ptq

Q4 2018

PETROLEUM TECHNOLOGY QUARTERLY

REFINING
GAS PROCESSING
PETROCHEMICALS

SPECIAL FEATURES

CORROSION & FOULING CONTROL

GAS PROCESSING

cover q4.indd 1 15/09/2018 07:34

 Your operations.

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 ULTIMet™ Unlocks Honeywell UOP’s high-activity ULTIMet™
hydrotreating catalyst breaks new ground by

Profits from efficiently processing opportunity crudes. You’ll

be able to process more difficult feeds, go longer
Challenging Feeds between catalyst change-outs, and operate at
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UOPUltimet
uop ULTIMet Ad_297x210mm.indd
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 ptq
PETROLEUM TECHNOLOGY QUARTERLY
5 Will they, won’t they?
Chris Cunningham

7 ptq&a

19 Hydrofluoric acid alkylation conversion and expansion

Shane Presley and Jason Nunez
DuPont Clean Technologies

29 Dynamic simulation to estimate tower relief

Harry Z Ha and Ben Leviton
Q4 (Oct, Nov, Dec) 2018 Fluor Canada
www.eptq.com
37 Advanced catalyst characterisation for improved hydrocracking performance
Maureen L Bricker, Sarika Goel, Marjorie Miranda and Tony Vranjes
Honeywell UOP

45 Corrosion management strategies for opportunity crudes

Kjell Wold and Tim Olsen
Emerson Automation Solutions

55 Mitigating overhead corrosion

Brandon J H Payne, Keyurkumar Patel, Collin W Cross, Matthew G Collins
and Pablo A Grieco
SUEZ Water Technologies & Solutions

61 Resisting metal dusting corrosion

Ramesh Venkat Tubacex

63 Front end filtering of unconventional oil

Timothy Houser, Stephen Gibson and Victor Scalco
General Atomics Electromagnetic Systems

69 Predictive analytics in corrosion management

Pierre Constantineau and Sridhar Srinivasan
Honeywell Process Solutions

79 Savings using divided wall columns

Prafull Patidar and Ajay Gupta
Reliance Industries

87 Feed conditioning technologies for gas processing plants

Scott Northrop ExxonMobil Upstream Research
David B Engel Nexo Solutions, Exion Systems Division

99 New insights into Claus waste heat boilers

Nathan A Hatcher, Clayton E Jones, Simon A Weiland, Steven M Fulk
and Matthew D Bailey
Optimized Gas Treating

107 Liquefaction technology selection for offshore FLNG projects

Saeid Mokhatab Gas Processing Consultant

113 New catalytic systems for converting hydrocarbons

Massimiliano Delferro
Argonne National Laboratory

119 Artificial intelligence for refiners

Jane Ren Atomiton

123 Technology in Action

Cover
Refining NZ’s Marsden Point at Whangarei is New Zealand’s only petroleum refinery

Photo: Refining NZ

©2018. 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 and its supplements the publisher cannot be held
responsible for any statements, opinions or views or for any inaccuracies.

ed com copy 19.indd 1 15/09/2018 07:28

 A CATALYST
FOR PROFITABILITY

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REAL PERFORMANCE.
WHERE IT COUNTS.

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catalysts, Albemarle AFX delivers the highest possible
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 ptqPETROLEUM TECHNOLOGY QUARTERLY
Vol 23 No 5
Q4 (Oct, Nov, Dec) 2018
Editor
Chris Cunningham
editor@petroleumtechnology.com
Production Editor
Rachel Storry
production@petroleumtechnology.com
Graphics Editor
Rob Fris
graphics@petroleumtechnology.com
Editorial
tel +44 844 5888 773
fax +44 844 5888 667
Business Development Director
Paul Mason
sales@petroleumtechnology.com
Advertising Sales Office
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Publisher
Nic Allen
publisher@petroleumtechnology.com
Circulation
Fran Havard
circulation@petroleumtechnology.com
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Hopesay, Craven Arms SY7 8HD, UK
tel +44 844 5888 776
fax +44 844 5888 667
Register to receive your regular copy of
PTQ at www.eptq.com/register
PTQ (Petroleum Technology Quarterly) (ISSN
No: 1632-363X, USPS No: 014-781) is published
quarterly plus annual Catalysis edition by Crambeth
Allen Publishing Ltd and is distributed in the US
by SP/Asendia, 17B South Middlesex Avenue,
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Back numbers available from the Publisher
at $30 per copy inc postage.
ed com copy 19.indd 2
Will they,
won’t they?
T
he public sell-off of a small but massively valuable stake in Saudi Aramco
hit a state of confusion as the northern summer approached its end. At
the outset, news agency reports were full of cancellation stories about
Aramco’s planned initial public offering (IPO). The very next day, the official
Saudi position from the ministry of energy dismissed the reports and insisted
that plans for selling off a stake of the oil major were very much on track and
it was all a matter of finding the right time, if a right time exists. (And if it
happens, the IPO is expected to cover just 5% of Saudi stock, but that is 5%
of a company valued somewhere between $1 trillion and $2 trillion and still
represents the biggest flotation ever, anywhere.)
At the moment, the big-money negotiations in Saudi Arabia have switched
direction (more of that in a moment). Also, the world of oil power plays has
changed considerably since the IPO was first mooted. At the time of that first
announcement, the price of a barrel of oil had reached its nadir in the $30s.
The much-vaunted US shale industry was having a bad year with doubts cast
over its future as a significant future energy source. That sunken price of crude
seemed to make the timing of the sell-off announcement less than auspicious,
but it is worth noting that the Saudi budget was in deficit at the time; it was
nonetheless seen as a mark of the nation’s developing, more liberal outlook,
driven by the crown prince; and Saudi Arabia was still, in the petroleum poli-
tics of supply-demand, the king of swing.
Times change. Shale may still have its naysayers, but its output – both oil
and gas – remains on an upward trajectory and so does its impact on the
wider world. It is a growing resource for Europe’s refiners, for instance, and as
a makeweight for China’s gas industry. The latter deal – crucial to US expan-
sion plans for LNG exports – highlights some insecurities about shale’s devel-
opment; the arrangement may be subject to the outcome of US-Sino confron-
tation over tariffs, and to a further supply deal for LNG developing between
China and Qatar.
Back to that cancellation, or otherwise, of the Saudi IPO: rather than mone-
tise its own holdings, Aramco is first looking to spend big internally by acquir-
ing a stake in Saudi Basic Industries (SABIC), one of the world’s largest petro-
chemicals companies. The deal would be for a reported 70% stake in SABIC at
a valuation of $70 billion. The stake is currently in the hands of Saudi Arabia’s
Public Investment Fund and would amount to shuffling cash between state
holdings. However, Aramco is looking to international banks to source funds
for the deal; this amounts to the same sort of outcome as the IPO.
The buy-out would, more significantly, represent a further step in Aramco’s
progression from crude oil supplier-in-chief to the world to a leading exporter
of value-added petroleum products and follows the company’s construction
of a fleet of megarefineries geared chiefly to production of finished fuels.
Meanwhile, export supplies of crude from the US move towards centre
stage.
CHRIS CUNNINGHAM
PTQ Q4 2018 5
13/09/2018 16:54
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 ptq&a
Q Is there potential for significant savings in running costs
by using dividing wall column technology for BTX separation?
A Joseph C Gentry, Sr Vice President Licensing and
Technology, GTC Technology US, jgentry@gtctech.com
Traditional designs for BTX separation use a sequence
of towers separating individual components. This
entails a thermodynamic inefficiency on account of
re-mixing separated components within the first tower.
ividing wall column ( C) technology uses a baffle
to create a pre-fractionation zone to avoid the back mix-
ing. Compared to a traditional two column system for
separating B/T and T/X, the DWC design is done in
one column. For a grassroots application of BTX puri-
fication, there will be capex savings of 25-30% and opex
savings of 25-30%. GT- C technology can simultane-
ously produce petrochemical grade benzene, toluene,
and xylenes in a single column; or high purity toluene,
xylenes, and C9+ in a single column. In an aromatics
complex, DWC technology is also applicable for refor-
mate splitting and naphtha splitting and for the stabi-
liser columns of transalkylation and isomerisation units.
Q We have been using boiler feed water as make-up wash
water in our desalter. Could this lead to downstream corrosion
issues?
A Francesco Ragone, Product Manager, Process Development
& Marketing, CHIMEC, fragone@chimec.it
The desalting stage is crucial for the whole process
downstream. Anything that enters the desalter but
should not can jeopardise one or more processes down-
stream. At the same time, whatever is expected to be
removed but is not will create some problems in the
next stages.
The main scope of the desalter is to ‘wash’ the crude
oil, hence remove, as much as possible, the salts present
in the crude, diluting what is dissolved in the water dis-
persed in the crude oil.
For this reason, working with the best quality wash
water available is always the best choice; of course, the
economic impact must be evaluated as well.
Coming to the question, it depends on what it is
meant by boiler feed water (BF ). By definition, BF
is a demineralised water, often obtained with several
stages of purification of sediments, anions and cations.
After this, it must be treated to be used in steam pro-
duction to prevent corrosion, scaling and foaming,
hence it is very important to know at which stage it is
used as wash water for the desalting stage: after deaer-
ation, with and without oxygen scavenger, with amines
and eventually phosphates already added to feed some
types of boilers.
In such cases, the kind of phosphates eventually
used must be evaluated to foresee the possible forma-
www.eptq.com
Q&A copy 33.indd 1
tion of insoluble calcium phosphates in the hot preheat
exchangers and the amines used must be considered
first in terms of oil water repartition, then in terms of
salts deposition in the overhead system, together with
the other amine sources.
As a rule of thumb, a good quality wash water should
match the following ranges:
• 5.5 pH 7.5: in this pH range the corrosion rate is
generally the lowest possible, considering both acidic
and sulphide corrosion, and the repartition of several
species between the oil and water phases
• NH3 10 ppmw, to avoid the formation of the ammo-
nia loop
• Total hardness as CaCO3 50 ppmw, to avoid precip-
itation of carbonates, in both the cold and hot train pre-
heat exchanger
• Chlorides 2000 ppmw, to reach the highest level of
washing of dispersed water drops
• Sulphates 200 ppmw
• Oxygen 1 ppmw, possibly even lower than, 0.2
ppmw, otherwise some O2 related corrosion can be
expected anywhere in the plant, especially in the
overhead.
Last but not least, it is important to evaluate eventual
incompatibilities between the wash water and the pro-
duced water arriving with the inlet crude.
Chimec relies upon several simulation software suites
that allow the closest possible simulation of real sys-
tems, considering oil/water repartition as well as the
ions’ water chemistries.
Q We are looking for higher conversion levels from our
FCC bottoms. Is there an effective catalyst additive route to
achieving this?
A Paul Diddams, Global FCC Additives Market Manager,
Johnson Matthey, Paul.Diddams@Matthey.com
To answer this, one first must know if the bottoms
product has the potential to be cracked or not. Bottoms
(typically 350 C boiling range) is highly aromatic, and
aromatic molecules are too stable to crack under FCC
conditions. So a key question is how much of the bot-
toms range material is non-aromatic (naphthenic, paraf-
finic, olefinic)
A quick rule of thumb can be applied to estimate
the approximate wt% aromatics in the bottoms, and
all you need to know is the bottoms density (DB). Two
basic assumptions are required: (1) the density (DA)
the bottoms would be if it was 100% aromatic, and (2)
the density (DP) the bottoms would have if it was 100%
non-aromatic. For bottoms with an end point of 500-
550 C you can use DA 1.15 and DP 0. 5 for estima-
tion purposes.
Now we are all set to estimate the wt% aromatics
assuming they are linear with bottoms density:
PTQ Q4 2018 7
13/09/2018 16:56

1.50
Matrix
Zeolite
1.25
Kinetic coke
1.00
0.75
0.50
0.25
0
0 1 2 3 4 5
Catalyst contact time
Figure 1 Kinetic coke on catalyst vs catalyst contact time
Aromatics (wt%) = 100 x ( DB – DP ) / ( DA – DP ) or, if
you prefer, ( DB – DP ) x 100/0.3
Example: bottoms density DB = 1.05
Aromatics (wt%) = 100 x ( 1.05 – 0.85 ) / ( 1.15 – 0.85 ) =
67%
And therefore by difference the non-aromatics (wt%)
100 – 67 = 33%
Which means with a bottoms density of 1.05 you have
a maximum potential reduction of the bottoms of 33%
(relative), so if your base case bottoms yield is 10 wt%
then you could at most crack 3.3% of it to lighter prod-
ucts, the remaining 6.7% cannot be cracked. Clearly
if the bottoms density is lower the potential bottoms
reduction increases.
Okay, so now we have a rule of thumb estimate of
how much bottoms can be cracked, so how do we do it?
Conversion of FCC bottoms requires acid sites in
pores big enough to accommodate the bottoms mole-
cules (mesopores), that is ‘matrix’ sites. Increasing the
proportion of matrix sites in the catalyst system (either
in the main catalyst or by using bottoms cracking addi-
tives) will increase the potential to crack these bottoms
molecules.
You can track the matrix activity in the Ecat by mon-
itoring the zeolite to matrix surface area ratio (Z/M) –
the aim here is to decrease the Z/M to increase matrix
cracking. Additives with high mesopores surface area
are rich in these matrix cracking sites – so the additive
of choice would not contain a zeolite (which would
serve to increase the M). One such additive is BCA-
105 supplied by Johnson Matthey.
A further consideration is coke make. Matrix sites
have historically been associated with increasing delta
coke. With the proliferation of advanced riser termi-
nation systems that have led to short catalyst con-
tact times this is no longer true. Delta coke (or coke
build-up on the catalyst) follows a kinetic equation of
the form kta as described by Voohries many years ago:
t is the catalyst contact tome, K is the delta coke after
one second contact time and a is an exponential factor
describing the rate of kinetic coke build-up.
It is important to note that kzeolite > kmatrix and azeolite
< amatrix therefore zeolite acid sites lead to high initial
8 PTQ Q4 2018
Q&A copy 33.indd 2
coke build-up over a short time, then the coke build-up
slows down and levels off, whereas matrix sites lead to
lower initial coke build-up than do eolites, but contin-
ues to build-up at longer times (see Figure 1). The net
result is that at very short contact times (<3 seconds)
matrix sites make less coke than zeolite sites, while at
longer contact times matrix sites go on to make more
coke than eolite sites. The cross-over point is typically
somewhere in the region of 2- seconds. Consequently,
using a bottoms cracking additive that contains a zeo-
lite is less effective due to rapid initial build-up of coke
6 7 8 by the zeolite that spills over and blocks matrix sites;
this is particularly important in the lower region of the
riser (shortest contact time range) where most of the
bottoms conversion in achieved.
It is also important to note that in FCC units with
advanced riser termination systems (operating with
short contact times) use of bottoms cracking additives
does not increase kinetic delta coke.
How much of the potential bottoms reduction can
be achieved using an additive? In principle if you add
enough matrix sites you should be able to get it all, but
the real world is never quite that simple. In practice,
you can typically get somewhere between 50- 5% of the
potential bottoms reduction with a bottoms cracking
additive.
A Stefano Riva, Technical Services Manager, BASF Refining
Catalysts, stefano.riva@basf.com
The question is a bit generic as it does not clearly distin-
guish between a desire to increase conversion through
bottoms cracking or just to move bottoms to distillate
at constant conversion. Depending on the constraints
against which the unit is running, different strategies
can be employed, particularly around optimisation
of the FCC operating conditions. This response will
assume the most challenging scenario where the unit is
fully optimised against at least the air blower and the
wet gas compressor limits. Catalytically speaking, the
answer is different depending on which of the above
two objectives the refinery aims for. For FCC units that
want to move slurry to less than 221 C ( 30 F) boiling
range, BASF would recommend adding a maximum
conversion co-catalyst. Unlike typical bottoms cracking
additives based purely on high activity matrix alumina,
the co-catalyst provides high activity so not only does
it not dilute the fresh catalyst make-up, it actually dis-
places at least the same amount by proportion, becom-
ing a very cost effective way to bring low value bottoms
all the way up to gasoline and LPG. A co-catalyst with
high zeolite content enables coke selective cracking
of heavy molecules on the external surface of the zeo-
lite crystals to middle distillates, while the high zeolite
surface area inside the crystals easily converts distil-
lates to lighter products. For units that desire to destroy
bottoms but not increase conversion, a low zeolite to
matrix ( M) co-catalyst deeply cracks FCC bottoms
to distillate, with a moderate zeolite content to avoid
over-cracking to lighter products. Both types of co-cata-
lysts have been used in several commercial applications
and remain the fastest way not only to crack bottoms
www.eptq.com
13/09/2018 16:56
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21:30
 Process Notes
Condensate is Crude
Ultra-light crudes and condensates are here to stay.
These streams have flooded the market in recent
years, and many of them are deeply discounted against
reference crudes. Refiners have been processing
increasing percentages of this light material through
their Crude Distillation Units (CDUs) up against unit
naphtha handling limits. On the surface, processing
condensate and other ultra-light crudes with high API
gravity and low sulfur should be easy. In reality, many
refiners have experienced significant challenges,
some of which are unique to ultra-light crudes and
condensate.
Although their bulk properties signal that these crudes
should be easy to process, new recovery techniques
tend to leave undesirable compounds in the crudes
that can adversely affect refinery CDUs or Condensate
Splitters. Some of the bad actors are:
• High melt point waxes / high paraffin content
• Tramp amines from production H2S scavengers
• Filterable solids
• Tramp phosphorous compounds
Severe crude column tray fouling
3400 Bissonnet St.
Suite 130
Houston, TX 77005, USA
pcs condensate.indd 1
Approach “easy” crudes with caution
These undesirable compounds are the source of
operating and reliability problems in CDUs and
Condensate Splitters worldwide, and the onset and
severity of certain problems can often be traced
back to the introduction of new ultra-light crudes and
condensates.
These supposedly “easy” crudes have been linked the
following problems:
• Fouling in the cold preheat train
• Poor desalter performance
• Fouling in the warm and hot preheat trains
• Crude heater fouling and hot spots
• Accelerated overhead system corrosion
• Salting in the top of the crude column
• Plugging of kerosene section trays and exchangers
• Plugging of stripping trays
Despite the impression that new ultra-light crudes
and condensates should all be easy to run, they are
not. Condensates and ultra-light crudes are crudes,
meaning that many of them can be difficult to process
and can present unique refining challenges.
Process Consulting Services, Inc. has experience with
these crudes and has addressed all of the problems
above through process and equipment design features.
Contact us today to maximize profitability and minimize
headaches while processing these discounted crudes.
+1 (713) 665-7046
info@revamps.com
www.revamps.com
13/09/2018 06:05
 but also to quickly steer the selectivities of any incum-
bent base FCC catalyst towards maximum conversion
or maximum distillates. Co-catalysts combine the flexi-
bility of the typical additives addition concept with the
strength of a catalyst change to keep the FCC unit up to
speed with quickly changing market economics.
A Francesco Ragone, PhD, Product Manager, Process
Development & Marketing, CHIMEC, fragone@chimec.it
FCC slurry properties and composition are greatly
dependent upon the feedstock processed in the unit, the
type of catalyst used, and the severity of the cracking
operation.
Fouling of the bottoms slurry loop is generally a com-
bination of inorganic and organic causes. The inor-
ganic components, apart from corrosion byproducts
and eventually salts when residues are processed, are
the catalyst fines: they are present in the process stream,
usually because the cyclones are not performing effi-
ciently. The inorganic fouling precursors can accumu-
late either in low velocity zones or become entrapped
in the resinous, organic deposit or they can even act as
nucleation sites for growth of organic fouling.
Organic fouling is usually formed by polymerisation
reactions, asphaltenes and polynuclear aromatics (PNA)
precipitation: being a loop, it is possible to speak about
aging of the slurry, with the reaction triggered espe-
cially by oxygen intake or metals present in the circuit.
A combination of attractive forces causes aggregation
between polymers. When the aggregation is allowed to
proceed, a highly viscous fraction is formed in the oil.
As this fraction contacts the cooler heat exchange sur-
faces, the viscosity increases such that this material
becomes tar-like and adheres to the surface. As viscos-
ity increases, fouling tendency generally increases as
well. High viscosity fluids tend to entrain more particu-
late matter. They also tend to produce less turbulence at
surface boundaries, resulting in lower heat dissipation
and increased coking rates at the heated surface, lead-
ing to:
• educed unit flow rate
• Reduced conversion
• Lower main fractionator bottom T, hence lower LCO
yield
• Reduced HEX duty, hence lower HP steam
production
• Shorter filters run length.
Some process operation may mitigate fouling devel-
opment and deposition, such as increasing the feed/cat
contact, contain catalyst carry-over, and maintain the
proper velocity in the slurry system to avoid particle
sedimentation.
The use of a proper antifouling program, together
with high level technical assistance, leads to great flexi-
bility since the fouling tendency can be controlled just
by adjusting the dosing rate of the chemical(s) and with
close monitoring of the unit in terms of fouling develop-
ment and simulation of the velocities in the slurry circuit.
Chimec’s antifouling portfolio for FCC slurry loops
accounts for the following classes of actives:
• Dispersing agents, which inhibit the growth of inor-
www.eptq.com
Q&A copy 33.indd 3
ganic and/or organic sediment, by neutralising their
mutual attraction, thus preventing sediments settling
down in the areas characterised by process stream low
velocity
• Stabilisers and antioxidants, which bind with free
radicals, thus stopping the di-olefins induced polymer
chemical chain reaction.
The chemical to be used has to be selected according
to operative unit parameters, the weight average char-
acteristics of the feedstocks processed, and possibly the
analyses of fouling collected during a recent opening of
the heat exchangers, to better tune the chemical treat-
ment and eliminate the unit bottleneck to achieve the
following results:
• Prevent agglomeration of organic particles present in
the slurry oil
• Improve the heat recovery in the slurry loop system
• Increase the filtering system cycle length.
Another kind of chemical treatment may be use-
ful to match the sediments content specification of the
slurry oil sold as fuel oil, especially during an upset in
the cyclone system: CHIMEC settling aid. This chemical
injection improves and accelerates (from weeks to days)
the sedimentation process.
Q We are expanding our alkylation capacity which will lead
to a heavy extra requirement for sulphuric acid regeneration.
We use a merchant operation at present but might in-house
regeneration have better economics?
A Steve Patterson, Process Engineer – MECS Technology,
DuPont Clean Technologies, steven.p.patterson@dupont.com
As the demand for high quality alkylate continues to
increase globally, refiners often find themselves asking
the same question. As alkylate capacities continually
increase to satiate this need, the merchant facility model
becomes less economically favourable as the associ-
ated logistical, infrastructure, utility, and acid process-
ing costs begin to balloon. At a certain point, the scale
tips in favour of the fully dedicated, highly flexible, and
always available on-site sulphuric acid regeneration
(SA ) plant. Additionally, refiners find value in gaining
the ability to process all sulphur-bearing gases, generate
additional HP steam, and further reduce their environ-
mental footprint.
The MECS Sulphuric Acid egeneration Technology
provided by DuPont Clean Technologies recognises
the increasing trend of on-site acid regeneration. To aid
refiners looking to shift away from the merchant model,
MECS technology experts have further improved
the value of on-site SA . The introduction of MECS
Advanced SAR substantially reduces both the capi-
tal investment and long term operating costs to tip the
scale sooner, making the choice of on-site acid regenera-
tion an easier one to make.
MECS Advanced SA lets refiners easily expand
their current on-site double absorption SAR capac-
ity by allowing them to retain their existing main gas
blower, since pressure drop savings achieved with
MECS Advanced SA avoids the high cost of blower
PTQ Q4 2018 11
13/09/2018 16:56
 P r o ce ss Not e s
Avoid Fired Heater Coking
For many refiners, heater coking in Crude and Vacuum
Distillation Units (CDU/VDUs) is a common occurrence.
Many units around the world are shut down every two
years, every year, or even every six months to deal
with chronic heater coking. However, with the right
design features driven by a solid understanding of
heater coking mechanisms, fired heater run length can
be extended beyond five years, even with relatively
challenging crudes.
The two primary drivers of heater tube coking in CDU/
VDU services are oil film temperature and residence
time. Secondary factors such as crude coking tendency,
solids content, and blend instability can further
accelerate heater tube coking. So, which heater design
parameters will maximize heater run length and avoid
shutdowns for high heater tube metal temperature or
high heater pass pressure drop?
MASS FLUX IS KING
Mass flux (lb/s/ft2 or kg/s/m2) is found by dividing the
mass flow through a heater tube by the tube’s cross-
sectional area. High mass flux begets high velocity and
suppresses coking in several important ways. First,
high mass flux means that the fluid moves through
the tube faster, minimizing residence time. Second,
high velocity results in high heat transfer coefficient,
which minimizes internal oil film temperature. Finally,
high mass flux creates high wall shear inside the tube,
minimizing build-up of solids or asphaltenes.
3400 Bissonnet St.
Suite 130
Houston, TX 77005, USA
pcs heater coking.indd 1
Heater coking is not inevitable
HEAT FLUX CAN SURPRISE
Heat flux (BTU/hr/ft2 or kcal/hr/m2) measures the
amount of heat absorbed through a given outside
surface area of a heater tube. High heat flux raises tube
metal temperature and causes high oil film temperature
inside the tube. Popular fired heater design programs
use a well-stirred firebox model and calculate peak
heat flux by applying a simple multiplier to the average
heat flux. In reality, heater design parameters such as
firebox height/width ratio, burner type, burner sizing,
burner placement, and air/flue gas flow patterns can
result in actual peak heat fluxes that are much higher
than the “calculated” peak heat flux on the heater
datasheet. Localized areas with very high heat flux will
coke and suffer from high tube metal temperature.
Of course there are many other variables that must
be considered, such as pass arrangement, vertical or
horizontal tubes, cylindrical or box or cabin, coil steam,
etc. Problems stemming from blend instability are
becoming more common as refiners are increasingly
mixing light shale crudes with heavy crudes. As the
crude begins to vaporize, asphaltenes can precipitate
out of unstable mixtures and coat the heater tubes,
forming coke and creating hot spots.
Even with challenging crudes, refiners have achieved
Crude Heater and Vacuum Heater run length goals
through careful design and respect for the basics of
coking. Contact Process Consulting Services, Inc. to
learn more.
+1 (713) 665-7046
info@revamps.com
www.revamps.com
13/09/2018 06:08

MECS SAR
MECS Advanced SAR
High concentration acid,
Fewer unit ops.
99.2%
Best in class emissions Best in class emissions
High onstream time High concentration acid,
99.2%
High onstream time
Better opex
Lower capex
Figure 1 Performance comparison of MECS SAR and MECS
Advanced SAR
replacement. The process allows the refiner to exceed
the performance of the more modern double absorption
process while simultaneously offering the reliability
and simplicity of a single absorption flow scheme. It is
precisely this transformation back to a single absorption
process that maintains a lower capital investment with-
out sacrificing performance (see Figure 1 ).
MECS Advanced SAR is made possible not by using
unreliable cutting edge technology but rather by a
novel combination of existing proven technologies and
incremental improvements to the gas cleaning sys-
tem. A robust selective SO2 regeneration unit, known
as the MECS Solv technology, effectively deletes the
final absorbing tower (and the associated pump and
acid cooler), two gas-gas heat exchangers, and up to
two converter passes from the process, resulting in an
overall improvement in utility balance and capital cost
(see Figure 2). Nearly 100% removal of SO2 is possible
in the SolvR absorbing column by utilising a low cost
and globally available solvent selective to SO2. Solvent
losses to the stack are negligible thanks to its charac-
teristically low vapour pressure. Furthermore, there is
nearly zero oxidative degradation of the solvent – less
than 1% of the solvent is oxidised in normal operations.
The non-toxic sodium sulphate salts are easily removed
through anion exchange and disposable by sewer in
most cases. Low grade steam is used to strip the rich
solvent of SO2 in the stripping column before it is recy-
cled back to the process for conversion. Reasonable
operating temperature and stability allow for FRP and
low grade stainless steels to be used as the material of
construction for the two columns to minimise cost.
In short, MECS Advanced SAR is a value proposition
that is helping refiners make the shift to dedicated, reli-
able, on-site acid regeneration.
Q What is the potential for operational and maintenance
savings by installing an integrated refinery information system?
A Rainer Rakoczy, Global Product Manager, Business Unit
Catalysts, Clariant, Rainer.rakoczy@clariant.com
Today’s refinery operation is a toolbox of well estab-
lished refinery processes, well understood analytical
methods, fully digitalised electronic process control,
and highly tailored economics optimisation calculation
tools. ith this set-up, refiners can operate their assets
with optimum margins and have high flexibility to fol-
low the changing properties of the crude oil available
on the market. An additional, deeper integrated infor-
mation system processing operation history of each sin-
gle device will help to indicate or forecast operational
upsets of these devices, enabling preventative measures
prior to any breakdown and reducing conflicting process
flows drastically. In addition to numerical computational
methods, recent developments in computational neuro-

Primary Dynawave
reverse jet scrubber Dynawave gas
cooling tower
scrubber

Decomposition Waste heat boiler

furnace
Spent acid
Acid gas
Fuel gas

Superheater

Main
gas blower
Air Absorbing
tower
Cold
Monplex
Hot Drying
Monplex tower

Steam SolvR Converter

Economiser Superheater

Figure 2 MECS Advanced SAR process scheme

www.eptq.com PTQ Q4 2018 13

Q&A copy 33.indd 4 15/09/2018 06:26

 Dewax with maximum yield

Challenged by
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properties?
TK-930 D-wax™ is Topsoe’s new isomerization dewaxing catalyst,
specifically designed for improvement of cold flow properties
with a minimal yield loss.

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haldor.indd 1 13/09/2018 10:48

 science and chaos theory should be part of the develop-
ment of such an integrated information system. Another
important part will be the contribution of catalyst and
process technology suppliers helping to optimise oper-
ational parameter set-up to improve results and to help
the determination of the cycle life times of the catalyst.
Q The cold flow properties of our diesel hydrotreater
product have been sub-spec recently. Is this likely to be a
downstream result of using tight oil feed? And what is the best
approach to improving those cold flow properties without
changing the crude feed?
A Stefano Cacciatori, Product Manager, Fuel Additives
Development & Marketing, CHIMEC, scacciatori@chimec.it
Especially in North America, tight oils – Bakken,
Permian, Eagle Ford and so on – became commercially
available on the market from the end of the first decade
of this century and are now spreading into the crude
assays of European refineries too. Such types of feeds
are challenging the refining industry since, among other
possible related issues, their quality rapidly changes
and they are rich in light cuts, which most of the time
are paraffinic. This clearly is reflected in the quality of
the final products, such as low octane number gasolines
and paraffinic gasoils.
Besides the opportunities given by changing the
crudes slate or by blending different cuts streams with
various cold flow properties, the latter can be improved
thanks to the adoption of middle distillate flow improv-
ers (M FI). These types of chemical additives are based
on low molecular weight polymers in organic solvents
which have the ability to co-crystallise with the n-par-
affins contained in gasoil, influencing the crystallisation
process and improving the low temperature operability
of the petroleum derivate in analysis.
M FIs typically have a nucleation and dispersant
effect. The two actions combined result in a change of
si e, shape and conformation of wax crystals.
ifferent chemical compounds are used as wax crys-
tal modifiers and it is always suggested to perform a
specific product selection to identify the most suitable
and effective chemical for a given gasoil.
For their application to be successful in enhancing the
cold filter plugging point (CFPP) and pour point (PP),
there is a need to follow specific rules. As the additive
improves the operability not by reacting chemically
with paraffins but by modifying the crystallisation pro-
cess, the best performance may be achieved only if the
chemical is injected before the crystallisation process
starts and thus the first crystal appears.
For gasoil, this means adding the chemical at a tem-
perature which is at least 10 C higher than the cloud
point temperature.
A Rainer Rakoczy, Global Product Manager, Business Unit
Catalysts, Clariant, Rainer.rakoczy@clariant.com
Specification of diesel fuel is quite sophisticated, espe-
cially when it comes to cold flow properties. Handling
tight oil crudes or opportunity crudes, refiners are fac-
www.eptq.com
Q&A copy 33.indd 5
ing deviations in cold flow properties in their hydro-
treating products. Clariant is in a position to supply a
fitting solution to overcome this issue giving high flex-
ibility in feedstock choice to the client. As a first step,
feed blending and cutting in combination with an
appropriate application of cold flow improving addi-
tives such as odiflow may help. As a second step,
application of a small dewaxing catalyst layer from the
Hydex series in the existing diesel hydrotreater will
help to overcome issues with diesel cold flow properties
and beyond, such as cetane index and product colour.
Q What is non-intrusive corrosion monitoring and how
could it benefit us?
A Jake Davies Global Marketing Director, Jake.Davies@
Emerson.com and Ivan Stubelj, Product Manager, Emerson
Automation Solutions
Non-intrusive corrosion and erosion monitoring is a
wide group of analysis methods which are based on
non-destructive testing techniques, that help hydrocar-
bon operators (upstream, midstream and downstream)
to quantify, either directly or indirectly, the metal loss
rate in process piping, pipelines, and vessels without
needing to modify the monitored structure or access
the transported fluid. It should be noted that intru-
sive weight loss coupons and electrical resistance (E )
probes provide additional insight for a more compre-
hensive corrosion mitigation programme.
Non-intrusive corrosion and erosion monitoring,
enhanced by wireless and battery powered features,
fosters information driven decisions by enabling per-
manent continuous monitoring in several locations.
(Corrosion can happen anywhere, so having additional
monitoring locations enables more visibility into poten-
tial asset integrity issues.) ireless corrosion moni-
toring products are not only cost effective and easy to
implement, they are supported and fully compliant
with the IEC 25 1 ( irelessHA T) standard. These
types of technologies play a fundamental role in the
current hydrocarbon industry’s digital transformation,
constantly supplying data historians, avoiding sending
people to ha ardous areas, and increased asset perfor-
mance through monitoring (ability to see corrosion and
make appropriate changes before problems escalate).
There are various non-intrusive corrosion erosion
technologies for use depending on the application:
• Ultrasonic wall thickness monitoring
• Field signature method (FSM) area monitoring
• Sand acoustic monitoring.
Ultrasonic wall thickness monitoring
Permanently installed, ultrasonic wireless wall thick-
ness monitoring sensors are ideal for corrosion mon-
itoring in several locations. The installation cost of
ultrasonic sensors is low because they are non-intrusive
and can therefore be mounted anywhere. ireless data
retrieval enables cable-free installation, further reducing
installation cost and removing any ongoing operating
costs. The sensor power packs are designed to last until
PTQ Q4 2018 15
13/09/2018 16:57
omparison of pre- andthe
post-revamp results
next plant turnaround, typically up to 10 years, so Sand acoustic monitoring
no maintenance is required between turnarounds. Pulling too much sand from the reservoir weakens the
Pre-revamp Post-revamp Results/comments
, t/h 147
This
182
simplicity of installation makes ultrasonic sen-
Feed rate increased by 124%
structural integrity and can ultimately result in a col-
0.26 sors 0.25
ideal for use in remote locations which are only lapse of the formation, reducing or killing off the abil-
125 116
accessible Reduction
during in stripper bottomTo
turnarounds. temperature
protectreduced
the ultra- ity to produce from the nearby area. Uncontrolled sand
reboiler duty
niser feed, % 0.132
sonic 0.05
electronics from heat, the sensor uses stain- and fines migration can also impair the permeability
164 less 170
steel waveguides
Fouled reboilerto keep
tubes limitedthe electronics safely
temperature of reservoir rock, reducing the natural productivity of
9.2 away 13.6from hot metal
Reboiler surfaces up to 00 C (1100 F).
duty debottlenecked the formation. eal time sand measurements provide
Advanced processing software makes use of previous greater insight into the performance of sand control
recorded ultrasonic waveforms to improve the resil- techniques and asset integrity, supporting a data driven
ience of the measurement when the internal metal sur- sand management strategy.
er at i tem- Reference face morphology is very rough, which is a situation The ability to establish sand production profiles
s ell side Kister H Z, Component trapping in distillation towers: causes,
e 1where normal
and cures,ultrasonic wall thickness measurements during well testing and determining maximum sand
ited due to t is symptoms
break down.
CEP, Aug 2004.
free rate (MSF ) and or maximum allowable sand free
f t e debutan- J Rajesh is Vice-President Process with Essar Oil Limited India. He has rate (MAS ), are important parameters when decid-
cleaned in t e over 20signature
Field years of experience
methodin –refinery operations and process and holds
area monitoring ing your production and sand management strategy.
a bachelor’s degree in chemical engineering from Annamalai University,
In critical locations, getting a deeper insight into cor- Operator insight and confidence are key in understand-
India.
rosion in a large area can provide valuable insight into ing maximum acceptable sand rate production through
Pawan Gupta is Deputy General Manager with Essar Oil Limited India.
understanding
He has over 12 years of asset health.
experience Fielddesign
in process signature method
and simulation the reservoir life cycle, ensuring maximum return on
and
n t e se - (FSM) measures the metal loss trend within a pre-
reservoir and asset. Acoustic sand monitor’s measure-
holds a bachelor’s degree in chemical engineering from MJP Rohilkhand
ed si nificantly defined India.
area and quantifies general and localised cor- ment principle is based on the noise that sand generates
University,
s a result t e
Rrosion.
Madhavan This allows
is General pipeline
Manager Processoperators and refineries
with Koch Chemical to
when it impacts the pipe wall, which is processed by
Technology
d recei er boot optimise
Group their Limited
India Private crude infeedstock, chemical
the Koch-Glitsch division.inhibitor pro-
He has over algorithm.
20
and intermit- years
Figureof2experience
gramme, (A)and
Gamma in mass
their transfershowing
scanintegrity
results technology
assessment
goodandliquid
holds an M. Tech. due to uniform response (B) Gamma scan results showing liquid mal-
programmes.
distribution
e corres ond- degree in chemical
distribution
The measurementsince engineering from
thereprinciple,
was no Indian
uniform
which Institute
response
is basedofamong the scanlines A Berthold Otzisk, Kurita Europe, berthold.otzisk@kurita.eu
Technology.
on electrical
a roximately Sandeep Yadav is a Senior Manager Process
potential drop, measures voltages at multiple sectionsEngineering with Koch Corrosion coupons and electrical resistance probes
ure of t e stri - Chemical
commonly Technology
on the pipe referred Group India
or vessel,togeneratingPrivate Limited
as a grida scan. in the Koch-Glitsch
When image
topography gamma of radiation through
(for instance, wire the
looptower must
probes, be kept
flush equal
probes, so χ
tubular
reduction in division. He has over 10 years of experience in mass transfer technology
scanning tower, Io remains fixed and µ is essen- remains
metal loss aphenomenon. a constant.
probes) are With
very useful I being
tools. Theymeasured, the equa-
require modification
and holds a bachelor’s degree in chemical engineering from Shivaji
tially a constant. For a grid scan, the multiple paths of tion is solved
of the for ρ,and
equipment the amaterial
defineddensity.
area, where corrosion
ca acity of t e University, India.
On the
occurs to basis
fix the that χ was indeed
monitoring kept equal,
equipment there.then the
alves,
d e results of multiple
pipe sockets sets and
of scan
otherdata from a have
hardware packed to column grid
be installed.
tion are s own scan
Localcould be simply
corrosion couldvisually
happen compared
soon before to oreach other.
after the
Since
coupon allorscan
probe parameters
installation, were constant,
reflecting wrong particularly
measur-
the
ing length
resultsorbecausepath ofcorrosion
radiation might
through notthebecolumn (χ),
indicated.
uniform
Another liquid distribution
disadvantage is thatwould be confirmed
the installed by all
monitoring
o er of water four scans detecting
equipment may change identical radiation.
the flow properties Figure 2a is a
in smaller
not easily re- typical
pipes. example of a grid scan showing all four scan-
ns and ydrau- lines matching, implying
Non-intrusive monitoring gooddevices
liquid distribution.
can be used with
ed closely wit farHowever, when there
higher flexibility. A was someofvariance
number different in technolo-
the radi-
to troubles oot ation
gies aremeasurement and the sets
available, providing helpful of scan data did
information not
about
t e unit es e- corrosion
seem potential.
to match veryAdditional
well, theninstallation of valves or
liquid maldistribution
ations to iden- pipe sockets
would is not required.
be diagnosed The Comparing
as the cause. sensor system the can
sets be
of
sym toms and fixeddata,
scan outsidelower of the metal surface
radiation to measure
counts (higher corrosion
density) indi-
nd debutaniser without
cated more changing
liquid and thehigher
flow characteristics.
counts (less density) Ultrasonic
indi-
ted t at water devices
cated lesscanliquid,
be used with aliquid
therefore singlemaldistribution.
sensor or multiple An
cause sensor system,
example of thiswhere
type of theconclusion
metal thickness is measured.
is demonstrated in
on enient way Figure 2b. instruments measure the hydrogen flux,
Hydrosteel
columns lead- permeating through
This is a totally the metal
subjective as anlacking
analysis indication of cor-
consistency,
t e se ara- rosion.to This
open varyingis a interpretation,
very helpful option and does when nothydrogen
translate
blem was fully induced
from tower cracking
to tower.(HIC) is observed.
Additionally, Field signature
this quantitative anal-
n t e se - method
ysis does(FSM)not giveis aany
monitoring
insight intotechnology
the severity where many
or quan-
neerin rou sensor
tity of pins
liquid aremaldistribution.
welded onto theTherefore,
metal surface. Feeding
the resulting
of t e existin an electricalfrom
conclusions current
thisthrough the monitored
purely qualitative section,
approach canitbeis
to remedy t e possible
very to determine
ambiguous general
regarding thecorrosion
presence or and localised
magnitude cor-
nd ro rietary rosion
of insidemaldistribution.
any liquid of the pipe in real time.
o ided a solu- In general, non-intrusive corrosion monitoring tools
oal y under- Advanced
provide the analytics:
advantage PackView
that they can be installed during
e roblem t e operation.
An advanced If theanalytical
area of corrosion
analysisattack slightly shifts
for gamma scan
e arator essel to another
data from position, it is possible
packed columns was to move thetosensor
developed con-
e erformance system to analyse
sistently that new gamma
location to keepdata
scan the corrosion
and reach moni- a
toring underresult.
conclusive control. Densities are calculated based

16 PTQ
PTQ Q2
Q4 2018
2018 PTQ Q4 2017 49 www.eptq.com
70 www.eptq.com

12/09/2017 16:51
Q&A
q2 copy 33.indd2 6
tracerco.indd 13/09/2018 10:46
13/03/2018 17:01
 180283_NBI_Lauch_Ad_PTQ_AQ1.pdf 1 5/11/18 4:01 PM

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IPCO_SPS-IPCO_PTQ_210x297.indd 1 13/09/2018
12/07/2018 06:14
16:30
 Hydrofluoric acid alkylation conversion
and expansion
Much of the cost of switching from hydrofluoric acid to sulphuric acid alkylation
can be avoided by using existing equipment
SHANE PRESLEY and JASON NUNEZ
DuPont Clean Technologies
A
t a time when refiners face
concerns around the rise
of electric vehicles and the
eventual peak in global gasoline
demand, alkylate as a gasoline
blend component is more popular
than ever. The unique properties
of alkylate, including high octane,
lack of olefins and aromatics, and
extremely low sulphur, make it the
only blending component that truly
enhances all aspects of the gasoline
pool, helping refiners meet tight-
ening specifications. ue to these
blend qualities, a transformation
has occurred in the last few years
whereby alkylate is sought out
worldwide and is now sold and
exported as a stand-alone product
to serve those regions of the world
where refining technology is not
able to keep up with changing fuel
specifications.
The commercially adopted alky-
lation processes in refineries utilise
two main catalyst types: sulphuric
acid and hydrofluoric acid (HF).
efiners that use HF in their alkyla-
tion units are burdened with safety
and environmental concerns, lead-
ing to tremendous pressure from
both regulatory agencies and com-
munity activists. This has led to a
recent resurgence in the interest in
conversion or replacement of HF
alkylation units with alternative
technologies.
As part of the 2017 Revamps edition
of PTQ, an article titled Advances
in HF alkylation conversion and
expansion’ was published, pro-
viding an overview of the uPont
ConvEx technology for converting
HF alkylation units to sulphuric
acid alkylation. This article explores
the technology in greater detail and
www.eptq.com
q4 dupont.indd 1
includes an in-depth case study uti-
lising the novel reactor solution.
DuPont ConvEx HF conversion and
expansion technology
uPont Clean Technologies devel-
oped the ConvEx HF conversion
and expansion technology for both
gravity-flow and pumped-flow HF
alkylation units to utilise sulphu-
ric acid as catalyst for the alkylation
reactions. The conversion options for
the reaction section include: tradi-
tional Stratco Contactor reactors and
a novel reactor design. The Stratco
The unique properties
of alkylate make it
the only blending
component that truly
enhances all aspects
of the gasoline pool
Contactor reactor option was dis-
cussed extensively in the 2017 article,
so this article will focus primarily on
the novel reactor approach.
The first conversion option using
Stratco Contactor reactors is suitable
for both gravity-flow and pumped-
flow HF alkylation units and will
match the performance of a grass-
roots Stratco alkylation unit. For
the conversion of a gravity-flow HF
alkylation unit, the acid coolers will
be replaced by Contactor reactors,
and the existing vertical acid settler
will be retrofitted to perform as an
acid settler for the converted sul-
phuric acid alkylation unit. For the
conversion of a pumped-flow HF
alkylation unit, the existing hori on-
tal HF acid settler will be reused as
a sulphuric acid settler.
The second conversion option
using a novel reactor design is also
suitable for both gravity-flow and
pumped-flow HF alkylation units.
For the conversion of a gravity-flow
HF alkylation unit, the existing ver-
tical acid settler will be retrofitted
with proprietary internals for mix-
ing and will perform the function
of an alkylation reactor, acid settler,
and compressor suction vessel. For
the conversion of a pumped-flow
HF alkylation unit, the existing hori-
ontal acid settler will be retrofitted
with proprietary internals for mix-
ing and will perform the function of
alkylation reactor, acid settler, and
compressor suction vessel. In both
bases, the reaction one modifica-
tions are limited to vessel retrofits,
new piping and new pumps. The
novel reactor design incorporates
innovations developed through
extensive research while utilising
proven design elements that are
familiar to refinery operators. ue to
the fact that no new reaction vessels
are required, this conversion solu-
tion can be very economical, while
still providing acid consumption and
alkylate product properties similar to
grassroots Stratco alkylation units.
Expansion through conversion
In both HF and sulphuric acid alky-
lation units, the ratio of isobutane to
olefins in the reaction one must be
maintained adequately high to pre-
vent unfavourable olefin-to-olefin
reactions from occurring that can
result in low quality alkylate and
higher acid consumption. How this
ratio is achieved in these processes
PTQ Q4 2018 19
13/09/2018 17:09
 from the fractionation section. As a
result, the fractionation equipment
HF alkylation
in HF alkylation units is signifi-
Olefins 100% isobutane cantly larger than in sulphuric acid
recycle
Isobutane alkylation units.
A comparison of isobutane flows
Feed Reaction Fractionation Product in HF and sulphuric acid alkylation
pre-treatment post-treatment
units is shown in Figure 1.
Propane
This difference between the isobu-
ASO tane recycle streams in HF and sul-
Butane
extraction phuric acid alkylation units is the
Alkylate basis for unit expansion capabili-
ties at the same time as conversion
Sulphuric acid alkylation with minimal additional cost. The
Olefins fractionation equipment and efflu-
~50% isobutane recycle
ent piping in HF alkylation units is
Isobutane
approximately twice the si e of that
Feed Dry alumina of a sulphuric acid alkylation unit
Reaction Fractionation
preparation adsorption of similar si e. As part of any HF
conversion to sulphuric acid alky-
Butane lation, a new refrigeration section
Alkylate is required to reduce reaction tem-
~50% isobutane
recycle
Refrigeration Propane peratures. This refrigeration section
will provide additional isobutane
(refrigerant recycle) flow to the reac-
tion one, unloading the fractiona-
Figure 1 Comparison of isobutane recycle streams in the HF and sulphuric acid alkylation tion equipment. Instead of operating
processes the unit in a very unloaded fashion,
it may be beneficial to utilise this
Capacity expansion case studies additional capacity to expand the
throughput of the unit.
Customer Feed type Design capacity, bpd Expansion capacity, bpd Capacity increase DuPont has evaluated many HF
A MTBE C3=/C4= 13 500 22 601 +67% alkylation units for conversion to
B FCC C3=/C4= 10 000 27 810 +178%
sulphuric acid alkylation using the
C MTBE C4= 13 500 24 435 +81%
D FCC C3=/C4= 10 500 20 569 +96% ConvEx technology. Table 1 shows
E FCC C4= 20 500 43 865 +114% the extent to which expansion was
F FCC C3=/C4= 10 000 24 309 +143% possible as part of this evaluation.
In each of these examples, the units
Table 1 were expanded up to the limits of
the fractionation equipment or other
is quite different, however. This refrigeration section. In sulphuric major unit constraints. Of the six
difference is leveraged as part of acid alkylation units, isobutane is examples shown in this table, three
the ConvEx technology to achieve flashed in the reaction one to pro- of these resulted in an expansion
a significant increase in throughput vide cooling for the reactors, which potential that more than doubled
by converting an HF alkylation unit typically operate at around 45-60°F the capacity of the existing HF alky-
to one using sulphuric acid as the (7-15 C). This flashed isobutane is lation unit. Doubling unit capacity
catalyst. then compressed, condensed and may not always be possible as part
For sulphuric acid alkylation cooled in the refrigeration section of a conversion of an HF alkylation
units, there are two sources of before being routed back to the unit, but in all the cases examined,
isobutane that circulate back to the reaction one as refrigerant recycle. considerable expansion was possi-
reaction one. The first source is The refrigerant recycle stream pro- ble, providing an economic incen-
the fractionation section, where net vides the remainder of the isobu- tive for refiners to consider HF
effluent is separated into its com- tane required in the reaction one. conversion.
ponents (isobutane, normal butane In HF alkylation units, the reac-
and alkylate). The isobutane stream tion one is operated at much Case study
from the top of the deisobutaniser higher temperatures, so no refriger- The case study presented here uti-
tower provides recycle isobutane ation section is required. Since there lises DuPont’s novel reactor design
to the reaction one. This stream is no refrigeration section providing to retrofit an existing pumped-flow
makes up about one half of the total refrigerant recycle back to the reac- HF alkylation unit (see Figure 2) for
isobutane required for the reaction tion one, all the isobutane required conversion to a sulphuric acid alky-
one. The second source is from the in the reaction one must come lation unit.

