ptq

Q4 2013

petroleum technology quarterly

refining
gas processing
petrochemicals

special features

Gas Processing Developments

Mass Transfer

cover and spine copy 17.indd 1 13/09/2013 17:02

 1221_e

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09.07.13 09:16
 ptq
PETROLEUM TECHNOLOGY QUARTERLY

3 Decision time for cellulosics
Chris Cunningham

5 ptq&a

17 Towards a zero gasoline production refinery: part 2

Blasis Stamateris Foster Wheeler
Dan Gillis Foster Wheeler, USA

29 Minimising transfer line vibrations

Rahul Patil, Randheer Yadav, Ajay Gupta and Asit Das Reliance Industries Ltd, Jamnagar
Q4 (Oct, Nov, Dec) 2013
www.eptq.com 39 High-acid crude processing enabled by unique use of computational fluid dynamics
Dr Collin Cross GE Water & Process Technologies

51 Processing strategies for metallic and high-acid crudes

Vivek Srinivasan, Mahesh Subramaniyam and Parag Shah Dorf Ketal Chemicals

59 Maintaining reliability when processing opportunity crudes

Eric Vetters and Dannie Clarida CorrMat International

69 How glycols affect acid gas removal

Torsten Katz, Georg Sieder and Justin Hearn BASF SE

81 Extending the treatment of highly sour gases: part 1

François Lallemand, Gauthier Perdu and Laurent Normand Prosernat
Claire Weiss Total EP
Julia Magne-Drisch and Sebastien Gonnard IFP Energies nouvelles

91 Gasification for hydrogen supply

Max-Michael Weiss, Helmut Heurich, Delphine Roma and Stefan Walter
Air Liquide Global E&C Solutions/Lurgi GmbH

99 Catalyst raises kero-treating performance

Woo Kyung Kim SK Innovation
Jessy Trucko and Eric Baker UOP, A Honeywell Company

103 Refinery power failures: causes, costs and solutions: part 2

William H Graf, William F Vukovich and Thomas W Yeung
Hydrocarbon Publishing Company

113 Heat integration projects for refining processes

Alişan Dogăn Turkish Petroleum Refineries Corporation

123 Applying pinch technology to energy recovery

Farbod Rikhtegar Iranian Fuel Conservation Company
Sepehr Sadighi Research Institute of Petroleum Industry

131 Multistage reaction catalyst with advanced metals tolerance

Yves-Alain Jollien Tamoil
Jeremy Mayol, Vasileios Komvokis and Carl Keeley Basf

139 Mitigating fouling in the caustic tower

Hua Mo and David Dixon Baker Hughes
Lowell Sykes Westlake Vinyls

145 Gasoline benzene reduction

El-Mekki El-Malki and Benjamin Umansky ExxonMobil Research and Engineering Company
Erik Moy, Grant Donahoe and Timothy Thom Badger Licensing

149 Technology in Action

Air Products’ Baytown, Texas, plant supplies hydrogen and other industrial gases to the regional refining industry.
Photo: Air Products

©2013. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means – electronic,
mechanical, photocopying, recording or otherwise – without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly the publisher cannot be held responsible for any
statements, opinions or views or for any inaccuracies.

ed com copy 2.indd 1 16/09/2013 12:50

 KBC Adv - PTQ Q4.pdf 1 9/9/2013 2:57:29 PM

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 p
T tq
he European Union has arguably
been the global leader in biodiesel
production and use, with overall
biodiesel production increasing from 1.9
PETROLEtonnes
million UM TECinHN2004
OLOGto
Y Qnearly
UARTE10.3
RLY million
tonnes in 2007. Biodiesel production in the
Decision time for
cellulosics
US has also increased dramatically in the
past fewNo
Vol 18 years
5 from 2 million gallons in
2000 to approximately 450 million gallons
Q4 (Oct, Nov, Dec) 2013
in 2007. According to the National Biodiesel

B
Board, 171 companies own biodiesel ack in 2008, there was a whiff of optimism in the air about the future of
manufacturing
Editor plants and are actively cellulosic biofuels and their role in the future of lower-carbon transportation.
marketing biodiesel.1. The global biodiesel
Chris Cunningham However, the cost of bringing second-generation biofuels to market, and
market is estimated to reach 37 billion
editor@petroleumtechnology.com uncertainties about the future of more conventional forms of biofuels, have
gallons by 2016, with an average annual dampened that enthusiasm. The coming 12 months looks to be a determining
Production
growth rateEditor
of 42%. Europe will continue to period for an industry based on fuel from farm waste and low-value crops.
Rachel Storry
be the major biodiesel market for the next A vote in September by the European parliament delivered a compromise on
production@petroleumtechnology.com
decade, followed closely by the US market. the future of biofuels, which amounts to a 6% cap on the contribution of biofu-
Although
Graphics Editor high energy prices, els to the regional renewable transport energy target of 10% by 2020. Although
increasing
Rob Fris global demand, drought the 6% cap represents an increase on the current 4.5%, a subsequent vote by
and other factors are the primary
graphics@petroleumtechnology.com MEPs on the issue of production of biofuels versus destruction of forests came
drivers for higher food prices, food down in favour of landscapes. They also backed a 2.5% target for the contribu-
Editorial
competitive feedstocks have long tion of second-generation biofuels made from non-food sources.
tel +44 844 5888 773
been and will continue to be a major From 2020, the debate on biofuels will take into account the impact caused
fax +44 844 5888 667
concern for the development of biofu- by switching swathes of crops from food output to biofuels production, not
els. To Development
Business compete, Director
the industry has so much in Europe as in developing regions, where demand for diesel —
responded
Paul Mason by developing methods to and, therefore, for biodiesel — from Europe leads farmers to clear forests.
increase process efficiency, utilise or
sales@petroleumtechnology.com This indirect land use change (iLUC) is said to have a net negative effect on
upgrade by-products and operate carbon dioxide higher than that of the fossil fuels that are being replaced.
Advertising
with Sales quality
lower lipids as Although biofuels producers dispute this, if it becomes a factor in EU policy
Bob Aldridge
feedstocks. then a further boost for producers of fuel from waste and biomass is implied.
sales@petroleumtechnology.com
Meanwhile, in the US, the Environmental Protection Agency issued its final
Feedstocks
Advertising Sales Office rule for the 2013 Renewable Fuel Standard (RFS) programme year. The rule
Biodiesel
tel +44 844refers to a diesel-equivalent
5888 771 sets a 6 million gallon target for cellulosic biofuels production in 2013, less
fuel consisting
fax +44 844 5888 662of short-chain alkyl than half the level in the proposed rule issued in February 2013, and barely
(methyl or ethyl) esters, made by the comparable to the 1 billion gallon target set in the Energy Independence and
Publisher
transesterification of triglycerides, Security Act of 2007.
Nic Allen
commonly known as vegetable oils or The issue of bioethanol is a lot more contentious in the US compared with
publisher@petroleumtechnology.com
animal fats. The most common form Europe. Significant numbers of legislators, encouraged by energetic lobbying,
uses methanol, the cheapest alcohol
Circulation would actually like to see the RFS repealed altogether. While that seems
available,
Jacki Watts to produce methyl esters. unlikely for now, opposition to the standard is hardly lessened by the system
The molecules in biodiesel are pri-
circulation@petroleumtechnology.com of credits, which refiners buy when they cannot meet blending quotas.
marily fatty acid methyl esters The RFS led to a compliance system in which refiners must submit credits
Crambeth Allen
(FAME), Publishing
usually createdLtd by trans- to prove that the required amount of renewable fuel is used or paid for by
Hopesay, Craven Arms SY7 8HD, UK
esterification between fats and metha- them each year. These credits, Renewable Identification Numbers (RIN), can
tel +44 844 5888 776
nol.
fax +44Currently,
844 5888 667 biodiesel is produced be bought or sold like commodities. Both refiners and blenders acquire RINs
from various vegetable and plant oils. by either blending the renewable fuel or buying credits in lieu of blending.
First-generation food-based feedstocks The cost of RINs has rocketed from an initially modest level.
are straight vegetable oils such as The original optimism for cellulosic biofuels may not be what it was, but
ptq (Petroleum Technology Quarterly) (ISSN
soybean
No: 1632-363X,oilUSPS
and animal
No: 014-781) fats such as
is published efforts to develop them are going ahead. A handful of companies are at the
tallow, lard,
quarterly plus yellow
annual Catalysisgrease, chicken fat
edition by Crambeth late stages of developing industrial-scale plants and some are already pro-
Allen Publishing Ltd and is distributed in the US
and the by-products of the
by SP/Asendia, 17B South Middlesex Avenue, production ducing small quantities. However, there is a further cloud on the horizon. As
of Omega-3
Monroe fatty acids
NJ 08831. Periodicals postagefrom fish oil.
paid at New producers of cellulosic ethanol prepare to enter the market at full scale,
Brunswick, NJ. Postmaster: send address changes to
Soybean
ptq (Petroleumoil and rapeseeds
Technology Quarterly), 17B oil
Southare the demand for fuel in any form is still falling as a result of increasingly efficient
common source
Middlesex Avenue, Monroefor biodiesel produc-
NJ 08831. engine technology and remaining economic weakness.
Back numbers available from the Publisher
tion
at $30 in theincUS
per copy and Europe in quanti-
postage. While only few years ago it appeared that the issues of replaced food crops
ties that can produce enough biodie- and deforestation would be short-lived when second-generation biofuels
sel to be used in a commercial market moved to centre stage, the reality, for now, is quite different.
with currently applicable
chris cunningham

PTQ Q4 2013 3

ed com copy 2.indd 2 13/09/2013 17:03

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 ptq&a
Q What is the best choice of packing material for minimal
liquid hold-up in a distillation column?
A Pat Quotson, Packing Product Manager, Koch-Glitsch,
Pat.Quotson@KochGlitsch.com
Liquid hold-up in a packed bed is a function of the
packing surface area, packing surface texturing, shape
of the packing, liquid viscosity and liquid rate. Surface
tension has only a moderate effect on the liquid
hold-up, and the vapour rate has little effect on the
liquid hold-up below the loading point of the packing.
At vapour rates higher than the loading point, the
vapour rate has an appreciable effect on the liquid
hold-up. Considering only the packing characteristics,
we can make the following generalisations:
• Liquid hold-up in random packing increases with
decreasing packing size
• Liquid hold-up in structured packing increases as
the surface area of the packing is increased. An
increase in surface area is generally equivalent to a
decrease in the crimp height
• Liquid hold-up in structured packing increases with
more aggressive surface texturing.
When trying to minimise the overall liquid hold-up,
structured packing with the largest crimp (lowest
surface area) that will satisfy the separation require-
ments should be used. Structured packing can be made
with no surface texturing to reduce the liquid hold–up;
however, omitting the surface texturing will reduce the
separation efficiency of the packing.
A Mark Pilling, Manager of Technology Applications & Process
Technology, Sulzer Chemtech USA, mark.pilling@sulzer.com
Studies by Suess and Spiegel, Hold-up of MellapakTM
Structured Packings, published in Chemical and
Engineering Progress in 1992, provides a correlation of
liquid hold-up as a function of liquid load, liquid
viscosity and the specific surface area for Mellapak. An
interesting observation was that the packing corruga-
tion angle (“Y” packings have an angle of 45 degrees
[from vertical] and “X” packings have an angle of 30
degrees) did not play a large part in the liquid
hold-up. The reason is that the liquid film is driven by
gravity and therefore the packing corrugation angle
has little impact on the liquid flow path below the
hydraulic loading point.
It should be noted that liquid hold-up is always
proportional to the packing height and thus the opti-
mal solution has to include the packing efficiency.
Also, although the packing corrugation angle does not
strongly affect hold-up, we do know that it plays a
significant role in efficiency.
In order to find the optimal technical solution, the
reason for the minimisation of liquid hold-up must be
known. Reasons could be:
www.eptq.com
Q&A copy 15.indd 1
• Minimising the residence time to avoid thermal or
chemical degradation
• Minimising liquid inventory for safety reasons
• Minimising start-up time to achieve steady state
• Dynamics of process control.
Therefore, the optimal packing type can vary from
case to case, but we can still say the following:
• In low to moderate vapour loaded applications, the
use of a Y-angled packing with the lowest installed
surface area is the best option. In this operating range,
the vapour load will have no relevant impact on the
liquid hold-up
• In highly vapour loaded applications, the use of a
high-performance, S-shaped packing, such as Sulzer
MellapakPlus, will have the lowest liquid hold-up. In
this operating range, the vapour load impacts the liquid
hold-up. For highly loaded applications, the high-
performance packing delays the onset of flooding and
so minimises the liquid hold-up in the packing itself.
A Jeremy Brauer, Packing Technology Leader, Separation &
Heat Transfer Products, UOP, A Honeywell Company, Jeremy.
Brauer@Honeywell.com
Structured packing has a lower liquid hold-up than
random packing, compared on the basis of equivalent
specific surface area. Within structured packing, the
liquid easily trickles down in the form of a film, which
results in a low residence time. This is important for
heat-sensitive products and is often used in vacuum
distillation to reduce temperature. In terms of random
packing, the liquid is guided downwards along the
individual metal surfaces in various directions, which
slows down the velocity and increases the liquid
hold-up. This enhances the absorption capacity
of a process solvent and is important in chemically
reacting systems, where the heat of reaction has to be
absorbed.
Q In what circumstances does partial oxidation compete
economically with continuous catalytic steam reforming in
hydrogen production?
A Ludo Boot, Market Development Manager, Albemarle, ludo.
boot@albemarle.com
Two technologies for partial oxidation exist: catalytic
partial oxidation (CPO) and non-catalytic partial
oxidation (POX). Of these two, POX has found wider
commercial success for producing syngas because of its
recognised ability to handle heavier hydrocarbons that
can also contain higher amounts of sulphur. However,
CPO is still being evaluated as a viable technology
for producing hydrogen. In principle, CPO is
less energy intensive, produces less CO2 overall and
can be applied at a smaller scale when needed. But
PTQ Q4 2013 5
12/09/2013 13:23
 PTQ&A copy 1 8/3/06 21:12 Page 3

A Luigi Bressan, Director of Process and Technologies, QUESTIONS & ANSWERS

challenges remain in process configuration, catalyst content of 5-8 wt% largely present in the unstripped Foster
Typical nitrogen balance: wt% feed nitrogen to FCC products
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erties and stripper efficiency. CokeReferences
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Q of coke combustion adequacy available testing and monitoring
presented configurations and catalysts to meet the Margaret Stin
reduced for
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corrosion
polycyclic rates by more
aromatic of existing
structures refinery Temperature
containing withWe particularly
are maximising programmed corrosive
propylene crudes.
in the FCC
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(TPO) would
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steam reformers by adding a CPO 1 Houlton
unit, whichG, Crude demand
is growing demand
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paraffin exchanger trains. What equipment re
than 80% inand
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study have coke been
xylenes used
combustion.
experience successfully
production In
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the more TPO in
ourthan these
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gasoline.
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in store, can be done to lower the equipment cost, such as the
Oil and Gas Journal, uop.com: Th
always
with aa smaller
TAN investment
of 5.0 mgKOH/g. in terms of(for size and capi- What tions, but
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Although coke may tobesteam
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Stuart such
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Foskett, BASF Mumbai
product sections,
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Technical
University.
line manager, have
Manager,
Axens, an innate
Stuart.
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most ofdramatic,
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Foskett@BASF.com
domergue@axens.net: due to Email: their higher
Gasoline thickness.
oxygenspecifications
paragshah@dorfketal.com
(and optionally Some are otherheavy,
getting some
processsuccess;
all f
There
tighteris when only limited
it comes flexibility
selected gases). The temperature is ramped (at, say,
to octane,when sulphur, adjusting olefins the and hydrocarbons
stripping. Ho
aromatics yield in FCC gasoline. Increasing the catalyst coupled
with somewith dif
15°C/min) to 730°C, then held isothermally. reach high iso
rare earth content
Combustion flue gases results areincontinuously
a small increase in aromat-
monitored by For vacuum
efficient and d
The Premium Alternative ics by hydrogen
infrared and mass spectroscopy.
isTheopposite
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Par-Isom
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in Process Simulation ene, where
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hydrogen
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species evolved
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generation
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converting an
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preserve olefins from cracking
starts at very low temperatures, already around 450°C by ZSM-5 to propylene. section, trays
is required, be
Otherwise,
(780°F). At this simply operating the
low temperature, the unit rate of to conversion
maximise major packing
tured equipm
additionaldrop fee
of HCN to thermodynamically more stable NO or Nand
conversion will enhance both the propylene yield
2
is pressure
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the highest-ac
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increasing the propylene
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concentra- 1. A case with
from water or cru
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as NO increases. for this are Thethe HCN cyclisation
is no longer reac- subject to foul
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stable enough to survive so it and subsequent N in olefins, although less clear, Stephan Zu
commercial
coke are converted data also intosuggest
NO or N a .possible
Despite being increase ther- in isomerisation
total aromatics associated with 2
a higher propylene Q
zuijdendorp@
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modynamically unstable under FCC regenerator chlorinated al
yield and/or
conditions, NZSM-5.
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2 platinum inve
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Since aromatics not crack, that FCC N2gasoline
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will also increase
reactive intermediate in the formation of NO. with a higher mono-aromatics A Girish
ATIS K In
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For units of the with a feed hydro-
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design, and
from 3 vol% to 4 vol% increases the rateorofseeking
treater, increasing the hydrotreating severity HCN improvements
Company, giris
catalysts with
conversion greater activity
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aromatics of NO saturation
in flue
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increase, with
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multi-ring
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interest. The l
will
These alsosimpleincrease. experiments show that HCN is readily clean fuels m
compensated b
Some
formed during coke refiners believe that higher
combustion at low aromatics temperatures, produc- heavier crudes
by cracking.
tion can
After be
you achieved
have
especially if oxygen concentrations used by processing
KIDExtractorFCC Ltd. gasoline Historically
P.O. Box are high at these
11, Zebbug
through it thethe first time, the
reformer, typically atemperature
heart-cut (170-300°F,
❝
hydrogen from
low temperatures. Once theMALTA is high With th
Kid Extractor
76-149°C). FCC will
gasoline is Tel.a poor
00356-21-462891 reformer feed, octane-e
gasoline produ
enough, the HCN becomes Fax. unstable and is readily
with become
higher your
nitrogen trusty and N+2A 00356-21-462755
than straight-run feedstock
gen demand.for
converted to NOx or N2. MOBILE: 00356-94-20596 what opport
feed, hydraulic-tube-
and olefinsof that must E-mail: be saturated in the has advanced
The implication
bundle-extractor this is that theidrojet@videobank.it
points of greatest capacity an
hydrotreater. Website: www.kidextractor.com
hydrogen
HCN formation in the FCC regenerator are likely to be similar to Figy
pressures,1,2 it

6 PTQ Q4 2013
ENQUIRY NO 214 www.eptq.com
82 PTQ Q2 2013 www.ptqenquiry.com www.eptq.com
www.eptq.com 8 PTQ Q3 2012 PTQ Q3 2013 18
121
P T Q Q2 2006

Q&A copy 15.indd 2 16/09/2013 13:55

j matthey.indd 2 11/03/2013 13:02
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8/20/2013 11:43
10:40:32 AM

0.70
0.65
wt% of fresh feed
0.60
Benzene yield,
0.55
0.50
0.45
0.40
0.35
0.30
4 5 6 7 8 9
Propylene yield, wt%
Figure 1 Commercial FCC data
Q We’re experiencing severe fouling in our FCC slurry/feed
exchangers, resulting in lost production during the exchangers’
regular downtime for cleaning operations. Is there a chemical
treatment we could use to eliminate the fouling on-line?
A Bruce Wright, Senior Technical Engineer, Baker Hughes,
Bruce.Wright@BakerHughes.com
FCC slurry pumparound exchanger fouling is quite
common and may result in severe economic penalties
for refiners. Deposits develop from two main interre-
lated mechanisms: agglomeration and deposition of
catalyst fines, and polynuclear aromatic compounds
(PNAs). There are additives that can be highly effective
in reducing the rate of normal fouling inside the heat
exchanger tubes in these units. Dispersants, asphaltene
stabilisers and various other chemistries interfere with
the recombination reactions of the PNA molecules.
These formulations will not completely eliminate foul-
ing, but when applied properly and at effective dose
rates will significantly reduce the rate of fouling. Other
mitigation actions include the use of slurry filters,
mechanical changes to maximise the slurry velocity
through the exchangers, and the injection of light cycle
oil to increase the aromaticity of the slurry oil.
Further reading: Modeling of FCC unit main fractionator bottoms
pumparound fouling, NPRA AM, 1995, Falker, Duggan AM-95-71.
A Stuart Foskett, BASF Regional Technical Manager, Stuart.
Foskett@BASF.com
Although not stated here, it is more common for foul-
ing in slurry/feed exchangers to occur on the slurry
side, which is usually the tube side. Fouling in slurry
exchangers is usually preventable. Slurry exchanger
fouling can occur by two mechanisms: tube blockage
by hard coke, or fouling by soft coke (asphaltenes).
Pieces of hard coke can be found in the slurry circuit
as a result of thermal cracking, typically due to high
temperature at a long residence time in the boot of the
main column. Coke formation can be controlled by
limiting the main column bottoms temperature.
Common operating limits in industry vary between
650°F and 680°F. Exchanger fouling by hard coke can
also be reduced by designing exchangers with 1-inch
tubes and higher tube velocity up to 12 ft/sec, install-
ing coke catching baskets in the exchanger heads and
8 PTQ Q4 2013 www.eptq.com
Q&A copy 15.indd 3
coke strainers in the suction line of the slurry pumps.
Fouling by asphaltene precipitation is an instability
of asphaltene solubility in the slurry, which can be
addressed by adjusting the cut-point between slurry
and cycle oil in the main column. Slurry viscosity is a
good control variable for preventing soft coke fouling,
with 15 cSt at 100°C being a common operating limit.
There have been many reported instances of anti-
fouling chemicals being used successfully in the slurry
circuit, generally to control soft coke fouling. With
chemical control of fouling, it may be possible to opti-
mise unit economics (for example, increasing the slurry
cut-point), and chemical control should only be consid-
ered once the operating conditions of the slurry circuit
have been reviewed properly.
A Xiomara Price, Global COE (Center of Excellence) Leader –
Fouling Control, GE Power&Water, Xiomara.Price@ge.com
Fouling in an FCC unit slurry pumparound loop is a
complex phenomenon that can cause significant opera-
tional problems. Slurry oil undergoes cracking and
recombination reactions every time it is returned to the
main fractionator to quench the hot gases that enter
the column at >950°F (510°C). In addition to the
temperature extremes experienced by the slurry liquid,
the catalyst fines still contain active cracking sites. As a
result of the temperature extremes and cat fines load-
ing, slurry circulating systems are often prone to
fouling. The slurry oil contains high molecular weight
aromatic compounds, a small amount of high molecu-
lar weight straight- and branched-chain alkanes,
asphaltenes, unsaturates, corrosion by-products and
catalyst fines. These materials can contribute to fouling
in the slurry loop system. The recombination reactions
of high molecular weight cracked hydrocarbons will
create long-chain polymeric material that can lay down
and dehydrogenate over time. Catalyst fines in the
slurry oil can also initiate cracking reactions in the
quench zone of the main fractionator, although at
reduced rates compared to the reactions that take place
in the riser. These undesired cracking reactions
increase the amount of materials in the slurry oil that
can recombine into larger molecules. Catalyst fines can
also agglomerate into the slurry oil fouling deposits:
the higher the fines loading, the more possible
mass for deposition. Additionally, aliphatic side
chains can be cleaved off asphaltene compounds,
enabling the asphaltene cores to layer together and
further dehydrogenate as they grow and precipitate
out onto the exchanger surfaces. The coke precursors
can continue to grow and dehydrogenate to the point
where coke chunks are moving through the slurry
system.
In cases where mechanical and operational changes
are not enough to fully cope with the slurry loop foul-
ing, GE Water & Process Technologies has successfully
provided slurry loop chemical treatment solutions to the
refining industry for more than 30 years. Due to the
multiple mechanisms involved in this type of system,
multifunctional products are often necessary. GE’s
Thermoflo antifoulant products consist of many
12/09/2013 13:25
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his words were Dmitry
nitrogen
Balandin
developers, the process
removal.
combinations of theThe
deliversof aFCC
extent
following
fuel yield
with improved
functionalities, improve-
selected to
“adequate
conversion organisation
catalyst suchof asdocumentation,
slurry oil circuit keeps the slurry heat exchangers in an amorphousboth in
silica-
e an end to the Chief Financial
performance
ments
Officer
over more conventional biodiesel and terms of management and data traceability”.
addresswere often
the driving amechanisms
function of desired
specific operational
to each system: alumina
excellent(ASA) or zeolite.
condition and allows the refiner to optimise
has persisted Gazprom Neftekhim
petroleum-based Salavat
diesel, including a cetane value of
cycle life and available hydrogen for the pretreat units. 80 Depending on the conversion and distillate selectiv-
• High-temperature organic and inorganic dispersant the heat recovery from the FCC main fractionator
hopeful that in compared with a cetane range of 40-60 in retail diesel.
Hydroprocessing
• Polymerisation catalyst inhibitorsystems were developed util- ity required,
bottom stream. all alumina, alumina/ASA or alumina/

W
dvance a true Eni
ising says
• Cokecobalt
e that are theliving
decision through
to
inhibitormolybdenum (CoMo) and nickel
convert the Venice site Petrochems
zeolite stacked from systems coal can be considered. Higher
recognises the to the difficult economic
production of renewable times.biofuels is aobjectives
response A
molybdenum
• Metal deactivator. (NiMo), depending on these conversions
Dharmeshcan be achieved
Panchal, Senior FCCby usingTechnologist,
Process alumina/ASA UOP
resources and Despite Union’sthis, theRenewablemarket Energy Directive, China’s Jiutai Energy
to
and the European
GEconstraints.
Water & Process Technologies’ analytical and stacks and
Ltd, Technology higher (Zhungeer)
evenServices, has licensed UOP’s
by using alumina/zeolite
Dharmesh.Panchal@Honeywell.com stacks
in rebuilding for
which oilmandates
and gasthat, production in of its 27 member methanol-to-olefins technology to convert methanola
In today’s
technical expertise fuelbyoperations,
clean enables 2020, 20%
us to provide much investment
effective treat- compared
Use of chemical to a total aluminatosystem.
additives mitigateIn main specifying
column
Russia
states’ remains
energy stable. The main from coal into key petrochemicals. The Hydro MTO
has
ment been mademust
solutions infor come and
ULSD fromFCC
FCC unit
renewable
naphtha
slurry
sources,
loopHDS, and
with
fouling. MHC
bottoms catalyst
circuit system,
fouling the has balance
generated of mixed
hydrotreating
results.
ly and friend source
greenhouse of thisgases stability
must be is high by 20%.
reduced process converts methanol from gasified coal or natu-
few refinersisnow
Thermoflo a mark achieving
of GE Power environmental
& Water. compliance versus
Applicationcracking catalyst and
of chemical additivesthe potential
is very unit addition
specificof
ources capable oilTheprices,
Venice whichrefinery allow
has a pretreatOJSC history of establish-
recent ral gas to produce ethylene and propylene. The
via previously designed units. Additional reactor
and willvolume dependis largely largely oninfluenced
the slurrybycomposition.
feed qualities In
prosperity and “Gazprom
ing Neftekhim
its ofgreen
A Berthold Salavat”Asandpart of an energy
credentials. technology enables producers in China, the world’s
results theOtzisk,
global drive towards
Consulting Engineer, clean fuels
Kurita are
Europe, and
casesthe desired
where theylevel haveofsucceeded,
conversion. As many
optimum of the
chemical
within the next other major programme
market participants largest miner of coal,
conservation
continued
otzisk@kurita.de advances in catalyst called technology
Stella Polare, thatit have
was feeds
additive processed areto high
injection concentrations
tap local in resources,
contaminant
have
rather
been reported
than
metals, in
panding shale to
the achieve
first in positive
Europe to margins.
obtain ISO The 16001
domestic market still
Certification for more expensive petroleum, to produce petrochemicals.
provided
Fouling insignificant
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system is and
caused HDN by sulphur
the 5-10 and wppm nitrogen,
range. the pretreat section
A reputable chemical is required
additive
the attacks on tends
its to
energy be influenced
management by the
system. activities of government Jiutai willthese produce 600 000 t/yensure of ethylene and
performance.
condensation These technologydehydrogenated
of asphaltenes, gains are being utilised polynu- to remove
supplier will request contaminates
a sample to of the slurry a sufficient
product
able feedstocks and The the regulatory
refinery waspretreat authorities,
selected for a pilotin particular
programme theto propylene at its facility in Ordos City, Inner Mongolia
to drive
clear new FCC
aromatics (PNAs) ordesigns to very
agglomeration high levels
of catalyst cycle life can tests
and perform be maintained while both
(stability, ability meeting
to reduce any
fouling
nd increasing measures
define government
methods to be takes
extended to toreduce
all of domestic
Eni’s industrialfuel Province, China.and In addition to nitrogen
technology licensing,
of performance
fines and coke and have particles provided refiners
(solids). with the
Destabilised product
tendency,targets and so on) minimising
to determine whatslip into theif
additive,
prices. During the second half of 2011, the government UOP willsection
provideofbasic engineering,
plants.
option
asphaltenesof revisiting
act as how glue best and to maximise
mortar the value the
in hardening of cracking
any, is suitable. the reactor. Feed catalysts,
quality and adsor-
the
L Pipeline, the implemented a new exportofduty the system (so-called “60- bents, speciality equipment, technical
The primary
existing
deposits.FCC
objective
pretreat
Deposition units. This
of asphaltenes,
project
has resultedis to in
solids and
identify
many
poly- reactor
UOP and catalyst system
recommends adhering specified determine and
services
to established the
and
the nation that 66”), whichthat benefits leadthe to upstream industry, but is less training for the project, which isremoval expected to start up
actions
units
mers can shifting willcatalyst
be controlled
asystem
by
reduction
the addition
in direct
designs of in
and
orderindi-
Kurita’s FCCto ultimate
widely proven sulphur and nitrogen
means to mitigate MCBcapability
fouling. These forina
domestic jobs advantageous
rect consumption for companies
as ofwell within
as energy-saving the downstream 2014.
provide higher levels
slurry antifoulants. nitrogen removal and measures aromatic given
provisions cycleinclude:
life. HDS functionality can remain an
mportantly, the sector.
through Thanks
the to ourof broad market appeal and The methanol-to-olefins (MTO) process was jointly
saturation by adoption
These antifoulants using more innovative
havehigh-activity
a high thermal
techniques.
NiMo catalysts,
stability
The
and important
• Reducingcriteria net lightfor somecycle MHC oil draw units to depending
shift slurry on
that the US is high-quality
certifying bodyofferings,
for ISOGazprom16001, Neftekhim
DNV, Salavat
highlighted developed by UOP and INEOS and converts methanol
maximising
excellent dispersingFCC conversionpower. Coke capability.
particles and catalyst existing
composition product specifications,
and reduce bottoms which temperatureare dependent
ependence and is findingofthe
elements export
the maximisation
Venice site’s and activities
domestic such markets to be
as manage- from crude oil and non-crude oilcapabilities.
sources such as coal
If distillate
fines are dispersed in the slurry, is desired, many
while polymerisation FCC on site
• Impose refinery constraints
an aggressive andand consistent However,
operations and
of ultimately profitable.
ment initiatives and activities aimed at operate reducing or natural gas to ethylene and propylene. The process
pretreat
is inhibited.units Kurita’s
can be revamped
FCC antifoulants to effectively are substitutes in HDN
laboratorycapability data is monitoring
often more important, program that as it tracks
influ-
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energy are challenges with thata resulting
Russian processfall in COindustry
emis- is based on UOP’s catalysts and isand saidperformance
to provide high
afor
MHC the mode.
naturalThis more
resins bysevere operation
surrounding theis asphaltenes
performed
2 ences
frequencycracking catalyst
of exchanger selection
clean-out. Examples include due
and political companies
sions. DNV operating in the oil
also temperatures
noted thatandand gas Venice
the market need refinery to yields with minimal byproducts. MTO can alsoreduce vary
with higher
molecules. reactor
This avoids destabilisation oftenof by modify-
asphaltenes to the remaining
monitoring nitrogen heteroatoms,
heat exchanger fouling rates,which frequency of
e for fuel and overcome
distinguished in the next
itselfsystem12 months.
for its to “excellent One key challenge
strategic evalua- is the relative quantities
ing
and the catalyst
precipitation of polymers, include
catalystafines more andactive
coke cracking
circulatingreactions.MCB pump As of propylenezeolite-containing
mentioned,
strainer cleaning,
and ethylene it
and daily
ent regulatory the high volatility of oil prices and
tion in identifying roles and responsibilities for the crack spreads for oil produces, so producers can adjust plant designs to
particles. A continuous antifoulant dosing into the products
tracking of can provide the
feed/slurry C7+ highest
insolubles,levelsAPI of conversion,
gravity and
ident Obama management of improvement objectives” and for the market
but theydemand.
viscosity tend to be the most sensitive to nitrogen slip,
ations to be UOP announced a similareffectiveness
project with in China’s Wison
reducing
• Maintaining their sufficient
long-term slurry circulation such
to thecases.
main
ic growth and (Nanjing) Clean Energy Company, which licensed the
Amorphous
column disk and silicadoughnut
alumina trays (ASA) cracking catalysts
till waiting. A first commercial-scale installation of the MTO process
provide
• Consider increased levels of
use of cooled nitrogen
slurry recycle tolerance
to sub-cool withthe a
needed to fix that combines the Hydro capabilityMTO process
lower
slurry level
pool of in conversion
the main column bottoms and, and the Total
for units with
htmare for the Petrochemicals/UOP Olefin Crackingpretreat Process. That
ry and an
merican public.
VAPOR PRESSURE limited
• Sustaining
project
can
HDN high
is expected
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severity,
and
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propylene.
capability,
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295
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PROCESS ANALYZER conversion
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sensible and (Comperj), a consider
major refinery andproblems
petrochemical
• Up to 2 Sample Streams should
Services.at least
Johnson some major
Matthey, Martin.Evans@matthey.com related
ut we believe construction project located in salts;
the city of Itaboraí,
• Adjustable Temperature to
Allwater
units composition:
experience some entrainedfouling, butentrained
in most caus- units
best be served Range: 20-60°C outside Rio de Janeiro.
tic;
this and
is notentrained
too muchsludge and sediments.
of a problem, and I am Entrained
not aware
enefit analyses The applications used impactwere on PDMS, Review and
• Adjustable V/L Ratio inorganics
of extensive, might if have
any, an use of antifoulants. the metallurgies
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ake sense and Global. JPNOR says that it selected the Aveva software
• Automatic Calibration the cutting
usually two tool,typescoke of drum and lines,
fouling together
in slurry with
circuit
because
potential of the flexibility and capacity of its object-
• Fast and Easy Maintenance exchangers:salts precipitation in the cutting tool’s
of Americans based data
• Automatic Lubrication nozzles.
• Coke “balls”Somestructures.
mitigation
blocking the
PDMS
of such and Review
tube phenomena
sheet. This is might were
usually be
resources and adopted as tools used at the individual project sites,
found in acidification
coke spalled from theand/or reactoranti-scalant
overhead system injection, andbut is
on is blessed while Global helped
all of that
commonly needs
worsetoafter be engineers
carefully to perform integration
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es that could tasks
Alsoacross
more consider
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, enhance our and inspection.
icals might act Ifasit continues
lem diminishes. emulsifiers then and youcan needpotentially
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ong fuel and The integration of ofPDMS models from over 20
stabilise the frothing
the fractionator bottoms coke and
level particles,
temperaturepreventing/
(lower
The decisions designers and EPCs enabled JPNOR to provide daily
limiting
coke forming theirtendency)
precipitation in the water recovery
in 2013 will progress updates to customers including Petrobras.
system
• Coke and catalyst creatingdepositing
coke particles in tubes. carry-over in the
This is caused
represent and, Construction of the Comperj refinery and petrochem-
cutting
by inadequatetool, which, in turns,
velocity, and can creates be plugging
overcomeand by
ical complex is estimated to cost $8.4 billion and marks
Phone +43 1 282 16 27-0 | Fax +43 1 280 73 34
info.grabner-instruments@ametek.at | www.grabner-instruments.com
possible
increasing erosion/corrosion.
the flow rate in the circuit.

6 PTQ Q2 2013 PTQ Q1 2013 11 www.eptq.com

/IMJJ-+)*+
10 PTQ Q4 2013 ppp'^imj'\hf
www.eptq.com

case studies copy 7.indd 2 08/03/2013 11:21

Q&A copy 15.indd 4 10/12/12 13:05:23 13/09/2013 14:46
Q&A copy 12.indd 2 11/9/12 13:23:03
 Aim for More Diesel, Better Diesel
ExxonMobil’s MIDW TM* technology is a commercially
proven process using an advanced proprietary
catalyst for the production of ultra-low sulfur and
low cloud-point diesel.
Benefits include:
• Low-pressure, fixed bed process — improves product
yield and quality

• Increased sulfur removal and reduced naphtha yields

• Proprietary catalyst** isomerizes waxy n-paraffins in

gas oil, tolerant to H2S, ammonia, and organic S and N

• Stand-alone or integrate with others

ExxonMobil Research and Engineering

Company’s MIDW* Technology
Improves Product Yield and Quality

* MIDW is a trademark of ExxonMobil Research and Engineering Company

** Available from ExxonMobil Catalyst Technologies LLC

3225 Gallows Road, Fairfax, Virginia 22037-0001, USA

www.exxonmobil.com/refiningtechnologies • +1-703-846-2568 • fax +1-703-846-3872 • tsl.email@exxonmobil.com

exxon.indd 1 07/06/2013 09:56

clg.indd 1 11/09/2013 14:07
 Q What level of performance should I expect from a NOx-
reducing additive for the FCC regenerator compared with a

Partner with
hardware alternative? Should I expect to rely on a scrubber
as well?

A Solly Ismail, BASF Modeling Specialist, Solly.Ismail@BASF.

the Best
com
There are two very different technologies for address-
ing the NOx issue. The hardware approach is a
capital-intensive solution, while the use of additives
results in a relatively minor increase in operating costs.
Although hardware solutions such as selective cata-
lytic reduction (SCR) or an ozone-based scrubber
system can reduce NOx to very low levels, lower than
4 ppm NOx in the flue gas, the capital costs are in the
order of $30 million. Most refineries do not have to
achieve such low levels of NOx emissions, as the norm
in the US is around 20 ppm. Additionally, there are
operating costs for hardware solutions such a catalyst
changes and on-going operating costs like ammonia
that have to be considered.
Additives cannot achieve such low NOx levels, but
could adequately meet the needs of many refineries.
Added to this, the total cost is substantially lower.
Typically, refineries use 1% of NOx additives in their
circulating inventory and, if the refinery NOx objective
is met, this is a superior economic solution. Other
advantages of the additive solution are:
• Additives can be implemented rapidly
• Changes in additive dosage rates can be made at
short notice to suit the changing operating conditions
• Additives can also be used in conjunction with a
hardware solution to reduce total ownership costs.
With regard to the use of additives for NOx reduc-
tion, a two-step approach is the best possible solution.
This includes:
• Use of non-platinum-based CO promoters, which
prevent or reduce the generation of NOx
• Use of NOx additives to reduce the NOx already
generated.
It is now well established that NOx formation in the
regenerator is not due to thermal oxidation of air, but
stems from the nitrogenous compounds in the feed With over 50 independent subsidiar-
and ends up as NH3 or HCN in the coke en route to ies and more than 220 engineering
the regenerator. These two compounds, ammonia and sales offices spread across the
(NH3) and hydrogen cyanide (HCN), are then oxidised world, SAMSON ensures the safety
to form NOx. As there is a large quantity of CO pres- and environmental compatibility of
ent in the regenerator, most of the NOx is chemically your plants on any continent.
reduced to inert nitrogen (N2), while the CO is
oxidised to CO2. On average, only 5 to 10% of NH3 and To offer the full range of high-quality
HCN, which is converted into NOx, remains unre- control equipment used in industrial
duced (to N2) and exits the regenerator in the flue processes, SAMSON has brought
gases. It is this small amount of NOx that has to be together highly specialized compa-
further reduced by either hardware or additive nies to form the SAMSON GROUP.
solutions.
The conversion of NH3 and HCN into NOx is a
complex chemical process and is affected by a large
number of variables. Some of the variables affecting
the formation of NOx are excess O2 in the flue gas, CO SAMSON AG · MESS- UND REGELTECHNIK
Weismüllerstraße 3
level in the flue gas, use of platinum CO promoters, 60314 Frankfurt am Main · Germany
dense bed temperature, metals on e-cat, residence time Phone: +49 69 4009-0 · Fax: +49 69 4009-1507
E-mail: samson@samson.de
Internet: www.samson.de
A01120EN

SAMSON GROUP · www.samsongroup.net

www.eptq.com

Q&A copy 15.indd 5 13/09/2013 11:39

 in the dense bed, pressure of the regenerator and cata-
lyst circulation.
Suppliers such as BASF have worked with a number
of refineries to reduce their NOx levels in the flue
gases. Due to the complex nature of NOx chemistry, a
refiner is advised to work with suppliers like BASF
that not only supply well-proven, field- demonstrated
additives, but also have technical and analytic support
to ensure a successful conclusion.
A Nick Confuorto, DuPont Clean Technologies, Belco
Technologies Corporation, confuorto@belcotech.com
Belco Technologies Corporation markets and sells
(under licence from the Linde Group) the LoTO tech-
nology worldwide to reduce flue gas NOx emissions.
This technology can, in conjunction with the Belco
EDV scrubbing system, achieve the level of NOx
reduction that is typically required by oil refineries.
The process entails the on-site generation of ozone
(from oxygen), which is then injected at a predesigned
location in the Belco scrubber, where a specific resi-
dence time is provided for a reaction with NOx to
form a soluble type of N2O5. The N2O5 is then removed
by the scrubber nozzles and neutralised by the scrub-
ber’s alkaline solution. This process allows the user to
consistently and reliably reduce NOx down to below
the 20 ppm or 10 ppm presently required.
There are, however, occasions where the untreated
NOx level is considerably high and therefore the cost
of generating the required ozone also becomes high. In
those cases, it may be an advantage to consider
combining multiple NOx technologies, such as a NOx
reductive additive and LoTOx technology, to achieve a
more effective total NOx reduction. In this situation,
the user may want to also consider other technologies
(such as SNCR) in combination with LoTOx to see if a
more effective approach can be found.
A Charles Radcliffe, Technical Consultant, FCC and Refining,
Johnson Matthey, Charles.Radcliffe@matthey.com
The level you can achieve depends on where you start
from, what the excess O2 is and what, if any, promoter is
being used. In a well-designed regenerator operating at
0.5-1.0% excess O2, with no CO promoter, a NOx level
of <50ppm should be achievable without additives. This
should be maintained with well-controlled additions of
a good non-Pt promoter such as Intercat’s COP-NP.
Q What is the best approach to capture heat from waste gas
incineration?
A Lorena Mosca, Technology Project Coordinator, KT- Kinetics
Technology, l.mosca@kt-met.it
Waste gas incineration poses the problem of a large
amount of heat to be recovered, since very high flow
rates and temperatures are involved. Depending on the
contaminants present and the composition of the waste
gas stream, thermal or catalytic incineration and
further treatment may be applied, and can vary from
case to case.
14 PTQ Q4 2013 www.eptq.com
Q&A copy 15.indd 6
Thermal incineration of acid gas streams, such as
those present at the tail gas of sulphur recovery units
or within gas processing plants, is typically operated in
a temperature range of 600 to 900°C and is realised by
combustion through special burners, under suitable
conditions of excess air and residence time within
combustion chambers.
Downstream of waste gas thermal incinerators there
is always a heat recovery unit, since the high-tempera-
ture effluent stream cannot be discharged as it is to the
atmosphere; the heat recovery is normally realised
through a heat transfer surface arranged inside the
refractory duct connecting the thermal incinerator with
the stack. Such a heat recovery surface operates under
natural draft conditions (flue gas side), with the gas
stream delivered through a stack to the atmosphere.
Due to temperature ranges and materials characteris-
tics, the most feasible and economic solution is to use
such a heat transfer surface for steam generation from
boiler feed water under natural draft conditions (with
the steam drum placed over the incinerator system).
The steam generated can also be superheated in a
separate bank, and sometimes steam superheating is
the only adopted heat recovery bank. Heat transfer
coils are realised as banks of tubes in Alloy 800H or SS
for the steam superheaters, and P11 or CS for the
steam generators, depending on the pressure and
temperature level of the steam produced. For the
smaller sizes, the heat recovery can be realised through
a kettle-type steam generator.
The cold end temperature of the waste gas stream is
fixed, considering a safe approach to the acid dew
point, which in this type of stream is normally high
(levels of 160-180°C are usual), as thermal incinerators
are designed to manage sulphur levels in the order of
a few per cent during plant upsets, depending on the
plant configuration upstream. On this basis, it is quite
normal to discharge the effluent stream in the range of
350-250°C and to avoid low-temperature heat recovery
such as the boiler feed water preheater or low-
pressure steam generation that would result in too low
skin temperatures.
To give an idea of the amounts, a waste gas stream of
about 250 t/h produces an incinerator effluent stream of
500 t/h and heat recovery of about 90 MW. Such large
amounts of heat are often available in industrial sites
like gas fields, oil fields and large refineries as a result of
waste gas treatment units. The most common and feasi-
ble solution to recover such heat amounts is, as said
above, steam generation. The level of temperature and
pressure, eventually more than one, may be fixed on the
basis of steam destination and, of course, on the site
utility network and the needs to be met.
In some cases, saturated or superheated HP steam or
MP steam is produced to be distributed to an industrial
complex nearby. One option is to generate
HP steam for electric power generation. Such an
option has to be evaluated economically on the basis of
site characteristics and economic background, and
becomes more attractive in cases where large heat quan-
tities are involved and economic incentives are present.
12/09/2013 13:24
 How Can KBR Answer Your
Refining Challenges?

Owners of refineries continue to confront

many challenges – rising feedstock prices,
shrinking margins, varying global demands
and a changing regulatory landscape that
includes ever-more stringent specifications
on sulfur and carbon footprints. As refinery
owners debottleneck and enhance existing
facilities, they call on KBR to deliver.
To learn how KBR can address your refining
challenges, go to:
refining.KBR.com/PTQ

refining.kbr.com / P TQ

K13009 © 2013 KBR, Inc. All Rights Reserved.

kbr.indd 1 08/03/2013 10:45


This exchanger has seen better crude slates
Nasty Stuff
Heavy crudes are here to stay.
As long as oil prices remain high,
Canadian, Venezuelan, Deep Water
Gulf of Mexico, Mexican and
other low API gravity crude oils
will play an ever more important
role in supplying world refineries.
And prices promise to remain high
because gainsayers notwithstanding,
Hubbert was right.
A big question is how to best handle
these nasty crudes? Do you
revamp existing units or invest in
new capacity? With refineries now
running flat out, the balance might
seem to favor grass roots expansion,
but given the substantial cost
multiplier over revamps, this could
pcs nasty.indd 1
be questioned. Whichever the case,
however, an inescapable fact is
that the process design of the project
will prove crucial. Between the
charge pump, the desalter and the
units' distillation columns there are
many places where miscalcula-
tions in the process design could
wreck the entire project.
Can you really be sure of attaining
desired crude rates? Desalting
viscous crude is extremely difficult.
Minimizing coking or asphaltene
precipitation in the heaters demands
extreme care. Can you reasonably
expect high diesel and HVGO
recoveries, acceptable levels of
nickel, vanadium, and microcarbon
3400 Bissonnet Ph: [1] (713) 665-7046
Suite 130 Fx: [1] (713) 665-7246
Houston, Texas 77005 info@revamps.com
USA www.revamps.com
residue (MCR)? Refiners who cut
deep should not be surprised when
the HVGO product MCR is over 2
wt % and the vanadium content is
in excess of 10 ppmw. Any one of
such difficulties can result in lower
revenue, unstable operation or
even unit shutdown. It is critical to
understand that the inherent
properties of these low API gravity
crudes dictate that exact process
design is of paramount importance.
The point of this litany of possible
problems is to remind you not to
skimp in the early phases of
engineering. From the start of the
LP work through the completion of
front-end process engineering,
actual product yield and qualities
depend on the process design.
The message is clear. Nasty crudes
will continue to make up an
increasing proportion of refineries'
crude slates. But time is precious.
The sooner we face this fact,
unwelcome as it may be, the more
expeditiously we can adapt.
For a more in depth review of
heavy crude challenges, ask us for
Technical Papers 173, 185 and
197.
1/6/12 11:58:35
 Towards a zero gasoline production
refinery: part 2
Refinery configurations can suit various processing objectives, such as variations to
the propylene-to-ethylene ratio and production of middle distillates and aromatics

BLASIS STAMATERIS Foster Wheeler, UK

DAN GILLIS Foster Wheeler, USA

T
he objective of this article is to
present alternative refinery
configurations that are able to
process relatively heavy crudes,
producing middle distillates, petro-
chemicals and aromatics, without
producing any gasoline at all. By
relying on well-proven refining
process technologies, the configura-
tions could be adapted to an
existing fluidised catalytic cracker
(FCC)-based refinery or used in a
grassroots project. The article illus-
trates options for integrating
products from the steam cracker,
aromatics complex and FCC unit
while rationalising investments.
Part 1 (PTQ, Q3 2013) presented
ways of upgrading streams
produced in refineries that have
traditionally been oriented towards
the production of transportation
fuels to petrochemicals. These solu-
tions may offer more attractive
returns and allow for diversifica-
tion of a refinery’s product slate.
The possibilities offered by the
streams from the FCC unit in terms
of propylene production and
aromatics production were also
illustrated.
The benefits of refinery and
petrochemical integration were
highlighted, in particular, diversify-
ing the product slate while
optimising capital costs, operating
costs and resources through fully
integrated production and shared
infrastructure for utilities supply
and offsites.
This second part outlines the
impact of these processes on the

LPG
Crude Heavy Benzene
Crude naphtha Aromatics
oil distillation SR naphtha Naphtha Naphtha
unit hydrotreater splitter Light complex Paraxylene
Kerosene
naphtha LPG
Diesel Fluidised
Raffinate catalytic
cracker Pygas
Kerosene Kerosene Steam naphtha
hydrotreater cracker Pygas Pygas and
Atmospheric catalytic
residue naphtha
Middle Diesel
hydrotreater
distillate
Propylene
hydrotreater
Diesel
Ethylene
ARDS Naphtha
Kerosene

Hydrotreated Diesel
residue C2 C4S
C3
C4
processing

Naphtha C 4S
To C4 sales
Propylene
Residue
fluidised Ethylene
catalytic
cracker

Diluted crude oil Light cycle oil

To fuel oil
sales

Figure 1 Refinery configuration with ARDS + RFCC

www.eptq.com PTQ Q4 2013 17

f wheeler.indd 1 12/09/2013 13:39

 LPG

Crude Heavy Benzene

Crude naphtha Aromatics
oil distillation SR naphtha Naphtha Naphtha
unit hydrotreater splitter Light complex Paraxylene
Kerosene
naphtha LPG
Diesel Fluidised
Raffinate catalytic
cracker Pygas
Kerosene Kerosene Steam naphtha
hydrotreater cracker Pygas Pygas and
Atmospheric catalytic
residue naphtha
Middle Diesel
hydrotreater
distillate
Propylene
hydrotreater Naphtha
Light Ethylene
vacuum LPG
gas oil Hydro- Kerosene Kerosene
cracker + diesel
Vacuum Diesel
distillation Kerosene
Heavy
unit vacuum + diesel
C2 C4S
gas oil Naphtha C3
Vacuum residue Diesel C4
Vacuum residue desulphurisation processing
Hydrotreater
residue
Naphtha C 4S
To C4 sales
Propylene
Residue
fluidised Ethylene
catalytic
cracker

Diluted crude oil Light cycle oil

To fuel oil
sales

Figure 2 Refinery configuration with HCU + VRDS + RFCC

product slate of the integrated
refinery/petrochemical complex for
different configurations.
Refinery configurations
A wide range of refinery configura-
tions for the production of
petrochemicals, aromatics and trans-
portation fuels has been studied.
Example material balances, devel-
oped with a linear programming
model, are presented to illustrate
ways to vary the product slate (C3=/
C2= ratio, aromatics, middle distil-
lates) and to demonstrate the effect
of C4s processing on the production
of propylene while optimising capi-
tal investment.
The basis for the cases presented
here are:
• Crude processing: 15 million t/y,
about 300 000 b/d
• Middle Eastern-type crudes of
around 28 API; capacities of process
units and/or product slates can be
adjusted to process heavier crudes
(17-22 API)
Complex configuration with
ARDS + RFCC
This configuration is typically used
for maximising gasoline and, more
recently, propylene yields from
atmospheric residues. For heavy
sour residues, such as those being
considered in this study, pretreating
the residue fluidised catalytic
cracker (RFCC) feed in an atmos-
pheric residue desulphurisation
(ARDS) unit is required to maximise
conversion to the desired products.
Figure 1 shows the schematic of a
refinery configuration, where an
ARDS unit is followed by the RFCC
unit.
The key feedstock properties that
impact the performance of an RFCC
unit are:
• Conradson carbon residue (CCR):
CCR is the main feed quality indica-
tor that affects the heat balance of
the reaction section, in particular the
regenerator temperature, which can
also affect the performance of the
catalyst (high temperatures produce
catalyst sintering with a negative
impact on yield pattern). The higher
the CCR content, the higher the coke
make and the higher the regenerator
temperature. For residues with a
CCR content under 8 wt%, the
RFCC unit could be equipped with
catalyst coolers to control the regen-
erator temperature
• Metals (mainly nickel and vana-
dium): these metals, especially
vanadium, reduce catalyst activity.
Additionally, nickel will non-
selectively crack the feed to undesir-
able light fractions. The higher the
metals content in the feed, the
higher the catalyst make-up to
maintain the high MAT activity
required to maximise the propylene
yield. (Note: Micro Activity Test
(MAT), defined by ASTM Procedure
D-3907, is widely used to determine
the relative activity and selectivity
of FCC catalysts for conversion of a
standard feedstock.)
• Hydrogen content: This affects
the RFCC feed’s conversion and

