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ptq
PETROLEUM TECHNOLOGY QUARTERLY
Q2 (Apr, May, Jun) 2024
3 Keeping refineries profitable
Rene Gonzalez

5 ptq&a

15 Optimising furnace run length in a steam cracker using AI

Surabhi Thorat and Vivek Srinivasan Dorf Ketal Chemical (I) Pvt Ltd
Sudarshan Vijayaraghavan Dorf Ketal Chemicals PTE Ltd

www.digitalrefining.com 21 Dryout design considerations for cryogenic gas plants: Part 2

Scott A Miller, David A Jelf, J A Anguiano and Joe T Lynch
Honeywell UOP

27 FCC co-processing of biogenic and recyclable feedstocks: Part 2

Jon Strohm, Darrell Rainer, Oscar Oyola-Rivera and Clifford Avery
Ketjen

33 Revamping a conventional naphtha splitter to a dividing wall column

Giuseppe Mosca, Joshi Chandrakant, Andrei Cimpeanu and Brad Fleming
Sulzer Chemtech

41 A refinery’s strategic journey towards sustainability

Aleix Carrillo, Duncan Manuel and Michelle Wicmandy
KBC (A Yokogawa Company)

47 SAF production via co-processing in the kerosene hydrotreater

Maria J L Perez, Gitte Thomsen Nygaard and Sylvain Verdier
Topsoe

53 Flexible downscaling of MAPD removal from C3/C4 olefin streams

Edgar Jordan, Charlotte Fritsch and Joachim Haertlé
hte GmbH

59 Sulphur reduction, sulphur removal, and spent caustic reuse

Richard Stambaugh
Merichem Technologies

65 Optimising compressor dry gas seal line design in FEED stage

Rajib Talukder
Saudi Aramco

71 Integrating refining/petrochemicals for increased chemicals production

Narendra Verma
HMEL (HPCL-Mittal Energy Ltd.)

77 Blue hydrogen – a low-carbon energy carrier: Part 1

Himmat Singh
Research Scientist

83 Effect of redundancy/voting in SIL calculation

Partha S Mondal
Fluor Daniel India Pvt. Ltd

90 Co-processing renewable feeds in hydrodesulphurisation units

Cristian S Spica
OLI Systems, Inc

94 Technology in Action

Cover
Commercial relevance of technology ranging from refinery FCC assets to chemical plastic waste recycling reflects
investments exceeding $185 billion to expand operations for meeting increased demand.

©2024. 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.

www.digitalrefining.com
www.decarbonisationtechnology.com
 Make every
molecule matter
At Shell Catalysts & Technologies, we understand how small, unseen chemical reactions
can affect the health of our loved ones, neighbours, and the planet at large. That is
what motivates us in our mission to Make Every Molecule Matter. Every member of
our team is focused on the same goal – developing cleaner energy solutions that
enable industries to tackle global climate challenges starting at the molecular level.
Our experienced scientists and expert engineers collaborate with customers to create
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Learn more at catalysts.shell.com/MEMM.

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002_Q2_Shell.indd 1 1 12/7/2311:16:43
11/03/2024 4:27 PM
ptq
PETROLEUM TECHNOLOGY QUARTERLY
Vol 29 No 3
Q2 (Apr, May, Jun) 2024
Editor
Rene Gonzalez
editor@petroleumtechnology.com
tel: +1 713 449 5817
Managing Editor
Rachel Storry
rachel.storry@emap.com
Editorial Assistant
Lisa Harrison
lisa.harrison@emap.com
Graphics
Peter Harper
Business Development Director
Paul Mason
sales@petroleumtechnology.com
tel: +44 7841 699431
Managing Director
Richard Watts
richard.watts@emap.com
Circulation
Fran Havard
circulation@petroleumtechnology.
com
EMAP, 10th Floor, Southern House,
Wellesley Grove, Croydon CR0 1XG
tel +44 208 253 8695
Register to receive your regular copy
of PTQ at https://bit.ly/370Tg1e
PTQ (Petroleum Technology Quarterly)
(ISSN No: 1632-363X, USPS No: 014-781)
is published quarterly plus annual Catalysis
edition by EMAP and is distributed in the US
by SP/Asendia, 17B South Middlesex Avenue,
Monroe NJ 08831. Periodicals postage paid at
New Brunswick, NJ. Postmaster: send address
changes to PTQ (Petroleum Technology
Quarterly), 17B South Middlesex Avenue,
Monroe NJ 08831. Back numbers available
from the Publisherat $30 per copy inc postage.
Keeping refineries
profitable
T
hroughout every quarterly issue of PTQ, we have seen the need to find new
ways to improve and apply existing technology for changing market forces
and regulatory requirements. So, with adaptation of carbon taxation, refiners
must produce higher yields of fuels per unit of CO2 from conversion units such as the
fluid catalytic cracking (FCC) unit. One interesting route is to operate FCCs more sus-
tainably by supporting the co-processing of alternative feeds. But how many FCC
units are co-processing alternative feedstocks?
The consensus is that co-processing is feasible if less than 5% of the feedstock
is from alternative sources. Above 5%, processing unknowns weigh in on the need
for additional expertise, such as the use of more active and poison-resistant cata-
lysts and absorbents for efficient conversion of renewable feedstocks to fuels and
chemicals, bringing new capabilities to existing facilities seen in Europe and North
America.
Elsewhere, project start-ups reflect strategies to increase fuel production and feed-
stock volumes for monetisation to petrochemicals, as seen in the Middle East and other
countries. For example, Saudi Arabia is building nine liquid-based ethylene steam
crackers to produce a wide range of products, such as a high-margin polymers.
Through joint ventures, steam cracker projects will process byproducts from
crude processing, including naphtha and off-gas, to produce ethylene, such as
with a multi-billion-dollar project between Saudi Aramco and South Korea to pro-
duce propylene, butadiene, and other basic chemicals by 2026. Petrochemicals
are set to account for nearly half of growth in oil demand to 2050, according to the
International Energy Agency. Petrochemicals are also poised to consume an addi-
tional 56 billion cubic metres of natural gas by 2030, the agency recently noted.
The global petrochemical market is projected to be worth roughly $800 billion by
2030, according to Precedence Research. At this juncture, there is a lot of pressure
to close refineries in Europe if old assets cannot be modified, such as with the ability
to co-process alternative fuels. What is happening with refinery growth in Africa
now could significantly impact European refineries, such as with a refinery in Nigeria
that includes a new 600,000 bpd single column crude unit. According to Honeywell
UOP’s Keith Couch, speaking at the January NARTC in Houston, “when that unit
starts up (i.e., at the Dangote refinery), the price pressure on European refineries will
approach $4 per barrel”. The Dangote refinery has ramped up its stock of imported
crude oil, including shipments of US light sweet crude oil, according to trader and
ship tracking data. So, the facility is well on its way to running at full capacity.
Will European refiners be able to stave off imports? Perhaps with government
subsidies and ESG-focused projects. Elsewhere, the rapid start-up of major capital
projects in China and India is taking 36 months, while projects in the Middle East
need perhaps 96 months to complete due to supply chain and labour restrictions.
This makes refineries such as Reliance in India more competitive, even as they
are leveraged by a lack of crude oil reserves. In almost every instance, the road
to success for refiners involves a shift to petrochemicals, such as with olefins and
aromatics.
For ‘older’ refinery facilities, such as in the US, that petrochemical opportunity
could begin with benzene, as its octane-enhancing importance in the gasoline mar-
ket is diminishing due to regulatory restrictions. Propylene is another bankable pet-
rochemical that can be considered with the right process and catalyst upgrades, as
discussed in this issue of PTQ. Further into the year, this narrative will discuss track-
ing a facility’s carbon footprint from new profitable and energy-efficient projects.
Rene Gonzalez
PTQ Q2 2024 3
 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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pcs cutpoint.indd 1 16/09/2020 12:05

 ptq&a
Q What technologies do you see dominating the long-
term development of alternative fuels like ammonia,
methanol, and hydrogen?
A Ujjal Mukherjee, Chief Technology Officer, Lummus
Technology
I see a variety of opportunities coming forth across a
broader spectrum of timelines. In the medium term, blue
hydrogen combined with carbon capture and storage will
continue as the dominant technology. With the advance-
ment of electrolysers incentivised by programmes such
as the Inflation Reduction Act in the US, the cost of green
hydrogen production will continue to drop. However, scal-
ing to match blue hydrogen capacities will require a level of
investment that only an enforceable penalty on CO2 pro-
duction could justify.
I see niche areas with plentiful solar, wind or hydroelec-
tric power as first adopters of large-scale green hydrogen
projects, such as Neom in Saudi Arabia. In countries with
an abundance of nuclear energy, such as Abu Dhabi, I soon
see the production of pink hydrogen as a reality, especially
post-COP28.
Pink hydrogen will be used first in the cement and steel
industries and later in the refining and petrochemicals sec-
tor. In the long term, turquoise hydrogen produced by the
direct conversion of methane to hydrogen and solid carbon
could become attractive at scale, especially if combined with
an electrical heat source from renewable power.
Ammonia and methanol will continue to see growth as
hydrogen carriers. The current cost of renewable hydrogen
production remains much higher than producing hydrogen
via steam methane reforming. In the long term, large-scale
use of renewable hydrogen will become economically via-
ble driven by governmental policy incentives, maturation
of electrolysers, and carbon dioxide (CO₂) taxation. Back
cracking of ammonia using a catalytic process to produce
hydrogen and nitrogen will become an attractive option.
Produced hydrogen can be used in fuel cells for power
packs. At scale, these power packs can replace marine fuel.
Firing of 100% hydrogen is technically feasible and
tested, and it avoids the challenges associated with the
use of ammonia as fuel. Using ammonia for direct firing
will require careful consideration of burner types and the
design of the selective catalytic reduction equipment. There
are also lingering concerns about fugitive ammonia emis-
sions leading to increased particulate matter (PM 2.5 and
PM 10.0) when combined with other pollutants found in
acid rain.
The use of methanol as a marine fuel will rise, especially
with the growth of green methanol. Green methanol pro-
duced from sustainable biomass will see large-scale adop-
tion in Asia, especially in India. Europe will see increased
adoption of methanol from hydrogen produced with renew-
able power and captured CO2 (e-methanol).
www.digitalrefining.com
Q2 q&a.indd 5
More answers to these questions can be
found at www.digitalrefining.com/qanda
Q What technology and strategies can resolve the huge
gaps between ethylene and propylene production in cer-
tain markets?
A Jeffery Nichols, Solutions Delivery Senior Advisor,
HSB Solomon Associates
The boom over the past 15 years in demand for olefinic
derivatives, most notably polyolefin plastics, has ushered
in a supply deficit in multiple markets, leaving producers
scrambling to capitalise on incremental margins. While the
introduction of new production lines has been realised, with
multiple fleet operators executing major capital projects
since 2010, existing facilities are examining their options
for squeezing every possible pound from their units.
The keys to maximising olefin production from any facility
– whether a new, world-scale complex or a vintage cracker,
and regardless of feed or technology – fall into four foun-
dational areas:
• Shrinking or eliminating losses
• Increasing yield
• Increasing capacity
• Sustaining high availability and minimising slowdowns
and downtime.
Robust mechanical maintenance
programmes, including sound
predictive and preventive
maintenance components, are
critical to increasing unit availability
As intuitive as these strategies for maximising produc-
tion may seem, applying them in the real world may not be
straightforward. In addition, they are likely to involve ini-
tial costs that hinge on the strategy or strategies adopted.
Furthermore, no action exists in a vacuum. In some cases,
improvement in one area will be complemented by positive
results in another, but sometimes there are trade-offs.
Robust mechanical maintenance programmes, including
sound predictive and preventive maintenance components,
are critical to increasing unit availability. Higher availabil-
ity, almost without fail, translates into reductions in losses
within a particular plant. Operational risk analysis that takes
into account a facility’s tolerance for approaching critical
plant limits or constraints is another essential element. Key
points to consider include excess utility capacity, redun-
dancy in contaminant removal, and safe operating limits
for major equipment such as compressors. Consider this:
For a 1,500-kiloton-per-year facility with a 98.5% service
factor, a four-day reliability event translates into a produc-
tion impact of more than 15 kilotons of product. Solomon
PTQ Q2 2024 5
11/03/2024 11:54:36
 can assist plant operators in evaluating the critical balance
between maintenance cost and reliability to improve long-
term performance.
Some loss mitigation programmes are not focused spe-
cifically on increasing plant reliability. These include capi-
tal-intensive projects aimed at recovering flare gas, taking
advantage of improved separation technologies (for exam-
ple, tower internals), and purifying recycle/fuel gas (and
thereby minimising olefin loss).
Frequent objectives such as improving plant yields or
expanding capacity can involve everything from unit opera-
tional debottlenecking to incremental marginal yield shifts.
Economic feasibility is a major factor in executing any pro-
gramme in these areas. Recent technological advances in
furnace coil design and metallurgy are having a significant
positive impact on once-through yields, with the bonus
of considerably extended run lengths. For furnace-limited
plants, a 50% average run length increase could translate
into an increase of 1-2% in annual furnace availability.
Another option is adding furnace capacity, but this can be
considerably more cost-intensive, at least initially.
Though attractive in principle, incorporating flexibil-
ity into a plant’s operation to take advantage of changes
in demand or price disparities for ethylene, propylene, or
another co-product may or may not be a practical pur-
suit. One must consider not only market demand but also
supply-side factors. For plants equipped to handle multiple
feed types, shifting to heavier feedstocks to increase pro-
pylene production is an intuitive response. Other options for
increasing propylene production include the incorporation
of metathesis units (at the expense of ethylene production)
and propane dehydrogenation (PDH). The current focus on
sustainability has also brought attention to methanol-to-
olefins (MTO) technology, especially when integrated with
blue hydrogen production from steam methane reforming
and with processes for carbon capture, utilisation, and stor-
age (CCUS).
The overriding takeaway is that there are numerous
options available for any particular producer to consider
when attempting to address deficiencies in olefins demand
vs supply. However, regardless of the technology consid-
ered or the strategies employed, an intense focus on avail-
ability must be maintained to keep the unit running and
running well. Solomon Advisors can assist plant operators
in achieving best-in-class performance.
A Ujjal Mukherjee, Chief Technology Officer, Lummus
Technology
When there is an abundance of cheap gas such as ethane,
producing ethylene from ethane is the most cost-effective
production pathway. However, the product slate is severely
tilted towards ethylene. Excess ethylene can be combined
with 2-butene to produce propylene using metathesis, a
low-cost energy-neutral process. Lummus’ olefins conver-
sion technology is the most widely used route to convert
ethylene to propylene to balance product slates in the most
economic manner. When both ethane and propane are in
abundance, we see a growing need for propane or propane/
butane dehydrogenation technology to produce a very high
6 PTQ Q2 2024
Q2 q&a.indd 6
yield of propylene. This approach has been adopted in the
US, the Middle East, and even in China with imported pro-
pane from the US.
The other way to reduce ethylene and propylene produc-
tion gaps is using mixed feed crackers designed to handle
a wide range of feedstocks from ethane, liquefied petro-
leum gas (LPG), naphtha, gasoils, and conditioned crudes
and condensates. Mixed feed steam crackers have specially
designed furnaces that can handle a wide range of liquids
while maintaining long heater run lengths. Mixed feed
crackers are particularly useful in the crude-to-chemicals
strategy being adopted in many regions of the world.
A Hernando Salgado, Technical Service Manager, BASF
Refining Catalysts
One strategy to adapt to changing market conditions, such
as seasonal changes in ethylene and propylene demand,
is having flexible process technologies that can adapt their
product slate to the changing demand of both products.
One of these process technologies is the always resilient
work-horse of the refining industry (and becoming increas-
ingly important to the petrochemical industry) – the fluid
catalytic cracking (FCC) process. The FCC process is char-
acterised by its inherent flexibility to manipulate severity,
and therefore, it can have the flexibility to shift between
types of light olefins produced.
This is particularly true for FCC units specially designed
to maximise light olefins – these can operate at very high
severity (with reactor outlet temperatures higher than
540°C/1,000°F) and are equipped with special hardware,
such as an additional riser to crack naphtha recycles or
other light streams, and/or special riser terminations to
maximise these secondary cracking reactions. Also, some
units are designed to crack naphtha streams exclusively
instead of conventional vacuum gasoil (VGO) or resid stock.
These specialised FCC designs combined with the appro-
priate FCC catalyst and additive systems are very effective
in maximising a variety of light olefins products.
The presence of this kind of process unit in a refining or
petrochemical complex can provide huge flexibility to play
between propylene and ethylene production by changing
operating conditions, particularly severity. In addition, the
selection of a proper catalyst, such as BASF MPS, MPS-R,
Fourte, Fourtune or Fourtitude, in combination with an
olefins additive to crack naphtha range material, such as
ZIP, will contribute to enhanced flexibility in the FCC unit,
allowing adjustment to shifting demand for propylene and
ethylene.
A Francy Barrios, Technology Engineer, Axens, Francy.
Barrios@axens.net
Ethylene and propylene are fundamental in the petrochemi-
cal industry and have a wide range of applications across
numerous industries, such as packaging, automotive, con-
struction, and textiles. The market for these chemicals is
growing due to the global demand for plastics and expand-
ing end-use industries. For this, it is important to solve the
huge gaps between ethylene and propylene production in
certain markets.
www.digitalrefining.com
11/03/2024 11:54:36
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 An increase in ethylene and propylene production can be
reached by applying simple strategies to existing technolo-
gies in the industry. For instance, increasing the severity in
FCC units and/or using specific catalyst technologies and
additives like ZSM-5 zeolite with high selectivity to olefins
provides the product flexibility required by market demand.
Even investment in additional and new technologies can be
evaluated to maximise olefins production, like the integration
of FlexEne technology, which is an innovative combination
of two well-proven technologies – FCC and oligomerisation
– to expand the capabilities of the FCC process to maximise
olefins production, especially propylene.
This flexibility is achieved by selective oligomerisation of
light FCC alkenes (olefins) for recycle cracking in the FCC
unit. Another important technology to be considered is
High Severity Fluid Catalytic Cracking (HS-FCC), an excel-
lent prospect for olefins maximisation. It is an evolution of
the well-known FCC process to reach a considerably higher
level of light olefins production, in particular propylene.
This technology is, therefore, bridging the gap between the
refining and petrochemicals industries.
Q What role does artificial intelligence (AI) play in
revamping downstream facilities that are scaling back on
conventional fuels production while upgrading to capture
value from new products?
A Bradley Ford, Global Process Optimisation Solution
Leader – Technology, KBC (A Yokogawa Company)
The growing scarcity of skilled labour is impacting the per-
formance of facilities worldwide. In fact, a study by Deloitte
and The Manufacturing Institute reports that the manufac-
turing skills gap in the US alone could result in 2.1 million
unfilled jobs by 2030, resulting in a projected cost total-
ling $1 trillion. As the industry pushes for optimisation, the
infrastructure’s increasing complexity poses a challenge.
KBC is observing the emergence of various types of AI
technologies that are starting to address these challenges.
For example, process simulation technologies are preva-
lent at nearly all global assets, operating as process digital
twins or online real-time optimisers. However, simulation
models that reflect reality still require calibration from engi-
neers. KBC now sees AI handling this critical task to:
u Monitor the asset and models
v Identify when calibration is lost
w Automatically recalibrate it.
The critical impact is allowing the available finite human
resources to focus on higher-value tasks.
Looking into the next steps, generative AI’s capabilities
are potentially game-changing in capturing organisational
knowledge that is dispersed across silos, contextualising
that knowledge, and allowing junior staff to use it for idea
generation. Careful oversight is needed to prevent genera-
tive AI systems from ‘hallucinating’ or producing theoretical
outputs that conflict with the data on which the algorithm
has been trained. Hence, training programmes are required
to educate staff on how to leverage generative AI to cre-
ate ideas for improvement, which still requires peer reviews
before implementation.
8 PTQ Q2 2024
Q2 q&a.indd 8
A Philippe Mege, Digital Services Factory Manager,
Axens, Philippe.MEGE@axens.net
Proposing a client upgrade a refinery plant from a conven-
tional market to new products is generally based on con-
sumer preferences, market trend analyses, and regulatory
changes. AI can use machine learning algorithms to analyse
historical data and make predictions about future market
trends. It can also help by running different market scenar-
ios to assess potential risks and associated impacts while
developing a new product. NLP can also be used to extract
valuable information from unstructured data sources to get
a better understanding of the market and, therefore, stay
ahead of the trends.
A Ujjal Mukherjee, Chief Technology Officer, Lummus
Technology
AI, an integral part of a digital strategy, can be used effec-
tively in retrofitting downstream units. We have a joint
venture with TCG Digital, called Lummus Digital, which
AI-driven digital solutions can
be adjusted within equipment,
product specification, and utility
constraints to minimise energy and
CO₂ emissions
leverages AI-based platforms such as tcgmcube. We couple
this with rigorous first principle-based process technology
tools to take available data, quickly create digital twins, and
develop unique hybrid solutions. These AI-driven digital
solutions can be adjusted within equipment, product speci-
fication, and utility constraints to minimise energy and CO₂
emissions while maximising production of the most valu-
able products. These techniques are applicable to optimis-
ing existing operations, designing new plants, or evaluating
potential retrofit options.
Once the products have been maximised within existing
constraints, new solutions are developed with retrofits. This
can include the change-out of catalyst systems, the addi-
tion of new equipment, and sometimes entire upstream or
downstream process technology. All of these impact the
overall product slate while remaining within the turndown
constraints of the base complex.
Examples of such strategies include:
• The introduction of biofeedstocks and waste plastic-
derived pyrolysis oils to existing refineries or petrochemical
complexes.
• The elimination of gasoline production while maximising
jet and diesel production, high-sulphur fuel oil production,
and high-sulphur coke production.
• Increasing chemicals production from 10-30% and
sometimes 50% production of needle coke and anode coke
from an existing coker, which is a dramatic shift in crude
slates and more.
www.digitalrefining.com
14/03/2024 11:52:59
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 The AI digital twin assesses plant performance under
various configurations and integrates with economic and
capital cost models to evaluate the full impact of the revamp
considered.
Q Under what conditions do you see opportunities for
blending petrochemical byproducts with refinery fuel
feedstocks to lower conversion costs?
A Romain Roux, VP Decarbonisation & Consulting,
Axens, Romain.ROUX@axens.net
Pygas is easily valorised in a refinery to produce an aro-
matic rich cut or a gasoline after different hydrogenation
steps. To produce an aromatic rich cut, a first step of hydro-
genation will remove the diolefins and styrene.
A second step of hydrogenation will remove the sulphur
and olefins. To produce a gasoline, the first step of hydro-
genation remains. It is then processed in a Prime-G+ unit to
produce ultra-low sulphur gasoline.
A Ujjal Mukherjee, Chief Technology Officer, Lummus
Technology
Whenever a refinery is being integrated with a petrochemi-
cals complex, the opportunity to upgrade low-value prod-
ucts from one unit to another increases. For example, the
extremely low-value pyrolysis fuel oil from an ethylene unit
is a good feedstock to a residue hydrocracking unit, where
it will be converted to transportation fuels and/or petro-
chemical feedstock. Hydrogen from propane dehydrogena-
tion, catalytic reforming, and ethylene units can significantly
reduce the hydrogen production demand in the refinery.
When demand for gasoline is high, which is still the case
in several parts of the developing world, the pyrolysis gaso-
line from the ethylene unit or reformate from an aromat-
ics unit can offer good value, especially when the price of
certain polymers is depressed. The C9+ aromatics from an
ethylene unit can be recycled back to a hydrocracker to pro-
duce incremental jet or heavy naphtha.
Q What heat and mass transfer technologies are helping
the industry lower Opex?
A Caroline Bird, Senior Marketing Specialist, Solenis
LLC, cbird@solenis.com
Heat exchanger efficiency is critical to the success of any
industrial operation, yet many plants rely on outdated
or inadequate data to assess the health of their heat
exchanger networks. As digitalisation is slowly becoming
accepted and explored in the industry, there are opportuni-
ties for refining and petrochemical operations to improve
data management and lower operating expenses.
Digital monitoring of heat exchanger reliability and per-
formance is allowing companies to identify problem heat
exchangers and create appropriate action plans to optimise
heat exchanger efficiency.
Solenis’ HexEval performance monitoring program for
heat exchangers is an example of this digitalisation. The
program allows plant operators to identify and monitor
problem heat exchangers that are operating outside of set
10 PTQ Q2 2024
Q2 q&a.indd 10
limits for fouling and scale. As a result, plant operators can
address fouling and scale issues in real time to help avoid a
plant shutdown or slowdown.
Additionally, Solenis’ HexEval program provides an online
repository for all heat exchanger activity, allowing access to
historical data when needed. This allows plant personnel to
devise action plans to proactively address system issues,
thereby maintaining plant productivity and generating
operational savings. The utilisation of the HexEval program
has enabled numerous Solenis customers to decrease cor-
rosion and corrosion-related pitting, cleanings outside of
turnarounds, and heat exchanger failures. Knowledge is
power, and having the knowledge of their heat exchangers
at their fingertips has enabled refining and petrochemical
operations to significantly reduce their operating costs.
A Jan Reneteau, Managing Director, Axens, Jan.
RENETEAU@axens.net
Very high-efficiency heat exchangers are key to lowering
the Opex of heavy energy consumption processes. While
standard S&T technology can offer limited thermal per-
formances, spiral tube heat exchanger technology greatly
enhances thermal and hydraulic performances.
This technology has been used for many years in the cryo-
genic liquefaction industry. For more than 30 years, ZPJE
has developed a unique state-of-the-art know-how of heat
exchange calculation, hydraulic simulation, and mechanical
modelling of spiral tubes design to enable this technology
to be used in refining and petrochemical applications.
The design of spiral tube heat exchangers consists of
many tubes arranged in multiple layers of helical coils,
around a centre pipe. This tube bundle is enclosed in a
cylindrical pressure vessel. The fluid on the tube side and
shell side flows in opposite directions, making the equip-
ment a true countercurrent heat exchanger, allowing a heat
transfer efficiency two to three times higher than conven-
tional S&T exchangers.
The minimum temperature difference between the two
fluids can be as low as 2°C, permitting the unlocking of heat
integration opportunities in demanding process services.
Those exchangers can be applied in reforming, aromatics
applications and also in hydroprocessing applications where
their high performance and high tolerance towards fouling
can drastically reduce the Opex, allowing, in some cases, the
end user to operate the furnace only during start-up phases.
The newly created joint venture between ZPJE and Axens
named Nectis aims to promote the application of spiral tube
heat exchangers in the refining and petrochemical busi-
nesses to help the industry lower its carbon intensity.
A Ujjal Mukherjee, Chief Technology Officer, Lummus
Technology
Some technologies that are especially useful include:
• New membrane technologies for separation and coil-
wound heat exchangers.
• Air preheat systems that can significantly reduce energy
consumption.
• Advanced integrated separation devices used in Lummus’
proprietary TC2C technology.
www.digitalrefining.com
11/03/2024 11:54:37
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 • The use of stripping media to eliminate expensive furnaces.
TC2C is a trademark of Lummus Technology.
Q How are technology suppliers dealing with attracting
young professionals to the industry?
A Louise Maratos, Head of Consulting Delivery, Lourdes
Cozzitorto, Vice President, Technology Services, KBC (A
Yokogawa Company)
Technology suppliers are increasingly recognising the
importance of attracting young professionals to the indus-
try. Companies are leveraging modern technologies not
only to enhance their products and services, but also to
streamline their recruitment and onboarding processes.
These companies are using applications that offer multi-
channel sourcing, making it more convenient for candidates
to apply for jobs matching their skills profile and interests.
They also encourage engagement via specific young pro-
fessional/graduate websites.
Emphasising a flexible work environment, work-life bal-
ance, and an innovative culture resonates with Gen Z’s
aspirations. Moreover, offering opportunities for skill devel-
opment and career growth, along with a commitment to
sustainability and social responsibility, must be actively
integrated into recruitment strategies.
Companies are leveraging modern
technologies not only to enhance
their products and services, but
also to streamline their recruitment
and onboarding processes
Adapting to the preferences and values of this younger
workforce is crucial to ensuring the industry remains vibrant
and competitive.
In Europe, collaborating with schools and colleges
encourages young adults to pursue STEM careers. We are
establishing partnerships with open opportunities within
our organisation for internships across technology and con-
sulting, giving young people insight and experience in our
industry. Additionally, a junior network is in place to facili-
tate discussions on various topics of interest with our global
experts, which actively engages with relevant universities.
A Mathilde Nerrant, Head of Talent Manager, Axens,
Mathilde.NERRANT@axens.net
Axens Group provides a complete range of solutions for the
conversion of oil and biomass to cleaner fuels, the produc-
tion and purification of major petrochemical intermediates,
the chemical recycling of plastics, all natural gas treatment
and conversion options along with water treatment and
carbon capture.
The offer includes technologies, equipment, furnaces,
modular units, catalysts, adsorbents and related ser-
vices. Axens is ideally positioned to cover the entire value
12 PTQ Q2 2024
Q2 q&a.indd 12
chain, from feasibility study to unit start-up and follow-up
throughout the entire unit life cycle.
This unique position ensures the highest level of perfor-
mance with a reduced environmental footprint. As a key
player in energy transition, Axens Group offers many guar-
antees to young professionals willing to join the energy
industry. These promises stand for both their professional
and personal development, which is facilitated by four
major HR levers that support our employer brand:
Empower yourself
At Axens, you can choose how to take your future into your
own hands: at your own pace, independently, but not alone.
Personalised training, career paths, taking on responsibili-
ties, geographical or intra-group mobility, you decide how
you venture forward, and we will build a secure future
together.
Worldwide
Working at Axens is also about building and living your
success story in France or abroad. Working in energy per-
formance for major industrial companies on a large scale,
international projects with our subsidiaries around the
world is a daily reality. As a young professional, you can
quickly meet our customers and suppliers from different
countries who speak different languages and exchange
with them on a daily basis.
Diversity and inclusion
Within the Group, we all interact with men and women of
more than 50 nationalities, different cultures, generations,
professions and backgrounds guided by a common ambi-
tion: to take the challenges of energy transition further. The
goal is that we like to live to the full at Axens by continu-
ously challenging stereotypes and clichés. It is the foun-
dation of our commitment to diversity and inclusion. Only
talent and personality matter to us.
Happy
Let us put it straight. Axens has obtained the label ‘Happy
at work’ for the ninth consecutive year. Young graduates
and professionals are also forging lasting relationships
thanks to strong values embodied by all Axens communi-
ties throughout the world. It is not by chance that most of
our people make the decision to build a long career path
with Axens.
A Nora Yap, Strategic Marketing Manager, Syngas and
Fuels, Clariant Catalysts, Nora.Yap@clariant.com
We need to ensure the fundamentals are right. Offering
candidates competitive salaries and benefits and ensuring
employees are supported in their continued growth with-
out compromising their work-life balance are key.
Fostering an innovative and inclusive work environment
is also about having a purpose they can believe in, where
their contribution matters.
Additionally, if we further foster openness and trust
within the organisation, we can ensure not only talent
attraction but also talent retention.
www.digitalrefining.com
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 Optimising furnace run length in a
steam cracker using AI
Case study on improving ethylene furnace run length by leveraging the synergy of
digitalisation and artificial intelligence to provide the necessary insights
Surabhi Thorat and Vivek Srinivasan Dorf Ketal Chemical (I) Pvt Ltd
Sudarshan Vijayaraghavan Dorf Ketal Chemicals PTE Ltd
E
thylene serves as a predominantly petrochemically
derived monomer essential for producing plastics,
fibres, and various organic chemicals. These end
-products find applications across industries such as pack-
aging, transportation, construction, and other industrial and
consumer markets. Notably, more than half of global ethyl-
ene derivative consumption is attributed to non-durable or
consumable end uses, especially in packaging.
The majority of this consumption is associated with poly-
ethylene, a plastic resin that constitutes most ethylene usage.
Given its status as one of the largest volume petrochemicals
globally, the consumption of ethylene is influenced by eco-
nomic and energy cycles. Its extensive and diverse derivative
portfolio, covering both non-durable and durable end uses,
positions ethylene as a benchmark for gauging the overall
performance of the petrochemical industry.
Furnace efficiency
In the complex realm of ethylene production, furnace efficiency
plays a pivotal role in determining overall operational success.
However, a significant challenge arises from shortened run
lengths, increasing downtime and production costs. This issue
is rooted in the increasing tube metal temperature (TMT) of
the furnace, a critical factor affecting operational longevity.
A decrease in run length in an ethylene furnace due to coke
formation and a rise in TMT can result in significant financial
losses for several reasons. Here are some potential factors
contributing to the financial impact:
• Production interruption: Reduced run length means the
ethylene furnace is not operating at its optimal capacity for
the intended duration. This interruption in production can
lead to lower yields of ethylene and other desired products,
resulting in lost revenue.
• Increased decoking: Coke formation and elevated TMT
may call for frequent decoking, resulting in higher energy
costs and reduced capacity utilisation rates. Frequent decok-
ing can also affect the overall reliability of the tubes, compro-
mising the life span of radiant tubes.
• Energy consumption: A less efficient furnace may require
more energy to maintain the desired operating conditions.
Higher energy consumption not only leads to increased
operational costs but also contributes to environmental con-
cerns if the energy source is not sustainable.
www.digitalrefining.com
DORF.indd 15
• Impact on selectivity: Inefficient furnace operation, com-
bined with a high potential for coking, leads to a critical
TMT threshold during mid-run cycles, constraining achiev-
able severity levels. Consequently, this limitation adversely
affects the overall selectivity for ethylene make.
• Market dynamics: In the competitive petrochemical indus-
try, delays or interruptions in production can affect a compa-
ny’s ability to meet customer demands. This can result in lost
market share and potential long-term damage to business
relationships.
• Increased emission and environmental impact: Poorly
optimised furnace operations tend to emit higher levels of
greenhouse gases, thereby exacerbating the carbon foot-
print, as furnaces are commonly fuelled by fossil fuels. The
frequent decoking process also introduces further emissions,
compounding an already elevated environmental impact.
To mitigate these financial losses, it is crucial for plant
operators to implement effective monitoring, maintenance,
and operational strategies to prevent or address issues
such as coke formation and elevated TMTs in a timely man-
ner. Regular inspections, proper decoking procedures, and
adherence to best practices in furnace operation can contrib-
ute to improved efficiency and extended run lengths.
Differentiator
Understanding and addressing elevated TMTs is key to
overcoming these aforementioned challenges. Dorf Ketal’s
proprietary artificial intelligence (AI) solution CokeNil offers
solutions to extend run lengths through predictive mainte-
nance, optimised process control, and improved fault detec-
tion. It is a data-driven, deep domain insight-based solution
where every process parameter is evaluated thoroughly in
the exploratory data analysis phase to ensure the accuracy of
the outcome. It is built on advanced deep learning methods
such as long short-term memory (LSTM) networks, Random
Forest regression, CatBoost regression, XGBoost regression,
and time series algorithms to help the model identify the pat-
tern and behaviour of each critical process parameter.
CokeNil is a unique AI solution for optimising the furnace
run length. This plant’s distributed control system (DCS)
feeds live operating conditions (such as naphtha feed com-
position, coil outlet temperature, steam-to-hydrocarbon ratio
[SHC], temperature, and fuel flow) to the CokeNil. These are
PTQ Q2 2024 15
11/03/2024 11:56:33
 1150
1050
950
850
1 4 7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52
Run length
Actual TMT Predicted TMT
Figure 1 Actual vs predicted TMT
processed by the AI model, and optimal values that need
to be set in the real process are recommended. A key point
is that the optimal values will never violate the acceptable
operational ranges of suggested critical parameters.
AI algorithms equipped with real-time data analysis
capabilities play a crucial role in predicting and proactively
addressing potential furnace issues. By dynamically adjust-
ing parameters and ensuring adaptive control, the AI system
prevents runway TMT and mitigates stress on critical com-
ponents. This dynamic optimisation lays the groundwork
for extended operational runs, minimising the interruptions
caused by unplanned downtime.
AI/digital twins symbiosis
AI-driven optimisation plays a key role in ensuring stable fur-
nace operation with reduced delta pressure and dilution steam,
as well as an optimised feed ratio. This leads to a more con-
trolled furnace temperature, contributing to operational stead-
iness. The nuanced control provided by AI not only enhances
operational efficiency but also contributes significantly to the
overall stability of the ethylene production process.
The discussion takes an intriguing turn with the introduc-
tion of advanced process modelling, including the concept of
digital twins. This innovative approach enables virtual test-
ing and scenario optimisation, allowing operators to explore
various conditions without impacting the physical furnace.
The symbiosis of AI and digital twins not only optimises cur-
rent operational parameters but also lays the groundwork for
future advancements in ethylene production processes.
However, challenges persist, and historical data serves
as both a hurdle and a guiding light. The initial phase of AI
1150
1100
1050
1000
950
900
1 4 7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52 55 58 61 64 67 70
Run length
Actual TMT Forecasted TMT
Figure 3 Scenario 2 where furnace run length is extended
by 18 days
16 PTQ Q2 2024
DORF.indd 16
1150
1100
1050
1000
950
900
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33
Run length
Actual TMT Forecasted TMT
Figure 2 Scenario 1
model building includes critical process parameters identifi-
cation, preliminary investigations, pattern discovery, anom-
aly spotting, hypothesis testing, and establishing correlations
between process parameters and run length by considering
TMT as the primary target.
AI leverages historical data to train the run length optimi-
sation model. Coking in the radiation coil is inevitable at high
cracking temperatures. As TMT reaches maximum threshold
values, the furnace undergoes decoking, compromising run
length. Furnace run length is directly linked to coke forma-
tion rate, with operational parameters such as TMT, dilution
steam ratio, firing rate, feed composition, feed rate, wall and
floor burners in operation, excess oxygen %, coil pressure
ratio (CPR), coil outlet pressure and venturi ratio determining
the end of furnace runs.
In response to these intricacies, the furnace is operated, and
parameters are controlled to minimise the rate of increase in
TMT throughout the run. This proactive approach mitigates
the rise in TMT, ultimately contributing to longer furnace run
lengths and improved operational efficiency.
TMT prediction model
The CokeNil TMT prediction model has demonstrated a com-
mendable accuracy rate of 98.2%, underscoring the efficacy
of our AI system. This high level of precision substantiates
the model’s reliability and underscores its potential impact
in practical applications. It is imperative to recognise that
model success extends beyond accuracy alone, encompass-
ing aspects such as generalisation to unseen data and robust
performance across diverse scenarios.
Furthermore, a holistic assessment that includes metrics
like precision, recall, and F1 score contributes to a more com-
prehensive evaluation of the model’s efficacy. The observed
effectiveness of the base model in predicting TMT for opti-
mal parameter recommendation holds promise for positively
influencing associated processes and systems. Continuous
monitoring, evaluation, and potential retraining with new data
are pivotal for sustaining and improving model performance.
Figure 1 shows the results of the TMT prediction model.
Whenever a new furnace run starts, the CokeNil model
captures critical parameters, which are the base for the model,
and generates optimal values for subsequent furnace runs.
The generated optimal values are typically in the acceptable
operational range, which the plant operator can incorporate
into the actual process and see the TMT improvement.
www.digitalrefining.com
11/03/2024 11:56:37
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 Figure 4 CokeNil dashboard
CokeNil scenario 1
Figure 2 shows Scenario 1, where our model is tested on his-
torical data to measure its impact on furnace performance. It
was identified that the ethylene furnace, operating under the
traditional pattern, reaches the threshold within 25 days from
the commencement of a new start. However, upon replac-
ing this conventional process with the CokeNil AI model, the
forecasted threshold reaches 33 days, signifying an extended
run length of roughly eight days (~27%), achieved through
the optimal parameters recommended by the AI model.
These bespoke enhancements ultimately contribute to
increased production, aligning with the organisation’s finan-
cial goals. Implementation of the parameters recommended
by the model is expected to yield a considerable benefit for
the 48 t/hr feed furnace, ranging from 140,000 to 150,000
$/year. This notable financial enhancement can be attributed
to the projected reduction of three decoking cycles.
CokeNil Scenario 2
Figure 3 illustrates Scenario 2, showing that the forecasted
TMT by CokeNil could extend the run length by 18 days
(~25%). These contrasting outcomes highlight the marked
difference between traditional and advanced approaches to
ethylene furnace operation.
Upon the implementation of the recommended parame-
ters by the model, it is anticipated that the 48 t/hr feed fur-
nace could yield a substantial benefit of 70,000-80,000 $/
year. This financial improvement is attributed to the expected
reduction in the decoking cycle by 1.6 instances.
CokeNil dashboard
Figure 4 shows the user interface dashboard for a cognitive
solution, analysing various furnace parameters (temperature,
pressure, and flow rate) in real-time and suggests adjust-
ments to optimise run length by providing actual and rec-
ommended parameters for each batch. This could involve
www.digitalrefining.com
DORF.indd 17
fine-tuning operating conditions, predicting potential issues
before they arise, and enabling preventative maintenance.
The dashboard includes an advanced analytics panel con-
sisting of the following:
• Predictive: Displays the actual vs predicted TMT trend with
the comparative trend of critical parameters like CPR.
• Descriptive: Generates alarms that promptly notify when
the TMT or CPR approaches the threshold and provides the
visualisation of critical parameters
• Prescriptive: Provides the overall benefits statistics.
CokeNil benefits for furnace run length include:
• Increased run length: The AI model’s ability to optimise
operations leads to longer furnace runs, resulting in higher
production capacity and reduced downtime.
• Improved efficiency: By optimising operating conditions,
the AI model helps reduce energy consumption, leading to
more efficient production.
• Reduced costs: Longer runs, improved efficiency, and fewer
unplanned shutdowns can translate to notable cost savings.
CokeNil trend analysis
The CokeNil trend analysis shown in Figure 5 indicates the
key elements of the dashboard:
• It displays the non-optimised run length of the furnace vs
the optimised run length and the next time the prediction will
be updated. It indicates the non-optimised run length is 35
days, and the optimised run length is 45 days, which means
the optimised run length is 10 days compared to the non-op-
timised prediction.
• The user can select process parameters, namely total
naphtha and coil outlet temperature (COT), for a specific
date range to see its individual behaviour and trends.
• The ‘Actual vs Predicted TMT’ graph indicates the accu-
racy of the TMT prediction model.
• The ‘Furnace RL Increase %’ chart shows that the AI model
has increased the furnace run length by 25%.
PTQ Q2 2024 17
11/03/2024 11:56:40
 Figure 5 CokeNil trend analysis
• The ‘Total Naphtha Vs Time’ graph shows the amount of
naphtha (feedstock) that has been used over time.
• The ‘COT Vs Time’ graph displays the COT of the furnace.
• The ‘Economics’ section highlights the economic benefits
of using the AI model, such as increased production and
reduced costs.
CokeNil alerts and alarms
These key elements of the dashboard include:
• TMT prediction and possible alert: Forecasts the TMT
and generates alert to take necessary action.
• Alert for critical parameters: If any critical parameters
exceed safe limits, an alert will be triggered, indicating
a potential concern. It is important to monitor and con-
trol these parameters to ensure efficient operation of the
furnace.
All triggered alarms due to specific conditions will be
emailed to the relevant authorities. This ensures that poten-
tial risks are addressed efficiently, contributing to a seam-
less and well-managed process.
CokeNil what-if analysis
The following elements are identified by the what-if analysis:
• Plant admin – diagnostic analysis: Explains the overall
purpose of the dashboard.
• Status of the furnace (online/offline): Indicates if the plant
is operational or not, which can affect the data displayed.
• Actual vs predicted TMT: Compares real-time TMT with
the AI’s prediction, aiming to optimise TMT for efficient and
safe operation.
• Specific input prompts: These allow the manual input of
specific feedstock or cycle time data for analysis.
• Recommendation and download: The AI suggest adjust-
ments based on the TMT comparison, which can be down-
loaded for implementation.
• Recommendation acceptance: Shows the user acceptance
18 PTQ Q2 2024
DORF.indd 18
rate for the AI’s recommendations regarding TMT, indicating
their effectiveness.
• Similar structure for CPR and SHC ratio: These follow the
same pattern as TMT, analysing and potentially optimising
parameters for improved performance.
Possible implications
• CokeNil’s AI tool plays a crucial role in analysing plant per-
formance, predicting key parameters and suggesting opti-
mising actions.
• By optimising TMT, CPR, and SHC ratio, CokeNil could
potentially improve process efficiency, reduce waste, and
enhance safety.
• The high recommendation acceptance rate suggests user
confidence in the CokeNil insights and its potential to deliver
positive outcomes.
Conclusion
It becomes imperative to strategically optimise operations
within steam crackers, with an emphasis on enhancing
furnace efficiency to address the economic constraints and
ensure sustainable performance. Central to this discussion
is the continuous learning capability of AI, empowering the
system to evolve and adapt based on new data and expe-
riences. In the context of ethylene furnaces, this continuous
learning contributes to data-driven decision making. The AI
system becomes not just a static tool but also a dynamic
partner in improving furnace performance and supporting
extended run lengths.
Surabhi Thorat is Head of Data Science at Dorf Ketal Chemical (I) Pvt Ltd.
Vivek Srinivasan, is Senior Manager, Global Technical Services at Dorf
Ketal Chemicals India Private Limited. Email viveks@dorfketal.com
Sudarshan Vijayaraghavan is District Manager at Dorf Ketal Chemicals
PTE Ltd.
www.digitalrefining.com
11/03/2024 11:56:41
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 Dryout design considerations for
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Closed-loop recirculation dryout removes water more efficiently, monitors dryout
progress more easily, and allows for a quicker transition to plant cooldown