20 PTQ Q4 2018 www.eptq.com

q4 dupont.indd 2 13/09/2018 17:09

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 Reuse
Abandon/demo Isostripper
Repurpose receiver

HF
stripper
1st stage
reactor
Depropaniser
Feed
dryers
Alumina
1st stage treaters
acid settler

Makeup
isobutane KOH
treaters
Olefin
feed
Feed
coalescer 2nd stage Propane
reactor

2nd stage
acid settler

Fresh
acid

Acid
storage drums
Isostripper
Acid
Tar regenerator
Alumina
Tar Polymer treaters
neutraliser surge drums

HC relief
header KOH
treaters

Acid relief
header n-butane
Relief gas
scrubber Alkylate

Figure 3 Original HF alkylation unit

This HF alkylation unit was orig- head stream was then routed to the
inally designed to produce 10 500 depropaniser as feed to the column.
Settler b/d of alkylate product using two The depropaniser overhead stream
effluent HF reactors, acid settlers, and acid was the propane product and the
HF circulation pumps with a feed con- bottoms product was routed back
Cooling reactor sisting of FCC butylene and propyl- to the reactor feed streams to sup-
water
supply ene (see Figure 3). ply approximately 30% of the recy-
Acid
settler The fractionation equipment for cle isobutane to the reaction section.
Cooling
water this unit included an isostripper col- The isostripper also included two
Acid
return umn and a depropaniser column. side streams. The first side stream
circulation
Combined pump Effluent from the two acid settlers was drawn off high in the stripping
feed was routed to the isostripper as section and, being rich in isobutane,
feed to the column. The isobutane was routed back to the reactor feed
Figure 2 Typical pumped-flow HF reactor and propane rich isostripper over- to supply the remaining 70% of the

22 PTQ Q4 2018 www.eptq.com

q4 dupont.indd 3 13/09/2018 17:11

 recycle isobutane to the reaction sec-
tion. The second side stream was Proprietary
Flashed vapour
internals
drawn off lower in the stripping sec- to compressor
tion as the n-butane product stream. Olefin feed and Olefin feed and
The isostripper bottoms stream was recycle isobutane recycle isobutane
the alkylate product stream.
Refrigerant Refrigerant
The conversion solution for this recycle recycle
case study involved converting the
existing acid settlers to novel sul- Acid emulsion Acid emulsion
recycle pumps recycle pumps
phuric acid alkylation reactors by
Fresh acid
retrofitting them with uPont’s
Net effluent
proprietary internals and adding Spent acid
product
acid emulsion recycle pumps (see
Figure 4).
Since sulphuric acid alkylation Figure 4 Novel reactor retrofit design
reactions are optimised at a much
lower temperature than HF acid a refrigerant recycle stream. Table Dry alumina adsorption
alkylation reactions, a new refriger- 3 provides a summary of feed and In sulphuric acid alkylation units,
ation section and new feed effluent product streams for the conversion stable droplets (or colloidal suspen-
heat exchangers were added to the solution offered for this case study, sions) of sulphuric acid and other
system. Other existing equipment while Table 4 provides a summary acidic compounds exist in the net
was repurposed for use as the acid of predicted alkylate properties. effluent. These droplets are formed
coalescer, dry alumina adsorption,
propane product treatment, and Case study: major equipment list
acid blowdown. Figure 5 illustrates
a simplified process flow diagram
of the conversion solution for this Existing equipment New equipment required Existing equipment not
HF alkylation unit. reused or repurposed for conversion used for conversion
Acid blowdown drum (remote) Acid emulsion recycle pumps Acid circulation pump
Most modern HF alkylation units Acid neutralisation pit Compressor K/O drum Acid regenerator
also have remote HF acid storage Acid settlers Feed/effluent exchangers Acid regenerator condenser
vessels and remote HF acid blow- Acid storage drums Fresh acid pumps Acid regenerator IC4 superheater
down drums. epending on the Alkylate cooler Net effluent pumps Acid regenerator overhead pump
Alkylate flush pump Propane purge pumps HF reactors
location of these vessels and the Alkylate product coolers Refrigerant condensers HF stripper
requirements of the conversion Depropaniser Refrigeration compressor Settled acid pump
solution offered, these may be uti- Depropaniser accumulator Spent acid pumps
lised as spent acid after-settlers, Depropaniser bottoms cooler
Depropaniser charge pumps
acid blowdown drums, or they Depropaniser condensers
may be converted to novel sulphu- Depropaniser feed/bottoms exchangers
ric acid alkylation reactors to take Depropaniser reboiler
full advantage of the additional Depropaniser reflux pumps
Feed coalescer
capacity available through conver- Feed dryers
sion to sulphuric acid. Potential Isobutane recycle pumps
opportunities to reuse these vessels Isostripper
will be determined on a case-by- Isostripper accumulator
Isostripper condensers
case basis. Table 2 provides a list of Isostripper feed/bottoms exchangers
existing and new major equipment Isostripper feed/IC4 recycle exchangers
in the alkylation unit. Isostripper reboiler
To maximise product quality Isostripper receiver
Isostripper reflux pumps
and to minimise acid consumption, Isostripper side stream cooler
uPont applied patented designs to KOH pumps
stage acid flows between the reac- n-Butane condensers
tion sections. n-Butane defluorinators
n-Butane draw vapour/liquid separator
Since the isostripper and depro- n-Butane KOH treaters
paniser were designed to pro- n-Butane product trim cooler
vide 100% of the isobutane recycle Polymer surge drums
Propane defluorinators
stream, a significant capacity
Propane KOH treaters
increase of nearly 100% was possible Relief gas scrubber
with the addition of a new refriger- Relief gas scrubber circulation pump
ation section. The new refrigeration Tar neutraliser
section provides approximately 50%
of the required isobutane recycle as Table 2

www.eptq.com PTQ Q4 2018 23

q4 dupont.indd 4 13/09/2018 17:11

 Refrigeration
compressor
Original equipment
New equipment Propane
Refrigerant
accumulator
Compressor
K/O drum Propane
treaters

Depropaniser
Feed
dryers

2nd stage
Makeup
isobutane
Olefin
feed
Feed
coalescer 1st stage

Fresh
acid

Acid
storage drums

Acid
coalescer Isostripper

Dry alumina
adsorption n-butane

HC relief Spent acid

header aftersettler

Acid relief
header Acid blowdown
drum
Relief gas
scrubber
Alkylate
Recovered
hydrocarbons
Spent acid

Figure 5 Converted alkylation unit

by the chemistry of the alkylation
reactions and cannot be avoided,
regardless of the technology used.
Additionally, these droplets exhibit
the characteristics of Brownian
motion and are not able to be effec-
tively removed by coalescing. If not
removed, these acidic components
will result in fouling and corrosion
in the downstream fractionation
equipment.
For many years, caustic based
treating was the standard for
removal of acidic components from
the net effluent stream. hile this
system is a very effective means of
effluent treating, a recent change
was made in the standard design
of Stratco alkylation units. Instead
of a caustic based treating sys-
tem, dry alumina adsorption was
adopted. Dry alumina adsorption
provides both a capital and operat-
ing expense benefit compared to the
caustic based system. Because the
vessels in this technology are ver-
tical, plot space requirements are
reduced. Finally, by not contacting
the effluent stream with caustic or
water, this stream and the recycle
isobutane stream from the deisobu-
taniser overhead is also completely
dry.
Because the recycle isobutane
stream is completely dry, water
removal is not required in the feed

24 PTQ Q4 2018 www.eptq.com

q4 dupont.indd 5 13/09/2018 17:11

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 Case study: feed and product stream summary Case study: product alkylate properties

Olefin feed, Isobutane Propane n-Butane Alkylate % Propylene/total olefins (feed) 42.1
% feed product product product % Isobutylene/total olefins (feed) 18.4
Volume flow, b/d 19 795 9564 2334 1,270 20,569 RON 93.5
Composition, vol% (R+M)/2 92.7
Ethane 0.03% 0.23% D-86 T90, °F (°C) <290 (143)
Propane 9.51% 1.99% 97.50% D-86 EP, °F (°C) <400 (204)
i-Butane 21.78% 95.00% 2.26% 16.71% 0.20% Acid consumption,
n-Butane 6.98% 3.01% 0.02% 82.29% 3.03% lbs acid/gal alkylate 0.45-0.55
i-Pentane 2.60% 0.98% 7.11% Alkylate Reid vapour pressure
n-Pentane 0.72% 0.02% 0.70% (RVP), psia 6.0
Propylene 24.61% Alkylate sulphur, ppm <2
Butylene 33.07%
Amylene 0.71%
C6+ 0.00% 88.96% Table 4

Table 3 offline mode, and the spent alumina

preparation section of the alkyla-
tion unit. HF alkylation technol-
ogy is very sensitive to water, so
feed dryers are required to remove
nearly all the water from the feed.
This is not the case in sulphuric acid
alkylation units. hile water does
dilute the sulphuric acid, resulting
in higher acid consumption rates,
larger amounts of water in the feed
are acceptable, so feed coalescers
are typically used instead of feed
dryers. Additionally, if dry alumina
adsorption is used for effluent treat-
ing and the recycle isobutane stream
is completely dry, feed coalescing
is not required. hen converting
from HF alkylation to sulphuric acid
alkylation, no changes are required
in the feed preparation section.
efiners have the option of contin-
uing to use the existing feed dryers
for removal of water from the olefin
feed stream if they are si ed appro-
priately. However, the olefin feed
stream is very small compared to
the recycle isobutane stream, so the
impact on acid consumption would
be negligible if this equipment was
abandoned instead.
ry alumina adsorption technol-
ogy works by flowing the effluent
stream across a packed bed of acti-
vated alumina. Acidic components
react in the pores of the alumina
beads through a process called
chemisorption. The basic reaction
mechanism is:
Al2O3 + 3H2SO4 ➝ Al2(SO4 )3 + 3H2O
The mechanism for alumina
deactivation in this service is that
the aluminum sulphate (produced
as part of the reaction mechanism
mentioned above) forms a crust’ on
the alumina beads that hinders fur-
ther reaction and removal of acidic
components. Acidic components
are still able to diffuse through this
crust for some period, but eventu-
ally the diffusion rate is such that
the alumina is no longer effective.
Figure 6 provides an illustration
of a typical dry alumina adsorption
treater.
Parallel treating vessels are
required so that the treating vessels
can be switched between online and
Untreated
effluent
Treated
effluent to
fractionation
Figure 6 Typical dry alumina adsorption
treater
from the offline treater can either
be removed and replaced or regen-
erated in place once the alumina
is deactivated. hile uPont has
done significant research to opti-
mise the selection of alumina prod-
ucts for this service, even the most
effective alumina products used
are very inexpensive, which is why
some refiners choose not to regener-
ate the alumina and simply replace
it once it becomes spent. For those
refiners that do choose to regen-
erate, this is done by washing the
alumina with water and then dry-
ing it before placing it back in ser-
vice. egeneration or replacement
frequency is a function of treater
si e, so refiners can choose a pre-
ferred frequency by selecting the
appropriate si e if new vessels are
used. hen converting an HF unit
to a sulphuric acid alkylation unit,
it is common to repurpose existing
vessels in the plant for the alumina
treaters. In this case, the frequency
of regeneration or replacement
is determined by the si e of the
repurposed vessel. hile regener-
ation and replacement frequency
can vary, it is common for regen-
erations to occur every 2- weeks
and replacement to occur every -
months. egenerated alumina can
typically withstand 0- 0 regen-
eration cycles before the alumina
requires complete replacement.
Conclusion
Community and regulatory pres-
sure surrounding HF alkylation
units is currently at an all-time high,
so refiners are being forced to con-
sider alternatives such as conver-
sion or replacement of their existing

26 PTQ Q4 2018 www.eptq.com

cat cat t
q4 dupont.indd 6 15/09/2018 06:28
 Results
HF alkylation units. emolishing
n ril t e unit was
and replacing existing assets can
successfully s ut down wit t e cat
be extremely expensive and result
alyst passivation technology. Figure
in lost opportunity costs due to the
3 compares and outlines the steps
downtime required for construc-
in ol ed in t e modified and rior
tion. The uPont ConvEx technol-
s utdown rocedures s can be
ogy seeks to make conversion of
seen elimination of t e ot ydro
HF alkylation units more feasible
gen strip and the ability to cool
for refiners by introducing solu-
under liquid oil circulation allowed
tions that not only solve the prob-
t e unit to be s ut down some
lem around safety in HF alkylation
hours earlier than the traditional
units, but also provide an economic
s utdown met od n o enin
justification for conversion projects.
t e reactor manways as sam les
This technology was developed
were ta en in all four reactors and
with four key objectives in mind:
found to be LEL free. The reac-
• evelop solutions that are safe
tors were quic ly and sequentially
alternatives to HF. In addition to
turned o er to air enablin cata
the safer chemical and physical
lyst unload o erations to be ex e
properties of sulphuric acid com-
dited in an atmos ere t at was
pared to HF, the alkylation designs
not immediately dangerous to life
by uPont have a long history of
or ealt e catalyst was
incorporating the highest safety
well assi ated s owin no si ns
standards. This is reflected by the
of reacti ity and all toxic dust and
positive safety record of refiners
pyrophoric material eliminated.
operating Stratco alkylation units.
e ma ority of catalyst ad
• evelop cost-effective conver-
to be remo ed by acuum extrac
sion solutions. A conversion from
tion as a consequence of its agglom-
an HF alkylation unit to a sulphuric
erated nature and reluctance to
acid alkylation unit is no small feat,
dum istorically t is would a e
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q4 dupont.indd 7
involved personnel entering a nitro-
regardless of which technology is
en filled confined s ace to erform
used. However, by value engineer-
t ese wor s n t is instance some
ing unique solutions to reuse as
ours of confined s ace wor s
much existing HF alkylation equip-
associated wit mec anical tray
ment as possible, the conversion
wor and catalyst remo al was all
solutions now offered by uPont
performed in an air atmosphere.
offer step-change reductions in cost
in comparison to other solutions
Conclusion
available on the market.
Catalyst Passivation Technology
• Create value for the refiner
provided an alternative methodol-
through unit expansion. An increase
ogy for ENAP to improve the safety
in throughput of 100% or more is
and reliability of catalyst changeout
possible when converting from HF
for t e l aro arrueto
alkylation to sulphuric acid alkyla-
Maintenance Engineer at the Bio Bio
tion by taking advantage of some of
refinery said e assi ation tec
the key design differences between
nology enabled us to apply a safer
these two alkylation technologies.
system of wor eliminatin two of
Even if conversion from HF catalyst
t e ma or a ards associated wit
is not a key driver, refiners have an
catalyst remo al nitro en w ile
opportunity to complete the expan-
unloading catalyst and inert entry
sion and be left with a safer technol-
into confined s aces e modi
ogy that has long term viability.
fied s utdown rocedure allowed
• Ensure the conversion technol-
us to reduce t e o erall downtime
ogy is proven, robust and opera-
and gave us access to the reactors
ble. Although many aspects of the
sooner.”
uPont ConvEx technology are
The foregoing is not intended to
unique and innovative, the design
be an endorsement of the passiva-
elements and know-how that have
tion tec nolo y by efiner as
made Stratco alkylation the lead-
S.A. Each reactor unit must undergo
a comprehensive engineering evalu-
ing global alkylation technology
ation to assess its suitability and the
have been incorporated into these
refiner must exercise t eir own inde
conversion solutions. The resulting
endent ud ment to decide w et er
product includes proven technology
the technology is appropriate for use.
applications, a robust design, and
equipment that is familiar to refin-
References
1
eryNACE – SP0170-2012, Protection of
operators.
Austenitic Stainless Steels and Other
Austenitic Alloys from Polythionic Acid Stress
Corrosion
ConvEx and cracking during
STRATCO are marksShutdown
of DuPont. of
Refinery Equipment.
Alvaro Barrueto works as a Maintenance
Shane Presley is the Technical Service and
Engineer for ENAP Bio Bio Refinery in Chile.
Development Manager for the alkylation and
He is in charge of the refinery’s catalyst
hydroprocessing businesses with DuPont Clean
replacement operations, as well as supporting
Technologies. With approximately 20 years of
maintenance activities in different units.
refining and technology licensing experience,
Ian Baxter is the Technical Manager with
and roles at Chevron and ExxonMobil prior
Cat Tech International Ltd and has over 25
to joining DuPont, he holds a BS degree in
years’ experience in the refining and chemical
chemical engineering from Mississippi State
Industry. Based in the UK, he provides technical
University.
expertise across a number of technologies
Jason Nunez is a Senior Technical Service
including Catalyst Passivation Technology.
Engineer for the alkylation and hydroprocessing
Gary Welch has over 40 years’ experience in
businesses with DuPont Clean Technologies.
the petroleum refining industry, specialising
With over 14 years of experience in the refining
in hydrotreating catalysts and operations. His
and petrochemical industries, and roles with
early career was spent with Shell Oil Company
Citgo Petroleum Corporation and the Saudi
in research and in positions of sales and
Aramco Mobil refinery prior to joining DuPont,
manufacturing of hydrotreating catalysts. He
he holds BS degrees in chemical engineering
now operates as an independent consultant
and environmental science from McNeese
and consults for Cat Tech International on the
State University.
Catalyst Passivation Technology.
14.06.2017 17:17:16
Catalysis 2018 43
PTQ Q4 2018 27
28/02/2018 12:23
13/09/2018 17:13
 Shell Global Solutions

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shell.indd
228646 1
GS_TechnologyDNA_A4_V07.indd 1 23/02/2018 08:55
06/03/2017 16:28
 Dynamic simulation to estimate
tower relief
When applied in the correct circumstances, dynamic analysis can help avoid
unnecessary scope and project delays

HARRY Z HA and BEN LEVITON

Fluor Canada

A
ccurately predicting the relief
loads for a distillation column Reaction Stripping Fractionation
is a challenge in engineering section section section
design. Most often, the unbalanced
heat (UBH) method1 is used in the
grassroots design of a project. The Off-gas
relief loads predicted by the UBH
Relief
method are typically conservative
due to the assumptions intrinsic to
the method of calculation. This level
of conservatism is normally accept-
able for a grassroots project as it
incorporates a safety margin into the
relief system design. For a revamp
or debottleneck project, however, Distillate
the acceptable column relief load is
limited by either the installed pres-
sure safety valve (PSV) size or by
the capacity of the existing flare
Bottoms
header. The relief load calculated by
the UBH method frequently exceeds
these physical limitations and can
lead to the installation of additional
PS s or extensive flare header mod- Feed
ifications, which are typically costly
and difficult to implement in an
operating plant.
Application of a steady state relief Figure 1 Typical flow scheme for a distillate hydrotreating process
model is often the next step to more
accurately predict the relief load by When facing these challenges on to the existing PS or flare system.
better characterisation of product a revamp project, dynamic simu- This article outlines the situa-
streams at relief conditions. Within lation can be employed to provide tions in which dynamic simulation
the limitations of steady state simu- the most reliable relief estimates. is most helpful in reducing calcu-
lation, the transitional changes of an Dynamic modelling accounts for lated relief loads. An example relief
upset case are still ignored or substi- the impact of stream compositional system for a product fractionator
tuted by conservative stream condi- changes, system volume contribu- in a hydrotreating unit is presented
tions. As a result, the column relief tions, and the available inventory in order to compare the relief loads
loads predicted by steady state sim- within the system during an upset predicted by UBH, steady state,
ulation also tend to be conservative. scenario. It also better character- and dynamic analysis for the same
Additionally, steady state models ises the relief stream by estimating system.
are not easily applied to upset sce- depletion of light ends, temper-
narios where the column trays run ature variations, and latent heat Hydrotreating unit product
dry due to loss of liquid loading changes over time. The column fractionator example
(for instance, reflux failure or loss of relief loads predicted by dynamic In order to compare the relief loads
feed) as the column generally fails simulation are often promising in predicted by UBH, steady state, and
to converge. eliminating potential modifications dynamic models, this article pre-

www.eptq.com PTQ Q4 2018 29

q4 fluor.indd 1 13/09/2018 17:20

 sents a case study which employs
all three calculation methods. In
this study, the total power failure
(TPF) relief load associated with
the product fractionator column of
a typical hydrotreating unit was
investigated using all three meth-
ods. A typical distillate hydrotreat-
ing process flow scheme is shown
in Figure 1.
The hydrotreating unit investi-
gated is divided into reaction, strip-
ping, and fractionation sections,
as shown in Figure 1. ey features
of the system configuration are as
follows:
• The reaction section includes a
recycle gas compressor loop along
with high and low pressure separa-
tor drums. The reactor effluent is
cooled by heat exchange with the
reactor feed and low pressure sep-
arator liquid.
• The stripping section includes two
columns in series. Flow from one
column to the next is driven by sys-
tem pressure.
• Feed to the fractionator section
is pumped from the stripping sec-
tion through a set of feed/bottoms
exchangers and a fired heater.
The relief scenario investigated
in this example is TPF which is a
global scenario with simultane-
ous relief loads from all units in
the plant. The detailed scenario is
defined by the following consider-
ations, driven by guidelines in API
Standard 521:2
1. All pumps and compres-
sors driven by electric motors are
assumed offline.
2. here both electric motor and
steam turbine drivers are availa-
ble for a given service, the turbine
driver is assumed to be in service
only if it favours higher relief loads.
3. Electric fans on air-cooled heat
exchangers are assumed offline.
Credit is taken for natural draft
cooling duty based on a detailed
HT I model.
. No credit is taken for any favour-
able instrument response from auto-
matic control valves during the
relieving period to mitigate relief.
5. The upset conditions in the
upstream (reaction) section of the
unit affect the downstream (strip-
ping and fractionation) sections and
must be accounted for.
30 PTQ Q4 2018
q4 fluor.indd 2
Off-gas
Relief
Distillate
Bottoms
Feed
ΣW = ΣW
F P
( W H +ΣQ ) − (ΣW H +ΣQ )
ΣW = Σ
A
F F 1
LA
P P
Figure 2 Illustration of column envelope
employed in the unbalanced heat method
Unbalanced heat (UBH) approach
The UBH method1 is a conven-
tional practice for calculating col-
umn relief loads and widely used
in industry. It is preferred in grass-
roots design where conserva-
tive PS and flare header si ing is
advantageous.
The method employs a heat and
material balance around the column
envelope (see Figure 2) at reliev-
ing conditions in order to estimate
excess heat input. The relief rate
(WA) is calculated from the excess
heat divided by the latent heat of
the relieving material.
The excess heat calculation con-
siders the enthalpy of each stream
at relieving pressure assuming
all product stream compositions
remain constant. An endless sup-
ply of relieving material is assumed
available (typically represented by
the top tray liquid of the column).
Normally, no credit is taken for the
following mitigating factors:
• Compositional changes including
depletion of light components
• Accumulation of mass within
the system volume as pressure
increases
• Hydraulic limitations
• Overhead cooling before the
reflux drum is flooded.
The UBH method is simple, effec-
tive and conservative. Aside from
typical over-estimation of relief
loads, it is also subject to the follow-
ing key limitations:
1. The UBH method is unreliable for
scenarios where the upset leads to
a significant compositional change
within the column envelope. A
typical example is a blow-through
of vapour from an upstream high
pressure section to the low pressure
column via a failed open control
valve.
2. UBH can over- or underestimate
relief loads for systems where the
column energy balance is sensitive
to minor compositional changes. In
these systems, the enthalpy of bot-
toms stream is typically affected by
the presence of light components
0
which skews the calculated relief
load. Some examples are:
• Stripping columns which remove
absorbed components from a sol-
vent (for instance, a sour water
stripper)
• Columns with low overhead to
bottoms flow ratio (for instance, a
stabiliser).
3. UBH is not normally suitable for
complex systems such as:
• Reactive distillation columns
• Columns with relief occurring
near the critical region
• Scenarios with significant tran-
sient effects such as a major upset
upstream affecting feed conditions.
UBH results
The UBH method was applied to
estimate the TPF relief load for a
hydrotreating unit product frac-
tionator. hile the UBH method
typically takes the feed at normal
conditions, in this case the feed
enthalpy was estimated based on
simulation of the upset conditions
upstream, since significant upsets
do occur in the reaction and strip-
ping sections during TPF. The cal-
culation resulted in a required relief
area of . in2. This is 172% of the
available relief area of 2 .0 in2.
Steady state simulation approach
Steady state modelling is recom-
mended as an alternative approach
www.eptq.com
17/09/2018 15:13
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 for column relief calculations where
the UBH method is not applicable. It
is most commonly employed in sce-
narios where compositional changes
affect the relief load (for instance, a
vapour blow-through case), as well
as systems that are highly sensitive
to product composition (strippers
or stabilisers). The upset cases are
directly simulated in a steady state
model at relief conditions along with
any feed changes, and the resulting
product stream compositions are
predicted by thermodynamics.
Steady state modelling is also
useful for relief cases where condi-
tions in the column are near critical
temperature and pressure. Because
the liquid and vapour densities
approach one another in these cases,
the reduction in liquid volume
through boiling is significant com-
pared to the generation of vapour
volume. Taking credit for this vol-
ume exchange can reduce the esti-
mated relief load significantly.
While steady state modelling
is valuable for the scenarios dis-
cussed above, for most systems it
offers only incremental advantages
over the UBH method. The tran-
sient effects of an upset case are
still ignored by assuming constant
stream conditions, and no credit is
taken for system volume or hydrau-
lic effects. Additionally, steady state
models fail to converge for some
upset cases where the column trays
run dry due to loss of liquid loading
(as a result of reflux failure or loss
of feed), limiting the application of
this method.
Steady state modelling results
The steady state method was
applied to estimate the TPF relief
load for a hydrotreating unit prod-
uct fractionator. As with the UBH
calculation, the feed enthalpy was
estimated based on simulation of the
upset conditions in the reaction and
stripping sections. The calculation
resulted in a required relief area of
31.5 in2. This is 121% of the available
relief area of 26.0 in2 – less than the
UBH estimated relief load but still
exceeding the existing PSV capacity.
Dynamic approach
A dynamic model can be employed
to simulate an upset event and pre-
www.eptq.com
q4 fluor.indd 3
Reaction section
Stripping section
Fractionation section
Temperature
Mass flow
0 5 10 15
Time, minutes
Figure 3 Dynamic propagation of upset conditions for total power failure in a
hydrotreating unit
dict the resulting relief profile as
it changes over time. This method
can account for transient effects that
would not be included in a steady
state model. In order to account
for these effects, a dynamic model
must include far more details than a
steady state simulation. The follow-
ing system input data are typically
included:
• Equipment geometry and elevation
• Piping volume based on isometric
drawings
• System pressure profile calibrated
with hydraulic calculations
• Performance curves for pumps
and compressors
• Valve characteristics
• Plant operation control parame-
ters for key control loops
• Column sump and drum liquid
levels
• Exchanger UA values based on a
detailed HTRI model.
Dynamic simulations present the
most accurate relief results and fre-
quently estimate lower relief loads
than the UBH or steady state meth-
ods. This is mainly attributed to the
rigorous estimation of vapour and
liquid composition within the col-
umn over time, particularly when
dealing with material having a wide
boiling range. As the lighter compo-
nents tend to vaporise earlier while
pressure is building in the column,
the latent heat of the remaining liq-
uid is elevated as it becomes heavier.
The following time-dependent
variables also impact the relief pro-
file during a relief event:
Mass flow Temperature
20 25 30 35 40 45
• Changes to stream temperatures
and compositions
• Accumulation and depletion of
material within system volumes
• Propagation of upset condi-
tions from an upstream system to a
downstream system
• Thermal limitations due to availa-
ble UA and changes to LMT
• Hydraulic limitations including
pump curves, frictional pressure
drop, and static head (consider the
circulation rate through a thermosi-
phon reboiler)
• Instrumentation control response
where plant parameters are available.
The decision to employ dynamic
modelling is normally made on a
case-by-case basis where the addi-
tional time and effort are war-
ranted by potential reductions in
scope. This is common in revamp
and debottleneck projects where a
change in configuration or increase
in capacity has the potential to
increase relief loads and dynamic
simulation provides the opportu-
nity to avoid costly relief system
modifications.3
In grassroots design, dynamic
modelling is normally consid-
ered for particularly complex sys-
tems such as reactive distillation4
or steam and condensate networks
where a significant potential for cost
savings is expected. Dynamic simu-
lation can also be employed to sim-
ulate transient operating scenarios
such as start-up, shutdown or unit
depressurising. Employing these
tools in the early stages of design
PTQ Q4 2018 33
17/09/2018 12:02
 25
tion cascade over time, eventually
impacting the feed to the fractiona-
tor. Mass flow from the reaction sec-
20 tion tapers off over time due to loss
of feed. However, the temperature of
the feed to the stripper section spikes
Area, in2

15
10
5 Dynamic orifice area
0 inventory of liquid in each column
0 5
Figure 4 Comparison of UBH, steady state, and dynamic relief loads for a hydrotreating
unit product fractionator
not only saves cost by optimising
the plant configuration, but also
improves operational reliability by
testing the potential impact of upset
scenarios, ensuring a safe design.
Dynamic results
The TPF relief profile for a hydro-
treating unit product fractiona-
No Sensitive system?
(stripper, stabiliser)
Governing/global Yes
scenario has significant
compositional changes?
No
Unbalanced
heat
Figure 5 When and where to apply UBH, steady state, and dynamic modelling
due to the initial loss of cooling duty
UBH orifice area in the feed effluent exchangers. The
SS orifice area increase in temperature and decrease
Installed orifice area in flow rate propagates through the
columns in the stripping section but
this effect is mediated by the initial
10 15 20 25 30 35 40 sump. By the time the temperature
Time, minutes peak reaches the fractionator col-
umn, the flow has decreased signifi-
cantly, mitigating the impact on the
relief load.
The peak required relief area esti-
tor was estimated using a dynamic mated by the dynamic model is
model. Rather than assume the 19.9 in2. This is 7 % of the available
feed conditions were constant, the relief area of 2 .0 in2. Based on these
upstream reaction and stripper sec- results, the potential PSV scope can
tions were fully modelled and the be eliminated. Figure 4 compares
upset conditions were propagated the estimated required relief area
through the system. by UBH, steady state, and dynamic
Figure 3 shows how the upset methods.
conditions from the reaction sec-
Recommendations: when and where
dynamic simulation should be used
Tower relief for column relief
calculation Dynamic modelling is the most rig-
orous method for column relief load
analysis and will typically result
in the most accurate relief loads.
Project
type With advances in the development
of process simulators, the time and
Grassroots
Revamp effort required to conduct dynamic
debottleneck studies are much more affordable
than a decade ago and can be war-
ranted by potential savings in pro-
Complex transient Yes ject cost and schedule.
scenario with potential
for cost savings? For a grassroots design, most
No relief loads are estimated using the
UBH method. Steady state analysis
No No
Preliminary UBH is employed by exception where it is
Near critical calculation shows relief
relief system undersized? warranted. This includes the follow-
Yes
Yes
ing commonplace situations:
• Governing or global scenarios
Governing/global
that include significant composi-
No
Yes scenario has significant tional changes such as vapour blow-
transient effects? through from an upstream high
Yes pressure system
• Columns that are sensitive to
Steady state
calculations show relief Yes changes in product composition
system undersized? such as a stripper or stabiliser
No • Relief systems at near critical
Steady state conditions.
Dynamic
Dynamic modelling may also be
employed in grassroots design for
particularly complex systems such

34 PTQ Q4 2018 www.eptq.com

q4 fluor.indd 4 17/09/2018 12:02

 aas DCII
reactivepressure of ~3.0
distillation 4
orbar is the
transient • Relief
Effect ofloads dependent
DCII pressure onhot
on the vapour
and 32.3%,
References 84.8% in medium pressure
optimum
scenarios where value significant
to minimise the
poten- orcold
liquid inventory
utility requirement of the process steam,
1 Sengupta cooling water
M, Staats F Y, Aand
newelectricity,
approach to
net
tial forprocess energy
cost savings requirement.
is expected. • Relief loads dependent on system respectively. The design
relief valve load calculations, pressure
43rd Proceedings
Subsequently,
For a revamp or a debottleneck
new processing pro- hydraulic of the
of DCIIRefining Section
is 4.5 bar.ofThus
American Petroleum
there is an
Pressure, orHotthermal
utility, limitations.
Cold utility,
sc
ject,eme wit modifi
a preliminary ed eatbyinte
evaluation the Figure 5 outlines
bar kW the hierarchy kW of Institute, Toronto, Canada, 1978.
o ortunity to reduce t e o erat
gration was isconceptualised (see 1.7 4898when and4252 2 APIcost
ing Standard
by 37.7%521. by
Pressure-relieving
revamping the and
UBH method normally employed. calculations for where
Depressuring Systems, American Petroleum
Figure
If this2). initial estimate of required to2 apply UBH, 5040
steady state, 4354
and existing process with the proposed
2.5 5276 4531 Institute, 6th Edition, 2014.
orifice area is within the available dynamic
3 modelling
3407 to estimate
2610 col- scheme. The payback period for the
3 Ha H Z, Harji A, Webber J, Accurate
Comparative
relief systemanalysis limitations, then the umn
3.5 relief loads.3630 2787 additional expenditure required for
prediction of tower relief, PTQ, Q2 2014.
on entional
relief analysis and can bero treated
osed the ro revamping
4 Ha H Z, Mercer the Dexisting
B, Dynamic aromatic
column
cesses
same as wit an o design.
in grassroots timum res Conclusion
Table 1 plant was
simulation found
delivers to berelief
reduced 10.3 months.
load, PTQ, Q1
sureIf for
the column
initial DCIIUBH ascalculations
shown in Due to advances in technology and Moreover,
2018. these energy savings
Figures
show that 1 andthe 2 were
reliefsimulated
system may in a was estimated
software, dynamic usingmodelling
the ratio has of will also result in a si nificant
closed
require loop for evaluation
modifications, steady of their
state ca ital cost
become to annual
a popular tool inrofi t t rou
engineering reduction in CO2 emissions from
actual
modelling energy requirement.
is normally the next Instep.
the ener
designy and sa operations
in s e support
cost ofwhere i the plant.
Harry Z Ha is a Principal Process Engineer
present
If the reliefstudy, the annual
loads based on operating
steady in modifi
it offers cation
insight intowas
system assumed
behaviour to with Fluor Canada Ltd. He has over 30 years’
cost
state was estimated
analysis for an existing
still exceed o erat be 30% specific
during of the installed
transient cost of new
scenarios or Conclusion
experience in R&D in the petrochemical
ing rate of then
limitations 8000 dynamic
h/y and modelling
for utility heat exchangers.
operating cases. Studies that would BTX is produced
industries. In addition to onprocess
a large scale
design, he
prices
shouldof besteam at Rs. In
considered. 1500some percases,
ton, haveetakenactualmonths a our
can now owbe com- in t eonrefi
focuses nin
data and etroc
and methods emi
development
cooling
steady state water at Rs.
analysis may 1.8/ton
be skippedand rofile in
pleted of weeks,indicates
making tit at t ere
feasible cal industries
to support small
process modelling andincrement
simulations.
electricity at Rs.
if it is clear that 4.2/kWH
the relief load will($ be= is a
to include reductionanalysis
dynamic in t eeven maxi in He ener
in holds y a MS degree inwould
e ciency environmental
result
Rs60).
impacted 3
Thesignificantly
capital costby of transient
the heat mum
the earlyalue of of engineering
stages on increasin pro- engineering
in si nififrom
cant Hong Kong University
financial sa in of s
exchanger network, reboiler and the Science and Technology
on entional andand ro a PhD in chemical
osed ro
effects. jects. DCII
The use reboiler pressure
of dynamic from
simulation
engineering from the University of Alberta.
condenser
Dynamic were analysis estimated using
is favoured 1.7
can bar
greatlyto improve
3.0 bar. theThisaccuracy
provides of cesses were simulated in a closed
Ben Leviton is a Process Engineer with Fluor
correlations
over steady state re ortedmodelling in in estab
the the
columnscope to load
relief increase the column
calculations. This loop to estimate the real value
Canada Ltd. He has five years’ experience in
lished
following and reliable literature.4,5,6,7
situations: throughput
article offers in case guide
a brief of an of increase
when of energy savings and the area
LNG, SAGD, and refining technologies with
The payback
• Systems period for
impacted by additional
upstream in
andthe toluene
where fraction simulation
a dynamic of the feed. is requirement
a primary focus for heat simulation
on process exchangers. and
expenditure
conditions that required
change for overnew timeheat Energy
required. saving analysis correctly,
When applied reveals The
relief results of holds
analysis. He the study
a BSc inreveal that
engineering
exchangers
• Relief loads and pipeline on
dependent rerouting
instru- scope
dynamic for analysis
savings ofcan around
help 40.1%,
avoid 40.1%,
chemistry32.3%, and 84.8%
from Queen’s savings
University, in
Kingston,
mented control response unnecessary scope and project delays. Ontario.

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www.eptq.com PTQ Q4 53
Q2 2018 35

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 Advanced catalyst characterisation for
improved hydrocracking performance
Advanced analytical techniques delivered new insights into catalyst structure
and manufacturing leading to improved performance material

MAUREEN L BRICKER, SARIKA GOEL, MARJORIE MIRANDA and TONY VRANJES

Honeywell UOP

W
hen choosing a hydroc-
racking catalyst, refiners +16
base their selection upon R2 = 0.9847
Total distillate yield, wt% +14
desired product properties and R2 = 0.9934
yield profile. Some refineries desire +12
a heavier product slate and hydro-
cracking catalysts that produce +10
high distillate yield. Other refin- +8
ers want the ability to use uncon-
verted oil (UCO) to produce higher +6
value lubricants. Having a catalyst +4
that hydrogenates across the entire
+2 HC-410LT
product slate to improve quality is
Last generation reference
important. The catalyst manufac- Base
turer now has the ability to produce
10

15

20

25

30

35
+5

+
hydrocracking catalysts to deliver
se

se

se

se

se

se

se

se
Ba

Ba

Ba

Ba

Ba

Ba

Ba

this functionality. The refiner may
obtain the desired product slate by
selecting an individual catalyst or
combining appropriate performance
aspects by staging multiple catalysts.
The use of improved advanced
analytical techniques has helped
explain phenomena that lead to per-
formance properties of catalysts. Of
particular value is the Titan 0-300
ke Super- aberration-corrected
electron microscope. This instru-
ment produces a surface level
representation of the catalyst at a
resolution that was not previously
possible. The application of char-
acterisation techniques to hydro-
cracking catalysts gives scientists
a better understanding of interac-
tions between the active metal and
the catalyst support. This infor-
mation sheds light on the effects
manufacturing processes and acti-
vation procedures have on catalyst
performance.
This article presents the results
of an advanced characterisation
study comparing two commer-
cially successful Honeywell UOP
hydrocracking catalysts. The goal
Ba
Conversion, wt% (691ºF)
Figure 1 Total distillate yield
was to explain, on a molecular met the performance targets of a
level, the reasons for differences in particular Asian refiner.
performance. The study compares HC- 10 to
UOP HC- 10 LT, a commercially a commercially proven reference
proven hydrocracking catalyst hydrocracking catalyst, HC-115 LT.
It was widely used in the same seg-
Having a catalyst ment for 10 years, before the 2015
introduction of HC- 10.
that hydrogenates nowledge obtained from the cat-
alyst comparison study was applied
across the entire in the development of Honeywell
UOP’s newest hydrocracking dis-
product slate to tillate catalyst, HC- 20 LT. This
has improved hydrogenation func-
improve quality is tion resulting from better metals
important utilisation and improves upon the
performance of Honeywell UOP’s
HC-32 LT, a proven, previous
known for high yield, high activ- generation hydrocracking cata-
ity and high viscosity index of the lyst. HC- 20 exhibits higher yield,
UCO, was chosen for the study. better activity and more hydrogen
HC- 10 has been accepted globally consumption. olume swell for
by base oil producers, with high hydrocracking of vacuum gas oils is
performance demonstrated in seven thereby increased. HC- 20 is com-
units. This article describes how it mercially available and has been

www.eptq.com PTQ Q4 2018 37

q4 uop.indd 1 13/09/2018 18:26


145
140
135
Viscosity index
130
125
120
115
110
105
100
0 10 20
Figure 2 UCO properties
sold into three commercial units in
201 .
This article also discusses perfor-
mance benefits that may be realised
from the increased hydrogenation
function of HC- 20 when used in
combination with other hydroc-
racking catalysts. This benefit was
demonstrated in pilot screening
studies of HC- 20 stacked with
HC- 10. This option would be bene-
ficial in applications processing dif-
ficult feeds.
Advanced characterisation study
The characterisation study com-
pares Honeywell UOP Unity
Portfolio hydrocracking catalyst
HC- 10 and a previous generation
catalyst HC-115, used as a reference.
Both catalysts are commercially
proven and are used in the lubes
segment. HC- 10 exhibits improved
yield (see Figure 1).
Background
HC-115, the reference catalyst, has
been successfully used for hydroc-
racking in the commercial lubes seg-
ment for over 10 years. HC- 10 was
introduced in 201 as a new genera-
tion hydrocracking catalyst for both
UCO for base oil plant feed and
distillate for fuels production. The
finely tuned hydrogenation func-
tion of this catalyst delivers a higher
dewaxed viscosity index than prior
generations, enabling production
of higher grade lube base oils. This
catalyst also offers proven higher
activity and diesel yields. HC- 10
delivers better metals utilisation for
38 PTQ Q4 2018
q4 uop.indd 2
Asia Pacific, North American, and
50 European regions.
45 The following example demon-
and nitrogen
40
strates successful performance by
HC- 10 in meeting the performance
35
targets of one particular Asian
Viscosity index 30
refiner. In 2017, HC- 10 replaced a
UCO sulphurUCO
Calculated viscosity index
25 catalyst from a different vendor in
Sulphur
20 this refiner’s hydrocracking unit.
Nitrogen
15 The prior catalyst system required
10 operation at higher than desired
5
conversion to meet the waxy I
target of greater than 13 , lowering
0
30 40 50 60 70 80 90 100 110 120 UCO yield. The refiner conducted
DOS its own pilot plant performance test-
ing to evaluate other catalyst ven-
dors and selected HC- 10.
HC- 10 met the waxy I target
at lower conversion, increasing the
improved hydrogenation and pro- yield of UCO, the desired product,
vides high distillate yield. and maximising profitability for
efiners require well-demon- the refiner. Commercial operation
strated improvements to risk chang- confirmed the predicted conversion
ing to a new catalyst. HC- 10 has at which the UCO I specification
received global acceptance by both would be met with HC- 10 (see
fuels and base oil producers and Figure 2). The sulphur and nitrogen
has been loaded in nine refineries in values were low in the UCO and
met specifications. HC- 10 con-
tinues to meet the refiner’s expec-
Stem micrograph tations, consistent with predicted
performance. Net conversion is at
target with higher middle distillate
yields than predicted.
Catalyst characterisations to
determine surface phenomena
HC- 10, a Ni catalyst, is prepared
using methods that differ from the
reference catalyst HC-115, resulting
Metal edge map
in superior total distillate yields.
Advanced analytical techniques
were used to characterise these cat-
alysts with the aim of determining
the phenomena responsible for per-
formance improvements.
The Titan 0-300 ke Super-
aberration-corrected scanning trans-
mission electron microscope (AC
STEM) uses atomic level imaging
to show catalyst surface morphol-
ogy not previously visible with
Si K-edge map
includes W M-edge traditional transmission electron
microscopy. In addition, spherical
Al K-edge map aberrations are reduced. Energy
dispersive -ray (E ) imaging
maps from the microscope showing
HC- 10 and HC-115 revealed new
information on catalyst support,
metal-metal interactions and inter-
actions between the support and
Figure 3 Chemical maps of HC-410 catalyst metals.
www.eptq.com
13/09/2018 18:26
dupont.indd 1 10/03/2017 10:54
cat tech.indd 1 26/02/2018 13:23
 The maps of HC-410 showed
localised areas of alumina, amor-
phous silica alumina, and zeolite
(see Figure 3). Individual metals
tended to locate preferentially in
selected localised zones of a par-
ticular base material, and to avoid
others. The micrograph shows the
localisation of elements. Some metal
species migrate to edges of stacks.
Alumina rich regions underlie the
stacks (nanostructures). The bulk
metal sulphide stacking stoichiome-
try was thus determined.
Figure 4 shows high angle annu-
lar dark-field scanning transmis-
sion microscopy (HAADF-STEM)
images displaying the differences in
catalyst structure observed with dif-
ferent preparation methods. HC-410
has shorter length flakes and less
layer stacking of the sulphided
metal particles.
Discoveries made during this
work about the inter-relationships
of these phenomena led to new
methods of catalyst preparation and
activation that optimise activity and
yield.
Development of new
distillate catalyst
A new molecular level understand-
production. Once-through screening
studies were performed to simulate
Reference catalyst
the first stage of a two-stage unit
for a potential commercial applica-
tion at a North American refinery.
Honeywell UOP proposed the com-
bined use of HC-620 and HC-410 in
a stacked configuration in response
to the specific goals of higher volume
swell and longer cycle life. The pilot
plant test shows the higher hydro-
gen consumption within the HC-620
stack (see Figure 6) which translates
HC-410 directionally to higher volume swell.
Higher activity is shown with the
HC-620 and HC-410 staged stacks
when compared to operation with
HC-410 only.
HC-620’s first commercial use
The North American refiner
selected HC-620 for its next
reload. It was chosen based on the
increased hydrogen consumption
and activity successfully demon-
Figure 4 Differences in catalyst structure strated in the pilot plant tests. The
with different preparation methods proven performance by HC-410 cat-
+22.5
+20.0
HC-620 commercial
HC-620 prototype
+17.5 Reference catalyst
Distillate yield

ing of metal behaviour was gained +15.0

in the HC-410 study and applied +12.5
during the development of a new +10.0
distillate catalyst, Honeywell UOP +7.5
HC-620. This is a new base with
+5.0
supported metals. During each step
+2.5
of manufacturing, characterisation
methods were used to verify that Base
20 30 40 50 60 70 80 90
the desired metals-to-support inter-
Distillate conversion
actions were produced. The result
was a considerably more active cat-
+70
alyst with higher yield. HC-620 prototype
Pilot plant tests confirmed +60 HC-620 prototype
that HC-620 achieved an activity
Distillate conversion

