Gulfpub HP 201001

www.HydrocarbonProcessing.
com
JANUARY 2010
HPIMPACT SPECIALREPORT TECHNOLOGY
GAS PROCESSING
DEVELOPMENTS
Innovations improve
gas treating
Continued struggles
for US refiners
The EUs Emissions
Trading Scheme
When carbon capture
makes sense
Managing equipment
costs and incidents
Select 55 at www.HydrocarbonProcessing.com/RS
www.HydrocarbonProcessing.com
JANUARY 2010 VOL. 89 NO. 1
SPECIAL REPORT: GAS PROCESSING DEVELOPMENTS
29
Advanced mercury removal technologies
New technologies can cost-effectively treat wet and dry natural gas
while protecting cryogenic equipment
N. Eckersley

37
A unique natural gas processing success story
Cost-effective expansion created high reliability operations
C. Baker and T. Barnette
39
Equilibrium considerations in choosing
a gas treating amine
Pursue these guidelines to understand solubility
S. A. Bedell
43
Designing a selective MDEA tail-gas treating unit
Following these protocols will enhance sulfur recovery efficiency
S. Nagpal
Cover Darwin LNG, located at Wickham
Point, Darwin Australia began operation
in 2006. This 3.7 MTPA facility, which
employs the ConocoPhillips Optimized
Cascade Process, establ i shed new
design benchmarks for LNG facilities by
being the first to apply high efficiency
aeroderivative gas turbines and the
first to use inlet air humidification to
enhance production during periods of
low humidity.
HPIMPACT
15 Struggles for US refiners
expected to continue
17 The EUs ETS at a glance
COLUMNS
9 HPIN RELIABILITY
More about
unreliability, global
procurement and you
11 HPIN EUROPE
Duh! Business as usual
will not be good for
the HPI
13 HPINTEGRATION
STRATEGIES
Applying tuneable
diode laser spectroscopy
to help reduce energy
consumption
82 HPIN WATER
MANAGEMENT
Wastewater discharge
permits; What should
you know?
ENVIRONMENT

49
When does carbon capture
make sense?
Here are several options in which carbon capture can provide
cost-effective solutions
S. Ferguson
MAINTENANCE/RELIABILITY

55
Managing costs and incidents in industrial plant equipment
Use this method to allogate limited maintenance resources to the most critical equipment
M. Gardella, E. Egusquiza, X. Escaler and A. Goti
PLANT SAFETY AND ENVIRONMENT

63
Designing for pressure safety valves in supercritical service
Use this rigorous method to prevent over-sizing
R. C. Doane
PIPING

69
New explicit friction factor equation for turbulent flow in
smooth pipes
A simple, explicit and high-accuracy equation is presented
A. Sasan-Amiri
INSTRUMENTATION

71
Implement a constrained optimal control in a conventional
level controllerPart 1
Novel tuning method enables a conventional PI controller to explicitly handle the three
important operational constraints of a liquid level loop in an optimal manner as well as
copes with a broad range of level control from tight to averaging control
M. Lee, J. Shin and J. Lee
ENGINEERING CASE HISTORIES

77
Case 54: Is it motor vibration
or some other cause?
Its not always the motor causing the vibration
T. Sofronas
DEPARTMENTS
7 HPIN BRIEF 15 HPIMPACT 19 HPINNOVATIONS
23 HPIN CONSTRUCTION 24 INDUSTRY FORECAST FORUM
25 LETTERS TO THE EDITOR 27 HPI CONSTRUCTION BOXSCORE UPDATE
78 HPI MARKETPLACE 81 ADVERTISER INDEX
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BT@HydrocarbonProcessing.com
HYDROCARBON PROCESSING JANUARY 2010

I

7

IEA speaks up
in Copenhagen
During the United Nations Climate
Change Conference in Copenhagen,
Denmark, the International Energy
Agency shared its blueprint on achiev-
ing ambitious climate change goals
while encouraging new investment for
clean energy.
With energy accounting for 84% of
global CO
2
emissions, the IEA said it
had analyzed what needs to be done
to limit the long-term concentration of
greenhouse gases in the atmosphere
to 450 parts per million (ppm) of CO
2

equivalent, in line with a 2C increase
in global temperature. The IEA believes
that, unless new measures are taken,
global energy-related CO
2
emissions
will reach 40 Gigatons (Gt) by 2030 (the
world stood at 29 Gt in 2007) and con-
tinue rising thereafter, whereas climate
stabilization requires emissions to peak
around 2020 and then decline.
According to the IEA, the world needs
to retire a significant portion of todays
coal-fired electricity plants by 2030.
These early closures around the world
would equal todays total coal-based
power generation in Japan, the EU and
the US. Around 60% of global electric-
ity production in 2030 would need to
come from a mix of renewables (37%),
nuclear (18%) and plants fitted with
carbon capture and storage (5%).
The bulk of the emissions reduction
could be delivered by energy efficiency,
accounting for over half of total abate-
ment by 2030 in the IEA 450 Scenario.
According to the IEA, energy efficiency
is necessary for the deployment of
the more expensive, low-carbon energy
supply as it helps lowering demand
first. IEA said that the additional invest-
ment can be recouped by end users
through lower energy bills; for industry,
the additional $8.3 trillion of required
investment would lead to $8.6 trillion
in savings between now and 2030. HP
Foster Wheeler AGs Global Engineering and Construction Group
plans to work with PetroAlgae to develop commercial solutions that will allow existing oil
refineries to convert micro-crop biomass into fuels that are functionally compatible with
petroleum-based fuels in the current market. For refineries, the solutions are expected to
evolve from the large-scale processing of PetroAlgaes micro-crop biomass into green fuels.
The two firms intend to create end-to-end market solutions for the large-scale production
of green gasoline, diesel, jet fuel and specialty chemicals.
A recent report from Companiesandmarkets.com shows that Latin
Americas thirst for oil has grown this decade. The region consumed 6.9 million bpd in
2001 and its appetite was expected to reach an estimated 7.7 million bpd by the end of
2009. For 2010, the region should have an average consumption of 7.9 million bpd, rising
to approximately 8.6 million bpd by 2013. While consumption in Latin America grew
from 20012009, overall oil production was flat and trending downward. The region pro-
duced 10.3 million bpd in 2001, while, in 2009, it averaged an estimated 9.6 million bpd.
The report sees this number rising to 10.8 million bpd by 2014. Meanwhile, oil exports
have been slipping because demand growth has exceeded the pace of supply expansion. In
2001, the region was exporting an average 3.4 million bpd. The total is expected to fall to
1.9 million bpd by the end of 2009 and then is forecast to recover to 2.2 million bpd in
2014. Companiesandmarkets.com says the principal exporters will be Mexico, Venezuela,
Ecuador and Brazil.
Caltex is planning to close its Kurnell refinery in Sydney, Australia. The
closure signals a cost efficiency drive and is in response to flat earnings in 2009. Global
refiner margins remained under pressure in the second half of 2009 because of depressed
demand and the expected growth in global surplus refinery capacity, a report from Caltex
said. Another contributing factor for closure was the stronger Australian dollar and higher
crude oil prices that caused a precipitous drop in Caltexs refining margins. Caltexs margins
fell to an average of about $2.60 a barrel in the second half of 2009, compared with an
average of $9 in the first half. The company believes the refinery is ripe for closing because
it manufactures outmoded lubricant products and faces declining feedstock sources. The
closure date has yet to be announced.
Chevron Corp. recently released its budget for 2010. The company
plans a $21.6 billion capital and exploratory spending program for 2010, a 5% decrease
from projected 2009 expenditures. About 80% of the 2010 spending program is for
upstream oil and gas exploration and production projects worldwide. Another 16% is
associated with the company's downstream businesses that manufacture, transport and sell
gasoline, diesel fuel and other refined products. Capital spending of $3.4 billion in 2010
is budgeted for global downstream operations. Included in the budget is $1.6 billion for
projects in the US, primarily for refinery projects. Outlays in 2010 include projects in the
company's refineries in Mississippi and California. The company's 50%-owned GS Caltex
affiliate is also expected to continue development work on the upgrading of its Yeosu refin-
ing complex in South Korea. In support of projects to commercialize the company's large
natural gas resource base, downstream expenditures will be made in 2010 on gas-to-liquids
manufacturing facilities.
Mission NewEnergy Ltd. has a five-year agreement to supply Valero
with up to 60 million gpy of Jatropha-extracted biodiesel. Valero has the right to
double that amount to 120 million gpy and to extend the term by an additional five
years. The agreement represents gross revenue potential to Mission of over $3.5 bil-
lion based on prevailing market prices, maximum volume and contract life. The first
product shipment under the agreement is expected to occur during the second quarter
of calendar year 2010. HP
HEINZ P. BLOCH, RELIABILITY/EQUIPMENT EDITOR
HPIN RELIABILITY
HB@HydrocarbonProcessing.com

I

9
We quite obviously believe that reading is the key to profes-
sional growth and that Mark Twain was right in stating that the
man who refuses to read is no different from the illiterate person
who cannot read. We also know that, while technical texts can be
pricey, a book costing $100 will often alert its reader to the solu-
tion to a million-dollar problem. In that case, the return on the
investment would be 10,000:1. And so, it makes a huge amount
of sense to put reading in your training plans and to have either
a budgetary item or subsidy for books at your refinery. Reading
and reliability improvements are related and should never be
separated. A recent column alluded to the reliability professionals
job of identifying critical parts and to write detailed specifications
that then facilitate their global procurement.
Coping with global procurement. Unless proven oth-
erwise, you should assume that the lowest bidder utilizes neither
quality control nor exacting specifications. Perhaps this explains
why an entity is the lowest bidder. Again, you must provide and
sometimes personally write a specification for these critical parts.
Once critical spare parts (even the ones originating from vendors
accepting your specifications and professing to have quality con-
trol) are delivered to your facility, the job is far from finished.
You must add value by personally verifying the full specification
compliance of these parts. Alternatively, take responsibility by
arranging for competent inspectors that verify specification com-
pliance of the critical spare parts received. These parts should be
accepted by the storeroom clerk only after compliance has been
verified. The clerk can then proceed to tag and preserve the parts
for future use.
As to the misguided direction where some in the HPI are headed,
we recently received a very strong message from a well-known asset
management consultant. After visiting a major refinery, he consid-
ered its management system completely broken. He expressed the
view that, due to past failures, decision makers now seem afraid
to make any decision that carries even a whiff of riskso they do
nothing! He met a young reliability engineer who had poured heart
and soul into a project, submitted it to the plant manager and heard
nothingnot even the simple courtesy of an acknowledgment!
The consultant was struck by this refinerys bewilderment why so
many of the young men and women who should be its lifeblood
and future were quitting their jobs. Those who remained seemed to
have the attitude, just tell me what you want, manager, and I will
get myself involved somehow. Of course, the manager doesnt have
a clue, so nothing of substance gets done at that location.
Then there are the many recurring accountability issues men-
tioned by the asset management consultant. In one review meeting
a reliability engineer was asked why he thought he had to spend
so much time in the plant during turnarounds watching things
like gasket replacements. His answer? Because Im held directly
responsible even though the fault may be solely attributable to the
carelessness of a mechanic. The mechanic will not be held account-
able, but I will be. Word spreads, and we heard rumors that, in
2007, not a single graduating engineer accepted the employment
offer made by one particular major oil company.
Shunning cheap temporary fixes. A huge problem at one
refinery seems to be its constant pursuit of cheap temporary fixes.
Managers at this location have no discernible concept of the bigger
overall picture and have enunciated neither sound strategy nor any-
thing resembling long-term improvement. At one location, a highly
experienced management consultant judged as totally inoperable
the functional asset hierarchy on which all cost and reliability data
are based. Upon being briefed about the issue, the refinery managers
considered corrective action too difficult and elected to again do
nothing but maintain a very precarious status quo.
Which gets us back to the original point and where global pro-
curement involves all kinds of service providers. Once we identify
the most successful service providers, we must ascertain that they
will continue to add value every step of the way. They will join us
in viewing every maintenance event as an opportunity to upgrade.
Upgrading means strengthening the weakest link in the compo-
nent chain whenever cost-justified. It will make the operators
life easier and will open wide the (presently very narrow) door to
operator-driven reliability (ODR). Conscientious upgrading will
have merit beyond that of traditional maintenance.
Whatever your job function, you can make a big difference and
be an effective change agent. Start by understanding or personally
defining critical spare parts and take it upon yourself to describe
them in an appropriate purchase specification. Read what others
have done in this regard, how they persevered and excelled not just
recently, but decades ago. Other facilities became best-practices
companies by having professional employees totally involved
these employees took the lead in advancing the reliability improve-
ment process. They were among the first to view every maintenance
event as an opportunity to upgrade components and machines and
initiated action where it was both feasible and cost-justified.
If you are not a manager, write down what you have found in the
various books and articles and discuss it with your manager. If he
doesnt take action, find someone who will. And if you are a manager,
do something about the critical situation we have accurately described
in this column. A bit of introspection will let you know who you
really are. Make adjustments in your course, which is another way of
asking you to either lead, follow, or move out of the way. HP
More about unreliability, global procurement and you
The author is HPs Reliability/Equipment editor. A practicing engineer and
ASME Life Fellow with close to 50 years of industrial experience, he advises process
plants on maintenance cost-reduction and reliability upgrade issues. Of his 17
textbooks on reliability improvement subjects, 11 are still in print and are being
updated periodically. His 2nd edition, Practical Lubrication for Industrial Facilities,
was released in May 2009.
In times like these, you need more than the right product in the right place. Thats
why, at Swagelok, we take training to heart. Working side by side with you to improve
your bottom line, well guide you in everything from correct component installation to
efcient steam systems and orbital welding. We even offer a variety of self-paced online
courses through Swagelok University, covering product and technology information
and applications. It all stems from our dedication to Continuous Improvement both for
ourselves and our customers. And its just one more way we continue to offer more than
you might expect. See for yourself at swagelok.com/training.
Because show me
works so much
better than tell me.

2
0
0
9

S
w
a
g
e
l
o
k

C
o
m
p
a
n
y
TIM LLOYD WRIGHT, EUROPEAN EDITOR
HPIN EUROPE
tim.wright@gulfpub.com

I

11

Where the common ground between my best friends in engineer-
ing and I becomes a parkland with fireworks is when we share the
aha moments. I suspect its from that curious, excited child in my
friends that they confide new ways of seeing things, such as saving
energy in their plants, or sharing a conventional wisdom or two.
Conventional wisdoms can be both oppressive and hugely diver-
sionary. For example, the English were laying steel cables from a
small beach in Southwest Cornwall to Newfoundland and the
Antipodes even as Marconi was having his aha moments with
an antenna at Pondhu station on a nearby
hillside. Yes, it turns out that there was a
scornful relative of the aha moment for
a sad lot of investors in this epic-age, deep-
sea, transglobal telegram cable project. Lets
call it the Duh! experience.
The golden age of Duh! We live in a golden age of these
duh moments; just think subprime. The stupidity of stacking
up derivatives on the back of people encouraged to lie about their
creditworthiness is enormous, and with, hindsight, it stops one in
ones tracks. After the fact, theres this rush of common sense, like
air entering a vacuum. In the sphere of energy and sustainability,
the Dubai crisis ticks all the boxes of a Duh! experience.
Dj vu all over again. At first, I get it. The United Arab
Emirates, the worlds second largest emitter of carbon dioxide
(CO
2
) from energy per capita, decides to diversify its economy.
The resource curse tells us that not much good comes from
having too much oil in centralized hands.
But for Dubai to diversify by building a long-haul tourist des-
tination and business hub with the most carbon-intensive attrac-
tions and accommodations imaginable, and at a time like this?
Consider that, since 2003 and with the worst dry period on record
locally, Australia has been desperately struggling to drought-proof
its desert and even its pastoral communities. The sandy, city state
of Dubai, meanwhile, has produced the innovative chilled swim-
ming pool, a shopping mall ski resort and desalinated irrigation
for a golf course.
Holiday destinations. I do know people whove taken a
vacation in the Middle East, but this idea hasnt exactly tickled
my familys fancy. Inspired by Ron Oxburgh, the former non-
executive chairman of Shell, my family hasnt traveled on vacation
by air since early 2006. Along with 63% of the European citizens,
were convinced that climate change is a very serious issue.
1

With a family goal to reduce our carbon footprint, even short-haul
flights are the worst CO
2
budget busters there are. Im not saying
that Dubais going to weep for not having the Wrights to stay, but
were not on our own over here.
Carbon-busting initiatives. In the UK recently, whole cities
have been signing up to the new 10:10 campaign, sponsored
by the makers of the Age of Stupid documentary. It encourages
individuals, companies and cities to reduce their greenhouse gas
emissions by 10% in 2010. The front benches of the governing
and opposition parties in the UK have already signed up.
So whats this got to do with the hydrocarbon processing indus-
try (HPI)? Well, from what I admit is a particularly European
perspective, and from an oil industry worker living in a coun-
try that still aims to eradicate oil largely
from private transport and home heating
by 2020, I think part of our industry (the
HPI), if not all, is heading for one of these
Duh! experiences.
The International Energy Agency
(IEA), financed by the OECD to warn
on energy security and climate change, says that a delay of just
a few years in enacting a massive decarbonization of the energy
industry could render a safe outcome for the worlds population
completely out of reach. If everything even vaguely on the
table for Copenhagen had been enacted, wed still be in line for
a scenario that calls for significantly more than a 2C increase in
global temperaturesthe level at which it is hoped would avoid
a dangerous outcome.
And yet, major energy companies, large refiners and other
vested interests are still trying to stop the US and Australia from
participating in any meaningful way, with their pump-top leaflets,
questionable rallies and constructed controversies. Well, they
can have business as usual. OECD oil demand will continue to
fall from its peak in 2005 because the costs are just so burden-
some. But sea levels, says the IEA, will eventually shut down every
coastal refiner under its business as usual, or reference scenario.
(As if that was all we would lose!)
And for the bright engineers who love the aha moment of solv-
ing real problems, the shame is they dont get to. The $10.5 trillion of
new investment to achieve the IEAs alternative scenario, and to keep
projected warming to below 2C, is a journey full of real challenge.
Its a journey that would reunite engineering with the enlight-
enment project set when the institutes and great academies were
being formed, which is of making the world a better place for all
humanity. HP
LITERATURE CITED

1
Eurobarometer Survey, December 2, 2009.
The author is HPs European Editor. He has been active as a reporter and confer-
ence chair in the European downstream industry since 1997, before which he was a
feature writer and reporter for the UK broadsheet press and BBC radio. Mr. Wright
lives in Sweden and is the founder of a local climate and sustainability initiative.
Duh! Business as usual will not be good for the HPI
Business as usual is not
an option anymore for the
HPI or modern industry.
PAULA HOLLYWOOD, CONTRIBUTING EDITOR
HPINTEGRATION STRATEGIES
editorial@HydrocarbonProcessing.com

I

13
Applying tuneable diode laser spectroscopy
to help reduce energy consumption
According to the US Department of Energy, industry accounts
for about a third of all energy used in the US. Despite the recent
drop in energy prices, energy remains the second leading cost pres-
sure (behind only raw materials) affecting manufacturers. Some of
the biggest culprits are incinerators, crackers, process heaters and
other energy-intensive combustion-based equipment.
The harsh operating conditions associated with combustion
analysis applications can eat up a sensor in no time, resulting in
inaccurate and unreliable sensor measurements. This can make it
nearly impossible to control these processes adequately. However,
new analysis techniques, such as tuneable diode laser spectroscopy
(TDLS), can improve efficiency, maximize throughput, reduce
emissions and improve safety in combustion analysis applications.
ABB, Siemens, Vaisala and Yokogawa all offer TDLS technology
for process measurements.
Reduce energy consumption. Most energy-intensive
operations, such as those found in a refinery or chemical plant,
experience considerable variability in energy consumption due
to changing operating conditions, equipment degradation, fluc-
tuating market conditions and inefficient control strategies. As a
result, plants typically consume more energy than necessary, yet
are unable to improve efficiency due to the inability to collect and
analyze real-time performance data. Frequently, the goals of opti-
mizing efficiency and maximizing throughput are at odds with the
need to reduce emissions and ensure plant and personnel safety.
Effective energy management is essential for a triple bottom line
business strategy that addresses social, economic and environmen-
tal concerns. TDLS contributes to a triple bottom line strategy
by helping increase throughput and reduce energy costs, while
supporting safe and environmentally responsible operations.
Advanced process control (APC) systems require sensitive
and accurate process measurements in real time, or near-real
time. APC reduces process variability and inefficiency, improves
product quality and provides for more stable operations. With
few exceptions, current process analytical techniques lack the
speed, accuracy and sensitivity to provide reliable measurements
for APC. Online optimization goes beyond APC to optimize a
process based on an economic objective function. This is becom-
ing more important in applications where profitability depends
upon improving quality while maximizing material utilization and
minimizing energy usage.
Historically, obtaining reliable quality measurements in time to
impact control has been an issue in combustion control applica-
tions. The current best practice utilizes a zirconia sensor for point
measurement of oxygen. In applications requiring multiple mea-
surements, point measurement cannot provide a representative
sample, making it both error-prone and potentially dangerous. Pro-
cess oxygen measurement requires samples to be extracted and then
transported to an analyzer for conditioning and analysis. This slows
response time, adds cost and degrades measurement accuracy.
TDLS in combustion analysis. Inefficient combustion can be
attributed to the air/fuel ratio. Too much excess air (air rich) results in
efficiency loss and increased NO
x
emissions, while too little excess air
(fuel rich) is downright dangerous. Carbon monoxide measurement
provides an indication of fuel-rich conditions, while oxygen measure-
ment indicate air-rich conditions. The optimum control point is the
lowest possible excess air value that does not cause the system to enter
into an unsafe condition or violate emissions limits.
TDLS technology is an innovative measurement technique
that utilizes semiconductor lasers to detect a variety of gases at
trace levels in the part-per-million (ppm) or part-per-billion (ppb)
range. Tuneable lasers, which enable miniaturization of transmis-
sion and receiving units, provide highly sensitive, quantitative
measurements with fast response times without the need for reca-
libration. The lasers can be tuned to detect specific constituents
independent of process gas concentrations.
TDLS enables high-performance measurements in real time,
even in challenging process environments. Exact performance
specifications may vary somewhat according to supplier; however,
the benefits are universal (Table 1).
To date, the most widely reported application of TDLS has
been for combustion control. However, the technology poten-
tially offers much wider applicability. In refineries, it can monitor
CO, CH
4
and O
2
in burner flameout applications, and identify
process tube leaks.
Energy can be the largest component of a manufacturers
cost structure. Despite the recent drop in energy prices, costs are
expected to trend upward over the long term. A willingness to
apply state-of-the-art technologies can have a significant impact
on the success of energy management programs. Technologies,
such as TDLS, that can improve performance and provide quick
ROI, can have a significant impact on the bottom line. HP
The author, a senior analyst at the ARC Advising Group in Dedham,
Massachusetts, has nearly 30 years experience in the areas of sales and product
marketing in industrial field instruments that utilize a vast array of technologies
including magnetic, Coriolis, radar, electrochemistry, capacitance and ultrasonic.
TABLE 1. Features and benefits of TDLS technology
Feature Benefit
In-situ analysis Sample conditioning not required
Fast response Real-time data for APC
Tuneable laser Interference-free analysis
Non-contact sensor Suitable for operation in harsh environments
Optical sensor Low maintenance

I

15
HPIMPACT
Struggles for US refiners
expected to continue
In a recent refining industry piece,
Deutsche Bank analysts took a gander at the
US refining industry and wondered if the
worst has passed for refiners. In short, they
think not. ConocoPhillips CEO Jim Mulva
told the analysts that the company will not
engage in any refinery sales, with the hope
that the market for refiners will turn around
over the next two years. If there is no market
improvement, Mr. Mulva said ConocoPhillips
would simply shutter the refineries in ques-
tion. Deutsche Bank sees this as good news
for independents, if they can last that long.
The report also said that Mr. Mulva is consid-
ering canceling both a major Saudi refinery
project at Yanbu and a major refinery upgrade
at Wilhelmshaven in Europe.
The Deutsche Bank analysts agree with
this train of thought, given that current US
utilization rates are at 80% and demand
continues to be down (Fig. 1), with total
products demand at its lowest level at the
end of October since 1998. The brave are
getting long with the idea that things cannot
get any worsewe disagree and have cited
the example of secularly challenged indus-
tries, such as newspapers versus the Internet,
to support this idea, the report said. The
bull argument is that oil demand recovers (it
is not, despite third quarter GDP growth)
and that will cause OPEC to increase pro-
duction (they already have) and that causes
wider heavy-light to widen (it has not).
While the current 80% utilization rate
has resulted in less backlog of refined prod-
ucts inventory (Fig. 3), the analysts are still
concerned with oversupply, especially when
factoring in inventory at sea. Still, recent
refinery shutdowns may assist in chipping
away at excess distillate inventory (Fig. 4).
Sunoco announced that it would indefi-
nitely idle Eagle Point, New Jersey; while
Valero announced in early September that
it would extend the Aruba shutdown, con-
tinue its Corpus Christi, Texas, coker and
FCC shutdown and run other cokers at
reduced rates until the coking economics
outlook improves, the report said. Other
recent decisions that may help with inven-
tory management include Valeros decision
to permanently close its refinery in Delaware
18,000
19,000
20,000
21,000
22,000
J
a
n
F
e
b
M
a
r
M
a
r
A
p
r
M
a
y
J
u
n
J
u
l
A
u
g
S
e
p
O
c
t
N
o
v
D
e
c
k
b
/
d
5-yr historical range 2009 2008
Source: Deutsche Bank, EIA
US oil product demand. Demand at the end of October was
at its lowest level since October 1998.
FIG. 1
J
a
n
F
e
b
M
a
r
M
a
r
A
p
r
M
a
y
J
u
n
J
u
l
A
u
g
S
e
p
O
c
t
N
o
v
D
e
c
20
25
30
35
40
45
50
55
D
a
y
s
US distillate inventories appear over-supplied. FIG. 3
J
a
n
F
e
b
M
a
r
M
a
r
A
p
r
M
a
y
J
u
n
J
u
l
A
u
g
S
e
p
O
c
t
N
o
v
D
e
c
3,200
3,600
4,000
4,400
4,800
k
b
/
d
US distillate demand for 2009 did not paint a pretty
picture.
FIG. 2
65
70
75
80
%
85
90
95
100
J
a
n
J
a
n
J
a
n
F
e
b
F
e
b
M
a
r
M
a
r
A
p
r
A
p
r
M
a
y
M
a
y
J
u
n
J
u
n
J
u
l
J
u
l
J
u
l
A
u
g
A
u
g
S
e
p
S
e
p
O
c
t
O
c
t
N
o
v
N
o
v
D
e
c
D
e
c
5-yr historical range 2009 2008 2007
When comparing US refining utilization from 20072009, it
should be noted that recent refinery shutdowns could help
the current situation.
FIG. 4
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when its time to deplane.
HPIMPACT

