Atmospheric Distillation Process - Fundamental Concepts - No Appendexes

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2008 Refining Processes Handbook HOME Processes Index Company Index
Hydrocarbon Processing’s 2008 Refining Processes Handbook reflects the

dynamic advancements now available in licensed process technologies, catalysts
and equipment. The refining industry is under tremendous pressure to process
“cleaner” transportation fuels with varying specifications for a global market.
Refiners must balance capital investment and operating strategies that provide
the optimum profitability for their organization. Hence, refining organizations
will apply leading-edge technology in conjunction with “best practices” for
refining fuels and petrochemical feedstocks from crude oil.
HP’s process handbooks are inclusive catalogs of established and emerging

refining technologies that can be applied to existing and grassroots facilities.
Economic stresses drive efforts to conserve energy consumption, minimize waste,
improve product qualities, and, most important, increase yields and throughput.
In further expansion, the process entries presented an expanded description

of the licensed technology including a process flow diagram, product description,
economic information and other vital information. Specific processing operations
to be emphasized include alkylation, biofuels, coking, (crude) distillation, catalytic
cracking (fluid and resid), gasification, hydrocracking, hydrotreating, hydrogen,
isomerization, desulfurization, lube treating, visbreaking, etc.
To maintain as complete a listing as possible, the 2008 Refining Processes

Handbook is available on CD-ROM and at our website for paid subscribers.
Additional copies may be ordered from our website.
Photo: Neste Oil’s Naantali special product refinery on the western coast of Finland.
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Processes Index
Alkylation Hydroprocessing
Aromatics Hydrotreating
Biofuels Isomerization
Catalytic cracking Isooctene/isooctane
Catalytic reforming Lubes
Coking Olefins
Deasphalting/asphalt Oxygen enrichment
Desulfurization-fuels Petrochemicals
Distillation-Crude Reactors
Distillation-Vacuum Sulfur recovery
Ethers Treating
Gasification Treating-acid gas
Hydroconversion Treating-flue gas
Hydrocracking Treating-fuels
Hydrodearomatization Treating-offgas
Hydrofinishing Upgrading-heavy oil
Hydrogen Visbreaking
Hydrogenation Waxes
Sponsors:
Premier sponsors:
Company Index
ABB Lummus Global B.V. Lummus Technology, a CB&I company
Air Products and Chemicals Inc. Lurgi GmbH
Akzo Nobel Lyondell Chemical Co.
Axens Merichem Chemical & Refinery Services LLC,
Bechtel Corp. Process Technology Division
Belco Technologies Corp. Merichem Chemical & Refinery Services LLC,
Gas Technology Products Division
CDTECH
Neste Jacobs OY
Chevron Lummus Global LLC
Quadrise Fuel International
Davy Process Technology
QuestAir Technologies Inc.
DuPont
Refining Hydrocarbon Technologies LLC
ExxonMobil Research and Engineering Co.
Shaw
Foster Wheeler USA Corp.
Shell Global Solutions International B.V.
GE Energy
Snamprogetti, a company of Saipem
Genoil Inc.
TECHNIP
Goar, Allison & Associates, Inc.,
an Air Products Company ThioSolv LLC
GTC Technology TOTAL
Haldor Topsøe A/S Uhde GmbH
Hamon Research-Cottrell UOP
KBR Viscolube SpA
Linde AG, Division Gas and Engineering Worley Parsons
Sponsors:
HYDROCARBON PROCESSING ®
ABB Lummus Global B.V.

Deep thermal conversion
Thermal gasoil
Visbreaking
Air Products and Chemicals Inc.

Hydrogen-recovery
Olefins recovery
Akzo Nobel
Emulsion residue upgrade
Processes
Fluid catalytic cracking
Resid catalytic cracking
Axens is a refining, petrochemical and natural gas market-focused
supplier of process technology, catalysts, adsorbents and services, Resid cracking
backed by nearly 50 years of commercial success. Axens is a world Catalytic reforming
leader in several areas, such as:
Hydroconversion—VGO and DAO
• Petroleum hydrotreating & hydroconversion
• FCC gasoline desulfurization Hydrocracking
• Catalytic Reforming Hydrocracking-residue
• BTX (benzene, toluene, xylenes) production & purification Hydrotreating, diesel
• Selective Hydrogenation of olefin cuts
• Sulfur recovery catalysts.
Hydrotreating-resid
Axens is a fully-owned subsidiary of IFP.
Isomerization
Lube oil refining, spent
Spent lube oil re-refining
Bechtel Corp.
Lube extraction (2 processes)
Lube hydrotreating (2 processes)
Dewaxing
Dewaxing/wax deoiling
Wax hydrotreating
Belco Technologies Corp.

NOX reduction, low temperature
SO2 removal, regenerative
Wet scrubbing system, EDV
CDTECH
Alkylate, butanes to alkylate
Alkylation, low-temperature acid catalyzed
Ethers-ETBE
Ethers-MTBE
TAEE, from refinery C5 feeds
TAME, from refinery and steam cracker C5 feeds
TAME, from refinery C5 feeds
Hydrogenation
Hydrogenation-benzene in reformate
Hydrogenation, selective for MTBE/ETBE C4 raffinate
Hydrogenation, selective for refinery C4 feeds
Hydrogenation-selective for refinery C5 feeds
Hydrotreating
Isomerization
Isooctene/isooctane, conversion of refinery MTBE units
Isobutylene, from MTBE decomposition
Chevron Lummus Global LLC

Hydrocracking
Hydrocracking, resid
Hydrofinishing
Hydrotreating
Hydrotreating-RDS/VRDS/UFR/OCR
Dewaxing
Davy Process Technology

Prereforming with feed ultra purification
DuPont
Alkylation
Hydrocracking
Hydrotreating
ExxonMobil Research and Engineering Co.