Reference catalyst
improvement and a higher distillate +50
yield over Honeywell UOP’s distil-
+40
late hydrocracking catalyst, DHC-32
(see Figure 5). For a once-through, +30
heavy vacuum gas oil test, the cat-
alyst exhibits very high hydrogen +20
consumption, maximising volume
+10
swell and higher liquid product
yield. Base
The commercial catalyst shows 670 680 690 700 710 720 730
identical activity and yields to the Average catalyst temperature
early prototypes of the catalyst. Thus
the performance benefits are main-
tained in large scale commercial Figure 5 Pilot plant test comparing HC-620 performance with reference catalyst

www.eptq.com PTQ Q4 2018 41

q4 uop.indd 3 13/09/2018 18:26


+55
Required temperature, ºF
+45
+35
+25
+15
+5
Base
45
+50
NMR H2 consumption, scfb
+40
+30
+20
+10
Base
45
Figure 6 Screening studies of HC-620 and HC-410 catalysts in a stacked configuration
alyst, equal or better to predictions,
weighed in the selection.
During 2018, HC-620 will be
loaded into a large two-stage hydro-
cracker to process a difficult heavy
vacuum gas oil feedstock with
very high metals content. Much
of the hydrocracker fixed reactor
volume is used by demetalisation
catalysts to remove nickel, vana-
dium, sodium, phosphorus, iron,
and silicon present in the feedstock.
Therefore, a high activity hydroc-
racking catalyst is required in the
first stage. The higher activity of
HC-620 will meet the objective of a
longer cycle length while maintain-
ing high distillate yields.
Conclusion
The use of state-of-the-art charac-
terisation instruments, such as the
Titan 80-300 keV Super-X aberra-
tion-corrected electron microscope,
aided in a characterisation study
comparing commercially success-
ful Honeywell UOP hydrocracking
catalysts. The study showed new
42 PTQ Q4 2018
q4 uop.indd 4
Pretreat + HC-410
Pretreat + Stack HC-680/HC-410
50 55 60 65 70 75
Gross conversion, wt% at 680ºF-
Pretreat + HC-410
Pretreat + Stack HC-680/HC-410
50 55 60 65 70 75
Gross conversion, wt% at 680ºF-
features of the catalyst and gave
insight into traditional catalyst man-
ufacturing techniques by providing
molecular level knowledge directly
correlating to performance.
The study showed that catalyst
metal-to-metal and metal-to-sup-
port interactions are affected by
manufacturing and activation.
Catalyst finishing and activation
techniques affect metals orienta-
tion and localisation with respect
to support. These phenomena and
their effects upon performance are
interrelated. Catalyst preparation
methods may be optimised by using
advanced characterisation.
Honeywell UOP applied innova-
tive research in the development
of the new HC-620 hydrocrack-
ing catalyst, with increased vol-
ume swell, C5+ yield and activity.
Characterisation studies also ver-
ified the basis for the superior per-
formance of HC-410 for fuels and
lubes applications.
The Honeywell UOP Unity
Catalyst Portfolio offers the opti-
mum combination of commercially
proven hydrocracking and hydro-
treating catalysts to meet processing
objectives whether maximising die-
sel, lubes, or naphtha production.
The authors acknowledge Honeywell UOP’s
Research Hydrocracking team, especially
Melanie Schaal and Sergio Sanchez.
Maureen Bricker is a Senior Fellow with
Honeywell UOP. Her current role is primarily
new catalyst invention and improvement
in hydrocracking technology. With 36 years
of experience at UOP, she holds 44 catalyst
patents and recently authored a chapter on
hydrocracking for distillate production in the
updated Springer Handbook of Petroleum
Processing. She holds a bachelor’s degree in
chemistry from the University of Alabama in
Birmingham, a PhD in chemistry from Ohio
State University, and a black belt in six sigma
methodologies.
Sarika Goel is a Senior R&D Scientist in the
Hydroprocessing Group with Honeywell
UOP, responsible for the development of
new and improved catalysts in hydrocracking
technology. Prior to this role, she worked
in exploratory research, responsible
for breakthrough technology ideas in
petrochemicals and refining. She has published
five scientific papers and holds two US patents,
and holds a bachelor of technology degree in
chemical engineering from the Indian Institute
of Technology, Delhi in India and a PhD in
chemical engineering from the University of
California, Berkeley.
Marjorie Miranda is a Principal Technical
Sales Engineer in the Hydroprocessing Sales
Support team with Honeywell UOP’s Catalysts,
Adsorbents & Specialties business. Her
responsibilities include developing technical
solutions for hydrocracking catalyst reload
opportunities. Prior to her current position,
she held roles in field operating services and
hydroprocessing sales support for the Process
Technology & Equipment business and holds a
bachelor’s degree in chemical engineering from
the University of Illinois at Chicago.
Tony Vranjes is Global Product Marketing
Manager for Hydrocracking Catalyst,
responsible for new product commercialisation,
marketing and manufacturing within
Honeywell UOP’s Catalyst, Adsorbents
and Specialties group. He has held regional
management positions in sales support and
product line management for UOP’s Refining
and Petrochemicals catalyst business in
Asia Pacific. Prior to joining UOP, he held
engineering and operations management
positions in refining/renewables businesses
in Australia and his native New Zealand. He
holds a degree in chemical and materials
engineering from the University of Auckland,
New Zealand.
www.eptq.com
13/09/2018 18:27
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jonell.indd 1 08/06/2018 19:32
 Corrosion management strategies for
opportunity crudes
Automation and wireless technologies and a combination of corrosion monitoring
techniques help refiners to be flexible in processing opportunity crudes

KJELL WOLD and TIM OLSEN

Emerson Automation Solutions

T
he refining industry is con-
tinuing to see pressures on
margins, making opportu-
nity crudes – the discounted, lower
price crude oil feedstocks purchased
on the spot market – an even more
financially attractive option.
Crude oil being the largest varia-
ble expense for a refinery, opportu-
nity crudes offer considerable cost
savings over other more traditional
crudes. For example, even a 1% use
of opportunity crudes discounted
to $ bbl in a medium si e refin-
ery (300 000 b d capacity) can lead
to crude oil cost savings of up to
$ .5 million y ($1 000 day). Some
larger refiners that are processing
discounted opportunity crudes
can potentially save hundreds of
millions of dollars on crude oil
purchases.
However, the use of opportunity
crudes comes with several potential
risks, such as increased total acid
number (TAN) levels, improper’
blending and the dangers of corro-
sion. This article will look at these
risks – in particular corrosion – and
analyse what technologies are avail-
able to tackle them.
The rise of opportunity crudes
Opportunity crudes are an impor-
tant part of the refinery mix, espe-
cially for coastal refineries that can
process over 50 different crude oils
during a year.
Crude oil imports from Canada
into the US, for example, have
increased by 10-12% year-on-year
with much of the crude coming from
the Alberta Sands, characterised by
heavy, sour and acidic crude, high
levels of TAN and high sulphur.
These characteristics – along with
nitrogen and aromatics content and
high viscosity – are often key ele-
ments of opportunity crudes.
The challenges – crude oil quality
and problem areas
The quality of opportunity crudes
has been a regular issue, with the

Overhead corrosion P Gas

and capacity limits
P
Naphtha
Fouling T stabiliser
Downstream unit
P F limits
Naphtha
Downstream
T
units
L F Steam FBP
T F Kerosene
H2S, API variability Fouling from Increased fouling L F Steam IBP FBP
and crude blending paraffin waxes and and asphahene F Light diesel
volume shrinkage filterable solids precipitation T
L F Steam IBP
O2 F Diesel
Emulsion T D360 Cong
Q’s CO L F Steam
instability
A Fired Flood
heaters T P F AGO
Q’s F
Stripping D360
F T tower
Feed T OFlash
Product property
B F T
Desalter Atmospheric differences
F
tower
F F Steam Naphthenic corrosion
Air T
Crude HV
blender Fuel
To vacuum
tower

Figure 1 Opportunity crudes can lead to a number of problem areas in a refinery

www.eptq.com PTQ Q4 2018 45

q4 emerson.indd 1 13/09/2018 17:40

 Crude Oil Quality Association
(COQA) supporting the recent
report from CME Group (which
operates an options and futures
exchange) on the quality specifica-
tions of light sweet crude as defined
in their futures contracts.
This includes five additional
parameters in characterising West
Texas Intermediate (WTI) and
domestic sweet crude oil: distillation
characteristics, vanadium content,
nickel content, TAN, and micro car-
bon residue content.
Opportunity crudes, however, can
lead to a number of problem areas
in a refinery, mainly due to qual-
ity issues, as Figure 1 illustrates. It
should also be noted that certain
opportunity crudes, such as tight
oil, will have different challenges
(filterable solids, waxes, H2S and
amine scavengers, potentially higher
vapour pressures, and so on) com-
pared to traditional crude oils. We
will discuss some of these elements
in more detail later in this article.
The challenges of crude oil blending
Many properties of opportunity
crudes typically do not match the
specifications of the refinery and
process equipment, and therefore
need to be blended. In these cases,
there is a need to blend two or more
crudes together to achieve the neces-
sary properties to meet and best lev-
erage the refinery’s capabilities. For
example, operating the refinery with
a light crude oil can result in the
under-utilisation of heavy crude oil
processing units, such as a delayed
coker.
Blending, however, is typically
performed on the back end for crude
oils to produce the required specifi-
cations in final fuel products, such
as gasoline and diesel, and is less
sophisticated (typically involving
just ratio blending) on the front end.
Furthermore, with numerous
crude oil feedstocks and varying
properties, modern and flexible
measurement capabilities when
blending are vital. This is important
not only to ensure the best utilisa-
tion of processing units within the
refinery, but also in managing the
expected yield and potential profita-
bility from the optimal crude blend.
Blending too much opportunity
46 PTQ Q4 2018
q4 emerson.indd 2
Crude oil
tanks Blend
controller
Blended
crude to
CDU-1
Blended
crude to
CDU-2
Blended
crude to
CDU-3
Figure 2 Real time monitoring contributes
to safer crude blending processes
crude into the mix, for example,
can potentially lead to accelerated
fouling, thus eliminating the bene-
fits of any discount. The percentage
of each blended crude used is also
vital with little margin for error.
For example, an 0-20% blend with
20% tight oil may not be enough to
see accelerated fouling, whereas a
70-30% blend may be unstable and
have unwanted accelerated fouling.
Asphaltenes also do not dissolve
in crude oil but exist as a colloidal
suspension; they are soluble in aro-
matic compounds such as xylene
but will precipitate in the presence
of light paraffinic compounds such
as pentane. Tight oils tend to have a
higher percentage of naphtha, thus
making conditions favourable for
asphaltenes to precipitate out when
too much of the crude blend con-
tains these lighter components.
Another point of vulnerability is
heat exchanger bundles which are
typically instrumented on the inlet
and outlet but not within individual
bundles. As fouling is not linear, it
is often therefore difficult to deter-
mine in which bundle fouling might
occur.
There is also the issue of blending
shrinkage. The blending of light and
heavy crude oils is seldom additive
and the blended volume is usually
less than the sum of the individ-
ual component volumes. Because
metering is usually by volume in the
US, shrinkage can be an important
source of volumetric error, having
a particular impact on the custody
transfer of large oil volumes.
Such volume shrinkage, however,
is not observed when using mass
flow to blend crude oils, as – while
the volume may change – mass
does not (see Figure 2). Measuring
mass based instead of volume based
flow for crudes provides the right
percentages required for the crude
blend, as is the case with direct mass
flow meters.
In all cases, real time monitoring
and measurement is vital in deter-
mining the maximum amount of
discounted blends and crudes that
can be safely processed.
TAN levels and the dangers
of corrosion
One of the main characteristics of
opportunity crudes is high TAN
levels. This includes high lev-
els of acidity and naphthenic acid
content – a mixture of naturally
occurring cycloaliphatic carboxylic
acids recovered from petroleum
distillates.
Typical elements of high TAN
crudes include fewer light compo-
nents, high density and viscosity,
high gel asphalt content, and high
salts and heavy metals content.
Such crudes also have the potential
to cause greater corrosion to key
refinery assets and other problems,
which might include emulsion insta-
bility, increased fouling and asphal-
tene precipitation, API variability
and volume shrinkage, and unin-
tended crude switch disturbances.
It is also important to note that the
types of acids in a crude oil vary and
that the boiling point distribution
can differ dramatically, according
to different crudes, as Figure 3 illus-
trates. The TAN value for a crude oil
indicates the potential for corrosion
problems, but this one acid number
measurement does not provide all
the details on acids within the crude
oil and the impact on refinery assets.
The cost benefits of high TAN
crudes, however, are clear as they
are discounted by availability, ease
www.eptq.com
13/09/2018 17:40
sinopec.indd 1 23/02/2018 14:45
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 of distribution and known risks.
The optimal blending of high TAN
crudes and conventional crudes can
therefore play a key role in refinery
profitability as long as the effects of
corrosion are closely monitored and
mitigated.
The most common forms of cor-
rosion in refineries caused by high
TAN levels are naphthenic acid cor-
rosion (NAC), sulphuric acid corro-
sion, hydrochloric acid corrosion,
and hydrofluoric acid corrosion. A
key challenge, however, is that these
different forms of corrosion often
behave differently and are found at
different plant locations.
NAC is a form of corrosion that
takes place in the high tempera-
ture parts of a plant, typically in
primary and vacuum distillation
units, as well as in associated pipe-
work. NAC increases when there is
higher TAN and sulphur content in
the crude and therefore when there
is more opportunity crude blend-
ing. NAC is also often triggered by
velocity, and therefore is found in
bends in pipework. Another chal-
lenge with NAC is that the impact is
localised and the exact impact point
is difficult to predict.
Meeting the challenges – wireless
technologies
It is in this context that refiners need
to learn how to successfully process
opportunity crudes while mitigat-
ing unwanted harm to the refinery
assets.
Effective methods and technolo-
gies to upgrade and process oppor-
tunity crudes can resolve these
problems and provide attractive
margins to the refinery as well as
offering a balance between integrity
risk and improved profitability.
How can this be achieved? There
needs to be a focus on online meas-
urement and the automated mon-
itoring of likely bottlenecks to
identify problems early and manage
expensive inhibitor additive usage.
Adding too much or too little corro-
sion inhibitor can cause problems, so
having online measurement ensures
proper use.
There is also a need to predict
when equipment is likely to have
problems detecting when the
rates of fouling accelerate (in heat
www.eptq.com
q4 emerson.indd 3
6
Ostra
5 Jubarte
TAN, mg KOH/g
Kearl
4 AWB
Altimira
3
WCS
2 Lloyd
Vasconia
1
0
0 200 400
Cut end boiling point, ºF
Figure 3 The types of acids in a crude oil can vary and the boiling point distribution can
differ dramatically, according to different crudes (Source: Improving refinery flexibility and
margins with high TAN crudes, D Comer, Dorf Ketal Chemicals, 2017 COQA)
exchangers, for example) and when
the percentage of discounted crudes
needs to be reduced. It is also impor-
tant to identify favourable condi-
tions for corrosion (process fluid)
and where corrosion is taking place
(wall thickness).
Finally, the early detection of
accelerated fouling, asphaltene pre-
cipitation and filterable solids plug-
ging is vital. In such cases, there is
a need for online health trending,
continuous monitoring and analysis,
and the ability to determine which
exchanger bundle needs cleaning.
To this end, high-density temper-
ature measurements (four sensors
and just one wireless transmitter)
– coupled with a single multi-input
wireless or wired digital transmitter
– can better identify where fouling
occurs, leading to the percentage
of opportunity crude in the blend
being immediately reduced.
Corrosion monitoring technologies
Along with corrosion mitiga-
tion measures, such as metallurgy
upgrades and chemical inhibitors,
another means of addressing the
issues of processing opportu-
nity crudes is that of corrosion
monitoring.
Such technologies can mitigate
safety and environmental incidents,
increase plant availability and asset
life, ensure process optimisation
and increased profitability, and
tackle the wide variety of corrosion
challenges, such as amine corro-
sion, ammonium chloride corrosion,
hydrochloric acid (HCI) corrosion,
NAC, ammonium bisulphide cor-
600 800 1000 1200 1400 1600
rosion, and more. Let us examine
some of the options.
Wall thickness monitoring
Wall thickness monitoring via ultra-
sonic (UT) measurements is a fast
and easy corrosion monitoring tool,
providing direct metal thickness
measurements.
Ultrasonic measurements are used
for wall thickness measurements
and for detecting defects over sev-
eral decades. Installing UT sensors
permanently on the pipe (clamped
or stud-welded to any pipe section
or asset) for regular measurements
on the spot provides increased sta-
bility and sensitivity. Real-life sen-
sitivity for UT measurements is
typically 10-20 µm for changes in
wall thickness. It is also possible
from the form of the wave signal to
determine surface conditions inside
the pipe.
UT can now be deployed on pipes
or vessels with temperatures up to
600°C. Wireless communications
also makes installation and data col-
lection rapid and cost effective, with
the sensors able to be installed any-
where. Arrays of UT sensors are also
used to cover for uneven corrosion
in the monitored area.
The limited maintenance require-
ments and ease of installation also
allow for a wide distribution of sen-
sors for integrity management and
corrosion and process insights.
Process fluid monitoring
hen it comes to process fluid mon-
itoring, options include probes and/
or coupons.
PTQ Q4 2018 49
13/09/2018 17:40
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Figure 4 A refinery probe from Emerson
Probes provide the highest sensi-
tivity and fastest response to chang-
ing corrosion rates. As an example,
a 20 mil element probe can detect a
corrosion rate of 5 m y (defined by
NACE International as moderate
severe) within hours and less than
a day, depending on measurement
frequency. This high sensitivity
makes probes valuable for the fast-
track monitoring of process changes
www.eptq.com
q4 emerson.indd 4
Figure 5 Probe data plot showing electrical resistance probe metal loss vs time with
slops production (blue) and corrosion from wireless transmitter (red)
and for tuning processes, such as
corrosion inhibitors. Figure 4 shows
a refinery probe from Emerson.
Electrical resistance (E ) probes
have been commonly used over dec-
ades for monitoring corrosion and
are based on measuring changes
in electrical resistance as the thick-
ness of the probe’s measurement
element decreases due to corrosion.
However, sensitivity, reliability and
visualisation capabilities have signif-
icantly increased over the years.
Figure 5 illustrates the data gen-
erated from an E probe installed
in a European refinery. The data
example shows a short period when
heavy slops were added to the pro-
cess. Observe that the scale (red
numbers) is in micrometers, and
that random variations in readings
are hardly visible in this scale. Also
observe how the changes in metal
loss (red line), which were due to
blending heavy slops with the feed,
can be tracked over the two day
period displayed.
There are also electrochemical
methods, such as linear polarisation
resistance (LP ) probes, that are
mostly used for water systems. Such
probes have an extensive history for
direct corrosion rate measurements.
More sophisticated electrochemical
methods, such as harmonic distor-
tion and electrochemical noise, are
also available.
Finally, there are in-line corrosion
coupons. Samples, pre-weighed to
0.1 mg, are inserted in the pipe or
vessel for a given period (say three
to six months). Upon retrieval, cou-
pons are cleaned, weighed again,
and from the weight loss the corro-
sion rate is calculated. The coupon
surface is also analysed with respect
to localised attacks (pits) and possi-
ble deposits. Coupons come with the
lowest equipment costs but the infor-
mation is not as readily accessible.
The field signature method
Another non-intrusive technology is
the field signature method (FSM, see
Figure 6). FSM is based on feeding
an electric current through a mon-
itored section of a pipe, pipeline or
vessel. The applied current sets up
an electric field that is monitored as
voltage drop values between a set of
sensing pins installed on the exter-
nal pipe wall.
The initial measurement sequence
measures the voltage drop between
all pairs of sensing pins and is called
the field signature. Later measure-
ments are compared to the field
signature, where general corrosion
can be seen as a uniform increase in
voltage drops between all pin pairs,
and localised corrosion can be seen
as a local increase in the values.
It is important to note that corro-
sion is measured between the sens-
ing pins, meaning that the complete
monitored area is covered, not only
under each sensing pin. The latter is
an important feature for monitoring
localised corrosion, such as naph-
thenic acid corrosion.
FSM data can be plotted as metal
loss versus time for the efficient
PTQ Q4 2018 51
13/09/2018 17:40

Figure 6 A field signature method sensing pin matrix installed on a pipe bend
tracking of changes in metal loss ver-
sus changes in process (inhibitors,
opportunity crude mix), or in 3D
plots that show the distribution of
corrosion over the monitored area.
Typical sensitivity for FSM is 0.1% of
wall thickness for general corrosion,
corresponding to 10-20 µm in most
cases. The maximum number of
sensing pins is 256, storage readings
capacity is 500, and FSM technology
can operate at up to 500°C.
An FSM refinery application
Figures 7 and 8 show data examples
from a European refinery appli-
cation. Figure 7 shows metal loss
versus time plots from FSM for a
vacuum distillation unit (VDU)
overpass bend. The total scale is -200
200
Pair 1
Pair 7
Metal loss, µm
Pair 13
100
0 feedstock selection, inspections dur-
−100
2012
Figure 7 Shows metal loss versus time plots from FSM for a VDU overpass bend
52 PTQ Q4 2018
q4 emerson.indd 5
µm to +200 µm. Observe the increase
in corrosion rates at time when
opportunity crude processing starts.
It can also be observed that the cor-
rosion rate is four times higher in
the VDU overpass bend compared
to the crude oil distillation unit
(CDU) overpass bend (not shown in
this plot).
Figure 8 features a three-dimen-
sional plot showing the distri-
bution of corrosion for the same
case. Observe the distribution of
corrosion for the VDU overpass
bend where significant corro-
sion is detected at the end of the
matrix. This has been observed
on several installations; hence,
sensing pin matrixes are now
installed in slightly further down-
2013 2014 2015 2016
stream bends compared to earlier
installations.
Tackling communication and data
management challenges
One of the key challenges in imple-
menting all the above technologies is
communications. Many older corro-
sion monitoring systems were based
on off-line data collection using
portable instruments, resulting in
difficult access, lack of information
ownership and fewer data points.
The standardisation and accept-
ance of wireless communication (for
instance, through the WirelessHART
standard), however, has revolution-
ised the industry, leading to unpar-
alleled quality and frequency of data.
Today, a wide number of appli-
cations are available with IEC
62591 (WirelessHART) standard
communications (pressure, tem-
perature, vibration, and so on),
and can be combined through the
same gateway, providing online
communication to a range of data
management solutions or control
systems. Ultrasonic wall thickness
sensors, for example, can provide
online wall thickness measurements
tracking wall losses of 10 µm or less,
and in-line probes can provide con-
tinuous measurements on the corro-
sivity of the fluid.
Finding the best combination
Combining technologies will often
give the best and most reliable mon-
itoring information.
For corrosion monitoring and the
effective processing of discounted
opportunity crudes and crude
blends, including high TAN crude
oils, a combination of monitoring
solutions for developing the best
and most reliable corrosion mitiga-
tion programme is recommended.
Online information from corrosion
monitoring sensors (both intrusive
and non-intrusive) can be utilised as
a comprehensive programme which
includes metallurgy upgrades, use of
chemical inhibitors, crude oil (blend)
ing turnarounds, and proper repair/
replacement of assets damaged by
corrosion when identified.
A well-designed corrosion mon-
itoring solution contributes to
improved integrity and safety and
www.eptq.com
13/09/2018 17:41
 the proposed approach is reliable 2 Antos G J, Aitani F M, Catalytic Naphtha ‘blocked-in’, th
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 Mitigating overhead corrosion
Advanced data handling and sensitivity analysis enable fuller understanding of
the influence of operating changes on salt formation
BRANDON J H PAYNE, KEYURKUMAR PATEL, COLLIN W CROSS, MATTHEW G COLLINS and PABLO A GRIECO
SUEZ Water Technologies & Solutions
I
n the pursuit of efficient and prof-
itable refinery operation, own-
er-operators must continuously
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ical availability and long short term
asset protection. Further complicat-
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One area where the ability to bal-
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hile the crude overhead system
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anisms typically controlled through
the implementation of a variety of
strategies, salt induced corrosion
is one of the most common. Salt
point is defined as the temperature
at which the first neutralisation
salt begins to precipitate from the
vapour phase. ue to the severity
of this commonplace mechanism,
www.eptq.com
q4 suez.indd 1
the overall success of an overhead
corrosion control application is
highly dependent on keeping salt
point temperatures for all amines
at least 15 F below the water dew
point ( P), or water wash injec-
tion temperature if a water wash is
in use. Because of the difficulty in
computing dynamic water wash
and salt point temperatures, as well
as their associated safety margins,
common industry practice is to tar-
get a tower top temperature (TTT)
that is at least 15-25 F above the
salt point. This criterion is a way of
helping to ensure that salt precip-
itation will occur downstream of
the P. eeping corrosive salts
from precipitating upstream of the
water’s initial condensation point
(ICP) is a desired condition because
they will then precipitate into a sig-
nificant amount of water to dilute
and wash them.
Salt formation temperatures
are driven by the product of chlo-
ride and amine partial pressures.
These partial pressures are, in turn,
related to the measured concen-
trations of amines and chlorides
in the overhead receiver water.
This relationship links salt precip-
itation to both chemical and oper-
ational factors, thereby allowing
many potential corrosion control
measures to negatively influence
product distribution and quality.
To better understand how prevail-
ing conditions can induce salt dep-
osition and associated reliability
problems, both the P and salt
points for all amine salts need to
be computed frequently and linked
to their inputs via sensitivity cal-
culations. Commonly there are
multiple key amines circulating in
the system with potential to show
dramatic day-to-day variability.
Understanding the variability of
amines and their associated salt
points can be key in effectively mit-
igating the corrosion process over
time.
Frequently measuring ion con-
centrations and computing salt
points for each amine species in a
dynamically varying unit can be a
tedious and time-consuming task.
Historically this has led to a lack
of visibility into dynamic linkages
between corrosion drivers and day-
to-day operational decision making.
Salt fouling and associated cor-
rosion can be more detrimental
to overhead reliability than ICP
corrosion via acid attack. To gain
a thorough understanding of the
corrosion process, salt points for
all amine chlorides in the system
need to be computed frequently
and salt point safety margins rig-
orously enforced. If this is done,
then overhead operations are much
more robust, stable, and optimised.
However, the necessary computa-
tions have historically had limited
application by primarily provid-
ing only retrospective information
with negligible predictive capabil-
ity on current or future conditions.
Additionally, neither the granu-
larity of data nor the sensitivity
analysis techniques necessary to
understand the relative influence
of operational inputs on simultane-
ous distillation and salt formation
have been available. The described
situation is somewhat analogous
to attempting to drive an automo-
bile with only a rear view mirror
and no ability to see the road ahead
to plan a safe and effective route
PTQ Q4 2018 55
13/09/2018 17:47

Greater frequency and
medium latency still misses
key corrosion events with
no predictive response
Salting events
Salt probability index
Low frequency,
high latency
sample results
Results latency period
Figure 1 Salt precipitation events comprehensively characterised with high frequency
and low latency amine speciation in a column overhead system
through driving ha ards. In the
world of overhead corrosion, it has
long been recognised colloquially
that 0% of metal loss occurs during
10% of the time in operation. Due
to the reasons above, and the con-
stantly changing tendency to form
corrosive salts in an operating unit,
it has remained difficult using tradi-
tional approaches to systematically
identify the proverbial 10% of time
where damage-causing episodes
occur so that effective mitigation is
possible.
An often overlooked aspect of
process system corrosion is that
what is typically measured as the
average corrosion rate is really the
sum of contributions from a series
of discrete random events mostly
occurring at unobserved points
in time. Corrosion loss is, there-
fore, not usually a continuous loss
of metallurgy over time. In tradi-
tional corrosion monitoring and
mitigation programs, the data upon
which key performance measures
are based are collected infrequently.
These substantial gaps in data col-
lection produce significant blind-
spots in the evaluation of asset
integrity, and many discrete corro-
sion events remain undetected. The
56 PTQ Q4 2018
q4 suez.indd 2
High frequency and low
latency enable real-time
response to a corrosion event
Medium frequency, High frequency,
medium latency low latency
sample results sample results
Salting probability index
Amine speciation performed
ability to detect individual corro-
sion events effectively is often most
limited by the relative difficulty of
obtaining frequent, timely, com-
plete, and accurate amine speciation
data and the inability to easily com-
pute the changing impact on salt
precipitation, fouling, and corro-
sion (see Figure 1). Historically, the
low frequency sample testing and
long laboratory turnaround time
required to receive detailed results
was inadequate for capturing and
characterising salt fouling quickly
enough to allow for broad based
proactive corrosion mitigation.
As advances in amine speciation
techniques have been made, lower
latency and higher frequency sam-
pling results can be incorporated
into the industry’s monitoring pro-
tocols. This is important because a
higher frequency and lower latency
of sampling can provide greater
granularity in corrosion monitoring
data with dramatically increased
reaction time. Many of the salting
events that were previously missed
can now be captured, and effective
mitigating actions can be ranked
and evaluated quickly enough to
allow both unit operations and the
corrosion process to be simultane-
ously manipulated on a day-to-day
basis.
ith the potential for significant
variability in both concentrations
and types of tramp amines enter-
ing the unit, the ability to charac-
terise a wide array of amine species
is crucial to properly mitigate over-
head system corrosion. If the focus
of amine speciation is limited to
only a few commonly problematic
amines arising from the use of H2S
scavengers, increased sampling fre-
quency may not allow for sufficient
breadth of coverage to effectively
mitigate overhead salt fouling and
corrosion in a repeatable way. SUE
ater Technologies Solutions has
addressed this dilemma by estab-
lishing a network of satellite field
laboratories in key locations. This
not only substantially reduces high
sample latency periods, but also
allows cost effective routine screen-
ing for over 22 different amines on
a bi-weekly or more frequent basis.
This combination of breadth of
coverage, high frequency, and low
latency provides a comprehensive
analytical protocol for the industry.
Unfortunately, due to the time
required to process manually
the amount of data generated by
enhanced amine speciation, as well
as the lack of available tools capa-
ble of a rigorous sensitivity analy-
sis, even when data are occasionally
available, a backward-looking view
is largely what has been practi-
cally possible to date. ith the
introduction of the computational
techniques in the Safe one proto-
col, a sensitivity analysis can now
be performed autonomously on
the highly detailed data described
above. This ability has enabled
operators to evaluate a wide range
of novel proactive chemical and
operational actions, used on a daily
basis to minimise active corrosion as
it occurs. This advance represents a
significant step forward in overhead
corrosion mitigation diagnostics
and prognostics that has not previ-
ously been available.
hile advances in metallurgy,
inhibitors, injection practices, and
monitoring techniques have stead-
ily occurred, overhead corrosion
measurement and predictive prac-
tices have not, due to the challenges
www.eptq.com
13/09/2018 17:47 cat Ark
 described above. With use of the
high concentrations
SafeZone technique, of theH2new
S (>30 000
com- When to stop injection and gasoil hydrodesulphurisation units
ppmv) because of potential dam- 250 equipment
disconnect DMDS and naphtha hydrotreaters.

Boot water amines,

putational framework allows con- NH3
age to metallurgy
tinuous and tosensitivity
and quantitative the recy- Once more 200 than the stoichiomet- e ser ice o ers
CHXA
cle compressor. But stabilisation
computations, leading to the rapid of ric amount of DMDS is injected, • Safe equipment: workers have
MEA
H S concentration at typically 10 000 how can one150 be sure that the cat- never been exposed to any H2S leak.

ppm
identifi
2 cation of seemingly random SafeZone indicated CXHA salting.
ppm is not
corrosion so easy
events because
and their H2S
precise alyst is fully 100sulphided? A con- • High reliability and accuracy:
Discussion with customer initiated.
results from the balance
causes. During an emerging corro- between venient test is as follows: DMDS continuous H2S monitoring has
catalyst consumption (full 50 on hold for a while been ac ie ed at all t e refineries
sion event, the onset can be flconver-
agged injection is put
sion of metal oxides
rapidly and alerted digitally to sulphides)
while and H2S is observed;
0 since a fresh that commissioned the service, and
H2S formation
anddriving either from feedstock containing1 2
sulphur 3 is 4con- 5 H S 6concentration
7 8 9 always
has 10 11been
the forces of salt formation 2
DMDS or from sulphur species in tinuously introduced, the H2S con- Time, in line with other analytical meth-
days
and their sensitivities are quantita-
the feedstock. Hence, continuous centration in the recycle hydrogen ods (reactive tubes, on-line gas
tively revealed. The demonstrated
measurement of H S concentration should increase due to the conver- chromatography, for instance).
method takes near 2 real-time data Figure 2 Selected overhead accumulator boot water amine concentrations, ppm
and its rate of decrease or growth is sion of sulphur compounds in H2S • A useful tool to better manage
from operating crude units and uses
key information to decide when and by the catalyst and no further H2S the catalyst sulphiding operation
them to compute how changing by SUEZ allows rapid, continuous, Also available is a ‘what if’ inter-
by ow muc t e ow rate consumption by the fully activated according to catalyst manufacturers’
factors, such as crude diet, process- and quantitative computations for face for evaluating potential miti-
needs to be adjusted. Figure 2 illus- catalyst. Figure 2 is an interesting procedures and guidelines.
ing objectives, operations, control amine hydrochloride salt forma- gating options on both current and
trates this optimisation of DMDS demonstration of this test: DMDS • Continuous H2S indication helps
schema, physical constraints, set tion in an operating crude unit to historically recorded events. The
ow rate durin a ydrocrac in injection was stopped after 18 hours to antici ate ow rate
points, and randomly varying be performed easily. When using sophisticated signal processing and
unit sulphiding operation. In addi- and H2S levels stabilised for two changes; DMDS consumption and
amine, and chloride levels, cause the technique, the driving forces of analytics algorithms of the platform
tion to the technical advantages for hours before they began to increase sul idin time can be si nificantly
corrosion events. The practical salt formation and their sensitivi- are then used to make a wide array
catalyst activation, this approach sharply. This test can be achieved reduced.
objective of the methodology is to ties are quantitatively revealed and of valuable capabilities become
minimises the excess of DMDS used safely and e ecti ely wit continu-
drive timely, precise, and proactive deconstructed graphically and in practical, seamless, and potentially
for the activation and leads to some ous H S measurement.
mitigation options in a detailed and tabular2 mode into a group of indi- Francis fully Humblot
automated.is NewImportantly,
Business Developer,
the
si nificant sa in s urin t is unit thiochemicals for the oil and subject
gas market
systematic
activation, fashion
53.2 tonnesacrossof a DMDS
wide cators which
Conclusion detail potential action- computations are done to
with Arkema, Lacq, France. He holds a PhD in
variety of event types
was finally consumed w ic is using graph- able options. The output is available the actual physical and operational
The Arkema analyser has been used heterogeneous catalysis from the University of
ically
only oriented
6% above reports
the and widgets.
stoichiometric to
forallmonitoring
parties dailyH2Sonin their mobile constraints affecting the unit during
the recycle Lyon, France.
The SafeZone platform
requirement of the catalyst. developed devices
hydrogen of hydrocracking report.
in a comprehensive units, its daily operation.
Email: francis.humblot@arkema.com

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BEST CATALYST avantium.com/rct

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www.eptq.com Catalysis 2018 6357
PTQ Q42018

q4cat Arkema.indd
suez.indd 3 3 26/02/2018
13/09/2018 16:19
17:47
 been detected in time. However, the
TTT-SDT (actual SafeZone optimised)
SafeZone engine’s ability to examine
TTT-SDT (what-if normal operations) multiple variables simultaneously
MET-SDT (actual SafeZone optimised) and quantify the relative impact
50
MET-SDT (what-if normal operations) on the system’s salt point allowed
40
the site to continue to evaluate
30 results and further optimise unit
20 performance and maximise asset
T, ºF

10 protection while production was

0 maintained. The SafeZone program
−10
−20
−30
−40
1 2 3 4 5 6 7 8 9 10 11
Time, days
Figure 3 Calculated temperature safety margins (°F) in the column overhead system
In a real world example taken corrective actions have historically
from an operating refinery on the been prohibitively time consum-
US Gulf Coast, the utility of the tech- ing and thus provided only a back-
nique was demonstrated in a crude ward-looking perspective to unit
unit constrained in both its desalter operational controls. The SafeZone
performance and crude overhead platform, on the other hand, rap-
safety factors. As is the case with idly alerted the operations team to
many refineries, a significant crude the changing corrosion conditions
dietary change driven by an unfore- and allowed them to evaluate a list
seen event rapidly changed both of potential mitigating actions that
product and operational economics typically fall outside of traditional
as well as the availability of usable evaluation methods (see Figure 2).
opportunity crude slates. This sit- The amine speciation protocol
uation forcibly altered the histori- used by SafeZone, which screens
cal ‘normal’ operating parameters for more than 22 different amine
of the unit. To maintain the deter- species several times each week,
mined safety margin of the refinery, detected the increased concen-
the TTT was targeted to remain at a tration of cyclohexylamine in the
minimum of 15°F higher than the overhead system and determined
calculated salt point to help mitigate it to have the most detrimental salt
corrosion in the overhead system. point. Following the automatic eval-
Historically, unit operations had uation of the emerging event by
allowed for an average TTT safety the SafeZone analytics engine, the
margin of 40°F above the computed quantitative output immediately
salt point. However, due to the rapid allowed the refinery team to take
and unforeseen change of crude diet, several key actions which prevented
several unit operational challenges the system from violating its corro-
altered this historical paradigm. Unit sion safety metrics.
operation was, therefore, adjusted to The calculations indicated a sub-
accommodate the new performance stantial decrease in both the TTT
envelope so as not to cross the min- safety margin as well as the over-
imum safety threshold. head chloride safety margin imme-
Driven by these changes to crude diately following the crude changes.
diet and operations, an additional The analysis reported by the
influx of the tramp amine cyclohex- SafeZone engine prompted the site
ylamine increased the salt precip- to increase rapidly the caustic injec-
itation potential in the overhead tion rate to counter the detrimental
system, threatening asset integrity effects of rising chlorides. Under
by narrowing the specified salt the traditional evaluation method-
point safety margin. Traditional ology, this singular move might
methods of calculating salt point have been deemed sufficient to cor-
safety margins and determining rect operational deficiencies had it
quantitatively demonstrated that
the unit could further reduce salting
potential by both raising steam rates
and lowering the rate of the top
pump around (TPA) while corre-
spondingly increasing the flow rate
of the tower’s upper naphtha reflux,
which was normally kept to a mini-
mum for trim control only. The off-
setting and balanced duties of these
changes kept tower temperature at
targeted levels while reducing salt
point. The reduction of TPA rate,
however, lessened the duty of asso-
ciated cold train exchangers, lead-
ing to a slight lowering of desalter
temperature below target range.
Desalter temperature was normally
controlled according to a predeter-
mined fixed temperature target. In
this case, however, the crude slates
viscosity and overall good desalter
performance allowed the refinery to
make a choice to effectively trade a
few degrees of desalter temperature,
along with a slight steam increase,
and a slight excess of caustic for
chloride reduction to obtain a sig-
nificantly reduced overhead salting
potential. The refinery operations
team decided these small projected
offsets from normal operation
offered an acceptable trade for risk
mitigation and so tower operations
were successfully adjusted, lead-
ing to significant improvements in
salt precipitation potentials with no
measured loss of operational per-
formance, product distribution, or
product quality.
Without the use of the SafeZone
program, this non-intuitive set of
linked actions could not have been
evaluated in a timely manner in
order to be effectively implemented
on the unit during the event. The
daily calculation of these factors
and the associated ongoing adjust-
ments of these variables allowed
the team to continuously improve
the TTT safety margin immediately

58 PTQ Q4 2018 www.eptq.com

q4 suez.indd 4 13/09/2018 17:47


beginning at 3-4°F above the tar-
geted safety margin of T 15 F.
As Figure 3 shows, by using the
on-stream predictive capabilities
of the Safe one platform, 10-15 F
dynamical salt point safety margin
improvements were realised with
respect to what would have been
obtained using the previous operat-
ing scheme (the dashed lines).
This case demonstrates that it is
often the balanced combination of
changes to multiple contributing fac-
tors that provide for the most robust
and efficient unit protection. The
adjustment of only one performance
parameter, such as temperature,
would not have been sufficient to
optimise corrosion mitigation with-
out leading to a loss against produc-
tion targets. SafeZone allows for the
rapid, automatic, and comprehen-
sive evaluation of multiple factors
that reveal action paths that would
have otherwise been obscured by
traditional evaluation paradigms.
By using the SafeZone platform,
it became possible to effectively bal-
ance corrosive interactions caused by
an unplanned introduction of new
crudes and production targets while
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PN11502.indd 1
q4 suez.indd 5
also considering practical equip-
ment challenges and unit constraints.
Balancing processing objectives
against corrosion risk to achieve
a customised processing strategy
was shown to reduce significantly
the corrosion potential for the frac-
tionator overhead. Importantly, this
was done while maintaining pro-
cessing targets and optimising the
use of existing corrosion mitigation
methods. The automated salt point
analytics framework engendered by
SafeZone provides the ability to opti-
mise salting risk against a refinery’s
production objectives in a flexible
and quantitative way.
SafeZone is a mark of SUEZ.
Pablo Grieco is Senior Regional Engineer with
SUEZ Water Technologies & Solutions and is
responsible for technical support, programme
development and application optimisation
for the company’s refinery process chemical
programmes used in refinery corrosion
management. With over 20 years of experience
of specialty chemicals, he holds a BSc degree
in chemical engineering from the National
Technological University of Argentina.
Matt Collins is Site Lead/Process Lead
with SUEZ Water Technologies & Solutions,
overseeing and managing numerous process
• Quickly switch between process streams:
saves €50,000/year
• Reduce instrument- and calibration maintenance:
saves €15,000/year
chemical applications including corrosion,
desalting, fouling, and finished fuel additives.
With over 25 years of specialty chemical
experience, he holds a BS in electrical
engineering from Texas A&M University.
Keyurkumar S Patel is a Lead Products
Application Engineer with SUEZ Water
Technologies & Solutions, and is responsible for
the development, deployment and technical
support of the company’s corrosion modelling
software applications used in refinery corrosion
management. With 10 years of professional
experience, he holds a PhD in chemical
engineering from the University of South Florida.
Brandon J H Payne is a Lead Products
Application Engineer with SUEZ Water
Technologies & Solutions and is responsible for
technical support, programme development
and application optimisation for the company’s
refinery process chemical programmes used
in refinery corrosion management. With over
20 years of experience in the hydrocarbon
processing industry, he holds a BSc degree in
chemical engineering from the University of
Illinois Urbana-Champaign.
Collin Cross occupies a role in the Product
Management organisation of SUEZ Water
Technologies & Solutions and leads the global
Center of Excellence for refinery corrosion
control. With specialities in structure activity
relationships, formulation, thermophysical
modelling, computer programming, and
software development, he holds a PhD in physical
chemistry from University of Oklahoma.
w
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ic
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PTQ Q4 2018 59
21/02/18 12:16
13/09/2018 17:47
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cri.indd 1 25/02/2018 15:09

