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Q3 2021

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 ptq
PETROLEUM TECHNOLOGY QUARTERLY
Q3 (Jul, Aug, Sep) 2021
www.digitalrefining.com
3 Signs of recovery
Chris Cunningham
5 ptq&a
13 Premature foam-flood in an amine absorber: Part 1
Henry Z. Kister Fluor
Rohit Kumar Bharat Petroleum Corporation Limited
21 Impact of chlorides on fluid catalytic cracking
Melissa Clough Mastry, Corbett Senter, Fernando Sanchez and Bilge Yilmaz
BASF Refining Catalysts
27 Desalter chemical programmes for opportunity crudes
Mike Dion And Peter Perez
SUEZ – Water Technologies & Solutions

35 Enhancing hydrocracking units potential with pretreat and tailored

hydrocracking catalysts
Xavier Ruiz Maldonado and Rahul Singh Haldor Topsoe
Pablo Dosdá Manzano Cepsa

43 Maximising yields and profits from the FCC unit

Silviu Serban, Chuck Ekeocha, Udayshankar Singh and Bani Cipriano
Grace Refining Catalyst Technologies

49 Lower operating costs with liquid phase hydroprocessing

Tony Chen, Sandeep Palit and Samantha Presley
DuPont Clean Technologies

55 Maximising stripping section performance

Edward Hartman and Bryan White
Process Consulting Services

63 Don’t let furnace emissions derail your expansion project

Shilpa Singh and Ankur Jain Engineers India Limited

69 Sulphidation corrosion in a Claus waste heat boiler

Simon Weiland and Nathan Hatcher Optimized Gas Treating, Inc.

73 Recovering silicon poisoned catalyst

Patricia Perez-Romo and Luis M Rodriguez Otal
Mexican Petroleum Institute

83 Improve profit with augmented digital twins

Mark Krawec, Mike Aylott and Simon Calverley
KBC (A Yokogawa Company)

87 Managing ammonium salts corrosion and fouling

Surjeet Kumar, Berthold Otzisk and Michael Urschey
Kurita Europe

91 Crude oil vapour pressure testing

Christian Schröder-Holzhacker eralytics

97 Modelling and optimising bitumen hydrocracking

Haiming Lai Dynamic Simulation & Consultancy

102 Technology in Action

Cover
Middle East Oil Refinery (Midor), Alexandria, Egypt will produce Euro V fuels following large scale expansion
Photo: Technip Energies

©2021. The entire content of this publication is protected by copyright. All rights reserved. No part of this publication may be reproduced,
stored in a retrieval system or transmitted in any form or by any means – electronic, mechanical, photocopying, recording or otherwise –
without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly and its supplements the publisher cannot be held
responsible for any statements, opinions or views or for any inaccuracies.

ed com copy 25.indd 1 14/06/2021 12:05

 Crack FCC issues with our experts
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 ptqPETROLEUM TECHNOLOGY QUARTERLY
Signs of recovery

Vol 26 No 4
Q3 (Jul, Aug, Sep) 2021

Editor
Chris Cunningham
editor@petroleumtechnology.com
Managing Editor
Rachel Storry
production@petroleumtechnology.com
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W
ith numbers of road journeys and volumes of freight increasing across
the globe, future prospects should be looking brighter for refiners. If
air transport achieves similar progress later this year, the chances of the
sector recovering to 2019 levels in 2022 are good.
While the attrition rate among petroleum refiners during the pandemic
has been severe as a result of closures, severe cutbacks, and bioconversions,
processing capacity is set to restore some of its upward trajectory in the near
future. Refinery losses and closures, in particular in Europe, Australasia, and
Japan, will be balanced by new capacity in China and the Middle East. Africa’s
refining sector is also set for growth in an effort to cut punitive bills for fuel
imports. The 650 000 b/d integrated Dangote plant in Nigeria is the most
striking instance of the continent’s centres of oil production driving to extract
more income from their resources.
These are among the findings of a recent Oil Market Report from the
International Energy Agency, the agency’s first detailed outlook on the pros-
pects for 2022. However, predictions of the petroleum industry’s future, even
a near term outlook, are beset by fast moving targets. In particular, meeting
expectations of recovery depends on the availability of sufficient raw material
for processing and decisions by refiners on whether mothballed capacity will
be worth reopening.
With regard to availability, the IEA says that the OPEC+ countries will need
to raise production levels to meet recovering demand. Crude stocks in import-
ing nations are already well below their five-year average and may not be able
to avoid further drawdown if predicted demand indeed passes the 100 mil-
lion b/d mark by the end of 2022. That would mark net growth from pre-pan-
demic levels. The agency reports that demand fell by a record 8.6 million b/d
in 2020, should recover by 5.4 million b/d this year, and will rise by a further
3.1 million b/d in 2022.
Vaccine supply may prove to be at least as big an issue as geopolitical events
if recovery is to meet these targets. Slow distribution of vaccine could limit
growth in output from countries outside the OECD. The resulting contin-
ued restrictions to air travel would mean jet fuel production maintaining its
lag in growth by comparison with other transportation fuels. Even gasoline
output, the fastest recovering sector of the fuels market, is likely to be shack-
led by domestic trends such as teleworking and, to a lesser extent, uptake of
electric vehicles.
Meanwhile, the IEA points out, the refining sector is expected to remain
under pressure. Next year’s demand for refined products will still not have
reached 2017 levels. Additions to refining capacity between 2017 and the onset
of the pandemic totalled 3.3 million b/d, while a further 1.5 million b/d of
additional crude distillation capacity is scheduled to come online by the end
of 2022. The result, according to the agency’s calculations, is that global aver-
age utilisation rates would be 78%, which would limit any recovery in refinery
margins from the low levels of 2020-21.
For refiners with simpler configurations and limited means of production of
petrochemicals, the future is very much uncertain.

CHRIS CUNNINGHAM

PTQ Q3 2021 3

ed com copy 25.indd 2 14/06/2021 12:17

 Process Notes

Vacuum tower cutpoint delivers profits

Cutpoint Concerns poorly designed heaters may experience coking with

COT below 700°F (370°C).
Crude unit vacuum tower performance is often critical
to a refiner’s bottom line. The vacuum tower bottoms Flash zone pressure is set by vacuum system
stream is valued far below the gas oil cuts, so most performance and column pressure drop. Lower flash
refineries look to minimize it. Many vacuum columns zone pressure increases cutpoint until the tower shell
are also designed or revamped to produce a diesel cut, C-factor limit is reached, at which point the packed
recovering diesel slipped from the atmospheric column beds begin to flood. Vacuum producing systems are
that would otherwise be downgraded to VGO product. mysterious to many in the industry, so a large number
of refiners unnecessarily accept poor vacuum system
Good vacuum column performance can maximize the
performance. With technical understanding and a good
profitability of downstream units by removing distillate
field survey, the root causes of high tower operating
hydrotreater feed (diesel) from FCCU or hydrocracker
pressure can be identified and remedied.
feed (VGO) and removing VGO from coker feed (resid).
In columns with stripping trays, stripping steam rate
One important measure of vacuum column
and tray performance are important. Stripping steam
performance is VGO/resid cutpoint. The cutpoint is the
rate is limited by vacuum column diameter (C-factor)
temperature on the crude TBP curve that corresponds
and vacuum system capacity. Any steam injected into
to the vacuum tower resid yield.
the bottom of the tower will act as load to the vacuum
system, so vacuum system size, tower operating
Vacuum column cutpoint depends on three variables:
pressure, and stripping steam rate must be optimized
1. Flash zone temperature
together. Depending on the design, a stripping section
2. Flash zone pressure
with 6 stripping trays can provide between zero and
3. Stripping section performance (if present)
two theoretical stages of fractionation, which can drive
Flash zone temperature is driven by vacuum heater coil a big improvement in VGO yield.
outlet temperature (COT). Increasing COT increases
Although the variables for maximizing vacuum tower
cutpoint. Vacuum heater outlet temperature is typically
cutpoint are simple, manipulating them to maximize
maximized against firing or coking limits. When
cutpoint without sacrificing unit reliability is not.
processing relatively stable crudes, vacuum heaters
Contact Process Consulting Services, Inc. to learn how
with better designs and optimized coil steam can avoid
to maximize the performance of your vacuum unit.
coking even at very high COT (800°F+, 425°C), but

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 ptq&a
Q We didn’t expect severe corrosion issues in the carbon steel
of our amine unit. What is causing it?
A Chris Claesen, Technical Director, Nalco Water, Chris
Claesen@ecolab.com
Corrosion in amine units can be due to a variety of rea-
sons. The most common ones are wrong operating con-
ditions and amine contamination and degradation. First,
you will have to do a root cause investigation looking at
operating conditions, amine composition, and the loca-
tion of the corrosion. An amine unit that is operated
within design guidelines and with good amine quality
will have very little corrosion issues even with carbon
steel. Refiners can end up in a situation where the oper-
ating conditions or amine quality cannot be controlled
within the recommended limits and in such a case cor-
rosion inhibitors such as the Nalco Water Intercept pro-
gramme can help control the corrosion in specific areas
of the unit. In the long term it is best to make the neces-
sary hardware modifications to bring the operating con-
ditions and amine quality back within the recommended
limits. Changes in crude slate and acid gas composition
(more H2S, NH3 or HSAS precursors) can change the cor-
rosion conditions in the amine unit and should trigger an
amine unit MOC check.
A Berthold Otzisk, Senior Product Manager, Kurita Europe,
berthold.otzisk@kurita-water.com
In amine plants, corrosion is a common problem when
acid gases are removed. When corrosion occurs, it is
highly localised – overall corrosion does not actually
occur. The alkanolamines bind the acid gases in the
absorber. Tertiary amines such as MDEA form much less
corrosive amine salts compared to secondary amines or
the even more corrosive primary amines.
If no corrosion has been noticed so far and now severe
corrosion is observed, this can have different causes.
In the first place, hydrogen sulphide (H2S) and carbon
dioxide (CO2) can be the reason for increased corrosion.
There is usually an equilibrium between acid gases and
the amine solution. If this equilibrium is shifted, the acid
gases can be released again and attack the metal surfaces.
Temperature increase or pressure reduction allow acid
gases to escape from the solution, which can then lead to
increased corrosion. The formation of a natural FeS pro-
tective layer is desired if the FeS scale is strong enough
to form a protective layer. Fluid dynamics, temperature,
pH, partial pressure of H2S and CO2, or the presence of
surfactants or corrosion inhibitors can have a negative
influence, which may increase corrosion. The strength
of the protective FeS film is highest at pH 7-8. Above pH
8, it is more porous and less protective. Too much iron
sulphide should be filtered out of the amine solution. If
corrosion occurs in the overhead system of the regen-
erator, the use of neutral amine can be useful, as H2S is
www.digitalrefining.com
Q&A copy 37 (original) copy 11.indd 5
More answers to these questions can be
found at www.digitalrefining.com/qanda
bounded in the liquid phase and NH3 is released. Heat
stable salts can also initiate higher corrosion rates. When
dissociation of the salt is observed, a corrosion cell is
formed with the metal. As a general rule, the concentra-
tion of heat stable amine salts should not exceed 10% of
the total amine concentration. By adding NaOH or KOH,
the concentration of heat stable salts can be kept stable.
More salts will preferentially form with the strong base,
NaOH, or KOH. Excessive injection of caustic should
also be avoided.
Q What is the best route for maximum propylene from a
resid feed to the FCC?
A Lynne Tan, Regional Technical Sales & Service Manager,
BASF Refining Catalysts Asia, lynne.tan@basf.com and Karen
Huang, Regional Technical Service Manager, BASF Refining
Catalysts Asia, karen.huang@basf.com
There are various routes for maximum propylene pro-
duction and the best route is what is suitable for the
respective refinery’s target and scope. Many licensors
provide technological solutions to revamp existing FCC
units for more propylene production but a significant
investment and a long lead time are expected. A suitable
catalyst design is a quick and easy alternative for FCC
units to maximise propylene under existing hardware
configurations.
To accomplish maximum propylene from a resid feed,
a catalyst needs to have high metals tolerance to prevent
activity and conversion loss due to contaminant metals,
and good coke selectivity to better manage heat balance
which is often a key challenge. An ideal maximum pro-
pylene catalyst will leverage on these unique character-
istics to deliver optimal bottoms conversion to produce
light naphtha, the precursor for propylene, and accentu-
ates the effects of ZSM-5 to produce high propylene yield
and selectivity.
A Gary Martin, Business Segment Leader (Dividing Wall
Column Technology), Sulzer Chemtech, Gary Martin@Sulzer.com
Whether you are producing propylene from a resid or
VGO FCC, the economic limit to maximising propyl-
ene often is constrained by the gas concentration sec-
tion (gascon). Modern FCC units provide an important
link between a fuel refinery and the production of light
olefins and aromatics for petrochemical use. FCC reac-
tor licensors are designing units to produce higher pro-
pylene production. Economic factors influence the
optimum propylene production with one factor being
the capex associated with recovering the propylene.
Revamps of older FCC units can provide for increased
propylene production at the expense of gasoline, but a
constraint to increasing production is the reuse of exist-
ing equipment to minimise capex. Increasing FCC unit
PTQ Q3 2021 5
15/06/2021 14:39
 severity, addition of ZSM-5 and varying the reactor
partial pressure, total pressure, and catalyst-to-oil ratio
enable increasing propylene production. However, this
can have a significant effect on the gascon. The shift in
additional propylene production produces more dry
gas, making it more difficult to recover the propylene. To
maintain high propylene recovery along with the shift
in product slate can lead to much higher loadings in the
sponge absorber, primary absorber, deethaniser, debu-
taniser, and the C3/C4 splitter. These columns are often
shell limited, and it is usually not economical to replace
or parallel these five columns by conventional means.
While shifting product slate to petrochemicals makes
sense for the forward-looking refiner, it must also make
economic sense for today’s business.
For existing processing units, achieving the shift in
yields requires an economical means of retooling exist-
ing assets. Dividing wall column (DWC) technology is
a technique providing a much lower capex revamp to
overcome the limitations of a light ends recovery sec-
tion. A DWC design using a single vessel that com-
bines the functions of a sponge absorber, primary
absorber, deethaniser, and C3/C4 splitter can be utilised.
This design can unload the existing gascon to enable
improved recoveries in the existing unit along with han-
dling additional load from shifting to increased propyl-
ene production. With the addition of only one vessel, this
design unloads the existing sponge absorber, primary
absorber, deethaniser, debutaniser, and C3/C4 splitter.
The DWC design can produce equal or higher propylene
recovery and product purities than that of a conventional
design configuration and add any additional capacity
needed. The only potential limitation is the bottom of the
debutaniser and bottom of the C3/C4 splitter but there
are other solutions if this is the case. Typically, this will
not be a problem as changes in the product slate result
in these areas not being a limitation or at least allow for
changes to handle the new design conditions. The shift
in product slate decreases gasoline yield which helps
unload the bottom of the debutaniser. The DWC can also
be used to overcome limitations in plot space and the
construction can often be completed prior to a shutdown
with only tie-ins required.
Q We’d like to produce less light naphtha and more liquid
fuels from our hydrocracker. How do we go about it?
A Bob Scheffer, Refinery Catalyst Technology and Hydro-
processing Expert, Petrogenium, Bob.Scheffer@petrogenium.com
There are several handles to tune the product composi-
tion of a hydrocracker. I would like to talk about these
on the basis of their timeframe, as operational, catalyst
selection, and revamp:
1.Operational
• Feedstock selection: various types of crudes (aromatic,
paraffinic and so on) give rise to different yield patterns
in a hydrocracker. However, usually the crude diet is
fixed (based on crude pricing) and little flexibility exists
here. The feed to the hydrocracker can be complemented
by other streams from the refinery that increase distillate
6 PTQ Q3 2021 www.digitalrefining.com
Q&A copy 37 (original) copy 11.indd 6
yield, such as cycle oils or extracts. We recommended to
study these options carefully as to not compromise the
expected life of the catalysts.
• Combined feed ratio: in recycle operation, the CFR is a
parameter that influences the yield structure: higher CFR
(at the same overall conversion level) means that a lower
conversion per pass is required and therefore a more
middle distillate selective yield is achieved.
• Recycle cut point: an increase in the RCP reduces
severity of operation, thereby producing a more distillate
selective yield pattern.
• Increasing the gas-to-oil ratio can shift the yield pat-
tern somewhat to the distillate range. The effect depends
on the type of catalysts used, so this should be evaluated
in pilot plant testing campaign. Supplying more (fresh
and recycle) gas also reduces the risk of maldistribution
and hotspots, which can be a cause of the formation of
lighter products.
• A hydrocracker usually contains multiple catalyst
beds, which contain different catalysts. There is some
flexibility in setting the temperature of each catalyst bed
by adjusting the quenches between the catalyst beds.
Optimising this temperature profile can shift the prod-
uct yield toward distillates by applying the higher tem-
peratures to the catalyst beds with the most selective
catalysts. Tuning a hydrocracker model and running dif-
ferent temperature profiles will support the refinery in
finding the optimum settings, while achieving maximum
run length.
• An effective way to maximise fuel production is by
minimising the downtime of the hydrocracker. Here we
can distinguish planned downtime (regular shutdown
for maintenance) and unplanned downtime. Just reduc-
ing the downtime by a few days per hydrocracker cycle
brings significant benefits, which go directly to the bot-
tom line of the refinery. To achieve this, we would do a
dedicate study investigating the causes of unplanned
downtime, in conjunction with smart maintenance man-
agement. A detailed review of the regular shutdown pro-
cedures, while closely managing the contractors involved
(optimising working in shifts, incentives for early deliv-
ery and so on) ,can yield strikingly good results.
2. Catalyst selection
• Key to optimisation of the hydrocracker is the selec-
tion of the catalysts that meet the objectives of the refin-
ery best. There are many suppliers, each with a large
portfolio of catalysts. Refiners do not always have the
resources to rigorously evaluate the proposals from cata-
lyst companies. We would enlist the support of an expert
consultancy to support the decision making, which
involves clever target setting, modelling of the hydroc-
racker, and – in some cases – pilot plant testing.
• During operation, the performance of the catalyst
should be monitored, in order to intervene at the earliest
possible time if some deviation from the expected per-
formance occurs. At an early stage, fixes are still possi-
ble, but if the malperformance endures for too long, the
catalysts may have been damaged irreparably and the
desired product yields cannot be obtained.
3. Revamp
• A major shift in yields is obtained if a hydrocracker
11/06/2021 17:10
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THE MOST TRUSTED TECHNOLOGY FOR SUPERIOR BASE OILS

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 is revamped from one-stage/series flow to a two-stage
operation.
• Minor revamps can also be effective. If maldistribu-
tion of hotspots is persistent, then revamping the reac-
tor internals can lead to better yields. Also re-traying
columns in the work-up/distillation section can lead to
better/sharper separation of products, maximising the
desired products.
Q Our air compressor trips off immediately after it powers
on. Is this a mechanical or process issue?
A Elkin Anaya, Senior Staff Consultant, KBC, Elkin.Anaya@
kbc.global
There are different types of air compressors with dif-
ferent control systems and process configurations. Let
us assume we are dealing with a process air centrifugal
compressor which has been in operation for several years
and trips off after it powers on.
In this case, the issue could be caused by the con-
trol system and motor protection. This type of unit
starts with minimum load and as the compressor delta
P increases the control system increases the load until
reaching operating conditions. Most air compressor
motors are not sized to start with the full load. If the
valve controlling the load malfunctions, the unit would
start with a full load, causing motor overload, which
would trigger the motor overload protection to shut off
the unit. Therefore, the issue is not related to a compres-
sor mechanical problem. It is due to a combination of
process conditions, load valve malfunction, and motor
protection.
Q For best product quality from vegetable oils should we
hydrotreat them with conventional petroleum feed or use them
as straight feed?
A Joris Mertens, Principal Consultant, KBC, Joris.Mertens@
kbc.global
Product quality from vegetable oil hardly depends on
whether the oils are co-processed or not.
Co-processing can provide a low capex option to
upgrade vegetable oils. The value of the product is
largely determined (and boosted) by legislation that
incentivises low carbon intensity produce and by the
availability of feedstocks that qualify as low carbon feed-
stock. There is a drive to only qualify waste vegetable
oils (and animal fats) as possible low carbon feeds. In
some regions legislation only incentivises pure vegetable
oil processing, not co-processing.
Co-processing to up to around 5% may be feasible
without investment at all but pretreatment normally is
required for waste bio-feeds. At higher percentages the
increase in hydrogen consumption (and reaction exo-
therm) will become very significant, as will catalyst activ-
ity inhibition due to CO formation, while the impact on
the product cloud point will become notable as well.
A unit treating only vegetable oils requires significant
changes in unit design i.e. The use of higher grade steels,
8 PTQ Q3 2021 www.digitalrefining.com
Q&A copy 37 (original) copy 11.indd 8
high and/or liquid quenches to control exotherms, the
requirement to remove CO2 and to isomerise the product
(the latter in order to reduce cloud point), and a differ-
ence in product separation due to the difference in yield
structure.
A Tom Ventham, Sales & Technical, Europe and Africa, Unicat
B. V. / G. W. Aru, LLC, tom.ventham@gwaru.com
Processing of vegetable based materials, such as FAME,
is known to be a highly hydrogen intensive process. The
incremental increase in hydrogen demand would also
be seen if blending with conventional feeds. If consid-
ering adding vegetable oils to the hydrotreater diet, it is
recommended to review the hydrogen balance to ensure
demand can be met. Many refiners now are tasked with
finding more hydrogen to satisfy the refinery hydrogen
balance. That may be a result of newly processing veg-
etable feeds, increased hydrotreatment requirements to
meet new road fuel specifications, changing crude slates,
or even hydrogen production for fuel cells. The steam
methane reformer remains the heart of the hydrogen
production system and is also the most adaptable tool
should hydrogen requirements increase for reasons such
as that posed in the question. Unicat has a long history
in the hydrogen catalyst market, and the recent acqui-
sition of the Magma group means it is now the lead-
ing company to offer catalytic solutions to refiners who
would like to increase hydrogen production from their
SMR unit. With MagCat SMR catalyst technology, hydro-
gen yields can be increased by 15-20% purely through
replacing the incumbent catalyst with pellet-like MagCat
catalyst. Using a nickel based catalytical system but with
a totally redesigned and reengineering pellet-type sub-
strate, MagCat radically improves fluid flow proper-
ties in the SMR tubes. If increased hydrogen production
is not the current driver, the same catalyst also signifi-
cantly improves hydrogen production efficiency which is
seen by the user as a reduction in energy or fuel require-
ments and a reduction in CO2 emissions. A reduction in
both reformer tube wall temperature (TWT) and hot
spots or banding increases tube lifetimes as a further cost
and safety driver. Therefore, with a view of moving to a
greener operation using vegetable feeds, MagCat catalyst
from Unicat gives many synergistic benefits to improve
the efficiency and effectiveness of the whole hydropro-
cessing operation in a simple and straightforward way
that can be implemented immediately without the need
for costly retrofits or redesigns.
Q Please suggest ways of reducing steam demand in our sour
water stripper.
A Chris Claesen, Technical Director, Nalco Water, Chris.
Claesen@ecolab.com
If some fouling is taking place in the sour water strip-
per this can lead to increased demand of steam to reach
the desired stripped sour water quality. In such a case
the use of a Nalco Water sour water stripper antifou-
lant programme can help control the fouling and reduce
the steam demand. In severe cases and if enough sour
11/06/2021 17:10
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 water tankage capacity is available and recycling of that
material is possible, a quick off-line cleaning can help to
recover SWS efficiency.
All the water streams going to the sour water stripper
should be evaluated. In some cases streams can bypass
the sour water stripper and for example be sent directly
to the desalter washwater. This can sometimes lead to
a significant reduction in steam use but all the effects
of such a bypass should be properly evaluated and the
effect on ammonia and amine recycle on the CDU over-
head salt formation should be checked with an ionic
modelling program such as Nalco Water Pathfinder.
In some cases better removal efficiencies can be
achieved with an improved stripped sour water pH
adjustment to reach sour water NH3 and H2S targets
A Simon Calverley: Consulting Product Integration Director,
KBC, Simon.Calverley@kbc.global
Sour water strippers are typically stripped with either
direct steam injection or via a steam heated reboiler.
The main specifications are typically on H2S and NH3 in
the stripped sour water. Modern design can produce a
stripped water effluent that contains less than 10 ppmw
of free NH3 and less than 1 ppmw H2S. Best practice
designs will use about 0.8-1 lb of steam to the reboiler
per gallon of sour water to achieve those levels. Over-
stripping or over-refluxing the tower (whether overhead
or via a top pumparound) will lead to higher steam rates,
thus these are potential ways to reduce steam. Reducing
the sour water load on the column (reducing the sour
water produced) will require less steam to meet the spec-
ifications, but may not be appropriate for the operation
of upstream units. A simulation of the sour water strip-
per can help with determining the amount of steam
required to achieve the desired specifications.
A Al Keller and Jim Asquith, Process Advisors, Becht, akeller@
becht.com
Steam demand in a sour water stripper (SWS) can be
reduced without affecting stripped sour water qual-
ity by reviewing a number of key operating parameters
including:
• Sour water generation: are you generating excessive
sour water or processing water in your SWS that does
not require treatment? If any water going to sour water
meets water treatment plant inlet specifications for
ammonia, COD, and BOD, it is not necessary to send it to
sour water stripper.
In addition to optimising exchanger water wash sys-
tems, if possible use low level ammonia containing water
as makeup water to water washes which will increase
the ammonia level. For instance, use 100 wtppm ammo-
nia water as makeup for a water wash where the ammo-
nia level will go up to 5000 wtppm.
• System fouling: a stripper consuming above design
steam to meet spec is most likely suffering from a fouled
feed effluent exchanger, fouled trays/packing, or con-
taminant load has increased. Simulating the tower and
comparing actual pressures, temperatures and flows to
design will help identify areas to optimise.
Crude or other process changes may lead to increased
Q&A copy 37 (original) copy 11.indd 10
fouling. If fouling is detected from significant process
change, routine mechanical cleaning of the reboiler and
stripped water side of the feed/effluent exchangers might
become necessary. Chemical cleaning may not be effective
with some heavy hydrocarbon fouling materials.
Keep hard water (cooling water, fire water, city water)
out of the SWS system. These contain water hard-
ness (calcium and silicon) that can affect SWS trays and
reboilers.
• Feed contaminants: the amount of ammonia allowed
in the stripped water usually sets the amount of steam
required in the stripper. The ability to strip ammonia
from water can be affected by the level of contaminants
in the sour water such as strong acids. Ammonium salts
of strong acid anions cannot be decomposed by steam
stripping at SWS conditions. To determine if this is hap-
pening, conduct a complete anion and cation ion chro-
matography scan of the sour water and compare the
strong acid anion charge equivalents (formate, acetate,
chloride) to cation equivalents. If anions exceed cat-
ions on a charge equivalent basis, caustic addition may
be needed to convert ammonium salts to sodium salts.
Measure ammonia in the bottoms with cation ion chro-
matography. Set the steam rate to achieve the desired
ammonia level by IC. Amines used for neutralisation or
from amine treating purges/upsets may interfere with
field test kits based on colorimetric chemical methods.
pH measurements do not give any indication of ammo-
nia content due to presence of many different anions and
cations. Do not control by pH.
• Phenolic and non-phenolic water: for systems that pro-
cess both phenolic and non-phenolic water, consider using
a separate SWS to process these streams. Phenolic water is
usually low in ammonia and takes less steam per gallon to
meet ammonia specs. Non-phenolic requires more steam
per gallon, but the volumes are generally lower.
A Marcello Ferrara, Chairman, ITW Technologies, mferrara@
itwtechnologies.com, Cristina Ferrara, Process Engineer, ITW
Technologies, cferrara@itwtechnologies.com
Sour water stripping is considered a ‘fouled service’, in
particular for phenolic sour water. Among the foulants,
the ones that have the greatest impact on steam con-
sumption are hydrocarbons and polymers.
The most common fouling is hydrocarbon based,
which occurs when large volumes of hydrocarbons
are carried over into SWS feed. Hydrocarbons tend to
agglomerate inside the equipment and form a sludge
that accumulates in the heat exchangers and in the bot-
tom of the tower, thereby directly impacting steam
consumption.
It is also common for phenolic water (for instance,
from the FCC unit and DCU) to contain polymer precur-
sors which create polymeric fouling inside the unit.
In general, polymer fouling may include: amine deg-
radation and oxidation products; red oil fouling (which
frequently occurs in olefin caustic treatment); peroxides
formed by the oxidation of various components (which
are initiators of polymerisation reactions); olefins, in par-
ticular conjugated diolefins (which form polymers or
gums in the presence of oxygen traces); thiophenes and
www.digitalrefining.com
11/06/2021 17:10
 thiophenols (which may form gum-like substances in the
presence of oxygen and diolefins) and phenols (which
form insoluble crosslinked polyphenols in the presence
of corrosion products).
Polymeric fouling will seriously contribute not only to
increased steam consumption, but to unit performance
by creating high delta P.
ITW can address both of the sludge and poly-
meric fouling issues by applying patented ITW Online
Cleaning or ITW Onstream Cleaning technologies.
Q We’ve increased the opportunity crude content of our feed
and are experiencing high calcium issues. How can we best
address this?
A Steven Van Vegten, Global Market Application Advisor,
Steven.vanVegten@Albemarle.com
Calcium may be removed through pretreatment of the
feed. If such pretreatment is unavailable or insufficient,
calcium will irreversibly poison the catalyst when the
feed is processed in an FCC unit.
Calcium deposits on the outer surface of FCC catalyst
particles, much the same as iron. Calcium is detrimental
to FCC catalyst performance as it causes sintering of the
surface, reducing the accessibility of the catalyst. With
reduced catalyst accessibility, it is more difficult for feed
molecules to reach actives sites, hampering conversion,
particularly in bottoms upgrading.
Because calcium and iron contamination hardly affect
Ecat activity, surface area, and pore volume, it may be
overlooked. As these lab tests employ long contact/dif-
fusion times, they do not capture the dynamic nature of
diffusion. To compensate for these oversights, Albemarle
developed a lab test to measure the accessibility of FCC
catalysts by allowing large probe molecules to diffuse
into the catalyst. The test result is known as the AAI
(Albemarle Accessibility Index). A diffusion limited cat-
alyst has a low AAI, while a catalyst whose structure
allows easy rapid diffusion has a high AAI.
As calcium poisoning is irreversible, a refiner may
choose to increase catalyst additions, perhaps with the
use of purchased Ecat, flushing the contaminants from
the unit inventory and reducing calcium contamina-
tion to a level the catalyst can cope with. Alternatively,
employing a high accessibility catalyst with intrinsic tol-
erance to calcium may provide for a more cost-effective
option, allowing for lower catalyst addition rates while
maintaining conversion. Albemarle offers a suite of cat-
alysts with high accessibility, such as ACTION for maxi-
mising butylenes and AFX for maximising propylene.
Q Are there options for online cleaning a preheat exchanger
network?
A Marcello Ferrara, Chairman, ITW Technologies, mferrara@
itwtechnologies.com, Cristina Ferrara, Process Engineer, ITW
Technologies, cferrara@itwtechnologies.com
ITW Online Cleaning can effectively address the cleaning
of organic deposits of heat exchangers, as well as any
www.digitalrefining.com
Q&A copy 37 (original) copy 11.indd 11
other equipment in the oil and gas industry. ITW Online
Cleaning is a patented cleaning technology based on
cleaning heat exchangers network and/or process
equipment in a closed loop, in the hydrocarbon phase.
An entire production unit can be cleaned in as little as 24
hours on a feed-out/feed-in basis.
ITW Online Cleaning is a patented cleaning technol-
ogy which includes all of:
• Patented method and process steps
• Patented chemicals
• Patented monitoring system
In a refinery the technology will dissolve asphaltenic/
paraffinic deposits, in order to reduce/eliminate mechan-
ical cleaning. When polymeric deposits are the concern,
a different proprietary chemistry is used to dissolve
the same. The dissolved material is fully stable and
can be fully reused/reprocessed. In the many applica-
tions worldwide, the washing fluids have been always
reused/reprocessed without any issues.
ITW Online Cleaning can be used:
a) in preparation of turnaround, during the shutdown
phase
b) pro-actively during a unit’s run
ITW Online Cleaning can be performed using the exist-
ing unit layout in most cases. By applying another pat-
ented technology, ITW Onstream Cleaning, a unit can be
cleaned during its run. ITW Onstream Cleaning implies
some plant modifications to be implemented under ITW
licence.
A Rob Turley, Senior Engineer, KBC, Rob.Turley@kbc.global
Yes. Chemicals or process fluids (such as LCO) can be
used for on-line heat exchanger cleaning. Cleaning chem-
icals can be injected into the process fluid upstream of
fouled exchangers at a specified dosage to dissolve and
disperse foulants such as asphaltenes. These chemicals,
however, can be harmful and so must be properly dis-
posed of – which can prove costly.
Likewise, process fluids can be used to dissolve fou-
lants – with paraffinic fluids being most effective at
removing waxy components, whilst naphthenic/aro-
matic fluids are most effective at dissolving asphaltenes.
Fouled exchangers are drained, before a suitable sol-
vent oil is added and left to soak for a sufficient time
to dissolve the fouling material. The solvent oil is then
removed from the exchanger, and with it the dissolved
material and any loosened solids deposits are repro-
cessed by conventional refinery operations.
An alternative option for online heat exchanger
cleaning is back flushing. A back flushing valve can
be installed which, when in use, reverses the direc-
tion of flow through a heat exchanger. This allows foul-
ing material that has built up in the inlet channels of the
exchanger to be flushed out through the same path that it
entered.
Online cleaning can extend unit run lengths
and reduce energy and maintenance costs. KBC’s
HX-Monitor utility in Petro-SIM can be used to quantify
the benefits associated with different cleaning methods
and recommend when is the right time to clean fouled
exchangers.
PTQ Q3 2021 11
11/06/2021 17:10
 AN UNRIVALED RESOURCE
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This publication represents the collective knowledge and experience built up over
75 years—part of a suite of resources including e-Catalysts.com, Catalagram
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experts. Written by Grace experts, the second edition includes new insights into recent
challenges in the industry.

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grace.indd 1 11/06/2021 13:56

 Premature foam-flood in an amine absorber:
Part 1
Troubleshooting and hydraulic analysis identified vapour channelling in fixed valve
trays as the root cause of premature foam-flooding in a high pressure amine absorber
HENRY Z. KISTER Fluor
ROHIT KUMAR Bharat Petroleum Corporation Limited
T
he lean amine flow rates in
the high pressure (HP) amine
absorber of the hydrocracker
unit at Kochi refinery were limited
by recurring foam-over events. To
increase liquid handling capac-
ity, the tower was retrayed by a
major tray supplier (Fluor was not
involved). The retray was quite
standard, using high-capacity valve
trays with small fixed valves and
push valves and increasing down-
comer top area. Surprisingly, higher
lean amine flow rates could not be
achieved without foam-overs. Even
at the same amine and gas rates,
the frequency of the foam-over
events jumped from once or twice
per month to once per day. Some 54
days after the new trays began oper-
ation, the bottom drain line from the
pre-knockout drum plugged, caus-
ing precondensed lighter hydrocar-
bons entrainment into the amine
system, and severely aggravating
the foaming issues. This required a
reduction in both the amine and gas
flow rates. The problem was eventu-
ally resolved by replacing the tower
with a random packed tower and a
new Pre-KOD and unplugging the
pre-KOD bottom drain line.1
Although the problem was
solved, the mystery remained.
Why did the revamp trays perform
worse than the original trays when
they should have performed bet-
ter? The refinery sought answers
from the supplier and the suppli-
er’s tray rating software, but nei-
ther of them were able to provide
any clues.
Aware of Fluor’s distillation
expertise, the refinery had Fluor
join their task force analysing data
and performing a ‘post mortem’.
www.digitalrefining.com
q3 Kister.indd 13
Process description
Recycle gas The vacuum gasoil mild hydro-
To D/S 12” cracker (VGO MHC) unit of the
KOD
Kochi refinery (1.7 million t/y)
treats VGO from the crude vacuum
8” distillation unit to produce low sul-
Lean
amine phur VGO feedstock for the FCC
unit, together with conversion of
excess VGO to low sulphur diesel.
8 spaces @ 600 = 4800
The design maximum feed sulphur
in VGO was 1.6 wt%.
The effluent from the MHC unit,
Gas
bypass consisting of the cracked products,
desulphurised VGO, hydrogen sul-
phide (H2S), ammonia, and excess
1150
hydrogen, are separated in separa-
tors/flash drums into liquid and
gas streams. The gas streams are
3750
further purified in hot and cold sep-
arators to remove heavier ends and
in a HP amine absorber to remove
H2S. The unit process is described
12”
in detail with the aid of a flow dia-
gram in a companion article.1
3900
Feed gas 12”
Figure 1 shows the HP amine
absorber. Feed gas containing less
Pre KOD
than 1.5 vol% H2S enters via a bare
nozzle into a pre-knockout drum
(Pre-KOD). A small amount of liq-
2” drain line uid knocked out in this drum drains
via the bottom 2” line. Gas from the
Figure 1 Hydrocracker high pressure amine drum ascends into the absorber,
absorber entering it via another bare nozzle.
The purified lean gas leaving the
This joint investigation disclosed HP amine absorber goes to a down-
a phenomenon that to the best of stream compressor knockout drum
our knowledge had not been pre- (D/S KOD) to remove any amine
viously reported: vapour chan- droplets before being routed to the
nelling inducing premature tray suction of a recycle gas compressor.
foam-flood. This first part of the There is a gas bypass that can divert
discussion presents our initial some of the feed gas to the absorber
analysis and findings. Details of overhead, at the expense of not
the follow-up investigation and its removing its H2S. The absorber
findings will appear in the second pressure is 105 kg/cm2g.
part of this article, to appear in the Vessel inspection during a unit
Q4 2021 issue of PTQ. turnaround in November 2017 iden-
PTQ Q3 2021 13
11/06/2021 14:35
 turi) orifices at 600 mm spacing. The
Tray dimensions
original trays were designed for 115
t/h of lean amine, but in practice
Old trays New high capacity trays
the absorber operated at 70-80 t/h
Tray type MR2 & MR63 Fixed small valve
Tower area, m2 3.14 3.14 of lean amine, with occasional runs
Active area, m2 2.43 2.47 just above 100 t/h. To increase the
Open area, m2 0.358 0.311 lean amine flow rate, and with the
Open area, % 14.5%1 12.6%
outlook of processing high sulphur
Downcomer top area, m² 0.354 0.447
Downcomer bottom area, m² 0.354 0.227 VGO, the tower was retrayed to
Downcomer area at top 11.3% 14.2% increase its liquid handling capacity
Downcomer top width, mm 340 400 to 150 t/h.
Downcomer bottom width, mm 340 250
The retray was designed and per-
Flow path length, mm 1320 1350
Outlet weir length, mm 1503 1600 formed by a major tray supplier
Weir height, mm 50 65 with mini-fixed valve trays, with
Downcomer clearance, mm 40 65 peripheral push valves along the
Tray thickness, mm 2 2
tower walls, pushing the liquid in
Note 1 the direction of flow. To increase
This is the open slot area of the moving valves the liquid handling capacity, the
straight downcomers were replaced
Table 1 by sloped downcomers, with larger
downcomer top areas and smaller
tified a number of internal cracks 0.50 mol/mol of methyl diethanol bottom areas, while keeping the tray
and hydrogen blisters in the HP amine (MDEA), well above the 0.40 active areas unchanged. The down-
amine absorber. Cracks were elimi- mol/mol maximum limit practised comer top to bottom area ratio was
nated by grinding the blistered sur- by the industry. The required lean 2:1, in accordance with good design
faces and weld filling the internal MDEA flow rate to maintain the practices.2,3 The clearances under
cracks followed by post-weld heat H2S loading below 0.40 mol/mol of the downcomers were also raised
treatment. In January-March 2019, MDEA was limited by the onset of to lower downcomer back-up. The
another unplanned shutdown was foam-over events. weir heights were raised to keep the
taken to partially replace the bottom downcomers at a zero static seal. A
portion of the absorber shell due to Retray details and preliminary comparison of the old to the revamp
aggravation in the cracks.1 hydraulic evaluation tray design is shown in Table 1.
The major reason identified for The amine absorber is 2.0 m in The absorber lean amine inlet,
hydrogen-induced cracking and diameter and had a total of nine rich amine outlet, gas entry,
hydrogen blisters was high rich single pass standard uncaged mov- and bottom seal pan remained
amine H2S loading of more than ing valve trays with sharp (not ven- unchanged. The bottom seal pan
overflow weir was 103 mm tall and
1500 mm long, 750 mm below the
90 50 bottom tray. The straight bottom
downcomer was replaced with a
80 45 sloped one of the same top and bot-
70 40 tom areas as the other revamp trays,
but its clearance was increased from
Lean amine flow rate, t/h

Absorber dP/tray, mbars

Lean gas flow rate, t/h

35
60 50 mm to 90 mm. No changes were
30 made to the pre-KOD vessel.
Levels, %

50
25
40 Operating trends during a foaming
20 event
30
15 Figure 2 shows the operating trends
20 during a foaming event, a short
10
time after the absorber returned to
10 5 service following the retray. The
0 0
tower operated steadily at a gas
24-Mar-2019 24-Mar-2019 24-Mar-2019 24-Mar-2019 flow rate of 43 t/h and a lean amine
16:19 16:33 16:48 17:02 flow rate of 74 t/h, with a differ-
Level in d/s KOD Level in absorber sump Pre-KOD level CV OP ential pressure (dP) of 11 mbar/
Amine flow rate Absorber DP Gas flow rate tray. At about 16:19, the dP started
to rise, slowly at first, then faster,
peaking at 19 mbar/tray at 16:23.
Figure 2 Operating trends during a foaming event: new trays, before pre-KOD bottom The absorber bottom level fell as
line plugging the dP rose. Both the rise in dP