Alkylation, sulfuric acid
Fluid catalytic cracking, high olefin
Fluid catalytic cracking, residual
Coking, fluid
Gasoline desulfurization, ultra-deep
Gasification
Hydrocracking, moderate pressure
Pressure swing adsorption-rapid cycle
Hydroprocessing, ULSD
Gas treating—H2S removal
Wet gas scrubbing (WGS), wet gas scrubbing plus
NOX abatement/SNCR
Catalytic dewaxing
Processes
Foster Wheeler USA Corpration is a global engineering and con- Coking
struction contractor and power equipment supplier, with a reputa-
tion for delivering high-quality, technically-advanced, reliable facili- Deasphalting
ties and equipment on time, on budget and with a world-class safety Crude distillation
record.
Our Engineering & Construction Group designs and constructs Hydrogen-steam reforming
leading-edge processing facilities for the upstream oil & gas, LNG &
gas-to-liquids, refining, chemicals & petrochemicals, power, environ- Visbreaking
mental, pharmaceuticals, biotechnology & healthcare industries. Fos-
ter Wheeler is a market leader in heavy oil upgrading technologies, Technical articles
offering world-leading technology in delayed coking, solvent deas-
phalting, and visbreaking, and providing cost-effective solutions for Integrated hydrogen solutions: Combining
the refining industry.
Services: hydrogen recovery and optimized steam
• Market studies Upgrade refinery residuals into value-added
• Master planning
• Feasibility studies products
• Concept screening Optimize turnaround projects
• Environmental engineering
• Front-end design (FEED) Drivers for additional delayed coking capacity in
• Project management (PMC) the refining industry
• Engineering (E)
• Procurement (P) When solvent deasphalting is the most appropri-
• Construction (C) & construction management (Cm)
• Commissioning & start-up
ate technology for upgrading residue
• Validation
• Plant operations & maintenance
• Training
Our Global Power Group, world-leading experts in combustion
technology, designs, manufactures and erects steam generating and
auxiliary equipment for power stations and industrial markets world-
wide, and also provides a range of after-market services.
GE Energy
Gasification
Genoil Inc.
Hydroprocessing-heavy oil and residue
Goar, Allison & Associates, Inc., an Air Products Company

Sulfur processing
Sulfur recovery
GTC Technology
Aromatics (3 processes)
Aromatics recovery
Benzene saturation
Paraxylene
Styrene recovery
Xylene isomerization
Desulfurization
Hydrotreating, pyrolysis gasoline
Carboxylic acid recovery
Dimethyl terephthlate
Haldor Topsøe A/S

Fluid catalytic cracking-pretreatment
Diesel upgrading
Diesel-ultra-low-sulfur diesel (ULSD)
Hydrocracking
Hydrodearomatization
Hydrogen-HTCR and HTCR twin plants
Hydrogen-HTER-p
Hydrogen—Methanol-to-shift
Hydrogen-Steam methane reforming (SMR)
Hydrotreating
Flue gas denitrification
Flue gas desulfurization-SNOX
Sour gas treatment
Spent acid regeneration
Hamon Research-Cottrell
Wet gas scrubbing, wet gas scrubbing plus
Processes
KBR is a leading global engineering, construction and services com- Fluid catalytic cracking
pany supporting the energy, petrochemicals, government services and Fluid catalytic cracking, high olefin
civil infrastructure sectors. KBR has been delivering high yields and
efficiency to its customers in the hydrocarbon processing industry for Fluid catalytic cracking, residual
over 80 years, when Morris Kellogg founded the M.W. Kellogg Com-
pany. KBR is one of the few leading engineering and construction Coking
companies to specialize in the development and licensing of process Asphaltene pelletization
technologies for petrochemicals, refining, ammonia production and
coal gasification, all founded on extensive research and development Deasphalting
at its Technology Center.
Isooctene/isooctane
With thousands of successful projects worldwide, KBR also com- Heavy oil upgrading
bines its technology expertise with full engineering, procurement
and construction services to help clients maximize the value of their
assets. This has become a critical factor as the world’s supply of con- Technical articles
ventional oil and gas resources is being depleted, and KBR technol-
ogy continues to help customers transform low value hydrocarbons To vacuum or not to vacuum
into high value products with processes that produce some of the
highest yields, efficiencies and reliability available in the hydrocarbon Unlocking current refinery constraints
processing industry.
Consider new technology to produce clean diesel
Email: technology@kbr.com Holding the key
Web: technology.kbr.com
Linde AG, Division Gas and Engineering

Oxygen enrichment for Claus units
Oxygen enrichment for FCC units
Lummus Technology, a CB&I company

Alkylation
Fluid catalytic cracking for maximum olefins
Coking
Lurgi GmbH
Biodiesel
Multipurpose gasification
Hydrogen (steam reforming)
Lyondell Chemical Co.