 Resisting metal dusting corrosion
Metal dusting corrosion can limit operating conditions, but recent developments
in alloys are helping to combat the phenomenon
RAMESH VENKAT
Tubacex
M
etal dusting occurs in envi-
ronments containing carbon
monoxide and hydrogen in
the temperature range 350-800°C.
Several industrial applications are
subject to metal dusting corrosion
such as plants producing hydrogen
by steam reforming processes in
industries including oil refining and
ammonia and methanol production.
Other examples could be coal gasi-
fication plants, synthetic gas pro-
duction and direct iron reduction
plants.
The extent of corrosion in terms
of general loss of material and/
or pitting corrosion is severe, and
pre-mature failure of tubes and
pipes can lead to loss of revenue
and jeopardise the safety of equip-
ment and plant. Lots of research
activity has taken place and several
studies are still in progress to miti-
gate metal dusting corrosion. Some
of the ways and means developed
by industry to increase the life of
tubes and pipes from metal dust-
ing include use of gas phase inhib-
itors and diffusion coatings. This
article is not going to discuss the
pros and cons of these alternatives
and we believe each solution could
be effective in given circumstances.
The article will discuss nickel alloys
and their performance and effec-
tiveness in combating metal dusting
corrosion.
Mechanism
Metal dusting involves the disinte-
gration of bulk metals and alloys to
metal particles, oxides and graph-
ite at high temperatures in envi-
ronments that are supersaturated
with carbon. It is generally believed
that the phenomenon is most wide-
www.eptq.com
q4 tubacex.indd 1
Figure 1 Surface resulting from severe
metal dusting
spread in the temperature range
400-800 °C. Such corrosion has been
observed in processes in chemical
and petrochemical industries where
hydrocarbons or other strongly car-
burising atmospheres are encoun-
tered. It is a catastrophic form of
corrosion that occurs when mate-
rials are exposed to environments
with high carbon activity. It breaks
up bulk metal to metal powder (see
Figure 1).
The suspected mechanism is
firstly the deposition of carbon on
the surface of the metal. The car-
bon is, for instance, derived from
carbon monoxide in a gas with a
carbon activity much higher than 1.
This carbon forms iron carbides in
the case of an iron alloy or diffuses
into the metal in the case of a nickel
alloy and, in both cases, after super
saturation the matrix decomposes
to carbon and fine metal particles
(and carbides). In a general under-
standing of the chemistry, at lower
temperatures the rate of reaction
is too low to be significant, and at
much higher temperatures carbon
activity and deposition decrease.
A critical item of equipment that
encounters metal dusting corro-
sion is a boiler where the operating
temperature zone is in the range
400-800°C.
Nickel alloys
The use of high nickel, high chro-
mium alloys is preferred as they
have much better corrosion resist-
ance to metal dusting than normal
austenitic steels. While alloying has
enabled an increase in resistance
to metal dusting corrosion, it also
leads to other non-desirable proper-
ties such as difficult workability and
weldability.
Importance of alloys in metal
dusting corrosion resistance
M Alloy A, an alloy devel-
oped by VDM and Tubacex in part-
nership, can produce seamless tubes
and pipes. Three key requirements
for steels in this application besides
resistance to metal dusting corro-
sion are creep strength, weldability
and workability.
Corrosion resistance
A high percentage of chromium is
important in any stainless steel and
in nickel alloys for metal dusting
corrosion resistance as it provides
a stable passive layer of chromium
oxide. As can be seen in Table 1,
the latest alloys developed to fight
metal dusting, such as M Alloy
A, have a maximum chromium
content of 30%, which makes it one
of the better alloys to be used in this
application.
However, any localised rupture
of the chromium oxide layer can
lead to significant intake of carbon
from the process atmosphere into
the alloy. Here, the addition of alu-
minium leads to the formation of a
PTQ Q4 2018 61
14/09/2018 13:09
 Nominal composition of commercial alloys
Weldability, workability and creep
VDM Alloy 699XA has good welda-
bility under argon. Welding recom-
Alloy Ni, % Cr, % Fe, % Mn, % Si, % Al, % Ti, % C, % Others mendations and requirements need
Nominal %
600 72 16 8 0.3 0.3 0.3 0.3 0.08
to be followed. Workability at room
601 60.5 23 13 0.2 0.2 1.4 0.4 0.05 temperature is comparable to 601.
602CA 62 25 9 2 0.18 Y, Zr Also creep resistance is similar to or
690 59 29 9 0.2 0.1 0.3 0.3 0.02 better than 601.
693 62 29 4 3 0.02 Nb, Zr
VDM Alloy
699XA Balance 30 Max. 2.5 2 0.02 Nb, Zr Conclusion
efiners would like to run their
Table 1 plant under peak operating con-
ditions to take advantage of cost
protective aluminium oxide scale to metal dusting corrosion in com- and efficiency but corrosion of steel
or sub-scale. From Table 1 we can bination with its good workabilty. alloys under such harsh conditions
see that VDM Alloy 699XA has an Laboratory results of metal loss has been a deterrent factor. While
aluminium content as high as 2%. through metal dusting in a highly a lot of effort is being put into the
A much higher aluminium con- carbonising gas (37% CO, 9% H2O, research and development of alloys
tent, such as 3%, would reduce 7% CO2, 46% H2, ac=163, p(02)= for metal dusting, recently devel-
workability. 2.5*10-27 bar at 600°C, 20 bar) shows oped alloys have so far shown
Increasing chromium to about that normalised maximum mass promising results.
30% together with a low iron con- loss for VDM Alloy 699XA was
tent is necessary for high metal close to 0.001 after 4000 hours of
dusting corrosion resistance in exposure. Also, no pitting showed
nickel alloys. in a total exposure time of 5692 Ramesh Venkat is Heat Exchanger Product
This combination of alloying ele- hours; the time to first pit was sig- Manager with Tubacex’s Group Global
ments makes VDM Alloy 699XA nificantly higher than 02CA, 01 Technical Marketing department.
one of the best alloys for resistance and 690. Email: vramesh@tubacex.com

34th
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q4 tubacex.indd 2 14/09/2018 13:09

 Front end filtering of unconventional oil
Processing unconventional oils requires technologies such as electrostatic
separation to handle higher amounts of filterable solids
TIMOTHY HOUSER, STEPHEN GIBSON and VICTOR SCALCO
General Atomics Electromagnetic Systems
I
ncreasing market demand for
cleaner fuels, both in quality
and quantity, is pushing refin-
eries to address the degrading
quality of crude oils as unconven-
tional oil reserves become more
predominant with a lower ini-
tial cost. To gain economic bene-
fit, refineries need to make better
use of lower quality oil resources
such as Venezuelan oils, Canadian
oil sands, and tight oil (also called
shale oil). Oil production in the
United States is predominantly
made up of tight oil which is pro-
jected to increase through the early
2040s.1 In 2017, tight oil made
up 54% of total US production.2
In 2040, tight oil is expected to
account for nearly 70% of total US
production.2 Recent analysis indi-
cates that tight oil formations are
located throughout the world and
constitute a substantial share of
global technically recoverable oil
resources.3
efineries process a variety
of crude oils to maintain a posi-
tive margin. Major investments
by refiners in the past incorpo-
rated equipment needed to match
the composition of available crude
oils to their refineries’ configura-
tions and to maintain the market
production levels set by each refin-
ery. Many of these investments
were made prior to the advances
in technology that enabled produc-
tion of tight oil. Successful refiner-
ies are characterised by their ability
to respond to market demands and
by their ability to adapt to a chang-
ing oil base by overcoming the
mismatch between their current
capabilities and those needed to
process tight oil.
www.eptq.com
q4 GA.indd 1
Challenges in processing
unconventional oils
While economically viable, uti-
lising unconventional oils pre-
sents challenges in downstream
maintenance and product quality.
Unconventional oils contain higher
levels of unwanted components
that promote corrosion, erosion and
fouling within process equipment,
poisoning of catalyst, increased
contaminants in end products, and
environmental pollution.7 The high
toxic nature of arsenic, cadmium,
lead and mercury in the environ-
ment has made them priority pol-
lutants. To maximise the benefits of
unconventional oils, refineries will
need new technologies and methods
to remove or reduce the unwanted
components contained in these oils
prior to transforming them into
fuels.
The growth in production of light
tight oil has made it more read-
ily available to US refiners, which
makes it a secure source of domes-
tic energy. However, refineries will
need to invest more in transpor-
tation and process modifications
required to process tight oil. Given
its variation in composition4 and
large amount of filterable solids,5
tight oil presents a number of chal-
lenges throughout the refining pro-
cess. These challenges cost time
and energy and reduce throughput
within the refinery which is why
tight oil generally costs less then
Brent (global crude oil benchmark)
or West Texas Intermediate (US
crude oil benchmark).
During the processing of tight oil
and other unconventional oils, refin-
eries need to address the increase of
filterable contaminants sediments
such as heteroatom compounds
(incorporating sulphur, nitrogen,
and oxygen), metals, solids, and
water. One of the significant chal-
lenges is the high level of solids
entrained within the crude oil, 100-
700 ppm. This level of solids is often
coupled with a large number of sol-
ids below 20µ. These solids tend to
destabilise emulsions in desalters
and carry over oil coated solids that
contribute to preheat fouling along
with crude oil distillation unit con-
version loss.6
What are solids?
There are two classes of solids
mostly referred to in refining: basic
sediments and filterable solids. The
former are particles greater than 20µ
that can settle out in the desalter
and in settling tanks for decant oil.
Smaller particles referred to as fil-
terable are typically smaller and
range below 20µ. The effects of con-
tamination from these solids can be
seen downstream of the desalting
process and after fluidised catalytic
cracking. Fouling, erosion, catalyst
poisoning, and inventory contami-
nation erode the profit potential of
the refiner when left to conventional
processing methods. Entire tank
farms may be impacted whereby
tank turnaround schedules are
shortened due to excess settling,
and large investments are required
to remove the hazardous waste cre-
ated in decanting these solids.6
Crude oil composition
Crude oil is a naturally occurring
complex hydrocarbon mixture con-
taining organic and inorganic com-
pounds and species which vary
depending on geological origin.7
PTQ Q4 2018 63
13/09/2018 18:04
 Figure 1 provides a general over-
view of the constituents that make
up crude oil. Hydrocarbons con-
stitute the largest group of organic
compounds found in crude oil.8 The
main hydrocarbon compounds are:
• n-paraffins and isoparaffins
(alkanes)
• Olefins (not usually found in
crude oils but produced in a num-
ber of refining processes)
• Naphthenes (cycloalkanes)
• Aromatic and polyaromatic
structures.7,
Crude oil contains varying
amounts of heteroatomic (sulphur,
nitrogen, and oxygen) compounds,
metals, emulsified water, and min-
erals. Table 1 provides a more
detailed breakdown of the constitu-
ents of crude oil.
Unconventional oil
Unconventional oil is crude oil
produced or extracted using tech-
niques other than the conventional
(oil well) method.9 Unconventional
oils are more difficult and costly to
process since added steps (hydro-
treatment, demetallisation, catalytic
dewaxing, and desulphurisation)
are required within the refinery to
convert these oils to lighter prod-
ucts. Unconventional oil feedstocks
tend to be heavy conventionally
produced crude oils, extra heavy
Breakdown of crude oil constituents11
Constituent
Hydrocarbons:
Paraffinic (alkanes)
Naphthenic
Aromatic
Dissolved gases
Sulphur compounds
Organic nitrogen compounds
Organic oxygen compounds
Organometallic compounds
Colloidal particles
Surfactants
Metals
Water (S&Wd or BS&W)d,e
Solids
Notes
a: Hydrogen sulphide is present as dissolved gas; b: Surfactants; c: Present in porphyrins;
d: Sediment and water; bottoms sediment and water; e: Microorganisms can be present in crude oils
Table 1
64 PTQ Q4 2018
q4 GA.indd 2
Organic
compounds
Heteroatom Hydrocarbons
compounds (C, H)
(S, N, O) Crude
oil
Inorganic Metals Organic
compounds compounds
(Na+, Ca++, Cl−) (Ni, V, Fe)
Figure 1 Constituents of crude oil8
oil that has a low degree of mobility
and tar sand bitumen diluted with
lighter hydrocarbons or synthetic
crude oils to meet pipeline gravity
and viscosity specifications.10
There are also lower density
crude oils that fall into the uncon-
ventional oil category, such as
tight oil, that are problematic due
to their high filterable solids con-
tent and paraffin levels. Although
tight oil is considered sweet (low
sulphur content), the processing of
this type of oil can be problematic.
Tight oil can contain over seven
times more filterable solids than
conventional crude oil.5 efineries
have reported filterable solids in
excess of 200 lbs per thousand bar-
Chemical type
Straight chain; branched chain alkyl cyclopentanes; alkyl
cyclohexanes alkyl benzenes; aromatic naphthenic fluorenes;
polynuclear aromatics
Nitrogen (N2); carbon dioxide (CO2)
Elemental sulphur (S8), hydrogen sulphide (H2S)a, mercaptans;
organic sulphides, disulphides and polysulphides thiophenes and
benzothiophones; sulphones
Pyridine, quinoline
Carboxylic acids (including naphthenic acids)b, alcohols,
phenolsb, aldehydes, ketones, esters, ethers, oxyacids
Porphyrins
Asphaltenes; resins; paraffin waxes
Sulphonic acids, sulphonates, sodium naphthenates
Vanadium, nickelc, ironc, aluminum, sodium, potassium,
calcium, copper
Fresh or saline
Sand, dirt, silt, soil dust, mud, corrosion products
(metals’ oxides, sulphides, salts)
rels of tight oil.5 For a refinery pro-
cessing 100 000 b d, this yields
more than 10 tonnes of solids per
day entering the refinery with the
crude oil.5 The increased level of
paraffin waxes creates operational
issues by fouling preheat sections
of crude oil heat exchangers and
other equipment and by remaining
on the walls of railcars, tanks, and
piping. Paraffin waxes that stick to
vessels walls and piping can trap
components within the crude oil
which creates localised corrosion if
not removed. Other issues include
increased asphaltenes, crude oil
incompatibility, and deficiencies in
product qualities (for instance, cold
flow properties such as cloud point,
pour point, and cold filter plugging
point).5
Typically, unconventional oils
have a high total acid number (TAN
0.5 mg OH g),11 higher density
and viscosity, high quantities of fil-
terable solids (sulphur, salts, and
metals), unstable asphaltene com-
pounds, and difficult-to-remove
chloride salts.10 These constituents
are concentrated in the low vola-
tile (bottoms) fractions which are
normally alkylated to lighter frac-
tions. They can also be coked, which
yields a lower value product than
the alkylated products.12
The main characteristics of heavy
oils (high viscosity and significant
content of heteroatoms) are directly
related to the significant presence
of higher polar compounds, such as
resins and asphaltenes.7 Asphaltenes
contain high amounts of molecules
of variable aromaticity with differ-
ent contents of heteroatoms, such
as sulphur, and complexed metals,
such as nickel and vanadium, which
are harmful compounds to refining
processes and to the environment.7
Metals in crude oils
Metal concentrations in crude oil
are influenced by several character-
istics including type of geological
formation, location, age of the rocks,
and depth. These factors can cause
metal concentrations to change
considerably from one source to
another. Metals are more concen-
trated in unconventional oils at
concentration levels between a few
tenths to several hundred parts per
www.eptq.com
13/09/2018 18:04

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1 12/14/17 12:21
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16:38
 million, while heteroatoms are pres-
ent at several percent.7,13
Metals in crude oil have adverse
impacts in the refinery including
deactivation poisoning of catalyst
during catalytic cracking, increased
coke formation, reduced quality
of finished products, and environ-
mentally adverse impacts includ-
ing release into the environment
during exploration, production
and refining. Nickel and vanadium
are the most abundant metals and
occur partly as organometallic com-
pounds (metalloporphyrins).3,7
Nickel and vanadium occur mainly
in crude oil in the following forms:
• Non-polar metalloporphyrin com-
pounds which complex principally
with nickel, vanadium, iron, or
copper
• Poorly characterised and hypo-
thetic (not confirmed) high molec-
ular weight polar non-porphyrinic
species
• Naphthenic acid salts which bind
principally with Ca, Mg, n, and Ti.7
There are no metalloporphyrins
in saturated fractions of crude oils.
Metalloporphyrins are predomi-
nantly present in the heavy polar
fractions of crude oil (about 5% of
total concentration in vacuum resid-
ual).7 Porphyrins are strongly asso-
ciated with asphaltenic compounds
by - bonding, or can be trapped in
asphaltene aggregates (see Figure 2).7
Crude oil issues treated prior to
transfer and processing
Crude oils vary greatly across the
worldwide supply and are pre-
treated to meet minimum quality,
composition and physical property
requirements, prior to trans-
port via pipeline or other method.
Transportation via a pipeline is the
most common method for conven-
tional oil. Common requirements
for pipeline transportation are den-
sity (max 0. g cm3) and viscos-
ity (max 350 cST),16 and the BS
content (0.2-0.5%)15 is generally low
to mitigate corrosion problems.
Operational temperature is also a
consideration and varies seasonally.
Unconventional oils, such as tight
oil, are normally transported by rail
or truck due to the limited pipeline
infrastructure available for those
crude oils.
66 PTQ Q4 2018
q4 GA.indd 3
: NH HN :
Figure 2 The 18-electron cycle of
porphyrin, the parent structure of
porphyrin highlighted5
The properties of crude oil
extracted from the field and poten-
tially at each well head need to be
determined so that existing or new
pretreatment processing methods
can be applied prior to its transfer to
storage, transport (pipeline, rail or
truck), and ultimately for process-
ing at the refinery. As demand for
processing higher levels of uncon-
ventional oil increases, new pre-
treatment methods are needed to
remove higher levels of metals, sol-
ids and other contaminants which
then allow more cost effective pro-
cessing within the refinery using
traditional methods.
Separation technology and methods
Unconventional oils contain higher
levels of unwanted components
that pose problems for most refin-
ery processes, especially heavy,
viscous oils requiring long resi-
dence time to allow for solids set-
tling or heavy metals separation.
Traditionally, refineries have relied
upon storage tanks and desalters to
separate the unwanted components
from received crude oil prior to dis-
tillation. ater, salts and sediments
are typically the components tar-
geted. Storage tanks allow oil to set-
tle under gravity prior to processing
within the refinery. esalting occurs
continuously at the front end of the
refinery and is intended to reduce
the salt content within the crude oil.
There is a need for improved
technologies, such as electro-
static separation, to handle the
higher amounts of solids and other
unwanted components in uncon-
ventional oils. By implementing
electrostatic separation or another
similar technology on the front end,
refineries could boost yields, reduce
fouling and maintenance require-
ments, and improve operational
performance. The challenge for
refineries is to overcome the mis-
match between current capabilities
and those needed to process uncon-
ventional oils.
Conclusion
Growth in the production of uncon-
ventional oils has made them more
readily available. hile economi-
cally viable, the processing of these
oils presents the refiner with a wide
range of challenges which cost time
and energy and reduced throughput
within the refinery. The processing
of unconventional oils will require
refineries to address an increase in
filterable contaminants sediments
using technologies designed to fill
a capabilities gap. Simply under-
standing the variety of solutions
available and focusing on the low-
est cost separation technology is not
sufficient to realise the economic
opportunity proper removal of sol-
ids represents to the bottom line. By
adopting a more universal and man-
aged approach to front end separa-
tion instead of dilution and common
settling techniques, it is possible to
raise profitability and reliability to
this downstream sector.
References and further reading
1 EIA, Annual Energy Outlook 2018, U.S. Energy
Information Administration (EIA) website.
[Online] 6 Feb 2018, www.eia.gov/outlooks/
aeo/pdf/AEO2018.pdf.
2 Tight oil remains the leading source
of future U.S. crude oil production, U.S.
Energy Information Administration (EIA)
website. [Online] 22 Feb 2018, www.eia.gov/
todayinenergy/detail.php?id=35052.
3 Bryden, Kenneth, et al, Processing tight oil in
FCC: issues, opportunities and flexible catalytic
solutions, Grace website. [Online] 2014,
https://grace.com/catalysts-and-fuels/en-us/
Documents/114-Processing%20Tight%20
Oils%20in%20FCC.pdf.
4 Gutierrez Sama, Sara, Study of two
chromatographic techniques (GPC and TLC)
for the separation and specification of S, V and
Ni in petroleum products, University Oviedo
website. [Online] July 2014, http://digibuo.
uniovi.es/dspace/bitstream/10651/28752/3/
TFM_SaraGuti%C3%A9rrezSama.pdf.
5 Baker Hughes, Overcoming shale oil
processing challenges, Baker Hughes website.
www.eptq.com
13/09/2018 18:04
 [Online] 2013. www.bakerhughes.com/ 14 The National Academies Press, Spills of Storage at U.S. Refineries. [Online] Reuters, 14
ity is calculated as almost 3200
news-and-media/resources/white-papers/ Sept 2015. [Cited:
Diluted Bitumen from Pipelines:Sulphur
A Comparative
balance for case study 2b 3 Jul 2018.] www.reuters.
t/d after considering the required
overcoming-shale-oil-processing-challenges- Study of Environmental Fate, Effects, and com/article/us-usa-refineries-oilstorage-
white-paper.
design margin. Response, The National Academies Press TPD kemp-idUSKCN0RE17620150914.
Sulphur, TPD of
Olsen T, Working
6 Selection of thewith tight oil,
sulphur plantEmerson
con- website. [Online] 2016. www.nap.edu/ ppmw sulphur
website. [Online] Apr 2015,
fi uration also needs to ta e into www.emerson. read/21834/chapter/4#25.
Feed
com/documents/automation/working-tight-
account a refinery confi uration of 15Very high sulphur
Al.Temeemi H, crude
Crude Oil Pretreatment 50 570 Timothy Houser39 700is a Principal Systems
1213.6 Engineer
oil-en-38168.pdf. Very high sulphur
(preparation crude oil for distillation):
of crude 50 430 with General 39 700 2002.1 systems
Atomics, providing
three crude trains, hence the sulphur Total feed 81 000 3215.7
7 Scalco V, Separation: a complex conundrum. (degassing-dehydration & desalting). qu.edu. engineering for the design and integration
plant needs to have at least three Products
Apr 2018, Hydrocarbon Processing, 25-29. iq. C[Online]
-C4 [Cited: 2 Jul 2018] http://qu.edu.5500 of developmental 10 systems and 0.055 established
8trains soChemical
that the shutdown and 3
Eser S, Constitution of crude iq/el/pluginfile.php/103933/mod_resource/
Naphtha 5500 product lines, 50 which includes experience
0.28 with
maintenance plan of any of
oil, College of Earth and Mineral Sciences, the SRU content/1/preperation%20of%20crude%20
DPK/ULS kerosene 9200 both government 8 and commercial systems and
0.07
trains
The may be grouped
Pennsylvania with any
State University, FSC one
432 ULS diesel
oil.pdf. 18 000 leading development
8 teams. He 0.14
has worked as
of the crude
Petroleum trains.website. [Online] 2017.
Processing 16IFOWikipedia, Porphyrin, Wikipedia website, 1500 a systems engineer
5000 for 20 years in 7.5the defence
LSFO 36 000 10 000 360.0
e selected confi uration
www.e-education.psu.edu/fsc432/node/5. [Online] 20 Apr 2018, https://en.wikipedia.org/ and oil and gas industries and holds a BS in
Total product 75 700 368.0
9is Wikipedia.
3 x 1000 Unconventional
t/d for the present Oil. Wikipedia
case, wiki/Porphyrin.
Balance - for sulphur plant capacity electrical engineering from San Diego State
2848
website.
ee in [Online]
t e ro1 ision May for2018,a fourt
https:// 17 Drugbank, Metalloporphyrins, Drugbank University.
en.wikipedia.org/wiki/Unconventional_oil.
train to cater for future needs. This website,
Table 2b [Online] 2018. www.drugbank.ca/ Stephen Gibson is a Senior Process Engineer
10 Speight
confi J, Chapter ro
uration 3 - Corrosion
ides t ine refinery
o ti categories/DBCAT001436. with General Atomics, providing process and
units. Oil and Gas Corrosion Prevention. s.l.: Gulf 18 Frames, Electrostatic coalescers, Frames mechanical engineering for the design and
mised installation cost for the pres- o erational exibility will be furt er and procurement cycle when the
Professional Publishing, 2014. website, [Online] 2017, www.frames-group. integration of existing equipment and process
ent scenario, yet it has the capability increased and t e refinery will be fourth train is installed.
11 Groysman A Corrosion Problems and com/getattachment/c3d546f8-fe64-4be6- systems for government and commercial
to i e in
Solutions t eOilrefi nery and
Refining exibility wit
Petrochemical able to operate at full capacity even contracts. He has worked as process engineer
a1e1-79151d82766e/Electrostatic-Coalescer-
respect to its shutdown and
Industry, Tel Aviv: Springer International mainte- with one SRU train out of operation for
pl-web.pdf.aspx?ext=.pdf. Case study
29 years and3:holds
multiple crude
a BS degree trains
in chemical
nance plans.
Publishing, 2017. Each of the three SRU as Otzisk
19 the three operating
B, Oil/water separationSRU
technologies, – major refi
trains engineering fromnery revamp
Kansas State University.
trains
12 can easily
Reynolds be linofed
J G, Removal to tande
Nickel (3 x 1000
[Online] Apr t/d
2013.= [Cited:
3000 2t/d) will meet
Jul 2018] The third
www. Victor Scalcocase study
is Global is for a brown-
Commercial Strategic
shutdown
Vanadium Fromand Heavymaintenance of any
Crude Oils By Exchange sulphur demand for the worst crude Business
digitalrefining.com/article/1000798,Oil_ field ro ect w ic Manager-Gulftronic
Development in ol es t e
Reactions,
of the three 1, s.l.:crude
American Chemical
trains. ThisSociety,
oper- water_separation_technologies.html#.Wzq-
case ase b of t e refinery e en Electrostatic Separators with of
capacity enhancement General Atomics
a 9 million
2004, Vol. 49.
ational exibility allows t e refinery fE2Wz3s.
with some design margin. Keeping Electromagnetic t y refinery toSystems Groupt (GA-EMS),
million y alon
to Horr,
13 operateClarence Albert,85%
at about et al,
evenGeological
when theWhat-When-How,
20 capacity of theSeparation
future trainProcesses,
the working
with a on process in
change design and assay.
crude developmental
Table
Survey Bulletin 1100: Uranium
one of the SRU trains becomes and Other Metals [Online] The-Crankshaft Publishing’s, [Cited: downstream
same as the installed SRU train 3 shows the sulphur balance solutions for hydrocarbon
for the
In Crude Oil, U.S. Geological Survey Publications 3 July 2018] http://what-when-how.com/ recovery, including development of new
unavailable. ca acity also o ers t e benefit of refinery wit t e re am ed ca acity
website. [Online] 1961. https://pubs.usgs.gov/ petroleum-refining/separation-processes/. filtration and separation systems. He holds a
When the future train is added, drastically reducing the engineering and crude assay.
bul/1100/report.pdf. 21 Kemp J, Operational Constraints Limit Crude MA degree from the University of San Diego.

www.eptq.com PTQ Q4 2018 67

www.eptq.com PTQ Q2 2018 59

q4 GA.indd 4 13/09/2018 18:04

q2 fluor.indd 3 09/03/2018 17:36
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 Predictive analytics in corrosion
management
Real time prediction models offer a corrosion software sensor framework, a new
way to quantify process corrosion
PIERRE CONSTANTINEAU and SRIDHAR SRINIVASAN
Honeywell Process Solutions
P
rocess corrosion quantification
and degradation management
has hitherto been achieved
through after the fact inspections or
hardware based (coupons, online
monitoring) historical averages. Such
reactive corrosion assessment has
often meant that corrosion mitiga-
tion did not lead to corrosion avoid-
ance; rather, it has been an activity of
detection and remediation.
New software and intelligent
modelling technologies developed
over the last 20 years have enabled
a proactive, predictive, data driven
approach to corrosion quantification.
A novel, award winning software
framework incorporating intelligent
predictive analytics linked to a pro-
cess historian (Predict-RT) has been
created to provide process operators
with the ability to see corrosion dam-
age in real time. Built on decades of
intense experimental corrosion data
and predictive model development,
this framework offers first of its kind
insights to proactively manage unit
operations, optimise throughput
management and derive enhanced
safety and reliability through
real time linkages to process data.
The system also enables easy
implementation of industry best
Comparison of corrosion data acquisition methods
Inspections Years
Coupons
Thickness sensors
Corrosion sensors
Integrity operating windows
Real time corrosion monitoring
Predictive analytics
Table 1
www.eptq.com
Q4 hps.indd 1
practices through support for
API RP584 (Integrity Operating
Windows) and API RP970
(Corrosion Control Documents).
What is effective corrosion
management?
The impact of unexpected corro-
sion damage is far beyond what
is obtained through instrument or
coupon measured corrosion rates,
which is often managed using timely
inspections and scheduled retro-
fits. The most effective corrosion
management system takes multiple
approaches (for instance, corrosion
coupons, ultrasonic thickness meas-
urements, LPR/ER devices) to detect
and monitor corrosion in order to
mitigate effects of unforeseen corro-
sion damage.
To be effective, a corrosion man-
agement system (CMS) must be able
to:
• Promptly detect high corrosion
rate events and their locations
• arn the refinery of locations
where inspections should be done
earlier
• arn the refinery of locations
where equipment may not reach the
desired life
• Adapt to changing operating
Corrosion rate detection timescale
Months
Months Weeks
Weeks Days
Days Minutes
Days Minutes
conditions and therefore varying
corrosiveness
• Enable engineers to evaluate dif-
ferent mitigation strategies prior to
their implementation
• Enable process engineers and
operators to see the impact of opera-
tion conditions on asset integrity.
In addition, such a system must
provide cost benefits and efficien-
cies that positively impact overall
operations.
Current status of corrosion
management
For years, corrosion management
has relied on carrying out regular
inspections to track cumulative cor-
rosion damage and identify when
equipment should be replaced. Due
to the high cost of carrying out such
inspections, methods to prioritise
inspections have been developed.
Risk based inspection methodolo-
gies1,2 have been developed to help
prioritise inspections by using a
very detailed and rational process
based on the risks and consequences
of equipment damage. Risk assess-
ment is based on quantification of
probability of failure and conse-
quence of failure; that is, the his-
torically observed corrosion rates
Corrosion damage prediction
Hours/Days Weeks Months Years
Now
Now
Now
Now Hours/Days Weeks Months Years
PTQ Q4 2018 69
15/09/2018 07:05
 (from multiple inspections) and wall
thicknesses observed (from the last
inspections). Generally, knowledge
about the damage mechanisms and
how they affect the life of equip-
ment as well as criticality of failure
is considered. However, it is gen-
erally assumed that corrosion rates
will remain constant and that asset
integrity will degrade at a constant
rate – the same rate as previously
observed. Unfortunately, too often
inspections highlight locations
where corrosion rates were higher
than expected. These inspections do
not provide any insight on when the
damage occurred or how to mitigate
or avoid any future damage. Nor do
we know which specific process or
metallurgical parameters caused the
damage. Table 1 shows a comparison
of historical methods and software
driven prediction analytics from a
damage quantification perspective.
efinery engineers have used
corrosion coupons as a means to
enhance visibility of corrosion rates
and enable them to detect and react
to high corrosion rate events more
rapidly than is possible with inspec-
tions. Due to the temporary nature
of corrosion coupons (meaning cou-
pons are consumed), they provide
quantifiable measurements and can
be used to compare the corrosion
rates of various materials. However,
as with inspections, they do not cap-
ture the timing of when high corro-
sion rate transients occur, nor do
they provide new insight for mitiga-
tion strategies.
Current corrosion measurement
methods are not sufficiently sensi-
tive to detect process transients that
accelerate or decelerate corrosion
rates. Such transients may cause sig-
nificant damage in a short period
and the actual damage of the event
would be blended or averaged
within the overall corrosion rate
that coupons and inspections meas-
ure. The opportunity to detect and
work to eliminate such transients is
therefore impossible. This is why the
industry developed and deployed
real time hardware sensors.
Hardware sensors: a picture of
real time asset integrity?
Many refineries have installed hard-
ware sensors at ‘purported’ most
70 PTQ Q4 2018
Q4 hps.indd 2
critical locations in order to derive
near real time feedback on how their
operations are impacting corrosion
rates. It is important to note that
most online sensors do provide pipe
thicknesses in real time but have a
few problems:
• Lagging measurement: they do
not measure the damage rate but the
thickness. For a corrosion rate to be
obtained, enough damage must have
occurred for the thickness change to
be measurable. The notion of using
thickness loss as a proxy for corro-
sion rate is flawed because in situ
thickness measurements do not cap-
ture the exact corrosion rate, only the
average rate. The sensitivity to high
corrosion rate events depends on
the magnitude and duration of such
events.
• Sensing area is generally very
localised. Due to the small area
monitored by thickness sensors
to measure pipe thicknesses, mul-
tiple sensors must be installed to
increase the likelihood of captur-
ing a corrosion event. Installations
of arrays of thickness measurement
sensors around pipe elbows that fail
to detect and warn of an upcoming
pipe failure are not uncommon. The
pipe may leak mere millimetres from
an installed thickness sensor, yet
nothing would have been detected.
• Due to the cost of installing and
maintaining such sensors, only the
most critical and accessible locations
will be monitored. This leaves the
potential for missing the ‘big picture’
and only focusing on locations that
were problematic historically.
Corrosion sensors (electrical resist-
ance, linear polarisation resistance,
electrochemical noise) do not have
the lagging problem of thickness
sensors. They can provide very rapid
(every minute) corrosion rates and
even provide insight into pitting
corrosion. Their main drawback is
that they are intrusive: the sensing
element must be immersed in the
corrosive fluid. Installation can be
expensive; they cannot simply be
clamped onto a pipe and maintained
(akin to corrosion coupons, the
sensing element must be regularly
replaced). They can be considered as
instrumented coupons.
Hardware sensors do play an
important role in corrosion manage-
ment. When monitored alongside
process parameters and corrosivity,
they provide feedback on whether
changes in operating conditions
have a positive impact on corrosion
rates. They can help with optimising
operating conditions and chemical/
inhibitor utilisation. Since they meas-
ure the current state of the process
and equipment, they are not really
predictive on their own. By build-
ing history, we can see trends and
extrapolate into the future; however,
any deviation outside the range of
current operation will make any
future prediction unreliable. One
must assume a ‘steady state’ in cor-
rosion rates.
Knowledge based corrosion
management
Over the last few decades, under-
standing of how each damage mech-
anism affects refinery equipment
has evolved to the point where the
most important operating varia-
bles affecting corrosion rates have
been identified and several operat-
ing guidelines have been set to help
control corrosion rates to be within
acceptable limits. For some damage
mechanisms, predictive models are
now available and can help engi-
neers make specific, quantitative
recommendations on design, mate-
rials and operating conditions. These
models include software programs
to predict naphthenic acid and sul-
phidic corrosion,3,4 sour water corro-
sion,5-7 as well as amine corrosion in
refinery operations.8
Effective corrosion management
systems include this knowledge so
that (excessive) corrosion damage
may be prevented before it occurs.
Too often, this knowledge is dis-
covered once an investigation into
a high corrosion damage location is
under way and mitigation steps are
urgently needed. Preventing exces-
sive corrosion damage starts with
bringing the design data and operat-
ing conditions together with the lat-
est damage mechanism knowledge.
In order to simplify this marriage
of domain expertise with process
data and unit operational specifics,
many refineries have gone through
the process of creating damage
control or corrosion control doc-
uments. API has recently pub-
www.eptq.com
14/09/2018 15:05
 unplanned or scheduled
lished Recommended downtime
Practice 970: im ro ed
Models e ciencies
of process data: and
is a furt er removal or total sulphur
to use regression reduction.to
or extrapolation
of one or more facilities.
Corrosion Control Documents.9 In reduced chemical volumes required.
statistical model truly a predictive Scavengers are a feasible
quantify corrosion rates. Corrosion tech-
Short-term
these andthe
documents, temporary facili-
unit operations Today,
model? inexpensive triazine based nology, both technically and
is generally a very slow integrating eco-
ties are a ery ood fi t for relati
are divided into ‘corrosion loops’ ely liquidwe
Can scavengers
‘mine’ thecoupled
mountainwith ofmore
pro- nomically able to remove H
process and corrosion rate measure-2
S in
high tonnage scavenger systems
each representing a specific corrosive ad anced and e cient equi
cess and inspection data available ment applications worldwide and
ment is generally deficient or non- in a
due to the relatively
environment. For eachquick and sys-
corrosion low options
at provideto producers,
each refinery get a model mid-pre- wide range of operating conditions.
existent, at least compared with real
cost installation of facilities.
tem, the active and potential damage stream companies
dicting corrosion? Any and facility oper-
statistical time process data. The notion that
mechanisms are described, the var- ators with
model a moresufficient
requires economical and
input probabilistic
Marc Schulz is methods
an Engineercan withbeUltrafab
used
Mercaptans
iables impactingand other eachsulphur
mechanism comprehensive solution to a
output or cause effect relationshipsbreadth to quantify
Industries and has corrosion
been using H2prediction
S scavengers
compounds
identified. ecommended moni- of H
to 2
S applications,
construct a model. including:
Unlike pre-gas has proven
exclusively in histo befora17fallacy
work years. Hebecause
has been
The most
toring, commontechniques
inspection sulphur com- and and NGL treatment in onshore
dicting failures of rotating equip- and the multivariate
involved directly in thecausal relationship
design and fabrication
mitigation steps are isdocumented.
pound to be removed H2S, as it is o s oreusing
ment o erations in amine
vibration and
analysis, of over 1500
between H2S removal
process application
parameters systems
and cor-
poisonous,
A natural corrosive
extension and the most
of Corrosion acid gas facilities and even
predicting corrosion failures using spe- and associated
rosion equipment installations, and
is not known.
prevalent sulphur
Control Documents is Integrity contaminant in cialty applications
process data facessuchsignificant H2S
as highchal- graduated
Unlike inother
chemical
plantengineering
failuresfrom
whichthe
roduction uids
Operating Windows (IOW). owe er many concentrations and large
lenges because it is not meaningfulsulphur University of Calgary.
occur much more rapidly, the oper-
gas sourcesAPI
Predating haveRP970, otherAPI sulphur
RP 584,
compounds that
IOW sets out a procedure may need to be
by which
removed as well,
damage mechanisms are identi- and triazine has
shown some success with
fied and their controlling variables respect to
these compounds.
are monitored. The goal of IOW is
10

H2S is lightofand
prevention will migrate
occurrence to the
of unan-
gas phase during transportation
ticipated or accelerated damage and
storage. Light mercaptans
leading to potential failure and/or behave
similarly.
prematureMethyl, equipment ethylreplacement.
and propyl
mercaptan can be
IOW limits are set to monitor found in the gas
meas-
phase quite often and,
urable and controllable variables that depending
on the application,
directly impact thethe total sulphur
damage mech-
limit may be exceeded
anisms. Operating within unlessthe some
IOW
of the other
limits ensures sulphur that compounds
damage rates are
removed. The triazine
are predictable and appropriately reaction with
mercaptans
managed. often competes with the
H2AS pitfall
reaction, potentially
in setting IOW reducing
limits is
the amount of mercaptans removed AdvaSulf TM

the incorrect assumption that there

when H2S is
is a clear and present. But when
predictable H2S
ongoing
is not present, triazine
relationship between monitored pro- systems can HySWEET®
be benefi cial to t e e
cess variables and corrosion rates. ecti eness of
COSWEET TM

mercaptans removal.
Without this quantitative model
Although
linking IOW the use of triazine
variables, sys-
damage
tems has not been used extensively SweetSulf TM

mechanisms and their rates, setting

for values
the mercaptans
of the removal,
limits williteither maybe: be Sprex®
a ood fi t for many
• Overly conservative and exces- a lications
Table 2limit
sively shows the an rangeexample of total
of operations, AdvAmine TM

sulphur reduction.
potentially crippling any potential
process optimisation
Conclusion
• Too inaccurate and not sufficiently
Sour oil and
sensitive to gas detect production,
conditions a strict
that
regulatory environment
increase damage rates above tolera- and chal-
lenging
ble economics have increased
thresholds. A UNIQUE TASTE OF SWEET FOR YOUR GAS
t Corrosion
e demand Control for Documents
cost e ecti ande
hydrogen sulphide
IOW are two critical pillars by which treatments.
Fortunately, advances
responsibility for corrosion in manage-
today’s 50 YEARS OF EXPERIENCE IN GAS SWEETENING AND
scavenging chemistries
ment can be extended to operations, and pro- SULPHUR RECOVERY PROCESSES
cesses have resulted
away from the world of reactive in improved
treatments forinspections. every phase of With its unique and complete proprietary technologies portfolio,
(post-damage) The two PROSERNAT offers optimized solutions to bring on specs any
production.
standards complement each other type of gas contaminated with CO2, H2S, COS and organic
andWhile triazine
represent theremains
fundamental the mostele- sulphur species, while producing sulphur with the most stringent
wides read and cost
ments of knowledge based corrosion e ecti e sca emissions standards.
enging chemistry,
management. Process and commodity
engineers and www.prosernat.com
operators have tools to treatment
pricing further reduces positively
cost, advancements
impact asset integrityin and the extend
appli-
cation
asset life. rocess a e si nifi cantly

www.eptq.com Gas 2018 23

www.eptq.com PTQ Q4 2018 71

gashps.indd
Q4 ultrafab.indd
3 9 12/03/2018 15:05
14/09/2018 11:24
 ating signatures (or statistical mod-
els) of ‘normal condition’, ‘early sign
of failure’ and ‘failure imminent’
cannot be obtained from the data.
Although hardware sensors may
help in obtaining thickness measure-
ments and the sign of imminent fail-
ures, they do not provide sufficient
data to be truly predictive. What
makes a model predictive? When
considering how a model could be
used by industry, we can establish a
few criteria to help decide whether
a model can be considered to be
predictive from a practical point of
view:
• Can the model be applied at mul-
tiple locations, circuits and processes
other than where the training data
came from?
• Can we ask the model: “What
would happen if we were to
change…”
Operating conditions (pressure,
temperature, flow)
Process variables (speciation,
phase behaviour)?
Materials: would upgrading the
metallurgy help?
Circuit design (pipe diameter,
configuration, and so on)
• Can the model provide insights
into how to minimise corrosion
rates?
• Can the model be used to establish
IOW limits?
• Does the model represent sound
corrosion science and engineering?
Models built on history cannot
always predict the future. Using sta-
tistical relationships derived from
historical data assumes that opera-
tions will operate similarly or within
the same operating window. They
assume that the process will oper-
ate at the same steady state with all
unknown parameters remaining the
same.
Not everything is recorded. For
example, it is widely known that sul-
phur is a critical element for sulphi-
dation corrosion in crude distillation
units. Unfortunately, it is also known
that not all crudes are created equal:
crudes of similar sulphur content
can behave very differently when it
comes to sulphidation. Something
else clearly influences how corro-
sive sulphur really is. Research at
Honeywell has shown that it is not
the total sulphur content that is
72 PTQ Q4 2018
Q4 hps.indd 4
important, it is the active sulphur
content or, more importantly, how
sulphur is bound to the hydrocar-
bons that is important. Some sulphur
species are very stable at distillation
temperatures while others are unsta-
ble and will lead to conditions where
sulphidation dominates. A data
mining exercise to create a statistical
corrosion model would not be suc-
cessful if such important variables
were left out.
Corrosion in refineries is inher-
ently complex. When consider-
ing thermodynamics, kinetics,
transport phenomena and metallur-
gical nuances, it is clear that multi-
ple processes occur simultaneously,
interact with each other, and are
non-linear. Additionally, it is very
common in a refinery for multiple
process variables to move in tan-
dem; they are correlated. It is naïve
to believe that using linear Gaussian
statistics on correlated process data
of non-linear and interactive pro-
cesses with insufficient incomplete
corrosion rate information would
lead to reliable corrosion prediction
models.
What is needed here are relia-
ble corrosion data sets to correlate
within specific parametric data
boundaries to describe unit specific
corrosion mechanisms, which leads
us to the value of corrosion predic-
tion models, predictive analytics and
software sensors.
Successfully decoding the message
encoded in process data: the
making of a software sensor
Over the past two decades, with
support from leading global refin-
ery operating companies, Honeywell
has developed engineering data-
bases and prediction models for the
most common refinery corrosion
problems: sour water corrosion,
naphthenic acid corrosion, amine
corrosion and sulphuric acid alky-
lation. Each of these models facili-
tates correlation of process data to
potential for corrosion propensity
and relevant corrosion mechanisms
and generates quantified corrosion
predictions. This provides a frame-
work to manage asset degradation
before such damage can cripple unit
operations.
Through Honeywell’s Joint
Industry Projects (JIP) initiative,
industry experts have developed
multiple models that utilise exten-
sive engineering data alongside
advanced phase behaviour and
numerical modelling to support
rigorous prediction quantifica-
tion of corrosion. Predictive mod-
elling applications3-8 have been
developed for the following process
applications:
• Sour water (NH4HS) corrosion in
refinery units (hydroprocessing, sour
water strippers, and so on)
• High temperature naphthenic acid
and sulphidation attack in crude
distillation and vacuum distillation
units
• Corrosion in amine treatment units
(MEA, DEA, DGA, MDEA)
• Corrosion in sulphuric acid alkyla-
tion units.
In order to build reliable predictive
corrosion models, Honeywell uses a
proven methodology to generate its
own corrosion data and eliminate all
of the issues that plague plant pro-
cess data:
• Measured corrosion rates repre-
sent a single operating point, not an
average of multiple operating con-
ditions for a single corrosion rate
measurement
• Process conditions are tightly con-
trolled around their operating point.
• Corrosion rates are measured pre-
cisely for a wide range of materials
• The number of operating points
far exceeds the range of operat-
ing conditions normally seen in
operations
• The flow conditions are accurately
modelled through appropriate char-
acterisation of vapour liquid equilib-
ria and multiphase flow
• Wild card conditions are added to
the experimental programs in order
to validate the model, identify any
hidden variables and test under-
standing of how specific damage
mechanisms operate
• Models are tuned and validated
through evaluation with actual refin-
ery measurements.4
Unlike ‘data scientists’ who look at
data through a lens of pure statistical
manipulation, Honeywell uses real
corrosion science, thermodynamics
and chemical engineering principles
to create truly predictive corrosion
prediction models. For example,
www.eptq.com
16/09/2018 09:05
 alyst formulatio
to similar activ
The New Standard in Sulfiding
thermodynamic and ionic modelling
TL catalysts. Th
is used to link ammonium bisul-
development o
phide (NH4HS), ammonia (NH3) and
DMDS, DMS, & TBPS SALES AND DELIVERY • ONLINE MONITORING OF H2S AND lutionary cataly
hydrogen sulphide (H2S) in the sour
H2 CONCENTRATION • TELEMETRY LINK TO THE WEB • SAFETY FIRST ATTITUDE • chose to modif
water corrosion prediction model. EXPERIENCED PROFESSIONAL TECHNICIANS • FULL SULFIDING REPORT TL shape and r
Another example of using estab-
the ATX shape.
lished engineering principles in our
predictive models resides in the use WIRELESS TELEMETRY
of a multiphase (gas liquid) flow
ATX-shaped cat
Criterion has be
model to link operating conditions
PLC CONTROL
lysts for hydroc
to wall shear stress: the actual flow
in the ATX sha
conditions observed where corro-
and the comm
sion occurs. This enables the cor-
astounding. The
rosion model to be applicable to a PATENTED
oped in part to p
very wide range of pipe diameters SMARTSKID
CORIOLIS METER ing units with a
and flow conditions. A data science INJECTION ressure dro a
approach would simply use veloci- SYSTEM increases in feed
ties to reduce volumetric flow rates
DUAL VARIABLE SPEED PUMPS ing hydraulic lim
of different pipe diameters to a com-
t ere are se era
mon variable and would miss the
by the ATX sha
fact that flow regimes are critical to
vice. All of Cr
accurate predictions.
eration mode
Because these corrosion prediction An integral part of our state-of-the-art sulfiding
service package is our Online Gas Analyzer
catalysts can b
models are built from comprehen-
Systems. These instruments continuously measure the ATX shape,
sive corrosion data correlated with
the H2S content and/or Hydrogen Purity of the crac in a lica
process conditions, they have proven
recycle gas while eliminating the hazardous task to benefit from
to help engineers working in multi- of sampling extremely sour gas with draeger tubes mance and capa
ple functions in refineries: from open sample ports.
e s a
• Engineering and design: equip-
In addition, the Analyzer Systems continuously shape with hig
ment design and material selection
TELEMETRY SCREENSHOT stream the H2S and H2 data to our web-connected area and slightly
• Operations and process engineer- SmartSkid™ Injection Pump. This allow you to ume. Catalysts
ing: evaluating the impact of changes constantly monitor the H2S and Hydrogen level of
the ATX shape
in operating conditions the recycle gas from any computer or smart phone
with an internet connection. bulk density wh
• Inspection and maintenance:
ing increased ca
inspection planning, equipment Additional advantages of our H2S and Hydrogen
si nificant incre
replacements, incident investigations Analyzer Systems:
essential to imp
• Operations planning, procurement
• Real-time data leads to more accurate control of sure drop as th
and logistics: evaluating the impact
the DMDS or TBPS injection rates during catalyst a sli tly lowe
of changes in feedstock, product mix
sulfiding, preventing H2S levels from reaching hydraulic diam
and safe processing of opportunity unacceptably high levels and hydrogen purity entional
crudes. from dropping too low. High concentrations of
c an es in bed
Some of these corrosion models H2S and low H2 levels will lead to purging of sour
particle hydraul
have changed how refinery equip- gas to the flare, causing excess sulfur emissions.
a reduction in c
ment is being designed. For instance,
• The systems ensure that H2S levels are always drop of 15-20% i
the API RP 932-B guideline docu-
high enough to prevent premature reduction of cations relative
ment (Design, Materials, Fabrication, the metal oxides on the catalyst, while hydrogen catalysts of the
Operation, and Inspection levels are maintained high enough to
eter depending o
Guidelines for Corrosion Control in prevent excess coke formation.
Lower bulk d
Hydroprocessing eactor Effluent
• The quantity of DMDS injected to the reactor a si nificant red
Air Cooler (REAC) Systems) refer- ONLINE H2S ANALYZER will be minimized, significantly reducing the lyst wei t req
ences Honeywell’s sour water corro-
total cost of the catalyst sulfiding project. vessels, aiding i
sion prediction model.
fill cost for a cat
With these corrosion models’
The ATX shape
ability to connect operating con-
boost in indiv
ditions to corrosion rates, refiner-
Reactor Resources BV formance due t
ies can avoid the futile exercise of
Scheepsbouwweg 8-K13 di usion len t
processing their own operating data
3089 JW Rotterdam, the Netherlands i er catalyst
(without the corrosion rate correla- email: Europe@reactor-resources.com e resultin im
tions) to try to infer useful statistical Phone: +31-646252145 tiveness leads t
models and go directly to using reli- www.reactor-resources.com
able predictive models to convert