I

17
City, Delaware, and Marathons scheduled
downtime for early 2010 at its refinery in
Garyville, Louisiana.
The EUs ETS at a glance
Carbon trading, carbon taxing and other
forms of regulating greenhouse gases have
been hot topics of conversation of late. Since
it appears that these concepts will be domi-
nating thought and affecting business plans
for companies in the HPI into the foresee-
able future, it is not a bad idea to examine
the most established cap-and-trade system
currently in existence, the one marshaled
into form by the European Union (EU).
The EUs Emissions Trading Scheme (ETS)
is basically a commodities marketa mar-
ket-based policy tool that sets a cap on CO
2

emissions from specific sectors. Analysts
from Orbeo (www.orbeo.com) have studied
the ETS extensively and have been briefing
interested parties on their findings. Orbeo
reports that ETS sources covered by the pro-
gram receive (or purchase through auctions)
emissions allowances. Flexibility is allowed;
plants can buy and
sell allowances on a
market according to needs. Carbon offsets
and carbon credits are flexibility mecha-
nisms that lower the cost of compliance to
cap-and-trade. Carbon credits are generated
from emissions-reducing projects and can be
used in addition to allowances (generally up
to a limit) in a cap and trade program.
Emissions of CO
2
by industry in Europe
are capped by quotas, known as European
Union Allowances (EUAs), and handed out
at the individual plant level. The CO
2
price
that emerges reflects the cost of reduction
the emissions. Carbon credits are allowed,
such as the Certified Emission Reductions
(CER) granted by the UN, for emission
reductions achieved in emerging countries.
The evolution of this price in the future will
depend on the industry constraints. Higher
emission reduction objectives thus mean a
higher CO
2
price.
Updated EU ETS balances. According
to Orbeo, EU ETS emission forecasts should
be revised down by 40 Mt for 2009, and
overall by 2% to 3% in the following years,
to account for slow recovery from the global
recession. CER issuances should stand at 1.3
Gt, which assumes significant acceleration.
For 2009, expected issuance volumes sink
down to 155 Mt. Orbeo believes the system
is still slightly short to 2012 (133 Mt).
First implications. It is now confirmed
that the EU ETS will exist to 2020 and
beyond. Thus, there will be one continuous
trading period, with full EUA banking from
Phase II (20082012) to Phase III (2012
plus) ensured. Orbeo predicts a large increase
in auctioned volumes. In Phase III, there will
be new rules on auctioning. Utilities will see
100% auctioning from 2013, with exemp-
tions for power plants in countries where
more than one-third of power is produced
from a single fossil-fuel source and income
per capita is less than half of the EU average.
Sectors with low carbon leakage risk will see
20% auctioning in 2013 increasing to 70%
through 2020, with full auctioning from
2027 onward. Sectors with high carbon
leakage risk are to have 100% of allowances
distributed for free. This free distribution is
based on 10% of the best available technol-
ogy benchmark in 20072008 and should
cover 80% to 90% of sector needs. HP
Imports mb/d (left-hand scale)
Imports as % of production (right-hand scale)
0
500
1,000
1,500
2,000
2,500
3,000
3,500
4,000
4,500
5,000
J
a
n
-
0
6
J
u
n
-
0
6
D
e
c
-
0
6
J
u
n
-
0
7
D
e
c
-
0
7
M
a
y
-
0
8
N
o
v
-
0
8
M
a
y
-
0
9
O
c
t
-
0
9
10
%
12
14
16
18
20
22
24
26
I
m
p
o
r
t
s

m
b
/
d
US product imports 20062009: Imports as a percentage of
US product production trended downward in 2009.
FIG. 5
0
500
1,000
1,500
2,000
2,500
3,000
3,500
4,000
4,500
5,000
EUA
2006
T
r
a
d
e
d

v
o
l
u
m
e
s

2
0
0
6
-
2
0
0
8

i
n

M
T
2007 2008
Secondary CER
Primary CER/ERU
Other markets
Source: SG Commodities Research
Carbon markets traded volumes from 20062008. FIG. 6
0
15
30
45
60
75
90
105
2006
T
o
t
a
l

E
U

E
T
S

a
n
d

C
D
M

t
r
a
n
s
a
c
t
i
o
n
v
a
l
u
e
s

i
n

b
i
l
l
i
o
n
2007 2008
EUA
Secondary CER
Primary CER
Other markets
Total EU ETS and Clean Development Mechanism (CDM)
transaction values.
FIG. 8
26%
30% 6%
8%
3%
11%
9%
7%
EUA exchange
EUA OTC cleared
EUA OTC
Primary CER/ERU
Secondary CER exchange
Secondary CER OTC cleared
Secondary CER OTC
Other markets
World traded carbon volumes in 2008 by market segment. FIG. 7
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HPINNOVATIONS

I

19
SELECTED BY HYDROCARBON PROCESSING EDITORS
editorial@gulfpub.com
Pressure-relief software awarded
first US patent
Farris Engineering Services, a business
unit of Curtiss-Wright Flow Control Com-
pany, has announced that its iPRSM prod-
uct, claimed to be a revolutionary software
for pressure-relief system management, has
been awarded a US patent, with a second
application approved for award. The product
has a unique Web-based design and contains
innovative impact analysis capabilities.
iPRSM is a multifunctional software
package for designing, auditing and docu-
menting the pressure-relieving capability
of process systems in the petroleum, petro-
chemical, hydrocarbon processing, refin-
ing and power-generation industries. The
software supports process system engineers
in maximizing the safety of personnel, pro-
cesses and facilities; minimizing operational
interruptions and losses related to overpres-
sure and documenting changes to pressure
relief systems.
By standardizing pressure-relief system
design and audit methodology, monitoring
pressure conditions and identifying poten-
tial problems, iPRSM makes compliance
activities efficient for various industries,
says Josh Kolenc, vice president, software
engineering. From a cost perspective, it
also reduces the risk of equipment repair,
downtime and lost production.
Web-based for system integrity. The
patented Web-based product allows iPRSM
to be deployed companywide for design
and sizing of overpressure equipment,
safety and change management, and regu-
latory documentation. With many users of
the product at multiple locations being able
to view and work on the process system
in real time, iPRSM protects the systems
integrity by preventing the duplication of
engineering changes or implementing con-
flicting changes.
When applied to evergreen system
design, iPRSM can integrate equipment,
instruments, piping and pressure-relief
devices across multiple locations to cre-
ate a protected system. Applied to exist-
ing systems, iPRSM creates a centralized
engineering drawing/document repository,
a pressure-relief database that includes as-
operating data from all sites, and a task list
for addressing concerns.
Impact analysis tool supports changes.
iPRSMs Impact Analysis Tool allows
modeling of code or engineering changes
at any stage in the process life cycle, from
design through full operation. When as-
operating data and the planned alteration
to the system configuration are input,
iPRSM identifies the protected system
and the various relief scenarios that could
be affected by that change prior to its
implementation. iPRSM can then vali-
date the adequacy of the safety relief sys-
tem under the new conditions or identify
necessary adjustments.
The Impact Analysis Tool, combined
with iPRSMs other capabilities helps ensure
that process plants effectively meet the
requirements of 29 CFR 1910.119 in a very
cost-effective manner, Kolenc explains.
iPRSM also has the capability of recreat-
ing previous system conditions that were in
effect prior to upgrades or other changes to
equipment, flow or pressures. This feature
simplifies troubleshooting and assists in
documenting the history and sequence of
changes to the process system.
First software to map
the automation genome
PAS, a global supplier of Operations
and Automation Effectiveness software
and services, announces the immediate
release of Integrity automation genome
software. This unique software maps the
automation genome, comprising the data-
bases, programs, displays, and intercon-
nections within and among all automation
systems in a plant, including distributed
control systems, SCADA systems, safety
instrumented systems, data historians,
advanced process controls and instrumen-
tation databases.
By mapping a plants automation
genome, Integrity software creates new
possibilities for fundamentally transform-
ing the productivity and safety perfor-
mance of industrial plants. By identifying
configuration defects and safety vulner-
abilities, costly operational problems can
be resolved quickly or avoided entirely.
Tracking and historization of configu-
ration changes ensures that the value of
automation systems does not deteriorate
over time. Users can access Integritys vast
knowledge base through the graphical
interfaces of their existing DCS and his-
torian workstations.
Integrity Software also serves as a
knowledge retention and collaboration
platform that captures implicit knowl-
edge, contextualizes it, and makes it acces-
sible. This ensures that knowledge from
experienced personnel is made available
to everyone who needs it. Additionally,
as e-mail has become a primary means of
exchanging significant plant information,
Integrity software includes the ability to
tag and incorporate important e-mails in
the knowledge base.
One of the killer applications of the
new Integrity automation genome software
is the Disaster Recovery module that pro-
vides a mechanism for automatic backup
and archiving of system and database files,
documenting restoration procedures, and
creating object-to-file associations.
In the event of a natural or man-made
disaster, it aids in system recovery, restoring
corrupted files, or providing the facility to
roll back to a point in time.
New virtual reality training
solution commercially available
Invensys Operations Management, a
global provider of technology systems, soft-
ware solutions and consulting services to
the process and manufacturing industries,
has announced the commercial availability
of its new EYESim virtual reality immersive
training solution. The first industrial virtual
reality training solution based on first-prin-
ciples simulation and augmented reality,
EYESim technology enables engineers and
operators to see and safely interact with the
plant and the processes they control.
As HP editors, we hear about new products,
patents, software, processes, services, etc.,
that are true industry innovationsa cut
above the typical product offerings. This sec-
tion enables us to highlight these significant
developments. For more information from
these companies, please go to our Website
at www.HydrocarbonProcessing.com/rs and
select the reader service number.
HPINNOVATIONS
Using and applying gaming and other
skill sets most familiar to younger employ-
ees, the EYESim solution also appeals to
employees new to the engineering and
plant workplace, as well as experienced
engineers. It combines virtual reality
technologies with high-fidelity process
and control simulation, computer-based
maintenance and documentation manage-
ment, and other applications to provide a
highly realistic and safe training environ-
ment for improving operating efficiency
and skills. Simulations are driven by the
companys DYNSIM high-fidelity process
simulator, FSIM Plus software, I/A Series
control system emulation and other com-
patible programs.
The increasing complexity of plants,
combined with a changing workforce,
demands next-generation tools that can
safely and interactively train new opera-
tors and engineers without putting them,
the community or the environment at
risk, said Tobias Scheele, vice president,
advanced applications, Invensys Opera-
tions Management. This system provides
a stable, realistic environment for practicing
routine operational and maintenance func-
tions, as well as rarely performed volatile
tasks such as plant shutdowns. In addition,
using computer models of real equipment
allows endless experimentation without
ever taking the equipment offline, mitigat-
ing risk to production as well.
By merging virtual plant imagery with
screens from asset management or other
application software, the Invensys solution
creates a computer-generated representa-
tion of either a real or proposed process
plant. Using a stereoscopic headset, trainees
enter a completely immersive environment
in which they can move throughout the
plant. Such freedom is possible because
the virtual environment is rendered at 60
frames per second, significantly faster than
what can be achieved by traditional, non-
real-time rendering.
EYESim technology is geared toward
the energy, chemical, oil and gas, and other
vital process industries as they face knowl-
edge management, training and retention
challenges brought on by an aging and
dwindling industry workforce.
New capability
improves performance
Emerson Process Management has inte-
grated machinery protection and predic-
tion of critical mechanical equipment with
its DeltaV digital automation system. This
new capability directly supports users goals
for improved availability and performance.
As turbomachinery and mechanical equip-
ment condition deteriorates, performance
and throughput decrease and unplanned
shutdowns become more probable. When
plant operators have visibility to the per-
formance of their high-stakes assets, they
can make process adjustments and reduce
process disruptions.
In traditional control systems, integra-
tion is complex and expensive, requiring
Modbus and system expertise as well as
specific machinery knowledge. Typical
machinery protection systems can require
more than 2,000 steps and up to five days
to complete the integration process. With
this many steps, network issues, additional
testing time and nuisance alarms are easily
introduced. The barriers to undertaking
integration are prohibitive, even though
Why can we say this
already at the beginning
of the year?
2010 was a very
w
w
w
.
h
o
e
r
b
i
g
e
r
.
c
o
m
HPINNOVATIONS
the payback from better information for
operators is significant.
Emersons integrated machinery pro-
tection and prediction solution, a key
component of the PlantWeb digital plant
architecture, easily connects to the Del-
taV system in three simple steps that take
less than 10 minutes. Asset parameters are
scanned, selected and imported into the
DeltaV system from AMS Suite predictive
maintenance software and the CSI 6500
Machinery Health Monitor. After import,
the DeltaV alarm banner is automatically
populated and the system is fully config-
ured with function blocks that can be fur-
ther used in control strategies.
Integration in the operator interface also
includes templates for vibration bar graphs,
vibration values and auto highlighters to
enable any DeltaV operator graphic to
come alive with valuable operator machin-
ery health information.
The benefits of combining process
information and machinery health have
long been understood, but this is the first
time the two have been integrated automat-
ically and so extensively for engineering,
operations and reliability personnel, said
Craig Llewellyn, president of Emersons
Asset Optimization division.
Emerson also provides PlantWeb Ser-
vices to help users design, install, and
implement machinery protection and
prediction. With these new capabilities,
the DeltaV system provides an integrated
solution for process control, process safety,
machinery protection and prediction.
Asset management expertise
creates valuable new capabilities
Emerson Process Management and
Meridium announced a unique partner-
ship to deliver enhanced asset management
capabilities to their customers in the pro-
cess industries. By combining the power of
Emersons PlantWeb predictive intelligence
with Meridiums advanced analytics and
decision support technology, customers can
now more effectively manage and maintain
their most critical production assets.
Emerson and Meridium have been work-
ing together for several months to develop the
new AMS Suite: Asset Portal v4.0 powered by
Meridium. The new product provides inte-
gration in realtime to other AMS Suite appli-
cations to link asset diagnostics with business
metrics and key performance indicators. Built
upon Meridiums Asset Performance Man-
agement Framework, the AMS Asset Portal
v4.0 includes pre-defined analysis, views and
reports of AMS Suite information. Power-
ful query, reporting, and graphing capabili-
ties enable users to perform custom analysis.
Select Meridium application modules are
also available for use with AMS Asset Portal.
These options provide advanced metrics and
scorecards, data management collected using
handheld devices, and integration with com-
puterized maintenance management systems
such as SAP PM and IBM MAXIMO.
Also announced was Emersons PlantWeb
Services offering to cost-effectively design,
implement and quantify the business benefits
of asset strategies for users. Meridiums best-
practice deployment models are available as
part of the PlantWeb Services offering. The
solution extends to mechanical equipment,
instruments, control valves, electrical switch-
gear, process equipment and fixed assets.
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HPIN CONSTRUCTION

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23
South America
BG Group has a joint venture agree-
ment with Petroleo Brasileiro SA focused
on developing floating liquefied natural gas
(FLNG) as an additional option to commer-
cialize the associated natural gas reserves in
the Santos Basin offshore Brazil. Under the
agreement, FEED contracts will be awarded
for a new FLNG vessel. The vessel will oper-
ate close to the planned Santos Basin floating
production, storage and off-loading (FPSO)
vessels. The vessel will process and liquefy the
associated natural gas from the pre-salt fields
before offloading to LNG ships.
The FLNG processing capacity is antici-
pated to be up to 14 million cubic meters
per day of associated gas. The 3 million tpy
of LNG produced would be shipped either
to Petrobras-operated regasification termi-
nals at Pecm and Guanabara Bay to supply
the Brazilian domestic market or exported
to other global markets.
CB&I has a contract valued in excess
of $1.4 billion with Refinera de Carta-
gena SA (REFICAR) for the engineering,
procurement services and construction of
a new refinery with processing capacity
of 165,000 bpd, adjacent to REFICARs
refinery in Cartagena, Colombia. CB&Is
scope also includes revamping the existing
80,000-bpd refinery. The overall project
aims to relieve regional refining constraints
and enable REFICAR to produce ultra-low-
sulfur gasoline and diesel from heavy crude.
CB&I will provide project management
and the engineering, procurement services,
fabrication and construction for the new
refinery, including the following major
components: crude and vacuum distillation;
fluid catalytic cracker naphtha hydrotreater;
diesel hydrotreater; hydrocracker; hydro-
gen plant; sulfur plant; delayed coker; and
power generation. The project is scheduled
for completion in 2012.
Europe
ABB has an order worth $26 million
from Hellenic Petroleum SA to provide an
integrated power and automation system for
the upgrade of Hellenic Petroleums Elefsina
refinery, west of Athens, Greece. ABB will
design, supply, install and commission the
electrical and automation system to power the
refinery. The turnkey electrical solution aims
to strengthen the reliability and quality of
power supply to the refinery, while improving
energy efficiency and reducing overall elec-
tricity consumption and costs. The project is
expected to be completed by 2010.
ABB will supply medium-voltage equip-
ment including the latest gas-insulated
switchgear and air-insulated switchgear.
ABB will also install intelligent low-volt-
age switchgear as well as a fully automated
power management and load shedding sys-
tem based on the companys automation
platform and compatible communication
networks. Integrating the electrical and
automation system on ABBs common plat-
form provides additional benefits includ-
ing reduced maintenance, engineering and
overall life-cycle costs.
The Shaw Group Inc. has a contract
with Petkim Petrochemical Holding AS
to provide engineering and procurement
services and additional study work for an
ethylene plant capacity expansion in Aliaga,
Turkey. Shaw built the original 300-ktpy
plant in 1986 and performed basic engi-
neering for the previous capacity revamp
to 520 ktpy in 1999. The new expansion
will increase ethylene production capacity
by approximately 10%.
Middle East
Samsung Engineering has a $2.73 bil-
lion contract from Abu Dhabi Oil Refin-
ing Co. for utilities and offsite work on the
Ruwais refinery expansion project (RRE).
Samsungs work is set for mechanical com-
pletion by April 2013 and is expected to
supply utilities into the complex to help
produce an additional 400,000 barrels of
oil. Samsung Engineering will perform engi-
neering, procurement and construction on
a lump-sum turnkey basis. The investment
for the RRE project exceeds $10 billion, and
is to be executed mainly by Korean contrac-
tors, including SK E&C and GS E&C.
Technip has a lump-sum turnkey EPC
contract from Abu Dhabi Gas Industries
Ltd. (GASCO) worth approximately $415
million for a project to revamp existing facil-
ities to support an increase in oil production
from the new Abu Dhabi Co. for Onshore
Oil Operations facilities and accommodate
up to 150 million scfd of additional associ-
ated gas from the existing Asab, Shah and
Sahil oil fields. Technip is responsible for
the installation of a new booster compres-
sion station, transfer lines, debottlenecking
of existing ASAB 0 facilities and diverting
feed flow from ASAB 0 to ASAB I/II by
installing a new compressor, transfer lines
and other associated facilities. This project
will be executed by Technips operating cen-
ter in Abu Dhabi, United Arab Emirates.
The first phase will be completed during
third quarter 2012 and the remaining phase
during second quarter 2013.
Asia-Pacific
Shell Chemicals Ltd. recently had a
successful startup of its new monoethylene
glycol (MEG) unit at the Shell Eastern Pet-
rochemicals complex in Jurong Island, Sin-
gapore. The capacity is 750,000 tpy of MEG.
The complex also includes a new 800,000-
tpy ethylene cracker, a butadiene plant and
modifications to Shells Bukom refinery,
which are planned to start up in early 2010.
TREND ANALYSIS FORECASTING
Hydrocarbon Processing maintains an
extensive database of historical HPI proj-
ect information. Current project activity
is published three times a year in the HPI
Construction Boxscore. When a project
is completed, it is removed from current
listings and retained in a database. The
database is a 35-year compilation of proj-
ects by type, operating company, licen-
sor, engineering/constructor, location, etc.
Many companies use the historical data for
trending or sales forecasting.
The historical information is available in
comma-delimited or Excel
and can be cus-

tom sorted to suit your needs. The cost of
the sort depends on the size and complex-
ity of the sort you request and whether a
customized program must be written. You
can focus on a narrow request such as the
history of a particular type of project or
you can obtain the entire 35-year Boxscore
database, or portions thereof.
Simply send a clear description of the data
you need and you will receive a prompt
cost quotation. Contact:
Lee Nichols
P. O. Box 2608
Houston, Texas, 77252-2608
Fax: 713-525-4626
e-mail: Lee.Nichols@gulfpub.com.
INDUSTRY FORECAST FORUM
24
In early December, Hydrocarbon Process-
ings editors and a panel of experts convened
a forum to discuss the outlook for the HPI
into 2010 and beyond. The forum took
place at the Omni Hotel in Houston, Texas,
and was thick with audience participation,
nuanced positions and well-researched pre-
dictions. One of the featured presentations
was by Bill Sanderson, president and CEO
of Purvin & Gertz. He said that he expects
global economic growth to resume, with
his outlook for US GDP growth to increase
2.5% to 3% in 2010. Challenges to this
prediction, he said, would be the strength
of the dollar and inflation.
We dont expect to be back to where we
were in 2007 until 2011, Mr. Sanderson
said. Weve lost several years of growth and
it had a significant effect on capacity utili-
zation. Looking forward, we see continued
growth in diesel gas oil demand combined
with flat petroleum gasoline demand.
Demand for bottom of the barrel prod-
ucts like residual fuel has been declining for
a long time globally because of displacement
by natural gas and efficiency improvements.
However, Mr. Sanderson noted that bun-
ker fuel for long distance marine travel has
increased due to the growth of the global
economy which propels the need to ship
goods around the world. With that in mind,
he said that global bunker fuel growth will
offset the decline in residual fuel.
Prices and margins. Mr. Sanderson
stressed an analysis of the feedstock slate
to determine future prices and margins. An
important part of profitability is the conver-
sion part of the refinery that converts resids
from heavy products to light products.
Weve got ourselves into a situation
where the difference between light and
heavy products is quite narrow. The reverse
will happen when we have to increase pro-
duction. That incremental production
increase will be the heavier grades of crude
oil, Mr. Sanderson said.
Rounding out his remarks, Mr. Sanderson
reiterated that recovery starts in 2010, with
Asia leading the way. He also said to expect
increased production from OPEC and refin-
ery closures in US and Europe. The specter
of closure looms large especially for weaker
facilities. In short, margins will recover for
refiners but 2010 will be a tough year.
Other featured speakers at the forum
included Kimberly Bowers of Valero,
Michaela Greenan of Ernst & Young and
Pierre Latour of Clifftent, Inc. Hydrocarbon
Processings editors also revealed research
from the HPI 2010 Market Data Book (to
order, visit www.gulfpub.com). For more
in depth profiles of each speakers remarks
and pictures from the event, please visit
our blog at www.hydrocarbonprocessing.
com/hpinformer. HP
Bill Sanderson of Purvin & Gertz was
a featured speaker at Gulf Publishing
Companys Industry Forecast Forum.
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LETTERS TO THE EDITOR

I

25
Advocating the abandonment
of MPC
Regarding Zak Friedmans three HPIn
Control columns on APC designs for
minimum maintenance in the June (p. 90),
July (p. 13) and August (p. 13) 2009 issues
of Hydrocarbon Processing, I fully agree with
Mr. Friedmans suggestions to prune multi-
variable controller (MPC) matrices in order
to mitigate maintenance and operations
difficulties. In many cases, I would go a
step further and consider abandoning the
MPC altogether in favor of revisiting what
can be accomplished with well-designed
DCS-level regulatory controls. In a surpris-
ing number of cases, this will result in more
optimal and robust performance, while the
demands of MPC go away altogether.
This may sound like strong medicine to
the MPC generation, but, in my opinion,
the downside of MPC over the past 20 years
has gone greatly under-reported. In recent
years, concerns are finding voice regarding
maintenance and sustainability issues,
but a closer look will often reveal that many
MPC applications have been problematic all
along, not withstanding the great tradition
of successful project completion rituals.
Typical distillation column regulatory
controls are well depicted by Mr. Friedmans
Fig. 1 (July issue), with the addition of a
steam-to-feed ratio control, a high-pressure
safety override and replacement of the top
temperature controller with a pressure-com-
pensated temperature or a more sophisticated
inferential where warranted. This fundamen-
tal configuration is often rearranged to fit the
particular column, but overall it is a good
starting point, and often a finishing point, for
many column control designs. MPC, whether
spartan, as Mr. Friedman recommends, or
fully dandified, as is the industry norm, has
little if anything more to contribute, except
expense and operational complexity.
Utilizing column pressure as an MV is a
good example of something MPC design-
ers habitually do, but which rarely works in
practice. Pressure is not a suitable handle for
composition control. I agree with its viabil-
ity on paper, but in practice Ive never met
a process engineer or operator who agreed
with throttling pressure like a valve for com-
position control. Column pressure is best
kept constant to preserve the composition
profile on which the other controls depend.
At most, pressure can float gradually on the
overhead condenser to capture the benefits
of minimized pressure or gracefully handle
a cooling limitation. Also, pressure should
normally override reboiler heat on high
column pressure, with a setting typically
510 PSIG above the regulatory setpoint
and below any safety function setting. All
of this is inherent in conventionally config-
ured regulatory controls, including smooth
response to saturated reflux or pressure con-
trol valves. No MPC required.
While MPC remains a sound and often
tantalizing technology in principle, its
practical applicability and rate of success
is not nearly what popular wisdom might
have you believe. I would hazard a guess
that only 1020% of all MPCs are earn-
ing money by doing something regulatory
controls cant do better, and that means a
whole lot of unnecessary MPC activity is
going on. The best thing many companies
can do for their process control budget,
especially in these lean times, is to prune
whole MPCs, not individual models, and
to re-allocate the liberated resources to
DCS-level work, an area that has received
altogether too much lip service throughout
the MPC era.
Allan G. Kern, P. E.
Authors response
Mr. Kern has a valid point about the
balance between APC complexity, main-
tainability and potential versus real bene-
fits. The quest to simplify APC should also
consider what can be done by advanced
regulatory control. When the applica-
tion dynamics and constraints are simple,
advanced regulatory control can deliver
benefits. It is important to remember, how-
ever, that when an application has mul-
tiple constraints and complex dynamics,
implementing it in the DCS does not make
it simple and maintainable. Simplify the
problem definition first, and then choose
the appropriate application platform.
Y. Zak Friedman
Hydrocarbon Processing welcomes
and encourages feedback from its
readers. Send your comments to:
Hydrocarbon Processing
Attention: Letters to the editor
P.O. Box 2608
Houston, Texas 77046
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HPI CONSTRUCTION BOXSCORE UPDATE
Company Plant Site Project Capacity Est. Cost Status Licensor Engineering Constructor
27
UNITED STATES
California BlueFire Ethanol Lancaster Biorefinery, Ethanol 3.7 MMgpy E 2010 BlueFire Ethanol
Colorado ClearFuels Commerce City Biorefinery 20 tpd 37 E 2010 Rentech
Florida INEOS Bio JV Vero Beach Biorefinery, Ethanol 8 Mgpy 100 F 2011 KBR
Hawaii Ensyn Corp Kapolei Biorefinery None 32 F 2010 UOP|Ensyn Corp
Illinois Haldor Topse Des Plaines Biorefinery 25 tpd 35 P 2011 Haldor Topse|ConocoPhillips Haldor Topse
Louisiana BioEnergy LLC Lake Providence Biorefinery, Ethanol 110 Mgpy 139 U 2011 BioEnergy LLC
Michigan American Process Inc Alpena Bio-ethanol 890 Mgpy 28 F 2011
Mississippi BlueFire Ethanol Fulton Biorefinery, Ethanol 19 MMgpy 311 E 2012
New Mexico Sapphire Energy Columbus Biorefinery 60 bpd 189 E 2012 Sapphire Energy
Oregon ZeaChem Inc Boardman Biorefinery, Ethanol 250 Mgpy 73 E 2010 ZeaChem Inc
Texas Algenol Biofuels Freeport Biorefinery, Ethanol 100 Mgpy 59 F 2011 Dow Chem
LATIN AMERICA
Brazil Petrobras\BG Group Santos LNG Floating (FLNG) 14 MMm3/d S
Colombia Reficar Cartagena Refinery, Heavy Ends RE 85 Mbpd 1400 F
EUROPE
Greece Hellenic Petroleum SA Elefsina Power Supply System RE None 26 E 2010 ABB
ASIA/PACIFIC
China Henan Jinkai Chemical Group Henan Ammonia TO 2000 m-tpd U 2012 ACSA ACSA ACSA
China Yanchang Petroleum Group Shaanxi Cracker, DCC BY 590 kty F 2013 Shaw SEIC
China Xinjiang Yili Coal Chemical Xinjiang Ammonia TO 1000 m-tpd U 2012 ACSA ACSA ACSA
Papua New Guinea InterOil Gulf Province Gas Stripping Unit None S 2012
Papua New Guinea Esso Highlands PNG LNG Kutubu Gas Treating None E 2014 CB&I|Clough
Papua New Guinea InterOil/Petromin/Pacific LNG JV Napa Napa LNG Liquefaction Plant 8 MMtpy 7000 F 2015
Papua New Guinea InterOil/Petromin/Pacific LNG JV Napa Napa Storage Train, LNG (1) 4 MMtpy 7000 F 2015
Papua New Guinea InterOil/Petromin/Pacific LNG JV Napa Napa Storage Train, LNG (2) 4 MMtpy 7000 F 2015
Singapore Linde Gas Singapore Singapore CO2 Liquefaction Plant 100 tpd 30 C 2009 Linde Gas Singapore
MIDDLE EAST
United Arab Emirates GASCO Abu Dhabi Compressor None 415 E 2013 Technip
United Arab Emirates GASCO Abu Dhabi Utilities RE None 415 E 2013 Technip
United Arab Emirates FERTIL Ruwais Ammonia 2 Mtpd 1200 E 2013 Uhde Samsung Eng
United Arab Emirates Abu Dhabi Oil Refining Co (TAKREER) Ruwais Offsites None 2730 E 2013 Samsung Eng
United Arab Emirates FERTIL Ruwais Urea 3.5 Mtpd 1200 E 2013 Uhde Samsung Eng
United Arab Emirates Abu Dhabi Oil Refining Co (TAKREER) Ruwais Utilities None 2730 E 2013 Samsung Eng
Yemen Total Balhaf LNG Liquefaction Plant 6.7 MMtpy 3200 C 2009
See http://www.HydrocarbonProcessing.com/bxsymbols for licensor, engineering and construction companies abbreviations,
along with the complete update of the HPI Construction Boxscore.
OHL Gutermuth Industrial Valves GmbH
Helmershuserstrae 9 D-63674 Altenstadt
Phone +49.60 47. 80 06-0 Fax +49.60 47.80 06-29
www.ohl-gutermuth.de og@ohl-gutermuth.de
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GAS PROCESSING DEVELOPMENTS SPECIALREPORT