Scott A Miller, David A Jelf, J A Anguiano and Joe T Lynch

Honeywell UOP

P
art 1 in PTQ Gas 2024 discussed the importance of
a properly conducted dryout for cryogenic gas plants
during start-up, the most common dryout options, and
the general design features needed for a closed-loop recircu-
lation dryout. Closed-loop recirculation dryout performs best
at effectively removing water from the system while easily
monitoring dryout progress This allows for a quick transition
to plant cooldown after dryout is completed. Part 2 will cover
some of the design challenges, the method for implementing
a closed-loop recirculation dryout, and monitoring progress.
Cold plant dryout challenges
Typical cold plant stagnant areas include:
• Thermosyphon reboiler loops
• Reflux system (propane recovery plant)
• Lower fractionator section (below expander outlet feed).
Thermosyphon reboiler loops
There is no obvious location to introduce dryout gas flow
into a thermosyphon reboiler loop unless isolation valves
are installed around the strainers for the exchanger. Some
cold plant designs include isolation valves for the strain-
ers to have the capability for removing a plugged strainer
without depressuring and clearing a much larger plant sec-
tion (if not the entire cold plant) of hydrocarbons. This is
the easiest location to introduce dryout flow because the
isolation valves can be used to direct flow where needed.
For this case, connect the dryout gas source between the
exchanger start-up screen isolation valves (see Figure 1). A
2in minimum dryout connection is recommended.
If strainer isolation valves are not installed, or another
means to direct flow through the stagnant pipe loop is
not provided, portions of the loop will likely see smaller
amounts of dryout flow (or no flow at all), potentially leav-
ing unknown water in the piping and equipment. Any flow
path that leaves the fractionator and then returns to the
fractionator will be stagnant. Therefore, consider the same
dryout approach as for a thermosyphon reboiler loop.
If strainer isolation valves are not
installed, or another means to direct
flow through the stagnant pipe loop
is not provided, portions of the loop
will likely see smaller amounts of
dryout flow (or no flow at all)
Reflux system (propane recovery plant)
Many technologies for propane recovery have a more com-
plex reflux system and can be difficult to dry out without
proper dryout connections. A section of the reflux system
from Figure 7 in Part 1, which typically is stagnant during
dryout, is shown in Figure 2. A 2in minimum dryout con-
nection is recommended.
The lowest point in the reflux system is the reflux pumps.
The reflux system should be designed to free-drain to the
lowest point. The dryout gas source can be connected to

Fractionator
Reflux
accum.
Dryout
gas supply
Dryout
Reboiler gas supply Reflux to
pass fractionator

Strainer
Low-point drain Reflux pump
Liquid product
Low-point drain

Figure 1 Possible dryout connection for reboiler loops Figure 2 Dryout connection for reflux system

www.digitalrefining.com PTQ Q2 2024 21

Q2 UOP.indd 21 11/03/2024 12:14:36

 Fractionator
Dryout
gas supply
Liquid product
Low-point drain
Figure 3 Fractionator dryout connection
the suction side of the reflux pumps inside the pump iso-
lation valves, as shown in Figure 2. The pump isolation
valves can then direct dryout gas flow downstream of
the pumps through the reflux piping to the de-ethaniser
column.
Lower fractionator section (below expander outlet feed)
The lower section of the fractionator column below the
expander outlet feed requires an external flow source to
remove water from the mass transfer equipment inside
the column. A pipe connecting dryout gas to the column
bottoms outlet piping should be designed and installed, as
shown in Figure 3. The piping and connection size must
be large enough for this dryout connection to be effective.
For a 200 MMSCFD (5.4 x 106 Nm3/hr) cold plant, a 4in
connection is recommended. As the cold plant nameplate
capacity decreases, so can the dryout connection size, but
use at least a 2in connection.
For propane recovery plants, it is important to note
that any water remaining inside the de-ethaniser column
after cooldown will become trapped, eventually freezing
because the column overhead is colder than the freezing
point of water, and the column bottom is warmer than the
boiling point of water.
Location to monitor cold plant water content
A sample location for monitoring the wet gas water content
at the outlet of the cold plant upstream of the residue gas
compressor must be available (see Figure 4). The wet gas at
this location is representative of the amount of water pres-
ent in the main dryout circulation loop. Any water carried
away by the warm dryout gas that will then be removed by
the dehydrators can be measured at this point.
Before starting dryout
Ensure the following before beginning a cold plant dryout:
• The pressure-reducing device is installed at the desig-
nated location.
• The residue gas compressor is operational and running
in total recycle before starting dryout gas flow through the
train.
• All dehydrator beds are available for service in their nor-
mal cycle. Each bed should have already had at least one
successful regeneration cycle, and the water content of
the dry gas exiting each bed should be less than 1 part
22 PTQ Q2 2024
Q2 UOP.indd 22
Residue gas AI
Air cooler compressor
To sales H2O
A A
Inlet
gas
Cold plant
B B
Dust filters
Dehydrators
Liquid
Dryout flow path Off-line product
Figure 4 Recommended location to monitor dryout water
content
per million by volume (ppmv). At least one bed should be
online with one bed in regeneration (assuming a two-bed
design).
• The dehydrator dust filters must be available for service.
A typical design includes two full-flow filters (one in service
and one off-line).
• All control valves and manual valves which would restrict
flow through the main flow path are open, except the J-T
valve.
• The fractionator bottom is isolated from its downstream
equipment.
• The expander/booster compressor is completely isolated,
with flow through the J-T valve and around the booster
compressor through its bypass line.
• The moisture analyser used to monitor the cold plant
water content is in service.
System design limitations
The following design limits must be adhered to keep from
damaging process equipment during dryout:
• The recommended maximum dryout gas feed tempera-
ture to the cold plant is 140°F (60°C), limited by the brazed
aluminum heat exchangers (BAHE) design temperature
of 150°F (65°C). Warmer dryout gas is better. Adjust the
louvres on the residue gas compressor discharge cooler to
provide a temperature near the maximum.
• Understand the flow rate limitations, which would result
in reaching the maximum velocity limitations across major
process equipment (dehydrators, filters, and mass transfer
equipment) during dryout because of system flow at lower
pressure. However, while it is prudent to know the plant
process design limits to keep from damaging equipment,
the maximum flow calculated to limit J-T expansion through
the cold plant will most likely be less than the process
equipment maximum velocity limits.
Dryout method
At this point, all process requirements should be met so
dryout can begin.
www.digitalrefining.com
11/03/2024 12:14:37
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1000
900 Water content (ppm)
800
700
600
500
400
300
200
100
0 a constant purge to flare throughout dryout may not be
0 50 100
Duration (hours)
Figure 5 Example water content trend during dryout
Summary of steps
 Initiate dryout gas flow through equipment
 Circulate dryout gas through the main flow path
 Periodically drain system low points
 Establish flow through stagnant piping loops.
 Initiate dryout gas flow through equipment
With the J-T valve pressure controller in ‘manual’, slowly open
the valve to 100% valve position. Increase the dryout gas flow,
if necessary, by increasing the residue gas compressor speed
until the calculated gas circulation flow target is reached. As
the circulation rate is established, continue to monitor the sys-
tem pressure. To maximise the velocity through the cold plant,
dryout system pressure should be set as low as the residue
compressor operation will allow. Add fresh gas as needed to
maintain the minimum system pressure during dryout.
Establish the baseline water
content in the cold plant when
dryout starts, and record water
content readings throughout
dryout to track progress
 Circulate dryout gas through the main flow path
The pressure drop across the fully open J-T valve should be
low enough so that no significant cooling occurs. In most
cases, a pressure drop of less than 30 psi (2 bar) should be
low enough to minimise cooling in the plant.
Monitor the cold plant temperatures. All the equipment
will cool slightly, but the temperatures should stabilise. If
equipment starts cooling significantly, slow down the res-
idue compressor until the pressure drop across the fully
open J-T valves decreases enough so that the cooling stops.
No hydrocarbon liquid should form.
If liquid accumulates in any vessel, it should be just the
free water moved to the vessel by the dryout gas flow.
24 PTQ Q2 2024
Q2 UOP.indd 24
 Periodically drain system low points
As circulation flow is established, free water will move to
the process low points where it can be drained. Mark all
low-point drains in the field and on a set of piping and
instrument diagrams (P&IDs) to ensure all low points are
drained during dryout. We recommend maintaining an
operator log listing all low-point drains and the times each
was blown down for the duration of dryout.
The best method for purging the plant is by opening all
low-point drains and allowing any water present to purge
to the closed drain system throughout dryout. However,
this approach increases the amount of flaring, and having
150
allowed. If a constant purge is not allowed, establish a rou-
tine frequency for draining all low points (say, once every
two hours). Open each drain for at least 30 seconds to
remove any free water at that location. The operator might
be able to hear the water draining and feel the water flow
as the drain valve opens. Add fresh gas as necessary to
maintain the minimum system pressure during dryout.
 Establish flow through stagnant piping loops
Once the main dryout flow path is dry, establish flow
through stagnant piping and equipment loops which would
otherwise not dry out. The stagnant piping loops discussed
in this paper should be designed to free-drain to the lowest
point. Drain any free water collected at the piping system
low point first. Use the method described in Step 3 for
draining water at each process low point. Once the free
water is drained, the remaining water in the loop should
be small enough to be picked up and carried away by the
warm dryout gas introduced.
Monitoring during dryout and time to completion
Once the dryout process has been established, how does
the operator know if dryout is progressing and when it is
complete?
Establish the baseline water content in the cold plant when
dryout starts, and record water content readings through-
out dryout to track progress. An online moisture analyser to
monitor dryout is helpful because water content readings
can be collected and trended in the plant’s data historian.
As discussed earlier, the recommended location to track the
water content is at the outlet of the cold plant upstream of
the residue gas compressor suction. In addition to monitor-
ing at this location, it is helpful to have a portable moisture
analyser to collect periodic readings in stagnant piping sys-
tems where additional dryout gas flow had to be introduced.
Figure 5 is an example of the general water content trend
during dryout. As process flow paths are changed and flow
is introduced into stagnant areas, do not be surprised if the
water content increases at times during dryout. This is an
indication that additional water has been absorbed by the
vapour stream and removed from the process equipment
and piping.
The suggested maximum water content for a cold plant
to avoid forming hydrates is 10 ppmv. Dryout is close to
completion once the water content decreases below 10
ppmv, but we recommend continuing dryout for a short
www.digitalrefining.com
11/03/2024 12:14:38
 duration afterwards (eight hours). During this time, reintro-
duce dryout flow into stagnant areas and force more flow
through portions of the main circulation path by manipulat-
ing valves to ensure the plant is completely dry. Dryout is
complete if the cold plant water content does not increase
above 10 ppmv after this period.
The time required to execute a closed-loop recirculation
dryout is dependent on the quantity of water in the cold
plant. Usually, four to six days is a reasonable estimation if the
guidelines described in this article are followed. In cold plants
where nitrogen cycling occ urs before a closed-loop recircu-
lation dryout, the time required may be as little as two days.
If the gas dew point is measured during dryout instead
of the actual water content, it is important to understand
that the pressure at which the dew point is measured has a
significant effect on the dew point reading.
Determine if the dew point analyser being used is reading
the dew point at line or atmospheric pressure and under-
stand the dew point conversion between the two pressure
points.
Establish the maximum allowable water content crite-
ria before dryout starts. The maximum set value will help
establish an agreement between all parties involved as to
when dryout is complete. At times, parties involved become
too eager and decide to begin cooldown prematurely, only
to have to go back into dryout mode again after freezing
the cold plant.

Conclusion
UOP Ortloff has witnessed many cold plant dryouts during
commissioning and initial start-up over the years (see Part
1 in PTQ Gas 2024).
A well-conducted cold plant dryout will help plant com-
missioning and ensure start-up goes smoothly and does
not last any longer than necessary. There are multiple
dryout options which can remove water from the system.
However, there are drawbacks to some of them.
The closed-loop recirculation dryout does the best job at
effectively removing water from the system while easily
monitoring dryout progress and allows for a quick transi-
tion to plant cooldown after dryout is completed.
Process integrated
Scott A Miller is a Principal Process Engineer with Honeywell UOP, solutions for Ejector
supporting Ortloff Cryogenic Gas Processing Technologies. He has
more than 23 years of experience in the petrochemical and gas pro-
Vacuum Systems
cessing industries, of which 15 are in the design and operation of NGL/
LPG recovery plants. Email: scott.a.miller@honeywell.com
GEA steam Jet Vacuum Systems help optimize
David A Jelf is a Principal Instrument and Controls Engineer with
production processes, reducing both costs
Honeywell UOP, supporting Ortloff Cryogenic Gas Processing and carbon emissions.
Technologies. He has more than 40 years of experience in the design Upgrade your system now!
and operation of NGL/LPG recovery plants.
J A Anguiano is a former Engineering Manager with Honeywell UOP,
previously supporting Ortloff Cryogenic Gas Processing Technologies.
He has more than 25 years of experience in the design and operation
of NGL/LPG recovery plants.
Joe T Lynch is a retired Engineering and Licensing Manager from
Honeywell UOP, previously supporting Ortloff Cryogenic Gas
Processing Technologies. He has more than 45 years of experience in
the design and operation of NGL/LPG recovery plants.

www.digitalrefining.com

Q2 UOP.indd 25 11/03/2024 12:14:42

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 FCC co-processing of biogenic and
recyclable feedstocks: Part 2
Part 1 provided a segue into operational concerns ranging from WPO co-processing to
maximising oxygen removal and flexible catalytic solutions for FCC operations
Jon Strohm, Darrell Rainer, Oscar Oyola-Rivera and Clifford Avery
Ketjen
E
merging corrosion concerns surrounding the pro-
cessing of fats, oils and greases (FOGs) are highly
paraffinic. They will vaporise and crack easily, but
some naphthenic acid (TAN) may be present, particularly
in tallow or used cooking oil (UCO). TAN has been known
to increase corrosion in distillation towers and hydrotreat-
ing units. For FCC units, it is generally accepted that the
TAN compounds will crack and pose little harm. However,
little has been documented on the feed section’s corrosion
effects before the riser.
As a rule of thumb, the presence of TAN in co-processing
feeds follows the order of bio-oils > animal tallow > vege-
table oils. Many refiners have a maximum TAN specification
to reduce the corrosion in the main column overhead (MC
OVHD). A careful inspection of the MC OVHD is important
during the turnaround after co-processing.
Some co-processing feeds may contain carboxylic acids
and other oxygenated species. When these feeds crack, they
will form smaller, oxygen-containing compounds. Most of
these compounds will crack into the lighter boiling fractions
(wet gas compressor [WGC] section). Elevated carbon diox-
ide (CO2), carbon monoxide (CO), and low levels of alcohols
are commonly seen. Other compounds observed are esters,
ketones, phenolics, and acids (acetic, formic, and propionic).
In most cases, the appearance of these compounds will
be in low concentrations (wppm or wppb levels). Better
analytical methods to measure them should be developed
for co-processing. These acids may increase the corrosion
concerns in the MC OVHD section. Elevated methyl acrylate
gas has been observed in tallow-based feeds in general
and UCO feedstocks in particular. Control of deoxygenation
pathways, as discussed later, is crucial to minimising light
oxygenate formation and the impact on these supporting
operations.
Light molecular weight (MW) products from co-process-
ing will primarily concentrate in the WGC section. The acids
will react with ammonia, and the pH of the systems will
decrease. Methyl acrylate will most likely form solids. Amine
units will have problems with elevated CO and CO2 levels.
In general, foaming issues may occur in high-pressure pro-
cess units, and corrosion concerns are more common.
Many industrial water and process chemical suppliers
have developed improved practices when co-processing.
www.digitalrefining.com
KETJEN.indd 27
While these issues have been documented, some FCC
WGC sections have recorded little to no problems. Process
units with no problems have used highly refined or refined/
bleached/deodorised (RBD) FOGs. While FCC units have
co-processed up to 100% FOGs,1 trials seldom exceed
10% of the total feed and are commonly below 5%.
Catalyst’s role in FCC co-processing
FCC catalysts drive the conversion and selectivity for
upgrading heavy feeds to value-added fuel and chemical
products. Conventional FCC catalysts are formulated within
the constraints of each unit to maximise product value and
unit objective. Examples include optimisation for slurry
To maximise product value
within the unit constraints and
drive towards incorporation of
renewable and circular carbon,
the co-processing catalyst can be
formulated and optimised for the
specific feed chemistry
conversion, metals tolerance, coke selectivity, and maxim-
ising gasoline and/or light olefins for a given feed, product
targets, and operational constraints.
The same holds true for catalyst technologies for FCC
co-processing of alternative feedstocks. In addition to the
different metals in the alterative feeds, the differences in the
hydrocarbon species present alter the conversion chemis-
try. To maximise product value within the unit constraints
and drive towards the incorporation of renewable and cir-
cular carbon, the co-processing catalyst can be formulated
and optimised for the specific feed chemistry.
Maximising deoxygenation
As previously stated, most units may only process small
quantities of FOGs. Typically, these units rely on the base cat-
alyst already in the unit without consideration of the change
in the feed chemistry, resulting in impacts on unit operations
PTQ Q2 2024 27
12/03/2024 10:07:52
 ketones, and acrylates. These light oxygenates can undergo
4
&
oligomerisation reactions, leading to gum and coke. In addi-
!"#$%#&%'()*+$,-,./'012'!34'56'!"#$%#&%'()*+$,-,./'784
Standard Technology 20%
SBO vs Standard
tion, these compounds will concentrate in the WGC section
9):);<=='012'!34'56'!"#$%#&%'()*+$,-,./'784
Technology-VGO of the unit if not converted in the riser. Decarbonylation
3
% ReNewFCC-20% SBO vs
Standard Technology-VGO rejects biogenic carbon as CO and can increase bottoms or
coke yields from both biogenic and conventional oil.
"2 While hydrodeoxygenation is dominant in hydroprocess-
ing units, it also occurs in FCC operations due to hydro-
∆Yield (wt%)
! "#$%&'()*+,

gen donation from the conventional feed to the biogenic

1
# oil. Removal of oxygen as water from the system results
-./$
Coke 01234
650F+
$
0
5-6
LCO
-1
!#
!"
-1.5
Figure 1 Delta yields during co-processing of 20 wt%
soybean oil in VGO over Ketjen’s standard catalyst
technology and ReNewFCC formulated for maximum
gasoline at an iso-conversion of 72 wt%
and the product slate. Successfully processing higher con-
centrations of FOGs requires maximising oxygen removal.
The deoxygenation efficiency of oxygenated molecules in
FOG is influenced by the surface chemistry of the catalyst
components, porosity, fatty acid composition, and synergy
between vacuum gas oil (VGO) and FOG. The ReNewFCC
technologies for FOG co-processing in FCC are designed to
maximise deoxygenation and drive it to increase the quality
of the hydrocarbon product slate.
To understand this, one must first consider the reaction
pathways for deoxygenation. The four main deoxygenation
pathways are dehydration, decarbonylation, hydrodeoxy-
genation, and decarboxylation. The net effect of dehydra-
tion results in the formation of biogenic coke, resulting in
higher losses of bio-carbon from useful products.
In the case of FOGs, the thermal decomposition of the
triglyceride followed by dehydration can result in the for-
mation of light unsaturated oxygenates such as aldehydes,
in a net decrease in the hydrogen-to-carbon (H/C) ratio of
5;7
LPG <=>'789
Dry gas the final hydrocarbon products. Not removing the oxygen
789.%#:$ as CO or CO₂ provides the advantage of higher biogenic
Gasoline
carbon retention in the final products (though CO and CO₂
are preferable to oxygen in the products).
In terms of FCC product slate, the net result from hydro-
deoxygenation can be a reduction in overall product value
as the reduction in the H/C ratio leads to an increase in
slurry and coke make from both biogenic and mineral feed-
stocks. From the perspective of FCC unit operations, deox-
ygenation of the biogenic oils through decarboxylation will
maximise the H/C ratio of the final products for an improved
FCC unit product slate with some loss of biogenic carbon
as CO₂.
Modification of deoxygenation pathways
Catalytically influencing the various deoxygenation path-
ways can have a significant impact on FCC product valori-
sation when processing unconventional FCC feedstocks
by optimising catalytic properties. Throughout the open
literature, there have been mixed reports regarding the
net impact of adding FOG to VGO feed under cracking test
conditions. Mixed results ranging from increased coke and
light cycle oil (LCO) make to reduced coke make during
testing are largely due to differences in catalyst technology
and balancing the catalytically active sites.
Baseline performance evaluation of Ketjen’s standard FCC
catalyst technology for maximising gasoline demonstrates
that when 20 wt% soybean oil is added to VGO, there is a
net positive feed impact of the soybean oil (see Figure 1).
The main feed effect is an increase in gasoline yields with
a reduction in coke, liquefied petroleum gas (LPG), and dry

70%
Influencing deoxygenation during Dehydration Biogenic coke and gum formation
co-processing 20% canola oil over
Hy

60% Water + coke (biogenic)

dr
De eoxy

various grades of ReNewFCC

od
hy ge
Oxygen balance, %

50%
dr

Rejects biogenic carbon

ati natio

Decarbonylation
n
tio

on

Higher slurry and coke make

la

40% Water + CO (biogenic)

xy
bo

n
r
ca

30%
De

Hydrodeoxygenation Highest biogenic-carbon retention

20% Water + coke (oil) Higher coke and reduced product H/C
Decarbonylation
10%
Decarboxylation Maximisation of product value
0% CO2 (biogenic) Biogenic carbon rejection as CO2
CO CO2 H2O

Figure 2 Oxygen balances during co-processing 20 wt% canola oil over various grades of ReNewFCC formulated for
maximum gasoline, illustrating the role of altering the catalytically active sites to influence deoxygenation pathways and
the generalised impact on the FCC