54 Catalysis 2018

www.eptq.com PTQ Q4 2018 73

cat criterion.indd 5

Q4 hps.indd 5 14/09/2018 15:05

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 Inputs Corrosion prediction Corrosion prediction results Asset integrity
models updated every 10 minutes updated daily

Temperatures
Real time data

Environment
Flow rates Ammonium bisulphide
corrosion
Pressures Amine corrosion Average corrosion rates

Composition Naphtenic acid Current wall thicknesses

corrosion Corrosion rates
Construction for multiple materials Remaining corrosion
Design data

materials Sulphidation corrosion allowances

Predicted
Pipe diameter Sulphuric acid corrosion risk threshold dates
Static data

Ammonium chloride
Pipe configuration corrosion
Design life
Asset data

Minimum wall
thickness
Initial corrosion
allowance

Figure 1 Corrosion prediction model: connecting corrosion rates and asset integrity to process parameters

real time operating process data into identification of process hotspots, tions can help validate where corro-
real time corrosion rates. This leads and determination of appropriate sion coupons and thickness sensors
us to the concept of a real time soft- action. should be installed
ware sensor. • Monitoring of non-critical areas:
Real time, predictive corrosion non-critical areas can be easily added
Predict-RT: a software sensor for management: the new paradigm to corrosion monitoring without the
predicting and monitoring corrosion Real time corrosion prediction com- need to install field devices. High
Many of the most important varia- plements all other areas of existing corrosion rate events will be detected
bles to predict corrosion are already corrosion management processes: and warn the integrity team that a
measured and updated in the con- • Risk based inspections (RBI) or non-critical area should be looked at
trol system in real time (see Figure standalone inspections: thicknesses more closely
1): temperature, pressure, flow rates. are updated from the predicted cor- • Operations optimisation and plan-
hen adding slowly changing data rosion rates. ith the updated thick- ning: changes in operating condi-
from the laboratory system and pro- nesses one can review inspection tions or feedstocks can be evaluated
cess piping design data, we have plans for their impact on corrosion rates
everything needed to perform a cor- • Coupons and thickness sensors for before making the decision for a trial
rosion rate calculation as part of the critical locations: real time predic- of the new conditions
real time process.
orking with its industry part-
ners, Honeywell has developed an Operations Integrity
intelligent data analytics framework management management
to provide proactive corrosion man-
agement through online, real time
corrosion prediction and monitor- Predict-RT
ing. This approach applies corro- Online corrosion
prediction
sion prediction models in real time Corrosion
Process data
to enable refinery operators to look Prediction engine engineer
historian
at corrosion as an operating process OPC compliant
Online corrosion
variable. This results in dynamically prediction Offline corrosion
updated and predicted corrosion models prediction
rate data as operational conditions models
change.
The corrosion prediction frame-
Inspection
work is depicted in Figure 2. personnel
The solution is designed, through Control and
Operators and instrumentation
intelligent, data driven analytics, to Plant assets
control system Inspections
provide a simple, visible and con-
nected set of insightful data, ena-
bling a real time view of key trends, Figure 2 Real time software driven corrosion prediction framework

www.eptq.com PTQ Q4 2018 75

Q4 hps.indd 6 14/09/2018 15:07


Warns of early
inspection requirements
Inspection
planning
Operations Real time
optimisation corrosion rate
and planning prediction and
asset integrity
indicators
Evaluates changes in
operating conditions
Validates IOW limits
Integrity
operating
windows
Detects upset conditions and
high-corrosion rate conditions
Figure 3 Intelligent predictive analytics: a multifunctional framework
• Corrosion control documents and
integrity operating windows: pre-
dicted corrosion rates validate that
operation within the preset IOW lim-
its will result in predictable, low cor-
rosion rate conditions. When IOW
limits are breached, a predictive cor-
rosion rate model enables engineers
to formulate a number of scenarios
and compare their effectiveness in
lowering corrosion rates before its
implementation.
This multifunctional framework is
depicted in Figure 3.
Conclusions
Traditional corrosion measurement
and monitoring methods, including
inspection and weight loss coupons,
represent off-line, manual processes
that lack the ability to capture the
present state of criticality of a cor-
roding system. eal time corrosion
models offer a new software sensor
framework providing scalable pre-
dictive correlations and a compelling
new way to access corrosion rate as a
process variable.
The availability of rigorous cor-
rosion prediction models is an
important industry paradigm shift
in bringing accuracy to a complex
and difficult task. However, the true
value of predictive models is only
realised when potential and actual
corrosion damage information can
be delivered in real time, as opposed
to running the tools as standalone
applications
With the advent of distributed
control systems, refineries have
76 PTQ Q4 2018
Q4 hps.indd 7
Updates current
thicknesses
Risk calculation
in RBI
Coupons and
thickness
sensors
Validates locations
before deploying
Maintenance,
equipment replacements
and project engineering
Calculates corrosion
rates for other materials
available an abundance of real time
process data. Monitoring process
control variables in real time and
maintaining the process within
well-defined IO s does help reduce
the likelihood of inspection and cor-
rosion coupons surprises. However,
the effectiveness of IO is dictated
by the process by which the IOWs
were defined and the quality of the
data utilised in setting IO limits.
Merely having an IO program will
not detect high corrosion rate opera-
tions nor will it protect against fail-
ure or excessive corrosion damage.
ith the arrival of Big ata ana-
lytics and its promise to change how
refinery data is processed to gain
actionable insight, one could expect
that the relationships between pro-
cess data and corrosion data would
be revealed. Unfortunately, any
models derived from historical plant
data would be of limited value to
predict the future behaviour of the
plant and inform the integrity team
on high corrosion rate events as they
occur.
Honeywell’s predictive corrosion
models provide a proactive para-
digm to quantify corrosion. These
models can transform the real time
process data available from control
systems into actionable real time cor-
rosion rate data. Consequently, high
corrosion rate events can be detected
in real time without the need to
install and maintain any new field
instrumentation. This enables the
deployment of real time monitoring
across a larger number of circuits at
relatively low cost. Further, the pre-
dictive analytics system offers a log-
ical path to implementing digitised
corrosion control documents and
true corrosion enabled IOWs, pro-
viding refinery operators with the
ability to proactively pursue flexible
unit operations and optimised pro-
cess management.
References
1 API RP 580, Risk Based Inspection – 3rd
Edition, 2016.
2 API RP 581, Risk Based Inspection Technology
– 3rd Edition, 2016.
3 Chambers B D, Srinivasan S, Kane R D,
Assessing and predicting the corrosive impact
of opportunity crudes, Opportunity Crude
Conference, Houston, Texas, USA, Oct 2012.
4 Srinivasan S, Yap K M, Kane R D, Role of
sulphur compounds in mitigating naphthenic
acid corrosion, EuroCorr/2013, Paper No 1506,
Estoril, Portugal, Sept 2013.
5 Srinivasan S, Horvath R, et al, Prediction and
assessment of ammonium bisulphide corrosion
under refinery sour water service conditions –
Part 3, Corrosion/2017, Paper No. 8929, New
Orleans, LA, Mar 2017.
6 Horvath R J, Lagad V, Srinivasan S, Kane R
D, Prediction and assessment of ammonium
bisulphide corrosion under refinery sour water
conditions: Part 2, Paper No. 10349, Corrosion
/2010, San Antonio, TX, USA.
7 Horvath R J, Kane R D, Cayard M, Prediction
and assessment of ammonium bisulphide
corrosion under refinery sour water conditions,
Paper No. 06576, Corrosion /2006, Denver, CO,
USA.
8 Lagad V, Srinivasan S, Williams D G,
Corrosion assessment in amine systems using
modeling and software tools, Paper No 18031,
Corrosion/2011, Mar 2011, Houston, Texas.
9 API RP 970, Corrosion Control Documents,
First Edition, Dec 2017.
10 API RP 584, Integrity Operating Windows,
First Edition, May 2014.
Pierre Constantineau is Solutions Consultant,
Corrosion Center of Excellence, with Honeywell
International, Inc. With over 10 years of
experience in designing and delivering real
time control and monitoring solutions, he is
responsible for the real time asset monitoring
and health assessment software portfolio of
the corrosion business.
Sridhar Srinivasan is Global Business Leader,
Corrosion Center of Excellence, with Honeywell
Process Solutions, USA, and Program Leader
for Honeywell’s Joint Industry Projects.
With over 25 years of experience developing
solutions for corrosion and asset integrity, he
holds a BS in mechanical engineering from
Bangalore University and an MS in mechanical
engineering from the University of Houston.
www.eptq.com
14/09/2018 15:11
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 Savings using divided wall columns
Divided wall columns can provide substantial energy and capital cost savings
compared to conventional distillation methods
PRAFULL PATIDAR and AJAY GUPTA
Reliance Industries
D
istillation is the most widely
applied separation tech-
nology in the petroleum
and chemical process industries.
However, inefficiencies in the dis-
tillation process lead to consider-
able energy consumption. With
energy costs rising, finding ways
to reduce energy consumption
has become an important require-
ment in the industry. Often simple
measures such as selecting proper
operating pressure, optimum feed
tray location, optimum reflux ratio,
avoiding over-purification and min-
imising recycle can help towards
reduction in energy consumption.1
The minimum energy required for
separation of components using
distillation for a reversible distilla-
tion process is given by the second
law of thermodynamics:
∫(Qrev/T) = ∆S (1)
However, to realise a reversible
distillation column, difficult practi-
cal requirements, like an infinites-
imal amount of heat supply and
removal from an infinite number
of column sections in the bottom
and top of a column respectively,
are needed (see Figure 1). In real
distillation columns, the change in
entropy is always greater than the
minimum due to irreversibilities
brought in by mixing of streams
which are not in equilibrium with
each other, such as where feed,
reflux and reboil streams mix with
other streams. Other sources of irre-
versibility are pressure loss in the
flow through a column and supply
and removal of heat to the column
at a non- ero temperature differ-
ence in the reboiler and condenser
www.eptq.com
q4 reliance.indd 1
a A
A
B
A
B
Infinite C B
C
coolers
B
C C
A
B
b
A
Infinite B
heaters A A
A B
B
C
B
B
C
Figure 1 A reversible binary distillation Figure 2 (a) Direct sequence (b) indirect
column sequence
respectively. Typical distillation nology. Let us first look at the evo-
columns used in real life consume lution of a DWC from conventional
more than 50% of the minimum distillation sequences.
required energy.
In order to make distillation Conventional column sequence
more energy efficient, heat inte- Single sidedraw column
In order to separate a multi-compo-
To make distillation nent mixture, a sequence of distilla-
tion columns is often used. Let us
more energy efficient, consider separation of three compo-
nents, A, B and C, where A is the
heat integration and lightest and C is the heaviest. In
some cases, it is possible to get pure
novel distillation B from a sidedraw stream in a sin-
configurations can gle column if the sidedraw is a liq-
uid stream from a stage above the
make a significant feed tray where the concentration
of B maximises, provided compo-
difference nent A is present in much smaller
quantity in the feed. Otherwise,
gration and novel distillation con- when component C is present in
figurations can make a significant much smaller quantity in the feed,
difference. A divided wall column a vapour sidestream rich in compo-
(DWC) is one such promising tech- nent B can be drawn from a stage
PTQ Q4 2018 79
13/09/2018 18:34
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separation by design
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sulzer.indd 1 13/09/2018 10:50

 tillation configurations are the
a
direct sequence and the indirect
sequence. As Figure 2 shows, in a
direct sequence, A is removed first, A
A
followed by B and C in the next
A
column, whereas in the indirect B
B sequence C is removed in the first A
A
column, followed by separation of B B
B
C
C A and B in the second column.
B B
C In these conventional configura- C
tions, in the first column the max-
imum concentration of middle
boiling component occurs at some C
C
intermediate tray and decreases
b towards the column exit. If this
component is not removed at its Figure 4 Fully thermocoupled Petlyuk
maximum concentration, thermal column arrangement
A inefficiency increases due to its
remixing with other components in side rectifier arrangement shown in
A the stages that follow. This remixing Figure 3a. Alternatively, we can also
B
A problem can be avoided by thermal get a side rectifier configuration
B coupling of the two columns. by removing the reboiler from the
C
second column and supplying the

B
C
Figure 3 (a) Thermally coupled side
rectifier arrangement; (b) thermally
coupled side stripper arrangement
DWCs in general necessary boil-up from the reboiler
of the first column. Similarly, in the
provide substantial indirect sequence, we can get rid of
the condenser from one of the two
energy as well as columns, with a single condenser
serving both the columns to pro-
capital cost savings vide the necessary liquid reflux
required. This results in the side
and promise to be stripper arrangement shown in

below the feed location with max-

a great alternative Figure 3b.

imum B concentration. However

in both cases, it is required that
the relative volatilities should be
high between the separating com-
ponents, and intermediate boiling
component B should be present in
large concentration in the feed. In
addition, taking out a vapour side-
stream is practically difficult.
Direct and indirect sequences
More commonly employed dis-
Studies of divided wall columns and potential savings
Separating system Company
C11-C13 heart cut
from C7 to C17 full range
kerosene UOP
C7+ aromatics from C7+
olefins/paraffins mixture UOP
Recovery of pure
aromatics from gasoline Uhde GmbH
LPG recovery from fuel gas GTC
Benzene rich cut removal
from reformate INA
Table 1
to conventional Fully thermally coupled columns
To further improve on the conven-
distillation methods tional sequences discussed above,
a better arrangement would be to
use the so-called Petlyuk column
Thermally coupled columns arrangement shown in Figure 4.3
Partially thermally coupled columns In this arrangement, we perform
In the direct sequence, if we a sharp split between A and C in
remove the reboiler from the first the prefractionator while B is dis-
column and supply the required tributed between the A and C rich
boil-up from the reboiler of the sec- streams. The top stream from the
ond column, we get the so-called prefractionator containing A and
B is fed to the upper part of the
second column while the bottom
stream containing B and C is fed
to the lower part of the second col-
Energy savings Capital cost savings Reference
umn. The upper part of the second
column performs separation of A
30% 28% Schultz et al4 and B whereas the bottom part per-
forms the B and C separation. Like
50% 35% Schultz et al4
the side rectifier or the side stripper
16% 20% Diehl et al5 configurations, these two columns
18.2% - Bhargava et al6 are further thermocoupled using
only one reboiler and condenser
51.7% 46.8% Dejanovic et al7
installed with the second column.
apour-liquid traffic in the prefrac-
tionator is maintained by provid-

www.eptq.com PTQ Q4 2018 81

q4 reliance.indd 2 13/09/2018 18:34

 ing part of the vapour and liquid
streams from the second column to
the bottom and top sections of the
prefractionator, respectively. A side
draw from the second column pro-
vides pure B product whereas the
top and bottom streams give pure
A and B.
Compared to the conventional
direct or indirect configurations,
the advantages of the Petlyuk
arrangement are a reduced number
of equipment as well as increased
thermodynamic efficiency, with
energy savings to the tune of
20-50% depending upon the com-
ponents being separated and the
design adopted. This energy saving
is primarily obtained by avoiding
the remixing problem discussed
earlier.
Divided wall column
The number of columns required
can be further reduced to a single
column if the prefractionator in the
Petlyuk arrangement is integrated
in the same shell as the second col-
umn. This is done by dividing the
column into two sections using a
partition wall (see Figure 5a), each
section taking the role of one of
the two columns discussed above.
Thermodynamically, this divided
wall column is equivalent to the
Petlyuk configuration, with the
added advantage of a lesser col-
umn. In addition to energy savings,
capital cost is reduced by typically
30%. Equivalent C configura-
tions with side rectifier and side
stripper distillation arrangements
are shown in Figures 5b and 5c,
respectively. Table 1 shows the sav-
ings realised using DWC, reported
by several companies.
Important aspects which make
Petlyuk columns thermodynami-
cally more efficient are:3
• The difference between the com-
position of the feed and the com-
position present at the feed stage
of the column is reduced. This
decreases losses due to mixing of
streams of different compositions
that are not in equilibrium with
each other.
• At the end of the first column,
mixing losses due to reflux and
reboiled vapour streams are neg-
ligible; these streams are from the
82 PTQ Q4 2018
q4 reliance.indd 3
middle boiling distributed com-
a
ponent is present in a substantial
amount in the feed, typically 20-60%
A of the feed. At lower concentrations,
other distillation arrangements may
be competent or better. This can
be understood as the middle boil-
A
B B ing component’s over-fractionation
C (repeated fractionation) in the two
columns of a conventional sequence
being avoided in a DWC. Thus the
larger the middle boiling compo-
nent’s composition in the feed, the
C
greater the energy savings realised
in a DWC compared to a conven-
b tional sequence.
• If there is an appreciable differ-
A B ence between the operating pres-
sures of different columns in a
conventional sequence, a DWC
operating at a single pressure might
A
B not be the preferred choice.
C • When evaluating the use of a
DWC, energy savings should be
evaluated, keeping in mind the
level at which energy is used in the
column.
C
• The partition wall should be ther-
mally insulated to avoid any heat
c
transfer across it. This is necessary
because the composition and tem-
A perature on the two sides of the
wall differ and any heat transfer
across the wall has an adverse effect
on the performance of the column.
A
B • If the temperature difference
C on both sides of the wall is large
(>40°C), then mechanical stresses
may cause undesirable bending in
the column due to differing thermal
expansion on the two sides. Finite
C B
element analysis studies should be
made to improve the mechanical
Figure 5 (a) Divided wall column; design. A more symmetrical con-
(b) divided wall side rectifier column; centric wall could be used instead
(c) divided wall side stripper column of a partition wall.
• When separating reactive com-
other column and are near to equi- ponents which may react to form
librium composition with the leav- lighter molecules in the bottom or
ing streams. high boiling components in the top
• Remixing of the intermediate section, use of a DWC is not recom-
component at the end of the first mended as the purity of the side
column and separation in the sec- draw product may be compromised
ond column, resulting in thermody- in such cases.
namic losses, are avoided. • Hydraulic design should take
care of pressure balancing on the
General guidelines two sides of the partition. This may
When considering the use of a involve providing the same num-
DWC, the following points need to ber of stages on the two sides of
be considered: the wall or using different types of
• A DWC is preferred when the internal packings in different sec-
www.eptq.com
15/09/2018 07:53
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grace.indd 1 13/09/2018 06:20

 tions to adjust the overall pressure
drop without compromising the
number of stages required in these
sections.
• When distilling heat sensitive
materials, a DWC can be advan-
tageous compared to conven-
tional arrangements since they are
reboiled only once and their resi-
dence time is minimised.2
Limitations
There are some major drawbacks to
a DWC:
• Requirement for taller columns: a
DWC has more stages and a bigger
diameter than either of the columns
in a conventional configuration.
• Increased pressure drop: a DWC
exhibits a larger pressure drop due
to its higher number of theoretical
stages. Since the pressure of the
column is usually dictated by the
temperature of the cooling utility
available for use in the condenser,
a similar top temperature means
a higher bottom temperature in
the DWC due to a higher pressure
drop in the column. This demands
heating utility at a higher tempera-
ture for use in the DWC which may
be costlier than using heating utility
at lower temperatures in conven-
tional columns, for instance using
medium pressure steam instead of
low pressure steam.
• Operation at single pressure: a
DWC being a single column can
operate only at a single pressure,
whereas in a conventional config-
uration there is the flexibility to
operate different columns at dif-
ferent pressures. Operation at dif-
ferent pressures might provide the
opportunity for heat integration
between the columns; this in part
compensates for the larger energy
requirement of the conventional
configuration.
• Process control: as the DWC has
greater numbers of degrees of free-
dom compared with a conventional
distillation column, it is necessary
to work with a larger number of
independent variables for satisfac-
tory operation.
• If one of the columns in a con-
ventional configuration requires
a different material of construc-
tion which costs more than that of
the other column, then the DWC
84 PTQ Q4 2018
q4 reliance.indd 4
time of designing the column. The
a number of stages in the different
B
sections of the column, location of
E feed and sidedraw are physically
E-rich fixed during construction of the
column and cannot be changed
B during operation. Moreover, the
vapour split is hydraulically fixed
A by the location of the partition wall
B and the pressure drop across the
sections on the two sides of the
wall. Thus it cannot be adjusted
during operation. As suggested
by olff and Skogestad,8 there are
A B four degrees of freedom that can
be adjusted during operation of
b a C: reflux flow rate, vapour
boil-up, sidestream flow rate, and
liquid split ratio. These degrees of
A B freedom could be used to control
S four variables, typical candidates
being the three product purities
A
and minimising energy consump-
B tion. In a simple three point control
structure suggested by olff and
Skogestad,8 distillate, sidestream
and bottom purities are controlled
by manipulating respectively the
reflux rate, the sidestream flow
rate and the vapour boil-up. An
c additional suggestion is use of the
liquid split to control the amount
of heavy component leaving in the
A top of the prefractionator. Many
B
more control structures have been
suggested in the literature.10
C
Applications in industry
DWCs have been successfully used
A for the separation of a large num-
ber of systems: hydrocarbons, alco-
hols, aldehydes, ketones, acetals,
B and amines, among others. Many
chemical companies have employed
DWCs for various ternary or qua-
Figure 6 Divided wall column used for ternary separations, BASF SE being
(a) azeotropic distillation; (b) extractive a pioneer amongst them.
distillation; (c) reactive distillation
Application to advanced distillation
needs to be constructed entirely configurations
from the more expensive material, DWC technology can also be used
which decreases the capital cost for more complex multiple column
advantage. distillation configurations such as
a eotropic distillation, extractive
Control of DWC distillation, or reactive distillation.
One of the major hurdles in the DWC schematics for these con-
adoption of DWCs in the industry figurations are shown in Figure 6.
is concern regarding the difficulty However, the pressure conditions
in their control and operability. A of the different columns being inte-
DWC has many degrees of free- grated in the single shell should
dom. Some of these are fixed at the match each other.
www.eptq.com
17/09/2018 12:04
 Designing a DWC
Designing of a DWC starts with shortcut calcula-
tions. Fenske–Underwood–Gilliland Equations can SERVICE
be used to calculate the minimum reflux ratio for the
different columns, taking a C equivalent Petlyuk
arrangement as the base case. Alternatively, a min-
imum vapour diagram method9 could be used for
preliminary calculation of operating parameters and
stages required. Once the shortcut calculations are
done, rigorous calculations and optimisation should
be done using commercial software to arrive at the
optimum configuration. At this point, a complete
process flowsheet should be considered to make use
of the heat integration possibilities. The final step is
detailed column si ing and hydraulic calculations.

Conclusion
In this article, various aspects of the C have
been discussed. Although we have kept discussion
only with respect to ternary systems, C concepts
could be extended to quaternary or even higher sys-
tems, albeit with increased complexity with respect
to control and operation. Cs in general provide
substantial energy as well as capital cost savings and
promise to be a great alternative to conventional dis-
tillation methods, especially when an intermediate
boiling component is present in substantial amounts
and is required in a pure form.

References
1 Faagau G, Reduce column energy consumption, Chemical
Processing, Jul 2008.
2 Smith R, Chemical Process Design and Integration, 2005, John Wiley
& Sons Ltd.
3 Petlyuk F B, Distillation Theory and Its Application to Optimal Design
of Separation Units, 2004, Cambridge University Press.
4 Schultz M A, Stewart D G, Harris J M, Rosenblum S P, Shakur M S,
O’Brien D E, Reduce costs with dividing wall columns, CEP, May 2002,
64-71.
5 Diehl T, Kolbe B, Gehrke H, Recovering pure aromatics, PTQ Q2
2006, 127-131.
SERVICE
YOUR PROFITS
6 Bhargava M, Nelson C, Gentry J, Siddamshetti V, Less is more: how
a dividing wall column maximises LPG recovery, Digital Refining, Oct
2014.
7 Dejanovic I, Matijasevic L, Jansen H, Olujic Z, Designing a packed
dividing wall column for an aromatics processing plant, Ind. Eng.
Chem. Res., 2011, 50, 5680-5692.
8 Wolff E A, Skogestad S, Operation of integrated three-product Tailor-made performance begins by putting
(Petlyuk) distillation columns, Industrial & Engineering Chemistry
Research 34, 1995, 2094-2103.
your needs center stage. Services offered by
9 Halvorsen I J, Skogestad S, Minimum energy consumption in HOERBIGER provide long-term improvements
multicomponent distillation. 1. Vmin diagram for a two-product in reliability, efficiency and environmental
column, Ind. Eng. Chem. Res., 2003, 42, 596-604.
10 Yildirim Ö, Kiss A A, Kenig E Y, Dividing wall columns in chemical
soundness. The goal: to make your plant run
process industry: a review on current activities, Separation and even more profitably.
Purification Technology 80, 2011, 403-417.
px.hoerbiger.com
Prafull Patidar is a Senior Manager in the Refining R&D division of
Reliance Industries Ltd. He has five years of industrial experience in
separation processes, process modelling and simulation in refining
units, and holds chemical engineering degrees (BE, MTech and PhD)
from MITS Gwalior, IIT Roorkee and IIT Bombay, respectively.
Ajay Gupta is Assistant Vice President, Refining R&D at Reliance
Industries Ltd, Jamnagar, Gujarat, India. He has bachelor’s, master’s
and doctoral degrees in chemical engineering from IIT, Delhi, India.

www.eptq.com PTQ Q4 2018 85

325_058_02_Anzeige_SERVICE_86x270+3_RZ-1.indd 1 10.09.18 10:22

q4 reliance.indd 5 15/09/2018 06:31

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jacobs.indd 1 13/09/2018 06:16

 Feed conditioning technologies for gas
processing plants
Recent contactor developments remove soluble gas phase contaminants from
the feed gas stream
SCOTT NORTHROP ExxonMobil Upstream Research
DAVID B ENGEL Nexo Solutions, Exion Systems Division
A
mine solvent foaming is a
common problem in gas
processing plants, including
those ahead of liquified natural gas
(LNG) manufacturing facilities. This
can lead to reduced gas throughput
and, in severe cases, solvent carry-
over and perhaps even plant shut-
down. This foaming is ultimately
caused by changes in the physical
and chemical properties of the sol-
vent. Chemical contaminants can
lower amine solution surface ten-
sion and change the surface rhe-
ology in such a way that foaming
tendency is augmented and foam is
stabilised. Earlier work has shown
that these contaminants are not
restricted to liquid hydrocarbons,
but can be from a variety of other
possible sources. While some of the
contaminants may originate from
within the amine unit itself, many
are introduced with the feed gas,
such as upstream production chem-
icals and produced water among
others. While antifoam products can
temporarily alleviate foaming epi-
sodes, they can also be a detriment
and build up over time, fouling ves-
sels and activated carbon beds.
Some LNG plants employ inlet
coalescers, filters or a water wash
to remove contaminants in the feed
gas. However, these systems may
not be completely effective for the
removal of certain contaminants.
Furthermore, the vessels or water
demands of these wash systems can
be large and relatively inefficient.
This article describes new technol-
ogies to prevent the introduction of
contaminants into amine units. The
novel systems are installed inline
with the feed gas pipe and com-
prises a compact water wash device
www.eptq.com
q3 nexo.indd 1
capable of removing water soluble
components such as surfactants and
salts from incoming feed gas. The
spent water can be treated and recy-
cled to minimise water make-up
and clean water consumption.
Gas treating for LNG manufacture
Natural gas is treated to remove
H2S and CO2 to meet pipeline or
other downstream process specifi-
cations. Removal of H2S and CO2,
known as acid gases, to low spec-
ifications such as those for LNG
production, demands much more
from processing units. For LNG
production, the H2S and CO2 spec-
ifications are usually ppm and
50 ppm, respectively. Very few,
if any, unprocessed natural gas
streams contain such low levels
of those acid gas contaminants.
Consequently, the vast majority of
natural gas (including pipeline gas
with ppm H2S and 1-2% CO2)
used for LNG worldwide (approx-
imately 2 million t y or about
22 billion cu ft d in 2015) must be
treated at least for CO2, often using
liquid reagents (also called sol-
vents) such as alkanol amines. The
chemistry of amine treating for CO2
removal is well known and docu-
mented elsewhere.
While many amine units function
well over the life of the LNG facil-
ity, some are prone to periodic or
even frequent foaming events. This
article discusses likely causes and
potential solutions to these foaming
episodes in amine units, which also
apply to gas treating in general.
Amine solvent foaming
When gas is routed through a liq-
uid such as an amine solvent flow-
ing across trays of an amine unit
contactor (or regenerator), a short-
lived, quick-breaking froth nor-
mally develops on top of the amine
solvent liquid layer. If the gas bub-
bles or pockets cannot break the
liquid-vapour interfacial structure
quickly, they become encapsulated
in the liquid phase and form what
is commonly referred to as foam.
Foam is essentially a collection of
gas bubbles encapsulated inside
a liquid film that will not easily
coalesce or rupture. Packed col-
umns are less prone to foaming as
upward flowing gas tends to flow
across the surface of the downward
flowing liquid instead of through
the liquid layer on a tray. However,
packed columns are not immune to
liquid hold-up and other symptoms
of foaming, hence the following
discussion applies to them as well.
To better understand foam, one
needs to consider two different
aspects of it: foaming tendency and
foam stability. Foaming tendency
refers to the ease with which liq-
uid film will encase gas bubbles.
There is not a completely standard-
ised measure for foaming tendency.
However, a relative measure can be
obtained by testing a fixed volume
of amine solvent in a graduated
cylinder and flowing air or nitro-
gen through a porous frit at a set
rate (1000 ml min), then measuring
the level of foam generated.
Foam stability is related to the
elasticity of the liquid layer around
the gas bubble and the ability of
the film to resist rupturing. Each
gas bubble has an interfacial layer
or ‘skin’ that confers resistance and
elasticity (hindering coalescence
and structural collapse), enabling
PTQ Q4 2018 87
15/09/2018 07:26

Figure 1 Example of a foam test column showing an amine solvent with significant
foaming tendency
the liquid film around it to flex as tendency as well as foam stability.
the gas bubble deforms, expands, When this type of foaming occurs,
or contracts. A rough measure it does not go unnoticed and a
of foam stability can be obtained number of process changes may be
using the test described previously observed, such as:
by turning off the gas flow and • ifferential pressure increase
determining the amount of time across the contactor and/or
(in seconds) it takes for the foam regenerator
to completely break. This is also • Decrease in contactor and/or
expressed as foam break rate. Figure regenerator bottoms liquid level
1 shows an apparatus used to test • Temperature bulge position
foaming in amine solvents. The col- changes inside the contactor tower
umn has a bottom porous glass frit • Increasing liquid level in the
for gas dispersion. Interestingly, amine contactor after-scrubber, as
some amine solvents display high amine solvent is carried over with
foam tendency, but the foam is the treated gas (leading also to
short-lived once gas is shut off, and amine solvent losses)
break rates are fast. In other cases, • Increase in H2S in the treated gas
the foam tendency is not as high, (and CO2 for LNG cases)
however the foam stability is strong • Amine contamination of the
with slow break rates. The worst regenerator reflux water.
scenario is an amine unit with a Note that mechanical damage to
solvent that has both high foam internals, solids fouling of internals
tendency and strong stability. or excessive gas velocity inside the
When an amine unit circulates a amine unit contactor (or regener-
solvent that displays foaming ten- ator) can result in tower flooding
dency and foam stability, foam is and mechanical frothing/foaming
initiated when process perturba- which is distinct from pure chem-
tions occur beyond what the unit ical foaming. However, the symp-
can tolerate. A decrease in surface toms are similar to those described
tension will sometimes correlate above, so it can be difficult to dis-
with an increased foaming ten- tinguish foaming from flooding
dency of the solvent, such as when based on operational observations
liquid hydrocarbons are intro- alone.
duced into the system. However, In a severe flooding-froth-
this foam can be short-lived and, ing-foaming event, the first action
in many cases, goes unnoticed. (after dosing antifoam into the sys-
Surfactants and other organic com- tem) is usually reducing the gas
pounds can increase the foaming rate to lower the differential pres-
88 PTQ Q4 2018
q3 nexo.indd 2
sure across the contactor and allow
any held-up liquid to fall into the
bottom of the contactor tower. It
can take a substantial reduction in
gas rate to recover control of the
system. In addition to the reduc-
tion of feed gas to the amine unit,
the upset must work itself through
the rest of the unit and may require
further operator intervention
such as flash tank and regenera-
tor adjustments. If frequent, these
foaming events can measurably
reduce the output of the LNG pro-
duction facility.
Foaming of the amine solvent can
often lead to carryover from the
contactor or regenerator caused by
entrained liquids with the treated
gas or acid gas, respectively. Most
amine units have separation ves-
sels such as a knockout drum at the
contactor outlet to recover most of
the amine solvent carryover. If the
amine unit is treating liquid hydro-
carbon (for instance, condensate
co-produced with gas), ‘foam’ can
be replaced by ‘emulsion’ in the
above discussion.
Any carryover from the amine
contactor in the treated hydrocar-
bon by emulsification is recovered
using a liquid coalescer and/or a
water wash stage. These devices
will remove any emulsified amine
solvent present in the treated liq-
uid hydrocarbon. An alternative
strategy is to inject 1-100 ppm
of an emulsiion breaker into the
hydrocarbon feed upstream of the
amine conatctor.t carryover may
reach downstream units such as
dehydration plants, mercaptan
removal plants or caustic treaters.
Sometimes the amine solvent carry-
over can infiltrate the main fuel gas
system. Foaming in a regenerator
is also detrimental as contaminated
amine solvents often do not regen-
erate fully. Furthermore, carryover
with the acid gas can reach the sul-
phur recovery unit, flare system or
other downstream process.
Antifoam addition is a common
method to temporarily control
the deleterious effects of foaming.
However, the effectiveness of a
given antifoam may be limited as
amine units sometimes use anti-
foam and experience little to no
apparent foam reduction. Some
www.eptq.com
13/09/2018 18:45
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 plants use antifoams in the amine
unit on a regular basis for short-
term relief, but this can harm the
solvent in the long term.1 In fact,
antifoams should not be used on a
constant or daily basis. Root cause
analysis of foaming and the elimi-
nation of its source is the best way
to deal with a foaming amine sol-
vent. Nevertheless, antifoams may
need to be used when sporadic
foaming incidents occur and the
source of foaming agent has not yet
been identified.
Antifoams in amine units can
accumulate on top of the solvent as
a separate phase in the amine con-
tactor flash tank or the regenerator
sump for example. Antifoams also
can render activated carbon beds
useless as they saturate the carbon
and hinder entry of contaminants
into the pore structure. Silicone
antifoams are actually small parti-
cles (1-10 microns in size) that are
very effective for reducing foam (10
times more effective than normal
polyglycol antifoams). However, sil-
icone-based antifoams should not be
used in amine units because of their
inherent physical incompatibility
with aqueous solvents. Most silicone
based antifoams are removed using
filters 10 or smaller.
Amine solvent foaming can usu-
ally be limited to a single root
cause: chemical contamination.
However, chemical contamina-
tion can originate from a number
of sources. Clean amine solutions
will not foam and should not froth.
Hence, standard design and oper-
ation advice for amine units typi-
cally includes: i) specifying efficient
inlet solids and liquids separation
systems to prevent ingress of most
feed contaminants; ii) setting the
lean amine temperature at least
10°F above the inlet gas tempera-
ture to avoid liquid hydrocarbon
condensation in the contactor; and
iii) including 15-25% slipstream of
carbon adsorption to adsorb sol-
uble contaminants in the solvent.
Additional measures include the
sparing use of effective antifoams
(applied efficiently), lean and rich
filtration to remove suspended
solids and andjusitng the amine
solvent concentation. A common
practice used during foaming in
90 PTQ Q4 2018
q3 nexo.indd 3
Hydrophillic
group
Hydrophobic group
+
O- Na
C
O
Figure 2 Example of a molecular surfactant
an amine unit is to discard the
returned condensted water at the
regenrator overhead condenser.
These can accumulate foaming
agents.
Despite appearing to follow these
heuristic rules, some amine units
still find themselves prone to foam-
ing events. Therefore, it becomes a
question of determining the source
of solvent contamination and elimi-
nating it. Below is a list of the most
common sources of amine solvent
chemical contamination:
• Ineffective inlet separation lead-
ing to contaminant ingress as solids
or liquids.
• Sub-micron aerosols:
Lubrication oils
Produced water
Surfactant based chemicals
from upstream treating such as cor-
rosion inhibitors.
• TEG from upstream dehydra-
tion units is frequently detected
in amine units, though TEG is not
generally regarded as a foam pro-
moter. However, TEG may react
with amine at regenerator tempera-
tures and thus has the potential of
generating foam promoters.
• Gas-phase contaminants carried
with the feed gas such as BTEX,
methanol, organic acids and espe-
cially pipeline chemicals such as
corrosion inhibitors; organic acids
in non-ionic form may have suffi-
cient vapour pressure to be carried
from upstream with the feed gas.
• Hydrocarbon condensation
inside the amine unit contactor by
not maintaining appropriated tem-
perature differential between lean
amine and inlet gas or by process-
ing heavy hydrocarbon rich gas.
Hydrocarbons will not cause the
amine solvent to foam, however,
they will lower the solution sur-
face tesion making the amine much
more prone to foaming.
• Incorrect activated carbon (acti-
vated carbon exposed to phospho-
rous based activation)
• Problems with activated carbon
changeout (insufficient backwash
to remove fines; post-filter passing
fines into system)
• Activated carbon bed spent or
carbon bed being bypassed
• High concentration of suspended
solids in the amine solvent (some
solids can stabilise foam)
• High soluble iron in the lean
amine (rapid solids formation in
the contactor)
• Excess antifoam injection (excess
antifoam use can actually induce
foam)
• Incorrect antifoam (Some anti-
foams will actually cause foam for-
mation, especially if overdosed.)
• Contaminants present in the fresh
amine solvent and or make-up
water
• In situ generation of contami-
nants through oxidation or high
regeneration temperatures.
It is important to emphasise that
amine solvent foaming can be elim-
inated or greatly reduced in sever-
ity and or frequency if efficient
inlet separation and filter coales-
cence is in place upstream of the
amine contactor. In addition, it is
necessary to have sufficient amine
solution filtration, effective acti-
vated carbon adsorption beds, and
to correctly operate and maintain
these units.
The physical chemistry of surfactant
contaminants
Surfactants are interfacially active
molecules. They can have a
wide range of molecular motifs.
However, molecular surfactants
usually consist of a polar section or
head, and a non-polar group, often
a hydrocarbon chain or tail (see
Figure 2). The polar part of the mol-
ecule can interact with polar sol-
vents like water, and it is therefore
also called the hydrophilic portion.
The non-polar part, on the other
hand, can interact with non-polar
materials such as hydrocarbons,
and is therefore called the lipo-
philic or hydrophobic portion.
Molecular surfactants can be clas-
sified according to the charge on
their polar head group:
www.eptq.com
13/09/2018 18:45
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Hydrocarbon phase,
gas or liquid
Water or air phase
Figure 3 Example of surfactants populating a hydrocarbon/water interface
Surface tension
Non-aggregated
surfactants (monomers)
Surfactant concentration
Figure 4 Example of surfactants and critical micellar concentration (CMC)
• Anionic surfactants have a nega-
tively charged head
• Cationic surfactants have a posi-
tively charged head
• Zwitterionic surfactants have a
zwitterionic head group (both pos-
itive and negative charge)
• Non-ionic surfactants have an
uncharged polar head group.
Surfactants adsorb preferably at
interfaces where they find the most
energetically favourable conditions
due to their two-part structure. At a
water surface, for example, the sur-
factants orient themselves in such
a way that the head group resides
in the water and the hydrocarbon
chain points to the gaseous phase
(see Figure 3). Thus, surfactants can
‘mediate’ between two phases as
they can form strong interactions
with both of them. The interfacial
tension consequently decreases,
since it is easier to generate more
interfacial area when those mole-
cules are present. The addition of
surfactants thus facilitates the mix-
ing of non-polar (in this case, gas)
and polar phases. This phenome-
non is used in the detergent indus-
try, for example, to bring oil into
the water phase.
92 PTQ Q4 2018
q3 nexo.indd 4
Nonpolar
tail
Polar
head
Critical micellar concentration
(CMC)
Aggregated surfactants
(micelles)
The decrease of the interfacial
tension caused by surfactants accel-
erates as more surfactant molecules
move to the gas/water interface.
Once the interface is saturated, the
addition of more surfactant will
not decrease the interfacial tension
any further. At this point, organ-
ised systems such as micelles may
appear in the aqueous phase (see
Figure 4).
Steel pipe wall
+ CnH2n+1
N (n = 8, 10, 12, 14, 16, 18)
- pared to distilled water when used
H3C CH3
Cl
Figure 5 Top: example of the mechanism
of a filming surfactant such as a
quaternary ammonium salt, cationic
corrosion inhibitor. Bottom: general
structure of a simple filming corrosion
inhibitor
It is important to mention that
solids such as iron sulphide (FeS)
can, under certain conditions, also
act as foam stabilisers because the
solids’ surfaces can interact with
both water and hydrocarbon (gas
and liquid) at the same time. FeS
is particularly notorious for this
because it tends to be in platelet
form. For the purposes of this arti-
cle, solid based foam stabilisers
(particles) will not be covered; only
molecular surfactants, as described
previously, will be considered.
Examples of surfactants com-
monly found in gas processing
feeds, such as amine unit and dehy-
dration unit feed gas, include lubri-
cation oils and upstream process
additives.2 Lubrication oils from gas
compressors typically contain high
percent of a heavy hydrocarbon
(most often petroleum fractions,
called mineral oils) and a small
percent of chemcial additives for
various functions, which often have
surface active properties. Additives
that reduce friction and wear,
increase viscosity, improve viscos-
ity index, as well as improve resist-
ance to corrosion, oxidation, aging,
and contamination in upstream
processes also often have surface
active properties. Upstream process
additives, on the other hand, can
be biocides, corrosion inhibitors,
H2S scavengers, hydrate inhibitors
or paraffin inhibitors, to name a
few. Corrosion inhibitors (filming
amines or quaternary ammonium
salts with alkanol segments) are
examples of process additives with
surface active properties. Figure 5
shows how a filming amine per-
forms, and a possible general
molecular structure. As with sur-
factants in general, a filming amine
has a hydrophobic section (long
alkyl chain), and a hydrophilic sec-
tion (polar ionic centre).
Figure 6 shows the change in sur-
face tension of distilled water com-
as a scrubbing agent for surfactants.
The decrease in surface tension from
72 mN/m to 46 mN/m is a clear
indication of the surfactant’s pres-
ence. Similar effects are observed
with some upstream process addi-
tives such as corrosion inhibitors.
The decrease in surface tension is
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13/09/2018 18:45
rezel.indd 1 08/03/2018 10:20

100
90
Surface tension, mN/m
80
70 72
60
50
40
30
20
10
0 ration and coalescence to minimise
Distilled water
Figure 6 Surface tension of distilled water in comparison with distilled water contacted
with surfactant and hexane
usually a good indicator of higher
foaming tendency, but low surface
tension alone does not mean that
a liquid will foam. A pure liquid
may have a low surface tension (for
instance, hexane at 1 mN m), but
without a surface active contami-
nant in the liquid, there is no mech-
anism for foam stabilisation.
Note that heat stable salts can
increase the surface tension of an
amine solvent, and thus may can-
cel out the lowering of surface ten-
sion due to surfactant. Therefore, a
working amine solvent may appear
to have a normal surface tension
value; however, it could have a
substantial surfactant concentra-
tion, and hence high foaming ten-
dency (see Figure 7).
A better, but not absolute correl-
ative, parameter to foam stability
is liquid surface dilational viscos-
ity. This has been measured using
100
90
Surface tension, mN/m
Pure water, 72
46
19
Scrubbing water Hexane
an oscillating bubble method.3
espite a number of detailed stud-
ies, foam stability is not completely
understood.4 However, part of
what stabilises foam is the ability
of the surfactant to dampen sur-
face tension perturbations when the
liquid surface area changes. A cur-
sory look at the literature does not
reveal any references that specifi-
cally examine the viscoelastic prop-
erties of amine solvent systems,
with or without contaminants.
However, a project along those
lines has been suggested.5
Minimising surfactants in amine
solvents
Excessive foaming can cause sol-
vent carryover out of the contactor
or regenerator. This can ultimately
result in liquid contaminants
appearing in downstream pro-
cesses since separation devices (like
demister pads) lose their separa-
tion efficiency as the liquid content
of the gas increases. Poor phase
separation can lead to multiple
downstream impacts in addition
to solvent loss. More importantly,
foaming events can reduce treating
capacity and consequently lower
throughput of the LNG plant.
Inlet filter and coalescers
The first line of defence against
surfactants is good inlet filter sepa-
solids, liquids and liquid aerosol
carry-in to the amine contactor.
There are many upstream chem-
icals such as those in slickwater
fracking fluid, compressor oils, and
amine corrosion inhibitors that can
contaminate amine and increase its
foaming tendency and stability.
Lean amine temperature
Though heavy hydrocarbons do
not have polar heads as described
above, they do seem to act as sur-
factants in amine solutions. To
ensure that they do not condense in
the amine absorber, standard prac-
tice is to run the lean amine at least
10 F above the temperature of the
inlet gas.
Amine carbon adsorption
If surfactant contaminants do make
it into the amine system, a car-
bon bed may be used to remove
them from the solution. The usual
arrangement is to take a slip stream
of lean amine and run it through
a mechanical filter, followed by a
carbon filter, followed by another
mechanical filter. The slip stream
is often 10-20% of full flow; how-
ever, a minimum of 25% is recom-
mended with 15 minutes contact

80 time. In many cases, activated car-

Pure water, 72 bon can remove surfactants from
70
the amine solvent; however, it can
60
take time to effectively remove the
50 contaminant.
40 In some cases, activated carbon
30 can only partially reduce foam-
20 Salts ing. In these cases, other materials
Methanol or BTX can be used for foam contaminant
10
Surfactants removal and amine purification.
0 Some novel adsorbents such as
Concentration NF-75 (from Nexo Solutions) can
remove foam when all other mate-
Figure 7 Effect of contaminants on the surface tension of pure water rials fail. Figure 8 shows the dual

94 PTQ Q4 2018 www.eptq.com

q3 nexo.indd 5 17/09/2018 12:06

 mixed-bed material used (left) for
the process and the resulting com-
parison (right). It can be clearly
observed that foam was reduced
and the amine solvent was also
clarified. This material can be used
in all existing activated carbon bed
vessels.
Despite having these three stand-
ard protocols for reducing amine
contaminants and their effects,
some amine systems still exhibit
substantial foaming tendency. Does
this mean that some amines have
inherent foaming tendency? Or can
there be another mechanism for
surfactant transport to the amine?
Organic acids – the Trojan horse?
For the ionic surfactants described
above, the only way for them to be
transported to amine is via aerosol.
Charged molecules cannot travel
in the gas phase. However, neutral
molecules can. An example is acetic
acid, the main component in vine-
gar. The reason one can detect its
odour is because it is transported in
the gas phase into one’s nose. The
protonated form of the acid can dis-
solve in aqueous solutions where it
can dissociate into ions. This is par-
ticularly true if the aqueous phase
has elevated pH, as does amine.
The foregoing situation would
apply to most organic acids present
in the hydrocarbon reservoir. For
sour gas reservoirs (with low pH
water), protonated organic acids
can vaporise and be transported
in the gas phase through the filter
coalescer. They could then be cap-
tured in the amine contactor and
become anionic surfactants.
NF-75 dual
bed adsorbent
Figure 8 Dual bed material NF-75 used for foam reduction and amine clarification
(left). Amine solvent presenting foam (right) before and after treating with NF-75
through the downstream filter coa-
lescer to the amine unit discourages
the use of corrosion inhibitor in the
wash system.)
The vessel and associated water
demand of these wash systems can
be relatively large, and thus diffi-
cult to justify in the plant design if
vapour phase surfactant intrusion is
not a known problem in that region.
What is needed is a compact sys-
tem that performs an effective water
wash, but consumes little excess
water, and can be easily retrofitted
into an existing amine facility. We
Two-stage cMIST
Stage 1
Feed gas
Droplet
generator
Mass transfer
section
Inline separator
contaminated processed
processed
amine solvent aminesolvent
amine solvent
describe here two novel water wash
systems that can be installed inline
with the feed gas pipe, and com-
prise compact water wash devices
capable of removing water solu-
ble components such as surfactants
and salts from incoming feed gas.
The spent water can be treated and
recycled to minimise water make-up
and clean water consumption.
The novel water wash systems can
be utilised separately, or in combi-
nation. One system utilises a modi-
fied cMIST contactor, and the other
is an Exion contactor, both of which
Stage 2
Product gas

Water wash
If conventional separation and fil- Exion Treated
ter coalescence are not completely contactor gas
effective at removing incoming LC

aerosols and surfactants, water

washing likely will be. A typi-
cal water wash tower consists of LT
three or four trays (or decks) and
employs a countercurrent flow of
LT
water (downward) relative to gas Water
LC
(upward). If there is appreciable recovery
acid gas (H2S and or CO2) in the
feed gas, the wash tower shell will
likely be fabricated from stainless Feed gas
steel to avoid corrosion. (The pos-
sibility of carryover of wash water Figure 9 cMIST contacting device (top), and Exion device (bottom)

www.eptq.com PTQ Q4 2018 95

q3 nexo.indd 6 17/09/2018 12:06

 a small mechanical followed by an
4.5 adsorbent bed.
In addition to absorbing water
4.0 soluble components, the water
3.5 droplets may coalesce with other
Foam height, mm
aerosols to make them easy to
3.0
capture and recover from the gas
2.5 stream. The cleaned gas then flows
2.0 to the amine unit.