Isomerization
Processes - PTD
Treating-phenolic caustic
Treating-spent caustic deep neutralization
Merichem Chemicals & Refinery Services LLC is a world leader Treating-gases
in providing services for management of caustic streams; the devel-
opment, engineering, fabrication, and sale of innovative technolo- Treating-coker LPG to low total sulfur levels
gies for treating H2S, mercaptans, and other impurities in gas and liq- Treating-gasoline and LPG
uid hydrocarbon streams; and the production of catalysts for treating
processes and naphthenic chemicals for a variety of industries. With Treating-gasoline desulfurization ultra deep
research facilities in Houston, Texas, Merichem continues to create,
innovate, and support new technologies, services and products for Treating-gasoline sweetening
all the industries it serves. Headquartered in Houston, with offices in Treating-jet fuel/kerosine
Illinois, Alabama, United Kingdom and Japan, Merichem is actively
engaged meeting the customers’ needs throughout the world, giving Treating-kerosine and heavy naphtha sweetening
you access to unmatched technical knowledge, applications exper-
tise, and worldwide service coverage. Treating-propane
Treating hydrocarbon streams and processing spent caustics Treating-reformer products
within the refinery
Since 1974, MCRS’s Process Technology Division (PTD) has been
providing technologies to the hydrocarbon process industry. The
most widely applied technologies employ the FIBER-FILM™ Contac-
tor, which essentially eliminates the problems associated with con-
ventional dispersive mass transfer methods to remove hydrocarbon
contaminants such as acid gases, sulfur, organic acids and basic com-
pounds.
PTD is also engaged in the design and fabrication of modularized
process systems applying its proprietary technology. With a fabrica-
tion facility in Houston, PTD can manage the entire project, from
design to start-up.
Processes - GTP
H2S removal (3 processes)
Meeting Today’s Challenges for H2S Removal/Recovery

MCRS’s Gas Technology Products division (GTP), with more
than 30 years of experience in H2S removal, provides a full line of
complementary hydrogen sulfide oxidation products: LO-CAT® and
LO-CAT® II and H2S scavenger process chemicals for use in its propri-
etary SULFUR-RITE® and THE ELIMINATOR™ processes, along with its
ARI®-100 mercaptan oxidation catalysts.
These processes are based on liquid and solid media desulfurization
technologies to sweeten natural gas, unconventional gas and syn-
gas streams, as well as ventilation air containing virtually any levels
of hydrogen sulfide or mercaptans – for streams of widely ranging
capacities. For any application, GTP offers engineering services and
complete turnkey systems with total system responsibility.
Neste Jacobs OY
Isooctene/isooctane
Quadrise Fuel International

QuestAir Technologies Inc.

Pressure swing adsorption-rapid cycle
Refining Hydrocarbon Technologies LLC

Alkylation
Biodiesel
Hydrogenation/hydrodesulfurization
Olefin etherification
Isooctene/isooctane
Shaw
Deep catalytic cracking
Refinery offgas-purification and olefins recovery
Processes
Shell Global Solutions provides business and operational con-
sultancy, catalysts, technical services and research and development Crude distillation
expertise to the energy and processing industries worldwide. Shell
Global Solutions has approximately 5,000 staff located in an exten-
Gasification
sive network of offices around the world, with primary commercial Hydrocracking
and technical centres operating in the USA, Europe and Asia Pacific.
Shell Global Solutions supports the Shell Group’s business activities
Reactor internals
in downstream manufacturing, downstream marketing, gas & LNG, Deep thermal conversion
production and project management. Outside of the Shell Group, the
company successfully services refining, chemicals, gas, metals, pulp Thermal gasoil
and paper and motor-sport customers worldwide. Visbreaking
Technical articles
Shell gasification technology: Generating profit
from the bottom of the barrel
Hydrocracking technology for clean fuels
Operating experience provides foundation for
innovative solutions
Market responsiveness through residue thermal
conversion technologies
Low NOx emission from FCC regenerators
Shell’s ultimate flexible FCC technology in
delivering diesel/propylene
Snamprogetti, a company of Saipem