28 PTQ Q2 2024 www.digitalrefining.com

KETJEN.indd 28 12/03/2024 10:07:55

 2.5
2 Standard Technology-20% SBO vs Standard
Technology-VGO
1.5 ReNewFCC-20% SBO vs Standard Technology-VGO
1 Gasoline
∆Yield (%)
0.5
Coke LCO
0
650F+
-0.5
-1
-1.5
2
Iso-Conversion = 74 wt%
-2.5
Figure 3 Delta yields during co-processing of 20 wt% soybean oil in VGO for Ketjen’s baseline max olefin catalyst
technology and ReNewFCC formulated for max olefins
gas. To achieve further valorisation of co-processing soy-
bean oil and leverage the conversion chemistry, that cata-
lyst can be further tailored.
ReNewFCC technology is designed to maximise deoxy-
genation and can be formulated to increase gasoline and
gasoline range olefins. At the same time, coke and bottoms
yields are reduced to maximise FCC unit profitability. This
is achieved by controlling the adsorption of oxygenated
molecules to balance deoxygenation mechanisms, reducing
hydrogen transfer to avoid olefins saturation, and reduction
of dehydrogenation reactions that lead to the conversion of
olefins to aromatics and coke.
Figure 2 provides an example of how the various grades
of ReNewFCC formulated to maximise gasoline can influ-
ence the removal of oxygen when co-processing canola oil
in VGO. With increased decarboxylation, reduced dehy-
dration and hydrodeoxygenation (as evident by increased
oxygen removal as CO₂ and H₂O), oxygen can be removed
while minimising hydrogen loss from the product.
While unique feed-feed interactions and unit constraints
should be considered, the know-how for manipulating
deoxygenation was applied to the previous case for co-pro-
cessing 20 wt% soybean oil. Figure 1 compares the addi-
tional changes in the product slate that ReNewFCC can
bring through the modification of deoxygenation pathways.
Compared to the standard catalyst technology, ReNewFCC
can significantly improve gasoline make while further
reducing coke, LPG (featuring improved olefinicity), and dry
gas.
Maximising light olefins
Alternatively, for units that target the light olefins produc-
tion (C₄=, C₃=, and C₂=), ReNewFCC can also be formulated
to maximise propylene with catalytic components that lead
to the maximisation of cracking from gasoline to light ole-
fins while maintaining the deoxygenation functionality.
Figure 3 compares how the performance of a standard max
olefin catalyst system can be further improved to increase
gasoline conversion to light olefins while improving overall
LPG olefinicity.
www.digitalrefining.com
KETJEN.indd 29
Dry gas
H2
LPG C3= C4= C2=
FCC co-processing of WPOs
Many waste plastic oils (WPO) are characterised by a
high naphtha content. Depending on its composition, this
naphtha may crack into lighter products or, in the case of
aromatics, more likely remain in the naphtha fraction. As
previously discussed, the composition of the WPO is highly
dependent on the waste plastic source and the conversion
technology.
Figure 3 in Part I (PTQ Catalysis 2024) showed an exam-
ple of a simulated distillation curve for various WPOs and
major hydrocarbon compounds within the various oils.
Comparing WPO from polypropylene (PP) and polysty-
rene (PS) clearly indicates that a large fraction of both is
within the naphtha range. However, the PP-WPO is pri-
marily comprised of iso-olefins, while styrene derivatives
are prevalent in the PS-WPO.
Generally, aromatics will not undergo catalytic cracking
beyond cracking alkyl side chains, while olefins and paraf-
fins can crack further into lighter components or cyclisation
to aromatics. This is an important factor to consider when
comparing the impact on product distribution during the
co-processing of different types of WPO.
Catalyst selection
During catalyst selection for conversion of WPO co-pro-
cessing applications, product distributions at constant
conversion can be misleading. Conventional FCC feeds are
primarily comprised of heavy boiling compounds, generally
in slurry and, to a lesser extent, LCO boiling ranges. Thus,
conventional conversion is often calculated and reported as
430F+ conversion by the yields of products not within LCO
and slurry cuts (430F+ conversion = 100 – LCO% – slurry%).
For example, in the co-processing of PP-WPO and
PS-WPO over a baseline catalyst technology, bottoms
yields may appear equal or higher compared to VGO pro-
cessing, as shown in Figure 4 (top). However, this is just
the effect of overestimating the conversion. Furthermore, it
is unclear if the observed increase in gasoline is due to the
addition of naphtha to the feed. To avoid this, we define an
effective conversion.
PTQ Q2 2024 29
12/03/2024 10:07:58
 3
2.4
20% PS 2.0 20% WPO conventional conversion - VGO @ 75% conversion
2
20% PP
∆Yield (%)

1.1
1 0.5 0.7
Dry gas LPG LCO Coke CTO Propylene
0
-0.3
Gasoline Bottoms -0.1 -0.3 -0.3 -0.1
-0.5 -0.5 -0.5 C4 Olefins
-1
-1.1 -1.0
-1.6 -1.4 -1.6
-2

-3
3
2.3 2.3 20% WPO effective conversion - VGO @ 75% conversion
20% PS_Corr
2
20% PP_Corr
∆Yield (%)

1.1 1.1
1 CTO 0.9

0.1 LCO Bottoms 0.3 0.1 0.2

0.0
0
-0.1
-0.3 Gasoline -0.3 Propylene C4 Olefins
-1 Dry gas LPG
-0.5
Coke
-0.5

-1.3
-2 -1.8
-2.4
-3

Figure 4 Delta yields comparing co-processing of 20 wt% PP-WPO in VGO and 20 wt% PS-WPO in VGO to a 100%
VGO baseline using a baseline Ketjen catalyst techology. The top plot uses the standard 430F+ conversion to compare
the changes in the product slate at an iso-conversion of 75%. The bottom plot uses the effective conversion to determine
the impact of introducing naphtha fractions from the WPO into the feed

This conversion subtracts the fraction of naphtha initially
present in the feed, leading to a more accurate interpreta-
tion of the impact of catalyst and feed on product distribu-
tion during WPO co-processing.
Applying this effective conversion leads to the observa-
tion that the slurry yield (bottom of Figure 4) is lower during
WPO co-processing compared to 100% VGO processing,
and clear differences in the product slate for the different
WPOs emerge.
The addition of PS-WPO shows a slight reduction in
LPG, LCO, and bottoms, while there is an increase in coke.
Compared to co-processing PP-WPO, there is an increase in
LPG that is mainly a result of increased C₄ olefins. The feed
impact differences between PS and PP-derived oils can be
directly related to their hydrocarbon composition. Due to the
aromatic nature of the PS-WPO, there is minimal impact
on LPG yield, LPG olefins, and increased coke selectivity.
However, the PP-WPO, comprised mainly of iso-olefins,
results in increased C₄= and a reduction in coke.
Flexibility
FCC units offer almost unparalleled flexibility for pro-
cessing a wide diversity of feedstocks. The International
Sustainability and Carbon Certification (ISCC) is a good
indicator of current trends for processing renewables and
recyclables (R&R). Reliable catalyst solutions to address the
introduction of a wide variety of R&R are being considered
and investigated for FCC co-processing.
Against this backdrop, ReNewFCC offers the same
degree of flexibility and effectiveness in addressing dif-
ferent operations, feeds, and yield objectives featured in
Ketjen’s established portfolio of more conventional FCC
catalysts, building on a foundation of industry-leading bot-
toms upgrading and metals tolerance to create solutions

3
Standard Technology-20% PP-WPO vs Standard Technology-VGO
2.5
ReNewFCC CircularMax -20% PP-WPO vs Standard Technology-VGO
2

1.5
∆Yield (%)

0.5
Coke LCO Dry gas H2
0
650F+ C4= C2=
-0.5 C3=
Gasoline LPG
-1

-1.5

Figure 5 Delta yields from processing 100% VGO over a standard light olefin catalyst technology, demonstrating the
comparative impact of co-processing 20 wt% PP-WPO over the standard and ReNewFCC catalyst technologies at a
standard (430F+) conversion of 75%

30 PTQ Q2 2024 www.digitalrefining.com

KETJEN.indd 30 12/03/2024 10:08:01

 addressing the unique, evolving challenges posed by
new feeds.
Within this framework, in co-operation with our col-
leagues at Fábrica Carioca de Catalisadores S.A (FCC SA),
who have recently published results detailing their experi-
ence running a 100% bio-feed in the FCC (Petrobras press
release), Ketjen is developing and has developed tailored
formulations for co-processing an array of R&R feeds in a
diversity of FCC applications, including those seeking to:
• Maximise gasoline yields and quality
• Maximise LPG and olefins
• Maximise plastic precursors from WPO types.
In addition, our high matrix activity/high accessibility
catalyst technologies lend themselves well as effective
platforms for tackling the full range of feeds and yield slate
targets across the entire array of feed compositions, con-
taminant profiles, and oxygen contents. This includes sig-
nificant advances in tuning the characteristics and ratios of
the catalyst active sites to promote maximum deoxygena-
tion, something that has never been a consideration in FCC
operations but is now of significant importance in co-pro-
cessing oxygen-containing feeds.
The refining world is changing, with an increasing empha-
sis on stewardship and sustainability that will forever alter
the face of the industry.
ReNewFCC is a trademark of Ketjen.
Part 1 of this article was published in PTQ Catalysis 2024.
References
1 Petrobras, partners process 100% renewable feedstock in Rio
Grandense in Refinery’s FCC, OGJ Newsletter, Dec. 4, 2023, www.
ogj.com/refining-processing/petrochemicals/article/14301266/
petrobras-processes-100-renewable-feed-in-riograndense-fcc
2 Nalco Water Solutions When Producing Biofuels, Chris Claesen,
presented at 2023 Ketjen FCC workshop, Hanoi.
Jon Strohm is an Research and Development Advisor within Ketjen’s
FCC R&D in Pasadena, Texas. He leads R&D efforts in the develop-
ment of new catalytic materials for current and emerging FCC technol-
ogies. He has more than 25 years of experience in thermochemical and
catalytic hydrocarbon conversions.
Darrell Rainer is the Global FCC VGO Specialist with Ketjen
Corporation, Houston, Texas. In this role, he works with R&D and busi-
ness groups to develop and market new catalyst technologies. He has
an R&D background, and more than 27 years of experience in FCC,
hydroprocessing, and biofuels.
Oscar Oyola-Rivera is an R&D Chemist at Ketjen’s FCC R&D and
Project Manager for ReNewFCC. He also leads R&D efforts to
develop new catalytic materials for current and future emerging FCC
catalysts. He has more than 10 years of experience in heterogeneous
catalytic processes for the conversion of hydrocarbons, biomass, and
CO2.
Clifford Avery is Global FCC Process Advisor with Ketjen Corporation,
Houston, Texas. In this role he leads the global FCC effort in training,
troubleshooting, and performing unit health checks. He has more than
38 years of experience with FCC and other refining processes.

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q1 eurotecnica.indd 1 12/12/2022 14:23:23

 Revamping a conventional naphtha
splitter to a dividing wall column
Installation of new equipment, performance results, and final commissioning of a
DWC and its ability to sharply fractionate three components in one single column

Giuseppe Mosca, Joshi Chandrakant, Andrei Cimpeanu and Brad Fleming

Sulzer Chemtech

A
dividing wall column1 (DWC) is a distillation column
combining the operation of two conventional col-
umns in one shell. The separation of a three-compo-
nent mixture into individual components is made possible
by the installation of a vertical wall in the middle of the col-
umn. The feed enters the column on one side of the wall,
and on the other side of the wall, a high concentration of
the middle boiling component is achieved.
The result is that three components can be sharply
fractionated in one single column. In the conventional
setup, two columns, two reboilers, and two condensers
are needed: the DWC needs only one vessel, one reboiler,
and one condenser. The DWC has shown its advantages
in many applications, typically for liquid mixtures of equal
amounts of three volatile components and for cases
where a high amount of middle boiling component must
be separated from smaller amounts of light and heavier
components.2
Rule of thumb: The bigger the side-stream portion of the
feed, the higher is the effectiveness of the dividing wall.
DWCs have been implemented in a large variety of refinery,
petrochemical, and chemical applications. Recently, they
have even been implemented for reactive distillation. More
complex DWCs (Dual3 DWCs) can be used for the separa-
tion of a stream in four cuts.
DWC: Benefits and limitations
From a unit operation point of view, a DWC eliminates the
thermodynamic inefficiency of the two-column setup,4
where the remixing of the middle and heavy boiling com-
ponents at the bottom of Tower 1 cannot be avoided (see
Figures 1 and 2).
DWCs allows for several benefits5 compared to the
two-column setup:
• Up to 40% reduction of investment cost
• Up to 40% reduction of operational cost
• Up to 40% additional theoretical stages
• Up to 50% energy savings
• Up to 40% reduction of plot plan space and consistent
reduction of greenhouse gas emissions.
DWCs also have limitations compared to the two-column
setup:

Qc1
Tower T1
T1 Top
A

Qc2 A
T2
B
Feed
A, B, C
Number of trays

Qr1 B

C
B, C
Remixing
Qr2
Bottom
0 0.2 0.4 0.6 0.8 1
C
Composition mole fraction

Figure 1 Composition profile in Tower 1 for two-column setup

www.digitalrefining.com PTQ Q2 2024 33

Q2 Sulzer.indd 33 11/03/2024 12:24:11

 Qc
Tower T1 Tower T2
T2 Top Top
A A
A

Number of trays

Number of trays
Feed T1
A, B, C B
B B

C C
Qr
Bottom Bottom
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
C
Composition mole fraction Composition mole fraction

Figure 2 Composition profile for a DWC

• Operational pressure variation between column sections The column is heat integrated with the FCC unit. The
is not possible heat duty to the column is provided by two reboilers: upper
• Increased temperature difference between reboiler and reboiler, where the heating medium is the light cycle oil
condenser (LCO) coming from the reboiler of the debutaniser, and lower
• Increased pressure drops reboiler, heated with the heavy cycle oil (LCO) coming from
• Increased length and diameter of the vessel the FCC main fractionator. The top condensation system
• Increased complexity for modelling in the process provides the cooling duty to draw off the light naphtha and
simulation generate the internal reflux required for the fractionation of
• Increased complexity for the hydraulic design of the mass the cuts. The feed is preheated at the preheat exchanger
transfer components by means of the side-cut draw before entering the tower in
• Lower operational flexibility. the middle section (see Figure 3).
The three cuts are further processed to the downstream
Existing naphtha splitter MOG and SCANfiner units to meet the quality of the gas-
The existing naphtha splitter is a conventional distillation oline pool.
column with a side draw. It splits the full naphtha coming
from the bottom of a depentaniser located at the GasCon Revamp motivation
of the fluid catalytic cracking (FCC) unit, into three streams: All three cuts were initially used for gasoline. The existing
light naphtha, middle naphtha and heavy naphtha. tower was able to achieve the required performances both

1.2 0.8

16.5 Light naphtha to SCANfiner

From De-C5 bottom

Middle naphtha to MOG
138

LCO from De-C4 reboiler

XX Pressure kg/cm2g
To De-C5 reboiler
YY Temperature ˚C

HCO from FCC MF

1.5
Heavy naphtha to SCANfiner
To FCC MF

Figure 3 Simplified process flow diagram of the tower before revamp

34 PTQ Q2 2024 www.digitalrefining.com

Q2 Sulzer.indd 34 11/03/2024 12:24:14

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035_Q2_endress.indd 1 11/03/2024 11:26:41

 Middle cut for Parex unit 1.2 0.8
Flow rate MTPH 160
Sp. Gr. – 0.829
D86 % Vol
IBP ˚C 110.5 Light naphtha
5 ˚C 118.6 16.5 to SCANfiner

10 ˚C 121.2
From De-C5
bottom Middle naphtha to
30 ˚C 127
138 Unionfining/Platformer
50 ˚C 134.1
70 ˚C 145.3 LCO from De-C4
reboiler
90 ˚C 163.9
95 ˚C 173.4 To De-C5 XX Pressure kg/cm2g
reboiler
FBP ˚C 181.3
YY Temperature ˚C

HCO from FCC MF

1.5
Heavy naphtha to SCANfiner
To FCC MF

Figure 4 Required middle cut quality as feed for the Parex unit

from the fractionation efficiency and the hydraulic capacity
points of view. Several years later, after the first start-up, the
tower was called for a different duty: top and bottom cuts
were still pro-gasoline, and the middle cut had to be used as
feed for the downstream Parex unit after being processed at
the Unionfining and Platformer units (see Figure 4).
A sharper separation between the three cuts is required
compared to the original design. To accomplish the new
service, several options were investigated, among others:
 Shifting the upper reboiler duty to the bottom reboiler
to maximise utilisation of the stripping section fractionation
trays.
 Increasing overall reboiler and condenser duties by
20% over the original design to maximise the reflux ratio in
the attempt to at least meet middle-cut specifications.
 Shifting the column’s feed location downward.
 Optimising the side-cut draw-off location.
None of the above options could be even close to the
required qualities of the three cuts:
• Insufficient separation between light naphtha and mid-
dle naphtha, resulting in higher C6 content than desired in
the middle naphtha.
• Poor separation between middle naphtha and heavy
naphtha, resulting in higher C10+ content than required in the
middle naphtha. It would cause over-coking at the down-
stream Platformer reactors with consequent high deactiva-
tion rate of the catalyst and lower yields of valuable aromatic
components.
Adding another distillation tower would achieve the
target, but it was not even considered due to the high
investment cost. To minimise the investment cost while
maximising energy savings and minimising GHG emissions,
it was decided to convert the tower into a DWC.
Revamping scope
The main revamping target was to increase tower
separation efficiency and produce three cuts with the fol-
lowing distillation boiling points (as D86):
• Light naphtha with a 98°C final boiling point.
• Middle naphtha with 110.5°C initial boiling point, and
final boiling point lower than 182°C for Case 1 and lower
than 179°C for Case 2.
• Heavy naphtha with initial boiling point >144°C at 300 t/h
feed flow rate.
• An operating range of 110-50% of design.
Major constraints
In attempting to minimise investment costs, the revamp
was implemented while considering several major con-
straints: reuse the existing equipment as much as possible,
minimise additional equipment, minimise tower modifica-
tions, and minimise modifications at the existing control
system.
A very narrow time frame for the project execution was
defined: licence, basic, and detailed engineering, manu-
facturing, and delivery of goods at the site in 18 weeks.
Implementation of the project at the site in less than 20
working days within the time frame of the planned unit
turnaround. All these items were under the responsibility of
one single company, GTC, now Sulzer CFCL.
Process simulation results
While simulating a middle DWC, several models can be
used. The most common are:
 Four columns interconnected: The first column mod-
els the section of the tower above the partition baffle. The
second column models the section of the column equipped
with the baffle and facing the feed. The third column mod-
els the section of the column equipped with the baffle and
facing the middle-cut draw-off. The fourth column models
the section of the column below the partition baffle.
 Two columns interconnected (see Figure 5): The first

36 PTQ Q2 2024 www.digitalrefining.com

Q2 Sulzer.indd 36 11/03/2024 12:24:15

 Main fractionator 512
Qc
S4
T2
500
A
S2
Prefractionator S6
510
581 511
T1
502

Z414_S17
501
Feed B
408

S14

!
Qr
Z414_C11A
Z414_C11B 529
S7
C S5

Figure 5 Process simulation model as per Petlyuk configuration

column models the section of the column equipped with
the partition baffle and facing the feed, also called the pre-
fractionator. The second column models three sections,
from top to bottom: the section of the column above the
partition baffle; the section of the column equipped with
the partition baffle and facing the middle-cut draw-off; and
the section of the column below the partition baffle. This
second column is also known as the main fractionator. This
second model is also known as the Petlyuk6 configuration,
in honour of the author who first studied and discussed this
topic in detail in 1965.
At Sulzer, Petlyuk‘s model is preferred. In addition, an
in-house optimised model has been developed. It allows for
a fast, solid, and reliable convergence of the process sim-
ulation. The output results can be automatically imported
into a dedicated hydraulic rating tool for the design of mass
transfer components and associated tower internals of a
DWC.
It must be underlined that this is the most critical step
while designing a DWC. The offset location of the dividing
wall to the axe of the column and the mass transfer com-
ponents at the right and left of the baffle should be prop-
erly designed to achieve the performance of the tower, as
expected from the process simulation model.
Ideally, the pressure drop at the left and right of the baf-
fle will be the same so that the vapour coming from the
section below the baffle will split between the prefraction-
ator and the main fractionator, as expected by the process
simulation model. In real life, this may not be possible due
to the required operational flexibility, not only in terms of
operating range (110-50% of design capacity) but also
in terms of cases with different feed composition and or

Light Middle Heavy 30

Feed Naphtha Naphtha Naphtha 103 1.2 0.8 75
Flow rate Kg/h 330,000 90,219 160,000 79,781
Density Kg/m3 799.2 762.3 804.4 834.2

D 86 % vol
Light naphtha
IBP ˚C 70.6 52.2 110.5 144.7 1.3 to SCANfiner
16.5
5 ˚C 86.4 63.7 113.7 157.2
10 ˚C 90.7 67.4 115.6 163.5 Middle naphtha to
138 Unionfining/Platformer
30 ˚C 105.0 70.7 122.4 172.1
13 161
50 ˚C 126.5 74.3 131.9 178.8
70 ˚C 150.0 78.9 143.6 187.2
90 ˚C 175.7 84.9 159.2 201.5
XX Pressure kg/cm2g
95 ˚C 184.8 89.0 165.6 208.3
FBP ˚C 198.0 97.2 181.0 214.6 YY Temperature ˚C

18 ex41
ZZ Duty MMKcal/h
GAP ˚C 24.7 -8.4
1.5 217
Heavy naphtha to SCANfiner

Figure 6 Material balance and main operating data after revamping

www.digitalrefining.com PTQ Q2 2024 37

Q2 Sulzer.indd 37 11/03/2024 12:24:17


Light naphtha
to SCANfiner
Feed
Middle naphtha
to MOG unit
LCO
HCO
Heavy naphtha
to SCANfiner
Figure 7 Major unit modifications after revamping
product qualities. Also, the extension of the dividing wall
should be properly designed to secure enough spare theo-
retical stages to mitigate the effects of the deviations from
ideality.
Post-revamp process simulation results
A simplified process flow diagram for Case 1 is shown in
Figure 6. This includes the material balance, the qualities of
the three cuts, and the main operating data (pressure pro-
file, temperature profile, and duties at both the reboilers).
In particular, the revamped naphtha splitter converted to
a DWC allows for an almost 25°C gap between light and
heavy naphtha. The overlap between middle and heavy
naphtha is as low as 8°C and consistently lower than the
existing setup. Also, the content of C10+ aromatic compo-
nents is far below the limits required by downstream units.
Major units modifications
Figure 7 shows the tower before the revamp on the left
side, and the tower after the revamp on the right side. For
easy interpretation, the new and/or modified equipment is
red in colour.
The tower has been completely retrofitted from top
to bottom by replacing existing conventional trays with
high-performance trays7 and high-performance structured
packing at the bottom of the tower. Two partition baffles
have been installed: one in the middle-bottom portion of
the large ID section of the tower, and one at the top of the
small ID portion of the column. To minimise the welding to
the tower wall with the final goal of minimising the instal-
lation time at site, a tailor-made partition baffle has been
implemented, also known as the ‘built-in dividing wall’.
The built-in dividing baffle is made by a combination of
thicker plate beams and lightweight bolted panels particu-
larly suitable for revamp projects. Two-pass high perfor-
mance trays8 have been installed in the main fractionator
38 PTQ Q2 2024
Q2 Sulzer.indd 38
Provisional
nozzles
Light naphtha
to SCANfiner
Feed
Middle naphtha
to Unionfining/
Platformer
LCO
ex41
HCO
Heavy naphtha
to SCANfiner
side of the wall and at the prefractionator above the feed.
Four-pass high-performance trays9 have been installed in
the prefractionator below the feed. A tailor-made chimney
tray has been installed above the partition baffle to control,
by gravity, the internal reflux split between the prefraction-
ator and main fractionator side of the dividing wall.
The existing middle-cut draw-off nozzle has been
blanked off and relocated a few trays above the existing
one. A chimney tray has been installed below the bottom
partition baffle to collect the liquid coming from both sides
of the wall and feed the distributor above the bed of struc-
tured packing. One new reboiler has been added at the bot-
tom, and a new bottom pump has been added for the heavy
naphtha draw-off, with associated piping and fittings.
No modifications were required at the top condenser sys-
tem, at the upper reboiler or at the feed preheat exchanger.
Two new provisional nozzles have been installed above
the partition baffle and blanked off. The purpose of these
nozzles is for external reflux control (for future implemen-
tation), but only in case the tower could not be operated
smoothly with the supplied internal reflux control system.
The existing unit control system has been maintained
unchanged. All tower modifications and external equip-
ment were implemented in 20 working days within the time
frame of the planned unit turnaround.
Conclusions
The DWC transformation allowed for a consistent improve-
ment of the fractionation of the three cuts, particularly
between middle and heavy naphtha: from a 40°C overlap
to a 2°C gap.
The unit ran for more than seven years after the revamp
without any significant issues. Last year, during the
planned shutdown, the column was opened for inspection,
and all the tower internals were found in place without any
damage.
www.digitalrefining.com
11/03/2024 12:24:18
 The external control system for the internal reflux split
was not implemented because the tower operation is steady
within the actual range of feed composition and throughput.
References
1 Dejanovic I, Matijasevic L, Olujic Z, Divided Wall Column applica-
tion for Platformate splitter, 20th European Symposium on Computer
Aided Process Engineers, Ischia, Naples, Italy, 6-9 June 2010.
2 Polovina S, Herceg S, Granic Sarac A, Designing a divided wall col-
umn, PTQ, Q1, 2016.
3 Halvorsen I, Skogestad S, Dejanovic I, Jansen H, Kaibel B, Olujic Z,
Layout and dimensioning multi-partition dividing wall column, AIChE
Spring Meeting, Houston, Texas, USA, 1-5 April 2012.
4 Bhargava M, Kalita R, Gentry J, Hydrocarbon Processing, Sept 2017.
5 Dejanovic I, Jansen H, Olujic Z, Dividing wall column as energy sav-
ing retrofit technology, AIChE Spring Meeting, New Orleans, Louisiana,
USA, 30 March-1 April 2014.
6 Petlyuk F B, Platanov V M, Slavinskii D M, Thermodynamically opti-
mal method for separating multicomponent mixtures, International
Chemical Engineering, 1965, Vol. 5, No. 3, pp.555-561
7 Mosca G, Tacchini E, Chandrakant J, Dave R R, Prabhakar N,
Shubhangi J, Debottlenecking an ACN heads and dry column with
VGAF (V-Grid anti-fouling) trays, AIChE Spring Meeting, Orlando,
Florida, USA, 24-27 April 2006.
8 Mosca G, Van Hemel G, Tocco R, Lestrade B, A Total success,
Hydrocarbon Engineering, Nov 2006.
9 Mosca G, Tacchini E, Sander S, Rotteger D, Wolf A, Rix A, Schilling
G, Upgrading a superfractionator C4S splitter with 4-pass high per-
formances trays at Evonik Degussa, Marl, Germany, AIChE Spring
Meeting, Tampa, Florida, USA, 28 April 2009.
Giuseppe Mosca is a Global Technical Expert and Head of the Refinery
Engineered Solutions INME of Sulzer Chemtech. He leads the design
of mass transfer components used in distillation towers, absorbers,
and strippers. He is also involved in process simulation, revamping
proposals, troubleshooting, commissioning, and start-up assistance of
fractionation equipment. He holds a Master’s in chemical engineering
from the University ‘La Sapienza’ Rome, Italy, is a registered profes-
sional engineer of the district of L’Aquila, Italy, and a senior member of
AIChE. Email: Giuseppe.mosca@sulzer.com
Joshi Chandraknt is Director Technology at Sulzer India Ltd., with
more than 30 years of experience in mass transfer technology, han-
dling various applications in chemical, petrochemicals, and oil refin-
ing industries. He is recognised as a Global Technology Expert in the
Sulzer Chemtec community. He holds a Bachelor’s degree in chemical
engineering. Email: Joshi.chandrakant@sulzer.com
Andrei Cimpeanu is Process Technology Expert, Sulzer Chemtech.
Houston, USA. He previously served as Process Technology Expert
with a demonstrated history of working in the refinery, petrochemical,
and chemicals industry. He is skilled in process modelling and simula-
tion, process development, engineering, and design activities. He holds
a MS in chemical engineering and is a licensed professional engineer.
Email: andrei.cimpeanu@sulzer.com
Brad Fleming is General Manager, Process Equipment Technology,
Chemtech Division, Clean Fuels and Chemicals Licensing (CFCL),
Dallas, USA, and a Global Technology Expert. He has more than 35
years of experience in process equipment design, R&D, testing, and
troubleshooting of mass and heat transfer systems in numerous petro-
leum refining and petrochemical applications. He holds a Bachelor’s
degree in chemical engineering from Texas A&M University and is a
member of AIChE. Email: brad.fleming@sulzer.com

ÞƷ‫ټ‬ȵƷ‫ژ‬ǠȄɫƷȽɋǠȄǒ‫ژ‬ǠȄ‫ژ‬
F‫ژ‬ȽȏǹɓɋǠȏȄȽِ
‚ɓȵ‫ژ‬ȄƷɬ‫ژ‬ƌɲȲȏȵɋً‫¾ژ‬ƷɱƌȽ‫ژ‬ǠȄɫƷȽɋȂƷȄɋ‫ژ‬ɬǠǹǹ‫ي‬

UȄƩȵƷƌȽƷ‫ژ‬ȏɓȵ‫ژ‬ȽɓȲȲǹɲ‫ژ‬ȏǑ‫ژ‬î°u‫ژדٮ‬ɋȏ‫ژ‬ȽɓȲȲȏȵɋ‫ژ‬
ȵƷ˟ȄƷȵȽ‫ژټ‬ȲȵȏȲɲǹƷȄƷ‫ژ‬ȲȵȏưɓƩɋǠȏȄ
-ȄȽɓȵƷ‫ژ‬ƌƩƩƷȽȽ‫ژ‬ɋȏ‫ژ‬ȵƷǹǠƌƨǹƷً‫ژ‬ǚǠǒǚ‫ٮ‬ȴɓƌǹǠɋɲ‫ژ‬
F‫ژ‬ƩƌɋƌǹɲȽɋȽ‫ژ‬ƌȄư‫ژ‬ƌưưǠɋǠɫƷȽ‫ژ‬
-ȄǚƌȄƩƷ‫ژ‬ȲȵȏưɓƩɋǠȏȄ‫ژ‬ȏǑ‫ژ‬ȏƩɋƌȄƷ‫ژ‬ƨƌȵȵƷǹȽ‫ژ‬
ǑȵȏȂ‫ژ‬Fً‫ژ‬ƌǹǵɲ‫ژ‬ƌȄư‫ژ‬u¾-‫ژ‬ɓȄǠɋȽ

Fȏǹǹȏɬ‫ژ‬ɓȽ‫ژ‬ȏȄ‫ژ‬kǠȄǵƷưUȄ‫ژ‬Ǒȏȵ‫ژ‬ȂȏȵƷ‫ژ‬ɓȲưƌɋƷȽٍ

www.digitalrefining.com PTQ Q2 2024 39

Q2 Sulzer.indd 39 11/03/2024 12:24:19

Rezel.indd 1 13/03/2024 10:08:22
 A refinery’s strategic journey
towards sustainability
A refinery’s strategic journey represents a delicate balance between profitability,
environmental commitments, and technological advancements

Aleix Carrillo, Duncan Manuel and Michelle Wicmandy

KBC (A Yokogawa Company)