14 PTQ Q3 2021 www.digitalrefining.com

q3 Kister.indd 14 11/06/2021 14:35

 and the reduction in bottom level
are symptoms of flooding. Just
before the dP peaked, the opera-
tors took the corrective action of
greatly reducing the lean amine
rate to 50 t/h. Amine carry-over to
the D/S KOD started at 16:23, as
seen by the rapid rise in level in the
drum. The drum filled up with liq-
uid within a minute or two. Upon
reduction in the lean amine rate,
the carry-over declined as seen by
the more gradual fall in liquid level
in the D/S drum, becoming low by
16:37. Simultaneous draining of the
D/S KOD was carried out at field.
Throughout the event, there was lit-
tle change in the gas flow rate and
in the Pre-KOD level.
Figure 3 shows the operating
trend during a foaming event, with
the old trays. The tower operated
steadily at a gas flow rate of 43 t/h
and a lean amine flow rate of 80
t/h, much the same as in Figure 2,
with a differential pressure (dP) of
19 mbar/tray, higher than in Figure
2. At about 18:43, the dP started to
rise, the rise being much less than
in Figure 2, peaking at 23 mbar/tray
at 18:44. The absorber bottom level
fell slightly as the dP rose. Both
the rise in dP and the reduction in
the bottom level are symptoms of
flooding. Just as the dP peaked,
the operators greatly reduced the
lean amine rate to 65 t/h, a higher
value than in Figure 2. Amine car-
ry-over to the D/S KOD started at
18:44, as seen by the rapid rise in
level in the drum. The drum level
only rose to 31%, much less than in
Figure 2, within two minutes. Upon
reduction in lean amine rate, the
carry-over declined, shown by the
more gradual fall in liquid level in
the D/S drum, becoming low by
18:53. Simultaneous draining of the
D/S KOD was carried out at field.
As in Figure 2, throughout the event
there was little change in the gas
flow rate and in the Pre-KOD level.
Figure 3 teaches that following
the retray, the events at equivalent
operating rates grew in severity and
amplitude. In addition, following the
retray, the foaming events frequency
rose from about one-two per month
to about one per day. Further, fol-
lowing the retray, there were events
experienced at as low a lean amine
www.digitalrefining.com
q3 Kister.indd 15
90
80
70
Lean amine flow rate, t/h
60
Levels, %
50
40
30
20
10
0 0
17-Jan-2018
18:28
Level in d/s KOD
Amine flow rate
Figure 3 Operating trends during a foaming event: old trays
rate as 65 t/h. In summary, follow-
ing the revamp the foaming events
grew in intensity and frequency.
Plugging of the pre-KOD drain line
The pre-KOD (see Figure 1), located
upstream of HP amine absorber,
knocks out condensed liquid hydro-
carbons to prevent their carry-over
into the amine absorber. The con-
densed hydrocarbons leave the
drum via a 2” bottom drain line. For
the first 54 days after the absorber
returned to service following the
revamp, there were no signs of
plugging of this 2” line, and the pre-
KOD drum level was operated and
controlled normally. On May 12,
2019, 54 days after the revamp, it
was observed during operation that
the drum level control valve became
100% open throughout the opera-
tion. There was no gas blow-by to
the downstream cold flash drum
from the pre-KOD. This indicated
that the 2” bottom line became
plugged. De-plugging of this line
during plant operation was risky as
it was operating under an extremely
high pressure of 105.0 kg/cm2g. At
a unit shutdown about a year later,
the 2” pre-KOD bottoms line was
indeed found to be heavily plugged,
shown in a photograph in a com-
panion article.1 Liquid knocked out
in the pre-KOD was unable to drain
and would build up until it was car-
50
45
40
Absorber dP/tray, mbars
Lean gas flow rate, t/h
35
30
25
20
15
10
5
17-Jan-2018 17-Jan-2018
18:43 18:57
Level in absorber sump Pre-KOD level CV OP
Absorber DP Gas flow rate
ried over by the gas stream into the
absorber bottom.
Following the plugging of the pre-
KOD drain line, the foaming events
became far more frequent and far
more severe. The lean amine flow
rate needed to be reduced from
the previous 70-80 t/h to below 40
t/h. The carry-over incidents used
to occur 10 to 15 times per eight-
hour shift when the amine flow
was raised beyond 50 t/h. This
would annoy the field operators
who needed to quickly drain the
carried-over amine by opening the
manual drain valve of the D/S KOD
to prevent its high level switch from
tripping the lean gas compressor.
The repeated carry-over events
forced keeping an operator full time
at the manual drain valve. The lean
amine rate was reduced to 40 t/h,
which lowered the frequency of
carry-over events to 2-3 times in an
eight-hour shift at 45 t/h of gas flow
rate. But this forced a costly reduc-
tion of unit throughput to bring rich
amine H2S loading under control.
It appears that carry-over of con-
densed hydrocarbons into the amine
system following the plugging of the
2” pre-KOD drain line caused the
severe escalation in foaming events.
Condensation of hydrocarbons into
an amine solution is a common cause
of intensified foaming frequency and
severity.4-6
PTQ Q3 2021 15
11/06/2021 14:35
 Troubleshooting and operational
improvements
A companion article1 lists in detail
an extensive troubleshooting and
simulation programme that shed
invaluable light on the absorber
operation. Several actions taken
to alleviate the severity and fre-
quency of the foaming events were
also described there. Steps were
taken to avoid hydrocarbon con-
densation into the amine solution,
including keeping the amine suffi-
ciently warmer than the gas to the
absorber and knocking out more
hydrocarbons in upstream separa-
tors by reducing the inlet tempera-
tures. Steps were taken to improve
amine quality, including improved
filtration, amine washing of the
absorber, and discontinuing amine
sharing with other units. These
were somewhat successful, but the
foam events persisted. Noteworthy
among these, antifoam injection did
not help much and was discontin-
ued after a trial.
The possibility of fouling in the
absorber was evaluated. Extensive
plugging of the trays was ruled out
as no plugging was observed in the
past, the pressure drop was not par-
ticularly high, and the carry-over
problem started immediately fol-
lowing the absorber’s return to ser-
vice after the revamp.
The one very successful action was
partial opening of gas bypass around
the amine absorber (see Figure 1),
allowing 30-40% of the gas flow
to bypass the amine absorber. The
gas flow rate through the absorber
declined to 25 t/h. This operation
brought huge relief to the plant as
the amine carry-over was completely
eliminated. On the debit side, the
unabsorbed H2S in the absorber
bypass necessitated downstream
purging of impure recycle gas
from the high pressure system to a
medium pressure system, where the
gas was amine treated and sent to
fuel gas. A downside of this measure
was loss of H2.
All these positive changes
allowed increasing charge rate
to the plant from 140 t/h to 245
t/h, with feed sulphur of 2.2 wt%.
Amine flow was increased to 125
t/h, keeping a H2S loading of 0.4
mole/mole of MDEA with amine
16 PTQ Q3 2021
q3 Kister.indd 16
strength of 40%. The continuous
filtration of amine also helped the
operators to slowly close the bypass
over a period of time without any
events of amine carry-over.
There is one more important oper-
ating data point. Most of the time,
the unit operated on VGO feed-
stock. However, from time to time
it was switched to diesel feedstock.
In the full diesel feedstock operat-
ing mode, no carry-over was ever
observed from the absorber, either
with the old or with the new trays,
even at 140 t/h of amine flow to the
absorber with the gas bypass line
fully closed. In this mode, the gas
rate was 30-32 t/h.
Although the gas bypass pro-
vided relief for the operators and
helped raise the charge rates, the
riddle of the intensified amine car-
ry-over events remained unsolved.
In the quest to explore the rea-
sons, a steady state simulation was
developed and provided a basis for
hydraulic evaluation. This simula-
tion is described in detail in a com-
panion article.1
Initial hydraulic evaluation and
problem fix
An initial hydraulic evaluation by
the refinery using the tray sup-
plier’s software failed to uncover
any smoking guns. The evaluation
showed that with a foaming factor
of 0.6 and without gas bypass (gas
flow of 45 t/h and amine flow of
100 t/h), the froth heights on trays
increased to 76% of tray spacing.
This arguably suggests the initial
stages of foaming in the absorber.
However, a foaming factor of 0.6
is lower than the 0.73-0.8 usually
used for these systems3, and even
this low 0.6 factor only reached a
froth height of 76% of the tray spac-
ing, which is still low to support a
flood diagnosis. The tray supplier
was consulted but did not have an
explanation to offer.
To explain the events at the lower
liquid rate (40-50 t/h lean amine
flow rate), there was a theory that
downcomers may have lost their
seal, with downcomer unsealing
flood causing the carry-over, a
mechanism similar to that described
for another amine absorber.7
Unfortunately, the tray supplier’s
software was unable to determine
whether downcomer unsealing was
likely and, if so, whether it would
lead to flood.
The carry-over events were
finally eliminated by replacement
of the amine absorber with a packed
tower (with random packing) and
by unplugging the drain line of the
pre-KOD. In addition, charcoal fil-
ters in the amine regeneration unit
were replaced. The issue of amine
foaming subsided and the unit has
been operating at full throughput
ever since. The tremendous savings
due to charge increment for just
three months is huge as described in
detail in a companion article.1
Rigorous hydraulic evaluation and
post mortem
Although the problem was solved,
the refinery continued to investigate
the yet unsolved mystery. Aware
of Fluor’s distillation expertise, the
refinery had Fluor join their task
force analysing data and perform-
ing a ‘post mortem’.
A review of Table 1 revealed noth-
ing unusual. Increasing the down-
comer top area and downcomer
clearances are common debottle-
necking techniques applied in foam-
ing service and should have helped
to alleviate the foaming events.
Even if unsuccessful, they should
not have brought the capacity
down.
Table 2 identifies the key cases
analysed for diagnosing the prob-
lem. Any mechanism postulated to
explain the absorber mystery must
be consistent with the plant experi-
ence in all these five key cases. The
flow rates were those measured at
the start of the various events, prior
to the pressure drop rise and the
carry-over. The physical properties
were per the refinery’s simulation.
The two left-hand columns in
Table 2 reflect typical operation
with the pre-KOD operating nor-
mally (drain line not plugged).
These provide a direct compar-
ison of the performance of the
old and new trays, unaffected by
the entrainment of condensed
hydrocarbons into the system that
occurred once the pre-KOD 2”
drain line plugged. The flow rates
are much the same for these col-
www.digitalrefining.com
11/06/2021 14:35
 T:210 mm

T:297 mm
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MECHANICAL
 T:210 mm

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MECHANICAL
 umns. Comparing these two cases
is central to understanding how the
changes in tray design affected the
absorber performance. It is impor-
tant to note that going from the old
trays to the new trays the frequency
of events rose from 1-2/month to 1/
day, and also increased in severity.
The third column in Table 2
reflects the performance of the trays
under the severe foaming condi-
tions generated by carry-over of
condensed hydrocarbons from the
pre-KOD into the amine system fol-
lowing the plugging of the 2” drain
line. Both gas and liquid rates are
considerably lower when the events
occurred, and the events were far
more frequent. The fourth column
reflects the absorber performance
with the gas bypass partly open.
The gas rate through the amine
absorber was quite low. At this gas
rate, no foaming events were expe-
rienced. The lean amine flow rate
could be largely increased with no
carry-over. The last column is the
diesel feedstock run. Under these
conditions, no carry-over events
were experienced, even at very high
lean amine rates.
Table 3 provides a flood eval-
uation for all five cases. The top
row expresses the gas load using
the C-factor based on the bubbling
(active) area, defined as:
rG
Cb = Ub [1]
r L - rG
where Cb is the capacity factor, m/s;
Ub is the gas superficial velocity
based on the bubbling area, m/s; ρG
and ρL are the gas and liquid densi-
ties, kg/m3.
The C-factors are low, compared
to typical values at jet flood for
trays spaced 600 mm apart about
0.13 m/s for non-foaming systems
and possibly slightly less for foam-
ing systems. The absorber C-factors
are not even close. This is echoed
by the jet flood calculations, none
of which exceeds 40% of flood for
cases where events were experi-
enced. Even allowing for a system
factor of 0.6, much lower than the
values 0.73-0.8 cited for amine sys-
tems3, the percent jet flood will
be below 67%. We conclude that
the carry-over in the absorber has
www.digitalrefining.com
q3 Kister.indd 17
Key cases considered in absorber hydraulic analysis
Old trays Revamp Revamp Revamp New trays
1-17-2018 trays trays gas bypass diesel
Event 3-24-2019 11-24-2019 partly mode
Event Event open operation
Frequency of events 1-2/month 1/day many/shift none none
Gas flow rate, t/h 43 44 30 25 31
Gas density, kg/m3 16.3 16.3 16.3 16.3 9.77
Gas volumetric flow rate, Am3/h 2630 2682 1825 1529 3201
Liquid flow rate, t/h 75 73 50 100 140
Liquid density, kg/m3 1028 1028 1028 1028 1028
Liquid flow rate, m3/h 72.9 71.0 48.6 97.3 136.2
Liquid viscosity, cP 2.88 2.88 2.88 2.88 2.88
Liquid surface tension, mN/m 48.3 48.3 48.3 48.3 48.3
Table 2
nothing to do with approaching jet recommended seven seconds min-
flood. imum for highly foaming systems.3
The downcomer backups are low, We conclude that insufficient down-
none exceeding 30.5%, for the cases comer residence time was not the
in which the carry-over events were issue in the absorber.
experienced, and for the revamp The one parameter that is close
trays it was 27.1% or less. Even to a limit for the cases in which the
when applying the conservative carry-over events were experienced
aeration factor for foaming systems is the downcomer inlet velocity.
of 0.33, the froth in the downcomer The recommended value for highly
would be only 90% of the tray spac- foaming recirculating systems
ing. Further, Table 3 shows that the (like amine absorber-regenerator
new trays would have reduced the systems) is 0.061-0.076 m/s.3 For
downcomer backup, thus debot- once-through foaming systems, the
tlenecking a downcomer back-up design values recommended are
issue. We conclude that downcomer lower, 0.031-0.046 m/s.3 The higher
backup flood was not the issue in values are recommended for recir-
the absorber. culating systems because foaming
The downcomer choke limit can be can be at least partially controlled
evaluated by considering the down- by antifoam addition. This is usu-
comer liquid inlet velocities and ally difficult with a once-through
the apparent downcomer residence system as the antifoam ends up
times. All the downcomer residence in the bottoms and contaminates
times for the cases in which the car- the product. Although the current
ry-over events were experienced absorber is part of a recirculating
exceeded 11 seconds, well above the amine system, no antifoam was
Flood hydraulic evaluation
Old trays Revamp Revamp Revamp New trays
1-17-2018 trays trays gas bypass diesel
Event 3-24-2019 11-24-2019 partly
Event Event open
Capacity factor, Cb, m/s 0.038 0.038 0.026 0.022 0.035
Outlet weir loading1, m3/h m 48 34 10 23 65
% Jet flood2, FRI 40.0% 35.3% 20.1% 21.0% 38.1%
% jet flood2, Glitsch eq. 13 39.6% 39.6% 27.0% 31.3% 46.6%
% Liquid flow rate, t/h 75 73 50 100 140
Liquid height in DC3, mm 198 180 134 157 238
% Liquid height in DC3 30.5% 27.1% 20.1% 23.6% 35.8%
Liquid velocity at DC inlet, m/s 0.057 0.043 0.030 0.060 0.085
DC apparent residence time, s 11.4 11.3 16.6 8.3 5.9
Notes
1. Only liquid flowing over the outlet weir, does not include weeping
2. No system factor included
3. Liquid head in downcomer (DC), does not account for aeration
Table 3
PTQ Q3 2021 17
11/06/2021 14:35
 injected, so it will behave like the
once-through systems. Our expe-
rience with once-through foaming
systems, including amine systems
with no antifoam injection, is that
downcomer choke flood occurs at
downcomer inlet velocities of 0.05-
0.055 m/s. This limit is slightly
exceeded in the old trays. We can
say with confidence that down-
comer choke flooding due to exces-
sive downcomer inlet velocity was
the cause of the carry-over events in
the old trays.
It appears that the tray supplier
was concerned about this issue and
successfully addressed it in the
revamp by increasing the down-
comer inlet area. The velocity at the
downcomer inlets of the new trays
during the foaming events was
well below the limit of 0.05 m/s. So,
downcomer choke due to excessive
inlet velocities is unable to explain
the events in the revamp trays.
Another unexplained issue is why
the flooding event was not experi-
enced when gas to the absorber was
partly bypassed, even though the
downcomer inlet velocity exceeded
the values at which downcomer
choke flood had been experienced.
Table 3 shows that both the crite-
ria of maximum downcomer inlet
velocity and the minimum down-
comer residence time for foaming
systems were violated in the diesel
run. With a foaming system, this
operation should have experienced
frequent carry-over events. The
fact that it did not experience any
strongly supports the refinery’s the-
ory that no foaming occurred under
diesel run conditions. A major dif-
ference between the diesel and VGO
modes is the cracking of heavy
hydrocarbons into lighter hydro-
carbons, which is far higher in VGO
mode. Due to the intrinsic proper-
ties of the catalyst, the refinery has
experienced almost negligible crack-
ing when operating in diesel mode.
In contrast, during the VGO run the
catalyst produced a large quantity
of these lighter hydrocarbons which
got into the amine solution and
made it foamy.
The experience of foaming tak-
ing place with one campaign but
18 PTQ Q3 2021
q3 Kister.indd 18
not with another is quite common.
One source reports some 15 cases
in which foaming in refinery FCC
secondary absorbers occurred when
light cycle oil (LCO) was used as the
lean oil, and replacing the LCO by
naphtha effectively eliminated the
foaming.8 A recent experience tells a
story of severe foaming when “sub-
stance X”, which was heavier than
the extractive distillation solvent,
was present, but no foaming when
it was absent.9
In summary, the flood analysis
invalidated any theories regarding
jet flood or downcomer back-up
flood or insufficient downcomer
residence time having any rele-
vance to the observed carry-over
The experience of
foaming taking place
with one campaign
but not with another
is quite common
events. The flood analysis explained
the event experience with the old
trays as downcomer choke flood
when the downcomer inlet velocity
exceeded a limit. The flood analysis
also explained the absence of events
when operating in diesel mode by
this mode being non-foaming.
The flood analysis was unable
to explain the events experienced
with the revamp trays. The joint
investigation revealed a previously
unreported phenomenon: vapour
channelling inducing premature
tray foam-flood. This will be dis-
cussed in detail in Part 2 of this arti-
cle, to appear in the Q4 2021 issue of
PTQ.
References
1 Mohan R, R Kumar, H S Kumar Gupta, B Zohail
N, Amine anomaly in a mild hydrocracker –
learning from simulation & field observations,
PTQ, Q2 2021.
2 Kister H Z, Distillation Operation, McGraw-
Hill, NY, 1990.
3 Kister H Z, P M Mathias, D E Steinmeyer, W
R Penney, V S Monical, J R Fair, Equipment for
distillation, gas absorption, phase dispersion
and phase separation, in D W Green and R H
Perry Perry’s Chemical Engineers’ Handbook
9th Ed., Section 14, McGraw Hill, New York,
2018.
4 Iyengar J N, P W Sibal, D S Clarke, Operations
and Recovery Improvement via Heavy
Hydrocarbon Extraction, 48th Laurence Reid
Gas Conditioning Conference, p161, Norman,
Oklahoma, 1-4 Mar 1998.
5 Mykitta R S, Operating Experiences of Shell’s
Yellowhammer Gas Plant, 49th Laurence
Reid Gas Conditioning Conference, Norman,
Oklahoma, Feb 1999.
6 Von Phul S A, Sweetening Process Foaming
and Abatement, 51st Laurence Reid Gas
Conditioning Conference, Norman, Oklahoma,
25-28 Feb 2001.
7 Kister H Z, N M Mohamed, Troubleshoot
and solve a gas treater downcomer unsealing
problem, Part 2, Gas Processing, p49, Mar/Apr
2015.
8 NPRA, Q & A Session on Refining and
Petrochemical Technology, 1983, p52.
9 Yarbrough B, T Cooper, C Davidson,
Extractive Tower Column Troubleshooting after
Internals Revamp, presented at the Distillation
Symposium of the AIChE Spring Meeting,
Virtual, 18 Aug 2020.
Henry Z Kister is a Fluor Corp. Senior Fellow
and Director of Fractionation Technology,
with over 35 years’ experience in design,
troubleshooting, revamping, field consulting,
control, and start-up of fractionation processes
and equipment. He is the author of three books,
the distillation equipment chapter in Perry’s
Handbook, the distillation chapter in the Kirk-
Othmer Encyclopedia of Chemical Technology,
and over 130 articles. He has taught the
IChemE-sponsored Practical Distillation
Technology online course over 530 times in 26
countries, and a recent online Troubleshooting
Distillation Controls course, also sponsored by
IChemE. A recipient of several awards, he holds
BE and ME degrees from the University of
NSW in Australia. He is a Fellow of IChemE and
AIChE, Member of the US National Academy
of Engineering, and has been serving on the
FRI Technical Advisory and Design Practices
Committees for more than 25 years.
Rohit Kumar is an Assistant Manager in the
VGO hydrocracker unit of Bharat Petroleum
Corporation Limited - Kochi refinery, with over
seven years’ experience, with special expertise
and qualifications in process modelling,
simulation and troubleshooting. He has worked
with major oil refineries in India where he has
led projects in commissioning, troubleshooting
and debottlenecking. He graduated in
Chemical engineering from Thapar Institute
of Engineering & Technology, Patiala (Punjab),
India.
www.digitalrefining.com
11/06/2021 14:35
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 Impact of chlorides on fluid catalytic cracking
A variety of issues can arise when chlorides enter an FCC unit
MELISSA CLOUGH MASTRY, CORBETT SENTER, FERNANDO SANCHEZ and BILGE YILMAZ
BASF Refining Catalysts
F
luid catalytic cracking (FCC)
is an important conversion
process in many refineries.
It produces transportation fuels,
including gasoline and diesel pre-
cursors, as well as feedstocks for
many chemical processes, includ-
ing propylene and ethylene. The
FCC process uses a fluidised solid
catalyst to crack feeds with a vari-
ety of properties. The need for a
sustainable FCC process is becom-
ing increasingly important as fuel
regulations become more stringent
and environmental regulations
become increasingly tight. In light
of this, the refining industry aspires
to make the most of every barrel
of crude oil processed. This often
means avoiding any byproducts
that reduce the amount of valuable
products (gasoline, diesel, propyl-
ene) produced by the FCC process.
Refineries that process residue-
containing feedstocks (resid feed)
face significant challenges to their
sustainability and even to reaching
their economic targets. Resid feeds
often introduce contaminants that
cause unwanted side reactions in an
FCC unit. Common contaminants in
resid feeds include vanadium, iron,
and nickel, each of which offers
obstacles by promoting unwanted
side reactions in an FCC unit.
Vanadium, for example, primarily
deactivates the fluidised catalyst,
leading to lower conversion and
unwanted heavy liquid products
(bottoms or slurry). Iron can cause
physical blockage on the surface of
catalyst particles, leading to a simi-
lar outcome.
Nickel, on the other hand, cataly-
ses the dehydrogenation of hydro-
carbon molecules. Nickel is a well
known dehydrogenation catalyst
that is often used in the petro-
chemical industry, and it can pro-
www.digitalrefining.com
q3 basf.indd 21
mote unwanted dehydrogenation
reactions in the FCC unit as well.
In the FCC unit, nickel increases
hydrogen and coke yields, which
decreases valuable product out-
puts (LPG, gasoline, and/or light
cycle oil will be decreased). Over
time, as nickel circulates through
the FCC unit, it loses its activity
and becomes relatively inactive
as a dehydrogenation catalyst by
becoming oxidised to the +2 oxi-
dation state. In this oxidation state,
nickel is essentially immobile.
Nickel in the Ni(0) oxidation state is
responsible for unwanted dehydro-
genation reactions and is consid-
ered relatively more mobile.1,2 Once
nickel is rendered relatively inac-
tive through oxidation, it remains
in this state until it is physically
removed from the unit. However,
in some cases, nickel can be reac-
tivated from its relatively inactive
state to its Ni(0) oxidation state.
One element in particular, chlorine,
can reactivate nickel.
In addition to their chemical
effects, chlorides can pose chal-
lenges to refiners by introducing
operational challenges. A promi-
nent example of this is the forma-
tion of chloride based deposits that
manifest downstream of the FCC
unit. The reactivation of nickel by
chlorides and operational chal-
lenges posed by chlorides will be
the focus of this article.
Reactivation of nickel
In other (non-FCC) processes, chlo-
ride-containing materials have been
shown to not only reactivate nick-
el’s dehydrogenation activity but
also increase its mobility on various
solid supports.1 Considering that
chloride-containing materials can
also enter an FCC unit, the chem-
istry of these reactions in an FCC
setting are of interest since this
would mean an increase in hydro-
gen and coke upon nickel reacti-
vation. For most refineries, this
is an unwanted side reaction and
can cause significant constraints
to operation. Therefore any chlo-
rides entering the FCC unit should
be scrutinised. Chlorides can enter
an FCC unit by various methods:
poor desalter operations, opportu-
nity feeds, residue or bio feeds, or
slops processing.3 Yet another ave-
nue for chlorides to enter the FCC
unit is through the fresh catalyst
itself, specifically through fresh cat-
alyst manufactured via an ‘incor-
porated’ technique that involves
chloride-containing ingredients. In
this manufacturing route, the use
of a binder, often an alumina-sol
based binder, is needed to provide
the catalyst its structural integ-
rity (its attrition resistance). Many
of these binders include chlorides
either as an integral component or
as a byproduct during the manufac-
turing step. Therefore some incor-
porated catalysts often come with
a significant amount of chlorides;
industrial reports detail up to 1.2
wt% chloride content. Regardless of
source, once in the FCC, chlorides
can have detrimental effects relat-
ing to the reactivation of nickel con-
taminant, among other issues.
Operational impact of chlorides in
the FCC unit
Aside from the chemical effects of
chlorides, which will be discussed
in more detail in the next section,
chlorides can also lead to unwanted
and unfavourable operational situ-
ations in an FCC unit. For example,
there have been many industrial
reports of main fractionator depos-
its that are heavy in chlorides. This
phenomenon is a result of the for-
PTQ Q3 2021 21
11/06/2021 14:46

250
200
Chlorides, ppm
150
100
50
0 0
Time
Figure 1 Chlorides content in the water purge draw from the main fractionator column
after a catalyst change at a refinery
mation of solid ammonium chloride
(NH4Cl) which forms according to
the following reaction:
NH3 (gas) + HCl (gas) ⇋ NH4Cl (solid)
Deposition takes place at the top
of the fractionator (downstream of
the FCC reactor) where tempera-
tures are relatively low compared
to the reactor itself. When both
ammonia (NH3) and hydrochlo-
ric acid (HCl) are present in the
vapour phase, the lower temper-
ature leads to their condensation
in the cold areas of the main frac-
tionator and their reaction to form
NH4Cl dissolved in water. When
water is later boiled off down-
stream, NH4Cl is deposited onto
the trays in the fractionator. NH3 is
formed upstream in the FCC unit,
especially in partial burn regener-
ators. Less NH3 is formed in a full
burn regenerator, as most N is oxi-
dised to NOx. But NH3 is rarely
ever the limiting reagent in the
above reaction mechanism so this
condensation mechanism is seen in
both partial and full burn regener-
ator FCC designs. Although NH4Cl
deposition will be made worse
with lower fractionator tempera-
tures (for example, if an FCC unit
has an HCN side-stream draw) or
increased partial pressure in the
fractionator, deposits have been
observed even for overhead frac-
tionator temperatures above the
water dew point since localised
cold spots (for instance, the top
pumparound return section) gener-
ate the same mechanism.
22 PTQ Q3 2021
q3 basf.indd 22
120
100
Turnover rate, %
80
60
40
Chlorides
Turnover 20
Such NH4Cl deposits will reduce
both the capacity and efficiency
of main fractionator operation.
These will manifest either as pres-
sure or temperature instabilities, an
increased pressure drop over the
trays, flooding of the top section of
the fractionator, or some combina-
tion of these. Another manifestation
might be poor performance over-
all, leading to, for example, poor
fractionation between LCO and
naphtha product streams. In addi-
tion, there could be long term det-
rimental effects like under-deposit
enhanced corrosion rates in tower
internals (trays, supports) and
external walls. Each of these nega-
tive effects has its own penalties in
terms of downtime and/or negative
economic impacts.
To mitigate these deleterious
effects, significant overhauls might
need to be taken, depending on the
extent of deposition and damage.
The operation of the fractionator
might have to be adjusted, which
can cause significant negative eco-
nomic impacts. A capital investment
might be needed to debottleneck
top pumparound hydraulics. Water
washing might be needed (its fre-
quency will depend on the severity
of the problem), which will require
the allocation of work hours to this
task. Continuous water washing
might not be an option for some
fractionator operations where the
top tray temperature is sufficiently
low. For those operating at rela-
tively high top tray temperatures,
the feed rate to the fractionator
might need to be reduced in order
to perform periodic water washes.
Yet another route is the use of
chemical additives to address the
deposition problem, which requires
its own assessment and feasibil-
ity programme (efficacy, costs, tri-
alling). All these mitigation steps
have their own (usually negative)
economic impacts on profitability.
Another cautionary area is caus-
ing off-spec products downstream,
where the chlorides are eventually
washed.
To demonstrate the effects of chlo-
ride deposits, three industrial case
studies are offered. The first is from
a refinery in which a catalyst con-
taining chlorides was introduced
and the effect of chlorides down-
stream was monitored. In the sec-
ond case study, a European refinery
was struggling with chloride depos-
its, and calculations to quantify the
problem are provided. In the third,
a back-to-back to back trial example
is compared in which water wash-
ing needs fluctuated based on cata-
lyst technology.
In the first example, during an
FCC unit industrial trial, a non-chlo-
ride containing FCC catalyst was
replaced with an incorporated FCC
catalyst containing chlorides. As
Figure 1 shows, since the begin-
ning of the industrial trial, a clear
increase in chlorides in the water
purge draw from the column was
observed as the catalyst turnover
progressed. Since the refinery was
not processing a chloride-contain-
ing crude, the increase in chlorides
in the water wash was attributed to
the new fresh catalyst, which was
known to use a chloride-containing
alumina based binder. We do note
that there is a continued increase in
chlorides content in the water purge
draw past the 100% turnover rate
(the last two data points in Figure
1), which could be attributed to the
lag in chloride purge from the water
wash system given the timing of
the wash itself relative to when the
chlorides entered the unit and main
fractionator.
In the second industrial example,
a case study offers a calculation of
the amount of deposits based on
unit operating data. We provide
these calculations in detail as an
example for FCC engineers, so that
www.digitalrefining.com
11/06/2021 14:46
 a similar exercise can be done on
their respective units if there are
concerns about NH4Cl deposits. The
details are as follows.
Inputs and assumptions
• 6000 kg/day of fresh catalyst
added to the FCC unit
• Fresh catalyst contains a moderate
amount of total chlorides: 0.8 wt%
• 80% of the fresh chlorides leave
the FCC regenerator through the
flue gas (best-case scenario is that
only 20% remain in the unit)3
• Fractionator tower diameter of
5 m (each tray has an area of 19 m2)
Calculations
• 6000 kg/day catalyst,* 0.8 wt%
Cl in the catalyst,* 0.2 Cl remains in
the unit = 9.6 kg Cl/day enter and
remain in the FCC unit
• 9.6 kg Cl/day* (53g/mol NH4Cl
/35 g/mol Cl) = 14.5 kg NH4Cl/day
or 436 NH4Cl kg/month
• 436 kg NH4Cl/month/1.53 kg/L
= 285 L NH4Cl/month or 0.285 m3
NH4Cl/month
• 0.285 m3 NH4Cl/month/19 m2
= 0.015 m or 1.5 cm layer of NH4Cl
per month
The calculations show that
approximately 1.5 cm of NH4Cl per
month is expected to deposit in the
main fractionator. In this case study,
the refinery had to conduct a water
wash of the fractionator every two
weeks to eliminate these NH4Cl
deposits, sometimes more often.
This high frequency of water wash-
ing indicated that the percentage
of chlorides leaving the regenera-
tor with flue gas was less than 80%
(so more than 20% remained in the
unit) or that the fresh catalyst total
chlorides content was higher than
0.8 wt%, or both. Because of this
deposit issue, among others, the
refinery decided to change from an
incorporated catalyst to an in situ
catalyst to alleviate its problems
with ammonium chloride deposits
and their associated costs. After the
refinery changed to an in situ cata-
lyst (which does not use chloride
based binders), the need for water
wash of the main fractionator was
eliminated.
Finally, a third industrial trial
is offered as an example. Figure 2
www.digitalrefining.com
q3 basf.indd 23
Overhead delta P
Figure 2 Main fractionator overhead delta P build-up during a trial with a high chloride
catalyst
shows similar experience observed
in a back-to-back-to-back trial
involving a chloride-containing
catalyst and two catalysts that do
not use chloride based binders. In
this example, similar to the case
described and calculated previ-
ously, the refinery had to undergo
frequent water washes during a trial
with a chloride-containing catalyst
(highlighted in blue in Figure 2) due
to delta P build-up in the main frac-
tionator overhead. Once the refinery
switched back to a catalyst without
a chloride based binder, the need
for water wash was eliminated.
Chemical impact of chlorides in the
FCC unit
The chemical impact of chlorides in
an FCC unit was recently explored
in a laboratory setting to comple-
ment the large body of knowledge
arising from industrial examples.1
H2/CH4 ratio
0.6
0.5
34% increase
0.4
wt% / wt%
0.3
0.2
0.1
0 5
Control
Figure 3 Effect of chloride exposure on H2/CH4 ratio and coke yield at 75% conversion
Trial period with
high Cl catalyst
Water wash
Time
In this study, equilibrium catalyst
(Ecat) containing 4600 ppm contam-
inant nickel was exposed to a chlo-
ride source and compared using
ACE analysis against a control sam-
ple of the same Ecat which was not
exposed to Cl. In this evaluation, as
expected, both hydrogen and coke
increased (see Figure 3).
This increase in non-value-added
products (hydrogen and coke) in
the chloride-exposed catalyst is
a testament to the reactivation of
nickel and suggests a move from
its relatively inactive state (Ni(2+))
to its more active state (Ni(0)). A
similar evaluation was done using
Ecat with a lower content, 630 ppm,
of contaminant nickel. Even with
this lower nickel regime, the effect
of chloride reactivation was still
noticeable: 32% higher H2/CH4
ratio and 15% higher coke yield. In
this lower nickel case, the absolute
Coke yield
10
19% increase
9
8
wt%
7
6
Chloride Control Chloride
exposure exposure
PTQ Q3 2021 23
11/06/2021 14:46

0.14
Inactive NiO on Ecat
2140 and 2160 cm-1 band area
0.12
0.10
0.08
0.06
0.04
0.02
0 ride content. This total chlorides
200
T (˚C)
Figure 4 CO DRIFTS results of nickel containing catalyst treated with N2 and HCl
changes in H2/CH4 ratio and coke
were smaller, since the cause of the
problem to begin with (nickel con-
tent) was lower, but, on a percentage
basis, the change was in line with
the high nickel case, as expected.
This demonstrates that, even in a
mild resid or VGO application, the
chloride effect would still be notice-
able. An increase in these magni-
tudes in either the H2/CH4 ratio or
coke yield would be genuinely con-
cerning in an industrial setting. In
FCC unit operation itself, the issue
could present itself as a problem
for downstream gas handling or on
coke burning capacity, particularly
if the gas plant is running against
its constraint, or if no catalyst cooler
is present, if the unit is operating
against a coke burn constraint.
In addition to ACE evaluation,
the nickel-containing Ecat samples
were studied via a specialised spec-
troscopic method called CO DRIFTS
(diffuse reflectance infrared Fourier
transform spectroscopy with car-
bon monoxide as the probe mole-
cule). This technique can provide
information on the oxidation state
of nickel.1,4 The results are shown
in Figure 4. The band areas at 2140
and 2160 cm-1 represent how much
nickel oxide (inactive nickel) is pres-
ent. At every temperature, samples
treated with Cl show that less inac-
tive nickel is present on the catalyst.
The results demonstrate that when
catalyst is exposed to chlorides, the
nickel present is rendered to a more
active state compared with the con-
trol and this supports the results
also seen in Figure 3.
24 PTQ Q3 2021
q3 basf.indd 24
N2
HCl
400 600
Minimising chlorides
Clearly, chlorides have negative
effects on FCC operation. All steps
should be taken to minimise chlo-
rides from entering the FCC unit.
The two main routes for chloride
entry into the unit – from the fresh
feed or crude oil and from the fresh
catalyst – should be minimised.
From the feed side, efficient
desalter operations and/or pro-
cessing of hydrotreated feeds (if
Clearly, chlorides
have negative effects
on FCC operation. All
steps should be taken
to minimise chlorides
from entering the
FCC unit
possible, as refinery configurations
allow) should be a priority. In addi-
tion, if slops are known to contain
a significant amount of chlorides,
they should be re-routed to other
units within the refinery for pro-
cessing to avoid the effects in the
FCC unit. Chlorides content in the
feed should be part of the feed mon-
itoring programme and should be
continuously measured or reported
to allow for efficient troubleshoot-
ing once a situation arises. In some
cases, the planning group might
want to set a maximum chloride
specification for the FCC feed.
From the catalyst side, refin-
ers and licensors should always
request information on the amount
of chlorides present from their cat-
alyst suppliers. Importantly, the
total amount of chlorides should
be reported, not just those that are
soluble in water. In some indus-
trial reports, only the water soluble
chlorides are reported by a vendor.
Sometimes water soluble chlorides
represent only half of the total chlo-
content can be upwards of 1.2 wt%.
As calculations in this article show,
this is a critical input to estimate
the severity of any problems down-
stream the FCC unit.
Minimising the introduction
of chlorides to the FCC unit will
avoid both the chemical effects in
the unit itself and the operational
effects downstream in the fraction-
ator, both of which will negatively
impact FCC margins. In addition,
minimising chlorides to the FCC
unit will free up the work-hours
devoted to resolving any chloride
related issues, both operationally
and chemically.
Conclusion
In this article, we have described
both the chemical and operational
impacts that chlorides can have
on an FCC unit. The chemical
issues arise from the reactivation of
nickel contaminant, which causes
unwanted dehydrogenation reac-
tions (higher hydrogen and coke
yields), lowering valuable product
yields and throughput. The problem
can be worse for heavy resid FCC
units in which the nickel content on
Ecat is very high (above 2000 ppm
for example). However, the problem
can still present itself in mild resid
or even VGO FCC units, given the
similar increase in H2/CH4 and coke
on a relative basis.
Therefore, regardless of the
type of operation (VGO to resid),
the reactivation of any amount of
nickel can cause serious concerns
in terms of yield profiles. The oper-
ational issues arise from the forma-
tion of NH4Cl deposits in the main
fractionator, leading to an array of
issues affecting both the through-
put and efficacy of FCC products
handling, which in turn can affect
www.digitalrefining.com
11/06/2021 14:46
 the way the FCC unit is operated.
In some cases, the throughput to the
unit might have to be decreased to
consider the lower efficiency of the
main fractionator.
Three real life case studies were
presented on this latter issue, NH4Cl
deposits. In multiple cases, the
refinery decided to switch to a cat-
alyst that did not contain chloride
based binders and did not cause
deposit issues. In both pathways,
chemical and operational, the effect
of chlorides introduces a significant
negative penalty on the economics
of an FCC unit.
Recommendations to mini-
mise chlorides in the FCC unit are
offered, mainly by feed manage-
ment and careful fresh catalyst eval-
uation and selection. If chlorides to
the FCC unit are not avoidable, an
example calculation is provided to
offer engineers another way to trou-
bleshoot and/or predict problems
that might arise downstream.
In a time when profitability and
sustainability are paramount, it is
even more important to minimise
the effects that chlorides will have
on the FCC unit to keep it operating
safely and profitably.
References
1 Senter C, Clough Mastry M, Zhang C C,
Maximuck W J, Gladysz J A, Yilmaz B, Role of
chlorides in reactivation of contaminant nickel
on fluid catalytic cracking (FCC) catalysts,
Applied Catalysis A: General 2021, 611.
2 Cadet V, Raatz F, Lynch J, Marcilly C, Nickel
contamination of fluidised cracking catalysts:
a model study, Applied Catalysis 1991, 68 (1),
263-275.
3 Melin M, Baillie C, McElhiney G, Salt
deposition in FCC gas concentration units, PTQ,
Q4, 2009, 135-139.
4 Zhang C C, Shi J, Hartlaub S, Palamara J P,
Petrovic I, Yilmaz B, In-situ diffuse reflective
infrared Fourier transform spectroscopy
(DRIFTS) study on Ni passivation in FCC
catalysts from boron-based technology,
Catalysis Communications 2021, 150.
Melissa Clough Mastry is a Technology
Manager with BASF’s Refining Catalysts group
in Iselin, New Jersey, serving Europe, the Middle
East, and Africa. Prior to refining catalysts, she
worked in procurement and R&D. She holds a
BSc from the University of Florida, a PhD from
Texas A&M University, and an MBA from the
University of North Carolina.
Email: melissa.mastry@basf.com
Corbett Senter is a Technology Manager
with BASF Refining Catalysts’ technical
service and technology teams in Houston,
Texas. He worked in catalyst research and
development prior to joining BASF and
holds a BS in chemical engineering from the
University of Mississippi and a PhD in chemical
& biomolecular engineering from Georgia
Institute of Technology.
Email: james.senter@basf.com
Fernando Sanchez is an Account Manager
with BASF Refining Catalysts, Barcelona, Spain,
with customer responsibilities in EMEA. With
over 24 years’ experience, he has worked in
troubleshooting as well as technical service in
fluid catalytic cracking. Prior to joining BASF, he
worked for CEPSA as a process and operating
engineer in an FCC unit. He holds a bachelor’s
degree in industrial chemistry from Granada
University, Spain.
Email: fernando.sanchez@basf.com
Bilge Yilmaz is Global Director of Technology
and Technical Services with BASF Refining
Catalysts. He holds a BS in chemical engineering
from Middle East Technical University, Ankara,
Turkey; an MS and PhD in chemical engineering
from Northeastern University, Boston, USA;
and an MBA from Columbia University, New
York, USA.
Email: bilge.yilmaz@basf.com

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 Desalter chemical programmes for
opportunity crudes
Opportunity crude processing can present many challenges including incompatibility,
high calcium, and tramp amines
MIKE DION and PETER PEREZ
SUEZ – Water Technologies & Solutions
O
pportunity crudes can be
categorised by their preva-
lent downstream processing
challenges. High calcium-containing
crudes such as Doba (Cameroon)
and Kraken (North Sea) pose emul-
sification challenges and down-
stream fouling potential. High
amines in crudes may be due to
upstream additives or naturally
occurring in the crude oil. Oil
shale crudes, such as Bakken (US
and Canada), Eagle Ford (US) and
Niobrara (US), can be blended with
other crudes, which may precipitate
asphaltenes, stabilising emulsions
that result in oily effluent brine or
increase fouling risk in crude unit
hot trains and furnaces. This arti-
cle will describe desalter chemical
programmes to mitigate processing
challenges from these opportunity
crudes and reduce customer carbon
footprint.
Incompatible crude blends
Crude oil is a complex mixture of
hydrocarbons with varying molec-
ular weights, bond structures, and
heteroatom functional groups.
Asphaltenes are the most polar frac-
tion in crude oil, typically consisting
of aromatic structures with five to
seven rings at the core of the asphal-
tene molecule with peripheral alkane
substituents.1 At low concentrations,
asphaltenes are predicted to exist as
a solution of dispersed molecules
but, as concentration increases, they
have a strong tendency to self-as-
sociate into nanoaggregates. These
nanoaggregates can also form big-
ger clusters that would have limited
solubility in crude oil.1 The entire
crude mixture, along with tempera-
ture and pressure, impacts the solu-
www.digitalrefining.com
q3 suez.indd 27
Index <1.5
Severity Stable
Stable emulsion, oily water & solids
R Potential
I unit
issues
X
Index <1.0 1.0 - 2.0
Severity Low Moderate
F
Conventional fouling
Potential
P unit
X issues
Figure 1 CrudePLUS interpretation guide
bility of the asphaltenes in solution.
Asphaltene precipitation can hinder
emulsion resolution in desalters and
foul downstream heat exchangers
and furnaces.
There are several methods to
measure crude compatibility. The
colloidal instability index1 (CII) is
one such method that uses a meas-
urement of a crude blend’s satu-
rate (S), aromatic (A), asphaltene
(As), and paraffin (P) content. This
defines as CII = (As + S) / (R + A).
When the index is less than 0.7,
the crude is deemed incompatible.
Above 0.9 is considered compatible,
and 0.7 to 0.9 is deemed a region of
uncertainty. However, most refinery
laboratories do not have the ability
to measure SARA. For the few who
have the equipment, it still takes a
considerable amount of time.
SUEZ – Water Technologies
& Solutions has developed
CrudePLUS, a model using spec-
troscopy, measured crude stability,
toluene insoluble solids, and tolu-
ene soluble solids to predict crude
compatibility. The output gener-
ated is a relative instability index
1.5 - 3.0 3.0 - 6.0 6 - 10
Unstable Critical Severe
Desalter
Cold preheat, hot preheat & heater fouling
2.0 - 3.0 3.0 - 6.0 6 - 10
Medium High Severe
Unconventional fouling
Hot preheat fouling
Heater fouling
(RIX – a measure of instability), a
crude precipitation index (CPI – a
measure of the amount of mass
that may precipitate), and a fouling
potential index (FPX – tendency to
foul downstream heat exchanger
and furnaces). An interpretation
guide is shown in Figure 1. RIX val-
ues between 1.5 and 5.0 have the
potential to stabilise desalter emul-
sions. In less than 30 minutes, with
less than 200 ml of sample, the sta-
bility and fouling potential of the
crude can be measured along with
the approximate location of occur-
rence: the desalter, the hot train
preheat, or the crude furnace. Due
to differences in unit configurations,
the data should be correlated to the
actual unit; this takes only about
two to three weeks. For instance, a
desalter with large residence times
and transformers may not have
issues until RIX is greater than 2,
whereas a smaller vessel or smaller
transformers may have stable emul-
sions with a RIX of 1.5.
The CrudePLUS model can also
predict instability and fouling
potential from crude names. For
PTQ Q3 2021 27
11/06/2021 15:21
 Mix valve

10.2
13.0
15.3
12.1
12.0
12.0
12.0
11.2
DP
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
2.9
2.0
2.0
2.0
2.8
2.5
2.6
3.6
3.1
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
7.6
Metal naphthenate Organic acid
2(RCOO-)Ca+2 RCOOH
5.0
4.5
4.0
Desalter height (feet)

3.5
Oil
3.0
Water
2.5
2.0
1.5
1.0
H+ Ca+2
0.0
Acid Water soluble calcium
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35
Day
Water Emulsion Oil
Figure 3 Calcium extraction from
Figure 2 Plot of SUEZ crude stabiliser’s impact on emulsion thickness naphthenate

new crude oils not previously ana- Western Canadian crudes. The mix Calcium naphthenate crudes
lysed, predictions are estimated valve pressure drop was reduced to Some specific opportunity crudes,
based on data from crudes with minimise oily effluent brine when such as Doba and Kraken, contain
similar characteristics. The ability to the emulsion band would expand calcium naphthenates. The calcium
predict potential processing issues to exit the bottom of the desalter is ionically bonded to an organic
in advance of crude sampling can vessel. SUEZ’s crude stabiliser molecule with a carboxylic func-
provide crude purchasers with data was employed to resolve emul- tional group. Under typical desalter
to make more informed decisions sion stability issues from incom- operations, ionically bound cal-
to enhance refinery profits from patible crude blends. It is ashless, cium is not extracted from crude
opportunity crudes. containing no metals or phospho- oil. Calcium naphthenate, depend-
Precipitation of asphaltenes when rous. Figure 2 depicts the emulsion ing on the number of carbons in the
processing incompatible opportu- height in the vessel before and after molecule, can be a surfactant which
nity crude blends may manifest as the crude stabiliser programme. stabilises emulsions in desalters.
a growing emulsion band that may With mitigation of emulsions from Calcium carried through the
eventually result in oil in the efflu- incompatible crude blends, the mix desalter may catalyse fouling or poi-
ent brine. Chemical additives can valve was increased to enhance son catalyst in residual processing.
be successfully utilised to disperse salt and solids removal to reduce An acidic effluent brine pH will
asphaltenes in solution when pro- overhead corrosion risk and down- extract calcium, exchanging a cal-
cessing incompatible crude blends. stream fouling potential. Best prac- cium ion with a hydrogen ion.
For example, a North American tice is to inject the crude stabiliser Figure 3 is a conceptual graphic of
refinery was experiencing emulsion into the most asphaltenic crude the exchange mechanism. Typically,
issues when processing lower cost prior to crude blending. a desalter brine’s pH is basic and
an acid is required to drive the pH
down to extract calcium. Mineral
100 acids such as sulphuric acid are
strong and difficult to control a con-
90 sistent pH. Several organic acids are
Avg. 92% easier to maintain pH control, such
80 removal as glycolic, acetic, and citric. Citric
Percentage

KPI target acid is contained in orange juice,

70 lemonade, used as a food preserv-
Avg. 84%
removal
ative, and is more environmentally
60
friendly than other types of acids.
Avg. 66% Due to high calcium concentrations,
50 Avg. 57%
removal
removal
there is a high calcium scale risk.
40
SUEZ has patented the use of citric
Parcel 1 Parcel 2 Parcel 3 acid with a scale inhibitor.
Suez 1 Competitor Suez 2 Suez 3
SUEZ’s patented Predator MR
series has proven effective in field
applications processing calcium
Figure 4 Calcium extraction efficiency per parcel of Doba naphthenate crudes. One refiner