Ethers
Isooctene/isooctane
Isooctene/isooctane, conversion of refinery MTBE units
Butene-1 recovery
Isobutylene, high-purity
TECHNIP
Crude distillation
Hydrogen
ThioSolv LLC
Treating
Treating-sour water stripper gas
TOTAL
Crude distillation
Uhde GmbH
Aromatics extractive distillation
Vacuum distillation
Ethers-ETBE
Ethers-MTBE
Gasification-PDQ
Gasification-PSG
Hydrogen
Hydrofinishing/hydrotreating
Lube treating
Olefins-butenes extractive distillation
Olefins-dehydrogenation of light paraffins to olefins
Slack wax deoiling
White oil and wax hydrotreating
Processes
Alkylation (2 processes)
Alkylation-HF
UOP LLC, a Honeywell company, has been delivering cutting-edge
technology to the petroleum refining, gas processing, petrochemi- Green diesel
cal production and major manufacturing industries for almost 100
years.
The company’s roots date back to 1914, when the revolutionary Catalytic reforming
Dubbs thermal cracking process created the technological founda-
tion for today’s modern refining industry. Since then, UOP engineers
Coking
have generated thousands of patents, leading to a complete port- Deasphalting
folio of licensed processes, catalysts, molecular sieve adsorbents and
key mechanical equipment that support the quality, efficiency and Hydrocracking
profitability needs of customers around the globe. These products
are backed by a broad array of engineering and technical services
Hydroprocessing-resid
that facilitate successful installation and operations. Hydrotreating (2 processes)
For more information, visit UOP online at www.uop.com.
Hydrotreating/desulfurization
Isomerization (4 processes)
Treating-pressure swing adsorption
Visbreaking
Technical articles
Technology advancements in benzene saturation
Process and catalyst innovations in hydrocracking
to maximize high-quality distillate fuel
Viscolube SpA
Worley Parsons
Sulfur recovery
Alkylation
Alkylate, butanes to alkylate - CDTECH
Alkylation - DuPont
Alkylation - Lummus Technology, a CB&I company
Alkylation - Refining Hydrocarbon Technologies LLC
Alkylation - UOP (2 processes)
Alkylation, low-temperature acid catalyzed - CDTECH
Alkylation, sulfuric acid - ExxonMobil Research and Engineering Co.
Alkylation-HF - UOP
Aromatics
Aromatics - GTC Technology (3 processes)
Aromatics extractive distillation - Uhde GmbH
Aromatics recovery - GTC Technology
Benzene saturation - GTC Technology
Paraxylene - GTC Technology
Styrene recovery - GTC Technology
Xylene isomerization - GTC Technology
Biofuels
Biodiesel - Lurgi GmbH
Biodiesel - Refining Hydrocarbon Technologies LLC
Green diesel - UOP
Catalytic cracking
Deep catalytic cracking - Shaw
Fluid catalytic cracking - ExxonMobil Research and Engineering Co.
Fluid catalytic cracking - KBR
Fluid catalytic cracking - Lummus Technology, a CB&I company
Fluid catalytic cracking - Shaw
Fluid catalytic cracking - Shell Global Solutions International B.V.
Fluid catalytic cracking - UOP
Fluid catalytic cracking for maximum olefins - Lummus Technology, a CB&I company
Fluid catalytic cracking, high olefin - KBR
Fluid catalytic cracking, residual - KBR
Fluid catalytic cracking-pretreatment - Haldor Topsøe A/S
Resid catalytic cracking - Shaw
Resid cracking - Axens
Catalytic reforming
Catalytic reforming - Axens
Catalytic reforming - UOP
Coking
Coking - Foster Wheeler USA Corp.
Coking - KBR
Coking - Lummus Technology, a CB&I company
Coking, fluid - ExxonMobil Research and Engineering Co.
Deasphalting/asphalt
Asphaltene pelletization - KBR
Deasphalting - Foster Wheeler USA Corp.
Deasphalting - KBR
Desulfurization-fuels
Desulfurizaton - GTC Technology
Diesel upgrading - Haldor Topsøe A/S
Diesel-ultra-low-sulfur diesel (ULSD) - Haldor Topsøe
Gasoline desulfurization, ultra-deep - ExxonMobil Research and Engineering Co.
Hydrogenation/hydrodesulfurization - Refining Hydrocarbon Technologies LLC
Distillation-Crude
Crude distillation - Foster Wheeler USA Corp.
Crude distillation - Shell Global Solutions International B.V.
Crude distillation - TECHNIP
Ethers
Ethers - Snamprogetti, a company of Saipem
Ethers-ETBE - CDTECH
Ethers-ETBE - Uhde GmbH
Ethers-MTBE - CDTECH
Ethers-MTBE - Uhde GmbH
Olefin etherification - Refining Hydrocarbon Technologies LLC
TAEE, from refinery C5 feeds - CDTECH
TAME, from refinery and steam cracker C5 feeds - CDTECH
TAME, from refinery C5 feeds - CDTECH
Gasification
Gasification - ExxonMobil Research and Engineering Co.
Gasification - GE Energy
Gasification - Shell Global Solutions International B.V.
Gasification-PDQ - Uhde GmbH
Gasification-PSG - Uhde GmbH
Multipurpose gasification - Lurgi GmbH
Hydrocracking
Hydrocracking - Axens
Hydrocracking - Chevron Lummus Global LLC
Hydrocracking - DuPont
Hydrocracking - Haldor Topsøe A/S
Hydrocracking - Shell Global Solutions International B.V.
Hydrocracking - UOP
Hydrocracking, moderate pressure - ExxonMobil Research and Engineering Co.
Hydrocracking, resid - Chevron Lummus Global LLC
Hydrocracking-residue - Axens
Hydrogen
Hydrogen - TECHNIP
Hydrogen - Uhde GmbH
Hydrogen (steam reforming) - Lurgi GmbH
Hydrogen-HTCR and HTCR twin plants - Haldor Topsøe
Hydrogen-HTER-p - Haldor Topsøe
Hydrogen—Methanol-to-shift - Haldor Topsøe
Hydrogen-recovery - Air Products and Chemicals Inc.
Hydrogen-steam methane reforming (SMR) - Haldor Topsøe A/S
Hydrogen-steam reforming - Foster Wheeler USA Corp.
Prereforming with feed ultra purification - Davy Process Technology
Pressure swing adsorption-rapid cycle - ExxonMobil Research and Engineering Co.
Hydrogenation
Hydrogenation - CDTECH
Hydrogenation, selective for MTBE/ETBE C4 raffinate - CDTECH
Hydrogenation, selective for refinery C4 feeds - CDTECH
Hydrogenation-benzene in reformate - CDTECH
Hydrogenation-selective for refinery C5 feeds - CDTECH
Hydroprocessing
Hydroprocessing-resid - UOP
Hydroprocessing, ULSD - ExxonMobil Research and Engineering Co.
Hydrotreating
Hydrotreating - CDTECH
Hydrotreating - Chevron Lummus Global LLC
Hydrotreating - DuPont
Hydrotreating - Haldor Topsøe A/S
Hydrotreating - UOP (2 processes)
Hydrotreating, diesel - Axens
Hydrotreating, pyrolysis gasoline - GTC Technology
Hydrotreating/desulfurization - UOP
Hydrotreating-RDS/VRDS/UFR/OCR - Chevron Lummus Global LLC
Hydrotreating-resid - Axens
Isomerization
Isomerization - Axens
Isomerization - CDTECH
Isomerization - UOP (4 processes)
Isooctene/isooctane
Isooctene/isooctane - KBR
Isooctene/isooctane - Refining Hydrocarbon Technologies LLC
Isooctene/isooctane - Snamprogetti, a company of Saipem
Isooctene/isooctane, conversion of refinery MTBE units - CDTECH
Lubes
Hydrofinishing/hydrotreating - Uhde GmbH
Lube extraction - Bechtel Corp. (2 processes)
Lube hydrotreating - Bechtel Corp. (2 processes)
Lube oil refining, spent - Axens
Lube treating - Uhde GmbH
Spent lube oil re-refining - Axens
Olefins
Butene-1 recovery - Snamprogetti, a company of Saipem
Isobutylene, from MTBE decomposition - CDTECH
Isobutylene, high purity - Snamprogetti, a company of Saipem
Olefins recovery - Air Products and Chemicals Inc.
Olefins-butenes extractive distillation - Uhde GmbH
Olefins-dehydrogenation of light paraffins to olefins - Uhde GmbH
Refinery offgas-purification and olefins recovery - Shaw
Oxygen enrichment
Oxygen enrichment for Claus units - Linde AG, Division Gas and Engineering
Oxygen enrichment for FCC units - Linde AG, Division Gas and Engineering
Petrochemicals
Carboxylic acid recovery - GTC Technology
Dimethyl terephthlate - GTC Technology
Sulfur recovery
Sulfur processing - Goar, Allison & Associates, Inc., an Air Products Company
Sulfur recovery - Goar, Allison & Associates, Inc., an Air Products Company
Sulfur recovery - Worley Parsons
Treating
Treating-phenolic caustic - Merichem Chemical & Refinery Services LLC, Process Technology Division
Treating-pressure swing adsorption - UOP
Treating-spent caustic deep neutralization - Merichem Chemical & Refinery Services LLC, Process
Technology Division
Treating-acid gases
Gas treating–H2S removal - ExxonMobil Research and Engineering Co.
H2S removal - Merichem Chemical & Refinery Services LLC, Gas Technology Products Division (3 processes)
Treating - ThioSolv LLC
Treating-gases - Merichem Chemical & Refinery Services LLC, Process Technology Division
Treating-sour water stripper gas - ThioSolv LLC
Wet gas scrubbing (WGS), wet gas scrubbing plus - ExxonMobil Research and Engineering Co.
Treating-flue gas
Flue gas denitrification - Haldor Topsøe A/S
NOX abatement - ExxonMobil Research and Engineering Co.
Treating-fuels
Treating-coker LPG to low total sulfur levels - Merichem Chemical & Refinery Services LLC,
Process Technology Division
Treating-gasoline and LPG - Merichem Chemical & Refinery Services LLC, Process Technology Division
Treating-gasoline desulfurization ultra deep - Merichem Chemical & Refinery Services LLC,
Treating-gasoline sweetening - Merichem Chemical & Refinery Services LLC, Process Technology Division
Treating-jet fuel/kerosine - Merichem Chemical & Refinery Services LLC, Process Technology Division
Treating-kerosine and heavy naphtha sweetening - Merichem Chemical & Refinery Services LLC,
Treating-propane - Merichem Chemical & Refinery Services LLC, Process Technology Division
Treating-reformer products - Merichem Chemical & Refinery Services LLC, Process Technology Division
Treating-offgas
Flue gas desulfurization-SNOX - Haldor Topsøe A/S
NOX reduction, low temperature - Belco Technologies Corp.
SO2 removal, regenerative - Belco Technologies Corp.
Sour gas treatment - Haldor Topsøe A/S
Spent acid regeneration - Haldor Topsøe A/S
Wet scrubbing system, EDV - Belco Technologies Corp.
Upgrading-heavy oil
Deep thermal conversion - Shell Global Solutions International B.V.
Emulsion residue upgrade - Quadrise Fuel International
Heavy oil upgrading - KBR
Hydroprocessing-heavy oil and residue - Genoil Inc.
Thermal gasoil - Shell Global Solutions International B.V.
Visbreaking
Visbreaking - Foster Wheeler USA Corp.
Visbreaking - Shell Global Solutions International B.V.
Waxes
Catalytic dewaxing - ExxonMobil Research and Engineering Co.
Dewaxing - Bechtel Corp.
Dewaxing - Chevron Lummus Global LLC
Dewaxing/wax deoiling - Bechtel Corp.
Slack wax deoiling - Uhde GmbH
Wax hydrotreating - Bechtel Corp.
White oil and wax hydrotreating - Uhde GmbH
Alkylate, butanes to alkylate