E
nergy consumption is a key cost factor in refinery
economics. About half of the refiner’s operating costs
are dedicated to meeting the demands of energy
consumption.1 Adding to this complexity, a Reuters report
revealed that 43% of surveyed global workers plan to leave
the energy sector by 2025.2
Amidst this financial and labour landscape, a mid-sized
refinery confronts rising energy costs, workforce shortages,
and the pressing need to meet net zero global commit-
ments by 2050. In addition, this journey unfolds in a setting
of diverse perspectives and agendas among the leadership
team and board of directors. Despite these obstacles, the
refinery committed to cutting Scope 1 and 2 emissions by
30%, benchmarked against a 2019 baseline, as depicted in
Figure 1.
Operating in a rapidly changing business environment,
the board sought to balance profitability by understanding
how the precise product mix, customer base, feedstocks,
and technologies interact. To reinforce this initiative, the
refinery’s Chief Operating Officer (COO) emphasised, “We
need to strategically invest for the long term, but we must
also remain profitable in the here and now. If we cannot
generate a positive cashflow today, how can we possibly
raise the funds for the investment we need to make?”
Achieving a balance between present performance
and long-term strategic investments required alignment,
commitment, and a clear and executable plan. Optimising
current performance while ensuring long-term success
required the refiner to keep one foot firmly planted in the
present and the other in the future.
The present – Project Catalyst
The refinery’s leadership team conducted a comprehensive
‘wall-to-wall’ operations assessment. This evaluation uncov-
ered several key focus areas, including soaring energy costs,
reliability issues, and team demographic challenges. Over a
six-week period, the following challenges were addressed:
• Asset reliability to overcome underinvestment
• Energy efficiency for quick wins
• Yield optimisation with digital twin software
• Turnaround optimisation for decarbonisation planning
• Recruitment and organisation to mitigate challenges
• Technology for digital transformation.
Rotating equipment issues significantly impacted asset
availability and throughput. This issue led to decreased
profit margins and hindered the site’s ability to capitalise
on a high-margin environment. The emphasis was on iden-
tifying reasons for underperforming asset reliability and
building consensus on corrective actions.
While historical underinvestment played a role in current
performance levels, the primary issue stemmed from a lack
of root cause analysis and follow-up actions, combined
with a lack of start-up readiness.
In Europe, rising energy costs have heightened the focus
on energy optimisation for many assets.3 A strategic energy
and maturity review identified that the refinery overlooked
the latest technology, monitoring tools, and efficient prac-
tices for energy management. Relying primarily on the
operators’ tacit knowledge, the asset fell short of industry
benchmarks, including KBC’s proprietary Best Technology
Index. However, through comparative analysis, the team
identified quick-win opportunities that required minimal or
no capital expenditures to swiftly improve the asset’s per-
formance. These opportunities not only delivered immedi-
ate value but also contributed to the programme’s overall
funding.
Additionally, long-term, mid-to-high Capex improve-
ments were identified and fed into the decarbonisation
workstream. Addressing no or low Capex opportunities
was integral to the refinery’s success in optimising energy
usage and achieving its goals.
120%
100%
95%
100%
90%
85%
80%
85%
70% 55%
60%
60%
40% 45%
Scope 1 & 2
20% Scope 3
0%
0%
2019 2025 2030 2035 2040 2050
Figure 1 Scope 1, 2, and 3 emissions reduction targets

www.digitalrefining.com PTQ Q2 2024 41

Q2 KBC.indd 41 11/03/2024 14:33:50


Purchased hydrogen
Process
Heater fuel
Hydrogen
Integrated Steam
Feedstock process models
Carbon Electricity
Detailed kinetic process
intensity
Detailed energy demand Fuel oil/gas
Heat integration analysis Natural gas
BT Benchmarking and Purchased
Energy Gaps electricity
Process GHG
Figure 2 Integrated Process, Energy, Emissions and Economics ModeI (IP3EM)
By creating a digital twin of the refinery, yield optimisation
opportunities could be thoroughly reviewed. This assess-
ment revealed numerous areas where operating parame-
ters and procedures could be improved. Furthermore, the
focus on no or low CapEx opportunities played an integral
role to the programme benefits and funding, similar to
energy efficiency opportunities.
Refinery margin erosion is largely attributed to turna-
rounds.4 This programme aimed to review both the overall
turnaround philosophy and the detailed scope of the next
two turnarounds. The focus was to identify activities that
could be descoped, moved off the critical path, and opti-
mised. Given two scheduled turnarounds between the
assessment and 2030, the turnaround review was inextri-
cably linked to the decarbonisation planning activities.
Many refiners struggle with dual challenges: an ageing
workforce and difficulty recruiting young engineers and
skilled operators.1,5 In addition, the oil and gas industry
is frequently perceived as contributing to climate change
rather than being part of the solution in the energy tran-
sition journey.3 The scale of the problem was assessed,
which has led to developing mitigation plans to address
potential gaps over one-, three-, five-, 10-, and 15-year
time horizons.
Technology is crucial for streamlining operations, rev-
olutionising work processes, and supporting necessary
productivity improvements to mitigate ongoing resourcing
issues. During this programme stage, the technology and
digitalisation vision were outlined for the operating assets,
consistent with the overall organisational vision. Having
defined the vision, a gap analysis was conducted, leading
to the development of a draft target application architec-
ture. This strategic approach ensured the technology was
leveraged optimally to achieve the refinery’s goals.
After completing the assessment phase, the next
step involved defining the resultant programme, Project
Catalyst. The process of defining the programme involved
overcoming the primary challenge of getting multiple
stakeholders with differing perceptions regarding priorities,
timescales, and resource requirements into agreement. To
42 PTQ Q2 2024
Q2 KBC.indd 42
Hydrogen
production Hydrogen plant GHG
SMR unit
Captured CO2
Electricity
Carbon capture
Steam CO2
Utility model MEA/MDEA
Utility Proprietary?
Steam system model
plant GHG
Detailed energy supply
Economic optimisation
GHG emissions
Refined products
Carbon intensity
address this, several highly facilitated programme design
workshops were held. These workshops were deliberately
not high tech. The team intentionally used basic tools such
as marker pens, sticky notes, a long sheet of brown paper,
and coloured voting dots.
Prioritising specific interventions was based on the cor-
porate goals, legislative frameworks (such as maintaining
a safe and compliant operation) and individual benefits
aligned with opportunities (such as maximising the trans-
formation investment). Engaging team members across
the organisation led to the development of a practical pro-
gramme where each workstream was assigned monthly
deliverables that were captured on a 4m-long poster. This
poster, shown in Figure 2, served as a key management
tool to communicate the programme’s progress and ensure
that everyone from the control room to the board room
understood the project.
The future – Project Horizon 2050
Building on the Project Catalyst programme, a similar exer-
cise was conducted to ensure the refiner met their decar-
bonisation targets. This initiative resulted in Project Horizon
2050. It should be noted that the ‘One Foot in the Present
– Project Catalyst’ and ‘One Foot in the Future – Project
Horizon’ workshops were held concurrently. The COO’s
vision was to transform the refinery into a future-ready
asset capable of meeting customer and societal demands
in a sustainable, affordable, and reliable way, including a
decarbonisation roadmap for reaching net zero with tech-
nology leading the way.
The main objective of Project Horizon 2050 was to
develop an agreed-upon decarbonisation roadmap that
balanced short-, medium-, and long-term initiatives to
achieve the refiner’s decarbonisation goals. To secure the
success of the roadmap and achieve net zero emissions by
2050, three pillars – strategy, operations and technology –
were defined, along with interim milestones.
The implementation of the refiner’s roadmap needed
to be anchored on technology and aligned with the other
two pillars to ensure sustained actions and results. This
www.digitalrefining.com
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 approach meant balancing current operations with a for-
ward-looking strategy.
As outlined in Project Catalyst, the roadmap started with
examining operations and implementing energy efficiency
to provide quick wins while balancing emissions reduction
with profitability. In this case, it involved reviewing existing
assets and operations to ensure optimal functionality. This
would achieve around a 15% emissions reduction, at best
20%. However, to reach the desired mid-30% emissions
reduction target and net zero by 2050, a clear strategy,
outside-the-box thinking, and alternative solutions were
needed to drive organisational change.
To achieve this first milestone of 30% emissions reduction,
the refiner built a green hydrogen plant to replace part of the
hydrogen produced at their steam methane reformer. This
step required various options to be evaluated to determine
the impact each alternative would have on energy, emis-
sions, and economics. Besides developing a solid business
case and a set of digital tools to analyse the green hydrogen
plant, additional actions and opportunities were explored to
achieve net zero emissions, such as electrification, carbon
capture storage and utilisation, and hydrogen firing.
Moreover, testing and verifying results were essential
to achieve top performance. As a result, tools capable of
incorporating the latest site modifications were essential
for real-time energy and emissions optimisation. By incor-
porating these measures, the refinery worked towards
achieving its emission reduction goals and contributing to a
more sustainable future.
Technology leads the way. Against this backdrop, and
to ensure alignment between strategy and current opera-
tions, two main technologies were adopted: the Integrated
Process, Energy, Emissions and Economics Model (IP3EM)
and digital energy management system.
The first technology implemented was the IP3EM. This
tool optimises renewable power options to reduce Scope 2
emissions while incorporating future Scope 3 projects.
As shown in Figure 2, this refinery-wide model compre-
hensively considered energy demanded from processing,
Renewable power
3.4 MW
4.8 MW
31.5 MW
33.5 MW
Traditional utility system
492 Kg/h
Electrolyser
H2
KPIs Fuels Emissions
Figure 3 Renewable and traditional energy management system
44 PTQ Q2 2024
Q2 KBC.indd 44
utility production and supply, and process and utility-gen-
erated emissions. Powered by a process simulator with
necessary modules, it addressed present and future energy
transition challenges. Moreover, the IP3EM model also
assessed the economic impact of the different alternatives
being evaluated and guided the refinery throughout its
entire decarbonisation journey.
The IP3EM revealed key benefits such as analysing refin-
ery margins, return on investment using emissions reduc-
tion scenarios, and accurately identifying and quantifying
major sources of Scope 1 greenhouse gas (GHG) emissions.
Several projects were considered. The IP3EM was key to
assessing the impact of Scope 1 and 2 emissions, energy
consumption, and economics regarding furnace electrifica-
tion, hydrogen firing, a green hydrogen plant (electrolyser),
and oxygen firing. Moreover, the analysis also included
future business cases that accounted for Scope 1 and 3
emissions. These projects included carbon capture and uti-
lisation (CCU) for sustainable aviation fuel, CCU urea pro-
duction, and a potential renewable hydroprocessing plant.
The second technology involved implementing a digital
energy management system to serve as the programme’s
foundation. This software optimised the energy system in
terms of economics and emissions to sustain long-term
value.
Simultaneously cutting costs and GHG emissions started
in a predominantly centralised, hydrocarbon-based energy
generation setting. During the energy transition, processes
improved, renewable energy vectors were introduced, and
assets were decentralised.
Ultimately, the goal is to achieve net zero GHG emis-
sions in a largely renewable energy system by maintaining
decentralised, low CO2 emissions energy generation, trans-
portation, as well as storage and utilisation.
The case in Figure 3 demonstrates a utility system that
blends traditional with renewable energy sources. This
scenario emphasises the importance of aligning short-term
scheduling with real-time operations for maintaining feasi-
bility and profitability.
Grid
AC
Process plant
HPS 28.5 TPH
V
MPS 85.0 TPH
LPS 14.1 TPH Ambient temp.
10 ˚C
www.digitalrefining.com
11/03/2024 14:33:53
 Resilience and innovation
In conclusion, the mid-sized refinery’s strategic journey
represents a delicate balance between profitability, envi-
ronmental commitments, and technological advancements
despite facing numerous challenges.
Through Project Catalyst, the refinery addressed opera-
tional deficiencies while optimising energy usage and man-
aging talent. These initiatives set the stage for the refinery’s
long-term success. By incorporating no or low Capex solu-
tions, the refinery not only improved immediate perfor-
mance but also laid a foundation for sustained success.
The simultaneous execution of the One Foot in the
Present and One Foot in the Future workshops via Project
Horizon 2050 demonstrated the refinery’s ability to bal-
ance financial viability with energy transformation.
The adoption of cutting-edge technologies, such as the
IP3EM model and the proprietary Visual MESA Energy
Optimizer, showcased the refinery’s commitment to precision
and efficiency. With a phased emissions reduction strategy and
initiatives like green hydrogen production and digital tools, the
refinery is set to meet net zero global commitments by 2050
and position itself as a leader in sustainable energy practices.
Visual MESA Energy Optimizer is a mark of KBC.
References
1 Bousso, R. (2021). Oil firms face workforce crunch as renewables
beckon – survey. Reuters. Retrieved from https://www.reuters.com/
markets/commodities/oil-firms-face-workforce-crunch-renewables-
beckon-survey-2021-11-30/
2 Worrell, E., & Galitsky, C. (2005). Energy efficiency improvement and
cost saving opportunities for petroleum refineries. U.S. Department of
Energy Office of Scientific and Technical information. Retrieved from
https://www.osti.gov/biblio/862119
3 International Energy Agency. (2020). The Oil and Gas Industry in
Energy Transitions – Analysis. Retrieved from https://www.iea.org/
reports/the-oil-and-gas-industry-in-energy-transitions
4 McGurty, J. (2022). Fires, outages and storms boost US refining mar-
gins. Retrieved from https://www.spglobal.com/commodityinsights/
en/market-insights/latest-news/oil/092622-refinery-margin-tracker-
fires-outages-and-storms-seen-boosting-us-margins
5 Dickson, D. (2021). The future of work in oil and gas | Deloitte
Insights. Retrieved from https://www2.deloitte.com/us/en/insights/
industry/oil-and-gas/future-of-work-oil-and-gas-chemicals.html
Aleix Carrillo is the Global Energy Transition Technology Solutions
Leader at KBC (A Yokogawa Company). With more than 17 years of
experience in the oil and gas industry, he brings value to KBC custom-
ers through digital solutions, consulting services and software applica-
tions for process, energy, and emissions optimisation.
Duncan Manuel serves as the Regional Head of Business Development
at KBC (A Yokogawa Company). He helps clients define how they
can leverage KBC’s SMEs, technology, and consulting capabilities to
address strategic and operational goals, whether they relate to cost
and efficiency and/or focus on the delivery of net zero goals.
Michelle Wicmandy is the Marketing Campaigns Manager at KBC
(A Yokogawa Company) in Houston, Texas, with more than 20
years of experience in marketing and communications. She serves
on the Forbes Communication Council and has contributed to both
academic and trade publications. She holds a DBA in business
administration.

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 SAF production via co-processing in
the kerosene hydrotreater
Guide to co-processing for SAF production, covering relevant regulations, why
kerosene hydrotreaters are preferred, and addressing challenges with solutions
Maria J L Perez, Gitte Thomsen Nygaard and Sylvain Verdier
Topsoe
S
ustainable aviation fuels (SAF) have been at the fore-
front of the fuel industry’s agenda for several years,
with increasing attention driven largely by regulatory
pressures. Across the globe, from the European Union and
the UK to Japan, Brazil, India, and Singapore, SAF man-
dates are being implemented, sometimes accompanied by
significant penalties for non-compliance, as exemplified by
the ReFuelEU aviation initiatives. These mandates are set
to significantly accelerate the deployment of SAF produc-
tion, and projections indicate that bolstered by such meas-
ures, SAF production could reach approximately 13 million
tons by 2030 and potentially soar to around 120 million
tons by 2050.1
Simultaneously, regulators are incentivising SAF supply
through attractive credit schemes. In the US, SAF suppliers
can benefit from Renewable Identification Number (RIN)
credits, Low Carbon Fuel Standard (LCFS) credits, Inflation
Reduction Act (IRA) production tax credits, and state-based
credits from states like Washington, Minnesota, and Illinois.
However, there are significant challenges to over-
come to increase the supply of SAF. Production of SAF in
standalone plants is capital intensive, and the process of
revamping an existing unit or constructing a new one can
span several years. This is where co-processing in a ker-
osene hydrotreater presents a compelling alternative. Not
only is it a low-capital expenditure (Capex) approach, but
it also allows for the rapid deployment of SAF production
within a few months (given the right conditions).
With more than 50 cycles of units co-processing renewa-
ble feedstocks in various hydroprocessing units worldwide
and with a wide range of renewable feedstocks, Topsoe has
accumulated extensive experience in this field. This article
is intended to offer a starting guide to anyone considering
going down the co-processing path by comprehensively
covering the regulations to be aware of, why co-processing
in the kerosene hydrotreater is the preferred choice for SAF
production, and the challenges and solutions.
What is co-processing?
In co-processing, even small amounts of fossil feedstock,
such as crude oil, can be replaced with renewable feed-
stock, such as vegetable oil, animal fat, and used cooking
oil (UCO). These are processed together in the hydrotreater
www.digitalrefining.com
q2 TOPSOE.indd 47
or hydrocracker (for example) to produce renewable fuel.
Co-processing of renewable feedstocks, such as virgin oils
or waste oils and fats, in hydroprocessing units has been
common practice for over a decade, primarily to produce
renewable diesel.
The amount of renewable feedstock added is typically at
relatively low levels of less than 5%. Such a low ratio gen-
erally only necessitates a catalyst change, which makes the
process relatively straightforward and makes co-process-
ing a simpler alternative to major revamps.
In cases where the co-processing ratio is increased to
10% or higher, revamps are typically required to address
common challenges, such as managing high exotherms or
mitigating corrosion issues.2
As written in the first quarter of 2024, most refineries
in the EU have become familiar with co-processing, and
few consider it a significant obstacle. Coupled with the
numerous benefits of co-processing for both producers
and off-takers, this is becoming an increasingly attractive
option for renewable fuel production.
Regulations on co-processing
As mentioned in the introduction, regulatory initiatives
supporting the supply or demand of SAF are being imple-
mented globally. This section outlines the key regulatory
initiatives introduced across various regions, as well as the
regulatory fuel compliance standards for co-processing.
In the EU, the ReFuelEU initiative targets a 70% SAF
share by 2050, split evenly between biogenic jet fuel and
eSAF. Non-compliance penalties enforce this obligation on
fuel suppliers. The UK is developing a similar SAF regula-
tory framework, potentially including a revenue certainty
scheme.
In the US, the SAF Grand Challenge promotes SAF
production, bolstered by incentives like RIN credits from
the Renewable Fuel Standard (RFS), LCFS credits from
California, Federal production tax credits (IRA), and addi-
tional credits from specific states. British Columbia, Canada,
has also issued SAF mandates, targeting 1% SAF by 2028
and 3% by 2030.
Other countries are also embarking on the SAF journey.
Japan aims for 10% SAF by 2030, India targets 1% SAF
by 2027 initially for international flights, Brazil seeks a 1%
PTQ Q2 2024 47
12/03/2024 13:48:51
 Eligible feedstocks for SAF production as per jurisdiction
EU-27
Feedstocks RED II Annex IX part B
(UCO, animal fat); Annex IX part A
(POME, CTO, MSW, etc.);
Other biogenic (not food and feed etc.)
Sustainability No food and feed crop
criteria No high ILUC feedstocks
Minimum GHG savings Min. 65% GHG saving
Fossil comparator 94 gCO2eq/MJ
LCA GHG calculation model RED II, Annex V
Table 1
reduction in GHG emissions by 2026, potentially rising to
10% by 2037, and Singapore announced that it is aiming
for a 1% SAF target from 2026 with plans to raise it to
3-5% by 2030.
Furthermore, discussions on mandates and incentives
are underway in numerous countries, including the United
Arab Emirates (UAE), Turkey, New Zealand, South Korea,
Australia, China, Chile, Colombia, Thailand, Malaysia,
Indonesia, and more.
From a fuel compliance perspective, the production of
SAF is guided by two key ASTM standards: ASTM D7566,
which currently outlines eight SAF pathways for standalone
plants, and ASTM D1655, which details the three current
co-processing pathways. The co-processing pathway dis-
cussed in this article involves the co-processing of mono-,
di-, and triglycerides, free fatty acids (FFAs), and fatty acid
esters (FAEs), allowing co-processing up to 5 vol% with
fossil feedstocks (further details can be found in Annex
A1.2.2.1 of ASTM D1655).
Regulatory considerations extend beyond fuel compli-
ance to also include questions about permissible feedstocks,
minimum greenhouse gas (GHG) savings, and GHG calcu-
lation methodologies. These complex issues are addressed
in various forums, but in this article, we will focus on regula-
tions related to co-processing. In the EU-27, the Delegated
Act on co-processing, issued on June 5, 2023, clarified the
methodologies for calculating the share of renewable fuels
via co-processing.3
This regulation supersedes the methodologies previously
established by specific member states like Spain and the
Netherlands, which were developed in the absence of a com-
mon EU approach. The Carbon Offsetting and Reduction
Scheme for International Aviation (CORSIA) scheme devel-
oped by the International Civil Aviation Organization (ICAO)
also covers SAF by co-processing, with the co-processing
methodology described in the methodology of a life-cycle
assessment (LCA) and default LCA values.4
What types of feedstocks?
The feedstocks eligible for SAF production via co-process-
ing vary by jurisdiction. In the EU, three types of biogenic
feedstocks are permitted (according to ReFuelEU Aviation):
• Waste listed in Annex IX part A
48 PTQ Q2 2024
q2 TOPSOE.indd 48
USA (RFS) CORSIA
Vegetable oil (no palm oil), Vegetable oils, waste oils and
waste oils and fats, some fats, solid waste, rotational crops
rotational crops, solid waste
Indirect ILUC criteria via 14 sustainability criteria
the minimum GHG savings (including ILUC)
Min. 50% for D4/D5 RIN; Min 10% GHG saving
Min. 60% for D3 RIN
_ 89 gCO2eq/MJ
GREET model CORSIA model
• Waste listed in Annex IX part B
• Other biogenic feedstocks not listed in Annex IX, pro-
vided they are not food and feed crops, intermediate crops,
palm fatty acid distillate, palm and soy-derived materials, or
soap stock and its derivatives. To comply, these feedstocks
must achieve a minimum of 65% GHG emission savings.
In the US, the choice of feedstocks depends on the type
of credits sought, such as RIN in the RFS scheme, LCFS in
California, or Clean Fuel Production Tax Credit (PTC) cred-
its. Each scheme has specific requirements and should be
examined individually. Both the RFS and IRA schemes also
require GHG savings, albeit with different methodologies.
Under the CORSIA, waste feedstocks are listed, and
default GHG values are provided for selected feedstocks.
The ICAO has also developed guidance to include addi-
tional materials in the positive list.
Kerosene hydrotreater: Preferred choice for SAF
production
Co-processing can be carried out in various refinery units,
including fluid catalytic cracking (FCC), diesel hydrotreat-
ers, hydrocrackers, and kerosene hydrotreaters. However,
the optimal choice often hinges on the principle of selectiv-
ity and optimal cost of production: Which unit will yield the
highest SAF output from the renewable feedstock at the
most optimal cost of production?
In this context, a kerosene hydrotreater emerges as the
most preferred choice. With the right catalysts, this unit can
maximise the conversion of biogenic carbon into the jet fuel
fraction, thereby optimising SAF production. Low-pressure
reactor operation (~25-30 bar g) makes co-processing in
the kerosene hydrotreater option unique with respect to the
high recovery of biogenic carbon.
Co-processing challenges and their solutions
While co-processing in general comes up with some
challenges, the limited catalyst volume, lower hydrogen
partial pressure, and use of relatively simple metallurgy
in a kerosene hydrotreater make this challenge even more
interesting.
If the end product is to obtain SAF certification, there
are three main challenges to be aware of when producing
SAF by means of co-processing in your kerosene unit. In
www.digitalrefining.com
12/03/2024 13:48:52
 this section, we will cover the three challenges and their
solutions. 10
It is crucial for certification to retain the biogenic carbon Kero. from HK unit
from the renewable feedstock in the liquid jet fuel product 0 Straight-run kero.

Freezing point of blend (˚C)

and meet the freezing point requirement. The key differen- -10
tiator between co-processing in a diesel unit vs a kerosene
hydrotreater is the requirement to achieve the product jet -20

freeze point. Thus, the first major challenge for kerosene

co-processing is meeting the freeze point requirement and
keeping the biogenic carbon in the jet fuel product. Jet A and
Jet A1 fuels have stringent product specifications, which
include a requirement for the freezing point to be below
-40°C for Jet A and -47°C for Jet A1 (as outlined in ASTM
D1655).
Even modest additions of renewable feedstock can
significantly increase the freezing point due to biogenic
n-paraffins formed during oxygen removal. As illustrated in
Figure 1, adding just 1% renewable feedstock can result in
an increase of the freezing point by more than 30°C, and
adding 5% renewable feedstock can result in a deteriora-
tion of the freezing point close to 50°C. To meet the cold
flow properties requirements of Jet A and Jet A1 fuels, deep
dewaxing of these biogenic n-paraffins is essential.
Freezing point improvement can be obtained through
hydrocracking, where the n-paraffins are cracked into
smaller molecules. This reaction, unfortunately, results in
high yield loss to gas and naphtha. A much more efficient
pathway to lower the freezing point is through hydroisom-
erisation. The n-paraffins are isomerised to iso-paraffins,
which have much better cold flow properties without losing
any biogenic carbons to the gas and naphtha (outlined in
Figure 2).
To meet the cold flow properties requirements of Jet A
and Jet A1 fuels, deep dewaxing of these biogenic paraf-
fins is essential. Fortunately, this process is made possible
by Topsoe’s highly selective dewaxing catalyst, TK-930
D-wax, which effectively facilitates the necessary deep
dewaxing and, at the same time, retains the biogenic car-
bon in the jet fuel product. This catalyst has been designed
to operate even at reactor pressure as low as 25 barg. To
-30
-40
Option 1 Option 2
-50
-60
0 1 2 3 4 5 6 7 8 9 10
Amount of n-C18 added (vol%)
Figure 1 How the freezing point is affected by even small
amounts of renewable feedstocks
this extent, a highly selective dewaxing catalyst and HDO
selective grading serve as a drop-in replacement for exist-
ing kerosene hydrotreaters.
Figure 3 demonstrates how to maximise SAF yield in a
kerosene hydrotreater with the right catalyst loading, with
selective HDO and isomerisation catalyst.
The second challenge is removing oxygen atoms from
lipidic feedstocks, converting FFAs and triglycerides into
n-paraffins. Two possible reaction routes are available:
hydrodeoxygenation (HDO), leading to water formation, or
decarboxylation (DCO), leading to CO2 formation (as illus-
trated in Figure 4). The preferred route is HDO, as it max-
imises the yield of the renewable fraction and retains the
biogenic carbon in the jet fuel fraction rather than convert-
ing it to CO2. Topsoe’s selective HDO catalyst can increase
HDO selectivity to 97%, resulting in a renewable yield that
is more than 2 vol% higher than when using traditional fos-
sil catalysts.
The third challenge is the contaminants of renewable
fuel. High levels of impurities in renewable feeds (met-
als, phosphorous, and unsaponifiables) can be reduced to

Number of carbon atoms: 14

50
Boiling point: 254 ˚C
Melting point: 6 ˚C
25
1
2 1
Freezing point (˚C)

0 Hydrocracking
Number of carbon atoms: 18
-25 Boiling point: 317 ˚C
Melting point: 28 ˚C

-50

-75 Normal alkanes Hydroisomerisation

2-methyl isomers 2
3-methyl isomers
-100 Number of carbon atoms: 18
0 12 14 16 18 20 Boiling point: 313 ˚C
Carbon atoms in molecule Melting point: -6 ˚C

Figure 2 Hydroisomerisation as a more efficient pathway for lowering the freezing point

www.digitalrefining.com PTQ Q2 2024 49

q2 TOPSOE.indd 49 12/03/2024 13:48:54

 in kerosene units can, as far as process compatibility is
Fossil kerosene Fossil naphtha + gases
Renewable feed Renewable propane
concerned, be done easily without modifications (aside
Hydrotreating from changing the catalyst) or with minor modifications,
reactor Splitter depending on the existing unit configuration and design
conditions.

Certification and biogenic carbon monitoring

HDO/HDS In addition to technical and regulatory considerations,
catalyst
sustainability certification plays a crucial role in ensuring
the SAF compliance produced via co-processing. As high-
lighted earlier, the EU-27’s Delegated Act on co-process-
Dewaxing ing, issued in May 2023, emphasises the importance of
catalyst monitoring the fate of biogenic carbon. This act approves
three methodologies: mass balance, energy balance, and
yield.5 However, the content of 14C biogenic carbon must
be verified to validate the chosen methodology. This verifi-
cation should occur at least every four months or whenever
Jet A or A1
2.7 %
SAF a change in operating conditions exceeds 5%. It is impor-
tant to note that if a discrepancy arises between the chosen
Biogenic methodology and 14C measurement, the 14C measure-
carbon
ments will be considered correct.
Fossil
carbon Several standards exist for 14C determination, as shown
in Table 2. The Accelerator Mass Spectrometry (AMS)
method is the most accurate, but only a few laboratories are
2.5 % currently equipped to conduct such analysis on oil samples.

Figure 3 The process of co-processing renewable Conclusion

feedstocks in kerosene hydrotreater
acceptable levels by a feed pretreatment step which, among
others, includes a degumming and bleaching process. The
feed pretreatment step can be avoided if pretreated renew-
able feeds can be procured. The feed impurities can be
further efficiently handled by a specially developed grading
catalyst to minimise the deactivation of bulk catalyst and
pressure drop-related issues to achieve higher unit reliabil-
ity and availability.
In conclusion, co-processing 5% renewable feedstocks
Demand for SAF is increasing, driven by regulatory pres-
sures across the world. However, SAF production faces
a crucial obstacle: standalone SAF production plants are
capital-intensive, and revamps of existing units require a
timeline of several years. Under these conditions, it will
take years before the supply of SAF can meet the expected
demand currently fostered by the mandates.
Co-processing is a fast track to SAF production that can
function as a short-term solution to comply with the upcom-
ing SAF mandates in the next few years. Among various
options, co-processing renewable feedstocks in kerosene

O O
H H H H Octadecane
Water Water
O O
HDO route H H H H Octadecane
Propane Water Water
+ 16 H2
O O
H H H H Docosane
Water Water
O Triglyceride Reverse water gas shift
O C O + H H O + +O C-
O O 9c-oleic acid H H

O Methanation
O 13c-eurcic acid H H
+O C- + H H CH4 + O
H H
O H H
9c 12c-linoleic acid

Decarboxylation O C O
route (DCO) Carbon dioxide Hepadecane
+ 7 H2 O C O
Propane Carbon dioxide Hepadecane
O C O
Carbon dioxide Henicosane

Figure 4 Two possible reaction routes for removing oxygen atoms from lipidic feedstocks converting free fatty acids and
triglycerides into n-paraffins

50 PTQ Q2 2024 www.digitalrefining.com

q2 TOPSOE.indd 50 12/03/2024 13:48:56

 The various standards for 14C determination

Technique Pros Cons Standard method Accuracy and uncertainty

Gas proportional Not commercial None
counters (GPC) Not sensitive

Beta Ionsation Low investment Low background lab and EN1 6640 (Annex D) 0.2-5% deviation
equipment gas purification device required

Liquid scintillation Fast/lower cost/easy LSC-Benzene: applicable D6866 (Method C); Maximum total error
counters (LSC) sample preparation/ to clear liquids only EN 16640 (Annex C); of +/-3% (absolute)
Referred in fast analysis (5-10h) DIN-51637
ASTM D1655

Accelerator mass Applicable to solid, Complex/time-consuming/ D6866 Instrumental error within 0.1-0.5%;
Spectrometry (AMS) gas, and liquids high cost/laborious (Method B); Interlaboratory total uncertainty
Referred in sample preparation EN 16640 +/-3% (absolute);
ASTM D1655 (Annex E) Lower detection limit 0.4%

Table 2

hydrotreaters is the best choice for SAF production with
respect to lower operating cost, lower capital investment,
higher recovery of biogenic carbon in the SAF product,
short implementation time, and low payback period. This
method can save up to two years of construction time com-
pared to building new facilities.
The main operational challenges of using a kerosene
hydrotreater as a co-processing unit to produce SAF are
Technology and a Diploma in Business Development and Management
from the Technical University of Denmark.
Sylvain Verdier is Senior Strategy Manager at Topsoe, Denmark, advis-
ing internal and external stakeholders on how to manage the energy
transition with a focus on technologies, regulations, sustainability, and
feedstocks. He holds an MSc in chemical engineering from ENSGTI and
a PhD in chemical engineering from the Technical University of Denmark.

the limited catalyst volume, operating temperature limita-

tions, and low hydrogen availability. These challenges can
be overcome in most cases, without major modifications in
the units, by limiting the amount of renewable feedstock to
less than 5 vol%.
Conclusively, producing SAF by co-processing 5%
renewable feedstocks in a kerosene hydrotreater will ena-
ble the acceleration of SAF production and a fast track to
increase the current supply.

TK-930 D-wax is a trademark of Topsoe.

References
1 SkyNRG, SkyNRG’s Sustainable Aviation Fuel Market Outlook May
2023, https://skynrg.com/safmo2023.
2 Nystrom S, Michaelsen N, Egeberg R, Improving the production of renew-
able diesel by co-processing, www.digitalrefining.com/article/1000060/
improving-the-production-of-renewable-diesel-by-co-processing
3 C_2023_3513_1_EN_ACT_part1_v3_0.pdf, https://energy.ec.eu-
ropa.eu/system/files/2023-06/C_2023_3513_1_EN_ACT_part1_
v3_0.pdf
4 CORSIA Eligible Fuels, www.icao.int/environmental-protection/
CORSIA/Pages/CORSIA-Eligible-Fuels.aspx
5 www.iscc-system.org/wp-content /uploads/2022/08/ISCC-
Guidance-Document-203-01_Co-processing-requirements.pdf

Maria J L Perez is Senior Product Line Director at Topsoe, Denmark.

Skilled in hydroprocessing catalyst, technical support, sales and per-
sonnel management, she holds a PhD in chemical engineering from
Universidad de Oviedo, Spain.