I

29
Advanced mercury removal
technologies
New technologies can cost-effectively treat wet and dry natural gas
while protecting cryogenic equipment
N. ECKERSLEY, UOP LLC, A Honeywell Company, Des Plaines, Illinois
M
ercury is present in many of the worlds natural gas fields.
Process plants with brazed aluminum heat exchangers,
including liquefied natural gas (LNG) facilities and
nitrogen-rejection units, are particularly susceptible to corrosive
attack by mercury. More awareness on the part of gas processors is
necessary to assure better protection of their assets and to address
environmental concerns by removing mercury. At present, mer-
cury levels have increased from 30 g/Nm
3
or 40 g/Nm
3
to levels
exceeding 1,000 g/Nm
3
in the Pacific Rim.
PROCESSING SOLUTIONS
In supplying purification solutions to the gas-processing indus-
try, a number of approaches for mercury removal have been devel-
oped. Several process options using both regenerable and non-
regenerable fixed-bed technologies are available. The protection of
aluminum heat exchangers can be accomplished by using a layer
of silver-containing molecular sieve inside the dehydration vessels.
The active silver forms an amalgam with any mercury present,
and its zeolitic substrate adsorbs moisture in the treated gas. This
approach offers flexibility in being regenerable, as the mercury-
containing gas is bypassed around any cryogenic equipment. If
necessary, condensed mercury can be collected, and the mercury-
entrained gas treated with a small non-regenerable guard bed.
Another approach uses non-regenerative metal sulfides to
remove mercury from the raw gas upstream of the dryers and the
amine unit. Utilizing larger vessels, this approach also protects
the brazed-aluminum heat exchanger and ensures less mercury
contamination in and around the process plant.
A comparison of mercury-removal processes will be described
via several case histories that examine regenerative zeolitic and
non-regenerable metal sulfide-based solutions. Plant-specific
drivers for each approach will be discussed as well as the efficacy
for each technology.
Contaminants of concern. Process systems designed to
purify hydrocarbon feed streams are commonly used in the natu-
ral gas (NG) industry and are becoming increasingly impor-
tant. Historically, NG components such as sulfur, carbon dioxide
(CO
2
) and water (H
2
O) have been effectively removed by using
regenerable molecular sieves, non-regenerable fixed-bed absor-
bents, membrane systems and amines.
Mercury is a naturally occurring element found in small but
measurable concentrations in many oil and gas fields. This metal
is most frequently detected in its elemental form and is prevalent
in NG processing and LNG facilities. Due to advances in detec-
tion systems, mercury can now be accurately measured down to
nanogram levels in the case of gases and to parts per billion (ppb)
levels in liquid hydrocarbons.
Metal embrittlement issues. Mercury, when present,
can cause severe and catastrophic corrosion of aluminum heat
exchangers, which are commonly used in gas-plant cryogenic
systems. Deposition of liquid elemental mercury in heat exchang-
ers can compromise their structural integrity. One mechanism is
referred to as liquid-metal embrittlement (LME). LME has been
responsible for a number of failures of aluminum heat exchangers
over the past 40 years. LME can cause crack initiation and propa-
gation within such equipment, particularly in the proximity of a
weld.
1
Several examples of mercury causing equipment failure in
gas processing facilities have been documented in North America,
North Africa and, more recently, in Asia Pacific.
2
Understanding
the effects associated with LME is particularly important as it is
difficult to detect prior to failure.
To avoid potential equipment failure, tight limits have been
placed on allowable mercury levels in NG passing through alu-
minum heat exchangers. The current typical level of mercury
removal commonly required is 10 nanograms/Nm
3
of NG passing
to the cryogenic section of a processing plant. This specification
can be achieved by using two types of mercury-removal technol-
ogy, located immediately upstream of the cryogenic unit:
Regenerable molecular sieve
Non-regenerable absorbent
Molecular sieve plus non-regenerable absorbent.
Mercury removal process options. These options meet
the required mercury specifications and each offers operational
advantages. The molecular sieve option relies on a portion of the
dryer vessel containing a silver impregnated molecular sieve, which
forms an amalgam with mercury. During the heating cycle of the
drying vessel, the mercury is desorbed into a regeneration stream
and bypassed around downstream cryogenic equipment.
Rather than removing mercury at a point immediately upstream
of the cryogenic unit, some operators have opted to purify gas as it
enters the plant. In this case, the heat-exchanger mercury specifica-
tion can be met using a larger, fixed-bed mercury-removal absor-
bent to treat raw gas as it enters the facility.
30

I

JANUARY 2010 HYDROCARBON PROCESSING
A recent variation in using either a silver-impregnated molecu-
lar sieve or a non-regenerable absorbent now combines the two
approaches. Installing a small vessel of non-regenerable absorbent
to treat desorbed mercury from the molecular sieve unit perma-
nently removes any mercury from the sales gas. Recognizing and
understanding the drivers involved in the decision-making process
when selecting the best available technology is the key and often
varies markedly from plant to plant.
Analysis and typical global levels. Table 1 lists the results
from a number of mercury surveys conducted over the years on
a diverse range of product streams found in Asia-Pacific, Europe,
North and South America, Middle East and Africa.
Analyzing the NG feeds. Mercury surveys were conducted
using two different analysis systems:
Cold vapor atomic fluorescence spectroscopy
Atomic absorption spectroscopy with Zeeman correction.
The cold vapor atomic fluorescence spectroscopy is typically
used to measure mercury in gases and the atomic absorption
spectroscopy has been used to measure mercury in both gaseous
and liquid streams. Accurately measuring mercury in the field
presents a complex challenge and requires a significant degree
of analytical understanding, including not only sample analysis
but also sample collection. Metallic sample collection containers
should be avoided when considering liquid samples since mercury
will readily plate out on metal surfaces. Sample line conditioning
is crucial, since mobile mercury will accumulate on the inner wall
pipe-work. The presence of different mercury species and other
chemical interference can also impact the measurements.
Non-regenerable absorbent technology. In addition
to forming amalgams with several metals, mercury is very mobile
and will adsorb onto pipeline surfaces and other equipment com-
monly found in gas processing plants. Mercury can then desorb
back into gas streams, passing through contaminated pipelines,
and prolonged periods can elapse between the installation of an
upstream mercury removal unit (MRU) and the complete purg-
ing of a pipeline.
3
MRUs have been developed to take advantage of the affinity
that the contaminant has with certain surfaces. Both metallic and
carbon-based sorbents have been developed to remove mercury
from a variety of hydrocarbon feeds. Collectively, these systems
can be termed non-regenerable as opposed to regenerable
molecular sieves. Non-regenerable sorbents contain sulfur, pres-
ent as metal sulfide in the case of metallic systems and impreg-
nated sulfur in the case of carbon. Potassium iodide promoted
activated carbon has also been used but is much less common
in NG processing.
Although sulfur-promoted activated carbon MRUs have pre-
vailed in gas processing plants, these units have recently been
superseded by metal-sulfide systems, for several reasons. Sulfur-
promoted carbon is only effective in treating dry gas. The exten-
sive micro-porous nature of activated carbon means that capillary
condensation is a problem when operating at or close to the dew
point of a gas.
4
Sulfur-promoted carbon is also prone to sulfur dissolution
when exposed to wet gas streams. This leaching of sulfur off the
carbon leads to sulfur slip from the MRU, potentially damaging
downstream equipment and reducing useful mercury capacity.
The presence of water in the gas to be treated has been shown
to elongate the reaction zone (mass transfer zone) resulting in
mercury slip over and above the required outlet specification. At
the same time, more gas processors are requesting that mercury
removal takes place either at the well head or close to the front
of the gas plant, where the gas can be wet. The objective is to
prevent mercury migration to various locations within a gas
plant and to avoid any subsequent partitioning into processed
NG and condensate streams.
5
The handling of mercury-contaminated pipe-work, which is
classified as hazardous waste must be considered in the context of
existing occupational health guidelines. Although mercury has a
high boiling point, it also has a relatively high vapor pressure. This
combined with its inherent toxicity means that extreme caution
is required when handling mercury contaminated pipe-work.
The American Conference of Governmental Industrial Hygien-
ists (ACGIH) has assigned mercury vapor a threshold limit value
(TLV) of 0.025 mg/m
3
of air as a time-weighted average (TWA)
for a normal 8-hour workday and a 40-hour workweek.
6
This TLV
has itself halved since 1991, when the previous assigned level was
0.05 mg/m
3
.
When up-front mercury removal is required on raw gas, the
challenge becomes one of how to treat NG that is not necessarily
bone-dry. In cases where a carbon-based MRU is positioned on
raw moist gas, the effective utilization of the carbon is compro-
mised. Co-adsorption of moisture into the micro-porous carbon
substrate proceeds, leading to a decline in mercury removal. The
length of the mass transfer zone of an adsorbent is an indication
of the rate of reaction the adsorbent has with the target contami-
nant. As little as 3 wt% to 4 wt% water adsorbed onto the carbon
MRU extends the mass transfer zone of the adsorbent by 12%.
4

In addition, since sulfur (S) is soluble in liquid hydrocarbons, the
presence of liquid hydrocarbon in natural gas leads to dissolution
of sulfur from the carbon. This loss of active sulfur diminishes
mercury (Hg) removal capacity of the activated carbon, thus
shortening the service life of the bed. The reaction between Hg
and S is stoichiometrically 1:1 according to:
Hg S HgS +
A 100% utilization of active S results in the removal of 1 mole
of mercury for every mole of sulfur. Table 2 looks at the effects
of entrained liquids on mercury adsorption capacity in an NG
application using a sulfur-promoted activated carbon MRU.
The achieved lifetime of the carbon MRU was half that of the
estimated lifetime quoted by the supplier.
The degree of liquid adsorbed onto carbon during the life
of the MRU is shown in terms of total wt% volatiles (200C).
Layer 1 represents carbon recovered from the inlet portion of the
bed and layers 2, 3 and 4 represent subsequent layers. Clearly,
TABLE 1. Reported elemental mercury levels detected
in natural gas
Region Mercury concentration / g/Nm
3
North Africa 1100
North America 120
South America 1105
Southeast Asia 102,000
Middle East 110
Europe 150
Source and survey from UOP
32

I

the carbon has co-adsorbed a significant quantity of liquid
(20%30%) from the raw NG causing its shortened service
life. This is not surprising since activated carbon has long been
used in hydrocarbon dew point control because it has a high
affinity with C
4
+ in NG.
The total wt% of active sulfur was measured on each layer of
discharged carbon. While sulfur levels on newly installed activated
carbon are typically 10 wt% to 18 wt%, the levels on spent mate-
rials were measured at 6 wt% to 9 wt%. To measure the mercury
removal efficiency of supplied carbon, the percentage of utilized
sulfur was also measured on a molar basis. The percentage of
sulfur utilized in the equilibrium section of the vessel (layers 1,
2 and 3) was measured at approximately 4 wt%. By comparison,
on a dry NG without the attendant issues of liquid entrainment,
this percentage utilization would be expected to be >10 wt%. The
data confirms that sulfided carbon is prone to sulfur dissolution
and micro-pore blocking when treating wet gas.
Apart from the basic requirement to ensure that adequate
mercury removal can be achieved on gases at or close to their dew
points, from the point of capital expenditure, it is important to
ensure that MRU reactor volumes are minimized where possible.
This is particularly important when positioning an MRU offshore
where spatial constraints are critical. The contact times required
by sulfided-carbon products often lead to a larger than practical
MRU footprint. The drive to reduce capital budgets and avoid
large volumes of spent material has led to gas processors examin-
ing technologies other than sulfided carbon.
After carbon is discharged from an MRU, it is usually sent to
a specialized plant where mercury is reclaimed via vacuum distil-
lation. There is no useful purpose for the remaining carbon and
it undergoes high-temperature incineration.
A better solution. A range of non-regenerable absorbents
has been developed to improve on existing
MRU technologies. Gas streams contain-
ing thousands of micrograms of mercury
can be successfully treated using advanced
new absorbents. Instead of carbon, transition
metal oxides and sulfides are utilized. The
active component of the advanced absor-
bents is a metallic sulfide, and the products
are supplied either in their oxide form and
are sulfided in-situ by the gas to be treated or
are supplied pre-sulfided.
After their useful life, the discharged absorbents can have
the mercury removed via vacuum distillation and sold into
specialist applications for re-use. Since the remaining active
metal is compatible with metal recycling programs, it is sent
for recovery via a smelting process and then sold back onto
the open market. This process ensures that the MRU product
is handled in an environmentally friendly way.
7
The absor-
bents have been developed to treat wet and dry gases, without
the same wet-gas limitations of other non-regenerable products.
Fig. 1 shows a commonly suggested flow-scheme location for the
advanced absorbent. This process product range is successfully
treating liquid hydrocarbon streams in addition to gaseous fluids.
Sulfur is anchored to the metallic substrate, preventing subsequent
dissolution and slippage onto downstream equipment.
Hg removal via regenerable molecular sieves. Remov-
ing mercury using molecular sieve technology represents a novel
and well-established approach in protecting cryogenic equip-
ment. Using two different types of molecular sieve within the
dehydration section of a gas plant, it is possible to ensure that the
NG is dry and mercury-free prior to entering the cryogenic unit.
Since the configuration and operating procedure of the dryers is
unaffected by installing this two sieve system, ease of operation is
assured. The silver-promoted molecular sieve, designed to remove
mercury in addition to water, is capable of passing through thou-
sands of regeneration cycles over the course of a long service life.
Contaminant removal proceeds via temperature swing adsorption,
with mercury forming a silver amalgam across the molecular sieve
structure and then desorbing when hot gas is passed through the
dehydration vessel. The mercury-containing regeneration gas is
safely bypassed around the cryogenic unit.
Removing mercury using silver-promoted molecular sieve in
existing dehydration vessels ensures that capital expenditure is
TABLE 2. Impact of liquids on mercury removal using activated carbon in
the gas phase
Total Total S, Total Hg,
Bed volatiles, wt% wt% Hg/S Hg/S Sulfur
position (200C) wt% (dry basis) (dry basis) weight basis molar basis utilization %
Layer 1 21.1 7.02 1.89 0.27 0.0429 4.29
Layer 2 21.0 6.57 1.71 0.26 0.0414 4.14
Layer 3 26.8 8.32 2.12 0.25 0.0406 4.06
Layer 4 24.4 7.97 0.29 0.04 0.0057 0.57
Raw
natural gas
CO
2
removal
Dryers
Feed-gas
separator
Non-regenerable
absorbent
Molecular
sieves
A flow scheme for treating wet gas up-stream of process
equipment using advanced absorbents.
FIG. 1
Raw
natural gas
CO
2
removal
Dryers
Feed-gas
separator
Molecular
sieves
Advanced
adsorbent
A flow scheme for removal of mercury using regenerable
silver-promoted molecular sieves.
FIG. 2
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34

I

reduced to a minimum without the need for an additional MRU.
Due to smaller quantities of the silver-promoted molecular sieve
adsorbent required, plants adopting this technology can load and
re-load the adsorbent quickly without any associated increase in
system pressure drop. Fig. 2 represents a typical flow scheme for
the silver-promoted molecular sieve adsorbents. Spent and prop-
erly regenerated adsorbent is mercury-free upon reactor discharge
and since it passes the EPA Toxicity Characteristic Leaching Pro-
cedure (TCLP) test, it is classified as non-hazardous waste for
disposal purposes.
8
To ensure the removal of mercury from sales gas and to protect
plant cryogenic equipment, some gas plant operators have taken
mercury removal with silver-promoted molecular sieves one step
further. By installing a vessel of advanced non-regenerable mer-
cury absorbent on the regeneration stream from the molecular
sieve drying unit, mercury is effectively removed and captured.
Fig. 3 represents a combined approach toward mercury removal
using both advanced molecular sieve and absorbent technologies.
Since the regeneration gas stream has a low flowrate (typically
10% of the inlet gas), the volume of the vessel containing the
non-regenerable absorbent is small. This results in a cost-effective
way of removing mercury, without the high capital expenditure
associated with installing a larger absorbent vessel upstream.
Clearly, there are several ways to remove mercury from NG
processing plants. Capital expenditure limitations, equipment
protection requirements and environmental factors must all be
considered. Both non-regenerable absorbents and molecular sieve
technology can be used to handle a very broad range of mercury
levels and process scenarios.
CASE STUDIES
These case studies illustrate factors involved when selecting
a mercury-removal system that is most applicable for a given
processing situation:
Case 1: PTT Thailand. The PTT GSP-5 gas plant located at
Map Ta Phut, Rayong, Thailand, was commissioned and started
up in 2004. The onshore facility processes raw gas via a pipeline
from offshore gas fields in the Gulf of Thailand. The raw gas
entering GSP-5 is conditioned to remove CO
2
, H
2
O and Hg, and
the total gas flow treated is 530 MMscfd. The MRU is designed to
protect a natural gas liquids (NGLs) recovery plant, incorporating
a cryogenic unit that includes a brazed aluminum heat exchanger.
The initial charge of mercury-removal adsorbent used from plant
startup was sulfur impregnated activated carbon.
The gas plant MRU configuration consists of two parallel
reactors, each designed to process 265 MMscfd of gas. The MRU
is located upstream of the amine plant and the dryers, and is
positioned to treat raw gas as it enters the facility. Historically, the
gas entering the MRU contained some liquid hydrocarbon with
a triethylene glycol carry-over component. The initial charge of
activated carbon experienced a premature mercury breakthrough
after two years in service. Table 3 provides a summary of the MRU
process conditions. After the activated carbon was discharged
from the reactors, the MRU was refilled with the non-regenerable
advanced absorbent. Fig. 4 shows the new installation with the
parallel flow reactors at GSP-5.
Since the change-over was commissioned, the plant has con-
tinuously recorded effluent mercury levels below the required
specification and maintained the start-of-run pressure drop, which
was a priority for the customer. This successful performance has
been achieved despite treating a liquid-entrained, water-saturated
natural gas. Fig. 5 details the actual mercury influent and effluent
levels at the GSP-5 facility in the first year following the startup of
the new MRU. Despite fluctuating mercury inlet levels, the new
absorbent continues to meet desired effluent specifications.
Case 2: Gasco Abu Dhabi. The original Adnoc (now
Gasco) Habshan gas plant, located in Abu Dhabi, was built in
1983 to process Thamama gas from the nearby Bab and Asab
fields. Following the completion of two major development
projects (OGD-1 in 1996 and OGD-II in 2001), the plant now
TABLE 3. PTT GSP-5 MRU process conditions
Gas treated Natural gas
Gas flowrate, MMscfd 265
Operating pressure, Kg/cm
2
48
Operating temperature, C 18
Hg influent range, g/Nm
3
50200
Hg effluent specification, g/Nm
3
< 0.01
Parallel fixed-bed reactors using advanced absorbents at
the PTT GSP-5 gas plant, Map Ta Phut, Rayong, Thailand.
FIG. 4
Raw
natural gas
CO
2
removal
Dryers
Feed-gas
separator
Molecular
sieves
Advanced
adsorbent
Non-regenerable
absorbent
A flow scheme for the combined removal of mercury
utilizing both regenerable molecular sieves and non-
regenerable absorbents.
FIG. 3

I

35
includes eight gas processing trains with the capacity to process
3.5 Bscfd of non-associated and associated gas. In addition to
network gas, the Habshan facility produces NGLs, condensate
and liquid sulfur.
The OGD-1 expansion raised output at Habshan from 450
MMscfd to 1,865 MMscfd. Three new trains were developed:
two 350-MMscfd trains for the treatment of non-associated and
associated gas (T1 and T2) and one 625-MMscfd train for the
treatment of non-associated gas (T3). In addition, condensate
recovery was raised from 5,000 bpd to 131,000 bpd. Raw gas
entering OGD-1 is currently conditioned to remove CO
2
, hydro-
gen sulfide (H
2
S), H
2
O and Hg.
From plant startup in 1996, the OGD-1 gas processing trains
have used molecular sieve adsorbents. In 1998 following a study
effort together with Gasco, a layer of silver-promoted molecular
sieve adsorbent was incorporated into each drying vessel as a retro-
fit solution to ensure that the gas passing to downstream cryogenic
equipment was mercury free. The combination of dehydration-
grade molecular sieves and advanced silver-promoted molecular
sieve adsorbent products has demonstrated excellent operating
performance in each of the three OGD-1 trains. Each train has
successfully used silver-promoted molecular sieve adsorbent in up
to six-year lifetime cycles, to reduce a design inlet mercury level
of 200 ng/Nm
3
250 ng/Nm
3
down to a cold box specification
of < 10 ng/Nm
3
.
Case 3: Enterprise US. The Enterprise Meeker I gas plant,
located in Colorados Piceance Basin, started up in 2007 with
an initial gas processing capacity of 750 MMscfd, incorporating
35,000 bpd of NGLs. A Phase II expansion in the form of sister
plant, Meeker II, started up in 2008 and doubled processing to
1.5 Bscfd of gas and 70,000 bpd of produced NGLs.
Both Meeker I and Meeker II condition raw gas to remove
CO
2
using amines and remove water and mercury using molecu-
lar sieve technology. Dehydration-grade molecular sieves and
silver-promoted molecular sieves are uitilized in the drying vessels
to remove water and mercury from the raw gas prior to the treated
gas passing to the cryogenic system. In addition, an advanced
absorbent is used to remove mercury from the molecular-sieve
regeneration stream. The molecular sieve dryers are configured
such that two vessels are in adsorption mode and one vessel is in
regeneration mode at any given time. Each molecular sieve vessel
processes 375 MMscfd of feed gas. Table 4 provides a summary
of the mercury removal process conditions for the combination
system at Enterprise Meeker I and II.
Summary. If mercury is allowed to reside in an NG plant un-
checked, it can cause severe damage to process equipment and
potentially compromise the health and safety of plant operators.
Two distinctive technologies have been developed to remove mer-
cury from various locations within a gas plant. Each technology
affords maximum mercury removal and protection and includes
within it a number of non-regenerable and regenerable fixed-bed
solutions. The well-established silver-impregnated molecular-sieve
technology ensures that the cryogenic component of a gas plant is
protected against potential mercury ingress. Applying such systems
can provide cost-effective (lower capital cost) options with longer
service life. The latest non-regenerable products offer the option
to remove mercury from raw gas as it enters the plant. Alterna-
tively, desorbed mercury can be removed from the molecular sieve
regeneration gas using a small cost-effective fixed bed. HP
ACKNOWLEDGMENT
The author acknowledges the cooperation of PTT, Gasco and Enterprise in
the writing of this article.
LITERATURE CITED

1
Willhelm, M. S., Risk analysis for Operation of Aluminium Heat Exchangers
Contaminated by Mercury, Annual AICHE Conference, April 2008, New
Orleans.

2
Lund, D.L., Causes and remedies for mercury exposure to aluminum cold-
boxes, 75th Annual GPA Convention, March 1113, 1996, Denver.

3
AIChE Paper Jointly authored by UOP and Equistar, Mercury removal from
cracked gas a liquid streams, Ethylene producers conference, April 2004.

4
Biscan, D. A., R. S. Gebhard, T. M., Matviya, Impact of process condi-
tions on mercury removal from natural gas using activated carbon, 8th
International Conference on Liquefied Natural Gas, 1986.

5
Edmonds, B., R. A. S. Moorwood and R. Szcepanski, Mercury partioning
In natural gases and condensates,GPA European Chapter Meeting, London,
March 1996.

6
2009 TLVs and BEIs ACGIH.