Application: With the conversion of butanes to high-value motor fuel al-
kylate using the CDAlkyPlus process, NGL producers now have another Recycle isobutane
n-Butane
route to upgrade butanes to gasoline blend stock. By using isobutylene Isobutylene/isobutane
feed Fresh
as the sole olefin source, the CDAlkyPlus technology allows for the prof- sulfuric acid
itable conversion of isobutylene and isobutane into high-value motor n-Butane
fuel alkylate. isomerization
Product
fractionation
Description: The patented CDAlkyPlus process is a low-temperature sul-
furic acid-catalyzed alkylation process coupled with a simple olefin pre- Olefin
Separation
treatment step. This combination provides significant benefits over direct Isobutane pretreatment
dehydrogenation
alkylation of isobutylene as well as other isobutylene upgrading pro- Alkylation Alkylate product
reaction
cesses such is isooctene production. Because isobutane and isobutylene
are incorporated together to produce a high-value alkylate product, the
CDAlkyPlus process produces two times the volume of gasoline blend-
stock compared with isooctene production. This process is ideal for use
downstream of an isobutane dehydrogentation process. The whole de-
hydrogenation unit product, a roughly 50/50 blend of isobutane and
Process advantages: The benefits of CDAlkyPlus process:
isobutylene, is fed directly to the CDAlkyPlus process.
Compared to direct alkylation of isobutylene
This technology also provides a unique opportunity for revamp-
• Lower acid consumption
ing an existing dehydrogenation unit-based methyl tertiary butyl ether
• Compressor horsepower requirements reduced by 50%
(MTBE) plant to produce alkylate. Much of the existing MTBE equip-
• Lower utilities
ment can be used in the CDAlkyPlus process, thus reducing capital
• No caustic waste streams
requirements. For these retrofit cases, the isobutane recycle around
• Higher octane alkylate product
the dehydrogenation unit is essentially eliminated. This means the n-
• Lower vapor pressure product.
butane capacity of the complex can be doubled without expanding the
Compared to iso-octene product alternative
existing dehydrogenation unit.
• Twice the product volume.
Licensor: CDTECH.
click here to e-mail for more information