Gitte Thomsen Nygaard is Senior Solutions Specialist for Renewable

Fuels at Topsoe, Denmark. She holds an MSc in Food Science and

www.digitalrefining.com PTQ Q2 2024 51

q2 TOPSOE.indd 51 12/03/2024 13:48:57

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 Flexible downscaling of MAPD
removal from C3/C4 olefin streams
This study simulates selective hydrogenation of a combined C3/C4 cut with
1,3-butadiene, aiming to retain the target products under relevant industrial conditions
Edgar Jordan, Charlotte Fritsch and Joachim Haertlé
hte GmbH
R
aw olefinic C3/C4 streams in integrated petrochem-
ical refineries, mainly the product of naphtha steam
crackers or FCC units, usually contain low-weight
percentages of acetylene derivatives, known as MAPD
compounds. MAPD stands for methylacetylene (propyne,
MA) and propadiene (PD), which are the most common
impurities; vinylacetylene (but-1-en-3-yne, VA) and ethy-
lacetylene (1-butyne, EA) can also be formed. These side
products must be removed to protect downstream pro-
cesses from severe catalyst poisoning and unwanted side
reactions of those highly reactive substances. For instance,
polymer-grade propylene must not exceed an MAPD impu-
rity level of 1 ppmw.
The predominant method for removing these compounds
is selective hydrogenation of the triple bonds while preserv-
ing the olefinic species. Whereas selective hydrogenation
of acetylene in the C2 fraction is performed in the gase-
ous phase, C3/C4 selective hydrogenation is predominantly
carried out in a liquid state. This is for reasons of energy
efficiency and the smaller reactor volume.
Another benefit of a liquid state reaction is that greenoil
formed as a byproduct during the hydrogenation reaction
is washed out of the catalyst bed. Greenoil is an unwanted
side product in C3-C4 selective hydrogenation, formed by
the oligomerisation of olefins to various heavier unsatu-
rated hydrocarbons. This greenoil can lead to catalyst deac-
tivation as well as contamination in the unit.
Commercial selective hydrogenation processes can be
differentiated into front-end and tail-end configurations.
Saturation feed
Upstream Downflow
pressure control configuration
Heater/cooler
H2
Reaction feed
Upflow
configuration
Figure 1 Unit set-up for up- and downflow configuration
www.digitalrefining.com
Q2 HTE.indd 53
Front-end hydrogenation processes are characterised by
an excess of hydrogen (H2) present in the raw product
stream from the steam cracking or FCC unit. In contrast,
tail-end selective hydrogenation, situated behind the
de-methaniser and de-ethaniser columns, is controlled by
feeding a stoichiometric amount of hydrogen to the hydro-
carbon stream. Whereas for front-end hydrogenation, NiCo
catalysts are common, tail-end hydrogenation catalysts are
precious metals, mainly based on promoted palladium (Pd).
Commercial process licensors and catalyst manufacturers
for selective hydrogenation include Axens, UOP, Evonik,
Lummus, Linde, KBR, and BASF.
Tail-end liquid state selective hydrogenation often incor-
porates multistage operation. In the first stage especially, a
recycle stream of the product can be integrated to control
the acetylene concentration and, in turn, the exothermicity
of the reaction.1-4
For operators of tail-end selective hydrogenation pro-
cesses, many aspects of the catalyst and process perfor-
mance are important to investigate, such as the long-term
stability of the catalyst, the acetylene derivatives conversion
level as a function of feed composition, the optimal operating
window of the process, and the control of greenoil formation.
Experimental set-up
The experimental unit was equipped with a flexible
up-and-downflow configuration. Liquid feed was pumped
by a two-piston syringe pump, whereas the hydrogen flow
was controlled by a mass flow controller (see Figure 1). The
Bypass
Downstream
pressure control
GC
Reactor
N2
PTQ Q2 2024 53
14/03/2024 10:09:06

Compound 1,3- 4-vinylcyclo- n-butane 1-butene c-2-butene
butadiene hexene acetylene
wt% 37.6 7.25 5.90
Table 1
pressure was controlled using a backpressure regulator sit-
uated after (liquid phase operation) or before (gas phase
operation) the reactor. The resulting product mixture was
diluted with N2 downstream, whereas any greenoil formed
was kept liquid and thus separated from the product stream.
The temperature of the catalyst bed was controlled by a
heating/cooling mantle connected to a thermostat equipped
with a parallel electrical heating circuit. The accessible tem-
peratures ranged from sub-ambient to 600°C.
With this flexible set-up, it was possible to run the reac-
tion at various pressures and temperatures in both liquid
and gas phase. Although most commercial selective hydro-
genations of these C3/C4 species are performed in the liquid
phase, the experiment additionally compared liquid and gas
phase performance to demonstrate the unit’s flexibility to
accommodate different light olefin selective hydrogenation
reactions. In liquid phase operation, the impact of upflow vs
downflow configuration was investigated.
The hydrocarbon feedstock simulates a C3-C4 olefin
stream. It should be noted that the feedstock contains
7.25 wt% 4-vinylcyclohexane as a dimerisation product of
1,3-butadiene, extending the educt spectrum up to C8.
The effluent stream was analysed with an Agilent gas
chromatograph (GC) equipped with a flame ionisation detec-
tor (FID) and an RTX-Alumina BOND column. Conversion
was calculated based on the weight and molar educt, and
product flow rates, with the educt flow rates defined by
repeated bypass measurements between the experiments.
Results and discussion
Operation under standard conditions
A commercial Lindlar catalyst was used (5 wt% Pd,
T = 16.7 ˚C T = 35.8 ˚C
11
10.5
Butadiene loss (%)
10
9.5
9
VA conversion MA conversion
Figure 2 Acetylene conversion (right axis) and butadiene
loss (left axis) vs reactor temperature (upflow, liq.), p = 24
barg, H2:VA = 2 mol/mol, LHSV = 22 h-1
54 PTQ Q2 2024
Q2 HTE.indd 54
Feed composition
Vinyl- Methyl- Ethyl- Propa- Propylene
acetylene acetylene diene
4.59 0.088 0.56 0.34 0.075 0.29 Balance
selectively poisoned by lead (Pb) on a calcium carbonate
carrier, Merck).5 The reactor with an inner diameter of 8 mm
was filled with a 2:3 (by volume) mixture of the Lindlar cat-
alyst and silicon carbide as inert material. The total catalyst
zone length was 77 mm. Reference conditions for testing
were a reactor temperature of 35°C, a pressure of 24 barg,
a molar hydrogen/VA ratio of 2, a hydrocarbon feed-based
liquid hourly space velocity (LHSV) of 22 h-1, and an upflow
configuration of the reactor system.
This approximates a typical operating window of com-
mercial units with a hydrogen dosage just below the sto-
ichiometric amount with respect to all acetylenes and PD.
These parameters were systematically varied during the
testing program, as will be further discussed.
Under these bespoke standard conditions, the following
conversions were observed: 78.6 wt% for VA, 49.4 wt%
for EA, and 54.1 wt% for MA. The higher conversion of
VA compared to MA and EA is characteristic of Pd-based
catalysts. Hydrogen was quantitatively consumed, which is
also typical for a tail-end selective hydrogenation process.
However, containing 5 wt% Pd, the commercially available
Lindlar catalyst provided a fivefold higher active metal load
than a typical industrially available catalyst for this reaction
and, hence, was significantly more active. This explains the
high BD loss of 9.53 wt%.
LHSV variation
Starting from the standard conditions, the hydrocar-
bon-based LHSV varied in a broad range between 7.2 h-1
and 82.4 h-1. Due to the high activity of the Lindlar cat-
alyst used, the hydrogen conversion remained at nearly
100 mol% over the whole LHSV range. At higher temper-
atures, a temperature increase of the catalyst zone could
be detected, with the zone temperature ranging from
T = 50.1 ˚C 80 35.5°C at LHSV = 7.2 h-1 to 36.7°C at LHSV = 82.4 h-1. The
heater/cooler system was able to keep the catalyst zone
75
Acetylenes conversion (%)
temperature constant within a narrow temperature range
70 also at high rates of heat production by the hydrogenation
65 reaction.
60
Temperature variation
55 Temperature was set to 15, 35 and 50°C, while the other
50 parameters were kept at their standard values (see Figure 2).
The highest acetylene conversion was observed at 15°C,
45
with a corresponding minimised butadiene (BD) loss. When
raising the temperature to 35 and 50°C, the acetylene con-
EA conversion BD loss
version decreases, with slightly rising butadiene conver-
sion. Quantitative hydrogen consumption was observed at
all temperatures, limiting the overall hydrogenation activity.
It is noteworthy that the relative shifts in BD conversion are
much smaller than the shifts in acetylene conversion due to
www.digitalrefining.com
14/03/2024 10:24:42
 the much higher absolute BD content with respect to the
acetylene species in the feed. These experiments neatly
90
show the importance of precise temperature control, espe-
cially when operating larger reactors.

Acetylenes conversion (%)

80

Hydrogen/VA molar ratio variation 70

As depicted in Figures 4 and 5, the molar hydrogen to VA 60

ratio was systematically varied between 0.3 and 7.2. With
50
the feed containing 1.6 mol% of acetylenes and PD, the
stoichiometric H2/VA ratio for quantitative hydrogenation 40
is 2.6. With an increasing H2/VA ratio, an increase in acet-
30
ylene conversion could be observed. However, 1,3-buta-
diene also began to be increasingly hydrogenated. At the 20
highest H2/VA ratio of 7.2, VA was nearly quantitatively VA conversion MA conversion EA conversion PD conversion
consumed, while MA and EA conversion reached around
90 wt%. Higher exothermicity is expected, as indicated by
slightly higher temperatures in the catalyst bed. With the Figure 3 Acetylene conversion at standard conditions,
heater/cooler system, the exothermicity could be controlled upflow vs downflow, p = 24 barg, T = 35°C, H2:VA = 2
at a maximum of 1°C at the highest H2/VA ratio. mol/mol, LHSV = 22 h-1

Influence of variable process conditions
Operating the unit under standard conditions as previously
described, the upflow configuration of the unit was tested
against a downflow configuration. In downflow operation,
a significant loss was observed in overall acetylenes con-
version (see Figure 3). The most probable reason for this is
that in the downflow regime, some gas-filled voids remain
between the catalyst particles, preventing the formation of
a uniform feed phase in the catalyst bed.
By reducing the reactor pressure to 0.6 barg, all hydro-
carbons could be evaporated, and the reaction could be
run in the gaseous phase (see Figure 4). As for the liquid
state experiments, the H2/VA ratio was systematically
changed at constant a hydrocarbon-based LHSV of 22 h-1.
At equal H2/VA ratios, much higher acetylene derivatives
conversions could be observed compared to liquid phase
operation at a significantly shorter contact time with the
catalyst. Correspondingly, the BD loss was significantly
lower (see Figure 5).
It is noteworthy that at the lowest H2/VA ratio, VA is
selectively hydrogenated to 1,3-butadiene, thus caus-
ing a negative butadiene conversion. This high selectiv-
ity is also targeted in commercial processes to maximise
1,3-butadiene yield. The most likely reasons for the higher
selectivity of gas phase operation are less restricted mass
transfer in the gas phase, plus the lower tendency for dou-
ble bonds to adsorb on the Pd active sites at lower pres-
sure. Furthermore, in a liquid state, H2 first needs to be
solved in liquid hydrocarbon; then, an equilibrium H2 con-
centration must be established in the hydrocarbon phase,
permitting the H2 concentration available at the active site
to be limited.

Conversions vs. H2/VA ratio, liquid phase upflow Conversions vs. H2/VA ratio, gas phase

36.8 36.8
100 100

34.6 34.6
80 80
Reactor temperature (˚C)

36.4 36.4
Conversion (%)

60 60
36.2 36.2

40 36 40 36

35.8 35.8
20 20

35.6 35.6

0 0
35.4 35.4
2 4 6 2 4 6
H2/VA Ratio in feed (mol/mol) H2/VA Ratio in feed (mol/mol)

VA conversion EA conversion MA conversion PD conversion BD conversion Temperature

Figure 4 Acetylene conversion vs H2 to vinylacetylene ratio (left axis), catalyst bed temperature (right axis); left: p = 24
barg, LHSV = 22 h-1 (liq., upflow), right: p = 0.6 barg, LHSV = 22 h-1 (gas phase)

www.digitalrefining.com PTQ Q2 2024 55

Q2 HTE.indd 55 14/03/2024 10:09:10

 MA conversion (liq., upflow) EA conversion (liq., upflow) VA conversion (liq., upflow)
40
Conversion of 1,3-Butadiene (wt. %)

20

0
MA conversion (gas) EA conversion (gas) VA conversion (gas)
40

20

0
50 100 50 100 50 100
Conversion of acetylenes (wt. %)

H2/VA ratio (liq.) = 0.99 H2/VA ratio (liq.) = 4.12 H2/VA ratio (liq.) = 0.29 H2/VA ratio (liq.) = 0.47 H2/VA ratio (liq.) = 6.91
H2/VA ratio (liq.) = 2.03 H2/VA ratio (liq.) = 7.2 H2/VA ratio (liq.) = 2.03 H2/VA ratio (liq.) = 1.44

Figure 5 1,3-butadiene loss vs acetylene conversion, liquid phase upflow (24 barg, 35°C, LHSV =22 h-1) vs gas phase
(0.6 barg, 35°C, LHSV =22 h-1)

Carbon monoxide (CO) dosage feed and further downstream nitrogen (N2) dilution. Figure
As for MAPD selective hydrogenation, front-end and 6 shows a significant drop in all acetylene conversions at
tail-end configurations are possible in acetylene selective the onset of the CO dosage. Also, H2 was no longer quanti-
hydrogenation in an ethylene matrix. In the case of front- tatively consumed, with H2 consumption instead dropping
end hydrogenation, an excess of H2 is present in the feed to about 75 mol%. A marginal temperature drop could be
gas, plus low levels of CO, which moderate the activity of observed in the catalyst zone. A shift of conversion levels
the hydrogenation catalyst towards acetylene. In tail-end toward triple bond hydrogenation was not observed, with
configuration, the H2 content can be controlled at stoichio- the BD conversion staying virtually stable.
metric levels, so it is therefore desirable to operate with an
intrinsically selective catalyst system.6 Greenoil formation and handling
To simulate a CO impurity in the feedstock, typical When running selective hydrogenation reactions in an
for front-end hydrogenation, a capillary for dosing CO, olefinic matrix, the control and handling of greenoil are
designed to dose 100 ppm CO in H2 at standard conditions, important aspects. During the operations, it was crucial to
was installed. The CO could not be detected by online GC, as separate greenoil from the C1-C8 product fraction before
the H2 itself became heavily diluted by excess hydrocarbon online GC analysis. This could be achieved by downstream

90

80
Onset of VA conversion 35.9
CO dosage BD conversion
70 Temperature 35.85
Reactor temperature (˚C)

60
35.8
Conversion (%)

50

40 35.75

30 35.7
20
35.65
10
35.6
0
580 585 590 595 600 605 610 615 620 625 630 635
TOS (h)

Figure 6 Effect of a 100 ppm level CO dosage on VA and BD conversion at standard conditions, 24 barg, 35 °C, H2:VA =
2, mol/mol, LHSV = 22 h-1.

56 PTQ Q2 2024 www.digitalrefining.com

Q2 HTE.indd 56 14/03/2024 10:14:16

 2.5
C16
120
2 100
80
1.5 60
Area (%)
40
20
1
0
0 100
0.5
0
0 100 200 300
Temperature (%)
Figure 7 SimDist analysis of greenoil accumulated downstream
N2 dilution followed by pressure regulation and controlled
evaporation of the main reaction products through a dome
pressure regulator.
Greenoil could then be separated from lighter products in
a liquid trap. Keeping a 50°C temperature at the pressure
regulator and the liquid trap during this step was of vital
importance, as at higher temperatures, increased greenoil
formation and carry-over led to downstream plugging of
pipes. At lower temperatures, lighter products were not
quantitatively carried over into the gas phase.
Samples of greenoil were collected and analysed via sim-
ulated distillation (SimDist: see Figure 7). Results showed
a boiling point range of 200°C up to >700°C, with a sig-
nificant peak for C16 species. It should be noted that the
greenoil was stored at 50°C for several days before the
analysis, potentially allowing for further oligomerisation. It
does not necessarily resemble the greenoil composition out
of the catalyst bed. The reaction network behind greenoil
formation is not yet fully understood and is still a topic of
debate in the available literature.1
Conclusions
In this case study, the selective hydrogenation of tail-end
acetylene derivatives and propadiene was successfully
downscaled in a highly unsaturated hydrocarbon matrix,
including 1,3-butadiene, in the laboratory environment.
The set-up allows for the testing of commercial catalyst
shapes under industrially relevant conditions. The high flex-
ibility of the unit allows for screening in a broad parameter
range for many types of commercial MAPD catalyst. An
optimum operating window was found to maximise MAPD
purification at low BD loss.
All trend data and performance data were measured in
parallel and automatically linked to corresponding online
GC data and can be reported on request. This unit is one
building block of olefin conversion capabilities in support-
ing the needs of refineries in integrating petrochemical
complexes.
The experimental concept can be transferred to other
www.digitalrefining.com
Q2 HTE.indd 57
Accumulated (%)
200 300 400 500 600 700 800
400 500 600 700 800
selective hydrogenation processes in the gas or liquid
phase, like acetylene in a C2 matrix, with stoichiometric or
excess levels of hydrogen. The influence of temperature,
H2/acetylenes ratio, liquid state upflow vs downflow, gas
phase vs liquid phase operation, and CO poisoning has
been tested and discussed.
Acknowledgement
We thank our colleagues at hte for their support in this study. Special
thanks to Tobias Zimmermann for his significant contributions to the
study within his occupational activities at hte.
Literature
1 Mohundro E L, Overview on C2 and C3 Selective Hydrogenation in
Ethylene Plants, AIChE 15th Ethylene Producers Conference, 2003.
2 Butadiene, IHS Markit Report, 2021.
3 Propylene, Technoeconomics – Energy and Chemicals, Nexant
Market Report, 2018.
4 Iselborn S, BASF selective and full hydrogenation technology Selop®,
Handbook of Petrochemicals Production Processes, Chap. 2.3, 2nd
ed., 2019, edited by R A Meyers, New York, McGraw-Hill Education.
5 Lindlar H, Ein neuer Katalysator für selektive Hydrierungen, Helv
Chim Acta 1952, 35, pp.446-450.
6 McCue A J, Anderson J A, Recent advances in selective acetylene
hydrogenation using palladium containing catalysts, Front. Chem. Sci.
Eng. 2015, 9(2), pp.142-153.
Edgar Jordan is Application and Project Manager focused on light ole-
fins conversion processes at hte GmbH, Heidelberg, Germany. He has
more than five years of experience in high throughput and pilot-scale
catalyst testing and holds a PhD in chemistry from the University of
Münster, Germany.
Charlotte Fritsch is Business Development Manager focused on
catalyst testing and process development at hte GmbH, Heidelberg.
She holds a PhD in chemistry from Karlsruhe Institute of Technology,
Germany.
Joachim Haertlé studied chemical and bioengineering at the University
of Erlangen and has been working as a project coordinator at hte since
2018.
PTQ Q2 2024 57
14/03/2024 10:14:33
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 Sulphur reduction, sulphur removal,
and spent caustic reuse
Demand for flexible sulphur recovery solutions is increasing, including wet air oxidation,
deep neutralisation, incineration, and processes that need sustainable strategies
Richard Stambaugh
Merichem Technologies
M
ore than a hundred different crude oils are traded on
the market today. The most desirable crudes are light
and sweet, containing less than 0.5% (by weight)
sulphur. They are highly efficient, leave minimal residue in
the refinement process, and the low density makes them
easy to distil and transport. Demand for light, sweet crude
grades rose exponentially across Europe, Africa, and the US
as refineries adjusted their slates ahead of the International
Maritime Organization (IMO) 2020 lower sulphur cap.
In contrast, heavy, sour crudes contain more than 0.5%
sulphur. They are generally extracted from the Gulf of
Mexico, Mexico, South America, Canada, and the 24 OPEC
Member Nations. Sour crudes are more complicated to
refine into lower-sulphur fuels, and the refiners who can
process them have a distinct advantage over those who
cannot, particularly considering IMO 2020. The impetus
has been on refineries to determine the best methods of
separating sulphur compounds from sour crude. In doing
so, US refineries can take in almost any crude oil and turn it
into clean-burning fuel.
The problem
Sitting midway to 2030 net zero goals, it has become
clear to scientists and environmentalists that incremen-
tal and fragmented change is insufficient to achieve the
Sustainable Development Goals (SDGs) in the seven years
remaining. Meeting (net zero goals) requires transforma-
tive and accelerated actions, outlined in the 2023 Global
Sustainable Development Report (GSDR), a new phase of
accelerated progress by UN member states towards the
Sustainable Development Goals leading up to 2030. It out-
lines the shifts required to transform the energy sector, and
the increasingly stringent fuel specifications have made
crude oil desulphurisation obligatory.
The sulphur-containing compounds in sour crudes are
among the most undesirable. Hydrogen sulphide (H2S) is
toxic to humans and particularly dangerous because, at suf-
ficiently high concentrations, it paralyses olfactory nerves
even when exposed to it for only a few minutes. According
to the National Institute for Occupational Safety and Health
(NIOSH), H2S environmental concentrations of 100 ppm
are immediately dangerous to life or health. Concentrations
greater than 500 ppm can cause a person to collapse
www.digitalrefining.com
Q2 Merichem.indd 59
within five minutes, and concentrations exceeding 700
ppm can cause immediate collapse and death within just
one or two breaths.
Spent caustics
When the malodorous and potentially dangerous sulphides
and mercaptans are expended from sweetened hydro-
carbons, the residual caustics are considered spent. The
complexities and numerous processes involved in treating
spent caustic are challenging. It is one of the most prob-
lematic industrial wastes in terms of disposal. When man-
aged poorly, spent caustic can cause significant harm to
health and the environment. Since 1997, the Environmental
Protection Agency (EPA), under the Resource Conservation
The complexities and numerous
processes involved in treating spent
caustic are challenging. It is one
of the most problematic industrial
wastes in terms of disposal
and Recovery Act (RCRA), has classified spent caustics as
hazardous waste, with strict handling and disposal require-
ments because of the high levels of contaminants.
Spent caustics typically have a high pH value (>12) and high
sulphide concentrations (2-3% w/w), not accounting for the
phenols, mercaptans, amines, or other organic compounds
that are emulsified in the caustic. Spent caustic is classified
as an EPA Hazardous Waste Number of DOO3, hazardous
waste under the US Resource Conservation and Recovery
Act (RCRA), and a Class 8 (corrosive) hazard throughout
United Nations (UN) participating countries use the UN
Globally Harmonized System of Classification and Labeling
of Chemicals (GHS), which is defined as substances that
can cause significant harm to living tissue and/or corrode
steel and aluminium upon contact. Spent caustic is also on
the Right to Know Hazardous Substance List cited by the
Occupational Safety and Health Administration (OSHA),
American Conference of Governmental Industrial Hygienists
PTQ Q2 2024 59
11/03/2024 14:36:41
 (ACGIH), Department of Transportation (DOT), National
Institute for Occupational Safety and. Health (NIOSH),
The National Fire Protection Association (NFPA), and
Environmental Protection Agency (EPA) – and is listed on the
Special Health Hazard Substance List.
Until the 1960s, most hazardous waste was dumped in
waterways, which caused pollution perilous to ecologies
and drinking water. Oil companies rectified the problem by
developing deep well injection sites to safely dispose of liq-
uids deep underground beneath aquifers to trap the liquid
waste under multiple impermeable layers of rock.
The severity of the effects of mismanaging spent caustics
is well documented.
In 2006, an oil trading company produced spent caus-
tic aboard a cargo ship that refined coker naphtha to mix
with gasoline to sell as fuel in the West African market. It
generated more than 500 cubic metres of toxic waste in
the ship’s waste tanks. After being turned away by several
countries, the company had the waste illegally dumped
in Côte d’Ivoire. Shortly afterwards, tens of thousands of
Ivorians suffered extreme health issues, and authorities
recorded 15 deaths – all of which caught the attention of
The goal of on-site treatment is
to neutralise the caustic, remove
impurities, and reduce both the
chemical oxygen demand and
biochemical oxygen demand
Amnesty International and Greenpeace.
In 2007, a spent caustic tank exploded in a major
Midwestern US refinery. The explosion occurred while the
operators were transferring spent caustic into the atmos-
pheric-relief cone roof storage tank that had been in service
since 1956. There were no injuries or fatalities, but property
damage was extensive enough to interrupt the spent caus-
tic disposal process. Unit operation was eventually restored
by commissioning an alternative, inherently safe, spent
caustic storage system.
Public policy solution
The OSHA, a department of the US Department of Labor,
requires chemical manufacturers, distributors, or importers
to provide applicable Safety Data Sheets to communicate
information and risks on hazardous materials. In 1974, US
refineries and petrochemical complexes were mandated
to treat spent caustic to prevent adverse environmental
impacts and meet environmental regulations.
The European Union (EU) developed a chemicals pol-
icy in the late 1960s that was regulated at the organisa-
tional level rather than within its 27 individual countries.
The policy was overhauled in 2007 with the launch of the
Registration, Evaluation, and Authorization of Chemicals
(REACH), which united chemicals regulation in Europe into
a single system.
60 PTQ Q2 2024
Q2 Merichem.indd 60
Canadian provincial governments play a role in the coun-
try’s environmental regulation, with the province of Ontario
leading in toxics reduction legislation. Its Toxics Reduction
Strategy helps protect the health and environment by
reducing toxic substances in air, land, water, and consumer
products. In 2009, the Ontario Legislature passed the Toxics
Reduction Act, the cornerstone of the Toxics Reduction
Strategy, which requires regulated facilities to track and
quantify toxic substances they produce and develop plans
to reduce their use and creation.
Although slower to adopt safety regulations compared to
the US, EU, and Canada, several other nations, including
Australia, China, Japan, New Zealand, and Singapore, are
instituting programmes and processes that ensure proper
compliance with safety and environmental policies.
There is also an extensive history of international col-
laboration on chemicals assessment and management,
resulting in binding conventions, such as the Stockholm
Convention, mandatory classification and labelling stand-
ards, and global chemicals institutions. Most notable is the
Inter-Organization Programme for the Sound Management
of Chemicals (IOMC), an international co-ordinating group
that promotes sound chemical management worldwide fol-
lowing the recommendations of the 1992 UN Conference
on Environment and Development (UNCED).
IMO 2020 was established in 2020 with regulations that
cap the sulphur content in marine fuels. It bans the use of
fuels with a sulphur content greater than 0.5% globally
to reduce sulphur emissions that are heavily produced by
standard variations of marine fuel. Refiners worldwide were
then required to produce higher volumes of IMO-compliant
low-sulphur fuel oil, including more valuable products like
marine gasoil and diesel.
A ripple effect of IMO 2020 was increased pressure
on the handling and disposal of spent caustics. The cost
of reclamation had begun to exceed the original cost of
materials, so most reclamation facilities were reconfig-
ured into disposal facilities. In the US, deep well injection,
which accounted for the disposal of more than 85% of toxic
wastes from refineries, was grandfathered into environ-
mental protection clauses. Deep well disposal was consid-
ered reasonably inexpensive and made disposal easy, but
environmentalists soon criticised the practice.
To avoid deep well injection, the toxic properties of spent
caustic must be removed sufficiently that it can be treated
in existing, above-ground, wastewater treatment facilities.
These facilities use biological oxidation to produce a treated
water effluent that is acceptable for discharge into water-
ways. Pretreating the spent caustic streams to remove their
most toxic components can sometimes require expensive
treatment technologies. The difficulty and cost depend on
the nature of the impurities.
Spent caustic treatment: Technical solutions
Spent caustic treatment technologies are deployed on-site,
eliminating the need to transport the spent caustic off-site
as waste to a treatment, disposal, or recycling facility.
The goal of on-site treatment is to neutralise the caustic,
remove impurities, and reduce both the chemical oxygen
www.digitalrefining.com
11/03/2024 14:36:41
 Steam, off-gas, nitrogen, PDC
air, water
Caustic
Sulphuric acid
Brine
Acid oils
LC
FC Scrubbing phase
Process separation
water
Oxidation
LC
TC
FC
Oxidation
air
TC
MP steam
Cooling water
FC
Spent
caustic
Figure 1 Spent caustic treatment system employing wet air oxidation
demand (COD) and biochemical oxygen demand (BOD). This
allows the treated brine to be sent to a wastewater treatment
facility for final polishing before release to the environment.
Treatment technologies typically utilise sulphuric acid,
atmospheric oxygen, nitrogen, fuel gas, electricity, steam,
and/or cooling water – all elements readily available at most
refineries. After treatment, a neutral pH, saltwater effluent
is produced that has minimal odour, presents no health
and safety issues, and is easily manageable in wastewater
treatment plants.
The most frequently used technologies include sim-
ple neutralisation, deep neutralisation, wet air oxidation
(WAO) and incineration. Although caustic neutralisation
and oxidation systems have been used for decades, their
seemingly simple processes are surprisingly complex. The
type and concentration of impurities affect the temperature
and pressure requirements, how many treatment steps are
required, the mixing and residence times for the reaction
and separation steps, and the selection of the metallurgy to
protect equipment from severe corrosion.
Simple neutralisation
Simple neutralisation is the most straightforward and least
expensive treating option for regenerated caustic streams
coming from light hydrocarbon streams such as LPG where
most of the toxicity and COD result from excess NaOH,
thiosulphate, and dissolved organics.
A simple acid, such as sulphuric or hydrochloric acid, is
added to the spent caustic to neutralise any free NaOH
remaining and drop the pH to an acceptable wastewater
discharge value, within the preferred range of 6-9, although
some publicly owned treatment works allow higher or
lower pH ranges. The acids are conveniently available and
add no COD to the treated brine. If the resulting sulphate or
chloride levels are too high, organic acids, such as formic or
acetic acid, can be substituted.
www.digitalrefining.com
Q2 Merichem.indd 61
PC
Off-gas
PC
Acid oils
FC FC
Nitrogen
Neutralisation
Cooling
AC LC
water Alkaline
solution
Fresh
FC AC Cooling caustic
water
Neutralised
brine
FC
M
Sulphuric acid
The simple neutralisation process is streamlined and
efficient. Spent caustic and acid are injected continuously
into a treatment unit, mixed, and then entered into a three-
phase separator. The acid flow is regulated by sensing the
pH of the released brine. Any acid gases or oils generated
by the reaction will separate. If necessary. to lower the COD
and odour, nitrogen or fuel gas can be added to strip away
dissolved acid gases.
When low levels of unregenerated sulphide, hydro-
sulphide, and mercaptide salts are present, a variation of
simple neutralisation adds a stripping column to the three-
phase separator where the nitrogen or fuel gas can effi-
ciently remove these dissolved acid gases. The degree of
removal of these dissolved acid gases is highly dependent
on the treatment pH, with a lower pH releasing more of
the gases. Where high levels of these impurities are pres-
ent, the pH must be lowered beyond the normal discharge
range, requiring the need for ‘deep neutralisation’.
Deep neutralisation
When spent caustic contains high concentrations of unre-
generated sulphides, mercaptides and organic compounds,
or the brine product specifications are more demanding,
deep neutralisation is utilised. This treatment method can
treat most sulphidic, phenolic, and naphthenic spent caus-
tics. ‘Deep’ refers to acidification of the spent caustic to a
low pH followed by re-neutralisation with caustic.
This process reconstitutes all the original acids that were
present in the treated hydrocarbon streams: sulphides,
mercaptides, and organic compounds, such as phenolics,
cresylics, and naphthenic acids. The organics form an oil
phase that separates from the brine. If deemed beneficial or
re-blended with another hydrocarbon stream, the organics
can be decanted for reclamation.
The deep neutralisation treatment system generally con-
sists of a low pH reactor, a three-phase separator, acid gas
PTQ Q2 2024 61
11/03/2024 14:36:43
 stripping, and re-neutralisation. As with simple neutralisa-
tion, sulphuric acid is added – except in excess – which is
needed to drive the pH to a low value to liberate the acidic
impurities. Any acid gases or oils liberated at the low pH
conditions separate in the three-phase separation drum.
If sulphide or mercaptide salts are present in significant
amounts, nitrogen or fuel gas is used to strip these away to
low ppm levels. The acidic brine is then re-neutralised back
to a neutral pH with fresh caustic. The effluent streams
become neutralised brine, a phenolic or naphthenic oil
phase, and an acid gas stream containing H2S and mer-
When treating high concentrations
of impurities, deep neutralisation has
the unique and distinct advantage
of utilising low temperature and
pressure operation
captans. If there is a significant acid gas stream, an amine
treater or Claus unit processes the H2S.
When treating high concentrations of impurities, espe-
cially sulphides and organics, deep neutralisation has the
unique and distinct advantage of utilising low temperature
and pressure operation, and it can recover the organics.
Wet air oxidation (WAO)
WAO is a well-established technology with great efficacy
for treating all spent caustic types. It is particularly suited
for high flow rate sulphidic caustic streams from ethylene
production plants.
WAO destroys impurities through oxidation. It converts
sulphides to sulphate and organic compounds to car-
bonate and low molecular weight carboxylic acids. During
the process, no acid gas is released, so the off-gas stream
contains mere traces of volatile organic compounds (VOC).
Highly coloured, malodorous liquors treated with wet air
oxidation become crystal clear and can be effectively man-
aged by a biological wastewater treatment system.
In the WAO process, hot caustic containing suspended
or dissolved pollutants is brought into contact with air at
elevated temperatures and pressures in a reactor unit.
The molecular oxygen dissolved in the caustic becomes
an oxidising agent that causes a chain reaction of free rad-
icals formed from organic and inorganic compounds in the
reaction mixture (see Figure 1). The organic pollutants are
mineralised or converted into biodegradable substances,
and the inorganic compounds are degraded.
The degree of oxidation hinges on the compound, the
reactor residence time, and the prescribed temperature
and pressure. Upon withdrawal from the reactor, the off-
gas separates from the oxidised caustic and flows to a
downstream incinerator. The oxidised caustic then flows to
a neutralisation system where sulphuric acid is added to
bring the pH within a desired final range, yielding a neutral
brine and off-gas (see Figure 2).
A very small number of providers offer WAO with varying
techniques and efficacy, with temperature being the most
critical variable in WAO system design. As the temperature
rises, there is a higher degree of oxidation. WAO reactor
temperatures range from as low as 100°C to as high as
320°C, with pressures ranging from 5 barg up to 120 barg.
The temperature and pressure selected depend on the feed
type and the product specifications required. Most sulphidic
systems operate in the middle of the range at 200°C and
30 barg, where all sulphides are fully oxidised to sulphate.
High-temperature systems (260-320°C) are applied where
organics such as phenolics, naphthenic acids, and amines
are prevalent. Although amines are difficult to oxidise, at
290°C and higher they are partially destroyed, depending
on the amine type.