18 PTQ Q4 2013 www.eptq.com

f wheeler.indd 2 12/09/2013 13:40


Oil Sands Crude
– Profits and
Problems?
Canadian bitumen production
currently runs about 1 MMbpd,
with some being sold as Synbit
and Dilbit. Over the next 10-12
years output is expected to
increase to 3.5 MMbpd and more
refiners will begin investing to
process it and come to depend
on the Synbit and Dilbit for a
significant part of their supply.
Few today, however, have ever
processed these feeds at high
blend ratios, and are unaware
that conventional process and
equipment designs are not up
to the job. Canadian oil sands
PROCESS
CONSULTING
SERVICES,INC.
pcs 2.indd 1
feedstocks are extremely hard
to desalt, difficult to vaporize,
thermally unstable, corrosive, and
produce high di-olefin product
from the coker. If you intend to
lock into a long-term supply,
therefore, it is imperative that you
consider reliability and run length
from a particular design.
Too low tube velocity in the
vacuum heater tubes will lead to
precipitation of asphaltenes. Too
fast a flow rate will erode the
tube bends. If coil layout, burner
configuration and steam rate are
not correct, run length will be
measured in months, not years.
Diluent recovery unit designs
must take into account possible
3400 Bissonnet
Suite 130
Houston, Texas 77005
USA
upsets from water slugs and
other unpredictable situations
that have damaged internals,
resulting in diluent losses and
high vacuum unit overhead con-
densable oil. Diluent is neither
cheap nor plentiful, and high
vacuum column operating pres-
sure will reduce overall liquid
volume yields. And if the design
of the delayed coker fractionator
is based on today’s experience
with conventional heavy feed-
stocks you will be lucky to run
six months.
What all this means is that
special process and equipment
designs are needed to satisfy
the special demands of pro-
cessing oil sands crudes. Such
processes are not generated by
computer based designers who
have little or no experience and
never leave the office. They are
developed only by engineers
with know-how who have real
experience wearing Nomex® suits
and measuring true unit per-
formance in Northern Alberta.
Shouldn’t this be kept in mind
by those considering long term
supply agreements?
For a discussion of factors
involved in designing refinery units
to process difficult oil sands feed-
stocks, ask for Technical Papers
#234 and 238.
Ph: [1] (713) 665-7046
Fx: [1] (713) 665-7246
info@revamps.com
www.revamps.com
1/6/12 21:05:28
 yield selectivity, in particular the initial investment and on-going configuration of ARDS + RFCC, the
propylene yield. The higher the catalyst replacement cost will be LVGO fraction of the crude is
hydrogen content, the higher the much higher than for most hydro- routed to a VGO hydrocracker
propylene
communicate yield. where the module processing constructionunits. of refineries are being Company (HCU) for
promise to the
in shift
derivingUK,the yieldsfrom
I value
designed ina the
For
will the types ofoncrude
be installed the plot oil plan.
Ammonia thatgas applied
The other to the key construction
features of of this sourdesired
smaller water direction.
stripper that
accumulations Figure
of eliminated2 shows a
unconven-
have been considered to sulphur theplantconfiguration
Connections between thehere, modules distributed GTL toplants. maximiseThe GTLthe the schematic
unnecessary
tional gas that of would
the refinery.
features of the unit
otherwise be
requires
typical
are CCRincreased
designed content of process
to be similar atmospheric
in config-unit production
process involves of petrochemicals
two operations:are: the shown Thein keyFigure
left underground, 2.such as
features of shale
this gas,
refinery
capabilities
residues
uration inthat
is soabout a number
12-14 of13 PSIG
wt%,
construction refining
and is • Process straight-run
conversion of natural gas light tonaph- a tight Figuregas,3 shows
configuration coal bed the essentials
are: methane of and a
190ºF
process
relatively
metals units, particularity
are straightforward.
80-90 wtppm. Ventech hydro-
Thus, tha mixture along of carbon Temp. 1
with Temp. 2 Temp. 3 Temp.
monoxide
light (CO) check-
catalytic correctA sour
1 Temp.
stranded
• gas
vacuum water
1 Temp.
(gas2 tower stripper
Temp.
fields 3
located design.
is installed too to
processingthat, Sour The90ºFmagnitude
assets. Feed is brought in at ambient
estimates
pretreatment of withfeed
the
water modularisation,
is required. and hydrogen
naphtha (LCN)
60 in(Hthe
2
), steam
knowncracker as back
farproduce
from existing
a diesel-type pipeline infra-
cut to be
(15)
of impact, of course, depends on
The ARDS unit is a specially • Process heavy straight-run naph- processed in the distillatefrom conditions (70-100°F, 21-38°C)

Normalised HDS temperature,

approximately 70%
feed of a project is syngas, followed by a Fischer- structure). A small, modularised hydro-
the particular
already
designed complete
hydrotreater feedeven processed,
thatbefore
pretreats the thaTropsch
in a(FT) process reforming
50catalytic to convert the unit the
GTL sour
plantwater
treater, ahasLVGO feedcut
the tank.
flexibility
to be Toprocessed
toheat
be
inherent flexibility
modules are shipped of the from facility’s
their syngas into paraffinic hydrocarbons the feed from
installed close 90°F to (32°C)
the to 250°F
trapped
the feed to the RFCC unit to reduce (CRU) to produce reformate in a two-stage, almost full-conver-
operations
facility. This and greatly the ability field
decreases to that can 40be further refined to (120°C) requires
and then about to16process
wt%
contaminants including sulphur, • Process heavy catalytic naphtha resource sion hydrocracker used unit oriented
offset this increased
construction time to deliver an produce processing a wide range steam fl ow, or about
of that resource locally. Associated gas 1.3-1.4lb of
nitrogen, organometallic
requirement.facility (see Figure 1).
metals and (HCN), pygas and reformate towards
steam
the
per gallon
production of
of
stripper
middle
operational hydrocarbon-based
30 products, includ- (gas produced along with oil) is

ºF
(8)
CCR.In Additionally,
making this it increases the throughMedium the aromatics
content complex to distillates
These methods alsomove,
facilitate proper
easy ing clean-burning,
NH3 water to sulphur-free bottoms, another which area ofis close to a typical
opportunity for
hydrogen
selection content
disassembly requiresand of the atmos-
a relocation,
good under- if produce
diesel and paraxylene
hydrotreaters and benzene
20jet fuel. Speciality prod- design • Thestripping
modularised
HVGO GTL steam
is combined
plants. ratio This gas forwith
pheric residue,
standing and
necessary, thus
at some improving
modelling point of the • The
in the ucts including
(1) C 4
s with relatively
food-grade waxes, sour high vacuum residue
water disposed
is typically strippers.ofThe to be
either pretreated
E-1byfeed re- in
crackability
facility as and
well selectivity
as a strong of
knowl- the olefins content
10 are either
DN-3651
future. For example, a remotely solvents and lubricants can also be injection, at considerable expense, sold
alternative or the
preheater,
feed vacuum refl
DN-3551 ux residue
pump
alternative desulphurisa-
(P-2)
feed and
residue.
edge ofFor
located asources
typicaland
the processing
gas ARDS HDS recycled
processing
facility could produced to from the second DN-3651
the riser of the
current
paraffinic GOthe tion
back refl
into(VRDS)
uxDN-3551
cooler
the unit
current
(E-2)
reservoir before
GOorshown processing
by in
the
Base
rate
be of 90%,
requirements
easily the apart
taken CCRthe
of reduction
and available
moved is FCC
to (directly
E-1
hydrocarbons. or through oligomeri- Figure it in the
wasteful 2 are RFCC
and unit
all eliminated.
environmentally How,
about new 65-70%
acrudes. Withand
natural gasthe
the metals
continued
source exist- sation)
if anreduc-
devel- Large, tocommercial-scale
maximise
Steam propylene
Alternative GTL then,
feed • Depending
damaging does feedonof
one
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tionopment
ing (HDM
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was isdepleted
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in plants, including the Sasol Oryx and design
its production is combined
subject shown
to in Figure
vacuum
increasing 3 will and
residue
regulation.
Catalyst age
wt%.of such
currentThefeeds,HDT
location. thisRFCC
knowledge feed needs will • Products
the Shell Pearl from the RFCC
plants unit and work?
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enable unit, a
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lessto in Qatar),
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ery wt% minimal
6 construction
to desalters
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content of single mous
Figure 15capital
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light cost.
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recovery plant, to HDS
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temperature
could intotaken
be UK) and
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thanregard Reviewing
10 wtppm. to productivity, TBP curves prod-
P-1 designed for
produce production
ethylene levels of it In
and propylene, worked
the larger
diluents justeconomic
such asasRFCC wellpicture,as thea oil
decanted
and
uct bulk
quality properties
and ensuringof whole
Due to the feed rate, nature of the minimising the crude
safety 34 000 b/d,
2 Dekkers C, Daane cost around
the R,capital
Oil & Gas $1.5 billion
investment conventional
modular
J., 1999, 97, Max(DCO) GTL
Ovchinnikov design
capability
andis light
a Seniorcycle shown
can
Research be(LCO) in to
the
oilChemist
or
of
Figureeven
constructionthe individual
4 Two-stage personnel.
sour water stripper cut-point
Since the
design to build.
without
145. feedThe Shell
preheat Pearl plant, with Figure
key
with factor2. that
Criterion enables
Catalysts andthe construc-
Technologies
feed, and processing objectives, a • Hydrogen from the CRU and produce some fuel oil. The VRDS
ranges
modules are built doesin a well-lit, not 3anPuri ultimate
B K, Irgolicdesign capacity
Geochem.of 140 based
relatively high pressure and low steam cracker K J, Environ.
is supplemented Health,
by tionunitinofwould upstream
Houston, Texas. projects
then beHeable tothat
is primarily
reduce
increased
necessarily
climate-controlledwater in
characterise the thesulphur
feed
environment, 1989, Figure
000 b/d 1. ofInGTL
11, 95. otherproducts
words, and a lot120 of engaged
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would in otherwise
thesour water
research and stripper
be cancelled
development of
space velocity
plant feed and design
thusaround
more is required
condensa- further hydrogen production from the CCR to the levels requiredand by
difficulty
work can or indicate
continue the full clock 4equipment
theimpact b/d is added
NielseofB, Villadsen,
natural to
gasCat.,liquids,
Appl. 1984,generate Figure
because4forshows
cost catalysts
11, 123. of poor a sour
hydroprocessing results water strip-
derived
applications
compared
tionthe
on
regardless
to sulphur
other processing
in individual
the of weather
hydroprocessing
plantconditions,
feed NH3 steam
units. refl
5
around
reforming
(a)ux Internal
when no to
$18-19 communication,
billion.
be used
fractionation in isthe has
Criterion
Conventional perthe
from with
12 RFCC
years a of
economic side feed, especially
draw-off.
experience
models. The exam-when the
partly
in heterogeneous
For
technologies.
gas knock-out
for greater Even so,
drum (and
productivity the cycle
and easier hydrotreaters.
Catalysts
thus required & Technologies;
GTL plantbetween designs rely (b) Merryfield
the on feedecono- R N,
and strippedCCR
catalysis and
ple, some sour content
refining
shale water of the
technologies. feed
He
is extracted
gas discoveries has to the
co-
are
length
water of the
that ARDS
has to unit
be is
recycled typically
back Gardner
overhead L E, Parks G D, Catalyst
product. Again,
quality control. Since module height mies of scale to drive positive being hampered by high develop-
References Characterization
the only VRDS
authored
from tray unit
over 8 exceeds
20 andtechnicaldirected24 wt%.
publications to and
the
only
to onesour
the
isHenke
1 K year. water
R, Arsenic,
restricted, For
safety the
stripper).caseChemistry,
Environmental
is enhanced, evalu- Science, ACS configuration
as Complex
purpose
financial of
Symposium Series 1985,
the tower
returns and are with
is to 1.
strip
viable out holds
only
a PhD degree in organic chemistry from
hydrotreaters
ment costs, which for result
use as make-up
in marginal
6 Bhan O K, Arsenic removal catalyst and Iowa State University.
ated The and
Health
workers buildARDS
Threats
design and Waste
shown
at limited in operating
Treatment,
heights2 HCU
FigureWiley, the
whereNH + VRDSand
there +
the
are RFCC
H S.
large supplies
3 making same,2 US Patent 6759364. of Complex
water
economics in the configuration
duesalt to (NHgas 4
HS)priceswith
removal
that
2009, 186. at least method for
objectives,
was
within common
the fabrication in two the reactor
facility. 1960s. The intention
low-priced of this
natural gas.refinery config- step areSDA
often + DCU
of low. + HCU
theThese reactor + RFCC
projects effl
canuent.
be
trains,
However,each with it alsothree suffersto five fromvery the uration
Correct
However, is to another
stripper increase the production
designoption being CompletelyThe refinery
enhanced by stripped configurations
converting water
the gas from toillus-
same
large and heat
Modularising balance
GTL drawbacks
thick-walled reactors, will and of In 1969, while
middle
developed — working
distillate at the for expense
smaller-sized the now and of the sour water
trated
higher-value above, stripper
clean fuelswherebottoms
produced is
residue
beneedless
The samecomplications
required. advantages ofasboth
Consequently, seenthe
modular vanished
distributedAmoco
in petrochemicals. International
GTL Relative
plants — theOil
to shows first sentthetoGTL theprocess.
in hydrotreaters crude reduce desalter. the While feed

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102 www.eptq.com
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20 PTQ Q4 2013 www.eptq.com

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 contaminants to levels required for
the RFCC unit to operate in an
economic manner, while increasing
the hydrogen content of the feed to
maximise high-value products, tend
to be capital intensive and have
high operating costs because of:
• The difficulty of removing
contaminants such as organometal-
lic and nitrogen compounds in the
heavier asphaltenic compounds
contained within vacuum residues.
This results in relatively high pres-
sures (160-200 bar(g)) and relatively
low space velocity (0.1-0.2 hr-1)
• The need to replace large
volumes of catalyst in the hydro-
treating unit (typically once a year)
• The RFCC unit requires a
two-stage regenerator, catalyst
cooler(s) and CO boiler, adding to
the cost of the unit
• A high catalyst make-up on the
RFCC unit to keep a high MAT
activity to favour the propylene
yield
• Additional investments required
in tankage to store hydrotreated
feed to continue running the RFCC
while the ARDS/VRDS catalyst is
changed in each reaction train
because of the comparatively longer
RFCC cycle length versus ARDS or
VRDS units.
An alternative solution would be
to have a refinery configuration
with unit processes capable of
separating the components of the
vacuum residue into two fractions:
one more easily hydrotreated,
which would then be processed in
a more conventional FCC unit, and
another where the impurities such
as polynuclear aromatics (PNA),
metals, CCR and asphaltenes could
be concentrated then processed in a
non-catalytic thermal conversion
process such as a delayed coking
unit (DCU).
Solvent deasphalting (SDA) is an
attractive solution for this type of
application, as it separates residues
by molecular type. An SDA unit is a
robust, relatively low-cost residue
separation process that uses an
aliphatic solvent (typical light
paraffinic solvents with carbon
chains of three to five) to separate
the more valuable oils and resins
from the aromatic and asphaltenic
components of its residue feedstock.
www.eptq.com
f wheeler.indd 4
Sulphur
CCR
Contaminant in DAO, %
Nickel
Vanadium
DAO, vol%
Figure 3 DAO contaminants versus DAO yield
Residue hydrotreating options
Option: VGO Light DAO Heavy DAO VR
% of VR N/A 35-50 50-75 100
Feed CCR, wt% 0-1 5-10 10-15 18-28
Feed C7 insolubles, wt% 0 <0.02 <0.05 5-30
Feed C5 insolubles, wt% 0 <0.1 <0.3 20-30+
% HDS 95+ 90-95 85-92 85-90
LHSV, hr-1 0.75-1.5 0.3-0.5 0.2-0.4 0.1-0.2
Pressure, bar(g) 70-100 100-125 120-140 160-200
Catalyst cycle, months 24+ 24 18-24 12
Table 1
The paraffinic solvent precipitates DAO yield. Although not shown in
the more polar, higher molecular Figure 3, even at DAO yields of 70
weight components, such as resins wt%, the DAO will be relatively
and asphaltenes, typically called free of asphaltenes, which are a
pitch, from the higher-quality, rela- significant factor in setting the
tively low contaminant and higher hydrotreater’s severity.
hydrogen content components When an SDA is integrated with
called deasphalted oil (DAO). The a DCU, the combination allows
heavier the solvent, the higher the DAO from the SDA unit and heavy
DAO yield and the higher the level coker gas oil (HCGO) from the
of contaminants it will contain. DCU to be sent along with the
This process has relatively low VGO from the vacuum distillation
capital and operating costs, as it unit to the FCC feed hydrotreating
operates at relatively low pressures unit and subsequently to a conven-
and temperatures, and no catalysts tional FCC unit.
are used. A well-designed SDA Foster Wheeler has taken this
unit, such as the UOP/Foster concept and optimised the integra-
Wheeler Solvent Deasphalting tion of SDA with delayed coking
Process, is highly reliable and will (see Figure 4). In this type of flow
typically have very long run scheme, the various streams are
lengths between planned shut- routed to where they are most
downs for inspections and general effectively processed. Another
maintenance. synergy that can be exploited with
Figure 3 shows the impact of this configuration is to eliminate
DAO yield on the percentage of the production of slurry oil from
feed contaminants in the DAO. For the FCC unit by processing it in the
most residues and from a hydro- DCU. This also has a side benefit of
treating processing perspective, the decreasing the coker feed’s viscos-
contaminants in the DAO are rela- ity, which would be relatively high
tively low, up to about 70 wt% of if only the SDA pitch was sent to
PTQ Q4 2013 21
12/09/2013 13:40
 SDA + 2 3
DAO
20%
HL coking 70 7 VGO
SDA + 7 6
Distillate
25%
ML coking 50 14 Naphtha

Coking 30%
29 29 14

0 5 10 15 20 25 30 35 0 20 40 60 80 100
ML = Medium lift – 50% Coke, wt% Liquid products, wt%
HL = High lift – 70%

Figure 4 Optimised SDA + DCU integration

the DCU’s heater. Likewise, uncon-
verted oil from the VGO
hydrocracker can be selectively
separated in the SDA unit. This
option would typically be used
when DAO is processed in a VGO
hydrocracker.
Due to the improved quality of
the feed to the hydrotreater, its
severity will be much lower in
comparison to the residue hydro-
treating configuration operations.
Table 1 shows the relative ranges of
process conditions when comparing
residues and VGO hydrotreating
options.
The benefits of this process
configuration are illustrated in
Figure 5; the combined liquid prod-
uct yields increase as the SDA lift
increases. (DAO yield is increased.)
Also, the coke yield decreases as
the SDA lift is increased.
Although there are two residue
processing units with SDA + DCU,
the overall capital cost is similar to
the cost of the DCU alone due to
the relatively low cost of a SDA
Coker
fractionator
Coke
drums
Heavy coker gasoil
Coke
Heavy
HCGO
Coker
feed
Heater
SDA pitch +
multiring aromatics
Figure 5 Integration between SDA and DCU: liquid yields versus coke production1
compared to a DCU, and because
the capacity of the DCU is lower
when combined with the SDA unit
versus a standalone DCU.
Figure 6 shows a schematic of a
refinery configuration that uses
SDA + DCU instead of VRDS +
RFCC to upgrade residues, elimi-
nating the operational/catalyst
management challenges of a VRDS
unit and a complex reactor/regen-
erator section associated with an
RFCC unit.
The key features of this refinery
configuration are:
• A vacuum tower is installed to
produce a diesel-type cut to be
processed in the distillate hydro-
treater, and a LVGO cut to be
processed in a two-stage, almost
full-conversion hydrocracker unit
oriented towards the production of
middle distillates. As an alternate
case, the impact of a partial-conver-
sion HCU, whose unconverted oil
is fed directly into the FCC unit, is
also presented
• The HVGO is combined with
Gas
Naphtha
Light coker gasoil
HDT/FCC
Hydrocracking
DAO
SDA
extractor HCU
unconverted
oil (UCO)
FCC slurry
oil (CSO)
Residue
feed
DAO and the HCGO to be
pretreated in a conventional VGO
HDT unit before its processing in
the FCC unit
• The vacuum residue is processed
in the SDA unit, and the pitch
combined with the FCC slurry is
processed in the DCU
• If the facility is located where
low-cost natural gas is not availa-
ble, the coke instead of being
exported could be used to generate
steam/electricity in circulating
fluidised bed boilers (CFBB).
Processing of mixed C4 streams:
metathesis
Metathesis is essentially used as a
way to adjust the propylene-to-
ethylene product ratio of the refin-
ery, thus upgrading the value of
butenes to high-value propylene,
improving economics and consum-
ing ethylene in addition to butenes.
In order to maximise propylene
production, the key to processing
C4 olefinic streams through metath-
esis is to prepare the feed such that
it is rich in 2-butenes, because
every molecule of ethylene that
reacts with a molecule of 2-butene
gives two molecules of propylene,
whereas all of the other C4 olefins
give only one molecule of propyl-
ene and other by-products,
competing with 2-butene for the
ethylene available.
The challenge is that the C4
components have close boiling
points and are difficult to separate
through fractionation (see Table 2).
Therefore, other means have to be
used to prepare the rich 2-butene
stream for metathesis.
Several processing routes have
been proposed to upgrade the C4
olefinic streams.2 The processing
steps to be taken to include

22 PTQ Q4 2013 www.eptq.com

f wheeler.indd 5 16/09/2013 13:56

 2
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8/28/13 3:55 PM
 status quo loves change
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basf.indd 1 11/09/2013 14:11

 LPG

Crude Heavy
Crude naphtha Benzene
distillation SR naphtha Naphtha Naphtha Aromatics
oil
unit Kerosene hydrotreater splitter Light complex
naphtha LPG Paraxylene
Diesel
Fluidised
Raffinate catalytic
cracker Pygas
Kerosene Kerosene
naphtha
hydrotreater Pygas Pygas and
Atmospheric catalytic
residue Steam naphtha
Middle cracker hydrotreater
Diesel
distillate
Propylene
hydrotreater Naphtha
Light Ethylene
vacuum LPG
gas oil Hydro- Kerosene Kerosene
cracker + diesel
Vacuum Diesel
distillation Kerosene
Heavy
unit vacuum + diesel
C2 C4S
gas oil Naphtha C3
Diesel C4
Vacuum processing
residue Naphtha Vacuum Hydrotreated feed
gas oil Naphtha C 4S
To C4 sales
Solvent hydrotreater
deasphalting Propylene
+ delayed Fluidised
coking unit Ethylene
catalytic
cracker
Light coker gas oil
Heavy coker gas oil
Coke Deasphalted oil Diluted crude oil Light cycle oil
To fuel oil
sales
Circulating Power
fluidised bed
boilers Steam

Figure 6 Refinery configuration with SDA + DCU

metathesis in the refinery configu-
rations are shown in Figures 1, 2
and 5:
• Extract butadiene from steam
cracker C4s and selectively hydro-
genate the raffinate-1 or selectively
hydrogenate the whole C4 olefinic
stream to reduce the butadiene
content to less than 10 wtppm. In
this case, the catalyst system and
operating conditions of the selec-
tive hydrotreating unit are adjusted
to isomerise 1-butene to 2-butene
• Remove iso-butylene through
MTBE decomposition: in this case,
separation by reaction takes advan-
tage of the fact that only the
iso-butylene reacts with alcohols to
produce ethers, which can be
converted back to high-purity
iso-butylene. This step could also
be required if high-purity 1-butene
is desired (for instance, as co-
monomer for the production of
polyethylene)
• Removal of 1-butene and lighter sent to the steam cracker. The
components: this process consists of bottom product is high-purity
two super fractionators. First, the C4 1-butene
stream is fed to the first column to • If high-purity iso-butylene and/
remove as a bottoms product the or 1-butene are not required, only
n-butane along with the bulk of the first super fractionator would
2-butene and some 1-butene. be required to produce the feed to
Second, from the top, the bulk of the metathesis unit. For the rest of
1-butene and other light compo- the C4s, there is potential to further
nents are taken to the second increase the production of ethylene
column, where iso-butane is and mainly propylene through
removed with some 1-butene and direct cracking or oligomerisation,
followed by cracking in a separate
riser in the (R)FCC unit.
Normal boiling point of C4 olefins
Results
Component Normal boiling point, °C
Iso-butane) -11.7 Table 3 summarises the material
1-butene -6.3 balances produced for each of the
Isobutylene configurations shown in Figures 1,
(2=-methyl propene) -6.9
2 and 5. The results show that,
1-3 butadiene -4.4
n-butane -0.5 regardless of the refinery configura-
Trans-2-butene 0.9 tion, when deep conversion units
Cis-2-butene 3.7 are considered and under certain
operating conditions designed to
Table 2 maximise the production of petro-

www.eptq.com PTQ Q4 2013 25

f wheeler.indd 6 12/09/2013 13:40

 higher middle distillates produc-
Material balances for different complex configurations tion than the ARDS + RFCC
configuration can achieve.
Product ARDS + ARDS + RFCC HCU + VRDS HCU + HCU + SDA/DCU
In the first case, propylene
RFCC with + RFCC SDA/DCU + + DAO HDT +
metathesis DAO HDT/FCC FCC + partial production decreases mainly due to
conversion HCU reduced FCC capacity, which in
+ metathesis this case was about 59 000 b/d as
C4s, KTA 1151 974 792 625 551
compared to the ARDS + RFCC
Gasoline, KBPD 0 0 0 0 0
Jet fuel, KBPD 15.6 15.6 23.5 36.2 27.4 configuration. The flexibility of the
Diesel, KBPD 128.8 128.8 147.3 131.6 128 SDA + DCU configuration in terms
Fuel oil, KBPD 7.2 7.2 6.1 1.3 1.3 of product slate is shown in the last
Ethylene, KTA 1123 907 1081 1106 975
case. Where the partial-conversion
Propylene, KTA 1100 1558 838 800 1312
Paraxylene, KTA 1600 1587 1573 1754 1830 HCU is feeding the unconverted
Benzene, KTA 490 501 509 563 582 bottoms to the FCC unit, the capac-
Coke 348 353 ity of the unit increases to 76 000
b/d. This, plus the metathesis,
Table 3 allows for an increase in propylene
production.
chemicals, world-scale production of direct cracking or oligomerisation In relation to paraxylene produc-
ethylene, propylene and aromatics of the C4s, followed by cracking in tion, since the amount of
with crude processing of 15 million a separate riser in the RFCC unit. straight-run material is the same
t/y — about 300 000 b/d — can be Paraxylene production is world for all cases, the contribution of the
produced. Choosing between the scale and is likely to require two naphtha produced in mid- and
ARDS + RFCC, VRDS + RFCC and trains of paraxylene recovery. deep conversion should be
SDA + DCU configurations is not The refinery configuration with analysed to understand the varia-
easy, as all can be adjusted to VRDS + RFCC shows the contribu- tions in paraxylene production.
produce similar amounts of distil- tion the HCU brings to the increase It should be noted that besides
lates, petrochemicals and aromatics. in middle distillates production, (R)FCC capacity, the feed quality
For the refinery configuration compared with the ARDS + RFCC also has a significant influence on
with ARDS + RFCC, both units are case, at the expense of propylene the catalytic naphtha yield. An
relatively large. The capacity of production, which decreases mainly RFCC unit processing a full range
ARDS and RFCC are 121 000 b/d because of the reduced RFCC unit of treated residue feedstock with a
and 108 000 b/d, respectively. capacity (in this case, about 65 000 relatively high content of resins and
Two cases were developed: one b/d). asphaltenes in the feed, as in the
where all of the C4s are sold and For the refinery configuration ARDS or VRDS + RFCC configura-
another one to show the impact a with SDA + DCU, two cases are tion, cannot be expected to produce
metathesis-based olefins conversion presented to show the flexibility the same naphtha yields as those
unit (OCU) has on the production this configuration offers to adjust that can be obtained in an FCC unit
of ethylene and propylene. the product slate to suit market with a VGO + DAO deeply hydro-
As can be observed, in the first requirements: a configuration treated feed.
case, both ethylene and propylene oriented to maximising middle The other key differentiator is the
production exceeds 1.1 million t/y. distillate production with a quantity and aromatics content of
In the second case, where an OCU full-conversion HCU, and another the heavy (R)FCC naphtha. It would
has been incorporated, propylene where the unconverted bottoms of be highly aromatic and naphthenic
production is increased by about a 70% conversion HCU are fed to because of the high severity and the
40% at the expense of ethylene. In the FCC unit and a metathesis unit use of additives required to maxim-
both cases, there is potential to is incorporated to maximise the ise propylene production. The
further increase the production of propylene production. aromatics content of the heavy cata-
ethylene and propylene through Both SDA + DCU cases show lytic naphtha produced from the
RFCC would be slightly higher than
Order of magnitude total installed cost (TIC) estimates that produced from an FCC unit
under similar operating conditions.
Fuel oil production is signifi-
[US$ million] ARDS+RFCC VRDS+RFCC SDA+DCU
ARDS/VRDS 601 465 - cantly reduced, as expected. Coke
RFCC 444 318 - can be either exported or used on
HCU - 371 371 site to produce steam/electricity in
VGO HT - - 235
a circulating fluidised-bed boiler.
FCC - - 169
SDA+DCU - - 360
Total 1045 1154 1135 Impact of capital investment costs
With regards to capital investment
Table 4 costs, Table 4 summarises the order

26 PTQ Q4 2013 www.eptq.com

f wheeler.indd 7 12/09/2013 13:40

 of magnitude total installed cost and competitive configuration. potentially to the revamp of exist-
tubular flow reactors with auto- by DN-3551. The points enclosed in customer conveyed the need to
(TIC) estimates that have been Certainly, if the objective is to ing facilities. The zero gasoline
mated process control and sampling. the highlighted areas labelled process more oil sands-derived
prepared, based on Foster maximise revenues with proven production refinery is a practical
The use of this multi-tube reactor DN-3651 represent samples tested coker gas oil. Consequently, the
Wheeler’s in-house cost estimating technology, in a reliable environ- and viable reality.
system allows significant accelera- as part of scale-up and manufactur- first initiative was to plan a transi-
database. ment, the configuration that has
tion of catalyst development relative ing optimisation. Use of high tion to a more metals-tolerant
As can be seen, the investments been developed by Foster Wheeler
to conventional testing techniques. throughput experimentation catalyst system, and Ascent
for the upgrading section of the utilising its SDA + DCU combina- References
Leads generated with the high allowed rapid development of a DN-3551 catalyst was selected for
refinery configurations are of the tion offers a competitive advantage. 1 Gillis D, Unique opportunities with proven
throughput equipment were reliable manufacturing process Cycle 2. This catalyst has
technologies to maximise residue conversion been
same order of magnitude. With
confirmed by conventional-scale
similar product slates and invest-
yielding the highest practical cata-
How to make the right decision &shown
refinerytomargins,
have superior feed poison
Asia Technology forum,
pilot plant testing. lyst performance. tolerance and was
Bangkok, 10-11 Oct 2012. considered to be
ments, the differences in economic The integration of refining and
The target performance level for Applying technology improve- 2better
Edwardssuited
S M, et to accommodate
al, Relative economics theof
indicators between the refinery petrochemical facilities offers
DN-3651 was an improvement in ments such as DN-3651 requires a expected
mixed poisons
C4s processing that
routes, PTQ, would
Q1 1998, 1.be
configurations will not be signifi- several opportunities for adding
HDN activity of at least 10°F holistic joint approach to ensure associated with processing incre-
cant enough to clearly favour one value to refinery streams by
(5.5°C) relative to DN-3551 (~20 that the full benefits of the technol- mentally higher percentage of oil
configuration over another. exploiting synergies between differ- is Downstream
RVA) with equivalent or better ogy can be taken advantage of by Blasis Stamateris coker
sands-derived gas oils.Business
Therefore, when it comes to the ent process units while rationalising Consultant in the Business Solutions Group
HDS activity with a challenging the operator, taking into account The second initiative included
decision of which refinery configu- investments that can positively of Foster Wheeler, UK, participating in refinery
design feed containing bitumen- the site-specific constraints and optimisation of the demet catalyst
ration to choose, other factors impact project economics. configuration studies, feasibility studies and
derived vacuum gas oil and heavy objectives. package to enhance catalyst stabil-
besides the product slate and Different refinery configurations FEED work for grassroots refin eries, CTL
coker gas oil. Figure 14 illustrates In this example, Criterion utilised ity. Prior
facilities to Cycle
and refinery 1’s Acompletion
upgrades. graduate in
investments, such as operating can be tailor-made to suit a range
the high throughput experimenta-
complexity and associated reliabil-
a collaborative approach with its
of processing objectives, including chemical engineering, he has loading,
and the DN-3551 we
over 25 years’
tion HDN and HDS activity data customer to improve catalyst advised the customer that the
experience in oil refining and upgrading. opera-
ity of the units, should be taken variations to the propylene-to-
obtained during the prototype performance and facilitate more tion blasis_stamateris@fwuk.fwc.com
Email: was being subjected to a higher
into consideration. ethylene ratio, and the production
development phase as well as difficult oil sands-derived feed feedGillis
Dan endpoint
is Director,and the forcatalyst
Refining Foster
Ultimately, the selected option is of middle distillates and aromatics.
during the scale-up and commer- processing capabilities. Three initia- systemUS.was
Wheeler, at risktechnical
He provides of accelerated
direction
based on an individual refiner’s Capacities of the process units can
cialisation phase. The activity as tives were implemented. aging
and due to feed
applications resid and
development for metals
Foster
objectives. The SDA + DCU options be adjusted to accommodate differ- Wheeler’s proprietary heavy oil technology. He
presented in these plots is the The original cycle 1 utilised entrainment. Subsequent detailed
represent well-proven technologies. ent crude oils. is an engineering graduate of the University of
decrease in temperature required to Criterion’s Centinel DN-3100 cata- feed component analysis at
If there is a suitable outlet for the The concepts outlined are appli- Saskatchewan, Canada.
achieve the target S or N level in lyst as the primary conversion Criterion’s Research facility
coke produced, this is a viable cable to grassroots projects and Email: dan_gillis@fwhou.fwc.com
the product relative to that required system. During the cycle, the confirmed elevated feed poisons

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 Minimising transfer line vibrations
Computational fluid dynamics was used effectively to solve start-up problems in
a transfer line
RAHUL PATIL, RANDHEER YADAV, AJAY GUPTA and ASIT DAS
Reliance Industries Ltd, Jamnagar
D
elayed coking is an important
process in a petroleum refin-
ery and adds significantly to
the gross refining margin. The
delayed coking unit (DCU) takes
vacuum residue as feed and ther-
mally cracks it into useful lighter
products such as liquefied petro-
leum gas (LPG), naphtha, gas oils
and residual coke. Vacuum residue
is first heated in a furnace to about
500°C for a very short time, to avoid
coking inside the furnace tubes, and
then cracked inside the coke drum,
where sufficient reaction time is
provided. Steam is added along
with vacuum residue in the furnace
to create additional turbulence for
better heat transfer and to avoid
coking inside the heater tubes.
Figure 1 depicts the flow scheme
for a vacuum residue and steam
mixture during start-up and normal
operation of the DCU. The vacuum
residue and steam mixture at the
furnace outlet enters a transfer line
connected to a header, which is
connected to the fractionator during
start-up for closed loop circulation
at a temperature of 300-350°C and a
pressure of 1.5-3.0 kg/cm2(g). After
establishing the desired flow circu-
lation, the header is disconnected
from the fractionator and connected
to the coker drum. During normal
operation of the coker unit, the
furnace outlet temperature is raised
to about 500°C and therefore the
vapour flow rate at the outlet
increases significantly due to
vaporisation and mild cracking of
vacuum residue even at higher
pressures of 3.5-6.0 kg/cm2(g).
During a start-up operation of the
DCU, the transfer line experienced
vibrations, giving rise to safety and
www.eptq.com
ril.indd 1
Normal
operation
Transfer line
where vibrations
were observed
Startup
Fractionator
Coke
drum
Heater
Figure 1 Block diagram for the coker
heater transfer line
reliability concerns. This article
presents an analysis carried out
using both conventional techniques
and computational fluid dynamics
(CFD), for determining the causes
of vibrations in the transfer line
exhibiting two-phase flow of
vapour and liquid.
What could cause vibrations in
the pipeline?
Large bubbles or slugs are the
usual suspects in the case of vibra-
tion of a pipeline carrying a
gas-liquid mixture. Therefore,
establishing the flow regime in the
pipeline is of prime importance.
The presence of a particular flow
regime (bubble, stratified, slug,
annular) within the pipe is a func-
tion of the volume fraction of the
phases and their properties. The
existence of a particular regime
may provide the desired results or
it can deteriorate performance or
cause reliability issues. For exam-
ple, mist flow can provide efficient
heat and mass transfer between
two phases; however, the presence
of a slug flow regime may cause
severe vibrations in equipment
because of the impact of high-
velocity slugs against bends or
other fittings. The flow regimes
existing in a pipe for a two-phase
system are complex and yet impor-
tant for better design and for
deciding the operating conditions
to achieve the desired outcome.
Determine flow regime in a pipeline:
conventional analysis vs CFD
Approximate prediction of flow
patterns can always be done using
flow pattern maps in the litera-
ture.1,2 For a horizontal pipe, a
Baker chart is widely used for the
prediction of flow regime in a
co-current flow of gas and liquid.
For a co-current vertical upflow of
gas-liquid mixture, the correlations
by Govier, et al, may be used for
quick estimates of flow regime.
Most of the flow maps or correla-
tions available in the literature are
generated using an air–water
system and may or may not be
applicable to the gas-liquid system
of interest. Studies correlating
results of CFD simulations with
Baker charts for gas-liquid systems
other than air-water, although
reported,2 are very few. The effect
of bends on flow regime cannot be
studied by conventional analysis.
Therefore, for a gas-liquid system
other than an air-water system, it is
advisable to study the complex
flow patterns in a pipeline using
computational models, which solve
constitutive equations for two-
phase flows.
Commercial CFD software, Fluent
6.3 from Ansys, has been used to
PTQ Q4 2013 29
12/09/2013 13:54
 100 Process conditions at the heater outlet
for Cases 1 and 2

Spray or dispersed Parameter Case 1 Case 2

Liquid volume fraction 0.2 0.04
10 Vapour volume fraction 0.8 0.96
Liquid density, kg/m3 900 880
Wave Annular Bubble or froth Vapour density, kg/m3 1.25 7.02
2

Liquid viscosity, cP 4 2
/ Λ, lb/s×ft

Vapour viscosity, cP 0.13 0.15

Surface tension, N/m 0.025 0.010
1
Slug
Table 1
GG

Stratified
volume fraction of the vapour
0.1
Plug phase in normal operation.
The process conditions mentioned
in Table 1 are used in conventional
as well as CFD analysis to deter-
0.01
0.1 1 10 100 1000 10,000
mine flow regime in the transfer
GLΛΨ /G G
line, and subsequently to find the
root cause of vibrations.

Figure 2 Flow regimes in co-current liquid-gas flow in horizontal pipes
solve the equations for two-phase
flow in a transfer line. The volume
of fluid (VOF) method3 has been
used to track the vapour-liquid
interface. The flow regimes from
conventional analysis are also
compared with CFD model
predictions.
Role of process conditions
As discussed above, the flow
regime in the pipe is dependent on
phase volume fractions and phase
properties. The process conditions
present during start-up and normal
operation thus play an important
role in deciding the flow regime
that exists in a transfer line. The
fluid properties at the heater outlet
based on process conditions at
start-up (start-up operation is
referred to as Case 1) and normal
operation (normal operation is
referred to as Case 2) are shown in
Table 1. Vaporisation is higher
during normal operation as
compared to start-up operation due
to the fact that, while temperature
and pressure are in the ranges of
300-350°C and 1.5-3.0 kg/cm2(g)
respectively during start-up, in
normal operation — although pres-
sure is higher (3.5-6.0 kg/cm2(g))
— some part of the hydrocarbon
liquid feed is cracked and vapor-
ised due to a higher temperature of
480-520°C. This vaporised gas adds
up to steam flow and increases the
Conventional analysis from flow
regime maps
Widely used Baker and Govier
charts1 were utilised to determine
the flow regimes for the co-current
flow of a vapour-liquid mixture in
horizontal and vertical transfer
lines, respectively.
Regime analysis for two-phase flow
through horizontal pipes
A Baker chart was used for predict-
ing the flow regime in co-current
liquid-gas flow in horizontal pipes.
Figure 2 shows the points marked
for regimes for Cases 1 and 2 for
flow through horizontal pipes. The
reference properties of air and
water are at 20°C and atmospheric
pressure. Equations 1 and 2 are
used for calculating λ and ψ:

(1)
10
(2)

The process conditions during

2
/ Λ, lb/s×ft

1
Ripple start-up (Case 1) lead to a slug flow
regime in the transfer line. As
Bubble Slug Froth Film
discussed, this may be the cause of
0.1 vibrations observed in the transfer
GG

line. During normal operation (Case

2), the process conditions are such
that the flow regime prevailing in
0.01 the transfer line is a dispersed/mist
0.1 1 10 100 1000 flow. In this regime, the liquid phase
GLΛΨ /G G
is dispersed completely in the gas
phase. This will lead to smooth
Figure 3 Flow regimes in co-current liquid-gas flow in vertical pipes operation during normal conditions.

30 PTQ Q4 2013 www.eptq.com

ril.indd 2 12/09/2013 13:54

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 Regime analysis for two-phase flow
through vertical pipes
A Govier, et al, (1957) chart was
used for the flow regime analysis of
co-current two-phase flow in verti-
cal pipes. The different regimes in a
Elevation 3
vertical transfer line corresponding
to different process conditions are
Elevation 2
shown in Figure 3. Again, slug flow
is observed for Case 1 and mist ∆E2 Y
flow is observed for Case 2.
From conventional flow regime
analysis, slug flow conditions exist
for Case 1 and mist flow exists X Z
for Case 2 in both horizontal and
vertical pipes. To see the effect of a
∆E1 = Elevation 2 – Elevation 1
combination of horizontal
∆E2 = Elevation 3 – Elevation 2
and vertical pipes connected by ∆E1
bends, CFD analysis was carried
out.

CFD analysis of flow regime: Elevation 1

geometry and boundary conditions
An isometric line diagram for the
transfer line is shown in Figure 4. Figure 4 Line diagram (isometric) of the transfer line for a coker furnace
2D approximation was done to
reduce the computational time. A CFD simulation results It is clear from Figure 6 that the
complexity involved with 2D Effect of geometry on flow flow pattern is similar in both cases
approximations of 3D piping simulations and large slugs of liquid are formed
systems is a lack of differentiation CFD simulations were carried out (red colour = liquid; blue colour =
of bends in horizontal and vertical for the start-up case using geome- vapour). These slugs are blocking
planes. The flow pattern for a verti- try 1 and 2 (Case 1-1 and Case 1-2, the path of gas flow. When there is
cal bend is supposed to be different respectively). The volume fraction enough build-up of gas pressure, it
to a bend in the horizontal plane, contours for Case 1-1 and Case 1-2 overcomes the resistance of the
because of the effect of gravity. To are shown in Figures 6a and 6b, liquid slugs, thereby splashing
rule out the ambiguity in flow respectively. these slugs on the wall/bends of
regimes due to 2D approximations,
two geometries of the transfer line
were generated in 2D using a Pressure
pre-processor, Gambit (see Figure outlet
A
5). The clouded portion (dotted
line) in these figures shows the ∆E2
approximated section for creating
2D geometry. The geometry was
meshed with about 1.5 lakhs
(150 000) grid points. ∆E1 Wall
CFD analysis was done using
Fluent 6.3 software from Ansys.
Velocity Pressure
The boundary conditions used for inlet outlet
the simulation are also shown in
Figure 5(a). A VOF approach was B
∆E2
used for predicting the flow regime
in the transfer line for different
process conditions at the coker
heater outlet. The unsteady state ∆E1
pressure-based formulation in
Fluent was used. A time step Velocity
of 5x10-4 s was used in simulation. inlet
The simulation was initialised
with the transfer line filled with Figure 5 2D geometry of the transfer line and boundary conditions (a) Geometry 1;
steam. (b) Geometry 2

www.eptq.com PTQ Q4 2013 33

ril.indd 3 12/09/2013 13:54

 A interpretations obtained with two
A
geometries would be similar. As
pressure fluctuations for Case 1-1
are bit more than for Case 1-2, for
future simulations to be on the
conservative side, Geometry 1 was
used to simulate the flow in the
transfer line under various process
B B conditions.

Start-up vs normal operation

Figure 6 Volume fraction contour of
vacuum residue at different flow times;
(a) Case 1-1 (b) Case 1-2
the transfer line. This results in the
large pressure variation of the wall
of the transfer line. Further, to
establish that the flow patterns are
similar, maximum pressure varia-
tions in the transfer line due to the
flow patterns were monitored (see
Figure 7) for two geometries.
Figure 7 shows the variation of
dimensionless pressure, the ratio of
maximum pressure to normal
A for Case 1. This leads to a change in
3.0
2.5
2.0
P
Figure 8 Volume fraction contour of
vacuum residue at different flow times;
(a) Case 1 (b) Case 2
operating pressure versus dimen-
sionless time, the ratio of flow time
(t) to the residence time (τ) of fluid
for a particular case. The simula-
tions were carried out for flow time
equal to two times the residence
time of fluid in the pipe for each
case. The pressure fluctuations for
Cases 1-1 and 1-2 are found to be
similar in nature. Thus, it was
concluded that the observations and
CFD simulations for Case 1 and
Case 2 were completed with
Geometry 1. Figures 8a and 8b
show the volume fraction contours
for Cases 1 and 2.
Figure 8a shows the large liquid
slugs formed in Case 1 (start-up
case). As was explained above, the
large slugs cause large pressure fluc-
tuations and result in vibration of
the transfer line. Figure 8b shows
the volume fraction contours for
Case 2, which corresponds to
normal operation. It can be observed
that no liquid slugs are present
during normal operation. This may
be because of the presence of a large
volume of vapour as compared to
liquid. Also, the temperature and
pressure for Case 2 is higher than
properties such as surface tension
and viscosity of the two phases.
It is evident that the flow regimes
in Cases 1 and 2 are significantly
different. While large slugs are pres-
ent in Case 1, no slugs are produced

in Case 2. The effect of presence or

absence of a slug on the forces
1.5 exerted on the pipe can be easily
understood by monitoring the maxi-
mum pressure acting on the transfer
1.0
0 0.5 1.0 1.5 2.0 line wall. The pressure fluctuations
t/τ in the transfer line with time for
B Cases 1 and 2 are shown in Figure 9.
3.0
The pressure fluctuations are
large for Case 1 compared to Case 2.
2.5
The large difference between base
and peak pressures leads to vibra-
tions in the transfer line, whereas no
2.0 such pressure peaks were observed
P

for Case 2. Case 2 is a high-tempera-

ture and high-pressure operation,
1.5 resulting in the physical properties
of the phases being significantly
different from Case 1. The disap-
1.0
0 0.5 1.0 1.5 2.0 pearance of vibrations during
t/τ
normal operation when compared
to start-up operation is explained by
Figure 7 Pressure fluctuation with time for Case 1-1 and Case 1-2 the analysis above.

34 PTQ Q4 2013 www.eptq.com

ril.indd 4 12/09/2013 13:54

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 A Process conditions at the heater outlet
3.0
for Cases 3 and 4

2.5 Parameter Case 3 Case 4

Liquid volume fraction 0.67 0.067
Vapour volume fraction 0.33 0.933
2.0 Liquid density, kg/m3 900 900
P

Vapour density, kg/m3 1.25 1.25

Liquid viscosity, cP 4 4
Vapour viscosity, cP 0.13 0.13
1.5 Surface tension, N/m 0.025 0.025

Table 2
1.0
0 0.5 1.0 1.5 2.0
t/τ Avoiding vibration in the transfer line
B Slug formation in the transfer line
3.0
was found to be the reason for
vibrations to occur and it was also
2.5 understood that normal operation,
because of the different proportions
of the vapour-liquid mixture and its
2.0 physical properties, is smooth. Now,
P

it was necessary to study the effect

of vapour volume fraction on pres-
1.5
sure fluctuations in the pipe during
the start-up process, so that condi-
1.0 tions for avoiding vibrations can be
0 0.5 1.0 1.5 2.0 provided. To accomplish this, two
t/τ more studies were carried out: one
with a lower vapour volume frac-
Figure 9 Pressure fluctuations vs flow time for case 1 and 2 tion (Case 3), the other with a higher
vapour volume fraction (Case 4) in a
A vapour-liquid mixture, as compared
3.0
to the start-up case (Case 1). The
process conditions for Cases 3 and 4
2.5 are given in Table 2.
The volume fraction contours for
Case 3, corresponding to the
2.0 start-up case with reduced vapour
P

flow, are shown in Figure 10a. The

flow regime for Case 3 is very
1.5 different when compared to Cases
1 and 2. In this case, liquid is the
primary phase and no slugs are
1.0
0 0.5 1.0 1.5 2.0
t/τ A
B
3.0

2.5

2.0 B
P

1.5

1.0
0 0.5 1.0 1.5 2.0
t/τ Figure 10 Volume fraction contour of
vacuum residue at different flow times;
Figure 11 Pressure fluctuations vs flow time for Cases 3 and 4 (a) Case 3 (b) Case 4

36 PTQ Q4 2013 www.eptq.com

ril.indd 5 12/09/2013 13:54

 efficiency trays must beline. usedThe to conventional
reduce refluxanaly- ratio cause sedime
forming
who are inside the transfer
not desk-bound and can benefit from access to
and lower the overhead cooling load. Flue gas fouling tende
sis real-time
showed data, plug trendsflow and and slugalertsflow in horizontal
— anytime, anywhere. and
turbines, energy recovery tially with con
for hydraulic turbines, energy-
A New Standard
verticalPlant pipes respectively
managers and production Case 3. engineers can use
saving motors, frequency conversion motors and for air the value ben
Figure
mobile 10b shows the
BI anytime, volumeinfraction
anywhere order tocontours first under-
flow regulation systems of compressors should be to fouling and
Case stand 4, anwhich issuecorresponds
and then propose to thesolutionsstart-uptocase problemswith

in Pressure
employed to recover pressure energy and reduce elec- version relatio
higher
in a vapour
time-frame flow. notThe flow regime
previously in Case 4with
experienced is similar
tradi-
tric advantage in d
slug energy
to tional flow.
desktop
consumption.
Even though the
solutions.
High-efficiency
The gasprevalence
volume fraction intensified
of mobile has
burners need to be used in furnaces are acceptable
increased
devices to 0.933 from 0.8
the in 1,tothe
Case industries. improve
slugMobile effi-
flow
Measurement
is transforming process result in lost c
ciency.
regime stillThe exhaust in
prevailed temperature
the transfer of line.
furnaces should be
Conventional
solutions empower decision-makers to have immediate improvement
reduced
analysis to improve thermal efficiency by 2-3%. New
access showed to important slug flow data,in both enablinghorizontal them and to verti-
make and run leng
insulation
calinformed
pipes for and material
Casequick needs to be employed
4. decisions to improve profitability. to reduce
the understand
heat loss of equipment and concept of op
ToEasy, digestible analysis the effect of plantof pipelines.
variation
information, of even vapour in
Low-temperature heat should rate of fouling
volume
remote fraction
locations, in the start-up
helps industry casebe on utilised byexerted
to pressure
react to adverse
apply-
ing
on changes low-pressure
the wall, steam generation technology,
andpressure
keep thefluctuations
operation performing in the transfer line
to targets. Fouling proble
over low-temperature Organic Rankine Cycle (ORC)
Thetime ability were to studied
access and (seeanalyse
Figurereal-time11). It was plantfound data Problem areas
that systems
pressure andfluctuations
Kalina Cycle systems.
forthe Case 3 are low compared
has enormous benefits. In past, users needed to be The sections m
to in Energy
Case optimisation of the area should be carried
the4.control
This isroom due to or liquid-dominated
in front of a monitor operation to track in
column, vacu
out.
theand Heatline.
transfer integration
The pressure between the refinery
fluctuations for Case and 4local are
manage manufacturing performance. Mobile BI very high con
very co-generation power plant isneeds to be the realised. A
hassimilar
provento to Case be 1.more This effective because when slug
usersflow are also suffer fro
large
regime quantity
prevailed of low-temperature heat in a refinery
provided within visualisation
the transfer line toolsfor Case(charts, 4. graphs,
ing of the
cannot be recovered because a heat sink is not availa-
portals and so on). unplanned sh
ble, and this
Conclusions andportion
recommendationsof low-temperature heat may be
For today’s engineers, the message is simple: mobile The same tr
CFD used as a heat
analysis ofprovides source
a two-phase forvapour-liquid
demineralised water flow
mixture and
intelligence the platform to achieve greater sediment gene
boiler
in profitability.feed
the transfer line water in a cogeneration
of a delayed power
coker software, plant.
unit was such Also,
carried
State-of-the-art mobile as of conversion
integration
outAspenat different with modes the local chemical plant
of operation. is important
The decision-mak-
flow during
InfoPlus.21 Mobile, enables faster certain limits
to achieve
start-up material
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ing and troubleshooting and displays critical, time cannot b
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the configuration of refining units avoid in China have continuous c
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the transfer line. Lowering the asteam long flow period rateinwas the
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and change unit configuration so as to improve the
linksD W,
1 Green allPerry
capabilities
H B, Perry’s of the business.
Chemical Engineering ItHandbook,
is an integrated
8thand
Edition. and the intrin
comprehensive utilisation rate of resources, to
set of production activity
2 De Schepper S C K, Heynderickx G J, Marin G B, CFD modeling and support software
of all Safety stability reser
meet the requirements of energy savings and emis-
designed
gas–liquid to harmonise
and vapour–liquid flowand optimise
regimes predicted thebyplant.the Baker chart, UÊʘ…iÀi˜ÌÞÊv>ˆ‡Ã>viÊÃi˜ÃœÀÊ܈̅ʘœÊ solubility will
sions reduction.
ChemicalTheEngineering
bottom Journal, line is138, that effective
349–357, 2008. production drives ՘`ˆÃVœÛiÀi`Êv>ˆÕÀiʓœ`iðÊÊ to generate co
More detailed classification ofInc,crude oil fractions
operational
3 Fluent excellence,
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Guide, Ansys betterUSA. and faster deci- UÊÊ
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and the consideration of various narrow-cut process-
sions.
Rahul C Patil Software
is Senior Manager technology helps
of the modelling refiners
andthe achieve
simulation group ÕÃiÊ-ÓÊ>˜`Ê`Õ>ÊÕÃiÊ-Î The amoun
ing technologies will actively promote low carbon
consistent performance across all assets.
of  refining R&D at Reliance Industries Ltd, Jamnagar, Gujarat, India. It also defines He sodium and
emission of refineries. Narrow-cut processing will
holdsthea Masters
importance in chemical ofengineering
real-timefrom IIT business
Kanpur performance
and a degree in process perfo
become the development trend in the overall process Robustness
management:
chemical plan, execute,
engineering from ICT Mumbai. monitor and respond to
and, in some
flow optimisation of refineries in theof21st century. fluid UÊÊ,Õ}}i`]ÊÞiÌÊVœ“«>VÌÊVœ˜ÃÌÀÕV̈œ˜
change immediately
Dr Randheer Yadav specialiseson all application
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showntothat systems involving multi-phase
manufacturing execution flows. He holdshave
systems a PhD in
laid precursors —
chemical engineering from to ICT Mumbai. i˜ÛˆÀœ˜“i˜ÌÃ
the foundations help refiners across the globe asphaltenes —
Dr Ajay Gupta is Assistant Vice President and leads the modelling and UÊʘ‡LՈÌʜÛiÀ«ÀiÃÃÕÀiʓiV…>˜ˆÃ“ÊvœÀÊ
strengthen is Vice their competitiveness and build upon the To avoid d
Sun Liligroup
simulation of President
refining R&D of Sinopec
at Reliance Engineering
IndustriesIncorporation
Ltd, Jamnagar, in ˆ˜VÀi>Ãi`ÊÀiˆ>LˆˆÌÞ
pillars of profitability.
charge of processing solution studies, engineering, construction and plays a major
Gujarat, India. He has Bachelors, Masters and Doctoral degrees in chemical
startup of
Engineering grassroots
from refineries
IIT, Delhi, India. and refinery modification projects. She process can h
has over
Marty
Dr Asit Das20is years’
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is thePresident
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Manager atengineering
AspenTech. design
During
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in the
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hydroprocessing
process industries, units,
he hashas won
worked several
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consultant ofinNational
over 65 Scientific
refineries,
Industries Ltd, Jamnagar. He holds a degree in chemical engineering from catalyst activi
and Technological
chemical, gas plantsProgress,
and anda holds
other a BS in petroleum
manufacturing refiningfrom
environments. from
He
Jadhavpur University, West Bengal, Masters in chemical engineering The effect of t
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IIT, holds aUniversity
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andpatent offor
Petroleum.
a doctoral multivariable control and
degree in chemical a degreefrom
engineering in chemical
Ghent
Email: sunlili.sei@sinopec.com
fouling can
engineering
University, from the University of Illinois.
Belgium.