Alkylation
Application: To combine propylene, butylenes and amylenes with isobutane Propane
product 5
in the presence of strong sulfuric acid to produce high-octane branched 2
chain hydrocarbons using the STRATCO Effluent Refrigeration Alkylation
process. 3 n-Butane
6 product
4
Products: Branched chain hydrocarbons for use in high-octane motor 1
fuel and aviation gasoline.
Alkylate
product
Description: Plants are designed to process a mixture of propylene, Olefin feed
butylenes and amylenes. Olefins and isobutane-rich streams along with START
a recycle stream of H2SO4 are charged to the STRATCO Contactor reac-

tor (1). The liquid contents of the Contactor reactor are circulated at high i-Butane
velocities and an extremely large amount of interfacial area is exposed START
between the reacting hydrocarbons and the acid catalyst from the acid
settler (2). The entire volume of the liquid in the Contactor reactor is main-
tained at a uniform temperature, less than 1°F between any two points
within the reaction mass. Contactor reactor products pass through a flash
drum (3) and deisobutanizer (4). The refrigeration section consists of a Economics (basis: butylene feed):
compressor (5) and depropanizer (6). Investment (basis: 10,000-bpsd unit), $ per bpsd 4,500
The overhead from the deisobutanizer (4) and effluent refrigerant Utilities, typical per bbl alkylate:
recycle (6) constitutes the total isobutane recycle to the reaction zone. Electricity, kWh 13.5
This total quantity of isobutane and all other hydrocarbons is maintained Steam, 150 psig, lb 180
in the liquid phase throughout the Contactor reactor, thereby serving to Water, cooling (20°F rise), 103 gal 1.85
promote the alkylation reaction. Onsite acid regeneration technology is Acid, lb 15
also available. Caustic, lb 0.1
Product quality: The total debutanized alkylate has RON of 92 to 96 Installation: Over 850,000 bpsd licensed capacity.
clear and MON of 90 to 94 clear. When processing straight butylenes,
the debutanized total alkylate has RON as high as 98 clear. Endpoint of Reference: Hydrocarbon Processing, Vol. 64, No. 9, September 1985,
the total alkylate from straight butylene feeds is less than 390°F, and less pp. 67–71.
than 420°F for mixed feeds containing amylenes in most cases.
Licensor: DuPont.

Alkylation
Application: The AlkyClean process converts light olefins into alkylate
by reacting the olefins with isobutane over a true solid acid catalyst.
AlkyClean’s unique catalyst, reactor design and process scheme allow *TPCVUBOF )ZESPHFO
operation at low external isobutane-to-olefin ratios while maintaining
excellent product quality. *TPCVUBOFGFFE
3FBDUPS 1SPEVDU
0MFmOGFFE
Products: Alkylate is a high-octane, low-Rvp gasoline component used TZTUFN EJTUJMMBUJPO
O#VUBOF

for blending in all grades of gasoline. "MLZMBUF

QSPEVDU
Description: The light olefin feed is combined with the isobutane make-
$BUBMZTU
up and recycle and sent to the alkylation reactors which convert the )ZESPHFO
SFHFOFSBUJPO
olefins into alkylate using a solid acid catalyst (1). The AlkyClean process
uses a true solid acid catalyst to produce alkylate, eliminating the safety
and environmental hazards associated with liquid acid technologies. Si-
multaneously, reactors are undergoing a mild liquid-phase regeneration
using isobutane and hydrogen and, periodically, a reactor undergoes a
higher temperature vapor phase hydrogen strip (2). The reactor and mild
regeneration effluent is sent to the product-fractionation section, which
produces n-butane and alkylate products, while also recycling isobutane
and recovering hydrogen used in regeneration for reuse in other refinery Installation: Demonstration unit at Neste Oil’s Porvoo, Finland Refinery.
hydroprocessing units (3). The AlkyClean process does not produce any
acid soluble oils (ASO) or require post treatment of the reactor effluent or Reference: “The AlkyClean process: New technology eliminates liquid
final products. acids,” NPRA 2006 Annual Meeting, March 19–21, 2006.
D’Amico, V., J. Gieseman, E. von Broekhoven, E. van Rooijen and
Product: The C5+ alkylate has a RON of 93–98 depending on processing H. Nousiainen, “Consider new methods to debottleneck clean alkylate
conditions and feed composition. production,” Hydrocarbon Processing, February 2006, pp. 65–70.
Economics: Licensor: Lummus Technology, Albemarle Catalysts and Neste Oil.
Investment (2007 USGC basis 10,000-bpsd unit) $/bpsd 5,200
Utility and catalyst costs, $/gal (2007) 0.10