28 PTQ Q3 2021 www.digitalrefining.com

q3 suez.indd 28 11/06/2021 15:21

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3/10/21 11:20
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 evaluated SUEZ and another spe-
cialty chemical supplier when pro-
cessing Doba crude. The Doba was
blended to achieve ~20 ppm cal-
cium in the crude charge. SUEZ
treated the first parcel of Doba
with an average extraction effi-
ciency of 84%. The competitor
treated the second parcel and only
achieved 57% removal efficiency
while also scaling the effluent brine
heat exchanger. The customer shut
down the competitive programme
and SUEZ treated the remainder of
the parcel. The heat exchanger was
cleaned prior to the third parcel
with 92% extraction efficiency with
no scale formation. Figure 4 is a rep-
resentation of extraction efficiency
during the trials.
Crudes with tramp amines
Some opportunity crudes contain
amines, either naturally occurring
in the crude, as byproducts from
the use of an H2S scavenger, or as
additives used upstream during
production, such as some biocides
or corrosion inhibitors. The amines
will partition between the bulk
oil and water phase in a desalter.
Partitioning will depend on sev-
eral factors including temperature,
the structure of the amine, and the
salinity of the brine. Small amines
such as monoethanolamine (MEA)
readily partition to the brine.
Amines that remain in crude or are
carried over in desalted crude resid-
ual water will vaporise in the crude
unit fractionator. In the overhead
system, amine chloride salts that
precipitate before the water con-
denses increase the risk of corrosion
in the overhead system.
Reducing the desalter effluent
2500
Liquid side
2000
1500
m/y
1000
500
40 25
0 0
Blank Blank
Conditions:- Syn. Naphtha: Milli Q water = 90:10, temp = 120˚C, time = 3hrs, RPM = 1000, N2 = 2.2 bar, dosages = 500 ppm.
Figure 6 Comparison of corrosion potentials of organic acids
30 PTQ Q3 2021
q3 suez.indd 30
Amine Water soluble acid drives
RNH2 equilibrium to aqueous
cationic amine
Oil
Water
RNH2 + NaCl + H + RNH3 + Cl –
Amine Acid Cationic amine
Figure 5 Amine partitioning
brine’s pH will increase the parti-
tioning of amines to the bulk water
phase. A hydrogen ion associates
with the amine to form an ammo-
nium cation. The ammonium salt
prefers the bulk water phase where
it is highly soluble. Acids similar
to those mentioned earlier are typ-
ically used to reduce brine pH and
enhance amine extraction. Figure 5
depicts the partitioning mechanism.
The type of acid employed to
enhance amine extraction may also
impact overhead corrosion. Glycolic
acid, for instance, will partition
almost entirely to the water phase.
However, glycolic acid carried into
the desalted crude from residual
water is volatile and will increase
acid loading in the overhead. If ace-
tic acid is employed, a portion will
partition to the bulk hydrocarbon
phase. It is also volatile and will
increase acid loading from both
partitioned acid in oil and that con-
tained in residual water in desalted
crude. An aldehyde like glyoxal will
degrade to glycolic acid over time
in storage. A portion will also con-
vert to glycolic acid in the desalter
wash water. SUEZ’s citric acid
based products, the Predator MR
series, will primarily decompose to
CO2 which is much less corrosive
50
Vapour side
1909 40
1335 30
m/y
1104
20
15
10
53
Acetic Glycolic Citric CO2 Blank
blanket
Test method: Rotating cage autoclave (ASTM G184)
than other acids examined. Figure 6
depicts the measured corrosivity of
various acids.2
Effluent brine pH is the con-
trolling parameter in amine extrac-
tion. It is the equilibrium pH after
acids and bases in the crude and
wash water are mixed. A pH of 5
or below is generally considered
corrosive for hot aqueous environ-
ments. Typical target pH for the
brine is 6 for manually controlled
pump adjustments. Best practice is
to inject the acid into the crude oil
after the cold train, but prior to the
mix valve, with an injection quill. If
injected into the wash water, there
may be occurrences where the wash
water pH may be 4 to achieve an
effluent brine pH of 6. Refiners that
do inject into the wash water line
usually install a stainless steel lining
to protect the wash water piping.
Almost all refiners use atmos-
pheric and vacuum condensate
as a portion of the desalter wash
water. Amines from the over-
head systems will recycle into the
desalter.3 For double stage desalter
systems, the wash water flow is
counter-current to the crude flow.
Amine laden wash water will
encounter the second stage desalter
where amines may partition back
into the crude phase. For this rea-
son, best practice is acid injection
into both the first and second stage
desalters. Controlling the effluent
brine of both stages will maximise
the extraction of amines from the
crude and assist in breaking amine
recycle loops in the crude unit. The
first stage will extract amines from
the crude oil and the second stage
will reduce amine cycling up in the
system.
39
35
24
18
14
Blank Acetic Glycolic Citric CO2
blanket
www.digitalrefining.com
11/06/2021 15:21
 Constructing a mass balance of
amines in the system can be prob-
lematic. Some higher molecular
weight organic amines in the crude
may not partition into the water
phase, but will degrade to lower
molecular weight amines in the
crude unit furnace. Unreacted tri-
azine (a common H2S scavenger)
may also degrade to MEA in the
furnace. Due to the potential for
compounds decomposing to amines
in the furnace, time series data to
track performance may not ade-
quately demonstrate programme
effectiveness.
For example, a refiner with a
single stage desalter occasionally
experienced high amine loading
in the overhead system when pro-
cessing certain opportunity crudes.
The higher amine content increased
the risk of overhead salting prior
to the water condensation, creating
a potential intermittent corrosive
event. SUEZ’s Predator MR pro-
gramme was employed to extract
amines from crude and break any
amine recycle loops with the crude
unit overhead. The overhead amine
content was tracked as a function
of effluent brine pH and is pre-
sented in Figure 7.
As the effluent brine pH
decreased, the overhead amines
decreased, indicating enhanced
amine partitioning into the efflu-
ent brine with lower brine pH. The
amine content entering the desalter
can vary due to many factors such
as changing crude slates, degra-
dation of more compounds into
amines in the crude unit furnace,
increased neutralising amine to
maintain targeted overhead con-
denser pH, and sour water stripper
operation (if used as a source for
desalter wash water). Manual pH
control usually entails crude unit
operators checking the effluent brine
pH every four hours and adjusting
the acid injection rate to increase or
reduce the pH accordingly. SUEZ
has developed and automated a
desalter effluent brine pH controller
containing self-cleaning and cali-
bration cycles. It has been in service
successfully for over two years and
does not require by-passing during
mud washing. It also reduces per-
sonnel exposure to operators meas-
www.digitalrefining.com
q3 suez.indd 31
210
Total of amines in overhead
140
70
0
4 4.5
Figure 7 Overhead amine vs desalter brine pH
Figure 8 Desalter effluent brine pH
controller
uring brine pH and activity with an
acid injection skid.The control skid
is shown in Figure 8.
Reducing demulsifier carbon
footprint
In view of societal concern for global
warming, many companies have
Figure 9 Surfactant accessibility with an oil based demulsifier in the wash water
R2 = 0.703
5 5.5 6 6.5 7 7.5 8 8.5 9
Effluent water pH
commitments to reduce their car-
bon footprint. One avenue SUEZ is
pursing to reduce carbon footprint
is patented water based demulsifi-
ers. Molecules typically used in oil
based demulsifiers are formulated as
a colloidal dispersion in water. Their
application is anticipated to have
similar or better performance than
prior benefits achieved with split
feed.4 First generation split feed tech-
nology involved feeding a portion of
an oil based demulsifier to the crude
and a portion to the wash water to
enhance emulsion resolution. The
mechanisms through which the pres-
ence of a demulsifier in the water
phase accelerates emulsion break-
ing are complex and have been the
subject of significant research.5,6,7
However, it is anticipated that an
appropriate demulsifier injected into
the water phase could have the fol-
lowing benefits:8
• Reduced travel time: water
is less viscous than crude oil. A
Emulsion stabilising
surfactants
Demulsifier molecules
PTQ Q3 2021 31
11/06/2021 15:21
 Others simply sell a product –
A control and shut off technique you can rely on. we offer a solution.
OHL Gutermuth

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MCRC and CBA processes, among others, have OHL Gutermuth
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ohl.indd 1 10/03/2017 16:12

 demulsifier molecule in water will
travel faster than a demulsifier mol-
ecule in the crude oil, allowing it to
reach the oil-water interface more
rapidly. This would be beneficial to
reduce the interfacial tension gradi-
ent that is created due to film thin-
ning during droplet coalescence
(Marangoni-Gibbs effects), thus
accelerating water separation.8
• Reduced travel distance: the
average distance that demulsifiers
must travel inside the water drop-
let to reach the oil water interface is
less than that of demulsifiers in the
oil phase.
• Surfactant accessibility: sur-
factants are stacked at the oil-water
interface with more polar or ionic,
emulsion-stabilising surfactants
closer to the interface. A demulsi-
fier injected solely into the oil phase
must first displace the upper layers
of surfactants before it can encoun-
ter the most active surfactants at the
interface. Injecting a portion of the
demulsifier into the water phase
facilitates encountering the strong-
est emulsion stabilising surfactants
more quickly, pushing them away
from the interface.
Figure 9 depicts surfactant acces-
sibility with an oil based demul-
sifier in the desalter wash water.
A portion of the oil based demul-
sifier will partition into the water
phase of the droplet and a portion
will remain in the demulsifier sol-
vent droplet. The molecules dis-
persed in the water droplet will
have the benefit of reduced travel
time whereas the demulsifier in
the solvent droplet must reach the
interface travelling at a reduced
velocity due to larger size and vis-
cous drag. Only a portion of the
demulsifier molecules have the
benefit of reduced travel time to
the interface.
Figure 10 portrays surfactant
accessibility with SUEZ’s patented
water based demulsifier in the
desalter wash water. The colloi-
dal dispersion of demulsifiers in
the water based demulsifier imme-
diately disperses into the water
droplet. All of the demulsifier mol-
ecules have the benefit of reduced
travel time to the oil water inter-
face, improving emulsion resolution
speed and completeness.
www.digitalrefining.com
q3 suez.indd 33
Emulsion stabilising
surfactants
Demulsifier molecules
Figure 10 Surfactant accessibility with a water based demulsifier in the wash water
SUEZ products for processing opportunity crudes
Challenge SUEZ solution
Incompatible crude blends Patent-pending ashless products and
CrudePLUS predictive modelling
Calcium extraction from calcium naphthenate crudes Patented Predator MR products that inhibit
scale formation
Extraction of tramp amines Patented environmentally friendly products
with less overhead corrosion risk and proven
automated control system
Reducing carbon footprint Next Gen Split Feed
Table1
Conclusion 7 McLean J D, Kilpatrick P K, Effects of
Opportunity crude processing can asphaltene solvency on stability of water-
present many challenges including in-crude-oil emulsions, Journal of Colloid and
incompatibility, high calcium, and Interface Science 1997, 189 (2), 242-253.
8 Kilpatrick P K, Water-in-crude oil emulsion
tramp amines. SUEZ has patented
stabilization: review and unanswered questions,
and patent-pending products to
Energy & Fuels 2012, 26 (7), 4017-4026.
assist customers in confidently pro- 9 Shetty C S, Nikolov A D, Wasan D T,
cessing opportunity crudes, while Bhattacharyya B R, Demulsification of
also reducing carbon footprint with water in oil emulsions using water soluble
SUEZ’s Next Gen Split Feed tech- demulsifiers, Journal of Dispersion Science and
nology (see Table 1). Technology,1992, 13 (2), 121-133.
References Mike Dion is a Product Applications Engineer
1 Mullins O C, The modified yen model, Energy for Refinery Process Separations with SUEZ –
Fuels 2010, 24 (4), 2179-2207. Water Technologies & Solutions. He has seven
2 Rathore V, Brahma R, Thorat Tr S, Rao P V C, years of oil field experience, 29 years of refining
Choudary N V, Assessment of Crude oil blends, experience, and is co-author of three patents.
PTQ, Q4 2011, https://cdn.digitalrefining.com/ He holds a BS degree in chemical engineering
data/articles/file/1530708289.pdf
from Michigan Technological University and a
3 K D Kuklenz, Degradation of carboxylic
acids and the associated impact on feed prep
MBA from Our Lady of the Lake University.
and overhead corrosion, NACE Corrosion
Peter Perez is a Senior Engineer with SUEZ -
Conference and Expo 2017. Paper No. 9289.
Water Technologies & Solutions at the Tomball
Technology & Innovation Center, Texas. With
4 Dion M, Payne B, Grotewold D, Operating
22 years’ experience in the refining industry,
philosophy can reduce overhead corrosion,
he has developed expertise in fuel formulation
Hydrocarbon Processing, Mar 2012.
and characterisation, fuel performance, and
5 Dion M, Desalting opportunity crudes, NPRA
fuel quality. He studied chemistry at the
Spring National Meeting, Mar 1995. AM-95-69.
6 Kokal S L, Crude oil emulsions: a state-of- Central University of Venezuela, and holds a
the-art review, SPE Production & Facilities, PhD in fuel science from Pennsylvania State
2005, 20 (01), 5-13. University. Email: peter.perezdiaz@suez.com
PTQ Q3 2021 33
11/06/2021 15:21
 New ultra-high activity TK-6001 HySwell™ catalyst for
hydrocracking pretreatment and ULSD production

Maximize volume
swell and produce
more barrels
Nitrogen in the feed limits aromatic saturation, density reduction and volume swell.
Removal of nitrogen is essential for the yield improvement both in your
hydrocracker and ultra-low sulfur diesel hydrotreating unit.

Our new ultra-high activity catalyst, TK-6001 HySwell™ is able

to remove 99.9% nitrogen from your feed,
enabling you to produce more barrels.

Scan the code or go to

www.topsoe.com/products/tk-6001-hyswelltm

www.topsoe.com

haldor.indd 1 11/06/2021 14:29

 Enhancing hydrocracking unit potential with
pretreat and tailored hydrocracking catalysts
A refiner uses pretreat and hydrocracking catalyst to maximise heavy naphtha,
kerosene, and diesel production with improved product properties
XAVIER RUIZ MALDONADO and RAHUL SINGH Haldor Topsoe
PABLO DOSDÁ MANZANO Cepsa
H
ydrocracking pretreatment
and zeolitic hydrocracking
catalysts are widely used in
refining to produce valuable finished
products. Selecting the right com-
bination of both catalyst systems is
imperative to maximise feed conver-
sion while maintaining the desired
selectivity towards the preferred
product fractions. Refiners will select
catalysts which generate maximum
profits for their hydrocrackers.
The primary objectives of hydro-
cracker pretreat catalysts are to
remove organic nitrogen and sul-
phur, particularly basic nitrogen
compounds, and to saturate aro-
matics. Nitrogen compounds have
a significant negative impact on
the activity of hydrocracking cata-
lysts and, consequently, on the per-
formance of the hydrocracker. In
addition, aromatic compounds are
difficult to crack and, by saturating
them with the pretreatment catalyst,
the resulting naphthenes are much
more easily cracked over the hydro-
cracking catalyst. The saturation of
these aromatic compounds also pro-
vides a higher volume swell which
increases unit profitability.
Optimal catalyst performance
does not depend on just one param-
eter, such as metals content or
porosity, but also on characteristics
of the support itself, the interaction
between support and active metals,
and the structure, acidity, porosity,
and surface conformation of the
zeolite.
TK-611 HyBRIM is one of Haldor
Topsoe’s latest HyBRIM catalysts.
Data from industrial operation
in the hydrocracker (NK) at the
La Rábida refinery of Compañia
Española de Petróleos, S.A. (Cepsa),
www.digitalrefining.com
q3 haldor.indd 35
Figure 1 Type I and Type II active sites and location of BRIM sites
shows that TK-611 HyBRIM is
7ºC/13ºF more active than TK-609
HyBRIM. In addition, both catalysts
showed the same deactivation rate.
Along with discussing its per-
formance in the Cepsa hydroc-
racking unit, this article describes
Selecting the right
combination of both
catalyst systems is
imperative to maximise
feed conversion while
maintaining the desired
selectivity towards
the preferred product
fractions
how Haldor Topsoe’s research has
played a key role in enhancing the
performance of hydrocrackers in
the refining industry. A case story
is presented to show the flexibility
that Topsoe’s hydrocracking cata-
lyst portfolio provides refiners with
an opportunity of adjusting product
yields to meet market demand and
maximise unit profitability.
The desired performance of
Topsoe catalysts is a result of the
company’s product development
and manufacturing techniques.
As a part of its technical support,
Topsoe uses customer feedback to
guide catalyst development which
addresses the objectives of various
hydrocrackers, supporting continu-
ous product improvement to meet
the industry requirements.
In 1984, Topsoe’s researchers
published results showing that
there was a modified Co-Mo-S
structure with substantially higher
activity per active site than tra-
ditional Co-Mo-S structures. The
two structures were called Type I
and Type II sites. In 2000, the com-
pany discovered another type of
active site using scanning tunnel-
ling microscopy (STM), which the
researchers named “BRIM” sites.
These BRIM sites are responsible for
initial hydrogenation reactions, a
key pathway to removing the most
sterically hindered sulphur com-
pounds, and are located on top of
the Co-Mo-S (or Ni-Mo-S) slabs.
As Figure 1 shows, the BRIM sites
are located close to the edges, where
their pi-electron clouds interact with
the pi-electron clouds of organo-sul-
phur reactants. This interaction
PTQ Q3 2021 35
11/06/2021 15:27
 with a proprietary catalyst prepa-
ration step. The technique ensures
better dispersion of active compo-
nents on the surface of the support
along with optimised metal-sup-
port interactions. Together, they
facilitate the formation of more
active Type II sites and maximise
the nickel promotion of the molyb-
denum slabs (see Figure 2). This
ultimately increases both hydrodes-
ulphurisation (HDS) and hydrode-
nitrogenation (HDN) activity. The
first application of this technology
Figure 2 STEM image of fully promoted hexagonal MoS2 slab in experimental NiMo catalyst was TK-609 HyBRIM. During the
last few years, HyBRIM technol-
draws the most difficult sulphur Topsoe’s latest catalyst technol- ogy has been further improved
molecules in for the initial hydro- ogy HyBRlM was commercialised and introduced to the market with
genation step, enhancing their abil- in 2013. It includes an improved second generation HyBRIM cata-
ity to interact with the nearby Type production technique in which lysts. Topsoe is now offering two
II sulphur vacancies. the BRlM technology is combined new catalysts: premium high activ-
ity TK-611 HyBRIM and ultra-high
activity TK-6001 HySwell for max-
imising volume swell.
The relative volume activity of
various NiMo catalysts is shown
in Figure 3. From the 1980s until
today, Topsoe’s NiMo catalysts
have increased in activity by 500%,
meaning that the amount of catalyst
required to meet a given objective
now is five times lower now than it
was in the 1980s.
Moreover, to fulfill refineries’
needs and provide flexible solutions
for all types of feedstock, the com-
pany has extensively researched
the synergy between hydrocracking
pretreatment catalysts and hydroc-
racking catalysts.
Topsoe manufactures its own zeo-
lites, which allows full control of
Figure 3 Relative activity of Topsoe NiMo catalysts since the 1980s the entire manufacturing process.
The performance of hydrocracking
catalysts depends on several fac-
tors, including zeolite types, zeolite
porosity, zeolite acidity, and acid
site proximity. The company also
Middle-distillate selectivity

TK-939 D-sel controls the production of aluminas,

TK-921 TK-926 alumina-silicas, metals, and metal/
TK-949 D-sel support relationships. Coupled with
TK-925/TK-927
tight quality control in manufactur-
TK-931 TK-943 TK-969 D-sel ing, this enables Topsoe to achieve
TK-947
TK-941 the desired catalyst performance.
TK-951 This understanding is further
TK-961 TK-971
enhanced by use of advanced pilot
plants and analytical tools.
As Figure 4 shows, Topsoe’s base
Activity
metal hydrocracking portfolio offers
three main types of catalysts. The
Figure 4 Topsoe hydrocracking catalysts portfolio red series offers maximum hydro-

36 PTQ Q3 2021 www.digitalrefining.com

q3 haldor.indd 36 11/06/2021 15:27

 Feed from Feed/product Recycle gas Make-up gas
tank heat heater 1 compressor Off-gas
exchanger

Stripper Fractionator
Filter Cold Heavy
Feed system Recycle separator Naphtha
Light
pump gas
Naphtha
heater 2
Kerosene
Low
Feed from vacuum pressure
distillation Lean steam
units (VDU) Recycle gas amine Heavy
compressor
diesel
Amine
scrubber Low pressure
stream
Hot
separator Rich
amine Unconverted
oil

Figure 5 Partial process layout of the Cepsa La Rábida hydrocracker unit

genation to enhance volume well, duced together with the liquid feed tionator splits the effluent into the
maximise naphtha and kerosene downstream from the feed/efflu- following product fractions: heavy
yields, and upgrade unconverted ent exchanger of the fractionation naphtha, kerosene, diesel, and
oil (UCO) for base oil services. The section, while the rest of the recy- UCO. The target product properties
blue series offers a balanced high cle gas is heated in the main fur- are show in Table 1.
yield of middle distillates and opti- nace of the unit. Downstream from The NK unit at Cepsa has been
mised diesel cold flow properties. the heater, the unit has two reactor operating with Topsoe catalyst for
Table
The D-sel series offers the maxi- trains. In both trains, the reactors five consecutive cycles. Early on,
mum yield of middle distillates in are loaded with pretreatment and cycle length was limited due to
both kerosene and diesel ranges. hydrocracking catalyst in an opti- pressure drop issues. These were
mal ratio in order to have equal addressed by the installation in 2018
Commercial experience cycle lengths and maximise middle of High-Efficiency Liquid Phase
Topsoe has worked for several distillates at 80% gross conversion. scale catchers (HELPsc). Addressing
cycles with Cepsa. This relation- The separation section is divided pressure drop issues allowed Cepsa
ship includes close collaboration into three zones: recycle gas purifi- to capture the activity improvement
with both Cepsa Research Center cation, stripper, and fractionator. In of TK-611 HyBRIM in subsequent
and La Rábida refinery, with the the purification section, H2S in the cycles.
aim of achieving maximum refin- recycle gas is scrubbed with lean Table 2 shows that the unit has
ery profits. La Rábida refinery is amine to reduce it to very low lev- used TK-609 HyBRIM since 2014,
located in Huelva, Andalucía, and els. The stripper operates to recover and in subsequent cycles it has used
has an annual capacity of 9.5 mil- light naphtha whilst the main frac- TK-611 HyBRIM.
lion tonnes. Together with the com-
pany’s Gibraltar San Roque and
Tenerife facilities, this provides Cepsa hydrocracker: typical product properties
a total refining capacity of nearly
500 000 b/d. Product Sulphur Nitrogen Aromatics Density Flash Smoke Cetane Cloud
The NK unit at La Rábida site fractions (mercaptans) reduction point point index point
operates in a single stage recycle Light naphtha X (*) X
Heavy naphtha X X X
(SSREC) manner. A partial lay- Kerosene X X X X X X X
out and process description of Diesel X X X X
the hydrocracker unit is shown in Unconverted oil X X X X
Figure 5.
The hydrocracker unit was orig- Table 1
inally designed to process 5800 t/d
of vacuum gasoil (VGO) but now Cepsa NK hydrocracking unit with Topsoe catalysts
operates at 33% higher capacity. The
VGO feed comes either from tanks Cycle Hydrocracking pretreatment Hydrocracking catalyst
and/or directly from two vacuum 2014 – 2016 TK-609 HyBRIM TK-92X
distillation units (VDU). 2016 – 2017 TK-609 HyBRIM TK-9X9 D-sel
2017 – 2018 TK-609 HyBRIM TK-9X9 D-sel
The liquid feed passes through 2018 – 2019 TK-611 HyBRIM TK-9X9 D-sel
a multiple filtration system to 2019 – 2023 TK-611 HyBRIM TK-9X9 D-sel
minimise pressure drop issues.
The recycle gas is partially intro- Table 2

www.digitalrefining.com PTQ Q3 2021 37

q3 haldor.indd 37 11/06/2021 15:27


Normalised HDN WABT, PTR
50 100
Run days
Figure 6 HDN activity and deactivation rates for TK-609 HyBRIM and TK-611 HyBRIM for
consecutive cycles
Extra volumetric yields fractions when
using TK-611 HyBRIM at the same gross
conversion with TK-9X9 D-sel
Yield fraction TK-611 HyBRIM -
at 80% conversion TK-609 HyBRIM
Light naphtha, vol% 0.2 +
Heavy naphtha, vol% 0.8 +
Kerosene, vol% 1.8 +
Diesel, vol% 0.3 +
Table 3
The hydrocracking catalyst was
chosen to maximise middle distil-
lates (kerosene and diesel). TK-9X9
D-sel catalysts have been selected
multiple times by Cepsa to provide
the highest selectivity towards these
product fractions.
Figure 6 compares the HDN
activity and deactivation rates
for TK-609 HyBRIM and TK-611
HyBRIM for consecutive cycles.
TK-611 HyBRIM shows 7ºC/13ºF
better activity than TK-609
HyBRIM. In addition, both catalyst
systems showed the same deactiva-
tion rate and the unit is free of pres-
sure drop issues.
Furthermore, Cepsa and Topsoe
conducted a performance guaran-
tee test run (PGTR) for each cycle
to evaluate the performance of the
catalyst in the unit. During the
PGTR for each cycle, the unit oper-
ated at similar feed rates and with
similar feedstock properties, while
aiming at 80 wt% gross conversion.
As Figure 7 shows, TK-611 HyBRIM
exhibited the same 7°C/15°F higher
HDN activity compared to TK-609
HyBRIM while producing the same
38 PTQ Q3 2021
q3 haldor.indd 38
7˚C (13˚F)
TK-609 HyBRIM cycle 2017–2018
TK-611 HyBRIM cycle 2018–2019
150 200
N-slip, thus allowing TK-9X9 D-sel
to operate at the same overall gross
conversion.
The applied gross conversion was
80 wt%, and the differences in volu-
metric product yields are shown in
Table 3.
As Table 3 shows, a higher vol-
ume swell is observed with TK-611
HyBRIM compared to TK-609
HyBRIM at the same gross conver-
sion. The higher volume swell is a
result of changes in feedstock boil-
ing point related to both sulphur
removal and aromatic saturation
over the HyBRIM catalyst before the
feed is cracked over TK-9X9 D-sel.
The density reduction of the product
fractions results in higher volumet-
ric yields, primarily in the kerosene
fraction, followed by heavy naphtha
diesel and light naphtha.
26.00
25.50
Kerosene smoke point, mm
25.00
24.50
24.00
23.50
TK-611
HyBRIM
23.00
22.50
Figure 8 Kerosene smoke point fractions
from TK-611 HyBRIM vs TK-609 HyBRIM
7˚C / 13˚F
HDN WABT
250
TK-611 TK-609
HyBRIM HyBRIM
Hydrocracking pretreatment
Test run conditions
Design feed rate
Feed sulphur, 1.8 wt%
Feed nitrogen, 1400 wt ppm
Feed, SG (0.93)
Feed aromatic, 40 wt%
Figure 7 Performance guarantee test run
In addition, a substantial upgrade
was observed in kerosene smoke
point for the TK-611 HyBRIM pre-
treat cycle. The gain in smoke point
is about two points at the same
overall gross conversion.
Monoaromatics, which are
responsible for smoke point,
mostly concentrate in the kerosene
fraction. The high improvement
in smoke point shown in Figure
8 is attributed to a higher degree
of deep hydrogenation with the
TK-611 HyBRIM cycle, resulting
in further reduction of monoaro-
matics during the TK-611 HyBRIM
cycle.
All in all, it can be concluded that
there is a significant advantage in
using hydrocracking pretreatment
catalysts with high hydrogenation
activity.
Cepsa’s business case
TK-609 Pilot plant tests in both Cepsa and
HyBRIM
Topsoe facilities were conducted
to evaluate the flexibility of the NK
unit to shift product yields to max-
imise heavy naphtha and kerosene
at the expense of the diesel frac-
tion. The pilot plant tests employed
www.digitalrefining.com
11/06/2021 15:27
 Sulzer Vacuum Distillation Unit Technology
The more things change, the more they stay the same
Within the volatile oil refining industry, some things remain critically the same. The Vacuum
Distillation Unit is a fundamental process technology within the refinery. As such, its performance
and reliability are of the utmost importance. Operating at vacuum conditions is expensive and
energy intensive. Sulzer Chemtech’s industry leading Mellapak™ and MellapakPlus™ packings
allow you to operate with the lowest possible pressure drop within the column, maximizing
yield while also minimizing energy consumption. Mellagrid™ AF grid packing and VG AF™
tray technology are ideal for use in your vacuum column wash section and stripping section,
respectively. They are both mechanically strong and fouling resistant.

Sulzer Chemtech has a long list of successful revamps of world scale vacuum columns. We
can provide anything from internals to process studies to complete revamps including ancillary
equipment such as pumps, exchangers, and fired heaters. Whatever your need, Sulzer Chemtech
is ready to be your single source for vacuum distillation unit engineering and expertise.

Because life is fluid – www.sulzer.com

sulzer.indd 1 11/06/2021 14:04

 TK-9X9 D-sel
Stacked red series

Product fractions yields @ fixed

Yields difference, wt%

conversion, wt%
27˚C / 50˚F
Activity difference

C1-C4 Light Heavy Kerosene Diesel

naphtha naphtha

TK-9X9 Stacked
D-sel red series
Figure 10 TK-9X9 D-sel vs stacked red series selectivity

ture was adjusted to give the same paraffinic  or low sulphur opportu-
N-slip and the hydrocracking con- nity crudes.
Figure 9 Activity difference between ditions were adjusted to obtain the Figure 10 shows the selectivity
TK-9X9 D-sel and stacked red series same overall gross conversion. of two different catalyst systems.
hydrocracking catalyst systems The results shown in Figure 9 The stacked red series system
demonstrate that the stacked red demonstrated appropriate crack-
a similar feed to one used for the series is 27°C (50°F) more active ing control and use of the hydro-
PGTR described earlier. than the current hydrocracking gen to minimise light ends and
TK-611 HyBRIM was chosen as catalyst, TK-9X9 D-sel. This signif- light naphtha while maximising
the hydrocracking pretreat cata- icantly higher activity allows the heavy naphtha and kerosene at
lyst and a combination of two base pretreatment catalyst to operate the expense of diesel. The reduc-
metal hydrocracking catalysts from at higher nitrogen slip if a longer tion of diesel resulted in increased
the red series were selected to pro- cycle length is desired. In addi- kerosene and heavy naphtha in
vide a higher yield of heavy naph- tion, lowering the gap between the same proportion. As expected,
tha and kerosene, while minimising the two required weighted aver- there was a slight increase in C1-C4
formation of light ends. In parallel, age bed temperatures reduces and light naphtha when using
the current TK-9X9 D-sel hydroc- the  dependence on heat release stacked red series system.
racking catalyst was tested at the in the upstream reactor (beds) In addition to the yields struc-
same conditions. and  imparts flexibility to oper- ture, a list of main product prop-
In both catalyst systems, the ate without ascending temper- erties of the fractions is shown in
hydrocracker pretreat tempera- ature profiles when processing Figure 11.
The light naphtha fraction pro-
duced by the stacked red series con-
tains higher iso-paraffins than the
one produced with TK-9X9 D-sel,
TK-9X9 D-sel
resulting in a favourable scenario
Product fraction properties

Stacked red series

for higher RON/MON in the gas-
Relative difference
oline pool. In addition, the heav-
ier naphtha contains higher N+2A
index, which is favourable for max-
imising BTX yields.
As expected, the kerosene frac-
tion showed an improved smoke
point due to the density improve-
ment from the stacked red series
Light naphtha Heavy Kerosene Diesel UCO VI (60˚C, (see Figure 11). The diesel frac-
iso-parafins, naphtha smoke point, cetane index, 100˚C), ASTMD-
wt% (N+2A), wt% mm ASTM D-4737 7042, adim tion substantially gained in cetane
index while the UCO showed an
enhanced viscosity index suita-
Figure 11 Product properties difference between TK-9X9 and stacked red series ble to produce Group III lube base
hydrocracking catalysts series stock.

40 PTQ Q3 2021 www.digitalrefining.com

q3 haldor.indd 40 11/06/2021 15:27

 Conclusion
By changing the current TK-9X9
D-sel to an optimal combination of
stacked red series catalysts, Cepsa
should be able to maximise heavy
naphtha and kerosene production
with substantially enhanced prod-
uct properties. The following prod-
uct property improvements would
be obtained:
• Higher paraffins in the light
naphtha for RON/MON retention
• Higher N+2A in the heavy naph-
tha cut to maximise BTX
• Enhanced smoke point in the ker-
osene fraction
• Better cetane index in the diesel
fraction
• Improved UCO VI for better lube
basestock production
The performance and prod-
uct properties could be further
improved by using TK-6001
HySwell as the pretreatment cata-
lyst. It has demonstrated a signifi-
cant boost in hydrogenation activity
in various industrial applications.
Topsoe and Cepsa will con-
tinue working in close collabora-
tion to optimise hydroprocessing
operations in the refiner’s system,
evaluating continually improving
solutions in the clean fuels era.
The authors acknowledge the continued
contribution of Haldor Topsoe A/S R&D to
fundamental knowledge of heterogeneous
catalysts and their impact on clean fuels
production.
Further reading
1 Robledo S, Zeuthen P, More from barrels,
PTQ, Q2 2021.
2 Zeuthen P, Schmidt M, Robledo S, A new
generation of catalyst is born, Hydrocarbon
Engineering, Mar 2021.
3 Singh R, Ticking all the right boxes.
Hydrocarbon Engineering, Mar 2020.
4 Hoces R, Romero M, Maldonado X,
Opportunity crudes and refinery challenges
during hydrocracking operation – Part 2,
Hydrocarbon Processing, Sept 2019.
5 Hoces R, Romero M A, Maldonado X,
Opportunity crudes and refinery challenges
during hydrocracking operation – Part 1,
Hydrocarbon Processing, Oct 2019.
Xavier Ruiz Maldonado is Principal Technical
Services & Sales with Haldor Topsoe Inc. With
more than 15 years’ experience in research and
industrial operation, he is currently working
in the Technical Support Group in Houston,
Texas where his main responsibility is to advise
refinery customers about start-up, monitoring
and troubleshooting of hydrocracking
and hydrotreating units. He also works in
collaboration with R&D on optimising start-
up procedures for all clean fuels applications.
He holds a MSc in chemical engineering from
Simon Bolivar University, Venezuela.
Pablo Dosdá Manzano is Senior Process
Plant Engineer at Cepsa La Rábida refinery
where he is in charge of the hydrocracking,
hydroprocessing, and hydrogen units, focusing
on daily catalyst monitoring, process and
energy optimisation and planning turnarounds,
including catalyst replacement. He joined
Cepsa as the Distillation Process Engineer
responsible for unit monitoring. He holds
a BS in chemical engineering from Jaume I
University and a MSc in energy and processes
from IFP School.
Rahul Singh is Technical Sales Manager,
Hydrocracking Catalyst and Technology
with Haldor Topsoe Inc, managing a group
of technical service engineers providing
technical sales and support for Topsoe’s
hydrocracking customers. In his more than
10 years with Haldor Topsoe, he has taken
on various responsibilities including catalyst
development, pilot plant testing, experimental
research, sales and technical support. He
holds a PhD in chemical engineering from
the University of Akron, Ohio with a focus
on application of heterogeneous catalysis for
industrial applications.

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 Maximising yields and profits from the
FCC unit
Comparative additive trials demonstrated a gain in petrochemicals output and profit
from an integrated refinery’s FCC unit

SILVIU SERBAN, CHUCK EKEOCHA, UDAYSHANKAR SINGH and BANI CIPRIANO

Grace Refining Catalyst Technologies

T
he growth in demand for fuels
worldwide is projected to
slow down as a result of the
electrification of the vehicle fleet
and maturing of advanced econo-
mies. On the other hand, demand
for petrochemicals is still on a
growth trajectory. Integrating pet-
rochemical production with their
operations provides refineries an
opportunity to profit from this
growth trend and ultimately avoid
risk of closure in the face of slowing
demand. This trend of integration
between refining and petrochem-
icals is well under way: in the past
several years, megaprojects were
announced in China, in which the
yield of petrochemicals from each
barrel of crude is slated to reach
~40%.1 New projects have been
announced, most notably by Saudi
Aramco, that seek to push this yield
up further.2
from using this technology in their
operations.
SATORP is one of the world’s
most efficient integrated refin-
ing and petrochemicals platforms.
Operational since 2014, it has one
of the most complex and efficient
sites, capable of converting a type
of heavy, high-sulphur crude oil
to high value added products. To
accomplish this, the refinery relies
on a broad range of processing units,
including two distillate hydroc-
rackers, an FCC unit, and a coking
unit. In early 2018, the SATORP
platform’s production capacity was
raised to 440 000 b/d of crude oil,
bringing annual output to around 22
million tonnes of refined petroleum
products, including 200 000 tonnes of
high purity propylene.
Feed specific gravity, g/ml
The key objectives of the SATORP
FCC unit are high conversion and
high yield of light olefins, includ-
ing C3= and C4=s. The feed is very
light and therefore easy to crack,
but it is very low in Concarbon and
metals which results in reduced
delta coke and regenerator temper-
ature. Consequently, combining a
catalyst that closes the heat balance
with an optimal ZSM-5 additive
to maximise light olefins is critical.
Additionally, due to the nature of
the feed and very high unit conver-
sion, the riser outlet temperature
(ROT) is depressed to below 505°C
which imposes further challenges.
The benchmarking plots in Figure
1 show SATORP’s FCC unit com-
pared with other FCC units in
the EMEA region in terms of key
Riser outlet temperature, ˚C

At Grace, we believe the fluid

catalytic cracking (FCC) unit facili-
tates the transition of refineries from
fuels to a focus on petrochemicals.
The reason for this is that the FCC
unit generates the highest yield of
light olefins, specifically propyl-
ene, compared to other units in the Rank Rank

refinery. Therefore, the company’s Industry SATORP

focus is on developing new tech-

nologies that allow refiners seeking
to integrate petrochemical produc-
C4= yield, wt%FF
C3= yield, wt%FF

tion to maintain or even increase

profitability in the face of slowing
growth in fuel demand. In this arti-
cle, we describe Zavanti additive,
Grace’s latest ZSM-5 technology for
maximum propylene FCC appli- Rank Rank
cations, and how the company
worked closely with Saudi Aramco Figure 1 Benchmarking plots indicate relative ranking of SATORP’s FCC unit compared
Total Refining and Petrochemicals with other FCC units in the EMEA region in terms of key properties: feed specific gravity,
(SATORP) to capture the most value riser outlet temperature, and yield of C3= and C4=

www.digitalrefining.com PTQ Q3 2021 43

q3 grace.indd 43 11/06/2021 15:31

 Activity retention
The higher severity conditions typ-
ical of max propylene units pose a
Zavanti additive is Grace’s newest additive designed specifically for maximum challenge to the stability of ZSM-
2019 propylene FCC units. 5, in terms of surface area, acid
2014 OlefinsUltra MZ additive is for very high propylene applications.
site density, and activity retention.
Therefore during the development
2010 OlefinsUltra HZ additive is for propylene focused applications. of Zavanti one goal was to show
high stability or activity retention
OlefinsUltra additive is for applications where moderate-to-high propylene
2002 production is required.
with respect to OlefinsUltra addi-
tives. These improvements were
1985- OlefinsPlus, OlefinsExtra and OlefinsMax additives were all developed by
2001 Grace. achieved with the use of a new
Additive O was the first ZSM-5 additive developed by Grace Davison in binder and changes in the processing
1984 collaboration with Mobil. technology. Surface area and activ-
ity retention can play a key role in
the effective activity of an additive
Figure 2 Grace’s developments in ZSM-5 additive technology to maximise propylene yield in the
unit. For two additives having equal
Typical physical properties of Zavanti vs OlefinsUltra additive grades starting activity for LPG olefins pro-
duction but different activity reten-
Zavanti additive OlefinsUltra MZ additive OlefinsUltra HZ additive tion with time (half-life decay), the
ABD, g/cm3 0.72 0.72 0.73 additive with the best activity reten-
Davison Index (attrition) 5 5 6
0-40% 7 7 6 tion or longer half-life decay will
APS µm: 80 78 80 have a higher effective activity in the
Surface area, m2/g High High Moderate unit.

Table 1 LPG olefin activity

parameters: feed specific gravity,
ROT, and C3= and total C4= yields.
The SATORP unit operates near
the lowest in terms of feed specific
gravity and ROT and near the high-
est in terms of C3= and C4= yields.
To achieve this performance,
Grace supported SATORP to meet
its objectives in two steps: (i) opti-
mal catalyst design to help close the
FCC unit’s heat balance and achieve
improved reliability and utilisation,
yet maximise gasoline olefins; and
(ii) optimisation of ZSM-5 additive
to crack gasoline olefins into valu-
able C3= and C4=s. Optimisation of
catalyst design was the subject of
a recent presentation.3 In this arti-
cle we will focus on the application
of Zavanti additive in the SATORP
FCC unit.
Developments in ZSM-5 catalyst
technology
In FCC, the ZSM-5 catalysts are also
known as ZSM-5 additives as they
are always used in combination
with FCC catalyst formulated with
Y-zeolite. Grace commercialised the
first ZSM-5 catalyst, Additive O, in
collaboration with Mobil in 1984.
Since then the company has made
advances in formulation and in the
technologies used to stabilise and
bind the ZSM-5 crystal in catalyst
particles. This is shown in Figure 2.
Zavanti additive
Zavanti additive has the follow-
ing features: physical properties
required for optimum circulation
in the unit, high retention of ZSM-5
activity, and maximum LPG olefin
activity. In this section we describe
each feature then present a compar-
ison of activity between the three
most recent generations of ZSM-5
additives from Grace. Finally, we
summarise the results of trialling
Zavanti in the SATORP FCC unit
and estimate the value delivered.
Physical properties
In FCC units, the physical prop-
erties of a catalyst are critical for
the smooth operation of a unit.
Properties such as attrition, appar-
ent bulk density (ABD), surface
area, and particle size distribution
are key to the retention, circula-
tion, and performance of a catalyst
in FCC units. When Grace devel-
oped Zavanti additive, it was
important to retain the same strong
physical properties (see Table 1) as
OlefinsUltra additives.
The activity of ZSM-5 additive can
be increased either by adding more
ZSM-5 to a catalyst particle or by
increasing the inherent activity of
the ZSM-5 crystal. Traditionally,
adding more ZSM-5 to an additive
particle to boost LPG olefin activ-
ity was a common approach. This
has been the case for OlefinsUltra
additives. This approach is not triv-
ial since it becomes increasingly
difficult to bind larger quantities
of ZSM-5 in an additive particle
and yet retain good physical prop-
erties (particle density and attri-
tion resistance). This approach has
limited potential towards increas-
ing LPG olefin activity since it is
very difficult to add more zeolite
beyond a certain point.
Grace’s R&D programme during
Zavanti’s development focused
more on increasing the inherent
activity of ZSM-5. The objective
was to increase propylene activity
by minimal to no increase in the
amount of ZSM-5 in a catalyst par-
ticle. This was achieved with use
of a better stabilisation and bind-
ing technology. As Figure 3 shows,
the result was a significant increase
in propylene activity for Zavanti
compared with OlefinsUltra
additives.