www.eptq.com
www.eptq.com
www.eptq.com

EJA-E-270x86.indd 1 07/09/12 13:50

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 High-acid crude processing enabled by
unique use of computational fluid dynamics
A methodology for applying CFD enables faster identification of pipe elements
that are the most vulnerable to attack by high-acid crudes
Dr COLLIN CROSS
GE Water & Process Technologies
I
n today’s refining marketplace,
the potential to process naph-
thenic acid-laden crudes often
appears very attractive from an
economic perspective. This is
because such crudes are usually
priced at a significant discount with
respect to more mainstream crudes.
Many of these naphthenic acid
crudes are extremely corrosive,
however, and can cause substantial
damage to refinery equipment
and/or have adverse impacts on
reliability and safety if not
processed correctly. Unfortunately,
estimations of the possible prob-
lems involved with processing
these crudes are often fraught with
uncertainty. Rules of thumb,
experiential-based strategies and
reactionary tactics have dominated
the industry in its approach to
managing the associated risks. Due
to the complexities involved with
these estimations, many refiners
adopt a conservative stance regard-
ing the rate at which they utilise
acidic crudes, or depend upon
capital-intensive upgrades to
equipment.
In order to gain the most benefit
from acidic crudes, new strategies
and tactics based on data-driven
decisions are needed. By better
understanding the interactions
between a particular blend of naph-
thenic crude, a particular crude
unit and a particular operating
envelope, it is possible to more
accurately estimate the feasibility of
successfully processing high-acid
crudes. Additionally, the refiner is
able to deploy a host of proactive
measures, allowing high-acid
crudes to be processed more confi-
dently and reliably.
www.eptq.com
ge.indd 1
Background
Naphthenic acid corrosion was first
recognised as a corrosive influence
in certain crudes as early as the
1920s.1 Since that time, the impact
of naphthenic acid corrosion has
been typified by its detrimental
effects, as well as its difficulty to
predict. While high-acid crudes
(HACs, crudes with substantial
amounts of naphthenic acid) have
been available for quite some time,
it has only been the last several
decades where their processing has
become more widespread. In fact,
the last 10 years have seen many
more refiners begin to explore the
possibilities of processing HACs
due to increasing pressures on
refinery profit margins. While refin-
ery economics provide a substantial
incentive to process these acidic
crudes, it remains difficult to
manage the long-term corrosive
impact of HACs.
Naphthenic acid corrosion, in
contrast to more traditional forms
of refinery corrosion, happens in
sections of the crude unit having
temperatures generally greater than
450°F (232°C). In these regions,
liquid water cannot exist and there
are often strong contributions from
sulphidic corrosion. Due to this
situation, traditional overhead
inhibitor chemistries, monitoring
tactics and concepts are no longer
effective. Overall, the best strategy
to deal with the ongoing processing
of HACs is to upgrade the metal-
lurgy of the refinery to high-grade
stainless steels, such as SS317 or
SS316. However, this is typically a
long-term and capital-intensive
effort. Due to the high cost of
advanced metallurgies, shorter-
term strategies to deal with the
impact of HACs often revolve
around controlling the blended
total acid number (TAN) of feed to
the unit and/or the TAN values in
selected side cuts of the crude frac-
tionators. Additionally, effective
high-temperature corrosion inhibi-
tors have been used in a
widespread fashion to mitigate the
impact of naphthenic acid
corrosion.
By adopting a crude blending
strategy, in concert with the use of
high-temperature inhibitors and
appropriate monitoring practices,
refineries can begin to benefit from
the attractive raw material costs of
HACs while reducing their poten-
tial impact on refinery operations.
Unfortunately, this strategy suffers
from several disadvantages, which
stem from two primary categories.
The first is that TAN is well known
to correlate very poorly with actual
manifested corrosion rates in a
refinery. Consequently, running
various crudes at similar targeted
blended feed TAN levels can give
rise to very different corrosion rates
within the crude unit. The second
is that naphthenic acid corrosion
from a particular crude blend is
typically highly localised. This high
degree of localisation, and the vari-
ability of localisation from crude to
crude, prevents traditional inspec-
tion and monitoring techniques
from being effective.
The two factors mentioned above
make it challenging to understand
the actual impact of long-term
processing of HACs either before
or during their processing.2-4 To
further exacerbate these problems,
significant non-linear variances for
PTQ Q4 2013 39
12/09/2013 14:16
 makes the application of any model
providing a single corrosion rate
from a set of fluid properties practi-

s
Su

ic
cally inadequate for understanding

m
lp

a
h

yn
ur
the true impact of long-term

od
m
processing of HACs. These condi-

er
Th
tions expose the refinery processing
HACs to significant risk in terms of
both reliability and safety. This
Temperature mpy? Acid characterisation situation is largely because there is
and concentration
usually not enough practical infor-
mation available that can be used
to proactively measure and control
active corrosion, as it is occurring,
during a given processing run.
ss

M
tre

In order to combat these chal-

et
rs

al
ea

lu
lenges, inspection departments

rg
Sh

Figure 1 Principal drivers of high temperature crude corrosion
actual corrosion rates are found at
equivalent TAN levels and caused
by blended crude interactions.5
Therefore, blending the same HAC
at the same feed TAN level with
different base crudes can lead to
significant variance both in terms of
corrosion rates and patterns.
Many attempts have been made
to predict actual refinery corrosion
rates based on individual and/or
blended crude properties.4 In large,
these techniques are inadequate for
real-world applications due to
the highly localised nature of
y
naphthenic acid corrosion.
Examples abound in which a single
circuit in a refinery side-cut circula-
tion system will experience
multiple corrosion rates over a rela-
tively short time period in varied
locations. Measured corrosion rate
variances within a side circuit, such
as an HVGO circuit, often occur
typically within a range of two to
five times. For instance, measured
wall corrosion rates may be 10 mpy
in one section of piping, but could
be 40 mpy a few pipe diameters
downstream. Such behaviour
often use risk-based inspection
programs in which the frequency of
inspection is based upon historical
corrosion rates. Corrosion probes
are also frequently placed into
available valve locations to meas-
ure fluid corrosion potential. These
techniques are not sufficient for the
reliable processing of HACs.
Corrosion probes placed in the
wrong location will not provide a
realistic view of active corrosion at
the pipe wall. Additionally, it is not
economically feasible to perform
wall thickness measurements over
an adequate number of locations
with enough frequency to proac-
tively identify and react to active
corrosion. If the locations where

Critical factors affecting crude oil corrosivity

Fluid properties and Operating Geometrical Metallurgy

composition parameters parameters

Naphthenic acid Flow rate Dimensions and Material of

content configuration component

Sulphur content Temperature

Thermophysical
and mechanical Pressure
properties of
crude

Phase
composition

Figure 2 Critical factors affecting crude corrosivity

40 PTQ Q4 2013 www.eptq.com

ge.indd 2 12/09/2013 14:16

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 active corrosion is likely to occur
could be identified in some fashion,
inspection efforts could be focused
on these regions with much higher
frequencies.
A new technique outlined in this
article enables a refiner to predict
the locations at which the probabil-
ity of localised corrosion will be
maximised within an extensive
piping network. By identifying and
prioritising these specific regions of
aggressive corrosion, monitoring
and inspection resources can be
selectively deployed with much
greater granularity and frequency
in an economical way. This tech-
nique, coupled with modern online
wall thickness measurements, can
allow the impact of a particular
crude slate, in a particular refinery,
to be quickly and accurately deter-
mined. These determinations can,
importantly, be obtained in a time
frame that is short enough to allow
informed responses and decisions
to be implemented mid-run. In
combination with chemical inhibi-
tion, these techniques can allow the
refiner to process HACs with much
greater reliability and safety than
traditional methods.
Drivers for naphthenic acid corrosion
Naphthenic acid corrosion is a
complex process that is influenced
by many factors.4 Figures 1 and 2
highlight many of the drivers.
While many of these factors are
easily understood and measurable
in the laboratory, several are
dynamically impacted by refinery
piping configurations and opera-
tions. Specifically, shear stress and
day-to-day crude blending prac-
tices give rise to changes in the
specific corrosion potential of fluids
in a given circuit and also the
actual manifestation of this corro-
sion potential as measured wall
loss.
In order to better understand the
likelihood for active corrosion to
occur at a specific location within
an operating refinery, the problem
should be divided into two broad
categories. These are corrosion
potential and manifest corrosion.
The corrosion potential is a combi-
nation of the intrinsic acid properties
of the crude oils and the thermody-
www.eptq.com
ge.indd 3
Corrosion rate
Shear stress (velocity)
Figure 3 Impact of shear stress on corrosion rate
namic state of the fluid. A particular
blend of crude or an oil being
processed at the same temperature
will have approximately the same
corrosion potential.
Manifest corrosion, on the other
hand, is the actual corrosion experi-
enced at a particular point on the
equipment wall. The factors that
cause corrosion potential to be
experienced as manifest corrosion
have historically been very difficult
to predict. However, it is primarily
these factors that drive the localised
behaviour of naphthenic acid
corrosion.
As an example, all parts of an
HVGO circuit operating at the
same temperature will experience
the same corrosion potential,
however; within this same circuit;
there may be several places at
which corrosion rates are much
higher than the baseline for the
circuit. These corrosion hot spots
are of primary importance to the
refiner, because it is at these loca-
tions where wall thickness losses
are the most dramatic.
The factors primarily responsible
for changing corrosion potential to
manifest corrosion are metallurgy
and shear stress. The impact of
metallurgy is easily understood and
categorised. Relative corrosion rates
on various metallurgies at constant
corrosion potential can be easily
measured in the laboratory, or by
online slipstream devices in the
field. Many groups have either
directly explored such behaviours or
reviewed them in the literature.1-5
The impact of shear stress on
corrosion rates can also be measured
in the laboratory. However, under-
standing shear stress regimes in
complex piping networks while they
are in operation has not been previ-
ously practical.
Shear stress relation to
corrosion rates
Shear stress is one of the most
elusive drivers of naphthenic acid
corrosion. Computational difficul-
ties in this arena have traditionally
prevented the practical prediction
of corrosion hot spots within an
operating refinery. The impact of
shear stress on corrosion rates can
be qualitatively understood by
referring to Figure 3.
For the purposes at hand, shear
stress can be defined as the
mechanical force exerted on a
specific surface element of a fluid/
metal interface, such as is found at
a pipe wall. In a refinery system,
certain sulphur compounds will
react with the metal of the wall to
form iron sulphide. Since iron
sulphide is not very soluble in the
surrounding fluid matrix, it forms a
passivating scale on the metal
surface.
This sulphide scale acts as a
diffusive barrier and will reduce
the ability of naphthenic acids to
reach the metal at the pipe wall,
thus lowering corrosion rates.
Unfortunately, iron sulphide scales
are not very robust towards
mechanical stress. If enough stress
is applied to the scale, it is
damaged and/or removed. Once
the iron sulphide scale is removed,
PTQ Q4 2013 43
12/09/2013 14:16
 the metal is again exposed to acid
attack.
Naphthenic acid reacts with the
metal to form oil-soluble iron
naphthenates. These corrosion
byproducts will not passivate the
metal wall as will iron sulphides.
Therefore, in a high shear stress
environment, where sulphide scales
cannot remain as a stable passivat-
ing layer, both sulphidic and
naphthenic acid attack will prevail.
This combined acid attack under
the influence of significant shear
stress moves the system from a
diffusion-limited regime into an
erosion corrosion regime.
The amount of shear stress
required to remove a particular
region’s passivating sulphide scale
depends on many factors. However,
there is generally a threshold level
of shear stress at which the system
will move into the erosion corrosion
regime. These factors are what give
rise to the qualitative shape
presented in Figure 3.
Due to the dynamic interplay of
fluid properties and shear stress in a
piping network, particular regions
of the pipe wall are affected more
than others. This situation is what
gives rise to the complex locational
Pressure
–1.33e–2
–7.84e–1
–9.64e–1
–9.83e–1
–1.18e0
–1.40e0
–1.76e0
–2.06e0
–2.38e0
–2.88e0
–2.98e0
–3.27e0
–3.57e0
–3.87e0
–4.17e0
–4.47e0
–4.77e0
–5.07e0 In
–5.37e0
–5.67e0
–5.96e0
Figure 5 Pressure field acting on the wall of a pipe elbow
44 PTQ Q4 2013
ge.indd 4
Figure 4 Numerical grid of a pipe elbow
for computational fluid dynamics
variation of manifest corrosion hot
spots in a piping network exposed
to equivalent fluid corrosion poten-
tial. What is needed to predict the
locations of active corrosion in a
piping network at equal corrosion
potential is a shear stress map of the
pipe wall at prevailing operating
conditions. Armed with such
powerful information, it is then
possible to identify specific locations
of probable elevated corrosion with
respect to baseline conditions.
Computation of shear stress
Analytical methods have existed for
many decades for computing shear
Out
stress and other flow-related
mechanical properties in non-linear
volumetric sections.6-9 Unfortunately,
these methodologies are mathemati-
cally complex and do not easily lend
themselves to use in large and inter-
connected piping networks or other
complex geometries.
Since the advent of cheap and
powerful computational platforms,
numerical methods have been more
frequently used to develop flow
fields in complex geometrical
spaces. This discipline is generally
referred to as computational fluid
dynamics (CFD).
When using the CFD formalism,
the volumetric space is digitised
into a grid of points that define the
boundary conditions of the mathe-
matical space.10 This digital
boundary then provides a template
upon which the guiding differential
equations can be solved by various
numerical methods.11 These tech-
niques give rise to the ability to
accurately model complex and
non-uniform geometrical spaces
toward heat and mass transfer, and
many other forms of engineering
science.
Figure 4 shows an example of a
grid boundary for a typical elbow
as might be found in a refinery
piping network.
Using CFD, the appropriate fluid
flow equations can be solved, to
provide all the mechanical proper-
ties acting on the pipe wall,
including the shear stress. Figure 5
shows an example of the pressure
field acting on the pipe wall for a
section of such an elbow.
CFD provides a very useful vehi-
cle that can provide a map of shear
stress and other important proper-
ties on a pipe wall. These
calculations, when used in combi-
nation with a refinery fluids
corrosion potential, can help iden-
tify specific geometrical regions of
active corrosion within a particular
pipe section.
According to the information
outlined above, CFD is a very
powerful tool that has the potential
to provide very specific geometrical
locations for corrosion hot spots in
a refinery piping network.
Unfortunately, the methods alone
are not practical. The reason for
www.eptq.com
12/09/2013 14:16
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j mathhey.indd 1 11/09/2013 14:05

 grid Raw
would be impractical
gas conditions from a
and analysis
To amine unit resource perspective. Furthermore,
even if this digitisation task was
Temperature, °F 100
4 somehow completed, 180
Pressure, psig
the computa-
tional time required to
Flow, MMscfd 55 render the
entire flow field would also be
1 Make up Composition
Wash column 3
impractical.
H2S, mol% 12.36
HCN, ppmv 100
Mixer Utilising
NH3, ppmvCFD to model a refinery
1000
31
piping network
Methane, mol% 36.14
Refinery piping Pipeline Corrosion models Ethane, mol% modelling9.27the entire
configuration configuration developed for Although
Raw gas 24
obtained during simplified in Tear
individual
Propene, mol%
piping
2.06
network of a 2.06
refinery crude
assessment terms of stream
components
Propane, mol%
unit using
1-Butene, CFD is impractical,
mol% 1.03 as
components and
geometry outlined above, this does
n-Butane, mol% 1.03 not mean
30 Hydrogen, mol% 36.04 be used
27analyser after installation of that the technique cannot
Figure 6 Percentage of oxygen Figure 7 Tag plot for total temperature of furnaces
furnace control to provide valuable information.
2 Chemical injection locations GE2 engineers and scientists have
Table
Corrosion29potential Purge to SWS
Pumpeffi- Divider extensive experience with CFD.
essential for optimum furnace and shutdown. In order placement
Monitoring equipment to protect equipment. During shutdown, all
Some
These processes
techniquesare arehigh producers;
routinely used
ciency. If necessary, a new analyser equipment, operational procedures fuel inputs to the furnace, except
others do not seem
to design advanced products to produce
rang-
should be installed. for startup and shutdown should for pilots, must be isolated. Pilots
Figure Water
Figure 16 A washing with
new approach recirculation
to CFD applied to refinery pipework HCN at all.jetOnce
ing from produced,
turbines HCN
to modern
The main hazard for furnaces is be followed completely, and a are kept alight as a safety precau-
finds its way into the amine
convection ovens. The GE Research system
gas accumulation in the firebox and purge sequence should be carried tion so that fuel does not
than
this the dieselCFD
is that and lighter fractions. complete conversion
take anywhere of byproduct
from 24-48 hours for with
Centersthe S-containing
CFDHlaboratory, gases.
in tandem
explosion. Explosioncalculations
will occur ifare a out to remove fuel from the firebox accumulate and 2
lead to an explo-
These
very processes break
expensive and up the
time larger molecules
consum- a single such as
six-foot HCN
pipe to ammo-
section. When HCN
with forms
its inHighvarious processes
Performance
source of ignition is introduced into before a burner is ignited. sion. Low process flow through
nitrogen-containing
ing. For example, molecules
the calculationsat nia as
considering ina refia nery
high-pressure
crude unit within
Computinga refinery,
facilities, whereas HSSs
has worked
a firebox containing a flammable the tubes is a good example of
high temperatures
required to map a and
smalllow hydro-
section of hydrotreater
piping network,or hydrocracker.
there is simply too form in the amine
with the GE Refinery Corrosionsystem. Once
mixture of fuel and air. The most Safe operation “heat off” shutdown.
gen
pipe,partial
such pressure
as that conditions
shown in that much
Figure Thus,piping
HCN occurs
to quite
allow the naturally
straight- in the ofamine
Center Excellence system, variousa
to develop
hazardous periods during the oper- The primary consideration is The very poor condition of the
may not enough
be as granularity
conducive to in refineries
forward andofhas many sources. conditions
patent-pending and the presence of
methodology to
4, with
ation of furnaces are during startup to safety forusage
operating these techniques.
personnel and furnace refractory has resulted in
provide the necessary accuracy in Even attempting to digitise the achieve the stated goals. These
terms of shear stress mapping, can entire piping network into a suitable novel techniques largely solve the

Triple eccentric
Butterfly Valves
Check Valves
Double Block and Bleed
ESD Valves

www.zwick-armaturen.de
de

104
46 PTQ
PTQ Q3
Q4 2013
2013 www.eptq.com
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ogrt.indd
ge.indd 52 10/06/2013
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14:16
tupras.indd 4 08/03/2013 13:30
 challenges outlined above. The
developed methodology allows
shear stresses to be computed in
critical areas of the refinery piping
network with enough accuracy to
allow the reliable prediction of
corrosion hot spot locations, caused
by naphthenic acid-induced erosion
corrosion.
Although the piping network in
even a small refinery is extensive, it
turns out that the network itself is
made up of a much smaller subset
of repeating and standardised indi-
vidual pieces. By breaking the
problem into a subset of standard-
ised components, it can be
modularised and brought into the
reasonable realm of solution by
extensive, but available, high-per-
formance computational resources.
Figure 6 provides a pictorial exam-
ple of this concept.
To a large degree, straight pipe
that is well separated from other
geometries has overall lower shear
stress contours than more complex
components that cause changes in
fluid direction and/or velocity.
While separating the network
components into discrete compo-
nents is an important first step,
when the individual components
are within a critical distance from
one another they have the ability to
interact.
That is to say, the flow field
perturbations induced by the first
component will cause changes in
the flow field of the downstream
components. Thus, interaction
terms must be accounted for when
the components are within a certain
distance from one another. Figure 7
shows several orientations of multi-
ple 90-degree elbows that each
cause different impacts on effective
shear stress magnitudes and
locations.
By utilising the methodology
outlined above, a refinery piping
network can be analysed to develop
a shear stress map of its critical
components. This information can
then be combined with fluid and
thermodynamic data that dictate
the local corrosion potential. Once
the corrosion potential of the fluid
is determined and combined with
the shear stress mapping of indi-
vidual circuits, a comprehensive
www.eptq.com
ge.indd 6
(a) (b) (c)
Figure 7 Different orientations of pipe elbows affect the area, magnitude and location of
shear stresses
understanding of locations for high sive crude oils that must be
probabilities of active corrosion can inspected.
be developed for the entire crude By utilising the methodologies
unit. outlined above, the entire crude
unit can be analysed to both reveal
Using corrosion hot-spot mapping and prioritise the specific surfaces
to improve reliability that have the highest probability of
As was outlined in the opening manifesting active corrosion, over
section, one of the primary chal- and above baseline levels. Armed
lenges for the refiner who wants to with this information, the refiner
maximise throughput of HACs can bring inhibitor chemistries and
is to understand the impact on a variety of monitoring tools to
the refinery in a short timeframe. bear on the most critical elements.
In this way, the impact of a This benefits the refiner by allow-
particular crude blend can be ing them a high probability of
rapidly determined and balanced measuring active corrosion at loca-
against its overall cost. Standard tions where it is greatest and then
inspection technologies are gener- using measured data to mitigate
ally not sufficient to provide the corrosion rate and assess the
this level of information. This is overall cost of the crude blend.
due to the availability of both By focusing chemical and moni-
manpower and time relative to the toring resources on the most critical
large surface area exposed to corro- regions, likelihood of any adverse
Crude characterisation
NAN
•NAS && TAN
TAN
+ Asset determination
• Flow pipe size
Fingerprint& &corrosion
•Fingerprint corrosion • Velocity
Characterisation sulphur,
•Characaterisation sulphur, etc.
etc. • Temperature
Corrosionmodel
•Corrosion model • Pipe configuration and
spatial relationship
• Pipe geometry
• Shear stress
• Metallurgy
Assessment
Assessment output
• Highlight critical impact areas
• Monitoring requirements/schedule, location and sensor type
• Analysis requirements/schedule and location
• Chemical injection requirements/chemistry and application
• Baseline conditions and entitlement (expected gain)
• Develop program controls, data interpretation, training, documentation
and improvements
Figure 8 Hot spot identification programme
PTQ Q4 2013 47
12/09/2013 14:17

Priority 8.5
Metallurgy
Temp. TAN
Velocity Priority
Element-31
Priority 7.3
Metallurgy
Temp. TAN
Velocity Priority
Element-02
Figure 9 Output from a hot spot identification programme
impacts to reliability and safety are
minimised. Conversely, TAN levels
can be adjusted to allow maximum
blending of HACs at fixed corro-
sion rates rather than blending to
an arbitrary spec and hoping that
damage to capital assets is not
occurring at any undiscovered
locations.
To achieve these goals, a compre-
hensive and structured hot spot
identification programme has been
developed by GE Water & Process
Technologies. The methodology has
been vetted and proven in the field
in many refineries worldwide.
Figure 8 outlines the overall process.
Figure 9 shows a specific output
from a typical study. This is an
example of the top six hot spots for
a medium-sized crude unit in
North America. The spider graphs
illustrate the drivers contributing to
the manifest corrosion priority at
each particular location.
When a study is done on a
particular crude unit, information
48 PTQ Q4 2013
ge.indd 7
be assigned to an individual
element.
Priority 8.0
At completion, a comprehensive
Metallurgy
table, listing the relative priorities
of each element and its drivers, is
Temp. TAN obtained. This hot spot priority
table can then be used to construct
a prioritised monitoring plan and
Velocity Priority Priority 7.8 chemical injection plan.
Element-26 Metallurgy As outlined in the text above, the
benefit of having such a prioritised
Temp. TAN list of hot spots is that it enables
resources to be focused on the criti-
cal regions of piping that need
Velocity Priority
utmost protection. This then
Element-55 maximises the probability that the
Priority greatest manifest corrosion can be
monitoring detected in a rapid and proactive
points Priority 7.6 way. This specific corrosion infor-
Metallurgy
mation can then be related to the
particular crude slate and operating
Temp. TAN envelope that was in place during
Priority 7.5 the timeframe of the corrosion.
Metallurgy The spider graphs shown in
Velocity Priority Figure 9 are a diagrammatic way to
Temp. TAN Element-45 illustrate the principal drivers for
each computational element. While
greater than 10 parameters are used
Velocity Priority to prioritise each element, only four
Element-06 are shown in the spider graphs
along with the overall priority for
the hot spot. These are: TAN, veloc-
ity and/or shear stress (listed
as velocity), temperature and
pertaining to each of the critical metallurgy.
factors listed in Figures 1 and 2 are It is important to note that high
collected. Fluid properties, opera- shear stress can be realised at low
tional data and geometrical velocities and that high velocity
information for sections of the does not always drive high shear
crude piping network in the appro- stress. However, for the purposes
priate temperature range are of visualisation, both of these driv-
included. A typical study includes ers are simply stated as “velocity”.
over 400 various line segment All principal drivers are obtained
elements and associated operational by the complete model output.
information. However, the simplified spider
Each element is assigned a unique graphs are often a quick and useful
identification number. After all of way to see how manifest corrosion
this data is organised and collated, a is driven for specific elements in a
model topology is generated specific quick and intuitive way. The
to the unit. Appropriate information number under each spider graph is
is then entered into the model. A set the element number. The priority is
of sophisticated calculations is the overall priority of that element
performed for each element. The ranked against all other elements in
results of the calculations provide a the study. The axes on the spider
set of driving parameters for each graph are a relative index from 0-10
element. These driving parameters showing the magnitude of the
allow the ranking of the potential particular contribution.
for manifest corrosion to occur in By using the output from the
each specific location. In all, each study, very valuable benefits are
element receives over 10 parameters obtained, as described above. At this
upon which a priority ranking can time, over 80 such studies have been
www.eptq.com
12/09/2013 14:17
 been coinedon
performed to describe
crude units the concept.
world- And this can be done even in loca-
References technology
10 Thompson J that
F, Warsiwill trigger
Z U A, Mastin Cthe
W,
3D visualisation
wide. The technique is very can be used
robustby tions
1 thatWwould
Derungs be inaccessible
A, Corrosion, 1956, 12, (12), 41.on development of lean construction
Numerical Grid Generation, 1985, Elsevier
new recruits for facility
and has a very high probability of familiarisa- thePiehl
2 physical
R, Proc.plant.
Conf. Corrosion, 1987, NACE methodologies.
Science Publishing. It enables existing
tion, in the
catching preparation
regions of for mostvisits
aggres- to 196. legacy assets
11 Chapra to be R,brought
S C, Canale Numericalinto the
Methods
remote facilities,
sive corrosion in each circuit.or for updating 3DPiehl
3 from start Perform.,
R, Mater. to finish1988, 27, (1), 37. digital environment
for Engineers, for more effi-
2001, McGraw-Hill.
skills and when procedures following 4 Slavcheva
3D is moving out A, Shone B, Turnbull
of the B, Brit.
design
Corr. cient management, and it supports
Typically comparing actual J., 1999, 34, (2), 125.
inspection data after long cover
plant modifi cation. It can HAC office to transform the entire asset highly efficient, safe and compliant
5 Yepez O, Fuel, 2005, 84, 97. Collin Cross has been with GE Water & Process
training
runs, in operations
the worst actual corrosion or safety hot lifecycle. Combining more powerful plant operations. The future plant
6 Lai Y G, So. R M C, Anwer M, Whang B C, Technologies since 1996 and currently serves in
procedures,
spots are captured testingwithin the themost top design functionalities with the abil- will be both a physical and a
a product management role, leading the global
Proc. Inst. Mech. Eng., 1991, (205), 231.
complex
five elements.what-if In one of these emergency
cases, ity to accurately capture the as-built
7 Kim N, Rhode D L, J. Turbo Mach., 2000,
digital
Center ofentity.
Excellence for refinery corrosion
response scenarios,
with a study just completed and a or collaborative asset 80.
(110), and associate both types of control.Bennett
Simon He holdsisa aPhD in physical
Senior Productchemistry
Business
planning between
chemical injectionmulti-site plan in teams.the information
8 Lacovides H,with every
Launder other
B E, Lee typeJ. of
H Y, Inter. is Manager with Aveva in Cambridge, He
from the University of Oklahoma. UK.then
He
However, there
process of being implemented, are even more a fundamentally
Heat changing
and Fluid Flow,1996, the way we
(17), 22. accepted
has a postdoctoral
over 10 fellowship
years of experience as a with the
software
powerful ways
dramatic failureto in usea it.vacuum
Information unit create,
9 operate
Pruvost andJ, maintain
J, Legrand Legentilhomme plants.
P, J. Keck Center
product for Computational
manager Biology for
and was responsible in
management
circuit resulted in technologies
a large fire. The like It now
Chem. Eng. Sci.,provides the enabling
2004, (59), 3345. Houston. Aveva’s Everything3D.
launching
Aveva Net enable
point of failure in this circuit was 3D data —
whether a CAD
identified and ranked as themodel, a laser scan
representation,
number two or both — hot
priority to be spot.
inte-
grated and cross-referenced with Compressed air, gas and vacuum solutions
Unfortunately, this study and an
every otherprotection
associated types of engineering
plan were not or
operational data.
implemented much earlier. Navigable 3D
models can not only be combined
with other information, they can be
Conclusion
used as a powerful
Techniques to determine tool forcorrosion
working
with the vast and complex
hot spot locations within a refinery digital
plant information asset.
have been outlined. In order to
mapFor the
example,
active iflocations
a leakingofvalve proba- is
reported, an engineer
ble aggressive corrosion in a could quickly
locate it ina the
refinery, 3D view
detailed andand view or
structured
navigate to all its
methodology has been developed. related informa-
tion,
A such ashot
corrosion its spot
locationstudy on isthe a
P&ID, its
comprehensive full specifi cation,
and mainte-
labour-
nance history,
intensive effort. spares
Typically, availability
250-500
and so on. Importantly,
hours are required to complete the abilitythe
to quickly
study. collate the P&ID,
Sophisticated and the patent3D
location of the valve
pending, state-of-the-art CFD tech- and the
HAZOP analysis
niques, which can require help deter- a
mine the severity
high-performance computing of the fault: is the
labo-
fluid water
ratory, or a flammable liquid?
are utilised.
What
At the conclusion onto?
is it dripping of such What else
a study,
is in the vicinity?
the refiner is armed with specific Are there any
personnel hazards?
information that details the priori-
Maintenance
tised corrosion locations management within the is
made easier by applications
refinery. Appropriate chemical and that
show the resources
monitoring physical locations can then be of Ener gy efficiency wins!
current and planned
allocated and focused. By utilising work orders
on aoutput
the 3D representation
of the study,ofinthecombi- facil- Change over to Aerzen product solutions and be a winner by
ity. This is a valuable
nation with proper monitoring means of reducing your energy costs! The innovative blowers, compressors
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ently unrelated
inspect with sufficienttasks. frequency to
• Increased energy efficiency up to 15%
Colour-coding
quickly catch active objects in theas3D
corrosion it
is occurring in mid-run. tasks such
model view can support • Lasting reduction of life-cycle-costs
asWith
risk-based
appropriate inspection (RBI) plan-
monitoring and • Guaranteed reliability provided by the leader in technology
ning. By colour-coding
chemistry in place, each cargo the various of
lines according
HAC that is run to, into
say, flthe uidrefinery
carried Benefit now from the the innovative solutions from Aerzen!
or the
can beindividual
quickly measured plant module, and
in terms For more information see www.aerzen.com
being able to “fl y”
of its corrosion impact. A proper through the
virtual plant, it becomes
and proactive response can then be possible to
do a virtual walk-down
rapidly determined, and the overall to trace the A erzener Maschinenfabr ik G mb H
route ofofa aparticular
impact processingline, checking
strategy can Reherweg 28 . 31855 Aerzen . Phone +49 5154 81-0 . www.aerzen.com . info@aerzener.de
be balanced against total cost.objects.
its proximity to adjacent

PTQ_120x190.indd 2 15.05.2013 16:27:11 Uhr

www.eptq.com
www.eptq.com PTQQ4
PTQ Q3 2013 51
2013 49

aveva.indd 4 10/06/2013 14:15

ge.indd 8 12/09/2013 14:17
 platinum standard

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For more information about UOP olefins solutions, visit www.uop.com/olefins.

© 2013 Honeywell International Inc. All rights reserved.

uop2.indd 1 12/09/2013 11:28

SPM-UOP-36 Olefins_A5.indd 1 4/8/13 1:48 PM
 Processing strategies for metallic and
high-acid crudes
Refiners can minimise the risk of processing crudes that are acidic with high
metals content through innovative treatment chemistries

VIVEK SRINIVASAN, MAHESH SUBRAMANIYAM and PARAG SHAH

Dorf Ketal Chemicals

A
lthough light, sweet crude
supplies are declining and
10,200 Libya Chad
prices are rising, increasing
Nigeria Equatorial Guinea
volumes of opportunity crudes are
Egypt Algeria
available at attractive prices. A 9700
Sudan Angola
number of African countries, Other Africa
including Chad and Sudan, 9200
produce crudes that pose chal-
lenges during processing. Examples 8700
such as Doba, Dar and Kuito are
Production, kb/d

trading at substantial discounts. 8200

Availability and attractive pricing
make these crudes appealing to 7700
refiners seeking to increase
throughput and enhance gross
7200
margins, especially in Asia.
Notably, African crude oil produc-
6700
tion has grown rapidly in the past
decade (see Figure 1).
This article discusses successful 6200
chemical treatment strategies to
overcome the challenges encoun- 5700
tered when processing these crudes
Base prod.
(see Table 1). Topics addressed 5200
include poor oil-water separation
01

02

03

04

05

06

07

08

09

10

11

12
20

20

20

20

20

20

20

20

20

20

20

20
with heavy, conductive crudes, and
n

n
Ja

Ja

Ja

Ja

Ja

Ja

Ja

Ja

Ja

Ja

Ja

Ja

rag layer formation and catalyst

deactivation due to calcium and
iron. Ammonia, tramp amines and
high wash water pH are discussed,
as is the corrosion that often occurs
with high-TAN crude.
Challenges of African crudes
Although some refineries are
investing in hardware and metal-
lurgy to deal with these heavier,
more acidic crudes, high costs
make the hardware difficult for
many others to justify, and some of
these crude slates pose problems
that cannot be resolved with availa-
ble hardware. Typically, desalter
upsets are among the first symp-
toms of the processing problems
these crudes entail (see Figure 2)
Figure 1 Crude oil production in African countries1
Problems associated with African crudes
Example crudes Origin Processing problems
Doba Chad High metal content (calcium naphthenate), high TAN and
high conductivity
Kuito Angola High TAN, high metal content
Dar Sudan Heavy crude with high TAN and high pour point, high pour point
of middle distillate
Dalia Angola Heavy crude with high TAN
Table 1
Emulsion problems indicates that the desalter current
Stable, hard-to-break desalter emul- often increases enough to cause
sions can form when processing grid voltages to decline, further
Doba, Dalia and other heavy decreasing emulsion-breaking effi-
African crudes. Experience ciency and causing oil under-carry,

www.eptq.com PTQ Q4 2013 51

dorf ketal.indd 1 12/09/2013 14:25

 Sulzer Chemtech

Tower Technical Bulletin

Separator Technology Reduces Refinery Operating Costs and Downtime

The Challenge
A US refining company contacted us to discuss a separation
problem in the feed to an alkylation process. Caustic
entrainment from their selective hydrogenation unit was
poisoning the hydrofluoric acid catalyst in the alkylation unit.
Two prefilters with 10 micron cut-off size were provided as
part of the package to protect the coalescer from particulate
contamination in the feed.

The continuous phase feed to the alkylation unit consisted of

~180m3/hr of mixed C4 hydrocarbons, mainly butanes and
butylenes, with varying levels of 10 – 20% caustic solution
entrained as a dispersed aqueous phase.

Sulzer was commissioned to design, engineer and

manufacture a solution to the problem which would reduce
the caustic entrainment to less than 30 ppmv.

The Solution
Examination of the process upstream of the alkylation
reactor revealed that separation of the caustic entrainment
should have occurred in a gravity separator. Calculations
suggested that the gravity separator would be capable of Coalescer Skid with Prefilters and Caustic Flash Drum
droplet removal down to about 60 microns. However, the
low interfacial tension in the hydrocarbon/caustic system
was likely to result in much more finely dispersed droplets Results
and coalescer internals were therefore recommended. The complete package was engineered, manufactured and
delivered within a 15 week lead time. Installation of the
Originally planned as a retro-fit project for the gravity equipment has reduced the entrainment levels from the original
separator, the customer decided that potential 10-20% to the target levels of < 30 ppmv providing the operator
contamination with hydrofluoric acid presented too many with substantial benefits in terms of:
safety issues and a decision was made to replace the
vessel with a new skid-mounted coalescer complete with 3 Reduced downtime
prefilters and caustic flash drum.
3 Increased catalyst life
The main feature of the package was a 78” diameter 3 Reduced catalyst cost
horizontal separator vessel complete with Enhanced DC
CoalescerTM internals and Enhanced flow distribution
device.
The Sulzer Refinery Applications Group
The Enhanced DC Coalescer was manufactured as Sulzer Chemtech has over 150 years of in-house
a co-knit composite packing of 316L SS and special operating and design experience in process applications.
multifilament fluoro-polymer fiber (PTFE). The combination We understand your process and your economic drivers.
of materials with different surface free energies provides Sulzer has the know-how and the technology to design
accelerated rates of droplet coalescence at each of the internals with reliable, high performance.
thousands of point contacts between the materials – a
property of the Sulzer DC Coalescer originally patented by
KnitMesh Ltd (now a part of Sulzer Chemtech). The use of Sulzer Chemtech, USA, Inc.
the fibrous PTFE multifilament provides exceptional direct 8505 E. North Belt Drive | Humble, TX 77396
interception efficiency for very small droplets, allowing Phone: (281) 604-4100 | Fax: (281) 540-2777
them to accumulate, coalesce and eventually drain to the TowerTech.CTUS@sulzer.com
bulk phase interface in the boot of the vessel. www.sulzer.com

Legal Notice: The information contained in this publication is believed to be accurate and reliable, but is not to be construed as implying any warranty or guarantee of performance.
Sulzer Chemtech waives any liability and indemnity for effects resulting from its application.

sulzer.indd 1 12/09/2013 11:24

 Highly Salt slippage and Crude column
conductive metal partitioning of overhead
High TAN crude ammonia and corrosion due to
and tramp amine amine in the crude ammonia and Water in oil
chlorides
Naphthanic acid
corrosion in crude
column and
vacuum column Thick interfacial pad
between
230ºC (430ºF) and
400ºC (750ºF)
Increased catalyst
Desalter emulsion costs due to Oil in water
stabilisation, Calcium in deactivation by
desalted crude calcium in
migration of ammonia
and amine, downstream units
high amperage, water
carryover and oil Desalter Increased effluent
undercarry effluent system treatment plant Figure 4 Interfacial pad caused by
scaling loading
naphthenates
Ammonia-rich,
Overloaded or amine-rich
Alkaline (high pH) underperforming Metals content
wash water sour water from
sour water stripper secondary units Some African crudes contain
calcium, iron and other metals in
naphthenate form. At high pH,
Figure 2 System impacts from opportunity crude processing calcium or iron naphthenate
migrates to the rag layer, where it
water carryover, salt slippage and Demulsifier case study stabilises the emulsion and forms a
overhead corrosion. A series of A refinery in Asia processed African thick interfacial pad (see Figure 4),
laboratory tests has been developed Dar, a heavy crude with an average increasing oil levels in the brine
by Dorf Ketal to evaluate these API of 25 and a particular affinity and effluent treatment plant
highly conductive crudes and for water. The refiner struggled with loading.
prescribe effective treatment. high levels of basic sediment and Doba African crude contains up
Solving emulsion problems in water (BS&W) in the desalter outlet to 250 ppm calcium in the form of
heavy, metallic crudes requires due to ineffective chemical treat- naphthenates. If this calcium is not
highly effective demulsifier chemis- ment. Dorf Ketal’s demulsifier removed in the desalter, it can find
try. Dorf Ketal’s approach relies on treatment substantially reduced its way through the vacuum resi-
formulations specifically designed BS&W, and the treatment was so due (and, occasionally, the vacuum
for crudes with an API below 25, effective that the refinery was able gas oil) to the hydrocracker, cata-
including a proprietary combination to increase the amount of Dar in the lytic cracker and gas oil
of high-performance dehydrating blend from a maximum of 18% to hydrotreater, where it will poison
compounds, solids wetting agents approximately 23%, increasing oper- the catalyst, adding substantially to
and reverse emulsion breakers. ating margins (see Figure 3). operating costs.

Previous chemical treatment programme Dorf Ketal programme

1.0 25
BS&W
0.9
Dar
0.8 20
0.7
BS&W, vol%

0.6 15
Dar, %

0.5
0.4 10
0.3
0.2 5
0.1
0 0
Ap il
7 ril

A il
A il
A il
A il
A il
M l
30 ay
7 ay

J e
J e
J e
J e
J e
Ju e
19 ne
22 ug

31 ug
25 g
28 ug

3 g
4 p
7 ct
10 ct
13 ct
25 ct
28 ct
31 ct
3 ct
6 ov
ov
27 pri
r

14 pr
17 pr
20 pr
23 pr
26 pr

10 n
13 un
18 un
21 un
24 un
29 un

Au

Au
Se
Ap

O
O
O
O
O
O
O
M

N
N
Ju

A
A
A
1
4

Figure 3 Dar crude blend levels and desalted crude BS&W

www.eptq.com PTQ Q4 2013 53

dorf ketal.indd 2 12/09/2013 14:25

 acids such as acetic acid. Mineral
Acid-based calcium Acid-free calcium
acids accelerate overhead corrosion
removal aids removal aid and react to produce salts that can
cause fouling and scaling. Acetic
acid must be used at high dosages
CRA-1 advantages CRA-2 advantages Advantages for maximum effectiveness, and its
• Forms water-soluble • For sour and heavy • Acid free oil solubility allows it to be carried
calcium salts crude (high H2S) • Requires no separate along with the crude, where it
• Low oil solubility • Forms water-soluble corrosion inhibitor or
• Includes corrosion calcium salts scale inhibitor distills into overheads and causes
and scale inhibitor to • Low oil solubility • Forms water-soluble corrosion problems.
protect brine system • Includes corrosion calcium adduct
• Biodegrades easily and scale inhibitor to • Biodegrades easily A novel calcium removal approach
protect brine system
Dorf Ketal has developed proprie-
tary CRAs that prevent these
Figure 5 Dorf Ketal CRA functionality and advantages problems: two acid-based formula-
tions and one that is acid free (see
Figure 5). The acid-based products
are water-soluble, organic acid-
Doba Dorf Ketal trial Dorf Ketal calcium removal efficiency
based CRAs that hydrolyse calcium
Doba competitor trial Competitor calcium removal efficiency
naphthenate to form water-soluble
Data-6 96
calcium salts, which are removed

Calcium removal efficiency, %

94 via the desalter brine. Desalted
Doba crude in blend, %

Data-5
92 crude treated with these products
Data-4 90
typically contains so little calcium
(less than 10% of inlet crude) that it
88
Data-3 does not cause downstream
86 problems.
Data-2 84 The acid-free CRA forms a
calcium adduct that is soluble in
82
Data-1 water. It is biodegradable, does not
80 cause corrosion and therefore does
78 not require dosing with corrosion
inhibitor or scale inhibitor.

CRA case study

Figure 6 Calcium removal efficiency vs Doba crude % in blend
Doba Dorf Ketal trial
Doba competitor trial
Data-6
Doba crude in blend, %
A large Asian refinery processed a
crude blend containing Doba in its
desalter. The calcium content in the
parcel was more than 200 ppm. The
Dorf Ketal oil in brine
results (see Figures 6 and 7)
Competitor oil in brine
demonstrate that the Dorf Ketal
1200
CRA outperformed alternative
chemistries in calcium removal effi-

Data-5 1000
ciency and brine oil control. The
Oil in brine, ppm

Data-4 800 treatment largely eliminated efflu-

ent treatment plant overloads even
Data-3 600 with relatively high percentages of
Doba in the blend.
Data-2 400
Ammonia and tramp amine
Data-1 200 Alkaline wash water can severely
constrain desalting efficiency, and
0 pH levels as high as 9 are typical in
refineries drawing wash water from
highly loaded or under-performing
sour water stripping units. High
Figure 7 Desalter brine oil and grease versus Doba crude % in blend wash water alkalinity is caused by
the presence of basic species such
Conventional calcium removal (CRA) that use acidification to as ammonia from cracking units
For many years, refineries have remove calcium with mineral acids and from tramp amines in the feed.
relied on calcium removal additives such as sulphuric acid or organic Ammonia and amine degrade

54 PTQ Q4 2013 www.eptq.com

dorf ketal.indd 3 12/09/2013 14:25

 efficiency by stabilising emulsions
in the desalter. Under high-pH 500 220
conditions, ammonia and tramp 450
210

Amine removal aid, ppm

amine also tend to be partitioned

Ammonia salt point, ºF

400
with the crude and carried to the 350 200
crude column overhead, where
300
they form their respective salts and 190
cause under-deposit corrosion. 250
180
Refiners strive to keep crude 200 Dorf Ketal
column overhead temperatures trial period
150 170
well above salting point tempera- 100 Ammonia salt point
tures to avoid under-deposit 50 Amine removal aid
160
corrosion, and higher temperatures
0 150
limit the production of valuable 1 2 3 4 5 6 7 8 9 10
lighter products. Data number
Dorf Ketal’s approach employs
one or both of two proprietary Figure 8 Amine removal and ammonia salt point
products: a pH-management
desalter additive and an innovative for a better way to reduce ammonia ing point temperature from 98.9°C
acid-free amine-removal aid. The and amine slippage into the crude (210°F) to 91.7°C (197°F) (see Figure
pH-management additive reduces column so that it could increase jet 8). The trial successfully increased
desalter alkalinity to pH 6-7 and fuel production, which was limited refinery operating flexibility by
the acid-free amine removal aid by the relatively high overhead expanding the margin between the
reacts with these basic species to temperatures needed to operate salting point and overhead
form a water-soluble imine, reduc- above the salting point. A trial with temperature.
ing partitioning of ammonia and Dorf Ketal’s amine removal aid
amine in the crude. reduced ammonia and amines in Naphthenic acid corrosion
the desalted crude, significantly African crudes contain substantial
Amine removal case study reducing partitioning of ammonia levels of naphthenic acids that are
A Gulf Coast refiner was looking and amines, and lowering the salt- known to cause corrosion between

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PTQ Q4 2013 (125x178) Sep 2013.indd 1 05/09/2013 14:56:53

www.eptq.com PTQ Q4 2013 55

dorf ketal.indd 4 12/09/2013 14:25

 230°C and 400°C (430°F and 750°F).
They are oil soluble, so they move
through the desalter and are carried
by the process stream into down-
stream units (see Figure 9).
Acidic crudes such as Doba are
typically characterised by their total
acid number (TAN), defined as the
number of milligrams of KOH
required to neutralise pH in a
one-gram oil sample. Although
crudes with TAN above 0.5 (and
cuts with TAN above 1.5) are typi-
cally said to be corrosive between
230°C and 400°C (430°F and 750°F),
TAN alone is not definitive. Other
important indicators of corrosion
potential must also be considered.
Total sulphur content is impor-
tant, especially reactive sulphur
content. Although sulphur reacts
with iron to produce a protective
sulphidic layer above 300°C (572°F),
naphthenic acids in the crude can
compete with the sulphur to react
with metal surfaces, removing this
protective film.
Naphthenic acid corrosion and
sulphidic corrosion interact and
occur together, as described by the
following reactions:2
Fe + 2RCOOH ⇔ Fe2+(RCOO–)2+ H2
Fe + H2S ⇔ FeS + H2
Fe2(RCOO–)2 + H2S ⇔ FeS + 2RCOOH
Affected areas
Figure 9 High-acid corrosion areas in the CDU/VDU
56 PTQ Q4 2013
dorf ketal.indd 5
Advantages of new “Low P”
Dorf Ketal HTCI
• High-temperature stability
• Forms protective film
• Minimal interaction with existing
iron sulphide layer
• Does not liberate phosphoric acid
Table 2
In Reaction 1, naphthenic acid
attacks the metal, forming oil-
soluble iron naphthenates.
Simultaneously in Reaction 2,
sulphur compounds decompose at
high temperatures, generating
hydrogen sulphide (H2S), which
reacts with the metal to form iron
sulphide (FeS), which is insoluble
in oil. The FeS deposits on the
metal, where it offers limited
protection against continued naph-
thenic acid attack. However, the
H2S also reacts with the soluble
iron naphthenate, regenerating
naphthenic acids and producing
more FeS particles that tend to
remain suspended in the liquid.
Since naphthenic acids are corro-
sive at or near their boiling points,
they can create severe problems in
the atmospheric distillation unit
(1)
and vacuum distillation unit.
Atmospheric furnace curves and
(2) expansion zones are at risk, as are
atmospheric tower heavy diesel and
(3) atmospheric residue zones, together
with vacuum furnace curves and
expansion zones, the vacuum tower
light vacuum gas oil (LVGO)
system, as well as MVGO, HVGO
and occasionally the vacuum resi-
due area (see Figure 9).
Maximum protection requires a
thorough understanding of the
following factors:
• Temperature
• Velocity and metal wall shear
stress
• Sulphur and sulphur compound
reactivity
• Naphthenic acid concentration
and boiling point
• Materials of construction.
Corrosion mitigation options
There are three options for corro-
sion mitigation available to
refineries that process high-acid
crudes: metallurgy, blend-slate
changes and high-temperature
corrosion inhibitors (HTCI). Of the
three, corrosion-resistant alloys
offer the best long-term protection
from sulphidic acid and naphthenic
acid corrosion.
Of course, metallurgical upgrades
are not always possible, let alone
cost effective. Although adding
low-TAN crude to the blend slate
can provide good control, availabil-
ity and cost of suitable crudes may
foreclose this option.
HTCI provide more cost-effective
protection than metallurgical
upgrades and, unlike crude blend
changes, they can be considered
regardless of crude blend econom-
ics or availability. The most
common HTCI products are based
on phosphate esters, but these
perform poorly at low tempera-
tures, require passivation of
vulnerable metal surfaces and form
salts that can cause fouling.
Dorf Ketal recently introduced a
proprietary alternative HTCI based
on polymeric “Low-P” phosphorus-
sulphur that solves these problems.
This new HTCI contains less phos-
phorus than conventional
formulations. It provides highly
effective filming activity without
releasing phosphoric acid, and with
minimal interaction with the exist-
ing protective iron sulphide layer.
This new chemistry offers a number
of advantages (see Table 2).
www.eptq.com
13/09/2013 14:48
 HTCI performance monitoring • Thickness survey uses ultrasonic treatment chemistries and by
is essential or radiography to measure pipe systematically monitoring treat-
High-temperature corrosion is a wall thickness and plot trends that ment performance with a
complex problem that can change help to identify pipe corrosion. combination of analytical testing
rapidly in response to normal vari- and real-time monitoring.
ations in blends and processing Invasive monitoring
conditions. Careful, continuous • Corrosion coupons are exposed to Hydrosteel is a mark of Ion Science Ltd. Ceion
monitoring is critical to the success system internals and periodically is a registered trademark of Teledyne Cormon.
of any HTCI treatment programme. removed for examination and
The best approaches employ a replacement. Measurements provide
References
combination of analytical testing corrosion rates in mils per year
1 Increase in crude oil production in African
and real-time monitoring tools. • Corrosion probes measure
countries, EIA International Energy Statistics.
Analytical testing provides TAN changes in electrical resistance and 2 Kane R D, Cayard M S, Understanding
estimates, characterises the acids, provide continuous information that critical factors that influence refinery crude
and identifies the sulphur correlates with corrosive activity corrosiveness, MP 1999, July, 48-54.
compounds in the crude and side- • Ceion probes measure changes in
cut streams to help refiners conductance/resistance and convert Vivek Srinivasan is Senior Engineer, Technical
anticipate and prevent corrosion the data to corrosion rates. Services with Dorf Ketal Chemicals, Mumbai.
problems as conditions change. He holds a degree in chemical engineering
Real-time monitoring adds valuable Conclusion from St Joseph’s College, India.
information about what is actually Refiners are under considerable Email: viveks@dorfketal.com
taking place at key locations in competitive pressure to enhance Mahesh Subramaniyam is Director of Research
vulnerable systems. A variety of profitability by processing attrac- & Development with Dorf Ketal Chemicals and
leads the company’s chemical development.
invasive and non-invasive real-time tively priced opportunity crudes
He holds a PhD in chemistry from the Indian
monitoring tools are available. that can be acidic and often contain
Institute of Technology, Mumbai.
high levels of metals, but such Email: drmaheshs@dorfketal.co.in
Non-invasive monitoring crudes carry significant risks of Parag Shah works in Global Refinery Technical
• Hydrosteel measures hydrogen upsets and costly damage to critical Services with Dorf Ketal Chemicals. He holds
flux across a given surface to systems. Refiners can minimise a BEng in chemical engineering from Mumbai
provide corrosion rates these risks by exploiting innovative University. Email: paragshah@dorfketal.com