PC

HP steam Oxidation

O2
PC AC
FC
M TC FC Off-gas
Spent
caustic
FC
M

Air Gas/liquid Sulphuric acid

Cooling separation
water M

Neutralisation
LC

Steam, air, off-gas LC

Caustic
AC Cooling water
Oxidised caustic
pH
Acid
Brine Neutralised brine

Figure 2 Merichem Mericon II spent caustic treatment system employing wet air oxidation

62 PTQ Q2 2024 www.digitalrefining.com

Q2 Merichem.indd 62 11/03/2024 14:36:48


Acid
FC pH
AC
M
Acid
Steam or
electric
heater
FC
Spent
caustic
FC
Spent
caustic
FC
Process
water
Figure 3 Mericon spent caustic neutralisation system featuring adjustable PH technology
Incineration
Incineration is another treatment method that can dispose
of all spent caustic impurities, including the most heat-
resistant compounds, such as amines. For these impurities,
only an exceedingly high flame temperature can catalyse
the oxidation. Fuel requirements for incineration are high,
resulting in high operating costs to maintain the flame as
atomised caustic is injected. Incineration is waste- and
facility-specific and can be problematic when treating high
total dissolved solids content.
Sustainable management option: Beneficial reuse
In its 2010 Petroleum Refining Operations Best Practice
Series, Ipieca, the global oil and gas association for environ-
mental and social issues, recommended companies explore
the possibility of spent caustic being sold to an adjacent
industry. In 2010, the Council of Australian Governments
endorsed a 10-year policy to produce less waste for dis-
posal, and manage waste as a resource to deliver economic,
environmental, and social benefits. The National Waste
Policy included reuse.
Beneficial reuse, which is defined by the EPA as reusing
a waste material that would otherwise be discarded in a
manner that makes it a valuable commodity, had already
been in practice for refineries when those reports were
made public.
When spent materials are beneficially reused without
reclamation, they become exempt from solid-waste require-
ments and are categorised as a product under US EPA reg-
ulations. Facilities can reuse byproducts or waste materials
in their own operations or send them elsewhere for reuse
as a fuel or substitute raw material in place of feedstock.
The lifecycle of the caustic is extended and creates an asset
from what may otherwise be perceived as a liability.
Beneficial reuse fits within the Guiding Principles of the
www.digitalrefining.com
Q2 Merichem.indd 63
PC
Off-gas to
incinerator
FC
Fuel gas
Oil or nitrogen
LC
Brine LC
M
Acid oils to
CWS refinery
pH
AC
FC
Neutralised
caustic
American Chemistry Council’s Responsible Care initiative
and reduces the need to harvest new raw materials, saves
energy, and reduces greenhouse gas emissions that con-
tribute to global climate change.
Conclusion
More than 80% of the global sulphur supply is extracted
from fossil fuels as waste. In the 1970s and 1980s, it
became clear that sulphur caused environmental and health
issues. Sulphur regulations were enacted, creating require-
ments for oil and gas companies to measure and reduce
sulphur content. Fortunately, oil and gas producers seized
the opportunity to address emissions through a series of
ready-to-implement and cost-effective sulphur reduction
technologies and techniques.
As the world races to meet net zero goals, the oil industry
is embracing the complexities of managing climate change
strategies and ESG (environmental, social, and governance)
performance while bridging the trust gap between indus-
try and society. The demand for adaptable sulphur recovery
solutions will increase.
The effective implementation of sustainable practices
aligned with corporate policies and processes will ensure
the integration of best practices for safely treating and
managing spent caustics. It is a clean demonstration of the
industry’s commitment to health, safety, the environment,
and social responsibility.
Richard G Stambaugh is Technology Manager – Liquid Treating at
Merichem Technologies, USA. He is responsible for integrating new
technologies into Merichem’s portfolio and improving existing technol-
ogies. He acts as liaison between sales, technical services, and process
engineering groups and helps cross-train other engineers. He holds a
Bachelor’s degree in chemical engineering from Texas Tech University
and an Associate degree in chemistry from Amarillo College.
PTQ Q2 2024 63
11/03/2024 14:36:49
 WHEN YOU SEE ARIEL,
you know your operation is built for unequaled reliability and environmental
sustainability. Our compressors go the distance, just like our people.
You can’t spell reliable without Ariel.

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064_Q2_Ariel Corp.indd 1 11/03/2024 11:29:25

 Optimising compressor dry gas seal
line design in FEED stage
A proactive approach to engineering excellence is presented by a strategic initiative
to enhance the design of compressor dry gas seal lines within FEED deliverables
Rajib Talukder
Saudi Aramco
L
everaging a rich pool of expertise from pre-commis-
sioning and commissioning phases, this initiative is
an effort to elevate front-end engineering design
(FEED) processes. It highlights the importance of a proactive
approach to design and standardisation, ensuring engineer-
ing solutions are robust and efficient from the start.
The narrative explores the process of revisiting and refin-
ing FEED deliverables, leveraging the author’s experience
in spearheading a FEED standardisation initiative within
a distinguished engineering firm. This initiative aimed to
streamline FEED deliverables by integrating the extensive
knowledge and expertise of the engineering community.
Optimising compressor dry gas seal (DGS) line design dur-
ing the FEED stage is crucial for several reasons:
• Reliability and performance: Proper design optimisation
ensures that the DGS system operates reliably and effi-
ciently. This is essential for maintaining the performance of
the compressor and avoiding unplanned downtime.
• Safety: A well-designed DGS system enhances safety by
minimising the risk of seal failure and gas leakage. Safety is a
critical consideration in the oil and gas industry, and a flawed
design could lead to hazardous situations.
• Environmental compliance: Efficient DGS systems help in
minimising fugitive emissions, contributing to environmental
compliance. Reducing leaks and emissions is essential for
meeting environmental regulations and sustainability goals.
• Operational costs: Optimisation in the FEED stage can
lead to cost savings during the operational phase. A well-de-
signed system may require less maintenance, resulting in
reduced operational and maintenance costs over the lifespan
of the compressor.
• Energy efficiency: Properly designed DGS systems con-
tribute to the overall energy efficiency of the compressor.
This can lead to lower energy consumption and reduced
operating costs.
• Long-term asset integrity: The design decisions made
during the FEED stage have a long-term impact on the
integrity of the compressor and associated equipment. A
well-optimised design helps in preserving the integrity of
assets, extending their operational life.
• Compliance with standards and codes: Adhering to
industry standards and codes is essential for ensuring the
reliability and safety of the compressor system. Design
www.digitalrefining.com
SAUDI ARAMCO.indd 65
optimisation in the FEED stage ensures that the system
aligns with relevant standards and codes.
• Early issue identification: Identifying and addressing
potential design issues early in the project life cycle is more
cost-effective than making corrections during the detailed
engineering or operational phases. FEED stage optimisation
allows for early issue identification and resolution.
• Ease of operation: A well-optimised design makes the
compressor system easier to operate and maintain. This is
important for the personnel managing the equipment, as
it reduces the complexity of operation and maintenance
procedures.
In summary, optimising compressor DGS line design
during the FEED stage is critical for achieving reliability,
safety, environmental compliance, and cost effectiveness
throughout the lifecycle of the compressor system. It allows
for proactive decision-making and sets the foundation for a
well-performing and efficient facility.
Key insights were gained from the collective experience
in pre-commissioning and commissioning, particularly in
enhancing compressor deliverables through modifications
in FEED documentation. Two primary recommendations
emerged:
 P&ID note enhancement
It was proposed to include a specific note on the compres-
sor’s piping and instrumentation diagram (P&ID) concerning
the seal gas line. This note would emphasise the importance
of minimising pockets, ensuring proper slopes, and providing
adequate heat tracing and insulation. The goal is to maintain
temperatures above the dew point, thereby pre-empting the
need for modifications during the engineering, procurement,
and construction (EPC) phase, which could lead to change
orders.
 Compressor datasheet improvement
Another recommendation focused on the compressor data-
sheet, suggesting the inclusion of precise dew point values
or graphs. This contrasts with the more generic directive
of maintaining temperatures ‘20°C above the dew point’.
Providing EPC contractors with specific, actionable infor-
mation from the outset is intended to facilitate a smoother
project execution.
PTQ Q2 2024 65
11/03/2024 14:47:24
 Dew point estimation for recycle gas compressor-DHT
Quoted liquid carryover from the various types of mist extraction devices are
usually in the range of 0.1-1 gal/MMscf. Ref GPSA Chapter 7 Separator Sealgas PIPE-100
RGC Discharge To Seal
RGS out
Ex HP amine Amb Cool
RGC Suc TEE-100

MIX-114 Comp Dis & Seal DE Spread sheet-1

SAT-100 QRGC
Sat Watr
RGC Suc RGC Discharge
Entrained Watr HC dew point 58.56 C RGComp HC dew point 62.97 C
Water dew point 70.00 C Water dew point 75.05 C

RT Dew Point
RGS Out Ex HP Amine Entrained WTR RGC Suc RGC Discharge Sat Watr CompDis& Seal DE Sealgas To Seal
Vapour fraction 1.0000 1.0000 0.0000 0.9999 1.0000 0.0000 1.0000 1.0000 0.9966
Temperature C 70.00 70.00 70.00 70.00 95.40 70.00 95.40 95.40 60.22
Pressure bar_g 49.00 49.00 49.00 49.00 60.00 49.00 60.00 60.00 57.40
Molecular weight 3.788 3.877 18.02 3.878 3.878 18.02 3.878 3.878 3.878
Mass flow kg/h 20,834.72 21,456.72 10.00 21,466.72 21,466.72 622.01 21,294 171.73 171.73
Phase comp mass flow (overall-H2O) kg/h 0.00 622.01 10.00 632.01 632.01 622.01 626.95 5.06 5.06
HC dew point 59 59 <empty> 59 63 <empty> 63 63 62
Water dew point <empty> 70 264 70 75 264 75 75 74

Figure 1 Hysys output for compressor.

However, these suggestions were perceived as exceed-
ing the traditional scope of FEED, which typically deals with
pipeline sizes of 4in and larger. The consideration of details
for a DGS line, which is only 1in in diameter, was viewed
as overly granular for the FEED stage. The argument was
that detailing such specifics in the datasheet might unduly
prolong FEED activities, with these aspects being more
appropriately addressed during the EPC phase.
While reviewing the EPC deliverables for a diesel hydro-
treater (DHT) recycle gas (RG) compressor, the author, draw-
ing upon extensive experience in project oversight, identified
critical areas of improvement. This analysis aimed to ensure
that the design and operational integrity of the compressor
system met the highest standards of efficiency and relia-
bility. The following sections detail specific observations
made during the review, an analytical process undertaken to
understand the implications of these findings, and mitigation
measures adopted to address these gaps effectively.
Dry gas seal line arrangement
Findings: The review of EPC deliverables for a DHT recycle
gas compressor revealed significant gaps in the DGS line
arrangement:
• The 1in seal gas line lacked tracing and insulation, a devi-
ation from the vendor’s P&ID, which showed tracing and
insulation post-seal gas filters.
• EPC P&ID documentation failed to specify the need for
sloping the 1in line back towards the tapping point.
• Additionally, the EPC contractor’s approach to dew point
temperature, set at 70°C based on compressor suction from
Compressor suction and discharge dew points
Compressor
suction
Hydrocarbon dew point (°C) 59
Water dew point (°C) 70
an RG gas scrubber treated with lean amine solution, was
identified as a key area of concern.
Analysis: The analysis commenced with the FEED contrac-
tor’s recommendation, anchored in API-692 guidelines,
which was added to the compressor mechanical datasheet.
This recommendation emphasised the need for the seal gas
line to be traced and insulated, potentially incorporating a
heater to maintain the temperature at least 20°C above the
dew point of the seal gas. The EPC contractor was then
tasked with carrying out detailed dew point calculations at
the compressor discharge, from where dry seal gas tapping
is taken.
The results from the Hysys simulation were pivotal in
understanding the dew point dynamics of the DGS system.
The Hysys simulation result shows the dew points of the
dry gas, as seen in Table 1.
Simulation output (see Figure 1) coupled with consider-
ations for entrained water, as per GPSA Chapter 7 recom-
mendations, called for a comprehensive analysis. The RG
compressor’s upstream knock-out drum (KOD) is equipped
with a demister to enhance gas purity.
A critical finding from the analysis was the gap between
the compressor discharge temperature (95°C) and the
water dew point (75°C). Heat loss calculation indicated a
significant risk of temperature drop in the DGS line, poten-
tially down to 60°C at the filter inlet. The analysis of heat
loss, considering ambient temperatures ranging from 21°C
to 30°C and wind speeds varying from 3 to 15 m/s, empha-
sised the considerable effect of wind velocity on heat dissi-
pation. This significant relationship is depicted in Figure 2.
Mitigated measure: In response to the comprehensive
Compressor analysis, the EPC contractor agreed to trace and insulate
discharge the DGS line, aligning with the detailed dew point and heat
63 loss calculations.
75

Absence of gas conditioning system for dry gas seal

Table 1 Findings: The review identified that the current system

66 PTQ Q2 2024 www.digitalrefining.com

SAUDI ARAMCO.indd 66 11/03/2024 14:47:26

zeeco.indd 1 11/03/2024 11:30:57
 with the necessary control systems, would require a signif-
Heat loss for 1in bare piping at different ambient temp and wind velocity icant investment.
700
Mitigation: Considering the risk of water cooler leakage and
600
the associated costs for a gas conditioning system, it has
Heat loss (W/m)

15 m/s
500 been decided to maintain the tracing temperature at 120°C.
400
9 m/s This approach ensures the dry gas temperature remains at
least 45°C above the dew point, effectively achieving a sim-
300
3 m/s ilar outcome to that of a gas conditioning system.
200

100
20 21 22 23 24 25
Ambient temperature (˚C)
3 m/s 6 m/s 9 m/s
Figure 2 Heat loss (w/m) in relation to wind speed (m/s)
and ambient temperature (°C).
lacked a gas conditioning system, as recommended by
API-692. The EPC contractor expressed concerns about
installing such a system, citing potential impacts on the pro-
ject’s schedule and cost. Additionally, the requirement for
a gas conditioning system was not explicitly stated in the
FEED deliverables, contributing to the decision against its
implementation.
Analysis: A gas conditioning system typically involves
cooling the gas to condense out water and hydrocarbon,
separating the condensed liquid, and then reheating the
dry gas. The proposed configuration would ensure that
the temperature across the heater raises the gas to at least
above the compressor discharge temperature, thereby
maintaining a substantial margin above the dew point.
The dew point improvement observed is at least 45ºC, as
depicted in Figure 3. Nonetheless, there is a risk of cooling
water leakage from the cooler, which could affect dry gas
quality. Implementing a cooler, separator, and heater, along
Dry gas filter set-up
26 27 28 29 30 Findings: During the evaluation of the compressor sys-
tem’s components, it was discovered that the vendor had
12 m/s 15 m/s not incorporated a separator downstream of the seal gas
filter. This omission meant that any liquid accumulating
within the filter could only be removed by isolating the fil-
ter, and the filter is isolated when the differential pressure
is high.
Analysis: The absence of a separator posed significant
operational challenges. The filter’s small size and the pres-
sure differential across it meant that detecting and remov-
ing liquid entrainment effectively was problematic. Liquid
that condenses and settles at the bottom of the filter can-
not be adequately measured or separated from the seal gas
under these conditions. This situation could lead to opera-
tional inefficiencies and potential damage to the DGS due
to the presence of liquid in the gas stream.
Mitigation: To address this critical gap, negotiations with
the vendor led to an agreement to install a separator on
the filter drain line. This addition is designed with capabil-
ities for proper liquid level detection and a draining option,
significantly enhancing the system’s ability to manage and
remove entrained liquids. The implementation of a separa-
tor ensures that the DGS operates under optimal conditions
by minimising the risk of liquid contamination.

Dew point estimation for gas conditioning system-DHT

Quoted liquid carryover from the various types of mist extraction devices are Heating
usually in the range of 0.1-1 gal/MMscf. Ref GPSA Chapter 7 Separator
WC cool Sel Gas V To Dry
Sealgas E-101 Gas Seal
RGC Out
RGS out Cooler Out
Ex HP amine E-100 V-100
RGC Suc TEE-100

Comp Dis & Seal DE Seal Gas L

SAT-100 MIX-114
Sat Watr
RGC Suc RGC Out Sel Gas V
QRGC
Entrained Watr HC dew point 58.56 C RGComp HC dew point 62.97 C HC dew point 50.00 C
Water dew point 70.00 C Water dew point 75.05 C Water dew point 49.99 C

RT Dew Point
Ex HP Entrained CompDis To Dry
RGS Out Amine WTR RGC Suc RGC Out Sat Watr & Seal DE Sealgas Cooler Out Sel Gas V Seal Gas L Gas Seal
Vapour fraction 1.0000 1.0000 0.0000 0.9999 1.0000 0.0000 1.0000 1.0000 0.9927 1.0000 0.0000 1.0000
Temperature C 70.00 70.00 70.00 70.00 95.40 70.00 95.40 95.40 50.00 50.00 50.00 95.00
Pressure bar_g 49.00 49.00 49.00 49.00 60.00 49.00 60.00 60.00 60.00 60.00 60.00 60.00
Molecular weight 3.788 3.877 18.02 3.878 3.878 18.02 3.878 3.878 3.878 3.552 48.14 3.552
Mass flow kg/h 20,834.72 21,456.72 10.00 21,466.72 21,466.72 622.01 21,294.99 171.73 171.73 156.15 15.59 156.15
Phase comp mass kg/h 0.00 622.01 10.00 632.01 632.01 622.01 626.95 5.06 5.06 1.60 3.45 1.60
flow (overall-H2O)
HC dew point 58.60 58.56 <empty> 58.56 62.97 <empty> 62.97 62.97 62.97 50.00 193.5 50.00
Water dew point <empty> 70 263.9 70.37 75.05 263.9 75.05 75.05 75.05 49.99 244.4 49.99

Figure 3 Hysys output for gas conditioning system

68 PTQ Q2 2024 www.digitalrefining.com

SAUDI ARAMCO.indd 68 11/03/2024 14:47:32

 Start-up seal gas arrangement
Findings: In the review of the compres-
sor system set-up, it was identified
that make-up hydrogen is employed
as a back-up seal gas for the start-up
phase, with procedural controls
intended to shut this make-up hydro-
gen line during regular operations.
This make-up hydrogen, delivered at a
substantially higher pressure than the
compressor discharge, originates from
a make-up gas compressor, which is
generally a lubricating type recipro-
cating machine.
Analysis: Concerns were raised with
the EPC contractor regarding the
operational risks linked to the make-up
hydrogen line. It was highlighted that if
operators fail to close this line by mis-
take, the make-up hydrogen, despite
its very low dew point, contains lubri-
cant oil, presenting a contamination
risk to the DGS system.
The make-up hydrogen’s movement
at a speed of 60 m/s, typical for gas
velocity within piping systems, signif-
icantly increases the likelihood of the
entrained lube oil being aerosolised.
This high-speed gas flow can mechan-
ically fragment the oil into extremely
fine droplets, which may then be con-
veyed as an aerosol through the DGS
filter. The potential for these aerosol
particles to be smaller than 1 micron,
the size for which the seal filter is
designed, poses a direct threat to sys-
tem cleanliness and functionality.
Mitigation: To address this issue,
a decision was made to enhance
the system’s control mechanisms.
A pressure control valve (PCV) was
introduced alongside the procedural
controls. This PCV is set to activate at
a pressure lower than the minimum
discharge pressure of the compres-
sor, ensuring the make-up hydrogen
line is automatically sealed off when
not needed. This additional layer of
control significantly minimises the risk
of operator error and the subsequent
contamination by lubricant oil.
Conclusion
The extensive discussions and negoti-
ations, while crucial, have underscored
the significant potential costs in terms
of both project schedule and budget.
www.digitalrefining.com
SAUDI ARAMCO.indd 69
This experience highlights the value of
adopting a conservative approach in
the FEED deliverables for compressor
systems. It is evident that incorporat-
ing specific considerations and rec-
ommendations at this early stage can
lead to substantial long-term benefits
and cost savings. To this end, the fol-
All from
lowing measures are recommended
for inclusion in FEED deliverables
related to centrifugal compressors:
one
• P&ID specifications: It should be
explicitly noted that the seal gas line
Source!
must be designed to minimise pockets
and ensure a slope back to the tapping
point from its highest point, with heat
tracing and insulation to maintain the
temperature well above the dew point.
• Compressor datasheet enhance-
Fast Delivery
ments: The datasheet should include
a dew point curve as illustrated in Worldwide
Annex-B of API-692, providing clear
guidelines for managing temperature
and condensation risks. Duranit®
Catalyst Support
• External source dry gas use: When
Material
dry gas is sourced externally, the data-
sheet and P&ID must highlight that it
Support Plates /
should not preferably be sourced from Grids
any lubricating type of compressor.
If such gas is utilised, its use should Droplet Separators /
be confined to start-up phases only, Demisters
controlled through a pressure control
valve to mitigate risks of contamina- Feed Devices:
tion during normal operation. Gas / Liquids
Implementing these proactive meas-
ures at the FEED stage could poten- Liquid Distributors /
tially result in significant cost savings Collectors
for a DHT unit for each shutdown.
Random Packings
Each shutdown event, triggered by
- Ceramic
liquid condensation in the dry gas
- Metall
seal, can lead to the tripping of the RG
- Plastic
compressor and result in a production
downtime of up to 72 hours for the Software and
DHT unit. Therefore, these recom- Consulting
mendations not only aim to enhance
operational reliability and efficiency www.vff.com
but also significantly contribute to the
overall economic performance of the
project.
Please
Rajib Talukder is a Process Specialist in visit us in
Aramco’s Global Manufacturing Excellence
Hall 4.0
department, with more than 30 years of expe-
rience in process engineering activities work-
Stand F66
ing on numerous projects around the world.
He is a chemical engineer who graduated from
NIT Tiruchirappalli, India. Vereinigte Füllkörper-Farbriken GmbH & Co.KG
P. O. Box 552, 56225 Ransbach-Baumbach,
Email: rajib.talukder@aramco.com Germany, +49 26 23 / 895 - 0, info@vff.com
PTQ Q2 2024 69
14/03/2024 11:56:20
 PAC-Petchem_PTQ-Print-Ad.pdf 3 3/11/2024 10:22:15 AM

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PAC.indd 1 11/03/2024 16:26:51

 Integrating refining/petrochemicals
for increased chemicals production
Case study of HMEL’s refinery and petrochemical integrated complex
Narendra Verma
HMEL (HPCL-Mittal Energy Ltd.)
P
etrochemicals are expected to be the largest driver
of world oil demand growth, surpassing gasoline
or diesel by 2030.1 Integrating refining and petro-
chemicals increases the gross refining margin (GRM) from
value-added products produced by petrochemical units.
In addition, advantages such as feed security and reliable
petrochemical units facilitate the blending of petrochemical
byproducts into refinery fuel products, leading to lower cost
of conversion and reduced Opex due to shared utilities, ser-
vices, and infrastructure.
Major refining and integrated oil and gas players reconfig-
uring their plants to maximise more petrochemicals, rather
than just fuel, can extract more value from new products
rather than just augmenting the existing product slate.
While standalone refineries are gradually exploring inte-
gration opportunities with petrochemical complexes, new
refineries should feature such integration from the start. The
extent of integration depends on technical feasibility and the
resulting economic benefits. This is a complex discussion
and requires further detailed study on a case-by-case basis.
On the one hand, the energy transition will reduce
demand for oil products due to hybrid and energy-efficient
vehicles, along with switching from fossil fuels to renewa-
bles and carbon footprint minimisation. On the other hand,
it increases opportunities to capture the growing demand
for petrochemicals. Forward-looking refiners are already
looking for opportunities to adjust or modify their produc-
tion modes to capture growing demand for petrochemicals,
such as by increasing output of naphtha, propylene, and
reformate. Against this backdrop, a case study of HMEL’s
refinery and petrochemical integrated Bathinda complex is
reviewed.
The Bathinda base refinery has a capacity of 9.0 MMTPA
and 5% crude oil-to-chemicals processing capability.
Integration with a new petrochemical complex comprising a
steam cracker and downstream polymer block will increase
this to 20%. Moreover, plans to increase chemicals to 25%
include diesel cracking as one option besides fuel gas, naph-
tha, LPG, and kerosene as feed to the cracker.
Existing refinery challenges
Analysts forecast that the world’s energy transition will soon
peak in the use of oil-based fuels, followed by a decline. The
transportation sector is at the forefront of this trend, with
total global demand expected to peak in the next one to two
www.digitalrefining.com
Q2 HMEL.indd 71
years and then gradually decline. Gasoline will experience
the greatest impact because it is primarily used for light-
duty passenger vehicles, and the market for these vehicles
is shifting toward electric.
In contrast, demand for petrochemical feedstocks will
continue to grow. The major oil-derived petrochemical feed-
stocks are ethane, liquid petroleum gas (LPG), and naphtha.
These are primarily used in the production of polymers for
plastics, synthetic fibre, and other petrochemical intermedi-
ates. Demand for these products will continue to grow with
rising global wealth.
These two developments pose a dual challenge for the
world’s 600 plus refiners. Lower overall demand means
less need for refining capacity. At the same time, remaining
refining capacity must evolve to match a shift in product mix
to meet petrochemical demand. Refiners will need to find
ways to make much less gasoline, marginally less diesel,
and more jet fuel and petrochemical feedstocks.
The world’s refiners must fundamentally rethink how
refineries are designed and operated. Globally, refiners have
the capacity to process nearly 100 million barrels of crude
oil per day. As global demand declines, refinery utilisation is
expected to drop in the key markets of Western Europe and
Asia. By the middle of this decade, utilisation in those mar-
kets could drop from the current rate of 85% to percentages
in the low 70s.4 Refinery utilisation in North America will
be slightly stronger due to location advantages for export
markets and crude supply. However, all markets will see a
significant contraction in profit margins due to the general
decline in utilisation.
Overall, the drop in utilisation and profitability could
result in capacity closures that will affect the least efficient
plants and those less able to adapt to new demands. This
scenario leaves most current plants operating but with
growing pressure to adapt to new conditions despite nar-
row margins and decreased cash flows to fund changes. As
demand declines for traditional refined crude oil products,
refiners and chemical companies should consider how to
take advantage of the growing oil-to-chemicals opportu-
nity. To develop the right strategy, refiners and chemical
incumbents will have to reflect on their current strengths,
capabilities, and positioning.
Internal competition for higher GRM due to uncertainty in
product cracks, fluctuating crude oil prices, and the geopo-
litical situation remains challenging. Also, stricter emission
PTQ Q2 2024 71
11/03/2024 14:50:18
 16000 10000
Ethylene capacity Propylene capacity
14000 Production Production
8000
Demand Demand
12000
Deficit Deficit

10000 6000

8000
4000
6000

4000 2000

2000
0

18
15
14

16

17

19

20

21

22

23

24

25
0

20
20
20

20

20

20

20

20

20

20

20

20
18
15
14

16

17

19

20

21

22

23

24

25
-2000
20
20
20

20

20

20

20

20

20

20

20

20
Figure 1 India – ethylene/propylene capacity vs total downstream demand2

norms have been regulating refinery processes. Today, most switching from one strategy to another as profit margins
brownfield projects are solely driven by these regulations. change. Figure 1 shows a huge gap between ethylene and
While costs are associated with these projects for improving propylene production (installed capacity) vs demand in India,
fuel quality, only a small fraction can be recovered from fuel which calls for petrochemical capacity additions.
product price hikes. Besides, market demand and new tech- When considering the projected strong demand for pet-
nologies are setting a platform for refineries to integrate with rochemical products in India (vs installed capacity), Table 1
petrochemical units to generate more value-added products. shows that by 2025/2030, there will be a shortfall in demand
by as much as 8/31.8 MMTPA (vs installed capacity).3
Petrochemicals industry status
Petrochemicals will likely remain the mainstay of all industrial Major challenges
and consumer-based products consumed by the world daily. Major petrochemical industry challenges in India include:
To maintain sustainable profitability, the refinery of the future • Lack of advantageous feedstock, like ethane and pro-
must respond quickly to challenging market conditions, pane, due to limited gas production. India still imports 55%
of required feedstocks and depends upon other
Future petrochemical demand in India countries.
• Surpluses that include ‘scattered’ liquid feed-
S.No. Product Nameplate Demand Shortfall Demand Shortfall
stock, like naphtha and kerosene. Currently, there
capacity 2025 2025 2025 2030 2030
10,048 4,233 13,701 7,886
is no common pool.
1 Polypropylene 5,815
2 LLDPE 2,275 4,154 1,879 5,853 3,578 • Alternate route via gasification demands high
3 HDPE 2,735 4,155 1,420 5,466 2,731 Capex.
4 PVC 1,550 5,147 3,597 6,573 5,023 • High utility and fuel cost; even fuel is required
5 MEG 1,919 3,249 1,330 3,969 2,050 for generation of utilities.
6 Formaldehyde 1,339 1,960 621 2,580 1,241 • Non-allocation of depleting domestic gas, and
7 PX 5,565 5,333 (-232] 6,378 813
there is no new allocation of reservoirs.
8 PTA 7,180 7,910 730 9,620 2,440
• Logistics, especially for cryogenics and natural
9 Butadiene 532 411 (-121] 568 36
10 LOPE 615 1,291 676 1,652 1,037 gas liquid (NGL), currently through ships only.
11 Acetic acid 215 1,256 1,041 1,442 1,227 • Plastic disposal remains a major concern since
12 PET 1,756 1,701 (-55) 2,320 564 it is not biodegradable. There is a need to educate
13 Styrene 0 899 899 1,082 1,082 people, and more effort is required to recycle the
14 Polyether polyol 70 401 331 496 426 waste.
15 Butyl acrylate 180 326 146 413 233
16 LAB 530 734 204 791 261
17 Glycol ethers 0 23 23 31 31 Shortfall MMTPA Shortfall MMTPA
18 Propylene glycol 20 110 90 134 114 Yr 2025 Yr 2030
19 Ethanolamine 30 128 98 170 140 • Commodity 11.7 • Commodity 23.2
20 EPR 30 69 39 90 60 • Niche 6.3 • Niche 8.6
21 Phenol 282 608 326 710 428 • Total 18.0 • Total 31.8
22 Acetone 182 247 65 268 86
23 Hexene-1 0 16 16 31 31 Estimated domestic demand of 25 major petrochemicals
24 Polycarbonate 0 195 195 242 242 products is 50 MMTPA and 65 MMTPA respectively in
25 SAP 0 55 55 71 71 years 2025 and 20303

Table 1

72 PTQ Q2 2024 www.digitalrefining.com

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073_Q2_Valmet.indd 1 11/03/2024 11:33:22

Butadiene
Styrene
PX
Toluene
Benzene
Propylene
Ethylene
Gasoline
Ref. Naphtha
Crude oil
0.5 1 1.5 2 2.5
Figure 2 Prices relative to naphtha: Key driver for integration
Integrating refineries with petrochemicals
Capturing more value from new products, rather than just
augmenting the existing product slate, is the way to go
for future revamps. Figure 2 depicts the prices of various
products relative to naphtha as a key driver for refinery and
petrochemical integration. This improves the GRM by add-
ing more value-added products produced by petrochemical
units.
Some of the other key drivers for refineries to integrate
with petrochemicals include:
• Paradigm shift with respect to integrated refinery/petro-
chemical complexes to hedge cyclic downturns and risks.
• Projected strong demand arising in petrochemical prod-
ucts in India vs installed capacity.
 By 2025/2030, shortfall in demand by 18/31.8 MMTPA
vs installed capacity.³
 Per capita consumption of petrochemicals in India is
lower (10 kg compared to global average of 34 kg).4
• Probable drop in future fuel oil demand due to energy-
efficient vehicles, hybrid vehicles, switch from fossil fuels to
renewables, and carbon footprint minimisation.
• Existing operating refineries have advantages for feed
security and reliability for petrochemical units.
• Leveraging refinery intermediate streams (naphtha, kero-
sene, LPG, and refinery fuel gas) as advantage feeds to the
petrochemical complex.
• Blending of petrochemical byproducts into refinery fuel
products, leading to lower cost of conversion.
• Demographic advantage for India as a low-cost manufac-
turing hub.
• Energy savings in well-integrated hydrocarbon
processing.
• Reduced Opex due to shared utilities, infrastructure, and
shared services, such as engineering, maintenance, pro-
3 curement, laboratory, HSE, security, HR, and admin.
Integration of a refinery and petrochemical complex
implies identifying synergies and optimising them for oper-
ational and economic gains. Figure 3 shows a typical inte-
grated petrochemical complex flow scheme.
The integrated complex provides optimum and better
return on investment (ROI) by capturing more value. Refinery
and petrochemical complexes can typically be integrated as:
• Refinery integrated with a steam cracker to produce eth-
ylene, propylene, and other derivatives.
• Refinery integrated with an aromatics complex to pro-
duce benzene, toluene, and xylene.
• Refinery integrated with an aromatic complex and a
steam cracker.
The extent of integration between any of these depends
on technical feasibility and the resulting economic benefits.
This is a complex discussion and requires detailed study on
a case-by-case basis.
Many refiners are considering shifting away from primar-
ily refining crude into fuels and are instead looking to refine
crude into chemicals, though few have begun the transi-
tion in earnest. Part of the challenge is that there is a wide
array of approaches, and they all require significant capital
investment. We see three ways for players to increase the
petrochemical yield of refinery operations: change individual
process units, change the mix of process units, or build more
direct crude-to-chemicals plants.