7
Private correspondence with Begemann Milieutechniek B.V. Mercury waste
reclaimers.

8
Corvini, Stiltner, Clark, Mercury removal from natural gas and liquid
streams.
TABLE 4. Enterprise Meeker I and II
Gas treated Natural gas
Gas flowrate to mol sieve vessels, MMscfd 750
Absorbent operating temperature, C 3040
Absorbent operating pressure, kg/cm
2
70
Raw gas Hg concentration to HgSIV 1, ng/Nm
3
Up to 800
Regeneration gas Hg concentration to absorbent, ng/Nm
3
Up to 2,000
Effluent Hg concentration from absorbent, ng/Nm
3
< 10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
0 1 2 3 4 5 6 7 8 9 1 01 11 2
Months online
M
e
r
c
u
r
y

c
o
n
c
e
n
t
r
a
t
i
o
n
,

g
/
N
m
3
MRU inlet
MRU outlet
Mercury influent and effluent levels at the PTT GSP-5 gas
plant with the new advanced absorbent system.
FIG. 5
Neil Eckersley is the UOP business manager for Aluminas and Specialties respon-
sible for its complete portfolio of alumina-based solutions including mercury and
sulfur removal products. He graduated from Sheffield Hallam University in the United
Kingdom with a BS degree in chemistry and has worked in the areas of Research,
Technical Service, Sales and Product Management.
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I

37
A unique natural gas processing
success story
Cost-effective expansion created high reliability operations
C. BAKER, Anadarko Pinnacle Gas Treating, Inc., East Central Texas;
T. BARNETTE, Merichem Chemicals and Refinery Services LLC, Schaumburg, Illinois
F
or the past decade Anadarko Petroleum has been operating two
liquid redox processing H
2
S removal systems. They managed
to maintain extremely high removal efficiencies along with
keeping the highest online time record in the area. For this reason,
Pinnacle Gas Treating is bringing on more natural gas wells in the
area and needs to expand the H
2
S removal capacity of their facility.
The ultimate goal of their expansion will require the removal of up
to 40 long tons per day (LTPD) of sulfur from the amine acid gas,
while maintaining their high turndown capacity that has consistently
given them their reputation for reliability. A modular approach
of adding multiple expansion gas processing systems in stages, as
needed, met their requirements in the most cost-effective way.
Background. In 1996, Western Gas Resources selected a liquid
redox process to treat the amine acid gas generated in their new
Pinnacle Gas processing plant located in Tennessee Colony, Texas.
Initially, Western Gas purchased a 2-LTPD liquid redox-based sul-
fur recovery unit (SRU), that started up in June 1997. However,
shortly into designing the first unit, it became apparent that the
units sulfur capacity would be exceeded. Consequently, Western
Gas purchased a 7-LTPD unit and it started up in November
1997. In 2001, the facility was purchased by Anadarko Petroleum,
which currently operates the facility.
The 7-LTPD SRU was originally designed to treat amine acid
gas at the processing conditions itemized in Table 1. As indicated,
the SRU was designed to remove 99.99+% of the H
2
S under
severe turndown conditions of 155:1 for the gas flow and 45:1
for the H
2
S concentration.
Additionally, while the unit was designed to handle a wide
range of flow and H
2
S concentrations totaling the design to 7
LTPD of sulfur, it would also be required to maintain operation
with a sulfur load turndown that could go from nearly nothing
(100 lb/day) up to the design capacity within a short time.
Because the increase in the sulfur removal requirement at the
gas plant was expected to continue to rise, and plans were begun
to add a 40-LTPD Claus plant to the SRU capacity at the facil-
ity. The goal was to use the liquid redox process up to 7 LTPD
removal and then use the Claus system above that, with the liquid
redox process acting as the tail-gas treater to achieve the high
removal efficiency required. Since flexibility was key, the operating
plan for the facility is illustrated in Table 2.
Let the expansion begin. From 1997 until 2000, the gas
processing systems were operated exclusively for H
2
S removal. In
2000, the Claus system was completed, consisting of:
Acid gas enrichment (AGE) to concentrate the 23% H
2
S
amine acid gas to 25% for minimum Claus feed concentration
40-LTPD Claus SRU
Tail-gas hydrotreatment to convert all sulfur species to
H
2
S
Cooling
Tail-gas feed to the existing 7-LTPD liquid redox process
unit as a tail-gas treater.
As this system was operated, several operational difficulties
were experienced, specifically with the hydrotreater system and
the Claus plant. The Claus plant operational difficulties were
related to the previously mentioned load swings, which the Claus
could not tolerate. After a year of difficult operation, Anadarko
decided to stop operation of the AGE/Claus/hydrotreater train
and to begin using the liquid redox processing systems exclusively
for the SRU. This was a problem, as it severely limited the com-
panys ability to further expand processing natural gas, as it was
now limited to a 7-LTPD sulfur throughput.
And stop. From 2001 to 2005, operation focused on optimiz-
ing the existing liquid redox processing operations and mainte-
nance to maximize online time and capacity. In 2005, however,
Anadarko began discussions with area gas producers, which would
potentially push the SRU requirements at Pinnacle beyond the
TABLE 1. Processing conditions for treating amine gas
Case 1 Case 2
Type of gas Amine acid gas Amine acid gas
Flowrate, MMscfd dry 9.3 0.06
% H
2
S in acid gas 2.0 90.0
Removal efficiency 99.99+% 99.99+%
Outlet H
2
S, lb/hr < 2 < 2
LTPD sulfur 7 7
TABLE 2. Operating plan for the facility
Sulfur load Operation
< 2 LTPD 2 LTPD liquid redox processing unit
2-LTPD 7-LTPD 7 LTPD liquid redox processing unit
> 7 LTPD Claus plant, with AGE/ hydrolysis/gas processing TGU
38

I

capacity of the existing liquid redox processing units. Over the
next year, expansion requirements expanded from 10 LTPD, to
15 LTPD, finally settling on 40-LTPD of total SRU capacity.
Several options were considered and dropped as the total sulfur
load increased, including, shortly, revamping and restarting the
Claus system (which was made unfeasible as the AGE unit had
been dismantled and moved). In 2007, two options remained:
Adding additional liquid redox gas processing system(s)
Direct oxidation with existing liquid redox process modified
and run as TGCU tail-gas clean-up unit (TGCU)
A lean feed acid gas process was initially considered for the DO
portion, as the sour acid gas would still normally have low H
2
S
concentrations (24 vol%). Further investigation of potential oper-
ating conditions showed that H
2
S levels could attain 8% for long
periods and periodically see levels as high as 16%. The lean acid
gas process could not tolerate these excursions and was pulled from
consideration. Pinnacles excellent operating experience and online
time with the liquid redox processing system and ease at which
the unit was operated with the highly variable sulfur load made
them very receptive to adding modular trains of larger liquid redox
processing systems. These systems are operating parallel to their
existing 7-LTPD unit, which is how the system is proceeding.
With a total sulfur capacity of 40-LTPD still planned, of which
the 7-LTPD would be considered part, 3 x 11 LTPD expan-
sion trains were planned, with the first 11-LTPD system ordered
in September 2007. This expansion will meet the plants needs
through new producers being brought online in June 2008, with
the liquid redox processing expansion planned to be operational
by that time. Future addition of gas producers tied to the Pinnacle
plant will require additional acid gas treatment capacity, with a
second 11-LTPD liquid redox processing expansion plant planned
for the future.
The liquid redox process. A single train flow, diagramming
the liquid redox process, is illustrated in Fig. 1.
The acid gas from the amine unit is passed through a knock-
out pot to remove any condensable liquids and/or amine car-
ryover. The acid gas then enters the proprietary autocirculation
liquid redox processing unit. In the autocirculation liquid redox
unit, the sour gas is sparged through a proprietary solution of
diluted chelated iron within the vessels absorber sections. Within
the absorbers, H
2
S is absorbed (reaction A) and converted to
elemental sulfur (reaction B) as follows:

H
2
S (gas) +H
2
OH
+
+HS
+H
2
O (A)
HS
+2Fe
+++
H
+
+SO+2Fe
++
(B)
The reduced iron solution then flows into the vessels oxidizer
sections where air is sparged through the solution to reoxidize
the chelated iron back to the ferric state (Fe
+++
) in accordance to
reaction C.

1
2
O
2
+H
2
O+2Fe
++
2OH
+2Fe
+++
(C)
Through a unique arrangement of weirs and baffles within
the proprietary autocirculation vessel, liquid circulation between
the absorber and oxidizer sections is maintained through a series
of airlifts, thus circulation pumps are not required. The air and
the sweetened acid gas streams are combined in the headspace of
the autocirculation vessel and directed to either an incinerator or
directly to the atmosphere.
The solid elemental sulfur, which is formed in the process, is
removed by directing a slipstream of solution to a settler vessel
where the slurry concentration is increased to approximately
10 wt%. The slurry is then pumped to a vacuum belt filter where
the sulfur is dewatered into a 60% dry cake.
Conclusion. Anadarkos decision to continue to employ the
liquid redox process as its primary sulfur recovery unit proved to
be not only an economical approach, but also a technical success,
even at sulfur loads that normally would be associated with a
Claus system. The liquid redox processing unit allowed them to
achieve removal efficiencies of greater than 99.9% while achieving
nearly 100% turndown. This wasnt only on their sulfur recovery,
but also on their gas flow, achieving > 99% online availability,
making their facility the most reliable in the area (Fig. 2). HP
Tony Barnette is the technology manager for Merichem
Chemicals and Refinery Services LLC Gas Technology Products in
Schaumburg, Illinois. Mr. Barnette has been employed at MCRS
Gas Technology Products for over 20 years, during which he has
held roles as sales engineer, pilot plant engineer, project manager,
applications engineer, senior applications engineer and applications manager before
his current position. His primary focus is desulfurization systems. Mr. Barnette received
a BS degree in chemical engineering from the South Dakota School of Mines and
Technology.
Sour gas
Filter and
silencer
Sulfur
settler
Settler feed pump
Vent gas
Air blower
To sulfur
separation
option
Autocirculation
(absorber/oxidizer)
Knock-out
pot
A single train flow diagram. FIG. 1
7 LTPD liquid redox plant, Pinnacle Gas plant. FIG. 2

I

39
Equilibrium considerations
in choosing a gas treating amine
Pursue these guidelines to understand solubility
S. A. BEDELL, The Dow Chemical Company, Freeport, Texas
S
olvents have been used for decades to remove acid gases
from a variety of gas streams.
1,2
The simplest type of solvent
is referred to as a physical solvent, usually a pure organic
compound that dissolves acid gases through nonreactive interac-
tions. The more commonly used solvent systems are aqueous
amine solutions that are called chemical solvents. In addition to
processing a certain degree of physical solubility, chemical solvents
(amines, in particular) can also react to form thermally regenerable
salts with acid gases.
Alkylamines are the simplest type of amine. An alkanolamine is
a particular type of amine that contains hydroxyethyl or hydroxy-
propyl groups in place of some or all alkyl groups. The introduc-
tion of hydroxyalkyl groups is considered to be an improvement
relative to an alkyl group since they increase the water solubility,
reduce the amine volatility and reduce hydrocarbon solubility.
However, hydroxyalkyl groups also reduce the amines basicity
(relative to an alkyl groups) which may not be an advantage from
an equilibrium viewpoint.
Equilibrium limitations. At the heart of any understand-
ing of amine treatments are equilibrium limitations of the reac-
tion between dissolved acid gas and the amine. The acid-base
interactions of the amine (Am) and the conjugate base of the
aqueous acid gas species, X
, are represented by the following

protonation equilibria:

X
+H
+
HX K
1
=[HX] / [H
+
][X
] (1)
Am+H
+
AmH
+
K
2
=[AmH
+
] / [H
+
][Am] (2)
The equilibrium constant for the solution reaction of the
amine and the dissolved acid gas can be represented by:

K
eq
= K
2
/ K
1
(3)
The following discussion is based only on the amines solution
properties and those of the dissolved acid gas. Gas phase concen-
tration differences (both inlet and desired outlet specification)
coupled with physical solubility differences of solvent/solute com-
binations will also play a role in solvent performance to determine
the actual equilibrium position. Such an analysis can be used to
calculate equilibrium partial pressures of acid gases over amine
solutions of various acid gas loadings.
Fig. 1 shows the protonation constants for two typical gas
treating amines, mono-ethanol amine (MEA) and methyl dietha-
nolamine (MDEA), along with several acid gases. Protonation
constants shown are for the species formed by acid gas dissolu-
tion in water. A larger protonation constant value represents a
molecules higher affinity for the proton. Thus, the acid molecules
shown at the bottom of the figure are more likely to give up
their protons to the amines above them. The temperature range
represents absorber conditions on the left and common stripper
conditions on the right. Fig. 1 can be used to illustrate several
aspects of amine acid gas interactions. Acid and base protonation
constants are from a National Institute of Standards and Technol-
ogy (NIST) database.
3
Values of protonation heats were used to
calculate constants by using the vant Hoff equation:
ln(K
T2
/K
T1
) =H/R(1/T
1
1/T
2
) (4)
Example 1. The reaction of MDEA with CO
2
shows a difference
in log K values of two at 40C. Thus, the equilibrium constant
for the reaction of MDEA and CO
2
under absorber conditions is
about 10
2
or 100. Under stripper conditions, the same equilibrium
constant drops to 10. This equilibrium constant reduction, com-
bined with a reduction of CO
2
partial pressure by the steam strip-
ping gas, facilitates the release of CO
2
from solution. The line for
H
2
S is similar to CO
2
which explains the use of MDEA for both
acid gases. This analysis takes into account only the equilibrium
0
2
4
6
8
10
12
14
40 60 80 100 120
Temperature, C
L
o
g

K

p
r
o
t
o
n
a
t
i
o
n
OH
-
CH
3
SH
SO
2
MDEA
H
2
S
CO
2
MEA
Comparative protonation equilibria used to assist gas
treating amine selection.
FIG. 1
40

I

limitations of the reactions: kinetic limitations for the reaction of
CO
2
with water can be used to selectively remove H
2
S.
Example 2. The protonation equilibrium line for methyl mer-
captan (CH
3
SH) is above MDEA. This means that the equi-
librium constant for their reaction at 40C is only 10
2
, which
explains why most alkanolamine systems are severely limited
with respect to mercaptan removal. Notice, that the use of caustic
solutions (OH
) provides a large enough equilibrium constant

(>10
3
) for efficient removal, but is not regenerable due to the
large constant (>10
2
) at regenerator conditions. Though MEA is
a stronger base than MDEA, its protonation equilibrium line is
substantially below CH
3
SH.
Example 3. Fig. 1 predicts that the reaction equilibrium con-
stant for MDEA with SO
2
under absorber conditions is about
10
6
, certainly much larger than that for H
2
S or CO
2
. Unfortu-
nately, the equilibrium constant under stripper conditions is also
very largemore than 10
4
too large to effectively strip the SO
2
.
This is typical for acids that are much stronger than H
2
S or CO
2

and the salts that they form with amines such as MDEA, MEA
and DEA are not regenerable under standard stripper configura-
tions. These salts are referred to as heat stable amine salts and will
reduce the capacity of the amine solution unless other methods
(vacuum distillation, electrodialysis or ion-exchange) are used to
regenerate the amine.
Example 4. Example 3 showed how the reaction of SO
2
with
MDEA is essentially irreversible in a typical gas-treating plant.
Fig. 1 can be used to design an amine that could be used for
reversible SO
2
scrubbing. Taking the reaction of MDEA with H
2
S
or CO
2
as a basis, one needs to find an amine of reduced basicity
such that its line in Fig. 1 would lie the same distance above the
SO
2
line. This is essentially what has been done in the develop-
ment of SO
2
removal processes.
1
The previous examples show only a consideration of equi-
librium constants. Actual amounts of neutralized acid gas will
depend on inlet or outlet gas concentrations.
Nonprotonation Equilibria. Total acid gas solubility can be
partitioned into physical and chemical with chemical solubility
depending on acid-base equilibrium properties as well as the
physical solubility. Thus, physical solubility in aqueous amine
solutions acts as a bottleneck in the overall acid gas capacity for
a given solvent. Fig. 2 illustrates the relative solubility of nitrous
oxide (N
2
O) in three amine solutions with the same water con-
centration. N
2
O is often used as a nonreactive gas to determine
relative physical solubilities of CO
2
in aqueous amine solutions.
Fig. 2 shows that:
1. N
2
O solubility drops by 10%20% (at zero CO
2
loading)
by replacing 30% of the water with amine. This should be expected
with CO
2
and perhaps H
2
S, but it has been noted that physical sol-
ubility of methyl mercaptan increases as water content is decreased
in alkanolamine solutions.
4
This is likely due to a higher affinity
between the more hydrophobic mercaptan and amine.
2. Physical solubility drops substantially as the acid gas load-
ing increases due to a salting-out effect. Though it appears that the
salting-out effect is less substantial for 30% DEA, data from that
same source at 20% amine concentration show a different relative
performance of these amines.
Thus far, the equilibria involved between CO
2
and a primary
or secondary amine to form carbamates have not been mentioned.
While Fig. 1 may be a good representation of MDEA reactions
with acid gases and MEA reactions with H
2
S and SO
2
, the ability
of MEA to form carbamates with CO
2
adds a degree of complexity
that is discussed in other literature.
6
An increase in amine basicity
(K
protonation
) results in both a higher degree of carbamate forma-
tion and faster reaction kinetics with CO
2
.
Although Example 2 demonstrates why mercaptan removal
with amines is severely limited, other more favorable equilibria
may be used to increase mercaptan removal by amine solutions.
The most common method is to find a co-solvent with high
physical solubilitysuch mixtures of water, amine and a physi-
cal solvent are called hybrid solvents. Other solution reaction
equilibria have been shown to provide favorable absorption/
desorption characteristics, including first-generation mercaptan
removal additives (MRAs) such as cyclodextrins.
7
Figs. 3 and
4 show the effect of -cyclodextrin on mercaptan vapor liquid
equilibrium in water. Not only is there an increase in the solubil-
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.0 0.1 0.2 0.3 0.4 0.5
Moles CO
2
/mole amine
R
e
l
a
t
i
v
e

N
2
O

s
o
l
u
b
i
l
i
t
y
30% MEA
30% DEA
30% MDEA
Solubility of N
2
O in aqueous amines solution compared to
water.
5
FIG. 2
0
50
100
150
200
250
300
350
400
450
500
0.00 0.04 0.02 0.06 0.08 0.10
mmoles RSH/L
p
p
m

R
S
H

i
n

v
a
p
o
r
MeSH
EtSH
nPrSH
nBuSH
VLE plot for mercaptans in water at 40C. FIG. 3
GAS PROCESSING DEVELOPMENTS
ity of all mercaptans but the cyclodextrin cavity size is best suited
for a larger mercaptan such as butyl (butanethiol). Normally, a
combination of low aqueous solubility and reduced acidity makes
it more difficult to remove higher mercaptans with aqueous scrub-
bing. Further refinements in MRA chemistry have led to a second
generation that shows a much higher affinity for mercaptans in
alkanolamine solutions.
8
These discussions of acid gas solubility and amine equilibria
are intended only as a guide to better understand the under-
lying principles of acid gas treating with amines. Many other
considerationsincluding reaction kinetics, energy requirements,
corrosion and degradationenter into the selection of a proper
amine system for acid gas removal. Also, in practice blends of
amines are often chosen to optimize operability for particular
applications. HP
LITERATURE CITED
1
Kohl, A. and R. Nielsen, Gas Purification, Fifth Edition, Gulf Publishing
Company, Houston, 1997.
2
Astarita, G., D. W. Savage and A. Bisio, Gas Treating with Chemical Solvents,
John Wiley, New York, 1983.
3
Martell, A. E., R. M. Smith and R. J. Motekaitis, NIST Critically Selected
Stability Constants of Metal Complexes Database, NIST Standard Reference
Database 46, Version 7, US Department of Commerce, 2003.
4
Bedell, S. A. and M. Miller, Industrial and Engineering Chemistry Research,
p. 46, 2007.
5
Browning, G. J. and R. H. Weiland, Journal of Chemical and Engineering
Data, p. 39, 1994.
6
da Silva, E. F. and H. F. Svendsen, International Journal of Greenhouse Gas
Control, p. 151, 2007.
7
Bedell, S. A., Improved control of organic sulfur, 12th Annual Green
Chemical Engineering Conference., Washington, DC, 2008.
8
Bedell, S. A., L. L. Pirtle and J. M. Griffin, Improve mercaptan solubility in
amine units, Hydrocarbon Processing, January 2007.
MeSH
EtSH
nPrSH
nBuSH
0
50
100
150
200
250
300
350
400
450
500
mmoles RSH/L
p
p
m

R
S
H

i
n

v
a
p
o
r
0.00 0.02 0.04 0.06 0.08 0.10
With 10% CD
VLE plot for mercaptans in 10% aqueous -cyclodextrin at
40C.
FIG. 4
Steve Bedell is a research scientist and senior technical person
for Dow Oil & Gas, working across multiple technologies in the
refining and processing market segment. Dr. Bedell received a BS
degree in chemistry from West Virginia University and a PhD in
chemistry from Texas A&M University. He holds 19 US patents and
is the author of over 50 external publications and presentations, most of which deal
with acid gas removal processes.
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I

43
Designing a selective
MDEA tail-gas treating unit
Following these protocols will enhance sulfur recovery efficiency
S. NAGPAL, Fluor, Gurgaon, India
S
elective amine-based Claus sulfur recovery units (SRUs)
tail-gas treating units (TGTUs) have become the preferred
option for enhancing sulfur recovery efficiency to above
99.8% while minimizing sulfur emissions. The most commonly
used selective amine is a generic methyl diethanol amine (MDEA).
The most commonly known process is the SCOT process. Over
400 such plants have been built and many others are under con-
struction that are using the SCOT process.
The TGTU process represents an extreme operating scenario
for an amine gas-sweetening unit. While the TGTU process con-
figuration is similar to a typical amine absorption-regeneration
system, both the absorber and regenerator operate at extreme
conditions. H
2
S and CO
2
absorption occurs at low pressure just
above atmospheric (typically 1 bara to 1.2 bara). Amine regen-
eration to very low lean amine H
2
S-loadings is required, leading
to operation with a high steam requirement.
*
TGTUs preferably
employ a selective amine solvent to minimize CO
2
co-absorption
and recycle it to the SRU.
The SRU converts acid-gas feed into elemental sulfur and
produces a tail-gas containing unconverted sulfur species. This gas
is hydrogenated to reduce all unconverted sulfur species to H
2
S
in a fixed-bed catalytic reactor, quench cooled with water and fed
to the TGTU absorber. The product from the TGTU is off-gas
that is sent to the incinerator while an acid-gas from the TGTU
regenerator is recycled to the Claus SRU furnace. Fig. 1 shows a
schematic of the SRU-TGTU process.
This article discusses some key issues that engineers need to
address when designing these
units. There are several pub-
lished articles that present quali-
tative effects of TGTU operating
parameters. This article gives a
more quantitative description
that can be used as a preliminary
design guideline, using several
commercial process simulators.
Variation among different simu-
lators will be highlighted.
Selective H
2
S removal.
MDEA is a tertiary amine that
does not react directly with CO
2
to form carbamate. The tri-
molecular reaction of MDEA with CO
2
(Eq. 1), is slow, while the
MDEA-H
2
S reaction (Eq. 2) is a fast proton transfer reaction that
can be considered to be almost instantaneous.
R'R
2
N+CO
2
+H
2
OR'R
2
NH
+
+HCO
3
(1)
R'R
2
N+H
2
S R'R
2
N
+
+HS
(2)
This results in the kinetic selectivity shown by MDEA toward
H
2
S absorption over CO
2
absorption. However, maximum equi-
librium loadings achievable for both H
2
S and CO
2
are ~1 mole
per mole of MDEA, provided that an adequate pressure-driving
force is available in the gas phase and adequate contacting time
is provided. Thus, selective H
2
S removal results are entirely due
to the choice of gas-liquid contacting time being long enough for
H
2
S removal but too short for equivalent CO
2
capture.
Optimum design for an amine contactor is required to allow
necessary H
2
S removal but minimal CO
2
co-absorption. Equip-
ment over-sizing is not advisable as it leads to excessive CO
2

absorption and recycle to the Claus SRU.
Accurate computer models that consider inter-phase mass-trans-
fer with simultaneous chemical reactions are required to simulate
the adsorption/stripping process for optimal design and retrofitting
of selective gas sweetening units. Use of equilibrium stage models
with user-experience-based H
2
S and CO
2
stage efficiencies, is a
common approach for designing gas-sweetening units. However,
this approach is not suitable for selective removal applications
where tray performance is highly
variable and can be sensitive to
factors such as tray type/design,
solvent loading, column tempera-
ture profile, etc. Also, tray effi-
ciency estimation is difficult.
Process simulation. The
performance of selective amine
sweetening process simulators
depends on two key model com-
ponents: Vapor-liquid equilib-
rium (VLE) and rate models.
Both H
2
S and CO
2
absorp-
tion in the amine solution are
reversible reactions. As men-
tioned above, the H
2
S-amine
Claus
furnace Air
Acid
gas
Converters,
reheaters and
condensers
Tail
gas
Hydrogenation
and quench
TGTU
absorber
TGTU
regenerator
Rich
amine
Off-gas
(to incineration)
Lean
amine
Acid gas (recycle to SRU furnace)
Sulfur
Sulfur recovery unit Tail-gas treating unit
Schematic of a sulfur recovery unit with a tail-gas treating
unit.
FIG. 1
* Loading is dened as mole H
2
S or CO
2

per mole amine in aqueous phase.
44

I

reaction is extremely fast, and the process operates close to vapor-
liquid equilibrium with respect to H
2
S absorption/regeneration.
On the other hand, the CO
2
-amine reactions for tertiary amines,
such as MDEA, are slow in the absence of the much faster car-
bamate formation reaction that occurs for primary and secondary
amines.
**
Thus, accurate rate models are required to determine
the extent of CO
2
removal while meeting H
2
S specification in
the off-gas for incineration.
VLE model. VLE models, comprising a gas phase equation-of-
state (EOS) model and a liquid phase activity coefficient model
are used to correlate experimental VLE data for the H
2
O-amine-
H
2
S-CO
2
system over a range of amine concentrations, H
2
S and
CO
2
loadings, and temperatures.
Fig. 2 compares VLE calculated with several simulators, with the
VLE data for 50 wt% MDEA at 40C and 120C.
1
Simulators 1, 2
and 3 are seen to fit the data quite well.
1
Recent VLE data for this
system reports significantly higher H
2
S partial pressures as a function
of amine loading.
2,3
Fig. 2 illustrates that Simulator 4 based VLE
calculations for 50 wt% MDEA at 40C matches the later data.
At 120C (regenerator condition), Simulators 1, 2 and 3 fit the
data fairly well.
1
At 120C, the lowest loading data reported was at
0.0095m/m.
1
Extrapolation of the VLE data to lower H
2
S load-
ings down to 0.0010.005m/m is required, as TGTU regenerators
are required to produce lean amine of this quality. Extrapolation
of VLE models into this low loading region with scanty data adds
to model prediction uncertainty.
The above VLE model comparison indicates that the process
simulator choice will have a significant impact on the design cal-
culations as the simulators use different VLE models and even use
different VLE databases for the VLE model parameter tuning.
Rate model. The rate model (also called the non-equilibrium
stage model) is used to calculate the approach to equilibrium on
each tray/packing section. With rate models, stage equations are
the traditional equations of mass and energy balances for each
stage, the vapor and liquid phases are now characterized by a
bulk composition and an interfacial composition. These models
typically assume that the bulk vapor and liquid phases are well-
mixed and the resistances to mass-transfer are located in the two
films at the vapor-liquid interface. Linear concentration profiles
are assumed in the two films. Mass-transfer correlations are used
to incorporate effects of system hydrodynamics. The vapor and
liquid mass-transfer coefficients are estimated using appropriate
correlations for the type of tray being simulated. Diffusivities in
the multi-component vapor and liquid mixturesalong with
other transport properties, such as density, viscosity, thermal
conductivityare required to calculate the mass-transfer coef-
ficients. Heat-transfer coefficients are commonly estimated using
the Chilton-Colburn analogy.
Rate model use requires the user to provide details of tray
type, column diameter, weir height, down-comer width, number
of passes, etc. These models report calculated tray efficiency for
H
2
S and CO
2
. The rate model accuracy determines how well H
2
S
selectivity or CO
2
slip is estimated.
***
Selective absorption at low pressure. There are several
challenges in the design of low-pressure tail-gas treating (TGT)
absorbers. A typical case is used to illustrate these issues. The feed gas
and lean amine to the absorber for this case are specified in Table 1.
1. Attainment of H
2
S specification in treated gas.
The overall sulfur recovery of the SRU-TGTU process is depen-
dent on the TGT absorber off-gas H
2
S concentration. Attainment
of sulfur recoveries in excess of 99.9% requires the off-gas H
2
S
spec to be 150 ppmv or less. (Note that a generic amine will be
able to achieve a 250 ppmv H
2
S spec, a selective amine ~150
ppmv and a formulated amine ~10 ppmv.) Attaining this H
2
S
spec in absorbers operating close to ambient pressure (1 to 1.2
bara) requires lean amine with very low H
2
S loading.
Fig. 3 shows the off-gas H
2
S concentration variation with H
2
S
lean amine loading at a column top temperature of 40C, esti-
mated with various process simulators. Fig. 3 also illustrates the
equilibrium H
2
S concentrations based on VLE data for 50 wt%
MDEA at 40C.
1,2
Note that the VLE data-based equilibrium
H
2
S concentrations represent the lower limit of off-gas H
2
S con-
centration achievable.
Off-gas H
2
S concentrations in the range 60150 ppmv are
obtained for a lean amine with 0.005 H
2
S loading. Simulators 1,
TABLE 1. Case study50 wt% MDEA absorber
Feed gas Lean amine
Flow, kmol/h 1,062 Flow, kmol/h 2,819 (88 TPH)
Temperature, C 43.3 Temperature, C 40
Pressure, bara 1.09 H
2
S loading, m/m 0.005
CO
2
, mol% 5.2 CO
2
loading, m/m 0.0001
H
2
S, mol% 1.7
Column Treated-gas spec
Diameter, m 2.1 H
2
S, ppmv 100
No. of Trays (Valve) 14
0.001
0.01
0.1
1
10
100
1,000
10,000
0.001 0.01 0.1 1
H
2
S loading, m/m
H
2
S

p
r
e
s
s
u
r
e
,

k
P
a
Jou data 120C
Simulator 1
Simulator 2
Simulator 3
Jou data 40C
Simulator 3
Simulator 1
Simulator 2
Rogers data 40C
Simulator 4
Simulator estimation of H
2
S VLE in 50 wt% MDEA. FIG. 2
** Carbamate formation for secondary amine: R
2
NH + CO
2
= R
2
NCOO
+
H
+
*** CO
2
slip (%) = 100 x moles of CO
2
in off-gas/moles of CO
2
in absorber
feed.
Natural Gas
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46