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 Maintaining reliability when processing
opportunity crudes
A risk-based approach that considers crude oil corrosivity can allow refiners to
safely and reliably process increasing levels of opportunity crude
ERIC VETTERS and DANNIE CLARIDA
CorrMat International
S
trong incentives exist in the
low-margin, highly competi-
tive petroleum refining
business to process low-cost oppor-
tunity crudes. There is also a strong
driver to reduce maintenance costs
and maximise uptime in order to
lower the per-barrel operating cost.
The problem is that, if the refiner is
not careful, these two objectives can
conflict with each other. While
some crudes of otherwise good
quality are price advantaged
because of transportation and logis-
tical issues, one of the more
common factors that drive the
discounting of opportunity crudes
is the presence of high concentra-
tions of corrosive compounds such
as sulphur and naphthenic acids. If
the refinery operator does not
understand how these feedstocks
will affect the facility, there is a risk
of excessive corrosion, leading to
increased maintenance costs and
expensive downtime.
While recent high-profile corro-
sion-related failures were not
linked to opportunity crude
processing, they illustrate the risk
involved with high-temperature
corrosion. Besides the cost of
replacing corroded equipment, a
fire resulting from the failure can
drive up the cost of the failure
exponentially. The potential for
extensive, widespread equipment
damage, loss of life and environ-
mental damage, with resulting
extended downtime for repair and
increased scrutiny from regulatory
agencies, make the cost of these
sorts of events truly staggering.
While it might be tempting for
refiners to forgo the risk of process-
ing opportunity crudes altogether,
www.eptq.com
corrmat.indd 1
Combined
Naphthenic acid
sulphur and
dominated
naphthenic acid
TAN
Sulphur
Low corrosivity
dominated
Sulphur
Figure 1 High-temperature corrosion
regimes
the consequences of shutting down
or selling unprofitable refineries is
equally unappealing. In the difficult
economic environment of recent
years, many European and US
refiners who could not or would
not process opportunity crudes
were forced to shut down or sell
their facilities at depressed prices.
The keys to successfully process-
ing opportunity crudes are in
High-temperature
corrosion can be
broken down into
three distinct
mechanisms
understanding the nature of the
feedstocks and how they will
process through the refinery, as
well as in understanding where the
greatest risks are, and then in
developing appropriate capital and
corrosion monitoring plans to
manage those risks.
The localised concentrations of
reactive sulphur and naphthenic
acids, measured as the total acid
number (TAN), in mg KOH/g oil,
are the primary factors that control
the high-temperature corrosivity of
the oil. Historically, sulphidic and
naphthenic acid corrosion are
considered to be a concern starting
at about 500°F and 450°F (260°C
and 230°C), respectively. More
recently, the industry has been
trending towards a lower threshold
temperature for sulphidation, and
an increasing number of incidents
of naphthenic acid corrosion at
temperatures as low as 350°F
(175°C) have been reported.
Besides occurring in the same
areas of the crude and vacuum
unit, the combination of sulphidic
and naphthenic acid corrosion can
be further complicated by the inter-
actions between the two
mechanisms. Sulphidic corrosion
produces metal sulphide scales that
limit the extent of attack by both
reactive sulphur compounds and
naphthenic acids. Naphthenic acids
also attack the metal sulphide
scales, thus impacting the ability of
the scales to protect against both
naphthenic acid and reactive
sulphur attack. High shear stress
due to process flow conditions is
also known to accelerate the corro-
sion process.
As Figure 1 shows, high-tempera-
ture corrosion can be broken down
into three distinct mechanisms:
sulphur dominated, naphthenic
acid dominated, and combined
naphthenic and sulphidic corrosion.
Corrosion based on the first two
mechanisms is relatively easy to
predict. The complex interactions
between sulphur, naphthenic acids,
shear stress and the different metal-
lurgies, however, can make
PTQ Q4 2013 59
12/09/2013 14:32
 predicting actual corrosion rates
very difficult when there are signif-
icant levels of both TAN and
sulphur present. Industry’s efforts
to develop models that combine the
effects of sulphur and TAN have
had limited success. What models
exist are generally proprietary
models developed by refiners using
internally generated research.
Opportunity crude impacts
If significant amounts of opportu-
nity crudes are to be processed
with minimal costly capital
upgrades and while still maintain-
ing reliability, then better strategies
for selecting feedstocks are
required. These strategies need to
move beyond traditional rules of
thumb to take a risk-based engi-
neering approach to selecting new
opportunity crudes.
In addition to high-temperature
corrosion, opportunity crudes can
impair refinery reliability through
decreased desalter performance,
increased fouling and shortened
hydrotreater run length. This article
will focus on factoring the
sulphur-dominated corrosion risk
into the assessment process when
evaluating new opportunity crudes.
The general approaches recom-
mended here are the same for
100
10
Corrosion rate, MPY
1 order of increasing complexity of
0.1
0.01
450
Figure 2 Modified McConomy curves
60 PTQ Q4 2013
corrmat.indd 2
naphthenic acid-dominated systems
and for combined naphthenic acid/
sulphur-dominated systems, but
these systems are beyond the scope
of this article because the use of
proprietary corrosion models is
required to estimate corrosion rates.
Crude oil selection
Traditionally, crude oil selection is
made by the refinery planning and
commercial functions. The refinery
planning group assesses which
crudes best fit in their configura-
tion, and the commercial group
goes out into the marketplace to
procure those crudes at the lowest
possible price.
Crude value is typically assessed
using linear computer programs to
estimate the actual expected refinery
product yields based on the proper-
ties of the crude oil and the
configuration of the refinery. The
actual crudes purchased are the
ones that generate the highest
margins (the difference between the
value of the products generated and
the crude price). Longer-term relia-
bility effects on the refinery, such as
corrosion, are often not considered
at all or are handled through some
simplified rules of thumb.
For instance, wt% sulphur limits
are typically set on refinery crude
CS
4-6% Cr
7% Cr
9% Cr
12% Cr
18-8 SS
500 550 600 650 700 750 800
Temperature, ºF
slates. These limits can be based on
a number of factors, such as the
sulphur-handling capacity of the
amine system and sulphur plants,
product specifications, emission
limits, or corrosion. Trying to
control refinery corrosion through a
total crude oil sulphur specification
is often not very effective for multi-
ple reasons.
High-temperature sulphidic
corrosion, often also referred to as
sulphidation, typically starts to
become a concern somewhere
around 450-500°F (230-260°C) on
carbon steel. The corrosion rate at
any point in the process is a func-
tion of the process conditions
(temperature and shear stress), the
metallurgy and the concentration of
reactive sulphur. The problem with
using total crude oil sulphur to
assess corrosion potential is that it
does not necessarily represent the
actual sulphur content at the loca-
tion experiencing the corrosion.
While increasing total sulphur in
crude oil typically corresponds to
increasing reactive sulphur, the
total sulphur content of the crude
oil is not a good predictor of the
reactive sulphur at any point in the
system. To maximise the sulphur in
the crude slate without sacrificing
reliability, it is important to under-
stand how the sulphur, especially
reactive sulphur, distributes in
crude fractions and how that
sulphur distribution matches up
with the actual metallurgy and
operating conditions.
Three different strategies for
setting corrosion-based sulphur
limits are presented here. There are
any number of possible variations
to these approaches, depending on
the specific needs of the refinery. In
analysis, the three approaches are:
• Fixed corrosion rate constraint
• Limits based on existing equip-
ment condition
• Limits based on existing equip-
ment condition and replacement
cost.
Fixed corrosion rate constraint
Proper setting of crude oil sulphur
limits usually requires a joint effort
of the planning or commercial func-
tions, as well as the corrosion
www.eptq.com
12/09/2013 14:32
enersul.indd 1 11/09/2013 14:19
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 engineer and process engineers.
Limits should be set based on the
actual metallurgy and operating
conditions. The most straightfor-
ward way is to look at each side
stream from the crude and vacuum
unit, and to set limits based on the
highest temperature for each metal-
lurgy in a given circuit, then to set
a maximum sulphur limit for each
stream based on a predetermined
maximum acceptable corrosion
rate.
Let us look at an example to see
how this process would work in a
refinery. The refinery in this exam-
ple processes a base crude slate that
is 30.5 API gravity and 1.22 wt% S.
Its goal is to run a more price-
advantaged crude slate by increas-
ing the wt% sulphur in the crude
slate. The refinery recognises that
increasing sulphur will increase
corrosion rates. Since sulphidation
is typically a uniform corrosion
mechanism, the refiner believes that
they can live with corrosion rates of
up to 10 mils per year (mpy) and
replace corroded equipment at
planned maintenance shutdowns
before failures occur.
The three alternative crudes that
are being considered are all of simi-
lar gravity and contain about 2%
sulphur. The sulphur distribution
in these crudes is shown in Table 1
along with the base crude. While
the total sulphur concentration of
all three new crudes is nearly iden-
tical, how that sulphur distributes
in the crude fractions varies
significantly.
The next step is to determine the
different temperature and metal-
lurgy combinations that occur on
each hot stream in the crude and
vacuum unit. This effort will
require involvement of the process
engineer to obtain the actual oper-
ating temperatures, and the use of
piping and instrumentation
diagrams to determine the actual
materials used in each system. With
this data, the corrosion engineer
can estimate corrosion rates for
both the base and alternative
crudes using the modified
McConomy curves shown in Figure
2 and the sulphur correction curves
shown in Figure 3.
If the refinery does not already
www.eptq.com
corrmat.indd 3
10
Sulphur, wt%
1.0
0.1
750ºF
550ºF
0.01
0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 16 1.7 1.8
Correction factor
Figure 3 Sulphur correction factor for modified McConomy curves
Crude and product sulphur distribution
Wt% S
Stream Base Crude A Crude B Crude C
Whole crude 1.22 1.90 1.95 1.94
Naphtha 0.10 0.34 0.05 0.05
Kerosine 0.33 0.89 0.33 0.29
Light diesel 0.83 1.72 1.02 1.32
Heavy diesel 1.16 2.16 1.62 2.33
Atmospheric resid 2.10 3.38 3.22 3.61
LVGO 1.38 2.35 1.83 2.77
HVGO 1.72 2.76 2.33 3.13
Vacuum resid 2.82 4.77 4.44 4.58
Table 1
have a positive materials identifica- corrosion failures. While most
tion (PMI) program in place to projects have PMI programs, rogue
retroactively assure the accuracy of components can work their way
the materials shown on the P&IDs, into the system during routine and
it should be considered. The pres- emergency maintenance activities
ence of undetected rogue materials unless a robust system is in place to
in existing systems can lead to prevent it. Running an advantaged
Corrosion rate estimates
Temperature, Corrosion rate, mpy
Material °F Base Crude A Crude B Crude C
Crude unit
Whole crude CS 500 5.1 5.9 5.9 5.9
Whole crude 9Cr 700 7.6 9.1 9.2 9.2
Naphtha CS 300 0 0 0 0
Kerosine CS 450 1.4 1.8 1.4 1.3
Light diesel CS 525 6.5 8.3 7 7.6
Heavy diesel 5Cr 625 8.3 11.2 10 11.5
Heavy diesel CS 525 7.3 9 8.2 9.2
Atmospheric resid 9Cr 690 8.8 10.7 10.5 11
Vacuum unit
Atmospheric resid 304 SS 750 1 1.2 1.2 1.3
LVGO CS 400 0 0 0 0
HVGO 5Cr 550 3.9 4.6 4.3 4.8
Vacuum resid 9Cr 675 8.8 10.9 10.5 10.7
Vacuum resid CS 500 6.7 7.9 7.7 7.8
Table 2
PTQ Q4 2013 63
12/09/2013 14:33
 Max percentage of opportunity crude in slate for 10 mpy limit
diesel circuit would set the maxi-
mum percentage in the crude slate
for all three crudes. In this case, the
Max sulphur for 10 mpy, Max % of new crude maximum percentage of new
Fraction wt% A B C
Heavy diesel 1.6 46 96 39
Crudes A, B, and C would drop to
Atmospheric resid 2.8 62 63 52 26%, 55% and 22%, respectively.
Vac resid 3.9 66 65 68 This strategy provides a logical
technical basis for setting limits on
Table 3 crude slate sulphur, and it is simple
to implement. The disadvantage of
crude slate is not required to have sulphur distribution in Crude B is this approach is that the setting of a
failures from the presence of rogue significantly different than in the maximum allowable corrosion rate
components, but it can significantly other two crudes, its limit is much is arbitrary. While many companies
increase the risk, especially if there higher and the limiting fraction is have targeted maximum corrosion
is a significant shift in the quality of the atmospheric resid instead of rates, this approach does not take
the crude processed. heavy diesel. If there were no other into consideration factors such as
Table 2 summarises the materials constraints, Crude B could be the condition of existing equipment
of construction, process conditions processed at a significantly higher and piping or the cost of replacing
and corrosion rate estimates for this percentage (63%) than either corroded materials.
example. It quickly becomes clear crude A or C (46% and 39%,
when inspecting Table 2 that a respectively). Limits based on existing
maximum allowable corrosion rate equipment condition
of 10 mpy is exceeded on the heavy Having a component A second strategy that is less arbi-
diesel, atmospheric resid and trary involves taking into
vacuum resid streams. These fail before the planned consideration the condition of exist-
results indicate that none of the ing equipment and setting corrosion
three crudes could be processed shutdown can cause limits based on targeted time frames
neat and stay under the maximum for replacement/upgrading of mate-
acceptable corrosion rate of 10 mpy. a very expensive rials. Typically, such replacements
Using the modified McConomy are done at routine maintenance
curves, the sulphur content that
unplanned outage on turnarounds, when the unit is
will produce a 10 mpy corrosion the whole unit scheduled to be shut down anyway.
rate can be estimated for each of It makes sense, then, to set corrosion
the limiting cases. Knowing the limits designed to ensure that piping
sulphur content and yield for each In this example, the maximum or equipment makes it to the desired
fraction of the base and alternative corrosion rate always occurred at turnaround before reaching retire-
crudes, the maximum percentage of the highest temperature in a given ment thickness. Since the corrosion
each alternative crude oil that can system, but if the metallurgy models used to make predictions
be blended into the base crude can changes as the temperature are less than perfect, it is generally
be calculated based on the three decreases there is no fundamental wise to apply some plus or minus to
limiting cuts. reason why the highest corrosion the corrosion rate estimates to build
Those results are shown in Table rate has to be at the highest temper- some conservatism into the predic-
3. The lowest percentage for a ature. For instance, if the heavy tions. Having a component fail
given crude indicates the limiting diesel transition from 5Cr to carbon before the planned shutdown can
stream for that crude. For crude A steel occurred at 540°F (280°C) cause a very expensive unplanned
and C, corrosion in the heavy diesel instead of 525°F (275°C), the outage on the whole unit.
cut sets the limit on the maximum predicted corrosion rate in the Working from the same hypo-
percentage in the slate. Since the carbon steel portion of the heavy thetical case from above, Table 4

Condition-based approach to setting maximum corrosion rates

Start date Next 2nd Max allowable predicted CR

Key dates 6/1/2013 3/1/2016 3/1/2021 No error 50% error allowance
allowance in predictions
Line Material Op temp, Historic Last Thickness, Retirement Est thickness To To To next To 2nd
°F CR, inspection inches thickness, at start date, next T/A, 2nd T/A, T/A, T/A,
mpy inches inches mpy mpy mpy mpy
6” Hvy diesel 5Cr 625 5 3/15/2011 0.29 0.15 0.279 47 17 31 11
12” Atmos resid 9Cr 690 7 3/15/2011 0.3 0.15 0.284 49 17 33 12
8” Vac resid 9Cr 675 9 3/20/2011 0.22 0.15 0.200 18 6 12 4

Table 4

64 PTQ Q4 2013 www.eptq.com

corrmat.indd 4 12/09/2013 14:33

 The new technology is profitable It is in Europe where the and refiner and He
DHP units. particularly
holds a degree the ability
in chemical
shows a simplified example of how
taking into account H2 fromtoday’s US difference between refinery
Maximum cut S foryield to anticipate
engineering
piping condition-based from market
approach Middle needsEast inTechnical
differ-
the equipment reduction condition-based Dedicated
market prices even if the middle structure and market demand is University, ent regions Turkey, and is a certified
as constraints evolve. Energy
approach might be applied to chlorine set trap Supervisor for industrial plants.
distillate price is lower than the critical, especially since conven-
Max allowable predicted CR
Maximum cut S
limits based on piping condition. In PolyFuel
Email: and PolyNaphtha
osman.karan@tupras.com.tr are trademarks of
gasoline price. Indeed, as a result of tional Line refining tools do not
Material Op have
temp, the To next T/A, To 2nd T/A, To next T/A, To 2nd T/A,
this example, the last inspection Axens. Asim Ay is CCR/NHT/ISOM Units
Mehmet
shale gas production, Reduction
LPG prices areRecycleflexibility

gas to reduce excess gasoline
°F
To booster mpy mpy wt% wt%
was done H2 toin LPG
March 2011;
chamberthe new 6” Heavy dieseland
5Cr increase
625 the 29 Process
Superintendent
11 with
>5 Tüpraş Manager
Kirikkale
2.1
low. Adding (C3 and/or C4) cut production to compressor Marielle Gagnière is Technology
crude slate is expected to start in
reduction 12” Atmospheric resid 9Cr 690 refinery.
33 He12holds
a degree
>8 in chemical
4.4
in a PolyFuel unit lowers feedstock amount of middle
8” Vacuum resid Separator
9Cr distillates.
675
for hydroprocessing
engineering
12 4from

and6.1 olefins technologies
Middle East Technical-
2013; and there are planned turna-
costs and contributes to increased Moreover, with drum
Reaction European refineries University, downstream FCC, especially oligomerisation
Turkey.
rounds in 2016 and 2021.
profitability, while maximisingsectionfacing increasing difficulty in find- Email: and etherification technologies, in Axens’
MehmetAsim.Ay@tupras.com.tr
The first step using this approach Table 5 Marketing, Technology and Technical
middle distillates production in the ing export markets for their excess Koray Kahraman is CCR/NHT/ISOM Units
is to estimate the condition of the Assistance Department. She is an engineering
refinery. Catalyst stream gasoline and given the tensions in Process Chief Engineer with Tüpraş Kirikkale
pipe at the time when Processprocessing
stream planned maintenance shutdown. In than graduate predicted
from the Ecole corrosion
Nationalerates, the
Supérieure
To reach 15% IRR for PolyFuel middle distillate supply, PolyFuel refinery. His six years of refinery experience
the new crude is expected to this example, the next two turna- maximum de Chimie de Paris, allowable predicted
and holds a post-graduate
with prices based in 2012 in the US should fulfil a primordial role in includes the process side of hydrocracker and
commence.
Figure Theadsorber
3 PFD after drum depart- rounds are being considered. Using corrosion
inspection engineering degree ratesfrom arethe then
sulphurreduced
IFP School.
Gulf Coast, the middle distillate adjusting the gasoline-distillate hydrogen Annick
production
Pucci is Deputy
plants,
Product
recovery,
Line Manager
ment should be able to provide the this approach, the maximum appropriately NHT, ISOM, CCR and basedDHP on the
units. He uncer-
holds a
price can be $96/t lower than gaso- production to better fit market in the field of light ends hydrotreatment and
measurements
measured pipe are takenfrom
thickness at the acceptable
year without a major rate
corrosion interruption,
is that tainty degree in inchemical
the corrosion engineering model.
from Middle
line. If the middle distillate price demand. a specialist in refining olefi ns processing,
outlet streaminspection
most recent of this adsorber
as welland indicating
as which would that put
the the vibration
pipe at prob- its East TheTechnical maximum
University, Turkey. allowable
were equal to the gasoline price In other regions, new tendencies Email: particularly for FCC effluent upgrading.
the resultscorrosion
historical are 0 ppm HCl,Based
rates. whereas lem was correctly
on retirement thickness identified.
just as This the predicted corrosion rates from
koray.kahraman@tupras.com.tr
($1129/t) and the LPG price kept at such as shale oil and shale gas are Arnaud She holds a bachelor’s degree in chemical
inlet
the last concentration
known conditionaverages case shows that a goodislicensorstarting.and If Table Selmen is Axens’be Technology Manager
$636/t, the IRR would reach 28%.
of the planned turnaround
revolutionising the US market, for engineering fromthen
5 can Ecole Nationaleused Supérieure
to esti-
30 ppmthe HCl. refinery relationship
only has istoessential
make it for to mate Naphtha Hydrotreatment and Reforming
pipe, time and the historic the piping
providing additional light products Technologies. des Industries Chimiques de Nancy, France. of
a maximum percentage
corrosion rate, it is easy to estimate the solving next problems that require
turnaround, a higher both sulphurEmilie Rousseau forHeeach has worked mainly with
is astream
Strategicsimilar
Marketing to
Conclusion and consequently influencing bottom-of the-barrel technologies, specialising
Conclusion
the thickness of the pipe at the time corrosion technological rate andwould operational
be more what Engineerwas doneMarketing
in Axens’ in the first example.
Department. She
With the world market for middle market balance and prices. Today in heavy crude oil upgrading. He has also been
Currently,
when processingthe H2-rich
the gasnewcompres- experience. than if it cannot be In
crude acceptable holds this case, the
a chemical 9Cr vacuum
engineering degree from resid
the
distillates growing and a reduced in the US, as a result of the impact involved in the process design of aromatics
sors are running
commences. smoothly without
The inspection depart- replaced until some turnaround piping
Ecole would
Nationale not
Supérieure make des it through
Ingénieurs en
demand for gasoline in certain Osman of shale Kubilay on is
gasKaran the the cost
Hydroprocessing
of LPG, complexes and NHT, as well as reforming
any
ment canproblem. The the
also supply compressors
retirement further
Units downSuperintendent
Process the road. Inwith case, aunits
this Tüpraş Artssecond
Chimiquesturnaround
startup and
et Technologiques
troubleshooting. cycle even
de Toulouse,
He holds
regions, the new process for olefinic PolyFuel is already profitable for a a master’s in chemical engineering from
were
thickness recently opened
for the pipe, by the it
allowing has been
Kirikkale assumed
refinery. His 25 that of refinery with
years predicted the current
an engineering degreefeedstock.
from the ByENSGTI
plan-
gasoline oligomerisation allows the mixed feed of LPG and C5/C6 cut. Imperial College in London and a master’s in
mechanical maintenance
remaining corrosion group and
allowance to corrosion rates using
experience includes the modified
the operational and ningengineeringto school
replaceandita DEA in the next
in refinery
refinery scheme to be adapted to a The flexibility of the new process energy economics and corporate management
no green oil formation was found, McConomy
be calculated. process sides curvesof crude, are +/-
vacuum50%.units, To turnaround,
process modellingand from the heavy diesel
IFP School.
maximum distillate mode. offers many advantages to CCR the Email:
from IFP School.
although
Normally, theypiping
ran forreplacements
almost one decrease
hydrocracker, the likelihood
hydrogen production plants,of an and atmospheric resid piping at
Arnaud.SELMEN@axens.net
would be done during a regularly unplanned failure due to higher the following turnaround, the

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OGT-0117 PTQ Half Horizontal Ad.indd 1 11/13/12 10:40 PM

www.eptq.com PTQ Q2 2013 21

www.eptq.com
www.eptq.com PTQ Q4
PTQ Q3 2013 33
2013 65

axens.indd 7 08/03/2013 11:49

tupras.indd 4 5
corrmat.indd 07/06/2013 14:33
12/09/2013 17:58
 Max % of crude in slate based on piping condition
Max sulphur, Max % of new crude
Fraction wt% A B C
Heavy diesel 2.1 95 100 81
Atmospheric resid 4.4 100 100 100
Vacuum resid 6.1 100 100 100
Table 6
maximum sulphur limits could be
increased, as shown in Table 6.
Those changes result in a signifi-
cant increase in the allowable
percentages of the crudes under
consideration, compared to the
approach above using fixed corro-
sion rate limits.
If this scope of piping replacement
is deemed too large then the time
frame for the analysis might need to
be extended to another turnaround
cycle. Requiring the piping to last to
the end of a third cycle would
significantly reduce the maximum
allowable corrosion rate, which
would reduce the amount of higher
sulphur crude that could be
processed, possibly showing any
increases to be impractical using the
criteria supplied.
There are a few key points to
keep in mind regarding this
approach. Since the analysis factors
in the condition of existing piping,
it is impossible to predict in
advance which parts of the system
will set the maximum limits. It is,
therefore, important to evaluate
each part of the system using actual
pipe thickness, historic corrosion
rates and predicted corrosion rates.
Depending on where it is in its life-
cycle, even a component corroding
at a low rate can potentially become
the constraint. With the use of
spreadsheets and conditional
formatting, limiting components in
the system can be quickly identified
using this approach.
Rather than assuming piping will
still have an acceptable life at an
arbitrary maximum corrosion rate,
this approach makes a best effort to
ensure that maximum corrosion
rates are consistent with unit oper-
ating and replacement objectives. In
some cases, this approach will
allow more aggressive opportunity
crude processing targets and, in
other cases, it could be more
66 PTQ Q4 2013
corrmat.indd 6
limiting, depending on the condi-
tion of existing equipment. The gap
in this approach is that it fails to
take into consideration the cost of
replacing corroded pipe.
Limits based on equipment
condition and replacement cost
That gap leads to the third
approach, which is a build-off of the
second strategy. This strategy also
factors the cost of piping and equip-
ment replacement into the equation
so that a full economic analysis of
replacement costs and benefits can
be done. For the case we have been
developing, Table 7 shows the
amount of piping that would need
to be replaced for each system.
Processing
opportunity crudes
does not have to
reduce refinery
reliability when a
systematic approach
to assessing corrosion
risk is used
In this particular unit, the limiting
section of heavy diesel piping is
only 20ft (6m) long. By also replac-
ing this short piece of pipe in the
next turnaround, the final constraint
limiting the maximum amount of
Piping replacement requirements
Line Material Length to
replace, ft
6” Heavy diesel 5Cr 20
12” Atmospheric resid 9Cr 1000
8” Vacuum resid 9Cr 150
Table 7
any of the new crudes is now
removed. This particular example
was selected to make the decision
obvious without the need for a
formal cost estimate. If the scope of
work required were more extensive,
the actual cost of piping replace-
ment could be compared with the
economic benefits of reducing refin-
ery feedstock cost to make the
optimum replacement decision.
In one project in which an author
was involved, a variation of this
approach was used to defer or
eliminate over $20 million from the
scope of a large capital project. In
this particular case, the crude slate
was set, and this approach was
used to take a more engineering-
based approach to materials deci-
sions. The particular crude slate
was both high TAN and high
sulphur, and a proprietary in-
house-developed corrosion model
was used to predict corrosion rates.
Corrosion monitoring
As was mentioned earlier, the avail-
able sulphidation corrosion models
are far from perfect. Even in simple
systems, there can be significant
differences between predicted and
measured corrosion rates. The modi-
fied McConomy curves are based on
total sulphur, but thiophenic
sulphur does not contribute to
corrosion. When the proportion of
reactive sulphur in the oil is signifi-
cantly above or below typical
proportions, predictions can vary
either high or low. When the system
is more complex, such as one with
two-phase flow and/or high shear
stress, the potential for significant
errors in predicted corrosion rates
increases even more.
It is important to have a robust
inspection and corrosion monitoring
program in place to minimise the
risk of equipment failures due to
corrosion. Since sulphidation corro-
sion is typically a fairly uniform
mechanism, traditional inspection
techniques such as ultrasonic thick-
ness and radiography are normally
effective. Other corrosion monitor-
ing techniques such as electrical
resistance probes and coupons can
also be used, dependent on process
conditions and the ability to select
safe installation locations. New
www.eptq.com
13/09/2013 14:49
 online,
the steam
control values non-intrusive
cracker
to drive the to corrosion
recover
process occur,
FCC
she a old
naphtha
holds in acorrosion
master’s secondary
in chemistry constraints
riser of thethe
from FCC amount
MBA fromA,the
9 Allen of capital.
University of Houston.
Refinery/petrochemical Processing
He is a
integration:
monitoring
ethylene
close to theor technologies
use athreshold
fouling common arewhere being
propyl- often
unit forshift,
University maximum
of Novi making
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Serbia, and a further
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registered andcrudes
professional
past, present into does
look engineer in not
the future, have
theOffshore
state
commercialised,
ene-propane
rapid exponential too,fouling
splitter whichforprovidestarts, full increases
Processing
chemistry inthethe
Technology,
from amount
2008 (89),
University or quality
864-873.
of Vienna. ofto reduce
Texas,
World, and
29 Decrefinery
is2007-Jan reliability
an inventor2008,or29-34. when a
co-inventor
real-time
integration datawithononly the the thickness
front end of 5 Ethylene, Chemsystems
of opportunity crude processed.
Email: silvia.ekres@bakerhughes.com PERP program, PERP onsystematic
10eight
ScottUSA,patents and has
al, Using
et approach published
microeconomics
to assessing nine to
thus maximising severity/conver-
the pipe. These new 08/09-5, Sept 2009.
Corrosion rates then increase in technical
guide papers.
investments
corrosion risk is used. in petrochemicals, McKinsey
of the
sion with FCC unit (consisting
respect to an technologies
acceptableof reac-
6 Kantorowicz
Bruce Wright isless S,a CBaker
processing options
Senior to
Hughessystems, on Chemicals, No 4, Spring 2012, 47.
andoffer the
tor,controllable potential
regenerator rate offorfouling.even The
and more
main previously 4corrosive
upgrade Support
Technical steam cracker
Engineer andinFCC
thestreams, 2nd
Industrial Robert
Eric ŽajdlíkD,
11 Dharia
Vetters isisaet
Slovnaft
a al, Bratislava
Catalytic
Consultant Refinery
cracking
with for
CorrMat
effective
fractionation)
approach cancorrosion
bewithused overhead monitoring,
to determine sent to requiring that they eventually be
Asian Petrochemicals
Technology DepartmentTechnology
in Sugar Land, Conference,
Texas, Technologist
integration with
of the MOL
refinery Group.
and
International LLC in Owasso, Oklahoma. During
steam the
cracker,
thewhich
the bestwetis gas critical when operating
compressor,
economical processing
whereas replaced/upgraded as well. past two years,
Korea, 7-8 May
specialising in 2002.
the hydrocarbon process Advances
He has over 30heCatalytic
in Fluid has been
years’ a technologist
Cracking,
experience CRC
in Press,
process
opportunity
the olefins
window, evenunitcrudes.
water quench
with Naphthenic
changes tower
in When an intentional approach is forengineering
the 119-126.
refinery’s LC Fining
7 NiccumHeP K,
industries. al, KBRthan
haset more catalytic olefins
30 years’ 2010, and corrosion withunit and 66.
Phillips FCC
acid
goes to
feedstock corrosion
the
andcracker tends
operations, gastocompressor
be more
because used to
technologies gradually
provide upgrade metal-
refinery/petrochemical
industry experience and is currently involved pretreater unit. He is aisgraduate
Blasis ewvetters@yahoo.com
Stamateris of the Slovak
Downstream Business
Email:
thelocalised
sharingdemonstratedthan
the sulphidicproduct
methods corrosion,
recovery
can inlurgy,
technical significant
balance, 25th
support increases
JPI andPetroleum in
Refining
troubleshooting Technical
Consultant
Dannie University, Bratislava,
in theisBusiness
Clarida President Faculty
Solutions of
Group
of CorrMat
so
rapidly corrosion
systems. 11
detect monitoring
the impact becomes of ofopportunity
Conference,
refinery fouling crude
Recent processing
Progress
problems. He in can
Petroleum
holds a BS Chemical Technology, and holds a
International LLC in Ponca City, Oklahoma, over
of Foster Wheeler, Reading, UK. He PhD
has in
and
even
Figure
fouling. more 4challenging. shows examples of inbe made
Process
chemical over
Technology, time
26-27without
engineering Oct 2010,
from sacrific-
Tokyo.
Rensselaer chemical
25 over
has engineering
years’40experience andinprocess
years’ experience theinoil control.
refining
refinery and
process
streams that are produced in refiner- ing refinery
8 Dupraz
Polytechnic C, (R)FCC
Institute,reliability
product
Troy, andand
New York, while
flexibility with
an Email: robert.zajdlik@slovnaft.sk
upgrading
corrosion atbusiness,
Conoco and andasholds a degree in
a consultant.
Ramping
ies that up can capabilities
be used on steam FlexEne, ARTC 2012, Bangkok.
spending the minimum possible chemical
Email: engineering.
Dannie.Clarida@corrmat.com
Any
crackers refiner suchthat as LPG embarks and/or on the an
LCadvantaged
use
Finingof common
is a mark crude
of Chevron program
facilities
Lummusfor expect-
Global.the
ing
This to isreduce
recovery
article based onfeedstock
of ethylene a paperand costsatwith
propylene.
presented the
noInincrease
International Bottominofrefinery
summary, maintenance
the Barrel andTechnology cost
petro-
and
Conference
chemical
to
no & capital
Exhibition,
be surprised.
• Allows
integration:
the upgrade
expenditure
Rome, May 2012.
Any ofincrease
is likely
low-value in Most proven.
sulphur
streams to in high-value
the crude products slate is very
likely
• Minimises
References
least
cal
to increase
somewhere
feedstocks,
the cost corrosion
in
since
of petrochemi-
the they
rates at
system, are
Most preferred.
1 Putek S, Gragnani A, First resid hydrocracker
which
readily will reduce
available fromthe working
the refinery life
to produce stable, low-sulphur diesel fuel
of existing
• Provides equipment. Reduced The global standard in coke drum unheading valves.
from ural vacuumstabilityresidue, over10th
ERTC the value
Annual
equipment
creation
Meeting, Vienna, chain life bymeans
2005. diversifying increased the
2 cost
product
Sherwoodfor equipment
D Eslate,
Jr, Barriers replacement.
which dampens
to high conversion
The profitability
cyclic
operations key is in being
in an ebullated-bed impact smart
unit about
relationship
how
• Reduces
between it is hydrogen
sedimentation done.and If operability,
the
productionstrategies
NCUTin
described
Workshop,
steam Edmonton, above2000.
reformers are applied when
by recovering the
McNamara
3 making
hydrogen D
decisionsJ, Sherwood
produced on new byD the Efeedstock,
Jr, steam
Bhan
Opinder
expensive K, Getting more out outages of your resid
cracker andunplanned catalytic reformer can
upgrading unit, 6th BBTC, Barcelona, 2008.
be avoided and
• Optimises the total
capital, operatingcost ofcosts the
4 Bartholdy J, Andersen S I, Changes in
change
and resources can be
through
asphaltene stability during hydrotreating,
limited.
shared The
infra-
approaches
structure
Energy and Fuels, 2000. described
for utilities here can also
supply,
improve a refinery’s
off-sites (tankage ability
allows to antic-
transfer of
ipate
refinery the need for replacingproducts
intermediate piping,
allowing
to petrochemicals,more effective common turnaround flare,
planning.
wastewater treating facilities)
and
Marco When equipment
infrastructure
Respini is a Baker Hughes reaches
(buildings, thelabo-
Technology end
of its life, decisions
Development
ratory), leading inwill
Specialist toneed
the to be
Industrial
lower
Technology
made
investments. on Group in Europe,
whether to specialising
replace the in
refinery process fouling control. He has 14
existing
The second metallurgy part ofinthis kind articleor
years’ refining experience and is currently
whether
will to upgrade
demonstrate thatthethe metallurgy.
full inte- Our innovative coke drum unheading valves have been in service for over 12 years,
involved in developing new technologies for
The
grated
monitoring
bestscheme decisions
fouling and leads are to
severity
made in the
significant
control in
and are installed in more refineries worldwide than any other unheading valve.
context
savings ofin long-term
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1 oil stability
Knight more
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J, Mehlberg aggressive
R, Maximise propylene crude
Email: marco.respini@bakerhughes.com roller screw technology.
purchasing decisions,
from your FCC unit, Hydrocarbon the upgraded
Processing,
Sep 2011, 91-95.will normally have a
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Silvia Ekres Coker
2 Kayode is a Baker HughesofAccount
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significantly longer life and can most proven, most preferred, worldwide.
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Industrial Portfolio product
Publishing, 237.
line When
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3 Bedell Ruziska P A, Steffen R, On purpose
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propylene fromapplications, made, typically
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Contact us at +1.801.984.1000 or visit http://deltavalve.cwfc.com

most
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Engineering Forum, Sept 2003, 3-4. systems
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4 Wang The G,authorC first. of As
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of cracking

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PTQ Q3 201335 67
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2013 19

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 KALDAIR

j zink.indd 1 13/09/2013 11:32

JZ-0182 PTQ-297mm x 210mm-Infographics Ad-Oct 2013 Q4.indd 1 4/26/13 12:07 PM
 How glycols affect acid gas removal

How to control the amine unit’s full acid gas capture performance over time and
so avoid operational surprises involving glycol build-up

TORSTEN KATZ, GEORG SIEDER and JUSTIN HEARN

BASF SE

R
aw natural gas usually comes
from oil wells, gas wells or
condensate wells. Besides
methane, it contains further valua-
ble components, such as ethane,
propane, butane and other hydro-
carbons. However, unwanted
components such as water, nitro-
gen, carbon dioxide, hydrogen
sulphide and other trace sulphur
components are quite common.
Before sending the gas to a sales
gas pipeline or before liquefaction,
some conditioning is required, to
purify the gas and to fulfill pipeline
or LNG specifications.
Conditioning takes place in
several steps and sometimes starts
near the wellhead. In many appli-
cations, several wells from one or
several fields are feeding raw natu-
ral gas via gathering pipelines to
one central processing plant.
Depending on project specifics, the
length of the gathering pipeline
system can consist of thousands of
miles of pipes, interconnecting the
processing plant to upwards of 100
wells in the area.1 Monoethylene
glycol (MEG) is sometimes injected
into the gathering systems. Its high
affinity towards water suppresses
hydrate formation and avoids plug-
ging of pipelines.
In the central processing plant,
the final purification takes place.
Here, pipeline or LNG specification
of the natural gas is ensured,
including the adjustment of the
acid gas content and the water dew
point. A common setup is shown in
Figure 1.
For sales gas applications, where
the natural gas is sent to a pipeline,
glycols or silica gels are common
means of adjusting the water dew
point. According to the Gas
Processors Association, a water
content of less than 7lb per million
cubic feet is a recommended value
for pipeline quality.4 For LNG
applications, molecular sieves are
the only option to achieve a water
specification of less than 0.5 ppmv,
which is necessary to avoid freez-
ing in the cryogenic section of the
plant. The dehydration unit is
usually downstream of the acid gas
removal unit (AGRU). For AGRUs
using amines, this is always

Train-A

DEG
regeneration Refrigeration

DEG Refigerant
Inlet solution
manifold
Inlet AGRU Dew point
(CO2 removal) Dehydration
separator control

HC CO2
liquid
Recycle HC liquid
gas
Raw
Sales gas
natural Stabiliser Incineration CO2 to atmosphere
to P/L
gas

Train-B

Train-C
NGL product
to export

Figure 1 Conditioning setup of a sales gas plant2

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 setup. This unusual pipeline/
Phase 1 (2004) processing setup will be found
more often in future: most of the
48" CNDG gas network
455km
US and Canadian LNG production
Krechba Hassi R’Mel facilities will receive their feedstock
compression
from the sales gas pipeline grid and
do not use dedicated pipelines. For
Field facility
38" these cases, the receiving gas has
60km Central processing facility already undergone a full condition-
Teg
Wells and gas gathering system ing process, thus the natural gas
24" 24" may have been processed by using
62km 13km glycols in the upstream condition-
Reg Phase 2 (future) ing process.
Another example of the use of
Hassi Moumene
glycols in natural gas applications
is Schroeter et al’s report3 about the
Gour setup of the In Salah gas plant in
In Salah Mahmoud
Algeria. This unit consists of three
Garet el pre-processing plants, in which,
Befinat
among others, the water dew point
of the natural gas is adjusted by
Figure 2 Overview of the In Salah gas processing plant3 using a triethylene glycol unit
(TEG) before compressing the gas
and sending it to a central process-
Molecular mass, boiling point and viscosity of MEG, DEG and TEG
ing facility, where a second TEG
dehydration downstream of the
Glycol Molecular mass Boiling point at atmospheric pressure Viscosity at 25°C (68°F) AGRU is installed (see Figure 2).
MEG 62.07 g/mol 197°C, 387°F 16.9 cP
The previous description shows
DEG 106.12 g/mol 244°C; 471°F 35.7 cP
TEG 150.17 g/mol 285°C; 545•F 49.0 cP that different glycols are being used
at different points in the production
Table 1 chain, in most cases downstream of
the AGRUs, but sometimes also
required, since the gas leaves the because major LNG production upstream of the AGRUs.
AGRU under more or less facilities always require seaport
water-saturated conditions. access, whereas the gas fields may Glycols in natural gas conditioning
In some applications, LNG plants be located far away from the The most common types of glycols
receive their feedstock from a processing site. SEGAS LNG in in natural gas application are
common pipeline grid. This is Egypt, for example, has such a monoethylene glycol (MEG), dieth-
ylene glycol (DEG) and triethylene
Dry
glycol (TEG). Whereas MEG is
gas mainly used as an alternative for
methanol for hydrate inhibition
Water (direct injection into the pipeline),
vapour DEG and TEG are being used for
1
Condenser dehydration purposes.
Glycol
pump Due to its higher boiling point,
TEG can be more easily regener-
ated to a higher purity; hence, it
Glycol achieves better water removal and
Wet 1
contactor
gas 3 Glycol lower dew point than either DEG
feed or MEG. A disadvantage of TEG is
Flash regenerator
Rich glycol
gas 2 its higher viscosity, which can
make liquid handling in plants
Skim
oil under low temperature conditions
Rich flash 3 very difficult. In these applications,
Reboiler DEG is the preferred glycol. The
setup of a glycol dehydration plant
Cross
exchanger is shown in Figure 3.
Lean
glycol To avoid condensation of hydro-
carbons in the glycol contactor, the
Figure 3 Process flow scheme of a glycol plant6 lean glycol temperature is

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bete.indd 1 26/02/2013 11:17
 be glycol saturated for the pressure
Treated gas Treated gas and temperature conditions in the
T = 30-80ºC (86-176ºF)
p = 40-75 bara (580-1088 psia)
T = 5-50ºC (41-122ºF)
p = 40-75 bara (580-1088 psia)
glycol absorber top (see Figure 4).
Even though glycol vapour pres-
sures are very low, a low
concentration of glycols will always
end up in the glycol absorber
Make-up water treated gas phase. Losses by
Lean amine Lean glycol entrainment will further increase
T = 30-55ºC (86-131ºF) T = 10-55ºC (51-131ºF) the content. Table 2 shows two gas
compositions, which will be used
for a case study in this article.
Amine absorber Glycol absorber Case 1 represents a CO2-rich gas,
Backwash section No backwash section
reduces amine losses possible which is also rich in C2 and C3+
components, whereas Case 2 repre-
Figure 4 Differences in glycol and amine absorber top sections sents a leaner gas, coming from a
pipeline.
Figure 5 shows the glycol satura-
100000 tion concentration over the
temperature range for gases with
compositions according to Case 1
10000
and Case 2 for pressures of 50 and
Glycol in gas, ppbv

70 bara (725 and 1015 psi). The

1000
100
10
1 content, neither of these two param-
0 20
(32)
Temperature, ºC (ºF)
Figure 5 Glycol content for feed gas conditions
recommended to stay 10°R (5.5 K)
above the gas inlet temperature.4,5
Common feed gas temperatures
between 5°C and 50°C (41-122°F)
result in lean glycol temperatures
between 10.5°C and 55.5°C
(51–132°F). Taking a usual TEG
flow rate of 6–8 US gal/lb H2O into
account,5 the resulting heat of water
condensation for common natural
gas pressures (p = 40–75 bara,
580–1088 psia) will only marginally
contribute to an increase in the feed
gas temperature (usually <3.6°R or
2 K). Lower feed gas pressures may
lead to somewhat higher tempera-
tures in the treated gas. However,
the assumption that the glycol
contactor dry gas temperature
equals the feed gas temperature
allows the approximation of the
minimum glycol content caused by
vapour pressure losses in the
treated gas.
MEG
DEG
TEG
40 60
(68) (104) (140)
In contrast to amine absorbers, a
glycol absorber can never have a
water backwash section to reduce
vapour pressure-induced solvent
losses, since the gas would immedi-
ately saturate with water again. As
a consequence, the treated gas exit-
ing the glycol absorber will always
Glycol treated gas conditions for the
case study
Case 1 Case 2
CO2, vol% 9.62 1.75
N2, vol% 0.76 0.50
CH4, vol% 81.3 96.05
C2H6, vol% 6.10 1.30
C3+, vol% 2.14 0.40
H2O, vol% Varies Varies
Temperature, °C 25 40
°F 77 104
Pressure, bara 59 50
psia 856 725
Table 2
values have been determined by
using the commercially available
software Multiflash,7 using the cubic
equation of state PR (advanced).
Even though the gases are quite
different with respect to acid gas
content and heavy hydrocarbon
eters has a substantial impact on
glycol solubility, at least not for
typical LNG feed gas conditions.
The glycol content in the gas
mainly depends upon the type of
glycol and the temperature. Glycol
concentrations between 1 ppbv and
100 ppmv are possible.
Liquid entrainment from the
absorber can further increase the
glycol content in the gas. In order
to minimise make-up costs, special
focus should be put on the selection
of the demister pad in glycol
absorbers.
As an example, the data from
Figure 5 shall be applied in the In
Salah Gas plant.3 The feed gas to
the AGRU had a temperature of
about 52°C/126°F at a pressure of
67 barg/972 psig. As reported, the
gas is being treated with TEG
further upstream. Assuming that
the AGRU feed gas temperature
equals the TEG dewpoint tempera-
ture, the gas contains about 350
ppbv of TEG according to Figure 5.
At 1000 MMscfd or 49 804 kmol/
hr, this equals 49 804 kmol/hr * 300
ppbv*150.17 kg/kmol = 2.61 kg/hr

72 PTQ Q4 2013 www.eptq.com

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 TEG ingress (5.75 lb/hr), or over a
period of one year = 22.9 mt. As 7
will be shown later in this article, 6
the losses of TEG via the treated

Glycol content, %
gas and the acid off-gas are rather 5
negligible; these 22.9 mt/year will
4
contribute to a TEG build-up in the
2.1wt%
system. Under consideration of a 3
total solution hold-up of 1060 mt, 1 year
this results in an annual TEG 2
Train 1
built-up rate of 2.1 wt%. A compar-
1 Train 2
ison with the results of a figure
Dilution
from Schroeter et al3 shows a good 0
fit (see Figure 6). Apr Nov Jun Dec Jul Jan Aug Feb Sep Apr
The significantly higher ingress 2007 2007 2008 2008 2009 2010 2010 2011 2011 2012
rate for Train 1 in December 2008
may be explained by additional Figure 6 Comparison of the In Salah glycol built up with results according to Figure 5
entrainment of liquid glycol drop-
lets into the unit.

How glycols affect the performance +15wt% MEG

of AGRUs +15wt% DEG
If the glycol-contaminated gas is fed +15wt% TEG
to an AGRU, traces of glycols also OASE
get into these units. In order to
PCO2

decide whether or not glycols affect

the performance of an AGRU, BASF
made lab measurements with a 45
wt% OASE purple solution by
adding 15 wt% MEG, DEG or TEG.
As Figure 7 shows, glycols have a
negative impact on the maximum
(= equilibrium) CO2 capture capac- Loading CO2, mol/mol
ity of the solvent. For a given CO2
partial pressure (pCO2) in the gas Figure 7 Impact of glycols on CO2 partial pressure and CO2 equilibrium loading
phase, the measured CO2 equilib-
rium loadings (Loading CO2) in the
OASE solution are lower in the
presence of glycols than for the +15wt% MEG
glycol-free solution. Glycols replace +15wt% DEG
water from the system, one of the +15wt% TEG
major CO2 capture reaction compo- OASE
Viscosity

nents, and thereby move the

equilibrium of the bicarbonate
formation reaction towards the
unprotonated (left) side, as shown
for the example of an MDEA-
containing solution:

MDEA + CO2 + H2O ⇔ MDEAH+ + HCO3-

This leads to a reduced CO2
capture capacity.
Also, the CO2 mass transfer is
negatively affected by the presence
of glycols, since they contribute to
an increased solvent viscosity. With
increased viscosity, however, the
mass transfer of CO2 into MDEA-
containing solutions slows down
(see Figure 8).
Temperature, ºC
Figure 8 Impact of glycols on solution viscosity and temperature
The implementation of the and viscosity, the model was
measured equilibrium and viscos- updated for all other required
ity data into BASF’s in-house physical properties (density,
simulation tool Chemasim allows surface tension and so on), as well
us to simulate the OASE process as for the enthalpy model taking
in the presence of glycols. In into account the impact of the
addition to the CO2 loading glycols.

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 losses. This, of course, will also
Treated gas Flash gas Acid off-gas reduce potential glycol emissions
from the amine absorber. Case 1
uses a two-stage regeneration
Stripper
system, which is common for gases
Make-up with the given high acid gas partial
Absorber
water Condenser pressure. The HP-flash drum
allows for hydrocarbon skimming.
HP flash The Case 2 design is simpler. Due
Lean to the low CO2 partial pressure in
solution
cooler
the feed gas, a conventional strip-
LP flash per is sufficient for regeneration,
and HP-flash is not required due to
the low C3+ content of the gas.
For both cases, the presence of
Feed
glycols in the regenerator is less
gas severe due to the high tempera-
ture/low viscosity effect. However,
Reboiler
the absorber is significantly affected
by increasing glycol concentrations
in the OASE solution.
Lean Figures 11 and 12 present the
solution Solvent/solvent results of the Case 1 study
pump heat exchanger (CO2-rich feed gas).
With increasing MEG content, the
Figure 9 Flow scheme for Case 1 (CO2-rich gas) liquid temperature and the CO2 gas
phase profile move upwards, indi-
cating that eventually the CO2 will
Treated gas Acid off-gas break through to the treated gas.
Condenser
The plant is capable of dealing with
MEG concentrations in the solution
Stripper
loop of up to 9.2 wt%. If MEG
Make-up accumulates to higher values, the
Absorber
water plant no longer meets its CO2 speci-
fication, as shown by the CO2
breakthrough curve for MEG-
Lean contaminated amine in Figure 12
solution
cooler on the left-hand side.
The temperature and CO2 concen-
tration profiles of DEG- and
TEG-contaminated amine solutions
for the Case 1 study show similar
Feed characteristics as for MEG. CO2
gas breakthrough, however, already
occurs at 8 wt% for DEG and 7.4
Reboiler wt% for TEG, as shown in the left-
hand side of Figure 12.
On the right-hand side, Figure 12
Lean shows the glycol feed gas concen-
solution Solvent/solvent trations that cause the accumulation
pump heat exchanger of the different glycols in the solu-
tion. In order to avoid CO2
Figure 10 Flow scheme for Case 2 (CO2-lean gas) breakthrough, glycol concentrations
in the feed gas have to stay below
Case study Case 2 (see Table 2) were simu- 350 ppbv (MEG), 19 ppbv (DEG) or
To estimate the impact of glycols lated. Simplified flow schemes of 2.3 ppbv (TEG). Any higher glycol
on the performance of a full the two plants are shown in Figures content in the feed gas will lead to
absorption/desorption process, 9 and 10. CO2 breakthrough over the long
AGRUs with a LNG specification Both plant designs have a water term.
(50 ppmv CO2 slip at the absorber backwash section in the absorber Figures 13 and 14 present the
overhead) according to Case 1 and top in order to minimise amine results of the Case 2 study (low

74 PTQ Q4 2013 www.eptq.com

q4 basf.indd 5 16/09/2013 13:58

 MEG content
13.4 wt%
12.4 wt%
10.4 wt%
8.9 wt%
0 wt%

Height

Absorber

40 50 60 70 80 90 0 2 4 6 8 10
(104) (149) (194)
Tsolution, ºC (ºF) y_CO2, mol%

Figure 11 Amine absorber liquid temperature and CO2 gas phase concentration profiles in presence of MEG for Case 1 (CO2-rich gas) conditions

CO2 content in feed gas). Changes

14
in the temperature profile for
MEG-contaminated OASE solution 12
Glycol in solution, wt%

are less distinct; the impact on

the CO2 profile, however, is still 10
significant. The treated gas is
8
off-spec for CO2, when the MEG
content in the OASE solution 6
exceeds 3 wt%.
MEG 4
Interestingly, there is no differ- DEG
ence in the maximum acceptable TEG 2
glycol content in the amine solution Spec. = 50ppmv
(see Figure 14) for all types of 0
glycols. This goes back to the 0 100 002 300 400 500 0.1 1 10 100 1000
viscosity-increasing effects of the CO2 slip, ppmv Glycol in feed gas, ppbv
glycols, which for higher tempera-
tures in the range of 60 to 90°C Figure 12 Case 1 (CO2-rich gas) breakthrough curves and corresponding glycol content in
(140°F–194°F) affect the mass feed gas

MEG content
13.3 wt%
11.8 wt%
8.7 wt%
7.1 wt%
0 wt%
Height

Absorber

40 50 60 70 80 90 100 0 0.5 1.0 1.5 2.0

(104) (158) (212)
Tsolution, ºC (ºF) y_CO2, mol%

Figure 13 Absorber liquid temperature and CO2 gas phase concentration profiles in the presence of MEG for Case 2 (CO2-lean gas) conditions

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Glycol in solution, wt%
Spec. = 50ppmv
0 100
CO2 slip, ppmv
Figure 14 Case 2 (CO2-lean gas) breakthrough curves and corresponding glycol content
in feed gas
transfer almost equally for all three
glycol types (see Figure 8).
The maximum acceptable glycol
contents in the feed gas are 280
ppbv (MEG), 210 ppbv (DEG) and
53 ppbv (TEG).
A further comparison between
Case 1 (CO2-rich gas) and Case 2
(CO2-lean gas) shows that a poten-
tial DEG or TEG contamination of
the feed gas is more severe for the
CO2-rich gas. This can be explained
by a discussion of the temperature
profiles. For Case 1 (CO2-rich gas),
the treated gas outlet temperature
almost equals the lean amine inlet
temperature into the absorber. Thus,
the treated gas is relatively cold and
14
12
10
8 MEG injection, can be operated (or,
6
MEG
4 into the AGRU absorber lies) with-
DEG
TEG
2 CO2 content in the treated gas.
0
002 300 400 500 10 100 1000 10000
Glycol in feed gas, ppbv
does not allow significant quantities
of glycols to be emitted. However,
Case 2 (CO2-lean gas) has a temper-
ature bulge in the top of the
absorber column, and the heat of the
CO2 absorption reaction leads to a
strong increase in the exiting gas
phase temperatures compared to the
incoming lean amine temperature.
This causes higher glycol vapour
pressure losses; thus, the plant can
accept higher glycol content in the
feed gas than applications with
higher CO2 content in the feed gas
(Case 1).
The combination of the maximum
allowable glycol content in the feed
gas, according to the heat and mass
balances of Case 1 and Case 2 (see
Figures 12 and 14), with the glycol
vapour pressure of the feed gases
(Figure 5) allows for the determina-
tion of the maximum temperature
under which a DEG or TEG unit, or
more precisely, where the glycol
dewpoint of the incoming feed gas
out causing production of off-spec
Figure 15 shows the following:
• A gas according to Case 1
(CO2-rich gas) must have a DEG
dewpoint of <1°C/34°F or TEG
dewpoint of <4°C/39°F, without
causing the production of off-spec
treated gas in the AGRU
• A gas according to Case 2
(CO2-lean gas) can have a DEG
dewpoint of <20°C/86°F or TEG
dewpoint of <35°C/95°F, without
causing the production of off-spec
treated gas in the AGRU
• MEG treatment of the gas
upstream of the AGRU absorber
will cause off-spec production for
Cases 1 and 2 for relevant MEG
dewpoint temperatures >0°C/32°F.
To treat gases with glycol
dewpoint temperatures above the
values according to Figure 15, addi-
tional glycol mitigation measures
are necessary to allow the produc-
tion of on-spec CO2 content in the
treated gas in the long term.

Case 1 (CO2-rich gas) Case 2 (CO2-lean gas)

100 000
MEG MEG
DEG DEG
TEG 10 000 TEG
Glycol in gas, ppbv

1000

100

MEG 350ppbv 10 MEG 280ppbv

DEG 19ppbv DEG 210ppbv
TEG 2.3ppbv TEG 53ppbv
1
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Temperature, ºC Temperature, ºC
<4ºC / <39ºF DEG DEG <30ºC / <86ºF
<1ºC / <34ºF TEG TEG <35ºC / <95ºF
MEG MEG

Figure 15 Maximum glycol dewpoint temperature for AGRU absorber feed gas

76 PTQ Q4 2013 www.eptq.com

q4 basf.indd 7 12/09/2013 16:18

 Options for mitigation
There
and the arelower
several options to reduce
temperature would ethylene yield increases; the recovery section of the steam
the impactcomplete
not allow of glycols coming into
vaporisation of propylene yield in the steam cracker and FCC unit are
the AGRU
main with the feed
feedstock, gas. To
leading to cracker decreases with increased integrated, because of the dilution

Vapour pressure, psia

decide which coke
unnecessary optionformation
is most appli- and severity, whereas it increases in the effect that the C4s from the FCC
cable, knowledge
deposition of the
in the feed use of any
zone. FCC unit. C4 yields remain about unit have on the combined C4s
glycol upstream
Another option of is totheuse AGRU
a sepa- is the same, but the naphtha yield stream.
very
rate important:
riser, where which the type of glycol
temperature decreases with increased severity, The main options for the produc-
was applied at which Water
and catalyst-to-oil ratio temperature,
can be opti- hence the once-through conversion tion of on-purpose propylene are:
Activator
what
misedisand thewhere
resultingthe glycol vapour
processing of of naphtha on the steam cracker is • Direct recycleMEG of C4s to a separate
pressure
the LCN in doesthenot
feed gas, and
interfere withso the
on. higher than on the FCC unit. FCC riser DEG
Not considering
cracking of the main glycolfeedstock.
in the feed In From a yields perspective, dispos- • Via metathesisMDEA
gas
this can
case,lead
the to malperformance
increase in propylene of ing of the LCN through the steam • Oligomerisation TEG combined with
the
yieldAGRU.
is still Even though
relatively this(about
small point cracker versus 50 a separate riser in recycle of the oligomerate 400 to be
may
2 wt%only on betop reached
of the one afterachieved
several the FCC could yield Temperature, better processed
ºF in a separate riser of the
years of operation,
with the mitigation
main feedstock), with meas-
low economic returns, but this needs to FCC unit.
ures will usually
conversion per bepass, required
a high sooner
gas be further investigated for each The direct recycle of the C4s cut
or later.
yield andIna the greatfollowing,
portion several
of the specifi
Figure 16c case. involves a secondary high-severity
Vapour pressure curves for thermal reclamation
options
olefins are presented:being further
produced riser parallel to the main riser
converted due to secondary reac- Option
Processing2 C4s backwash
designed tosection.
upgradeOmitting
the C4s intothe
tions 1into aromatics. Another
Option Instead
There are of increasing the capex, backwash
several commercially section is and
ethylene, propylene therefore
catalytica
Consider
option to the glycol
dispose of content
the LCNinisthe to there
proven is also
waysan option to go ahead
to upgrade C4s means
naphtha.to Sometolerate
fuelhigher
gas isglycol
also
feed
send gas during
it along withthethe design phase;
straight-run with
produced a standard
from the design
FCC unit of and
the content
produced.in the
Thefeed gas. However,
products from both it
additional
light naphtha margins
to a steam in the solvent
cracker. AGRU by accepting
steam crackers. 6 increased
Figure oper- will
1 illustrates risersalso leadattothe
merge increased
reactor amine
outlet
circulation rate, heat
Table 2 compares exchanger
the yields that ational
some of the expenditures
options. (opex). Not losses (higher
and travel as aopex)
common and stream
is there-
to
duties
can be and absorber
obtained when height can
cracking installing
Although a water-backwash section fore
the butadiene content the mainnotfractionator.
the most preferred
compensate
naphtha on aforsteam glycol ingress
cracker into
versus in
of Cthe
4
absorber
s from the top
steamwill slightly
cracker is mitigation
An advantage measure.
of thisAlso,
processthisis
the
in a AGRU
separatewithin
riser on a acertain range.
FCC unit. increase
significantlythe vapour pressure
higher than losses
that of the glycol mitigationhydrotreatment
that selective measure is limited for
AsThea consequence,
trends are similar mainlyincapitalboth of
FCC glycol
unit, exiting the absorber
the potential top to
to recover thea certain glycol feed gas
diene conversion concen-
of the C4s
expenditures
cases. As the (capex)
severitywill increase.
increases, the compared
butadiene isto lost a when
plant thewithlighta tration
stream range
as well only.
as the removal of

www.eptq.com PTQ Q4 2013 77

14 PTQ Q3 2013 www.eptq.com

q4 basf.indd 8 12/09/2013 16:18

fw.indd 3 10/06/2013 12:33

 the AGRU. This requires additional
equipment. A water scrubber is the
Treated gas 60
easiest and most beneficial way of
Make-up doing this.