44 PTQ Q3 2021 www.digitalrefining.com

q3 grace.indd 44 11/06/2021 15:31

 ACE performance data in wt% delta yields: yield of olefins additives blend minus
250 yield of base FCC catalyst at 75 wt% conversion (5% additive comparison)
Relative propylene activity, %
200 5 wt% Zavanti in 5 wt% OlefinsUltra 5 wt% OlefinsUltra HZ
catalyst blend vs MZ in catalyst blend in catalyst blend vs
150 base FCC catalyst vs base FCC catalyst base FCC catalyst
Cat-to-oil ratio 0.21 0.31 0.38
100
Hydrogen -0.02 -0.01 -0.01
Ethylene 0.85 0.61 0.39
Dry gas 0.55 0.57 0.30
50
Propylene 6.49 5.39 4.30
0 Propane 0.44 0.39 0.29
a®

HZ

I™
Isobutylene 1.50 1.26 1.01
M

NT
tr

a®

a®
l

Total C4=s 2.99 2.58 2.06

sU

VA
tr

tr
fin

ZA
sU

sU

Isobutane 0.44 0.45 0.36

le

fin

fin
O

Total C4s 3.44 3.07 2.43

le

le
O

LPG wt% 10.31 8.85 7.02

Gasoline -10.98 -9.45 -7.60

Figure 3 Propylene yield in OlefinsUltra
RON 1.57 1.59 1.19
ZSM-5 additives (previous generation) MON 0.79 0.95 0.69 Table 2
increases with the increased zeolite con-
tent of the additive. In Zavanti additive, LCO -0.45 -0.39 -0.12
the increase is due to improvement in the Bottoms 0.45 0.39 0.10
inherent activity of ZSM-5 Coke 0.12 0.03 0.28

Table 2
Laboratory testing
To show the difference in activ- ACE performance data in wt% delta yields: yields of olefins additives blend minus
ity between Zavanti and previ- yields of base FCC catalyst at 75 wt% conversion (23% additive comparison)
ous generations of ZSM-5 additive
technology, Grace tested against 23 wt% Zavanti in 23 wt% OlefinsUltra 23 wt% OlefinsUltra HZ
OlefinsUltra HZ and OlefinsUltra catalyst blend vs MZ in catalyst blend vs in catalyst blend vs
base FCC catalyst base FCC catalyst base FCC catalyst
MZ additives in an Advanced Cat-to-oil ratio 0.99 0.94 0.95
Catalytic Evaluation (ACE) unit Hydrogen -0.02 -0.02 -0.01
using a VGO feed. Ethylene 2.67 2.04 1.58
For performance testing, the Dry gas 2.49 1.90 1.55
ZSM-5 catalysts were deactivated Propylene 9.23 8.90 8.42
separately and then blended at two Propane 1.03 0.79 0.69
different levels with the base FCC Isobutylene 1.88 1.85 1.83
catalyst containing Y-zeolite. The Total C4=s 3.49 3.60 3.61
Isobutane 0.32 0.31 0.47
base catalyst chosen for this study is Total C4s 3.99 4.01 4.17
a low rare earth catalyst to minimise LPG wt% 14.25 13.70 13.28
hydrogen transfer reactions and
maximise gasoline olefins. The base Gasoline -16.95 -15.83 -15.36
RON 2.63 2.51 2.55
FCC catalyst was deactivated using MON 1.51 1.42 1.52
a milder hydrothermal deactiva-
tion protocol of four hours in 100% LCO -0.45 -0.46 -0.36
steam at 1500°F (815°C) whereas a Bottoms 0.45 0.46 0.36
Coke 0.21 0.22 0.53
severe deactivation protocol was
followed for olefins additives. The
olefins additives were hydrother- Table 3
mally deactivated for 50h in 100%
steam at 1500°F (815°C) compared at constant conversion, expressed as lyst, Zavanti shows a ~20% increase
to the standard deactivation proto- deltas in wt% yield between cata- in delta propylene yield over
col of 24h.3 lysts with and without olefins addi- OlefinsUltra MZ. The higher activ-
For ACE testing, the deactivated tive, are shown in Tables 2 and ity of Zavanti is also reflected in
olefins additives were blended at 5 3, compared at 5% and 23% higher yields of ethylene and buty-
wt% and 23 wt% level with the base additive blend levels, respectively. lene. A corresponding decrease in
FCC catalyst. The low blending ratio The data reveal that Zavanti tech- gasoline is observed, which is due
was used for better differentiation of nology produces higher propylene to cracking of gasoline range olefins
two high activity olefins additives yield compared to OlefinsUltra MZ to light olefins.
whereas the high blending ratio was as well as OlefinsUltra HZ at both At higher blend level (23 wt%),
used to evaluate its application for low and high blending levels. Zavanti still shows about 6%
max propylene FCC units. ACE data, At 5 wt% blend in the base cata- higher delta propylene yield over

www.digitalrefining.com PTQ Q3 2021 45

q3 grace.indd 45 11/06/2021 15:31

 Raw data and FCC SIM comparison shifts
Reactor product Raw data yield shifts: Zavanti FCC-SIM yield shifts: Zavanti minus
minus OlefinsUltra HZ additive, wt% OlefinsUltra HZ additive, wt%
C2- offgas yield (C2=) +0.20 +0.18
C3= +0.41 +0.65
Total C4=s +0.33 +0.39
Gasoline -0.94 -1.22
Table 4
OlefinsUltra MZ. The advantage
of Zavanti is lower at high addi-
tive level since there is less gasoline
range material left to crack and what
remains are mostly C5 and C6 olefins
which are more difficult to crack.
The results indicate that greater
yields of LPG olefin yields can be
obtained at constant additive level
of Zavanti versus OlefinsUltra MZ,
or similar LPG olefin yields can be
obtained by using lower percentages
of Zavanti versus OlefinsUltra MZ.
The lower usage of olefins additive
in max propylene FCC units will
help to maintain the high activity
of base catalyst by minimising the
dilution effect. The higher catalyst
activity can be leveraged to increase
conversion, therefore improving the
profitability of the FCC unit.
The data reveal that Zavanti
achieves a higher propylene yield
compared to OlefinsUltra HZ. At 23
wt% blend, Zavanti shows a ~11%
increase in delta propylene yield
over OlefinsUltra HZ, the incum-
bent ZSM-5 catalyst at SATORP.
The data clearly show the ranking
in activity: Zavanti > OlefinsUltra
MZ > OlefinsUltra HZ.
The data demonstrate that Zavanti
formulated with Grace’s binding
and stabilisation technology delivers
a much higher boost in propylene
yield over the incumbent additive
technology and is the clear choice
for the SATORP unit to maximise
propylene yield. Therefore, Zavanti
was preferred over OlefinsUltra MZ
for the SATORP trial.
Summary of SATORP FCC unit data
The performance of Zavanti in the
SATORP FCC unit was assessed by
comparing the commercial test run
data during the period of its use
against that of OlefinsUltra HZ, the
incumbent ZSM-5 additive. Table
4 summarises the shifts in yields
both for the raw data and the data
46 PTQ Q3 2021
q3 grace.indd 46
normalised for operating and feed
conditions via FCC-SIM model-
ling. OlefinsUltra HZ in inventory
was slightly higher than that of
the Zavanti test run. Despite this,
as can be seen, the raw data indi-
cates higher LPG olefin yields with
Zavanti vs OlefinsUltra HZ and the
modelling indicates that, once the
test run conditions are normalised,
Zavanti outperforms further. It is
worth noting that in Table 4 the C2-
offgas delta is composed of C2=.
Using the generic price set in
Table 5 and the yield shifts in Table
4, we can estimate the value uplift
delivered by Zavanti additive over
OlefinsUltra HZ additive.
In the case of SATORP, the expec-
tation is that the improvement in
C3= and C4= could have been even
higher if the ROT could have been
increased. However, this is not possi-
ble at present due to unit constraints.
Assuming typical specific gravity
values for various products, we pro-
ject uplift of between $0.38/bbl and
$0.58/bbl. Maximising LPG olefins
can be highly profitable for a refiner
and Zavanti additive technology
can be a tool for refineries with this
objective to unlock that value.
Conclusion
Facing the prospect of decreasing
fuels demand, refineries are opt-
ing to produce higher yields of
petrochemical products. The FCC
unit, with its high yield of C3=, can
facilitate this transition from fuels
to a petrochemicals focus. The
value delivered at SATORP ranged
between $0.38/bbl and $0.58/bbl
with Zavanti additive. This example
illustrates the value that petrochem-
ical yields and new additive tech-
nologies can deliver for a refinery.
This article includes contributions from the
SATORP FCC team.
ZAVANTI is a mark of W.R. Grace & Co.
FCC-SIM is a mark of KBC.
Generic price set for various
refinery products
Product Price, $/t (generic)
C2= 700
C3= 989
Total C4=s 531
Gasoline 483
Table 5
References
1 Large integrated crude-to-chemicals sites in
China – the next mega-trend, Wood Mackenzie,
Apr 2018.
2 Crude-to-Chemicals: Opportunity or Threat?,
Wood Mackenzie webinar, Mar 5, 2019.
3 FCC Petrochemical Maximization by
Catalyst Selection, Presentation at BBTC Mena
& ME-CAT, SATORP, Dec 2020.
4 Cipriano et al, ZAVANTI™ catalyst: Newest
ZSM-5 technology for max propylene Units,
Grace Catalagram, Vol 125, 2020
Silviu Serban is a Technical Sales Manager
with Grace Refining Catalyst Technologies
Middle East & Africa. With 18 years’ experience,
especially in FCC and other refinery units, he
previously worked on the SATORP refinery
project in Saudi Arabia, as a Production Engineer
for Amromco Energy in Romania and in the
US, and at the S.C. Petrotel – Lukoil refinery in
Romania. He holds a MSc degree from the “Oil
and Gas” University of Ploiesti, Romania.
Chuck Ekeocha is Technical Service Manager
with Grace FCC, Middle East & Africa. With 14
years’ experience, he has worked in refining
operations, design and project management
with a focus on catalytic reforming, fluid
catalytic cracking, hydrotreating, crude
distillation, sulphur recovery, and refinery
utilities. He holds BSc & MSc degrees in chemical
engineering from the University of Science
and Technology, Ghana and the University of
Newcastle-upon-Tyne, UK, and is a member of
the Institute of Chemical Engineers.
Udayshankar Singh is Senior Principal Research
and Development Scientist in the Refining
Technologies business with W.R. Grace & Co.-
Conn., Columbia, Maryland. He has 14 years’
experience in the development and scale-up
of new catalysts for various FCC applications
and provides technical support to customers.
He holds a PhD in chemistry from The Open
University, UK, spent two years as a postdoctoral
research fellow at the University of Exeter, UK,
three years as a postdoctoral research fellow at
the University of California-Santa Barbara, and
is an inventor of several patents.
Bani H Cipriano is FCC Segment Marketing
Manager, Light Olefins with W.R. Grace & Co
and manages the company’s portfolio of max
propylene catalysts and ZSM-5 additives. His
priority is to commercialise technologies that
will enable customers to maximise yields of
petrochemical feedstocks from the FCC unit.
He holds BS and PhD degrees in chemical
engineering from the University of Maryland.
www.digitalrefining.com
11/06/2021 15:31
sabin.indd 1 11/06/2021 14:01
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 Lower operating costs with liquid phase
hydroprocessing
Liquid phase hydroprocessing demonstrated its economic and environmental
advantages over trickle bed technology in a Chinese refinery
TONY CHEN, SANDEEP PALIT and SAMANTHA PRESLEY
DuPont Clean Technologies
A
ir quality concerns have
led to increasingly strin-
gent environmental legisla-
tion globally. In the case of China,
diesel sulphur specifications have
seen a marked change in the last
10 years. The country made dras-
tic cuts to sulphur levels in diesel
and introduced a limit of 10 wppm
in densely populated areas in 2010.
As a result, refiners face strict
national regulations both for grass-
roots and existing plants. When
the government-owned China
National Offshore Oil Corporation
(CNOOC), the largest offshore oil
and gas producer in China, received
approval to construct Phase II of its
expansion project at the Huizhou
refinery, the organisation turned
to DuPont Clean Technologies to
help it achieve not only the desired
increase in crude processing capac-
ity, but also to enable it to produce
high quality, low sulphur fuel effi-
ciently, safely and in compliance
with local environment regula-
tions. Implementing IsoTherming
hydroprocessing technology allows
CNOOC to meet all of these goals as
well as decrease energy consump-
tion and operating costs compared
to conventional trickle bed hydro-
processing technologies.
Project parameters
Phase II of the Huizhou refinery
was designed to more than double
crude processing capacity at the
plant from 11 million t/y (220 000
b/d) to 22 million t/y (440 000 b/d).
CNOOC also wanted to improve
its flexibility in processing a wider
range of more economically attrac-
tive sour Arabian Gulf crudes. In
October 2017, after three years
www.digitalrefining.com
q4 dupont.indd 49
400
350
300
250
Sulphur, µg/g (ppm)
200
150
100
50
0
2010
Figure 1 China’s historical diesel sulphur specifications
of construction, the refinery suc-
cessfully started up and tested 15
processing units, auxiliary produc-
tion units, and supporting pub-
lic works for the Phase II refinery
project. These included new and
modified units from a crude unit
to an FCC unit, diesel hydrotreat-
ing, VGO hydrotreating, residue
hydrotreating and a gasoline hydro-
treating unit. Among them were a
China National V diesel compliant
(≤10 wtppm sulphur) 3.4 million
t/y (71 637 b/d) grassroots diesel
hydrotreater and a 2.6 million t/y
(51 419 b/d) grassroots vacuum
gas oil hydrotreater for the FCC
feed, designed for output of <1000
wtppm sulphur and <600 wtppm
nitrogen, both licensed by DuPont
Clean Technologies.
At the outset of the refinery expan-
sion, the CNOOC Phase II pro-
ject included grassroots diesel and
VGO hydrotreating units, which
presented the company with an
opportunity to evaluate its options,
including IsoTherming technology
On-road
Off-road
2011 2012 2013 2014 2015 2016 2017 2018
which has been commercialised
since 2005. Trickle bed hydropro-
cessing technology has been demon-
strated globally for decades in
numerous refinery applications.
However, trickle bed technology
relies on maintaining a high hydro-
gen gas to oil ratio. This leads to
high energy consumption and capi-
tal investment arising from the con-
siderable amount of hydrogen gas
circulation needed for maintaining
hydrogen partial pressure, con-
trolling temperature rise, and pro-
viding the necessary hydrogen for
the reactions. CNOOC wanted to
explore IsoTherming technology as
it is characterised by low energy con-
sumption, low capital investment,
low operating costs, ease of main-
tenance and simple operation. In
addition, at the time of the CNOOC
technology evaluation, there were
more than 10 IsoTherming units in
commercial operation processing
kerosene through 100% light cycle
oil feeds in a variety of hydropro-
cessing applications.
PTQ Q3 2021 49
11/06/2021 15:34

Make-up Compressor
hydrogen
Feed
IsoTherming
reactor
Recycle To LP flash/
pump stabiliser
Figure 2 IsoTherming process
CNOOC undertook a thorough
investigation of the technology, bas-
ing its final selection on confirmed
process, environmental and safety
benefits, commercially proven
results, as well as capital and oper-
ating costs. The process of evaluat-
ing, selecting and commissioning
this technology at the Huizhou
refinery therefore spanned a five-
year time frame and included tech-
nical discussions, an evaluation of
IsoTherming and trickle bed hydro-
processing technologies in terms of
process, investment and operating
costs, and visits to existing commer-
cial unit installations.
CNOOC’s technology evaluation
In IsoTherming hydroprocess-
ing technology (see Figure 2), the
hydrogen required for the reaction
is supplied using a saturated liq-
uid stream rather than a recycle gas
stream. The liquid recycle rate is set
so that the amount of hydrogen dis-
solved in the combined (fresh and
product liquid) feed is much greater
CNOOC’s comparison of high-pressure equipment requirements for IsoTherming
and trickle bed technologies
Key equipment
Reactor
Amine scrubber
Amine scrubber knockout drum
Reactor feed/product heat exchanger
Hot HP separator gas cooler
Hot HP separator gas/recycle H2 heat exchanger
Hot HP separator
Cold HP separator
Recycle H2 compressor knockout drum
Recycle hydrogen compressor
Recycle canned motor pump
Table 1
50 PTQ Q3 2021
q4 dupont.indd 50
Trickle bed reactor
Vapour and liquid phases
Requires almost perfect
feed distribution
IsoTherming reactor
Single liquid phase
Lower temperature rise
Lower light ends yield
Lower catalyst
deactivation rates
Figure 3 Liquid distribution differences
between trickle bed and IsoTherming
technologies
than the reaction requirements. This
liquid-full design ensures excess
hydrogen availability at the reactor
inlet/outlet. To replace hydrogen
that has been consumed throughout
the catalyst bed, hydrogen is contin-
uously injected between each cata-
lyst bed to re-saturate the feed prior
to the next catalyst bed. A nominal,
continuous flow of excess hydro-
gen/off-gas is vented from each
catalyst bed as an indicator that suf-
ficient hydrogen is flowing to the
inter-bed resaturation point. Liquid
distribution differences between
IsoTherming and trickle bed reac-
tors are illustrated in Figure 3.
CNOOC realised the reactor
IsoTherming Trickle bed
√ √
√
√
√ √
√ fuel gas savings. Further, CNOOC
√ opted to incorporate a twisted-tube
√
√
√ for the feed/effluent exchanger,
√ proving for the first time that this
√ type of heat exchanger can be reli-
design of IsoTherming technology
would address areas of concern
related to conventional trickle bed
technology including multiphase
flow, pressure drop and mainte-
nance of the correct flow regime. In
the IsoTherming reactor, the lack
of a vapour phase and resultant
reduced volumetric flow rate results
in significantly lower pressure drop.
In addition, the liquid-full reactor
and even distribution of reactants
minimises the possibility of form-
ing isolated pockets of low flow
and resultant ‘hot spots’ within
the reactor bed. With the more effi-
cient use of catalyst and a more
uniform distribution of bed tem-
perature due to the total liquid reac-
tor feed, CNOOC concluded that
IsoTherming technology is inher-
ently safer and simpler than trickle
bed technology.
Comparison summary
In summary, CNOOC viewed
IsoTherming as offering the follow-
ing advantages over conventional
hydroprocessing technology:
• Lower capital requirements for
both high pressure (HP) related
equipment and the IsoTherming
feed/effluent exchanger. Table 1
provides a summary of differences
in high pressure equipment require-
ments for IsoTherming and trickle
bed technologies. Depending on the
application, IsoTherming’s capital
cost savings can be as much as 25%
compared to a conventional trickle
bed design.
Another key part of the
IsoTherming design is direct reactor
feed/effluent heat exchange which
recovers much of the heat of reac-
tion energy by heating the reactor
feed directly by combining it with
the reactor effluent. Direct heat
transfer enables the unit to recover
high-level energy without the heat
loss associated with indirect heat
exchange (use of a heat exchanger),
and this leads directly to significant
bundle type heat exchanger design
ably operated in an IsoTherming
unit.
www.digitalrefining.com
11/06/2021 15:34
 • Lower maintenance and operat-
ing costs by eliminating the hydro-
gen recycle gas compressor and its
ancillary recycle loop equipment.
• Reduced energy consumption
as IsoTherming has consistently
demonstrated 40-60% utility savings
over trickle bed technology, for the
following reasons:
■ By using a canned motor pump
for hydrogen delivery which con-
sumes substantially less energy
than a comparable trickle bed
recycle gas compressor, the unit
power consumption is reduced,
on average, by 30-40% for any
application.
■ By eliminating the hydrogen
recycle gas loop, the low-level
energy loss to cooling water or air
that is associated with the hydro-
gen recycle loop is eliminated.
■ By direct heat exchange (vs
indirect heat exchange) using
a liquid recycle, the high-level
energy is recovered fully and
leads directly to fuel gas sav-
ings at the reactor charge heater.
The technology has consistently
demonstrated a 30-60% drop in
fuel gas costs.
• Any excess reactor bottoms heat,
beyond what is required to pre-
heat the reactor feed, can be used
to generate steam. This results in a
net reduction of steam usage within
the unit and, in some extremely
exothermic applications, the unit
becomes a net producer of steam.
Overall, IsoTherming not only
offers significant utility cost sav-
ings as well as substantial capital
cost reductions compared to trickle
bed technology but also a reduc-
tion in CO2 emissions (due to mini-
mal reactor charge heater duty). At
the same time as comparing tech-
nologies, CNOOC also considered
past commercial experience with
IsoTherming. Since its first com-
mercialisation in 2003 and at the
time of the CNOOC evaluation, it
has been licensed for more than 20
units around the world, of which
seven were located in China. Today,
IsoTherming hydroprocessing tech-
nology has 28 licences globally with
15 of these in commercial operation.
In view of these benefits, CNOOC
concluded that the technology
would be able to operate with lower
www.digitalrefining.com
q4 dupont.indd 51
CNOOC ULSD hydrotreating engineering and equipment cost analysis
Total engineering and bare Trickle bed IsoTherming Difference
equipment cost estimate ¥362 759 800 ¥279 628 000 ¥83 131 800
$54 413 970 $41 944 200 $12 469 770
Bare equipment cost breakdown Trickle bed IsoTherming Difference
Static equipment ¥108 132,000 ¥64 910 900 ¥43 221 100
$16 219 800 $9 736 635 $6 483 165
Mechanical equipment ¥62 560 300 ¥43 857 700 ¥18 702 600
$9 384 045 $6 578 655 $2 805 390
Process pipe ¥57 255 200 ¥32 280 500 ¥24 974 700
$8 588 280 $4 842 075 $3 746 205
Automation ¥32 639 900 ¥26 406 500 ¥6 233 400
$4 895 985 $3 960 975 $935 010
Total savings approx. 25 MM USD (Chinese installation factor = 2-3 x equipment)
Table 2
investment and lower operating ability to reduce catalyst coke for-
cost. CNOOC therefore decided mation, compared to conventional
that it was feasible for the Huizhou trickle bed technology.
Refining & Chemical Project (Phase CNOOC indicated that it has
II) to utilise it in its ULSD and VGO demonstrated successful appli-
hydroprocessing units. cations of the technology at the
Huizhou refinery, with all technical
Operational highlights indicators showing that the technol-
CNOOC broke ground for the ogy works well.
ULSD unit on 16 October 2014,
followed by a successful start-up Economic and social benefits
in September 2017. At the time of analysis
start-up, the ULSD unit’s operation CNOOC developed estimates for
complied with the design specifica- engineering and bare equipment
tions and the ULSD product met or costs during the company’s evalua-
exceeded the China V standards at tion of hydroprocessing technology.
a lower than design feed rate due The results are summarised in Table
to available feedstock limitations. 2. It should be noted that these
The ULSD unit underwent a per- results do not represent the full cap-
formance test at the full design feed ital cost or savings associated with
rate in September 2018. During the either technology as the information
performance test, all the product’s is for the cost of bare equipment
properties and waste emissions met only, plus engineering fees (and
or exceeded unit design specifica- does not include any installation
tions and performance guarantees related costs).
indicating that IsoTherming oper- The total capital cost savings
ated as intended. associated with IsoTherming for
CNOOC broke ground on the the CNOOC ULSD hydrotreating
VGO hydrotreating unit on October unit were approximately $25 mil-
16, 2014 and initiated a successful lion (Chinese installation factor =
start-up in October 2017. Due to 2-3 x bare equipment). It is worth
reduced refinery throughput due to noting that the actual cost sav-
market conditions, the IsoTherming ings would be greater outside of
VGO hydrotreater ran at reduced China where installation factors
rates until recently. A success- are typically in the range 4-6 x bare
ful performance test for this unit equipment.
was completed in July 2020, where CNOOC determined that an
the results exceeded performance average IsoTherming ULSD hydro-
guarantees. In particular, the unit treater requires approximately
demonstrated that it maintained 50% of the energy used by a com-
catalyst activity over the three-year parable Chinese conventional
period, demonstrating one of the trickle bed design. A portion of the
advantages of the technology in its IsoTherming unit’s operating cost
PTQ Q3 2021 51
11/06/2021 15:34
 treater realises total annual oper-
18 ating cost savings of ¥27.3 million
Fuel gas consumption
500
($4 095 000) compared to a conven-
16 Fresh feed tional trickle bed design.
14 CNOOC concluded that the pro-
400 jects, when built and put into oper-
12 ation, yielded a high reduction in
m3 per ton of fresh feed

energy consumption. The antici-

Fuel gas consumption,

10 300
pated savings of large amounts of
8 fuel gas and steam were realised

Fresh feed, ton/h

200 along with a considerable reduction
6
in emissions. Overall, the projects
4 had a positive impact on environ-
100
mental protection.
2

0 0 Conclusion
Currently, two hydroprocessing
8

18

18

18

18

18

19
01

20

20

20

20

20

20
options are available for the pro-
r2

ay

ct

ec

b
Ju
Ap

Se

Fe
O

duction of ULSD and the treatment

M

D
19
10

27

4
7

16
30

of FCC feeds. These include con-

ventional trickle bed and liquid
Figure 4 CNOOC Phase II ULSD feed heater fuel gas consumption phase (IsoTherming hydroprocess-
ing) technologies. CNOOC selected
advantage comes from reduced China showed an average energy IsoTherming, enabling the com-
fuel gas use due to optimised consumption of 9.71 kg EO/t for pany to realise both economic and
feed/product heat integration. The 2016. As such, the CNOOC ULSD social benefits. Overall, the com-
remainder comes from the method hydrotreater energy consumption pany achieved significant capital
for delivering hydrogen to the cat- is 5.52 kg EO/t less, equating to and operating cost savings while
alyst beds. For many IsoTherming a total annual operating cost sav- meeting or exceeding the expected
units, the reactor charge heater ings of 65.7 million CNY/year (US product yields of conventional
duty is determined by start-up con- $9 853 200/year). trickle bed technology. CNOOC
ditions when there is insufficient benefits from a safer, simpler, more
product heat to exchange with the efficient, and cost-effective pro-
feed. As a result, the charge heaters Overall, the company cess with lower emissions as com-
typically operate with significantly pared to conventional trickle bed
lower duty than design conditions
achieved significant technology.
once the unit is stabilised. For the capital and operating
CNOOC ULSD hydrotreater, the
reactor charge heater operates at cost savings while
approximately 23% of the design Tony Chen is Senior Technical Manager with
duty, leading to annual fuel gas sav- meeting or exceeding DuPont Clean Technologies for IsoTherming
ings of ¥7.854 million ($1 168 360) hydroprocessing technology. Prior to
compared to an equivalent trickle the expected joining DuPont, he spent 20 years in the oil
refining industry, with most of his time in
bed design.
Figure 4 shows the unit total product yields of hydroprocessing. He holds a PhD in chemical
engineering from Oklahoma State University.
fuel gas consumption on a per-ton
basis of fresh feed plotted against
conventional trickle
Sandeep Palit is a Senior Technical Sales
the unit total fresh feed rate. The bed technology Manager with DuPont Clean Technologies
graph demonstrates that greater for IsoTherming hydroprocessing technology.
energy savings can be realised He graduated from Worcester Polytechnic
(within design limits) when more CNOOC carried out a simi- Institute then held positions in process
feed is processed. CNOOC believes lar evaluation for the Phase II engineering in refining and chemicals,
this to be one of the advantages IsoTherming VGO hydrotreater. hydrocracking and dewaxing.
of IsoTherming. Overall utility CNOOC determined an average
Samantha Presley is Global Licensing
consumption including power IsoTherming VGO hydrotreater
Manager with DuPont Clean Technologies
and steam generation for the requires approximately 60% of the
for IsoTherming hydroprocessing technology
IsoTherming ULSD hydrotreater is energy consumed in a comparable and is responsible for the technical and
4.19 kg EO/t (kilogram oil equiv- Chinese trickle bed design. While a commercial sale of the technology. She holds
alent per metric ton) whereas data portion of the unit’s operating cost a bachelor of science degree in chemical
on energy consumption for a con- advantage comes from reduced fuel engineering and a minor in business from the
ventional diesel hydrotreater in gas consumption, the VGO hydro- University of Kansas.

52 PTQ Q3 2021 www.digitalrefining.com

q4 dupont.indd 52 11/06/2021 15:34

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 Maximising stripping section performance
The design of a crude unit stripping section affects diesel and gasoil yields, energy
usage, and unit reliability
EDWARD HARTMAN and BRYAN WHITE
Process Consulting Services
M
aximising stripping section
performance in crude and
vacuum units is traditionally
used as a tool to enhance recovery
of diesel, atmospheric gasoil, and
vacuum gasoil. Refinery econom-
ics have long favoured projects that
aim to increase profitability through
yield and/or charge rate improve-
ments. In one documented case,
revamping a crude unit stripping
section, combined with flow scheme
changes and modifications to the
diesel fractionation section inter-
nals, allowed an Australian refiner
to raise diesel production by 14.5
vol% on crude.1 This article focuses
on the benefits of optimisation of
stripping sections for both revamps
and grassroots projects and the
impact on reducing energy con-
sumption. In today’s environment
of low refining margins, emphasis
on energy efficiency and reduc-
tion of greenhouse gases emission,
and extremely constrained capital
budgets, optimisation of stripping
sections presents refiners with a
cost effective and focused means to
improve their competitiveness.
Common stripping section problems
Stripping sections in crude atmos-
pheric and vacuum towers are often
troubled by process, hydraulic, and
mechanical design errors or inade-
quacies that result in poor stripping
performance and low vaporisation
of atmospheric and vacuum resi-
dues. At first, the process design
for a stripping section must con-
sider the type of crudes that will be
processed, as well as cut point and
product yield requirements. Many
older units were designed with only
three or four stripping trays and
low steam rates of less than 3 lb/bbl
of residue. While these factors may
not carry a large penalty for light
www.digitalrefining.com
q3 pcs.indd 55
crudes, they significantly reduce
diesel and vacuum gasoil yields for
heavy crudes.2,3
The hydraulic design of the
stripping section affects tray effi-
ciency in several ways. Modern
crude atmospheric towers normally
have a smaller diameter cylindri-
cal shroud near the bottom of the
column that serves as a stripping
section. In older crude towers, it is
common to find the stripping trays
located in the same diameter as the
Optimisation of
stripping sections
presents refiners
with a cost effective
and focused means
to improve their
competitiveness
flash zone. Either way, the result-
ing cross-sectional area is often too
large to promote good vapour and
liquid contact, which leads to low
tray efficiency and fouling on tray
decks. In vacuum towers, the major-
ity of stripping sections are located
in smaller diameter vessel sections
which frequently are still too large,
resulting in poor tray efficiency and
fouling.
Another fundamental error in the
design of atmospheric and vacuum
towers stripping sections is to use
the same open area for all stripping
trays. With this approach, open
area is usually set by the highest
vapour load, which occurs at the
top stripping tray. The lower trays
operate with gradually less vapour
with the bottom tray handling only
stripping steam. The strip-out ratio
(ratio between total vapour gener-
ated in the stripping section and
stripping steam on a volumetric
basis) is a function of crude blend,
flash zone pressure and tempera-
ture conditions, number of stripping
trays, and steam to residue ratio.
The strip-out ratio is approximately
2:1 in crude towers and 4:1 in vac-
uum towers. Imparting the same
tray design and open area through-
out the stripping section results in
weeping and poor vapour-liquid
contact in the lower trays.
Based on the authors’ experience,
the combination of these hydraulic
design errors results in low strip-
ping section tray efficiencies, in the
10% range or even lower. These
low efficiencies reduce diesel and
vacuum gasoil yields at constant
flash zone conditions in the crude
and vacuum columns, respectively.
In order to maintain yields and
compensate for poor stripping sec-
tion efficiencies, higher duties are
needed in the crude and vacuum
heaters.
Fouling in stripping sections typ-
ically occurs due to deposition of
asphaltene compounds on tray
decks and inside downcomers. This
deposition tends to be more pro-
nounced with heavy crudes prone
to lower thermal stability and when
running incompatible crude blends
of aromatic and paraffinic crudes.
Some crudes are also known for
having high amounts of solids and
sediment. For example, solids in
some shale crudes have been meas-
ured as high as 350 lb per thou-
sand barrels. In addition to causing
emulsion problems in desalters and
fouling in preheat train exchangers
and crude heaters, solids have also
caused plugging of crude tower
stripping section trays. Poorly
PTQ Q3 2021 55
11/06/2021 15:43
 designed trays with excessively
large diameters and small open
areas aggravate fouling and plug-
ging. In the most severe instances of
fouling, refiners are forced to reduce
stripping steam rates and even take
unscheduled shutdowns.
Tray features and details such as
type of valve, opening size on the
tray decks, weir height, and down-
comer clearance also impact fouling
tendency in the stripping section.
For example, moveable valves or
fixed valves with small openings,
as well as small diameter sieve
holes, tend to foul and plug quickly.
High outlet weirs promote accumu-
lation of fouling material on tray
decks. Small downcomer clearances
can lead to downcomer plugging.
Additionally, the inherent liquid
flow pattern of conventional cir-
cular trays leads to stagnant pools
of liquid on the deck (see Figure 1).
Downcomer bottom edge length
is normally between 50% and 60%
of tower diameter. As liquid exits
the downcomer and flows towards
the outlet weir, it does not spread
evenly across the deck. This uneven
flow pattern is especially poor on
single pass trays and results in stag-
Existing elevation
#5
#4
#3
#2
#1
Full diameter trays with stagnant areas
5 trays at 30” spacing
High weir height
Same open area
One theoretical stage or less
Figure 2 Crude tower stripping section revamp
56 PTQ Q3 2021
q3 pcs.indd 56
Stagnant area prone to fouling
Inlet area
Downcomer
Figure 1 Single pass tray flow pattern and
stagnant zones
nant areas near the periphery where
more fouling materials tend to accu-
mulate. The same problem occurs to
a lesser extent on two and four pass
tray designs.
Improving tray mechanical integ-
rity is paramount to achieving
good stripping section performance
and maintaining that performance
between turnarounds. Damaged
stripping sections can cause crude
and vacuum distillate yield losses as
high as 4% and 3% on whole crude,
respectively.4 Crude and vacuum
towers commonly have episodes
Revamp elevation
#7
#6
#5
#4
#3
#2
#1
Trays in rectangular shroud with no
stagnant areas
7 trays at 18” spacing
Low weir height
Varying open area
Collector tray feeding top active tray
More than two theoretical stages
of high bottoms liquid level and
‘wet’ steam, especially during unit
start-up. In vacuum towers, intro-
duction of wet steam can be very
destructive due to the expansion of
condensate from liquid to vapour
phase under vacuum pressure.
Trays designed with normal metal
thickness and frictional assembly
methods do not resist uplift forces
resulting from these operational
upsets. The result is often partially
damaged trays or all stripping trays
laying in the tower bottom head.
With this kind of disastrous dam-
age, the trays do not contribute to
atmospheric or vacuum residue
vaporisation, no matter how well
intended the process and hydraulic
designs.
Stripping section improvements
Improvements to crude atmospheric
and vacuum tower stripping sec-
tions can be applied in grassroots
and revamp projects. These projects
should focus on maximising tray
count and efficiency, minimising
their fouling tendency, and upgrad-
ing mechanical resistance against
operational upsets. Stripping steam
rate should also be reviewed and
adjusted if necessary. The goal is to
optimise the ratio of steam to resi-
due and to increase vaporisation of
light material, considering unit con-
straints such as overhead condenser
capacity and the effect on tower
operating pressure.
An effective way to achieve these
goals in crude atmospheric strip-
ping sections is to locate the trays
inside a shroud constructed as par-
allel walls. This design results in
rectangular active areas with no
stagnant zones. Shroud width and
number of tray passes are selected
to obtain a high weir liquid loading.
The resulting liquid velocity profile
on the tray decks is analogous to a
plug flow regime, which reduces
fouling potential. Outlet weirs have
low height and are also configured
to minimise fouling. Downcomers
are properly sized and with a high
clearance to avoid stagnation and
plugging. Finally, active panels
are fitted with ¾” or 1” sieve holes
and the open area of each tray is
adjusted according to the increas-
ing vapour rate from bottom to
www.digitalrefining.com
11/06/2021 15:43
 top. The overall effect of this design
approach in projects executed by Customary design PCS design
Process Consulting Services (PCS)
has been tray efficiencies of 35%
or higher with minimal fouling
tendency.
Maximising tray count should
also be part of the parallel wall #7 #7
shroud design. The number of trays #6 #6
that can be installed is a function of #5 #5
the difference in elevation between #4 #4
flash zone and residue high liquid #3 #3
level control point, as well as tray #2 #2
spacing. Decreasing tray spacing #1 #1
allows the designer to maximise
tray count in the available space
while adjusting the shroud design to
achieve the required tray capacity.
Figure 2 illustrates this design
approach which was developed
during a PCS revamp design of
a US West Coast refiner’s crude Same area on all trays Tray areas proportional to vapour rate
atmospheric tower. An important Lower trays oversized and inefficient Efficiency maintained on all trays
One theoretical stage or less More than two theoretical stages
detail of the existing column is that
the top tray #5 is extremely inef-
ficient, even more so than trays Figure 3 Vacuum tower stripping section configurations
#1-4. This inefficiency results from
poor liquid distribution, which is to avoid liquid weeping or dump- API blend of heavy crudes, where
affected by the flow pattern from ing through the sieve holes which the vacuum tower strip-out ratio
the tangential feed nozzle and worsens efficiency. As a result, exceeds 4:1.
flash zone feed distributor. As one the conical design achieves a more As another feature of the PCS
feature of the revamp configura- uniform sieve holes density and design, side downcomers are
tion, a collector tray is located at avoids large ‘dead’ or unpunched designed with a special multi-
the top of the shroud to provide areas on all trays, thus contribut- chordal profile to minimise periph-
good liquid distribution to the first ing to better efficiency. To illustrate eral zones prone to stagnation and
active tray (#7), thus preserving its this, Figure 4 compares the den- fouling. Other custom features dis-
efficiency. sity of sieve holes on the bottom cussed previously related to weirs,
For vacuum towers, PCS uses tray achieved with the PCS design, downcomers, and active panels
an innovative design to handle the against a customary design, for a are also applied. Similar to crude
large difference in vapour rates constant vapour velocity through towers, overall results are tray effi-
between the top and bottom strip- the holes. This example is based on ciencies in the 35% range with min-
ping trays. As Figure 3 shows, the a US Gulf Coast 275 000 b/d crude imal fouling tendency. The conical
stripping trays are located in a ves- and vacuum unit designed for a 24° stripping section has been applied
sel section with a conical shape, as
opposed to the customary design
with a straight section. In the cus- Customary design PCS design
tomary design, the top tray where
the highest vapour and liquid loads
occur sets the section diameter. As
a consequence, the lower trays are
over-sized, which leads to low tray
efficiency and fouling. In the PCS
design, the conical shape progres-
sively reduces each tray diameter
and area, thus maintaining tray effi-
ciency and reducing fouling.
In addition to the decreasing tray
area from top to bottom provided
by the conical section, the open area
on each tray is adjusted according
to the vapour rate. The objective is Figure 4 Bottom tray sieve hole layout

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q3 pcs.indd 57 11/06/2021 15:43

 residue stripping. Additionally,
improving crude tower stripping
impacts the vacuum heater in two
ways:
• Since the energy required for oil
vaporisation in the stripping sec-
tion comes from the liquid itself,
improved stripping reduces atmos-
pheric residue temperature.
• The atmospheric residue becomes
heavier and therefore more difficult
to vaporise.
All of these effects need to be
taken into account and each unit
should be analysed individu-
ally when it comes to quantifying
energy impacts. The following cases
illustrate different ways the benefits
of stripping section improvements
can be realised.
 
Figure 5 The stripping trays heavy-duty construction features highlighting shear clips and Case 1: Crude tower stripping impact
through-bolting on crude heater firing
Large modern refining complexes
to new vacuum towers and also port rings as well as to downcomers configured with a crude distillation
as part of revamps. For revamps, • Through-bolting to support ring unit (CDU) that feeds atmospheric
the existing stripping section is or peripheral clamping on a tight residue to a fluid catalytic cracking
removed from the bottom of the spacing (RFCC) unit have been built in the
tower and the new conical section is developing world. Normally they
welded in its place. Stripping section revamp benefits produce light and heavy diesel as
Mechanically, all of the strip- Every crude and vacuum unit is the lowest side products from the
ping section trays are designed for unique. There is no standard flow crude tower. Downstream hydro-
higher uplift resistance so that they scheme and each unit has its own processing units dictate light and
are more likely to withstand opera- set of constraints. Crude types, heavy diesel product specifications,
tional upsets caused by wet steam products yield structure, preheat which limits the benefit of increas-
or high liquid level. Trays should train integration with products ing distillate yields. In such cases,
be of heavy duty construction (see and pumparounds, and heat rejec- crude heater firing can be directly
Figure 5), with features such as: tion to utilities affect the impact of reduced by stripping section
• Active and downcomer panels stripping section improvements on improvements. The curve in Figure
made of thicker sheet metal energy usage. For integrated crude 6 is based on a modern grassroots
• Through-bolting of adjacent and vacuum units, the level of heat design that PCS recently completed
panels integration greatly affects energy and is under construction. It corre-
• Shear clips from panels to sup- benefits associated with improved lates reduction in crude heater fired
duty to number of theoretical stages
in the stripping section. This curve
0.0% is based on a 35 °API crude charge
at a constant ratio of stripping
Percent change in heater fired duty

steam per barrel of atmospheric

-1.0%
residue, and constant heavy diesel
cut point. The curve also accounts
-2.0% for the heat recovery effects on the
crude preheat train and, therefore,
-3.0% heater inlet temperature.
For a CDU processing a 200 000
-4.0% b/d crude charge, improving
atmospheric tower stripping sec-
tion from one to three theoretical
-5.0%
1 2 3 4 stages reduces crude heater firing
Number of theoretical stages by 16 MMBtu/h. At a fuel value of
$4.00/MMBtu, this translates to fuel
Figure 6 Crude heater firing reduction savings of approximately $515 000

58 PTQ Q3 2021 www.digitalrefining.com

q3 pcs.indd 58 11/06/2021 15:43

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35
Suction pressure (mmHg absolute)
30
25
20
2 crude stripping stages –
15
10
5
0 ping to two theoretical stages cuts
0 1000
Figure 7 Ejector performance curve
per year. Finally, the lower crude
heater duty results in a reduction in
CO2 emissions of roughly 7300 t/y
based on a typical refinery fuel gas
composition.
Case 2: Crude tower stripping
impact on ejector motive steam
The vacuum system at a US
Midwest 250 000 b/d crude and
vacuum unit has three parallel
first stage ejectors in operation.
The vacuum unit’s mode of opera-
tion is ‘wet’ with heater coil steam,
bottoms stripping steam, and no
pre-condenser. With this config-
uration, vacuum system suction
pressure is a function of first stage
ejector load and its performance
curve, as long as its discharge pres-
sure is below its maximum dis-
charge pressure. First stage ejector
load consists of non-condensable
gas, condensable oil, and water
0.0%
Percent change in heater fired duty
-0.5%
-1.0%
-1.5%
-2.0%
-2.5%
-3.0%
1 2
Figure 8 Vacuum heater firing reduction
60 PTQ Q3 2021
q3 pcs.indd 60
2 crude stripping stages –
2 ejectors in operation
3 ejectors in operation
1 crude stripping stage –
3 ejectors in operation
2000 3000 4000 5000 6000 7000
Equivalent water vapour load @ 70˚F (lb/hr)
vapour. Non-condensable gas is
the summation of cracked gas gen-
erated in the vacuum heater and
bottoms liquid pool and any air
leakage in the system. Condensable
oil consists of 300-700°F (150-370°C)
boiling range hydrocarbons present
in the vacuum unit feed that are not
condensed at the tower top operat-
ing temperature. Water vapour is
composed of coil steam, stripping
steam and a minor amount of water
that comes in equilibrium with the
reduced crude.
Typically, water vapour repre-
sents the largest first stage ejec-
tor load in a ‘wet’ unit. However,
a poorly performing crude tower
stripping section increases the
300-700°F boiling range hydrocar-
bons in the atmospheric bottoms.
Consequently, the first stage ejector
load increases and raises the vac-
uum tower pressure with it.
3 design that PCS recently com-
Number of theoretical stages
The first stage ejector perfor-
mance curve in Figure 7 illustrates
how improving the crude tower
stripping section impacts ejector
system and vacuum tower oper-
ation. The red operating point
marks the equivalent water vapour
load to each of three ejectors, all
operating in parallel and with one
theoretical stage of crude tower
stripping. The red operating point
is at 10.0 mmHgA suction pres-
sure. Improving crude tower strip-
the condensable hydrocarbon rate
in the vacuum overhead vapour
by 60%, at the same vacuum tower
top temperature. When refinery
economics do not favour maxi-
mum vacuum gasoil cut point,
this reduction in first ejector load
allows the refiner to shut down the
motive steam to one of the ejectors,
leaving two operating in parallel.
The new equivalent water vapour
load to each operating ejector is
represented by the green point and
results in a suction pressure of 11.4
mmHgA, which increases vacuum
residue yield by less than 0.2 vol%
on crude.
Shutting down one of the first
stage ejectors reduces motive
steam usage by a third and results
in annual savings of $175 000.
Conversely, when economics favour
maximum gasoil cut point, the
refiner has the ability to maintain
the three parallel ejectors in oper-
ation and reduce suction pressure
to 8.0 mmHgA, represented by
the blue point on the performance
curve. This case demonstrates how
improved atmospheric residue
stripping can improve vacuum
tower operation.
Case 3: Vacuum tower stripping
impact on vacuum heater firing
In some refineries, standalone vac-
uum units process long residue
from storage tanks via a simple
train of preheat exchangers. In such
cases, vacuum heater firing can be
directly reduced by stripping sec-
tion improvements. The curve in
Figure 8 is based on a grassroots
pleted and is in operation in Asia.
It correlates reduction in vacuum
heater fired duty to number of
www.digitalrefining.com
11/06/2021 15:43
 theoretical stages in the stripping
section and is based on a 21°API
long residue charge at a constant
ratio of stripping steam per barrel
of vacuum residue, and constant
HVGO cut point of 1025°F (550°C).
The curve also accounts for the
effects on recovery of heat in the
preheat exchangers and the result-
ing heater   inlet temperature. The
vacuum unit was designed for a
heater outlet temperature of about
785°F (420°C) and tower pressure of
20 mmHgA.
For a standalone VDU processing
100 000 b/d long residue charge,
improving the vacuum tower strip-
ping section from one to two the-
oretical stages reduces vacuum
heater firing by 7.5 MMBtu/h. At
a fuel value of $4.00/MMBtu, this
translates to annual fuel savings of
approximately $240 000. The corre-
sponding reduction in CO2 emissions
is roughly 3400 t/y based on a typi-
cal refinery fuel gas composition.
The performance of a vacuum
stripping section also critically
impacts the vacuum unit’s reliabil-
ity. In this example, consider the
www.digitalrefining.com
q3 pcs.indd 61
effect of ‘wet’ steam blowing up the
stripping trays such that the num-
ber of equivalent theoretical stages
drops from two to zero. Vacuum
heater fired duty increases by 10.5
MMBtu/h and the outlet temper-
ature must be raised by 10°F to
compensate for less vapour strip-
out and maintain gasoil cut point.
The resulting vacuum heater out-
let temperature reaches approxi-
mately 795°F (425°C), making the
vacuum heater and vacuum tower
wash zone more prone to coking
and requiring careful monitoring of
heater tubes and wash bed packing.
Conclusion
Stripping section trays comprise
an important aspect of crude and
vacuum unit performance. They
affect diesel as well as atmospheric
and vacuum gasoil yields, energy
usage, and unit reliability. All too
often little attention is paid to strip-
ping tray details, which can result
in lost opportunities if they are not
designed well. Through the skilful
application of process, hydraulic,
and mechanical design features,
stripping trays present refiners with
a cost effective and flexible way to
improve energy efficiency, reduce
greenhouse gases emissions, and
improve product yields.
References
1 Barletta T et al, Crude unit revamp increases
diesel yield, PTQ, Spring 2000, 45-51.
2 Golden S W, Martin G R, Controlling
vanadium from high metals crude oils, 1995
NPRA Annual Meeting, Paper AM-95-18.
3 Hanson D W et al, Low-capital crude unit
revamp increases product yield, Oil & Gas
Journal, Mar 24 2003, 65-70.
4 Erasmus N M, Barletta T, Crude unit start-
ups: results of high liquid level, PTQ Revamps &
Operations, Autumn 2003, 38-40.
Edward Hartman is a process engineer with
Process Consulting Services Inc, in Houston, TX,
USA. He specialises in distillation equipment
design, leading studies and design packages for
new and revamped refinery units.
Email: ehartman@revamps.com
Bryan White is a Chemical Engineer with
Process Consulting Services, Inc. in Houston,
Texas. Process Consulting Services provides
grassroots and revamp front-end process
engineering to the refinery industry worldwide.
Mr. White has more than 30 years of experience
working in 75 different refineries across the
globe, with a focus on crude and vacuum units.
PTQ Q3 2021 61
14/06/2021 13:57
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 Don’t let furnace emissions derail your
expansion project
Predicting emissions prior to actual furnace design is not just a mathematical calculation
SHILPA SINGH and ANKUR JAIN
Engineers India Limited
I
ndia’s national Ministry of
Environment, Forest and Climate
Change (MoEFCC) promulgated
an environmental impact assessment
(EIA) notification, making environ-
mental clearance mandatory under
the Environmental (Protection) Act
1986 for expansion or modernisation
of an existing industrial set-up or for
setting up new projects. Hence, to set
up a new oil refinery or to revamp
an existing refinery for capacity
expansion, and so on, environmen-
tal clearance is required to ensure
that emissions from the industrial
installation remain within permis-
sible limits. For the energy intensive
hydrocarbon processing industry,
fuel firing is a necessary evil which
cannot be done away with com-
pletely. Hence, every effort is made
to maximise the heating potential
of all fuels being burnt. If allowed
to go uncontrolled, their emissions
can create havoc for flora, fauna and
habitation in and around the refinery
complex. Over the years, emissions
norms have been made more and
more stringent in order to minimise
impact on the environment and cli-
mate. This article explores various
means for optimising gaseous emis-
sions from fuel fired refinery fur-
naces. The article addresses the topic
from an Indian perspective, although
the strategies can be extended to any
other scenario’s or country’s specific
guidelines.
Regulations restricting furnace
stack gaseous emissions fall into two
categories. The first is the maximum
concentration limit of pollutants like
SOx, NOx, and CO in the flue gas
discharged from individual stacks.
Limiting values for these pollutants
as per the MoEFCC notification are
shown in Table 1.
The second regulation limits the
www.digitalrefining.com
q3 EIL.indd 63
Limiting emissions values from refinery fired heater stacks
S. No. Parameter Maximum emission limit Maximum emission limit
concentration (mg/Nm3) concentration (mg/Nm3)
in existing plants in new plants/expansions
(corrected to 3% O2) (corrected to 3% O2)
1 SOx oil firing 1700 850
2 SOx gas firing 50 50
3 NOx oil firing 450 350
4 NOx gas firing 350 250
5 CO oil firing 200 150
6 CO gas firing 150 100
7 Particulate matter oil firing 100 50
8 Particulate matter gas firing 10 5
Table 1
total allowable quantity of each allocated for the overall complex on
pollutant emitted from a complex account of significant augmentation
undergoing revamp or installation. of capacity.
The total allowable value is provided Predicting emissions prior to actual
by the authority concerned on a case furnace design is not just a mathe-
to case basis after due review of mul- matical calculation. A consultant’s
tiple factors including the effects past experience brings a lot of value
of pollution on people living in the through optimisation and revisit-
vicinity. Accordingly, the maximum ing critical design aspects at the unit
allowable limit may be lower near conceptualisation stage, helping to
densely populated cities, whereas achieve the desired emissions as well
in a sparsely populated coastal area, as optimum engineering. This arti-
where there is less risk to humans, cle discusses a number of strategies
higher values may be allowed. including process duty optimisa-
Within the same location or plant, tion, heat recovery, alternative fuels,
the current allowable limit is much burner replacement, and so on, in
lower than might have been allowed an expansion revamp or in a grass-
10 years ago. Meeting the total allow- root refinery project. Through these,
able limit requirement for a complex a reduction in emissions can be real-
is critical. Even if the concentrations ised for environment clearance and
of pollutants in individual stacks as compliance with statutory require-
per Table 1 are met, it may be that the ments. The special point about the
total quantity or flow rate of pollut- strategies discussed here is the ‘least
ants will exceed the allowable limit investment’ nature of the ideas com-
O P T I M I S AT I O N OF EMISSIONS
PROCESS DUTY HEAT RECOVERY TYPE OF FUEL BURNER
Figure 1 Strategies for optimisation of emissions
PTQ Q3 2021 63
11/06/2021 15:47
 furnace design duty will also project
Configuration and emissions details of a refinery, base case
an inflated figure.
For example, it is quite often
S. No. No. of Type Total absorbed Fuel type Fired duty, SOx, NOx,
heaters duty, MM kcal/h MM kcal/h kg/h kg/h (*) observed that the heater design duty
1. 3 Balanced draft 60 Fuel oil 68.1 69.6 45.2 quoted by the unit licensor is twice
2. 4 Natural draft 48 Fuel oil 58.6 59.8 38.8 that required for all normal operating
3. 3 Natural draft 18 Fuel gas 21.4 1.9 10.7 scenarios. Because of this variation in
Total 10 126 148.1 131.3 94.7
normal operating and design duty,
*NOx emissions are reported considering conventional burners with 450 mg/Nm3 achievable NOx in the the firebox temperature for normal
existing facility. The case study presented here is developed solely for illustration purposes.
Not to be correlated with any particular case or any real installation. duty sometimes falls below the API
recommended value for safe oper-
Table 2 ation since, at lower temperatures,
emissions like CO tend to increase
pared with capital intensive routes NOx is required to be limited to 45.3 beyond allowable limits. At times,
such as DeNOx or DeSOx systems. kg/h to meet a 140 kg/h total limit. it emerges that the substantial duty
In other words, these ‘low hanging To comply with these targets, it of an upstream exchanger is added
fruit’ strategies may be explored first is evident that replicating the exist- as an over-design margin in heater
before opting for capital intensive ing configuration will not suffice. duty, taking into account non-avail-
equipment. Therefore thought has to be put into ability of the exchanger. For such
For a fair understanding of the reducing emissions significantly. instances, after detailed deliberation
strategies shown in Figure 1, a step- With this aim in mind, the following of furnace optimisation and safety,
wise approach is taken with the aid avenues were explored for the addi- the licensor may be required to prune
of a case study of a typical refinery, tional capacity. additional over-design built into the
operating for 15 years, with the mul- furnace design duty, bringing it closer
tiple heaters described in Table 2. Can you further optimise furnace to normal requirements. This results
An expansion is planned for the absorbed duty? in optimisation of fired duty along
refinery to add 100% additional The first critical step in estimating with a welcome reduction in overall
capacity with a similar configuration emissions is finalisation of the fired installation cost and improvements
of units/heaters. Hence after revamp duty of the new heaters. Fired duty in operating parameters like bridge
pollution is expected to double: total depends on the process requirements wall temperature and tube metal tem-
SOx will be 262.6 kg/h and NOx will and efficiency of the system. Exact perature. Corresponding emissions
be 189.4 kg/h. process data may not be available at are also reduced significantly. Thus,
But in view of stringent pollution such an early stage of project concep- selection of furnace duty and its oper-
norms, similar emission limits may tualisation. At this point, past expe- ating range can play a crucial role.
not be permitted by the regulatory rience comes in handy in making Applying a similar strategy for the
authority. initial estimates of process loads. Due case study, reducing unnecessary
Typically, the allowable emissions corrections become necessary as soon margins after due evaluation of pro-
cap for a new refinery is approxi- as the licensor’s/designer’s data is cess requirements, heater duties are
mately half of what was allowed made available. A fundamental step revised according to Table 3. For ease
a few decades back. Therefore it is is to check carefully the process duty of understanding, only new revamp
assumed for the case study that the requirement as unnecessary margins duties corresponding to a 100%
total allowed value of SOx for the for an infrequent operating scenario capacity increment are shown here.
combined revamp capacity (100% may add up in firing duty, with a Thus, with the use of a duty opti-
original capcity + 100% new capac- corresponding increase in emissions. misation exercise, there is a 10.3%
ity) is 200 kg/h and the allowable This is quite common in hydropro- reduction in fired duty for new
NOx value is 140 kg/h. To arrive at cessing units where the furnace’s capacity furnaces with respect to
a limiting value of 200 kg/hr, SOx actual operating duty is considerably existing duty, with a corresponding
emissions from the new capacity less compared to the furnace design reduction in SOx and NOx values.
must be limited to 68.7 kg/h and duty. Thus emissions worked out for
Does additional investment in the
Optimised duties with corresponding emissions for a new facility form of residual heat recovery suit
the optimisation case?
S. No. No. of Type Total absorbed Fuel type Fired duty, SOx, NOx, For a given process, total firing
heaters duty, MM kcal/h MM kcal/h kg/h kg/h (*) requirement depends on the fuel effi-
1. 3 Balanced draft 54 Fuel oil 60 61.4 30.9
ciency of the system. For a less effi-
2. 4 Natural draft 43 Fuel oil 52.4 53.5 26.9
3. 3 Natural draft 16 Fuel gas 19.1 1.7 6.8 cient heater, the corresponding firing
Total 10 113 131.5 118 65.3 requirement will increase, resulting
in higher emissions. A heater may
* NOx emissions are reported considering low NOx burners in the new facility with limiting NOx emission as
350 mg/Nm3 for fuel oil firing and 250 mg/Nm3 for gas firing.
be designed as natural draft, forced
draft or balanced draft. A balanced
Table 3 draft system with an air preheater