Alkylation
Application: The RHT-Alkylation process is an improved method to react Mix olefin feed
C3– C5 olefins with isobutane using the classical sulfuric acid alkylation
C3 purge
process. This process uses a unique mixing device — eductor(s) — that
Condensed 5 C3 6
provides low-temperature (25°F – 30°F) operations at isothermal condi- C4s removal
Absorber C4 system Depropanizer
tions. This eductor mixing device is more cost-effective than other de-
vices being used or proposed. It is maintenance free and does not re- C4s
quire replacement every two to three years. This mixing device can be a Olefin/HC reactor feed Isobutane
retrofit replacement for existing contactors. In addition, the auto refrig- 1
Reactor Reactor 2 Crude 7
eration vapor can be condensed by enhancing pressure and then easily Reactor
system effluent
HC/separation
Finishing alkylate Alkylate n-Butane
feed coalescer separation
absorbed in hydrocarbon liquid, without revamping the compressor. Acid recycle
Alkylate product
Description: In the RHT-Alkylation, C3 – C5 feed from FCC or any other Acid makeup Acid return
source including steam cracker, etc., with isobutane make-up, recycle Spent acid
isobutene, and recovered hydrocarbons from the depropanizer bottom

and refrigeration vapors are collected in a surge drum — the C4 system
(5). The mixture is pumped to the reactor (1) to the eductor suction port.
The motive fluid is sent to the eductor nozzle from the bottom of reac-
tor, which is essentially sulfuric acid, through pumps to mix the reactants
with the sulfuric-acid catalyst.
The mixing is vigorous to move the reaction to completion. The The hydrocarbon is sent to distillation column(s) (7), to separate alky-
makeup acid and acid-soluble oil (ASO) is removed from the pump dis- late product and isobutane, which is recycled. The butane is sent to offsites
charge. The process has provisions to install a static mixer at the pump or can be converted back to isobutane for processing units requirements.
discharge. Some feed can be injected here to provide higher OSV, which The auto refrigeration occurs in the reactor at temperatures 25 –30°F. The
is required for C3 alkylation. Reactor effluent is withdrawn from the isothermal condition lowers acid consumption and yields higher octane
reactor as a side draw and is sent to acid/ hydrocarbon coalescer (2) product due to improved selectivity of 2,4,4 trimethylpentane.
where most of the acid is removed and recycled to the reactor (1). The The auto-refrigeration vapor is first enhanced by the ejector and
coalescers are being used by conventional process to reduce the acid in then absorbed in a heavy liquid — alkylate, which provides a low-cost
the hydrocarbon phase to 7–15 wppm. The enhanced coalescer design option and then condensed. Some liquid is sent to depropanizer (6);
RHT can reduce the sulfuric acid content in the hydrocarbon phase to propane and light ends are removed. The bottoms are recycled to C4
negligible levels (below <1 wppm). system and sent to the reactor.
After the coalescer, the hydrocarbon phase is heated and flashed The major advances of RHT process are threefold: eductor mixing
increasing the alkylate concentration in the hydrocarbon, which is sent device, advance coalescer system to remove acid from hydrocarbon (dry
through the finishing coalescer (4) where essentially all of the remaining system), and C4 autorefrigeration vapors recovery by absorption, mak-
acid is removed. ing compressor redundant.
Continued 
Alkylation, continued Commercial units: Technology is ready for commercialization.
References:
Economics: For a US Gulf Coast unit 1Q 2006 with a capacity of 10,000 US patent 5,095168.
bpd alkylate unit US Patent 4,130593.
CAPEX ISBL, MM USD 29.5 Kranz, K., “Alkylation Chemistry,” Stratco, Inc., 2001.
Power, kWh 2,800 Branzaru, J., “Introduction to Sulfuric Acid Alkylation,” Stratco, Inc.,
Water, cooling, m3/ h 1,750 2001.
Steam, kg / h 25,600 Nelson, Handbook of Refining.
FCC Feed (about 15% isobutelene in C4 mixed stream) Meyers, R. A., Handbook of Refining, McGraw Hill, New York,
1997.
Product properties: Octane (R+M) / 2:94.8 – 95.4
Licensor: Refining Hydrocarbon Technologies LLC.

Alkylation
Application: The modified HF Alkylation technology is used with HF al- HF to isostripper
(internal regeneration)
kylation technology to reduce aerosol formation in the event of an HF
HF to Rx section
release, while maintaining unit operability and product quality. The UOP
Alkad Modified HF Alkylation process and the UOP ReVap Modified Al-
Additive
kylation process are both passive mitigation systems that will reduce stripper
aerosol from any leak that occurs while additive is in the system. i-C4 Acid
HF from recycled regeneration
Rx section column
Description: The additive stripper sends acid, water and light-acid sol-
uble oils overhead and on to the acid regenerator. Heavy acid soluble Polymer to i-C4
i-C4 neutralization
oils and the concentrated HF-additive complex are sent to the additive
stripper bottoms separator. From this separator the polymer is sent to
neutralization, and the HF-additive complex is recycled to the reactor
section. The acid regenerator removes water and light-acid soluble oils Light acid
soluble oils and CBM
from the additive stripper overhead stream. The water is in the form of HF – additive to Rx section to neutralization
a constant boiling mixture (CBM) of water and HF.
There is no expected increase in the need for operator manpower.
Maintenance requirements are similar to equipment currently in stan-
dard operation in an HF alkylation unit in similar service.
Installation: Twelve units have been licensed at present. Three are in

operation.
Licensor: UOP.