MEG content treated gas, ppbv

water
50 For the Case 1 scenario, some
scrubber simulations were
Water 40 performed, assuming 1 ppmv of
wash MEG in the feed gas. Figure 17
shows the configuration. The water-
30
wash section can be designed with
a pumparound, allowing a signifi-
20 cant removal rate of glycol so that
only a small portion of make-up
10 water is needed. Per 100 MMscfd of
Feed gas feed gas, roughly 0.7 GPM of
with glycol make-up water is needed to reduce
0
0 1 2 3 4 5 6 the MEG content down to 10 ppbv,

Water bleed
Make-up water
/
Feed gas,
which is lower than the critical
concentration of MEG (<350 ppbv),
(glycol) GPM/100mmSCFD
where some impact has to be
expected on the performance.
Figure 17 Performance of the removal of MEG (1 ppmv in feed gas) for Case 1 using a
water wash Option 7
Another option to avoid getting
Option 3 pressure and therefore cannot be glycols into amine-operated AGRUs
Continuous, or intermittent, bleed- thermally separated at all with is to replace them with alternative
ing of solvent and substituting it reasonable effort processes. Instead of MEG, metha-
with fresh solvent offers another • TEG is the heaviest boiling nol offers an alternative, which,
option to operate the plant at full component and therefore requires due to its lower boiling point, is
capacity and to balance the incom- evaporation of all other compo- much easier to handle in an AGRU
ing glycol quantities with the exiting nents first. This is very costly. than MEG. In other applications,
quantities. To minimise accompany- Thermal reclamation always glycols have been replaced with
ing amine losses, the stream with requires vacuum distillation in adsorption processes operating
the highest glycol-to-amine ratio order to avoid thermal degradation with silica gels such as Sorbead. As
should be selected. This is usually of the amines. well as dehydration, they allow the
the lean amine stream. Increased recovery of natural gas liquids
opex and potentially complicated Not considering (NGL), which for some applications
solvent disposal are unwanted increases their attractiveness. They
consequences of this approach. glycol in the feed also facilitate the operation of pipe-
Practically, it is expected that a lines, since glycol fouling is not an
combination of a slight adjustment gas can lead to issue any more.
to the plant design and allowing a
bleed stream is the most cost- malperformance Summary
effective way to mitigate the impact Glycols in natural gas applications
of glycols on the performance of
of the AGRU are widely used for hydrate
the AGRU. suppression or dehydration
purposes. Even though they have
Option 4 Option 5 relatively low vapour pressures,
Thermal reclamation of glycol- Reclamation by applying ion traces of glycols will end up in the
containing amine solutions is exchange is a possible way to sepa- natural gas. Gas phase concentra-
extremely difficult and depends rate amines from glycols. In this tions between several ppbv up to
very much on the solvent compo- case, the amines (and not the several hundred ppmv are possible.
nents and glycols in use. The glycols) will be removed from the The use of demisters can only
vapour pressure curves (see Figure solution, which makes it a very reduce liquid entrainment of
16) show that for MDEA-containing costly method. glycols into the natural gas. Gas
solvents: phase losses, however, will always
• MEG boils in-between MDEA and Option 6 contribute significantly to overall
one activator component, which Option 6 offers the most sophisti- glycol losses.
makes thermal separation difficult cated way to deal with glycols in In most natural gas applications,
• DEG and MDEA have more or gas conditioning: removing them in glycols are being used downstream
less exactly the same vapour a pre-treatment step upstream of of AGRUs; some companies,

78 PTQ Q4 2013 www.eptq.com

q4 basf.indd 9 12/09/2013 16:18


however, operate glycol units
upstream of AGRUs. For these
applications, it is important to
know the glycol dewpoint of the
natural gas at the AGRU inlet in
order to determine the absolute
glycol ingress to the amine units.
Major quantities of the incoming
glycols will accumulate in the
amine units up to significant
concentrations (>15 wt%), since
glycols are heavy boiling compo-
nents and do not easily leave the
system. They have a negative
impact on the acid gas capture
capacity and on the absorption
kinetics, and thus may limit the
treatment capacity of a natural gas
conditioning plant.
To mitigate the effects of glycols,
Bryan Research & Engineering Technical Papers,
www.bre.com/portals/0/technicalarticles/
Design%20Glycol%20Units%20for%20
Maximum%20Efficiency.pdf
6 en.wikipedia.org/wiki/Glycol_dehydration
7 Multiflash: DLL Version 4.0.08 February
2011, Infochem.
Torsten Katz heads the Global Technology
Group of BASF SE in Ludwigshaven, Germany,
and coordinates new business development
activities in the gas treatment field. He holds
a degree in mechanical engineering and a PhD
in desalination technology from the Technical
University of Aachen, Germany.
Georg Sieder is Research Manager for Sour
Have you got used to the
Gas Treatment with BASF SE in Ludwigshaven
and was previously Technology Manager for
Gas Treatment Process Technology and project
leader for BASF’s Flue Gas Carbon Capture
Technology development. He holds a master’s
degree and a PhD in mechanical engineering
from the Technical University of Kaiserslautern,
Germany.
Justin Hearn joined BASF in Dubai, and
since 1998 he has been located in Germany
and working in the Gas Treating Group. His
focus has been the process design, start-
up and continuing optimisation of BASF’s
gas sweetening plants in Europe, the Middle
East and Africa. He graduated in chemical
engineering from Bradford University, UK.

oil consumption
several counter-measures are possi-
ble. These range from accepting
glycols in the feed to the AGRU
and considering extra design
margins to the AGRU, bleeding for granted?
part of the glycol-containing
solvent or avoiding significant
glycol ingress to the units. This can Have you
be done either by applying a water-
wash step upstream of the AGRU got used to the

oil leakage
or by replacing glycol processes
with alternatives, such as methanol
(hydrate inhibition) or silica gels
(dehydration). Reclaiming of
glycol-contaminated amine is
another possible but costly means.
In any case, the knowledge that of your metallic oil wiper rings?
the natural gas to be treated in an
AGRU will contain glycols requires
adequate glycol mitigation measures Packings featuring metallic ring designs cause piston rod wear and,
to avoid running into operational
paired with oil losses, result in large costs over time.
surprises once the AGRU is in oper-
ation for several years. The design of the new non-metallic OFD oil wiper ring incorporates
HOERBIGER’s expert knowledge on reciprocating compressors and is the
OASE and Sorbead are marks of BASF
SE. Multiflash is a mark of KBC Advanced result of substantial research work. Take advantage of our experience!
Technologies plc.
The new OFD wiper ring at a glance:
References
1 NaturalGas.Org: www.naturalgas.org/ „ No oil leakage thanks to superior sealing
naturalgas/processing_ng.asp efficiency and use of elasto-hydrodynamic effects
2 Tanaka K, Fujimura Y, Katz T, Spuhl O, HiPACT
– advanced CO2 capture technology for green „ Optimal conformity between ring and rod
natural gas exploration, LRGCC conference „ Long service life of wiper rings and piston rod
proceedings 2010.
3 Schroeter R W, Eguren R, Hearn J, Koelmeyer
P, Bensot M, Investigating constraints on CO2 For more information:
removal at the In Salah gas plant, LRGCC ringsandpacking@hoerbiger.com
conference proceedings 2012.
4 GPSA Handbook, 10th edition. www.hoerbiger.com
5 Hernandez-Valencia V N, Hlavinka M W,
Bullin J A, Glycol units for maximum efficiency,
OFD_PTQ_4.indd 1 05.09.2013 11:57:12

www.eptq.com PTQ Q4 2013 79

q4 basf.indd 10 13/09/2013 14:50

 ThyssenKrupp Uhde –
Engineering with ideas.
The key to our success is the creativity and resourcefulness of
our employees. And it is this that keeps turning major challenges
into solutions that are not only brilliant and innovative, but often
set the standard for the entire engineering sector.

www.thyssenkrupp-uhde.de

ThyssenKrupp Uhde

uhde.indd 1 11/09/2013 14:03

 Extending the treatment of highly sour
gases: part 1
The removal of acid gas components from highly or super-sour gases requires the
optimum choice of process
FRANÇOIS LALLEMAND, GAUTHIER PERDU and LAURENT NORMAND Prosernat
CLAIRE WEISS Total EP
JULIA MAGNE-DRISCH and SEBASTIEN GONNARD IFP Energies nouvelles
F
or decades to come, gas will be
an energy source of choice to
meet increasing energy
demands. Oil and gas operators
have always preferentially produced
the gas from those reservoirs that
are technically the easiest and the
cheapest to develop, but they will
have to develop fields with a higher
acid gas content in the future.
Effectively, over 40% of the world’s
conventional gas resources currently
identified as remaining reserves to
be produced, representing over 2600
trillion cubic feet (tcf), are sour, with
both H2S and CO2 present most of
the time. Among these sour
reserves, more than 350 tcf contain
H2S in excess of 10%, and almost
700 tcf contain over 10% CO2.1
The Middle East, the Caspian Sea
area and China have gas reserves
with a high H2S content, while large
amounts of gases with a high CO2
content are encountered in South
East Asia and, to some extent, in
South America and North Africa.
Removing the undesired acid
gases from highly sour gases is a
costly operation. The size and cost
of the acid gas separation units and
of the acid gas-handling facilities
(transformation of the H2S into
sulphur and forming/shipping of
the produced sulphur, or acid gas
compression/pumping and reinjec-
tion facilities) increase with the
amount of acid gases to separate. In
the meantime, the volume of sales
gas exported decreases because of
the reduced hydrocarbon content of
the inlet raw gas, and because of the
increased auto-consumption for gas
treatment. As a consequence, the
technical cost per volume of
exported sales gas is roughly
www.eptq.com
prosernat.indd 1
doubled every 20-25% of additional Most experts consider that this
acid gases present in the raw gas situation is set to continue for
(see Table 1). several decades, at least in several
To ensure economic develop- parts of the world. The production
ment of these fields, very efficient of major oil or gas fields in the
technologies are therefore needed Middle East or in the Caspian Sea
to separate large amounts of acid area could lead to the production of
gases at controlled costs. Prosernat considerable quantities of additional
implements several solutions sulphur in an already saturated
within the AdvAmine series of market, while the storage of extra
processes, some of them developed sulphur in the long term is also an
in a collaboration between Total issue that requires significant capital
and IFP Energies nouvelles/ to be resolved. This is why new
Prosernat. This article presents production methods give the green
some optimisations of the process light to develop ultra-rich H2S gas
scheme that give rise to new devel- fields in places where economic
opments at demonstrated and interest does not rely on the addi-
attractive economic duties. tional production of sulphur.
Sulphur, the traditional sub- Companies willing to produce
product from the treatment of gases large gas fields with very high
containing high amounts of H2S, amounts of CO2 have to face a
formerly represented a substantial different constraint, related to the
part of the revenues drawn from the essential need to reduce atmospheric
production of such gases. It is no emissions of greenhouse gases.
longer of economic interest to sell Economics may also be improved
sulphur from several areas today, by the growing acceptance of the
especially those locations far from reinjection of separated H2S and
the sea and the sulphur users. The CO2, for enhanced oil recovery
world sulphur market is globally (EOR). Separated acid gas reinjec-
saturated, as the supply of sulphur, tion into a depleted reservoir or an
mainly obtained from H2S separated aquifer, as a feasible alternative to
from sour natural gases or sour costly sulphur recovery to a dimin-
crude, has exceeded demand, essen- ishing sulphur market, or to
tially from the fertilizer industry. limit atmospheric emissions of
Relative technical cost of sour gas production versus acid gas content
Production of pipeline Sweet gas Highly sour Ultra-sour
gas, with AGI 20% acid gas 40% acid gas
Sales gas, % of raw 98 75 52
Capex, MM$ % 100 140 185
Opex, MM$/year % 100 160 200
Technical cost, $/mmBtu % 100 200 400
Note: Acid gas = H2S + CO2
Table 1
PTQ Q4 2013 81
12/09/2013 16:39

Lean solvent
Sour Rich solvent
gas
Figure 1 Acid gas removal unit design
greenhouse gases, increases the
number of highly sour gas fields
that can be reconsidered as exploit-
able to produce much-needed
natural gas.
These new constraints lead to the
development of more energy-
efficient technologies for acid gas
separation, adapted to these new
production schemes. With this
objective, in addition to the
AdvAmine series of gas sweetening
processes using amine-based
solvents, Total, IFP Energies
nouvelles and Prosernat have
developed the Sprex and SprexCO2
processes for the production of
Lean solvent
Semi-lean solvent
Sour
gas
Figure 2 The conventional double-split flow design
82 PTQ Q4 2013
prosernat.indd 2
Treated
gas
Acid
gas
LP steam
Fuel
gas
highly sour gas reserves with acid
gas reinjection. Discussion of these
processes will be the subject of the
second part of this article, to be
published in PTQ at a later date.
Optimisation of amine processes for
highly sour gas treatment
Amine processes (see Figure 1)
have been used for many years to
remove acid gases from natural and
associated gas streams. They are
very versatile processes, which can
be used to treat all types of sour
gases, regardless of the H2S and/or
CO2 content, down to the most
severe specifications, such as those
Treated
gas
Acid
gas
LP steam
Fuel
gas
imposed by gas liquefaction plants.
But the cost of gas sweetening
increases with the amount of acid
gases to be separated, requiring
larger amine solution flow rates and
higher energy consumption for
amine solution regeneration. On the
other hand, amine processes,
because of the variety of amines that
can be used and the possibility to
adapt and improve the process flow
schemes, can be efficiently used for
almost any type of gas sweetening
application. Amine-based technol-
ogy can therefore actually be
considered as the workhorse of the
sour gas processing industry and, as
such, still justifies continuous tech-
nological improvements to extend
the economical limits of its applica-
tions. Issues such as treatment costs
and energy consumption are
addressed by such developments.
Treatment of such highly sour gas
goes far beyond the usual basic
design practices employed in the
first stage of a process design of an
acid gas removal unit. One usual
criterion is the need to stick to
moderate acid gas loading of the
amine solution.
Capital and operational savings
cannot be met without attractive
solvent loading and deep thermal
integration of the rich solvent regen-
eration section, based on the
self-regenerating properties of
highly loaded solvents when they
are moderately flashed or heated.
The base use of highly loaded
solvent at high temperatures should
nevertheless be coupled with new
recommendations for unit design,
especially in terms of sizing criteria
and metallurgy requirements.
This article primarily discusses
design perspectives to handle high
contents of acid gas in the feed and
describes some improvements to
optimise plant design in such condi-
tions. It also describes how such
perspectives have been secured by
the long-term operation of Total in
its highly sour gas treatment plants.
The article also presents solutions
proposed by Prosernat for efficient
and economic treatment of gases
with high acid gas contents, either
H2S or CO2. Among these solutions,
some are now widely proposed by
several licensors, while others have
www.eptq.com
12/09/2013 16:40
 been developed through the joint
R&D effort of Total, IFP Energies
nouvelles and Prosernat.
Double-split flow process
configuration
Among the oldest process configu-
rations, the double-split flow design,
sometimes called split-flow design,
has been used as an alternative
flowsheet to minimise capital and
operating costs in several sour gas
processing plants. Generally used
with primary or secondary amines,
this design enables very severe
treated gas specifications for the
same reboiler duty as in the conven-
tional process flow scheme and was
documented, probably for the first
time, in 1962.2 But the double-split
flow design also enables the same
treated gas specification as the
conventional amine plant scheme
with a much-reduced reboiler duty
when treating very sour gases. The
conventional double-split flow
design is shown in Figure 2.
In this design, part of the amine
solution is withdrawn from the
regenerator as a side stream, then
cooled and pumped into the lower
section of the absorber. The amine
in the side draw is not fully regener-
ated and has a higher residual acid
gas loading. However, as this semi-
lean solution contacts the incoming
sour gas, it can still pick up the bulk
of the acid gas. Due to the semi-lean
amine side draw, the amine flow to
the regenerator reboiler is reduced,
and the duty of the reboiler can be
decreased to achieve the same lean
amine quality required on top of the
absorber column to meet the treated
gas specification.
energizedMDEA for the treatment of
very sour gases
The main factors affecting a
solvent’s performance for acid gas
absorption are its ease of regenera-
tion, and the related solubility and
reactivity of acid gases.
Tertiary amines require less regen-
eration energy than primary and
secondary amines. Being a tertiary
amine, MDEA therefore requires
less reboiling duty than DEA. It is,
however, well known that MDEA
reacts slowly with CO2. This particu-
larity, which is used to advantage
www.eptq.com
prosernat.indd 3
MDEA
DEA
10000
Pressure, mbar
1000
100
0.2 0.3
Figure 3 Equilibrium solubility of CO2 in aqueous amine solutions
for the selective H2S and controlled
CO2 removal, becomes a handicap
to complete acid gas removal, espe-
cially when a substantial quantity of
CO2 has to be removed. To over-
come this kinetic obstacle, energisers
were sought among secondary
amines having high speeds of reac-
tion with CO2 to blend into the
otherwise desirable MDEA solvent.
Several energisers were selected by
Total from among those best suited
to industrial conditions, taking into
account commercial availability, cost
and impact on the environment.3
While the reactivity of CO2 with
MDEA is lower than with DEA, its
solubility in MDEA is more strongly
influenced by CO2 partial pressure
than by its solubility in DEA. This
can be shown by the slopes of the
equilibrium solubility curves (see
Figure 3).
The basic concept of an efficient
process for the removal of large
quantities of acid gases consists of
taking advantage of the slope of the
equilibrium solubility curves of CO2
in aqueous MDEA solutions, to be
able to liberate a maximum amount
of the acid gas from the solution by
simple physical pressure letdown
flash and thus substantially reduce
the thermal regeneration duty. For
example, as shown in Figure 3, the
MDEA solution releases almost
twice as much CO2 as the DEA solu-
tion by a pressure letdown from 10
bar to 1 bar. In addition, the equilib-
rium solubility of H2S in aqueous
MDEA exhibits similar behaviour
to CO2, allowing an equivalent
DEA
MDEA
0.4 0.5 0.6 0.7 0.8
CO2
/ Amine, mol
amount of H2S liberation by pres-
sure letdown. energizedMDEA
approaches the equilibrium curve of
MDEA at high pressure, but
behaves like DEA at low acid gas
partial pressures. This is achieved
thanks to the blend of an energiser
with MDEA, generally a secondary
amine.3,5
This particularity of energizedM-
DEA to release a substantial part of
the absorbed acid gases in a
low-pressure flash can be combined
with the introduction of a semi-lean
solvent in the bottom part of the
absorber, as in the double-split
flow design described above (see
Figure 4). The specificity of ener-
gizedMDEA is that it combines the
characteristics of secondary and
tertiary amines, based on the blend
of various amine molecules. Given a
certain concentration of secondary
amine, it is possible to associate its
performance at low acid gas partial
pressures (the ones encountered in
the upper section of the absorber) to
the capacity of tertiary amines, to
load greater contents of acid gases
at high acid gas partial pressures
(the ones encountered in the lower
section of absorber). This is espe-
cially valid for CO2, because it does
not react directly with MDEA but
with secondary amines.
The rich amine solution after
letdown through a hydraulic turbine
is divested of co-absorbed light
hydrocarbons in a first flash drum,
as in the conventional process, then
further expanded to a low pressure
in a second flash drum, to partially
PTQ Q4 2013 83
12/09/2013 16:40
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 liberate CO2 and H2S. The greater
part of the rich amine thus partially
regenerated is returned to an inter-
mediate level of the absorber as a
semi-lean solvent. This semi-lean
solvent loop is particularly
economic, as it reduces the thermal
regenerator load and consumes only
pumping energy.
When H2S is present and/or the
treated gas specification calls for the
removal of CO2 below the 2 vol%
range, thoroughly regenerated,
virtually H2S- and CO2-free amine is
required. This is accomplished in a
conventional thermal regenerator,
returning a small flow of the leanest
amine to the top section of the
absorber.
In 1990, the new solvent and
regeneration system was tested on
an existing DEA unit at the Lacq
sour gas plant in southwest France,
which was then converted to the
energizedMDEA process.4,5 This
process was also used in several
other locations, such as offshore
North Sea, at Elgin Franklin for
controlled CO2 removal, and in
Venezuela, Egypt, Iran and Yemen.
Different energisers have been
patented to suit specific cases: total,
partial or controlled CO2 removal,
with or without H2S.
The performance of the process is
closely related to site-specific treat-
ment conditions, notably feed gas
composition and treated gas
specifications. Some practical rules
of thumb to highlight the general
interest of regeneration by flash
include:6
• The greater the H2S and/or CO2
partial pressure in the feed gas, the
greater the efficiency of the flash. In
the case of the Lacq sour gas plant,
the acid gas partial pressure of the
feed is approximately 15 bar in
comparison to a total pressure of
2 bar in the second flash drum. This
gives a ratio of 7.5/1 (acid gas
partial pressure/flash pressure). In
general, the advantage of the
flash-procured regeneration starts
above a ratio of 3
• Targeting low H2S content in the
treated gas requires a thermal regen-
erator to clean up the solvent down
to low H2S residual loading. The
overall energy consumption of the
energizedMDEA unit increases as
www.eptq.com
prosernat.indd 4
Lean solvent
Semi-lean solvent
Sour
gas
Figure 4 Split-flow design with energizedMDEA
the treated gas specification becomes
more stringent, since the amount of
lean, totally regenerated amine from
the thermal regeneration increases.
In some bulk CO2 removal cases,
with no H2S, as mentioned, it may
even be possible to completely elim-
inate the thermal regenerator.
As a consequence of the above
attributes, the energizedMDEA
process is well adapted to the treat-
ment of high-pressure and very sour
gases, where the advantages of
flash-procured regeneration will be
maximised to reduce the energy
footprint of the sweetening.
High loading in amine sweetening
The effort towards moderating the
solvent flow rate along with the
reboiler duty quickly brought some
process developers and, later on,
plant operators to consider increas-
ing the acid gas loading of the rich
amine leaving the absorber.7 The
maximum achievable loading is
controlled by the thermodynamic
equilibrium between the sour gas
entering the absorber and the rich
amine, and by the efficiency of the
mass transfer in the absorber: the
higher the acid gases’ partial pres-
sure in the sour gas, the higher the
amine loading at thermodynamic
equilibrium. High H2S and CO2
partial pressures will therefore
invariably allow a high amine load-
Treated
gas
Acid
gas
LP steam
Fuel
gas
ing, with the benefit of improved
process efficiency. Loadings higher
than 0.8 (mole of acid gases per
mole of amine) can theoretically be
achieved when the acid gases’
partial pressure is above 15-20 bar;
that is to say, when treating a very
sour gas at high pressure.
The pH of the rich amine solution
decreases with its acid gas loading,
in turn increasing the tendency of
the amine solution to corrode
carbon steel. This is the reason why
some operators prefer to limit the
loading at values below the 0.5 to
0.6 level. As a matter of fact,
erosion/corrosion of carbon steel
can be controlled and maintained to
acceptable levels at high solvent
loading under the operating condi-
tions of an amine sweetening plant,
provided the design of the unit and
the operating procedures follow
basic rules8, such as limiting the
flow velocity in the rich amine lines.
In some cases, for instance when
treating gases with very high CO2
content and little or no H2S, the use
of 316L stainless steel will be neces-
sary in limited susceptible areas of
the amine unit. It should be noted
that using stainless steel piping
lowers the bulk piping weight of
the unit.
High amine loadings are well
known to Total, which has operated
plants for several decades, first of all
PTQ Q4 2013 85
12/09/2013 16:40

Partial pressure H2S, bar
Figure 5 Rich amine loading as a function of temperature
the Lacq plant, with rich amine
loadings above 0.6 and up to
0.85/0.90 without corrosion issues.
Several AdvAmine units have also
been licensed to other operators.
Table 2 gives examples of such
amine units.
Case study: energizedMDEA for very
sour gas sweetening
A noteworthy example of the use of
the energizedMDEA process is
given below for the sweetening of a
sour natural gas with very high H2S
content. The sour gas composition is
given in Table 3.
This case study compares three
different process configurations for
the removal of H2S and CO2 down
to a usual commercial gas specifica-
tion; namely, 4 ppm vol H2S and
2 vol% CO2:
• Single-flow (conventional) process
• Double-split flow process, with
thermal regenerator (conventional
double-split flow design, as shown
in Figure 1)
• Split-flow process, with flash-
supported regeneration to produce
20
T = 85ºC
18
T = 55ºC
16
14
12
10
8 consumptions for treatment of the
6 gas with the three schemes, as well
4 as the relative capital costs of the
2 corresponding units.
∆= 0.15
0
0 0.25 0.5 0.75 1.0
Loading, mol H2S mol MDEA
/ amine solutions
the semi-lean amine solution (see
Figure 3).
Both split-flow process configura-
tions entail a larger amount of
equipment than the single-flow
process. This is due to the addition
of a semi-lean amine circuit, which
includes a rich/semi-lean amine
exchanger or a rich amine preheater,
a semi-lean amine cooler and
pumps. In addition, the flash-
procured split-flow scheme needs
an amine heater and an additional
flash drum at regenerator pressure.
Both split-flow process configura-
tions also need an absorber with a
slightly increased height compared
to the conventional process configu-
ration, to take into account the
additional liquid feed. As only a
fraction of the amine solution is
fully regenerated, the total amine
solution flow rate (lean plus semi-
lean) is also larger than that of the
conventional process.
On the other hand, the reboiler
duty is substantially decreased in
both split-flow configurations, and
the whole regeneration section is
considerably reduced in size in the
flash-procured split-flow configura-
tion. In large plants necessitating
multiple treatment trains, there may
even be a reduced number of regen-
erator trains because of this reduced
regenerator capacity.
Table 4 shows comparative energy
Further increasing the loading of
The loading of the rich amine solu-
tion is limited by thermodynamic
equilibrium at the absorber bottom
and by the approach to this
equilibrium. The thermodynamic
equilibrium is a function of the acid
gases’ partial pressures in the feed
sour gas, and high loadings are
favoured by low temperature (see
Figure 5). Lowering the rich amine
solution’s temperature on the lower
part of the absorber is therefore a
means to increasing the loading of
the rich amine solution leaving the
absorber.
It is generally not practical to
reduce the temperature of the feed
sour gas. This would require an
expensive high-pressure gas cooler
and the use of a refrigeration loop in
many fields. In any case, cooling
would be limited by the hydrate
formation temperature of the gas. In
addition, the gas cooler needs an
additional pressure drop on the gas
route that is detrimental to the effi-
ciency of downstream units.
Eventually, the low temperature of
solvent at the absorber top slows the
reaction rate of CO2 with amines,
Case study: high H2S content sour
gas composition

Some AdvAmine units operated with high acid gas loading Composition, vol%
H2S 21.5
CO2 14.8
Amine Feed gas Feed gas Feed gas
Nitrogen 2.8
type pressure, bar H2S, vol% CO2, vol% Loading Start-up year
Methane 57.0
HiLoadDEA 65 4.2 6.0 0.64 1984
Ethane 1.8
MDEAmax 70 4.0 5.6 0.71 2001
Propane 1.1
energizedMDEA 105 Traces 9.2 0.72 1996
Butanes 0.4
HiLoadDEA 66 8.5 9.5 0.77 1980
Pentanes plus 0.5
HiLoadDEA 66 21.5 14.7 0.85 1987
Organic sulphur 0.1
HiLoadDEA 70 15.8 9.8 0.85 1957
Temperature, °C 40
HiLoadDEA 70 34.6 6.1 0.90 1972
Pressure, bar 70

Table 2 Table 3

86 PTQ Q4 2013 www.eptq.com

prosernat.indd 5 12/09/2013 16:40

 requiring additional transfer height
to achieve tight CO2 specification for
some cases.
The solution, to lower the Lean
solvent
absorber bottom temperature with- 820m3/h
out cooling the feed gas and without
decreasing the top trays’ tempera- 180 MMSCFD
ture, consists of the installation of a H2S = 11%mol
C2O =11%mol
liquid intercooler. This will remove P = 66 bar abs
some heat from the amine solution
from an intermediate tray, or section Rich solvent
of packing, in the absorber column, 85.2ºC
where the temperature of the gas
and the liquid is the highest because
of the exothermicity of the acid
gases’ absorption. In this process Lean
configuration, the semi-lean amine solvent
solution is withdrawn from a chim- 690m3/h
ney tray, pumped through a cooler Intercooling
and reinjected to the tray just below to 55ºC
the withdrawal tray.
The example below demonstrates
the incidence of the absorber inter-
Rich solvent
cooler in the case of the sweetening 71.2ºC
of a very sour gas, with the compo-
sition given in Table 5.
The amine solution temperature is Figure 6 Incidence of the intercooler on
decreased to 55°C in the intercooler. absorber operating conditions
As a consequence, the absorber
bottom temperature is reduced from often because of the equilibrium
85.2°C to 71.2°C, and the rich amine conditions, with high concentrations
loading can be increased from 0.60 of sulphur compounds in the reser-
to 0.71 (see Figure 6). voir. The presence of high
Table 6 shows the comparative concentrations of mercaptans
energy consumptions for treatment becomes an issue, as the capability
of the gas with the two schemes, as of amine solvents to remove
well as the relative capital costs of mercaptans may not be sufficient to
the corresponding units meet current stringent commercial
gas specifications with regards to
Mercaptans removal in highly organic sulphur species.
sour gas Amine solvents feature good
Gases with H2S also contain variable capabilities for the removal of
amounts of organic sulphur mercaptans with, however, some
compounds, such as mercaptans, limitations:
Case study: energy consumption and capital cost comparison
energizedMDEA process scheme Conventional Double-split Split-flow process
single-flow flow process with flash-
process supported
regeneration
Acid gas loading (rich amine solution), mol/mol 0.85 0.86 0.92
Rich amine solution concentration, g/l 458 461 458
Thermal energy:
Reboiler 77 67.5 39
Rich amine preheater, MW 10
Power consumption, MW 2.7 2.7 3.6
Total energy demand, MW* 100. 5 89.1 69.6
(base) (88.7% of base) (69.3% of base)
Capital cost, arbitrary unit 100 (base) 113.7 123.1
* Steam boiler efficiency 83%, power generation efficiency 33%
• As weak acidic species (at least
compared to H2S and CO2), mercap-
tans compete with H2S and CO2 for
absorption by alkaline amine-based
solvent. The disadvantageous acidic
strength in comparison with those
of H2S or CO2 means that they are
absorbed more slowly than H2S and
CO2
• At highest solvent loadings, the
reduced pH of the solution in the
bottom section of the absorber
evenly reduces the solvent strength
to further absorb mercaptans
• Looking at the problem more
precisely, it has been demonstrated
for some years now that the solubil-
ity of mercaptans in highly loaded
solvent is much lower than the one
in lean solvent of the upper part of
absorber. In some cases, high
solvent loadings and high tempera-
tures in the bottom part of the
absorber even stop any form of
absorption of mercaptans. This
results in slippage of sulphur
species in treated gas and in
increased difficulties targeting the
required sulphur specification.
When significant mercaptans
removal is looked at, the solution
given to the plant designer is to
increase the solvent flow and
marginally reduce the solvent
temperature. This approach reduces
the solvent loading. As such, the
increase in solvent flow has a signif-
icant impact on the economics of the
plant, because of increased equip-
ment size and increased energy
consumption. This is why hybrid
solvents have been developed for
such applications.
Hybrid solvent processes for
enhanced mercaptan removal
Hybrid solvent processes, such as
the recently developed HySweet
from Total, 9,10 may be considered, as
they show a greater affinity for
mercaptans.
Case study: sour gas composition
Composition, vol% H2S 11
CO2 11
Hydrocarbons Balance
Gas flow rate, 106 Sm3/d 5.1
Temperature, °C 50
Pressure, bar 66

Table 4 Table 5

www.eptq.com PTQ Q4 2013 87

prosernat.indd 6 12/09/2013 16:40

 References
Energy consumption and capital cost comparison
1 Lallemand F, Aimard N and Rocher A, Sour
gas production: moving from conventional to
energizedMDEA process scheme Conventional absorber Absorber advanced environmentally friendly schemes,
No intercooler with intercooler Sogat Conference, Abu-Dhabi, 29 Apr–3 May
Absorber bottom temperature, °C 85.2 71.2 2007.
Acid gas loading (rich amine solution), mol/mol 0.60 0.71 2 Estep J W, McBride G T Jr, West J R, The
Amine solution flow rate, m3/hr 820 690
Recovery of sulphur from sour natural and
Thermal energy: reboiler, MW 67.0 59.5
Power consumption, MW 2.40 2.05 refinery gases, Advances in Petroleum Chemistry
Total energy demand, MW* 87.6 77.6 and Refining, Vol. 6, 1962.
(base) (88.5% of base) 3 Elgue J, Peytavy J L, Tournier-Lasserve J,
Capital cost, arbitrary unit 100 (base) 96.4 Recent industrial developments in natural
gas sweetening by MDEA, 18th World Gas
* Steam boiler efficiency 83%, power generation efficiency 33% Conference, Berlin, Germany, 1991.
4 Elgue J, Lallemand F, MDEA based solvents
Table 6 used at the Lacq processing plant, Gas
Processors Association European Chapter
meeting, London, UK, 18 Jan 1996.
The drawback of hybrid solvent maximised to reduce the required
5 Elf Activated MDEA: an important
processes is their limited selectivity amine solution flow rate. Operating
improvement in natural gas sweetening
towards hydrocarbons, and their amine plants at high loadings has processes, 19th World Gas Conference, Milan,
use should be limited to the been proven by Total through Italy, 1994.
sweetening of natural gases with extensive operating experience, and 6 Lallemand F, Minkkinen A, Processes
a low heavy hydrocarbons a liquid-side cooler scheme on the combine to assist acid gas handling, reinjection,
content. This is why, when devel- acid gas absorber was developed to Oil and Gas Journal, 21 Jan 2002.
oping the HySweet technology, further increase this loading and 7 Streicher C, Lallemand F, Minkkinen A,
Total focused on the selection of a reduce the cost of highly sour gas Lecomte F, A new look at amines: extending the
hybrid solvent composition with a sweetening. gas industry “workhorse” to new limits, 83rd
very limited hydrocarbon absorp- When the mercaptans content of GPA Convention, New Orleans, LA, Mar 2004.
8 Kittel J, Bonis M, Perdu, G, Corrosion control
tion capability. highly sour gas becomes an issue to
on amine plants: new compact unit design for
Thus, co-absorption of heavy meet a stringent total sulphur
high acid gas loadings, Sogat Conference, Abu-
hydrocarbons is maintained within commercial gas specification, the Dhabi, 28 Apr–1 May 2008, and at the GPA
acceptable limits in the HySweet HySweet process from Total may Europe Conference, Barcelona, Spain, 13-15
process. The process has been be considered. May 2009.
commercially used at Lacq since In the second part of this article 9 Cadours R, Shah V, Weiss C, Roquet
2008, treating feed gas with more about solutions for the treatment of D, Lallemand F, Industrial operation of
than 20% mol H2S + CO2, and a highly sour gases, it will be shown HySWEET, a new hybrid solvent for improved
second unit is under construction that, even though amine-based mercaptan removal, 2nd Annual Gas Processing
for another operator in France, sweetening has proven to be a very Symposium, Doha, Qatar, 10-14 Jan 2010.
designed by Prosernat. efficient technology, cryogenic bulk 10 Shah V, Cadours R, Weiss C, HySWEET
process: an improvement in energy efficiency,
removal of H2S or CO2 offers an
Abu Dhabi International Petroleum Exhibition
Conclusions economic advantage when the
and Conference, Abu-Dhabi, 1-4 Nov 2010.
Technologies to treat sour natural separated acid gases from super-
or associated gas are numerous on sour gas are reinjected. The Sprex
Francois Lallemand is Senior Advisor at
the market, but none has shown to and SprexCO2 processes, jointly Prosernat.
be as versatile and economic as developed by Total, IFP Energies Gauthier Perdu is Deputy Process Director
those using amine-based solvents. nouvelles and Prosernat, can be at Prosernat and Head of the Amine Process
To be truly competitive, the combined with an amine unit to Technology Group within Prosernat’s Process
removal of acid gas components reduce the cost of the production of department. He holds a Dipl. Engineer and Post
H2S and CO2 from highly or super- gases containing more than 25-30% Graduate certificate in chemical engineering
sour gases requires the optimum H2S or over 40-45% CO2. They from ENSIGC Toulouse.
choice of process. Within the provide an economic and Laurent Normand is Business Development
AdvAmine series of processes, the easy-to-operate alternative to Manager at Prosernat. He holds a PhD in
material science and graduated as an engineer
energizedMDEA process can be amines, to membranes and to other
in physics from the École Nationale Supérieure
optimised to reduce energy require- more complex cryogenic fractiona-
des Mines de Paris.
ments, taking advantage of the tion processes for the treatment Claire Weiss works for Total EP in the process
ability of MDEA to release a of such highly sour gases. The department within the Acid Gas group.
substantial part of the absorbed Sprex series of processes was Julia Magne-Drisch is Gas Treatment Project
acid gases in a low- demonstrated in a unit installed Manager at IFP Energies nouvelles. She holds a
pressure flash to produce the semi- at the Lacq sour gas plant and PhD in hydrotreatment.
lean stream in a split-flow process the technology is now ready Sebastien Gonnard is Process Engineer at
configuration. The acid gas loading to be implemented at industrial IFP Energies nouvelles, in charge of process
of amine solutions needs to be scale. development and techno-economic evaluations.

88 PTQ Q4 2013 www.eptq.com

prosernat.indd 7 12/09/2013 16:40

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LNG value chain.

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onis.indd 1 10/06/2013 13:10

 Gasification for hydrogen supply
Integrating the gasification of liquid residues into a refinery balances the
hydrogen demand of hydroprocessing units
MAX-MICHAEL WEISS, HELMUT HEURICH, DELPHINE ROMA and STEFAN WALTER
Air Liquide Global E&C Solutions/Lurgi GmbH
H
ydroprocessing is used in
refineries for producing
transportation fuels such as
gasoline and diesel from crude oil.
These technologies ensure that the
emissions from the fuels after they
are burnt in a combustion engine
are meeting today’s environmental
requirements. The refining
processes are consuming hydrogen.
For instance, in a hydrotreater,
impurities such as sulphur, nitro-
gen and metals are removed and
replaced by hydrogen. In a hydroc-
racker complex, petroleum
molecules are converted into
smaller molecules, boiling in the
diesel range, and saturated by
adding hydrogen.
The required hydrogen can be
produced inside the refinery using
several technologies:
• Steam reforming of natural gas,
LPG naphtha, refinery off-gases (or
a combination of those)
• Gasification of liquid residues or
pet coke
• Recovery of hydrogen from
naphtha reformer or hydroprocess-
ing off-gases using membranes
and/or pressure swing adsorption
units (PSA).
Alternatively, a third-party indus-
trial gas company can supply the
required hydrogen over the fence.
This article describes Air Liquide
Global E&C Solutions’ Lurgi Multi
Purpose Gasification (MPG) tech-
nology as a reliable source for
hydrogen supply to refineries. The
North West Redwater (NWR)
upgrader project in Alberta,
Canada, is the latest example of
integrating the gasification of liquid
residues into a refinery for balanc-
ing the hydrogen demand of the
www.eptq.com
air liquide.indd 1
Diluent and
naphtha
32 501 bpd
Bitumen blend Crude and Hydrocracker
feedstock vacuum unit and hydrotreater ULS diesel
36 178 bpd
77 080 bpd
Dilbit 51 760 bpd
Synbit 25 320 bpd
Residuals
hydrocracker LS vacuum
gas oil 8276 bpd
Butane 771 bpd
Hydrogen
Multi-purpose High-quality
gasification CO2
Figure 1 NWR block flow diagram (numbers given are for one phase out of three)
hydroprocessing units in the the upgrading and refining
complex. processes enables the capture of a
The NWR complex processes substantial portion of the produced
bitumen, the heavy oil extracted CO2. This CO2 is of high purity and
from oil sands, from different ideal for enhanced oil recovery
sources and converts this extra- (EOR).
heavy oil, not into a synthetic crude
but into high-value finished prod- North West Redwater
ucts such as ultra-low-sulphur upgrader project
diesel, which accounts for approxi- A block flow diagram of the NWR
mately 50% of the products and complex is shown in Figure 1. The
diluents recycled back to the bitu- feedstock is a bitumen blend. In the
men producers. For the production atmospheric distillation process,
of hydrogen, the project will utilise most of the diluent is recovered.
Lurgi MPG technology. The feed- Together with the naphtha
stock is unconverted oil from the produced in the hydroprocessing
hydrocracker. The gasification tech- units, it is recycled back to the
nology allows for the efficient bitumen producers. Vacuum resi-
elimination of upgrading by-prod- due is fed to the hydrocracker. The
ucts such as pet coke and/or heavy main product of the complex is
residues, solving any issues regard- ultra-low-sulphur diesel. The
ing marketing and logistics of these unconverted oil from the hydroc-
products for a “land-locked” refin- racker is used as feed for the MPG
ery, as well as a significant unit, which provides the hydrogen
reduction in natural gas and water consumed in the hydrotreating and
consumption. The decision to use hydrocracking units. High-purity
gasification as an integral part of CO2 is recovered by a Lurgi
PTQ Q4 2013 91
12/09/2013 16:46
 the reactor, to obtain a low viscos-
ity at the burner tip. If the feedstock
Feed Feed A Feed B
has a low flash point, vaporisation
O2 + steam O2 Steam
of the low-boiling constituents of
Cooling water
the feedstock starts in the burner
nozzle, which disturbs the feed-
stock flow and results in damage to
the burner tip. To avoid this, the
MPG burner uses steam to atomise
the oil into fine droplets in a
Quench
water
proprietary diffuser nozzle system.
Gas Thus, additional hydrocarbon
offtake vapours generated by heating the
feedstock do not affect the feed-
stock flow at the burner tip. Due to
Soot the atomisation of the feedstock
slurry with steam, the burner can handle
highly viscous feedstock and also
Figure 2 Special features of Air Liquide Global E&C Solutions’ Lurgi MPG technology particles in the low mm range. The
MPG reactors afford good availabil-
Rectisol unit, and sold for EOR The second special feature is the ity and reliability, thanks to a
application and final storage. quench technology. This allows for combination of long on-stream
a feed of ash-containing feedstock. times and the option to restart the
Lurgi MPG technology The ash, if present in the feedstock, reactor without burner inspection.
The special features of the MPG melts in the special reactor, forming This increases the operational flexi-
process are, inter alia, the very relia- a slag, which flows along the bility and reduces the downtime
ble burner and the quench (see refractory-lined wall. The hot gas for maintenance work. The burner
Figure 2). The burner uses a special and the slag, together with the high is equipped with a pressurised
diffuser nozzle system to atomise amount of soot, are shock-cooled cooling water system, which gives
the feedstock into fine droplets, by water injection in the quench an inherent safety to the burner
which are required for good pipe. The slag is vitrified to a operation. A surveillance system
conversion. This differentiates it non-leachable solid and is routed detects and records any deteriora-
from other burner systems, which with the soot water to the solids tion of the front plate and the
need a high-pressure differential separation system, designated as burner nozzles. This information is
for atomising into droplets. Due to the metals ash recovery system analysed and trips a safe shutdown
the segmentation into several (MARS) unit. of the reactor, if necessary. The
nozzles, the burner allows the The MPG burner affords high burner creates a low pressure drop
simultaneous feed of two or more feedstock flexibility. No limitations across the feed system, which
different feedstocks into the reactor exist regarding the flash point of allows for the use of inexpensive
via one burner. This is important the feedstock. This is often an issue feedstock pumps. The burner is
for applications where the feeds are with highly viscous feedstock, equipped with an integrated
immiscible or, worse, tend to react which has to be heated to high heat-up burner, so manipulation of
with each other. temperatures before feeding it to burner system in the hot reactor is
not necessary during startup.
An overview of MPG’s flexibility
MPG flexibility for liquids and slurries in operating modes is shown in
Table 1.
Actual operating ranges Operating limits
Quench configuration Boiler configuration Hydrogen production unit
Component Oil mode Waste/slurry mode Figure 3 shows a block flow
C, %wf 65-90 90 65-90 diagram of the hydrogen unit. The
H, %wf 9-14 14 9-14
main process steps are the conver-
S, %wf 6 6 6
Cl, %wf 2 8 50 ppm (wt) sion of feedstock in quench-type
LHV, MBTU/JQ 15-18 2-13 15-18 gasification reactors, ash and soot
MJ/kg (35-42) (5-30) (35-42) removal from the raw gas, the CO
Toluene insolubles, %wf 6 45
shift unit, gas cooling followed by
Ash, %wf 3 25 0.4
Water, %wf 2 5-30 acid gas removal and hydrogen
Viscosity, cSt (at burner) 200 300 200 purification. The hydrogen capacity
Particle size, mm 2 of the unit is 3.2 MM mn3/d.
Feedstock to the gasification
Table 1 block is hydrocracker residue from

92 PTQ Q4 2013 www.eptq.com

air liquide.indd 2 12/09/2013 16:47

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as fields mature and production peaks.
n Result:
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for extended, cost-efficient operations.

They turned to Elliott

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elliott.indd 1 12/03/2013 14:20

 CO2 Pure dry CO2
compression to EOR
Feedstock
~52 t/h LP steam 148 t/h

Steam
~26 t/h MPG quench Raw gas shift Gas cooling Rectisol Methanation Hydrogen
3 × 50% 97% pure
~129 000 nm3/h
H2S + CO2
O2
~37 000 nm3/h Carbon Sulphur
slurry Air + O2 Claus
Claus off-gas

ASU Filter Waste water

Process water
treatment

Filter cake
Air

Figure 3 NWR hydrogen plant block flow diagram

the hydrocracking unit. A quench
configuration has been selected due
to the high ash content of this feed-
stock and to minimise investment
costs. The quench also adds the
major portion of the steam required
for the CO shift conversion to the
gas, which results in considerable
process simplification and invest-
ment cost savings.
Raw gas from the quench is first
treated in a fine wash section,
which removes ash and soot parti-
cles. The particle-free gas is then
routed to a sulphur-tolerant CO
shift unit, where CO reacts with
steam to produce hydrogen accord-
ing to the following reaction:
CO + H2O ⇔ H2 + CO2
The shifted gas is cooled, with
the energy recovered as low- or
medium-pressure steam. The
options for acid gas removal and
hydrogen purification are discussed
in the next section.
The main design target of the
hydrogen unit in the upgrader is to
maximise hydrogen production.
The hydrocracker and hydrotreat-
ing units allow for some percentage
of impurities in the hydrogen. CO2
is produced as a separate, pure and
bone-dry stream. The CO2 is
compressed to fit into the nearby
trunk pipeline of the CO2 off-taker
and is used for enhanced oil recov-
ery in the Alberta oil fields. Figure
3 shows the selected process route.
The CO shift unit is designed for
maximum CO conversion, since all
unconverted CO ends up in the
hydrogen product. It has to be
finally shifted in the methanation
unit. The Lurgi Rectisol process
separates all sulphur components
from the shifted gas and produces
an acid gas stream suitable for the
Claus process. In addition, bulk
CO2 removal is efficiently
performed by Lurgi Rectisol to the
low ppm level and a pure CO2
stream is produced. A final meth-
anation reactor converts all traces
of carbon oxides left in the hydro-
gen to methane.
The wash water from gasification
is treated in the MARS unit. The
dissolved gases are flashed in the
slurry tank, before the solids are
separated from the water in a filter
press. The filtrate water is recycled

High BTU,
Feedstock LP steam Pure CO2 low sulphur
fuel gas
Steam
MPG quench Raw gas shift Gas cooling Rectisol PSA Hydrogen

H2S + CO2
O2
Carbon
slurry O2 OxyClaus Sulphur

ASU MARS Waste water

Process water
treatment

Metals/ash
Air

Figure 4 Lurgi Rectisol-based acid gas removal in a gasification-based hydrogen unit

94 PTQ Q4 2013 www.eptq.com

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Feedstock
Steam
MPG quench
O2
Carbon
slurry
ASU MARS
Air
Figure 5 Selective acid gas removal in a gasification-based hydrogen unit
back to the wash section of the
gasification reactors. At the NWR
complex, the filter cake is trucked
to a suitable landfill site. In other
cases, the soot in this cake might be
burned off in a specialised oven.
The metal-ash would be a saleable
product, whereby specialised finer-
ies might recover valuable metals
such as vanadium and nickel.
Gas purification options for
gasification-based hydrogen plants
The selection of an appropriate gas
purification technology depends on
the required hydrogen purity, the
value of the byproducts, such as
fuel gas and CO2, and the plant
emission regulations.
Acid gases have to be removed
from the raw hydrogen down-
stream of the sulphur-tolerant shift
Feedstock
Steam
MPG quench
O2
Carbon
slurry
ASU MARS
Air
Figure 6 Gasification-based hydrogen unit with methanation for hydrogen purification (as used for the NWR hydrogen plant)
www.eptq.com
air liquide.indd 4
LP steam Impure CO2
Raw gas shift Gas cooling
H2S + CO2
O2
Waste water
treatment
unit. This can be achieved with
various processes.
In the first case, the Lurgi Rectisol
process produces an H2S-rich sour
gas suitable for the Claus unit. In
addition, CO2 bulk removal is
economical and a pure CO2 stream
is generated, which can be used for
sequestration, industrial gas or
vented without further treatment.
A PSA unit is used to free the
raw hydrogen from trace compo-
nents, such as methane, nitrogen,
carbon monoxide and argon, which
are concentrated into the PSA
off-gas. This off-gas is a high-BTU,
low-sulphur gas, since Rectisol
economically removes all the CO2
and other trace acid components, in
addition to H2S (see Figure 4).
In the second case, Lurgi Rectisol
is replaced by a selective acid gas
LP steam
Raw gas shift Gas cooling
H2S + CO2
O2
Waste water
treatment
Low BTU,
S >100ppm
fuel gas
Selective PSA Hydrogen
AGR
OxyClaus Sulphur
Process water
Metals/ash
removal (AGR) process such as
Purisol or Selexol. This also
produces an H2S-rich sour gas suita-
ble for the Claus unit. Typically,
20-30% of the CO2 content of the
raw gas is removed in a selective
gas purification process. This CO2 is
produced as a separate, impure CO2
stream with a significant sulphur
concentration. The sulphur impurity
in the CO2 stream is normally not a
problem for sequestration purposes.
Venting, however, is usually not
permitted (see Figure 5).
Since the AGR is selective, a
considerable amount of CO2 passes
to the PSA unit and is separated
there. The PSA unit also separates
the remaining sulphur impurities.
Due to the high CO2 content, the
PSA off-gas exhibits a low heating
value. It also contains a significant
Pure CO2
Rectisol Methanation Hydrogen
97% pure
OxyClaus Sulphur
Process water
Metals/ash
PTQ Q4 2013 95
12/09/2013 16:47
 This technology directly delivers
Lurgi Rectisol for five tasks
syngas qualities with extremely low
total sulphur content. There is no
1. Trace contaminants removal COS, CS2, NH3, HCN, Hg… need for any further gas purifica-
2. Deep desulphurisation Directly to synthesis feed quality (for sensible catalysts), total tion in guard beds.
sulphur <0.1 ppm v (w/o guard bed!)
3. Bulk CO2 removal Up to 100% CO2 may be recovered This process is equally well
4. CO2 purification Total S <5 ppm v in CO2 stream suited to the removal of bulk CO2.
5. Acid gas enrichment Claus-suited acid gas even at a very unfavourable CO2/H2S ratio CO2 concentrations in the low ppm
of >500 range are economically achieved in
One Lurgi Rectisol unit compares with five tasks to be performed in five process steps the purified gas. Due to the physi-
cal nature of the absorption
Table 2 process, the energy required to
remove large amounts of CO2
amount of sulphur because applica- Comparison of the three hydro- depends only on the total gas flow
ble processes such as Selexol and gen purification options with the and gas pressure, and not on the
Purisol leave traces of H2S in the requirements of the NWR upgrader CO2 concentration in the feed gas.
low ppm range in the purified gas project revealed that only option The CO2 product stream is of a
and remove carbonyl sulphide three, applying the Lurgi Rectisol good quality with a low sulphur
(COS) only partly. process, meets all specifications. content. It can be used for all
In the third case, if hydrogen This option also has the lowest purposes such as the chemical
production is to be maximised but investment costs and utility industry (urea production), the
is not required to have a high consumption. beverage industry and for
purity, and additional fuel gas is of sequestration.
low value, the PSA unit can be Lurgi Rectisol process This process also has the ability
replaced by a methanation reactor, The Lurgi Rectisol process is often to produce H2S-rich acid gas
which converts CO and CO2 to described as an expensive process streams from raw gases with high
methane. Since all impurities end for gas purification. This has to be CO2-to-H2S ratios, which are typi-
up in the product hydrogen, the put into perspective, considering cally found in gases downstream of
gas purification unit must remove the features of the process, which CO shift units.
all sulphur species to the ppb range allow it to perform five tasks in one For an evaluation of the process
and remove bulk CO2 to the low process (see Table 2). economics, one Lurgi Rectisol unit
ppm range. Lurgi Rectisol is the The process removes all trace has to be compared against five
process of choice for this configura- contaminants contained in the raw process steps such as HCN and
tion. A hydrogen purity of 97% can gas from the gasification unit such COS hydrolysis reactors upstream
be achieved and no fuel gas is as organic sulphur compounds, and guard beds downstream of the
produced. This hydrogen purity is ammonia and cyanide. Volatile AGR unit. The advantages of the
normally sufficient for hydrotreat- metal components such as carbon- process are fully utilised when the
ing and hydrocracking applications. yls are also completely removed by downstream processes require high
This process configuration gives the this process. Mercury is equally syngas purity, as demonstrated in
highest specific hydrogen produc- trapped, which is important in coal the investigation for the NWR
tion (see Figure 6). gasification. upgrade project.
Today, 75% of the syngas
produced from coal, heavy oil and
wastes is purified in Lurgi Rectisol
Different oil LPG units (source: Gasification
fractions Hydrocracker
Technologies Council/GTC Data
from refinery Diesel Base). This share increases to 90%
for the syngas produced for chemi-
Vacuum Off- Acid cal synthesis such as ammonia and
Solvent
gases gases Hydrogen
residue from de-asphalting
refinery Chemicals methanol (non-IGCC use).