1.5 Production and pipeline chemicals –

1.0
0.5
Control
0 with a water wash to scrub the con-
0 100 200 300 400 500 600 700 800 900
Time, s
Figure 10 Foaming tests of laboratory grade 50% MDEA in distilled water with added
corrosion inhibitors (1000 ppm). Each line represents a different corrosion inhibitor used
in pipelines. The red line represents the control sample containing no corrosion inhibitor
are depicted in Figure 9. The cMIST the water to be reused by removing
contactor is a co-current gas-liquid any surfactants from the spent water
contactor that has been successfully using a proprietary resin.
applied to gas dehydration with For the combination case, water
TEG, and is being tested for selec- would be injected upstream of the
tive H2S removal.6 Exion has been Exion device where it would be coa-
used for removing H2S and mercap- lesced and collected. That ‘polishing’
tans from liquid7 and gas streams8; water would be pumped upstream
however, it can also be used for to the cMIST unit where it would
surfactant removal from feed gas be sprayed into the gas steam and
streams. These systems can also be a short mass transfer zone, with
used in combination to effectively the liquid being recovered by an
remove virtually all soluble gas inline separator. A small amount of
phase contaminants from the feed the recovered water would be bled
gas stream. The Exion system also off, while the remainder (with a lit-
has a water reuse stage that allows tle clean make-up water) flows to
air
air
scrubbing
Scrubbing
distilled water
water
water
with
corrosion
inhibitor
corrosion
inhibitor
Figure 11 Set-up to test gas phase transport of corrosion inhibitors and scrubbed with
distilled water. The pipeline corrosion inhibition chemical is shown in the centre and is a
significant foam promoter
the hidden foaming agent?
ecent field tests using a gas slip
stream and a test unit equipped
taminants from the gas revealed that
often production or pipeline chem-
icals are vapour borne and carried
with the feed gas into the amine
unit. The gas phase contaminants
caused the wash water to have a
significant foaming tendency and
considerable stability. Laboratory
testing at the Nexo Solutions labo-
ratories of common corrosion inhib-
itors added to 50% MDEA caused
significant foaming. Figure 10 sum-
marises the laboratory test per-
formed to screen various corrosion
inhibitors promoting amine foam.
All tested chemicals produced foam
given the foam column height. The
foam stability was also significant,
with some chemicals stabilising
foam for several hours.
To support the hypothesis that
surfactants such as corrosion inhib-
itors can be carried in the vapour
phase with the gas stream, a simple
but important experiment was con-
ducted. The experiment consisted of
passing air over the surface of water
containing a known surfactant based
corrosion inhibitor in a glass bot-
tle (see Figure 11). The air flow was
passed over the surface of the water
phase with no possibility of aerosol
formation. The air was then routed
into another bottle containing dis-
tilled water only. The air stream was
bubbled into the distilled water to
scrub any gas phase components.
Initially, the experiment did not
reveal any appreciable foam forma-
tion. However, after aproximately
~6 hours, a small stable froth head
was observed at the surface of the
scrubbing water reservoir. This
froth was short-lived, but indi-
cated that the water was starting
to be contaminated with compo-

96 PTQ Q4 2018 www.eptq.com

q3 nexo.indd 7 17/09/2018 12:05

 nents that can stabilise foam. After
12 hours, the froth became stronger
and more stable, leading to the
initial stages of foam. The surface
tension of the scrubbing distilled
water decreased 9% compared to
pure distilled water. This was clear
evidence that gas phase surfactants
can travel in the gas stream and
likely penetrate any filter and coa-
lescer before ingression into an
amine unit or glycol unit. Filters
can remove solid particles, while
coalescers can remove liquid drop-
lets or liquid aerosols. However,
gas phase components will not be
removed by either method. Hence,
the need for a water wash system
to greatly reduce the chance of sur-
factant carry-in to the amine unit.
Conclusion
Virtually every natural gas stream
with H2S or CO2 should be treated
by amine or other solvents to meet
gas specifications for pipeline, LNG
or other cryogenic processes.
Solvent foaming tendency and
foam stability are complex phe-
nomena in both amine and glycol
units, and generally originate from
multiple sources. The foaming
of amine and glycol solvents has
not been thoroughly investigated,
largely because such a wide range
of factors and variables present in
actual processing units make its
understanding difficult.
Increased foaming tendency is
usually the result of lowering surface
tension by organic components such
as certain solvents, hydrocarbons
and specific surfactants that enter
the unit. However, surface tension
alone cannot always explain foam
tendency or foam stability because
of the multiple contaminants pres-
ent in amine or glycol solvents that
can actually increase surface tension.
More complete surface rheology
tests must be conducted to deter-
mine foam film elasticity and better
correlate to foam formation.
Foam stability is attributed to
contaminants that can stabilise
foam, primarily surfactants. These
form elastic films capable of self-
assembling at critical interfaces,
leading to foam stabilisation.
Compact water wash upstream of
processing units may be an effec-
www.eptq.com
q3 nexo.indd 8
tive means of absorbing gas phase
contaminants and, by implication,
reduce foaming tendency and stabil-
ity in the downstream amine unit.
References
1 Sczesny J S, Keller A, Perils of foaming and too You require special
much antifoam in amine treatment, presented technology services
at the 68th Laurance Reid Gas Conditioning or operational quality
Conference, Norman, OK, 26-28 Feb 2018. support for catalyst
2 Engel D, Burns H, Williams S, Surfactant
shutdown peak coverage?
contaminants in feed gas streams to amine
units: the hidden foaming agent, presented
at the 96th GPA Midstream Convention, San
Antonio, TX, April 2017.
3 Fruhner H, Wantke K-D, Lunkenheimer
K, Relationship between surface dilational
properties and foam stability, Physicochemical
Engineering Aspects, v. 162, 2000, 193–202.
4 Georgieva D, Cagna A, Langevina D, Link
Between Surface Elasticity and Foam Stability,
Soft Matter, v. 5, 2009, 2063–2071.
5 Bryant J, Univ. of Kentucky, personal
communication, 2017.
6 Ramkumar S, Philbrook S, Northrop S, Yeh N,
Shatto D, Shaunfield P, cMISTTM: Inline selective
H2S removal technology, presented at the 68th
Laurance Reid Gas Conditioning Conference,
Norman, OK, 26-28 Feb 2018.
7 Engel D, Burns H, Williams S, Remove
mercaptans from hydrocarbon condensates
and NGL streams, Gas Processing & LNG
Magazine, Mar-Apr 2016.
8 Engel D, Burns H, Williams S, New H2S
removing technology proven in gas treating
field tests, Oil & Gas Journal, Jun 2017. GO BEYOND YOUR
LIMITS WITH US!
Scott Northrop is a Gas Treating Advisor
in the Production Technologies Function of
ExxonMobil Upstream Research Co. in Spring, With our experienced
TX, USA. He has 28 years’ experience in the personnel for:
industry, and is the author/co-author of a shutdown planning & project
number of patents, presentations and articles support
in a variety of related subjects. He sits on catalyst shutdown services
Technical Section F of the Gas Processors
loading technology services
Association (GPA), and is on the board of
directors of Alberta Sulphur Research Ltd., user trainings
Calgary, Canada. He holds a BSc degree from project supervision
Washington University in St. Louis, Missouri,
OEM services
and an MSc degree and PhD from the California
Institute of Technology, all in chemical A wide range of rental
engineering. equipment on stock!
David Engel is the Managing Director of Nexo
Solutions and Technology Leader for Exion You‘ll get know-how,
Systems. He has over 20 years’ experience experience and technology
in chemical engineering and chemistry, from one source!
specialising in process optimisation and
contaminant separation technologies. He is the
Edelhoff Technologies GmbH
inventor in 18 US Invention Patents and author Iserlohn, NRW · Germany
of over 70 technical and scientific papers.
Edelhoff Technologies USA LLC
He holds a BS in industrial chemistry, a MS Houston, Texas · USA
in chemistry and a PhD in organic chemistry.
He is also 6-Sigma and Project Management www.edelhoff-technologies.com
certified, and is currently President of the
American Filtration Society, Southwest Region
and Member of the GPA Technical Section M.
PTQ Q4 2018 97
13/09/2018 18:46
 TEXAS INGENUITY.
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rentech.indd 1 13/09/2018 10:51

 New insights into Claus waste
heat boilers
The real plant performance of a waste heat boiler depends on many factors
besides heat transfer

NATHAN A HATCHER, CLAYTON E JONES, SIMON A WEILAND, STEVEN M FULK and MATTHEW D BAILEY
Optimized Gas Treating

T
he Claus waste heat boiler
(WHB) is a critical piece of
equipment in the sulphur
recovery unit (SRU). As processors
move towards higher sulphur feed-
stocks, more load is placed on the
SRU, and WHB failures are becom-
ing more common. Higher failure
rates have come at the very time
when uptime metrics and envi-
ronmental constraints have also
become stricter.
A set of case studies is reported
using a newly developed rate based
heat transfer and chemical reaction
model of the WHB which provides
quantitative insights into several
aspects of the HB that affect S U
performance:
• Recombination reactions that
occur at the front of the WHB are: Figure 1 Waste heat boiler (Courtesy of Schmidtsche Schack, Düsseldorf)

H2 + ½ S2 ⇌ H2S
CO + ½ S2⇌ COS
These reactions not only influ-
ence sulphur recovery, air demand,
and hydrogen production in the
S U, but they also affect the heat
flux and performance of the HB.
These reactions occur towards
the front (inlet) side of the WHB
and are exothermic. The hidden’
heat associated with them tends to
increase heat flux near the critical
tube to tubesheet joint.
• adiation affects heat transfer,
primarily towards the inlet of the
WHB.
• Radiative heat transfer, coupled
with the exothermic recombination
reactions, collectively increase the
peak heat flux at the front of the
boiler well above predictions from
models that ignore or discount
these factors. Tube wall tempera-
tures, heat flux, and corrosion rate
predictions from the model are
examined down the length of the
tubes for an oxygen enriched and
air only sulphur plant as a func-
tion of tube size and mass velocity.
Surprising findings show elevated
tube wall temperatures well down-
stream of the area of protection
provided by ceramic ferrules for
the higher mass velocity cases, val-
idating documented failures in the
industry. The implications of sul-
phidic corrosion and the resulting
impact on boiler tube life and sul-
phur plant reliability are examined
with this new information.
Background
The WHB (see Figure 1) is argu-
ably the most fragile part of an
SRU and is subject to sudden and
very costly failure. The most com-
mon failure point is the tube to
tubesheet joint where temperatures
can become unacceptably high,
causing the welds there to fracture
and the joints to fail. To provide
operability, this region of the WHB
is protected by ceramic ferrules (see
Figure 2) inserted a short distance
into the tubes and which usually
also completely cover the face of
the tubesheet (see Figure 3). On the
utility side, high or medium pres-
sure steam is usually generated
(heat recovery) by cooling the hot
gas on the process side. Sulphur is
not usually condensed in the WHB
except at turndown conditions.
As heat is removed in the WHB,
a number of interesting reactions
take place (see Equations 1-4). The
S2 vapour allotrope is exothermally
converted into the S6 and S8 forms
as the gas is cooled (see Equations
1 and 2). Reactions of at least equal
importance involve hydrogen

www.eptq.com PTQ Q4 2018 99

q4 OGT.indd 1 14/09/2018 08:59


Figure 2 Thermal protection by ceramic ferrules
recombination with S2 vapour (see
Equation 3) and COS formation from
carbon monoxide and S2 vapour (see
Equation 4). These reactions are also
exothermic and take place primarily
at the HB’s front end:1-5
3S2 ⇌ S6 + heat
4S2 ⇌ S8 + heat
2H2 + S2 ⇌ 2H2S + heat
2CO + S2 ⇌ 2COS + heat
Because of the high inlet temper-
ature of the process gas, radiation
also plays a significant role in heat
transfer in the HB. This is quite
unlike the heat exchangers further
downstream.
Approaches to recombination
modelling
The recombination reactions can
generate significant heat near the
Castable refractory
Tubesheet
Tube to tubesheet joint
Point of maximum metal temperature
(<315ºC or 600ºF)
Ceramic ferrule insert
WHB tubesheet
Point of maximum heat flux:
Maximum turbulence
Maximum process temperature
Steam blanketing possible
Eddy shedding
front of the HB (close to the frag-
ile tube to tubesheet joint area),
so getting the simulated tempera-
ture there as correct as possible is
important. Until very recently, the
models used by all commercially
available S U simulators handled
(1) recombination by one of several
(2) obfuscation techniques:
(3) • Ignore local recombination and
(4) assume the reaction furnace is at
equilibrium
• Lump these reactions into the
reaction furnace effluent
• Free e the reactions by assuming
they reach equilibrium at a user
supplied quench temperature.
The only correct approach is
to model the reactions as they
truly are: fully reaction kinet-
ics rate based. ith the advent
of the SulphurPro simulator, this
approach is now available.
The SulphurPro simulator uses
a first principles, rate based model
that incorporates the effects of
• eaction kinetics
• igorous heat transfer (includ-
ing temperature, composition, and
geometry dependent radiation)
• Condensation calculations of liq-
uid sulphur (including thermody-
namic and physical property effects
resulting from the varying distribu-
tion of sulphur allotropes).
The interdependency of physi-
cal properties, reaction rates (and
their heats of reaction redistribu-
tion), bulk heat transfer, and stream
enthalpies (both latent and sensible)
are all considered together to pro-
vide a consistent and powerfully
predictive modelling tool. The set
of equations governing the HB,
including recombination reactions,
is numerically integrated along the
boiler tube length. Adaptable seg-
mentation is used to yield more
accurate results by placing more
segments in the locations where
properties are changing fastest
and consequently require greater
numerical resolution.
eaction kinetics modelled in
SulphurPro are based on work
whose original purpose was explo-
ration of the two main recombi-
nation reactions that occur in the
HB, and in which Arrhenius
kinetics parameters were tuned
to match sets of experimental,
pilot, and full-scale S U data.
Implementation of kinetics in
SulphurPro are consistent with the
ProTreat simulator’s thermodynam-
ics, with additional refinements
made to match internal sets of
plant data for both normal opera-
tions and off-spec conditions in real
operating sulphur plants. All other
transport coefficients and physical
properties are calculated from pro-
prietary or well-established litera-
ture correlations. Case studies will
illustrate the importance and rele-
vance of these reactions.

Case studies
The case studies are based on the
flowsheet in Figure 4. Because HB
failures have tended to be more
common during the harsher con-
Figure 3 Types of ceramic ferrules, installed view: (a) Conventional ferrules before final ditions of oxygen enrichment, the
refractory installation; (b) Hex-head ferrules (Courtesy of Blasch Precision Ceramics) basis plant selected for study was

100 PTQ Q4 2018 www.eptq.com

q4 OGT.indd 2 15/09/2018 06:35

 IS WHO WE ARE
Ariel’s knowledgeable
aftermarket workforce is
what makes us the number
one authority in natural
gas compression.

ariel.indd 1 13/09/2018 10:52

 S S
%O2 control ADA
Oxygen MULT
30% O2 wet
O2 air
2 MULT MULT

Feed Trim
Intake air forward air
Heat loss
Claus air blower
SWS preheat
SWS AG Thermo transfer-1

AG preheat
RHTR-1 RHTR-2 RHTR-3
Amine AG +
TGU recycle
24 7 Conv-1 Conv-2 Conv-3
20 Tall gas
36 35 32 42

Rxn WHB 30 34 31 33
furnace Cond-1 Cond-2 Cond-3 Cond-4
Sulphur

Figure 4 Flowsheet for case study

designed originally for approxi-
mately 100 lt/d (101.6 mt/d) sul-
phur on air operations, but that
was to be revamped using low
level oxygen enrichment (to 30%
O2 wet basis) in order to gain 25%
more throughput. Typical compo-
sitions of refinery amine acid gas
(90% H2S, 0.5% C1, balance CO2,
water saturated) and SWS gas
(55% NH3, 45% H2S, water satu-
rated) were used with a 5.6:1 ratio
of amine acid gas to SWS gas. This
resulted in nominally 6% NH3 in
the combined acid gas feeds.
Table 1 shows the WHB tube
configuration chosen for rating.
Failures above mass velocities of
5.0 lb/ ft2.s (24 kg/m2.s) have been
reported to be more common,5 so
WHB configuration and parameters
a design was chosen that would
operate at just under this mass
velocity on air operations. A range
of utility side heat transfer coef-
ficients from the literature6 was
chosen for the sensitivity study to
encompass expected ranges to rep-
resent operating over a range from
poor to good utility side circulation.
Table 2 summarises the results
of the study specifically for the
boiler rating. Quite profound differ-
ences between the air and oxygen
enriched operations can be seen.
The inlet temperature from the reac-
tion furnace climbs from 2360°F
(1293°C) on air operations to nom-
inally 2680°F (1471°C) on oxygen.
Peak boiler tube wall temperatures
and heat fluxes also elevate substan-
tially on oxygen compared to air.
Sulphidic corrosion rates at the fer-
rule outlet and the process piping
outlet (assuming no refractory lin-
ing) were calculated by a curve fit
of the chart in reference 6 knowing
the percentage H2S and wall tem-
perature. Expected corrosion rates
under oxygen operations are about
twice those for air only. It should be
noted that the heat fluxes that were
computed do not take into account
the insulating effect of the ferrules,
nor do they account for the effect of
eddies that typically amplify heat
flux at the ferrule outlet.
Referring to Table 2, an unex-
pected finding is just how sensi-
tive the results appear to be to the
assumed steam side heat transfer
coefficient. If water circulation is
poor near the tube inlet (150 Btu/h.
ft2.°F case), then corrosion rates well
above 10 mil/year can be expected

Number of tubes 120 WHB rating results

Tube OD/ID, inches 2/1.783
Tube length, ft 32 Parameter Air only 30% O2
Steam generation pressure, psig 350 Steam side HTC, Btu/h.ft2.°F 150 350 500 150 350 500
BFW temperature, °F 280 % H2S in/out 4.4/7.0 4.0/10.0
Mass velocity, lb/ft2.s 4.45/4.9 Temperature in/out, °F 2361/598 2359/577 2358/572 2681/664 2678/631 2677/623
Inside tube wall emissivity 0.9 Mass velocity, lb.ft2.s (inlet) 4.45 4.9
Fouling resistances, process/ Max tube wall temp, °F 706 602 576 783 651 621
steam sides, h.ft2.°F/Btu 0.008/0.002 Max heat flux, Btu/h.ft2 37,400 39,900 40,500 48,200 51,900 52,700
Steam side HTC range, Corrosion rate in/out, m/y 13/4.7 4.5/3.8 3.4/3.5 27/10 7.4/7.3 5.4/6.7
Btu/h.ft2 °F
.
150 to 500

Table 1 Table 2

102 PTQ Q4 2018 www.eptq.com

q4 OGT.indd 3 14/09/2018 09:00

 for both air and oxygen enriched
operations. Eddy heat flux ampli-
fication on the process side would a 100 O2 enriched, % of H2
Air only, % of H2
undoubtedly make matters even 90
O2 enriched, COS ratio
worse. These findings point to the

Inlet H2 reacted, %
80
Air only, COS ratio
importance of maintaining good 70
water side circulation and water
60
quality to prevent scale formation.
More steam side resistance increases 50
tube wall temperature while higher 40
process side fouling will tend to 30
insulate the tube and lower the tube 20
wall temperature. Better circulation 10
(higher steam side HTC) lowers the
0
maximum tube wall temperature, 0 5 10 15 20 25 30 35
but increases heat flux. The oxygen Cumulative tube length, ft
enriched operations show heat flux
in excess of 50 000 Btu h.ft2, which b 900
O2 enriched wall temperature
in the authors’ experience can be a 850 60000
O2 enriched heat flux
red flag for reliability. A CF study 800 Air only heat flux
50000

Heat flux, BTu/h.ft2

of this boiler plus water side model-
Temperature, ºF

750 Air only wall temperature

ling would be wise.
700 40000
Figure 5 shows sample plots of
several parameters as a function of 650
30000
cumulative tube length. The lines 600
for air only operations assume a 550 20000
steam side heat transfer coefficient 500
of 500 Btu h.ft2. F while the lines 10000
450
for 30% O2 operations assume a
value of 150 Btu h.ft2. F for the 400 0
0 5 10 15 20 25 30 35
steam side heat transfer coefficient.
Cumulative tube length, ft
These conditions were chosen to
bracket the extremes of the study c
3000 30
that was conducted to contrast dif- O2 enriched process temperature
ferences. Plotted parameters are: Air only process temperature
• eacting species, H2 and COS 2500 O2 enriched corrosion rate

Corrosion rate, mpy

Temperature, ºF

(top most plots) Air only corrosion rate

• Tube wall temperature and heat
flux (middle plots)
• Process temperature and pre-
dicted corrosion rate (bottom plots).
A number of interesting obser-
vations follow from Figure 5. First,
the hydrogen and COS reactions
are finished in the first 5-10ft of the
tube bundle. Hydrogen losses are
much higher on oxygen than for air
while the COS formation tendency
is also much higher with oxygen.
Tube wall temperatures on oxy-
gen operations remain quite high
well past the insertion length typi-
cal for ceramic ferrules ( in). Given
the right conditions, such as poor
water side heat transfer, corrosion
rates and heat flux will also be high
past the ferrule protected length.
Tube wall temperature and heat
flux (middle charts) exhibit an
inflection at approximately 10ft
along the tube length. Looking fur-
20
2000
1500
10
1000
500 0
0 5 10 15 20 25 30 35
Cumulative tube length, ft
Figure 5 How process metrics change with distance along WHB tubes
(a) H2 and COS vs cumulative length; (b) Tube wall temperature and heat flux vs length;
(c) Process temperature and corrosion rate vs length
ther at the bottom plots, the pro- study for the entire sulphur plant.
cess temperatures are in the range Hydrogen in the Claus tail gas is a
where sulphur species begin shift- weakly increasing function of the
ing from S2 vapour to S and S8 assumed steam side heat transfer
vapour (1200-1 00 F, -7 0 C). coefficient. Both hydrogen make in
the Claus unit and COS production
Process performance considerations are higher under oxygen opera-
Table 3 outlines key process perfor- tions. In general, sulphur recovery
mance predictions from the rating efficiency under oxygen enrichment

www.eptq.com PTQ Q4 2018 103

q4 OGT.indd 4 14/09/2018 09:00


Key process performance predictions
Parameter
Steam side HTC (Btu/h.ft2.°F) 150
H2 in tail gas, % (wet) 2.35
Sulphur recovery, % 97.44
COS in tail gas, ppmv (wet) 401
Condenser-1 effluent NH3, ppmv
Table 3
is higher than on air operation for
the Claus unit. Note that SO2 emis-
sions from the TGU stack may not
follow the same relationship since
oxygen enrichment leads to more
COS in the tail gas.
The SulphurPro ammonia
destruction model predicts that
ammonia concentration is higher
leaving the thermal stage under
oxygen enrichment than under air
operations. This counter-intuitive
finding results from two factors:
1. Although the reaction furnace
runs hotter on oxygen, residence
time for an overall hydraulic load
equivalent to air operations is actu-
ally lower because of the higher
temperature (lower actual gas
density).
2. While NH3 destruction efficiency
is comparable on oxygen, the lower
concentration of inert gases from
combustion air increases the con-
centrations of all the other species
across the board.
Sulphur recovery efficiency is
a competition between the Claus
reaction and tendency to COS for-
mation in the thermal stage and
efficiency of destruction in the cat-
alytic stages. The minimum recov-
ery efficiency on air only operations
and maximum recovery efficiency
on oxygen enriched operations at
Differences using less rigorous models (30% O2 at 150 Btu/h.ft2 .°F steam side HTC)
Parameter Kinetics rate
model
Enriched air flow, lbmol/h 698.3
Furnace temperature, °F 2681
WHB outlet, °F 664
WHB duty, MMBtu/h 30.2
Peak wall temperature, °F 783
Peak heat flux, Btu/h.ft2.°F 48,200
H2 in tail gas, mole% (wet) 2.70
Sulphur recovery, % 97.57
Table 4
104 PTQ Q4 2018
q4 OGT.indd 5
furnace temperature being over-
predicted by 220°F (2902°F vs
2681°F). In the authors’ experi-
Air only 30% O2 ence, this is a common problem
350 500 150 350 500 with most commercial sulphur
2.42 2.44 2.70 2.77 2.79
97.42 97.46 97.57 97.60 97.58 simulation packages. Because the
387 384 587 570 566 temperature prediction in the fur-
36 63 nace is wrong to begin with, soft-
ware using this reaction lumping
approach will often require multi-
ple regression models to predict the
350 Btu/h.ft2.°F steam side coef- thermal section performance. The
ficient are a reflection of this engineer then has to decide which
competition. regression model to select, a choice
that is often unclear when pro-
Weaknesses of less rigorous models cess conditions overlap regression
The study to this point has focused boundaries.
on the reaction kinetics rate based The freeze quench method works
heat transfer model in SulphurPro. to capture the hydrogen make,
So the natural question most engi- combustion air demand, and sul-
neers will ask is: “What do less rig- phur recovery, but only for the
orous models predict in these two one set of equilibration tempera-
circumstances of air vs O2 opera- tures that is assumed for tuning the
tions?” A sensitivity analysis was model. Because the reaction furnace
run using SulphurPro on the most temperature is contrived by the
severe oxygen enriched operating assumption of equilibrium, there
case with 150 Btu/h.ft2.°F steam is no true temperature to represent
side heat transfer coefficient. Table the real process stream entering the
4 summarises the results. WHB, so the WHB simply cannot
Using a thermodynamic equilib- be rated rigorously. There is noth-
rium based furnace without taking ing predictive about this sort of
into account recombination under- approach. Again, the engineer is
predicts the air demand to the unit forced to use judgment as to how
by a stunning 15%. The model also far away from the tuning point or
overpredicts unrecovered sulphur rule of thumb the results can be
by 20%, and results in gross over- safely applied.
prediction of hydrogen produc- A final test (not shown in Table 4 )
tion by a factor of 3.7. None of the was conducted to ignore radiation
equilibrium results reflect anything in the WHB. The predicted outlet
like what can be expected in a real temperature would be about 20°F
operating plant. higher for the exchanger rating con-
Assuming that the same hydro- ducted in this manner.
gen and COS production predicted
by SulphurPro’s rate model both Conclusions
occur, but in the reaction furnace The real plant performance of
itself vs the WHB, results in the a WHB depends on many fac-
tors besides heat transfer. When
the chemistry of the recombina-
tion reactions is properly handled
by the model as reaction kinetics
Equilibrium Lumped reaction Freeze quench based, new insights into the per-
furnace method method formance of the WHB and the
603.5 698.3 698 Claus unit can be gleaned. We
2510 2902 2680
have demonstrated, quantitatively,
648 658.5 664 (spec’d)
25.8 30.3 30.2 that corrosion beyond the ferrule
736 796 N/A outlet can become quite high, and
41,800 50,000 N/A it is highly sensitive to the steam
8.7 2.70 2.70
side heat transfer characteristics.
98.05 97.58 97.62
Corrosion is excruciatingly costly
when it results in tube failure and
Claus unit downtime to re-tube the
www.eptq.com
14/09/2018 09:00
 boiler with concomitant loss of pro-
duction. SulphurPro’s rate based
model used here demonstrates the
importance of water side hygiene –
to maintain reasonable boiler tube
life, keeping fouling in check is
important under normal air opera-
tions, and even more so under oxy-
gen enriched conditions.
A further important conclusion is
that the true reaction furnace tem-
perature on oxygen enrichment is
considerably lower (220 F) than
is predicted by many models that
lump the recombination reactions
into the furnace effluent stream.
Furnace temperature measuring
devices have acquired a bad repu-
tation over the years because they
almost invariably read lower than
most models predict. Some of this
thumping may be undeserved. The
SulphurPro approach to modelling
completely eliminates the need to
use lumped parameter empirical
models to fit different operating
modes such as oxygen enrichment.
Finally, equilibrium based fur-
nace model predictions have been
Visit us at Sulphur 2018, Stand #27
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q4 OGT.indd 6
demonstrated not to reflect many
important aspects of Claus unit
performance. Air demand to the
unit was underpredicted by nearly
15%. Unrecovered sulphur was
missed by 20%, and hydrogen pro-
duction was overpredicted by a fac-
tor of 3.7.
SulphurPro and ProTreat are marks of
Optimized Gas Treating, Inc.
References
1 Karan K, Mehrotra A K, Behie L A, Including
radiative heat transfer and reaction quenching
in modeling a Claus plant waste heat boiler,
Ind. Eng. Chem. Res., 33, 1994, 2651-2655.
2 Nasato L V, Karan K, Mehrotra A K, Behie L A,
Modeling reaction quench times in the waste
heat boiler of a Claus plant, Ind. Eng. Chem.
Res., 33, 1994, 7-13.
3 Karan K, Mehrotra A K, Behie L A, COS-
forming reaction between CO and sulphur: a
high-temperature intrinsic kinetics study, Ind.
Eng. Chem. Res., 37, 1998, 4609-4616.
4 Dowling N I, Hyne J B, Brown D M, Kinetics
of the reaction between hydrogen and sulphur
under high-temperature Claus furnace
conditions, Ind. Eng. Chem. Res., 29, 1990,
2327-2332.
5 Martens D H, Porter McGuffie Inc., Tube and
Higher Reliability / Uptimes
- Better structural integrity vs conventional
checkerwalls
- Eliminate SRU plugging and catalyst
poisoning
- 50 -75% faster installations
Tube Weld Corrosion and Tube Collapse, 2011
Brimstone Sulphur Symposium, Vail, CO.
6 www.engineeringtoolbox.com/convective-
heat-transfer-d_430.html, accessed 14 Sept
2017.
Nathan (Nate) A Hatcher is Technical
Development Lead with OGT. He holds a BS
in chemical engineering from the University of
Kansas. Email: Nathan.Hatcher@ogtrt.com
Clayton E Jones joined Optimized Gas Treating,
Inc as a Software Development Engineer in
2012. He holds a BS in chemical engineering
from McNeese State University and a MS in
chemical engineering from the University of
New Mexico.
Simon A Weiland joined Optimized Gas
Treating in 2014 as a Software Development
Engineer. He holds a BS in chemical engineering
from the University of Oklahoma.
Steven M Fulk has been a Software
Development Engineer with Optimized Gas
Treating since 2016. He holds a BS in chemical
engineering from Texas A&M University and a
PhD in chemical engineering (2016) from the
University of Texas at Austin.
Matt Bailey joined Optimized Gas Treating
in 2014 and provides technical sales and
marketing support. He holds a BS in Chemical
Engineering from Texas A&M University and an
MBA from the University of Houston.
Timothy Connors
Senior Market Manager
Energy & Chemicals
PTQ Q4 2018 105
15/09/2018 06:34
 ®

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zeeco.indd 1 12/09/2018 19:01

 Liquefaction technology selection for
offshore FLNG projects
Development of a successful offshore floating LNG project depends on an
appropriate liquefaction process that best meets project objectives
SAEID MOKHATAB
Gas Processing Consultant
A
s global demand for LNG
increases, interest grows in
unlocking and monetising
stranded gas reserves in deepwater
locations. This makes floating lique-
fied natural gas (FLNG) technology
a technically innovative solution
and a commercially viable means
of exploiting remote offshore gas
reserves, while at the same time pro-
viding an economically preferable
option to flaring associated gas at oil
fields.
FLNG technology offers lower
production costs, reduced time to
first production, and less environ-
mental impacts than land based
alternatives. In addition, a potential
advantage of a floating facility is that
it can be moved relatively easily to
an alternative offshore location as
the original gas resources decline or
economics change. This allows the
operator to save money on future
gas field developments or earn rev-
enue by charging third parties to
process their gas through the FLNG
facility.
hile principally aimed at remote
offshore gas reserves, FLNG produc-
tion technology can be considered
for the development of nearshore
gas fields with limited infrastructure.
Alternatively, FLNG can be used to
liquefy pretreated, onshore pipeline
quality gas for export to markets
that require small to midscale LNG
supply volumes. It may also be used
where the shoreline is too rugged
and difficult to build infrastructure
like LNG tanks onshore, for instance
Western Canada.1
Initial offshore FLNG develop-
ments are focused on building large
scale facilities that can move and
process large quantities of LNG,
www.eptq.com
q4 mokhatab.indd 1
FLNG projects development models2
Characteristics Small to midscale FLNG facilities
Liquefaction capacity, MMt/y Less than 3.0
Required gas reserves, Bcm 14 to 85
Hull shape Ship
Storage capacity, m3 Up to 220 000
Liquefaction processes Simpler processes
Table 1
typically 5 million t y and up, that
require significant capital invest-
ment. However, global LNG prices
have recently dropped considerably
and industry leaders are currently
planning to mitigate project risks by
developing small to midscale FLNG
projects, limiting production capac-
ities to 0.5-3 million t y. One excep-
tion is Shell’s Prelude FLNG facility
with a nameplate production capac-
ity of 3. million t y, located off-
shore NW Australia.
In large scale FLNG projects, the
liquefaction facilities are mounted
on a barge-like structure or a ship-
shaped vessel (depending on the
location) with the LNG stored in the
hull underneath. In small to midscale
FLNG projects, the liquefaction facil-
ity is built on a purpose-built vessel
that is sized as a conventional LNG
ship. Table 1 provides the key char-
acteristics of both small to midscale
and large scale FLNG facilities which
are considered by project developers.
Offshore production challenges
Although the FLNG production con-
cept has been the focus of research
and development for decades, it
is only in the last 10 years that any
FLNG projects have progressed to
the detailed design and construc-
tion phase. In fact, some special
Large scale FLNG facilities
3.5-6.0
More than 85
Ship or barge (depending on the location)
More than 250 000
Baseload type processes or multiple simpler
process trains
challenges exist in the design, con-
struction and operation of an FLNG
facility in the harsh offshore environ-
ment that require special solutions.
The key technical challenges,
which influence the liquefaction pro-
cess and equipment selection for a
floating gas liquefaction facility, can
be summarised as follows.
Space and weight requirements
Floating systems are space limited,
requiring more compact and lighter
equipment to fit the deck space.
These systems have high equipment
density and lower equipment count
to overcome space and weight con-
straints. High equipment density
substantially increases the potential
for explosions (as opposed to defla-
grations). In the event of gas release
and ignition, this would result in
higher impact severities, perhaps
escalating to total facility loss. An
FLNG facility must meet both fire
loads and escape route requirements.
Note should be made that due to
the space constraint, equipment is
designed with fit-for-purpose’ crite-
ria. This reduces the flexibility that
may be desired. For example, gas
turbine waste heat recovery may not
be justifiable due to the additional
weight and space or centre of gravity
requirements.
PTQ Q4 2018 107
14/09/2018 09:02
 The PIONA characterisation and
kinetic approach used in this work A
allow for the ability to predict the 2.5
reactivity
Ease
stream
Conditioning ofConference
equipment a wide
of operation/start-up/shutdownrange
such as the
(LRGCC), of vac-
FCC
Norman, when field Conference
Conditioning gas quality differs.
(LRGCC), Gas and
Norman, the otherthreats
formation
K, Materials standard
ofin aging
insoluble marine safety
sulphide
amine units, NACE
Bad
uum weather/extreme
residues. This would environmen-
mean not processing
Oklahoma, Feb equipment capable Toof value
requirements by increasing
add to the the destruc-
complexity
unit
4800and
Oklahoma,
b/dthe
Feb hydrotreater
1995.
slurry oil product and * ini-365 ble energy sources.
2015.
2.0 Millions of CDU salts
tion
dol- 4 Minyard ofoforganic
Corrosion W magnesium
Conference
F, Woodson
&
sulphur
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T S,
2013. calcium,
compounds
Upgrade FCC
tal
only
3 API
tiate conditions
that
Recommended
the corrosion may
optimisation require
Practice
cycle. 945 (APIrapid
studies RPcan
They also 945 handling
MDEA
12 Nassef well
reference fluids with varying
A S, solvent
Banazadeh-Neshabouri of
19 safety
N, slurry
which Daughtry
results management
J,in:Teletzke and
E, emer-
Controlling

Reactivity index
days
shutdown
be
*
carried
$2.0/
of
b/d = $
the FLNG
3.5 million/y
facility.
lars in revenue
conditions will add
to India’s
to facility
oil and (COS
E V, gency
cost, and
oil with
response ) at lower
CSstudies
chemical
2 procedures
settling
operating
aids,
of
World
such
the out (blend of feeds, differ-
(R2008): Avoiding Environmental Cracking in Formulated
Keller M W, MDEA Roberts reference
K P, Rybicki Analyser
solvent
E F, Iski corrosion: case from amine plant
affect catalyst, which
Simulated results gas sector are1.5beingDesalter lost daily • Reduced
with- Refining, Nov/Dec1999.
temperatures heat transferItin
(<220°C). also heaters,
has a
Thus,
ent
Amine
in more floating
operating
Units,
frequent liquefaction
conditions,
Apr 2008. upset
need facilities
scaling
ends
for up,
catalyst
Jefftreat
Shirazi Desalter
S Ultra
A, Comparison of erosion resistance facilities.
equipment count, and operational 5 Motaghi M, Shree K, Krishnamurthy S, Anode
operation,
causing
Laurance
more
Reid
fuelNorman,
Gas
consumption
Conditioning
and
The only meaningful process of cost outironconsidering the impact of envi- low pressure drop, which of iscontain-
impor-
1 2
are
and
4 De generally
so
Waard
change-out. on), considered
C,butLotzalso impliesfor benign
U, Prediction poten-
CO2 complexity.
of carbonate protective layer with grade Thecoke
Conference
higher potential
cost
(LRGCC),
from for loss
traditional Oklahoma,
crudes, PTQ, Q2 Feb
for the electrostatic separator is for ronmental waste and the cost of tant as the SCOT process operates at
waters.
corrosion
tial monetaryLiquefaction
of carbon
saving byprocess
steel,
Preventative actions that are taken
paper
reducing trains
no. 69
the calcium carbonate 1.0 particles vs. sand, Society 2010. ment
• Hotmust
2016.
spotsalso in heatingbe addressed tubes,and when
which
recycle
presented flow.
at NACEFor this
1993. scale, the recy- lostPetroleum
of revenue from Engineersthe bottom of the 6 Elliott
SPE-188531-MS, near atmospheric pressure an
are
need most
totherun efficient
cracking when
experiments.operated considering hull fabrication. A cat-
H2S in treated gas

Safety J D, Impact of feed properties and

inside
5 cle flow
Ehmke distillation
Erate
F, would betower
Polysulphide stopsand
2 vol% in
ofFCCU
the barrel.
presented
Analyser
Inatthe theeffort
Analyser
Abu Dhabi to become reduces their operational
self- operating parameters on delayed coker petcoke
International excessive pressure dropcould life
can require
continuously with
Simulated very
the overhead system do not replace infrequent Design
Crude and operation of the FLNG astrophic
• Reduced tankflow failure
rates result
inwhich of over-
effluent, or demand
100
Proc.,b/d. At 149-155.
$1.0/ b/d, sufficient, 0.5
increased and refinery mar-
corrosion,
shutdowns.
Hydro.
References upset
air
However,
Jul 1981,
an increaseto
oil
Petroleum
facilities
Exhibition
present a set of
Conference,
safety chal- more
Robert air
in subsequent blower duty
Abu quality, presented at the ERTC 2008 Coking and
James is Vice
large
President
scale the sulphur
discharge
Global
the
6 thisneed
Ehmke, to
costE F,is:
Use remove
starts
ammonium the maximum
polysulphide gins
Dhabi, alone
UAE, Nov will
2017.not sustain the ris- loads
Marketing,
recovery pumping
Oil &
unit units,
Gas/Refining making
with Pall them
Canada.
the (SRU) to would
maintain
Wash Gasification Conference.
in operational
1 Liang
amount interruptions
X, Yan W, Thomsen
of andsalthydrogen
content should
K, Kontogeorgis
from the
G lenges
ing costas of
below:
R,crude efficiency 7of LNG overinto
less efficient sea. This with be
stop corrosion blistering, paper 13 James
water 0 refining.
Arshad A, HighIncluding With
flow.
35 years of experience
U.S. Energy Information Administration, India Pall
be
M, Onexpected
crude
100 b/d
no. 59,
petroleum fluid
oil before
NACE offshore,
recycle it* 365
Corrosion/81, and
characterization
enters the
* $1.0/
Ontario, this
with
crude
b/d =
Canada, • Potentially
contaminant large
removal inventories
improves new of
and followed
• by a rapid
Blockages in tubes which lowers
the installation of the GES to exist-VR Ministry of Petroleum & Natural Gas, Oil
Corporation
density in fluid separation phase and transition,
clarification
& Gas
will adversely
the PC-SAFT
distillation unit.
6-10
$ 36Apr
500 1981.
equation impact
of state,operational
Fluid Phase hydrocarbon
existing
ing refineries B Desalter
sweetening refrigerants
and those control
processes,
with (such
room as Journal, FGE.
Laurance
failing which
across acould cause
their capacities and efficiencies.
broad range serious
of heavy structural
industries, he has
Equilibria, 2014, 375, 254-268.
efficiency.
7 NACE (National Association of Corrosion propane)
Reid Gas represent
Conditioning a hazard
Conference which
(LRGCC), Green-
damage
been and
to
involved thebrownfield
in offshore
the development benefits
facility, of with
many
The salt content of crude oils var-
2 Riazi M, Characterization and properties of mechanical 2.5 filtration could effec- Optimisedwithdesalting
8 Paraskos
Compared
J, Scalco V, Optimize
aloss.
currently processes
value from
applied
Engineers)
ies
standard
with fractions,
Ignoring origin, theASTM MR-0175/ISO
the
labour water
15156,
andcontent
mate- may
Norman, require
Oklahoma, adding
Feb to
2017. safety miti- possible
leading-edge
FCC
tively increase India’s energy sup- are inevitable to guarantee mini- bottoms, stability
application
Hydrocarbon Prevention
solutions to
Processing, advanceof
Apr
petroleum
Availability
international,
Corrosion Cracking Resistant materials for Oil gation
2005,
14 Fontana in terms
M G, of separation
Greene or
N D, Corrosion fire combination
such an
plant and
2013. occurrence
process of performance.
catalyst is a and
key amine
He safety
holds a
in the
Volrial emulsion
50. costs of tank and the amount
cleaning, consider of Figure
ply, 1reduceArrangement environmental
of salt-in-crude waste
oil mum
solvent shutdowns
bachelor ofinengineeringTGT and
line-ups, maintenance
existing
The
Field process
3 the
Equipment.
cost
emulsion-forming
Nji G, oftechnology
Svrcek landfill foroptions
particles
W, Yarranton the
H, in cho-
sludge
Satyro the walls.
Engineering, McGraw-Hill,
and35
analysers
M, 30 create
in40
2.0
a more
desalter
NY, NY, 1967.
efficiency in crude requirement
of those refinery of offshore degree from
units that designs.
can
McGill
be
sen
0
for the FLNG
5 10
facility
15 20
should
25
take
45 50 refineries and gas plants can ben-
1. • Process related accidental hydro- Victor The use of concrete for theCommercial
hull pro-
8 Friedman B, Craig B, Understanding the 15 Lagad V V, Cayard M S, Srinivasan S, University. Email: robert_h_james@pall.com