Butene-1
LLDPE/HDPE
Ethylene

Alpha Alpha
olefins alcohol
HDPE

Ethylene Ethylene
Off-gases oxide glycol
Cracker Poly-
Propylene propylene

Mixed C4 1, 3 Butadiene Cumene/

BdEU PBR bisphenol/
LPG
epoxy resins
C4 raffinate MTBE MMA/PMMA
C5+
Naphtha
Refinery Styrene
PBR
recovery unit
Kero/diesel C6 fraction
BzEU Benzene
PGHU
C6 raffinate C7/C8
C9+
Diesel pool
CBFS

Figure 3 Typical integrated petrochemical complex flow scheme

74 PTQ Q2 2024 www.digitalrefining.com

Q2 HMEL.indd 74 11/03/2024 14:50:22

 MS Block (NHT/ISOM/CCR) LPG
Design
(1300/525/550)
Crudes H2
AH: Doba CDU/VDU Licensor - Axens
2 x 44 HTAS PP
AM 11300
Designer – EIL DHDT 4340
Revamp - Technip Licensor - Axens Naphtha
PPU
2 x 220 + 3rd reactor
VGO HDT 3650 Licensor - Novolene BS-IV gasoline
Licensor - Axens Revamp - EIL
Revamp - EIL
Kerosene/
DCU 2700 ATF/MTO
Licensor - ABB Off-gases
PFCC 2700 SRU Block
Licensor - Shaw (Technip) BS-IV diesel
(ARU/SWS/SRU)
CPP 2 x 375 TPD
(GT/HRSG) Revamp - EIL Coke

Figure 4 HMEL refinery capacity at 11.3 MMTPA

Refinery block Petrochemical block

LPG
LPG LLDPE/ (Refinery)
MS Block
HDPE swing
Naphtha
CDU/VDU Ethylene unit HD/LLD-PE
11300 Kero (Petchem)
DHDT HDPE unit
PP
Butene-1 (Refinery +
unit Petchem)
VGO PPU Cracker +
Propylene
HDT fractionation PP unit Gasoline
(Refinery)
Benzene
DCU
Kero/ATF
FCC HPG (Refinery)
Offgas Offgas Wash oil
Offgas treatment unit Diesel
(Refinery)
LSFO
(low sulphur
fuel oil) Bitumen
(Refinery)

Figure 5 Refinery/petrochemical integration at HPCL-Mittal Energy Ltd., Bathinda, India

Integrated complex HMEL plans to increase chemicals to 25% by primarily

HMEL started with a base refinery of 9.0 MMTPA with 5%
of chemicals production as polypropylene on crude oil pro-
cessing. The refinery was expanded to 11.3 MMTPA (see
Figure 4) and integrated with a new petrochemical complex
to increase chemicals to 20% by adding more polypropylene
and new linear low density polyethylene (LLDPE), high den-
sity polyethylene (HDPE), and benzene units (see Figure 5)
to maximise value by meeting domestic consumption needs.
For the integration shown in Figure 5, an LP model was
developed and validated for the new base case of 11.3
MMTPA with BS-VI fuels production. The product slate
from this model served as the basis for economic analysis.
Capacities of existing process units were utilised. Various
configuration options for petrochemical integration were
studied before arriving at the final configuration, including a
dual feed cracker unit (1,200 KTPA) and downstream units:
LLDPE/HDPE swing units (2 x 400 KTPA), HDPE unit (450
KPTA), polypropylene unit (500 KTPA), butene-1 unit (55
KTPA), and matching utilities and off-sites. The integration
increased chemicals production and maximised value and
profitability by meeting domestic consumption needs.
increasing polypropylene and various percentages of poly-
ethylene and benzene. This includes diesel cracking as one
of the preferred options over and above refinery fuel gas,
naphtha, LPG, and kerosene as feed to cracker in an inte-
grated complex.
This article is based on a presentation from the Refining India 2023
conference, 9-10 October 2023, New Delhi.
References
1 https://www2.deloitte.com/content/dam/Deloitte/us/Documents/
energy-resources/us-the-future-of-petrochemicals.pdf
2 Department of Chemicals and Petrochemicals; Chemical and
Petrochemical Statistics at a Glance-2018
3 https://economictimes.indiatimes.com/industry/energy/oil-gas/cen-
tre-plans-to-set-up-petrochemical-clusters-dharmendra-pradhan/
articleshow/59821662.cms
4 Crude oil to chemicals: How refineries can adapt | McKinsey
Narendra Verma is DGM-Petrochemicals at HPCL-Mittal Energy Ltd.,
Bathinda, India, with 28 years of experience in crude oil refineries, gas
and petrochemical plants. He holds a B.Tech in chemical from HBTU,
Kanpur, and a PGDM in business administration from Welingkar
Institute of Management, Mumbai, India.

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076_Q2 Watlow.indd 1 11/03/2024 11:34:22
 Blue hydrogen – a low-carbon energy
carrier: Part 1
Through the capture and storage of CO2 generated during hydrogen production, blue
hydrogen can achieve carbon neutrality or even yield negative emissions
Himmat Singh
Research Scientist
T
he global blue hydrogen (H2) market size is anticipated
to grow at a compound annual growth rate (CAGR) of
14.8% in the present decade. The growing emphasis
on clean hydrogen energy with low carbon content, rising
usage of hydrogen fuel as an active propulsion system in
the automotive industry, and speculation of blue hydrogen
working as an enabler of green hydrogen are some reasons
behind the growth of the market. Blue hydrogen has a strong
role to play in the energy transition by helping to build a
hydrogen market while continuing to lower emissions.
Like the green variety, blue hydrogen at present is expen-
sive to produce compared to the traditional carbon-intensive
production processes used today. By reducing blue hydro-
gen’s costs, companies could speed up hydrogen’s much-
vaunted replacement of fossil fuels. European countries have
been working on several projects to boost the adoption of
blue hydrogen in various regions.
Part 1 is an overview of hydrogen and blue hydrogen in
terms of their role in energy mix, estimated demand in the
coming decades, and committed huge investments. The
overview also covers emerging and matured blue hydro-
gen technologies, namely steam methane reforming (SMR),
autothermal reforming (ATR), natural gas decomposition
(NGD), and the newly introduced Shell SGP process.
Part 2 concludes in PTQ Q3 2024 with a detailed compar-
ative assessment of cost, greenhouse gas (GHG) emissions,
and other parameters relating to three mature technologies,
with a brief appraisal of blue hydrogen market dynamics,
end-use insights, and concluding remarks.
CO2-to-H2 ratio
Hydrogen is the most abundant element in the universe,
and it could play an essential role in tomorrow’s energy mix,
from fuelling all modes of transport to generating electricity
and powering industry. Colours of hydrogen are increasingly
used to distinguish different production methods and as a
proxy to represent the associated environmental impact.
Today, close to 95% of hydrogen production comes from
fossil resources. As a result, the carbon dioxide (CO2) emis-
sions from hydrogen production are quite high. Grey, black,
and brown hydrogen refer to fossil-based production. Grey is
the most common form of production and comes from natu-
ral gas, or methane (CH4), using steam methane reformation
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Q2 SINGH.indd 77
but without capturing CO2. It creates around 10 tons of CO2
for every ton of hydrogen produced. Therefore, there is a
need to find a way to produce clean hydrogen that is less
carbon intensive.
There are two ways to move toward cleaner hydrogen pro-
duction. One is applying carbon capture and storage (CCS)
for fossil fuel-based hydrogen production processes. Natural
gas-based hydrogen production with CCS is referred to as
blue hydrogen – a low-carbon energy carrier. CO2 storage
is typically accomplished by injecting the gas into geologi-
cal formations such as saline aquifers or depleted oil fields.
Green hydrogen is produced by using electricity generated
from renewable sources, such as wind and solar, to produce
hydrogen via electrolysis.
The IEA estimates that the demand for hydrogen today
is about 90 mtpa, almost all of which is used for ammonia
production and refining and is forecast to reach about 200
mtpa by 2030 and more than 500 mtpa by 2050. There are
other estimates as well, but they are at variance with the IEA.
Meeting this demand will require an unparalleled transfor-
mation in how clean hydrogen is produced.
Europe and China have committed huge investments
through to 2030 to lower carbon via blue and green hydro-
gen projects, for an estimated production capacity of more
than 10 mtpa by 2030. However, this is far below the
demand forecast, leaving a considerable need for further
projects and investments. While green hydrogen may be the
better economic option in some locations, blue hydrogen has
an advantage in others, and therefore both are needed in the
short and medium term. In short, both types of hydrogen
reinforce each other’s strength.
To meet their Paris Agreement commitments, many coun-
tries are turning to blue hydrogen projects as a medium-term
solution for hydrogen mass production while also developing
green hydrogen for future production. The UK, for example,
has prioritised driving the growth of blue hydrogen as part of
its Ten Point Plan to reach its net zero ambitions.
Blue hydrogen shares similarities with grey hydrogen, the
key difference being that instead of releasing CO2 into the
atmosphere, it is captured and stored. Blue hydrogen has
been a clear leader in the evolution of the hydrogen industry.
Carbon capture technologies can be retrofitted onto existing
hydrogen processes or integrated into new plants by design.
PTQ Q2 2024 77
11/03/2024 15:06:52
 Methane Coal Biomass
(natural gas, biogas, Novel processes
renewable natural gas
Sorption-enhanced Biomass
Conventional processes SMR (SE-SMR) processes

Steam methane Electrified SMR Biomass

reforming (SMR) (eSMR) gasification
Microwave-assisted
Partial oxidation SMR Conventional Biomass pyrolysis
(POX) process
Membrane-assisted
reforming Coal gasification Dark fermentation
Autothermal reforming (CG)
(ATR) Dry methane
reforming (DMR) Microbial electrolysis

Catalytic partial Other novel

oxidation (CPOX) thermochemical
processes
Advanced autothermal
gasification (AATG)
Emerging processes
Chemical looping
Methane pyrolysis combustion (CLC)
reforming

Turquoise hydrogen Blue hydrogen

Figure 1 Technologies identified and covered by IDTechEx for blue hydrogen production Source: IDTechEx2

Notable plans for hydrogen projects include Air Product’s
announced plans for Europe’s largest blue hydrogen pro-
duction plant, and RAG Austria says it has commissioned
“the world’s first 100% hydrogen storage facility in a porous
underground reservoir”. The global blue hydrogen market is
projected to grow at a CAGR of 8.0% by 2033.
Further discussions relate to different ways to produce
blue hydrogen using different technological paths, taking
into consideration major innovations and challenges, with
brief appraisal of blue hydrogen market dynamics, end-use
insights, and concluding remarks (including future outlook).
Blue hydrogen technologies
Producing hydrogen in a carbon-neutral manner is chal-
lenging (and potentially expensive), but the many colourful
means of producing hydrogen provide exciting opportuni-
ties. Once available, it can be used in almost every vertical
in the energy space. This includes power generation, energy
storage, e-fuels production for aviation and heavy road and
rail transport, as well as cement and steel manufacturing,
along with applications in other carbon-intensive industries.
Blue hydrogen, produced from fossil fuels with CO2 capture,
is currently viewed as the bridge between the high-emissions
grey hydrogen and the limited-scale zero-emission green
hydrogen. Two recent reports on blue hydrogen production
technologies highlight different commercially deployed and
emerging hydrogen production processes from fossil fuels
and biofuels, along with recent advancements in hydrogen
storage and transport.
Progressive Energy1 for the Bacton Energy Hub (BEH)
Hydrogen Supply Special Interest Group (SIG) documents
technologies for blue hydrogen production from natural gas
with CCS, along with the auxiliary process stages required.
As many as 13 technologies have been listed, along with their
readiness level. SMR and autothermal and POX processes
are the mature processes, followed by one modified version
of SMR and two modified versions of ATR. The remaining
seven technologies are still at a low level of readiness.
The Hafenstorm report includes a comparison of the six
main blue hydrogen production technologies, its 10-year
market forecasts for 2023-2033, and supply chains, along
with seven application areas, major innovations and pro-
jects. The report also examines applicable carbon capture,
utilisation, and storage (CCUS) technologies and discusses
the prospects and challenges of producing blue hydrogen.
Blue hydrogen is going to grow due to global decarbonisa-
tion efforts in hard-to-abate sectors, such as oil refining and
ammonia production.
IDTechEx2 forecasts that the global blue hydrogen mar-
ket will grow to reach $34 billion by 2033. Overviewing the
production methods indicates SMR is the most developed
and widespread hydrogen production technology (grey
hydrogen) used throughout the world. Coal gasification (CG)
is another popular technology used to produce hydrogen
(black/brown hydrogen), especially in China. Other processes
include partial oxidation (POX), which is useful in converting
waste oil/refining products to hydrogen, as well as the more
recently developed ATR of methane. This self-heating steam
reforming process that is more cost-effective than SMR for
producing blue hydrogen. Air Liquide and Topsoe are the
major players in this field.
The IDTechEx report further provides coverage of meth-
ane pyrolysis, which produces hydrogen and solid carbon
products, the latter being carbon black in most cases. This
technological path is mostly occupied by start-ups and small-
er-to-medium enterprises (SMEs), some of which are quickly
commercialising their technologies termed ‘promising tech-
nologies’. Other processes fall under the categories of novel

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 processes and biomass processes.
Figure 1 shows the technologies iden-
tified and covered by IDTechEx for blue
hydrogen production.2
Al Humaidan et al have also reviewed
blue hydrogen in terms of status and
future technologies. The bespoke publi-
cation highlights the following aspects:
“Significant transition is expected in
world energy system over the next
30 years, inclusion of blue hydrogen
is inevitable for the transition toward
hydrogen-economy.” The techno-eco-
nomical assessment of many recent
studies has indicated that the oxy-
gen-based system, such as ATR and
partial oxidation, is the most efficient
for producing greenfield blue hydrogen.
The Shell Blue Hydrogen Process
(SBHP) reflects a new way to produce
blue hydrogen from natural gas or other
hydrocarbon gases (refinery off-gases)
that integrates other proven Shell tech-
nologies, which is another important
route that has been well reported in
recent publications.3
Blue hydrogen: Mature production
processes
Steam methane reforming
SMR, a proven catalytic technology,
is widely applied for grey and blue
hydrogen production, primarily due
to its cost effectiveness and ability to
obtain high-purity hydrogen. Globally,
it is estimated that 75% of all hydrogen
supply comes from SMR technology.
Initially, natural gas (methane) is des-
ulphurised to remove small amounts
of sulphur and pretreated to convert
higher hydrocarbons to methane,
hydrogen, and carbon monoxide (CO)
and to prevent coke formation leading
to catalyst deactivation. The mixture
is then preheated and passed over an
alumina-supported nickel catalyst (Ni/
Al2O3) in the pre-reformer unit, typically
operating at a pressure of 35 bars and
under high temperature (697-827ºC).
At this stage, reacts with the steam,
leading to the production of CO and
methane, as indicated in Equation 1:
CH4 + H2O  CO + 3H2 , ΔH°298K = +241 kJ/
mol (1)
After that, at ~197-247ºC and 347-
547°C, CO undergoes another reform-
ing process to convert it to CO2 using
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Q2 SINGH.indd 79
water-gas shift (WGS) reactors, result-
ing in additional hydrogen production,
as shown by Equation 2:
CO + H2O  CO2 + H2, ΔH°298K = -41.1 kJ/mol
(2)
The overall reaction is highly endo-
thermic. The reformer consists of
catalyst-packed tubes inside a fired The future
industrial furnace that uses a portion of
the natural gas feedstock as fuel to pro- is now
vide heat to the endothermic reaction.
Finally, the impurities and produced with our
CO2 are captured from the off-gas by
different methods depending on the technologies
amount of CO2 to enhance the quality of
produced hydrogen. More recently, the
for tomorrow.
Shell Cansolv CO2 capture system was
introduced to capture nearly all the CO2
(99%) from low-pressure, post-com-
bustion flue gas. The system can be
retrofitted to convert grey hydrogen
production to blue.
Autothermal reforming of methane
The ATR process4 aims for hydrogen
production while saving significant
amounts of energy for the reaction com-
pared with the SMR endothermic reac-
tion. However, an air separation unit
(ASU) is required to provide a pure oxy-
gen supply for the process. Initially, in
the presence of a nickel catalyst, steam,
natural gas, and oxygen react in an
adiabatic ATR reactor to form syngas,
which contains steam, hydrogen, CO, Discover our innovative
process technology and get
CO2, and some trace gases. The heat the future started today.
generated due to POX is simultaneously
used for the endothermic reforming → process gas compressors
reaction without the need for additional e.g. hydrogen, CO2
fuel. After that, the resulting syngas is
cooled and fed to the WGS unit, where → membrane systems
emission control,
steam reacts with CO over an Fe and Cr gas separation and OSN
catalyst to produce hydrogen and CO2.
CO2 is then separated from the hydro- → ball valves
gen-rich gas using an amine-based for midstream and down-
syngas purification unit or liquefied nat- stream applications
ural gas (LNG)-based cold energy sys-
→ heat transfer systems
tem. Additionally, the hydrogen-rich gas for hydrogen and syngas
is further purified from any unconverted projects and many more.
CO, argon, and other impurities, using a
PSA unit, up to 99.9% hydrogen.4 www.borsig.de
Partial oxidation (POX)
In this process,1 methane is partially
ACHEMA 2024
oxidised as per Equation 3, with oxy- Hall 4.0 Booth B26
gen typically sourced from a cryogenic
ASU. The CO shift reaction, Equation
PTQ Q2 2024 79
11/03/2024 15:06:53
 Lower methane slip Energy sufficiency Higher operating pressure
as SGP operates at high Produced steam satisfies Hydrogen compression duty and ADIP
reactor temperatures most internal users Ultra CO2 capture efficiency are improved

Saturated steam Superheated steam To internal users (air separation unit,

Bolier feed CO2 removal unit, triethylene glycol
water dehydration and power generation)
Natural
gas Syngas Water ADIP Ultra Hydrogen
and/or SGP effluent gas CO2 removal Hydrogen Hydrogen product
refinery reactor Hot cooler Cooled shift Shift unit purification compression export
syngas syngas effluent Impure Hydrogen
fuel gas hydrogen product
Oxygen
Medium pressure CO2
Air Integrated SBHP
Air separation CO2 compression High-pressure CO2
unit and dehydration to storage
Low-pressure CO2

Feed flexibility: Intermediate flash: High capture pressure means most

Non-catalytic process means robustness against of the CO2 can be regenerated at a medium pressure
feed contaminents (sulphur, olefins, C2 +) to minimise CO2 compressor size

Shell proprietary technology Shell technology embedded Open source technology

Figure 2 The SBHP and advantages of integration with other technologies Source: Shell Catalysts & Technologies3

4, is then used, as in previous technologies, to increase the
hydrogen yield and maximise CO2 available for capture in the
process stream. Heat released from this exothermic reaction
is used to generate steam for the downstream process and
more general preheating of other processes:
CH4 + ½ O2  CO + 2H2 (3)
CO + H2O  CO2 + H2 (4)
According to the Shell Blue Hydrogen Process (SBHP), POX
technology provides substantial savings compared with ATR
– a 22% lower levelised cost of hydrogen that derives from
lower Capex. This saving comes from a lower Capex owing
to the potential for a higher operating pressure, leading to
smaller hydrogen compressors, CO2 capture and CO2 com-
pressor units, and lower Opex.

As with many industrially mature chemical processes, POX SGP process

units can be designed as thermal POX or catalytic POX reac-
tors. The main difference between the two is the operating
temperature, with catalytic POX requiring significantly lower
temperatures at the cost of being vulnerable to poisoning by
sulphur species in the feed.
Soot formation and deposition on catalyst beds are risks
associated with feed composition, temperature, pressure,
burner design, and flow conditions in the combustion zone4,
resulting in less effective heat transfer and reduction in cata-
lyst performance. This can be controlled and mitigated using
catalysts, which ensure the destruction of soot precursors, as
well as optimising burner design and flow control solutions.
In thermal POX units, soot formation is tolerated in the reac-
tor to a degree determined by downstream equipment and
can be removed by a water wash to prevent carryover into
the CO Shift reactors.
Compared to SMR, POX technology saves money by max-
imising carbon capture efficiency and simplifying the pro-
cess line-up, both of which offset the cost of O2 production.
Additionally, it does not require steam as a reactant, which
reduces the need for gas pretreatment.
Compared to ATR, a key advantage is, again, that the
POX reaction does not require steam as a reactant. Instead,
high-pressure steam is generated by using waste heat from
the reaction, which can satisfy the steam consumption within
the blue hydrogen process, as well as some internal power
consumers. Also, with no need for feed gas pretreatment,
POX technology has a far simpler process line-up than ATR.
Shell gas partial oxidation (SGP) technology has a far simpler
process line-up and, as a non-catalytic, direct-fired system, it
is robust against feed contaminants such as sulphur and can
thereby accommodate a large range of natural gas quality
and thus give refiners greater feed flexibility to decarbonise
refinery fuel gas.
SGP technology is also an oxygen-based system with
direct firing in a refractory-lined reactor that does not con-
sume steam and has no direct CO2 emissions. Compared
with SMR, SGP technology saves money by maximising car-
bon capture efficiency and simplifying the process line-up,
both of which offset the cost of oxygen production.
A key advantage of SGP technology over ATR is that the
POX reaction does not require steam as a reactant. Instead,
high-pressure steam is generated by using waste heat from
the reaction. It is a mature Technology Readiness Level 9
(TRL9), ‘low carbon’ technology with more than 30 active
residue and gas gasification licensees, and more than 100
SGP gasifiers have been built worldwide.
The SBHP is a new way to produce blue hydrogen from
natural gas or other hydrocarbon gases (refinery off-gases)
by integrating proven technologies that can be deployed
rapidly (see Figure 2). The SBHP, which integrates Shell SGP
and ADIP Ultra technologies, offers key advantages over
ATR, including a 10-25% lower levelised cost of hydrogen,
a 20% lower capital expenditure, a 35% lower operating
expenditure (excluding natural gas feedstock price), >99%
CO2 captured, and overall process simplicity.3

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 Methane pyrolysis technologies
Methane pyrolysis is an important, economically attractive,
emerging clean hydrogen production process along with
solid carbon (char). It can be affected in three ways: ther-
mal, plasma, and catalytic. Currently, technology is at a lower
maturity level than electrolysis or SMR with CCUS. Research
efforts are focused on improving the reliability of the pyroly-
sis process and attaining economy-of-scale operations. The
hydrogen produced is termed ‘turquoise’, on the colour spec-
trum between blue and green.
The thermal process in the absence of oxygen proceeds as
per the following reaction:
CH₄ (gas)  C (solid) + 2H₂ (gas) ΔH -76KJ/Mole
The reaction is highly endothermic with an equilibrium that
shifts toward hydrogen and carbon around 300°C and goes
to completion around 1,300°C.
Compared to SMR with CCUS, the methane pyrolysis pro-
cess has a major advantage. It does not produce CO2 and
avoids the need for CCS. Compared to water electrolysis, the
process needs no renewable electricity or water as a feed-
stock. The carbon produced is in the elemental solid form.
Part 2: Looking ahead
Fostering the creation of appropriate technologies and their
applications is essential to promote environmentally friendly
blue hydrogen technologies. To enhance effectiveness, and
to overcome current limitations while improving economic
viability, additional research and development efforts are
ac24_Decarbonisation Technology Magazine_178x125.indd 1
www.digitalrefining.com
Q2 SINGH.indd 81
needed in blue hydrogen production techniques. Advancing
blue hydrogen production techniques necessitates critical
investments in new technologies and pilot initiatives.
Part 2, to be presented in PTQ Q3 2024, will focus on col-
laborative partnerships involving governments, businesses,
and academia that can expedite the development of novel
and environmentally friendly methods for hydrogen pro-
duction, contributing to the overall progress in sustainable
energy solutions. The findings of this study may prove useful
for decision-making at various levels.
References
1 Progressive Energy. Blue Hydrogen Production Review (Report on
Behalf of Becton Energy Hub), 20 Sept 2022.
2 IDTechEx Forecasts the Global Blue Hydrogen Market to Reach
US$34 Billion by 2033, 21 Feb 2023,
3 Liu N, Shell blue hydrogen process. https://decarbonisationtechnol-
ogy.com/article/64/shell-blue-hydrogen-process
4 Oni A O, et al, Comparative assessment of blue hydrogen from steam
methane reforming, autothermal reforming, and natural gas decom-
position technologies for natural gas-producing regions, https://www.
sciencedirect.com/science/article/pii/S0196890422000413
Dr Himmat Singh is a consultant in petroleum refining and natural
gas. He was previously a Scientist ‘G’ at the CSIR Indian Institute of
Petroleum and a professor/head of department with several institutions
of higher education/universities. He holds an MSc in chemistry, Diplome
D’Ingeniuer form ENSPM of IFP France, and a PhD in refining of lube
basestocks. He has published 200+ articles, 12 patents, and three
books. He has served on CSIR and government of India committees/
academic councils and been the recipient of many prestigious awards.
23.10.2023 07:52:37
PTQ Q2 2024 81
11/03/2024 15:06:58
 www.zwick-armaturen.de

082_Q2_Zwick.indd 1 11/03/2024 11:35:26

 Effect of redundancy/voting in
SIL calculation
Developing safeguard strategies in the early stages of refinery and petrochemical
project system design helps achieve optimal protection and prevent false alarms

Partha S Mondal
Fluor Daniel India Pvt. Ltd

E
ngineers designing protective systems for a process
plant often encounter and justify the use of redun-
dancy. The questions encountered are:
• How are hardware fault tolerance (HFT) and redundancy
related, and how are they applied in design?
• How much redundancy is required to achieve a targeted
safety integrity level (SIL)?
• Why and when can we use route 2H to assess HFT?
• How is redundancy achieved using multiple devices with
similar technology or diversified technology?
• What type of redundancy is required in system design
(1oo2, 2oo2, 2oo2D, 2oo3)?
• How can redundancy affect the PFD value during SIL
calculation, and how does selected architecture affect SIL
verification?
The primary objective of redundancy is to avert any inter-
ruption in system operation in the event of a technical failure
in one of the systems. This implies that if a single sensor fails
to meet performance requirements, leading to a technical fail-
ure, redundant or multiple sensors are available without a loss
of functionality. Redundancy is not solely designed to ensure
plant safety but also to forestall false trips or false alarms and
ensure availability. Parameters to consider when implement-
ing redundancy in any system architecture will be reviewed
to help system designers configure and justify redundancy.
2oo3, 1oo2D, 2oo2D, and more. The term 1 ‘hardware fault
tolerance’ of N means that N+1 is the minimum number of
faults that could lead to a safety loss.
The relationship between redundancy (MooN) and HFT
is expressed by the formula M-N. For a 1oo2 redundant
architecture, the HFT will be 1; for 2oo2, the HFT will be
0; and for 2oo3, the HFT will be 1. It is important to note
that redundancy is not the same as HFT. Table 1 provides
examples of HFT and redundancy to illustrate the concept.
Redundancy required to achieve SIL
While evaluating SIL of a safety instrumented function
(SIF), major factors deciding achieved SIL include:
u Architectural constraints (redundancy)
 Target PFDavg or RRF to be achieved
 Requirement of systematic capability (SC).
IEC 61508 and IEC 61511 both define the minimum HFT
(architectural constraint) requirement, which is required to
meet the target SIL.
IEC 61508:2010 provides two routes to satisfy the archi-
tecture constraints to meet a particular SIL for a particular
safety instrumented function:1
• Route 1H: It is based on safe failure fraction and hardware
fault tolerance of each element.
• Route 2H: It is based on component reliability data from

Applying HFT and redundancy

SFF vs SIL vs HFT
in design
Various types of redundant architecture Safe failure fraction Instrument type Hardware fault tolerance
can be applied in a safety instrumented of an element 0 1 2
<60% Type A SIL1 SIL2 SIL3
system, such as 1oo1, 1oo2, 2oo2,
<60% Type B Not allowed SIL1 SIL2
60-<90% Type A SIL2 SIL3 SIL4
Redundancy and HFT examples 60-<90% Type B SIL1 SIL2 SIL3
90-<99% Type A SIL3 SIL4 SIL4
Redundancy HFT
90-<99% Type B SIL2 SIL3 SIL4
1oo1 0
>=99% Type A SIL3 SIL4 SIL4
1oo2 1 >=99% Type B SIL3 SIL4 SIL4
2oo2 0
2oo3 1 ‘Type A’ devices have well-defined failure modes of all constituents, the behaviour of the element under
fault conditions cannot be completely determined, and they have sufficient dependable failure data.
1oo3 2
‘Type B’ devices have complex behaviour and failure modes, and typically contain embedded
1oo2D 1 microprocessors and software.
3oo3 0 Example of Type A: Pressure switch. Example of Type B: Electronic pressure transmitter.

Table 1 Table 21

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Architecture constraint vs SIL
SIL Mode
1 High Demand Mode or
Continuous Mode
(7.4.4.3.1 e_IEC-61508 P2)
2 Low Demand Mode
(7.4.4.3.1 d_IEC-61508 P2)
2 High Demand Mode or
Continuous Mode
(7.4.4.3.1 c_IEC-61508 P2)
3 High Demand Mode or
Continuous Mode
(7.4.4.3.1 b_IEC-61508 P2)
3 Low Demand Mode
(7.4.4.3.1 b_IEC-61508 P2)
4 Low Demand Mode
(7.4.4.3.1 a_IEC-61508 P2)
of 1 is sufficient for SIL 3, Similarly HFT of 0 is acceptable
for SIL 2 application.
Please note that while comparing the historical data, it
Minimum HFT
0
must be referenced from a similar application (compar-
ing a subsea instrument data with an instrument used in
clean water service should not be done).3 The failure rate
0 will always be different in these two bespoke services.
Generally, if the failure data is evaluated based on route
1 2H, it will be shown on the SIL certificate of the device. For
example:
1
1
Hence, if you have accurate data (high confidence, 90%
quality of data), the architectural constraints can be reduced
2 using Table 3.

Table 3
field feedback/based on data collected in accordance with
international standards (such as IEC 60300-3-2 or ISO
14224).
It is important to note that if route 2H is selected, the relia-
bility data uncertainties will be considered when calculating
the target failure measure (PFDavg or PFH), and the system
will be improved until there is confidence greater than 90%
that the target failure measure is achieved. As per route
1H of IEC 61508, the HFT constraint to SIL is described in
Table 2.
Hence, as per Table 2, if route 1H is selected for type B
element, SIL 2 can be achieved by HFT=0 and SFF greater
than 90%.
If IEC 61508:2010 route 2H is followed, Table 3 can be
constructed. This is the same as IEC 61511-2016.
Example: Two level transmitters are used to design a SIF.
The logic solver (PLC) is designed to trip if either transmit-
ter detects a dangerous condition (1oo2). To what SIL can
this configuration qualify per IEC 61511 or 61508 Route
2H? Since the HFT of this configuration is ‘1’, it means if
one transmitter fails, the other transmitter can still perform
the safety function. As per Table 3, the sensor configuration
can qualify for SIL 3 for any mode.
The Type A device (valve) can be better understood
with the following example: If we follow Route 1H and if
SFF is <60%, then as per Table 2, we require three valves
in a series to achieve SIL 3, and if SFF is >= to 60%, then
we require two valves in series. Hence, designers and
equipment manufacturers have always tried to prove that
SFF>=60% to reduce the cost of having an additional valve
while achieving SIL 3.
Route 2H is a method to calculate the target failure meas-
ure (PFDavg) based on the reliability data uncertainty for the
entire element according to IEC 61508. It is based on the
historical data of the device, where the confidence level
is more than 90%. Instead of determining the safe failure
fraction (SFF), Table 3 can be used to determine the max-
imum possible SIL against each hardware fault tolerance.
So, if the confidence level can be demonstrated, then HFT
Achieving redundancy4
When incorporating redundant sensors, design engineers
must account for the impact of common cause failures. To
mitigate this common cause of failure, redundant sensors
may be physically separated (for example, separate tap-
ping) and electrically isolated (for example, wiring with
separate junction boxes and cables). This serves to dimin-
ish common environmental stress.
An alternative approach to reducing common causes of
failure in redundant architecture involves using devices
from different manufacturers. While this approach miti-
gates common design and manufacturing defects to some
extent, it is important to note that, as the sensors share the
same technology, they will respond similarly to external
disturbances.
Diversity in technology presents another avenue for min-
imising common mode failures. In this scenario, different
sensor technologies are employed to measure the same
variable in a redundant configuration.
This helps decrease common faults but introduces new
challenges, such as differing calibration procedures, varied
repair methods, potential data mismatches due to distinct
digital rounding practices, diverse maintenance cycles, dis-
parate spare part requirements, and increased operational
complexity.
Therefore, when selecting various sensor technologies
or manufacturers, it is crucial to weigh multiple trade-
offs, considering their impact on operations and mainte-
nance processes at sites, as indicated by the Site Safety
Index (SSI). The SSI, a straightforward five-level model, is
designed to evaluate the influence of operations and main-
tenance processes at a given site.
Redundancy and selected architecture affect
How does redundancy affect PFD value during SIL calcu-
lation, and how does selected architecture affect SIL veri-
fication? To understand different types of voting logic and
their impact, simple mathematical equations for PFDavg and
spurious trip rate (STR) can be used.
These simple approximate equations do not include the
common cause, diagnostic, proof test coverage, and other
key variables.