Air Liquide plants

Alternative bottom-of-the-barrel
Asphalt Power / solutions
Integrated power HP steam
Oxygen
In combination with solvent deas-
Gasification Sulphur phalting units, trickle- or
Hydrogen ebullated-bed hydrocrackers, MPG
Common off-site Chemicals gasification can solve the bottom-
CO2 for
facilities Steam sequestration of-the-barrel issues in refineries by
Sulphur
combining the production of high-
value products with the elimination
Figure 7 Comprehensive bottom-of-the-barrel solution of pet coke production, elimination

96 PTQ Q4 2013 www.eptq.com

air liquide.indd 5 12/09/2013 16:47

 of Heavy
Very most Crude refinery 10
Upgrading off-gases,
– Long Term reduc-
R&D 11 also integrated
Wadsworth solutions
D, LC-Fining forfor
options steam/
heavy technology,
properties, as Res,
Ind Eng Chem
Projected yields the worldwide
for1989, 28, 1278.
commercial

Absolute deltas, wt% of feed

tion in natural
Opportunities, 1994.
8
gas and water energy
oil generation
upgrading, Proceedings of theandNPRA AnnualCO2 industrial
19 standard
Yuiapplication
S, Removing for clean
diolefins
of OptiFuel fromsyngas
Technologycoker
2consumption,
Yui S, Chung K H,and Syncrude theupgrader
recovery revamp handling.
of Meeting, Air CA,Liquide
San Diego, 9-11 Marchcan 2008. also production,
naphtha necessaryit before
provides a clean
hydrotreating, Oil
improves 6 1999, 97, 36.
CO2 forproductEOR or quality, Oil Gas J, 2007, Vol. 12
sequestration. Ordorica-Garcia
provide G, Croiset E, Douglas
an (over-the-fence) supply P, Gas J,
hydrogen product Base
and Predicted
enables
105,With
46, 52.the configuration
4 Elkamel A,
shown in of air gases, power and steam,Gupta M, Modeling the energy 20 Chang A-F,carbon
economic Liu Y A, capture.
Predictive modeling of
Coke 32.2% 28.5%
3 Chrones J, Germain R R, Bitumen and heavy demands and greenhouse gas emissions of the large-scale
Dry gas integrated refinery reaction
4.4% and
Figure 7, the feedstock 2
to the MPG CO2 compression/liquefaction and Lurgi Rectisol,systems
5.6%
MPG, OxyClaus and Purisol
oil upgrading in Canada, Fuel Sci Tech Int, 1989, Canadian oil sands industry, Energy Fuels, 2007, fractionation
C3+ liquid yields from
62.2% plant data. Part are
67.1% 1:
unit is normally reduced to that transportation. marks of Air processes,
Liquide Global
7, 783. 0 21, 2098. hydrocracking EnergyE&C Solutions
Fuels, 2011,
amount needed to satisfy the
4 Rana M S, Samano V, Ancheyta J, Diaz J 13 Morawski I, Mosio-Mosiewski J, Effects of (Lurgi
25, GmbH). Selexol is a mark of UOP, a
5264.
Table 4 company.
A I, A review of recent advances If
demand of the
-2 complex. on syngas Conclusion
process parameters in Ni-Mo catalysed hydrocracking Honeywell
productionfor upgrading
technologies exceeds
–4 of the
heavy amount
oils and Invacuum
of the context
residue on of composition
ever moreand stringent
quality
needed
residua, Fuel,to 2007, produce
86, 1216. the required of environmental
obtained products, regulations
Fuel Process forTechnol,
refin- cracking reactions
Max-Michael Weiss is overDirectortheInnovation,
strictly
5hydrogen
Speight J G,
–6
(depending
The Chemistry first
and of all
Technology on ers,
2006, there
87, 659. is a trend to increase thermal
Clean cokingwith
Conversion, reactions
Air Liquidethat
Globaloccur
E&C
A1 A2 A3 A4 B1 B2 B3 B4 Solutions/Lurgi GmbH. He graduated
the
of crude
Petroleum, Coke, % quality/origin),
2007, 4th –4.32
ed, CRC–4.01 –3.38 the
Press/Taylor residue
& –4.4314 –1.44 conversion
Danial-Fortain
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T, Merdrignac in the traditional delayedas Diplom
coker
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operation. (chemical
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development, it
surplus
Francis, Boca C syngas
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+ liquid, %FL. can
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3
the Technical University of Karlsruhe, Germany.
Sayles generation
6power S,Fuel
Romero
gas, % S, –4.51
Understand –4.76 differences 1.42vacuum 0.99residue
with gas turbines rate of the units, the heavy bottom
–3.14 2.25in hydroconversion
1.85 1.79 conditions, has Alvarez-Majmutov
Anton been observedis an that
NSERC OptiFuel
Visiting
Helmut Heurich is Director for Refinery
between thermal
or the production and of hydrocracking, Feed andCatal
chemicals/ yield will2010,
Today,
formulation range 150,from
255. 10-20%. Using Technology
Fellow shifts the
at CanmetENERGY delayed
working coker
on bitumen
Applications in the HyCO Product Line in
Hydrocarbon Process, 2011, Sept, 37.
fuels. Air Liquide Global E&C Air Liquide Global E&C Solutions’ 15 Ding F, Ng S H, Xu C, Yui S, Reduction of yields
upgrading towards
process more
modelling valuable
and simulation.
Global Engineering & Construction Solutions
Martinez
7Figure J, Sanchez J L, Ancheyta J, Ruiz light cycleof
R application oilOptiFuel
in catalytic cracking ofpilot bitumen- He holds a PhD from
products, Mexicanamounts
Institute of
Solutions 3 Changes
can providein pilot plant
theyields with
applica- Lurgi MPG Technology: technology-based plant of Air Liquide.with reduced
He studied process technology of
S,runs
A review
at Penn of process
State aspects
University and modeling derived crude HGOs through catalyst selection, Petroleum
dry gas (IMP).
and coke.
ble technologies (see Figure 7). hydrogen production allows a
of ebullated bed reactors for hydrocracking of Fuel Process Technol, 2007, 88, 833.
at the Technical University of Braunschweig.
Besides
heavy oils, MPG
Catal Rev technology,
Sci Eng, 2010, including
52, 60. refiner
16 Botchwey to C, transform these J,residues
Dalai A K, Adjaye Kinetics
Delphine Roma is the Global Marketing
Jinwen Chen is a Senior Research Scientist and
Albemarle
8airYuiseparation,
has CO
S, Producing quality
designed shift, an
synthetic
addi-
syngas
crude oil of
vessels
into an needed
amount
bitumen-derived
foroiladditive
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upgrading
mixing
that
using a
Pilot plant
Manager verification
in charge of the refining industry
Group Leader at CanmetENERGY. He holds
tion system
cleaning,
from CanadianLurgi to ensure
oil sandsRectisol, proper
bitumen, PSA mixing and
and commercial
J Jpn Petrol storage.
balances the NiMo/Alrefinery’s
O needs.
catalyst, Can J Chem Albemarle
within Air Liquide and
Global E&C
a PhD in chemical engineering OFTGSolutions.have
from Tianjin
She
of 2008,
the solid
51, 1. and theliquid portionsalso and The
2004,yield aimprovements
proven andseen with conducted a series of pilot plant
2 3
methanation, company has Eng,MPG is 478. reliable holds an MSc and engineering degree from the
Inst, 82, University.
to avoid solids settling. The supply this technology are hypothesised to École
runsdes at Ponts
PennetState
Chaussées in Paris. (PSU).
University
9technologies
Yui S, Athabasca for sulphur
oil sands produce recovery
quality 17 technology
Yui S, Sanford for E,securing
Kinetics of thearomatics
hydro-
Stefan
The scope Walter is Head
of these of Department,
consists
diesel and of
jet a
fuels, liquid
Oil Gas carrier
J, 2000, and
Vol. 98, the
(preferably OxyClaus, since oxygen gen supply to a refinery. It further
47, be the
hydrogenation result of of reactions
bitumen-derived in
gas both
oils, the
Can Mugurel Munteanu is studies
a Leadhas been
Process
Gasification Technologies, with Air Liquide
additive
58.
is available), supplied to the refinery
technologies for chem- liquid
in Javoids
Chem Eng, and
the1991,vapour
69, 1087.
production phases, which are
of petroleum to quantify
Engineer theTechnology,
at CoSyn benefits of the tech-
a division of
Global E&C Solutions/Lurgi GmbH. He
bags
10 Yui or
S, bulk
Chung shipments
K H, Processing for
icals (such as methanol and coke, and helps to consumeoilmixing
sands 18directly
Yui S, influenced
Sanford E, Mildby the additive.
hydrocracking muchof nology as inaEdmonton,
WorleyParsons, functionCanada.
of additive
He holds
graduated as Diplom Verfahrensingenieur
on-site.
bitumen The
is syncrude’s additive
R&D focus, injection The
Oil Gas J, bitumen-derived active sites
coker ofandthe additive
hydrocracker are
heavy acomposition,
PhD in chemicalfeed properties
engineering and
from Laval
propylene) and fuels production less natural gas and water. In (process engineering) from the Technical
2001,
systemVol. 99, 17, 46.minimises the size of gas
design oils: kinetics,
intended to product yields, andcatalyse
preferentially product University,
operating Canada.
conditions.
(for instance, Fischer-Tropsch), but combination with the Lurgi Rectisol University of Aachen, Germany.

The team of CS Combustion

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Harsh operating conditions. Challenging waste streams.

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 Catalyst raises kero-treating performance
The activity and stability of a replacement catalyst in a kerosene treater enabled
a refiner to process difficult-to-treat condensate in greater quantities
WOO KYUNG KIM SK Innovation
JESSY TRUCKO and ERIC BAKER UOP, A Honeywell Company
T
he recent boom in gas field
production, by utilising new
technologies such as hydraulic
fracturing, has resulted in abundant
production of natural gas. As natu-
ral gas exits the wellhead, it
decompresses, causing heavier
hydrocarbons to condense out of
the vapour phase as the tempera-
ture and pressure decrease. These
condensed heavy hydrocarbons are
recovered as liquids, commonly
referred to as natural gas conden-
sates. These condensates can cover
a wide boiling point range, from
pentanes, through the light and
heavy naphtha ranges, and all
the way through the jet fuel and
diesel ranges.
Although natural gas condensates
fractionate into boiling point ranges
that refiners are familiar with, they
exhibit very different concentrations
and species of mercaptan molecules.
The mercaptans present in these
condensates are typically linear
mercaptans. This, combined with
high concentration levels, make
these feeds challenging to treat. Two
effective options exist for the refiner
who would like to refine these
lower-cost condensates into kero-
sene or jet fuel: hydrotreating and
mercaptan oxidation via sweetening
(conversion of mercaptan to disul-
phide) technology. Although
hydrotreating removes these
mercaptans, it requires increased
hydrogen supply and capacity in an
existing hydrotreater or a large capi-
tal cost investment to realise.
Alternatively, the UOP Merox Fixed
Bed Sweetening Unit with Merox
No. 10 catalyst technology requires
a low capital investment and mini-
mum operating cost, while
www.eptq.com
uop.indd 1
10MPD
10MPD
No. 2
CDU 40MPD
RSH = 100ppm
10MPD
10MPD
Figure 1 Jet fuel production at Incheon
producing on-specification kerosene
or jet fuel.
Treating unit comparison
and challenges
SK Innovation in Incheon, South
Korea, produces jet fuel from two
kerosene-sweetening units receiv-
ing the same feed blend for the
production of jet fuel. The smaller
kerosene treater (No. 1 KMX) was
designed by UOP and loaded with
Merox No. 10 catalyst. This unit
has a history of operating well, but
was brought down when a new
and larger kerosene treater (No. 2
KMX) was installed. No. 2 KMX
was not designed by UOP and was
initially loaded with a competitor’s
catalyst. Although SK historically
processed a blend of various
streams to make jet fuel, it began to
produce off-specification jet fuel in
No. 2 KMX when the mercaptan
content increased, due to blending
RasGas condensate from the South
Pars field (Qatar) in the feed.
Unfortunately, the company could
not make its desired jet fuel specifi-
cation consistently with the treating
technology and catalyst in No. 2
KMX. It reduced the RasGas
No. 1
KGHT
No. 1 20MPD
Jet fuel
KMX Merox No. 10
No. 2 10MPD
KGHT
ULSD blending
No. 2 10MPD
Jet fuel
KMX
Non-UOP
technology
condensate portion of its feed and
brought No. 1 KMX back on line to
handle the turned-down capacity of
No. 2 KMX. It needed to process jet
fuel through its hydrotreater No. 1
KGHT, so its product could blend
with the jet fuel pool and be on
specification by offsetting the high
mercaptan product from No. 2
KMX. Figure 1 illustrates this setup.
Operating data showed that No. 1
KMX with Merox No. 10 catalyst
ran at over twice the space velocity
of No. 2 KMX, while performing
better. SK reloaded a high-activity
version of the non-UOP catalyst
into No. 2 KMX in late 2009, in an
attempt to achieve conversion
equivalent to No. 1 KMX. UOP
worked with SK Incheon to opti-
mise the operation of No. 1 KMX,
and showed that it performed to
specification and outperformed the
new No. 2 KMX catalyst load, even
though the current load of Merox
No. 10 was three years old in 2011.
Once again, SK reduced No. 2
KMX’s throughput to meet specifi-
cation. Further addition of the
RasGas condensate to the feed
caused the catalyst performance in
No. 2 KMX to deteriorate quickly
PTQ Q4 2013 99
12/09/2013 16:54

No. 2
CDU 30MPD
RSH = 100ppm
Ulsan
CLX 10MPD
Figure 2 SK switched to an easier-to-treat feed with less mercaptan
Catalyst comparison: mercaptan removal in Incheon’s kerosene treaters
Licensor
Design capacity, BD/LHSV 5500/1.0
Current capacity, BD/LHSV
Catalyst
Measured loaded catalyst vol, m3
Normal life cycle, year
Feed mercaptan, ppm
Product mercaptan, ppm
Table 1
and exceed the maximum internal
mercaptan sulphur specification of
20 wppm sulphur and the sales
maximum of 30 wppm sulphur (see
Table 1). Ultimately, SK switched to
an easier-to-treat feed with less
feed mercaptan until a better
alternative could be found (see
Figure 2).
SK continued to compare the
performance of No. 1 KMX with
Merox No. 10 catalyst against the
catalyst in No. 2 KMX with the
same feed. Over a two-month
60
Product mercaptan sulphur,
Beneficial replacement
After further evaluation of the data,
10MPD No. 1 UOP and SK agreed that, despite
KGHT the differences in reactor vessel
10MPD No. 1 20MPD design, Merox No. 10 catalyst
Jet fuel
KMX Merox No. 10 would be a beneficial replacement
10MPD No. 2 10MPD for the catalyst in No. 2 KMX. UOP
ULSD blending
KGHT proposed two options:
• The first option replaced the
No. 2 10MPD
KMX
Jet fuel existing catalyst with UOP Merox
Non-UOP
technology
No. 10 and kept the current unit
design flow rate of 20 000 BPSD.
This approach minimised the unit’s
down time and allowed SK to test
the performance of Merox No. 10
catalyst in a non-UOP reactor
• The revamp option replaced the
existing reactor internals of No. 2
No. 1 KMX No. 2 KMX KMX and increased active catalyst
UOP Other
20 000/1.33
volume by about 50%, increasing
Normal 8000/1.5 20 000/1.33 feed throughput to 30 000 BPSD.
Max 14 000/2.6 SK selected option 1 for its low
Merox No. 10 Non-UOP capital cost and quick turnaround
36 99
4 2
schedule. It reloaded with Merox
100 100 No. 10 catalyst without revamping
Less than 20 10~30 the unit.
The company loaded No. 2 KMX
with Merox No. 10 catalyst and
evaluated the performance of the
period, SK observed higher levels of new catalyst. During testing, it
conversion across the Merox No. 10 processed a higher portion of
catalyst despite the age of the cata- RasGas condensate to No. 1 KMX
lyst in No. 1 KMX. The formulation and No. 2 KMX units, increasing the
of the Merox No. 10 catalyst mercaptan load by over 250%. In
increases activity over other treating addition, it realised product mercap-
catalysts, while maintaining activity tan concentrations of less than
in difficult-to-treat environments by 8 wppm sulphur with decreased air
providing increased resistance to injection rates (see Table 2).
fouling by organic acids such as Merox No. 10 catalyst has been in
sodium phenolate and sodium service in the No. 2 KMX reactor for
naphthenate. Figure 3 shows the almost two years now with excellent
increased stability of Merox No. 10 performance. The catalyst change
standard fixed-bed catalyst. has allowed No. 2 KMX to process
72% more mercaptan sulphur, while
reducing off-spec product by more
than 50% (see Table 3).

In the original configuration,

50
hydrotreated kerosene needed to be
40
added to the jet fuel blend to reduce
the amount of mercaptan sulphur in
wtppm

30 the jet fuel product. This is an

expensive product to use for the
20 dilution of jet fuel. The Merox No.
10 catalyst performance meets the
10 specifications of mercaptan sulphur
in jet fuel without the need for dilu-
0 tion with hydrotreated kerosene.
0 1 2 3 4 5 6 10
Months of operation Economic benefit
There are two ways in which the
Figure 3 Increased stability of Merox No. 10 standard fixed-bed catalyst economic benefit of using Merox

100 PTQ Q4 2013 www.eptq.com

uop.indd 2 12/09/2013 16:54

 No. 10 catalyst can be realised. The
Lower product mercaptan with higher mercaptan feed
flow scheme in Figure 4 shuts
down the No. 1 Hydrotreater (No.
1 KGHT), thus reducing operating Case Original conditions UOP guaranteed condition Test run result
Capacity, BPSD Base Base Base
costs. Figure 4 shows a flow scheme Feed mercaptan, ppm Base Base + 350% Base + 200%
where the No. 1 KGHT flow is Air rate, % of theoretical Base 80% of base 60% of base
reduced to zero and the No. 2 KMX Product S-RSH, wppm
flow is increased to 20 MBPD. The Internal spec: • S <20wppm S Less than 30 Less than 20 Less than 8
No. 2 KMX unit operates at 10% of
the No. 1 KGHT unit operating Table 2
cost, resulting in about six million hydrotreating, SRU, utility and wastewater
US dollars ($6 MM) in operational Mercaptan removal performance
treatment. Prior to his current role, he was
before and after catalyst change
savings to the refinery. This allows part of the aromatic and BTX technical service
the No. 1 KMX to treat another team. RSH represented 18-month 18-month
feed at lower severity and higher Jessy Trucko is a Lead Technical Specialist as mercaptan average average
throughput. with UOP, A Honeywell Company. His 15 years sulphur before UOP after UOP
with UOP include work with the UOP Parex Merox Merox
Conversely, an increase in profit No. 10 No. 10
process and experience with the development
to the refinery can also be calcu- No. 2 KMX feed, MBPSD Base Base + 10%
of alkylation processes as well as for the fluid
lated by considering the feed costs. LHSV Base Base + 10%
catalytic cracker (FCC) development group. Average feed RSH Base Base + 65%
Use of the catalyst allows SK the Subsequently, he worked as a project engineer Average product RSH Base 75% of base
option of operating with the origi- in the gas processing engineering department, Peak feed RSH Base Base + 12%
nal flow configuration, leaving the concentrating on the Merox process and Peak feed product RSH Base 23% of base
No. 1 KGHT running to make jet improving the designs of individual units and Off spec, % Base 46% of base
fuel. The increased processing unit complexes, for which he has been awarded Lbs RSH converted Base Base + 72%
RSH removal Base Base + 10%
capacity of No. 2 KMX leaves No. 1 patents.
KMX available to process another Eric Baker is Senior Product Line Manager,
stream and increases jet fuel Merox Products, Catalysts, Adsorbents and Table 3
production by 33% (see Figure 5). Specialties with UOP, A Honeywell Company.
Over the past 14 years, his responsibilities in wide initiatives. He holds a bachelor’s degree
In this case, the increased profit is
manufacturing, research and development, in chemical engineering from the University
due to processing a larger amount of Notre Dame and a master’s in business
and the business, have been associated with
of cheaper condensate feed. An a range of refining, petrochemical and gas administration from the University of Chicago
additional refinery profit of $6 purification technologies, as well as plant- Booth School of Business.
million can be realised by the abil-
ity to treat less expensive and more
difficult-to-treat feed. 0MPD No. 1
KGHT
Conclusion
No. 2 20MPD No. 2 20MPD
Merox No. 10 was able to signifi- CDU 30MPD KMX
Jet fuel
Merox No. 10
cantly improve the profitability of RSH = 400ppm
10MPD No. 2 10MPD
the SK-Incheon refinery. The activ- ULSD blending
KGHT
ity and stability benefit of the
catalyst allowed the company to Ulsan No. 1 10MPD
Jet fuel
process a difficult-to-treat conden- CLX 10MPD KMX
Merox No. 10
sate in higher quantities and
permitted it to offload one of its
hydrotreaters. UOP has completed Figure 4 No. 1 hydrotreater was shut down to reduce operating costs
the design of two more Merox
process units for the company and
is currently in discussions to 10MPD No. 1
revamp the existing No. 2 KMX to KGHT
a UOP jet fuel Merox Reactor. No. 2 20MPD No. 2 30MPD
Jet fuel
CDU 40MPD KMX Merox No. 10
RSH = 400ppm
Woo Kyung Kim is Technical Service Team 10MPD No. 2 10MPD
ULSD blending
Leader with SK Energy Incheon Complex. With KGHT
21 years of experience, his responsibilities
Ulsan No. 1 10MPD
include technical support for production Jet fuel
CLX 10MPD KMX
departments and mid-scale projects. RSH = 150ppm
Merox No. 10
Previously, he worked as a section manager
at the production department, responsible
for operational optimisation, technical Figure 5 The increased processing capacity of No. 2 kerosene treater leaves No. 1
service and labour management for the CDU, kerosene treater available to process another stream and increases jet fuel production

www.eptq.com PTQ Q4 2013 101

uop.indd 3 13/09/2013 14:53

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 Refinery power failures: causes, costs and
solutions: part 2
Technologies are discussed to help refiners formulate strategies in managing
risks and crisis due to emergency shutdowns, thereby minimising financial loss
WILLIAM H GRAF, WILLIAM F VUKOVICH and THOMAS W YEUNG
Hydrocarbon Publishing Company
P
art 1 of this series (PTQ, Q3
2013) discussed how electrical
disruptions and power failures
at refineries regularly cause enor-
mous damage in terms of lost
production, excessive repair costs,
and can lead to environmental and
safety concerns, raising the ques-
tions of how these outages can be
prevented and how an affected
refinery can be brought back online
as quickly as possible. In this arti-
cle, vital prevention techniques,
protective devices, quick restart
equipment, and supply security
methods will be discussed.
Electricity is the lifeblood of the
refinery operation. Optimal design
and excellent construction mean
nothing if the plant cannot receive
a consistent and reliable power
supply. Plant shutdowns, whether
planned or unplanned, will
decrease production and reduce
profits, as shown by US refiner
HollyFrontier, which reported a
loss of $98 million for Q1 2013
because of planned and unplanned
shutdowns.1
Not only is power reliability
essential for profits, it is also impor-
tant for national fuel supply
security and environmental
concerns. On 8 July 2013, Eni’s
Taranto refinery in Italy suffered a
leak of untreated fluid following a
power outage. Italy’s industry
ministry declared that the refinery
must invest in a power feed system
to prevent further blackouts, or else
the refinery would lose its permits.2
The necessity of flaring following
electrical failure is common, as on
30 May 2013 when a simple Mylar
balloon caused a short circuit in
a substation at ExxonMobil’s
www.eptq.com
hpc.indd 1
Refinery outage
mitigations
Risk
management
Prevention Protection
Figure 1 Refinery outage mitigations
Torrance, California, refinery in the
US resulting in the evacuation of
workers and elevated flaring.
Refineries require a lot of power
to operate. The overall mitigation
strategy primarily consists of two
parts: risk management and crisis
management (see Figure 1). In
handling risk management, a refin-
ery must install the most reliable
equipment available in the market
that can withstand disruptions
caused by weather, power surges,
blackouts, and any other outside
elements. Since no equipment is
perfect, reliability engineers and
operators still need to prepare for
worst-case scenarios as well as the
most frequently occurring possibili-
ties. This is where they utilise
prevention techniques to detect and
fix problems before they lead to a
power failure, and select protective
equipment accordingly. When a
problem does arise, the second part
of the strategy — crisis manage-
ment — comes into play. This
involves the recovery technologies
that allow for safe shutdown and
continued operation, and the restart
Crisis
management
Recovery Restart
methods that will not lead to the
same problem that caused the
previous failure.
Prevention and protection
One of the most important
preventative measures a refinery
can take is to have an efficient
maintenance programme. Studies
show thatthe failure rate of electri-
cal equipment is three times higher
for components that are not part of
a scheduled preventative mainte-
nance programme as compared to
those that are.3 Accordingly, main-
tenance is often a high priority for
refiners; at a National Petrochemical
& Refiners Association’s (NPRA)
conference in the US, a Gulf Coast
refinery representative said that his
company spends about 20% of
the maintenance budget on
proactive activities. It focuses on
rotating equipment and predictive
and preventative maintenance
programmes such as oil analysis,
vibration analysis, thermal imaging,
and craft training programmes. An
East Coast refinery representative
added that his company spends
PTQ Q4 2013 103
13/09/2013 14:53
 about 15% to 20% on proactive
maintenance and in the long term
will have it up to 65% to 70% of the
budget.4
Protective measures will keep
refining equipment from being
damaged or failing when exposed
to hazards such as arc flashes or
short circuits. This requires the
proper selection of distributive
equipment including transformers,
switchgears, motor control centres,
motors and cables that can handle
extreme conditions, and are able to
withstand dangerous events. This
also necessitates the proper selec-
tion and use of equipment such as
protective relays, circuit breakers
and grounding devices in order to
protect distributive equipment from
dangerous conditions. Good protec-
tive technology can also protect
operators and other personnel from
injury. The following sections
discuss the causes of and remedies
to major equipment failures in a
refinery, with specific refinery
applications to show the latest tech-
nologies adopted.
Transformers
Transformers are an essential part
of power distribution. They
increase or decrease voltage for
downstream distribution and oper-
ation. A properly operating
transformer keeps the electrical
system and load at optimal utilisa-
tion voltage levels.
Almost every malfunction is a
result of the failure of the device’s
insulation system. The insulation is
what keeps the transformer in elec-
trical balance and, when the
insulation ceases to function, the
entire transformer is susceptible to
immediate failure. Faults, heat and
mechanical damage will lead to
insulation failure, but the electrical
engineer can avoid these issues by
selecting a unit capable of with-
standing expected operating and
fault conditions.
A study done by Hartford Steam
Boiler during a 20-year period
showed that 13% of all transformer
failures in the US were caused by
inadequate maintenance. It is
important for maintenance person-
nel to check the insulator fluid.
These tests will indicate the health
104 PTQ Q4 2013
hpc.indd 2
of the transformer. Regular testing
such as an insulation resistance test,
dielectric absorption test, power
factor test, dissolved gas in oil test,
acidity test, colour test, and insulat-
ing liquid test will allow reliability
engineers to track a transformer’s
degradation and determine if
replacement or repair is necessary.3
The right transformer will
provide the correct level of power
for refinery units. In May 2013, it
was announced that Siemens will
be providing 220kV/110kV power
transformers and 35kV/10kV distri-
bution transformers as part of the
electrical system for China National
Petroleum Corporation’s planned
Guangdong Petrochemical Refinery.5
Switchgears
Switchgear is a combination of elec-
trical enclosures, buses, protective
relays, circuit breakers, fuses,
controls and indicating devices that
are used to distribute power to and
protect other electric equipment.
An arcing event can
cost a refinery as
much as $15 million
per incident
Receiving power from generators
or transmission cables, they will
distribute their power to other
switchgear (or switchboards) and
motor control centres.
Arcing is a major threat to
switchgear safety and reliability.
Major arc flashes and blasts will
ruin the switchgear and nearby
equipment, and endanger nearby
workers. An arcing event can cost a
refinery as much as $15 million per
incident.6 Plant engineers should
select arc-resistant models that
utilise quick sensing and switching
to de-energise arcs.
An easy maintenance programme
can be set up for switchgears. A
maintenance engineer should
inspect insulators and conductor
supports for signs of cracking,
broken pieces and other physical
damage or deterioration. Operators
should examine all bolts and
connecting devices for signs of
deterioration, corrosion or overheat-
ing, and ensure that bolts and
connecting devices are tight, accord-
ing to manufacturer’s specifications.3
Switchgear is an extremely
important electrical unit for refiner-
ies. Outdated units should be
upgraded to protect the refinery
from arc flashes and other possible
failures. In July 2013, ABB installed
its 11 kV Unigear ZSI switchgear
with REA arc-quenching technol-
ogy at the Total Lindsey Oil
Refinery (LOR) in the UK.
Motor control centres
A motor control centre (MCC)
is used to group a number of
combinations of motor controllers
together with a common power
bus. A MCC gives operators easy
and safe control over a number of
different motors throughout the
facility. Motor controllers serve
several key functions: starting or
stopping the motor it controls,
interrupting the current of the
motor, and providing overcurrent
protection.
Since its construction is very
similar to that of switchgear, MCCs
can experience similar failures. This
includes failure to the protective
circuit breakers and fuses, loose
connections in the cables and, of
course, arcing. Manufacturers are
employing the same arc-mitigating
technology used in switchgear to
protect MCCs from failing or harm-
ing personnel, so an engineer
would be wise to choose units with
this feature.
Motors are the most important
unit for refinery processing units to
operate. The motor control centre is
even more critical in providing
protection and the right electrical
levels for the motors. Eaton was
rewarded a $3 million contract
from Valero Energy (US) in July
2013 for its arc-preventative
FlashGuard motor control centres,
285 of which were installed in new
or existing units.7
Motors
As far as consumption of electric
energy goes, nothing in a refinery
comes close to the amount of
power provided to motor-driven
devices. Motor-driven equipment
www.eptq.com
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 will typically account for 70% of
energy consumption in refineries,
so special attention must be paid to
their proper selection and opera-
tion.8 The number of motors in any
refinery will be in the thousands,
and the safe operation of all of
them is essential to smooth
production.
Everything from pumps,
compressors, fans and other rotary
devices is considered motor driven,
and steps can be made to protect
and improve the reliability of these
essential parts of any refining
process. One of the main reasons
for motor failures is overheating.
Overheating will degrade a motor’s
insulation and necessitate de-rating
of the motor. This can be a result of
excessive current from faults or
frequent start-ups. Technological
considerations such as switching to
variable-speed drives (VSDs) or
soft starters, and good maintenance
practices will improve reliability.
Using modern motors can help
increase efficiency, which then
decreases operating costs. An April
2011 case study by Rockwell
Automation reported a 30-41%
reduction in energy consumption
and decreased downtime for
China’s Daqing Refinery Plant after
it switched from its throttling
system to Rockwell’s PowerFlex
7000 MV VSD and a 6kV inverter.9
Cables
A refinery will use miles of cable
for power distribution, motor oper-
ation and process control. Its ability
to transport signals and current
will impact the entire refinery’s
ability to operate. Protection of all
the cables is vital for any part of a
process.
Cables will suffer from degrada-
tion to their insulation through heat
and contamination. Parts of a cable
that heat up from excessive current
or external factors will be vulnera-
ble to water trees and short circuits.
Cables surrounded by polymer
insulation are especially vulnerable
to the damage caused by water
trees.
Cables should be inspected for
sharp bends, physical damage,
excessive tension, oil leaks, pits,
cable movement, soft spots, cracked
106 PTQ Q4 2013
hpc.indd 3
jackets, damaged fireproofing, poor
ground connections, deterioration,
and corroded or weakened cable
supports. Maintenance workers
should inspect for wear at entrance
points and at supports, and inspect
potheads for oil or compound leak-
age and for cracked or chipped
porcelain.3
A rejuvenation technique called
cable injection is one option to fix
damaged polymer insulation.
Novinium provided this service to
the Hess Port Reading Refinery in
Perth Amboy, New Jersey (US), in
2010 to rejuvenate its medium-
voltage cable after the refinery
suffered from short circuits.10
Protective relays
Relays are essential to any electrical
system. They are used in all parts
of the system, from the generators
and substation to the transmission
lines and load. Protective relays
detect abnormal system conditions
and direct the circuit breakers to
operate in the proper manner, to
correct any abnormality.
A condition known as hot-switch-
ing is a common cause of relay
degradation, especially in older elec-
tro-mechanical equipment. Large
differences in potential across a
relay will cause this to happen. The
electrical engineer must be sure that
the relay chosen is capable of with-
standing the voltage and current
levels that occur during normal
operation and fault conditions.
Inspection, maintenance, and test-
ing of protective relays should be
done annually by an operator to
ensure proper and reliable opera-
tion. Relays should be inspected for
physical damage and deterioration,
gaskets and covers checked for
damage and excessive wear, and
repaired or replaced as necessary.
Refinery maintenance personnel
must also examine and clean the
relay and enclosure of foreign
materials, such as dust, dirt and
moisture contamination.3
Upgrading old electro-mechanical
relays to modern digital relays can
help refineries better protect their
units and monitor their electrical
usage. Motor Oil Hellas Corinth
Refineries S.A. (MOH) in Greece
upgraded to SEL PowerMAX
Power Management and Control
System, a microprocessor relay
system, to boost reliability after a
2005 power outage.11
Circuit breakers
Circuit breakers protect circuits and
equipment from current and volt-
age spikes. Circuit breakers are
designed to open and close by
non-automatic means and to open
the circuit automatically on a
predetermined over-current with-
out damaging itself. The device
protects other units from overload
or short circuit. Its basic function is
to detect a fault condition. Unlike a
fuse, circuit breakers can be reset
after they have been tripped.
Circuit breakers will face issues
due to mechanical wear when over-
used, and dried-up lubrication when
underused. Contaminants in the
insulation, or the insulating medium
escaping the breaker, are certain to
lead to failure. Failure of a breaker
will cause false trips that can harm
operation and nearby workers.
To maintain a circuit breaker,
maintenance personnel should
inspect for damage and broken or
missing parts, make sure breaker
contacts are clean and aligned, be
sure that spring pressures are
correct, check for leakage, see if the
oil gauge is correct, and conduct an
insulating oil test.3
Circuit breakers are the infantry
of the electrical grid. Incorporating
units that are robust for any condi-
tion and the correct setting for its
position distribution line can save
the refinery from failures. Back in
2010, Petroplus Coryton Refinery in
Essex (UK) replaced LV circuit
breakers with 3200A 3-pole
Masterpact NW circuit breakers
made by Schneider Electric, a
model more suited to intense
weather conditions.12
Grounding
A properly grounded (earthed)
system will protect equipment and
personnel from exposure to fault
currents. Well-placed and -designed
grounding will divert any faults to
earth or a grounded bus. It is
utilised throughout an electric
system for equipment such as
transformers and motors, and on
www.eptq.com
12/09/2013 16:59
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 conductive structures like storage
tanks and pipes.
Most electrical systems at refinery
utilisation levels will use resistance
grounding, where there is a resistor
between the equipment and
ground. This resistor, through
factors such as corrosion and
mechanical wear, can wear out and
consequently leave a system
ungrounded. Neutral grounding
resistor (NGR) monitoring will
immediately detect when a NGR
has failed, and greatly decrease the
amount of time a system is vulner-
able to ground faults. I-Gard’s
Sleuth high-resistance grounder has
been installed during projects such
as PetroCanada’s (now Suncor)
2005-2009 Refinery Conversion
Project.
Recovery and restart
Preventative and protective meas-
ures will make great strides
towards decreasing downtime aris-
ing from power failures. But if a
failure does occur, it is necessary to
minimise loss in production and
resume normal operation as quickly
as possible. Even if the units are
running at reduced rates, flaring
can be reduced and production will
not completely halt. The use of
backup generators and uninter-
ruptible power supply (UPS) can
help get units back up and running,
and get control rooms back online
without missing a beat.
Backup generators
When the power goes down, all the
units have to stop. On-site genera-
tors give operators the ability to
continue running units when the
primary power goes down. These
units are not usually used as the
primary power due to fuel costs.
The failure of the cooling system
will lead to a rapid deterioration of
the core insulation and conductors.
Generator failures can be due to
excessive rotor coil foreshortening,
electrical grounds, mechanical
imbalances and overheating. Again,
the solution for these problems is an
effective maintenance regimen to
spot the problems before they occur.
Backup generators can keep the
power going when the utility fails
or when maintenance requires the
108 PTQ Q4 2013
hpc.indd 4
shutdown of the primary feed. In
June 2012, Mid Refinery Company,
part of Iraq’s Ministry of Oil, was
provided with Cummins Power
Generation’s C3300 D5 generator
set to operate at 6.6kV for its refin-
ery outside of Baghdad.13
Uninterruptible power supply
UPS is a device that acts as a
backup power source. It is designed
to detect power dips and power
failures, and initiate a battery
backup power once a problem is
detected.14 A UPS should only be
used in an environment that it is
rated for. UPS system loads consist
of digital control systems, program-
mable logic controllers, critical
process instruments, fire and gas
alarm panels, safety shutdown
systems, process equipment control
panels (boiler controls, compressor
controls, and so on) and other criti-
cal electrical loads.15
A properly grounded
system will protect
equipment and
personnel from
exposure to fault
currents
The battery of a UPS is the weak
link in the system. If the UPS is in
a hot environment then battery life
will be reduced. Vented lead acid
batteries have an average life of
10- 15 years for plate arrangement
and 15-20 years for tubular design.
The Plante plate arrangement has
increased battery life to 20-25
years. Nickel cadmium batteries,
in vented or recombination
arrangement, can have a life time
of up to 25 years. Batteries should
be kept below 25°C (77°F) to main-
tain good operation.16
Maintenance for UPS systems
can be challenging and require
certified personnel. Trained work-
ers should ensure that any areas of
corrosion and deterioration are
repaired as needed. They should
clean and examine all electrical
connections for signs of corrosion
or deterioration, repair or replace
as necessary, and ensure that all
connections are tightened according
to manufacturer’s specifications.
They should also, as applicable,
clean and test all breakers, discon-
nects and relays as prescribed
elsewhere in these standards and
as specified by the manufacturer,
and check all system alarms and
indicator lights for proper
operation.3
UPS systems can not only
provide backup power for control
units, but can also be set to balance
the electrical feed when the voltage
is fluctuating. In July 2011, Emerson
provided a UPS and generator
package to Chevron’s (now Valero)
Pembroke Oil Refinery (UK) for the
sulphur recovery unit as a way to
operate in the event of a grid fail-
ure and to operate emergency
shutdown procedures without
environmental impacts.17
Formulating strategies to mitigate
power failures
Every processing unit within an oil
refinery was meticulously designed
and planned on the assumption that
it would receive a constant power
supply. With that in mind, it is
necessary to consider the steps that
could be taken to ensure 24/7
production from every process. Risk
management and crisis management
must be practised to maximise
productivity of the plant.
Understand the impacts
Plant owners and managers must
understand the lasting impacts
outages will have on a company in
order to appreciate the importance
of mitigating refinery power fail-
ures. Figure 2 illustrates the
impacts of refinery power failures.
The financial implications have
been stated earlier, where more
downtime means less product and
increased maintenance and repair
expenditures. The sudden shut-
down of large units presents a large
array of safety and environmental
concerns, where large amounts of
dangerous chemicals can be
released through flaring or
ruptured lines; poor plant safety
and environmental hazards are
certain to lead to sanctions, lawsuits
www.eptq.com
16/09/2013 13:59
 and, of course, bad media coverage
and negative publicity. Sudden,
unplanned shutdowns are never Energy Financial Plant safety
efficiency performance and liability
good for the reliability of a refin-
ery’s operating units, especially the
larger ones. Motors and rotary
equipment are damaged when
suddenly taken from full speed to a
dead stop, and consume a great Power failure Negative
Reliability publicity
deal of energy while restarting. But impacts
if steps are taken to minimise
unplanned failures, all of these
consequences can be reduced.

Finding the most reliable electrical Asset Environmental

equipment
Refineries need to work with elec-
trical technology vendors to design
and construct the most reliable grid
for each unit. This cooperation can
help refineries improve their energy
security and efficiency. Table 1
shows a list of selected major
companies from those that were
surveyed by Hydrocarbon
Publishing Company in preparation
of its report. The survey covers 120
companies from around the world
that provide various technologies
management
Figure 2 Impacts of refinery power failures
that are further discussed in the
report.
Six Sigma
Strategies for process improvement
such as Six Sigma rely on identify-
ing and removing defects within a
process and carrying out proper
operational practices by qualified
concern and
liability
personnel. This starts with the initial
design of the power system by the
electrical engineer, where all factors
such as steady-state load require-
ments, ambient conditions, and
quantified fault conditions are thor-
oughly considered. Management
and engineers must also work with
the vendors to be certain that all the

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www.eptq.com PTQ Q4 2013 109

hpc.indd 5 13/09/2013 11:51

 Technology suppliers surveyed advancing age and potential
cyber-attacks. Power disruptions
Technology Companies due to poor infrastructure are
Transformers ABB, Eaton, GE, Schneider Electric, and Siemens AG common problems around the
Switchgears ABB, Caterpillar, Eaton, GE, Schneider Electric, and Siemens AG world.
Motor control centres ABB, Eaton, GE, Schneider Electric, and Siemens AG
Motors ABB, Baldor Electric Co., GE, Rockwell Automation, Siemens AG,
and Teco Westinghouse Get everybody on board to save
Cables General Cable, Nexans, and Novinium bottom line
Protective relays ABB, Eaton, GE, Schneider Electric, Schweitzer Engineering Refiners are advised to set a goal of
Laboratories, and Siemens AG
“zero” power failure and “fastest”
Circuit breakers ABB, Eaton, GE, Schneider Electric, and Siemens AG
Grounding technologies i-Gard and Littlefuse power recovery and share the goal
Backup generators Aggreko, Caterpillar, Cummins Power Generation, GE, Kohler and Siemens with all the employees, including
Uninterruptible power people working outside the plant.
supply units Ametek Solid State Controls, Eaton, and Emerson
When a refinery shuts down, busi-
ness profit is gone, thereby
Table 1 affecting everybody in the
company, from the CEO to the
electric equipment installed is rated tify the most vulnerable equipment maintenance worker. Any employ-
for the appropriate operating condi- and units. The results assist in ees that offer key contribution in
tions. Operators and maintenance sound decision-making on what terms of ideas and innovations to
personnel must be properly trained options and investments to choose increased reliability and availability
and educated by the vendors to in minimising power failures. of a power system should be
know how to correctly run and Disciplines such as predictive offered financial incentive for
check up on newly provided equip- analytics, actuarial science and avoiding power failures.
ment. Reliability engineers should enterprise asset management
have access to operating and should be included in overall refin- Conclusion
condition-based data to assess the ery operations management. No refinery can afford and tolerate
state of all equipment and notice power interruptions, as financial
any future problems. Power independence costs and potential liabilities due to
Onsite power generation via environmental and safety incidents
Big data combined heat and power (CHP) can run into millions of dollars a
Models should be developed not day. The responsibility of keeping a
just for faults and degradation, but Risk management and smooth operation not only lies with
also for weather tracking in case of reliability engineers, operation
incoming storms and lightning crisis management managers and maintenance person-
through cloud, temperature and nel, but also with senior
wind sensing. A refiner may want must be practised management, who should allocate
to borrow the idea from IBM, resources to invest in advanced
which recently announced that a to maximise technologies in protection, preven-
combination of big data analytics tion and recovery now available in
and weather modelling technology
productivity of the market. Refiners are advised to
can predict the performance of
renewable energy.18 Since over 16%
the plant take a holistic approach by manag-
ing risks and crisis in terms of
of refinery power disruptions were mitigating power failures.
caused by weather in the US from units and microgrids are worth Otherwise, stockholders, communi-
2009-2012, refiners must ensure consideration. The latest CHP and ties near the refineries and
there are adequate investments in microgrid technologies can be incor- consumers are paying the price.
on-site weather monitoring equip- porated into the design of a new
ment, and also cooperate with local refinery power grid that can be
weather authorities and tracking combined with other renewable
services so that steps can be taken energy generation units as a way to
in a quick and efficient manner to improve power supply security and
prepare for any weather-related reduce plant carbon footprint. This This article is an excerpt from a multi-client
emergency and quickly mitigate will also help refineries track the use strategic report called Refinery Power Outage
any potential damage. of electricity to maximise efficiency Mitigations: Latest Technologies and Strategies
Since there are many options and discover problems before they to Minimize Financial Impacts, published in
September 2013.
available and refiners are often occur to keep power disruptions to
limited by tight budgets, the a minimum, instead of depending
cost-effective strategy is first to on their utility provider. Special thanks to Mr Baldwin A Yeung, P.E. of
combine electrical outage data, and Furthermore, power grids are prone SAIC, who provided technical assistance for
process reliability models and iden- to outages because of weather, this article.

110 PTQ Q4 2013 www.eptq.com

hpc.indd 6 12/09/2013 17:00

 Potential legal liabilities 245 000 b/d Richmond, California, explosion and subsequent fire at its
Aside
References from missed production, refinery in helps
drive solution AugustChina’s2012
Daqing had forced
refinery plant Texas City, Texas, refinery on 23
EmersonNetworkPower’sChlorideIntegrated
outages
1 Zawadzkiprompt unnecessaryvows
S, HollyFrontier flaringless Chevron
reduce annual to energy
pay $10 millionbyto41%,
consumption indi-
Apr March 2005 that resulted in 15
PowerSolutionKeepsPembrokePetroleum
ofdowntime
hydrocarbons
at refineries, to Thomson
avoid Reuters,
unsafe7 viduals,
2011, area hospitals,
www.emea.rockwellautomation.com/ city worker deaths and over 170
PumpingNewfacilityatChevron’sPembroke
conditions.
May 2013. Over the past 10 years, agencies and the Hazardous
oilandgas/en/docs/mv.pdf injuries.
refinerygets.aspx
7

2 Paraskova
the US EPA T, Italy has
orders Eni to install into
entered power 10 Case study:
Materials Hess PortasReading
Program Refinery,
of January 18 IBM’s press release on 12 Aug 2013, Made
feed at Taranto refinery, Power Market Review, Perth Amboy, NJ, 2010. in IBM Labs: IBM drives the future of renewable
settlements with 28 different refin- 2013. There are approximately Conclusion
6 Aug 2013, www.powermarket.seenews.com/ 11 Case study: automated power management energy with new wind and solar forecasting
eries that are aimed at restricting 24 000 civil claims that have been As previously noted, about 19% of
news system — an economical approach to greater system.
emissions
3 Recommended by the oil industry.
maintenance practicesThefor levied against
operational the firm as a result of
dependability. refinery emergency shutdowns in
EPA has distribution
electrical acquiredsystem consent decrees
equipment, The the flaring atrefines
12 Petroplus Richmond.
its technology with the US between 2009 and 2012 were
from 105Steam
Hartford US Boiler,
refineries in 32 states
2010, www.hsb.com Emergency
retrofit shutdowns
from Schneider because
Electric, of
Schneider caused by power disruptions
and
4 56th territories
Annual NPRAsince December
2002 Technology Q&A, power failure
Electric, Mar 2011.can also pose safety because of severe weather, poor
2000.
NPRA, All
2002 of the21.settlements have
p8, 20, issues.
13 CumminsSometimes
Power Blogapress refinery
release on shut-
6 Jun power
William quality
H Graf isand electrical
Technology equip-
Analyst with
involved
5 Siemens at and least one ofPetroleum
China National four down will force the need to
2012, MICTA supplies and installs Cummins ment malfunctions. Costs to refiners
Hydrocarbon Publishing Company and holds
Corporation conclude
primary pollution types: NOx, framework agreement,
SOx, Power Generation
evacuate Prime Power
workers for Solution
safetyat a BS degreetoinmillions
amount physics from ofHampden-Sydney
dollars every
29 May 2013, Siemens Global, www. third site for Mid Refinery Company in Iraq. College.
benzene and volatile organic reasons. In April 2010, BP’s Texas year due to lost production, repairs
siemens.com/press/en/pressrelease/?press=/ 14 Stout M, Effects of extreme temperatures.
compounds (VOCs). Furthermore, City, Texas, plant experienced an to damaged equipment, sending
en/pressrelease/2013/energ y/oil-gas/ electrical construction and maintenance, 2012. William F Vukovich is Technology Analyst with
alleog201305036.htm
of the violations involved one or electrical
15 Cosse R outage
Jr, Dunn D,that
Spiewak shutR, Isoff all
my UPS
valuable material to flare, possible
Hydrocarbon Publishing Company and holds a
more four key
6 Franklin refinery components:
J, De-energizing arc-flash in oil & power and steam to the refinery
distribution system coordinated?, IEEE, 2004. fines for excessive
BS degree in chemical emissions,
engineering and
from Lehigh
the
gasFCC unit,
facilities, Oil SRU, flares and
& Gas Monitor, 6 Marheat-
2013, and forced
16 Eaton’s the FMX
Power Xpert evacuation
Medium-Voltage of so on. Therefore, equipment
University.
ers/boilers. Excessive flaring can
http://oilgasmonitor.com/de-energizing-arc- non-essential
Switchgear Systemworkers optimized with from the
SASensor vendors, maintenance and reliabil-
lead to environmental concerns and
flash-oil-gas-facilities/4406/ plant. Safety-related
for tomorrow’s Smart Grid, incidents
Eaton, 25can Jan ity
Thomasservicing companies
W Yeung is Principal and
and Managing
incur fines
7 Eaton’s pressimposed
release on Julby16 environ-
2013, Eaton result
2012, in the loss of life along with
www.eaton.com/Eaton/OurCompany/ refinery
Consultant withtechnology
Hydrocarbondevelopers
Publishing
to Enhance
mental agencies.Safety, Equipment Reliability NewEvents/NewsReleases/PCT_333811
the potential for millions of dollars Company. been
have He is aseeking
licensed professional
technical
for
TheValero Energy Corporation’s
potential liability due St. Charles
to a Emerson
in17 fines andNetwork Power’s not
civil lawsuits, Chloride
to approaches to preventand
engineer (New York State) holds afail-
power BS
Petroleum Refinery. Integrated Power solution keeps degree in chemical engineering from University
prolonged flaring can cost a refiner mention any negative publicity ures, protect equipment, speed up
8 Electrical installations in petroleum Pembroke Petroleum Pumping, 13 Jul of Wisconsin-Madison, a MS degree in chemical
a processing
huge sum. For illustration
plants, American Petroleum
from the event. Previously, BP paid
2011, Emerson News Release, www.
restarts and salvage damaged
engineering from University of Connecticut-
purposes,
Institute, Jul 2004, p12. caused by a
a fire over $87 million in fines issued by
emersonnetworkpower.com/en-EMEA/ components. A few
Storrs, and a MBA from of University.
New York the tech-
corroded
9 Rockwellpipe that led
automation’s to subse-
medium voltage OSHA along with undisclosed
About/NewsRoom/NewsReleases/Pages/ niques available include approaches
Email: info@hydrocarbonpublishing.com
quent excessive emission at its amounts in civil suits related to an to examine transformer failure due

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26 PTQ Q3 2013 www.eptq.com

www.eptq.com PTQ Q4 2013 111

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 Heat integration projects for
refining processes
Heat integration projects can deliver substantial savings, but they require
detailed simulation and case-specific heat integration analysis
ALişAN DOgĂN
Turkish Petroleum Refineries Corporation
R
efining is a complex operation
involving many kinds of
processes. All these processes
have different principles; some
involve fractionation, some involve
different reactions and some have
both. All these processes have one
thing in common: they need
energy. It may be a need to heat
“cold streams”: energy to make the
required separation between cuts,
energy to strip off unwanted gases,
energy to perform a reaction and so
on. The processes also have ener-
gy-giving streams (hot streams):
column pumparounds, overhead
streams, reactor effluents and so
on, which are available to supply a
portion of the necessary heat;
furnaces burning fuel take care of
the rest. Some processes are inte-
grated; the product or residue of
one process may be the feed to
another. The better the heat integra-
tion in or between process units,
the less fuel is burned in furnaces,
which leads to more profit. In this
article, the basics of heat integration
studies performed in various heat
integration projects for different
refinery process units are consid-
ered. The methods, equipment and
approaches used for heat integra-
tion (pinch) studies of various
refining processes, their similarities
and differences are discussed.
In order to make a pinch study of
an existing unit, one should first
define the overall picture, which is
the energy balance and the temper-
ature profile of all the related cold
and hot streams. The heating cool-
ing curves and potentials saving
should be determined. A test run
performed in the unit will give all
the necessary information, such as
www.eptq.com
tupras.indd 1
flow rates, temperatures and lab
results. Based on this test run, a
simulation model of the unit should
be made. For a start, only the heat
exchanger network consisting of
simple heat exchanger models may
be enough to define the overall heat
balance. However, when it comes
to adding equipment, making accu-
rate cost estimations and defining
design data for retrofits and new
equipment, a unit model with
rigorous heat exchangers, columns
and other equipment will be neces-
sary. Furthermore, a complete unit
model will let you find additional
and more accurate saving opportu-
nities through case studies and
trial-and-error studies. At the end
of the day, it is all about making
the necessary investment in an
existing unit to gain air- or water-
cooled waste heat to decrease
furnace loads or generate steam.
Case studies will be necessary to be
able to select the best investment
option. When deciding on the
design data of new equipment and
retrofits, rating them with a second
set of simulation data representing
the unit (or units) will be wise in
order to select the equipment based
on a range of operations.
Main steps to making a detailed
heat integration engineering study
are given below. The procedure
may change from study to study,
but the principles remain the same:
• Rigorous simulation modelling of
the existing unit or units within the
boundary
• Formation of base case heating –
cooling composite curves
• Determination of base case mini-
mum approach temperature and
potential savings
• Determination of possible retrofit
paths to achieve potential savings
• Making the necessary equipment
additions to the unit model and
simulating the new retrofit paths
• Repeating the first five steps for
another base case simulation
model, preferably a case at the
opposite end of the operation
envelope
• Rating the equipment to supply
the needs of both operation cases
• Determination of investment
costs and benefits of all the differ-
ent saving opportunities (options)
• Selecting the most appropriate
case
• Extracting the process data neces-
sary for new equipment design.
Savings may be further increased
during the latter simulation stages
by changing/shifting reflux duties
and operation variables.
Heat integration studies
performed on different refining
units will now be discussed, taking
into account similarities and differ-
ences in the approaches and their
effects.
Crude and vacuum distillation
processes
The first important step for a heat
integration study of a crude distil-
lation unit is drawing the
boundary: is the unit integrated
with the vacuum unit and, if not,
should it be? Integrating a crude
unit with the downstream vacuum
unit is, most of the time, more prof-
itable. Even if they are not
integrated, the overall boundary
should be drawn to include the
vacuum side — the atmospheric
residue (vacuum charge) preheat-
ing train.
PTQ Q4 2013 113
12/09/2013 20:12

Crude Heating
Crude unit
AR
357ºC
AR
duty
Crude unit
HVGOPA
duty
AR
~357ºC
Figure 1 Drawing the CDU/VDU heat integration boundary
Drawing the boundary
In an integrated CDU/VDU config-
uration, vacuum unit hot streams
are used to heat the crude charge,
and hot atmospheric residue is sent
directly to the vacuum furnace to be
heated. In a non-integrated configu-
ration, atmospheric residue is sent
colder to the vacuum unit after heat-
ing the crude oil. Therefore, in a
non-integrated layout, atmospheric
residue is first a hot stream giving
energy to the crude side, then a cold
stream, which is heated by vacuum
unit hot streams such as the HVGO
pumparound and vacuum residue
run-down. This is an inefficient
design from a heat integration point
600
500
Temperature, ºC
residue preheating should be
AR Heating included in the heat integration
study when drawing boundaries.
Unintegrated
Including only the crude unit will
prevent one from seeing the poten-
tial modifications, retrofits and
benefits, which result in hotter
atmospheric residue going to the
Vacuum vacuum unit.
furnace Figure 2 is the composite curve
127ºC 300ºC
HVGOPA VR and unit for the CDU unit in Figure 1, which
duty duty is not integrated with the VDU. The
hot-side pinch point is 129°C and
Integrated the atmospheric residue outlet from
crude preheating is at 127°C.
Therefore, the atmospheric residue
temperature is at the closest point
VR
duty to the heating curve of the cold
streams. The minimum temperature
Vacuum
furnace difference (DTmin) between the
~357ºC curves is 30°C. Although there is 44
and unit
Gcal/h of waste heat, the saving
potential is limited to 7 Gcal/h
even when you target a minimum
temperature difference of 10°C,
of view. Heat exchanger area is which is very hard to achieve.
needed to first cool down the hot The reason for this is that if you
atmospheric residue in the crude bring only the CDU into the
side, and additional area is needed picture, it is not possible to gain
to heat it in the vacuum side. substantially from the waste heat
Furthermore, the heat that could be and keep the atmospheric residue
recovered would be higher in the temperature close to 129°C at the
integrated case, the HVGO pumpa- same time.
round (at high flow) and vacuum However, when atmospheric resi-
residue (at high temperature) being due preheating in the VDU is
able to give more duty to the crude brought into the picture, there is no
side and the atmospheric residue need to keep the atmospheric resi-
going much hotter to the vacuum due temperature close to the cold
furnace directly from the atmos- curve, because it is a cold stream
pheric column. that is heated by VDU hot streams.
Even if integration of the CDU Sending atmospheric residue hotter
and VDU is not desired for a to the VDU is desirable, therefore a
specific reason, atmospheric potential is generated even when
the two units are not integrated. If
the units are to be integrated, the
potential is much higher.
Atmospheric residue will then be
going to the VDU furnace directly

in its hottest form, and the VDU

400
hot streams will be used in crude
heating (see Figure 1).
300
When atmospheric residue
200 preheating is added within the
Pinch = 129ºC
boundaries, DTmin automatically
100 dTmin = 30ºC increases to 46°C, creating a poten-
Pinch = 99ºC tial of 15 Gcal/h for DTmin = 10,
0 already doubled even though the
0 50 100 150 200 250 same atmospheric residue tempera-
Enthalpy, Gcal/h ture is targeted. The real potential,
in fact, is much higher than this,
Figure 2 Drawing the boundary and composite curves considering that there is no