I

2 and 3, although all based on VLE data,
1
reported significantly
different results, essentially from different rate models. Simulator
4, which is based on the VLE data
2
reported, gives higher off-gas
H
2
S concentrations than all the other simulators at H
2
S lean
loadings above 0.0040.005. Comparing Simulator 4 results with
the equilibrium limit of H
2
S concentrations suggests that it is
essentially an equilibrium based model with super imposed CO
2
kinetic effects (to estimate CO
2
selectivity). Operating experience
has shown that absorber off-gas will typically approach 34 times
the equilibrium H
2
S partial pressure on the absorber top tray.
6
These simulator results indicate that attaining an off-gas spec
of 100 ppmv will require a lean amine H
2
S loading of 0.005
m/m or lower. Use of a typical refinery gas-sweetening unit lean
amine H
2
S loading of 0.010.015 m/m would allow the reduc-
tion of H
2
S to 250500 ppmv, which may not suffice to meet the
required overall sulfur recovery target.
2. Maximizing CO
2
slip. The low pres-
sure TGT absorber is usually designed with
just enough trays/packing height to ensure
that the gas leaving the column top is close
to equilibrium with the lean amine entering
the column with respect to H
2
S. Avoid over
design to minimize CO
2
absorption.
Table 2 illustrates the impact of number
of trays on column performance. Increasing
the number of trays allows some reduction
in off-gas H
2
S concentration, but this comes
at the cost of increased CO
2
co-absorption and it will eventual
recycle to the Claus SRU. Typical CO
2
slip observed in trayed
MDEA TGTU absorbers ranges from 6085%, but this can vary
considerably based on column design. Yet, Simulators 3 and 4
simulate an unrealistically high CO
2
slip, and show no impact
on the number of trays for treated gas H
2
S concentration. This
suggests that 10 trays are adequate to reach H
2
S equilibrium
composition w.r.t feed lean amine.
It should be noted that commercial-grade MDEA commonly
has some DEA impurity, which can reduce CO
2
slip, and result in
increased off-gas H
2
S concentrations. Use of high-purity MDEA
can enhance TGTU performance.
3. Optimal amine concentration. The maximum H
2
S
loading achievable in the rich amine leaving the absorber bottom
is controlled by the feed gas H
2
S partial pressure and amine con-
centration used. MDEA use became popular for refinery amine
systems as it could be used at higher concentrations and with
higher acid-gas loadings than the earlier generation primary and
secondary amines, viz. MEA and DEA. MDEA also allows reduced
CO
2
pick-up in the absorbers. These factors resulted in operation
with significantly reduced amine circulation rates. However, for the
low-pressure TGTU absorber, operation with high amine concen-
tration at high H
2
S loading is not feasible due to column bottom
pinch. This leads to the question, Is there any benefit to operating
TGTU absorbers at high amine concentrations?
This is examined in Fig. 4, which illustrates the variation in
off-gas H
2
S and CO
2
concentrations with amine circulation
TABLE 2. Impact of number of trays
H
2
S out, ppmv CO
2
slip, %
Simulator Simulator Simulator Simulator Simulator Simulator Simulator Simulator
No. of trays 1 2 3 4 1 2 3 4
10 307 244 61 141 84.4 84.8 96.3 98.5
14 135 100 61 141 79.1 79.5 96 98.0
20 93 70 61 141 71.3 72.1 92.8 97.2
25 85 66 61 141 65.1 66.7 91.1 96.8
Simulator 1
Simulator 2
Simulator 3
Simulator 4
Equilibrium limit @ 40C
1
Equilibrium limit @ 40C
2
0
50
100
150
200
250
300
350
400
450
500
0.000 0.015 0.005 0.010
Lean amine H
2
S loading, m/m
O
f
f
-
g
a
s

H
2
S
,

p
p
m
v
Off-gas H
2
S concentration dependence on H
2
S lean amine
loading for the TGT absorber defined in Table 1. Absorber
top pressure considered is 105 kPa.
FIG. 3
0
100
40 60 80 100 120
200
300
400
500
600
700
800
900
1,000
Amine circulation rate, TPH
H
2
S

i
n

t
r
e
a
t
e
d

g
a
s
,

p
p
m
v

4.0
4.1
4.2
4.3
4.4
4.5
C
O
2

i
n

t
r
e
a
t
e
d

g
a
s
,

%
m
o
l
H
2
S (50 wt% MDEA)
H
2
S (20 wt% MDEA)
CO
2
(50 wt% MDEA)
CO
2
(20 wt% MDEA)
Effect of amine concentration and amine circulation rate
on off-gas H
2
S and CO
2
concentration estimated with
Simulator 2. Lean amine H
2
S and CO
2
loadings considered
were 0.005 m/m and 0.0001 m/m, respectively.
FIG. 4
TABLE 3. Case study- regenerator column
Rich amine feed Column
Temperature, C 104 Condensor pressure 2.35 bara
Flow, kmol/h 7544 Reboiler pressure 2.6 bara
MDEA concentration 50wt% Condensor temperature 40C
H
2
S loading, m/m 0.077 Diameter, m 3.3
CO
2
loading, m/m 0.027 Trays (total) 27
Trays (below feed location) 24
Weir Height, cm 5

I

47
rate for two amine concentrations, 20 wt% MDEA and 50 wt%
MDEA. For the 50 wt% MDEA case, a sharp increase in off-gas
H
2
S concentration is calculated at amine circulation rates below
50 TPH, which is indicative of a column bottom pinch. However,
for the 20 wt% MDEA case, onset of pinch conditions occurs at a
higher amine circulation rate of ~90 TPH. Thus, higher MDEA
concentration use is estimated to allow operation with a lower
amine circulation rate and a higher CO
2
slip. (Typical MDEA
application range is between 35 wt% and 50 wt%).
Amine regeneration. A typical rich amine feed to a TGTU
regeneration column is considered to illustrate some design issues;
this data is listed in Table 3.
1. Steam requirement. As previously discussed, a very low lean
amine H
2
S loading of 0.005 m/m or lower is estimated to achieve
off-gas H
2
S concentration below 100 ppmv. Attaining such low
lean amine loading requires high steam input to the amine regen-
erator column (ARC) reboilers. For the ARC case in Table 3, Fig. 5
shows a specific steam consumption (SSC) variation with H
2
S lean
amine loading estimated with various simulators. All the simulators
estimate a sharp increase in steam consumption as H
2
S lean loading
decreases below 0.01 m/m. However, there is considerable variability
in the calculated magnitude of specific steam consumption.
Medium- and high-pressure refinery/gas plant absorbers
required to reduce treated gas H
2
S to 440 ppmv can operate with
H
2
S lean loading of 0.01-0.015m/m with a corresponding SSC
of ~1 lb-steam/gal-amine. However, for the low-pressure TGTU
that requires an H
2
S lean loading of ~0.005, ARC operates at sig-
nificantly higher SSC of 1.5 lb-steam/gal-amine and is estimated
with Simulators 2 and 3. However, Simulator 4 allows very low
lean amine H
2
S loadings down to 0.003 m/m to be achieved with
an SSC of 1 lb-steam/gal-rich amine.
From an overall unit design perspective, it is useful to look at
ARC steam requirements for attaining a target absorber off-gas
H
2
S concentration. This is illustrated in Fig. 6. For off-gas H
2
S
concentration >400 ppmv, the discrepancy between the simulators
is fairly small, with SSC of 0.60.8 lb-steam/gal-rich amine for all
simulators. However, for off-gas H
2
S concentrations below 200
ppmv, the simulator results deviate significantly. For instance, for
100ppmv H
2
S in off-gas, Simulator 2 estimates SSC two times
that obtained from Simulator 4. This suggests that different simu-
lator use can lead to significantly different design when targeting
off-gas H
2
S that is below 200 ppmv.
Reliability of these estimations is subject to the VLE data
accuracy, especially at low H
2
S loading. Published VLE data
Simulator 3
Simulator 1
Simulator 2
Simulator 4
0.00
0.50
1.00
1.50
2.00
2.50
3.00
0.000 0.002 0.004 0.006 0.008 0.010 0.012 0.014
Lean H
2
S loading, m/m
R
e
b
o
i
l
e
r

s
t
e
a
m

c
o
n
s
u
m
p
t
i
o
n

(
S
S
C
)
,
l
b

s
t
e
a
m
/
g
a
l

r
i
c
h

a
m
i
n
e
Reboiler specific steam consumption for producing lean
amine of varying quality estimated with various simulators
for the regenerator defined in Table 3.
FIG. 5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
0 200 400 600 800 1,000
Off-gas H
2
S, ppmv
S
S
C
,

l
b

s
t
e
a
m
/
g
a
l

r
i
c
h

a
m
i
n
e
Simulator 2
Simulator 3
Simulator 4
Simulator 1
Reboiler specific steam consumption required for
associated tail-gas absorber off-gas H
2
S concentration
estimated with various simulators.
FIG. 6
(a)
1.00
1.25
1.50
1.75
2.00
20 25 30 35 40 45 50
Number of trays
S
S
C
,

l
b

s
t
e
a
m
/
g
a
l

r
i
c
h

a
m
i
n
e
(b)
1.70
1.80
1.90
2.00
195 215 235 255
Reboiler pressure, kPa
S
S
C
,

l
b

s
t
e
a
m
/
g
a
l

r
i
c
h

a
m
i
n
e
120
125
130
135
R
e
b
o
i
l
e
r

t
e
m
p
e
r
a
t
u
r
e
,

C Temperature
SSC
Impact of number of trays and column pressure on reboiler
specific steam consumption (SSC) for the case described
in Table 3. Lean amine H
2
S loading considered was
0.005 m/m. Estimations were done with Simulator 2.
FIG. 7
48

I

at the ARC bottom conditions (H
2
S loading below 0.01 m/m,
and temperature above 120C) are scanty and of relatively lower
accuracy. Thus, the estimations from the simulators should be
validated using reliable operating data.
ARC lean amine CO
2
loading is calculated to be significantly
lower than the H
2
S loading. This is due to the higher volatility/K
value of CO
2
compared to H
2
S. The bulk of the CO
2
in the
rich amine strips out rapidly in the trays
below the rich amine feed, while H
2
S
stripping continues all the way down
to the bottom of the column. At high
specific steam consumptions, increase
in CO
2
loading in the rich amine feed
does not result in an increase in the spe-
cific steam consumption (SSC can even
decrease at increased feed rich-amine
CO
2
loading). To a certain extent, the
presence of CO
2
acts as a strippping gas
for H
2
S. This is in contrast to conven-
tional regenerators designed to produce
lean amine with acid-gas loadings of 0.015 m/m (or higher) in
which the specific steam consumption increases in proportion to
the feed rich amine acid-gas loading.
2. Number of trays. Using a higher number of trays in the
stripping section of the ARC can be employed to reduce steam
requirement for attaining a low lean amine H
2
S loading. Fig. 7a
shows the effect of increasing the total tray number in the ARC on
steam required (SSC) to obtain a lean amine H
2
S loading of 0.005.
The rate of reduction in SSC decreases as the number of trays
increases. Typically, 2025 trays are used in the TGTU ARC.
3. Column pressure. ARC operation at higher pressure leads
to higher column temperatures and better regeneration. ARC
operating pressures are limited on the lower side by back-pressure
requirement from the downstream SRU and on the higher side
by temperature limit for keeping amine degradation rates down
at acceptable levels. Fig. 7b shows the effect of column pressure
variation on steam consumption (SSC) and reboiler temperature,
using Simulator 2. Simulators 1 and 3 give a lower sensitivity of
SSC to column pressure. A low sensitivity due to counter balanc-
ing effects of higher acid-gas vapor pressure at higher tempera-
ture and higher column pressure has been previously reported.
6

Reduction in SSC at higher pressures/temperatures comes at a
cost of increased amine degradation rates. For generic MDEA
solutions, recommended reboiler process-side temperatures are
125C or less (with steam temperature below 150C) to keep
degradation rates in check.
4
Conclusions. Accurate rate-based process simulators are
required for optimal design of SRUsTGTUs. The TGTU
absorber and regenerator columns operate at extreme conditions
with respect to H
2
S lean amine loadings and steam consumption.
Lean amine with H
2
S loading below 0.01 m/m is estimated to
achieve TGT off-gas H
2
S spec below 200 ppmv. This, in turn,
entails ARC operation with high steam consumption, with steam
consumption increasing exponentially with decreasing lean amine
H
2
S loading. Unlike conventional ARC where SSC is controlled
by the feed rich amine acid gas loading, the TGT ARC SSC is
controlled by the required off-gas H
2
S concentration and lean
amine H
2
S loading.
Considerable variability was found among commercial simula-
tors with respect to SSC required for attaining off-gas H
2
S level
below 200ppmv. Scanty VLE data at low H
2
S loadings results in
uncertainty in the simulator estimation of steam requirements,
and off-gas H
2
S concentrations at low loadings. Reliable operating
data from existing units are thus required to validate the simula-
tor results, and to optimize the steam consumption required to
attain low off-gas H
2
S concentration
and high overall sulfur recovery for
the SRU-TGT plant. A literature scan
found just a few relevant reports on
operating data with TGT amine units.
The gas industry would benefit from
a common database of reliable plant
operating data that can be used in all
commercial simulators.
Options that have been explored to
reduce steam consumption for TGT
units include acid-addition and split-
flow processes.
5
Acid addition can
allow production of lean amines with very low H
2
S loading
(~0.001 m/m) with lower steam consumption. Split-flow ARC
are sometimes used for refinery units that have critical users, e.g.
TGTU and fuel gas absorbers where any H
2
S slip ultimately
results in more SO
2
emissions and less-critical users (e.g., absorb-
ers for recycle gas in hydro-processing units) where bulk removal
is sufficient. HP
LITERATURE CITED

1
Jou, F., A. E. Mather and F. D. Otto,Solubility of H
2
S and CO
2
in Aqueous
Methyldiethanolamine Solutions, Industrial & Engineering Chemistry Process
Design Development, Vol. 21, pp. 539544, 1982.

2
Rogers, W., J. A. Bullin and R. R. Davison, FTIR measurements of acid-
gas-methyldiethanolamine systems, AIChE Journal, Vol. 44 Issue 11, pp.
24232430, November 1998.

3
Huttenhuis, P. J. G., N. J. Agrawal, J. A. Hogendoorn, and G. F. Versteeg,
Gas Solubility of H
2
S and CO
2
in aqueous solutions of n-methyldieth-
anolamine, Journal of Petroleum Science and Engineering, Volume 55, pp.
122134, 2007.

4
Dupart, M. S., T. S. Bacon and D. J. Edwards, Understanding corrosion in
alkanolamine gas treating plants, Hydrocarbon Processing, April 1993.

5
Wong, V. W., J. Y. Mak and T. K. Chow, The DAP and STREP Processes
for Acid Gas Removal, Acid Gas Enrichment, and Claus Tail-Gas Treating,
Brimstone Sulfur Recovery Symposium, 2007.

6
Huffmaster, M. A., Stripping requirements for selective treating with sulfinol
and amine systems, Laurance Reid Gas Conditioning Conference, p. 262,
1997.
ACKNOWLEDGMENT
The author thanks Ashwin Nagarajan and Michiel Baerends of Fluor for their
assistance in preparing and reviewing the article.
The gas industry would
benefit from a common database
of reliable plant operating
data that can be used in all
commercial simulators.
Soumitro Nagpal is a process specialist with Fluor India. He
has over 20 years experience in process design and development.
Dr. Nagpals primary areas of work have been gas processing, gas-
treating, sulfur recovery, CO
2
and SO
2
capture, petcoke gasification
and alumina refining. He developed rate-based models for selective
gas-treating applications and used these models for process design and the revamp
of gas-treating units in India. In the past, Dr. Nagpal has worked at Engineers India
Limited and Imperial College, London. He received a BE in chemical engineering from
Birla Institute of Technology & Science, Pilani and a PhD in chemical engineering from
the University of Utah.
ENVIRONMENT

I

49
C
apture and storage of carbon dioxide (CO
2
) is a techni-
cally feasible method for making deep-reductions in CO
2

emissions. As more governments mandate tighter emission
rules for carbon emissions, HPI companies must make thoroughly
reasoned decisions when considering carbon captured and storage
(CCS) projects. This case history investigates the economics of a
CCS project with CO2 recovery.
Climate change. The capture and storage of carbon dioxide
is a technically feasible method of making deep reductions in CO
2

emissions.
1
This statement, made by the Intergovernmental Panel
on Climate Change, is widely accepted, as is the need for timely
development of carbon capture and storage (CCS) demonstra-
tion projects. However, without a clear projection of the future
CO
2
market value, the business case to make these demonstra-
tion projects economically viable may be questionable. However,
using CCS for enhanced oil recovery (EOR) via captured CO
2

can provide economic drivers in some situations.
Economic solutions. Using captured CO
2
for EOR may raise
an interesting question for project stakeholders: if the captured
CO
2
from a CCS project is used for EOR, does the project still
result in a net reduction in CO
2
emissions to the atmosphere?
This question could be answered by suggesting that the oil would
be extracted anyway and that injecting CO
2
for EOR does not
affect the total global crude production rate. However, using
CO
2
for EOR implies significant reservoir depletion and that the
incremental oil recovered as a direct result of CO
2
injection would
have remained unrecovered otherwise. We will discuss whether or
not a CCS project with EOR would result in a net reduction in
CO
2
emissions to the atmosphere and to identify key factors that
determine the total overall carbon emissions avoidance resulting
from such projects. Simplified calculations may be done by bal-
ancing the carbon extracted in the form of oil against the carbon
permanently stored as CO
2
, as well as considering the emissions
resulting from the likely use of extracted oil.
CO
2
STORAGE OPTIONS
A number of storage options have been postulated, including
storage in geological formations or deep-sea storage, where pressure
of the overlying water column maintains the CO
2
in supercritical
form. There are significant technical and environmental risks asso-
ciated with deep-sea storage that are at present unresolved.
The geological storage options include saline aquifers, depleted
oil wells and depleted natural gas wells. Enhanced hydrocar-
bon recovery is an option that can be considered for the two-
well scenarios. Depleted wells have a significant advantage over
saline aquifers, not only for the economic potential of EOR and
enhanced gas recovery (EGR) but also because the containment
integrity has been proven, although additional surveys may still
be required to confirm this parameter.
For saline aquifers, more extensive geological surveys are
required to characterize the storage location and caprock and to
determine that the location is free from faults and discontinuities
within the caprock, thus preventing injected CO
2
from leaking
back to the surface. In all permanent geological storage cases,
continuous monitoring is required during, and for a significant
period after CO
2
injection.
The characteristics of each geological site will have a significant
effect on the possible injection rate and, for oil and gas wells, the
enhanced hydrocarbon recovery potential. Well permeability,
depth and pressure are key factors to be considered, and these
result in a wide range of experienced and anticipated recovery rates
per unit of CO
2
injected from one site to the next. Issues such as
public acceptance and legal aspects of permanent CO
2
storage,
such as long-term operator liability will not be considered within
the scope of this article.
Methodology. Three CCS with EOR project cases will be
considered:
Case AFossil-fuel power station with CCS, EOR, down-
stream refinery or conventional power plant.
Case BFossil-fuel power station with CCS, EOR, power
plant with CCS sequestered in a saline aquifer.
Case CFossil-fuel power station with CCS, EOR, power
plant with CCS, EOR in a closed loop.
The CCS project cases will then be compared against control
cases:
Case DConventional power plant without CCS
Case EFossil-fuel power station with CCS, CO
2
seques-
tered in a saline aquifer.
The analyses will be conducted over three main steps for each
case. Step 1 considers only the emissions avoidance of the carbon-
capture power plant. Step 2 calculates the expected net storage of
carbon when CO
2
is applied for EOR. Step 3 considers the emis-
sions resultant from the likely use of incremental oil extracted.
When does carbon capture
make sense?
Here are several options in which carbon capture can provide
cost-effective solutions
S. FERGUSON, Foster Wheeler Energy, Reading, Berkshire, UK
ENVIRONMENT
50

I

The analysis will consider the following example fossil-fuel
fired plant for all cases; natural-gas fired combined cycle with
net power output of approximately 350 MW, annually emitting
1.3 metric million tons of CO
2
before carbon capture (Fig. 1).
Step 1Fossil-fuel power plant with CCS. The global
demand for power is ever increasing, and it can be assumed that
a significant number of new, conventional power plants will be
required to prevent a significant supply shortfall. We can begin
our analysis by drawing a system boundary around a generic,
90% carbon-capture power station, which is proposed in place of
a conventional power station (Fig. 2). Since a power station was
required anyway, building one which emits only 10% of the CO
2

that would otherwise have been emitted clearly results in a 90%
net carbon emission reduction.
Step 2Fossil-fuel power plant with CCS and EOR. If
the CO
2
is intended for EOR, then the total carbon storage of the
project is impacted. Although a significant quantity of carbon will
be stored in the reservoir as CO
2
, a significant quantity of carbon
will be released from the reservoir in the form of oil. The balance
between the mass of carbon stored vs. the mass of carbon recovered
is key to the total carbon storage level of this project (Fig. 3).
The expected quantity of oil that can be recovered per unit
of CO
2
stored depends on the characteristics of the individual
reservoir, such as permeability and pressure. This projected figure
for the reservoir enables calculation of the net carbon storage.
Step 3CO
2
resulting from using extracted oil. The
majority of crude oil used globally is processed in refineries into
a wide range of products, mostly fuelsalthough some crude is
also fired or co-fired directly to generate power. This study will
consider three cases for the end-use of oil:
Refinery or conventional power plant feedstock
Carbon-capture power plant feedstockstorage in saline
aquifer
Carbon-capture power plant feedstockEOR.
TOTAL CARBON AVOIDANCE
For CCS projects with EOR, the total carbon avoidance should
be calculated to include all three steps of the project chain: carbon
emitted and stored across the power plant, in the reservoir and
resultant from the recovered-oil end use.
Power plant net output and carbon avoidance. Power
requirements for the CO
2
capture and compression units of the
power plant with CCS result in a reduced overall efficiency, requir-
ing more consumption of fuel per MW of electricity net produced.
To account for this efficiency reduction, a 90% carbon capture
avoided power plant with CCS would actually need to capture
approximately 92% of its CO
2
emissions, if it fired natural gas (or
93%94% for coal-fired plants) to meet the 90% avoided target,
as compared to a conventional fossil-fuel fired power plant. For this
analysis, the carbon-capture power plant is defined as 90% carbon
avoided overall, with a net power output of 350 MW.
Construction phase and other emissions. CO
2
emis-
sions resulting from the construction phase of the facility were
assumed to be small as compared to the operational phase. Simi-
larly, a full life-cycle analysis was not done as other contributing
factors, such as land use change, are anticipated to be of lower
impact as compared to the variables considered in this study.
CO
2
recycle at the wellhead. It was also assumed that
100% of the CO
2
that returns to the surface with the extracted
oil is separated and re-injected as per normal practice.
9
Without
the CO
2
injection, it would not be possible to extract further oil
from the reservoir in question. Any additional process equipment
and operational CO
2
emissions at the injection site have not been
considered. No consideration has been made for additional power
required to recycle or compress CO
2
at the wellhead.
ANALYSES
This example will consider a natural-gas fired power plant as
the base case.
Fossil-fuel
power plant
Natural gas
100% of CO
2
to atmosphere
Electrical
power
System
boundary
Step 1Block flow diagram of a natural-gas fired power
plant with no CCS.
FIG. 1
Fossil-fuel
power plant
Natural
gas
10% of CO
2
to atmosphere
Electrical
power
System
boundary
CO
2
capture and
compression
90% of CO
2
to sequestration
Step 1 Block flow diagram of a natural-gas fired power
plant with CCS.
FIG. 2
Fossil-fuel
power plant
Natural
gas
10% of CO
2
to atmosphere
Electrical
power
System
boundary
CO
2
capture
and
compression
Incremental
crude oil
Partially
depleted
reservoir
Step 2 Block flow diagram of a natural-gas fired power
plant with EOR.
FIG. 3
Converting poisonous Hydrogen Sulphide (H
2
S) into non-polluting
useable elemental Sulphur
Engineered to cover the full range of needed materials
When the right
reaction matters ...
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Unit (SRU) Catalysts
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2
S, COS
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2
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ENVIRONMENT
52

I

Step 1Carbon-capture power plant. In the study, a
conventional 350 MW (net) natural-gas fired power plant would
have annually emitted 1.1 million metric ton (mMMtpy) of
CO
2
. Instead, a 350 MW (net) natural-gas fired power plant with
carbon capture is built, producing 1.3 mMMtpy of CO
2
of which
0.1 mMMtons is emitted to the atmosphere and 1.2 mMMtons
are transported to storage. The total CO
2
emissions avoided are
1 mMMtpy, or 90%:

CCS power plant CO
2
=1.10.1=0.1 mMMtpy (1)
CCS power plant CO
2
=1.30.1=1.2 mMMtpy (2)
Where F denotes carbon or CO
2
emitted and f denotes car-
bon or CO
2
permanently stored.
Note: that had a saline aquifer or other permanent storage
location been selected for the CO
2
storage, then the analysis
would end here, with the total carbon avoidance being equal to
the carbon avoidance of the CCS power plant.
Step 2Carbon capture power plant with EOR. The
350 MW natural-gas fired carbon capture power station captures
1.2 mMMtpy of CO
2
, as shown in Eq. 2:
Molar rate of:
CO
2
=
1.210
9
3652444.01
=3,112.6 kmol/h (3)
Mass rate of carbon injected
:
C =
3112.612.018760
1, 000
=
327, 500 metric tpy (4)
In our example case, the maximum expected additional output
from the reservoir is 40 MMbbl of oil over 15 to 20 years.
2
Making
an assumption based on the 20-year case, the oil resultant from stor-
ing 1.22 mMMtons of CO
2
is 2 MMbbl per year, on average.
The composition of a typical crude can be used to calculate
the carbon recovered in the form of oil. For example, a Middle
Eastern heavy crude is composed of approximately 85 wt% car-
bon, 12 wt% hydrogen and 3 wt% sulfur. For a lighter crude, the
hydrogen content will be higher and the sulfur content lower; yet,
the carbon content will remain essentially the same. The typical
specific gravity for this Middle Eastern crude is 0.89 and thus:

Carbon in extracted oil:
C =
210
6
0.890.85
6.29
=240,800 metric tpy (5)
(Converting barrels of oil to cubic meters using 6.29 bbl/m
3
)

The net carbon stored:
C =327, 500240,800 =86, 700 metric tpy (6)
Therefore, 26% more carbon is stored than is recovered using
CO
2
for EOR and 74% of the carbon returns to the surface. The
CO
2
emissions resulting from the return of this carbon to the
surface depend entirely on the end use of the extracted oil.
Step 3CO
2
resulting from the use of extracted oil.
In Case A, we will consider a refinery or conventional power plant
feedstock. For the refinery case, most of the final products will be
combusted as fuels. Although some carbon will be consumed as
feedstock for petrochemical/chemical processes, and are therefore
not combusted, a significant amount of carbon will be used to
provide heat and power to the refinery itself, therefore the CO
2

emissions resulting from the refinery are equivalent to having
combusted 100% of that oil. A conventional power plant will
also result in combustion of 100% of the extracted oil. For this
analysis, the two end uses can be assumed to result in the same
emissions level:

100% combustion of oil
CO
2
=
240,80044.01
12.01
=880, 000 metric tpy (7)
Case B. Carbon capture power plant feedstock
storage in saline aquifer. If the extracted oil is fired in
a power plant designed for 90% carbon capture, then the total
resulting emissions will depend on the use of that captured CO
2
.
If the CO
2
is stored in a saline aquifer, then only the emissions
from the plant must be considered:
Emissions from 90% CCS plant:
CO
2
=880, 000 tpy 0.1=88, 000 metric tpy (8)
Case C. Carbon capture power plant feedstock
with EOR. If a CCS power station is operated in a closed loop
with storage and an EOR reservoir then the total CO
2
emissions
avoided, including the EOR component, remains 90%, as shown
in Fig. 4. (Note: This assumes that the power plant is oil-fired
rather than gas-fired and that oil recovered through EOR is less
than the total fuel requirement of the power plant, with the deficit
being made up with imported fuel from elsewhere.)
The only streams crossing the system boundary are imported
makeup fuel (if required to maintain power output at 350 MW
net) and 10% of combustion generated CO
2
, which is released to
the atmosphere from the original capture plant. Therefore, the addi-
tional CO
2
emissions due to the end use of the recovered oil are:

Additional emissions from CCS plant:
CO
2
=0 metric tpy (9)
OVERALL CARBON AVOIDANCE RESULTS
We have calculated the carbon balance across each step in the
process from the original power plant, the EOR reservoir and end
use of the recovered oil. The total carbon avoidance results can be
calculated for each end-use case presented here:
Case A consists of a carbon-capture power plant with CCS for
EOR. The resultant oil is subsequently combusted, either as power-
plant feedstock, or as refinery products such as transport fuels:
Fossil-fuel
power plant
Makeup
fuel
10% of CO
2
to atmosphere
Electrical
power
System
boundary
CO
2
capture
and
compression
Incremental
crude oil
Partially
depleted
reservoir
Step 3Block flow diagram of a natural-gas fired power
plant in a closed loop with an EOR reservoir.
FIG. 4
ENVIRONMENT

I

53

Case A total emissions:
CO
2
=110,000 +880, 000 =990, 000 metric tpy (10)
Case A carbon avoidance:
CO
2
=
1,100, 000990,000
1,110, 000
100 =10% (11)
Case B consists of a power plant with CCS for EOR. The
resultant oil is subsequently combusted in a second 90% carbon-
capture power plant from which the CO
2
is stored in a saline
aquifer:

Case B total emissions:
CO
2
=110,000 +88, 000 =198, 000 metric tpy (12)
Case B carbon avoidance:
CO
2
=
1,100, 000198, 000
1,110, 000
100 =82% (13)
Case C consists of a power plant with CCS for EOR. The
plant is operated in closed loop with the reservoir; combusting the
recovered oil as fuel with a makeup stream imported, operating at
90% carbon capture:

Case C total emissions:
CO
2
=110,000 +0 =110, 000 metric tpy (14)
Case C carbon avoidance:
CO
2
=
1,100, 000110, 000
1,100,000
100 =90% (15)
Conventional-power station case, Case D. For compar-
ison, the same calculation can easily be done for the conventional
power plant case, Case D:

Case D total emissions: CO
2
=1,100, 000 metric tpy (16)
Case D carbon avoidance:
CO
2
=
1,100, 0000
1,100,000
100 =0% (17)
Permanent storage case, Case E. The same can be applied
to a carbon-capture power station for which the CO
2
is stored
directly in a saline aquifer, or similar permanent storage location,
instead of being used for enhanced hydrocarbon recovery, Case E:

Case E total emissions: CO
2
=110, 000 metric tpy (18)
Case E carbon avoidance:
CO
2
=
1,100, 000110, 000
1,100,000
100 =90% (19)
The total carbon emissions and avoidance for each case are
summarized in Table 1.
Sensitivity analysis. The analysis conducted is highly sensi-
tive to the quantity of oil recovered per unit of CO
2
injected into
the reservoir. The calculations above are based on assuming that
40 million barrels are recovered over 20 years. Any change in the
assumed recovery rate could have a significant impact on the bal-
ance of carbon stored vs. carbon recovered from the reservoir.
Considering the high impact of this variation, a sensitivity to
the expected rate of oil recovered per metric ton of CO
2
injected
was done. Table 2 shows a range of figures for the quantity of oil
recovered as a function of the CO
2
injection rate from different
data sources for different example locations:
Calculating the resultant proportion of carbon that remains
stored in the reservoir over this range of figures is shown in Fig. 5,
where the proportion of carbon stored is calculated as:

CO
2
=
(carbon in injected CO
2
) (carbon in extracted oil)
(carbon in injected CO
2
)
100
Fig. 5 shows that carbon storage in the reservoir can range
from 0% to 37% depending on the mass of CO
2
stored per bar-
rel of incremental oil recovered. This clearly has a very significant
impact on the total carbon avoidance of the project and must be
assessed for each project rather than relying upon any generic
assumption of recovery or storage.
For our example project, the site-specific data gave a 26%
carbon storage averaged over the life of the project. This shows
that the very lowest figures would result in zero or negative carbon
storage in the reservoir. Therefore, the end use of the recovered oil
TABLE 1. Overall emissions and carbon avoidance
of the example CCS project
Case Total CO
2
, mMMtpy CO
2
avoided, %
A CCS plant, EOR, refinery .99 10
B CCS plant, EOR, CCS plant, aquifer .198 82
C CCS plant, EOR, CCS plant, EOR, loop .11 90
D Conventional power plant 1.1 0
E CCS plant, saline aquifer storage .11 90
TABLE 2. EOR incremental oil recovery per metric ton
of CO
2
injected
te CO
2
/ bbl incremental oil Data source
0.45 to 0.6 Projected for Miller Field, North Sea
2
0.44 Weyburn-Midale typical, Canada
3
0.5 to 0.68 BERR projection for North Sea, 2007
6
0.68 USA averaged typical
6
0.6 Paper example project
Reservoir net storage of carbon
-10
0
10
20
30
40
0.3 0.5 0.7 0.4 0.6 0.8
Metric tons of CO
2
stored per bbl incremental oil recovered
P
r
o
p
o
r
t
i
o
n

o
f

c
a
r
b
o
n

p
e
r
m
e
n
a
n
t
l
y

s
t
o
r
e
d
,

%
Example project
Sensitivity graph of carbon stored in different locations. FIG. 5
ENVIRONMENT
54

I

would be key to the project total emissions avoidance. Conversely,
in cases with high CO
2
storage per bbl recovered, the end use has
significantly less impact on the total balance of emissions avoided
by the project.
Outlook. It can be seen in Table 1 that, in our example case,
a 90% carbon-capture power station with EOR stores approxi-
mately 26% more carbon as CO
2
than is extracted as oil. A total
project carbon emissions avoidance level of 10% is achieved,
assuming that the extracted oil is eventually combusted. How-
ever, if the recovered oil was subsequently combusted in a similar
90% carbon-capture power plant, then the total project carbon
emissions avoidance level would be increased to between 82%
and 90%.
It can be concluded that, despite the large quantity of carbon
that is brought back to the surface as a result of using captured
CO
2
for EOR, the total project still provides a significant net
environmental benefit in terms of CO
2
emissions avoided, even
if, as in the worst case, 100% of the recovered oil is combusted.
The extent of total CO
2
emissions avoided for a specific project
is highly dependent on:
End use of the extracted oil
Reservoir characteristics, particularly the projected oil recov-
ery per metric ton of CO
2
injected.
Thus, before the total carbon emissions avoided can be calcu-
lated for a proposed CCS project with EOR, both of these factors
must be quantified. HP
LITERATURE CITED

1
IPPC, Intergovernmental Panel on Climate Change Special Report on
Carbon Dioxide Capture and Storage, 2005. Prepared by Working Group III
of the Intergovernmental Panel on Climate Change; Metz, B., O. Davidson,
H. C. de Coninck, M. Loos and A. Meyer (Eds.).; Cambridge University
Press, Cambridge, UK, and New York, NY, p. 442.

2
http://www.bpalternativenergy.com/liveassets/bp_internet/alternativenergy/
next_generation_hydrogen_peterhead.html.

3
http://www.ptrc.ca/weyburn_overview.php.

4
http://www.netl.doe.gov/publications/proceedings/01/carbon_seq/2a1.pdf.

5
http://www.ptrc.ca/siteimages/Summary_Report_2000_2004.pdf.
6
Becky, A., D. Hughes and M. Raistrick, Introduction to the Geological
Storage of Carbon Dioxide, Senergy Training Course, Guildford, UK,
October 2008.

7
Wehner, S., Operators apply CRP to a giant, Hart Publications, Houston,
Texas.

8
CO
2
EOR Technology, Technologies for Tomorrows E&P Paradigms,
US Department of Energy, Office for Fossil Fuel Energy, National Energy
Technology Laboratory, March 2006.

9
Storing CO
2
with Enhanced Oil Recovery, US Department of Energy,
National Energy Technologies Laboratory, February 2008.
Suzanne Ferguson graduated with an MEng (Hons) in chemi-
cal engineering from the University of Surrey in 2004 and joined
the Foster Wheeler Energy Ltd. (FWEL) graduate training program.
In her first three years at Foster Wheeler, she worked on refinery
and hydrogen unit front-end engineering design (FEED) projects
and performed basis of design, FEED and EPC-phase dynamic simulation for LNG
projects, obtaining her chartership as a chemical engineer in 2007. Ms. Ferguson is
now a member of the CCS and gasification team in FWELs Business Solutions Group
where she has worked on a range of CCS studies, FEED and pre-FEED projects. In
2008, she completed a training assignment at Foster Wheelers Italian operation in
Milan during which she worked on power island design.
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andling eq
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Corrosive and toxi
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Temperatures to TT 1100 F
d
t In h
y s u dust in r
g handlin eq
p orm aw e e awl rm f er
tough requireme h re iremen
Corrosive and toxi
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I

55
Managing costs and incidents
in industrial plant equipment
Use this method to allogate limited maintenance resources
to the most critical equipment
M. GARDELLA, E. EGUSQUIZA, X. ESCALER, Technical University of Catalonia,
Barcelona, Spain; and A. GOTI, University of Mondragn, Guipzcoa, Spain
T
he purpose of this research is implementing a continuous
improvement initiative in terms of reliability, availability,
maintainability and safety. This article presents a method
with the goal of showing in which equipment, how and with which
cost incidents related to maintenance appear in industrial plant
equipment. The approach will be developed through performance
ratios. The goal of the initiative is to extract the information required
to know where the maintenance resources are spent and which criti-
cal points reduce the availability of industrial plant equipment.
The study centers on three ratios: the number of incidents,
their cost and the fraction between the cost and the number of
incidents, all of them grouping incidents by equipment type or
considering each piece of equipment. Each of these groups is
presented in a structured way to back up plant managers in the
decisions they make.
With the methodology designed, it is possible to know the
number of events of a specific type of incident per machine type
and its associated cost.
Thus, a procedure is defined for establishing reference values
for indicating the importance of the frequent repetition and the
cost of plant incidents.
The developed approach is applied to a chemical plant for
several types of equipment: several incidents and costs related to
pumps are systematically detailed.
The study aims at showing the importance of organizing the
information in a structured way, which can be applied in the
maintenance management of an industrial plant to improve the
assigned resources, reducing costs and rocketing productivity.
Introduction. This work presents a method to extract informa-
tion about incidents related to maintenance performed on indus-
trial plant equipment, based on the studies developed by Bradley
and Dhillon.
1,2
In each of their works a compilation of incidents is
performed, studying the periodicities that happen over the time.
A main difference between maintenance management as a
business unit and maintenance benchmarking relies on the fact
that the first aims at maximizing the maintenance department
performance whereas the second is oriented to maximizing the
plant profitability, as is indicated by Kelly and Levitt.
3,4
Both
maintenance as a business unit and benchmarking related to
maintenance are taken as a basis for the presented research, as both
goals are pursued jointly.
The objective herein is to establish a path that allows visual-
izing the types of incidents that happen in a plant, categorized
by different types. Thus, it is possible to focus the limited plant
resources on improving the effectiveness of its resources, as Souris,
Wireman and Goti recommend.
5,6,7
To structure the maintenance activity information three main
management ratios are presented: the amount of incidents, their
cost and the ratio between these costs and number of incidents.
Next, the ranges of the necessary values to size the importance of
the ratio are presented. Machines with high values in their ratios
are critical points for maintenance so that resources may be pri-
oritized toward this machinery.
The diminution in the values of these ratios represents that the
plant is managed more efficiently, increasing its productivity, as is
affirmed by Juric,
8
thanks to reductions in stoppages and unavail-
ability, as Amendola and Garca Garrido indicate.
9,10
Literature review. Failures producing anomalies in equip-
ment operation are presented according to their relevance and
gravity, as proposed by Narayan.
11
These failures should be quan-
tified, as proposed by Wireman.
12
Industrial companies try to maximize the productivity of their
equipment through management models that organize the human
and technical resources they have, as Campbell and Tomlingson
indicate.
13,14
Performance indexes utilized herein are frequently
related to productivity and quality, always trying to respect envi-
ronmental regulations, as stated by Narayan and Wireman.
11,12
The aim of any management model or philosophy, such as
RCM, TPM, etc., is to try to maximize resource effectiveness, to
avoid unscheduled stoppages and obtain the desired performance
ratio values, as proposed by Amendola.
9
MTBF is a reliability ratio consisting of the averaged value
of working time between stoppages. It is scientifically related to
reliability laws throught the failure rate.
15,1,16
MTBF is comple-
mented with the maintainability parameter MTTR. These ratios
are useful to measure the amount of incidents in a system during
a period of time.
Once events are technically analyzed, it is very important to
perform a profitability study of the actions to be made, as Ber-
man indicates.
17
Thanks to the literature review, it is shown that the models and
methods related to optimizing maintenance productivity and reli-
56

I

ability propose an overall framework. In this framework ways to
detect significant productive inefficiencies through performance
ratios must be developed, considering both economic impacts of
incidents and how many times these events are repeated. Addition-
ally, the proposed structure has to be helpful to propose actions
that are profitable for the company.
The mentioned references also help in understanding how pro-
duction and maintenance departments work, their needs and their
objectives. But as a conclusion of the literature review a gap is detected
in defining a method for the practical identification and prioritization
of productive inefficiencies caused by equipment or system failures.
This gap is also extended to the way the method results are presented,
which should permit production and maintenance work together.
Industrial plant maintenance departments that act in a mainly
corrective way have to somehow justify their usually high costs
related to maintenance. The MTBF and MTTR values of their
equipment are a function of their own effectiveness, being rela-
tively difficult to be compared with other plants. This may hap-
pen because of their deficiency in management, more specifically
due to the lack of organization for identifying and being short of
preventive maintenance interventions.
Thus, the next section proposes a methodology to detect sig-
nificant productive inefficiencies through performance ratios, con-
sidering both economic impacts of incidents and how many times
these events are repeated. The work is then tested and applied to
different cases to analyze its validity.
This way of working makes it easy to analyze the plant effi-
ciency level. By sizing the parameters in the methodology pro-
posed in the next section properly which combinations of failure
modes and systems are more important can be determined.
In these critical points is where more human and technical
resources can be used to diminish the value of the index, and thus
obtain a higher efficiency. This procedure leads to the implanta-
tion under the concepts of economic reliability and feasibility.
Methodology. The methodology proposed herein follows the
steps presented in the scheme detailed in Fig. 1.
The information reported in the daily operative by all the
departments is varied and complex, with several input and out-
put values in the computerized management systems they use. In
this study it is necessary to extract the information related to the
maintenance actions in the different plant areas. It is also really
important to have access to data about time and cost associated
with these interventions.
Thus, it is important to integrate into a worksheet the follow-
ing variables:
Incident number
Industrial plant area
System affected by the incident
Incident description
Incident date
Number of hours to solve the incident
Cost associated with the incident repair.
Once the information is properly arranged, it is necessary to
obtain the performance indexes to control the information and,
therefore, manage the plant maintenance.
The indexes proposed in this article are the cost of the inci-
dents, their numbers and the fraction obtained by dividing the
cost with the number. Prior to the estimation, it is essential to
define the incident and equipment types, and this work is a func-
tion of the equipment type we have within our industrial plant.
Reckoning process. Eqs. 1 to 12 indicate the way to count
maintenance incidents and costs in a structured way. Eqs. 1, 2,
3 and 4 count the total, per equipment, equipment and incident
type and number of incidents, respectively.

I
tot
= I
ij
(k.l ),
j
k and l (1)

I
j
e
= I
ij
e
(k.l ),
i
k and l (2)

I
l
e
= I
ij
(k.l ),
j
with I
ij
(k.l ) =1 l =l
e
and
with I
ij
(k.l ) =0 1l
e
, and k (3)

I
k
e
= I
ij
(k.l ),
j
with I
ij
(k.l ) =1 k =k
e
and
with I
ij
(k.l ) =0 k k
e
, and 1 (4)
Eqs. 5, 6, 7 and 8 count the total, per equipment, equipment
and incident types and cost incidents, respectively.

C
tot
= C
ij
(k.l ),
j
k and l
i
(5)

C
j
e
= C
ij
e
(k.l ),
i
k and l (6)
Denition of incidents
and equipment types
Information summary
of maintenance
Incident assignment types
To add incidents and costs for
incident and cost types
To establish indicator
range values of incidents,
costs and ratios
Contribution of technical and
economic improvements
Obtaining and analysis
of new results
Good results?
No
Optimized system
Yes
Representation and results
analysis
Scheme for managing incidents. FIG. 1

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58

I


C
l
e
= C
ij
(k.l ),
j
with C
ij
(k.l ) =1 l = l
e
and
with C
ij
(k.l ) =0 l l
e
, and k (7)

C
k
e
= C
ij
(k.l ),
j
with C
ij
(k.l ) =1 k = k
e
and
with C
ij
(k.l ) =0 k k
e
, and l (8)
Eqs. 9, 10, 11 and 12 count the total, per equipment, equip-
ment type and incident cost/incidents fraction, respectively.

C
I
tot
=
C
tot
I
tot
, k and l (9)

C
I
je
=
C
j
e
I
j
e
, k and l (10)

C
I
l
e
=
C
l
e
I
l
e
, with C
ij
(k.l ) =1 and I
ij
(k.l ) =1 l = l
e
.
with C
ij
(k.l ) =0 and I
ij
(k.l ) =0 1l
e
, and k (11)

C
I
k
e
=
C
k
e
I
k
e
, with C
ij
(k.l ) =1 and I
ij
(k.l ) =1 k = k
e
and
with C
ij
(k.l ) =0 and I
ij
(k.l ) =0 k k
e
, and l (12)
Once the values from theses management ratios have been
calculated then they have to be discussed. To do that, where the
highest and lowest values are obtained must be analyzed. These
values must represent a unique group of importance or gravity
defined for each group for a range of values for each ratio.
The lowest and highest points of each range of values are as well
a function of the frequency we perform the analysis, being possible
to apply a weekly, monthly, quarterly, annual, etc., periodicity.
Fig. 2 indicates the relationship existent between the ratio val-
Frequency
Variables
Seriousness
10 years
4,000
1,000
2,000
110
5
210
5
210
5
510
5
10,000
25,000
7,500
500
200
10
20
400
1,500
1
A
I
B
I
A
C
A
C
A
C/I
B
C/I
2
20
V
e
r
y

l
o
w
L
o
w
N
o
r
m
a
l
H
i
g
h
V
e
r
y

h
i
g
h
100
20
40 40 40 40
50 50 50 50 50
5 years
1 year
1 month
1 week
Value ranges for performance indexes per equipment
types.
FIG. 2
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DEFINING THE ART OF ENGINEERING EXCELLENCE
59
ues and the number of incidents, along with their costs and costs
incidents relationships. Some example values are given as well.
Eqs. 13, 14 and 15 indicate the value ranges for the number of
incidents, incident costs, and ratio values per incident management
indexes. These equations are adapted to the equipment type.
A
I
and B
I
in Eq. 13 indicate the lower and upper values for the
number of incidents per equipment type. In addition, A
C
and B
C

in Eq. 14 represent the lower and upper values for the incident
cost per equipment type. Lastly, A
C/I
and B
C/I
in Eq. 15 present
the lower and upper values for the cost/number of incidents ratio
per equipment type.

I
l
e
A
I
and I
l
e
B
I
, with I
ij
(k.l ) =1 l = l
e
and
with I
ij
(k.l ) =0 l le, and k (13)

C
l
e
A
C
and C
l
e
B
C
, with C
ij
(k.l ) =1 l = l
e
and
with C
ij
(k.l ) =0 l l
e
, and k (14)

C
I
l
e
A
C / I
and C
I
l
e
B
C /I
, with C
ij
(k.l ) =1 and
I
ij
(k.l ) =1 l = l
e
. with C
ij
(k.l ) =0 and
I
ij
(k.l ) =0 l l
e
, and k (15)
Eqs. 16, 17 and 18 present the management ratio values related
to the number of incidents and costs. These equations are related
to a specific piece of equipment.
D
I
and E
I
in Eq. 16 represent the lower and upper values of
the range of the number of incidents per piece of equipment. D
C
and E
C
in Eq. 17 indicate the very same index but considering
costs, while D
C/I
and E
C/I
in Eq. 18 are the same but for the costs/
number of incidents ratio.

I
j
e
D
I
and I
j
e
E
I
, k and l (16)

C
j
e
D
C
and C
j
e
E
C
, k and l (17)

C
I
j
e
D
C /I
and C
I
j
e
E
C / I
, k and l (18)
The ratio range values are established by production and main-
tenance managers. They are established through an extrapolation
of the values obtained in the daily management ratios to the values
to be obtained by these new indexes; thus, these complementary
ratios help improve plant performance by complementing, with
little effort, the operative ones identifying critical points that may
not be identified with classical procedures.
Chemical plant application. This application is based on
the information compiled in a Spanish chemical plant during a
year.
18
Specifically, all data necessary to calculate the variables pre-
sented in the methodology section are exported to a spreadsheet.
This information is sorted taking into account the classifica-
tion for equipment types and incidents shown in Table 1 based on
the works of Gardella, August, Mobley and Moubray.
19,18,20,21
Reckoning process. Using Eqs. 1 to 12, Tables 2, 3 and 4
show the number of incidents, their related costs and the costs/
number of incidents ratio, for the types of incidents detailed in
Table 1. Tables 5 and 6 present the information related to the
TABLE 2. Number of incidents per incident and
equipment type
Agitator 0 29 9 1 26 3 1 69
Pump 104 728 165 146 256 580 7 1986
Boiler 44 5 0 5 1 16 0 71
Distillation 38 1 1 54 5 32 0 131
column
Heat exchanger 30 0 0 110 0 48 0 188
Reactor 347 23 15 210 178 61 0 834
Tank 127 70 3 79 0 160 1 440
Total 690 858 193 605 466 906 9 3,727
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TABLE 1. Equipment types and incidents
Equipment types Incident types
Agitator Instrumentation
Pump Magnetothermic off
Boiler Fastener leak
Column distillation Joint leak
Heat exchanger Lubrication
Reactor Planned revision
Tank Nailed pump
60

I

number of incidents with their costs. It is worth noting that for
this case the studied elements are pumps.
Three groups or value ranges are defined for gravity, indicated
with green, yellow and red colors depending on the lower or
higher importance, respectively. White-colored cells represent
noncritical equipment (Table 7).
In a cell in Table 2 there appears a 580 value (high gravity (red))
for the type of incident planned revision of the pump equipment. In
Table 3 it is possible to observe that its cost is 60.548 (average grav-
ity (yellow)) and a fraction of 104,39 /incident (low gravity (green)),
in Table 4. This third ratio is an example since it shows the relative
importance of a specific incident in the studied chemical plant.
Table 7 shows the lower and upper limits for the ranges of values
for the management ratios presented in the previous tables, using
Eqs. 1318. It is worth remembering that these values are specific for
this example, being necessary to adapt these limits to this situation.
Once the management ratios are detailed, it is necessary to
establish priorities in assigning resources with the objective of
diminishing the value of the indexes presented herein.
The reduction in the number of incidents and their costs in a
machine is based on finding the best combination of economic
and technological solutions, to guarantee that the interaction
among the productive process, maintenance, technical and mana-
gerial concepts improves the plant performance.
Discussion of results. It can be observed in Tables 2, 3 and 4
that the type of incident magnetothermic off shows 728 incidents
(red), being a very high value, costing 27,779 (green) and a frac-
tion of 38 /incident, being a noncritical incident. Once analyzed
from the study results it is clear that each incident of this type is
not important, but it is significant on the whole.
After having studied and analyzed the causes of the incident
type, magnetothermic off, it is concluded that it may happen because
of an overcharge in the equipment, a lack of lubrication or refrig-
eration, etc. In these cases the problem cannot be assumed by the
maintenance department, because the equipment is not working in
the conditions it should and the total annual cost is very high.
Concerning the reactor equipment, only 61 incidents have
happened (green (low gravity)) with the reason planned revision,
with a total cost of 163,320 (red (high gravity)), with a costs/
number of incidents ratio that is also critical.
TABLE 4. Cost/number of incidents ratio per incident
and equipment types
Agitator 0 175 133 25 183 541 8 152
Pump 73 38 428 223 73 104 600 220
Boiler 275 4 0 75 10 1.498 0 266
Distillation 106 1 45 153 1.031 937 0 325
column
Heat exchanger 50 0 0 336 0 2.123 0 358
Reactor 122 49 30 284 22 2.676 0 455
Tank 109 18 179 174 0 41 60 83
Cost/incidents in 105 41 116 181 188 1.132 96
incidents types
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TABLE 3. Costs per incident and equipment types in
1
Agitator 0 5.089 1.193 25 4.762 1.624 8 12.702
Pump 7.614 27.779 70.590 32.560 18.693 60.548 4.201 221.985
Boiler 12.086 19 0 377 10 23.974 0 36.465
Distillation 4.038 1 45 8.251 5.155 29.979 0 47.469
column
Heat 1.494 0 0 36.941 0 101.920 0 140.355
exchanger
Reactor 42.199 1.126 457 59.555 3.974 163.220 0 270.531
Tank 13.839 1.258 538 13.771 0 6.570 60 6.037
Total 81.269 35.273 72.823 151.480 32.593 387.835 4.270 765.544
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TABLE 5. Number of incidents per incident type and
specific pump
P-060 1 1 0 4 0 0 0 6
P-061 8 42 0 0 0 9 0 59
P-062 4 1 8 1 0 0 0 14
P-063 0 0 1 0 0 0 0 1
P-064 0 0 0 0 0 0 0 0
P-065 2 2 22 3 1 6 0 36
P-066 1 2 7 0 0 0 0 10
P-067 12 0 5 1 31 0 0 49
P-068 2 0 0 0 0 5 0 7
P-069 0 0 5 0 0 0 0 5
P-070 1 1 5 3 2 5 0 17
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TABLE 6. Cost per incident type and specific pump
P-060 109 119 0 533 0 0 0 762
P-061 195 441 0 0 0 2.011 0 2.647
P-062 269 0 2.775 25 0 0 0 3.068
P-063 0 0 364 0 0 0 0 364
P-064 0 0 0 0 0 0 0 0
P-065 41 256 18.274 4.202 479 139 0 23.392
P-066 62 28 2.779 0 0 0 0 2.868
P-067 677 0 2.153 31 1.464 0 0 4.324
P-068 251 0 0 0 0 26 0 278
P-069 0 0 1.604 0 0 0 0 1.604
P-070 201 0 5.791 186 173 21 0 6.372
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I

61
Going deep into detail in the management of such reactors, it
was concluded that these planned interventions are due to com-
pulsory actions related to strict regulations must be performed,
so there was little to do in this case.
Cells in Tables 5 and 6 present respectively 22 incidents (yel-
low) for pump P-065, for the incident type fastener leak, with the
associated cost of 18,274 (red); with a 831 /incident ratio,
a nonindicated value. When a pump locker is loose, the locker
has to be repaired, and this operation is usually very expensive.
Thanks to this analysis it was concluded that it is not possible
to afford more than 10 incidents per year for this incident type,
as otherwise the maintenance profitability is seriously damaged,
being reflected in the maintenance department budget.
Thus, the 22 incidents that in this case have to be faced are
an excessive value although it is shown in yellow; this situation
happens because several pumps with a high failure rate exist and
there is little that can be done about it unless a substitution of the
whole pump is performed.
As a summary, it has been proved that the results obtained
permit finding the root causes that must be reduced to increase
the chemical plant efficiency. HP
NOMENCLATURE
I
tot
Total number of incidents
I Number of incidents
C
tot
Total incident cost,
C Incident cost,
C
I
tot
Total incident cost ratio,
Euro
C
I
Incident ratio cost,
i Incident number i
j, j
e
Equipment
k, k
e
Incident type
l, l
e
Equipment type
A
I
, B
I
Lower and upper values of the number of incidents per
equipment type
A
C
, B
C
Lower and upper values of the cost per equipment type
A
C/I
, B
C/I
Lower and upper values of the cost/incident ratio per
equipment type
D
I
, E
I
Lower and upper values of the number of incidents per
equipment
D
C
, E
C
Lower and upper values of the cost per equipment
D
C/I
, E
C/I
Lower and upper values of the cost/incident ratio per
equipment
MTBF Mean-time-between failures
MTTR Mean-time-to-repair
RCM Reliability-centered-maintenance
TPM Total productive maintenance
LITERATURE CITED

1
Bradley, Jones, R., Risk-Based Management: A Reliability Centered Approach,
Gulf Professional Publishing, 1995.

2
Dhillon, B., Engineering Maintenance: A Modern Approach, CRC Press, 2002.

3
Kelly, A., Benchmarking for School Improvement: Practical Guide for Comparing
and Achieving Effectiveness, Routledge, 2001.