64 PTQ Q3 2021 www.digitalrefining.com

q3 EIL.indd 64 11/06/2021 15:47

 provides higher efficiency than a nat-
ural draft system because of recovery
of waste heat. In a balanced draft sys-
tem, flue gas exiting the convection
section is passed through an air pre-
heater to transfer the residual heat
of flue gas to air. An induced draft
fan is provided to induce flue gas
into the air preheater and then to the
stack. Forced draft fans send atmos-
pheric air to the preheater.
A decision on whether a balanced
draft system is feasible depends on
multiple parameters like total fired
duty, process inlet/outlet condi-
tions, and type of fluid handled.
Sometimes, because of very low
duty and low heat recovery poten-
tial, installation of a balanced draft
system needing an elaborate set of
equipment may not be economically
feasible.
In the case of multiple low duty
heaters in a unit, the possibility of a
common APH/heat recovery system
may need to be evaluated based on
operating scenario and other process
considerations decided by the licen-
sor and unit designer. In the current
case study, the possibility of combin-
ing natural draft heaters to install a
common balanced draft system was
evaluated. After careful optimisation,
three heaters from S. No. 2 and two
heaters from S. No. 3 (see Table 3)
were converted from natural draft to
balanced draft mode. The remaining
heater from S. No. 2, and from S. No.
3, were not changed to balanced draft
due to the typical location/proximity
constraints usually encountered in
refinery furnace installations.
Revised emissions considering combination firing in heaters
S. No. of Type Total absorbed Fuel Fired duty, SOx, NOx,
No. heaters duty, MM kcal/h type MM kcal/h kg/h kg/h
After After After After
heat comb. heat comb.
recovery firing recovery firing
1. 6 Balanced draft 89 Fuel oil+ 97.8 101.1 54.3 50.8 42.5
Fuel gas (50:50)
2. 1 Natural draft (*) 8 Fuel oil + 9.7 9.9 5.4 4.9 4.2
Fuel gas (50:50)
3. 2 Balanced draft 10 Fuel gas 10.8 0.96 0.96 3.9 3.9
4. 1 Natural draft (*) 6 Fuel gas 7.1 0.63 0.63 2.5 2.5
Total 10 113 125.4 112.6 61.3 62.1 53.1
*No heat recovery provision available for these furnaces due to proximity or location constraints. Total
SOx emissions are reduced to 61.3 kg/h. However, a revised NOx value of 53.1 kg/h is still higher than the
allowable value of 45.3 kg/h.
Table 4
Through this exercise of combin- product in oil refineries, fuel oil was
ing natural draft heaters to convert abundantly available. Hence, most
them to balanced draft, fired duty refinery installations were designed
reduced to 125.4 MM kcal/h from with fuel oil firing, typically with a
131.5 MM kcal/h, so a 4.6% reduc- sulphur content as high as 5 wt%.
tion in fired duty is achieved with a Regulations have limited the maxi-
corresponding reduction in pollut- mum permitted sulphur in fuel oil
ants (see Table 4). to 0.5 wt% for new refineries. With
this lower sulphur level in fuel oil,
Fuel oil or fuel gas: rise above the SOx emissions have reduced, but
dilemma this may not be enough in view of
The type and composition of fuel for stringent total emission limits. For
firing is another important parameter further reduction of total SOx emis-
that needs attention while optimising sions, combination firing or fuel gas-
emissions. The main pollutants emit- only firing may need to be adopted,
ted from a heater stack are SOx and depending upon the target value.
NOx. While SOx emissions depend Availability of cleaner fuel like fuel
directly on the sulphur content of gas has increased over time due
fuel, NOx depends on the nitrogen to the adoption of technologies for
content of fuel as well as on thermal processing heavy residues like resi-
NOx resulting from combustion. due upgrading units. This has made
A heater may be designed with combination firing a good option,
burners firing either gas fuel or fuel although fuel oil firing is still not
oil. In the past, when there was less completely out of the picture due to
processing of bottom of the barrel its lower price.

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q3 EIL.indd 65 11/06/2021 15:47

 Ultra-low NOx: next generation
500 burners
>450
NOx emission in mg/Nm3 450 As Figure 2 shows, burners can vary
400
350 widely with respect to NOx emission
350
figures. For example, conventional oil
300
250
250 fired burners installed under the ear-
200 lier regime of emissions limits may
150
150
emit higher than 450 mg/Nm3 of NOx,
100 high compared to the latest standards.
50 More advanced low NOx burners
0
Conventional burners Low NOx oil Low NOx gas Ultra low NOx gas
employ a number of fuel and air stag-
with oil firing fired burners fired burners fired burners ing strategies and thus can reduce the
NOx emission level to 350 mg/Nm3
Figure 2 Generations of burners for oil firing and 250 mg/Nm3 for gas
firing. Further, ultra-low NOx fuel gas
Revised emissions with ultra-low NOx burners for fuel gas fired furnaces fired burners have evolved in recent
years. They can achieve very low NOx
S. No. No. of Type Total absorbed Fuel type Fired duty, SOx, NOx, emission levels in the order of 100-150
heaters duty, MM kcal/h MM kcal/h kg/h kg/h mg/Nm3. These burners are designed
1. (a) 5 Balanced draft 74 Fuel oil+ 81.3 45.1 35.3
to minimise flame temperature
Fuel gas (50:50)
(b) 1 Balanced draft 15 Fuel gas 16.2 1.4 3.4 through staging of air and/or fuel, as
2. 1 Natural draft 8 Fuel gas 9.5 0.8 2.0 well as internal circulation of flue gas
3. 2 Balanced draft 10 Fuel gas 10.8 0.96 5.7 to minimise NOx.
4. 1 Natural draft 6 Fuel gas 7.1 0.63 1.5
As ultra-low NOx technology
Total 10 113 124.9 48.9 44.5
applies to gas fired burners only, one
Table 5 fired heater of 15 MM kcal/h duty
out of the six mentioned in S. No. 1
To achieve NOx emissions to Table 4). SOx emissions are sig- in Table 4 is changed from combina-
MoEFCC guidelines in the fuel oil nificantly reduced to 65.8 kg/h, tion firing to fuel gas firing (balanced
firing case, the nitrogen content of and are within the allowable value draft), reflected in S.No. 1(b) in Table
fuel oil also has to be limited. A typ- of 68.7 kg/h. The NOx value is 5. In addition, the natural draft heater
ical nitrogen content of 1000-1300 reduced to 53.8 kg/h, but it is still mentioned in S. No. 2 in Table 4 is
wtppm may be allowed in fuel oil higher than the allowable value of changed from combination firing to
to meet NOx concentration limits 45.3 kg/h. 100% fuel gas firing.
in the stack (see Table 1), depend- For further NOx reduction, one Using ultra-low NOx burners for all
ing on confirmation from the burner remaining natural draft heater out fuel gas fired furnaces, the resulting
vendor. A further reduction in NOx of four (see S.No. 2 in Table 3) is parameters are shown in Table 5.
can be achieved by adopting fuel changed to combination firing from In Table 5 it can be seen that NOx
gas firing with low/ultra-low NOx fuel oil firing. emissions for the new facility are
burners. The resulting parameters after reduced to 44.5 kg/h which is within
To continue with the study case, optimisation of heat recovery the allowable value of 45.3 kg/h.
fuel oil firing for balanced draft options and types of fuel are shown With a careful and well thought-out
furnaces is changed to combina- in Table 4. approach, emissions from the case
tion firing in a fired duty ratio of For further NOx reduction, an study project are brought within the
fuel gas:fuel oil of 50:50 as a first exercise involving advanced burner benchmarks needed to meet environ-
trial (see reflected in S. No. 1 in technology was explored. mental regulations. A comparison of
baseline data against optimised data
is shown in Figure 3.
250
NOx in Kg/hr, SOx in Kg/hr

Existing facility Combined overall refinery Conclusion

Fired duty in MMKcal/hr

200 New add-on facility Allowable figure

A major oil refinery project or a
brownfield expansion of any refin-
150
ery installation starts with obtaining
environmental approval, which can
100
be a major hurdle unless valuable
experience of strategies is employed.
50
Expertise in customising furnace
emissions to suit environmental stip-
0
Fired duty NOx SOx ulations can turn the table in favour
of the project even where there is very
Figure 3 Comparison of parameters little room to manoeuvre.

66 PTQ Q3 2021 www.digitalrefining.com

q3 EIL.indd 66 11/06/2021 15:47

 of
5. AMeasure
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approach, Thus, the the
focus heterogeneous catalyst in the previous
aisthree-day
analysing issues
References
oils
Such and
byproducts streams
iswell-controlled
heavy of which
crudes the can
cracking
often build
optimised
have reactionsup on
blending
alifetime,
high the
that acatalyst
operations
occur
viscosity, in and
high the
1 content
commercial
immediately
and
upcoming minimised coke unit formation.
after
requirements using
through start-up, Z-HD20.Over
use
for
Christensen P, Hearn A, Yeung T, The future for hydrocracking, part I, PTQ, whereas
of itsDeSOx
cleaning. technologies.
Predictive catalyst break-in
ana-may
Both
which exhibits
known
upstream
salt
experience result
content, to
maximise both
cause
in
reactor,
some high higher
a
deactivation.
the problem
while use
concentrations
sintering yield
ofof
all such
In
low
the
active and the as
cost
chlorides
of selectivity
sites. vibration
FCC unit
refinery
solidsThis in orthe
is for
in
a
one a
streams
feed
unstablemono-
typicalpump
of are
the nisms were ins
of For
period
lytics
Q4 2017. these a istechnologies
turns European
typically
a lagging refiner
required
are
indicator well operating
forproven,in situ
into a 300 indicator
sulphiding.
however
a leading t/hthey Atwo- typ-
have
and or borylated
convertedcompressor.
asphaltenes,
reasons catalyst
ensure why to the methane
poison
meeting Sonic
hydrochloric
high activity is
the
sulphur than
monitors
organic
of required
a acid.
levels,thecan
regenerated The homogeneous
vanadium be added
specifications
high reactions found
naphthenic
catalyst to are: the
iscatalyst.
in device
closest the
acid
signif- process safety.
stage
2 andicalallows
their
American timewith
own recycle
savings
operating
action
Petroleum to hydrocracker
comparison
be
Institute, costs
taken along between
before
Recommended withhaving
losses in situ
significant
Practice are a 932-B,
three-year
sulphiding
incurred. capital
Design,
to and Importantly,
the when
feed
limits vibration
stream. the team
Catalyst exceeds found a certain
fouling 6that in MOF
level,
aFigure
FCC UiO-67-Mix
alerts
has can
been be The system i
or
icantly
cycle,
and
costs.
The
Materials,high UltraCAT
Thus
finalmetals
restored
estimates
Fabrication, it (to
step iscontent.
after reduce
indicate
preactivation
always
is coke
adding
Operation, the
This removal.
that
prudent
andAI quality
causes
is orMACH
shown
to
Inspection explore
knowledge giveaway)
significant
Around intechnology
Guidelines other80-90%
based 1.
for are
problems
ideas of
could
ana-
Corrosion thethe
first
sentwithout to
caused advise iridium
by operators
organic+had no that
iron effect remedial
which on methane
can action
block borylation.
is the needed. and, because o
main
such
through
lytics
NH3 (g)+ ininstruments
as
hydrodesulphurisation
improve that low
the
effective
HCl can(g)desalting
bottom
→ generate
NH to4 Reactor
and increase
line
Cl efficiency
and
best by
(s)correct refinery
$10–20
utilisation because
hydrodenitrification
advice millionprofitability.
of ofper
commonly
taking uncontrolla-
incycle. allpores
activity ele-is
availa-
-
Control Hydroprocessing Effluent Air Cooler (REAC) Systems, Third
bleAIn-line The
Prescriptive
of
emulsions, theteam
blending catalyst
wateralso
analytics
(to carried
and when
a adds
product
salt out
the a new
carry-over detailed
level
tank, layer
becomes
ship,
or oiloptimisation
of or sophisti-
carry-un- very
pipe- oil supply and
typically
ble of
ments technologies
Edition, Jun 2019. of
Francis restored
thecatalytic
situation
Humblot, with
which a
and simple
canthen
New meetBusinesscokeregulatory
provide burn-off, clear
Developer, depending
requirements,
actions Arkema, to
cation the
high Hto S–(g)the
this often + reaction
methodology, depends conditions
moving on theare using
itspecific
from a UiO-67-
product in different mo
line),
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3 onwithout
NH into
how(g) when
+it.the
theopting
2This
all
desalter
commercialblending
→action for
NH effluent
4 such
components
(s)middle
Lin H, Lagad V, Evaluating ammonium chloride corrosion potential with
resolve HSmay capital water.
require distillate
intensive
human Vijaycatalyst
continuously
(without
infrastructure.
intervention Ni/V
-
Conclusion
Thiochemicals,
Mix-Ir
francis.humblot@arkema.com; Srinivas,
based to as the
a broader catalyst process by screening
based approach. several Indifferent
deliver- • High tempera
3
sourced
in
Shell
Such
or, Drawbacks
feed)
where
Principal designfrom
Catalysts
strategies theand
hydrotreating
Scientist, the
are and
process production
&processing
reduced reactor
water partial pressure, NACE International Conference and Expo, Paper No.
Technologies,
Arkema,ideas isUsing have
trusted, process.
units
throughput,
was
Thiochemicals been then and/or
operated
in collaboration
discussed
automated,
R&D, storage
increased
during in detail
vijay.srinivas@ tanks
its foul-
auto- life-
with in
ing C-H inert
prescriptive solvents. analytics, C
there D has as tothe be solvent
a recognition led to furnaces run pa
and
ing These
8960, 2017.
time.
Zeolyst,
this
matic and
2
High
article
arkema.com Sintering
simultaneously
has
maintenancereactions
corrosion,
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developedthe of passed
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demulsifier less
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When toon
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process ofoptimising
3.3% adds
Prescriptive
ammonium chloride corrosion in refineries, Corrosion, 2001, 67 (5). for furnace
large
analytics
duty
amount at
looks
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methane.
at
data
data system could s
over
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tion
mesopores
sulphide
stage
processing which
temperature
the
ishydrogen
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and controls
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oil/water catalyst. on
enable
activity
calculations, thewhere
options
defined
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the Any VGO heat
catalyst for
as
deviation the
and transfer
that blending
salt
surface,
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angle be leads
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procedure
a canaver-
reached,
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large also to
of
Conversely,
streams across when
these, the
and
6 Shargay C, Marciniec S, Analyzing water washing requirements for low common
pinpoints solvent
sophisticated tetrahydrofu- signa- ing three bitum
andpushed
rated
coke
heavier
should
be
amount an age
finished
easily
formationfeeds
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fromtoon
reviewed
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to adapt
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In
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3catalyst
Extra aoil 30-day
fat to the
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However, on unit
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period to does
salts
nameplate
it pro-
often can
with
and
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tures was
and employed,
patterns of 98%
data
severity hydroprocessing units, NACE International, Paper No. 04646, 2004. conversion
that are happening of the borylation
in advance duction lines, t
in
EOR form
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Refiners
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Similarly,
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However,
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ing
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Exchange Minutes, St. Louis, MO, 2019. ain
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products,
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dutyKPIs depropaniser/debutaniser
act
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where
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stable
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chlorides on refinery corrosion and fouling, NACE
impending >99%, turnover
failure
Its emulsion
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Treese S A, The origin and fate of chlorides in hydroprocessing units, PTQ,
consideration.
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tain
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Dimethyl
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and
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relief of
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contaminant more
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References structure
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products.
in
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refinery, of
hydrocarbon
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and
refineries
rate phase.
SOxand
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validation to
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emissions
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optimiseby
concomitant
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modelslevel themonitor-– is
amount
increase
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they work
streams, PTQ, Q3 2017.
the hydrogenation for catalyst
need toof understand
functionalised that the requirement
nitro-aromatics heaters.
most
1
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advantaged
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crudes. are
deactivation that
analyticswith
Recommended aThe can
class frequent
reducing
reductions and melt
of
in ability compounds
commercial
data
Practice by at
changes
related
to to
584,anyregener-
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ensure costs
stand-
practice,
Integrity to
of
for workers
is molecular
employed willtoevolve. Organisations and people(ani- will
the
high
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products
OperatingBelow
Catalysis
ard,
need
ator
refinery
issues.
without
system temperatures
iscrude
beyond
240°C,
Today 154, 2010, 256-263.
to retrain
weight,
considering
operating
Windows, First Edition, May 2014.themanufacture
oil
themselves.
diet and
ability anydamage
and/or
soluble
reduction
correctly. of inuse
major
aromatic
toluene or
conventional
reaction or‘import’
capital destroy
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Ben
The
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Elsevier ISBN 978-0-444-53556-6. pharmaceutical
Leviton is a process engineer with Fluor Canada Ltd. With eight years’
and on of will
gasoline
downstream drop.
complex industries.
into is
units. product
soluble Nitro-aromatic
in tanks
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difficult
flow rate
Nevertheless,
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Conclusion ofin or higher
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compounds consist of at least one nitro group (NO be2)
experience
3 Accelerated deactivation and upgrading
studies technologies,
of hydrotreating his primary
catalysts focus
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or
ics ships
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The
producing
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ultimate
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decision today
paraffins
dispersant
further in are in confirmed
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specification.many
reaction.
reductions
support non-solvent.
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in refineries.
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following
For are faster
refin- war-
on industry
process
attached
plant, Applied co-opetition’.
simulation
to
Catalysis an and relief
A,aromatic Thering.
analysis.
General 548, 2017, 114-121. opportunity
He holds
Typically, a BSc totheir
in seamlessly
engineering
hydro- the storage tan
From the
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Asphaltenes
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tensioactive point of can
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genation
Accelerated or
chemicals
elements
chemistry from Queen’s University. one
stricter
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industries.
required the to
value (diesel
have cap
Digitalisation
use
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higher cetane
applies.
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ciple
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Harry advantage
Z to companies asItwhich
Ha is a Technical Fellow, Process Technology with Fluor Canada
precious metals such platinum, recognise that and can the furnaces i
itpalladium, or for- rho-
long-term deactivation in a commercial plant, Catalysis Today 45, 1998,
blending
sion
injected of
characteristic
This metal
can the into
inin bethepassivation
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Ltd. He has over 30 years of experience in R&D in petrochemical industries,
take
319-325. dium. advantageOther researchers opportunity to build
reported that business changing alli- flowing throug
realise
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aromatics,
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droplets,
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properties, of areas
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targets for
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supported value
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Catalysis, 2019, 1-5.
nanoparticles to has done
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control
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the
University of Science and Technology and a PhD in chemical engineering
environmental approval, and
place. process
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liquid
without Na feed.
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Sulphiding
immediate in be the need CDU
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6 Decrease catalyst costs by regeneration, analysis and sorting, PTQ furnace outlet,
withdispersed consumer clusters goods shipping and
or single-atom delivery
catalytic sitessupply a
erable.
•oil desalters
matrix,
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After Thus,
reaction
from the University of Alberta.
ried
capital
focused out in
intensive
on are
the
two
identifying
Catalysis, 2012, Article no 1000352. can
taking
able with
yield
phases: betoasalts,
spending. optimised
of decision
minimise the molecule
premium
primary
exceptions by
and to
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and selecting
implement
fuels interaction
secondary. becomes
anomalies. through the most
direct
polar,
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chains, process manufacturers
iron oxide will
PtRodwell is Senior Director, Process Technology with Fluor Canada
catalyst with (FeOdo ) to react
support to market
resulted the required h
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Morgan
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selectivity diameter of the
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MACH
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analysis
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technology
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configuration, trouble-shooting, and project execution. He holds a BSc in
engineering from IIT Kanpur and a PhD in catalysis engineering from Delft and models
catalytic across
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Professional Engineer in the Provinces of Alberta and British Columbia.
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Email: shilpa@eil.co.in.is a Hydrotreating a
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Jain isand
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sal.torrisi@shell.com
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Fluor
achieve
experimental physics from the University of Leiden and a PhD in molecular
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Researcher
240°C.
US. With 38 years of experience in metallurgy, welding, corrosion control, of
withof dispute,
the
Shella
Maximising vanadium
system which
Catalysts & may
requires
DMDS passiva-
Technologies pose this
flowin
and meaningful
istroubleshooting
based in Amsterdam, ofand
physics from the University of Amsterdam, The Netherlands.
and fired compete
heater
Netherlands.systems, in 2019 he holds and abeyond. BTech degree from 50mm to
additional
Naphthenic
approach
rate tion
above programme
challenges.
as220°C, acids
well. can such
ascertaining affect
materials selection, and fabrication, she is active in NACE and API, with over
Email:
chemical
Duncan ouwerkerk@catalyst-intelligence.com
engineering
Micklem is from
Executive SDCET, Vice as
India. Nalco
President,emulsion
Email:a MVP.
controlled stability
ankur.jain@eil.co.in
Strategy and exothermeither
Marketing
Email: johan.den-breejen@shell.com
70 publications in her field.
with www.eptq.com
KBC (A Yokogawa Company).
www.eptq.com 88 PTQ Q2 2019 PTQ Q1 2019 13
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Catalysis
Catalysis Q2
2019
2021
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q4 argonne.indd 3 14/09/2018 09:35

outlook .indd 7 q2 tupras.indd 2 17/12/2018 13:12

Q&A
q4
cat Q&A
Q&A copy
copy
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fluor.indd
Q8.indd
Q&A 37.indd
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copy 37.indd
37
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27 copy 13
376 (original)
44(original) copy 8.indd
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12copy.indd 13 13/12/2019
13/09/2019
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14/09/2020
15/03/2021 17:46
17:28 11:53
10:56
12:08
16/03/2020
23/02/2021 11:59
16:28
q3q3
cat EIL.indd
shell.indd
kbc.indd 67
6 11/06/2021
24/02/2020
15/06/2019 15:47
12:13
07:36
 ----A---WORLD---LeADeR---
-------in---suLphuR�
----------pROcessing----------
�AnD---hAnDLing-----
End-to-end systems from receipt of molten sulphur to loading
of solid material – single source supply by IPCO.

• Premium Rotoform pastillation.

• Duplex steel belts specifically alloyed to resist corrosion.
• High capacity drum granulation.
• Downstream storage – silo and open/closed stockpiles.
• Custom-built reclaimers for any location.
• Truck, rail and ship loading and bagging systems.
• Large scale block pouring.

ipco.com/sulphur

IPCO_Sulphur_ad_210x297.indd
ipco.indd 1 1 02/12/2020 13:58
11/06/2021 16:10
 Sulphidation corrosion in a Claus waste
heat boiler
Simulation enabled a refiner to avoid potentially dangerous operating conditions in a
sulphur recovery unit
SIMON WEILAND and NATHAN HATCHER
Optimized Gas Treating, Inc.
S
ulphidation corrosion and ther-
mal cycling in Claus waste
heat boilers (WHB) are the
two leading causes of unexpected
failures that result in unscheduled
shutdowns of sulphur recovery
units (SRU). Sulphidation corrosion
is caused by two main factors: high
temperatures, typically exceeding
650°F (343°C), and hydrogen sul-
phide (H2S). Hot hydrogen sulphide
is prevalent in an SRU, especially
at the front end where the thermal
reactor (originally called a reac-
tion furnace) and WHB operate.
Refractory lining is used as protec-
tion wherever metal surfaces may
see high temperatures and H2S.
Other special protection measures
are put in place in the front end of
the WHB in the form of ceramic fer-
rules to protect the tube-to-tubesheet
transition joint as well as the first
6–12 inches of heat transfer tubing.
It is in this region of the WHB where
most failures occur.
Although metal temperature and
H2S concentration are the two basic
factors that go into determining the
ADA valve
MULT
Oxygen
Air
intake
Claus air
blower
Ejector steam
Sour water
acid gas
Amine acid gas
& TGU recycle
Figure 1 SRU configuration
www.digitalrefining.com
q3 OGT.indd 1
rate of sulphidation corrosion, tube
metal temperature itself is influ-
enced by several parameters. In a
WHB, one of these factors is the heat
flux. Heat flux is the rate at which
heat is exchanged from the hot pro-
cess gas through the tube wall to the
cool utility water/steam. The faster
that heat is transferred through the
tube walls, the hotter the tube walls
become, making it a vital considera-
tion when designing a WHB or when
managing changes in an SRU’s oper-
ating conditions. Oxygen enrichment
also can have a profound effect on
heat flux and capsize a border-line
issue into a catastrophic failure.
Sulphidic corrosion is generally
calculated based on the widely
accepted Couper-Gorman curves1
which, at least for high heat fluxes,
have been very closely confirmed
by measurements made by Alberta
Sulphur Research Limited (ASRL)
for carbon steel. Couper-Gorman
curves are also available for a vari-
ety of chromium-containing met-
allurgies and are generally used to
assess corrosion in systems contain-
S
Air demand analyser control
Rh 1
RF zone 1
RF zone 2 WHB WHB
pass 1 pass 2
Cv 1
Cd 1
ing H2 and H2S. Claus WHBs are
typical examples of such systems.
The curves were created based on
an industry survey conducted by the
National Association of Corrosion
Engineers (NACE) Committee T-8.
An excellent NACE article2 summa-
rises much of what is known about
the corrosion of carbon steels and
higher metallurgies in this context.
The Couper-Gorman curves were
modified downwards by a factor of
between two and three by Martens3
based solely on anecdotal evidence
but the original curves have been
validated by the already-cited ASRL
work.
Case study
A North American refinery was
considering adding oxygen enrich-
ment to the Claus unit in an effort
to increase capacity. Using oxygen
enrichment in an SRU can be a sim-
ple and inexpensive way to squeeze
more hydraulic capacity through a
plant without requiring a huge capi-
tal expenditure. This is achieved by
increasing the oxygen content of the
Rh 2 Rh 3
Tail gas
Cv 2 Cv 3
Cd 2 Cd 3 Cd 4
Thermal Sulphur
Total
Sulphur
PTQ Q3 2021 69
11/06/2021 15:49
 perature of 650°F (345°C). The blue
750 line in Figure 3 shows the sulphida-
28% Oxygen
tion corrosion rate in the first pass
700 of this WHB for this air-only base
Tube wall temperature, ˚F

650
600
550
500
0 5
Cumulative tube length, ft
Figure 2 Tube wall temperature in WHB Pass 1
air, which replaces the diluent nitro-
gen that otherwise simply takes up
volume. Oxygen enrichment has been
successfully practised for many years,
but there is an increased tendency
for failures caused by the resulting
higher operating temperatures.
Figure 1 shows the facility as a
typical three conversion stage SRU
with a front-side split design on
the thermal reactor, and a two-
pass WHB. In addition to amine
acid gas (AAG), this plant pro-
cesses sour water acid gas (SWAG)
with high ammonia content. As
designed, the SRU operates on air
only. Consideration is being given
to upgrading to low level oxygen
enrichment (up to 28% oxygen).
The WHB steam generation pres-
sure in this plant operates with a
somewhat elevated pressure of 657
psig (45.3 barg). Normally, WHBs
are designed to operate somewhere
between 300 and 600 psig (20-40
barg). This will be important later in
the discussion.
35
Sulphidation corrosion rate, m/y
Air only
10 15 20
To gain a better understanding of
how oxygen enrichment will affect
the SRU and to reveal any possible
pitfalls, the unit’s present operating
conditions were used in a simula-
tion model of the facility using the
SulphurPro simulator. The cor-
rosion calculations are built into
SulphurPro and are based on carbon
steel tube metallurgy using recent
research data from ASRL and the
Couper-Gorman plots reduced to
correlations. The model provided
a good picture of the heat transfer
characteristics along with an esti-
mate of the present corrosion rate
in the WHB. The blue line in Figure
2 shows the tube wall tempera-
ture through the first pass of the
WHB under current air-only base
conditions.
The front of the WHB (Pass 1) is
where the tube wall temperature
(and the heat flux) are highest. The
tube wall temperature is slightly
elevated at just over the recom-
mended maximum tube wall tem-
case. The peak corrosion rate is just
over 21 mils per year (m/y) based
on the Couper-Gorman corrosion
curves. It is a bit alarming that, on
air-only operations, the peak corro-
sion rate is already twice the recom-
mended limit of 10 m/y where most
of the last 20 feet of tubing hovers.
Returning to the steam generation
25
pressure of just over 657 psig, the
higher the steam generation pres-
sure, the higher the heat flux needs
to be to meet that demand. A higher
heat flux will necessitate a higher
tube wall temperature and cause the
corrosion rate to increase.
With the base case understood,
oxygen enrichment was added to
the simulation and the acid gas rates
adjusted to keep the same overall
hydraulic throughput in the unit.
The red lines in Figures 2 and 3 cor-
respond to enrichment to 28% oxy-
gen. The tube wall temperature has
increased to over 700°F (370°C) at the
inlet and the sulphidic corrosion rate
is just over 29 m/y. Although that
may not sound like a big increase, it
is 50% higher than the base-case air-
only operation.
This particular plant was already
operating with a higher than normal
WHB steam generation pressure,
causing the tube wall temperatures
to be in the ‘caution’ region at just
over 650°F. This resulted in a much
higher than advisable corrosion
rate of over 21 m/y when operating
on air only. Even low level oxygen
enrichment compounds the prob-
lems already present, increasing the
corrosion rate to over 30 m/y (by
more than 50%), thereby reducing
the life expectancy of the WHB tubes

30 28% Oxygen
Air only even further. Increased sulphidic
25 corrosion stems in part from the
20 unusually high utility-side pressure
causing higher tube temperatures,
15 and in part from higher tempera-
tures consequent to using oxygen
10
enriched air. The effect of utility-side
5 pressure is instructive.
Figures 4 and 5 show boiler tube
0
0 5 10 15 20 25 temperatures and sulphidic corro-
Cumulative tube length, ft sion rates when using 28% oxygen
enriched air and utility-side pres-
Figure 3 Sulphidation corrosion in WHB Pass 1 – base case air only sures of 150, 300, 600 and 657 psig

70 PTQ Q3 2021 www.digitalrefining.com

q3 OGT.indd 2 11/06/2021 15:49

 (current operating pressure). At the
tube-to-tubesheet joint where tem-
peratures and therefore corrosion
rates are highest, the predicted cor-
rosion rate increases from about 12
m/y to above 30 m/y over that range
of pressures. The increase with pres-
sure is slightly sub-linear but is none-
theless quite substantial and explains
why WHB failures have become
more commonplace with high pres-
sure steam generation, especially
when using oxygen enrichment.
An interesting learning is that
even with a very modest level of
oxygen enrichment and quite a low
utility-side pressure it is possible for
a WHB to show concerning levels
of sulphidic corrosion at and near
the tubesheet end of the boiler. This
suggests that when considering oxy-
gen enrichment there must be careful
attention given to the possibility for
elevated corrosion. Furthermore, it
may not be enough just to lower the
steam generation pressure to com-
pensate. Oxygen enrichment can
be a risky undertaking demanding
assessment of multiple unforeseen
consequences. There is no substitute
for a well-founded SRU simulation
tool with high reliability that takes
fully into account all the fundamen-
tals of radiative and convective heat
transfer, process chemistry, and the
kinetics of all the reactions.
Conclusion
The corrosion prediction feature
in SulphurPro uses state-of-the-art
research results and allows areas of
the plant that cannot be monitored
easily with instrumentation to be
much better understood. In this par-
ticular plant, the real limitation may
have been the original WHB design
and the choice of steam generation
pressure. With the WHB rating fea-
ture in SulphurPro, a what-if anal-
ysis such as the one just described
can be conducted to help engineer
out a previously hidden problem.
Indeed, because corrosion in this
kind of equipment cannot be readily
seen until the equipment itself under-
goes multimillion dollar failure and
remains offline maybe for months
while a new WHB is fabricated, the
ability to identify and predict dan-
gerous operating conditions has
enormous economic value. For a cost
www.digitalrefining.com
q3 OGT.indd 3
750
700
Tube wall temperature, ˚F
650
600
550
500
450
400
0 5
Cumulative tube length, ft
Figure 4 Tube wall temperatures at various WHB steam pressures
35
Sulphidation corrosion rate, m/y
30
25
20
15
10
5
0
0 5
Cumulative tube length, ft
Figure 5 Sulphidic corrosion rates depend on WHB utility-side pressure
far less than would be needed to hire
an expert to evaluate the system, the
operator of this plant licensed a sim-
ulation tool to identify a previously
hidden problem, and to determine
the corrosion consequences of the
proposed oxygen enrichment pro-
gram, not only today but into the
future.
To get an idea of limitations on
equipment life in a sulphur plant
from sulphidic corrosion, operating
companies usually resort to either
(a) doing nothing and waiting for
the equipment to fail or (b) paying a
consultant or engineering company
a high price to conduct a study, get
the results once and wait until they
have to repeat the exercise the next
time they need to assess the conse-
quences of further changes to plant
conditions. A third economical alter-
native is (c) to pay a licence fee for
the SulphurPro simulator and for the
small amount of time to set up the
150 psig
300 psig
600 psig
657 psig
10 15 20 25
150 psig
300 psig
600 psig
657 psig
10 15 20 25
model then use the model whenever
process changes are contemplated.
References
1 Couper A S, Gorman J W, Computer
correlations to estimate high temperature
H2S corrosion in refinery streams, Materials
Protection and Performance 10(1) 31-37, 1971.
2 NACE Technical Committee Reports,
Overview of Sulphidic Corrosion in Petroleum
Refining, Item No. 24222, NACE International
Publication 34103, 2004.
3 Martens D H, Tube and tube weld corrosion
and tube collapse, Brimstone Conference, Vail,
CO, 12-16 Sept 2011.
Simon Weiland is a Technical Applications
Engineer with OGT, responsible for key
accounts, employee and customer training,
and workshops. He holds a BS in chemical
Engineering with a minor in German from the
University of Oklahoma.
Nate Hatcher is an Engineering Consultant
with OGT following several years as Director
of Technical Development. He holds a BS in
chemical engineering from the University
of Kansas and is currently a member of the
industry Amine Best Practices Group.
Email: Nathan.Hatcher@ogtrt.com
PTQ Q3 2021 71
14/06/2021 13:59
 WWW.ZWICK-ARMATUREN.DE

H2-Re
ady!

TRI-CON
SERIES FOR H2
APPLICATIONS

zwick.indd 1 12/03/2021 12:51

 Recovering silicon poisoned catalyst
Silicon poisoning usually spells the end for hydrotreating catalysts, but a rejuvenation
process can extend the effective life of silicon trap catalysts

PATRICIA PEREZ-ROMO and LUIS M RODRIGUEZ OTAL

Mexican Petroleum Institute

I
n recent years, the oil refining
industry has been character- CH3 CH3 CH3 CH3
ised by an increase in crude oil (CH3)3Si O Si O Si Si O Si O Si(CH3)3
demand, the need to increase con-
version of barrel bottoms into val- CH3 CH3 CH3 CH3
uable hydrocarbon streams like Polydimethysiloxane

naphtha, jet fuel and diesel, and

tighter control of contaminants in
products. Therefore an important
increase in residue conversion tech-
nologies, both thermal and catalytic,
such as hydrocracking, mild hydro-
cracking, visbreaking and coking of
vacuum residue, has been observed.
In the last 20 years, adoption of
thermal processes has expanded
significantly, particularly coking
processes including delayed coking
and Flexicoking.
Delayed coking is the most impor-
tant source of petroleum coke with
low ash content, which is necessary
to manufacture the electrodes used
in the aluminum and steel indus-
try. Coke from delayed coker units
is used as calcination coke in the
cement industry. Coker units also
produce important quantities of
gases, naphtha, light coker gas oil
(LCGO), and heavy coker gas oil
(HCGO). Coker naphtha is used as
feedstock for catalytic reforming
units (CRU), while LCGO is used to
produce diesel, and HCGO is fed to
fluid catalytic cracking (FCC) units.
Products obtained in the coker
unit are the result of decomposition
and condensation reactions of the
compounds contained in vacuum
residue. The formation of coke takes
place before maximum conversion
of the liquid products is reached.
In order to accomplish long opera-
tion cycles, a heater output stream
is introduced to the coker cham-
bers where the reaction processes
continue in adiabatic mode to com-
pletion, maximising the liquid prod-
H3C CH3 CH3
H3C Si O Si O Si CH3
CH3
CH3 H3C CH3 H3C CH3
CH3
H3C O Si O Si
Si O Dimers and trimers H3C
H3C
CH3
of dimethysiloxane
Si O
O Si H3C
Si O CH3 O Si
H3C
CH3 H3C CH3
Octamethylcyclotetrasiloxane Hexamethylcyclotrisiloxane
Figure 1 Chemical structures of the most important siloxanes produced in coker chambers
ucts and coke. Finally, the products liquid products, mainly in the naph-
are sent to a fractionator system. tha stream.
Once fractionated, they flow to The distribution and con-
downstream units where they are centration of silicon in delayed
finished. coking products depend on a poly-
dimethylsiloxane’s properties
Origin of the problem (molecular weight, viscosity, and
Due to the dynamic fluid in coke polydispersity). However, regard-
chambers, foam formation takes less of its properties, silicon is dis-
place. This must be avoided in tributed in all the liquid products
order to prevent the foam being of the coker units; the highest con-
dragged to the separation system. centration is found in the naphtha
For this purpose, an antifoaming stream.
agent such as polydimethylsilox- The products from the coker
ane (PDMS) is introduced into units have high sulphur and nitro-
the coker chambers. This polymer gen levels, therefore they must be
breaks down under the chamber’s hydrotreated, especially naphtha
operating conditions (480-500°C) which is fed to the CRU, and LCGO
to form dimethylsiloxane com- which is used to produce ultra low
pounds, where typical fragments sulphur diesel (ULSD). But these
are hexamehyltricyclosiloxane and streams also contain silicon com-
octamethylcyclotetrasiloxane (see pounds which poison hydrotreat-
Figure 1). Since these compounds ing and reforming catalysts. In this
have boiling points of 134-245°C, context, until today silicon has been
they tend to be concentrated in the considered a permanent poison, so

www.digitalrefining.com PTQ Q3 2021 73

Q3 MPI.indd 73 11/06/2021 15:55

 Silicon based fluids used in the oil industry
Viscosity Oil/gas Delayed
(cSt) separation coking
1000
12 500 Yes
60 000 Yes Yes
100 000 Yes Yes
600 000 Yes Yes
1 000 000 Yes Yes
Table 1
poisoned catalyst cannot be regen-
erated or reactivated and is sent for
disposal. This has a negative impact
on refinery profitability while spent
hydrotreating catalysts are consid-
ered a hazardous waste.
Coker products are the most
important silicon sources in refin-
ery streams, however refineries
without coker units in some cases
also encounter silicon poisoning in
hydrotreating catalysts. This hap-
pens because siloxanes are used as
surfactants in drilling muds as well
as in the extraction and transport of
crude oil for refineries. To be frac-
tionated, crude oil must be heated
to 330-340°C before being intro-
duced into the distillation tower.
This temperature is above the initial
thermal decomposition temperature
of PDMS (about 315°C), therefore
the slow degradation to lighter sil-
icon compounds begins during the
crude oil fractionation. An over-
view of the silicon based fluids used
in the oil industry is presented in
Table 1.1
Crude Vacuum Cracking Asphalt
distillation distillation process processing
Yes Yes Yes
Yes
Yes Yes
Silicon poisoning pathways
Coker naphtha exhibits important
differences with respect to other
naphtha streams. It contains the
highest olefin and diolefin levels
and consequently has the highest
tendency to form gums, with high
concentrations of nitrogen, sulphur,
and silicon. Therefore, it is not com-
mon practice to hydrotreat it (alone
or co-processed with other naph-
thas) in units traditionally used to
hydrotreat straight-run naphtha
because:
a) It presents high exothermic-
ity due to its olefin and diolefin
concentrations.
b) At typical HDT conditions
(T<280°C), polymerisation reactions
of diolefins will deposit gum on the
top layer of the catalyst bed.
c) It is important to trap all silicon
in order to avoid poisoning cata-
lysts in downstream units such as
naphtha catalytic reforming.
d) Harsher conditions are necessary
to meet the specification for down-
stream units due to the high nitro-
gen and sulphur contents in this
stream.
Units where coker naphtha is
processed or co-processed with
other naphtha streams have a sep-
arate design. The recommended
configuration has three reac-
tors: a diolefin saturation reactor
(DIO), a silicon trap reactor (STR),
and a main hydrotreating reactor
(MHTR). Figure 2 shows a typical
unit with three reactors.
Each one of these three reactors
and the catalysts loaded in them
have very specific goals in order to
ensure the specifications needed
for catalytic reforming units (S <0.3
wtppm, N <0.3 wtppm, no olefins,
arsenic, and silicon).
The DIO reactor is designed to
saturate diolefins in the feedstock
in order to avoid gum formation.
For this reason, the severity in this
reactor is the lowest; the operating
temperature is typically lower than
210°C.
The function of the STR is to
remove heavy contaminants, espe-
cially silicon and arsenic. Olefin sat-
uration, HDS, and HDN also take
place. Because of the temperature
of the reactions (260°C on average),
only the least difficult HDS and
HDN reactions can be carried out.
In the MHTR, the temperature is
higher than in the previous reactor
(315-330°C) and the most difficult
HDS and HDN reactions are carried
out. In this reactor it is also impor-
tant to eliminate any mercaptans

Make-up Gases
Hydrogen
Feedstock pump Heater

Recycling
compressor

Feedstock Silica Main HDT Separator

filter Treat gas trap reactor
reactors C1-C4 w/H2S

DIO
Treat gas Stabiliser
reactor

Separator

Product (S< 0.5 wppm)