Reactivity index
removed.
crude oils,
Characterization Assuming
like
of heavypolar landfill
oils resins
and is $1.0/
bitumens.and oil production. affected.
M Scalco III is Global
basics of corrosion in sweet and sour gas Prediction and assessment of rich amine efit from reduced operating costs,
Time, minutes
into
Lb,account
the costand maintaining
is: critical constant
asphaltenes. To prevent corrosion, it the prediction
highest carbon releases (both of refrigerants vides benefits in the storage Manager, of cryo-
treating plants, Laurance Reid Gas Conditioning content and1.5 emulsion properties AliAs the cost ofDevelopment
desalting depends
Vapor pressure
corrosion under simulated refinery conditions, Strategic
lowerArshad Business
emissions,
is Senior improved
Director oper-
– Technology/
availability
is essential possible.
toresilience
pre-processSometimes the crudethis and partially processed natural gas genic fluids as it retains
primarily on crude oil quality, refin- its structural
Feb will
NACE frequently fluctuate according
method for heavy hydrocarbons, Energy & Gulftronic Electrostatic Separators with
Conference
may
Figure
1600
Fuels, result
2
2007,
(LRGCC),
22,in
Upset
tons/year a *
Norman,
less
1, 455-462.$ of Oklahoma,
efficient
Jefftreat
2000/ton design
=Ultra
$ 3.2 or LNG)
Further
Corrosion Conference
are
reading also Source: andShell
considered
Expo, 2010.
to be
analysis ability
FTAP (Fluidand
integrity
General
Technologies
when
Atomics increased
in
and Asset capacity.
contact
Electromagnetic with
Protection)
LNG,
Systems
oil
2005.in the desalter which breaks the to 16 the crude
Chambers B,1.0feed V,in
Lagad Corrosion in amine eries
the desalter. with Pallmust
Additionally, Corporation. make
for With
new a facilities,
compromise
over 26 years of
but willH,
4 million/year
Kumar enable
Froment Grobust operations
F, Mechanistic kinetic key safety
1 Guercio V risks.
J, US producing, exporting more Group. but traditional
He has worked steel ship
for than cap-
designs
more are
20
oil/water
9 NACE
levels and emulsion,
MR0103-2003,
treated gas separating
Materials
specifications. the
Resistant Some
(Criterion)crudes
gas treating: findings
C-834are ofdifficult
laboratoryto
high activity, desalt,
simulations
low between
extensive
ital costs the
separation
are maximum
expected
and fluid
to allowable
clarification
be lower
during
modeling
water changing
of
from
the
the sea states.
hydrocracking
crudeagas oil,
of
and
complex •
thus such Control
slurry oil, Oil of
& process
Gas related
Journal, 4 Oct 2010. hazards cheaper
years
salt
in
content to
the build.
design and implementation
as Venezuelan extra heavy to theand lowest costseparation
of desalt-
to Sulphide Stress Cracking in Corrosive of rich amine conditions, Materials Science and experience in gas processing, refinery, and
Critical
feedstocks,
The tosuch
annual achieving
as vacuum
savings step change
oils,$3.5
are Industrial
mil- temperature
(for instance,
2 Platts, Methodology SCOT
0.5 andcatalyst.
mechanical integrity
Specifications of
Guide, owing
of hydrocarbon smaller
filtration equipment
and size
removing the salt.
Petroleum
in
Refining
the– $0.04
performance
Environments.
of$3.2
the estab- crude,
Technology, Doba
Productcrude
Houston TX, and
2010. Canadian ing when choosing
chemical/petrochemical their development
crude
applications, oilfor
he or
has
17The
2007, PetroleumJefftreat
46,= process Ultra
& Gas Liquids:solvent
US Caribbean and
has systems, reduced
involved equipment
in technical count
Kittel equipment, ignition source
& Engineering Chemistry Research,
10lion
Flexibility
NACE and
standard million
efficiency +
TM0284-2003, million
Evaluation J, Bonis M, Perdu G, Mitigating Vessel
authored motion
several technical papers, instructed
To
lished
18, increase
process
5881-5897. the refining
hasfacilities
been the margin,
devel- crudes,
superior
and Latin and Hsweet form
S selectivity
America, Jan 2012. HCl in the
over pre- blend.
car- Vessel
the enhanced process.
and training with EPC and FCC/RFCC licensors
Designing
of$6.7
Pipeline
refineries FLNG
million/year
and Pressure
purchase
Vessels
crude intended
Steels
oils and
for control
corrosion insystems, 2 0 gas and units: a explosion
comparison separation motion
courses due
at to wind
technical forums,and and
5opment,
Quann R jointly J, Modeling with Huntsman
the chemistry of heater of the desalter.
3 Silverman L D, Winkler S, Tiethof J A, worldwide. With experience in programme
bon dioxide (CO ) at high temper-
to
crudereceive
Resistance to
blends feed
Hydrogen gas from
Induced
atmixtures,
the multiple
Cracking.
lowest cost, overpressure)
between
High and
Witoshkin
laboratory
salt require
data
2
content
A, Matrix more
and field
in heavy
effects robust
VR density survey,
and
in catalytic waves
and C
presented
7
development
Significanceis histhe
asphaltenes work
for key limiting
at various
ofcommercial
on-line factor
conferences.
crudeapplications,
oil in
He
Corporation,
complex
fields
petroleum
introduces of the
the 106, highly
need selec-
Environmental
for6,addi- atures
designs is therefore capable of Smaller
deploying plantsfloating LNG facilities in
cracking, and operating systems.
11 Jones
The road C E, Hatcher
ahead1998, N A, Weiland G S Laurance Reid Gas Conditioning Conference holds a PhD in chemical engineering from the
often as heavy
Health Perspectives, and sour andopportu-
Suppl 1441. opportunity
achieving
presented
ultra crudes at the also
lowcollision
SO
NPRA plays
emissions. an scoping studies and commissioning, he holds
annual analysis
Smaller for
plants optimised costindex desalting
less
tive
tional Jefftreat
gas Ultra
conditioning solvent and •
facilities Control of vessel hazards harsh environments. Once as to build.
aa function
FLNG
A,India
Weiland is R H,
looking Predicting
to further mitigating
develop (LRGCC), Norman, Oklahoma, Feb 2014. University of Oklahoma.
a MA degree from the University of San Diego.
6 Quann R J, Jaffe S B, Structure-oriented important role in scale accumula- The desalting process comprises
nity crudes which are blended with Figure 8 (A) Reactivity
meeting, 23-25 Mar 1986, index
W 2vs vacuum
estin Bonaventure residue density (B) Reactivity the
Criterion
corrosion
and in Catalysts
harnessamine its &Laurance
units,various Reid Gas The
Technologies’
renewa- 18 van C-834
Roji J, catalyst
Klinkenbijl J, adds
Nellen P, further
Sourisseau However,
Email: if
ali_arshad@pall.com
California. there is substantial
of density and C7 asphaltenes
Hotel Los Angeles, California.
other
lumping:crude
describing oils.
theTherefore
chemistry ofthe salt tion in heat exchanger
complex tubes due to following operations:

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OHL Gutermuth
Helmershäuser Straße 9+12 · 63674 Altenstadt / Germany Industrial Valves GmbH
Phone +49 6047.8006-0 · Telefax +49 6047.8006-29
www.ohl-gutermuth.de · E-Mail: og@ohl-gutermuth.de

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 facility is in operation, moving decks
may present major challenges on the
operability and efficiency of process
equipment with two-phase flow.
The sea’s wave motions can also
cause sloshing in the partly filled
membrane tanks. As such, process
equipment that is sensitive to vessel
movement should be located close
to the floating vessel’s centre line to
reduce the forces exacted by move-
ment in the six degrees of freedom.
In addition, utilising hull storage
in twin row tanks cuts down the
sloshing issues while also providing
a robust deck with support in the
middle to help take heavy topsides
loads.
In addition, safe offloading of liq-
uefied gas products to visiting LNG
carriers under harsh environmen-
tal conditions requires more robust
mooring and loading arm technolo-
gies than those developed for shel-
tered, land based ports. If offloading
is considered with a typical spread-
moored configuration, then side-by-
side offloading could be considered.
This provides the benefit that most
LNG carriers load at midships, pro-
viding more flexibility. However, in
less benign seas, weathervaning and
tandem offloading configurations
are more appropriate. To facilitate
this, several technology suppliers
have designed flexible loading arms
for the transfer of LNG between the
production vessel and the tanker
such as the SBM soft yoke mooring
and offloading system.3
Note that the Sevan Marine cylin-
drical hull FLNG concept provides
a more stable and economical plat-
form for offshore FLNG produc-
tion, storage and offloading than
traditional ship shaped vessels in
harsh environments such as extreme
cyclonic situations. In fact, the cylin-
drical hull has significantly less pitch
and roll motion than a conventional
ship shaped hull and eliminates the
need for expensive turret and swivel
solutions.4
Offshore liquefaction processes
From the foregoing discussion, it is
clear that the design criteria of an
offshore FLNG facility are quite dif-
ferent to a land based LNG plant
in terms of process safety, storage,
compactness, sensitivity to motion,
www.eptq.com
q4 mokhatab.indd 3
as well as flexibility and simplicity
of operation. The heart of the FLNG
facility is the liquefaction section. As
such, for a successful FLNG appli-
cation, the liquefaction technology
must be proven, reliable, relatively
lightweight, space efficient, cost
efficient, and relatively simple to
operate. It must also have high flex-
ibility to operate under varying feed
gas and other conditions. Before
discussing the relative benefits of
the various liquefaction cycles, it is
therefore useful to review the cycles
themselves.
Alternative liquefaction cycles
Two generic types of refrigeration
cycles have been considered for
offshore natural gas liquefaction:
the mixed refrigerant and nitrogen
expander cycles. There are variants
of each cycle with some common
features between them.
For offshore applications, the
cascade cycle has disadvantages
despite its high efficiency. It has
three refrigeration circuits driven by
individual compressors, and each
refrigerant has its own liquid stor-
age. The large equipment count and
the large plot requirement increase
the cost of FLNG where space is a
premium. This technology could
only be commercially viable for very
large capacities, as demonstrated by
ConocoPhillips evaluations on off-
shore FLNG facilities of 5 million
t y.5
Mixed refrigerant
The mixed refrigerant (MR) tech-
nology, which employs refrigerant
comprising nitrogen and hydrocar-
bons, has been assessed for offshore
liquefaction based on both single
mixed refrigerant (SMR) and dual
mixed refrigerant ( M ) cycles. The
SMR cycle is suitable for capacities
of around 2 million t y of LNG pro-
duction per train whilst the DMR
cycle is suitable for capacities up to
million t y in a single train. The
SM process provides the benefit
of reduced equipment count, but it
comes at the cost of slightly lower
efficiency than the M cycle, which
better matches the overall MR boil-
ing curve to the feed condensation
curve.
The propane pre-cooled single
mixed refrigerant (C3-MR) process
developed by Air Products and
Chemicals Inc. (APCI), in which
pre-cooling is performed in multiple
kettle-type heat exchangers with a
propane refrigeration loop, achieves
higher efficiency than the SM
process due to the ability to better
match the MR boiling curve to the
feed condensation curve. However,
the large inventory of propane and
the relatively large plot space that is
required for the propane evaporators
make the C3-MR process less attrac-
tive for offshore FLNG projects.
Nitrogen expander
The nitrogen expander process is
based on a reverse Brayton refriger-
ation cycle, which uses non-flamma-
ble gaseous nitrogen as refrigerant.
The single expander cycle has rela-
tively low efficiency, but higher pro-
cess efficiencies can be achieved by
adding a second expander. Adding
a precooling cycle, based on pro-
pane or other refrigerants (hydro-
fluorocarbons, for example), can also
further improve overall efficiency.
Increased FLNG facility complexity,
reduced overall reliability, and the
need for increased refrigerant stor-
age are potential disadvantages of
adding a precooling refrigeration
circuit.6
The dual nitrogen expander cycle,
which is widely used in peak shav-
ing LNG plants, has been proposed
for a couple of offshore FLNG pro-
jects due to its high inherent safety
level and insensitivity to vessel
motion. However, the applicabil-
ity of the nitrogen expander cycles
will be limited to trains of smaller
capacity (up to 0. million t y per
train) due to the fact that refrigerant
exists entirely as vapour, making
pipe sizes very large as train capacity
increases.7 There are some licensed
processes available that increase
the capacity from a single train of a
nitrogen expander cycle up to 1.5
million t/y, but those processes
currently have no references in the
industry.
Technology selection
Selection of the liquefaction tech-
nology for offshore FLNG facilities
will be influenced by the needs of
the owner. arious process features
PTQ Q4 2018 109
14/09/2018 09:02

Comparing liquefaction cycles for mid to large scale offshore FLNG projects8
Train capacity, million t/y
Thermal efficiency
Equipment count
Storage of liquid hydrocarbon
refrigerants
Reliability
Capital investment
Offshore suitability
Availability
Motion impacts
Table 2
including the production capacity,
thermal efficiency, equipment count,
refrigerant type, reliability, specific
capital investment, simplicity of
operations, offshore suitability, avail-
ability and impact of vessel motion
must also be considered. Table 2
compares SM , M , and nitrogen
expander cycles, taking into consid-
eration these factors, for mid to large
scale FLNG applications.
As can been from Table 2, the
nitrogen expander cycle offers lower
efficiency than other technology
the presence of a hydrocarbon liquid
phase in the cycle.
The SMR cycles are normally
SMR DMR Nitrogen expander
appropriate options for small to
1-2 >2 ≤0.8
Medium High Low mid-scale offshore floating lique-
Low Medium Medium faction systems due to their lower
Medium Medium None equipment count, resulting in a
smaller footprint and lighter weight,
High High High
Low Medium High thereby lowering associated capi-
High High High tal costs. The M cycles, offering
High High Medium higher efficiency, are optimal solu-
Medium Medium Low
tions for single, larger train FLNG
applications. Larger trains can offer
economies of scale (thereby reducing
capital expenditure) and a reduced
options, but it can be used for small footprint, but less operational redun-
scale FLNG production because of dancy and flexibility. In this case,
its simplicity and ease of sourcing the choices around equipment will
the non-flammable refrigerant from be also limited with longer deliv-
onboard nitrogen generators. ery periods, which could potentially
As production capacities move affect economies of scale.
into the mid-scale and large scale
ranges, there is a preference towards Outstanding liquefaction process
MR cycles because they are more Selecting the appropriate liquefac-
efficient than nitrogen expander tion process is a key focus for off-
cycles and have lower unit capital shore FLNG projects. ecently, a
and operating costs at larger LNG few processes have been proposed
capacities. However, M cycles may for offshore applications, but none
be affected by sea motions due to have yet been put into operation.9

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q4 mokhatab.indd 4 15/09/2018 06:42

 Unproven processes present a sig-
nificant risk to investment in FLNG
projects. A potential solution to these
challenges is Black eatch’s Prico-
SMR liquefaction process, which has
been proven in onshore applications.
It contains the following elements
required to meet the needs of off-
shore FLNG projects:10
• Single refrigeration system; no
series systems
• Reduced equipment count
• Compact layout; no complex cold
box (due to the use of compact, lower
weight, and well proven brazed alu-
minum heat exchanger for the refrig-
erant exchangers, as compared to the
very tall and heavy exchangers used
in other technologies)
• Motion insensitive due to the use
of a unique brazed aluminum heat
exchanger, where all connections are
external to the box with no moving
parts, valves or vessels inside, leav-
ing the process performance unaf-
fected by motion
• Single module for entire liquefac-
tion train
• Simplified operation
• Modular philosophy and process
concerning available drivers
• Small refrigerant inventory
• No venting or flaring of refriger-
ant during shutdown
• Currently applied across a broad
range of production sizes up to 7.8
million t y in multiple (four) trains
• Efficiency competitive with base-
load systems
• Use of single body compressor
• High turndown ratio
• eaping the benefit of economy of
scale from small scale solutions and
does not stretch the boundaries of
available and proven equipment
• Quick start-up after shutdown
• Lower capital and operating
expenses.
The Prico-SM (see Figure 1) is
the best fit for small to mid scale
offshore liquefaction systems due
to its low equipment count (which
simplifies operation and minimises
costs), and flexibility in handling
a broad range of feed gases. In this
process, the final refrigerant sep-
arator produces liquid and vapour
streams, where the liquid flow rate
can be set in the distributed control
system. The liquid flow rate, com-
bined with a constant high pressure
www.eptq.com
q4 mokhatab.indd 5
Low pressure refrigerant
Separator
Suction
drum
Refrigerant
compressor
Refrigerant
pump
Separator
Interstage
pump
Figure 1 Prico-SMR process12
vapour, determines the molecu-
lar weight of the refrigerant in the
main cryogenic heat exchanger.
Therefore, the refrigerant can easily
be adjusted for changes in feed gas
conditions while the facility is in
operation.11
When larger production rates or
operational flexibility for chang-
ing feed rates are required, multi-
ple trains can be used. However,
the Prico-DMR process utilising the
same characteristics of the Prico-
SMR process, but with two mixed
refrigeration circuits and four brazed
aluminum heat exchanger zones
contained in either one or two cold
boxes, provides the option of higher
LNG production in a single larger
train.
A wide range of single train capac-
ities is available from the Prico pro-
cesses based on gas turbine driver
selection. For Prico-SMR, a single
Figure 2 Golar Hilli Episeyo FLNG facility (Source: Offshore Energy Today)
Treated
feed gas
Refrigerant
heat exchanger
Separator
Heavy
liquid
LNG to
storage
train capacity up to 2.0 million t/y
can be achieved with proven gas
turbines or motor drivers. For Prico-
DMR, the maximum capacity of a
single train can be in the range 3.0-
3.5 million t/y.10
The Prico-DMR is an optimal
solution for offshore FLNG applica-
tions where a single larger train is
preferred by owners and operators.
However, the current trend is to use
multiple trains which have the fol-
lowing features:13
• Lower economy of scale partially
offset by increased competition as
more suppliers become available
• Operational flexibility (easier
start-up and improved turndown)
• Wider selection of fabrication
yards
• Shutdown of one train does not
stop production from other trains
• Annual maintenance can be stag-
gered by train
PTQ Q4 2018 111
15/09/2018 06:42
 • Incremental capacity build-up for
off-takers (alignment with prevailing
LNG market conditions)
• Phased approach to align
upstream development and feed gas
supply.
Black eatch is a low cost
FLNG trend setter and has gained
leadership in FLNG projects hav-
ing completed the world’s first
barge based LNG project (Exmar
Caribbean FLNG) and the world’s
first LNG carrier conversion FLNG
project (Golar Hilli Episeyo) utilis-
ing Prico-SMR liquefaction technol-
ogy. In fact, Golar Hilli Episeyo (see
Figure 2) is the only FLNG vessel in
the world in commercial operation
today.
Conclusion
A key step in the development of a
successful offshore FLNG project is
the selection of an appropriate liq-
uefaction process that best meets
the project objectives. Evaluating the
most important criteria for selecting
the best fit liquefaction process for
offshore application has shown that
the Black eatch Prico-SM is an
outstanding candidate by providing
an optimised design that will best
align with the owner’s needs.
PRICO-SMR is a trademark of Black & Veatch.
References
1 Mokhatab S, Nearshore FLNG enables new
opportunities, Gas Processing, 13-14, May/Jun
2016.
2 Kerbers I, Hartnell G, A Breakthrough for
floating LNG?, paper presented at the 24th
World Gas Conference, Buenos Aires, Argentina,
5-9 Oct 2009.
3 Faber F, Resweber L R, Jones P S, Bliault A E J,
Floating LNG solutions from the drawing board
to reality, paper presented at the Offshore
Technology Conference, Houston, TX, USA, 6-9
May 2002.
4 Odeskaug L, Mokhatab S, Cylindrical hull
concept improves design for offshore FLNG
Production, Hydrocarbon Processing, 95, 8, 39-
44, 2016.
5 Wilkes M, Design and operation of floating
gas processing and LNG liquefaction facilities,
paper presented at the GPA Europe Spring
Conference, Ashford, UK, 14-16 May 2008.
6 Mokhatab S, Basi S, Hunter P, Develop
successful nearshore FLNG solutions – Part 2:
natural gas liquefaction, Gas Processing, 17-22,
Sept/Oct 2016.
7 Bronfenbrenner J C, Pillarella M R, Solomon
J, Selecting a suitable process, LNG Industry,
17-25, Summer 2009.
8 Chiu C-H, Commercial and technical
considerations in the developments of offshore
liquefaction plants, paper presented at the
23rd World Gas Conference, Amsterdam, the
Netherlands, 5-9 Jun 2006.
9 Breckenridge B, Germinder B, Talib J H,
Competitive at-shore FLNG solutions, paper
presented at the Gastech 2017 Conference and
Exhibition, Tokyo, Japan, 4-7 Apr 2017.
10 Talib J H, Germinder B, Game-changing
floating LNG solutions, paper presented at the
Offshore Technology Conference, Houston, TX,
USA, 2–5 May 2016.
11 Price B, Mahaley M, Shimer W, Optimize
small-scale LNG production with modular SMR
technology, Gas Processing, 21-26, Mar/Apr
2014.
12 Talib J H, Hoffart S D, Barte W L, Flexibility
is key to FLNG project success, Gas Processing,
41-46, Mar/Apr 2014.
13 Talib J H, Private Communication, Floating
Technology Applications, Black & Veatch,
Overland Park, KS, USA, Aug 2018.
Saeid Mokhatab is a world-class expert in the
natural gas processing industry who has worked
on the design and operation of several gas
processing plants, and has contributed to gas
processing technology improvements through
300 technical papers and two handbooks
published by Elsevier in the US. He has held
technical advisory positions for leading
professional journals, societies and conferences
in the field of gas processing, and has received a
number of international awards in recognition
of his work in the natural gas industry.

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 New catalytic systems for converting
hydrocarbons
Novel schemes for the development of catalysts with high selectivity for
hydrocarbon processing
MASSIMILIANO DELFERRO
Argonne National Laboratory
M
anufacturing chemicals for
industrial processes often
involves use of a cata-
lyst, which speeds up the chemi-
cal reaction involved and lessens
the amount of energy required.
Ideally, the catalyst has high selec-
tivity for the desired end products
and a practical lifetime. In collabo-
ration with researchers from Ames
Laboratory, Iowa State University,
and Northwestern University, a
basic research group at Argonne
National Laboratory is finding
novel catalytic systems with which
to more cheaply and efficiently
manufacture products derived
from methane in the natural gas
being generated from underground
shale gas deposits. It is also iden-
tifying new routes to making
higher performance catalysts for
hydrogenation.
The research on three newly
developed catalytic systems
includes:
• An iridium-containing catalyst
supported on a microporous metal-
organic framework. This material
facilitates the borylation of methane
in a gas phase, which has applica-
tion in the oil and gas industries.
• A platinum-containing catalyst
on a inc-modified silica support
for chemoselective hydrogenation
of functionalised nitro-aromatics to
aromatic amines in a liquid or gas
phase. This product has application
in a variety of industries.
• A vanadium-containing catalyst
on silica support for hydrogenation
of alkenes and alkynes in a liquid
phase.
This basic research encompasses
computer modelling of catalytic
mechanisms, catalyst synthesis, cat-
www.eptq.com
q4 argonne.indd 1
alyst characterisation in advanced
analytical facilities, and state of
the art catalyst testing. The lat-
ter makes use of Argonne’s High-
Throughput Research Facility,
which provides highly automated
technology not found in the private
sector that accelerates the discovery
of materials and screening of pro-
cess conditions.
Iridium-containing catalyst for
activation of methane
In the last two decades, the energy
industry has been transformed by
the widespread use of fracking;
that is, the extraction of shale gas
by hydraulic fracturing in shale for-
mations buried deep underground.
Shale gas is natural gas found in
shale rock formations created hun-
dreds of millions of years ago. This
capability to tap previously inacces-
sible shale gas deposits has created
an abundant source of methane and
other hydrocarbon gases in North
America, which can be chemically
converted to a mixture of carbon
monoxide and hydrogen that can
be used as a low cost feedstock for
making synthetic chemicals such as
methanol or ammonia.
The first of the catalysts to be dis-
cussed, iridium on a microporous
metal-organic framework support,
expedites the conversion of the
methane in natural gas to metha-
nol. Methane constitutes the larg-
est fraction of natural gas. Given
the large reservoir of natural gas
in shale formations within the US,
methane could be a low cost and
abundant starting material for the
manufacture of value added chem-
icals and fuel. While methane com-
busts at very high temperatures
(approximately 2000°C), it is one
of the more difficult hydrocarbons
to transform into other products
at lower temperatures because of
its strong hydrogen-carbon bonds.
Metal-catalysed borylation has
recently emerged as a promising
route for the catalytic functionalisa-
tion of methane. A major challenge
in this regard is selective borylation
towards the desired monoborylated
product.
Since the 1960s, zeolites have
been commonly used as a support-
ing material to perform catalysis.
Zeolites are microporous crystal-
line minerals that often include sil-
icon, aluminum, and oxygen. They
are commonly used as commercial
adsorbents and catalysts and have a
cage-like framework in which reac-
tant molecules can become trapped.
However, if the molecules are too
big to fit inside the framework, no
catalysis will occur. Metal-organic
frameworks are attractive alter-
native candidates for performing
shape selective catalysis because
they are structurally tunable. They
can be synthesised with pore and
aperture sizes tailor-made for tar-
geted molecules.
Argonne built upon earlier work
from different research teams.
They showed how they could intro-
duce a boron based compound,
in a process called borylation, and
thereby found a promising route
for transition metal-catalysed meth-
ane activation under much less
demanding chemical conditions
than would otherwise be possible.
The teams separately observed the
borylation process, yielding prod-
ucts that were both monoborylated
(technologically valuable) and bis-
PTQ Q4 2018 113
14/09/2018 09:35
 Figure 1 Methane borylation by conversion of CH4 and bis(pinacolborane) (B2pin2)
to monoborylated methane (CH3Bpin) and the thermodynamically more favoured
diborylated methane (CH2Bpin2). The molecular sizes of B2pin2, CH3Bpin, and CH2Bpin2
are shown in the ball and stick models with the van der Waals surface in wire mesh1 Figure 2 Three-dimensional structure of
(Reproduced with permission from Ref. 1. Copyright 2018 Springer Nature)
shape selective catalyst UiO-67-Mix-Ir.
The purple rods and turquoise truncated
borylated (undesired). The catalytic linkers with an aperture size of octahedra represent the linkers and nodes
of the UiO-67-Mix-Ir, respectively. Orange,
reaction scheme is represented in 0.8 nm and an octahedral cavity of
turquoise, grey, blue, red and light grey
Figure 1. By inserting an iridium 1.1 nm3 in solvent accessible vol- spheres represent Ir, Zr, C, N, O and H,
based catalyst inside the metal- ume. The team prepared a shape respectively. Cl and some of the H atoms
organic framework, our team has selective catalyst by the mixed have been omitted for clarity1
been able to produce a reaction that linker synthesis of the UiO-67-Mix (Reproduced with permission from Ref. 1.
formed only the monoborylated and subsequent metallation with Copyright 2018 Springer Nature)
product because the pores of the an iridium-containing precursor,
metal-organic framework were too Ir(1,5-cyclooctadiene) -Cl) 2 (see cyclohexane at 150°C and 34 atm
small for the bisborylated product Figure 2). of CH4 gas for 14 hours, employ-
to form. Borylation of methane was ing 5 mol% of iridium catalyst.
As part of this research, the conducted in the Argonne high Under this catalytic condition, the
Argonne team investigated a pressure, high throughput reac- UiO-67-Mix-Ir system fully con-
metal-organic framework first tor with the heterogeneous cat- verts bis(pinacolborane) and yields
developed at the University of alyst UiO-67-Mix-Ir and, for about 17% of monoborylated meth-
Oslo, Norway, and referred to as comparison, a homogeneous catalyst ane with a turnover number of 32,
‘Universitetet i Oslo-67’ (UiO-67). that consisted of the iridium cata- which is slightly higher than the
This highly stable material is com- lyst Ir(1,5-cyclooctadiene) -Cl) 2 value for the homogeneous catalyst
posed of Zr6 inorganic nodes and plus phenanthroline. Initial meth- sample. Under this condition, the
4,4’-biphenyl dicarboxylate organic ane borylation was performed in major product is a monoborylated

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T +65 6702 3707

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q4 argonne.indd 2 14/09/2018 09:35

 cyclohexane. Remarkably, the selectivity ratio of mono-
borylated versus diborylated methane products is 15:1
with the heterogeneous catalyst. In comparison, the
homogeneous catalyst gives a monoborylated methane
yield of only 5.6%. Thus, the heterogeneous catalyst
exhibits both higher yield and selectivity for mono-
borylated methane than the homogeneous catalyst.
Importantly, the team found that MOF UiO-67-Mix
without iridium had no effect on methane borylation.
The team also carried out detailed optimisation
of the catalytic reaction conditions using UiO-67-
Mix-Ir as the catalyst by screening several different
C-H inert solvents. Using C6D12 as the solvent led to
bis(pinacolborane) conversion of 19% and a much
lower yield of 3.3% for monoborylated methane.
Conversely, when the common solvent tetrahydrofu-
ran was employed, 98% conversion of the borylation
reagent was achieved; however, the major product
was borylated tetrahydrofuran, with only 3.8% yield
of monoborylated methane. Among the solvents
tested, dodecane gave the best results: a conversion
of >99%, turnover number of 67, a monoborylated
methane yield of 19.5%, and no detectable amount of
diborylated methane or borylated dodecane (<1%),
which amounts to an extraordinarily high selectivity
of >99% for the monoborylated product.
Experiment strongly suggests that the UiO-67-
Mix-Ir structure with metal-organic framework allows
bis(pinacolborane) and methane molecules to react
inside the pores to yield monoborylated methane
while preventing the formation of the thermodynam-
ically more favoured diborylated methane. In the
next phase of our research, the team plans to activate
methane with the same chemistry, but will substitute
Earth-abundant metals such as iron, cobalt, nickel and
copper for iridium, which is rare and expensive.

Platinum-containing catalyst for functionalisation

of nitro-aromatics
Catalysis with hydrogen (hydrogenation) is a key pro-
cess in refining, among other industries. In particular,
the hydrogenation of functionalised nitro-aromatics
is employed to manufacture aromatic amines (ani-
lines), which are important to the agrochemical, pig-
ment, and pharmaceutical industries. Nitro-aromatic
compounds consist of at least one nitro group (NO2)
attached to an aromatic ring. Typically, their hydro-
genation has required use of catalysts containing
precious metals such as platinum, palladium, or rho-
dium. Other researchers have reported that changing
the supported Pt sites from nanoparticles to highly
dispersed clusters or single-atom catalytic sites in a
Pt catalyst with iron oxide (FeOx) support resulted
in unprecedented reactivity and enhanced selectivity
for hydrogenation of nitro-aromatics to the aromatic
amines. However, the low surface area of this system
limits the number of accessible catalytic surface sites.
A promising alternative would be to use a support
material composed of a high-surface area oxide, such
as silica, instead of iron oxide. The problem is that
because of its low acidity and weak interaction, SiO2

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q4 argonne.indd 3 14/09/2018 09:35

 Figure 3 Solution phase synthesis of highly dispersed organoplatinum sites on a Zn/SiO2 support with a molecular precursor [(MeCp)
PtMe3] in toluene at room temperature and hydrogenolysis of 1 [(MeCp)PtMe/Zn/SiO2] to form 2 [(MeCp)PtH/Zn/SiO] at 135°C under
an atmosphere of hydrogen. (ALD = atomic layer deposition; SOMC = surface organometallic chemistry)2
(Reproduced with permission from Ref. 2. Copyright 2018 American Chemical Society)
has not been effective in stabilising
noble metal active sites.
Surface organometallic chemistry
represents an alternative synthe-
sis strategy for the deposition of
single-atom site catalysts on tradi-
tional high-surface-area supports.
Argonne researchers have found
unprecedented catalytic activity
and selectivity with an ‘organoplat-
inum’ catalyst (to be exact, methyl-
cyclopentadienyltrimethylplatinum)
deposited on a inc-modified silica
support. This material is prepared
by the atomic layer deposition of
a submonolayer of Zn2+ anchoring
sites on SiO2 to stabilise highly dis-
persed organoplatinum fragments.
The Sn/SiO2 support contains both
isolated Sn2+ sites and SnO-rich
areas. Because only surface hydrox-
yls associated with isolated Sn2+
have increased acidity, the Sn/SiO2
support is more capable of stabilis-
ing Pt4+ sites relative to traditional
SiO2. The use of atomic layer dep-
osition was critical in achieving
uniform distribution of the zinc
anchoring sites.
As Figure 3 shows, the precur-
sor material was treated by surface
organometallic chemistry at room
temperature to yield pre-catalyst 1
[(MeCp)PtMe/Zn/SiO2], which was
then activated at high temperature
in hydrogen to yield the hydrogena-
tion catalyst 2 [(MeCp)PtH/Zn/
SiO]. In tests at 40ºC and 50 psi for
24 hours, the resulting Pt4+/Zn2+/
SiO2 catalyst exhibited hydrogena-
tion activity significantly improved
over its PtZn/SiO2 alloy nanopar-
ticle counterparts. The surface sup-
ported organoplatinum sites were
fully characterised by a combination
of ex situ and in situ spectroscopic
techniques. The Zn anchoring sites
were found to stabilise high oxida-
tion state metals (Pt4+), promote in
116 PTQ Q4 2018
q4 argonne.indd 4
situ formation of a probable metal
hydride, and prevent sintering and
catalyst deactivation. The organ-
oplatinum catalyst was found to
be selective for the hydrogenation
of 1,3-butadiene to a mixture of
butenes and reduction of function-
alised nitro-aromatics with excel-
lent tolerance of sensitive functional
groups (for example, olefins, carbon-
yls, nitriles, and halogens).
The team’s work also demon-
strated that, under mild conditions
(room temperature), isolated organ-
oplatinum catalyst can be grafted
onto a silica support equipped with
Lewis acid anchoring sites (Zn2+).
The catalyst design strategy in
Figure 3 provides a potential tem-
plate for the rational development
of new classes of mono- and mul-
timetallic selective catalysts. Further
studies are ongoing to explore and
demonstrate the generality of this
catalyst design strategy and syn-
thetic approach. In particular, Lewis
acids and/or redox active cationic
anchoring sites, such as Al3+, Ga3+,
and Ce4+, are being employed in the
development of a series of surface
supported organoplatinum catalysts.
Figure 4 Structure of organovanadium(III)
catalyst on silica.3
(Reproduced with permission from Ref. 3.
Copyright 2017 Royal Society of Chemistry)
Vanadium-containing catalyst
for hydrogenation of alkenes and
alkynes
Argonne researchers also discov-
ered an abundant and low cost
organovanadium on silica catalyst
that works for hydrogenation in a
liquid or gas phase to yield alkenes
and alkynes. These catalytic prod-
ucts are used for making everything
from petrochemical products to
vegetable oils to vitamins.
Vanadium on its own will not
work for the hydrogenation pro-
cess. To make the vanadium work
required a three-step process. First,
the vanadium has to be in its 3+
oxidation state, a very reactive but
unstable state. Second, the vana-
dium had to be relatively dispersed
on the support surface – if the
clumps of vanadium atoms were
too big, they would cease to be
active. Last, the vanadium atoms
had to be ‘low coordinated’, which
means that there must be electronic
room for the target molecules to
bind.
The structure that solved those
problems is shown in Figure 4. It
consists of organovanadium sites
on a bulk silica surface, fabricated
via surface organometallic chemis-
try technique. This strategy yielded
the first example of a well-defined
low coordinate organovanadium
catalyst on SiO2 with remarkable
activity for liquid and gas phase
hydrogenation of alkenes and
alkynes under mild conditions
(temperature of 75ºC, pressure of
200 psi, and duration of 20 hours).
The catalyst thermal stability and
recyclability were also studied
under liquid and gas phase hydro-
genation conditions. Kinetic poi-
soning experiments confirmed that
about 100% of all vanadium sites
are catalytically active.
www.eptq.com
14/09/2018 09:35
 hot utility, cold
by implementin
BTX processing
Conclusion
The first commercial Methaformer (see Figure 4) is overall savings
Inundergoing
addition topre-commissioning
the above, the team’s withwork hasby
start-up resulted
June back period fo
in2018.
several US patent applications. One is
The 150 b/d (6000 t/y) unit will process a vari- for multi-me- installing new h
tallic
ety of catalysts
naphthathat selectively
feedstocks. Withconvert
a projectedn-butaneupliftto would be aroun
1,3-butadiene, a primary building block
of >$23/bbl ($200/t), it will validate the predicted of synthetic proposed schem
rubber,
yields and which polymer
scale-up manufacturers have used to
factors. sions significant
make car tyres. Another patent
Because of Methaforming’s similarity application is for
to the a cat-
hydro- It can be obse
alytic process for the purification of shale gas and syn-
treating process, there is a low cost and high return
thesis of desired products.
Together facing a ventional proce
opportunity in converting an existing idle hydro- proposed metho
Basic research
treater on theThe
or reformer. novel catalyst
basic cost forsystems described
this might be brighter tomorrow and can be impl
here is expected to lead to a knowledge
as low as $5 million, mostly for the methanol base that one
han- configuration fo
day will find diverse applications in the
dling facilities. Because most refiners have some low real world. To At Yokogawa, we believe the sky’s the limit.
ings and increas
that end, we are already working with
octane naphtha for blending to gasoline, those with several compa- And to reach beyond today’s horizons,
nies involved
an idle processwith unitthehave
production of various
a low cost opportunity products
for we work step-by-step with you to make References
ranging from oil
upgrading that stream. and gas processing to biofuels. the unimagined a reality. That’s how we 1 Halvorsen I J, Skog
Many potential customers are interested in quick move forward, through the synergy of
of Petlyuk distillation
2 Yildirim O, Kiss A
delivery, low cost skid mounted units. We have com-
Acknowledgments
co-innovation partnership. Join hands with
This work was supported by the US Department of Energy (DOE), Office process industry: A re
pleted the detailed mechanical design for two ver- us, and together we can sustain a brighter
of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and 80:403–417.
sions (see Figure 5). The contractor will build these in future. Yokogawa: Building a better 3 Dejanović I, Matij
Biosciences, under Contract DE-AC02-06CH11357. Use of the Advanced
Russia at a fixed price of $900 000 for a 150 b/d (6000 dividing wall column
Photon Source at Argonne is supported by DOE, Office of Science, and tomorrow with you today.
t/y)ofunit
Office Basicand
Energy$2Sciences,
million forContract
under a 460 b/d (20 000 t/y)
DE-AC-02-06CH11357. Res., 2011, 50:5680-
unit. These can be delivered within six
Use of the transmission electron microscope at the Center months and
for Nanoscale 4 Kumar S, Gupta
will include all of the equipment necessary
Materials at Argonne National Laboratory is supported by DOE, Office inside top, middle and b
ofbattery limit.ofThe
Science, Office Basicoutside batteryunder
Energy Sciences, limitContract
depends on
DE-AC02- Benzene, Toluene a
existing customer
06CH11357. Calculationsfacilities. Much of
were performed thisthe
using may already
computational plant, Separation Sci
be available
resources providedorby can be available
the Laboratory on an
Computing incremental
Resource Center at 10.1080/01496395.2
cost basis.
Argonne and National Energy Research Scientific Computing Center. 5 Douglas J M, C
International edition
Our first customer in the CIS will soon order a 460
References engineering series, 19
1 Zhang(20
b/d X, 000
Huangt/y) unit.
Z, Ferrandon M, Yang D, Robison L, Li P, Wang T C, 6 Couper J R, Penney
Delferro M, Farha O K, Catalytic chemoselective functionalization of (Selection and Design
Conclusion
methane in a metal-organic framework, Nature Catalysis 1, 2018, 356- 7 Sinnott R, Towler G
Methaforming
362, upgrades low octane streams by $15-
doi.org/10.1038/s41929-018-0069-6. Heinemann, 2010.
2 35/bbl ($130-330/t)
Camacho-Bunquin thereby
J, Ferrandon M,producing
Sohn H, Yanggasoline from
D, Liu C, Ignacio-
denaphtha and methanol
Leon P A, Perras F A, Pruski M, atStair
onePthird the cost
C, Delferro of current
M, Chemoselective Sunil Kumar is a
technologywith
hydrogenation forsupported
new units. It can generate
organoplatinum (IV) catalystover $50
on Zn(II)- Petroleum (IIP)Dehr
modified silica, Journal of the American Chemical Society 140, 2018,
million/y of yield improvements by converting an areas include solvent
3940-3951, DOI: 10.1021/jacs.7b11981.
existing semi-regenerative reformer. extractive desulphur
3 Sohn H, Camacho-Bunquin J, Langeslay R R, Ignacio-de Leon P A, integration, producti
Niklas J, Poluektov O G, Liu C, Connell J G, Yang D, Kropf J, Kim H, Stair P fuels. Technologies a
Please visit www.yokogawa.com/eu
C, Ferrandona M, Delferro M, Isolated, well-defined organovanadium(III) commercialised, inc
onStephen Sims is President,
silica: single-site catalyst New Gas Technologies
for hydrogenation – Synthesis
of alkenes and North
alkynes, include Certificate o
America and an Energy Advisor at Houston Technology Center.
Chemical Communications 53, 2017, 7325-7328, DOI: 10.1039/ and Institution of En
With over 40 years’ industry experience in more than 15 countries
c7cc01876b. Engineering. He hold
4 spanning the entireS D,
Cook A K, Schimler value chain
Matzger A J,ofSanford
the downstream sector, he
M S, Catalyst-controlled Prasenjit Ghosh is
previously served in technical and management
selectivity in the C-H borylation of methane and ethane, Science roles with Exxon,
351, aromatic extraction
Citgo1421-1424,
2016, and ConocoPhillips.
DOI: 10.1126/science.aad9289. of interest are proce
5 Elena K T, Berritt is
SmithLobichenko S, aGonzález-Moreiras
Research Engineer with M, Ahn New S, Gas Technologies
Smith III M R, Mu- reaction engineering
Hyun Baik, Mindiola D J, Catalytic borylation of methane,inScience
– Synthesis LLC. With over five years’ experience chemical 351, engineering from Jad
analysis and synthesis, working
2016, 1424-1427, DOI: 10.1126/science.aad9730. at major chemistry laboratories of
engineering from IIT
6 Moscow State University,
Serna P, Corma she holds
A, Transforming nanoa MSc
metal in nonselective
materials science from
particulates Shrikant Nanoti ret
Skoltech
into (Russia)/MITcatalysts
chemoselective (USA). for hydrogenation of substituted
CSIR-IIP Dehradun in
Iosif Lishchiner is
nitrobenzenes, ACS CatalysisChief Technologist with New Gas Technologies –
5, 2015, 7114-7121. With over 30 years
7 Wei H, Liu X, Wang A, Zhang L, Qiao B,with
Synthesis LLC and Head of Laboratory YangtheX, High
Huang Temperatures
Y, Miao S, Liu separation based tec
J, Institute
Zhang T, of the Russian Academy
FeOx-supported platinum of Sciences.
single-atom He has
andover 30 years’
pseudo-single- pinch analysis for th
experience
atom catalystsin for
the chemoselective
research and development
hydrogenationofofnovel refining
functionalized the technologies he
technologies in the downstream
nitroarenes, Nature Communications 5, 2014, 5634. sector and is the author of 25 refineries. He has pu
patents. patents, and receiv
Massimiliano
Olga Malova(Max) is Head Delferro is the with
of Catalysis GroupNew Leader
Gas Catalysis
Technologies Science
– Shield for developme
Program
Synthesisin the
LLCChemical
and Assistant Sciences and Engineering
Professor DivisionofofOrganic
in the Department Argonne
technologies. He hol
National Laboratory.
Chemistry, GubkinHis research
Russian spans
State the synthesis
University andand
of Oil characterisation
Gas. She is Institute of Technolo
ofamultimetallic
co-developer single-site hydrogenation/dehydrogenation
of the Methaforming process catalyst with catalysts
over
to25 atomic
patents. Prior to her current role at New Gas Technologies and
layer deposition, additives for tribological applications, –
supported
Synthesisorganometallic
LLC, she worked catalysis for C-H
with Bayer andtransformation.
Eni in developing refining
Email: delferro@anl.gov
catalysts.

www.eptq.com
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Q3 13:23
103
2018 117
2018
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q4 argonne.indd 5 14/09/2018 09:35
 Information for Reliability and Instrumentation Engineers

INTELLIGENT
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Within 200 milliseconds

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The meaning of SIL and Functional Safety

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prognost.indd 1 13/09/2018 06:24

 Artificial intelligence for refiners
First define the problem, then artificial intelligence can be the way forward to
higher operational efficiencies
JANE REN
Atomiton
A
rtificial intelligence (AI) is
an umbrella term that covers
many things. By its name, it is
using computer programs to do what
intelligent humans could do, and
often doing it even better. Artificial
intelligence is also called cognitive
science, which is the most popu-
lar computer science course now in
universities.
At its core, AI facilitates the ability
of machines to learn from experience,
adjust to new inputs and perform
human-like tasks. Most examples
encompass deep learning and nat-
ural language processing. Using
these technologies, computers can be
trained to accomplish specific tasks
by processing large amounts of data
and recognising patterns in the data.
In the 1 50s, the foundation of AI
research covered problem solving
and symbolic methods before the US
epartment of efence took interest
in this type of work with the efence
Advanced esearch Projects Agency
( A PA) projects in the 1 70s.
They had some early success with
A PA, producing intelligent per-
sonal assistants in 2003, long before
Siri, Alexa or Cortana were house-
hold names. This early work paved
the way for the automation and for-
mal reasoning that we see in comput-
ers today, including decision support
systems and smart search systems
that can be designed to complement
and augment human abilities.
Five attributes of AI
The cognitive tasks of AI can be
divided into five categories: percep-
tion, learning, forecasting, reasoning,
and coordinating. ith perception,
AI can understand the environment
with sensing, and detect and rec-
ognise occurrences; is that smell a
fuel leak From this it can learn by
www.eptq.com
q4 atomiton.indd 1
synthesising that information into
knowledge; this could be learning
the relationship between tempera-
ture set points and distillate yield.
ou begin to extract value from
this data by being able to forecast
with high precision and simulate
outcomes such as the diesel fuel
demand at your terminal next week.
hen it comes to solving logical
problems, or reasoning, AI can make
decisions or suggest the best solu-
tions; given what I know, what is the
optimal distribution of my products
at different terminal sites
Finally, coordinating, or what
economists call playing games’,
is behaving with the assumption
of other autonomous agents and
responding rationally.
espite the expanding range of
problems AI can solve, there is one
thing which no AI program has been
able to replace humans in: defining
the problem itself.
Given the obvious benefits that
can be derived from adopting AI,
what are the challenges that down-
stream oil and gas companies
face when they embark on a pro-
gramme One of the biggest mis-
takes that companies make is that
they embark on AI without first
defining the problem. They col-
lect lots of data, but do not know
what to do with it, since they do not
know what problem they are trying
to solve by collecting all this data.
Other industries have made this
mistake before. A familiar example
is the auto industry, which spent
fortunes on telemetry programmes,
collected terabytes of data, and have
not yet figured out what to do with
them. That fervour did not save
the auto industry from its 200 cri-
sis, nor is it protecting the industry
from disruptive forces.
Machine learning
One of the most popular subcate-
gories today is machine learning. In
fact, machine learning has become
so popular that many people equate
machine learning to AI. In fact,
machine learning is only a small part
of AI.
Machine learning is popu-
lar because it overcomes scientific
unknowns through large quanti-
ties of historical data, and hence has
made fortunes for companies that in
the past found their data too com-
plex to interpret (Google, Ama on,
Facebook). Machine learning is based
on pattern recognition, and machine
learning methods consider all data
as either inputs (features) or outputs
(prediction). Multiple inputs are fed
into an algorithm that produces an
output. If the output does not match
the actual data, the algorithm is
tweaked to do better next time. This
is called training in machine learning.
The IT world has been using
machine learning for many years, in
Ama on’s recommendation engine,
Gmail’s spam filters, and Google’s
search engine ranking algorithm.
Because machine learning relies
on large quantities of data about
the same subject, it is better at very
focused problems and parame-
ters, such as what is the relationship
between vibration and engine failure
Machine learning behaves poorly
when the problem is a system prob-
lem with more complexity, such as
a refining process or a logistics sup-
ply chain for oil that has many mov-
ing parts, which prevents repeating
patterns.
It can also struggle when most
of the information is domain spe-
cific, such as the pressure setting
on the steam boiler that has a cer-
tain relationship with the steam
PTQ Q4 2018 119
14/09/2018 09:37
 supply chain and complex activities.
To manage cost and ensure quality in
Seven steps to create a successful IIoT AI project today’s oil price market, supply chain
1. Identify a problem with tangible impact. transparency and asset performance
2. Depict the what-if scenario. offer the biggest returns on invest-
Example 1: if we could know A and B and get information on C 24 hours earlier ment. Digitised supply chains gain
than we do now, our operations would be entirely different, because we would insight from across terminals to bet-
be able to perform D intelligently. This is the prediction problem. ter forecast demand and plan supply,
Example 2: if we had a real-time computer that could help our people calculate while smart assets improve asset pro-
all the possibilities (permutations) and consequences, we would be able to make ductivity and reduce energy costs.
the best decision all the time. This is an optimisation problem. Terminals and refineries are dis-
3. Understand what category of intelligence is needed. This would determine covering efficiencies by imple-
what AI methods are a good fit. menting IIoT (Industrial Internet
4. Understand time and location dependency/sensitivity of the solution. of Things) software that leverages
a. Most intelligence in downstream is time sensitive. Decisions relying on them AI and machine learning. In these
are on a minute, hour, or daily basis. This means if your AI program always sectors, margins are very low and
needs human intervention, for instance by a data scientist in the loop, it is going therefore efficiency is vital. There
to be useless. This determines how your AI programs runs – inline or offline, and are ways that IIoT software can inte-
how often it needs to get data, immediately or every week. grate AI into day to day operations
b. Where are the sources of most data? Onsite, distributed, or centralised? If for the downstream oil and gas sec-
you found you have to transport most of the data through the wires for analy- tor to manage and reduce the use of
sis, it is probably not efficient or secure. resources and optimise supply chain
c. Understand what data are needed and what data are available, and if the logistics.
data are available at the right time window at the right location.
6. Select technology, but more importantly have someone define an end-to-end Energy challenges in refineries
solution specific to your problem. Do not buy generic services that assume all Peak energy usage
problems are the same. There simply has not been sufficient domain informa- One of the main resources used in
tion fed into today’s AI technologies. Without domain specificity to your prob- refining and processing is energy,
lems, most AI programs or services are useless. and peak energy use can be very
7. Remember to define and document the business impacts of the programme. costly. Peak energy use may also
Then iterate and expand the scope of your first selected problem. impact future costs based on higher
demand costs and has a greater neg-
ative environmental impact. Energy
energy generated and subsequently time series problems from most other use typically suffers from low visi-
the processes in the distillation col- statistical problems is that in a time bility, meaning it is difficult to attrib-
umn. Such domain-specific informa- series observations are not mutually ute energy costs to different assets
tion from the data cannot be utilised independent. Rather a single chance and processing activities. In refining
unless an engineer or data scientist event may affect all later data points. operations, there are many opera-
has spent time to structure and cor- Yet, existing time series technol- tional constraints that make manual
relate the data to correctly represent ogy alone does not solve all the new optimisation of energy infeasible.
the relationship between them; this problems either. Enterprises are try- By monitoring and profiling energy
is something that machine learn- ing to aggregate and store all data used for assets and activities (distill-
ing cannot replace. The cost of this in time series format, which under- ing, cracking, mixing), predictions for
manual work is often ignored when stands time, but misses all domain energy load against operational plans
companies want to train their data. correlations. This correlation across and schedules can be made. Working
They end up not having meaningful the domain of operations is critical within operational constraints and
conclusions. for gaining contextual intelligence. priorities, activity schedules can be
Another problem occurs when Even though historian has been a optimised using Atomiton IoT oper-
time and sequence are important. familiar technology to first use, it is ating stack (A-Stack) software. Peak
Most machine learning programs do not sufficient. energy use can be reduced by lev-
not incorporate time based patterns. Companies should consider the eraging optimised schedules, thus
For example, the best way to predict nature of the problems before they reducing energy costs.
the loading queue at the terminal in invest. You need the right AI tool
the next hour is to count the current based on the problem you have Steam usage
queue length. Fuel demand estimates defined. Be sure to define the prob- Steam is another resource which is
at a retail fuel station require infor- lem first, so that you can select the challenging to manage. A very small
mation such as which month of the right tool. Do not make the auto refinery could spend over $1 million
year and which day of the week it is industry’s mistake. each year just on steam to heat the
in order to predict more accurately. AI is already making inroads into process. Steam is a resource where
This is where time series come in. the downstream sector. The oil and you must use it or lose it. If you gen-
The central point that differentiates gas industry is known for its long erate more than you need during