84 PTQ Q2 2024 www.digitalrefining.com

FLUOR.indd 84 11/03/2024 15:12:23

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 channel. This allows either channel to handle the safety
Equation for various voting function.
STR PFDavg In case one channel experiences a dangerous failure (such
Equations 1oo1 λS λdu*TI/2 as a short circuit), the other channel acts as a safeguard for
Equations 1oo2 2*λS (λdu * TI)²/3 the system. However, if both channels fail simultaneously,
Equations 2oo2 2 * λS²/3 * λS + 2/TI λdu * TI the safety function fails upon demand.
Equations 1oo3 3*λS (λdu * TI)³/4 PFDavg and STR can be calculated using the Table 4 equa-
Equations 2oo3 6 * λS²/5 * λS + 2/TI (λdu * TI)² tions. In this architecture, the spurious trip does not improve
1oo1 0.01/yr 0.01
much, but the PFDavg improves significantly.
1oo2 0.02/yr 0.00013
2oo2 0.0001/yr 0.02
2oo3 0.0003/yr 0.0004 2oo2 voting
In the 2002 voting design, two channels are linked in par-
Table 4 allel, requiring both channels to initiate the safety function
before it activates. If one channel is open, the system will
The following equations are used only to explain the dif- not trip because the other channel remains active and
ference between various architectures. Do not use these energised.
formulas for real PFDavg calculations. The consideration of PFDavg and STR can be calculated using the Table 4 equa-
case is de-energised to trip the circuit, with reference to the tion. In this architecture, the spurious trip improves signifi-
following terms: cantly, but the PFDavg does not improve much.
• MRT: Mean repair time
• TI: Time interval between proof tests 1oo3 voting
• MT: Mission time The 1oo3 voting consists of three channels (three separate
• λdu: Dangerous failure rates undetected sensors with an IO channel) connected in parallel so that
• λds: Dangerous failure rates detected either channel can process the safety function. If two chan-
• λs: Safe failure rates nels fail dangerously (short-circuited), the other channel
• λsu: Safe failure rates undetected will protect the system. If all three channels fail simultane-
• λsd: Safe failure rates detected ously, a safety function fails on demand.
For the calculation, let us consider the below failure rates: PFDavg and STR can be calculated using the Table 4 equa-
• λdu=0.02 failures/year tions. In this architecture, the spurious trip does not improve
• λs=0.01 failures/year much, but the PFDavg improves significantly.
• TI=1 year
2oo3 voting
Design variatons The architectures discussed so far aim to enhance PFDavg or
1oo1 voting minimise spurious trips. To address both issues, the 2oo3
In the 1oo1 voting design, there is a single channel without voting architecture shown in Figure 3 can be considered.
fault protection. When a demand occurs, the circuit opens This setup involves the use of three channels running in
to de-energise the final element. However, there is a risk of parallel, utilising a majority voting system for output sig-
a dangerous failure where the output remains energised in nals. This ensures that the output state remains unchanged
a closed circuit. if only one channel produces a result that differs from the
PFDavg and STR can be calculated using the Table 4 other two.
equations. To explain the 2oo3 voting architecture, consider the 2oo3
voting circuit in Figure 3, which consists of three channels,
1oo2 voting and each channel consists of two output switches. This
The 1oo2 configuration comprises two channels, each total of six switches are wired such that two are in series
connected in parallel with its own sensor and input/output and three in parallel. Now, if subsystem ‘A’ fails dangerously

1oo3
Input Logic Output
Sensor
circuit solver circuit
2oo2
Input Logic Output
Sensor
circuit solver circuit
Input Logic Output
Sensor
circuit solver circuit

Input Logic Output

Sensor
circuit solver circuit
Final Input Logic Output
Sensor
element circuit solver circuit
Final
element

Figure 1 2oo2 architecture⁷ Figure 2 1oo3 architecture⁷

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Sulphur.indd 1 11/03/2024 10:09:41

 1oo1D voting
The 1oo1D voting design involves a single channel with
2oo3
diagnostic capability. Unlike the 1oo1 voting, a diagnostic
A Output
circuit 1 circuit is connected in series with the switch (see Figure 4),
Input Logic
Sensor circuit solver causing the output to de-energise in the event of a diagnos-
Output
circuit 2 tic fault. Any dangerous fault detected through diagnostics
will be transformed into a safe failure. When conducting
quantitative analysis, it is essential to account for the added
B Output
circuit 1 failure rates associated with the supplementary diagnostic
Input Logic
Sensor circuit solver channel.
Output
circuit 2
2oo2D voting
When two 1oo1Ds are wired in parallel, as per Figure 5, it
C Output
circuit 1 is called 2oo2D voting architecture. So even if one diagnos-
Input Logic
Sensor circuit solver tic channel fails, the other channel keeps running the plant.
Output
circuit 2 Effective diagnostics are essential to this architecture as an
undetected dangerous failure on either channel will fail the
Final
element system.

A A
B C
Figure 3 2oo3 architecture⁷ and 2oo3 voting circuit
(short-circuited), the remaining switch ‘B’ is still in a healthy
condition to de-energise, open, and bring the system to a
safe state when demand occurs. If one has failed safely (for
example, ‘A’ switch is open circuit), the final element is still
energised as ‘B’ and ‘C’ are healthy and continue to provide
power supply to the final element.
PFDavg and STR can be calculated using the equations
in Table 4. In this architecture, both the spurious trip and
PFDavg improve significantly but are still no better than
1oo2 voting in terms of PFDavg and 2oo2 voting (in terms
of spurious trip). Microcomputer engineers have introduced
automatic diagnostics in the redundancy architectures,
as discussed in the following examples of these types of
redundancy configurations.
1oo2D voting
The 1oo2D architecture (see Figure 6) resembles 2oo2D
voting, with the key distinction being that the diagnostic
B
unit of one channel can can also diagnose the other chan-
nel. To facilitate this, additional control lines were incorpo-
rated, allowing each unit to control both its own diagnostics
and that of the other channel. This significantly enhances
C safety compared to 2oo2D voting architecture. However, it
is important to note that the effectiveness of 1oo2D voting
relies heavily on reliable diagnostics.
Based on all reviewed architectures, Table 5 can be for-
mulated to describe different types of architectures.
Hybrid-based architectures⁶
Hybrid fault tolerance/diagnostic-based architectures
incorporate various combinations of architectures, such as
2oo(1oo2D). For instance, hybrid architecture is a combi-
nation of 1oo2 and 1oo1D. This hybrid approach ensures
high safety integrity with a minimal number of modules.
The following examples are derived from a hybrid system
that offers flexibility in architecture with multiple variations.
Configuration 1 (see Figure 7) aims to achieve maximum
2oo2D
Diagnostic circuit
Input Logic Output
Sensor
circuit solver circuit

1oo1D

Diagnostic circuit Diagnostic circuit

Input Logic Output Input Logic Output

Sensor Sensor
circuit solver circuit circuit solver circuit
Final Final
element element

Figure 4 1oo1D architecture⁷ Figure 5 2oo2D architecture7

88 PTQ Q2 2024 www.digitalrefining.com

FLUOR.indd 88 11/03/2024 15:12:28

 Description of all reviewed architectures
1oo2D
Architecture Number Output Objective
Diagnostic circuit
of units switches
1oo1 1 1 Base unit
1oo2 2 2 High safety
Input Logic Output
2oo2 2 2 Maintain output Sensor
circuit solver circuit
1oo1D 1 2 High safety
2oo3 3 6 Safety and
availability
Diagnostic circuit
2oo2D 2 4 Safety and
availability
1oo2D 2 4 Safety and
Input Logic Output
availability – Sensor
circuit solver circuit
biased toward Final
element
safety

Table 5⁵ Figure 6 1oo2D architecture7

safety integrity with SIL 3 capability using minimal hard-

Con iguration 16
ware, while configuration 2 (Figure 7) prioritises both max-
imum availability and safety integrity with SIL 3 capability. Input
module
Node
processor
This type of hybrid system provides high safety integrity Chasis Digital
processor output
and high availability. Input Node
module processor
Analysis of different redundant architectures with dif-
1oo2 1oo2 1oo1D 1oo1D
ferent PFDavg and STR is done to understand their effect
on integrity and availability. The designer has to consider Configuration 26
appropriate redundant architecture (better to use the term
Input Node
HFT) during system design based on the SIL target to be module processor
Chasis Digital
achieved and accepted spurious trip rate. processor output
Input Node
module processor
Takeaways Chasis
Digital
processor
HFT and redundancy are interrelated aspects crucial to the Input Node
module processor
development of a robust safety design, particularly when
2oo3 2oo3 2oo2D 2oo2D
aiming to achieve a specified SIL.
Route 2H allows for a redundant architecture with fewer
restrictive limitations than Route 1H, provided there is a Figure 7 Configurations 1 and 2
high degree of confidence (90%) in the integrity of instru-
ment failure data. We can consider Route 1H if we plan to References
use the component in a safety system that has both high 1 International Electrotechnical Commission (IEC) 61508 (2010),
and low demand. Functional safety of electrical/ electronic/programmable electronic
The creation of a well-structured, diverse redundant sen- safety-related systems.
sor subsystem necessitates careful consideration of various 2 International Electrotechnical Commission (IEC) 61511 (2016),
trade-offs during the system design phase. These include Functional safety – Safety instrumented systems for the process
decisions on achieving redundancy through the utilisation industry sector.
of multiple devices with the same technology from differ- 3 Back to basics 19 – Route 2H. Online: www.exida.com/Blog/
back-to-the-basics-19-route-2h
ent manufacturers or employing diversified technologies.
4 W M Goble, I van Beurden, Safety Instrumented System Design
Different types of redundancy, such as 1oo2, 2oo2, 2oo2D,
Techniques and Design Verification.
and 2oo3, come with distinct (PFDavg and STR. Therefore,
5 W M Goble, H Cheddie, Safety Instrumented Systems Verification:
the selection of the most suitable redundant architecture
Practical Probabilistic Calculations.
depends on the required SIL and the acceptable level of
6 W M Goble, A Hybrid Fault Tolerant Architecture. Project RTP 3000
spurious trips in the plant.
system. Online: https://rtpcorp.com/wp-content/uploads/2021/03/
An effective safety system should not only be capable
Exida-ArchitectureWhitePaperRTP3000.pdf
of achieving shutdown but also require precision to avoid 7 Exida Presentations.
triggering false alarms.
Partha S Mondal is a Certified Functional Safety Expert (CFSE 100821
001, Exida) and Instrumentation Engineer at Fluor Daniel India Pvt. Ltd,
Acknowledgement with 15 years of experience in the oil and gas industry. He has worked
I wish to thank Amit K Aglave for reviewing this article and providing on various FEED and detailed engineering projects on activities such as
his valuable input. P&ID development and HAZOP/SIL reviews, analysers, and automation.

www.digitalrefining.com PTQ Q2 2024 89

FLUOR.indd 89 11/03/2024 15:12:29

 Co-processing renewable feeds in
hydrodesulphurisation units: Part 1
Ionic modelling’s contribution to designing crucial modifications in HDS unit process
schemes to minimise the risk to operations while maximising renewable feed utilisation
Cristian S Spica
OLI Systems, Inc
T
he call for the energy transition underscores the need
to decarbonise our lifestyles. Numerous pathways
have been identified to contribute to the decarboni-
sation of the transportation sector. It is imperative to incor-
porate existing assets into these initiatives to swiftly attain
decarbonisation benefits in the transportation fuel sector.
The refining industry has responded to the target of
reducing fossil carbon emissions by integrating renewable
feedstock components into refinery operations, aiming to
lower the carbon intensity of the resulting fuels. Refiners
are employing diverse strategies for processing renewa-
ble feeds. Some are undertaking the construction of new
units dedicated to renewable diesel or sustainable aviation
fuel (SAF). Simultaneously, others are actively engaged in
adapting their existing facilities – hydrotreaters or fluid cat-
alytic crackers (FCCs) – to co-process a portion of renew-
able feeds.
The introduction of new feed components triggers
entirely new reactions, resulting in the formation of new
products that may introduce fresh challenges. Thus, before
introducing even a minor number of new feedstocks into
an existing facility, it is crucial to understand the potential
implications and have a clear strategy for mitigating any
associated risks. In such a scenario, having access to a
robust tool becomes paramount, aiding in identifying the
type and safe percentage of renewable feed that can be
incorporated into the existing feed.
Ionic modelling tools offer a solution by enabling the
H2–C–OO–C
H2
H–C–OO–C
H2–C–OO–C
1 2 1 Hydrogenolysis / Hydrogenation
TG + 12 H2 3 C18H38 + 6 H2O + C3H8
2 Decarboxylation / Hydrogenation
TG + 3 H2 3 C17H36 + C3H8 + 3 CO2
3 Methanation / WGS
CO2 + 4 H2 CH4 + 2 H2O
CO2 + H2 CO + H2O
Figure 1 Triglycerides reaction pathways
90 PTQ Q2 2024
OLI SYSTEMS.indd 90
identification of plant bottlenecks and the development of
mitigation strategies. This includes material of construction
selection, integrity operating window identification, corro-
sion inhibition package definition, and wash water injection
design. By accurately predicting corrosion and fouling risk
well ahead of introducing renewable feedstock in the unit,
these tools can validate the actual risks post-introduction.
Co-processing impact on hydrotreatment units
Hydrotreating units (HDTs) are key facilities in upgrading
renewable feedstocks, such as vegetable oils (for example,
palm, soybean, rapeseed, sunflower, corn, and jatropha)
and alternative or waste-based oils, such as used cooking
oil (UCO), waste cooking oils (WCOs), fatty acid methyl
esters (FAMEs), free fatty acid (FFA), palm fatty acid distil-
late (PFAD), palm oil mill effluent (POME), tall oil fatty acid
(TOFA), into high-quality biodiesel and renewable diesel.
While these feedstocks may vary in appearance and
contain differing levels of impurities, such as alkalis and
phosphorus, they are provided in the form of triglycerides
(TG), which can be viewed as the condensation of glycer-
ols and three carboxylic acids. The desired reaction is the
deoxygenation of the glycerides and free fatty acids in the
presence of hydrogen to form linear paraffins, according to
the mechanism in Figure 1.
There are two pathways for the main reaction. The first
favours high yields (increased return), while the second
minimises hydrogen consumption (decreases costs). The
first pathway (1) involves complete hydrogenation to form
six moles of water, one mole of propane (C3H8), and three
moles of normal paraffins with the same chain length as the
fatty acid chains (n-C18 and n-C22 in the case of rapeseed
oil) per mole of reacted triglyceride. This pathway is usually
termed hydrodeoxygenation (HDO).
The second pathway (2) involves a decarboxylation step,
where three moles of carbon dioxide (CO2), one mole of
propane, and three moles of normal paraffins with a chain
length that is one carbon atom shorter than the fatty acid
chains (n-C17 and n-C21 in the case of rapeseed oil) are
produced.
Since both CO2 and carbon monoxide (CO) are produced,
two additional reactions need to be considered, as shown
in Figure 1 (3). Hydrotreating catalysts are known to be
www.digitalrefining.com
15/03/2024 10:13:26
 Recycle gas compressor
Lean amine

Impact on catalyst activity Reduced H2 purity

Rich amine
CO/CO2 build-up
Increased light ends
Tail gas

HDS Amine
reactors Wild naphtha
Additional H2 absorber
consumption Sour
H2 Water
gas Gasoil
stripper

H2
Stripper
reboiler
Wash water Increased CO2
injection concentration

HP separator

Corrosion risk
Product
H2 LP separator
Improved cetane number
Lower density
No impact on CFP
Feed

Vegetable oil injection Water Increased H2O production

Figure 2 Co-processing impact on HDT unit

active for both reverse water gas shift (CO2 + H2  CO +
H2O) and methanation (CO + 3H2  CH4 + H2O). The rela-
tive extent of these two reactions determines the observed
distribution between CO, CO2, and methane (CH4).
If all triglycerides undergo the decarboxylation route,
seven moles of H2 will be consumed, compared to the 16
moles of H2 consumed when all triglycerides are converted
via the HDO route. In other words, there would be a 63%
reduction in hydrogen (H2) consumption. However, if all the
CO2 produced is shifted to CO, and all the CO formed is
subsequently converted into CH4, a total of 19 moles of H2
will be consumed by the decarboxylation route, resulting in
a 19% increase in H2 consumption. Indeed, co-processing
biofeeds in an HDT (see Figure 2) can have various effects,
both positive (pros) and negative (cons):
Pros:
• Co-processing biofeeds can lead to the production of
intermediate and linear paraffins, thereby improving prod-
uct properties.
• Increased H2 consumption (lipids HDT reactions).
• Reactors cycle length reduction and performance
decrease:
 Catalyst deactivation and reactor pressure drops
increase:
 Production of CH4/CO/CO2/H2O by conversion of
lipids followed by water gas shift (WGS) equilibrium
and production of C3H8 by removal of the glycerol
group.
 CoMo catalyst active sites partial Inhibition due to
CO.
 H2 partial pressure decrease.
 Catalyst active sites partial deactivation due to Ca
and Mg phosphate.
 Fouling issues (phospholipids, peroxides, olefins and
di-olefins, metals).
• Reactor effluent air cooler (REAC) – fouling, uniform cor-
rosion and pitting corrosion risk by chlorides in the effluent
reactor side:
 Increased organic and inorganic chloride concentration

 This increase in volume swell enhances the profitability in biogenic feedstock.

of the hydroprocessing unit.  H2O increased production and increased relative
 It boosts the Cetane number, facilitating easier blend- humidity (RH):
ing into the commercial pool or reducing the need for  HDO pathway.
additives.  Increased water quenching due to higher exother-
 Cold flow properties (CFP) are minimally impacted by micity because of the lipids HDT reaction.
biofeeds co-processing options. • Low-pressure (LP) separator/stripper overhead/amine
section – wet CO2 corrosion risk:
Cons:  CO2 production.

• Upstream reactors uniform corrosion risk – FFAs • Compressor capacity limitations:

corrosion.  Light ends load increase.

www.digitalrefining.com PTQ Q2 2024 91

OLI SYSTEMS.indd 91 14/03/2024 09:49:54

 Fossil feed contaminants Wash water quality

Fossil feed Average Max Wash water Average Max

Nitrogen-based 1,000 ppmwt 1,500 ppmwt Chlorides 5 ppmwt 10 ppmwt
Sulphur-based 10,000 ppmwt 20,000 ppmwt Ammonia 100 ppmwt 200 ppmwt
Chlorides* 1 ppmwt 3 ppmwt Sulphides 200 ppmwt 300 ppmwt
Oxygenated 120 ppmwt 300 ppmwt Oxygen 25 ppbwt 70 ppbwt
Phosphorus 1 ppmwt 2 ppmwt Carbonates 2 ppmwt 5 ppmwt
Metals 2 ppmwt 4 ppmwt Metals 1 ppmwt 2 ppmwt
Cyanides 15 ppmwt 30 ppmwt
*Due both to the presence of organic chlorides solvents in the imported gasoil and
from the H2 make-up streams coming from the CCR unit, due to upsets of the chloride
guard beds (the catalyst is regenerated via the injection of perchloroethylene or similar Table 2
chlorine-based organic agents)

This is especially crucial in HDT units, which are highly sus-

Table 1
Ionic modelling
Electrolyte models provide insights into corrosion and foul-
ing risk in HDT units.
Thermodynamic analysis of HDT streams at varying
feedstock qualities and operating conditions (temperature,
pressure, pH, and composition) can be used to evaluate
fouling and corrosion potential.
Ionic mass balance throughout the unit aids in the com-
prehensive assessment of fouling and corrosion risks across
the process scheme. By establishing operating envelopes,
operators can determine the safe introduction of biogenic
feedstock, avoiding highly corrosive conditions and thereby
extending the life and reliability of the units. Ionic mod-
els also assist in identifying significant modifications to
the process scheme, guiding the design and selection of
appropriate materials for tower internals, heat exchangers,
overhead systems, and piping systems, ensuring the safe
incorporation of a higher percentage of biogenic feedstock.
Electrolyte chemistry modelling plays a critical role in
understanding the behaviour of complex water and hydro-
carbon streams in downstream oil and gas process units.
ceptible to upsets due to substantial changes in feedstock
qualities and operating conditions. An electrolyte model
provides in-depth insights into these complex systems,
informing reliability and design engineers about operating
efficiencies, as well as corrosion and fouling risks.
Case study: DHT co-processing feasibility study
A European refinery aiming to produce ultra-low sulphur
second-generation renewable diesel has outlined plans to
co-process renewable feeds at its existing diesel hydro-
treater (DHT). In pursuit of this goal, the refinery has
engaged OLI Systems Inc. to conduct a feasibility study.
The primary objective of the study was to assess the
impact of the biogenic feedstocks on the unit’s operations.
This included identifying potential process bottlenecks,
establishing quality and incorporation rate limits, and defin-
ing a safe operating envelope. Additionally, the study aimed
to provide recommendations for key modifications to opera-
tional parameters and suggest the installation of new equip-
ment to ensure the safe and profitable operation of the unit.
The first phase of the project focused on evaluating the
status of the unit, including quantifying bottlenecks and
limitations associated with running the plant with 100%

Recycled compressed gas Recycle gas

Gas compressor
Reactor
effluent 01 out 02 out 03 out
Sweet
gas Sep-1 AA sour
Hex 01 Hex 02 Hex 03 Lean amine S-2 gas
S-3
04 out 05 out 06 out
Rich
Intermittent Amine amine
wash water NH4HS corrosion & fouling risk absorber
Hex 04 Hex 05 Hex 06
Continuous S-4 Flash
ww inj. mixer Mix-3 tank
AA rich amine
09 out 10 out
07 out 08 out 09 out 10 out AC01 out
ww Diesel stripper
Hex 10 ww condensate
Hex 07 Hex 08 Hex 09 Intermittent Diesel
ww inj. mixer HP separator stripper DS OVHD
Solid OVHDs DS OVHD receiver
Continuous HP sep. sour gas coolers
injection
system HP separator To diesel
Tail
HC LP stripper Diesel gas
separator stripper
NH4Cl corrosion & fouling risk DS
Pre-heat water

LP separator
HC Wild
HP
Stripping Diesel naphtha
separator LP separator
water water steam product

Figure 3 OLI Flowsheet ESP – 100% fossil feed – ionic survey

92 PTQ Q2 2024 www.digitalrefining.com

OLI SYSTEMS.indd 92 15/03/2024 10:25:59

 NH4HS corrosion risk table

Stream Temperature (⁰C) Corrosion rate (mm/y)* pH Metallurgy [NH4HS] (%wt )

HEX 10 out 135 0.35 7.0 CS 0.6
AC 01 out 70 0.50 7.6 CS 3.1
HP sep. water out 50 0.45 7.8 CS 4.1
LP sep. water out 40 0.75 8.0 CS 5.5
Diesel stripper condensate 35 1.25 8.0 CS 8.0

* For long-term service to be deemed acceptable, the corrosion rate must remain below 0.125 mm per year. The corrosion rates were determined based on the operational fluid velocity,
which consistently remained below 6 m/s.

Table 3

balance was carried out on OLI Systems’ proprietary leg-
acy process simulator, Flowsheet ESP, by reproducing the
DHT process scheme and simulating its behaviour at aver-
age process and contaminant level conditions (see Table
1). Each stream was then analysed in the proprietary OLI
Studio: Corrosion & Stream Analyzer to gain insights into
the electrolyte chemistry and assess the corrosion and foul-
ing risk of each of the streams.
It is worth noting that the unit is equipped with both inter-
mittent and continuous wash water injection facilities. These
are situated upstream and downstream of HEX 10, respec-
tively, with an overall injection rate of 15-20 t/h of wash
water. The wash water mainly originates from the vacuum
distillation unit (VDU), which explains the elevated concen-
trations of ammonia, sulphides, and observed oxygen.
The result of the ionic survey evidenced the following
issues:
• Fouling issue: Dry NH4Cl β-solid formation in HEX 08-09
tube bundles with a RH of 0.7%.
• Fouling issue: NH4Cl α-solid formation in HEX 09-10
tube bundles (the NH4Cl β-crystalline form transition to the
α-form at 185⁰C) with a RH of 1.0%.
• NH4HS corrosion: AC 01 outlet – HP and LP separator
outlet (NH4HS concentration 3.0-5.5%wt ).
NH4Cl deposition in HEX 08-09 is a commonly over-
looked occurrence, with no proactive measures taken to
address it (for example, feedstock quality control, feed
pretreatment, wash water or salt dispersant injection, or
operational parameter change). However, it is widely rec-
ognised in both literature and practical plant experience
that there is a significant risk of pitting corrosion when rel-
ative humidity exceeds 10-15% for carbon steel material.
While NH4Cl is not corrosive and primarily causes fouling
when dry, it becomes corrosive when exposed to moisture
due to its hygroscopic nature.
The NH4HS corrosion issue is relatively mild, extending
from the AC01 outlet to the LP separator cold and diesel
stripper overhead areas (see Table 3). This corrosion is sen-
sitive to both concentration and velocity. While engineering
best practices suggest that a concentration of 2%wt and a
velocity of 6.0 m/sec are the safe operation limits for carbon
steel, rather than solely relying on these practices, we con-
ducted an analysis of corrosion rates and the risk of pitting
corrosion to which the unit is exposed by surveying the
streams highlighted in purple in the proprietary OLI Studio:
Corrosion Analyzer (see Figure 3).
Another factor contributing to NH4HS corrosion is the
presence of oxygen, which can accelerate corrosion. It is
recommended that wash water be oxygen-free, with a
suggested oxygen limit of <15 ppbwt.
From the first phase evaluation, it is evident that the unit
is already experiencing some issues, with corrosion and
fouling, particularly chloride salt deposition, being the most
problematic. Therefore, any increase in chloride intake does
not seem feasible. Additionally, the chloride content in the
fossil feed should be limited. Alternatively, a new intermit-
tent wash water injection facility with a capacity of 15-20
Another factor contributing to
NH4HS corrosion is the presence
of oxygen, which can accelerate
corrosion
t/h should be installed upstream of HEX 08 to dissolve the
dry chloride salts formed. Additionally, an upgrade in the
material of construction (MoC) for the carbon steel HEX tube
bundles and piping should be implemented. This upgrade is
necessary to protect HEX 08-09 from chloride stress cor-
rosion cracking due to intermittent water washing and to
resist NH4HS corrosion in REAC downstream cold areas.
Going forward
The second phase of the project to be discussed in PTQ Q3
2024 assesses the behaviour of the unit when incorporat-
ing different biogenic feedstocks and different rates, with
a minimum target of 10 wt%. The feasibility study results
revealed that achieving the targeted minimum biofeedstock
incorporation rate of 10% was not feasible with the cur-
rent DHT configuration, necessitating significant capital
expenditure (Capex) for implementation.
Cristian Spica is a Senior Application Engineer with OLI Systems,
Inc. He has 12 years of experience in chemical engineering activities
including process engineering, modelling and simulation, engineering,
design and construction, project management, technical support and
training. He holds a chemical engineering degree from the University
of L’ Aquila, Italy (MSc equivalent) and is an Executive MBA candidate
at Luiss Business School in Rome.
Email:cristian.spica@olisystems.com

www.digitalrefining.com PTQ Q2 2024 93

OLI SYSTEMS.indd 93 14/03/2024 09:49:58

 Technology in Action
Emerging LOHC technology
The use of liquid organic hydrogen carriers (LOHCs) is part
of broader research into hydrogen as a clean and sustainable
energy carrier. LOHCs are a class of chemical compounds
that can be used to store and transport hydrogen. The idea
behind them is to use liquid organic compounds, such as
toluene, as carriers for hydrogen molecules, allowing for a
safer and more convenient means of handling and transport-
ing hydrogen gas (see Figure 1).
The process typically involves chemically binding hydrogen
to a liquid organic compound, forming a stable LOHC. This
LOHC can then be easily transported and stored at ambient
conditions so the hydrogen can be released when needed by
various methods, such as heating or using a catalyst.
One advantage of LOHCs is that they offer a way to over-
come some of the challenges associated with the storage and
transportation of gaseous hydrogen. Hydrogen, in its natu-
ral state, is a lightweight and highly flammable gas, which
poses safety concerns. A trifecta of market developments,
regulations, and technical advancements could accelerate
LOHC commercialisation. PTQ recently discussed LOHC
opportunities with Ian Clarke, Honeywell UOP’s Business
Director, Naphtha and Aromatics/Derivatives, UOP Process
Technologies (UPT):
 What market and regulatory incentives could accelerate
LOHC implementation? Market, regulatory, and government
incentives currently seem key to driving clean hydrogen
solutions, whether green or blue hydrogen projects. These
incentives will enable hydrogen producers to reduce the cost
of hydrogen either through subsidising electricity prices or
Figure 1 Integration of LOHC infrastructure into industrial operations
94 PTQ Q2 2024
TIA Q1.indd 94
contributing towards the capital of the projects. The use of
LOHC is closely connected to the same incentives. A hydro-
gen economy is created only when it is more cost-effective
for countries to generate hydrogen at a lower price than
another country can generate the same clean hydrogen.
The Honeywell LOHC Solution has been optimised in
terms of hydrogen recovery, capital cost, and operating costs
to become a minor part of the overall hydrogen pricing. For
example, with the Honeywell LOHC Solution, we can recover
more than 98.5% of the hydrogen generated in Country A
as a final hydrogen product in Country B without post-treat-
ment, with carrier make-ups of significantly less than 1 wt%.
These two factors alone make the Honeywell LOHC solution
a highly attractive hydrogen transport solution compared to
other pathways and offerings.
 What technical advances will facilitate the integration of
LOHC with refinery infrastructure in 2024 and beyond? The
Honeywell LOHC Solution is based on commercially proven
technology and catalysts that have been operating in refin-
eries for more than 50 years. LOHC allows integration with
existing transfer and storage systems, refinery operations,
and existing hazardous clarifications. This allows customers to
select a solution that is not only ready to implement now but
has the potential to revamp existing refining assets so they
can fast-track clean hydrogen projects. This technical solution
is now ready at commercial-scale capacities with options for
new unit installations or low-Capex retrofits of existing plants.
Honeywell UOP
Contact: charles.brandl@honeywell.com
ian.clarke@honeywell.com
www.digitalrefining.com
12/03/2024 13:51:48

Innovative vessel internals for enhanced
safety when changing media beds
In our previous article (PTQ Q1 2024), we discussed the
challenges inherent in performing scheduled inspections
within confined spaces of fixed-bed downflow reactors.
We noted that process safety managers are experts at
maintaining compliance with rigorous OSHA and industry
safety standards for entering ‘permit-required’ confined
spaces. These safety teams are professionals who are
expertly trained as to what is needed to mitigate the many
significant worker safety hazards present during media bed
replacements, including potential explosions, asphyxi-
ation, continuous changes to the internal atmosphere,
and much more.
Although planned maintenance is critical to keep a
plant at peak productivity and operating dependably,
shutting down profitable production for maintenance
turnarounds is always disruptive and expensive. As a
result, many process managers have been challenged
by their companies to streamline and speed up the
turnaround process and increase the efficiency of their
teams to reduce costs.
In response, process engineers and safety managers
are looking at ways to eliminate the need for workers to
enter a reactor vessel for a simple media bed change.
Since there are no shortcuts to maintaining worker safety
and compliance with industry safety standards, the focus
has shifted to analysing the maintenance process.
StaySafe products enhance workers’ safety by eliminating the
Eliminating manway entry need to enter potentially hazardous, confined spaces
With fixed-bed reactors that utilise hold-down screens
at the top of the bed, accessing the media requires the
screen to first be removed from the vessel. Traditionally,
this requires that a worker enter the confined space of the
vessel to dismantle the manway in the centre of the screen,
or for ‘floating’ screens, dismantle and remove the entire
screen through the vessel manway. Senior process lead-
ers have concluded that this initial stage can be eliminated
Both new products are hold-down
screens with the same StaySafe
‘no-entry’ disassembly and
removal concept, but they have
quite distinctive designs based on
how they sit in a vessel
and have started to mandate that workers will no longer be
allowed to enter a vessel just to remove a screen or man-
way for simple media bed changes.
Johnson Screens was engaged to help address this issue
by responding with the creation of two innovative hold-
down screen solutions in a new StaySafe product platform.
While both new products are hold-down screens with the
www.digitalrefining.com
TIA Q1.indd 95
same StaySafe ‘no-entry’ disassembly and removal con-
cept, they have quite distinctive designs based on how they
sit in a vessel.
The first new product is a ‘floating’ hold-down screen
that rests directly on the top of the media bed. These
screens sit on the media bed and must be removed from
the vessel before media extraction and replacement can
begin. Traditional designs of this type of screen are bolted
together, and a worker must enter the vessel to disassem-
ble the screen and remove it from the vessel.
This innovative design approach incorporates interlock-
ing components assembled in the vessel without tools and
secured in place with a central locking hub. This design
allows for easy disassembly and removal of the screens
from outside the vessel and eliminates the need for work-
ers to enter the vessel to remove the screen. Working from
outside the vessel simplifies compliance with regulatory
safety protocols by eliminating the need for confined space
entry permits in the initial stage of media bed replacement.
The second new StaySafe product is a ‘supported’ hold-
down screen with a manway, which rests on support beams
within the vessel. Although the screen follows a standard
bolted design, the manway incorporates a unique design
so it can be disengaged and removed from the screen from
outside the vessel. An integrated manway screen seal
ensures media containment with an easily released panel.
This allows the turnaround team to remove the manway
from the vessel or set it aside in the vessel while the media
bed is replaced. The manway can then be reinstalled and
locked back into position from outside the vessel.
Both new StaySafe products are already in use today and
have been designed to the high-performance specifica-
tions and rigorous manufacturing standards that Johnson
Screens has been delivering to the gas processing industry
for decades.
StaySafe is a mark of Johnson Screens.
Johnson Screens
Contact: kevin.chase@johnsonscreens.com
PTQ Q2 2024 95
11/03/2024 15:35:16
 Alphabetical list of advertisers

ACHEMA 2024 81 Merichem 20

AMETEK Grabner Instruments 31 PAC 70
Ariel International Corporation 64 Process Consulting Services 4
Axens 7 Reactor Resources 14
Becht 19 Refcomm 2024 85
Borsig 79 Refining India 2024 OBC
Crystaphase Insert 16/17 Rezel 40
Endress+Hauser 35 Sabin Metal Corporation 52
ERTC Ask The Experts IBC Saint-Gobain NorPro 13
Eurotechnica 32 Shell Catalysts & Technologies 2
FTC Corporation 58 Sulphur + Sulphuric Acid 2024 87
GEA Wiegand 25 Sulzer Chemtech 11
Halliburton Multi-Chem 46 Valmet 73
Honeywell UOP IFC VEGA 23
Idrojet 51 Vereinigte Füllkörper-Fabriken 69
ITW Technologies 26 W R Grace & Co 9
Johnson Screens 43 Watlow 76
Ketjen 39 Zeeco 67
Lechler 45 Zwick Armaturen 82

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