Figure 2 Typical three-reactor unit for processing coker naphtha

74 PTQ Q3 2021 www.digitalrefining.com

Q3 MPI.indd 74 11/06/2021 15:55

 due to recombination reactions. The
MHTR is also the last opportunity
to trap silicon that could leak from
the STR.
Catalysts used to trap silicon are
characterised by their higher spe-
cific surface area. There is a direct
relationship between the specific
surface area of the catalyst and the
amount of trapped silicon. It is also
accepted that this poison is seized
by OH groups on the surface of
γ-alumina which is used as a sup-
port in hydrotreating catalysts.
Coker naphtha also contains arse-
nic, which is another aggressive poi-
son for hydrotreating and reforming
catalysts and must be eliminated.
Refineries generally use the same
reactor and the same catalysts to
eliminate silicon, arsenic, olefins,
and other potential poisons as well
as routine poisons such as sulphur
and nitrogen; for these reasons,
the most common industrial cata-
lysts in the STR contain nickel and
molybdenum. However, there are
also metal-free catalysts on the mar-
ket. The metal component does not
participate directly in the reaction
to trap silicon, but it is necessary
to trap arsenic and hydrogenate
olefins.
The amount of trapped silicon is
affected by the reaction tempera-
ture, liquid hourly space velocity
(LHSV), and catalyst size. There
is another accepted issue: the sili-
con trap reaction does not follow
a piston flow pattern. The afore-
mentioned information strongly
suggests that the global deactiva-
tion reaction by silicon is a mass
transfer-controlled reaction. A typ-
ical pattern of silicon poisoning
observed in Pemex coker naphtha
hydrotreating (CNHDT) units is
presented in Figure 3. This perfor-
mance explains why there is a sili-
con leak from STRs before all their
capacity to trap silicon has been
reached. In fact, some catalyst sup-
pliers suggest that the silicon leak
begins when only 50 wt% of the
total capacity is reached.
In order to understand and clar-
ify the reaction pathway among
the chemical structures of silicon
compounds, it is important to point
out that the -OH groups present
on γ-alumina are not homogene-
www.digitalrefining.com
Q3 MPI.indd 75
(a)
Silica on the catalysts, wt%
Figure 3 Profile of silicon content on catalysts: a) start of run plus three months; b) start
of run plus nine months
ous. They feature varying acidity
depending on the oxygen atoms
around them. The presence of
molybdenum atoms also affects the
acidity of these -OH groups.
Bruce Wright2 revealed that the
chemical bond between silicon
and oxygen in siloxane molecules
is stronger than the silicon-carbon
bond, and the latter is more sus-
ceptible to being degraded by the
action of the -OH groups on the
alumina surface, creating a silicon-
oxygen-aluminum bridge, which
is the first step in the poisoning
reaction of HDT alumina catalyst.
This first step is a kinetically con-
trolled reaction. For a given cata-
lyst, around 8-9% of the total silicon
to be trapped is seized by alumina
through this pathway. However,
when this first silicon layer is
formed, the kinetics is no longer the
controlled pathway. Once the first
layer is formed on some of the -OH
groups of the alumina surface, the
siloxanes are eliminated from the
hydrocarbon stream through reac-
tions with other -OH groups on alu-
mina that are free and active, and
through condensation reactions.
The condensation reactions pro-
duce very stable structures where
methyl groups are progressively
eliminated.
By nuclear magnetic resonance
(NMR), it is possible to identify
different structures of silicon com-
pounds, depending on the methyl
and hydroxyl groups bound to the
silicon atom. Analysis of industrial
spent catalysts has shown a set of
silicon structures on the surface
of the catalysts and helped iden-
(b)
Silica on the catalysts, wt%
tify the heterogeneity of the silicon
compounds present at the end of
the operation cycle of the catalysts
used as silicon traps in industrial
units. It is possible to classify the
silicon compounds on the cata-
lyst surface according to two major
groups: organic and inorganic
compounds. The organic types are
those structures where silicon is
bound to methyl groups and they
are labelled as Type T (one methyl
group) and Type D (two methyl
groups) structures. The inorganic
silicon compounds have chemical
silicon-oxygen bridges with silicon
or aluminum or hydrogen and are
labelled as Type Q structures.
The evolution of silicon com-
pounds on alumina over cycle time
was studied using an industrial
fresh catalyst. Four samples were
analysed by NMR:
a) The first was a spent sample
obtained from the STR of an indus-
trial coker naphtha hydrotreating
unit after being downloaded from
the reactor once its operational cycle
came to an end.
b) Three fresh samples of the same
catalyst were activated and poi-
soned in a pilot plant using a coker
naphtha stream doped with silicon
compounds. The doped naphtha was
prepared using the PDMS cracked at
450°C, which is a condition used in
the drums of delayed coker units.
From this study, it was possible to
observe and conclude the following
points:
a) The silicon deposition increased
with time on stream, indicating
an important retention capacity of
silicon species by the catalyst.
PTQ Q3 2021 75
11/06/2021 15:55
 H
O
HO O OH
HO Si Si

CH 3
CH
OH O O

CH 3
HO O O

3
Si
Si Si Si OH
3
CH

O H
CH3 CH3 O O O nO
Si

H3C H3C O O HO O O O O O
3
CH
O

H3C Si H3C Si Si Si HO Si Si Si Si Si Si OH
O OH OH OH O O O O OH O O O O O O O
Al Al Al Al Al Al Al Al Al Al Al Al Al Al Al Al Al
O O O O O O O O O O O O O O O O O O O

7
global pathway of silicon deposition
6 D% T% Q% on γ-alumina catalysts is presented
in Figure 4.
Distribution, wppm

5
The silicon condensate structures
4 build up on the catalyst surface,
limiting access to active sites situ-
3
ated in the pores of the catalysts.
2 This phenomenon is referred to in
1
the literature as “pore mouth plug-
ging” and affects the activity of
0 hydrotreating reactions. The surface
Doped (1.6%) Doped (3.2%) Doped (3.5%) Spent (7.4%)
area of an industrial fresh catalyst
from a Pemex refinery was reduced
Figure 4 Evolution of the silicon species on γ-alumina from 292 to 136 m2/g, and the pore
volume evolved from an average
b) The amount of retained silicon of silicon compounds in the feed- of 0.51 to 0.29 m3/g. Figure 5 shows
was almost the same as the one cal- stock, LHSV (inverse of contact qualitatively the impact of silicon on
culated for the first days. However, time), catalyst size, and reaction two of the most important reactions
after 30 days on stream, an increas- temperature. of the hydrotreating process.
ing difference between the content c) There is a change in the chemical Among hydrotreating catalyst
of measured silicon and calculated nature of silicon compounds as their suppliers, there is a consensus on
values is observed. The previous content increases on the catalyst. two points:
event is in good agreement with This change is reflected through the a) Catalysts used in STRs lose their
the fact that condensation reactions modification with the time of distri- activity due mainly to silicon poi-
are controlled by the mass transfer bution between organic/inorganic soning rather than carbon build-up.
produced by reduction of the global compounds. This is a key conclu- b) Catalysts poisoned with silicon
reaction rate. This would explain sion in order to develop a process cannot be regenerated and/or reac-
that the silicon content in the spent to rejuvenate these catalysts, thus tivated because during carbon burn-
catalysts is affected by the amount avoiding their final disposal. A ing, the silicon compounds react
with γ-alumina, modifying their
structures and properties.
Catalyst suppliers agree that the
100
size of the silicon trap catalyst must
90
be between 1.3 mm (1/20”) and 3
80 mm (1/8”) in order to fulfill a com-
70 promise between the accessibility of
Relative activity, %

60 silicon compounds and the pressure

50 differential along the catalyst bed.
40 The last point is a very important
30 functional parameter for an indus-
20 HDS
trial unit and must be considered
in the preparation and production
10 HDN
of industrial catalysts. A scanning
0
0 2 4 6 8 10 electron microscope (SEM) image
Si on catalyst, wt% of an industrial spent catalyst from
the STR of a CNHDT unit is shown
Figure 5 Effect of silicon deposition on HDS and HDN reactions in Figure 6; it is possible to observe

76 PTQ Q3 2021 www.digitalrefining.com

Q3 MPI.indd 76 11/06/2021 15:55

 fully exploited. In as much as green waxy oil, University of Pretoria Press, Pretoria, Marcio Wagner da Silva is a Process Engineer
coke silicon
that enablesisdelayed coking to pro-
homogeneously dis- 2011. and Project Manager with Petrobras in São José
tributed in the catalyst. sulphur, its
vide a stable ‘sink’ for 3 Clark J, MSc (Eng) dissertation: Delayed dos Campos, Brazil. He has extensive experience
incineration effectively reverses this coking of South African petroleum heavy in research, design, and construction in the oil
benefit, contributing
Selective extraction oftosilicon
substantial
from
residues for the production of anode grade and gas industry, developing and coordinating
coke and automotive fuels, University of the projects for operational improvement and
SOx emissions,
poisoned catalysts negating initiatives
Witwatersrand Press, Johannesburg, 2008. debottlenecking bottom of the barrel units.
to restrict
To this day, sulphur levels inpoisoned
all catalysts automo-
4 Congressional Research Service, Petroleum He holds a bachelor’s degree in chemical
tive fuels. As cleaner,
with silicon are sent for final more efficient
dis- coke: Industry and environmental issues, engineering from the University of Maringa
energy technologies
posal. However, the Mexican replace heavy 2013, CRS, www.everycrsreport.com/reports/ (UEM), Brazil, a PhD in chemical engineering
petroleum Institute
Petroleum residues (IMP)
in fuel mar-
patented R43263.html
Figure 6 SEM image of spent catalyst from thefrom thetrap
silicon University
reactorofofCampinas (UNICAMP),
a coker naphtha
kets, they will need to be
a process in 2008 to remove silicon processed 5 EPA, Types6. unit
hydrotreating
Figure ofTheeconomic
SEM imageincentive and catalyst
of a spent Brazil, MBA
from ainsilica
project
trapmanagement
reactor of a from
in an environmentally
compounds sustainable
from spent catalysts. 3 hybrid-based approaches, 2017,CokerEPA, www.Hydrotreating
Naphtha Federal University
unit. of Rio de Janeiro (UFRJ) and
manner to affect an absolute
A semi-industrial test was carried reduc- epa.gov/environmental-economics/economic- is certified in business from Getulio Vargas
tion using
of SOx incentivesEffect of the rejuvenation process onFoundation
structural (FGV).
properties of catalysts
out 50 kgemissions.
of industrial Delayed
spent
coking offers a realistic
catalyst from a Pemex Refinación enabling 6 Etter R, Production and use of a premium John Clark is a fossil fuel scientist and industrial
option naphtha
coker in terms unit.
of refinery integra-
The semi-in-
fuel grade petroleum coke, Patent publication development
Ni-Mo/γ-Al2O3 Specific area, cm2/g
specialist. He has substantial
number WO2000010914A1, World Intellectual experience in fossil fuels
Rejuv 3research and
tion, distressed heavy
dustrial test was supported by residues, SOxa Fresh Spent Rejuv 1 Rejuv 2
Property
CatalystOrganization, 1999, www.patents. sustainable product and business development.
emission targets, and lighter
large number of studies and eval- hydro- A 184 288
google.com/patent/WO2000010914A1/en
Catalyst B 198 He283specialises in delayed coking chemistry
carbon carried
uations production to drive
out with spentbusi-
cat- Catalyst
7 Liu C Z, Yang P,292
G, Peng Wang G, Sulphur135in coal and 208coke markets, 215 and has 228
made considerable
ness initiatives in an
alysts with various shapes, from increasingly and its environmental impact from Yanzhou contributions in aluminium, steel, bunker fuel,
environmentally
diff erent suppliers restricted
and from market.
dif- mining district, China, Chinese JournalPore volume,
of cm
3
heavy/g petroleum residues, coal to oil, bitumen,
By removing fuel grade
ferent Pemex Refinación CNHDT coke from Catalyst A
Geochemistry, 2001, vol. 20, no. 273.
0.42 0.81
and energy value chains.6 He has lectured as an
Catalyst B 0.75 1.27
energy markets, significant contri-
units. 8 Petro Industry
Catalyst C News,0.51
2020, What is Petcoke?
0.29 honorary
0.44 professor
0.47 on a pro bono basis at the
0.49
butions
As hasare made
been to reduce in
mentioned, absolute
spent And What is it Used For?, International Labmate University of the Witwatersrand (South Africa)
SOx emissions.
catalysts two kinds of silicon com-
Limited, www.petro-online.com/news/fuel-for- and held a seat on the executive council of
Table 2
thought/13/breaking-news/what-is-petcoke- an international coal industry consortium in
pounds are present: organic and and-what-is-it-used-for/33235
Further reading the USA. A seasoned international lecturer
inorganic.
1 Calkins W H,Throughout
The chemical forms the ofrejuve-
sulphur The inorganic
9 Speight J G, Heavy compounds
and Extra-Heavy wereOil remained
and industrialinadviser
the to catalyst.
academic,Figure 7
industry,
nation process, fi rstly the organic
in coal: a review, Fuel, vol. 73, no. 4, 1994, 475- removed step by step as the reac- shows the silicon compounds
Upgrading Technologies, 1st ed., Elsevier Press, and government audiences, he holds a BSc that
structures
484. are detached, being 2013. time grew. However, some evolved
tion in chemistry, onMSc the(Eng)
catalyst
in heavyafter dif-
petroleum
totally
2 Clark J, removed after
PhD Thesis: The some ofhours.
production highly inorganic
10 Robinson compounds
P R, HSU C (Q Handbook of ferent
S, structures) timesandina PhD
shipping fuels the(Applied
rejuvenation
Materials
anisotropic needle-like coke from aliphatic Petroleum Technology, 1st ed., Springer, 2017. Engineering) in sustainable needle coke.

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www.digitalrefining.com PTQ Q3 2021 77

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Q3 MPI.indd 77 11/06/2021 15:55

 H3C H3C CH3
CH3 CH3 H3C O CH3 OH CH3 H3C O O CH3
H3C Si OH Si H3C Si Si CH3 HO Si OH Si OH Si Si Si
O O O O O O O O O O O O
Al Al Al Al Al Al Al Al Al Al Al Al
O O O O O O O O O O O O O O O O O O
Type ‘D’ Type ‘T’

H
O
HO O OH
HO Si Si
OH O O
HO O O
Spent
Si Si Si OH
H
2h O O O O
HO O O O O O n
4h HO Si Si Si Si Si Si OH
8h O O O O O O O
Al Al Al Al Al Al Al
12 h
O O O O O O O O
0 -20 -40 -60 -80 -100 -120 -140 -160
Chemical shift, ppm Inorganic /Type ‘Q’

Figure 7 NMR analysis of an industrial catalyst at different rejuvenation times by the IMP process

process. After 12 hours, 80-85 wt%

12 of the silicon compounds were
removed from the spent catalyst.
Spent
A higher quantity of silicon can be
10
removed, although the time needed
to do that is not justified.
8 The effect of the rejuvenation
process on alumina’s textural prop-
Si, wt%

erties was evaluated through the

6 evolution of surface area and pore
volume. The changes in these prop-
Rejuvenated erties of two catalysts with differ-
4 ent shapes are presented in Table 2.
Catalyst A was a cylinder catalyst
0
0 100 200 300 400 500 and the second was a tetralobal cat-
Distance, µm alyst. Both were industrial Ni-Mo/
Al2O3 catalysts specifically designed
Figure 8 SEM image of spent sample and rejuvenated catalyst to trap silicon. As expected, the
surface area and pore volume of
both rejuvenated catalysts were
partially recovered. Total recovery
% Molybdenum of the textural properties was not
% Nickel possible due to the carbon formed
during normal operation and sili-
Metal content, wt%

con remaining on the catalysts. It

can be assumed that the deblock-
ing of pores is only attributed to the
removal of silicon compounds. Only
activity to remove carbon from the
catalysts was carried out. Therefore
it is expected that the higher the
removal of silicon compounds, the
Cat 1 Cat 1 Cat 2 Cat 2 Cat 3 Cat 3 Cat 4 Cat 4 Cat 5 Cat 5 Cat 6 Cat 6 higher the recovery of surface area
(*) (*) (*) (*) (*) (*) and pore volume.
SEM studies of spent and reju-
Figure 9 Catalyst metal content before and after rejuvenation by the CleanSil-IMP process. venated catalysts (eight hours of
Rejuvenated catalyst (*) treatment) were also carried out in

78 PTQ Q3 2021 www.digitalrefining.com

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 order to establish whether silicon
removal was homogenous through-
out the catalyst. Figure 8 shows that
the remaining silicon was homog-
enously distributed on the catalyst
pellet.4
A concern in the rejuvenation
process is related to its selectivity
towards the removal of only sili-
con compounds without modify-
ing the active metal concentrations.
In order to establish that the metal
content (nickel and molybdenum)
suffered insignificant changes after
the rejuvenation process, spent cat-
alysts rejuvenated from different
suppliers were analysed (see Figure
9). These changes were within the
limits of the method’s sensitivity,
so it is possible to suggest that the
rejuvenation process selectively
removes silicon compounds while
the content of active metals remains
unchanged regardless of the shape
and size of the catalysts.
The most important role of the
catalyst loaded in the STR is its
capacity to trap silicon in the naph-
tha stream, but the recovery of cat-
alytic activity is another important
www.digitalrefining.com
Q3 MPI.indd 79
Effect of the rejuvenation procedure on the activity of Catalyst C (85% removed
silicon) at feed = 1.58 h-1 and pressure = 55 bar
Test time (days) 0 10 20 40 60 80 100
Temperature (°C) 260 260 300 300 300 300 300
Feed (Sulphur wt%) 0.44 0.44 0.44 0.44 0.44 0.44 0.44
Spent (Sulphur wt%) 0.20 0.23 0.01 0.011 0.018 0.017 0.017
Rejuv (Sulphur wt%) 0.079 0.080 0.012 0.01 0.008 0.007 0.007
Feed (Nitrogen wtppm) 37 37 37 37 37 37 37
Spent (Nitrogen wtppm) 29 28 10 11 11 11 12
Rejuv (Nitrogen wtppm) 13 13 4 3 3 3 3
Feed (Silicon wtppm) 14 14 14 14 14 14 14
Spent (Silicon wtppm) 10 4 5 4 6 9
Rejuv (Silicon wtppm) <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2
Table 3
factor to be taken into account when unit. The operating conditions, feed
the rejuvenation process is applied. properties, and activity results are
In order to evaluate these proper- shown in Table 3. The capacity to
ties, the rejuvenated catalyst was trap silicon and the HDS and HDN
unloaded from the semi-industrial activity were evaluated under two
unit and loaded into a pilot plant typical operating conditions of an
unit. In order to ensure that all the industrial Pemex STR: start of run
metal species were sulphurated, (260°C) and end of run (300°C). The
a brief check-up procedure pro- silicon content of the product was
vided by the catalyst supplier was evaluated by atomic adsorption
applied. The capacity to trap silicon, analysis.
and the HDS and HDN activity, From the results shown in Table 3,
were tested using a coker naphtha it is possible to conclude the follow-
stream from a Pemex Refinación ing points:
PTQ Q3 2021 79
11/06/2021 15:55

To process
Steam
Water
Figure 10 The rejuvenation process adapted to a coker naphtha hydrotreating unit with
two silicon trap reactors
a) The rejuvenated catalyst recov-
ered its capacity to trap silicon.
b) HDS and HDN catalyst activ-
ity was affected mainly by silicon;
if silicon is removed, a significant
amount of activity is recovered.
c) The most important silicon poi-
soning effect is exerted on HDN
activity; if the catalyst is rejuve-
nated, the impact will be more evi-
dent on HDN activity.
d) The silicon impact on HDS activity
is lower than on HDN activity, how-
ever at start of run an increase in HDS
activity of around 30% is observed. At
end of run conditions, the improve-
ment is marginal, as expected.
In order to evaluate the impact of
successive rejuvenations, an indus-
trial spent catalyst was rejuvenated,
poisoned, and rejuvenated succes-
sively three times. The pilot plant
tests were carried out in series,
which means that the catalyst was
not unloaded. The procedures used
to poison, rejuvenate, and evaluate
the catalysts were those mentioned
previously. The results for a trilobal
catalyst (Catalyst C) are shown in
Table 2. The initially used spent cat-
alyst was the one unloaded from
one of the Pemex Refinación indus-
trial units. The silicon level in each
poisoning step of the pilot plant test
was the same as when the industrial
catalyst was unloaded. The refer-
ence catalyst was a sample of the
fresh catalyst unloaded from the
industrial unit.
80 PTQ Q3 2021
Q3 MPI.indd 80
From process
Silica
trap
reactors
Reposition
It is possible to elicit from the
results shown in Table 2 that the
physical and structural properties of
the catalyst are not affected by suc-
cessive rejuvenations, which sug-
gests that it is possible to eliminate
silicon several times from the same
catalyst. After the third rejuvena-
tion, the catalyst activity was evalu-
The physical and
structural properties
of the catalyst are not
affected by successive
rejuvenations, which
suggests that it is
possible to eliminate
silicon several times
from the same
catalyst
ated and the results were similar to
those obtained and reported for the
catalyst rejuvenation (see Table 3).
From deep characterisation of the
catalysts, it is possible to conclude
that, according to the percentage of
silicon removed, an important frac-
tion of alumina’s textural properties
are restructured through the reju-
venation process. These changes in
physical and structural properties
improve accessibility to the active
sites of the catalysts and allow the
recovery of HDS and HDN activity
and capacity to trap silicon.
Potential application of the process
The results obtained from the IMP
studies let us suggest that it is possi-
ble to avoid final disposal of silicon
trap catalysts once they are satu-
rated with silicon in the first cycle.
The rejuvenation procedure allows
the reuse of these catalysts, at least
for three operation cycles, which
reduces the generation of hazard-
ous refinery materials.5 Due to the
operating conditions of the reju-
venation process, it is possible to
integrate the equipment required to
carry it out in a CNHD unit. Figure
10 shows potential integration into
a unit with two STRs.
Once the silicon trap shows a sil-
icon leak, it is blocked and purged
with nitrogen in order to eliminate
all hydrocarbons from the reactor.
Once the reactor is empty, solvent
is introduced into the rejuvenation
circuit and preheated with the out-
let stream from the lag STR using
heat generated by the reactions
that take place in the reactor. To
reach the required temperature, a
heat exchanger is needed, where
a vapour stream delivers the
requested energy. The solvent
is preserved in the liquid phase
throughout the rejuvenation pro-
cess. When operating conditions are
fixed (pressure, temperature, and
solvent flux), a small temperature
differential is observed. This is the
first indication that silicon is being
desorbed from the catalysts. A cycle
of 72 hours is enough to eliminate
80-85% of silicon from the catalyst;
then, the solvent is removed and the
reactor is purged with nitrogen in
order to prepare it for a brief reac-
tivation process before it is recon-
nected with the reaction loop as the
lag STR. The reactivation process
is a short version of the sulphiding
process and is carried out to avoid a
severe restart.
During the rejuvenation process,
some of the solvent is degraded. In
order to preserve the solvent’s con-
centration and monitor the degrada-
tion process, some control analyses
www.digitalrefining.com
11/06/2021 15:55
 should
vary greatly
ring. be
In carried
by geography,
total, out and,
four hot taps according
source to the results,
of production,
were installed onand a
the
small
other purge
factors. 3 of the solvent would have to be fixed. The
The net emissions
pressure shell, two in the side downcomers of Tray 8 in the case of HVO naph-
removed
tha and twosolvent
compared with isnatural
replaced gaswithare fresh
much solvent.
lower, since the
feedsump.
below the normal
emissions (main overall contributor) are zero in the
liquid level in the column
WHAT CAN ENSURE MY
case
and
ofThe
Conclusion
Silicon
renewable
bypass lines
found in
HVO were
crude
naphtha.
oil
put When
streams
2018. The steam cracker unit operating rate emis-
blue hydrogen, although there arecomes
lower
comparing
into operation
not only
overall
in grey
mid-
from
could
PLANT‘S LONG-TERM
thebeantifoaming
sions, the incremental
increased agents
to 97% used
compression
ethylene in coker power units.
production Different
requirement
capacity. EFFICIENCY?
polysiloxanes
diminishes the are
overall used net in the
effect.
On-specification overhead and bottom products were extraction, transport, and
The
refining present of analysis
crude oil deliberately
and these
produced while the bypass was in operation. The debu- are did not
cracked consider
in the the
dif-
cost
ferentof any
refiningcarbon credits
processes. associated
The
taniser was opened in a later turnaround and severe thermal with the recovery
decomposition
and/or
products sequestering
polymerisation of polysiloxanes of CO2was
fouling so are
the
found reader
concentrated
on the can bottom
appreciate
mainly tray
the impact
in active
naphtha of these
areas streams
and in subsidies
their and which
they poison
downcomers vary(see byFigure
geography,
hydrotreat-7).
local/regional
ing, reforming, policies, political appetite,
and isomerisation environmental
catalysts via their
restrictions,
adsorption
Conclusion and onto otherthefactors.
alumina Neither
surface,was blocking
the incremental access
cost
to In and
active logistics
summary, for CO2 sequestration/
sites. thorough analysis of field storage
data and consid- tray
ered.In There
order are
hydraulics multiple with
to together
eliminate initiatives
silicon gamma aimed
compounds at CO
scanning from capture
2were naph- key
ortha,
reuse,
these
factors asformentioned
streamsa time- wereandinhydrotreated
the previous in
cost-efficient section.
units that Carbon
troubleshooting. use
credits
catalysts
Close and economics
specially
collaboration of sequestration
designed
between tothe trap are
silicon;
plant owner,essential
these cata-
Tracerco to
bridge
lysts
scan the
have gap in
a higher
experts, cost
and between
surface grey and
area thancompany
engineering blue hydrogen.
traditional hydro-
personnel
treating
made the catalysts. The silicon
troubleshooting adsorption
discussed here aprocess
success. on
Conclusions
alumina occurs by a different reaction pathway and
Hydrogen
two kindsis of
References nowadays
silicon compoundslabelled with werea colour
formed: associated
organic
with 1 its production
H, Green D process,
and inorganic. Until today, silicon has been considered
Perry R W, Perry’s feedstock,
Chemical and
Engineers’ emissions,
Handbook, New
among York,other considerations.
McGraw-Hill, 2008.
a permanent poison. In order to avoid final disposal Grey, blue, and green hydro-
gens 2 are
Kister
of catalysts theHmostZ, What common
poisoned
caused tower
with known types;
malfunctions
silicon, each
in the
a rejuvenation one lastwith its
50 years,
pro-
pros
cess and
Trans. cons.
Inst. Chem.
wasL,developed, Blue
Eng., hydrogen
2003, Vol.
whichtower (fossil
81, 5-26.
enables fuelthe base with
possibilitythan CO of2
sequestered)
3 Pless
reusing theseis viewed
Simon
catalysts as aatbridge
Xu, Distillation
least between
flooding
three low complex
– more
times. cost,
The high
reju-
you think, Chemical Engineering, Jun 2002.
emissions grey hydrogen andcoupled
high cost, to limited scale, zero

EXPERIENCE!
venation
4 Lockettprocess can be
M J, Distillation Tray Fundamentals, current
CambridgeCNHDT University
emissions green hydrogen. Compared to grey hydrogen,
units
Press,fitted
Cambridge, with1986. STRs. The rejuvenation process can
blue hydrogen requires a higher capital and variable cost
be carried out without unloading the catalyst from the
for CO recovery
Pless wasand the sequestration. The know-how of more than 60 years empowers Böhmer
reactor.
Lowell
2 Business Development Manager – Distillation
The emissions
Applications withfromTracerco, incremental
located in Pasadena,use of Texas,energy and is(pri-
now
to build Ball Valves that help customers to realize their
projects efficiently & successfully for the long term.
marilya
References
power)
consultant required
for the for
company. compression,
He has been separation,
applying and
radioisotope
sequestration
1 techniques inofprocess
Pape P G, Silicones: COUnique
2
must also befor
troubleshooting
Chemicals accounted
for for. Carbon
over 30 Processing,
Petroleum years, originally
SPE,
credits,
with availability
Tru-Tec
Dow Corning Corp. Services of sequestration
(acquired by sites,
Tracerco in and
2006)processing
and started 1/8 TO OIL, GAS, STEAM, CHEMICALS UP TO
56 INCH & SPECIAL APPLICATIONS 800 BAR
costs thearetower
2 Radhakrishnanessential
scanningfor
T S, Newthe
service deployment
for Tru-Tec in Western
Method for Evaluation ofofblue hydrogen.
Europe
Kinetic
and the
Parameters
Green hydrogen
Middle must
East. He holds a use renewable
BS degree in chemical
and Mechanism of Degradation from Pyrolysis – GC Studies: Thermal sources to
engineering produce
from the
true zero emissions
University
Degradation
of Texas in the production
at Austin,
of Polydimethylsiloxanes;
is a registered process;
Analytical this repre-
Professional
and Spectroscopy
Engineer
in the State of Texas, participates on the Design and Practices
sents challenges
Division, Polymers and in terms of cost and
Special Chemicals Group,scale
Vikram of Sarabhai
production Space
committee for Fractionation Research (FRI), and is a member of the
among other factors.
Centre, Thiruvananthapuram 695 022, India, 1998.
American Institute of Chemical Engineers.
Governments
3 US Patent 8,716,159 haveB2. a critical role to play in addressing
key challenges.P,Blue
4 Pérez-Romo and greenC,hydrogen
Aguilar-Barrera Laredo G C,can be profitable
Ángeles-Chávez C,
André Perschmann is anforequipment process designsilicon
expertfromwith HDTLinde
with carbon credits.
Fripiat J, Novel solution removing poisonous
Engineering
catalysts, for eight
Applied Catal.years.
611He (2021).
designs all types of columns and
https://doi.org/10.1016/j.
References
separators
apcata.2020.117964 for petrochemical, natural gas, hydrogen, and synthesis gas
1 Theplants.
FutureHe of isHydrogen, report prepared by the IEA for the G20, Japan
also
5 Pérez-Romo P, involved in root cause
Aguilar-Barrera C, analysis,
Nueva troubleshooting,
tecnología para and
(Jun 2019).
revampselectivamente
activities. He holds a diploma de degree in bioprocess engineering
remover compuestos silicio de catalizadores de
2 Marquez M, Bumgarner B, Optimum
from the Technical use of H2 in theGermany.
production of drop-
hidrotratamiento, 5° University
CongresoofLatinoamericano
Braunschweig, y del Caribe de
in green fuels, 2020 AFPM Summit, www.hydrocarbonprocessing.com/
Refinación, Aug 27-30, 2018, Mendoza, Argentina.
conference-news/2020/08/2020-afpm-summit-optimum-use-of-h2-in-
David Bruder is a process and operation expert for petrochemical
the-production-of-drop-in-green-fuels
plants with Linde Engineering, planning, simulating, and optimising
3 Methodology for the calculation of GHG emissions from Biofuels and
all relevant processes within the Linde petrochemical portfolio with
Bioliquids,
Patricia Doc. 2BS-PRO-03,
Perez-Romo www.2bsvs.org/documents/public/2BSvs_
is a Research Project Leader with theinvolved
Mexicanin
a focus on steam cracker separation
PRO_03_Methodologie_de_Calcul_des_GES__F__v1.pdf technology. He is
Petroleum Institute. With 20 years’ experience in research
brownfield/revamp projects such as capacity increase, optimisation, projects for
thelife
Tarun oil refining industry, she holds a PhD in chemical
plants,sciences
Vakil is Director of Hydrogen Technology for Nippon Sanso Holding
cycle, energy, or troubleshooting existing and in the from the
analysis
University
Corporation’s
of process Pierre
US et Marie Curie,
andsubsidiary
operation France.He has more than
Matheson.
performance/optimisation 45 years
of running of
plants.
Email: pperezr@imp.mx
experience in engineering and industrial gases and holds a BS degree in
chemical engineering from The Indian Institute of Technology, Bombay, and
Thomas Walter heads the Equipment Process Design &
a MS degree in chemical engineering from Pennsylvania State University.
LuisComputational
M Rodriguez Otal is a Senior
Mechanics Engineerofin Linde
department the oilEngineering
refining industry.
where
Email:
Hehistvakil@mathesongas.com
has 40 years’ experience in process
evaluation, selection,
group is responsible for the design of staticand operation
equipment for
Marco Márquez
of petrochemical,
refining is Global
catalysts. He Director
previously of worked
Hydrogen at Business
Pemex Development
and Albemarle
natural gas, air separation, and hydrogen/synthesis gas
– Corporation
Refining with Matheson. He has more in than 30 years of combined
plants. Heand holdsholds a PhD
a master’s degree
degree in chemical
process sciences
engineering from
from the
the
experience
Autonomous in the oil industry
National University and with industrial
of Mexico. gas companies and
holds Technical
MSc and University,
PhD in Dresden,
chemical Germany.
engineering from North Carolina State
Email: lmrotal@gmail.com
University. Email: mamarquez@mathesongas.com www.boehmer.de

www.digitalrefining.com
www.digitalrefining.com
www.digitalrefining.com PTQ Q3 2021 81

gas matheson copy.indd 8 17/03/2021 11:18

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Q3 MPI.indd 81 11/06/2021 15:55
 Measurement in the Hydrocracker
Hydrocracking is a process used to process
heavy feedstock residues, such as atmospheric
and vacuum residue. Fresh catalyst is
continuously added and used catalyst is
withdrawn, improving product quality over
time. To promote safe and efficient heavy oil
processing, a reliable measurement and
density profiling is needed for control of
critical process stages.

+1 800 FOR LEVEL

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Reliable Convenient Cost-effective

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vega.indd 1 11/06/2021 14:06

 Improve profit with augmented digital twins
Artificial intelligence and machine learning deliver greater, more sustainable value
from simulation models
MARK KRAWEC, MIKE AYLOTT and SIMON CALVERLEY
KBC (A Yokogawa Company)
O
il refiners are struggling
to command their share of
reducing profit pools. Profit
margins are tight, and the energy
transition is exacerbating already
tough operating conditions as a
result of economic loss of significant
parts of the barrel through reduced
air and road travel. In many
regions, growing availability of
lower cost energy sources is increas-
ingly undermining demand for
transportation fuel product. Even if
alternative energy sources are not
cheaper, ambitious net zero carbon
policies are driving the switch of
fuel away from conventional, fossil
based sources.
Oil refiners must adapt or die. The
more progressive refiners are taking
deliberate steps to future-proof their
relevance:
1. Scale: boldly increase scale,
thereby reducing unit cost of out-
put, the assumption being that
markets will be found for increased
product volumes.
2. Scope: others are not betting on
availability of export markets to
simply expand their scale, and are,
instead, altering the scope of their
operations:
a. Re-tool conventional refineries
to produce ‘greener’ products such
as biodiesel from alternative feed-
stocks such as waste agricultural
products and animal fats. In doing
so, make a more meaningful contri-
bution to society through the pro-
cessing of materials such as cooking
oil, fats, greases, and soybean oils.
b. Downstream integration to pro-
duce a wider petrochemical product
slate, including ethylene, propyl-
ene, polyethylene, ethylene glycol,
paraxylene, and/or styrene.
Historically, improving refinery
profit has focused on opening up
www.digitalrefining.com
q3 kbc.indd 1
the crude oil basket and changing
associated process operating con-
ditions to most efficiently drive a
desired change in yield slate. Whilst
these options remain relevant
today, the upstream and down-
stream optimisation envelope has
expanded greatly.
Feedstock optimisation must now
include crude oils, as well as alter-
native biofeedstocks. Similarly,
downstream integration must con-
sider conventional transportation
fuels, petrochemicals, as well as
emerging inter-connected econo-
mies such as hydrogen.
Enhanced complexity around
these expanded inputs, outputs, and
processes requires new technologies
to aid evaluation and realisation of
available opportunities for improv-
ing profits.
Same goal, different pressures,
higher expectations
Operational excellence must deliver
a measurable change in profitabil-
ity. Unfortunately, this can be over-
looked in the rush for adoption of
the latest digital technology and
enthusiasm for proof of concepts
and articulation of blue-sky visions.
Understanding where value can be
sourced, how to unlock it, and then
putting in place the right people,
processes, and technology to sustain
it has been the staple of KBC’s Profit
Improvement Program (PIP) over
the past 40 years. Billions of dol-
lars in benefits have been realised
to date by KBC by exploiting the
full range of refinery optimisation
levers, but in particular improving
margin through optimisation of
yields and energy.
Subject matter experts, specialist
reactor simulation models, and use
of full Petro-SIM flowsheets have
enabled significant benefits from
complex inter-unit improvements.
All of these have contributed to rea-
lignment of multiple refineries to
maximise profit against their limita-
tions and constraints.
However, in a world where agile
approaches are critical and delivery
expectations have changed, value
must be realised faster despite the
increasing complexity of problems
arising and the range of options.
This comes both from the ability to
implement faster but also to mon-
itor and adapt continuously to
market signals, disturbances, and
changes in operating conditions.
Continuous, holistic optimisation
on a real-time basis has become an
imperative. A shift away from ad
hoc and highly manual approaches
is needed. To achieve this shift
requires a strong data founda-
tion, digital-enabled technology,
and agile delivery with progres-
sive deployment of integrated tools
which avoid large scale retooling of
IT systems and workflow changes.
Certain sites may also require
reskilling of staff to adopt the avail-
able benefits more rapidly and
sustainably.
Whereas a number of expectations
have changed, those that have not
changed are the need for industry
expertise, sound work processes,
and accurate technology. Core
to integrating these fundamental
expectations with new ones is digi-
tal twin technology.
In with the new – the digital twin
that works
A digital twin is a virtual or digital
copy of a human, device, system, or
process that accurately mimics actual
performance in real-time, and that is
executable and can be manipulated,
PTQ Q3 2021 83
11/06/2021 15:57

Traditional simulator
An accurate representation of a particular
operating case
Static provision of a snapshot in time
Built on an ad-hoc basis to answer
a question
Owned and used by isolated groups
on an ad-hoc basis
Figure 1 A digital twin is always aligned with driving a business data model
allowing better performance to be
developed.
Digital twins of process units
that are built from rigorous sim-
ulation models made operational
with real-time data are currently
used for monitoring and optimis-
ing unit performance (see Figure 1).
They enable a real asset to accom-
modate real constraints and physics
by providing the ability to forecast,
predict, and optimise molecular
behaviour under different pres-
sures, temperatures, volumes/
flows, and catalyst service. In doing
so, the rigorous models handle asso-
ciated non-linear relationships and
infer information that cannot be
directly measured. But we cannot
yet explain everything by physics
alone, or at least provide answers at
the speed and cost which business
can more readily afford.
This is why artificial intelligence
(AI) and machine learning (ML)
techniques have become important
for providing ways of extending the
reach of process simulation in criti-
cal areas like fouling and corrosion
prediction, as well as increasing the
speed of optimisation.
One of the challenges of
expanded applications of digital
twin models has been the associ-
ated increase in model upkeep and
maintenance due to disturbances
from market and process/equip-
ment conditions. However, rapid
enhancements in technology have
allowed AI and ML techniques to
shoulder much of the burden of
model maintenance. Previously,
both structured, ad hoc and man-
ual optimisation of process units
required expertise in in-depth tech-
no-economic subject matter, but
can now be undertaken in a con-
84 PTQ Q3 2021
q3 kbc.indd 2
VS Digital twin
An accurate representation of the asset over
its full range of operation, all the time
Captures the full history and
future of the asset
Automated, regular model runs.
Built in to business workflows
Centralised single version of the truth,
used by everyone, outputs delivered directly
to the business, strong governance systems
tinuous and automated manner
through AI and ML that:
• Takes account of long-term oper-
ating history to ensure all intercon-
nectivities are understood
• Reviews inferred parameters and
qualities to cover those which can-
not be measured on-line
• Provides understandable out-
puts to both panel operator and
advanced process control (APC) to
deliver meaningful change
• Deploys/operates in a modular
approach to ensure safe and con-
trolled operation
• Monitors equipment health and
continuously identifies opportu-
nities for improvement to ensure
direction of the unit is aligned to
strategy
•Adapts models to changes in unit
performance bounded by first prin-
ciples and constraints to ensure safe
operation
Value delivery is significant
Petro-SIM is purpose-built to be
able to validate mass balances and
reconcile process data automati-
cally. The integration of real-time
production data and enhancements
in automated data validation ena-
bles rapid comparison of meas-
ured plant performance against
model performance (both simula-
tion model, as well as refinery lin-
ear programming (LP) model). This
automated comparison indicates the
necessity of a retune in simulation
calibration and/or LP vectors much
earlier than before and also allows
for generation of new LP vectors.
The value generated is significant,
in the order of 5¢/bbl of unit feed
from improved monitoring and
10c/bbl from having an LP that bet-
ter reflects the plant.
PIPs see huge benefits from
implementing opportunities and
considering the associated site-
wide impact of potential changes
in feed, product, or configuration.
Combining the benefits of each unit
digital twin is no different, with
expected margin improvement in
the order of 30-70¢/bbl of refinery
feed. Digitalisation of the PIP is uti-
lising digital twins, refinery wide
models, AI/ML, and subject matter
expertise to deliver and sustain the
benefits.
Case study 1
A leading European refinery
wanted to maintain maximum
energy efficiency in a crude dis-
tillation unit while achieving the
production plan, regardless of dis-
turbances in the process. The unit
KPIs did not adequately reflect per-
formance objectives and APC did
not fully optimise the operation due
to limited ability to manipulate all
independent variables with some
key operating parameters (such as
liquid and vapour rates not being
measured). Historical operating
data was also not being analysed
automatically to identify improve-
ments in different production situ-
ations, for example crude switching
which had a significant impact on
the crude unit and downstream
units.
The solution combined first prin-
ciple Petro-SIM models with ML.
The in-built optimiser in Petro-SIM
was used to train the ML model
with optimised solutions for many
different production situations.
Based on what the ML model was
able to ‘learn’ from multiple auto-
mated Petro-SIM runs against many
different scenarios, faster and more
automated optimisation by the ML
model was achieved.
The Petro-SIM model used was
an accurate representation of the
crude unit and was calibrated using
at least two years of historical data.
Examples of the data automatically
provided to Petro-SIM comprised
operating and crude data sourced
directly from the process histo-
rian, as well as laboratory and yield
accounting data. The ML model
was trained on the same historical
data as well as additional optimised
www.digitalrefining.com
11/06/2021 15:57
 solutions from Petro-SIM. The ML
model was able to assess the cur-
rent data and rapidly provide new
optimised targets to APC systems in
place.
As opposed to alternative solu-
tions, the ML model also progres-
sively learned from experience,
taking both fresh plant data and
new synthetic data and optimums
from the Petro-SIM model. This
data driven solution was tested
and maintained the process unit at
maximum energy efficiency while
achieving the production plan. The
main users were the unit engineer
and shift supervisor, as well as the
APC engineer and the panel oper-
ators. In future, the solution could
also provide inputs to maintenance,
planning and control, and instru-
mentation teams as the ML model
continues to learn unit operations
(see Figure 2).
Case study 2
A Middle Eastern ethylene pro-
ducer wanted to use artificial intel-
ligence to solve two particularly
difficult operating challenges:
• Predicting benzene reactor cat-
alyst performance was challeng-
ing. Changing the catalyst too early
risked wasting significant active cat-
alyst, whereas too late risked pro-
duction of off-spec product due to
deactivated catalyst.
• Unidentified cooling restrictions
caused quench tower(s) to lose effi-
cacy, leading to reduction in the
yield of desirable products.
AI was applied to both problems
using a combination of plant data
and inferred data generated from
Petro-SIM. The entire data set was
used to train ML models to generate
better outcomes.
The outcomes were the identifi-
cation of new and different param-
eters to monitor. In the first case
this enabled better prediction of
catalyst life, leading to more effec-
tive planning of catalyst change-out,
less down-time, and less off-spec
product. In the second case, the
operators’ application of the new
parameters enabled the quench
tower temperature to be more effec-
tively controlled in the summer
months, leading to an increase in
yields of desirable products.
www.digitalrefining.com
q3 kbc.indd 3
Input sources
APC
Assays CV limits
Scheduling
Historian
Feed quality
calculation
Crude
composition
& assays
Figure 2 Deployment of machine learning
Tight margin environment
and Energy Transition pressures
Asset-wide models built as part of
Digital PIP ‘operationalised’
as digital twins
Constant up-to-date asset-wide
model for capital investment studies
Figure 3 Simulation technology applying real-time data is augmented by AI and ML
Conclusion
Refining industry revenues have
fallen and a tight environment for
margin means a lot of capital invest-
ments have been cut. Whilst digi-
talising deeper and faster is a way
to boost the industry’s resilience
and competitiveness, refiners need
to first buy themselves time to dig-
italise. Thereafter, changes to asset
portfolios can be made in order to
embrace the energy transition:
• Short-term productivity and effi-
ciency optimisation to improve
financial returns
• Digitalisation to help change
short-term gains into sustained
improvements
• Asset portfolio optimisation/
diversification (M&A, expansions,
upgrades, revamps, and so on) to
position for longer term success (see
Figure 3).
Experienced subject matter exper-
tise, proven process simulation
technology, real-time data with AI
and ML unlock significant value.
The simulation technology made
operational with real-time data (for
digital twin capabilities) is aug-
mented by AI and ML to deliver
larger and more sustainable value.
On-line Petro-SIM calculation
MVP
ML model using
Petro-SIM optimisations
Optimum
APC
energy
Feed MVP open loop
qualities COT
PA duties
Stripping steam rates
Digital Profit Improvement Program Buy time
(PIP) returns $MM - c. 10x it’s cost
Digital twins used for further margin
improvement – real-time unit Digitalise
surveillance, re-optimisation, APC
input and benchmarking
Portfolio transition to address Transition
the Energy Transition
The technology is then readily
available for further real-time unit
surveillance, re-optimisation, and
benchmarking, as well as providing
a constantly updated, asset-wide
model for capital investment studies
to address the energy transition.
Profit Improvement Program and Petro-SIM are
trademarks of KBC (A Yokogawa Company).
Mark Krawec is Global Product Manager –
Process Optimization with KBC, based in
London, UK. He focuses on improving the
delivery of process optimisation consulting
at KBC, considering the standards, tools,
capability and development, and has worked on
numerous performance improvement studies
in the hydrocarbon processing industries all
over the world.
Mike Aylott is Chief Technology Officer with
KBC, based in Calgary, Canada. He is responsible
for the technical direction of KBC, directly
leading the technology R&D programme and
the technology delivery teams, covering digital,
IT and modelling services, support and training.
Simon Calverley is Consulting Product
Integration Director, based in London,
UK. He has worked in the hydrocarbon
processing industries since graduating and
has spent a significant portion of that time
executing profit improvement programmes,
working on both opportunity identification
and implementation. He is a Fellow of the
Institution of Chemical Engineers.
PTQ Q3 2021 85
11/06/2021 15:57
 7th Opportunity Conference theme:

CrudesConference Refining in Transition: Crudes

for Fuels & Petrochemicals in
Demand
OCT. 25-27, 2021 | Par t 1—Vir tual

OPEN FOR REGISTRATION

Register today to take advantage of pre-conference discount by visiting:
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The global upstream and downstream sectors are riding tough waves—one after the other. High hopes of recovery from demand de-
struction due to the coronavirus pandemic have been frustrated by persistent climate scrutiny. Therefore, you are cordially invited to
attend the upcoming two-part Opportunity Crudes conference, which features hands-on industry strategists and technology experts
with knowledge, experiences, and insights on how to tackle challenges and gain benefits during these changing times.