4
Levitt, J., The Handbook of Maintenance Management, Industrial Press Inc.
New York, 1997.

5
Souris, J., Maintenace, source of profits, Ed. Les ditions dorganisation, 1990.

6
Wireman, T., Benchmarking Best Practices in Maintenance Management,
Industrial Press, New York, 2004.

7
Goti, A., Sound-based predictive maintenance: a cost-effective approach, Special
Report on Maintenance and Reliability, Hydrocarbon Processing, vol. 87, no.
5, pp. 3740, 2008.
8
Juric, Z., Ingeniera de Planta S.L., Seminary on Maintenance and
Profitability Ratios (in Spanish), 2004.

9
Amendola, L., The Theory of Constraints, TurnaroundShutdowns
Maintenance, Espuela de Plata. Sevilla, 1999.

10
Garca Garrido, S., Integral Organization and Management of Maintenance (in
Spanish), Ed. Daz de Santos, 2003.

11
Narayan, V., Effective Maintenance Management: Risk and Reliability Strategies
for Optimizing Performance, Industrial Press Inc., 2004.

12
Wireman, T., Developing Performance Indicators For Managing Maintenance,
Industrial Press Inc., 2005.

13
Campbell, J., and Reyes-Picknell, J., Uptime: Strategies for Excellence in
Maintenance Management, Productivity Press, 2006.

14
Tomlingson, P., Effective Maintenance: The Key to Profitability: A Managers
Guide to Effective Industrial, John Wiley and Sons, 1993.

15
Birolini, A., Reliability Engineering: Theory and Practice, Springer, 2004.

16
Lyonnet, P., Tools of Total Quality, Ed. Chapman & Hall, 2007.

17
Berman, J., Maximizing Project Value: Defining, Managing, and Measuring
for Optimal Return, AMACOM, 2007.

18
Gardella, M., Incidents in Chemical Plant Equipment (in Spanish), IGM, n
4950, Ed. Alcion, Madrid 20062007.

19
August, J., Applied Reliability Centered Maintenance, PennWell Books, 1999.

20
Mobley, R., Root Cause Failure Analysis, Elseiver, 1999.

21
Moubray, J., Reliability-Centered Maintenance, Industrial Press Inc., 2001.

22
Campbell, J., Maintenance Excellence: Optimizing Equipment Life Cycle
Decisions, CRC Press, 2001.

23
Wireman, T., Maintenance Management and Regulatory Compliance Strategies,
Industrial Press Inc., 2003.
Marc Gardella is an industrial engineer doing his PhD in the
Polytechnic University of Catalonia (UPC) since 2004. His PhD work
is aimed at improving the Reliability Centred Maintenance meth-
odology in the petrochemical industry. In addition, Mr. Gardella
has worked as maintenance manager in a chemical plant and as a
trainer in a petroleum company.
Xavier Escaler holds a PhD in industrial engineering and is
a member of the Department of Fluid Mechanics of the UPC. He
teaches courses on fluid mechanics and hydraulic machines. Dr.
Escaler simultaneously heads CDIF projects and provides services
for companies, including vibration analysis, damage detection
and applying predictive maintenance techniques for turbomachines both online
and offline. His main research line is predicting erosive cavitation and the dynamic
behaviour of large hydraulic machines.
Aitor Goti holds a PhD in Engineering. He teaches subjects related
to project management and operations research in the Engineering
School of the University of Mondragon (MU). Dr. Goti has taken part
in over 20 research projects supported by private and public funding
and written over 40 national and international publications.
Eduard Egusquiza holds a PhD in industrial engineering and
is Professor of Fluid Mechanics at the School of Industrial Engineer-
ing of Barcelona (ETSEIB) (UPC). Dr. Egusquiza has been secretary of
the Hydraulic Machinery and Systems section of the International
Association of Hydraulic Engineering and Research (IAHR) since
2002. He is a member of the TC-10 Technical Diagnostics Committee (IMEKO) and
of the ISO/IEC JWG1 Committee.
TABLE 7. Value ranges for the proposed management
ratios
Low Medium High
A
I
50 151 > 500
B
I
150 500 > 500
A
C
10,000 50,000,001 > 100,000
B
C
50,000 100,000 > 100,000
A
C/I
200 500,001 > 1,000
B
C/I
500 1,000 > 1,000
D
I
10 16 > 25
E
I
15 25 > 25
D
C
900 3,000,001 > 6,000
E
C
3,000 6,000 > 6,000
A
L

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63
PLANTY SAFETY AND ENVIRONMENT
Designing for pressure safety valves
in supercritical service
Use this rigorous method to prevent over-sizing
R. C. DOANE, S&B Engineers and Constructors Inc., Houston, Texas
P
ressure safety valves (PSVs) on vessels containing liquid
hydrocarbon that may be blocked in during a fire can relieve
a supercritical fluid, if the relieving pressure is higher than
the critical point. The conventional method for calculating an
orifice size is presented in API RP-521.
1
This method, however,
treats all un-wetted vessels the same, whether the fluid contained
is supercritical, a vapor or a gas. Caution is given in the API text
and states that the given equations are based on the physical
properties of air and the perfect gas laws with no change in fluid
temperature. The reader is cautioned to review these assumptions
to ensure they are appropriate for any particular situation.
Supercritical fluids are not obedient to the perfect gas laws.
Compressibility factors can range from 0.5 to 0.7 and are not con-
stant while the vessel is relieving. Also, the fluid temperature is not
constant. Fortunately, it can be shown that the API method is con-
servative, producing larger orifice areas than required. On the other
hand, an over-sized valve has two problems: there is a potential for
destructive valve chatter and larger PSVs are more expensive.
The method presented adheres to basic thermodynamic prin-
ciples, not the perfect gas laws. The resulting orifice areas are
significantly smaller than those derived from the API method.
Sonic flow through the PSV orifice is taken into account.
Fire case scenario. Fig. 1 illustrates a typical fire case situation
for a pressure vessel containing a hydrocarbon liquid. Both the
inlet and outlet lines have a valve capable of being closed, inadver-
tently or not. If all the valves are shut, this is considered a blocked
in condition. The vessel is only 10 ft from grade level. According
to the API RP-521 standard, the entire vessel can be exposed to an
external fire. The pressure in the drum will rise until the PSV set
pressure is reached. At this point, the PSV will start to open. The
valve will be fully open at the relieving pressure, normally 21%
above the set pressure for a fire case design.
The relieved fluid condition depends on the critical pressures
relation to the relieving pressure. If the relieving pressure is less
than the fluids critical pressure, the liquid will boil when the
PSV opens. Relieving pressure will continue until the liquid is
all vaporized. The temperature will only vary during the relieving
process if the fluid is multi-component having a boiling range.
If the relieving pressure is above the critical pressure, the liquid
will not boil. The fluid becomes supercritical, having the proper-
ties of one phase, somewhere between a liquid and a vapor. The
fire will continue to heat the drum and its contents, even if the
fluid is composed of only one compound. Eventually the pres-
sure will reach the PSV relieving pressure. The PSV will open
and relieve a vapor below the critical pressure. Relieving pressure
will continue until no more moles of fluid remain in the drum to
maintain the pressure.
Vent to process
To are
10 ft To pump
Typical vesssel subject to fire case study (and possibly
supercritical relief).
FIG. 1
Enthalpy
Critical pressure
Critical
temperature
Relieving pressure
Maximum
back-pressure
Critical
point
Two-phase
region
Liquid region
Vapor
region
Line of constant specic volume
Initial
condition
Choke
conditions
Lines of
constant
entropy
P
r
e
s
s
u
r
e

Typical hydrocarbon P-H Diagram (showing path of fluid
conditions into the supercritical).
FIG. 2
64

I

PLANT SAFETY AND ENVIRONMENT
The path to supercritical. Fig. 2 shows a pressure-enthalpy
(P-H diagram) to illustrate the path taken by the fluid from the
initial condition to the relieving conditionafter the drum is
blocked in and a fire starts. The vapor remains in equilibrium as
the temperature increases.
The pressure follows the liquids vapor pressure up the boundary
of the two-phase region to the critical point. If the relieving pressure
is above the critical point, the pressure and temperature will con-
tinue to increase along the path of constant specific volume, from
the critical point to the horizontal relieving pressure line. The fluid
must remain at constant volume because, with no fluid relief, both
the mass of fluid and the vessel volume remain essentially constant.
The distinction between vapor and liquid phases has been lost.
After reaching the relieving pressure, the fluid will continue to
be heated by the fire. The pressure must remain the same to avoid
over-pressuring the drum. The temperature and required relieving
rate will vary as the relieving process continues.
Fig. 2 also shows five points, corresponding to different PSV
inlet conditions along the relieving pressure line. These points will
be needed to verify location of the condition requiring the largest
PSV orifice area. It has been shown that the mass relieving rate,
volume relieving rate and maximum orifice area are not necessarily
found at the same temperature.
3
Also illustrated are four points corresponding to a choked
condition at the outlet of the orifice. The velocity through the
orifice is sonic for these conditions and the relieving rate must be
calculated accordingly. Sonic flow is typical for supercritical relief.
The remaining four points, along the back-pressure line, are only
needed when the orifice flow is not sonic.
Procedure and calculations. The procedure consists of
transcribing property data obtained from a process simulator onto
a spreadsheet that calculates relieving rates and required orifice
areas (Table 1). The calculations follow the logic diagram in Fig. 3.
The fluid in this example is normal butane. The vessel is assumed
to be essentially full, with a small vapor space. Table 2 shows the
fluid and vessel data that should be gathered and entered into the
spreadsheet.
To calculate the heat transfer rate from a fire, use Eq. 1:
1

Q =21, 000 fA
e
0.18
(1)
It is assumed that Eq. 1, derived for wetted surface areas, is also
applicable for supercritical fluids, where the concept of wetted
becomes nebulous. Any error is on the safe side, since the heat trans-
fer rate to a wetted surface is higher than for an unwetted surface.
TABLE 2. Fluid and vessel information gathered and
inputted into the spreadsheet
Data required Comment
Vessel exposed area Include both heads
Insulation factor Usually 1.0; see Table 5 in API RP-521 3.15
PSV relieving pressure For a fire case, the relieving pressure is 1.21 times
the set pressure.
Maximum PSV back pressure The flare system is usually designed to provide a
maximum value at each PSV
Fluid mole weight and The process simulator may be needed to calculate
critical properties the critical properties.
TABLE 3. API RP-521 method vs. the rigorous method
Max. orifice Relief Orifice
Method area (in.
2
) mass rate (lb/hr) velocity (ft/sec)
API RP-521 0.186 14,351 287
Rigorous 0.0651 13,405 950
TABLE 1. Supercritical relief valve sizing example problemnormal butane
Choked Choked Orifice Mass Volume Mass Orifice
Enthalpy Entropy Cp/Cv pres flow velocity flux flow flow area
Segment Point T P rho V h s k Pc ? v G Q W A
points number (F) (psia) (lb/ft
3
) (ft
3
/lb) (Btu/lb) (Btu/lb-F) (psia) (ft/sec) (lb/ft
2
sec) (ft
3
/hr) (lb/hr) (sq in.)
critical 306 550 10.74 0.0931
1 to 2 1
in
424.0 983 10.74 0.0931 815.8 0.5797 1.522 499.9 yes 953 4,658 1,304 6,374 0.0644
1
sonic
359.0 499.9 4.889 0.2045 0.5797 1.295
1
subout
200.8 40.0 0.3430 2.9155 881.7 0.5797
2 to 3 2
in
434.0 983 10.19 0.0981 807.0 0.5896 1.464 508.9 yes 950 9,685 1,315 1,3405 0.0651
2
sonic
372.3 508.9 4.775 0.2094 0.5896 1.268
2
subout
214.3 40.0 0.3352 2.9833 875.1 0.5896
3 to 4 3
in
444.0 983 9.711 0.1030 798.6 0.5990 1.415 516.8 yes 949 9,219 1,274 12,371 0.0631
3
sonic
385.0 516.8 4.671 0.2141 0.5990 1.246
3
subout
227.3 40.0 0.3281 3.0479 868.6 0.5990
4 to 5 4
in
454.0 983 9.293 0.1076 790.3 0.6081 1.375 523.5 yes 949 8,819 1,250 11,620 0.0620
4
sonic
397.4 523.5 4.57 0.2188 0.6081 1.227
4
subout
239.8 40.0 0.3216 3.1095 862.3 0.6081
5
in
464 983 8.925 0.1120 782.2
Vessel diameter (ft): 6 T
normal
90 F
Vessel tan-tan (ft): 12 Molecular weight: 58.12 P
normal
44 psia
A
e
(exposed area) (sq ft) 304 Relieving pressure (psia) 983 Kd 0.85 (2)
f (insulation factor) 1.0 = found by trial Kb 1
q (mBTU/hr) 2.283 (5) Back-pressure, Pa (psia) 40 Kc 1

I

65
Using a simulator program, define the first point 1
in
, on the
relieving pressure line. The specific volume must equal the fluids
critical volume. Knowing P and V, find T by trial. This is equiva-
lent to drawing a line of constant specific volume from the critical
point to the horizontal relieving pressure line. Record h, s and k
for point 1
in
.
Move to the next point by incrementing T by 10F. A higher
accuracy can be achieved with smaller temperature increments,
but 10
o
is sufficient for this example. Knowing P and T, use the
simulator to find V, h, s and k for point 2
in
. Repeat the temperature
increments until all five PSV inlet pressures have been defined.
For each point it must be known whether or not the flow
through the orifice is sonic. The choke pressure at the orifice is
calculated from Eq. 2.
4
P
ch
= P
in
[2 / (1+k
in
)]
(k
in
/(k
in
1)
(2)
Compare P
ch
with P
back
. If the choke pressure is higher than
the back-pressure, sonic flow exists at the orifice.
Sonic flow. Since the change in condition from upstream of
the orifice to the orifice itself is adiabatic and almost reversible,
the change is virtually isentropic. We can determine the other
properties for i
sonic
by keeping s the same as for the inlet point,
i
in
and setting P = P
ch
. The temperature is found by trial. This is
equivalent to drawing an isentropic line from point i
in
to P
ch
on
the P-H diagram. Record k
sonic
and V.
The sonic velocity is found using Eq. 3:
4

v
son
= k
son
g
c
(R/M)T (3)
The orifice area equation will need a value for the mass flux,
G, found from the velocity and specific volume:

G =v
son
/ V
son
(4)
Subsonic flow. For subsonic flow, the procedure and equa-
tions are similar to the sonic case. At constant s and with P =
P
back
, define point i
subout
. The temperature is found by trial. This
is equivalent to drawing an isentropic line from i
in
to the back-
Calculate the heat transfer rate from
the re to the vessel:
q = 21,000 f A
e
-0.18
Using a process simulator, nd point 1
in
,
at the relieving pressure and the critical
volume.
Determine: Vessel exposed area
Vessel insulation factor
PSV relieving pressure
Maximum PSV back-pressure
Assume: Adequate drainage exists
under the vessel
Fluid critical properties (pressure,
temperature and specic volume)
Fluid molecular weight
Record h, s and k for point 1
Increment T by 10F
Let i = point number 1
Using the simulator, nd V, h, s and k for
point i. Maintain P at the relieving pressure.
The temperature is found by trial.
No Yes
i = 5 ?
Next point
i = i + 1
Back to rst point
i = 1
Calculate the choke pressure for point i
in
:
P
ch
= P
in
[ 2/(1 + k
in
]
(k
in
/ (k
in
1)
Flow through
the PSV orice
is sonic.
Flow through
the PSV orice
is subsonic.
At constant s and with P = P
ch
,
nd point i
sonic
. The temperature
is found by trial. Record V and k.
At constant s and with P = P
back
,
nd point i
subout
. The temperature
is found by trial. Record V and h.
Calculate the uid velocity
through the orice:
v
son
= k
son
g
c
(R/M) T
Calculate the uid velocity
through the orice:
v
sub
= 2(h
in
h
subout
) g
c
(778)
Calculate the uid mass ux
through the orice:
G = v
son
/v
son
Calculate the uid volumetric ow:
Q = q(V
in,i+1
V
in,i
) /(h
in,i+1
h
in,i
)
Calculate the mass ow:
W = G/ V
Calculate the required orice area:
Select the largest required
orice area.
A = 0.04 W/ (K
d
K
b
K
c
G)
Next point
i = i + 1
G = v
sub
/V
sub
Calculate the uid mass ux
through the orice:
No Yes
Is P
ch
P
back
?
No Yes
i = ?
Logic diagram for supercritical relief valve sizing. FIG. 3

I

67
pressure line on the P-H diagram. Record h and V.
The subsonic velocity can be found using Eq. 5, derived from
the first law of thermodynamics, neglecting the relatively low
velocity upstream of the orifice.
4

v
sub
= 2(h
in
h
subout
)g
c
(778) (5)
The mass flux equation for the subsonic case is very similar to
that of the sonic case. Note that the subscripts in Eq. 6 are not
the same as in Eq. 4.

G =v
sub
/V
sub
(6)
Perform the velocity and mass flux calculations, including the
sonic/subsonic flow analysis, for each point 1 through 4.
Orifice sizing. After calculating G for each of points 1 through
4, the fluid volumetric flow is found using Eq. 7.

Q =q(V
in,i +1
V
in,i
) / (h
in,i +1
h
in,i
) (7)
This is an approximation to the differential equation resulting
from a heat and mass balance around the vessel, with constant
relieving pressure:
3
Q =q(dV /dh)
p
(8)
Knowing Q and G, the mass relieving flow and required orifice
area are found from Eqs. 9 and 10 as follows:
2

W =G/V (9)

A =0.04W/(K
d
K
b
K
c
G) (10)
The PSV discharge coefficient is assumed to be 0.85, as rec-
ommended in the API RP-521 standard for preliminary sizing
when vendor data is unavailable. The back pressure correction is
normally 1 for supercritical relief, since the relieving pressure is
so high. The combination factor is also 1, since a rupture disk is
not included in this example.
When the spreadsheet is complete, there are four values for
the orifice area to choose from. Simply select the maximum value
for the design. In the example spreadsheet, the area for point 2,
0.0651 in.
2
, is the largest of the four. It may be necessary to define
more points and expand the spreadsheet if the maximum area
occurs at point 4 or beyond.
Comparison with the conventional method. Table 3
compares the results of the conventional method in the API
RP-521 3.15 standard with the more rigorous method pre-
sented. The results of both methods are based on the previous
example problem. For the conventional method, the relieving
temperature is the same as for the rigorous method. Using the
ideal gas law to find the relieving temperature, as suggested in the
API RP-521 standard, may lead to unrealistic results.
It is readily seen that the conventional method in the API
RP-521 standard produces conservative results for relief of
supercritical fluids. The orifice design size is about three times
the area calculated using the more rigorous method. The mass rate
is higher, but the orifice velocity is far below sonic.
Conclusion. PSV orifice areas calculated using the method
in the API RP-521 standard when relieving supercritical fluids
are conservatively large. Orifices sized using a more rigorous
approach, based on thermodynamic principles, can be signifi-
cantly smaller, resulting in cost savings. HP
LITERATURE CITED
1
Guide for pressure-relieving and depressuring systems, American Petroleum
Institute, API RP 521, Fourth Edition, March 1997.
2
Sizing, selection and installation of pressure-relieving devices in refineries,
American Petroleum Institute, API RP 521, Seventh Edition, January, 2000.
3
Ouderkirk, R., Rigorously size relief valves for supercritical fluids, CEP,
August 2002, pp. 3443.
4
Weber, H. C. and H. P. Meissner, Thermodynamics for Chemical Engineers,
Second Edition, New York, 1963.
NOMENCLATURE
P Fluid pressure, psia
T Fluid temperature, degrees Rankine
rho Fluid density, lb/ft
3
V Fluid specific volume, ft
3
/lb
v Fluid velocity, ft/sec
h Fluid specific enthalpy, Btu/lb
s Fluid specific entropy, Btu/lb-F
k Specific heat ratio, Cp/Cv
G Fluid mass flux, lb/ft
2
-sec
W Fluid mass flow, lb/hr
A PSV orifice area, in.
2
Ae Surface area of vessel exposed to the fire, ft
2
i Fluid point number on the relieving pressure line
gc Newtons law conversion factor, lbm-ft/lbfsec
2
M Fluid molecular weight
K
d
PSV discharge coefficient
K
b
PSV back pressure correction factor
K
c
PSV combination correction factor
Q Fluid volumetric flow rate, ft
3
/hr
q Heat transfer rate from external fire to the fluid,
millions of BTU/hr
f Vessel insulation factor
R Gas constant, 1, 546
lbs ft
lb
mol
R
SUBSCRIPTS
in Fluid data at PSV inlet
sonic or son Fluid sonic velocity data at the PSV orifice outlet
subout Subsonic fluid data at the outlet of the PSV orifice
norm Normal fluid condition
ch Choke flow condition
Richard Doane recently retired following 37 years experience
in engineering and construction, plant start-up, and operation
supervision. When this article was written, Mr. Doane was a senior
process engineer with S&B Engineers and Constructors in Houston,
Texas. He holds BS and MS degrees in chemical engineering from
Northeastern University in Boston, Massachusetts and an MS degree in accounting
from the University of Houston in Clear Lake, Texas.
The PSV discharge coefficient is
assumed to be 0.85, as recommended in
the API RP-521 standard for preliminary
sizing when vendor data is unavailable.
The back pressure is normally 1 for
supercritical relief, since the relieving
pressure is so high.
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PIPING

I

69
C
alculating the factor is an essential step with piping sys-
tems for laminar and turbulent flows in smooth or rough
pipes. The Moody diagram is the most widely accepted
graphical method for determining factor but there are also many
equations for this purpose. Eqs. 1, 2 and 3 are used for calcula-
tion for laminar flow in pipes, turbulent flow in rough pipes
and turbulent flow in smooth pipes respectively.
f =
64
Re
(1)
Re
1
f
= 2log
10
/ D
3.7
+
2.51
Re f
(2)

1
f
= 4log
10
Re f
( )
0.4 (3)
The last two equations are very accurate but have the disad-
vantage of being implicit in that need an iterative estimation
method hence, considerable effort has been expended to introduce
an explicit equation to determine and simplify the calculation
for turbulent flow in rough and smooth pipes but this work just
focuses on Eq. 3 to introduce a new explicit friction factor equa-
tion for turbulent flow in smooth pipes.
In 1913, Blasius proposed Eq. 4 that is valid for the
range 3,000 < Re < 10
5
. Drew, et al. also introduced Eq.
5 that is good for the range 3,000 < Re < 310
6
in 1932 but
recently Goudar and Sonnad
1
recommended a very accu-
rate equation (Eq. 6) that is valid over the entire range of
turbulent flow regime in pipes 4,000 < Re < 10
8
and com-
pared the range of error in , % for nine explicit equations.

f =0.0791Re
0.25
(4)
f =0.0014 +0.125Re
0.32
(5)
1
f
=aW
Re
a
e
b
a
1
)
l
l
l
l
(6)
where:
a = 4/ln(10)
b = 0.4
W (x) =ln
x
ln
x
(ln x)
h
h =exp
1.124491989777808
0.4225028202459761+(ln(x))
Proposed explicit equation for . To represent the new

equation, the first step is deriving the factor from Eq. 3 for
3,000 points by the iterative method over 4,000 < Re < 10
8
and
then accurate and uniform relations are obtained between Re and
for five regions by data fitting and the final form Eq. 7 is derived
by selecting an average value for coefficients (Fig. 1).

f =
1.5114978x10
4
+
0.59501296
(ln(Re))
+
2.3501318
(ln(Re))
2

3.3218937
(ln(Re ))
3
2
(7)
New explicit friction factor equation
for turbulent flow in smooth pipes
A simple, explicit and high-accuracy equation is presented
A. SASAN-AMIRI, Bouali Sina Petrochemical Company, Khuzestan, Iran
0.000
10
3

f
a
c
t
o
r
Re
10
4
10
5
10
6
10
7
10
8
1E+09
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0.009
0.010
0.011
Friction factor from Eq. 3
factor derived from Eq. 3. FIG. 1
TABLE 1. Max., min. and average error in percent for 99,997 points
Equation name Eq. 7 Sonnad Nikuradse Blasius McAdams Bhatti Drew, et al.
Average -0.000243024 0.006791315 0.209029792 -39.84423026 -16.77314702 -9.155504298 11.58937747
Min. -0.000752998 0.006131462 -14.4272666 -46.75906704 -22.22733063 -18.85983705 -0.484544169
Max. -0.000208474 0.011714088 1.139429761 2.7564055 2.419757397 2.338352892 17.40457569
70

I

PIPING
Sonnad and Goudar have compared the range of error in per-
cent for nine equations and Fig. 2 shows the mentioned compari-
son for five equations that vary in a wide range and Fig. 3 compares
the mentioned error for Sonnad and Goudar and Eq. 7. Table 1
also represents the average error in percent for 99,997 points in
the range 4,000 < Re < 10
8
by the interval 1,000 and max. and
min. values. Hence, the recommended equation seems to be proper
to calculate the factor and estimate a more reliable and accurate
value in smooth pipes and the turbulent flow regime. HP
NOMENCLATURE
= Friction factor
/D = Pipe roughness
Re = Reynolds number
W = Lambert W function
LITERATURE CITED

1
Sonnad, J. R. and C. T. Goudar, Explicit friction factor correlation for pipe
flow analysis, Hydrocarbon Processing, June 2005, pp. 103105.