114 PTQ Q4 2013 www.eptq.com

tupras.indd 2 12/09/2013 20:12

 constraint on the atmospheric
residue temperature, and even
more when the units are to be
integrated.
In the example below, a heat inte-
gration study performed on another
CDU/VDU unit is explained in
detail. The configuration, number
of pumparound streams, reboiler
hot streams and so on may differ in
different process layouts.
Case 1: CDU/VDU unit
In the integrated unit discussed
below, the preheat train consists of
three different sections. Before the
desalter, the heat required is
provided by the atmospheric
column overhead and some portion
of the diesel pumparound duty.
After the desalter, crude is sepa-
rated into three streams to be
heated by product run-downs, the
diesel pumparound and the HVGO
pumparound. Afterwards, the
combination crude is further heated
by vacuum residue before going
into the atmospheric furnace. The
reboiler and naphtha splitter
reboiler duties are supplied by
HVGO and diesel pumparounds.
The DTmin of the light crude base
case is ~70°C, with nearly 62
Gcal/h of furnace process duty and
42 Gcal/h of wasted “hot stream”
energy.
The main waste heat streams in
this configuration are as follows:
• HVGO PA air cooler duty (after
crude heating)
• LVGO PA air cooler duty
• Atmospheric column overhead
duty after the top condenser
• Run-down air cooler duties (after
crude and desalter water heating),
especially heavy diesel run-down.
Basic design considerations for
the project are:
• Increasing the HVGO pumpa-
round duty in the vacuum column
automatically decreases the
air-cooled LVGO pumparound
duty. Even in the low HVGO
pumparound base case, a substan-
tial amount of duty is lost through
air coolers. The desired HVGO
temperature to the hydrocracker is
150°C. Therefore, a HVGO pumpa-
round temperature of 150°C is
targeted. In order to make up room
in the crude network for the exist-
www.eptq.com
tupras.indd 3
Crude
Desalter
OVHD HADPA2
Crude
Desalter
OVHD HADPA2
Figure 3 CDU/VDU example crude preheat train before and after the project
ing air-cooled duty and this
additional duty in the HVGO
pumparound, some duty has to be
shifted towards the hotter side of
the train. Therefore, a new hot
HVGO pumparound exchanger is
added before the existing hot VR
exchanger, and the new cold
HVGO pumparound heat
exchanger is added to the cold side
to recover the additional duties
• The remaining LVGO pumpa-
round duty is partially recovered
before the HADPA exchangers in
the second branch
• A portion of the heavy diesel
duty is recovered in the second
branch, following the new LVGO
heat exchanger
• Additional surface area is added
to the HADPA heat exchanger. The
reason for this is that the crude
temperature is much higher now
because of the LVGO and heavy
diesel heat exchangers
• The new cold vacuum residue
exchanger drops the temperature to
its initial value before going to
steam production
• The overhead vapour duty after
the first condenser (crude oil
heater) is very high, and this is lost
through air and water coolers.
However, it needs a higher-grade
material heat exchanger to recover
because of its corrosive nature
• Putting an additional high-grade
material overhead exchanger and
recovering the energy across the
Kero. LAD HAD To
furnace
HADPA1 VR
HVGOPA
Kero. LAD HAD1 To
furnace
LVGOPA HADPA1 HVGOPA1
HAD2 VR1
HVGOPA2 VR2
dew point was considered. This
would enable more heat recovery
by shifting the diesel pumparound
duty towards the hotter side of the
train, making room for the over-
head duty before the desalter.
Diesel pumparound duty would
be shifted by closing the bypass
and putting additional area on the
existing HADPA exchanger.
However, because of the tight
equipment layout, enough space
could not be found in the actual
unit conditions. This option is laid
aside for the time being as a
possibility.
The simplified crude preheat
train before and after the project is
shown in Figure 3.
The key to this study is that all of
the new heat exchangers are
considered to be plate-type heat
exchangers. All welded-type plate
heat exchangers, because of their
area and space efficiency (high heat
transfer coefficient), are well suited
to tighter applications. If shell and
tubes were to be selected for this
project, a huge number of shells in
series and the space they occupy
would have been required. This
would have increased the invest-
ment cost, pressure drop and space
requirements. With this project,
over 15 Gcal/h of furnace duty will
be saved even without the addi-
tional overhead exchanger. Overall
payback time of the project is
almost half a year.
PTQ Q4 2013 115
12/09/2013 20:12

Desalter
Crude
OVHD HADPA2
Figure 4 Preflash drum option for the project
Preflash drum option
The feasibility of adding a preflash
drum depends on the column oper-
ation, pumparounds and how they
are located in the structure of the
heat exchanger network and the
tray where preflash vapour is intro-
duced. Adding a preflash drum
changes the pinch structure, the
potential energy savings and the
additional area of new heat
exchanger needed. It is a case-
specific study, and it should not be
decided whether an option with the
preflash drum will be feasible or
not without making a detailed
study. However, the existing unit
column and heat exchanger
network structure will give a hint.
It is certain that preflash vapour
will bypass the furnace and the
liquid load will decrease.
Furthermore, the preflash drum
bottom temperature will be much
lower than the inlet. This will create
a driving force in temperatures and
make an opportunity for this
stream to be heated more effi-
ciently, which may result in duty
shifts and savings.
However, the main point to be
considered in a preflash drum study
is the cooling effect of preflash
vapour on the tray to which it is
introduced. If this vapour is given
directly to the flash zone, the
column bottom temperature will be
lower and the direct benefit will be
small. In fact, the only real potential
in this case is the temperature drop
in the preflash bottoms and the abil-
ity to heat this stream more
effectively. If preflash vapour is
given to the upper trays based on its
temperature, the pumparound duty
on the column will decrease.
Therefore, the question is where is
this pumparound duty used?
116 PTQ Q4 2013
tupras.indd 4
Kero. LAD HAD1
LVGOPA HADPA1
HAD2 Flash drum
HVGOPA2 VR2
• If pumparound duty is used
directly in the preheat, potential
duty gained by bypassing the
furnace is lost as reflux duty in the
preheat train, cancelling out the
energy benefit
• If pumparound duty is air cooled,
the preflash vapour will decrease
this duty. Energy-wise, there will
be no loss and the furnace duty
will be decreased
• The saving related to the driving
force effect with the preflash option
depends on the waste heat availa-
ble in the heat integration study
and the configuration.
Simulations are made such that
there is no loss of valuable prod-
ucts to less valuable ones. Some
examples regarding the preflash
studies made are given below.
Preflash example 1
In the CDU/VDU study given as
the example project, a preflash
study was made. A brief summary
of the preflash option for this
particular unit follows.
When the preflash vapour is
given to the flash zone, duty gained
in the atmospheric furnace is lost in
the vacuum furnace.
When the preflash vapour is given
to the upper trays at a suitable
temperature, column pumparound
duty decreases. There is only one
pumparound in this particular unit
(HADPA) and all of the duty is used
in crude oil preheat. The potential
duty gained by preflash vapours
bypassing the furnace is lost in
crude oil preheating. The column
atmospheric residue temperature
increases and the vacuum furnace
load decreases. However, overall
saving in this aspect is close to zero.
There is a 20°C temperature drop
in the preflash drum bottom. This
To
column
To
furnace
HADPA HVGOPA1 VR1
(new)
driving force effect creates room for
additional savings potential in the
cold side of the train and decreases
the heat exchanger investment to
be made. In this specific layout, the
cold preflash bottom temperature
makes HADPA duty shift to the
hotter side of the preheat train,
creating room for an additional
savings opportunity before the
desalter. The only air-cooled stream
available for this is the overhead
stream. Therefore, the driving force
effect would make additional
savings if overhead duty were to be
used. This effect also decreases the
investment cost of exchangers and
decreases the vacuum residue
temperature going to steam
production (by shifting some
portion of the vacuum residue
steam duty to crude oil heating
furnace duty). The additional
saving would be in the range of
2 Gcal/hour in the light crude case
and close to zero in the heavy
crude case. Based on these results,
the preflash drum option for this
study was laid aside because of its
low overall benefits and unit space
constraints.
Preflash example 2
Another example is the initially
non-integrated CDU/VDU unit
illustrated in Figures 1 and 2. The
effects of the preflash drum and
also the importance of drawing the
overall boundary correctly will be
discussed in this example. When a
typical non-integrated CDU such as
in Figure 1 is considered, atmos-
pheric residue is used in preheating
crude oil, and colder atmospheric
residue is heated again with
vacuum-side hot streams.
If there is an air-cooled pumpa-
round, introducing preflash vapour
www.eptq.com
12/09/2013 20:12
 f
or warming up
and cooling down

bronswerk.com

bronswerke.indd 1 11/09/2013 14:16

 in the upper trays creates a benefit,
as discussed in the previous
example.
If all pumparound duties are used
in preheating, one does not expect
large amounts of savings. However,
if you draw the boundary on the
CDU only, the results will be differ-
ent. The pumparound duties (there
may be more than one pumpa-
round) will be lower with the upper
tray preflash option. This would
automatically mean that crude inlet
temperatures to the existing atmos-
pheric residue exchangers would
decrease, creating a driving force
effect. This would also automatically
mean that more duty can be recov-
ered from atmospheric residue,
making up for the lost duty in
pumparounds, and the atmospheric
residue temperature leaving the
CDU will be lower. This is an
energy saving if you are only
considering the CDU. However, the
atmospheric residue is sent directly
to the vacuum unit, and this poten-
tial saving is lost in the vacuum
furnace. Therefore, if you draw the
boundary on the CDU only, you
will be evaluating a potential that is
not actually there. There will be
some shifts from steam production
duty to furnace duty, but this is not
an energy-saving potential in the
CDU/VDU. It is a matter of the
value of steam in that particular
refinery. If the unit is integrated,
project saving potentials are much
bigger. However, the effect of a
preflash drum will be similar.
Hydrocracker and
hydrodesulphurisation (HDS) units
A typical hydrocracker or a HDS
preheat train can be divided into
two sections: the reactor effluent
side with high pressure and
Effluent
EFF1 EFF2
To reactor furnace
Figure 5 Hydrocracker project existing simplified network
section will be discussed with
regard to the hydrocracker example.
Example: hydrocracker
In the unit studied, HVGO, hydro-
gen and stripper feed is heated
with reactor effluent. Before going
into this high-pressure network, the
stripper charge is heated with
diesel and fractionator bottom
product. Debutaniser and naphtha
splitter reboiler duties are supplied
by the diesel pumparound in the
fractionator. Kerosene pumpa-
round, kerosene run-down, stripper
and fractionator overhead streams,
and the reactor effluent stream
going to the air cooler are the main
sources of waste energy. There are
two furnaces: one reactor charge
furnace and the other fractionator
charge (stripper bottom) furnace. A
simplified existing heat exchanger
layout is shown in Figure 5.
In the base case, the furnaces
have a process duty of 26.4 Gcal/h.
600
dT = 75.38ºC
Qh = 26.4
500
Qc = 60.3
Temperature, ºC
To
air-cooler
EFF3 EFF4 EFF5 EFF6 EFF7
Fractionator
bottom
product
Diesel
product
To stripper HVGO feed Stripper feed Hydrogen
Waste heat through air or water
coolers is in total 60.3 Gcal/h.
Nearly 24 Gcal/h is wasted
through the effluent air cooler
(operating from 190°C to 62°C). The
minimum temperature difference is
75°C between the curves. The hot
pinch is 230°C and the cold pinch is
154.5°C (see Figure 6).
The link between the high-
pressure and low-pressure heat
exchanger trains is the stripper
charge. Stripper feed is heated from
~60°C to ~110°C with fractionator
streams before going to the
high-pressure effluent exchangers,
where it is heated to 255°C.
Therefore, if the stripper charge
stream is further heated with addi-
tional heat exchangers on the
stripper-fractionator side (the
low-pressure side), there will be
available duty potential in the efflu-
ent side to heat reactor feed streams
or the fractionator feed stream. In
this way, a portion of the wasted

temperature; and the stripper–

400
fractionation side with run-downs,
pumparounds, reboilers and so on. 300
The main cold streams in this
layout are the reactor input 200
streams: HVGO for the hydroc-
racker (diesel for HDS), hydrogen 100
and stripper-fractionator feeds.
In hydrocracker and HDS heat 0
integration studies performed, 0 20 40 60 80 100 120 140 160
similar principles were followed Enthalpy, Gcal/h
(except for the fact that there is no
fractionator in a HDS), therefore this Figure 6 Hydrocracker project base case curves

118 PTQ Q4 2013 www.eptq.com

tupras.indd 5 12/09/2013 20:13

 column overhead energy (together with other frac-
tionation side heat) will be recovered as furnace
duty. Once again, for the low-pressure side, weld-
ed-type plate heat exchangers are selected.
This approach can be applied either to keep the
reactor effluent temperature as it is (~190°C; after
wash water injection it is ~160°C) or maximise the
www.contitech.de/alw
benefits by decreasing (gaining from) the reactor
effluent air cooler duty as well. The choice is a
matter of the additional heat exchange area required
in the high-pressure network to shift this duty to
feed streams and the furnace duty benefits achieved
from it. However, it is also a matter of corrosion. A
lower reactor effluent air cooler temperature means
that temperatures are shifted towards cold stream
heating. Therefore, corrosion mechanisms will be
shifted towards the existing or new heat exchangers.
On the low-pressure side, diesel pumparound has
a high flow rate and temperature to be able to heat
up the fractionator charge with a plate-type heat
exchanger. In order to achieve this, reboiler duties
have to be shifted as much as possible towards the
lower-grade heat sources. Air-cooled kerosene
pumparound, diesel run-down and kerosene
run-down are suitable to take a portion of this duty.
Therefore, lower-grade heat sources are used for
lower-grade heat, freeing up higher-grade heat to be
used elsewhere – in this case, for heating the frac-
tionator charge. The temperatures are tight, so DAMPF TRIX® 6000 OIL
plate-type heat exchangers are suitable for this
purpose. highest quality for conveying
An alternative approach is to further raise the
fractionator feed temperature by introducing it to
steam according to
the high-pressure reactor effluent network. EN ISO 6134 - 2B -
Including this stream on the effluent side by means
of the optional exchanger shown in Figure 7 The new, oil resistant DAMPF TRIX® 6000 OIL is an
increases the amount of savings made per amount innovative hightech version in ContiTech's extremely
of additional investment. Furthermore, the saving is successful steam hose family. It is especially suitable
for conveying steam in the chemical and petrochemical
directly from the furnace. However, introducing the industry, in refineries, the building industry, in shipyards
fractionator feed to the high-pressure network may and for various other industrial applications under the
not be desirable because of relief load and safety most grueling conditions – in all places, where existing
concerns. steam hoses fail at an early stage due to oil contamina-
tion from outside.
In the HDS unit example without a fractionator, no
pumparound duty may be available. However, heat- q heat resistant EPDM inner layer material
ing the stripper feed more effectively with stripper q temperature range for saturated steam up to
max. +210°C, short term +220°C at 23 bar
overhead and diesel product before it enters the
(saturated steam)
high-pressure preheat train creates the opportunity to q working pressure up to 18 bar
further heat up the reactor furnace feed streams. q burst pressure: min. 180 bar, safety factor 10:1
Therefore, the principle is similar. q reinforcements: 2 steel wire braids, excellent
resistance to corrosion
Alternative options q oil resistant special cover, resistant to ozone,
weather, UV and abrasion
Introducing a preflash drum
q electrically conductive, R < 106 Ω
Similar to the crude preflash study, introducing a
q meets all requirements as per EN ISO 6134 2B
preflash drum to the fractionator feed creates a 20°C
temperature difference driving force. This stream
can be heated with heavy diesel (heavy diesel
pumparound) or reactor effluent, or both. This driv-
ing force creates an additional energy-saving ContiTech Schlauch GmbH
opportunity and decreases the amount of additional Postfach 1120
area needed. However, the main saving comes D-34481 Korbach
industrial.hoses@fluid.contitech.de
because the kero pumparound is air cooled. Preflash
vapour duty directly decreases from the air cooler if

www.eptq.com PTQ Q4 2013 119

Conti Anzeige Dampf Trix OEL GB 86x270 01-2013.indd 1 04.02.13 14:18

tupras.indd 6 12/09/2013 20:13

 To reactor
furnace
Effluent
EFF1 EFF2 Optional EFF3
HADPA
Fractionator feed
(Preflash bottom)
Figure 7 Hydrocracker project simplified network after possible modifications
vapours are introduced to the
upper trays according to the
temperature profile. Therefore, frac-
tionator furnace duty is decreased
directly. Together with the shifting
of reboiler duties to lower-grade
heat sources and using diesel
pumparound duty to heat up the
preflash bottoms (fractionator feed)
with a new heat exchanger, furnace
and air-cooled pumparound or
overhead reflux duties are
decreased substantially.
Taking into account all of the
design considerations discussed, a
simplified heat exchanger configu-
ration looks like the one shown in
Figure 7 (new positions are shown
in red).
The total furnace process duty
saved with this configuration, even
without affecting the reactor efflu-
ent cooler and without adding
additional area to the existing
exchangers, is 9 Gcal/h, which is
actually higher when furnace effi-
ciency is considered. Together with
kero run-down steam production
and considering firing efficiencies,
the total saving is nearer 13 Gcal/h.
By adding the new heat exchang-
ers shown and adding new shells
to the existing heat exchangers,
savings can rise to 18 Gcal/h,
taking into account increased
120 PTQ Q4 2013
tupras.indd 7
To fractionator
furnace
EFF4 EFF5 EFF6
To stripper HVGO feed
Debut reboiler duty shifted to
HAD rundown.
Portion of naphtha splitter
reboiler duty shifted to kero
pumparound.
Stripper feed
investment costs. Payback times of
all the different scenarios are
around, or less than, one year.
Introducing a hot separator
The stripper feed can be described
as the cold reactor effluent stream
after the air cooler and pressure
separators. Therefore, in a way, it is
being cooled with an air cooler and
heated again with reactor effluent.
From an energy point of view,
instead of cooling it to 60°C, it can
be kept at the desired temperature,
say 255°C, with a new separator
configuration including a hot
separator. In this way, the effluent
air cooler duty will be lower and
duty will be transferred to the other
cold streams, decreasing furnace
loads. However, low-pressure side
hot streams heating the stripper
charge will be freed up, and they
have to be used in steam production
in order not to waste them and gain
some energy overall. Whether this
steam is needed or not is a critical
issue when evaluating this option. If
steam is not a good alternative in
the refinery’s utility balance, hot
separator designs do not bring any
energy benefit at all when compared
to other heat recovery scenarios.
Furthermore, introducing a hot
separator means more soluble
To air cooler
EFF7
Fractionator
bottom
product
Diesel product
from deb. reb.
Fractionator
overhead
Hydrogen
hydrogen through stripper charge
and loss of hydrogen to fuel gas. It
also means loss of C3-C4 (LPG prod-
uct). Four separator designs can be
selected to lower the amount of
product lost, but cannot prevent it.
Therefore, even though steam
production is acceptable with the
low-pressure fractionation streams
and more energy is recovered over-
all, hydrogen and LPG losses,
together with major changes in the
high-pressure section of the unit
(adding two separator drums),
make this alternative much less
attractive among the other heat
recovery scenarios.
Targeting the reactor effluent
air cooler
The effluent air cooler is the biggest
source of waste heat in a hydroc-
racker. Introducing this source of
heat to the recovery options will
increase the potential overall savings
and decrease the overall investment
cost. However, the corrosive nature
of this stream and the modifications
that need to be done in the fraction-
ation section of the heat exchanger
network require a detailed analysis
and a change of approach.
Considering its positive effects on
unit shutdown periods as well, this
option may be a very good selec-
www.eptq.com
12/09/2013 20:13
 test run’s results, it could be
Key performance indicators for ConSep trays
concluded
tion,
Substations, thatwhether
in combination the revampwith owned thetargetsby effectively
key from sources
types of switchgear are that
oil would
or gas sometimes
Texas, complex
the ebullated-bed very critical
had inor
a power
reactor heatfed inte-
surge
to a
for utility
the CDU-1 Properties
main of coker
fractionator and hydroconverter liquid products a
points
the taken from the
company orother
the refinery, otherwise
options. insulated. A prove
strayvery sparkcostlycan cause and gration
that studies.
coker unit. For this study, it pipe
triggered a The
small freedom
fire in a wasto
(C-150)
tend were achieved.
to break down if not Noproperly
hydrau- involve these to high
catchpressure
Parameters on fire and drops fail.if shell
Design produce
rack at steam
the
considered that this may
refinery’s
Test run bring addi-
chemical
stream is recy-
lic constraint In
Conclusion was October
experienced in and Froth backup/CS
tubes were height,
to % be theused.obscure 68
Plate- tional benefits 60to overall fuel
maintained. Coker 2009, Then there
Hydroconverter
Tray pressure
are
drop, mbar 12.3
plant.
cled back Power to surges
the can cause fires
9.2 hydroconversion
achieving
Heat
Valero’s integration
Property the Naphtha
McKee, design
optionsplant
Texas, intake
and
LGO stud-
had of
HGOa type
reasons
Naphtha heatthat
Tube flood , % LGO exchanger
cannot
HGO be
Vacuumusage
predicted
residue is
73 consumption
and cause
reactor, meaning in
breakdown the
60 that refinery,
in there or is
different it
13Yield,
ies 000
substation wt%t/d and
should theconsidered
be26.8
malfunction, required34.1 prod-
which as
39.1 limited
and in pressure
14.0 parameter
Flow happen 37.9 27.8(to 40 bar)
so infrequently 20.4 0.17 may not be needed
that it units. In April
complete overall residue conver-
0.19 at
2011,all. Sunoco’s
SG 60/60°F 0.7363 0.8715
uct
forced quality
case-specific
API gravity unitswas achieved.
evaluations.
offline.
60.7
There 0.9736
Substation
30.9
0.7365
is • Using
13.8 is Flooding
a 0.8710
hardcolumn
Overall
60.6
flash
to
31.0
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factor, before
protect
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against. a frac-
-5.6
In even
In Philadelphia,
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Pennsylvania,
0.10
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no rule of thumb whether an option (CS tray), % a driving force 133 112
malfunctions
Sulphur, wt% have1.79 occurred 3.67 more 4.43 tionator
November
0.25 creates
2012,1.37
0.71 Valero’s 6.90 Corpus optionsconversion reported in Table with
ery had should a be
power evaluated
surge 2thatis
is the best
Conclusions
frequently
Nitrogen, for amany
than
wppm specific
316 people unitthink.
1694 or 3973
a effect 393 that
Christi, Texas,may had
1582 enable
3063 a some power8905addi-loss detailed
knocked
78%. simulation
compressors and heat
offline. inte-In
The
specific
In performance
Aromatics,
March refinery.
wt%
2010, 27.1 of Chevron’s
Unit Shell 58.0 ConSep
layout, inte-66.0 tional
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Table 3
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products from
Nickel, wppm - - 8.2 - - 3.0 262.9
trays in with
gration
Segundo, the other HGO refinery
California, pumparound
downstream shut shift from
contacting steamthe production
primary to cold
power should
California, be considered
facility
the VTB conversion step, hadin a acase-spe-
power
along
Vanadium, wppm - - 27.4 - - 6.2 458.3
section
units,
down
CCR, wt% ofoverall
due thetoCDU-1 atmain
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a substation.utility such- cases.
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transformer. -In this
Transformers
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(furnace project,
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that can cific
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3 De Villiers W
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J L, Wilkinson P M,
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capacity However,
be of only three
main of
theshould bethese
point trays to
in making
protected in and
Summers
ting
lates, taking
down D R,general
require
Further guidelines
several
furtherPTQ
advances in into
refinery
hydrotreating
light
units.
enhancement
(such as the without
hydrocracker any drawback
effluent the most capacity-constrained hydrocarbon fractionation, Q3 2004.
had a aallow preflash drum a working
feasible option is account. Most of the time, heat inte-
a) Yield values are based on total liquid product.
Kapolei, Hawaii, complex only those on them Normal
to reduce operations
sulphur, were
nitrogen restored and
compared
air
power cooleroutageto the
example)due pre-revamp
toalla affect
failurecondi-
the section
at whether
to get to ofthere
the
them. column
is wasted, made
In February it possi-
air-cooled
2010, gration
the next
aromatic projects
day.
Kaushik Majumder contents will bring
for producing
is Distillation large
Team Lead of
tions.3ofDuring
selection
one
Table process:
the the test
local run, the
electric utility’s ble to retrofit
trays pumparound
Western the existing
duty
Refining’s column
near Yorktown,
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Shell Projects
suitable &ofTechnology
blending savings involving
in Bangalore,
components India.
for
were operating
• Drawing
substations. at 10-15%
the overall lower than
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is flash
Virginia, vapour.
had theancapexGiving option
unidentified more
preflashunit millions
Multiple
He holds a of
unit dollars
shutdowns
bachelor’s
SCO. The properties of the hydro- per
degree year,
from with
Jadavpur
the
very design
In important,
May 2010, capacity BP’s even
especially Texas atCity,
in CDU/ attractive
the vapour
shutdown over
due athe
to higher traysother
temporarymaydebottle-
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power be usually
Since less
most
University,
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and aone-to–one-and-a-
India,refinery units
master’s
and final andare
SCO inte-
doctorate
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Texas, intake Integration
refinery ofhad13Properties
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a power will ofdue
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blip options.
because
products
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by SCO of liquid
a goose flying entrain-
into a half-year
from Indian
grated andpayback
Institute of periods.
sometimes
provided in Table 4. The SCO has
Technology, Delhi. the
share
heavier
of the time
caused crude
bybring feed
switchgear and lower
additional feed ment
benefits
failure. nearbyconcerns;
power line. therefore,
Unless specialpower same Email: Kaushik.Majumder@shell.com
no power and
residue supply, verypower failures
low sulphur
temperature.
in energy savings However, and the
area built-in
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* Shell ConSep, should
Shell be
CS and Shell given
HiFi to
areitShell Giuseppe Mosca is the Global Refinery
Switchgear failures also occur quite lines are put underground, is could
and lead to
nitrogen the shutdown of these
capacity
Coker-based scheme Hydroconverter-based scheme Alişan Doğan
Technology is a Process
Manager ofcontents.
and Equipment
Sulzer Chemtech.The
Property margin
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TheNaphtha
relay thethat stable
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LGO failed oper-
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API gravity 60.4 33.1 23.5 31.5 60.4 33.6 23.7 31.8 Technical
engineering Services
from the Management
University with
“La Turkish
Sapienza”
the option
ble capacityinfeasible,
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Sulphur, wt% 0.018 0.112 0.16 References
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tion
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Nitrogen,
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Switchgears
204 740 preflash
Power tower
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fluctuations damages.
scheme.
336 self specialising Table
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Email: Giuseppe.Mosca@sulzer.com summarises and heat the
1 482
Refinery 21
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The drum
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wt% aexample)
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Kent Mahon is of 2009,
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They
Table 4 generation
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Technical outage.
University,
Commissioning
coker products requires higher The
Ankara,
Process hydrocracker
Turkey.
Engineer during the
trays
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maintained are heat limited.
to efficiently
avoid ConSep
failures. andAtrayscost
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ExxonMobil’s
propylene yield using ultrasteam
systembalance
Baytown,
fractionation is Email:
and Alisan.Dogan@tupras.com.tr
Point isomerisation
Forward Project. unit were shut to
provide an attractive solution for trays, ERTC 2006. Email: Kent.Mahon@refiningnz.com

www.eptq.com PTQ Q1 2013 77

www.eptq.com
www.eptq.com PTQ
PTQ Q4 2013 121
23
www.eptq.com PTQ Q3
Q2 2013
2013 41

sulzer.indd 5 11/12/12 18:05:58

tupras.indd
hpc.indd 3 84 12/09/2013
07/06/2013 20:13
canmet.indd 08/03/2013 17:53
13:04
 advanced burner technology

UOP Callidus CUBL process burners provide value to the refining and
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leaning and extremely low NOx levels in reformer applications for hydrogen, ammonia and methanol applications.
• The CUBLX utilizes pre-mix technology to provide outstanding performance in furnaces with low draft
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• The CUBL-HC is designed for use in high capacity, forced draft applications in which there is a need for large
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©2013 Honeywell International Inc. All rights reserved.

uop2.indd 1 11/09/2013 14:17

 Applying pinch technology to
energy recovery
A pinch technology-based study of heating and cooling of material streams in a
large-scale olefins plant identifies major opportunities for energy savings

FARBOD RIKHTEGAR Iranian Fuel Conservation Company

SEPEHR SADIGHI Research Institute of Petroleum Industry

E
nergy saving is one of the most Pinch technology
important issues associated with Composite curve
cost, regulations and environ- For analysing a heat exchanger
Separator
mental performance in the network, sources of hot and cold
petroleum and petrochemical indus- Utilities streams (source and sink) should be
tries. Most of the available methods Reactor first identified using material and
for energy targeting, retrofitting and Heat energy balances. For instance, the
design of heat exchanger networks exchanger current typical flow sheet of a
network
are based on the pinch method. chemical process is shown in Figure
The term “pinch technology” was 2. The supply and target tempera-
introduced by Bodo Linnhoff in ture and enthalpy changes of four
1991 to represent a thermodynami- Figure 1 Onion model process streams are also given in
cally based methodology that Table 1.
guarantees minimum energy levels demonstrates how the technology’s Consider steam at 200°C and
in the design of heat exchanger design methodology can be used cooling water at 20° for heating and
networks (HEN); therefore, this for improving the heat recovery cooling utilities, respectively. It is
approach has been used to save networks of an olefin plant, as a preferable to recover as much heat
energy in processes and across case study. as possible between process
complete sites. Wherever heating
and cooling of material streams Stream data
take place, there is a potential
opportunity to save energy. The
design philosophy starts at the Stream no Stream type Supply temp, °C Target temp, °C ∆H, kW CP, kW°C
1 Hot 180 80 2000 20
heart of the onion model, the reac- 2 Hot 130 40 3600 40
tor, and moves out to the 3 Cold 60 100 3200 80
separation system (see Figure 1). 4 Cold 30 120 3240 36
Heating and cooling duties for the
next layer of the onion are the heat Table 1
recovery systems. Consequently,
targets can be set for the HEN to
evaluate the performance of the 60ºC
process design, and it can enable Condenser
both the energy and capital costs of
100ºC
the HEN to be assessed. It is obvi- 72ºC
∆H 3200
ous that, without a screening heater
approach, selection between many
design options cannot be easily Reboiler
afforded in terms of the time and 120ºC ∆H 3600
effort required. 30ºC cooler
130ºC
In this article, the discussion ∆H 3240
40ºC
covers the basic principles and heater
180ºC
capabilities of pinch technology, 80ºC
and how the technology can be Reactor Reactor
1 2 ∆H 2000
utilised to determine scope for cooler
reducing energy consumption and
costs. In particular, the article Figure 2 Flow sheet of a case study

www.eptq.com PTQ Q4 2013 123

iranian.indd 1 12/09/2013 20:18

 250
The key in capital
Hot composite curve
Cold composite curve cost targeting is the
Temperature, ºC
180 surface area required
150
for exchangers that
100 are included in the
50
∆Tmin = 10ºC network
the grand composite curve (GCC) is
H an appropriate tool to show the
interface between the process and
Figure 3 Current case composite curve the utility system (see Figure 6).
In this method, our aim is to use
the specified utility at an appropri-
ate level. Thus, for the hot utility,
Hot composite curve
250 QHmin = 960 we should use the lowest tempera-
Cold composite curve
ture and generate the highest
200 temperature. In contrast, for the
cold utility, we should use the
Temperature, ºC

highest temperature and generate

150
the lowest temperature.

100 Heat exchanger area target

∆Tmin = 10ºC It is possible to predict the required
50 surface area for the whole problem
by using vertical enthalpy intervals.
QCmin = 120
The area calculated with this model
0 is minimised when the heat transfer
H coefficients of all streams are equal.
For each enthalpy interval, we can
Figure 4 Composite curve of targeting case predict the required area from the
composite curves. The duty and
streams. The scope for heat recov- and capital cost. In Figure 5, the heat transfer coefficients of the
ery can be determined by plotting trade-off between energy, capital streams are obtained from the
all streams on a T-H diagram (see cost and economic amount of stream data, and the log-mean
Figure 3). This figure shows energy recovery is illustrated; thus, temperature difference (DTLM) is
DTmin=10°C for the proposed flow the trade-off can be carried out derived from the composite curves
sheet; therefore, the hot and cold using energy and capital cost (see Figure 7).
utility recoveries are 960 and 120 targets.
units, respectively (see Figure 4). It Capital cost target
can be concluded that DTmin deter- Utility selection The capital cost of a heat exchanger
mines the relative location of the After recovering the heat using network is mainly dependent on
hot and cold streams, so it is an process-process heat exchangers, the surface area of each heat
important variable for setting the the remaining required heat for the exchanger, the number of shells,
amount of heat recovery. plant should be obtained by the the material of construction, the
utility system. In pinch analysis, heat exchanger type and the pres-
Heat recovery pinch sure rating. However, the key in
To achieve the lowest DTmin, the capital cost targeting is the surface
Industrial recommended DTmin
type of heat exchanger and fluid area required for exchangers that
regime are important. In Table 2, are included in the network. For
the minimum approach tempera- Industrial sector Experience the total cost targeting procedure,
DTmin value
ture for several industries is shown. Oil refineries 20-40°C
lots of appropriate software has
As a rule of thumb, rating with a Petrochemicals 10-20°C been introduced, but SuperTarget
DTmin less than 10°C should be Chemical plants 10-20°C from KBC is particularly regarded
avoided. The correct setting of Low-temperature processes 3-5°C for handling energy targeting
composite curves is defined by an projects. SuperTarget is a suite of
economic trade-off between energy Table 2 programs to optimise the energy

124 PTQ Q4 2013 www.eptq.com

iranian.indd 2 12/09/2013 20:19

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 of ethylene product. Process data
A was taken from design process flow
diagrams and from discussions
with operating engineers. Due to
the significant differences in
temperatures and economics of
operation, the olefin unit was sepa-
Cost

Total
rated into cold and the hot sections.
Energy A DTmin of 10°C was chosen to
Capital identify future potential savings.
The stream data and composite
curves of the process obtained
using SuperTarget software are
shown in Table 3 and Figure 8,
∆Tmin respectively.
Additionally, the energy targets
B
Hot composite curve QHmin and the pinch temperatures
Cold composite curve obtained by pinch analysis are
shown in Table 4. This table
confirms that the total potential
Temperature

savings for the plant studied

amount to 194.8 GJ/h. The majority
of the savings were achieved
through reducing steam consump-
∆Tmin tion and also by increasing
high-pressure steam generation.
The GCC related to the utility
QCmin
system is shown in Figure 9.
H According to this figure, it is
recommended that medium-
Figure 5 Balanced composite curve pressure steam should be used to
increase high-pressure steam gener-
consumption and utilities of a plant heat exchanger network’s design. ation at a higher level to be more
by applying pinch analysis. Additionally, the software can be beneficial for the plant.
Furthermore, it enables the user to integrated with other process simu- Moreover, to obtain a cycle effi-
determine the absolute maximum lators, such as PRO II and Hysys. ciency of 60.7% for the utility
potential for heat recovery, estimate system, there are several potential
utility and capital costs for a given Case study routes that are dependent on site
heat recovery, determine the mini- As a case study, an olefin plant economics and impacts on the
mum approach temperature located in the south of Iran at steam and power system. The aim
(DTmin), examine capital/energy Bandar Imam was considered. The is to minimise consumption in the
trade-off, and set the basis for the capacity of the plant is 411 000 t/y condensing turbine and generate

QHmin
Temperature interval
Temperature

α α

QCmin

H H H
Composite curves Shifted composite curves Grand composite
curve

Figure 6 GCC of a case study

126 PTQ Q4 2013 www.eptq.com

iranian.indd 3 12/09/2013 20:19

 Energy targets and gaps

Target, Now, To save,

Heating GJ/h GJ/h GJ/h 7
H: MP steam 68.2 133.9 65.7

Temperature
6
H: PS steam 19.1 50.8 31.7
Total hot 87.3 184.7 97.4
5
Target, Now, To save, 4
Cooling GJ/h GJ/h GJ/h
C: PS steam (gen) 0 62.1 62.1 3
Network area:
C: Cooling water 114.2 321 .1 206.9 2
7

Σ
C: HP Steam (gen) 148.7 135.1 -13.6 1 qstream
C: Seawater 151.5 0 -151.5
1 Amin = Σ
∆TLM h
C: C3{20C} 6.46 0 -6.46 interval
Total cold 420.9 518.3 97.4 H
Total energy 508.2 703.0 194.8

Table 4 Figure 7 Area integrity of a heat exchanger network

power using a combination of a gas

900
turbine (associated with the waste Hot composite
heat boiler to generate high- 800
Cold composite
pressure steam) and a back-pres- 700
Temperature, ºC

sure turbine. Table 5 shows all 600

projects that can be implemented 500
Naphtha furnace
product
according to the study of the olefin
400
site. Savings and costs are calcu- Ethane furnace
product
lated according to financial criteria. 300
It should be noted that only rele- 200 Quench oil Dilution steam

vant, feasible and achievable 100 Quench water heat recovery

Column reboilers
projects are included in this report. 0
Liquid feed

This means that other projects with 0 100 200 300 400 500 600 700
payback times longer than five Enthalpy, GJ/h
years are ignored. These projects
typically demand huge invest- Figure 8 Composite curves for ethylene hot section
ments, and they also need gas
turbines with heat recovery steam
generators or a high-pressure 900
Process GCC
(100+barg) steam level. 800
Utility GCC
Interval temperature, ºC

700 Naphtha furnace

product
Conclusion 600 Ethane furnace
The best design for an efficient heat 500
product

exchanger network is the result of a

400
trade-off between fixed and operat-
ing costs. Pinch technology can 300 U: HP steam (gen)
U: MP steam
help to perform the best process 200 U: PS steam Pygas rec. cooler
Dilution steam
modifications as long as the trade- 100 Quench water heat recovery Liquid feed
off in costs is followed accurately. 0
U: cooling water

In this article, first the principles of 0 100 200 300 400

pinch technology, including
composite curve, heat recovery
pinch, utility selection, pinch prin-
ciples, capital cost target and
retrofit of heat exchanger networks,
were introduced. Then, an olefin
plant located in the south of Iran
(BIPC) with a nominal capacity of
411 000 metric t/y of ethylene
product was selected as a case
study. The plant was separated into
cold and hot sections to perform a
pinch analysis. Moreover, a crack-
Enthalpy, GJ/h
Figure 9 GCC for ethylene hot section
ing furnace and super-heater were increasing high-pressure steam
excluded from the analysis. A DTmin generation.
value of 10°C was chosen to
express the future potential savings.
It was confirmed that the total
potential savings are 194.8 GJ/h, Further reading
and that the majority of these 1 Polly G T, Heat exchanger design and process
savings could be achieved by integration, Chem. Eng, 1993.
reducing steam consumption and 2 Catier M, Pinch analysis revisited: new

www.eptq.com PTQ Q4 2013 127

iranian.indd 4 12/09/2013 20:19

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 rules for utility targeting, Applied Thermal
Engineering, 27, 2007, 1653–1656.
3 Linnhoff B, Flower J R, Synthesis of heat
exchanger network, AICHE, 1978.
4 Yoon S G, Lee J, Park S, Heat integration
analysis for an industrial ethylbenzene
plant using pinch analysis, Applied Thermal
Engineering, 27, 2007, 886–893.
5 Ahmad S, Smith R, Targets and design for
minimum number of shells in heat exchanger
network, Trans ICHeme, 1989.
6 Linnhoff B, Ahmad S, Cost optimum heat
exchanger networks, Chem. Eng, 1990.
7 Smith R, Chemical Process Design and
Integration, 2005, McGraw Hill.
8 Matijaseviae L, Otmaeiae H, Energy recovery
by pinch technology, Applied Thermal
Engineering, 22(4), 2002, 477-484.
Farbod Rikhtegar is a Senior Process/Energy
Engineer with the Iranian Fuel Conservation
Company’s (IFCO) Industry Sector. He holds a
MSc in chemical engineering.
Email: f.rikhtegar@ifco.ir
Sapehr Sadighi is Project Manager, Catalysis
and Nanotechnology Division in the Catalytic
Reaction Engineering Department of the
Research Institute of Petroleum Industry (RIPI).
He holds a PhD in chemical engineering.
Email: sadighis @ripi.ir
Ethylene plant hot section stream data
Splits and mixers Matches (showing specified temperatures)
Stream HX dH, TS, TT, Utility
UpStrm DownStrm Value Name GJ/h C C
Liquid feed EA119 4.9 37 60
EA120 10.4 60 105
Ethane feed EA121 3.2 30 60
Ethane furnace product EA107-11 60.3 832 338 HP steam (qen)
EA111 24.5 338 210
Naphtha furnace product EA101-10 74.8 841 447 HP stearn (gen)
Quench oil S1 1 166 166
S1 M1 0.0937 EA128 7.4 166 155
S1 M1 0.9063 EA124 62.1 166 155 PS steam (qenl
M1 1 155 155
Upper quench oil EA120 10.4 155 108
Process water EA126 3.2 119 127.1
EA128 7.4 127.1 145
Dilution steam 1 EA125 122.2 145 170.5 MP steam
EA129 2 170.5 182.6 MP steam
Dilution stream 2 EA111 24.5 145 168.5
Oil steam blowdown EA126 3.2 170.5 130.1
EA127 6.2 130.1 43 Coolinq water
Fuel oil rundown EA122 0.4 142.6 65
Quench water cooling 3 EA131 45.3 55 43 Cooling water
Quench water reheating EA122 0.4 55.28 65
Quench water heat recovery TEE-100 1 80.39 80.39
TEE-100 MIX-100 0.3842 80.39 80.39
TEE-100 MIX-100 0.0438 EA119 4.9 80.39 65.41
TEE-100 MIX-101-2 0.012 EA211 1.8 80.39 60.51
TEE-100 MIX-101-2 0.0172 EA206 2.5 80.39 60.42
TEE-100 MIX-100 0.0647 EA428 7.2 80.39 65.41
TEE-100 MIX-101-2 0.0215 EA121 3.2 80.39 60.41
TEE-100 MIX-100 0.4454 EA424 49.4 80.39 65.42
TEE-100 MIX-100 0.0111 EA426 1.2 80.39 65.39
Table 3

Bandar Imam olefins plant energy savings

Energy savings
Fuel Steam saving Elect power
ProjectID Description Type saving, GJ/h HP, t/h MP, t/h LP, t/h saving, MW
01-01 Cracking furnace improvement Furnace 86.4
01-02 Increase steam pressure generation in gas cracker TLEs Furnace 0.6
01-03 Reduce steam pressure generation in liquid cracker TLEs Furnace -0.9 1.2
01-08 Quench water interchange - deethaniser feed preheat Heat integration 3.7
01-09 Quench water tower top cooling Yield opportunity 0.2
01-10 Recover blowdown to dilution steam vessel Heat integration 0 .1
01-11 Condensate stripper temperature control Other 0.1
01-12 Optimise dryer regen Furnace 0.261
01-13 Hydrogen product purity Yield opportunity
01-14 Preheat demethaniser lower feed Heat integration 3.5
01-18 Acetylene heat integration Heat integration 4
01-19 C2= fractionator analysis Other 1.4
01-20 Recover cold from LLP ethylene Utilities & power 0.04
01-22 Reduce operation of depentaniser Yield opportunity 1 .8
01-24 Reboilers using propylene refrigeration Other 1
01-25 Install O2 analysers Furnace 12.5
01-26 Install stack temperature measurement Furnace 16.4
01-27 Steam loss reduction program Vent reduction 7
01-29 Reinstatement of insulation Other 1.65
01-30 Increase cooling effectiveness Utilities & power 0.7
01-31 Compressor sophisticated anti-surge controller Utilities & power 5.8
01-32 Program of seawater surface condensers backflushing Utilities & power 0.7
01-33 Implementation of furnace operation improvement Furnace 13.2
01-35 Furnace severity and decoking Yield Opportunity
01-37 Switch small condensing turbine to motor Utilities & power 19 -1.7
01-41 Replace propylene turbine with electric motor Utilities & power 103 -18.1
01-42 Commission secondary TLEs Furnace 9
01-43 Commission turbo expander Utilities & power 0.3
01-44 Increase HP steam temperature exit superheater Furnace -2.0 0.8
01-47 Use oil steam BD to reboil cond stripper Heat integration 1
01-48 Use C3= 20°C recup to reboil DeMeth Heat integration 4.9
01-49 Recover L P-HP transfer cold Heat integration 5.5
ME-10 Energy management organisation Other 17.9
ME-11 Energy management tools Other 17.9

Table 4

www.eptq.com PTQ Q4 2013 129

iranian.indd 5 12/09/2013 20:19


Process Insight:
The design and optimization of separation processes is
carried out using process simulators, which utilize various calcula-
tion approaches. Two techniques that are widely used for modeling
distillation are the ideal stage model and the mass transfer model.
IDEAL STAGE MODELS
The ideal stage model requires a minimum amount of
data—only equilibrium relationships and enthalpy data for the heat
balance. The assumptions of the ideal stage approach are: 1) that
the vapor and liquid are both perfectly mixed so that the vapor and
liquid leaving a stage are at the same composition as the material
on the stage and 2) that thermodynamic equilibrium is obtained on
each stage. The equilibrium assumption also means liquid and va-
por leaving a stage are at the same temperature. Ideal stage mod-
els can also account for non-ideal column performance through the
use of reaction kinetics as is done for amine sweetening columns.
Obviously, the main disadvantage of the ideal stage
approach is just that—the use of ideal stages to model real trays
or packing depths. However, for most processes encountered in
gas processing and other industries, the overall efficiencies are
well established for proper operating conditions of the column. For
systems that are unavailable, similar systems often exist to allow for
efficiency estimation. If not, the mass transfer approach is available
as an option.
MASS TRANSFER MODELS
For the end user, the notable feature made available via
the mass transfer approach is the ability to model a column with the
actual number of trays in the unit or the actual depth of packing.
However, there are still several assumptions that are made in this
approach that can have a significant impact on results. Two that are
worth mentioning include the mixing model for trayed columns and
the discretization of the packing depth for packed towers.
Application of the mass transfer model to random or
structured packing requires the column height to be discretized into
vertical segments or stages. For trayed columns, various mixing
models can be used for the liquid and vapor phases. The most
basic assumption is that of complete mixing in both the liquid and
vapor phases. However, the concentration gradients that develop
on a tray can significantly impact the predictions made by this model
since this gradient is the driving force for mass transfer. As the
column diameter becomes larger, the perfectly mixed flow model is
less applicable.
For modeling both liquid phase chemical reaction and
mass transfer, the use of the enhancement factor technique may be
considered. The enhancement factor describes the increased rate
of absorption due to the effect of a chemical reaction. The material
ProMax® process simulation software by Bryan Research & Engineering, Inc.
Engineering Solutions for the Oil, Gas, Refining & Chemical Industries
· ·
sales@bre.com www.bre.com 979 776-5220 US 800 776-5220
bre.indd 1
Ideal Stage or Mass Transfer...
Which Model Should Be Used?
balance requires kinetic rate expressions for all chemical reac-
tions occurring in the system. As with equations for a non-reacting
system, an appropriate model for interface behavior must be used.
Mass transfer models require data necessary to calculate
interphase mass and heat transfer coefficients and interfacial area
based on correlations of the following transport and thermal proper-
ties: diffusivities, viscosities, densities, heat capacities, thermal
conductivities, etc. Furthermore, mass transfer models require
detailed information on the column internals. For trays, this includes
information such as weir heights and fraction active area. For pack-
ing, this includes surface area per unit volume and void fraction.
If the simulator allows the user to select from various
alternatives for these parameters, knowing the correct selection
may be problematic. Further, the prediction of multicomponent
mass transfer coefficients is of questionable accuracy. These facts
prompt the recommendation that columns modeled with the mass
transfer approach be checked against an ideal stage model with
an expected efficiency until sufficient experience with the particular
application is achieved.
CONCLUSIONS
When performed properly, both the ideal stage and mass
transfer approach as implemented in ProMax 4.0 can calculate ac-
curate results for a variety of separation processes with and without
reactions. The ideal stage approach can be used initially to deter-
mine appropriate equipment sizes and operating conditions. More
detailed studies can be performed using the ideal stage approach,
the mass transfer approach, or both. Although significant operat-
ing experience provides reasonable efficiency estimates for most
processes, the empiricism in scaling up from ideal to real stages or
ideal stages to real bed lengths can be a disadvantage when ac-
curate overall efficiencies or HETP’s are unavailable.
The mass transfer approach requires more equipment
design details and does not make use of overall efficiencies or
HETP’s. More detailed composition and temperature profiles are
produced by this method at the expense of longer calculation time.
The mass transfer approach may appear more predictive in nature,
but is not necessarily more accurate. It relies on more parameters
that must be estimated, as both require thermodynamic data to
model equilibrium—for the tray composition in the ideal stage
approach and for the interface composition in the mass transfer
approach. Many of these mass transfer parameters are of limited
accuracy but also may be of limited sensitivity in some systems.
Both techniques are useful tools in process simulation.
For more information about this study, see the full article at
www.bre.com/support/technical-articles.aspx.
·
12/09/2013 11:21
 Multistage reaction catalyst with
advanced metals tolerance
The metal trapping capabilities of a catalyst gave a refiner greater flexibility to
upgrade heavy residue feed with increased metals content in its RFCC unit
YVES-ALAIN JOLLIEN Tamoil
JEREMY MAYOL, VASILEIOS KOMVOKIS and CARL KEELEY BASF
T
amoil’s Collombey refinery in
Switzerland operates an R2R
design residue fluidised-bed
catalytic cracking (RFCC) unit. (The
R2R process is offered through the
FCC alliance between Axens, IFP
Energies Nouvelles and Technip
Stone & Webster Process
Technology.) It has a two-stage
regenerator. The feedstock is 100%
atmospheric residue derived from
crudes such as Es Sider, El Sharara,
Saharan Blend and Brega with a
moderate-to-high metals content
and a high Conradson carbon
residue (CCR) content (typically
4-6 wt%).
Increased flexibility to upgrade
heavy residue feed with even
higher metals is a key enabler for
further improving the profitability
of the Collombey refinery.
Base catalyst in use
Collombey changed to BASF’s
Aegis catalyst during the first half
of 2012. This catalyst combines the
benefit of BASF’s DMS and Prox-
SMZ technology platforms. It is
designed for resid feed applications
where moderate-to-high metals
tolerance is needed, and it offers
the flexibility to improve both
diesel and gasoline yields.
Compared to the best-proposed
solution of a competitor, Aegis
delivered improved LPG/gasoline
selectivity at a low equilibrium
catalyst (e-cat) rare earth level,
similar gasoline and coke yields,
and better bottoms upgrading, all
leading to a profitability increase of
$0.40/bbl of fresh feed.1
To satisfy changing feed quality
and product slate demand, and to
continuously maximise the unit’s
www.eptq.com
basf2.indd 1
profitability, the Aegis catalyst was
fine-tuned several times during the
first year of operation.
Unit operating data are routinely
reviewed using BASF’s Technical
Support Service (TSS), and this
identified that catalyst performance
could be further improved through
even better feed metals passivation.
This triggered a review of catalyst
technology options.
Using BASF’s Catalyst Change
Management Process, Fortress cata-
lyst, based on the company’s
Distributed Matrix Structures
Contaminant metals
vanadium and nickel
increase catalyst
deactivation and
hydrogen yield
(DMS) and Multi-stage Reaction
Catalyst (MSRC) technologies, was
selected as the best option.2
The changeover to the custom-
ised Fortress catalyst proceeded
smoothly, and the new catalyst
delivered excellent performance.
Using typical feed and product
values, the profitability has been
increased by $0.30/bbl of fresh feed
compared to the Aegis catalyst.
Thus, this past year, the refinery
has improved profitability by
approximately $0.70/bbl (Aegis
and Fortress).
This article shows how advanced
FCC catalysts and value-added
technical service are supporting
Collombey refinery. This is made
possible by Collombey’s good
approach to data sharing and
collaboration to form the best team.
Impact of feed metals on
FCC operation
The contaminant metals in residue
feed that need to be controlled by
the FCC unit are mainly vanadium
(V) and nickel (Ni), with iron (Fe)
and calcium (Ca) also high from
some crudes. Sodium (Na) is typi-
cally reduced to low levels by crude
desalting. The potential detrimental
effects of these metals on FCC
performance are summarised below:
• Ni: dehydrogenation activity
leading to increased H2 and coke
• V: catalyst deactivation, with
some dehydrogenation activity
• Fe and Ca: surface pore plugging
and nodules formation at higher
levels, leading to conversion loss,
higher dry gas yield and possibly
catalyst circulation problems
• Na: involved in catalyst deactiva-
tion (more information below).
This article focuses on mitigating
the deactivation/dehydrogenation
effects of Ni and V through the
application of the appropriate cata-
lyst technology to passivate these
metals.
Improving FCC catalyst vanadium
tolerance
As previously indicated, V deacti-
vates the catalyst, and increased
feed V will require higher catalyst
additions to maintain the optimum
target e-cat activity. The deactiva-
tion steps are:6
• V is deposited onto the catalyst
and is oxidised in the FCC
regenerator
• The oxidised form undergoes
further reactions to form several
PTQ Q4 2013 131
16/09/2013 09:32
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 highly mobile types of vanadic acids
• These vanadic acids remove Na+
from the zeolite exchange sites
• The sodium vanadate hydrolyses
to sodium hydroxide (Na+OH-)
• The hydroxyl group (OH-) then
attacks the silica-oxygen zeolite
framework, leading to zeolite
collapse, destruction and catalyst
deactivation.
There is residual Na+ on the fresh
catalyst from the manufacturing
process. In BASF FCC catalysts, the
amount of residual Na+ on zeolite
is reduced to ultra-low levels by a
unique combination of calcination
and ion exchange steps, which
improves resistance to Na-V zeolite
deactivation.
Impact of H2 and coke on FCC
operation
Additional production of H2 and
coke from processing high metals
content and high CCR feeds has a
significant impact on FCC unit
operation, as most units operate to
gas and coke handling limits.
High volumetric flow from the
low molecular weight H2 may lead
to wet gas compressor and gas
concentration unit capacity limits.
In addition, at many refineries, H2
Zeolite crystallites Macropore
SEM = Scanning electron microscopy
TEM = Transmission electron microscopy
SEM
TEM
Matrix crystallites
Figure 1 DMS selective pre-cracking by exposed outer surface of zeolite
in the absorber off-gas from the limits or mechanical design temper-
FCC’s gas concentration unit is atures limits. There are four types
routed to the refinery fuel gas of contribution to FCC coke:
system, where it has a low contaminant metals, feed additive,
economic value — ample reasons to cat-to-oil (strippable) and catalytic.
focus on minimising the formation This article focuses on controlling
of H2 in the FCC unit. contaminant metals and catalytic
Coke is any carbonaceous, high coke. Contaminant metals coke
molecular weight, non-volatile resi- results from reactions due to feed
due formed from cracking. The metals acting as dehydrogenation
maximum tolerable coke yield/ catalysts; for example, Ni and V,
production may be constrained by which remove H2 from hydrocar-
regenerator operating limits; for bon molecules, thereby increasing
instance, due to air blower capacity the tendency to form coke. Catalytic