The first part will be held virtually during Oct. 25-27 this year to address uncertainties related to the pandemic recovery and increasing
calls for decarbonization of refining operations in terms of crude processing and products output. The second part of the conference
will be held in person in Houston, TX, during Oct. 24-26, 2022, with presentations on strategies and technologies to meet the new era
of fuel demand and environmental requirements as market and legislation transition pictures become clearer.

Why should you come to this well-known crude-focused, refining-tailored event? You will benefit from our speakers in tackling timely
crude and refining issues centered on four matrices.

• How to stay profitable in an environment of shifting fuel demand and unstable crude prices due to supply dominance by OPEC+
producers

• Ways of decarbonization to meet greenhouse gas emissions-reduction targets, e.g., via crude selection and trades based on car-
bon intensity and carbon taxes, co-processing of conventional oil and biofeeds, and prevention of fouling and corrosion to improve
energy efficiency

• Portfolio adjustments to sustain long-term business viability, i.e., balancing petrochemicals, bitumen asphalt, base oil lubricants,
etc.

• Technology solutions to facilitate both business and energy makeovers, i.e., digitalization and IoT innovations, refinery-PC integra-
tion, crude-to-chemicals, etc.

This 2-1/2 day event consists of five topical sessions covering (1) Global Oil Market Outlook, (2) Crude Procurement Strategies amid
Shifting Crude Market and Changing Quality, (3) Refiners' Game Plan, Revamps, and Technology Requirements to Tackle Urgent Is-
sues, (4) Big Data Analytics & the Emerging Adoption of the Internet of Things (IoT), and (5) Crude Management.

Visit https://opportunitycrudes.com/agenda21.php to review a preliminary agenda of this problem-solving conference.

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opp crudes.indd 1 14/06/2021 09:55

 Managing ammonium salts corrosion
and fouling
An additive overcame corrosion and fouling issues in a FCC unit, avoiding costs arising
from water wash
SURJEET KUMAR, BERTHOLD OTZISK and MICHAEL URSCHEY
Kurita Europe
F
luid catalytic cracker (FCC) and
residue fluid catalytic crack-
ing (RFCC) are important parts
of modern refineries and are used
for converting lower value petro-
leum fractions to valuable compo-
nents. Feedstock to FCC is becoming
increasingly heavy with the process-
ing of atmospheric residue, which
increases the potential for formation
of ammonium salts.
Ammonium salts and their
management
Fractionators in a FCC unit are prone
to corrosion and fouling by ammo-
nium chloride (NH4Cl) and ammo-
nium bisulphide (NH4HS) salts.
Corrosion and fouling are observed
in the fractionator overhead, top
section, and pumparound circuits.
Depending on the partial pressure of
the reactants, and conditions in the
tower, salts can deposit and accu-
mulate at temperatures above the
water dew point. The consequences
of ammonium salts formation in FCC
units are:
• High corrosion in the overhead
line, top section and pumparound
circuit due to absorption of moisture
by ammonium salts
• High delta pressure due to fouling
of trays in the top section which can
result in flooding and loss of tower
efficiency
• Reduced heat exchange across
pumparound circuits due to
exchanger fouling resulting in
reduced heat removal from the tower
Ammonium chloride formation is a
function of localised conditions: tem-
perature, concentration of HCl, and
concentration of NH3:
NH3 (gas) + HCl (gas) → NH4Cl (solid)
www.digitalrefining.com
q3 kurita.indd 1
As the partial pressures of NH3 and
HCl increase and the temperature
decreases, the potential for ammo-
nium chloride fouling increases.
Under-deposit pitting corrosion is
predominantly caused by ammo-
nium chloride salt due to its hygro-
scopic nature. Chloride ions react
with iron to form iron chloride which
results in severe localised corrosion.
In the presence of H2S, iron chloride
reacts to form iron sulphide, and
chloride ion is released again to con-
tinue the process of corrosion.
Refineries sometimes also face the
problem of amine chloride salt for-
mation (RNH3Cl) due to overdosing
of amine to meet the pH of overhead
condensed water which, like NH4Cl,
results in localised under-deposit
corrosion.
Ammonium bisulphide is formed
by the reaction of ammonia and
hydrogen sulphide:
NH3 + H2S → (NH4)HS
Ammonium bisulphide is also
corrosive towards steel and forms
hydrogen gas and iron sulphide in
the corrosion process. Normally, the
iron sulphide formed coats the sur-
face of the metal to stop further corro-
sion and the corrosion mechanism is
terminated. But if cyanide is present
then it will react with iron sulphide to
form a soluble ferrocyanide complex
which will remove the protective iron
sulphide layer so that the corrosion
reaction of ammonium bisulphide
with the metal surface can continue:
FeS + 6 CN- → Fe(CN)64- + S2-
If corrosion due to ammonium
bisulphide continues then this can
lead to hydrogen blistering in the
system due to the formation of
hydrogen atoms that penetrate the
metal surface.
Refineries often use oil soluble
filming amines to mitigate corrosion.
At higher concentrations they act as
salt dispersants to stop fouling prob-
lems due to ammonium salt forma-
tion. These products just transport
salts from one location to another
and hence the problem is shifted to
another downstream location and is
not completely resolved. They work
by chemically binding to salts, and
if sufficient free water is not present
to solubilise the salts then it can be
found in product streams as well.
Filming amines are surface active
products and can stabilise emulsions.
Refineries also use continuous or
intermittent wash water to remove
ammonium salt deposits and thus
minimise under-deposit corrosion
and fouling. These water wash sys-
tems can be counter-productive in a
refinery because the choice of wash
water quality is defined by availa-
bility of water, and the right quality
of water is not always available in
abundance. The best source for water
wash is either steam condensate or
properly stripped water from the
sour water stripper unit. Generally,
water wash is 6-7 vol% on fresh feed
to the FCC unit.
An insufficient or poorly designed
wash water system can lead to
increased corrosion as ammonium
salts form acidic solutions when dis-
solved in water. Dead areas, bends,
and low flow areas are prone to
acidic under-deposit corrosion if
the wash water is not sufficient; this
leads to formation of highly concen-
trated thick and viscous salt solu-
PTQ Q3 2021 87
11/06/2021 15:59

Figure 1 Dried ACF-Cl salts convert from solid to liquid form on exposure to atmospheric
humidity inside the laboratory, illustrating the highly hygroscopic nature of ACF-Cl salt
tions. Wash water can also lead to
reduced productivity due to off-spec
product, thus increasing reprocessing
costs.
Ammonium Chloride Free (ACF)
technology
Kurita’s ACF technology is a solution
which can eliminate problems related
to ammonium and amine salts in var-
ious refinery units including the FCC
unit. Features of ACF technology
include:
1. Liquid formulation of a very
strong organic base. The pKb value
of ACF product is close to zero which
indicates a very strong base.
2. Instantaneous reaction with HCl
and ammonium salt deposits, hence
quick results can be achieved.
3. Water soluble and does not react
with hydrocarbons, hence no con-
tamination of hydrocarbon product
streams.
4. A single product can be used to
handle ammonium chloride, organic
Salt
fouling
Salt fouling
Figure 3 Salts fouling in a RFCC fractionator
88 PTQ Q3 2021
q3 kurita.indd 2
amine chloride, and ammonium
bisulphide related corrosion and
deposition problems.
5. The reaction product with salts
is ACF-Cl, which has neutral pH,
unlike ammonium salts which form
acidic reaction products.
6. ACF-Cl salts are highly hygro-
scopic and are easily removed from
the system with free water in the sys-
tem (see Figure 1).
7. The corrosion potential of ACF-Cl
salts is very low, unlike ammonium
salts which are highly corrosive.
Kurita ACF works via two modes
(see Figure 2):
1. Removal of existing deposits from
piping, trays, and heat exchanger
surfaces:
NH4Cl (solid deposit) + ACF → ACF-Cl (Liquid)
+ NH3
2. Reaction with HCl to neutralise it
and form non-corrosive ACF-Cl in
the column overhead and tower:
Gasoline
base material
LCO
HCl NH3
NH3 ACF ACF HCl
Metal surface Metal surface
Liquid ACF-Cl
Excellent fluidity
ACF Low corrosion
potential
NH3 HCl
NH4Cl deposit
High corrosion Metal surface
potential
Figure 2 ACF reaction mechanisms
HCl + ACF → ACF-Cl
Depending on the application,
ACF can be dosed intermittently as
an online cleaner for removing exist-
ing ammonium salt deposits, or it
can be added on a continuous basis
to avoid corrosion and deposition
due to HCl and ammonium salt for-
mation in the system.
Case study: ammonium chloride
fouling removal
Since its commissioning, a refinery
experienced ammonium salts depo-
sition in the RFCC fractionator’s col-
umn top trays and heavy gasoline
pumparound circuit (see Figure 3).
The plant began a regular water
wash to dissolve the ammonium
chloride salts, but this resulted in
increased corrosion potential and
violation of product specification,
leading to reduced productivity and
high reprocessing costs.
Normally, the chloride content in
overhead condensed water are up to
approximately 70 ppm, but during
water washing they are up to 13 900
ppm, which is a clear indication of a
high amount of ammonium chloride
salts deposition.
The plant also introduced salt
dispersants in the tower reflux
and heavy gasoline circuit with-
out much success. In spite of add-
ing high amounts of salt dispersant,
water wash was needed to sustain
operations.
For this plant there was the pos-
sibility to inject ACF in the tower
reflux or heavy gasoline pump-
around circuit and the latter was
selected for dosing. No water wash
www.digitalrefining.com
11/06/2021 15:59
 30.0
29.0
28.0
27.0
26.0
25.0
24.0
23.0
22.0
Delta temperature, ˚C

21.0
20.0
19.0 F
18.0 g AC
rtin
17.0 r sta
afte
16.0 ture
15.0 pera
tem
14.0 elta
in D
ease
Random Packings,
13.0
12.0 Incr
11.0

Catalyst Support
10.0
9.0
8.0
7.0
6.0
5.0 Material and
Column Equipment
Da 1 5 0:00 M
Da -1 00:0 PM
Da 11 0:00 M
Da 2 2 0:0 M
Da 2 5 :00 M
Da y-2 00:0 AM
Da 11 0:00 M
Da 2 2 :00 M
Da 2 5 :00 M
Da y-2 00:0 PM
Da 11 0:0 M
Da 3 2 0:0 M
Da 3 5 :00 M
Da -3 00:0 AM
Da 11 0:00 M
Da 3 2 0:00 M
Da 3 5 :00 M
Da -3 00:0 PM
Da 11 0:00 M
Da -4 2 0:0 M
Da 4 5 :00 M
Da -4 00:0 AM
Da 11 0:00 M
Da 4 2 0:00 M
Da -4 5 0:00 M
Da -4 00:0 PM
Da 11 0:00 M
Da 5 2 0:0 M
Da 5 5 0:00 M
Da -5 00:0 AM

Da 11 0:00 M
Da 5 2 0:00 M
Da 5 5 0:00 M
Da y-5 00:0 PM
Da 11 0:0 M
Da -6 2 0:0 PM
Da 6 5 0:00 M
Da -6 0:0 AM

11 0:00 M
0: M
AM
y- 8:0 0 P
y- :0 P
y- :00 0 P

P
y- :0 0 P
y- :00 0 P

y- 8:0 0 P
y :0 P
y- :00 0 P

P
y- :0 P
y- 0 P

y- :0 P
y- :0 0 A

A
y- :00 A
y- :00 A

y- 8:0 0 A
y- :0 A
y- :00 A

y- 8:0 0 A
y- :0 A
y :0 A

y- 8:0 0 A

y- :0 A
y- :0 A

y- 8:0 0 A
:0 A
y- 8:0 0

y- 8:0 0

y- 8:0 0
y :0 0
0
y- 8:0 0

00
Da -1 2 0:0
y :0

y :0
y :

y :

y :

:
:

y :

y :

:
y :
Da 11

5
1

6
y-
Da

Figure 4 Immediate recovery in delta temperature across a heat exchanger after injection Largest Capacity and
of ACF. Recovery in delta temperature was higher than the target value
Biggest Stock in Europe

1.30
1.28
Cost-Saving due to
1.25 Modern High Performance
1.23
1.20 Random Packings
1.18
1.15
1.13 Catalyst Support
Delta pressure, bar

1.10 Material
1.08
1.05
1.03
1.00
0.98
0.95
0.93
0.90
0.88
0.85 High Performance
0.83 Random Packings
0.80
Da 1 5 0:00 M
Da -1 00:0 PM
Da 11 0:00 M
Da 2 2 0:0 M
Da 2 5 :00 M
Da y-2 00:0 AM
Da 11 0:00 M
Da 2 2 0:00 M
Da 2 5 :00 M
Da y-2 00:0 PM
Da 11 0:0 M
Da 3 2 0:0 M
Da 3 5 :00 M
Da -3 00:0 AM
Da 11 0:00 M
Da 3 2 0:00 M
Da 3 5 :00 M
Da -3 00:0 PM
Da 11 0:00 M
Da -4 2 0:0 M
Da 4 5 :00 M
Da -4 00:0 AM
Da 11 0:00 M
Da 4 2 0:00 M
Da -4 5 0:00 M
Da -4 00:0 PM
Da 11 0:00 M
Da 5 2 0:0 M
Da 5 5 0:00 M
Da -5 00:0 AM

Da 11 0:00 M
Da 5 2 0:00 M
Da 5 5 0:00 M
Da y-5 00:0 PM
Da 11 0:0 M
Da -6 2 0:0 PM
Da 6 5 0:00 M
Da -6 0:0 AM

11 0:00 M
0: M
AM
y- 8:0 0 P
y- :0 P
y- :00 0 P

P
y- :0 0 P
y- :00 0 P

y- 8:0 0 P
y :0 P
y- :00 0 P

P
y- :0 P
y- :0 P

y- :0 P
y- :0 0 A

A
y- :0 A
y- :00 A

y- 8:0 0 A
y- :0 A
y- :00 A

y- 8:0 0 A
y- :0 A
y :0 A

y- 8:0 0 A

y- :0 A
y- :0 A

y- 8:0 0 A
:0 A
y- 8:0 0

y- 8:0 0

y- 8:0 0
y :0 0
0
y- 8:0 0

00
Da -1 2 0:0
y :0

y :0
y :

y :

y :

:
:

y :

y :

y :
Da 11

5
1

6
y-
Da

Figure 5 Immediate reduction in delta pressure across a heat exchanger after starting
ACF injection
was done during application of ACF
for online removal of ammonium
salts from the heavy gasoline pump-
around circuit.
The results of online ACF injection
are shown in Figures 4 and 5.
Other benefits observed were
increased depropaniser bottom tem-
perature, reduction in LCO flow, and
steam to the depropaniser reboilers.
No water wash during the trial
ensured no reduction in unit
throughput and no off-spec product
for reprocessing.
Conclusions
Ammonium salts formation can lead
to unplanned shutdowns and high
operating costs if not managed prop-
erly in the FCC unit. Kurita’s ACF
technology is a solution to avoid
ammonium salts corrosion and foul-
ing in FCC units. Generally, refin-
Ceramic
Random Packings
eries use oil soluble filming amines
or periodic water wash that may
increase corrosion potential, reduce
productivity, and can shift problems
to downstream systems.
ACF technology can completely Plastic
remove deposited ammonium salts Random Packings
and can also avoid formation of new
ammonium salt deposits in the FCC.
The reaction of ACF with ammonium
salts is instantaneous and immediate
results can be achieved. The correct
application will eliminate the need Demister and
Column Internals
for water wash, hence improving
plant integrity and productivity.
Surjeet Kumar is Technical & Marketing Manager
for the Middle East with Kurita Europe.
Email: Surjeet.kumar@kurita-water.com
Berthold Otzisk is Senior Product Manager for
Please visit: www.vff.com
refinery and petrochemical applications with
Kurita Europe.
Email: Berthold.Otzisk@kurita-water.com Vereinigte Füllkörper-Farbriken GmbH & Co.KG
Michael Urschey is R&D Manager with Kurita P. O. Box 552, 56225 Ransbach-Baumbach,
Europe. Email: Michael.Urschey@kurita-water.com Germany, +49 26 23 / 895 - 0, info@vff.com

www.digitalrefining.com PTQ Q3 2021 89

q3 kurita.indd 3 11/06/2021 15:59

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ertc.indd 1 11/06/2021 13:54

 Crude oil vapour pressure testing
Why a higher shaker speed improves the accuracy of measurement

CHRISTIAN SCHRÖDER-HOLZHACKER
eralytics

T
he vapour pressure of crude
oil (VPCR) is a major safety 78
parameter for storage, trans-
port, and handling of crudes. Its reli- 76
able determination is of high interest
74
in the petroleum industry, in par-
Ptot (KPa)

ticular for crude oils featuring a high 72

vapour pressure.
For an ASTM D6377 crude oil 70
measurement, the specimen is intro- 5.7 c/s 4.3 c/s
68
duced into the measuring cell, the 2.9 c/s 1.5 c/s
piston expands against vacuum 66
adjusting a vapour to liquid ratio 0 100 200 300 400 500 600
of 4:1, and the temperature is regu- t (s)
lated to 37.8°C. When the pressure
is stable within a maximum pressure Figure 1 Crude oil 1 measured with a V/L ratio of 4.00 and variable shaking speeds
variation of 0.3 kPa/60s the VPCR is between 1.5 c/s to 5.7 c/s. The equilibrium points according to ASTM D6377 are marked
determined.
Compared to simple spark ignition 78
fuels or other petroleum based final
products, crude oils have a much 76
more complex composition, and
74
their volatility (vapour pressure) may
Ptot (KPa)

range from <1 kPa up to atmospheric 72

pressure or even above. Furthermore,
other crude oil properties like viscos- 70
ity play an important role for vapour
68 4.3 c/s 1.5 c/s
pressure measurement. A higher
viscosity significantly influences the 66
degassing process and delays the for- 0 300 600 900 1200 1500 1800
mation of a thermodynamic pressure t (s)
equilibrium. Therefore, to improve Figure 2 Crude oil 1 measured with a V/L ratio of 4.00 and variable shaking speeds of 1.5
repeatability and to speed up the c/s and 4.3 c/s up to 1800 s. The equilibrium points according to ASTM D6377 are marked
measurement, shaking of the meas-
urement cell during the measurement
is mandatory in ASTM D6377. 12
The first vapour pressure instru-
11
ments on the market could only
shake the sample with about 1.5 10
cycles per second, and therefore
Ptot (KPa)

ASTM D6377 required the relatively 9

ambiguous shaking speed minimum
8
frequency of 1.5 c/s. In contrast, mod-
ern instruments such as eralytics’ 7
5.7 c/s 4.3 c/s
2.9 c/s 1.5 c/s
Eravap can apply much higher shak-
ing speeds, leading to the question of 6
0 100 200 300 400 500 600
the influence of shaking speed on the t (s)
ASTM D6377 measurement.
The intention of this article is to Figure 3 Crude oil 2 measured with a V/L ratio of 4.00 and variable shaking speeds
clarify the following questions: between 1.5 c/s to 5.7 c/s. The equilibrium points according to ASTM D6377 are marked

www.digitalrefining.com PTQ Q3 2021 91

Q3 eralytics.indd 91 11/06/2021 16:05

 an integrated density meter mod-
12 ule EV10-D4052. The density (ASTM
D4052) and vapour pressure (ASTM
11 D6377) were determined simultane-
ously for each sample.
10
To demonstrate the impact of
Ptot (KPa)

9 shaking speed and measuring time,

initially two different crude oils were
8 measured with a V/L ratio of 4.00
at 37.8°C (100°F). Crude oil 1 (ρ  =
7 4.3 c/s 1.5 c/s
0.8364 g/cm³) had a considerable
6
fraction of volatiles and was stored
0 300 600 900 1200 1500 1800 in a floating piston cylinder (FPC)
t (s) with a back pressure of 300 kPa.
Crude oil 2 (ρ = 0.8374 g/cm³) can be
Figure 4 Crude oil 2 measured with a V/L ratio of 4.00 and variable shaking speeds of 1.5 considered as ‘dead’ and was sam-
c/s and 4.3 c/s up to 1800 s. The equilibrium points according to ASTM D6377 are marked pled with a standard tube from an
open sample container. Both crudes
were measured at various shaking
64 speeds, ranging from 0 c/s to 5.7 c/s
and each measurement was repeated
60
two times to verify the result.
56 Initially, the conducted shaking
speeds were reported as 1.5, 3.0, 4.5,
Ptot (KPa)

52 and 6.0 c/s. Further investigation

showed that for the higher shak-
48
ing speeds these values had to be
44 4.3 c/s 2.9 c/s 1.5 c/s revised to 2.9, 4.3, and 5.7 c/s.  
To expand the investigation, two
40 additional crude oils from Canada
0 100 200 300 400 500 600
were investigated, as reports have
t (s)
indicated that these crudes show a
particularly large sensitivity to shak-
Figure 5 Crude oil 3 measured with a V/L ratio of 4.00 and variable shaking speeds ing speed. Crude oil 3 (ρ = 0.9274 g/
between 1.5 c/s to 4.3 c/s. The equilibrium points according to ASTM D6377 are marked cm³) features a significantly higher
viscosity than the previous two
samples and a vapour pressure
64 comparable to crude oil 1. Crude
oil 4 (ρ = 0.8193 g/cm³) showed a
60 low viscosity while having an even
56
higher vapour pressure than any
of the other samples. Both crudes
Ptot (KPa)

52 were kept in an FPC and the vapour

48
44
40
0 300 600
Figure 6 Crude oil 3 measured with a V/L ratio of 4.00 and variable shaking speeds of 1.5
c/s and 4.3 c/s up to 1800 s. The equilibrium points according to ASTM D6377 are marked
• How is the VPCR result affected by
changes in the shaking speed?
• Is there a bias between the VPCR
and an “equilibrium vapour pres-
sure result” and does this depend on
the shaking speed?
• Does a higher shaking speed
pressure was determined at shaking
speeds ranging from 1.5 c/s to 4.3
c/s.
4.3 c/s 1.5 c/s
The measurement curves (see
Figures 1 to 8) depict the pressure
900 1200 1500 1800
during the progressing measurement
t (s)
in dependence of the applied shaking
speed. The point of the ASTM D6377
stability criterion is marked.
Discussion
reduce the measurement time? The measurements of the four differ-
• Is there an optimum shaking ent crude oils shown in Figures 1 to
speed? 8 all demonstrate the strong impact
of shaking speed on the vapour
Experimental pressure measurement. The higher
The following measurements were the shaking speed, the higher the
conducted on an Eravap EV10 with recorded pressures. Also, a higher

92 PTQ Q3 2021 www.digitalrefining.com

Q3 eralytics.indd 92 11/06/2021 16:05

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 shaking speed significantly speeds
110
up the formation of a stable pressure.
Table 1 contains the time and
100
VPCR results (the pressure readings
when the stability criterion accord-
90
Ptot (KPa)

ing to ASTM D6377 is reached). The

difference between a VPCR result
80
obtained with a shaking speed of 1.5
c/s 4.3 c/s ranges from 1.9 kPa (0.28
70
4.3 c/s 2.9 c/s 1.5 c/s psi) for crude oil 1 to 7.4 kPa (1.07 psi)
for crude oil 3. Also significant is the
60
0 100 200 300 400 500 600 difference in measurement time. The
t (s) time for reaching the stability crite-
rion of ASTM D6377 correlates with
Figure 7 Crude oil 4 measured with a V/L ratio of 4.00 and variable shaking speeds the shaking speed and the viscosity:
between 1.5 c/s to 4.3 c/s. The equilibrium points according to ASTM D6377 are marked for crude oil 3, at the minimum fre-
quency of 1.5 c/s this pressure stabil-
ity is reached after 884 s, whereas at
4.3 c/s it takes only 342 s.
At the minimum shaking speed of
1.5 c/s, the pressure continues to rise
significantly even after the ASTM
D6377 cut-off criterion is reached.
This results in a large difference
between the VPCR result and the
equilibrium vapour pressure. The
bias between the VPCR and the actual
equilibrium vapour pressure result
(pressure at 1800 s with shaking
speed of 4.3 c/s) can be as large as 7.4
kPa when a minimum shaking speed
of 1.5 c/s is applied. For a shaking

Technical
speed of 4.3 c/s, this bias is signif-
icantly smaller, implying a higher
accuracy for these measurements.

competence
Clearly visible for all four crudes
at shaking speeds of 4.3 c/s (or
above), the pressure eventually
does not change any more. It can be
argued that at this point a thermody-
namic vapour pressure equilibrium
has been achieved. In this regard,
a shaking frequency of 4.3 c/s can
be considered a critical threshold.
When using a slower shaking speed,
the formation of a thermodynamic
Service with passion
vapour pressure equilibrium could
not be observed within a reasona-
We at MAN PrimeServ understand that performance
and reliability are paramount to your business.
ble measurement time. On the other
You need technical competence that drives your hand, applying shaking speeds
success. MAN PrimeServ’s many decades of hands- above 4.3 c/s does not change the
on experience and its diverse portfolio provide this.
With MAN PrimeServ as your partner you benefit final VPCR result any further, even
from state-of-the-art technical and digital solutions though the final pressure level is
that fit your individual situation. What’s more, these
benefits are brought directly to your business through
reached slightly faster.
a global network of local experts. Whatever the time
and wherever you are in the world, you can count on Conclusions
MAN PrimeServ as a strong service solution provider
for your needs. • A higher shaking speed leads to a
higher VPCR.
To find out more about our technical competence,
please visit:
• The difference between a VPCR
result obtained with a shaking speed
www.man-es.com of 1.5 c/s and 4.3 c/s can be as large
as 7.4 kPa (1.07 psi).

94 PTQ Q3 2021 www.digitalrefining.com

2106_19645_MAN_PS_Anzeige_TechnicalCompetence_ENG_reSe_115x190mm_USWebCoated.indd 1 25.05.21 15:59

Q3 eralytics.indd 94 11/06/2021 16:05

 • Applying shaking speeds of 4.3
c/s or above eventually leads to the 110
formation of a thermodynamic equi-
librium vapour pressure. 100
• A VPCR result obtained at a
higher shaking speed (4.3 c/s or 90

Ptot (KPa)
above) is closer to (or at) the actual
thermodynamic equilibrium vapour 80
pressure, meaning this result is more
accurate. 70
4.3 c/s 1.5 c/s
• The measurement time for ASTM
D6377 can be reduced significantly 60
0 300 600 900 1200 1500 1800
by increasing the shaking speed. t (s)
• For Eravap, a shaking speed
of 4.3 c/s (= “36” in the method Figure 8 Crude oil 4 measured with a V/L ratio of 4.00 and variable shaking speeds of 1.5
parameters) was found to be the c/s and 4.3 c/s up to 1800 s. The equilibrium points according to ASTM D6377 are marked
optimum setting for ASTM D6377
measurements. Time and pressure readings when the stability criterion of 0.3 kPa/60 s (ASTM
D6377) is reached and the bias to the final pressure
Recommendations
Measurement Equilibrium: time and pressure
• Always agitate the sample with Sample Parameter 0 c/s 1.5 c/s 2.9 c/s 4.3 c/s 5.7 c/s
the highest shaking speed possible. Crude 1 Time (VPCR) 354 s 352 s 222 s 128 s 110 s
This results in a VPCR closer to (or VPCR 74.6 kPa 74.6 kPa 75.9 kPa 76.5 kPa 76.5 kPa
at) the actual thermodynamic equi- Bias 2.1 kPa 2.1 kPa 1.8 kPa 0.2 kPa 0.2 kPa
Time (eq.) - - - 230 s 210 s
librium vapour pressure. Pressure (eq.) - - - 76.7 kPa 76.7 kPa
• Include the shaking speed when-
ever comparing or reporting results. Crude 2 Time (VPCR) 124 s 126 s 210 s 82 s 60 s
Many established vapour pressure VPCR 7.9 kPa 7.9 kPa 9.0 kPa 10.5 kPa 10.6 kPa
Bias 2.7 kPa 2.7 kPa 1.6 kPa 0.1 kPa 0 kPa
testers provide only limited shaking Time (eq.) - - - 128 s 90 s
speed (<< 4.3 c/s) and will therefore Pressure (eq.) - - - 10.6 kPa 10.6 kPa
not reach thermodynamic equilib-
rium vapour pressure and report a Crude 3 Time (VPCR) 884 s 638 s 584 s 342 s -
VPCR 54.5 kPa 53.3 kPa 59.3 kPa 61.0 kPa -
too low VPCR result. Bias 7.4 kPa 8.6 kPa 2.6 kPa 0.9 kPa -
ERAVAP is a mark of eralytics GmbH. Time (eq.) - - - 1240 s -
Pressure (eq.) - - - 61.9 kPa -
Christian Schröder-Holzhacker is a Product
Manager with eralytics GmbH, Vienna, Crude 4 Time (VPCR) 866 s 840 s 440 s 124 s -
Austria. With prior experience in academia, VPCR 95.1 kPa 95.3 kPa 98.5 kPa 99.0 kPa -
his expertise is vapour pressure and flashpoint Bias 4.2 kPa 4.0 kPa 0.8 kPa 0.3 kPa -
Time (eq.) - - 856 s 354 s -
determination of various products throughout
Pressure (eq.) - - 99.3 kPa 99.3 kPa -
the petroleum industry. He holds a PhD in
synthetic chemistry from the Vienna University
of Technology, Austria. Table 1

T +49 2961 7405-0

T +65 6702 3707

Made
in
Germany

Your Specialist for

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PRESSURE RELIEF
SOLUTIONS in the
OIL & GAS INDUSTRY
Consulting. Engineering. Products. Service.

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 Bringing Together the Global Distillation Expertise
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 Modelling and optimising bitumen
hydrocracking
A rigorous hydrocracking model for the quoted catalysts is used for predicting
hydrogen consumption and product yields to maximise operating revenues
HAIMING LAI
Dynamic Simulation & Consultancy
T
he Canadian oil sands indus-
try reached peak production
of roughly 3.4 million barrels
of combined mining and in situ
bitumen at the end of 2018. Only
55% of these barrels is upgraded
to sweet synthetic crude oil (SCO).
Despite low oil prices and sev-
eral months of lockdown during
the pandemic, Canadian oil sands
production remains resilient and
maintained about 3.0 million b/d in
March 2020.
Two business factors have been the
driving forces behind the bitumen
upgrading process in the Canadian
oil sands industry. One factor is to
recover the expensive diluent which
is then recycled back to steam-
assisted gravity drainage (SAGD)
central processing facilities, and the
other is to produce high value-added
SCO to eliminate the impacts of the
volatile market price spread between
WTI and WCS on the SAGD or min-
ing operations. So far there is still a
lack of adequate capacity to upgrade
most produced bitumen to SCO. The
production of finished oil products
from Canadian bitumen requires
either new, integrated upgrading
and refining facilities, or the revamp-
ing or debottlenecking of existing
upgrading/refining plants. There
are two primary bitumen upgrad-
ing technologies: coking and hydro-
conversion. Currently, coking based
upgraders have predominated in the
bitumen upgrading market. In this,
asphaltene residue is converted to
petroleum coke and hydrogen is pro-
duced by reforming natural gas. This
coking based upgrading scheme has
become the standard template for
building an upgrader in Alberta.
The primary challenge with
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Q3 dynasim.indd 97
Diluent
Diluent Vacuum
Dilbit
recovery
AR
Distillation
VR
unit unit
VGO
AGO
Hydrocracker
unit
SCO LE
Light end
recovery
SCO blending
Figure 1 Integrated bitumen upgrading process with SDA, hydrocracker, and gasifiers
Canadian bitumen is the large
percentage of bottoms to be dealt
with, as well as the relatively high
asphaltenes, sulphur, and metals
content of those bottoms. To use
fixed-bed hydrocracking technol-
ogies, a feed clean-up unit such
as a solvent deasphalter (SDA)
should be installed upstream of the
hydrocrackers to reject the heaviest
CCR and metals as a pitch stream.
Recently most commercial applica-
tions on bitumen upgrading config-
urations have focused on selection
of primary upgrading technology
and how to deal with low-valued
unconverted pitch/asphaltene.
There is a growing trend in the
industry to utilise asphaltene gas-
ification for hydrogen production
to eliminate coking waste and its
on-site storage. Examples include
Long Lake upgrader and the North
West Surgeon refinery.1
A proposed bitumen upgrading
scheme based on the above con-
siderations is shown in Figure 1.
The bitumen upgrading process is
integrated with a SDA for primary
Air separation
unit
Solvent
Deasphalting
Asphaltene O2
unit
Asphaltene
gasification
DAO unit
H2
Syngas
Synthetic crude oil
upgrading, fixed-bed hydrocracking
for second upgrading, and asphal-
tene gasification for hydrogen pro-
duction. Once the asphaltene has
been separated from the vacuum
residue, the deasphalted oil (DAO),
along with atmospheric gasoil
(AGO) and vacuum gasoil (VGO), is
easier to process in the hydrocrack-
ing unit. The heavy asphaltene or
pitch can be completely converted
to synthesis gas and hydrogen
products through gasification. This
configuration has no undesired or
low-value coke byproducts and is
therefore truly bottomless. Detailed
research work on bitumen upgrad-
ing configurations will be published
later. As a key hydroconversion
process, this article mainly focuses
on process modelling and optimisa-
tion of the hydrocracking unit and
light end recovery (LER) system.
 
Predictive hydrocracking model
Process description
Figure 2 shows the process flow
diagram of a single stage AGO/
VGO/DAO hydrocracking unit
PTQ Q3 2021 97
14/06/2021 10:33
 Vapour Vapour
R1
Vapour
RG
MU H2 Compressor
RG
Purge
Amine
scruper Depropaniser
LE
R1
HP
Furnace steam
feed Vapour
MU H2

Feed mix
Furnace
feed
R1

R1

MP
steam
RG
Compressor

Amine
scruper

H2S
RG
Purge

HPS

HP steam
Vapour

LPS
Vapour

LE

SCO stripper

LP steam
Depropaniser

HP
steam
Vapour

Debutaniser

MP
steam

SCO
C5+
C4
Vapour

Blending
SCO
H2S
Debutaniser
LPS
HPS
C4
SCO stripper MP
Feed mix MP steam
steam
Blending
C5+ SCO
LP steam
HP steam

SCO

Figure 2 Process flowsheet of hydrocracking unit, light end recovery, and SCO blending

and LER unit. The purpose of the from the reactor effluent, the efflu-
hydrocracking unit is to process ent is routed to the high pressure
AGO from the diluents recovery separator (HPS) to separate recycle
unit (DRU), VGO from the vacuum hydrogen stream, sour water, and
distillation unit (VDU), and DAO hydrocarbon. Recycle hydrogen
from the SDA, convert these feeds will be routed to an amine scrub-
into SCO, and blend with C4 and C5+ ber to remove sulphur and ammo-
from the LER unit into the final SCO nia compounds prior to recycle.
products. Compressed recycle hydrogen will
The AGO/VGO/DAO feed be supplemented with make-up
is mixed with recycled gas and hydrogen from the gasifiers as
make-up hydrogen and heated up required for the hydrocracker unit
by the effluent heat exchangers operation. Hydrocarbon products
and feed furnace. The combined will be stripped of sulphur com-
feed enters through two fixed- pounds and light hydrocarbon
bed reactors in series – R1 of the
hydrotreater and R2 of the hydro- Feed properties and product yields
cracker, each consisting of three
beds. Within the R1 reactor, a cat- Feed properties Data
alyst guard zone is utilised to trap Gravity, API 18.9
Sulphur, wt% 3.6
metals present in the feed, while Nitrogen, wtppm 2041
the high activity hydrotreating Metal (Ni+V), wtppm 48
catalysts reduce the sulphur and
nitrogen contents. The produced Operating conditions
LHSV of R1/R2, hr-1 1.18/1.75
hydrogen sulphide and ammonia Pressure, MPa 18.0
can then be removed from the recy- Inlet temperature to R1, °C 370
cle gas loop. Hydrotreated feed will Gas/oil ratio, Sm3/m3 620
be quenched with recycle hydrogen H2 consumption, Sm3/m3 297
Product yields
and then routed to the R2 reactor NH3, wt% 0.18
for hydrocracking processes. In the H2S, wt% 3.50
hydrocracker, long-chain mole- Gas (C1-C4), wt% 4.78
cules will be cracked to short-chain Naphtha (C5-221°C), wt% 34.87
Distillate (221-371°C), wt% 38.65
molecules. Both R1 and R2 reactors Gas oil (371-538°C), wt% 19.20
contain specially ordered fixed-bed Resid (538°C+), wt% 1.09
catalysts. Total yields, wt% 102.27
After process heats are recov-
ered and MP steams are generated Table 1
products. The stripper bottom prod-
ucts will become the primary SCO
blending component. The stripper
overhead distillate will be routed to
the LER unit for further separation
in the depropaniser and debutaniser
to recover usable fuel gas and C4
and C5+ components. The C4 and C5+
components will be blended with
the primary SCO to produce the
final SCO products.
Predictive hydrocracking model
To perform a parametric sensitivity
analysis and optimise the operation
of the hydrocracker, a system model
is needed for the hydrocracker and
LER system. Fundamentally, sys-
tem modelling of the hydrocracking
processes consists of three layers of
modelling scope2:
• Hydrocracking kinetic model
• Reactor model
• Process system model
The key layer is the kinetic model
which focuses on the kinetic anal-
ysis of complex reaction networks
to study reaction mechanisms, cat-
alyst activities, and deactivations,
as well as the influence of reac-
tion conditions. The reactor model
quantifies the reactor performance
– product yields, hydrogen con-
sumption, utility usages. A process
system model is used for the opti-
misation of unit or upgrader-wide
operating conditions to maximise

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 profits and enhance process safety.
There are two types of refining reac- 45 88
tion modelling: correlation model- 40 86

Conversion, %
Mass yields, %
ling and first principles modelling. 35 84
Correlation modelling is empiri- 30 82
cally a ‘cause and effect’ model that 25 80
20 78
correlates one variable to another,
15 76
whereas first principles modelling 10 74
is based on the chemical reaction 360 365 370 375 380 385 390 395 400
fundamentals of kinetics, mass, and WART of HCR,˚C
heat balances, with consideration of Naphtha yields Distillate yields Gas oil yields Conversion
the following factors of the petro-
leum species:
• The large number of (unknown) Figure 3 Mass yields vs hydrocracker WART
chemical compositions present
• Knowledge of true kinetic behav- mine the economics of hydroc- ibrated Hysys model is used to pre-
iour with the presence of thousands racking operation. The deeper the dict product yields and hydrogen
of system compounds is largely hydrocracker severities, the higher consumption. The major operating
incomplete or unknown the SCO API and product volume variables that affect hydrocracking
A combination of first princi- yields, which generate higher sales performance include the reactor tem-
ples and correlational approach to revenues based on the product vol- perature and gas-to-oil ratio.
kinetic lumping modelling is uti- umes. On the other hand, this also
lised to develop practical models of consumes more hydrogen, result- Reactor temperature
the hydrocracking system.3 A first ing in significantly higher operating Reactor temperature is the primary
principles framework is preferred to costs. To reach maximum operating mean for severity control of the
form the kinetic basis, while corre- profit there exists an optimal hydro- hydrocracking reactions. Figures
lated calibration is also required to cracker severity. In order to optimise 3-5 illustrate the effects of the
bridge the gap between the model’s the hydrocracking processes, the cal- weighted average reactor temper-
results and actual unit performance.
In this case study, the hydroc-
racker unit model (HCR) of Aspen 350
Hysys Petroleum Refining is used
H2 consumption, Sm3/m3

300
to simulate the single-stage hydroc- 250
racking process system.
200
To find cost effective solutions to
the upgrading operation, a list of 150
revamps and debottleneck options 100
has been evaluated, which would 50
affect hydrocracker feed and avail-
0
ability of hydrogen for the hydroc- 360 365 370 375 380 385 390 395 400
racker. To align with and validate WART of HCR,˚C
the hydrogen consumption and H2 Chem cons Purge H2 H2 losses Total MU H2
economics of revamp options, the
recommended catalyst types, load-
ings, and estimated yields for the Figure 4 Hydrogen consumption vs hydrocracker WART
HCU from several catalyst ven-
dors was collected and reviewed.
Table 1 lists the hydrocracker feed 46 65
properties and product yields for 44
SCO production, kB/d

60
selected commercial catalysts. This 42 55
set of process data along with the 40
SCO API

50
38
reactor geometries, catalyst load- 45
36
ings, reactor operating pressure and 40
34
temperature, and expected product 35
32
distribution is used to calibrate the 30 30
catalyst reaction activity parameters 360 365 370 375 380 385 390 395 400
of the hydrocracker. WART of HCR,˚C

SCO API Blending API SCO prod Blending prod

Parametric sensitivity analysis
The hydrocracker’s reaction severity
is a key operating factor to deter- Figure 5 SCO API and production vs hydrocracker WART

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 Gas-to-oil ratio
40 90
There is a limited operating range
of gas-to-oil ratios for the existing
35 88
hydrocracking system. The higher
Mass yields, %

Conversion, %
86
30 gas-to-oil ratio demands higher
25
84 compressed capacities in the recy-
82 cle gas compressors and higher
20
80 reactor inlet pressure to overcome
15 78 the higher pressure drops for
10 76 both reactors and the recycle gas
400 600 800 1000 1200 1400 1600
loop system. A higher operating
Gas/oil ratio
pressure leads to a higher hydro-
Naphtha yields Distillate yields Gas oil yields Conversion gen partial pressure which can
enhance aromatic hydrogenation,
increase the H/C ratio of prod-
Figure 6 Mass yields vs gas-to-oil ratio ucts, and extend catalyst life by
reducing coke depositions. On the
other hand, a higher hydrogen par-
400 tial pressure also leads to higher
380 hydrogen consumption, which
H2 consumption, Sm3/m3

360 increases operating costs.

340
Figures 6 and 7 illustrate the
320
effects of gas-to-oil ratios on prod-
300
280
uct yields, conversion, and hydro-
260 gen consumption. As the ratio
240 increases, conversion and hydro-
220 gen consumption also increase,
200 and gasoil yields decrease. In con-
400 600 800 1000 1200 1400 1600
sideration of optimum conversion
Gas/oil ratio
and process profitability, gas-to-oil
ratios of 600-700 are recommended
Figure 7 Hydrogen consumption vs gas-to-oil ratio as optimal.

ature (WART) of the hydrocracker hydrocracking processing of middle Economic analysis

reactor on product yields, hydrogen distillate, causing the distillate yield The economic basis for a bitumen
consumptions, as well as effluent/ to drop. From the predictive simu- upgrader in Western Canada has
blending SCO API and production lation results, we can conclude that been to convert the bottom of the
capacities. The total hydrogen con- the optimum WART temperature is barrel to sweet synthetic crude oil
sumptions in Figure 4 are estimated within the range 380-385°C and the as well as to capture the volatile
by three parts: hydrogen chemical corresponding SCO capacities reach price spread between discounted
consumptions, purge hydrogen, a maximum production of approx- Canadian heavy oil/bitumen of
and hydrogen losses. The responses imately 59 000 b/d with a volume Western Canadian Select and light/
of the two SCO products’ API and yield of 110%. synthetic crude oil. The major
capacities (reactor effluent SCO operating costs considered for the
and final blending SCO) to changes Assumed hydrocracking cost data hydrocracking and LER systems
in reactor operating temperature are divided into two groups: uncon-
is shown in Figure 5. Conversion, trolled market pricing of WTI and
Item description Data Unit
hydrogen consumption, and blend- WCS, and variable and controllable
Upgrader reliability 92%
ing SCO API increases while WART Days per year 335.8 d operating costs. The key control-
increases. A rise in the hydrocracker USD to CAD rate 1.3 $/USD$ lable cost items include hydrogen
reactor temperature enhances reac- WTI price 30 USD$/Bbl energy cost, electricity power con-
SCO discounted 0%
tion severity. For product yields, sumption, and HP, MP, and LP
SCO price 39.0 $/Bbl
the naphtha yield increases, and the WCS price 20 USD$/Bbl steam usages. Table 2 lists the
gasoil yield decreases significantly Crude feed discounted -20% assumed unit cost data for the base
while WART increases. Increasing Crude feed price 31.2 $/Bbl case.
H2 energy price 0.138 $/Sm3
the reactor temperature shifts prod- Under the fixed process condi-
Electricity price 50 $/MWh
uct distribution from heavier to HP steam (4000 kPag) 16 $/ton tions of the base case, the impacts
lighter products. However, increas- MP steam (1100 kPag) 12 $/ton of the hydrocracker reactor tem-
ing WART does not always benefit LP steam (350 kPag) 6 $/ton perature of WART on SCO vol-
the hydrocracker and may acceler- ume yields, hydrogen costs, total
ate coke formation and secondary Table 2 operating costs, and operating

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 revenues are analysed in Figures 8
and 9. As the WART of the hydro-
cracker increases, the unit severity, 140

Operating cost/revenue, MM$/yr

hydrogen costs, and blending SCO 130
API always increase. In the WART 120
operating range of 360-400°C, the
100
maximum SCO volume yield is
about 110.5 vol% at a WART of 100
389°C, and the maximum operat- 90
ing revenues are $88.6 million per
80
year at a WART of 380°C with a
SCO gravity of 42°API. The optimal 70
360 365 370 375 380 385 390 395 400
WART for maximising operating WART of HCR,˚C
profits is roughly 10°C lower than
the WART value for maximising Operating revenue H2 cost Operating cost

SCO yield.