2
Holland, F. A. and Dr. Dragg, R., Fluid Flow for Chemical Engineers,
Edward Arnold publishing, Great Britain, 1995, pp. 7175.
10
3
Re
10
4
10
5
10
6
10
7
10
8
1E+09
-0.0005
0.0015
0.0035
0.0055
0.0075
0.0095
0.0115
0.0135

f
a
c
t
o
r
Sonnad, e%
New eq., e%
Error in percent for Sonnad and Goudar and the new
equations.
FIG. 3
Amir Sasan-Amiri works in the paraxylene unit in the pro-
cess engineering department of Bouali Sina Petrochemical Co.
as a process senior engineer. He holds a BSc degee in chemical
engineering from Arak Azad University, Iran, and an MSc degree in
construction management from Grenoble University in France. Mr.
Sasan-Amiris interests include fluid mechanics, heat transfer, separation processes
and process simulation.
Blasius, e%
McAdams, e%
Bhatti, e%
Drew, et al., e%
Nikuradse, e%
-50
-40
-30
-20
-10
0
10
20
E
r
r
o
r

i
n

,
%
10
3
Re
10
4
10
5
10
6
10
7
10
8
1E+09
Error in percent for five former explicit equations. FIG. 2
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I

71
INSTRUMENTATION
Implement a constrained optimal
control in a conventional level
controllerPart 1
Novel tuning method enables a conventional PI controller to explicitly
handle the three important operational constraints of a liquid level
loop in an optimal manner as well as copes with a broad range of level
control from tight to averaging control
M. LEE, Yeungnam University, Kyongsan, Korea; and J. SHIN and J. LEE, LG Chem.,
Daejeon, Korea
D
ue to the importance of liquid level loops for success-
ful plant operation, extensive research has been done to
enhance their control performance.
19
A level controller
is often required to not only minimize level deviation but also
to provide nonaggressive control action. Controlling outflow
behavior is as crucial as controlling the liquid level itself, especially
when the outflow is situated upstream of a critical unit such as a
reactor or a separation column. Furthermore, a liquid level loop
generally has three important operational constraints: the rate of
change in the outflow should be kept below an allowable limit
for smooth control action, the level deviation should be within
an allowable inventory limit and the outflow overshoot should
also be within an allowable limit to avoid severe overflow and
downstream oscillations.
For these reasons, level control problems can be considered
as typical constrained optimal control problems. In spite of its
industrial importance, the constrained optimal control strategy
has rarely been employed in level loops because of the lack of a
proper design method to implement it in the conventional PI con-
troller. Recently, a novel constrained optimization-based approach
has been proposed to cope with the constrained optimal control of
a level loop in a unified manner.
10,11
In this article, we introduce
a practical PI controller tuning method for optimal level control
by extending this approach to explicitly handle the three typical
constraints previously mentioned.
Optimal level control formulation. The liquid level loop
in Fig. 1 can be simply described by the following equation:

H(s ) =
1
As
Q
i
(s )
1
As
Q
o
(s) (1)
where:

Q
o
(s) = K
L
1+
1
I
s
H(s) H
set
(s )
( )
(2)
and
K
L
=K
c
Q
ovmax
H
span
(3)
The closed-loop transfer functions for the regulatory problem
are then:
H(s ) =
I
A
s
I
s
2
+
I
s +1
Q
i
(s ) (4)
Q
o
(s) =

I
s +1
I
s
2
+
I
s +1
Q
i
(s ) (5)
where:
H
=
A
K
L
=
V
K
c
(6)
and
V
=
AH
span
Q
ovmax
=
V
T
Q
ovmax
(7)
Q
i
Q
o
LT
LC
Typical level control loop. FIG. 1
72

I

INSTRUMENTATION
The damping factor of the above closed-loop characteristic
equation is expressed as:

=
1
2
H
(8)
The control objective is to minimize both the rate of change
in the outflow and the level deviation against the variation of the
inflow, which is the main concern in a level loop. The level loop
should also be operated under the following three operational
constraints or specifications: a maximum allowable rate of outflow
change, Q'
o max
; maximum allowable level deviation, H
max
; and a
maximum allowable outflow, Q
o max
, to a given inflow variation.
Therefore, the optimal control problem of a level loop can be
formulated as:

min =
H(t )
^H
span
l
l
l
l
l
2
0
]
dt +(1)
Q'
o
(t )
Q'
ov max
l
l
l
l
l
2
0
]
dt (9a
subject to:

Q'
o
(t ) Q'
o max
(9b)
H(t ) H
max
(9c)
Q
o
(t ) Q
o max
(9d)
Consider a regulatory problem with regard to a step change
of magnitude Q
i
in the inflow (i.e., Q
i
(s)=Q
i
/s). Through
some mathematical manipulations, the optimal control problem
defined by Eqs. 9ad can be converted into the following con-
strained optimization problem expressed in terms of
H
and (see
the Appendix for the details of its derivation):

min=(
H
,) =
H
3
2
+
1
H
1+
1
4
2
(10a)
subject to:
H
+
h
h() 0 (10b)

H

g
g()
0 (10c)
f ()
f
0 (10d)
where:
=2
Q
i
AH
span
2
; =
1
2
Q
i
Q'
ovmax
2
;
h
=
Q
i
Q'
o max
;
g
=
AH
max
Q
i
;
f
=
Q
o max
Q
i
(11)
where h(), g() and f () are given by Eqs. (A9), (A13) and (A6)
in the appendix, respectively.
Optimal PI controller design. Applying the Lagrangian
multiplier
12
converts the constrained problem in Eqs. 10ad into
the equivalent unconstrained problem:

min L(
H
,,
1
,
2
,
3
,
1
,
2
,
3
)
=
3
H
2
+
1
H
1+
1
4
2
+
1
(
H

h
h()
1
2
)+
H
g()
2
2
+
3
(
f
f ()
3
2
) (12)
If
h
h(
H

If
*f
H

vl
H
If
min

*h

vr
If
min

*g

vr
If
*g

>
vr
If
*h

>
vr
If
H

h
h(
)
If
H
>
K
c
= =;
I
V
T
If
vu
H

*f
H

vl
H
If
*f
H
>
vu
H
Global optimum
(
H
)
(
min
,
vl
H
)
(
min
,
*f
H
)
(
*h
,
*h
H
)
(
*g
,
*g
H
)
(
vr
,
vr
H
)
(
vr
,
vr
H
)
(
opt
,
opt
H
)
= 4(
opt
)
2

opt
H
(
min

,
vu
H
)
(
min

,
vl
H
)
(
min

,
vl
H
)
(
min

,
*f
H
)
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
N
N
N
N
N
N
Y
g(
g
g(
g
If
min

Q
omax
opt
H
Flow chart for finding the global optimum and optimal PI
parameters.
FIG. 3
Case A Case B
Case C
Case E Case F Case G
Case D
T
H
= G
g
/g(Z)
T
H
T
H
= G
h
h(Z)
Z
T
H
Z
T
H
Z
T
H
Z
T
H
Z
T
H
Z
T
H
Z
G
f

= f(Z)
(Z
+
T
H
+
)
(Z
*h
, T
H
*h
)
(Z
vr
, T
H
vr
)
(Z
*g
, T
H
*g
)
(Z
vl
, T
H
vl
)
(Z
vu
, T
H
vu
)
(Z
*f
, T
H
*f
)
Typical contours and constraints for the seven possible
cases with respect to the global optimum location. The
shaded part denotes the feasible region.
FIG. 2
Proof only. Copyrighted material.
May not be reproduced without permission.
Proof only. Copyrighted material.
May not be reproduced without permission.
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74

I

INSTRUMENTATION
where
1
is a Lagrange multiplier (
1
^0) and
i
is a slack
variable.
The necessary conditions for a stationary point are:

L
H
=3
2
H
2
H
1+
1
4
2
+
1
2
H
=0 (13a)

L
=2
3
H
2
1
3

2
g '()
3
f '()=0 (13b)
L
1
=
H

h
h()
1
2
=0 (13c)
L
2
=

g
H
g()
2
2
=0 (13d)
L
3
=
f
f ()
3
2
=0 (13e)
L
1
=2
1
1
=0;
L
2
=2
2
2
=0;
L
3
=2
3
3
=0 (13f )
The simultaneous solutions of Eqs. 13af for various combina-
tions of
i
=0,
i
0,
i
=0 and
i
0 are associated with the cor-
responding optimum cases. Fig. 2 shows the seven possible cases
with respect to the global optimum location of the optimization
problem in Eqs. 10ad. As depicted in Fig. 2, the global optimum
can be located in the interior of the three constraints (case A), on
the boundary of one constraint (cases C, B and E) or on the vertex
formed by two constraints (cases D, F and G). The conditions
associated with these seven possible cases can be evaluated by
investigating the geometrical characteristics of the contours and
constraints shown in Fig. 2 and are summarized in Table 1.
For example, case A corresponds to the situation where
1
=
2
=
3
=0 in Eq. 12.
This case is likely to occur when the three specifications,
Q'
o max
, H
max
and Q'
o max
are mild (i.e., have large values). In
particular, case A happens when
min
^
and
h
h(

g
g(
)
.
In this case, the extreme point (
H
) in the interior of the
three constraints is the global optimum. The global optimum (
H
) is calculated from Eqs. 13ab as given in Table 1:
=
1
2
and
H
=

1
4
Once the global optimum of (,
H
) is evaluated for a given
specification set, the corresponding optimal PI parameters can be
directly calculated from Eqs. 6, 7 and 8 as follows:
K
C
=
V
T
Q
ov max
H
;
I
=4
2
H
(14)
The shortcut procedure for finding the global optimum and
PI parameters is illustrated in Fig. 3. Since Q
o max
is only a func-
tion of for a given Q
i
, setting the value of Q
o max
is equivalent
to setting that of the minimum allowable damping factor,
min
.
Furthermore, it is clear that
*f
,
vu
and
vl
are equal to
min
. As
seen in Table 1, most of the equations employed for finding the
optimal are expressed in their implicit forms. However, cal-
culating the optimal can be easily achieved by using a simple
root-finding method.
It should be noted that when
h
<
g
, no vertex point is formed
by
H
=

g
g()
and
H
=
h
h
(). This situation is likely to occur when the
specification Q'
o max
and/or H
max
are mildly set with relatively large
values. In this case, it should be noted that case D does not exist
and the value of
vr
can be simply considered as extremely large
for evaluating the conditions in Table 1.
Effect of weighting factor. The weighting factor, w, is a
crucial parameter to adjust the control performance and robust-
ness. When a larger w is chosen, the optimal control performance
measure is mainly determined by the level response. Therefore,
the PI controller yields a tighter level response, which corresponds
to tight level control, and the response is likely constrained by
Q'
o max
. When a smaller w is used, the performance measure is
mainly weighted by the rate of change in the outflow. The control-
ler gives a smoother control action, i.e., averaging level control
and the response is likely constrained by H
max
.
Constraint set feasibility. It is often desirable to control a
level loop on the tightest possible constraint set. However, since
all three specifications are interrelated, they cannot be selected
arbitrarily or independently. Therefore, the constraint set should
be determined not only by considering the process requirement
but also by satisfying the feasibility.
Remark 1. For any given Q'
o max
(or H
max
), the tightest avail-
able H
max
(or Q'
o max
) always occurs at
t
= 0.4040 and thus satis-
fies
11

H
max
Q'
o max
=0.5206(Q
i
2
/ A) (15)
A g i v e n ( Q'
o ma x
, H
ma x
) s e t i s f e a s i b l e i f
H
max
Q'
o max
0.5206(Q
i
2
/ A). Otherwise, the (Q'
o max
, H
max
)
set is infeasible.
if
min

vr
if
h

g
Feasible (Q
omax
, H
max
, Q
omax
)
Given (Q
omax
, H
max
, Q
omax
)
Increase Q
omax
Increase (Q
omax
, H
max
)
If H
max
Q'
omax
0.5206 (Q
2
i
/ A)
Infeasible
Infeasible
Y
Y
Y
N
N
N
Feasibility check and design of a constraint set. FIG. 4
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76

I

INSTRUMENTATION
Remark 2. Q
o max
can be specified only between Q
i
and
2Q
i
. Any (Q'
o max
, Q
o max
) and (H
max
, Q
o max
) set is feasible with
this available Q
o max
. The tight (Q'
omax
, Q
o max
) (or (H
max
, Q
o max
))
specification set requires the mild H
max
(or Q'
o max
) specification
for it to be feasible.
Fig. 4 illustrates the overall procedure for checking the fea-
sibility of a given constraint set and designing a feasible con-
straint set.
Part 2 of this article will be published in February and dis-
cuss PI controller design for tight constraint control and provide
some examples.
TABLE 1. Conditions associated with and calculation of global optimums for the constrained optimization problem
in Eqs. 10
Lagrangian Typical Global optimum Global optimum
Case parameter specification Condition and its location calculation
A
1
=
2
=
3
=0
Mild Q
o max
,
Mild H
max
,
Mild Q
o max
min
and
h
h(
H

g
g( )

(
H
)
In the interior
of the constraint set

=
1
2
;
H
=

1
4
B
1
=
2
=
3
=0
Tight Q
o max
,
Mild H
max
,
Mild Q
o max
min
*h
vr
and
H

h
h(
)

(
*h
,
*h
H
)
On
H
=
h
h()
*h
=
1
2
h
h(
*h
)

*h
H
=
h
h(
*h
)
C
2
=
1
=
3
=0
Mild Q
o max
,
Tight H
max
,
Mild Q
o max
min
* g
vr
and
H

g
g(
)
(
* g
,
* g
H
)
On
H
=

g
g()
F(
* g
) =0
* g
H
=

g
*
D
1
=
2
=0
Tight Q'
o max
,
Tight H
max
,
Mild Q
o max
*h
vr
and
H

h
h(
or
* g
vr
and
H

g
g(

(
vr
,
vr
H
)
On the vertex vr by
H
=

g
g()
and
H
=
h
h()

g(
vr
)h(
vr
) =

g
h

vr
H
=
h
h(
vr
)
E w
1
=w
2
=
3
=0
Mild Q'
o max
,
Mild H
max
,
Tight Q
o max
min
>
and
vl
H
<
* f
H
<
vu
H
(
min
,
* f
H
)
On
f
= f (), i.e., =
min

f
= f (
min
)
* f
H
=
1+4
2
min
12
4
min
1
4
F
1
=
3
=0
Mild Q
o max
,
Tight H
max
,
Tight Q
o max
[
min
>
and
* f
H

vu
H
]
or
min

* g
and
H

g
g(
(
min
,
vu
H
)
On the vertex vu by
f
= f () and
H
=

g
g()

f
= f (
min
)
vu
H
=

g
g(
min
)
G
2
=
3
=0
Tight Q
o max
,
Mild H
max
,
Tight Q
o max
[
min
>
and
* f
H

vl
H
]
or [
min
*h
and
H

h
h(
)]
(
min
,
vl
H
)
On the vertex vl by
f
= f () and
H
=
h
h()

f
= f (
min
)
vl
H
=
h
h(
min
)
If
h
<
g
, the vertex vr or case D is not available and set
vr
by an infinite or extremely large values.
F(
* g
) is 2
3
g
* g
g(
* g
)

2
g
g
5
(
* g
)
(
* g
)
3
3
3
g
(
* g
)
2
g
g
4
(
* g
) 1+
1
4(
* g
)
2
1
)
'
!
1
1
1
+
1
1
1
'
!
1
1
1
+
1
1
1
g '(
* g
)
ENGINEERING CASE HISTORIES

I

77
Vertical pump vibrations are usually
written up by the operator as a motor
vibration problem. It has been the writers
experience that 80% of the time it wasnt
the motor vibrating at all. There are many
causes for vibration problems (Fig. 1), but
the first observation is usually made on
the motor.
Fig. 2 shows another reason why the
motor can be reported as the vibration
source. With only one measurement on
the motor the value would be four mils. At
3,600 cpm, this would appear very rough.
However, when data are taken on the verti-
cal as shown, only one mil of vibration is on
the motor, and none is on the foundation.
All of the vibratory motion is taking place
through the I beam structure. If this was
a new installation, filling the structure with
grout material could be required. However,
if it is an old installation, loose anchor bolts
may be the cause.
Shutting the motor down and noticing
how the system responds can be productive.
Even with no vibration-monitoring equip-
ment available, if the vibration disappears
immediately when the power is removed
this can indicate an electrical problem.
A shudder or vibration level increase
and then decrease on shut down can reveal
a resonance problem. Try to identify an
external source of the vibration by repeat-
ing the startup and shut down, if safety isnt
a concern.
A vibration level that drops as the sys-
tem coasts down can signal several prob-
lems. Bent shafts, bad couplings or fouled
impellers all cause imbalance forces that are
reduced as the speed is reduced and come
down as the square of the speed.
1
With horizontal motors locked out, the
motor and driven device can be rotated by
hand. A heavy spot while turning could
indicate misalignment.
Sometimes corrections havent been
made for thermal misalignment. The
motor or driven equipment is supported
in such a way that if the machines are not
offset during cold alignment they will be
out of alignment and vibrating when at
operating temperature. When the hot
alignment condition is not considered an
indication of this is that the machine runs
smoothly when first started but vibrates
when hot. When a machine vibrates when
it is cold but smoothes out when at operat-
ing temperature, the hot corrections were
probably made.
Many times when there is motor vibra-
tion, usually on smaller motors, a soft
foot can be the problem. This occurs when
one of the motor feet pulls down more
than the rest. It is generally thought that
this causes internal misalignment which
can result in vibration. When the suspect
bolt is loosened the vibration drops sig-
nificantly. Shimming of the soft foot is
usually the remedy. The motor shouldnt
be operated with the loose bolt, even if it
runs smoother.
At one time the writer was on the plat-
form with a 7,000 hp motor with vibration
problems. As he contemplated the cause
and leaned against the air intake filter
screen, the vibration stopped. The cause
was local resonance of a loose screen and
shows the importance of a walk around.
There are many other causes of motor
problems,
2
however, a few rather unsophis-
ticated checks may allow the plant special-
ist to save the time and the expense of an
extended outage. HP
LITERATURE CITED

1
Sofronas, A., Analytical Troubleshooting of Process
Machinery and Pressure Vessels: Including Real-
World Case Studies, (p. 35), ISBN: 0-471-73211-
7, John Wiley & Sons.

2
Bloch, H. P. , Geitner, F. K., Machinery Failure
Analysis and Troubleshooting, (p.343), ISBN
0-88415-662-1, Gulf Publishing Co.
Case 54: Is it motor vibration
or some other cause?
Its not always the motor causing the vibration
T. SOFRONAS, Consulting Engineer, Houston, Texas
Unbalance rotor, bearings
Locked, unbalanced,
misaligned coupling
Loose bolts
Oil-soaked grout
Bent or misaligned shaft
Imbalanced, corroded or
fouled impellers
Bushing wear
System resonance
NPSH problem plugged screen
Loose anchors
Electrical problem
Vertical pump vibration reported
as a vibrating motor problem.
FIG. 1
0 1 2 3 4
mils p-p
Motor
Foundation
Structure
Displacement
3,600 rpm
Motor vibration shown as problem
with single measurement.
FIG. 2
Dr. Tony Sofronas, P.E., was
worldwide lead mechanical engineer
for ExxonMobil before his retirement.
The case studies are from companies
the writer has consulted for. Informa-
tion on his books, seminars and consulting are available
at the Web site http://www.mechanicalengineeringhelp.
com.
78
I
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H y d r o c a r b o n P r o c e s s i n g . c o m
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HPI Outlook 2010
ABB Automation
Technologies Division . . . . . 42 (69)
www.info.hotims.com/29415-69
Alstom Power, Inc. . . . . . . . . . 27 (156)
Axens . . . . . . . . . . . . . . . . . . 84 (53)
BASF Catalysts LLC . . . . . . . . 51 (75)
Cameron . . . . . . . . . . . . . . . . . 2 (55)
CB&I . . . . . . . . . . . . . . . . . . . . 8 (98)
CB&I . . . . . . . . . . . . . . . . . . . 66 (68)
Chas. S. Lewis & Co., Inc. . . . . 36 (67)
Emerson Process Mgmt
Delta V . . . . . . . . . . . . . . . . 28 (92)
Emirates . . . . . . . . . . . . . . . . 16 (85)
Fisher Controls . . . . . . . . . . . 12 (84)
Flexitallic LP . . . . . . . . . . . . . . 5 (93)
Gas Technology Products LLC . 26 (59)
Construction Boxscore . . . . . 75
Events, IRC . . . . . . . . . . . . . 68
HPI Marketdata Book . . . . . 73
Products . . . . . . . . . . . . . . . 58 (159)
Software . . . . . . . . . . . . . . . 70
Webcast . . . . . . . . . . . . . . . 80 (163)
Hoerbiger . . . . . . . . . . . . . 20-21 (152)
HPI Marketplace . . . . . . . . 78-79
Hytorc . . . . . . . . . . . . . . . . . . 14 (91)
Idrojet . . . . . . . . . . . . . . . . . . 27 (155)
Inpro / Seal Company . . . . . . . 6 (78)
Kobe Steel Ltd . . . . . . . . . . . . 22 (103)
LA Turbine . . . . . . . . . . . . . . . 41 (157)
Linde Process Plants . . . . . . . 45 (81)
Lurgi GmbH . . . . . . . . . . . . . 18 (95)
OHL . . . . . . . . . . . . . . . . . . . 27 (154)
ONS . . . . . . . . . . . . . . . . . . . 62 (104)
Prosernat . . . . . . . . . . . . . . . 24 (153)
Prosim . . . . . . . . . . . . . . . . . 59 (160)
Samson GmbH . . . . . . . . . . . . 4 (151)
SNC-Lavalin Engineers
& Construction Inc. . . . . . . . 24 (161)
Spencer Turbine . . . . . . . . . . . 54 (158)
Swagelok Co. . . . . . . . . . . . . 10 (63)
T.D. Williamson . . . . . . . . . . . 83 (66)
Team Industrial Services . . . . 57 (73)
Toyo Engineering Corporation 31 (57)
URS Corporation . . . . . . . . . . 33 (108)
Veolia Environment . . . . . . . . 31 (94)
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81
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Website
Company Page RS#
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LORAINE A. HUCHLER, CONTRIBUTING EDITOR
HPIN WATER MANAGEMENT
Huchler@martechsystems.com
82

I

Title IV, Permits and Licenses, of the Federal Water Protection
Control Act, also known as the Clean Water Act (CWA) created
the system for permitting wastewater discharges, known as the
National Pollutant Discharge Elimination System (NPDES).
Under NPDES, all facilities that discharge pollutants from any
point source into waters of the US must obtain a wastewater dis-
charge permit. Environmental personnel are directly responsible
for reporting compliance to wastewater discharge permits. These
environmental regulations impact the decisions and choices for
chemical treatment in the water utilities.
Water permits. States regulate the volume and concentration
of contaminants in treated wastewater and industrial storm water
discharged to the local watershed. State regulators customize per-
mits for each plant based on contaminants consistent with the
manufacturing process and characteristics of the local watershed.
Each permit is unique and subject to renewal every several
years. With each renewal cycle, the environmental regulations
usually become stricter. The EPA limits the circumstances under
which an existing permit can be modified or reissued with less
stringent effluent limits, standards or conditions than those
already imposed. Table 1 shows two examples of impacts by
stricter permit limits on water utility operations.
The permit provides two levels of control: technology-based
limits the ability of plants in the same industrial category to treat
wastewater and water quality-based limits apply if the technology-
based limits are insufficient to provide protection.
Pollutant categories. Regulators have grouped pollutants
into three general categories under the NPDES program: con-
ventional, toxic (priority) and nonconventional. CWA designated
these five parameters as conventional pollutants:
Five day biochemical oxygen demand (BOD5)
Total suspended solids (TSS)
pH
Fecal coliform
Oil and grease (O&G).
Toxic (priority) pollutants include metals and man-made organic
compounds. The remaining pollutants are non-conventional pollut-
ants including chlorine, ammonia, nitrogen, phosphorus-, chemical
oxygen demand (COD) and whole effluent toxicity (WET).
Best control methods. Regulators initially defined treat-
ment as Best Conventional Pollutant Control Technology (BCT)
and Best Practical Control Technology (BPT). Later, regulators
increased the requirements for treatment by imposing the eco-
nomically Best Available Technology (BAT). New Source Perfor-
mance Standards (NSPS) reflect effluent reductions that are achiev-
able based on BAT. These standards are the most stringent controls;
they require permit applicants to install high-efficiency wastewater
treatment technologies. Environmental regulators must consider
the cost of achieving effluent reductions and any non-water quality
environmental impacts and energy requirements.
Pretreatment Standards for New Sources (PSNS) and Pre-
treatment Standards for Existing Sources (PSES) are national and
uniform, technology-based standards that apply to dischargers to
publicly owned treatment works (POTWs) from specific industrial
categories (i.e., indirect dischargers). PSNS and PSES prevent the
discharges of pollutants that pass through, interfere with, or are oth-
erwise incompatible with the operation of POTWs. Environmental
regulators consider the same factors and issue PSNS and NSPS at
the same time. Tables 2 and 3 summarize these requirements.
The EPA annually reviews and revises its technology-based
regulations, called effluent limitations guidelines or effluent
guidelines, that limit the discharge of pollutants from various
categories of industrial facilities.
Summary. Wastewater discharge permits will become stricter.
Environmental personnel can provide valuable information about
potential changes in specific contaminant limits that will impact
decisions for chemical treatment in the water utilities. HP
The author is president of MarTech Systems, Inc., an engineering consult-
ing firm that provides technical services to optimize energy and water-related
systems including steam, cooling and wastewater in refineries and petro-
chemical plants. She holds a BS degree in chemical engineering and is a licensed
professional engineer in New Jersey and Maryland. She can be reached at:
huchler@martechsystems.com.
Wastewater discharge permits; What should you know?
TABLE 1. Sample impacts on permit limits
State Regulation Impact
TX, IL Ultra-low [zinc] in discharge Use of zinc-corrosion inhibitors in
cooling water may violate permit limits
KY No gluteraldehyde Must choose alternate non-oxidizing
biocides
TABLE 2. Relevant standards
Types of sites regulated BPT BCT BAT NSPS PSES PSNS
Existing direct dischargers
New direct dischargers
Existing indirect dischargers
New indirect dischargers
TABLE 3. Pollutants regulated
Pollutants regulated BPT BCT BAT NSPS PSES PSNS
Priority pollutants
Nonconventional pollutants
Conventional pollutants
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