Electron micro-probing Scanning electron microscopy

0.6
V
0.5 Ni
Concentration, wt%

0.4

0.3

0.2
Nickel
0.1

0
–50 –25 0 25 50
Distance from centre, microns

Two-stage Fortress catalyst

Alumina

Flex-Tec Fortress catalyst

Figure 2 Development story for Multi-stage Reaction Catalyst and Fortress catalyst

www.eptq.com PTQ Q4 2013 133

basf2.indd 2 16/09/2013 09:32

 coke is formed by thermal and oil), leading to an increased yield of
catalytic reactions. Operating valuable products.
The formation of coke on the data It is generally accepted that the
catalyst results in catalyst deactiva- dehydrogenation activity of metals
tion due to the blocking of active can be expressed in terms of equiv-
Performance Progress
acid sites. Thus, the coke must be evaluation check alent nickel as Ni + V/4 + Fe/10 +
burnt off the catalyst in the regen- 5Cu. Typically, residue feeds
erator to restore its activity. The contain large amounts of Ni and V,
coke burning requires oxygen from Operation Process and sometimes Fe, while copper
the air supplied from the air optimisation analysis (Cu) levels are usually very low.
blower, and the reaction generates This relationship shows that it is
a significant heat release. Figure 3 Information flow using BASF’s TSS especially important to mitigate the
Heat generated from burning coke dehydrogenation effect of feed
drives up the regenerator tempera- zeolite outer surface, rather than on contaminant Ni. This is done within
ture. This can contribute to higher the active amorphous matrix mate- FCC catalysts by incorporating an
catalyst deactivation and fresh cata- rial. This difference provides the active speciality alumina into the
lyst consumption, reduced potential for improved selectivities matrix to trap the Ni.
equipment operating life, as well as with the reduced coke formation Equilibrium FCC catalysts have
lower conversion due to reduced characteristic of zeolite cracking. been examined under electron
cat-to-oil. Thus, it is always very microscopy. From this work, it has
important to control the production The formation of been generally observed that V is
of coke, and this is particularly chal- distributed throughout the particle,
lenging when processing residue coke on the catalyst and Ni mainly deposits and accu-
feed. mulates on the outer 5-15 micron
The risk of excessive H2 and coke results in catalyst layer of the e-cat4,5 when processing
production associated with process- resid (see Figures 2a and 2b).
ing residue feed can be mitigated deactivation due to Conventional manufacturing
by the use of advanced FCC cata- techniques, practised by all FCC
lyst technologies.
the blocking of catalyst suppliers, result in the
active acid sites active speciality alumina being
Advanced FCC catalyst technologies more or less evenly dispersed
To improve coke selectivity, BASF throughout the particle. This leads
developed the unique DMS tech- The secondary diffusion pathway to a large proportion of the interior
nology platform.3 In DMS, the of the cracked products to the inter- alumina being unavailable to react
matrix is designed to provide nal crystalline zeolite surface is also with the surface-deposited Ni; this
enhanced diffusion of the feed minimised, resulting in less interior alumina is essentially
molecules to pre-cracking sites over-cracking (undesirable conver- wasted. By using BASF’s MSRC
located on the external, exposed sion of gasoline to LPG, dry gas technology (see Figures 2c and 2d),
surface of highly dispersed zeolite and coke). The net result is higher the spatial distribution of the speci-
crystals (see Figure 1). bottoms upgrading, with lower ality alumina within the particle is
The feed initially cracks on the delta coke (wt% coke yield/cat-to- optimised to maximise its efficiency
in Ni trapping and this leads to
improved catalyst performance.2
Process This technology has been incorpo-
Appraise Select Define Implement Improve rated into BASF’s Fortress catalyst.
Fortress catalyst is a two-stage
Value addition catalyst based on the MSRC tech-
Data review Catalyst Risk Trial All aspects nology. The catalyst outer-stage is
Cold eyes Additives minimisation procedures of FCC based on the DMS technology3 (see
review plan Monitoring operation
Services Figure 1), but is enriched with
Process Trial etc
Logistics procedures speciality alumina to trap Ni where
Modelling
(statistical etc it enters and deposits on the cata-
and kinetic) lyst surface. The catalyst inner-stage
also has the DMS structure (see
Results Figure 1) to allow enhanced diffu-
Forming the best team Tailored solution Deliver culture change sion of heavy molecules and
Challenges the Addresses all needs Shifts focus to selective pre-cracking on the
status quo! continuous profit exposed outer zeolite surface,
improvement
maximising conversion. Using the
MSRC technology, these stages are
Figure 4 BASF’s Catalyst Change Management Process chemically bound together by

134 PTQ Q4 2013 www.eptq.com

basf2.indd 3 16/09/2013 09:36

 zeolite and the catalyst particle is
manufactured in such a way that
80 Aegis–TC3 to –TC6
all physical properties, including
78 Fortress–TC7
attrition resistance, are similar to
Fortress–TC8
other DMS based products (for 76

Conversion, wt%
instance, Flex-Tec catalyst, which is 74
used for targeting conversion maxi- 72
misation. It cracks severe resid
70
feeds while maintaining high activ-
68
ity with low coke and gas
formation). In addition, the 66
improved spatial distribution of the 64
Fortress Ni-trapping alumina offers 62
better performance potential. 60
The features described above that 1.0 1.5 2.0 2.5 3.0 3.5
improve Ni and V tolerance have Catalyst consumption, kg/MT feed
been incorporated into the Fortress
catalyst tested in the Collombey
refinery RFCC unit. The excellent Figure 5 TSS corrected conversion (221°C minus) vs catalyst consumption
results achieved by this catalyst and
technology are described below. conversion increased by a remarka- iso-metals in feed, the fresh catalyst
ble 3-4% at iso-catalyst addition consumption was reduced to a
Trial results rate (see Figure 5). record low rate of 4 MT/d (see
The typical feed processed by A reduction in the catalyst Figure 6a). During the trial,
Collombey’s RFCC unit is 100% consumption was enabled by improvements were also made in
atmospheric residue with moder- higher activity retention. At the approach to control e-cat
ate-to-high metals content and a
high CCR (typically 4-6 wt%).
Routine unit data reviews using A 11
Aegis–TC3 to –TC6
BASF’s Technical Support Service
Catalyst addition, MT/day

10 Fortress–TC7
(TSS, see Figure 3), revealed that Fortress–TC8
9
FCC profitability could be further
improved through better feed 8
metals passivation. 7

Trial objectives 6
The trial’s objectives were to reduce 5
H2 production to minimise the
4
amount of H2 sent to refinery fuel
gas, and to control LPG/gasoline 3
selectivity and total LPG+gasoline
2

13

13

13

13

13

13

13
01

01

01

20

20

20

20

20

20

20
/2

/2

/2

production at the same delta coke,

1/

2/

3/

4/

5/

6/

7/
10

11

12

1/

1/

1/

1/

1/

1/

1/
1/

1/

1/

conversion level and bottoms

upgrading performance delivered
B 77
by the Aegis catalyst.
FACT), wt%

76
Using BASF’s Catalyst Change 75
Management Process (see Figure 4), 74
Fortress catalyst was selected and 73
wt%

customised during the trial to 72

(using

improve profitability. This process 71

FACT,

combines FCC operations review 70

(cold eyes review), state-of-the-art 69
E-cat activity

modelling (statistical and kinetic), 68 Aegis–TC3 to –TC6

basic and advanced ACE pilot unit 67 Fortress–TC7
testing, and a proactive risk mini- 66 Fortress–TC8
misation plan, to ensure a flawless 65
2

13

13

13

13

13

13

13

catalyst change to deliver an

01

01

01

20

20

20

20

20

20

20
/2

/2

/2

improvement in unit profitability

1/

2/

3/

4/

5/

6/

7/
10

11

12

1/

1/

1/

1/

1/

1/

1/
1/

1/

1/

(measured in $/bbl).
Using TSS (see Figure 3) to stand-
ardise the unit data, the average Figure 6 TSS corrected a) catalyst addition rate, b) e-cat activity vs time

www.eptq.com PTQ Q4 2013 135

basf2.indd 4 16/09/2013 09:32

 0.70
Using TSS to
A
0.65
Aegis–TC3 to –TC6
Fortress–TC7
standardise the unit
0.60
0.55
Fortress–TC8
data, the average
0.50 conversion increased
H2, wt%

0.45
0.40 by a remarkable
0.35 3-4% at iso-catalyst
0.30
0.25 addition rate
0.20
2000 2500 3000 3500 4000 4500 5000 trapping speciality alumina is
Ni + V/4 – 4/3Sb, ppm concentrated in the outer-stage,
2.2 which improves Ni tolerance and
B
2.1 Aegis–TC3 to –TC6 performance. Consistent with the
2.0 Fortress–TC7 lower H2 yield, Figure 7b shows
1.9 Fortress–TC8 improved coke selectivity.
1.8 Dry gas yield was on the lower
Coke factor

1.7 side (see Table 1) and total

1.6 LPG+gasoline yields were similar
1.5 to the previous results with the
1.4 Aegis catalyst (see Figure 8a).
1.3
Similar performance was achieved
1.2
by optimising the catalyst formula-
1.1
tion (zeolite surface area, matrix
1.0
2000 2500 3000 3500 4000 4500 5000 surface area, rare earth level on
Ni + V/4 – 4/3Sb, ppm zeolite and so on). However,
bottoms upgrading to LCO was
Figure 7 ACE unit a) hydrogen yield, b) coke factor vs equivalent Ni significantly increased using
Fortress catalyst, compared to the
previous unit record that was set
BASF Fortress catalyst trial summary
by the Aegis catalyst.1 The increase
in the LCO/slurry ratio at higher
Competitor (base) BASF Aegis BASF Fortress conversion was 12-15% (see Figure
High Z/M Optimised Z/M Optimised Z/M 8b).
Base ZSA Higher ZSA than base Higher ZSA than base
Base MSA Higher MSA than base Higher MSA than base
Collombey refinery did not
%RE = 3.3 %RE = 2.8 %RE = 2.6 observe any problems with attrition
Feed-specific gravity 0.933 0.935 0.928 resistance. In Fortress catalyst,
Feed rate, bbl/day 16 596 16 756 16 152 the stages are chemically bound
Catalyst consumption, kg cat/MT feed 2.9 2.5 2.0
Dry gas, wt% 3.30 3.28 3.22
together by zeolite in such a
LPG/gasoline, wt%/wt% 0.307 0.214 0.300 way that all physical properties,
LCO/slurry, wt%/wt% 0.763 0.893 1.001 including attrition resistance, are
Coke, wt% 7.93 7.83 7.88 similar to other DMS based prod-
Economics, $/bbl of FCC feed Base Base +0.40 Base +0.70
ucts (for example, Flex-Tec).

Table 1 Economic assessment

activity within the desired range,
with the result that more often the
e-cat activity is controlled within
the target operating window (see
Figure 6b). BASF’s Fresh Catalyst
Addition Tool was helpful in this
regard.
At a lower fresh catalyst addi-
tion rate, the level of contaminant
metals increased on the e-cat. The
Ni+V on e-cat increased to 8000-
9000 ppm. To eliminate the effect
of varying feed quality and operat-
ing conditions during the trial, an
ACE unit was used to assess the
improvement in coke selectivity
using standardised feed and oper-
ating conditions. Figure 7a shows
a hydrogen yield reduction even
though the Ni level on e-cat
increased during the trial. In the
Fortress catalyst, the Ni-
The increased refinery profitability
estimated using typical feed and
products values is summarised in
Table 1.
Conclusions
This article has shown how
advanced FCC catalysts and value-
added technical service are
supporting Collombey refinery.
This is all made possible by
Collombey’s good approach to data

136 PTQ Q4 2013 www.eptq.com

basf2.indd 5 16/09/2013 09:32

 US), with similar results observed
A 65 at all locations.
63
61
LPG + gasoline, wt%
59
Acknowledgements
57 The authors would like to thank Steve Challis
55 of Chalcat Consulting Limited, UK, for chairing
numerous cold eyes reviews at site and
53
providing consulting during the BASF catalyst
51 trials.
49 Aegis–TC3 to –TC6
Fortress–TC7
47
Fortress–TC8 References
45
60 62 64 66 68 70 72 74 76 78 80 1 Jollien Y-A, et al, Use an innovative cracking
catalyst to upgrade residue feedstock,
Conversion, wt%
Hydrocarbon Processing, Feb 2013, 63-67.
2 McLean J B, et al, Multi Stage Reaction
1.4 Catalyst: a breakthrough in fcc catalyst
B technology, NPRA AM-11-01.
1.3
3 McLean J B, et al, Distributed matrix
LCO/slurry, wt%/wt%

1.2 structures – a technology platform for

1.1 advanced fcc catalyst solutions, NPRA AM-
03-38.
1.0
4 Kugler E L, et al, Nickel and vanadium on
0.9 equilibrium cracking catalyst by imaging
0.8 secondary ion mass spectrometry, Journal of
0.7 Aegis–TC3 to –TC6 Catalysis, 109, 1988, 387,
Fortress–TC7 5 Lappas A A, et al, Effect of metals poisoning
0.6
Fortress–TC8 on FCC products yields: studies in an FCC short
0.5 contact time pilot plant unit, Catalysis Today,
60 62 64 66 68 70 72 74 76 78 80 65, 2001, 233–240.
Conversion, wt% 6 Xu M, et al, Pathways for Y zeolite destruction:
the role of sodium and vanadium, Journal of
Catalysis, 207, 2002, 237-246.
Figure 8 TSS corrected a) Total LPG + gasoline yield, b) LCO/slurry ratio vs conversion

sharing and collaboration to form • Due to high activity retention, at

the best team. Combining the refin-
ery’s operating expertise and
BASF’s catalysts and technical
support, it was possible to further
improve flexibility to upgrade
heavy residue with even higher
metals content. Fortress catalyst
was selected for a trial in 2013. This
is a two-stage reaction catalyst
based on BASF’s DMS and MSRC
technologies. The outer-stage of the
catalyst is enriched with speciality
alumina to trap Ni where it enters
and accumulates on the catalyst.
The improved metals tolerance
delivered by this catalyst has
increased the profitability of
Collombey’s RFCC unit by $0.30/
bbl of FCC feed compared to the
Aegis catalyst. Thus, this past year,
the refinery has improved profita-
bility by approximately $0.70/bbl
(Aegis and Fortress).
The Fortress catalyst delivered:
• A 3-4% conversion increase at
iso-catalyst addition rate
iso-feed metals, fresh catalyst addi-
tion can be reduced to a record low
rate of 4 MT/d
• Bottoms upgrading to LCO was
significantly increased. The increase
in the LCO/slurry ratio at higher
The outer-stage of the
catalyst is enriched
with speciality
alumina to trap Ni
where it enters and
accumulates on the
catalyst
conversion was 12-15%
• Attrition resistance was similar to
previously used catalysts.
Fortress catalyst is currently in
operation at four other refineries
(one in the UK and three in the
Yves-Alain Jollien is a Process Engineer for
Tamoil S.A. Raffinerie de Collombey and is
the FCC Unit Process Engineer. With over six
years of experience, he holds an MEng degree
from the Swiss Federal Institute of Technology
Lausanne and later studied for one year at the
IFP School near Paris.
Jeremy Mayol is a Technical Account Manager,
Refining Catalysts for EMEA with BASF
Corporation. With over 15 years of experience,
he is a recognised technical specialist in FCC
unit operation. He has worked for BASF for four
years and previously spent 12 years working for
INEOS and BP.
Vasileios Komvokis is the Technology
Manager, Refining Catalysts for EMEA with
BASF Corporation. He holds BS and MS degrees
in chemistry and a PhD in chemical engineering
from Aristotle University, and was a researcher
at CPERI and a research Professor at the
University of South Carolina.
Carl Keeley is the Marketing Manager, Refining
Catalysts for EMEA with BASF Corporation.
He holds a MEng in chemical engineering and
applied chemistry from Aston University, UK, is
a professional engineer (CEng) and has over 12
years of experience. Previously, he worked with
UOP, BP and Dow.

www.eptq.com PTQ Q4 2013 137

basf2.indd 6 16/09/2013 09:32

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 Mitigating fouling in the caustic tower

Comprehensive analysis of foulants in an ethylene plant’s caustic tower led to

the identification of an effective treatment programme

HUA MO and DAVID DIXON Baker Hughes

LOWELL SYKES Westlake Vinyls

A
n ethylene plant experienced
severe fouling in its caustic Cracked gas to
tower. The degraded perfor- secondary compression
mance of the caustic tower WW make-up
threatened ethylene production. WW circulation

The progression of fouling in the WW blowdown

caustic tower indicated that the
treatment programme at that time
could not control the fouling.
To reduce caustic system fouling
and extend unit run length, exten-
sive testing was conducted to
identify all fouling mechanisms
prior to initiation of a new treat-
ment programme. Identification of
fouling mechanisms provides a
clear understanding of the root
causes of fouling. It also helps to
identify the right chemistries to
apply for a successful treatment
programme.
The Baker Hughes treatment
programme, based on the identified
fouling mechanisms, improved the
performance of the caustic tower.
System degradation dramatically
slowed and the run length was
extended. This article reviews the
ways to identify fouling mecha-
nisms and the impact of modifying
a treatment programme based upon
the identified fouling mechanisms.
Description of unit
The caustic tower in the ethylene
plant is used to remove acid gases
from cracked gas. A general flow
Quench
water
Weak caustic circulation
Cracked gas
from amine unit or
primary compression
Figure 1 The ethylene plant’s caustic tower
diagram of the caustic tower is
shown in Figure 1.
There are typically four sections
in a caustic tower: weak section,
intermediate section, strong section
and water wash section. The caustic
solutions are circulated in the
strong and weak sections. Boiler
feed water is circulated in the water
wash section, and the cracked gas
from the compressor feeds into the
caustic tower weak section. When
the cracked gas contacts caustic
solution, the acid in the cracked gas
is removed by an acid-base reac-
tion. Some hydrocarbons are also
captured by caustic solution at the
Fresh caustic make-up
Strong caustic circulation
Intermediate circulation
Liquid HC
Spent caustic
coalescer
To spent caustic treatment
same time. After the acid removal,
the cracked gas leaves the tower
overhead and feeds the next stage
of compression.
Fouling mechanisms
Polymeric hydrocarbon precursors
present in the caustic solution can
form various polymeric materials
by different reaction mechanisms.
These polymers can deposit and
agglomerate in the caustic column,
causing fouling, reduced through-
put and decreased tower efficiency.
There are three major organic
fouling mechanisms: aldol conden-
sation polymerisation, free-radical

O O O OH O O
OH– –H2O
R1CH2CH R1CHCH + R2CH2CH R2CH2CHCHCH R2CH2CH=CCH

R1 R1

Figure 2 Aldol condensation

www.eptq.com PTQ Q4 2013 139

b hughes.indd 1 13/09/2013 10:09


Chain initiation
1. R–H  R• + H•
2a. M++ + R–H  M+R• + H+
2b. M++ + R–O–O–H  M+R–O–O• + H+
Chain propagation
1. R• + O2  R–O–O•
2. R–O–O• + R’–H  R–O–O–H + R’•
3. R• + C=C  R–C–C•  Growing polymer
Figure 3 Free-radical polymerisation
polymerisation and Diels-Alder
reaction polymerisation.
Aldol condensation
The aldol condensation reaction
mechanism is shown in Figure 2.
As an anionic reaction, it only
occurs in the base condition; the
condensation reaction initiates and
propagates in the circulating caus-
tic solution. The precursors for the
aldol condensation reaction include
various aldehydes, ketones and
unsaturated esters. The two most
commonly identified aldol conden-
sation precursors identified in
olefin cracked gas streams are acet-
aldehyde and vinyl acetate.
Free-radical polymerisation
The free-radical reaction mechanism
is shown in Figure 3. The presence of
free-radical initiators, such as perox-
ides, may initiate the reaction. In
addition, monomers such as styrene
will readily self-initiate free-radical
polymerisation reactions at typical
caustic tower operating tempera-
tures. The presence of olefins, such as
conjugated olefin, styrene and
indene, provides the monomers for
chain propagation. The polymer
chain length will depend on temper-
ature, stability of the initiator or
monomer concentration.
Diels-Alder reaction
The mechanism of a Diels-Alder
reaction is shown in Figure 4. Diels-
Alder reactions are self-initiated
Figure 4 Diels-Alder reaction
140 PTQ Q4 2013
b hughes.indd 2
Chain termination
1. R• + R’•  R–R’
2. R• + R’–O–O• +  R’–O–O–R’
R• = Reactive polymer,
monomer or oligomer
M = Metal
reactions and may occur at low
temperatures. The precursors for
Diels-Alder reactions are conjugated
dienes, such as cyclopentadiene
derivatives.
Although many mechanisms may
co-exist in the caustic tower, one or
more reaction mechanisms cannot
significantly contribute to the foul-
ing. Different caustic tower systems
will have different fouling mecha-
nisms. To ensure successful treatment,
each fouling mechanism or combi-
nation of fouling mechanisms must
be identified for each system.
Fouling control
Aldol inhibitor, free-radical inhibi-
tor and dispersant are used to
control the fouling.
Aldol inhibitor (Polyfree 305C)
The aldol inhibitor from Baker
Hughes is used to quickly convert
carbonyl in aldol to another non-re-
active functional group. After the
reaction, the aldol condensation is
completely inhibited; there is no
side reaction of this inhibitor.
Free-radical inhibitor
(Polyfree 300R1)
The active component in the free-
radical inhibitor reacts with the
free-radical, either carbon or oxygen
centred, in the caustic tower. After
the free-radical reacts with the
free-radical inhibitor, free-radical
polymerisation is inhibited.
Dispersant
Dispersant is used to disperse
foulants that could not be inhibited
by the aldol inhibitor and free-radi-
cal inhibitor, such as products of a
Diels-Alder reaction. Dispersant
could prevent foulant from
precipitation. The dispersed foulant
will be carried out of the caustic
tower by the spent caustic system.
Identification of fouling mechanism
Methodology
Fouling in the caustic tower is
influenced by two factors: the accu-
mulation of existing foulant and the
formation of new foulant. The accu-
mulation of existing foulant can be
evaluated and monitored with
filterable solids analysis and solu-
ble polymers analysis. The potential
to form new foulants is influenced
by many factors, including reaction
mechanisms, fouling precursors,
process temperatures and initiators.
Although the existing foulant was
investigated, this article will
primarily focus on identifying and
controlling foulant-forming reaction
mechanism(s) to reduce and/or
eliminate the accumulation of new
foulant material.
Analytical results and discussion
Existing foulants
The following method is widely
used as an effective caustic tower
monitoring programme. The test
results are shown in Table 1.
Analysis of the filterable solids is
used to measure the precipitated
foulants. The soluble polymer anal-
ysis is used to measure the
total polymers in the caustic tower.
After the soluble polymer agglom-
erates, it will precipitate out of
solution to form filterable solids.
The particle size of filterable
solids can continue growing until
eventually it will stop moving in
the caustic system and deposit
in the pipeline and exchanger,
and foul the caustic system. A
high level of filterable solids and
soluble polymer indicated a high
fouling rate in the caustic tower
system.
The existing foulants in this unit
were significantly higher than those
units that were treated by Baker
Existing foulants
Filterable Soluble
solids, ppm polymer, ppm
Strong section 329 490
Weak section 1986 1895
Table 1
www.eptq.com
13/09/2013 10:09
 HydrocarbonChina.com
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 Hughes. The results suggested that Functional group vs mechanism analysing the functional group in
there is room to improve with a the deposit. The relationship
treatment programme. between the functional group and
Functional group Reaction mechanism reaction mechanism is shown in
Carbonyl Aldol condensation
Skim oil investigation Conjugated vinyl Free-radical Table 2.
Condensed fouling precursors are monomer (styrene, polymerisation Several instrumentation tech-
concentrated in the skim oil. The butadiene, indene, etc) niques, such as weight loss,
concentration of these fouling Cyclopentadiene Diels-Alder reaction elemental analysis, spectroscopy
precursors influences the fouling and chromatography, were used to
rate. A high concentration will Table 2 identify the functional group in the
increase the fouling rate. deposits. The results showed that
A skim oil sample was collected were involved in the caustic tower more than one reaction mechanism
from the caustic tower. Visual fouling. As a result, free-radical had contributed to fouling in the
examination revealed that the polymerisation and aldol condensa- caustic tower. The majority of the
sample was very cloudy. There was tion inhibitors could be used to deposit was organic components
an organic layer on the top of the control fouling. The results were such as cyclopentadiene derivatives,
sample. Spectroscopy and chroma- confirmed by the caustic tower styrene derivatives, carbonyl deriv-
tography analytical results showed reflux. atives and other oxygenate species.
that the organic layer of skim oil The cyclopentadiene derivatives
contained a significant amount of Deposit analysis indicated the presence of a Diels-
components with aldol and vinyl The skim oil analysis confirmed Alder reaction. The styrene
functional groups. The presence of that aldol condensation and derivatives and oxygenated species
aldol and vinyl-type components free-radical polymerisation were indicated the presence of free-radi-
provides a significant amount of involved in the fouling reaction. To cal polymerisation. The carbonyl
precursors in both aldol condensa- confirm the hypothesis, a deposit derivatives indicated the presence
tion and free-radical polymerisation. was collected from the caustic of aldol condensation. Another
This indicated that aldol condensa- tower. The fouling reaction mecha- effect of the deposit is that it could
tion and free-radical polymerisation nism can be determined by absorb some monomers, such as
styrene and indene. The organic
component, which was absorbed in
a 4.0 the deposits, could contribute to
y = 0.0158x – 642.7 free-radical polymerisation as the
chain propagation reagent.
3.5
Caustic reflux test
Caustic tower DP

The stream and deposit analyses

3.0 indicated that both aldol condensa-
tion and free-radical polymerisation
were involved in the caustic foul-
2.5
ing. Baker Hughes’ Polyfree
Flow corrected DP
programme was recommended,
Linear (flow corrected DP)
2.0
including a free-radical inhibitor
22/1/12 1/2/12 21/2/12 12/3/12 1/4/12 11/4/12 and aldol condensation inhibitor to
Date inhibit the polymerisation reaction.
An additional Polyfree dispersant
b 10
was recommended to remove the
y = 0.0076x – 305.68
foulants formed by other reactions,
such as a Diels-Alder reaction.
To test the efficiency of the inhib-
Caustic tower DP

itors, caustic reflux was used. The

5 samples from the caustic tower
were spiked with antifoulants and
refluxed. After the reflux, the
foulants that formed were meas-
Flow corrected DP ured. If the inhibitor is effective, the
Linear (flow corrected DP) amount of foulant with inhibitors
0 will be lower than that without any
2/5/12 10/7/12 18/10/12 26/1/13 6/5/13 14/8/13
inhibitors. The test results are
Date shown in Table 3.
The reflux results showed that
Figure 5a Before treatment 5b After treatment both the Polyfree 300R1 and

142 PTQ Q4 2013 www.eptq.com

b hughes.indd 3 13/09/2013 10:09

 identified. The results showed that appreciation to Westlake unit personnel for
Caustic sample reflux test results
free-radical polymerisation and their collaboration on this project.
aldol condensation were involved POLYFREE is a trademark of Baker Hughes
Chemical Percentage in the caustic tower fouling. Based Incorporated.
additives inhibition, %*
Blank n/a
on the analyses, a successful chemi-
Polyfree 300R1 additive 18.9 cal treatment programme was Hua Mo is a Senior Chemist with Baker Hughes.
Polyfree 305C additive 27.9 recommended to the customer. He holds a PhD in organic chemistry from Rice
Polyfree 300R1/ Field test data indicated that the University.
Polyfree 305C additive 81.5 David Dixon is a Field Support Technologist
fouling was controlled and the run
length of the tower was extended. with Baker Hughes. He holds a BS in toxicology
*Percentage Inhibition (%)= [(Foulants with
additive) – (Foulant without additives)]/ from Northeast Louisiana University.
Foulant without additives x 100 Acknowledgement Lowell Sykes is the Process Engineering
The authors wish to extend their gratitude Supervisor for Westlake Vinyls Calvert City,
Table 3 to the analytical group at Baker Hughes Kentucky, Ethylene Plant. He holds a BS in
Incorporated for their help in providing the chemical engineering from Purdue University
Polyfree 305C additives could analysis work. We also wish to express our and an MBA from Murray State University.
significantly decrease the polymer
formation. This confirmed that
free-radical polymerisation and
aldol condensation contributed to
caustic tower fouling. The combina-
tion of Polyfree 300R1 and Polyfree
305C additives showed the best
performance.

Treatment results
Based on the test results, Polyfree
305C, Polyfree 300R1 and Polyfree
350C additives were recommended
to the unit’s operators. The process
information in Figures 5a and 5b
shows the effect the new chemical
treatment programme had on the
unit.
The performance of the caustic
tower was measured by the tower
differential pressure (∆P). ∆P
increased dramatically before the
treatment. The slope was 0.0158.
When the Baker Hughes programme
was applied to substitute the previ- We Process Your Energy
ous treatment programme, the
tower’s ∆P did not climb signifi- TECHNOlOGIES aND EquIPmENT FOR OIl & GaS TREaTmENT
cantly. The ∆P fouling rate was YOuR EFFICIENCY, OuR FlExIBIlTY
0.0076, indicating about a 50% foul-
ing reduction. The field test result Because Oil & Gas projects require highly reliable and cost effective solutions
we timely deliver since over 35 years fully guaranteed modular process-
showed that fouling was success- equipment packages tailored to meet specific customer’s requirements; for
fully controlled in the caustic tower. all kind of Oil & Gas processing applications.
In addition, the run length of the Because each project is unique and highest quality design is paramount to
caustic tower has been extended. It success we offer a unique portfolio of proprietary gas treatment technologies
is still performing well at the time of licensed by Prosernat. Backed by our strong investment and partnerships
in R&D, with IFP Energies nouvelles and Total, we are proud to bring to
writing. This successful treatment the market the most advanced technologies in the following areas: Natural
indicated that the Baker Hughes Gas Sweetening, Natural Gas Dehydration, Sulfur Recovery, Hydrocarbon
proprietary caustic system analysis Dewpointing, Separation and CO2 Capture from Flue Gases.
mode, which includes foulant analy-
sis, a caustic reflux test and skim oil
analysis, can be used to minimise
caustic tower fouling.

Conclusion
In this article, the fouling mecha-
nism of a caustic tower was

www.eptq.com PTQ Q4 2013 143

b hughes.indd 4 13/09/2013 10:09

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 Gasoline benzene reduction
By adding a new unit that reacts a benzene-rich stream with light olefins, a refiner
complied with current regulations for benzene and achieved a payback in 20 months
EL-MEKKI EL-MALKI and BENJAMIN UMANSKY ExxonMobil Research and Engineering Company
ERIK MOY, GRANT DONAHOE and TIMOTHY THOM Badger Licensing
U
nder clean fuels regulation in
the US, specifically Mobil
Source Air Toxics II (MSAT
II), refiners are required to reduce
the benzene in gasoline to 0.62 vol%
on an average annual basis. This has
been in effect since January 2011 for
large refiners, with a deferment for
small refiners until 2015. In Europe
and in many other regions, a regula-
tion of 1.0 vol% maximum benzene
in gasoline has been in effect and
others are expected to adopt similar
regulations. The challenge for refin-
ers is to meet the tightening gasoline
specifications for benzene at the
lowest cost and without significant
octane loss.
Refiner’s options
There are several approaches availa-
ble to refiners to reduce the benzene
in their finished gasoline. Since
naphtha reforming is the predomi-
nant source of benzene in a typical
refinery, the prevention of the
formation of benzene in the
reformer is accomplished by
pre-fractionation of the naphtha
feed to remove the benzene precur-
sors. However, for many refiners,
pre-fractionation of the reformer
feed does not provide sufficient
benzene reduction to achieve 0.62
vol% in the gasoline pool.
Alternatively, the conversion of
benzene produced in the reformer is
implemented downstream of a
reformate splitter. The benzene
containing light reformate fraction
from this splitter is sent to a hydro-
genation reactor, where benzene is
converted to cyclohexane. Both of
these strategies result in a loss of
octane barrels and an additional
burden on the hydrogen balance in
www.eptq.com
exxon.indd 1
the refinery. The third approach is
benzene extraction for the petro-
chemical market. While
petrochemical benzene can be an
attractive product, there is signifi-
cant investment required to recover
benzene. And unless the refinery
has existing facilities or capacity for
such a process, it is very difficult to
justify this investment on a small
scale.
An alternative technology,
BenzOUT, has been developed by
ExxonMobil Research and
Engineering Company (EMRE) and
is licensed by Badger Licensing. The
technology provides a low-cost
alternative solution for refiners to
meet benzene regulation without
the octane and hydrogen debits
associated with alternative options.
In this article, we will discuss a
project where significant benefits
were achieved from the implemen-
tation of this technology.
Process description
EMRE developed the BenzOUT
technology and catalyst to convert
benzene into high-octane alkylaro-
matic blending components by
reacting a benzene-rich stream with
light olefins, such as ethylene or
Propylene
Light
Reformate reformate
splitter
BenzOUT
Reformate reaction
Heavy
reformate
Figure 1 BenzOUT process flow
propylene. In December 2009, EMRE
and Badger agreed to jointly market
the technology to third parties, and
ever since licences and related engi-
neering services are provided
exclusively through Badger.
In a typical application, the tech-
nology reduces benzene in
reformate by reacting benzene
contained in a light-cut reformate
with refinery-grade propylene from
an FCC unit over a proprietary
EMRE zeolite catalyst. The typical
benzene concentration in a light-cut
reformate, which is produced in a
reformate splitter, ranges from 10-30
vol%. A simple flow diagram of the
process is shown in Figure 1. The
key features are:
• Fixed-bed catalyst technology The
process uses a fixed-bed liquid-
phase reactor, resulting in low
utility requirements. The reactor
may be a single bed (stage) or multi-
ple beds, depending on the benzene
content of the feed and the desired
benzene conversion. In revamp
projects, it is possible to retrofit
existing tubular or fixed-bed reac-
tors for this application
• Catalyst The process utilises an
EMRE proprietary highly active
zeolite catalyst with long cycle
LPG
Stabiliser
Mogas
PTQ Q4 2013 145
13/09/2013 14:58

FCC propylene
Benzene-containing
feedstock
Two-stage
once-through
reactor system
Figure 2 Calumet Superior process flow
lengths. In addition, the catalyst is
regenerated ex-situ to further extend
catalyst life
• Stabilisation Propane fed to the
unit with propylene is removed
from the BenzOUT product in a
product stabiliser. This can produce
a propane product of HD-5 quality.
The product from the technology is
a light reformate with a reduced
RVP.
Besides benzene reduction, the
process provides several advantages
that make it economically attractive.
The reaction of benzene with light
olefin results in a volume swell,
which largely depends on the
benzene content in the feed and the
degree of benzene conversion. Also,
an octane gain of 2 to 3 numbers of
(R+M)/2 in the total reformate is
typical. Moreover, the BenzOUT
unit offers reformer flexibility, since
it allows refineries to process the
full-range naphtha feed in the
reformer to achieve increased
hydrogen production and significant
octane gain.
Commercial experience
Construction
The first grassroots BenzOUT unit
was started in December 2011 at
Calumet Superior refinery in
Wisconsin. A schematic of the unit’s
process flow is shown in Figure 2.
The naphtha feed splitter at the
refinery was changed to become the
reformate product splitter for the
unit. Two new benzene alkylation
reactors and a new product stabi-
liser with all associated equipment
were installed.
The refinery had an aggressive
timeline for the project’s execution,
146 PTQ Q4 2013
exxon.indd 2
Propane
Stabiliser
BenzOUT
product
with a target mechanical completion
date of November 2011. Given the
climatic conditions at the refinery’s
location, the short seasonal construc-
tion window was given full
consideration. The selection of
modular design accelerated the
construction of the unit and allowed
for a minimal footprint in the refin-
ery. Six separate structural modules
containing equipment, piping and
instrumentation were delivered to
the refinery to create a three-level
structure. The major vessels such as
alkylation reactors, the stabiliser and
pumps were placed on the perime-
ter of this three-level structure.
Figure 3 shows a photograph of the
installed unit.
Benzout unit operation
Initial plant commissioning activities
were commenced in mid-November
2011 with the assistance of opera-
tions and technology experts from
Figure 3 Calumet Superior BenzOUT unit
EMRE, Badger and the client’s
contractor. Catalyst was loaded on 9
and 10 November and, after a
subsequent two-week period to set
up rotational equipment and process
controls, the unit began operation
on 1 December, reaching steady-
state operation within a matter of
days. Operating and process control
strategies were fine-tuned in the
following weeks, and at the end of
December the start-up was officially
completed.
The operation of the unit has been
straightforward and easy to control.
No additional staffing is required to
operate the unit. It is run without
any online analysis and one daily
set of samples.
Performance has been at or
beyond the design expectations, in
terms of benzene conversion and
consumption of propylene. The
quality of the product from the unit
has proven to be consistent with the
projections made at the onset of the
project, and Calumet is benefiting
from an increase of about 4 points
octane (R+M)/2 across the unit,
which is equivalent to an increase of
about 2 to 3 points on the basis of
total reformate. The unit has enabled
Calumet to improve the hydrogen
management in the refinery. The
Calumet Superior unit is designed
to process 5500 b/d of feedstock.
Benefits to the Calumet
Superior refinery
The installation of the BenzOUT
unit was achieved by Calumet on an
aggressive project timeline using
creative and forward-thinking
execution strategies. The plant was
installed at a cost of approximately
$19 million, within the budget allo-
cated at the early stages of the
project. With the addition of the unit
to its refinery, Calumet complied
with the MSAT II regulations for
benzene and gained several
economic benefits, which resulted in
a simple payback on its investment
in approximately 20 months.
With this technology, Calumet
meets benzene compliance, while
allowing for full reformer operation.
Recovering more hydrogen at the
reformer has averted the installation
of a hydrogen unit. With the addi-
tional octane increase across the
www.eptq.com
13/09/2013 14:58
 Second, software
1.0 advances have the real and the virtual worlds can opportunity
enabling of lean by construction
eliminating meth- the
brought new ways in which to use be integrated in a common environ- hydrogen
odologies. consumption
Casting an envious associated
eye
0.9
3D surveys. Early developments ment (see Figure 3). with
on thesaturation
many benefitsunits. brought by the
enabled the0.8accurate but relatively This brings important benefits. lean manufacturing revolution, the
sparse “point 0.7cloud” representations One is the ability to efficiently plant industries have long sought
Benzene, wt%
of the as-operating
0.6 plant to be refer- reverse-engineer existing plant the key to unlock lean construction.
enced within 0.5 a 3D design system, construction. Software can now Thatarticle
This key ishas now
based on abeen
papercreated.
presented By
at
enabling new design to be aligned recognise, for example, that a cylin- the AFPM Annual
exploiting theMeeting,
ease and San affordability
Antonio, Texas,
0.4 USA, March scanning
2013.
accurately with existing construc- drical array of 3D scan data points of laser at every stage in
0.3
tion. This substantially reduced the represents a pipe run. By comparing the fabrication and construction
commercial0.2 risk in revamp projects, its diameter with available pipes in sequence, and integrating the data
El-Mekki El-Malki is Licensing Manager with
as new design 0.1 could be created and the system catalogue, it then offers with theResearch
ExxonMobil as-designed model,Fairfax,
and Engineering, the
fabricated in 0the confidence that it the designer a shortlist of candidate feedback loop can be closed between
Virginia, USA. He is chiefly responsible for
would fit right first time during Time pipe specifications. The correct spec- design, fabrication
marketing the company’sand construction.
refining technologies
on-site installation. ification is determined from the In Middle
in the one-off capital
East and Africa. projects, if a
Rapid
Figure development
4 Benzene has product
level in BenzOUT taken P&ID and selected from the short- costly
Email: or long-lead item is made
el-mekki.el-malki@exxonmobil.com
this further. The latest software list, whereupon the software creates incorrectly,
Benjamin the programme
Umansky impact
is a Senior Engineering
unit, Calumet
releases enablecan,
bothatdesign
times, models
lessen Conclusion
a native, intelligent pipe object accu- can be considerable.
Associate with ExxonMobil ButResearch
if the devi-
and
the severity
and laser scanofdatatheto bereformer
combined to Refiners are facing with
rately co-aligned a challenging
its scan Engineering.
ation can be identified immediately
produce
in the samemore gasoline
3D design environ- market
volume. as they Current
representation. comply with envi-
capabilities Erik
andMoyin is Technology
detail, Manager with
an informed Badger
decision
With regard Licensing, and is responsible for design and
ment. The to improved design ronmental
benzene compli- cover pipes, regulations.
nozzles Often
and theysteel can be made to mitigate its impact
development work with BenzOUT technology.
ance, Figure 4 described
visualisation shows theabove benzene is are
beams,faced with theproductivity
increasing challenge on of and protect the programme. For
Timothy Thom is Engineering Manager
level in thebyBenzOUT product.“real-The investing capital
mostwith no payback. example, suppose
matched high-definition some of the repetitive aspects with Calumet SuperioraRefining,
project Wisconsin,
requires
benzene
world” laserlevel in the blurring
scans, product has the BenzOUT technology provides a
of reverse engineering. a concrete base with a number
USA, where he is responsible for planning of
consistently been below
visual distinction between wt%. process advantage to help refiners
1.0 design mounting points for key
turnarounds and for project management. modules.
When
objectstheandproduct is blended
surveyed the such
objects.in The Lean as Calumet meet benzene regu-
revolution The concrete
Grant Donahoe is is poured,
Director ofbut only
Business
gasoline
designer pool,
can the
work Superior intui- lations,
equallyrefinery However, whilethe atmost
the far-reaching
same time when the with
Development modules Badgerare Licensing,
being
meets
tively the with0.62 both
vol% typesmaximum of achieving
benefit ofan integrating
attractive economic
the as- installed several
Cambridge, weeksUSA,
Massachusetts, laterandis isit
benzene level.Now,
information. The for
product
the first fully return
is time, designed on and
investment. In lies
the as-built addition,
in the discovered
responsible that some new
for commercialising mounting
process
blendable into gasoline. the technology can provide margin technologies.

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sulphur.indd 1 13/09/2013 11:28

 Technology in Action
Automated temperature control
aids HDS process development
The introduction of precise, automated temperature
control is enabling more efficient development of
desulphurisation and other processes for Taiwan’s
petrochemicals industry. Accurate, individual control
of heating elements means that catalysts in the devel-
opment reactor are maintained in an isothermal state,
which, in turn, enables consistent reaction conditions
for the Refining and Manufacturing Research Institute
(RMRI).
RMRI is the research institute of the CPC
Corporation, a state-owned gas, petroleum and chemi-
cals company in Taiwan. Approximately 300
employees research and develop refining and petro-
chemical processes, focusing on catalyst systems and
process design for the refinery and petrochemicals
industry, but also for other companies in the chemicals
industry. The company has been operating pilot plants
for this purpose in Taiwan since 1985. These plants
employ various processes and systems, such as cata-
lytic reforming, hydrodesulphurisation and
hydrotreating. However, other technologies can also
be tested and evaluated, such as isomerisation,
catalytic distillation or oxidative desulphurisation.
RMRI also has an analysis laboratory for catalysts,
where the physical properties, including loss on igni-
tion, bulk density, crush strength and attrition index,
can be determined in accordance with ASTM
standards.
The processes and catalysts validated at RMRI pilot
plants are used later at full industrial scale at refineries
of the CPC Corporation, Taiwan, and at chemical
companies throughout the world. These processes
focus on methods for removing sulphur from crude oil.
The path from crude oil through fractional distillation
to the end product is a lengthy one. In particular,
naphtha, middle distillates or vacuum gas oils contain
sulphur compounds that not only violate environmen-
tal legislation but also poison catalysts during further
processing such as catalytic reforming. In hydrotreat-
ing residue, the heaviest fraction of crude oil,
hydrocarbons are mixed with hydrogen and heated to
at least 350oC under pressure of 2000 psig. Apart from
sulphur, nitrogen, oxygen, metals and other aromatic
compounds are removed. It is this process that RMRI
investigates. The catalyst and the reaction conditions
are the key points of reference in this investigation.
The catalysts are tested intensively and approved after
a series of lengthy tests. For example, only catalysts
with an “A grade” certificate are approved for CPC
refineries.
www.eptq.com
case studies copy 7.indd 1
Precise temperature control
The precise temperature control of the reactor is an
issue that poses challenges for research teams devel-
oping a new desulphurisation process. Each tubular
reactor is heated by multiple-zone heating elements,
each of which has to be individually controlled in
order to maintain the catalysts inside the reactor in an
isothermal state. This is the only way that a regular
reaction can be achieved. To do this, the temperatures
of the catalyst bed are measured using separate ther-
mocouples. The control process is very complicated,
as the temperature is influenced by numerous factors,
such as material flows, heat transport, the reaction
heat of the exothermal process and the interaction
between the neighbouring thermocouples. Until now,
a great deal of sensitivity was required to achieve
isothermal control of the catalyst temperature.
Previously, this was solved by means of a multi-in-
put, multi-output system and, although this has been
in use for 20 years, the system relies on numerous
manual operations. At the same time, the energy costs
for even temperature control were high. While these
costs are still not a significant factor in a research
reactor, they are certain to become relevant when the
process is transferred to large plants, or even
before then.
Migration
RMRI wanted to replace the existing and now
outdated control system and began an extensive
search to select a new one. The Simatic PCS 7 control
system has been deployed in Taiwan for a long time,
in particular because a large number of these systems
are installed in the semiconductor industry there. The
advanced process control (APC) module, which is
fully integrated into PCS 7, played a significant part
in RMRI’s selection. The APC module is a controller
based on predictive algorithms. These algorithms
allow even complex interrelations of process parame-
ters or variables to be described mathematically and
be used for automatic and flexible operation of the
plant. This so-called lean predictive controller (model
predictive control [MPC]) only needs a few matrix
multiplications to calculate the manipulated variable
online. It is fully integrated and thus requires less
engineering effort. This permits not only optimised
process control but also a consistent method of
procedure.
An attempt had already been made to implement a
comparable function in the process, but failed because
suitable tools were not available. RMRI was
concerned that such a system would be too expensive
or too powerful for its research environment. Would
additional servers and know-how be needed? How
would the operating personnel respond to this
PTQ Q4 2013 149
13/09/2013 10:28
 technology? The APC from Siemens appeared to be
easy to implement and suited to the required, compli-
cated temperature control. The standard library of
Simatic PCS 7 contains numerous controllers for APC
functions, which cover most of the higher-level
control tasks in the process industry.
The entire project, the migration to PCS 7 with the
integrated APC controllers, started in May 2009 and
was completed by June 2010. Altogether, it was not
possible to shut down the system for longer than four
months. The old hardware had to be removed and
new field devices, including the system and program-
ming, had to be installed and commissioned in this
period. The entire installation encompasses an engi-
neering system, two OS servers (one of which is to
provide redundancy), four OS clients (including a
DataMonitor server) and four Simatic S7-414H CPUs
with 1200 I/OS. Also included were training sessions
for PCS 7, an APC workshop, and support in the
implementation and commissioning. In future, more-
over, it is planned to replace the weighing system
with Siemens products.
It has been possible to reduce
manual interventions by 80%,
while temperature fluctuations
are now at +/-0.2°C
Temperature control of catalyst beds
In the meantime, the system is running effectively. In
particular, the temperature control of the catalyst beds
is convincing. RMRI uses the control system to control
the six temperature zones in the same setpoint. This
was not possible with the previous system. It has been
possible to reduce manual interventions by 80%, while
temperature fluctuations are now at +/-0.2°C.
Previously, fluctuations of about 2°C were common.
Energy consumption has also been reduced. The lean
predictive controller can be used directly, as it requires
no extra server.
The precise control of temperature now increases
the accuracy of the trials in the pilot plant and
makes it easier to compare the catalysts. The
CFC library contains numerous built-in function
blocks, allowing the required control schematics to be
created quickly. RMRI also gains from easier data
handling; for example, automatic reports are sent by
email.
Today’s Instruments, a partner of Siemens in Taiwan,
was responsible for integration of the instrumentation
and the control system, including the cabling and proj-
ect programming. Siemens Taiwan provided
engineering assistance in setting up the PCS 7 worksta-
tions and organised the training sessions. The next
steps are already planned: now that the optimisation of
two processes has been completed, an additional
desulphurisation process, the so-called HDS project, is
currently being examined.
150 PTQ Q4 2013
case studies copy 7.indd 2
Hydrotreating upgrade delivers
low-sulphur diesel specification
An IsoTherming diesel hydrotreating unit recently
started up at PetroChina Changqing Petrochemical
Company’s refinery in Xianyang, China, to meet local
diesel sulphur specifications of less than 50 wppm.
DuPont Sustainable Solutions licensed the unit to
PetroChina in 2011; it was designed to produce
low-sulphur diesel when processing 600 000 t/y (12
487 b/d) of a 67% light cycle oil/33% straight-run
diesel blend. The project’s overall duration from the
start of DuPont’s process design work to unit commis-
sioning was approximately two years. Unit
commissioning activities were completed during June
2013, with on-spec product being produced immedi-
ately upon completion of catalyst sulphiding and
initial introduction of feedstock. A successful perfor-
mance test run at design throughput, with the design
basis feed while meeting the diesel product specifica-
tions, was carried out in July 2013.
PetroChina is the largest oil and gas producer and
distributor in China, and hence plays a dominant role
in the industry. It is not only among the companies
with the biggest sales revenue in China, but also one of
the largest oil companies in the world. By introducing
IsoTherming hydroprocessing technology, PetroChina
Changqing is able to produce low-sulphur diesel
compliant with local environmental regulations, and is
also able to decrease energy consumption and operat-
ing costs.
IsoTherming meets low-sulphur specifications
through hydrotreating or mild hydrocracking. The tech-
nology provides the hydrogen necessary for reactions
through a saturated liquid recycle stream. It eliminates
the need for a recycle gas compressor and associated
equipment, and makes the flow through the reactor a
single, liquid phase. This reduces capital costs and
lowers annual operating costs, according to DuPont,
while meeting ultra-low-sulphur specifications in motor
fuels. The hydrotreated liquid recycle stream also acts as
a heat sink, resulting in less unwanted cracking, less
coking, reduced light-ends make, reduced maintenance
and increased catalyst life.
By removing hydrogen dissolution from the reactor,
IsoTherming also removes any mass transfer limitation
from reactions, kinetically controlling the reaction rate
for faster processing. As a result, the reactor can be
sized for the hydroprocessing reactions themselves,
rather than for dissolving hydrogen in the reaction
mixture.
Currently, there are 10 commercial IsoTherming
operations in both hydrotreating and mild hydrocrack-
ing applications; 21 units have been licensed
globally. Their capacities range from 2264 b/d to 78
501 b/d (3.750 MMTPA). Feedstocks include various
mixtures of distillates and heavy gas oils, including
coker gas oil blends, 100% light cycle oil and 100%
kerosene.
www.eptq.com
13/09/2013 10:28

Design integration aids aromatics build
Saudi Aramco and Sumitomo Chemical awarded
Petrofac the $5 billion Rabigh II refining and petro-
chemical project to develop a new aromatics complex
and expand the facility to process 30 million cu ft/d of
ethane and 3 million t/y year of naphtha. These prod-
ucts provide feedstock for various high-value
petrochemical products.
Petrofac used Intergraph’s Caesar II to design 248
systems requiring stress analysis. Project deliverables
included: stress isometrics using the Isogen tool;
graphical plots; expansion joint datasheets; reports on
input, stress summary, displacement summary,
restraint summary, equipment nozzle compliance, civil
and structural loadings data; calculations for API 650
appendix P.2, flange leakage, wear pad requirements,
and trunnion loading.
For such a large-scale project involving numerous
vendors and companies working together, errors and
over-design are not uncommon as a result of different
contractors using or developing different systems. For
the Rabigh II project, Petrofac had 198 “interface
points” with other contractors. Even with this
complexity, the flow and sharing of engineering infor-
mation among the contractors was said to be smooth
and efficient because many of them use Intergraph’s
CADWorx & Analysis Solutions that interface with
design and engineering products including Caesar II.
Geotechnical investigations of the site revealed clay
at several site locations, and the settlement analysis
indicated large, long-term settlement values.
Considering these values in the compliance checks
resulted in nozzle connection overloads. This meant
that Petrofac had to achieve equipment nozzle compli-
ance on piping without special aids such as spring
supports or lateral expansion joints, and without soil
improvements. Caesar II’s tools for dynamic analysis,
API-650 nozzle flexibilities and centre of gravity calcu-
lations addressed these issues. Using built-in codes
and post-processing tools, Petrofac was able to validate
equipment nozzle loads for more than 500 nozzle
connections. It achieved this without Teflon pads and
low-friction sliding plates — specifications that are not
recommended in the prevailing desert-like conditions
at the site. These tools helped save additional
man-hours and money, and helped expedite the
schedule.
Automated valve actuation for
tank farm
A modernisation programme under way at Tupras’s
Izmit refinery in Turkey includes a retrofit project that
will deliver automated actuation and control for over
900 valves at the refinery’s tank farms. The retrofit proj-
ect involves the installation of Rotork intelligent valve
actuation and two-wire digital control technologies and
www.eptq.com
case studies copy 7.indd 3
is part of an expansion programme that also includes
the construction of new facilities on an adjacent site, for
which more than 400 IQ electric actuators are being
fitted by Técnicas Reunidas.
The four-stage project is motorising manually oper-
ated valves. Nearly 800 of the actuators will be
retrofitted on existing valves, while the balance will
consist of new actuated valve packages. Many of the
actuators will be factory fitted with intumescent fire-
proof coatings, and all will be monitored and
controlled on Pakscan two-wire digital networks.
The two-wire digital control system will enable
Rotork to extend the retrofit from valves in the field
into the control room with a continuous chain of actu-
ation and control equipment. Pakscan provides a
direct interface with host control and SCADA
systems, while simplifying the overall control
network, optimising actuator functionality and
increasing reliability.
Nearly 800 of the actuators will
be retrofitted on existing valves,
while the balance will consist of
new actuated valve packages
The retrofit is being performed by local company
Omas Teknik Pazarlama Temsilcilik, which will design
and fabricate valve adaptation, install the new actua-
tors and commission the work.
A handheld instrument and a bidirectional link will
be used for setting control parameters, commissioning
and downloading integral data loggers. This system is
used to perform all the switch setting and commission-
ing functions that previously were only achieved by
removing electrical covers.
The same instrument can be used to download data
and upload it to other IQ actuators with similar
commissioning parameters, or to download actuator
operating information from the actuator’s data logger
to provide diagnostic information for asset manage-
ment programmes.
The inclusion of a data logger enables a history of
valve activity to be generated, including the torque
profiles produced during each opening and closing.
Using Rotork’s IQ-Insight software on a PC, this data
can be compared with the valve torque signature
profile logged during the commissioning process to
identify the trend of valve operating wear or isolate
tight spots and other problems. Analysis of this data
improves asset management through fault diagnostics
and preventative maintenance.
In view of the size of the Izmit refinery site, groups
of IQ actuators in different areas will be monitored and
controlled by 20 Rotork Pakscan P3 digital bus
networks. Each network is controlled by a Pakscan P3
master station, which provides a local centre for moni-
toring and control and links the network to the site’s
SCADA system.
PTQ Q4 2013 151
13/09/2013 10:28
 Alphabetical list of advertisers

Air Liquide Global E&C Solutions IFC ITW Technologies 20 & 112
ABB Consulting 55 John Zink Company 68
Aerzener 49 Johnson Matthey 45
Air Products and Chemicals 23 KBC Advanced Technologies 2
Euro Petroleum Consultants 144 KBR Technology 15
Axens OBC Koch-Glitsch 84
BASF Corporation, Catalysts Division 24 Kurita Europe 27
Belco Clean Air Technologies 41 Linde 89
Bete Fog Nozzle 71 Linde North America 58
Bilfinger Water Technologies 125 MAN Diesel & Turbo 62
Bronswerke Heat Transfer 117 Merichem Company 138
Bryan Research & Engineering 130 Metso Automation 102
Burckhardt Compression 105 OHL Gutermuth Industrial Valves 121
Cameron Process & Compression System 128 Onis International 90
CB&I 7 Optimised Gas Treating 65
Chevron Lummus Global 9 Process Consulting Services 16 & 19
ContiTech Schlauch 119 Prognost Systems 35
Criterion Catalyst & Technologies 4 Prosernat 143
CS Combustion Solutions 97 Prosim 6
Delta Valve 67 Rentech Boiler Systems 32
DuPont Sustainable Solutions 77 Sabin Metal Corporation 31
Elliott Group 93 Saint-Gobain NorPro 132
Enersul 61 Samson 13
DigitalRefining.com IBC Spectro Analytical Instruments 109
ExxonMobil Research and Engineering Company 11 Streamlight 147
Foster Wheeler 28 Sulphur 2013 148
Gastech 2014 57 Sulzer Chemtech 52
GE Oil & Gas, Surface Pumping Systems 38 ThyssenKrupp Uhde 80
GEA Heat Exchangers 42 UOP 50
Grabner Instruments 10 UOP Callidus Technologies 122
Grace Catalysts Technologies 12 Weir Minerals Lewis Pumps 107
Hoerbiger Kompressortechnik Holding 79 Yokogawa Europe 37
HydrocarbonChina.com 141 Zeeco 98
Hydrocarbon Publishing Company 111 Zwick Armaturen 46

For more information on these advertisers, go to www.ptqenquiry.com

152 PTQ Q4 2013 www.eptq.com

ad index copy.indd 1 13/09/2013 17:15

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