Conclusion Figure 8 Operating revenue/costs vs WART

Hydrocracking is one of most ver-
satile processing steps currently
available for modern upgraders or
refineries. This case study presents 111.0 45
detailed modelling and optimi- 44
110.5
sation of a deasphalting bitumen 43
SCO yield, v%

hydrocracking process using Hysys 110.0

SCO API
42
Petroleum Refining. The hydroc-
racking model was developed and 109.5 41
calibrated based on representa- 40
tive data from catalyst vendors. 109.0
39
Operating parameter sensitivity
108.5 38
analyses of the reactor tempera- 360 365 370 375 380 385 390 395 400
ture of WART and gas-to-oil ratio WART of HCR,˚C
on product yields and hydrogen
Volume yield SCO API
consumptions were performed.
It was concluded that under the
charged feed properties, the fixed Figure 9 SCO yield and API vs hydrocracker WART
operating conditions, and the
ordered catalyst activities shown
in Table 1, the rigorous simulation Integrating process References
1 K Heal, K Kemp, North West Sturgeon
model predicted the following unit
performance: modelling and Refinery project overview – carbon capture
through innovative commercial structuring in
• Maximum annual operating rev-
enue is about $88.6 million at the
simulation flowsheets the Canadian Oil Sands, Energy Procedia 37,
7046-7055, 2013.
optimal R2 WART of 380°C with can be considered an 2 A-F Chang, K Pashikanti, Y A Liu, Refinery
SCO gravity of 42°API and produc- Engineering: Integrated Process modelling and
tion of 59 000 b/d important and useful Optimization, WILEY-VCH Verlag GmbH & Co.
• The maximum SCO volume yield KGaA, 2012.
is about 110.5 vol% at a R2 WART tool to aid bitumen 3 R T Powell, C-y Yu, Refinery reaction
of 389°C modelling trends, Hydrocarbon Engineering, Jan
• Hydrocracker conversion of upgrading process 2004.
roughly 82% and hydrogen con-
sumption of roughly 297 Sm3/m3 for design, operation, and HaiMing Lai is a Principal Consultant with
the optimal operating point.
Integrating process modelling
optimisation Dynamic Simulation & Consultancy Ltd, Calgary,
Canada. He has over 20 years’ experience in
and simulation flowsheets is a cost modelling and dynamic simulation, process
effective way to optimise operat- design and operation in the upgrader/refinery
ing scenarios. Therefore, it can be HYSYS is a mark of Aspen Technology. and petrochemical industries. He holds a PhD
considered an important and use- in chemical engineering from Beijing University
ful tool to aid bitumen upgrad- Acknowledgement of Chemical Technology and is a registered
ing process design, operation, and The author is grateful for the support of Li’s professional engineer in Alberta, Canada.
optimisation. Process Consulting Services Inc. Email: hmlai@shaw.ca

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 Technology in Action
Multi-phase project enables switch to heavier crude
In recent years, deasphalted oil (DAO) hydrocracking
has emerged as a highly attractive investment option,
principally because it provides the opportunity to simul-
taneously address two key objectives. First, it enables
refiners to include greater proportions of lower-priced
opportunity crudes in their diets, which has the potential
to increase margin significantly. Secondly, it offers the
opportunity to reduce fuel oil production.
In today’s new reality, refiners are likely to adopt a
more conservative approach to capital investment, but
a recent project by Hyundai Oilbank provides a compel-
ling demonstration of how refiners can unlock business
improvements by taking a phased approach. The South
Korean refiner began to generate cash with a series of
strategic investments, which it then used to fund addi-
tional projects.
Hyundai Oilbank’s project began in 2016, when it iden-
tified an opportunity to improve margins at its Daesan
refinery by moving from a medium-sour Middle East
crude blend towards super-heavy crudes such as Maya
and Basrah Heavy. These low-priced crudes can provide
high margins but are extremely challenging to process.
One of the site’s key constraints for processing a more
difficult crude slate had been the maximum allowable
metals content that the existing atmospheric residue des-
ulphurisation (ARDS) unit could process. This unit con-
sisted of two identical reactor trains (modules) that had
fully independent high pressure sections and a common
work-up section.
Phase 1: Deasphalting and moving to mild hydrocracking
(MHC) service
In Phase 1, Hyundai Oilbank installed a new C5 sol-
vent deasphalting (SDA) unit (a residuum oil super-
critical extraction, or ROSE, unit licensed by KBR) and
revamped the existing delayed coker to enable co-pro-
cessing of vacuum residue and ROSE pitch feed.
Together with Shell Catalysts & Technologies,
Hyundai converted one ARDS module to 100% DAO
MHC service. The feed rate increased to 50% above the
original design, at 50% conversion.
High sulphur
heavy crude
AR VGO
CDU-1 VDU
VR
CHGO
High sulphur
C5 SDA
SDA
DCU
heavy crude
DAO PITCH
CDU-2
AR LIGHT DAO
DAO MHC
T-DAO
AR AR
RDS
T-AR
Figure 1 Block flow scheme of Hyundai Oilbank refinery after the revamps For more information: mike.street@shell.com
102 PTQ Q3 2021
tia copy 12.indd 102
Also in this phase, Hyundai Oilbank and Shell
Catalysts & Technologies revamped the second ARDS
module. This was to enable it to process 50% more
atmospheric residue above original design, at 20%
conversion.
The products (0.5% sulphur, 4.5% micro-carbon resi-
due) feed the existing residue fluidised catalytic cracker
and will supply a future petrochemicals complex. These
changes had a substantial impact on the site’s ability to
process more difficult crudes, because the SDA unit con-
centrates the crude impurities, such as sulphur, nitro-
gen and metals, in the asphalt stream that is routed to the
delayed coker.
For the project to begin to generate returns, speed of
implementation was also important. It took the project
team just 30 months from the beginning of the feasibility
study to start-up.
Phase 2: Adding additional capacity
The two organisations also worked together in
Phase 2, which began in 2018. The original, com-
mon ARDS work-up section was augmented so that
each reactor module had its own fractionation section.
Debottlenecking the fractionation facilitated further
revamps to both reactor modules.
Reactors were added to the DAO MHC module to
enable a further 10% capacity increase and a 50% cycle-
length extension. The ARDS module was revamped from
a single train to two parallel trains. Adding more fixed-
bed reactors helped to increase the capacity by an addi-
tional 30% and the cycle length by 50%.
These changes enabled the refinery to be further inte-
grated with a new heavy-feed petrochemical complex
that was being built, and the updated refinery flow
scheme is shown in Figure 1.
For this phase, it took just 20 months from starting the
feasibility study to starting up the revamped unit.
Conclusion
To enable the processing of super-heavy crudes while
minimising capital investment, Hyundai Oilbank made a
series of changes to the refinery configuration in a care-
fully designed combination of adding new hardware and
revamping existing assets.
As a result, Hyundai Oilbank unlocked a major
improvement in its refining margin. Also, in 2018
Hyundai reported it had the nation’s highest heavy
HCU
oil upgrading ratio, and in 2019 it posted the indus-
try’s highest ratio of net income to sales. The Phase
IGCC 1 project, which ended in 2018, was a key contribu-
Petrochemicals
tor to these achievements.
Complex Haeil Jo, Saudi Aramco
(formerly of Hyundai Oilbank)
RFCC/LSFO Changduk Cho, Hyundai Oilbank
Mike Street, Shell Catalysts & Technologies
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11/06/2021 16:17

Upgrading a vacuum distillation tower
When a major oil refinery in India was constrained by
its vacuum tower, it turned to Sulzer Chemtech to find a
solution that would not only solve existing issues in the
plant but also achieve capacity increases of over 10%.
For a decade, the refinery had been suffering from fre-
quent failures at the tower of its vacuum distillation unit
(VDU), causing considerable unplanned downtime. The
VDU was started up in 1995 with a capacity of 1.8 mil-
lion t/y. The reduced crude oil, coming from the atmos-
pheric distillation unit, was heated from 635°F (335°C) to
784.4°F (418°C) and partially vaporised in a fired heater,
then transferred to the tower flash zone at absolute pres-
sures of 35 mmHg via a transfer line and a tangential
vapour horn feed inlet device. There, the liquid and the
vapour phases would be separated. Liquids would drop
down to the stripping trays at the bottom of the tower,
while vapours would be fractionated into heavy vacuum
gasoil (HVGO) and light vacuum gasoil (LVGO) in the
upper sections.
To recover various useful distillation fractions, the vac-
uum column was structured over the following sections:
a wash bed, a HVGO and a LVGO pumparound cir-
cuit to condense the VGO for the downstream fluid cata-
lytic cracking (FCC) and hydrocracking (HDC) units. Two
additional beds at the top were present to recover vacuum
diesel that would be further processed at the diesel hydro-
treating (DHDT) unit before reaching the diesel pool.
The problem
Over the years, the vacuum tower was pushed to its lim-
its, increasing its capacity to 2.1 million t/y. This strain
caused instabilities within the unit, thus resulting in
pressure surges that would frequently dislodge the tan-
gential feed inlet, which was falling down to the strip-
ping area at the bottom of the tower.
The sudden pressure variations also damaged the
structured packings located in the wash bed and the
HVGO pumparound section, which could not frac-
tionate the bottoms anymore. In addition, entrainment
of reduced crude oil to the HVGO was experienced.
Therefore, large volumes of contaminants could not be
removed, resulting in off-specification VGO being fed to
the HDC and FCC units.
As a result, along with frequent downtime, the refin-
ery needed to lower the furnace temperature, thus reduc-
ing the overall VDU efficiency, in order to counteract the
release of sub-standard VGO.
To upgrade the existing VDU, Sulzer Chemtech’s team
first conducted an in-depth analysis to determine the
VDU operating conditions, stream data, and the feed
quality, as well as to predict the resulting process param-
eters after the upgrade.
More precisely, the new system needed to be able
to process 2.4 million t/y while maintaining the fur-
nace outlet temperature at 784.4°F (418°C) and 35
mmHg absolute pressure at the flash zone of the vac-
uum tower. Also, the contaminants in the vacuum gasoil
should be kept below the allowable limits with respect to
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Conradson carbon residue (CCR), asphaltene, and metal
content such as nickel and vanadium.
Innovative design of feed inlet device
On the basis of the analysis conducted, Sulzer Chemtech
suggested turning the tangential feed entry into a radial
access to address the system failure issues and increase
yields. This required the replacement of the vapour horn
with a Shell Schoepentoeter Plus feed inlet device.
In contrast to the tangential vapour horn inlet, the
Schoepentoeter Plus device dissipates the kinetic energy
and momentum of the feed, as well as provide it with
centrifugal acceleration to promote the separation of liq-
uids from the vapour. As a result, it featured a higher
mechanical integrity and greater de-entrainments and
separation efficiencies, even with higher loads.
The different arrangement of the inlet device required
the 60 in (1.5 m) feed nozzle and the transfer line to be
modified. In particular, the first needed to be relocated
while the latter needed to be rerouted and shortened in
order to fit with the radial inlet. Sulzer Chemtech per-
formed a number of engineering simulations to deter-
mine the feasibility of the new arrangement in terms of
stream and process operations, and the mechanical integ-
rity of the transfer line and the vacuum tower.
The vacuum tower, the heater, and transfer line were
first checked by mean of hydraulic calculations and pro-
cess simulations. To cross-check the results, computational
fluid dynamics (CFD) studies were also performed to
identify flow regime type and the ratio between the actual
velocity and the critical one. This would ensure that the
predicted distillates yields would not be jeopardised.
The mechanical review used a piping stress analysis to
determine the presence of critical areas, and finite element
analysis (FEA) studies highlighted load and boundary
conditions within the system. The results of these simula-
tions allowed Sulzer Chemtech to design a reliable VDU
with respect to process and mechanical performance.
As a result of these simulations, Sulzer Chemtech
determined the optimal reroute of the transfer line. In
addition, it was found that the existing design of the fur-
nace did not require any modifications.
To further strengthen the HVGO and wash beds, an
enhanced support system was implemented at both sec-
tions. Also, after careful inspection, the mist eliminator at
the top of the tower and bed #5 were replaced, as they
showed signs of degradation.
Immediate results
Despite the large scale of the project, the retrofit of the
VDU was completed in record time, minimising refin-
ery downtime. The analysis and simulations required
less than eight months, while the actual installation and
maintenance activities were completed within a month.
As a consequence of the retrofit, the VDU has been oper-
ating smoothly and efficiently for several years. The qual-
ity of the VGO improved, as the level of contaminants was
reduced. Furthermore, the refinery improved its competi-
tiveness, reaching the desired vacuum tower capacity.
Sulzer Chemtech
For more information: dorota.zoldosova@sulzer.com
PTQ Q3 2021 103
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 ptq&a extra
Q We didn’t expect severe corrosion issues in the carbon
steel of our amine unit. What is causing it?
A Andrew Layton: Principal Consultant, KBC, Andrew.
Layton@kbc.global
Typically, materials selection in an amine unit is related
to the H2S loading designed for the amine units.
Carbon steel is often adequate at modest H2S loading
with well controlled levels of contaminants. A change
in corrosion rates can be triggered by several events:
• Increase in H2S loading of the rich amine (also max
loadings dependent on amine type)
• Increase in CO2 loading as if started co-processing of
biofeed on a hydrotreater
• Increase in circulation rates – corrosion erosion
related to high contaminant concentrations and velocity
• O2 increase leading to organic acids such as water
washing issues on FCC offgas systems upstream of the
amine unit
• Too low a H2S concentration in lean amine lines
through over stripping in the amine regenerator. Very
low H2S loading removes the protective sulphide layer
from the piping
• Increase in ammonia concentration in regenerator
overheads such as through hydrotreating higher N2
feeds or deeper HDS/HDN levels of the hydrotreaters
• High levels of heat stable inorganic and organic salts
formed via O2 and often in gases from FCC or other
cracking units
• Inorganic salts such as chlorides from exchanger
leaks and fouling leading to under deposit pitting
corrosion
• Change in amine type used
A Celso Pajaro, Head Engineered Solutions Refinery AME,
Sulzer Chemtech, Celso.Pajaro@sulzer.com
We will provide several potential explanations to the
corrosion phenomenon:
Amine appearance: one indication of corrosion is the
increased presence of solids in the amine solution.
Allowing a high solid content in the amine accelerates
erosion – corrosion problems as well as will increase
fouling problems. The refiner will need to operate the
filters at the maximum flow rate.
Check filters: take samples of the amine solution
upstream and downstream of the filter to verify it
is properly working, as some filters have had prob-
lems with poor sealing that allows unfiltered amine to
bypass the filtration element.
Check the amine appearance of the rich and lean
amine. If the rich amine is dirtier (darker) than the lean
amine, please check the amine quality for
• High CO2 content in lean amine (for units treating
streams with H2S and CO2) will keep iron carbonate in
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solution, and once it enters the amine absorber it will
precipitate iron sulphide. Increasing amine regenerator
reboiler duty should reduce CO2 in the lean amine
• Another mechanism is the presence of amine degra-
dation compounds that keeps iron soluble until it gets
in contact with H2S in the absorber. There are several
public guidelines on the maximum amount of amine
degradation products for each type of amine.
■ Excessive acid gas loading in the rich amine. High
acid gas loading produces amine bisulphide that can
penetrate the iron sulphide protective layer on the car-
bon steel and accelerate corrosion.
■ High pipe velocities will produce an erosion-corro-
sion effect, and amine solution velocity in carbon steel
piping should be kept 6 ft/s maximum.
■ Two phase flow can also accelerate corrosion in car-
bon steel piping.
• Rich amine pipe located downstream of the rich/
lean amine heat exchanger should be checked for two
phase flow, and the rich amine control valve that feeds
the regenerator should be as closed as possible to the
regenerator inlet.
• Rich amine pipe located downstream of the amine
contactors control valve should also be checked for two
phase flow, as it is preferred to have the control valves
as closed as possible to the amine flash drum.
• Equipment showing signs of corrosion due to wall
thickness measurements or visual inspection
■ Amine regenerator acid gas overhead drum. The
presence of ammonium bisulphide or cyanides can
penetrate the iron sulphide layer and attack the steel.
An analysis of the reflux will help to determine if there
are high concentrations of either component. If this is a
problem, a portion of the reflux should be diverted to a
sour water stripper unit.
■ Amine regenerator reboiler. Poor amine regen-
eration can increase the acid gas content in the amine
going to the reboiler. Once amine reaches the reboiler,
it will be heated, allowing the release of the acid gas,
which will produce corrosion. Taking a sample of the
amine before going to the reboiler will indicate if more
regeneration is needed.
■ Bottom of amine regenerator. Poor amine regen-
eration and high momentum of the vapours (or
vapour-liquid) coming from the reboiler can impinge
on the vessel wall and remove the protective iron sul-
phide layer.
■ Amine contactor can suffer from corrosion prob-
lems in the bottom due to feed high momentum that
impinges on the vessel wall.
■ Any equipment made of carbon steel will suffer
from cracking problems if it is not properly processed
using the right chemistry, welded properly, checked for
hardness and, if required, post weld heat treated.
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 A Gerrit Buchheim, Refining Metallurgical & Corrosion
Engineering, Becht, Gbuchheim@becht.com
Severe corrosion in amine units is not rare and should
be expected. Depending on where in the unit (absorber,
hot rich exchangers/piping, regenerator bottom, regen-
erator top, or in the hot lean amine) corrosion is occur-
ring will have different root causes. Typical culprits are
excessive amine loading of H2S or CO2 or high veloci-
ties in the rich amine system, particularly in the hottest
sections. Regenerator bottoms and hot lean amine pip-
ing and the reboiler return piping can be quite corrosive
due to a lack of FeS protective scale, in hot lean amine
systems, high heat stable salt loading and specific
salts can be very corrosive. High velocity in the lean
amine system aggravates corrosion rates. The regener-
ator overhead can be corrosive due to acid gases (H2S)
and can be very corrosive if NH3 builds up if there is
no purge on the regenerator acid gas outlet overhead
drum reflux stream, to prevent ammonium bisulphide
corrosion. Many units have upgraded austenitic stain-
less steel in the hottest rich and lean amine parts of the
unit because of excessive corrosion. Beyond corrosion,
PWHT is important to minimise amine SCC in lean
amine and wet H2S SOHIC cracking in rich amine.
A Marcello Ferrara, Chairman, ITW Technologies, mferrara@
itwtechnologies.com and Domenico Ferrara, Process engineer,
ITW Technologies, dferrara@itwtechnologies.com
One common cause of corrosion is the formation of
heat stable salts (HSS). HSS cause an irreversible con-
sumption of amine with subsequent loss in acid loading
capacity and increasing the level of contaminants, caus-
ing corrosion in the amine unit and operating problems
in the SRU.
Additional corrosion is due to HSS penetrating the
protective FeS layer on the metal surface exposing the
metal to further attack. Several HSS anion species have
been directly related to increased corrosion in car-
bon steel in amine solvent systems; in particular they
appear to act as corrosion accelerators by displacing the
iron sulphide film.
The corrosion rates increase with higher concentra-
tions of all of the HSS species. The corrosion from HSS
occurs in hot areas of the plant, wherein the liquid and
vapour phases are present: the reboiler, reboiler outlet
line, the regenerator column between the lean amine
level and the bottom trays. HSS start causing evident
corrosion problems when the total HSS level exceeds
2%.
ITW has developed and patented technologies,
together with proprietary know-how, to dissolve HSS
and hence remove them from the equipment. A pro-ac-
tive approach has also been developed for preventing
HSS formation.
ITW technologies’ applications range from normal
run to turnaround. Equipment can be cleaned online
without having to open the same. This is particularly
beneficial in severe applications such as heat exchang-
ers placed at elevated location or columns/vessels.
The ITW cleaning method involves the injection of a
proprietary chemical that transforms the fouling into a
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Q&A copy 37 (original) copy 12.indd 109
fully reusable liquid, thereby removing deposits from
metal surfaces.
Avoidance of opening the equipment is particularly
important at unit start-up and during maintenance
turnarounds because of pipe scale/rust formation; this
readily forms when carbon steel is exposed to air, espe-
cially in the presence of moisture. Any pipe scale or rust
is immediately converted to iron sulphide when H2S is
introduced in the unit. Because FeS is not bonded to the
pipe it will be carried by the circulating solution and
contribute to fouling.
This is an important additional benefit of ITW Online
Cleaning in that it will improve performance upon
restarting.
Q What’s the best route for maximum propylene from a
resid feed to the FCC?
A Carel Pouwels, Technical Service Advisor, Albemarle, Carel.
Pouwels@Albemarle.com
Producing propylene from a resid feed is not as easy as
processing the VGO fraction. Propylene make is gov-
erned by the ability to create and preserve gasoline
olefins, the potential of which is reduced when pro-
cessing higher boiling fractions. Nevertheless, it is cer-
tainly a profitable route given the lower price of resid
feed. The choice of the residue, however, is important.
The less refractory the feed, the more conversion can be
obtained, thereby more gasoline olefins. Gasoline ole-
fins are the precursors for the generation of propylene.
It is thus key to maximise these by maximising conver-
sion. While the crackability of the feed is of paramount
importance, unit limitations ultimately determine how
severely an operation can be pushed. In resid applica-
tions, this often comes down to regenerator tempera-
ture, air rate, and the maximum duty of a cat cooler, if
present.
Several options are available to maximise propylene
from an FCC unit, all related to the requirements the
client has and the starting point. Considering a com-
pletely new FCC unit begins with the process technol-
ogy. Process licensors are the right partners to work
with to determine the best choices for strategic and eco-
nomic long-term solutions. One can choose from con-
ventional process designs that yield between 10 wt%
and 12+ wt% of propylene. There are also several high
severity applications that target propylene yields in the
15-20 wt% range. These applications commonly operate
at 550-600°C with cat-to-oil ratios about double those of
conventional FCC operations.
In the case of an existing FCC unit where debottle-
necking downstream units is considered, or where
hardware changes to the FCC unit are feasible, process
licensors are again good partners. They can suggest
various scenarios and help customers make the right
choices for their goals.
When the refiner is not planning an overhaul of the
FCC unit or its downstream units, the options to maxi-
mise propylene are restricted to process conditions, the
choice of feed, and catalyst design. The catalyst supplier
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 can be consulted to provide good insight into the opti-
mal operation combined with the best catalyst technol-
ogy and design for customer goals.
Albemarle provides such expertise and offers maxi-
mum propylene catalysts AFX and DENALI AFX. Both
are proven in all current process technologies offered
by licensors today. While a good catalyst technology is
a prerequisite, more important is catalyst application
knowledge. At Albemarle, using collected data from
all our industrial applications, our Technical Services,
Applications, Modelling Department, and R&D teams
work together to build deeper understanding of catal-
ysis in relation to process conditions and catalyst
technology.
A Charlie Chou, Business Segment Leader (Refining,
Aromatics & Derivatives), Sulzer Chemtech, Charlie Chou@
Sulzer.com
The FCC heavy naphtha/gasoline portion actually has
a lot of olefins that can be re-cracked in the FCC for pro-
pylene. However, the FCC heavy naphtha/gasoline
also has significant aromatics which is not preferred
in the FCC. GTC offers a GT-BTX PluS technology
that utilises a simple extraction process to extract aro-
matics from FCC heavy naphtha/gasoline to produce
high-purity BTX (extract) as petrochemical products;
and the remaining FCC heavy naphtha/gasoline (raffi-
nate) would be non-aromatics and rich in olefins, which
would be an ideal stream to recycle back to the FCC
to crack for additional propylene. By doing this, the
propylene yield can increase by 2-6% if there is a sec-
ond riser to be recycled to (or to add a second riser), or
increase by absolute 1-3% if recycling to the only/first
riser together with resid feed.
A Tom Ventham, Sales & Technical, Europe and Africa, Unicat
B. V. / G. W. Aru, LLC, tom.ventham@gwaru.com and Natalie
Herring, Director of Technology and Business Development, G.
W. Aru, LLC, natalie.herring@gwaru.com
To consider the twin objectives of maximum propyl-
ene production with residue processing was once the
antithesis of FCC operation. However, advances in FCC
catalyst technology and unit design mean this is now
a common strategy to maximise unit profitability and
is no longer the insurmountable challenge it may once
have seemed. For a long time, an outdated myth existed
suggesting that increasing ZSM-5 addition to the FCC
would at some point lead to no further increase in pro-
pylene production – a ceiling or plateau existed beyond
which further increases in propylene were no longer
possible. Laboratory analysis by visionary FCC experts
and the challenging of these conventions by pioneering
refiners showed increasing ZSM-5 use will continue to
improve propylene yield, albeit at admittedly reduc-
ing effectiveness.1 Therefore, increased use of an effec-
tive ZSM-5 additive, in the absence of advanced FCC
redesigns or retrofits, presents refiners with the oppor-
tunity to immediately increase propylene yield beyond
the current level. Today, ZSM-5 additives, such as Ultra
C3Booster from Unicat & G. W. Aru, LLC, remain flex-
ible and cost-effective means to achieve propylene tar-
106 PTQ Q3 2021 www.digitalrefining.com
Q&A copy 37 (original) copy 12.indd 110
gets. But what else can be improved in the resid FCC to
aid effectiveness of ZSM-5 to maximise propylene out-
put? Once the most appropriate ZSM-5 additive has
been selected, normally a factor of cost, activity, and
technical support and expertise offered by the supplier,
reviewing FCC operation with the view of boosting
effectiveness and propylene maximisation is critical.
In this response we look at the best approaches
under assumptions that feed quality remains fixed and
mechanical design of the unit cannot be changed. The
first area to review is to ensure feed molecules that can
be converted to LPG olefins, such as propylene, using
ZSM-5 are maximised. This centres around avoidance of
hydrogen transfer reactions that saturate gasoline range
olefins to retain these molecules for catalytic cracking
with ZSM-5. Hydrogen transfer is a bi-molecular reac-
tion that takes place between an olefin and naphthene
with final products being paraffins and aromatics.
Therefore, hydrogen transfer reactions should be min-
imised to avoid conversion of gasoline olefins in the
C6-C9 range that could be cracked to propylene using
ZSM-5. Hydrogen transfer increases with increasing
FCC catalyst rare earth on zeolite, as measured by unit
cell size (UCS). High rare earth content catalysts tend
to be favoured in residue FCC applications due to the
advantages of rare earth stabilisation on zeolite activ-
ity retention in high contaminant metal environments.
Furthermore, in some technology platforms rare earth
based vanadium traps are a common feature of catalysts
offered for residue operations.
An experienced refiner looking to increase propylene
production from a residue FCC unit will consider suit-
able alternatives to high rare earth on catalyst. The chal-
lenges of high metals operation warrant an alternative
and more advanced solution than a simple high rare
earth catalyst. Advanced metals traps, including Ultra
CokeBuster supplied by Unicat/G. W. Aru, LLC, offer
protection from deleterious FCC contaminants. Separate
particle metals traps have proven effective in a number
of FCC applications by protecting the main FCC cata-
lyst to retain or improve inventory catalytic activity or
unit conversion. This alternative metals protection capa-
bility allows the catalyst to be reformulated to further
increase unit propylene production without sacrificing
other valued yields.
In parallel with metals trap option discussed, another
approach to be considered by the advanced refiner
includes an operational spin to fully optimise the whole
system when faced with this challenge of operating in
maximum propylene mode with resid feed. When fur-
ther increasing light-ends production a common limita-
tion that will be reached is wet gas compressor (WGC),
or associated gas plant, hydraulic constraint. This is
common with residue feed units due to relatively high
dry gas production, even when using metals trapping
or passivation technologies. Another common lim-
itation in residue units is maximum regenerator tem-
perature due to the high coking tendency of the heavy
feed. In both of these cases, a reduction in riser outlet
temperature acts to alleviate the constraint. Any collat-
eral loss in propylene yield through a reduction in riser
28/06/2021 14:07
 temperature, including if reducing below ‘overcracking’
temperature, will be more than fully compensated by
an increased addition of ZSM-5. ZSM-5 only generates
LPG olefins whilst overcracking operation creates a mix
of thermal cracked products including low molecular
weight C2- species, low value light paraffins, and prob-
lematic di-olefins. Reducing the yield of low molecu-
lar weight species through riser temperature reduction
alleviates WGC volumetric capacity limitations creat-
ing an opportunity to efficiently refill the space with a
higher proportion and mass of LPG olefins generated
from an increase in ZSM-5 addition. Furthermore, riser
temperature reduction will lead to a decrease in cat-
to-oil ratio (C:O) at constant other parameters. Lower
C:O will tend to a reduction in hydrogen transfer reac-
tions, the negative effect of which is described above.
The complex dynamics and balance of this optimisa-
tion, coupled with expected variations in residue feed
quality, necessitates separate ZSM-5 and other additive
addition to allow for a careful online tuning that will
ensure profitability is consistently maximised.
Once riser temperatures have been stepped down to
a new propylene-led optimum, another challenge will
be faced, that of a reduction in conversion and conse-
quent increase in bottoms product yield. This again
can be resolved by considering the additive approach.
Refiners who have reduced riser severity of their FCC
or RFCC operation, whether because of rate limita-
tions or shift to diesel-mode type operation, use bot-
toms upgrading type additives to maintain minimal
bottoms yield despite a deliberate reduction in con-
version or riser severity. These matrix based additives,
of which Ultra MCBuster can be supplied by Unicat
& G. W. Aru, LLC, crack paraffinic slurry range mol-
ecules to more useful products to maintain maximum
profitability. A further benefit of using a high matrix
additive such as Ultra MCBuster is that the shift in the
zeolite-to-matrix ratio (Z:M) of the catalyst inventory
is in the direction that favours a reduction in hydrogen
transfer reactions.
Further operational improvements that can be made
if targeting maximum propylene with a resid feed
would be to increase riser steam and nozzle steam
rates. Not only does the increase in nozzle steam
give the possibility of improving feed dispersion that
would reduce WGC limiting dry gas production, but
the presence of more steam in the FCC riser reduces
hydrocarbon partial pressure which is unfavour-
able for the progression of the bi-molecular hydrogen
transfer reaction.
The recommendations discussed, focused around
short-term catalyst, additive and operational improve-
ments, give a robust methodology for how to optimise
a unit for maximum propylene while processing resi-
due feed. These recommendations are based on the vast
FCC experience within the Unicat and G. W. Aru, LLC
group and gives operators the tools and knowledge to
proceed with confidence to achieve these goals.
1 How ZSM-5 works in FCC, Bart De Graaf, Johnson Matthey Process
Technologies Inc., AFPM 113th Annual Meeting, March 24, 2015.
www.digitalrefining.com
Q&A copy 37 (original) copy 12.indd 111
A Sanjay Bhargava: Director – Global Value Solutions, KBC,
Sanjay.Bhargava@kbc.global
Propylene production from resid feed in a FCC depends
on several factors including feed characteristics, oper-
ating conditions, base catalyst, catalyst additives and
equipment design. At a fixed feed, the variables that
will have the maximum effect will depend on unit con-
straints and you will need a sophisticated calibrated
simulation model that includes the reactor/regen, cata-
lyst characterisation and gas plant to determine the best
route for maximising C3=.
Feed characteristics: residue is heavy and aromatic and
is H2 deficient. C3= production is favoured by paraf-
finic resids. So the more paraffinic the resid, the higher
the tendency to make C3=. Low metals and low concar-
bon is also preferred when processing resid in FCCs.
Hydrotreating resid also increases the H2 content and
conversion
Operating conditions: maximising the riser out-
let temperature (ROT) will result in increasing C3=.
Lowering the preheat will also increase C3= content.
Unfortunately, maximising ROT makes more dry gas
and the increase will be limited either by wet gas com-
pressor limits or gas plant limits. Increasing injection
steam rates also helps increase C3= yield but this needs
to be optimised based on effects on atomisation, ero-
sion of feed nozzles, main fractionator flooding and
sour water handling constraints. Lift steam and cat-
alyst make-up rate also affect C3= production. This is
a complicated optimisation and will need a sophis-
ticated simulation model with calibrated catalyst
factors.
Catalyst composition and additives: best way to increase
C3= with catalyst additives is with the use of ZSM-5 as
an additive (preferred) or impregnated into the base
catalyst.
Equipment design: resid processing through the RFCC
poses challenges mainly with high regenerator tem-
peratures that has a major impact on conversion which
in turn affects C3= production. RFCC designs now
incorporate catalyst coolers and/or two-stage regen-
erators with partial combustion. Both designs result
in lower regenerator temperatures resulting in higher
conversion.
Q We’d like to produce less light naphtha and more liquid
fuels from our hydrocracker. How do we go about it?
A Matt Lehr: Senior Consultant, KBC, Matt.Lehr@kbc.global
There are a variety of process variables available to
reduce hydrocracker light naphtha production and
increase heavier liquid fuels from the hydrocracker.
These range from feedstock selection, catalyst selec-
tion, reactor operation and severity, use of liquid recycle
within the unit (if available), and fractionator cutpoint
changes. The selection of any of those variables, or
a combination, to meet the yield objective is deter-
mined by existing unit constraints, and also consider-
ation of the hydrocracker’s position and strategy within
the refinery. While directional movements (increase/
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 decrease) of yields are roughly understood for each
variable above, this is not always the case, especially if
multiple reactors and liquid recycle are involved. It is
recommended to use a simulation model tuned to the
unit’s operation to both validate and quantify the direc-
tional yield movements expected from these variable
changes.
Product quality will also be affected as the yield pro-
file shifts towards heavier liquid fuels, which must
also be considered in the final decision of hydrocracker
yields.
Catalyst management must also be considered, as
changes in reactor severity typically lead to longer/
shorter catalyst life. Shorter catalyst cycles imply more
frequent catalyst change-outs and costs. Shorter cata-
lyst cycles may be justified, but must first be considered
against the expected economic benefit.
The final decision of optimal hydrocracker yields is
typically determined via the LP model, which consid-
ers the economics of running various feeds and produc-
ing different amounts of each hydrocracker product. A
robust and representative hydrocracker LP submodel,
validated with plant data on a regular basis using a
digital twin, is critical to reaching the optimal yield
decision.
A Steve DeLude, Process Advisor, Becht, SDeLude@becht.com
and Doug Clarke, Process Advisor, Becht, DClarke@becht.com
For changes mid-run with an existing hydrocracker
catalyst load, facilities and feed, the most effective
way of lowering light naphtha yield is to reduce the
conversion in the hydrocracking catalyst portion of
the load. This is usually accomplished by reducing
the hydrocracking catalyst temperature, reducing liq-
uid recycle rate and/or increasing recycle cut point.
Often the extent of de-conversion is limited by prod-
uct specifications (sulphur, nitrogen, Cetane, PNAs) or
equipment constraints within the unit (product pump
rates, hydrocracking catalyst quench/cooling, product
fractionator stripping rate). Some temperature adjust-
ments to the hydrotreating catalyst may be required
to meet product specifications while equipment
constraint can often be determined by doing some
planned rate and performance tests. Note that reduc-
ing the conversion will also likely reduce the total
liquid product yield thereby leading to an economic
trade-off with light naphtha yield.
For long term reduced light naphtha yield reduction
with the same/increased total liquid product yield,
a combination of changes to the loaded catalyst sys-
tem and debottlenecking of unit equipment is typi-
cally required. Working with the catalyst vendors can
help identify catalyst systems that have reduced naph-
tha selectivity/increased diesel selectivity as well as
increased liquid swell for a more desirable product
yield slate. Some unit constraints may be known from
past operations; however, typically a good project basis
for identifying and relaxing equipment constraints can
be accomplished by doing a unit performance test. The
performance data can then be used in simulations and
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to check performance against equipment data sheets
limits. Upgrades to product pumps, quench valves,
fractionator internals and safety valves are common
for modest upgrades to run in a de-converted mode.
Experience shows that desired product yield pro-
files shift often with economics, so some flexibility to
run in both low and high conversion modes is usually
maintained.
Q For best product quality from vegetable oils, should we
hydrotreat them with conventional petroleum feed or use
them as straight feed?
A Robert Ohmes, Division Manager, Strategic Business
Planning, Becht, ROhmes@Becht.com
Addressing this question requires review of multiple
factors:
1. Type and quality of vegetable oils
2. Capabilities of existing hydroprocessing unit
3. Product blending system
For item 1, each of the vegetable oils (canola, soy-
bean, corn, and so on) have their own distinct prop-
erties, both before and after hydroprocessing. After
hydrotreating, these streams should meet or exceed
typical specifications of ultra low sulphur diesel,
such for specific gravity, distillation, cetane, and sul-
phur. The key quality that impacts this decision is
cold properties. Given the highly paraffinic nature
of the resultant products, the renewable diesel prod-
uct will not meet cloud, pour, and/or CFPP with-
out additional processing or blending. The primary
options for meeting cold properties are 1) blend-
ing with conventional fossil fuel distillate streams,
2) cold property enhancement additives, or 3) use
of dewaxing catalysts within the hydrotreater.
Processing vegetable oils with conventional fossil
fuel distillates in a hydrotreater is the most straight
forward path to making renewable diesel, but the
percentage of vegetable oil allowed may be dictated
by the resultant cold properties. Blending of other
hydrotreated fossil fuel distillate streams with the
co-processing unit’s product can allow for additional
vegetable oil processing up to the same controlling
limit. Maximising vegetable oil processing likely
requires use of a dewaxing catalyst to isomerise the
paraffins, improve cold properties, and meet final
product blending requirements.
Building off this element is the capability of the
existing hydroprocessing unit (item 2). The high
organically bound oxygen content of vegetables oils
(at least 10%+) requires significant hydrogen addi-
tion to meet final product specifications, along with
breaking the backbone of the triglycerides. Hence, the
hydrotreating unit must have the assets to manage
and complete hydrodeoxygenation. For instance, the
make-up hydrogen compressors, as well as hydro-
gen generation assets, must have sufficient capacity
to meet the vegetable oil processing target. If either
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 of these elements is limited, then the percentage of
vegetable oil processed will be limited. Similarly, this
high level of hydrogen consumption requires suffi-
cient recycle gas capacity not only for sufficient treat
gas into the reactor to ensure proper catalyst distri-
bution, hydrogen availability for the reactions at the
catalyst site, and a heat sink for the resulting exo-
therm, but also quench capacity to maintain reac-
tor heat balance and avoiding runaway reactions. In
addition, the metallurgy and contacting systems must
be able to handle the CO, CO2 and water that are gen-
erated by the oxygen removal reactions. If the unit
is designed for a significant percentage of vegetable
oil processing, then the unit should have capacity
for higher processing levels. However, if an existing
asset was repurposed and moderately modified to
allow for a small percentage of co-processing, then
increasing that processing percentage will be a chal-
lenge. For existing assets, if some of the reactor cata-
lyst volume was used for dewaxing catalyst, then the
conventional fossil fuel processing and vegetable oil
processing will be impacted as one balances improv-
ing cold properties while hydrotreating the renew-
able and conventional feeds to meet oxygen, sulphur,
and cetane requirements. In summary, the asset
capacity and capabilities of the hydroprocessing unit
will impact this decision.
Finally, hydrotreated vegetable oils produces high
quality diesel material – high API gravity/low SG,
high cetane, low sulphur, and ideal distillation range.
However, as stated above, the poor cold properties
require processing or blending mitigations to meet
specifications. The advantage of co-processing and
co-blending of hydrotreated vegetable oils with con-
ventional distillate streams is that the organisation can
use each blendstock to create a product that meets all
the diesel qualities with minimal giveaway. Hence,
a typical refiner with cold property giveaway and
‘spare’ hydrotreater capacity can examine co-process-
ing of vegetable oils to not only take up that giveaway
but generate renewable credits and reduce carbon
intensity. Similarly, a facility that is cetane limited can
co-process or blend renewable diesel to create space
within the cetane pool to allow for further optimisa-
tion of upstream fractionation and/or additional pro-
cessing of low cetane feedstocks. Producing a pure
renewable diesel product does give the most flexibil-
ity from a blend perspective and, in some regions, pro-
vides clearer accounting and capturing of renewable
credits, but making pure renewable diesel does require
a robust processing scheme and hydroprocessing unit
as well as the ability to manage cold properties of the
standalone stream.
In summary, the decision on achieving best qual-
ities is multifactorial and is a combination of sources
for vegetable oils, capability of the treating assets
and auxiliary systems, blending infrastructure, abil-
ity to capture renewable credits, and target market.
A holistic analysis is required to review the process-
ing capabilities, limitations, feedstock sources, market
potential, incentives, and blending approaches.
www.digitalrefining.com
Q&A copy 37 (original) copy 12.indd 113
Q We’ve increased the opportunity crude content of our
feed and are experiencing high calcium issues. How can we
best address this?
A Marcel Foet, Senior Staff Consultant, KBC, Marcel.Foet@
kbc.global
When calcium is present as inorganic salt in crude oil,
typically 10% is from calcium. The majority is sodium
and the rest is magnesium. Salts of chlorides hydro-
lyse to evolve HCl when exposed to high tempera-
tures in crude units. The HCl condenses with water
in the crude unit overhead and can cause severe cor-
rosion. The main source of chlorides in a crude top
system is coming from magnesium chloride and
some from calcium chloride. Sodium chloride leaves
the crude tower with the bottom stream. Essential in
removing chlorides is the efficiency of the desalter
and if necessary, by polishing with caustic soda
downstream the desalter. Other control strategies are
the addition of neutraliser and filming agent, an over-
head water wash and overhead temperature (at least
10°C higher than the water dew point). With a good
desalting system more than 95% of calcium, magne-
sium and sodium should leave the desalter with the
brine.
Calcium can also be present as an organometallic
component in the form of a soap. Problems for refin-
ers associated with high calcium (>100 ppm) include
exceeding metal specs for fuels oils that have resids
blended in, poisoning catalysts for residual catalytic
crackers, adversely affecting coke specs for metals,
and contributing to crude unit fouling and delayed
coker furnace fouling. Several methods are available
for the removal of calcium from crude oil, essentially
using the desalter. All involve the use of organic car-
boxylic acids like citric acid. High calcium crude oil is
contacted with the acid to form a sequestered calcium
containing complex that partitions to the water phase
in the resolved emulsion.
A Chris Claesen, Technical Director, Nalco Water, Chris
Claesen@ecolab.com
Increased levels of calcium due to opportunity crude
processing can be effectively handled in the desalters
as described in articles in the PTQ Q3 2017 and PTQ
Q1 2018, Opening the crude flexibility window. The
calcium that can create problems in downstream pro-
cesses is in the form of a calcium naphthenate salt that
is oil soluble.
Using a suited calcium removal programme con-
sisting of an acidification additive and an efficient
corrosion inhibitor, combined with a high-perfor-
mance emulsion breaker the calcium can be extracted
to the desalter brine with a high efficiency while
minimising potential downstream impacts of the
treatment. Key is to have real-time control of the
washwater and brine pH and quality, this can be the
best achieved by an automation system such as Nalco
Water’s 3DT for brine.
PTQ Q3 2021 109
28/06/2021 14:07
 Q Are there options for online cleaning a preheat exchanger
network?
A Berthold Otzisk, Senior Product Manager – Process
Chemicals, Kurita Europe, berthold.otzisk@kurita-water.com
The options of online cleaning of preheat exchangers
are often limited because larger product quantities are
flowing through the heat exchangers. Because of high
treat rates, online cleaning quickly becomes commer-
cially uninteresting compared to mechanical cleaning,
when individual exchangers can be separated.
Nevertheless, there are various cleaning methods
and possibilities to clean entire heat exchanger net-
works during operation. Experience has shown that
coke deposits or completely polymerised deposits
cannot be removed, or usually only to a small extent.
If organic salt deposits or corrosion products are
the cause of fouling, these deposits can be removed
quickly and easily using Kurita’s ACF technology.
Water-soluble ACF salts are mobilised and trans-
ported with the product stream. Mobilised metals then
remain in the residue.
If asphaltenes, maltenes or other tenacious hydro-
carbon deposits are causing the fouling, these depos-
its can be removed with a cleaning product from
the Kurita CD series or an asphaltene dispersant.
The cleaning product dissolves hydrocarbon depos-
its. An asphaltene dispersant from the Kurita AP
series transports smaller particles and prevents them
from agglomerating into larger molecules to avoid
precipitation.
Online cleaning requires much higher dosing rates
in the range of 20-200 ppm or more compared to con-
tinuous antifoulant treatment.
A Chris Claesen, Technical Director, Nalco Water, Chris
Claesen@ecolab.com
The individual exchangers can be cleaned with a
chemical programme such as Nalco Water Enterfast,
while bypassed on the fouled side, if they can be iso-
lated and have access nozzles for the cleaning pro-
gramme. The advantage of such cleaning is that it can
be done in a short time span and without opening and
pulling the exchanger. This will also reduce safety and
environmental risks and will typically be a lot cheaper
than mechanical cleaning. Using heat exchanger mod-
elling software such as Monitor can help evaluate
which exchanger is most fouled and what the energy
gain will be if a particular exchanger is cleaned. This
will also give the benefits in terms of CO2 emission
reductions.
A Steve DeLude, Process Advisor, Becht, SDeLude@
becht.com and Roberto Tomotaki, Process Advisor, Becht,
RTomotaki@becht.com
There are a number of options either using chemi-
cal additives/solvents or mechanical means available
that can be used to on-line clean preheat exchanger
networks.
110 PTQ Q3 2021 www.digitalrefining.com
Q&A copy 37 (original) copy 12.indd 114
For chemical or solvent approaches, the most appro-
priate choice of cleaning option and its effectiveness
is dependent on the nature of the fouling that has
occurred in the exchangers and the ability to ensure
flow through all the exchanger tubes. Your chemi-
cal suppliers should be involved and can provide any
information from past turnarounds on the deposit
chemistry/characteristics to determine the most
appropriate on-line cleaning chemistry to apply. The
chosen solution will often be a combination of pro-
prietary chemical formulations customised by your
chemical supplier for your specific situation.
Care should be taken to ensure that chemical and
deposits removed from the exchanger network does
not have an adverse impact on downstream equip-
ment or catalyst.
If the fouling is caused by deposition of asphaltenes
or other heavy hydrocarbons, then a highly aromatic
stream or solvent additive can assist in redissolv-
ing and dispersing the heavy deposit. If the fouled
exchanger is upstream of the desalter, it may be pos-
sible to remove some of the heavy deposit with the
desalter mud. Temporarily bypassing or shutting
down one side of parallel banks of exchangers can
increase flows and temperatures to also help move
very heavy deposits.
If the deposit is mainly corrosion products, these
can sometimes be removed by acidic or other chemical
reactants additives.
If the deposit is an inorganic salt, a water wash may
temporarily improve the exchanger heat transfer but
extreme care is required to not cause any materials
damage due to rapid corrosion that can occur with wet
salts if they are not completely removed. This can be
especially true where the exchanger pressure drop is
high and there is evidence of partially plugged tubes.
However, even with the correct chemistry, there will
always be some risk that the on-line cleaning will not
be fully effective due to an inability to get good flow
through all the fouled areas of the exchanger on both
the tube side and the shell side of the exchanger.
In addition to chemical cleaning methods, sev-
eral mechanical cleaning methods can also be utilised
often in conjunction with chemical cleaning methods.
Such methods include, attaching ultrasonic transduc-
ers to the exchanger tubesheet. This method utilises
ultrasonic transducers to generate vibration, acous-
tic streaming and cavitation to ‘shake loose’ deposits
from the exchanger surface.
Another option includes the use of internal vibrat-
ing systems to keep the inside of the exchanger tubes
clean by installing a vibrating device or spring secured
on both tube ends by a fixing wire. The energy of the
fluid flow in the tubes causes these devices to vibrate
creating a continuous online mechanical cleaning
effect of the tube interior.
In cases where on-line cleaning is not completely
successful, then improved techniques for off-line
cleaning such as those applying ultra-sonic cleaning
technology can be applied to regain most of the origi-
nal heat transfer performance of the equipment.
28/06/2021 14:07
 digitalrefining.com is the most extensive It provides a constantly growing
source of freely available information on database of technical articles,
all aspects of the refining, gas and company literature, videos, industry
petrochemical processing industries. news and events.

dr copy 20.indd 1 15/03/2021 15:10

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