120 PTQ Q4 2018 www.eptq.com

q4 atomiton.indd 2 14/09/2018 09:37

 the day, you then lose it. Not only is
that expensive, but it affects the envi-
ronment. On the other hand, if you
have a steam shortage, it may cause
a shutdown or interruption to opera-
tions. Planning steam sources is com-
plex, with different types of steam
generation, steam sources, and asso-
ciated costs and reliability.
By connecting to steam meters
and boilers at a refinery, A-Stack
uses real-time data to profile steam
demand and solve for the most eco-
nomical combination of steam gen-
eration and purchasing sources, to
reduce steam costs while meeting the
refinery’s process needs. Additional
relevant data such as weather condi-
tions (humidity) can be incorporated
into the models to predict the impact
on steam production and allow for
dynamic optimisation.
Terminal efficiency
In downstream terminals, maximis-
ing loading efficiency can have a sig-
nificant impact on the performance
of terminal operations. Scheduling
is a complex process due to the
many inputs (truck arrival time, ter-
minal queue, loading bay queue,
loading time, and so on) and the
multiple combinations of trucks that
require different products, against
the required volumes and flow rates
from pumps into different loading
bays. The number of calculations
becomes exponential as you consider
all the variables in this process and
becomes a nearly impossible task for
humans. Today’s manual process
is typically experience based with
some amount of guess work, which
does not optimise terminal opera-
tions. But with predictive analysis
from A-Stack, these different vari-
ables can be used to calculate opti-
mised scheduling, to determine for
each truck which particular loading
bay it should use. This orchestra-
tion minimises overall queuing for
the terminal and maximises loading
efficiency, improving supply chain
logistics.
Strategic decision making
One of the main strategic benefits
that IIoT software with embedded
AI can deliver is that you can now
move from operational data to intel-
ligent business decisions. There are
www.eptq.com
q4 atomiton.indd 3
Categories of problems in downstream oil and gas
1. Scheduling/allocation/coordination problems: crude scheduling; inventory
distribution across terminals, loading and unloading coordination. Fleet (fuel
distribution) coordination
2. Process optimisation: for instance, optimising the FCC and crude distillation
unit to optimise or control yield
3. Monitoring, detection, faster responses: leak detection; equipment
performance monitoring and failure detection
4. Supply chain logistics: optimising supply and demand.
a few areas that positively impact oil energy optimisation, demand predic-
and gas companies. tion, inventory optimisation, sched-
One is pricing. In this sector, there uling or loading optimisation. Next,
are different pricing structures at dif- define the goals for the initiative –
ferent stages for each commodity reduce energy costs by 20%, increase
and these can rapidly change. This terminal throughput by 10% Then
will depend on whether the trading pull together your operations and IT
has a day or hour boundary. Having teams. There is often a lack of shared
full visibility of the distribution of knowledge between these groups.
inventory is vital. Sometimes it is sit- hen IT starts a digitisation project
ting in tanks, sometimes it is being without understanding operational
transported in boats or trucks, and processes or activities, it can lead
having this data will make it much to failure. Teams working together
easier and faster for people to make leads to a much higher success rate
the pricing decisions, and this also and to projects that give the busi-
includes products that flow through ness valuable operations intelligence
pipelines. and often rapid OI. Start small and
The second is about planning develop an innovation pilot that can
and coordination. eal-time data then be scaled easily once proven.
extracted from tanks, equipment, The technology is complex, and
loading bays, and trucks can perform the ecosystems have not all come
intelligent predictions and optimi- together, so it is important to work
sations through automated actions. with good partners to ensure suc-
Optimising supply chain logistics cess. The interest level is extremely
by leveraging this integrated intel- high, and it is almost becoming a
ligence enables better demand fore- mandate, particularly in the oil and
casting and supply planning. gas sector where the industry has got
The third area concerns new busi- a wake-up call with the price of oil.
ness models. A company that dig- Higher efficiency is essential.
itises can be more competitive not
only through cost reduction and effi- Conclusion
ciencies, but also can provide cus- Five categories of intelligence
tomers with new kinds of visibility. • Future intelligence: the ability to
Continuous and dynamic optimisa- forecast future events with good
tion of operations turns a business confidence
advantage into a strategic advantage. • Historical intelligence: the ability
to understand what happened
Starting the IIoT AI journey • Contextual intelligence: the abil-
Even though interest in the tech- ity to correlate multiple factors in a
nology is high, it is the responsibil- context and make sense of what is
ity of IIoT AI vendors to ensure that happening
it is targeted against solutions that • omain intelligence: the ability to
can provide clear business benefits. deepen domain knowledge science
This begins with enterprises defining • Logical intelligence: the ability
the problems that need to be solved. to compute numerous logical con-
Start with a focus area and quickly ditions constraints simultaneously
identify low-hanging fruit and con- and find the solution.
centrate on those – for example, Jane Ren is the CEO of Atomiton.
PTQ Q4 2018 121
14/09/2018 09:37
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 Technology in Action

Evaluating quickly deactivating

catalytic systems Catalyst A
2.0 Catalyst B RON base

Relative C5+ RON

Catalyst C RON + 2
Avantium provides contract research services for 1.5
Catalyst D
high throughput catalysis R&D. For some years now, 1.0
Avantium has been helping refineries select the best 0.5
reforming catalysts. The tools, methods applied and 0.0
resulting data quality (precision, accuracy and repro-
−0.5
ducibility) have been independently verified and 50 75 100 125 150 175
accepted by the catalyst vendors. Time
Time onstream,
on stream,hh
Axens wanted to evaluate the performance of some 12.5
naphtha reforming catalysts. Four Axens CCR reform-

Relative C5+ _Y, wt%

ing catalysts were evaluated in a fixed bed 1 parallel 10.0

reactor high throughput Flowrence micro-pilot plant. 7.5

The performance of the catalysts, defined by activity
5.0
(temperature required), selectivity (C5+ yield) and sta-
bility, was evaluated at fixed product severity. For this 2.5
test, two octane targets were used but aromatic yield
0.0
can also be targeted. The so-called iso-RON operation is 50 75 100 125 150 175
achieved by using an automated feedback loop between Time
Timeonstream, hh
on stream,
the gas chromatographic analysis of the effluent and
the reactor’s temperature which is thus continuously 50
Relative reactor
temperature, ºC

adjusted.
The key results with time onstream are shown in
Figure 1.
Results obtained through iso-RON operation
are easy to interpret for fixed bed units (S reforming)
but also provide invaluable information about cata-
lyst performance for moving bed CCR units, which
would otherwise be too difficult to operate on a lab
scale.
The lower temperature required (higher activity)
to reach the specific octane means greater flexibility
for CCR operation, while a lower temperature slope
is typically indicative of a low coke make. For a CCR
unit, the lower coke make will provide greater flex-
ibility to increase the product severity (for instance,
increased aromatic yield) or to process more demand-
ing feeds like thermal cracked naphtha. Finally, high
catalyst selectivity (C5+ yield) is always desired as long
as product severity can be maintained. The stability of
the selectivity is typically measured by the length and
slope of the stable C5+ yield output before the tempera-
ture rises sharply.
Relative coke content, wt%, on spent samples
Catalyst Coke, wt%, for RON Coke, wt%, for RON
= base samples = base+2 samples
A REF±0.02 REF±0.1
B +2.4±0.01 +2.33±0.04
C +5.99±0.07 +4.11±0.22
D +2.71±0.23 +1.99±0.12
Table 1
40
30
20
10
0
50 75 100 125 150 175
Time
Timeonstream, hh
on stream,
Figure 1 Catalyst performance with time onstream
Analysis of the coke content (see Table 1) of all the
spent catalysts confirms the relationship between coke
make and catalyst stability.
These trends are completed with the continuous anal-
ysis of the product effluent, which provides vendors
and refineries with a complete hydrocarbon break-
down for every point in time. The baseline separation
of ethyl-benzene and all xylenes isomers, or the break-
down of the C1 to C products for example, are crucial
for economic and integration studies.
Thanks to the availability of multiple reactors in the
micro-pilot plant, each catalyst system was tested in
duplicate for each octane target in order to provide
repeatability and confidence interval on the results. The
ability to test all catalysts simultaneously, under rigor-
ously the same feed and conditions, combined with the
proprietary Flowrence technology used to accurately
control all the key process parameters, provides unpar-
alleled precision to discriminate between the various
fine catalyst differences.
An example of the precision and discriminative

www.eptq.com PTQ Q4 2018 123

tia copy 3.indd 1 14/09/2018 09:43

 power obtained is illustrated in occur, resulting in a serious increase
Figure 2, where key selectivities of bacterial count in the cooling
Catalyst A
are plotted against temperature Catalyst B RON base
water, before counter measures
required at a fixed time onstream, Catalyst C RON + 2 were taken. As the microbiologi-
with clearly non-overlapping confi- Catalyst D cal growth rate depends on various
dence intervals. 12 external factors it was impossible to

Relative C5+ _Y, wt%

The approach presented here for control all of them at the same time.
CCR catalysts can be applied to any 10 Microbiological investigations
system that has a noticeable deacti- can easily take one week before
8
vation over the duration of days, or the results are available. Counter
even up to months. 6 measures consequently are also
Every reforming unit has its own one week late. Kurita’s HydroBio
constraints, and the portfolio of cat- 4 Advance measures the fouling
0 20 40 60
alyst vendors often tries to strike tendency online when it occurs.
Relative reactor
the right balance between perfor- temperature, ºC Therefore, adequate counter actions
mance and the ability to accommo- can be taken at a much earlier stage
6
date those constraints. Further than avoiding over dosages of prod-
paper estimates, the possibility to aromatic, wt% ucts and ensuring smooth plant
Relative total

simultaneously compare catalysts 4 operation.

under various plant conditions
and with specific feed properties
(amount of coke precursors, pres-
ence of contaminants such as sul-
phur, and so on) is thus critical to
determine the right catalyst.
Avantium
produced, wt%
The system was installed in
2 January in the cooling water to
monitor fouling tendencies by using
0 the approach biofilm elevated’.
0 20 40 60 This programme is using a slightly
Relative reactor elevated temperature profile on the
temperature, ºC
sensor surface, making it possible to
predict biofilm formation tendency

0.6
Relative H2

For more information: in the system. With this early warn-

Tiago.Vilela@avantium.com 0.4 ing system, corrective actions can
be initiated, even before biofilm for-
0.2
mation occurs.
Online monitor slashes 0.0 Online monitoring of this cool-
biocide dosage 0 20 40 60 ing system with HydroBio Advance
Relative reactor indicated no fouling tendency with
In many systems, fouling and temperature, ºC the biocide dosing programme in
deposits are a serious problem place. After stopping the biocide
which results in shutdowns, clean- Figure 2 Selectivity vs activity, interpolated dosage, HydroBio Advance imme-
ing actions and unexpected costs at 80 hours onstream diately detected that there was a
for the customer. Proper treat- continuous fouling tendency in the
ments are available and applied in many systems but recirculation water of the cooling system, even during
changing side conditions still can lead to unexpected the cold winter time conditions (see Figure 1).
and unpredictable fouling or deposit formation. After stopping the biocide dosage, some extra bioc-
eal time monitoring of these effects, independent ide dosages were applied during a short intermedi-
of the reason, would give a much better control pos-
sibility for the application of the right products at the
right time. HydroBio Advance is a monitoring system 30 Cooling water temperature 60
which fulfils this real time tracking of deposit forma- 25 Biofilm thickness 50
Biofilm thickness, µm

tion for practically any kind of fouling.

20 40
Temperature, ºC

A petrochemical plant wanted to evaluate the real

biocide demand of its cooling system during a winter 15 30

period. With HydroBio Advance, biocide consumption 10 20

was reduced by 75%. 5 10
In this plant the biocide has been dosed throughout 0 0
the whole year on a constant level. Only in the case Stop biocide
−5 −10
of special events or out of spec measurements were dosage

additional biocide dosages applied. The main reason −10 −20

8 Jan 11 Jan 14 Jan 17 Jan 20 Jan 23 Jan 26 Jan 29 Jan
behind this approach was the lack of a suitable online
e

o nd

th

e
of ng
K

as

as
O

ea ow
Lo wth
ilm

gr a
bi wi

ph

ph

monitoring device which could detect fouling occur-

re off
ro

gr
y

dy
G

g
gh
d
ea

rence in real time. Indirect measurements using micro-

ou
St

St
Sl

biological parameters were used to conclude if serious

fouling occurred in the system. So fouling first had to Figure 1 Biofilm monitoring by HydroBio Advance

124 PTQ Q4 2018 www.eptq.com

tia copy 3.indd 2 14/09/2018 09:44

 American
Fuel & Petrochemical
Manufacturers
www.afpm.org/conferences

2019 AFPM
MEETINGS
Annual Meeting Labor Relations/
March 17 – 19 Human Resources Conference
Marriott Rivercenter May 2 – 3
San Antonio, TX Sheraton Austin at the Capital
  Austin, TX
International Petrochemical  
Conference Reliability & Maintenance
March 24 – 26 Conference and Exhibition
Grand Hyatt May 21 – 24
San Antonio, TX The Gaylord Texan
  Grapevine, TX
International Base Oils &  
Waxes Conference Board of Directors Meeting
March 24 – 26 September 8 – 10
Grand Hyatt The Broadmoor
San Antonio, TX Colorado Springs, CO
   
National Occupational & Operations & Process
Process Safety Conference Technology Summit
April 24 – 25 October 14 – 16
The Gaylord Texan Marriott Rivercenter
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Security Conference Environmental Conference
April 30 – May 1 October 27 – 29
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afpm.indd 1
SAVE THE DATES
3757_AFPM_2018_QA_ShowDaily_Ad_v2.indd 1 9/7/18 8:33
12/09/2018 AM
18:57

30 Cooling water temperature
25 Biofilm thickness
20
Temperature, ºC
15
10
5 10
0 0
−5
Restart biocide dosage
reduced to a quarter
−10
31 Jan 3 Feb 6 Feb 9 Feb
Clean out Under control
with extra dosage
Figure 2 Biofilm monitoring by HydroBio Advance during biocide
optimisation
ate phase to remove accumulated biomass from the
system.
Following the cleaning, the regular biocide dosage
was restarted at one quarter the original dosage. The
results showed that this was already enough to keep
microbiology and fouling under control during winter-
time conditions (see Figure 2).
The HydroBio Advance series of online monitors is
available for various applications and with different
configurations. The standard sensor is a 1in tube sen-
sor. It is available in stainless steel but also in seawater
resistant steel. The tube material itself has practically no
impact on the measurement result. Therefore, the sen-
sors can be made from any type of alloy, matching the
requirements of each application.
The standard sensors are used at ambient tempera-
tures in cooling water or similar applications. In addi-
tion, the tube sensor is available for applications at
elevated temperatures up to 110 C. Special strap-on
sensors for geothermal applications are currently being
developed and will be able to detect deposits at temper-
atures as high as 250 C.
HydroBio Advance is a robust but sensitive fouling
monitor to track fouling occurrences in different appli-
cations. As fouling is measured directly all side impacts
are taken into account. At the same time, parameters
like turbidity or suspended solids have no impact on
the measurement.
Kurita
For more information: rainer.haug@kurita.eu
Best practices in boiler replacement
hen you are processing 100 000 barrels or more of
crude in a day, reliability is of the utmost importance.
There is no justification for unscheduled shutdowns
due to a lack of process steam. Boiler replacement, then,
must be done smoothly and efficiently. Here are best
practices observed in the field from several refinery and
petrochemical projects conducted by Rentech Boiler
Systems of Abilene, Texas.
126 PTQ Q4 2018
tia copy 3.indd 3
Boiler selection
60 Several boiler options are available. Package boilers are
50 those fabricated in a factory and shipped to be installed
Biofilm thickness, µm
40 on site. There are also stick-built boilers which are
built at the site itself. There are also hybrid approaches
30
which combine elements of package and stick-built
20
boilers.
Package boilers are standardised, come in specific
sizes, and are the less expensive option. If the design
−10 fits exactly the needs of a facility, they are a good
choice. However, with refineries this is rarely the case.
−20
12 Feb 15 Feb Often, a package boiler will not be sized appropriately
for the specific needs of the facility. Further, large refin-
eries require large boilers and a packaged unit of that
si e can be difficult, if not impossible, to transport.
Some refineries seek to get around that by specify-
ing a stick-built boiler. They are designed specifically
for the petrochemical application. Further, the si e of
the boiler is less of an issue as there is no need to trans-
port it from a factory to the refinery. Components are
shipped to the site and everything is manufactured and
assembled there. The down side includes the fact that
they are more costly and take a lot longer to install. But
where huge boilers are required, this may be the only
option.
A hybrid approach, favoured by Rentech, takes ele-
ments from both approaches. Each boiler is custom
built to customer specifications, pre-assembled and
then tested. The boiler can be shipped to the site in one
or more pieces for final installation and commission-
ing. Smaller boilers can be shipped in one piece. Larger
units are shipped in two or more pieces. As each part is
pre-assembled and tested before shipping, only a small
amount of work is needed on site to combine the parts
at the refinery. Since these boilers are factory built, they
are less expensive and do not require the extensive site
work required for stick-built boilers.
Conservative sizing
Some companies size boilers with little margin, oth-
ers conservatively. Rentech advises the latter. Those
building smaller, hot rod boilers may be a little
cheaper. However, this approach can impact reliabil-
ity. By building conservatively, warranty problems
are avoided and petrochemical sites gain a more relia-
ble boiler in the end. This manifests in ways such as a
design with a slightly larger steam drum.
A good example is water to carry over from the steam
drum into the superheater. If the boiler allows that, it
will eventually blow out the superheater. Having a
larger steam drum, on the other hand, allows better
separation to remove water from the steam before it
arrives at the superheater. Additionally, if feed water
flow is lost to the boiler, a larger steam drum allows
more time to correct the water issue before steam lev-
els fall. This is far more desirable than scrambling with
only a minute or so from normal operating level on the
steam drum to low level trip. That can be a disaster for
a refinery in terms of lost production as it can some-
times leave too little time to correct the situation. With
a larger steam drum, a five minute interval should offer
www.eptq.com
14/09/2018 09:45
 OPEN FOR REGISTRATION
Register today to take advantage of early bird discount by visiting: https://opportunitycrudes.com/houston2018/

Conference theme: Crude Disruptors: Accelerating Changes in Global Refining

Change is not new in the refining world, but sudden shifts are disruptive to steady operations. Geopolitical tensions
and supply fluctuations add big risk premiums to the crude market, threatening feedstock delivery to global
refineries. To name a few disruptors, which have already created market volatility and supply uncertainties:

• US announced to exit the Iran nuclear deal,

• Deterioration in Venezuela's oil production and exports,
• Russia's pivot of oil shipments to Asia from Europe,
• OPEC/non-OPEC producers reducing medium sour grade exports to meet agreed quotas,
• Increasing US oil export to Europe, Asia, and Latin America but trade tension could disrupt this trend.

Refiners also face shifting product demand because of consumption (e.g. higher gasoline octane, increasing demand
for petrochemical feedstocks) and environmental (e.g. ultra-low sulfur diesel and gasoline, IMO's 2020 low-sulfur
bunker fuel) reasons. Can refiners fight both changing feedstock and product battles at the same time?

As in our previous meetings, this biennial conference has assembled a team of well-known business strategists and
technology gurus to help refiners tackle urgent challenges and identify exceptional opportunities.

Join us in this highly productive and rewarding event, thanks to excellent speakers, timely theme, well-organized
agenda, and stimulating atmosphere to encourage the exchange of ideas! The agenda of the 2-1/2 day event
consists of five topical sessions covering global crude supply and export trends, crude management and blending,
processing light tight and residual oils, and advanced refinery IOT applications.

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our upstream, midstream, and downstream colleagues worldwide.

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opp crudes.indd 1 08/06/2018 19:37

 enough time to react to any feed water situation that
may crop up.
Achieving lower emissions
unning a smaller boiler flat out is going to raise the
emissions profile of any facility. And that could mean
running foul of legislators and air quality control
authorities. By sizing for a larger replacement furnace,
a platform is provided to lower emissions and mini-
mise problems with flame impingement. Plants that
keep their furnaces larger find that it is easier to achieve
lower NOx.
Additionally, by augmenting the new boiler with
selective catalytic reduction (SCR) technology, emis-
sions can be lowered further. Coen LoNOx burners too
can help to minimise NOx production from boilers. One
university campus in California, for example, attained
NOx levels of 3 ppm from its Rentech boilers. This kept
them well below the 5 ppm demanded by the local air
quality management district.
The combination of the right burners and SCR can
keep emissions down without the mass flow and par-
asitic losses of flue gas recirculation. As a result, not as
much reactant is required. This allows the use of a more
compact SCR since it does not need to deal with the
higher mass flow or higher NOx levels.
By observing these best practices, replacement boil-
ers will be more efficient, will have lower emissions and
will require much less maintenance.
Rentech
For more information: hkumpula@rentechboilers.com
Characterising heterogeneous catalysts with
laser diffraction
Heterogeneous catalysts, where the catalyst is in solid
form, enhance many of the gas and liquid phase reac-
tions that underpin routine chemical processing. Prime
examples include Raney catalysts for the hydrogenation
of liquid fats, fluid catalytic cracking (FCC) catalysts
for hydrocarbon processing and three-way catalysts for
the in situ treatment of car exhaust fumes. The extent to
which such catalysts enhance reaction rates is directly
dependent on the specific surface area they present to
the reactants, which for particulate catalysts is a func-
tion of particle size – a decrease in particle size results
in an inversely proportional increase in surface area,
and hence reaction rate. hile finer particles may be
advantageous from the point of view of reaction poten-
tial, there are downsides too: health and safety issues;
poor fluidisation properties; and a tendency to agglom-
erate, which inhibits reaction. It is therefore necessary
to balance the need to maximise reaction efficacy with
the need to reduce the risks associated with overly fine
particle size, which means that there is usually an opti-
mum particle size range for a catalyst.
A common analytical technique for measuring parti-
cle si e is laser diffraction.1 This is an ensemble particle
sizing technique that reports a particle size distribution
128 PTQ Q4 2018
tia copy 3.indd 4
20
Catalyst A
Catalyst B
Volume density, %
15 Catalyst C
10
5
0
0.01 0.1 1 10 100 1000 10 000
Size classes, µm
Figure 1 Particle size distributions for FCC catalyst samples A, B
and C measured with wet dispersion show sample B to have a
much narrower particle size distribution
for the entire sample. Particles illuminated by a laser
beam scatter light over a range of angles depending on
their size, and give a distinctive scattering pattern from
which the particle size distribution can be determined
using an appropriate scattering model, ideally Mie the-
ory. For catalyst applications the particle size data gen-
erated can also be used to calculate a specific surface
area (SSA) by converting the reported volume distri-
bution into a surface area distribution using the Hatch-
Choate equations, for example.2 The general equation
linking SSA with particle size is:
SSA=6/D[3,2]
where D[3,2] is the surface area moment mean or Sauter
mean diameter (SMD).
As was touched upon earlier, SSA is a critical metric
for defining catalyst activity and achieving an optimum
particle size distribution. Traditionally this has been per-
formed using Brunauer-Emmett-Teller (BET) physisorp-
tion techniques; however, catalyst specialists are increas-
ingly turning to laser diffraction techniques for faster and
more efficient assessment. To this end, laser diffraction
particle si ing is finding widespread application for the
characterisation and development of catalyst powders.
Case study: using laser diffraction to measure specific
surface area
The particle si e distributions of three different FCC
catalysts were measured using wet dispersion laser dif-
fraction on a Mastersizer 3000 (Malvern Panalytical)
Comparison of the Sauter mean diameter (D) and the specific
surface area (SSA) of FCC catalysts A-C undertaken with wet
dispersion laser diffraction
Catalyst D[3,2]/microns SSA/m2.kg
A 40.9 54.4
B 74.8 33.2
C 38.5 57.7
Table 1
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asia downstream.indd 1 12/09/2018 19:41

4.8
R2 = 0.9509
4.6
4.4
BET, SSA/m2 g-1
4.2
4.0
3.8
3.6
3.4
3.2
3.0
0.065 0.070 0.075 0.080
Laser diffraction, SSA/m2 g-1
Figure 2 Comparison of SSA derived with BET and laser diffraction.
Results show excellent linearity confirming laser diffraction as a
viable alternative to BET
using dispersion conditions based on standard wet
method development strategies.3
Figure 1 shows particle size results and indicates that
all catalyst samples have a median particle size of 60-80
m. Catalyst B, however, has a markedly narrower par-
ticle size distribution compared with A and C, which
are relatively similar.
Table 1 shows the calculated SSA values for each cat-
alyst as determined from laser diffraction data. These
results indicate that the SSA of catalysts A and C are
similar, whereas catalyst B has a much smaller SSA. The
higher SSA for samples A and C are attributable to the
higher levels of fine material present which is absent
from catalyst B.
Figure 2 shows a comparison between the laser dif-
fraction SSA results and analogous data produced
using BET techniques. The results show excellent cor-
relation with one another, indicating that laser diffrac-
tion can be used in place of BET to predict likely cata-
lytic activity or provide a method for quality control
analysis.
References
1 ISO 13320:2009 Particle size analysis – Laser diffraction methods.
2 Hatch T, Choate S P, Statistical description of the size properties of
non-uniform particulate substances, J. Franklin Inst., 207, 369-387,1929.
3 Wet method development for laser diffraction measurements,
Malvern Instruments Application Note available for download from
www.malvernpanalytical.com
Malvern Panalytical
For more information: john.duffy@malvernpanalytical.com
Measuring level in a molten sulphur pit
Not every level measurement application is straight-
forward. In some instances, the nature of the substance
being measured creates a hostile measurement atmos-
phere requiring creative solutions. ithout reliable
instruments in these environments, the level measure-
ment readings can be inaccurate and cause significant
problems.
Magnetrol produces a broad portfolio of level instru-
130 PTQ Q4 2018
tia copy 3.indd 5
mentation designed to tackle tough challenges. This
article shares the story of a company that found a reli-
able way to measure its most challenging application, a
sulphur pit, using Magnetrol instrumentation.
Application challenges
A gas production company required an accurate level
measurement in a molten sulphur pit. Previously, the
company used a bubble system that required regular
maintenance and recalibration to keep it operational.
0.085 0.090 Obtaining an accurate level measurement is difficult
in this application due to both the low dielectric of the
process medium and dry sulphur build-up. In addition,
the relatively high temperature (300°F/150 °C) and the
corrosive properties of molten sulphur increased the
demand for service and maintenance.
Application solution
The Magnetrol Eclipse Model 706 guided wave radar
transmitter provides accurate and reliable level meas-
urements in difficult process conditions. hen com-
pared to other technologies, the Eclipse requires
less maintenance and does not need calibration. To
ensure maximum accuracy and reliability, Magnetrol
equipped the Model 706 with a Model 7YF single-rod
probe.
Before the Eclipse was accepted as the molten sulphur
pit level control device, it was tested and monitored.
Plant operators using the manual hand-dipped method
checked each measurement it made. After two weeks of
testing, its performance was verified and its application
was endorsed.
The single-rod probe performed well despite the
problems that can be caused by sulphur build-up or
coating. A strong pulse was still detected from the liq-
uid surface despite the build-up.
Reliable level measurement of molten sulphur in a pit
is difficult to obtain. The Eclipse proved to be the solu-
tion for process level control that was not adversely
affected by high temperature, probe build-up, or the
corrosive properties of the media measured.
Eclipse Model 706 loop-powered, 24 VDC transmit-
ters are designed with guided wave radar technology,
which represents best in class liquid level instrumen-
tation. The 706 is ideal for wellhead equipment includ-
ing separators and oil tanks. This level transmitter is
designed to provide measurement performance well
beyond that of many more traditional technologies:
• Fast start-up and stabilisation times reduce energy
consumption
• Accurate top level and interface measurement delivers
precise tank capacity control to reduce production costs
• Powerful diagnostics and data storage enable effi-
cient remote monitoring
• Complete probe line ensures reliable performance,
regardless of media
• Compatible with industry standard remote terminal
units (RTU).
Magnetrol
For more information: info@magnetrol.com
www.eptq.com
14/09/2018 09:46
 digitalrefining.com is the most extensive It provides a constantly growing
source of freely available information on database of technical articles,
all aspects of the refining, gas and company literature, videos, industry
petrochemical processing industries. news and events.

063_dig ref full page ad.indd 1 15/12/2016 09:28

 Option 1 Option 2
Virgin AGO, 52 lv%
Kerosene, 30 lv%
LCO, 18 lv%
Light gas / LPG

HDT HDT
HDT Naphtha MIDW
MIDW

Diesel
Diesel Value Spec. Figure 2 Option 1 (selected): Optimise placement of MIDW catalyst in the existing reactor LCO;
Pour point, ºF − − Option 2: Use an additional reactor to provide added flexibility
Cloud point, ºF 0.0 0.0
D86 T90 %off 577ºF 640ºF
350

Figure 1 Diesel specification from a 340

Spec= 640ºF 639ºF
800 psig hydrotreater

Temperature, ºC
330

= 62ºF
320
Drop-in catalyst generates more jet fuel and
full range diesel 310
577ºF
300
A North American refiner was producing ultra low sul-
290
phur diesel (ULS ) in a 00 psig hydrotreater. Meeting Pre MIDW Using MIDW
pour point and cloud point specifications required the D86 T90 %off
refiner to blend kerosene into the hydrotreater feed,
resulting in downgrading jet fuel to diesel and signifi-
Feed composition, pre MIDW Feed composition, using MIDW
cant giveaway on the product end point. The refiner’s
LCO, 18% LCO, 18%
goal was to increase profitability by eliminating this Kero, 7%
end point giveaway to meet the hydraulic constraints of Kero, 30%
the unit. (see Figure 1).
AGO, 75%

Introduce proprietary technology and services

ExxonMobil applied its technical expertise and owner-
operator experience while working closely with the
refiner to analyse the situation and identify the best
possible solution. Two options were proposed:
1. Optimise placement of MI catalyst within the
reactor, which enables production of high cetane and
low cloud and pour point diesel at higher yields, elimi-
nating the need for kerosene blending to meet cold flow
properties.
2. Use an additional reactor to provide additional flex-
ibility. After evaluating both options, the refiner chose
to optimise placement of MI catalyst in the existing
reactor (Option 1 in Figure 2).
Improved profitability and elimination of giveaway
The implementation of ExxonMobil’s robust catalyst
solution enabled feed rebalancing, resulting in com-
pletely eliminating the end point reduction issue. The
lighter kerosene component was routed to a separate,
pre-existing H T unit to make jet, which allowed the
AGO end point to be increased, thereby netting more
higher value products. Pour point remained at -5.3 F
and cloud point remained at 0.0 F (on-spec). This led to
a jet fuel yield increase and an AGO upgrade to diesel,
AGO, 52%
Figure 3 Benefits of a jet fuel yield increase and an AGO upgrade
resulting in estimated annual benefits greater than $20
million/y (see Figure 3).
ExxonMobil
For more information: www.exxonmobilchemical.com/midw
Activity still key for FCC catalyst to improve
profit margin
Nowadays, the gasoline economy still prevails in most
markets. The US market has been favouring gasoline
yields for a long time. Even in the Indian refining market
where petrochemicals have been strongly focused, gasoil
or resid feed still needs to be cracked to gasoline before
they are further converted to LPG. The FCC reaction sys-
tem is highly complicated but, to simplify, the ability
to crack diesel range molecules to a gasoline fraction is
defined as the conventional cracking activity, best facil-

132 PTQ Q4 2018 www.eptq.com

tia copy 3.indd 6 14/09/2018 09:46

 84 80 72 50
Conversion, wt% 82 Conversion Conversion
Inventory 78

LPG + gasoline, wt%

70 Inventory

Inventory, %
80 40
78 76

Inventory, %
68
76 30
74
66
74
72 20
72 64
70 70 10
Time, dates 62

Figure 1 Conversion improved by 1.8 wt% with increased
inventory replacement of HCpect catalyst
itated by Y-zeolite. The cracking of the bottoms fraction
into diesel range molecules mostly occurs on the matrix.
HCpect (Qingdao Huicheng Environmental
Technology) has been focusing on improving both
matrix and Y-zeolite activity to create value for refin-
ing customers, all while maintaining or improving
coke selectivity. The Y synthesis and treatment has
been optimised to offer improved activity, while the
treatment of non-framework aluminum improves coke
selectivity. On matrix technology, HCpect has a com-
binatorial system using compensating natural clays
to form desirable pore size structure. Moreover, the
clay and specialty alumina complement each other
for optimised pore size distribution. Both technolo-
gies were deployed in a commercial trial in a Sinopec
refinery. For a fair comparison, both the current and
the incumbent catalyst were without metal trapping
60 0
Time, dates
Figure 2 LPG+gasoline yield improved by 1.7 wt% with increased
inventory replacement of HCpect catalyst
technology, despite notable levels of metals on the Ecat.
The FCC unit throughput is 28 000 b/d with a dual
reaction zone design. The secondary reaction zone pro-
motes hydride transfer and isomerisation reaction to
reduce olefin content in the gasoline product. The cat-
alyst inventory was 380-400 t and the catalyst addi-
tion rate was 3.0 t/d. During the otherwise smooth tri-
als without major operating disruptions or cut point
shifts, the feed API was consistent at 21.2±0.6°. The com-
bined Ni+V content on the Ecat was approximately 4000
ppmw, with an uptick toward the end of the second trial.
The conversion showed a 1.8 wt% increase when sig-
nificant inventory was replaced with HCpect catalyst
(while far from an ideal catalyst inventory replacement,
here comparison was done at ≥20% vs ≤20% inven-

www.eptq.com PTQ Q4 2018 133

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 8
bottom line of the FCC optimisation. In this trial, the
Traditional matrix profit margin was improved by $1.13 bbl at the current
Incumbent catalyst inventory replacement level. This margin can be further
Improved matrix
improved when the catalyst replacement reaches an
ideal 70- 0% level, primarily due to the improved activ-
6
ity through bottoms cracking and - eolite cracking.
Slurry, wt%

HCpect FCC Catalyst

(Qingdao Huicheng Environmental Technology)
4
For more information: tpshi@hcpect.com

2
Online hydrogen purity analysis
74 76 78 80 boosts sulphiding
Conversion, wt%

Figure 3 Improved matrix resulted in lower slurry yield and
selectivity compared against the incumbent and the catalyst with
traditional matrix
tory replacement levels), as shown in Figure 1 . uring
the trial, small amounts of SM-5 additives were used
throughout the trial. To eliminate the artefacts of the
inconsistent addition of SM-5, the combined weight
yield of LPG and gasoline is shown in Figure 2 ; an aver-
age increase of 1.7 wt% was evident. Also shown in
Figure 3 is the slurry yield comparison against conver-
sion. The new matrix showed improved slurry yield
and selectivity when compared against the catalyst with
traditional matrix and the incumbent catalyst.
Overall, the value creation through activity and bot-
toms cracking improvement still proved pivotal to the
eactor esources has utilised the Online Hydrogen
Purity Analy er to assist with the sulphiding of 0
hydrotreating units. efiners have found that real time
analysis of the recycle gas composition speeds up the
catalyst sulphiding process while minimising the envi-
ronmental issues resulting from purging sour gas to the
flare or fuel gas system.
uring sulphiding, dimethyl sulphide ( M S) is
typically injected into the reactor feed, decompos-
ing to form hydrogen sulphide (H2S). H2S reacts with
the metal oxides on the hydrotreating catalyst, form-
ing active metal sulphides on the catalyst surface. The
decomposition of M S also forms byproduct meth-
ane (CH ) that will dilute the recycle gas stream and
increase the gas density.
A low hydrogen concentration resulting from H2S

WEBINAR: WEDNESDAY 10 OCTOBER 2018

FROM HYDROGEN PRODUCTION TO SULPHUR RECOVERY:

LET CERAMICS PAVE THE WAY
Brought to you from the publishers of PTQ and DigitalRefining.com

On 10 October 2018, learn how to boost the reliability and performance of your hydrogen
production and sulphur recovery plants through the deployment of Blasch’s ceramic systems.

• Higher plant reliability and much longer run lengths

PRESENTER
UDAY PAREKH
Senior Global Director,
Energy and Chemicals,
Blasch Precision Ceramics
• 60-90% faster installation times
• Capacity increase
• Annual energy savings of several hundred thousand dollars for SRUs
• Lower emissions
Flue gas tunnels in steam methane reformers warp and fail, causing non-uniform flow and costly
catalyst tube failures. In sulphur recovery units, checker walls or choke rings in the reaction
furnace collapse, causing contaminant breakthroughs, downstream pressure build-up and catalyst
poisoning. All of this results in more frequent and costly turnarounds and loss of precious
production. See how these problems can be eliminated with Blasch’s innovative technologies.

This webinar will illustrate the design and technologies underpinning these robust solutions,
followed by examples from a variety of case studies demonstrating the benefits from deployment
of these systems worldwide. The 45-minute presentation will be followed by a live 15-minute Q&A.

To register, visit www.digitalrefining.com/news/1005209

tia copy 3.indd 8 14/09/2018 15:03

 and methane formation slows the kinetic rate of the sul-
phiding reaction. Catalyst manufacturers recommend
a minimum hydrogen concentration of 0% in order to
maintain an adequate kinetic rate and to minimise coke
formation. Increased gas density associated with excess
methane make can also cause compressor issues and
may lead to compressor trips, depressuring the unit.
In order to avoid these issues, refiners typically take
gas samples in ‘sample bombs’ and send them to the lab
for analysis. hile this approach works in many cases,
the time lag waiting on lab results can be - hours.
By this time, adjustments to the gas composition have
typically been made based on ‘best guesses’ instead of
actual data. These adjustments involve excessive purg-
ing of extremely sour gas with fresh make-up hydrogen
brought in to the system. However, purging of sour gas
can cause environmental issues when excess sulphur is
sent to the flare header or fuel gas system.
An Online Hydrogen Purity Analyzer will minimise
and possibly eliminate the need to purge sour recy-
cle gas since the real time data the analyser provides
make the process much easier to precisely manage. This
allows the sulphiding team to maintain hydrogen con-
centration above the minimum target level. In addition,
the analyser provides meaningful safety enhancements
since operations personnel will no longer be exposed to
hazardous levels of H2S during the sampling procedure.
Case study
A US Midwest refiner utilised eactor esources’
Hydrogen Purity Analyzer for the start-up of a ULSD
unit. The customer was able to monitor the gas concen-
tration in real time via our cloud-connected system as
the recycle gas hydrogen concentration dropped from
100% to below 70% less than four hours after DMDS
injection began. With a continuous stream of accurate
data, the refiner reacted quickly, purging the optimum
amount of sour hydrogen and adding fresh make-up
hydrogen only as needed. By using data from the
eactor esources system, the refiner stayed below the
stack sulphur limit of 1 0 ppm during the start-up.
With the ability to monitor the recycle gas concentra-
tion and injection process in real time, the refiner was
able to complete the sulphiding process by using only
55.3 tonnes of DMDS, a saving of over €50 000 in chem-
ical costs. It was later learned that the feed used dur-
ing sulphiding also contained sulphur that was con-
verted to H2S during the start-up. By also measuring
the H2S concentration in real time, the sulphur from the
feed was accurately accounted for, and the correspond-
ing amount of DMDS was not injected. Instead of ‘fol-
lowing the script’ from the previous start-up of this unit
when 72 tonnes of M S was injected, the refiner was
able to use real time data to inject the optimum amount
of spiking agent. Furthermore, issues resulting from
over-injection, such as compressor trips and purging of
excessively sour gas, were totally avoided.
eactor esources’ SmartSkid M S Injection
System and Online Gas Analyzers have now been used
to successfully sulphide over 300 hydroprocessing units
across the US, Canada, and Europe.
Reactor Resources
For more information: info@reactor-resources.com

WEBINAR: WEDNESDAY 23 OCTOBER 2018

INTELLIGENTLY PREDICT AND PREVENT CORROSION
ACROSS YOUR OPERATIONS
Brought to you from the publishers of PTQ and DigitalRefining.com

The fight against corrosion never stops. What if you could have insight into real time corrosion rates
in your process? Honeywell Predict Corrosion Suite provides the next generation of corrosion
management solutions, intelligent software providing real time corrosion quantification. Unlike
conventional corrosion management methods, unique prediction models are employed that
encapsulate deep domain expertise and extensive process data to correlate corrosion rates to
specific process units, damage mechanisms, and operating conditions.
PRESENTER
Join us for a webinar focused on Predict-RT, software that gives real time visibility on internal SRIDHAR SRINIVASAN
corrosion in piping and equipment and enables proactive corrosion management across operations.
Global Business Leader,
Learn how you can evolve your corrosion management approach to:
Corrosion Center of
Excellence, Honeywell
• Understand – Use prediction models and what-if analyses to identify critical corrosion conditions
Process Solutions
and locations
• Monitor – See corrosion rates and correlate with operating data in real time
• Prioritise – Leverage up-to-date, real time information for a proactive approach to deploying
corrosion management resources

Using Honeywell’s tools, global leaders in oil and gas and refining have achieved significant benefits
in safety and reliability, supply chain, operating and maintenance costs, and capital expenditures.

To register, visit www.digitalrefining.com/news/1005223

tia copy 3.indd 9 14/09/2018 15:03

 Alphabetical list of advertisers

6th Opportunity Crudes Conference 127 Idrojet 16

Advanced Refining Technologies 78 IPCO 18
AFPM 2019 Events 125 ITW Technologies 53 & 74
Albemarle Catalysts Company 4 Jacobs Comprimo Sulfur Solutions 86
Aqseptence Group (Johnson Screens) 54 Johnson Matthey IBC
Ariel Corporation 101 Jonell Filtration Group 44
Asian Downstream Summit 129 Koch-Glitsch 89
Avantium 57 Kurita Europe 48
Axens OBC Magnetrol International IFC & 1
Blasch Precision Ceramics 105 Malvern Panalytical 59
Burckhardt Compression 36 MetsoFlow Control 68
Cat Tech 40 Neste Engineering Solutions 35
Chevron Lummus Global 9 OHL Gutermuth Industrial Valves 108
CRI Catalyst 60 Process Consulting Services 10 & 12
Criterion Catalyst & Technologies 6 Prognost Systems 118
Crystaphase Products 43 Prosernat 71
CS Combustion Solutions 67 Reactor Resources 73
Dunn Heat Exchangers 133 Rembe 114
Dupont Clean Technologies 39 Rentech Boiler Systems 98
Edelhoff Technologies 97 Rezel Catalytic Technologies 93
ERTC 2018 122 Sabin Metal Corporation 32
ExxonMobil Catalysts and Technology Shell Global Solutions 28
Licensing 17 Shell Global Solutions - Gas Processing 25
DigitalRefining 131 Silobau Thorwesten 112
Gemini Industries 50 Sinopec Catalyst Company 47
Grabner Instruments 27 Sulphur 2018 62
Haldor Topsøe 14 Sulzer Chemtech 80
HarbisonWalker International 21 Tubacex 110
HCpect 115 W. R. Grace & Co 83
Heraeus Precious Metals 91 Webinar: Blasch Precision Ceramics 134
Hoerbiger Wien 85 Webinar: Honeywell Process Solutions 135
Honeywell UOP 2 Yokagawa Europe 117
Honeywell UOP Connected Plant 31 Zeeco 106
Honeywell UOP Callidus 65 Zwick Armaturen 77

Register to receive your regular copy of PTQ at www.eptq.com/register

136 PTQ Q4 2018 www.eptq.com

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j matthey.indd 1 13/09/2018 06:39
 Axens is a leading global
provider of technologies, OIL REFINING
catalysts, adsorbents,
services and equipment.
Axens solutions are used
at major industrial plants
PETROCHEMICALS
around the world.

GASES

RENEWABLES
& ALTERNATIVES
TOGETHER
SUCCEED

WATER

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