Alkylation
Application: The UOP Indirect Alkylation (InAlk) process uses solid cata-
Polymerization Debutanizer Saturation Product
lysts to convert light olefins (mainly C4 but also C3 and C5 ) to alkylate. reactors column reactor stripper Offgas
Olefin
feed Raffinate
Description: The InAlk process makes premium alkylate using a combi-
nation of commercially proven technologies. Iso-butene reacts with itself
or with other C3 – C5 olefins via polymerization. The resulting mixture of
1
higher molecular weight iso-olefins may then be hydrogenated to form 4 5
2 3
a high-octane paraffinic gasoline blendstock that is similar to alkylate,
but usually higher in octane, or it may be left as an olefinic high-octane
gasoline blending component.
Either resin or solid phosphoric acid (SPA) catalysts are used to po-
lymerize the olefins. Resin catalyst primarily converts iso-butene. SPA
catalyst also converts n-butenes. The saturation section uses either a
Alkylate
base-metal or noble-metal catalyst. Makeup hydrogen
Feed: A wide variety of feeds can be processed in the InAlk process.

Typical feeds include FCC-derived light olefins, steam-cracker olefins
and iC4 dehydrogenation olefins.
Installation: The InAlk process is an extension of UOP’s catalytic con-

densation and olefin saturation technologies. UOP has licensed and de-
signed more than 400 catalytic condensation units for the production of
polygasoline and petrochemical olefins and more than 200 hydrogena-
tion units of various types. Currently, 10 InAlk units are in operation.
Licensor: UOP.

Alkylation, low-temperature acid Propane to storage
catalyzed
DeC3
Application: The patented CDAlky process is an advanced sulfuric acid-
catalyzed alkylation process for the production of motor fuel alkylate.
Description: The CDAlky low-temperature sulfuric acid alkylation tech-

nology reacts light olefin streams from refinery sources such as fluid Olefin feed iC4 recycle
iC4 Makeup
catalytic cracking units or from steam-cracking units with isoparaffins
to produce motor fuel alkylate. Central to the CDAlky process is a novel
scalable contactor/reactor design. The CDAlky process is available for
Fractionator
license to the petroleum refining and petrochemical industries. Reaction
The process flow diagram shows the basic configuration to process Separation
n-Butane to storage
a mixed-C4 olefin feed and produce a high-octane motor fuel alkylate,
without the need for a reactor effluent alkaline water wash. The CDAlky Alkylate product to storage
Acid recycle
process yields a higher quality product while consuming significantly
less acid than conventional sulfuric acid-based technologies. The flow Fresh acid Spent acid
scheme is also less complex than conventional designs, which reduces
capital and operating costs.
Conventional sulfuric acid alkylation units use mechanical mixing in Advantages. The benefits of the CDAlky process:
their contactors, which are characterized by their high acid consump- • Lower acid consumption
tion. In addition, they are unable to take full benefit of operating at very • Lower utilities
low temperature, which substantially improves alkylate quality and re- • Reduced operating cost
duces acid consumption. This scalable, vertical reactor also reduces capi- • Reduced environmental exposure
tal costs and plot space requirements. This process has also eliminated • Higher octane product
the need for reactor effluent alkaline water wash, thus reducing caustic • Lower CAPEX—simpler flowsheet with fewer pieces of equipment
waste. In addition, this dry fractionation section reduces the potential • Highly flexible operation range—maximum absolute product oc-
for downstream corrosion and thereby reducing overall maintenance tane or maximum octane barrels
costs. • Lower maintenance—no mechanical agitator or complex seals
• Less corrosion due to dry system
• No caustic waste stream.
Licensor: CDTECH.

Alkylation, sulfuric acid

Propane product
Application: ExxonMobil’s Research & Engineering (EMRE’s) autore-
frigerated sulfuric-acid catalyzed process that combines butylene (and
propylene or pentylene if desired) with isobutane to produce high-oc- 3
tane gasoline components that are particularly attractive in locations 2
that are MON limited. Technology can be installed rassroots or retrofit Refrigerant Recycle Butane
isobutane product
into existing alkylation facilities.
Products: A low-sulfur, low-Rvp, highly isoparaffinic, high-octane (es- 1

4
pecially MON) gasoline blendstock is produced from this alkylation pro- 5 6
cess.
Olefin feed
Description: Olefin feed and recycled isobutane are introduced into the START
stirred, autorefrigerated reactor (1). Mixers provide intimate contact be- Makeup Alkylate
Recycle acid isobutane product
tween the reactants and acid catalyst. Highly efficient autorefrigeration
removes heat of reaction heat from the reactor. Hydrocarbons, vaporized
from the reactor to provide cooling, are compressed (2) and returned to
the reactor. A depropanizer (3), which is fed by a slipstream from the
refrigeration section, is designed to remove any propane introduced to Utilities: typical per barrel of alkylate produced:
the plant with the feeds. Water, cooling, M gal 2
Power, kWH 9
Hydrocarbon products are separated from the acid in the settler con- Steam, lb 200
taining proprietary internals (4). In the deisobutanizer (5), isobutane is H2SO4, lb 19
recovered and recycled along with makeup isobutane to the reactor. NaOH, 100%, lb 0.1
Butane is removed from alkylate in the debutanizer (6) to produce a Operating experience: Extensive commercial experience in both
low-Rvp, high-octane alkylate product. A small acid stream containing ExxonMobil and licensee refineries, with a total operating capacity of
acid soluble oil byproducts is removed from the unit and is either regen- 137 bpsd at 13 locations worldwide. Unit capacities currently range
erated on site or sent to an off-site sulfuric acid regeneration facility to from 2,000 bpsd to 30,000 bpsd. In addition, the world’s largest alkyla-
recover acid strength. tion unit, with a capacity of 83,000 bpsd will be starting up in 2008 at
Reliance ’Petroleum Limited’s Export Refinery in Jamnagar, India. Anoth-
Yields:
er licensed unit is in the design phase with a capacity of 16,000 bpsd.
Alkylate yield 1.8 bbl C5+ / bbl butylene feed
The larger units take advantage of the single reactor/settler trains with
Isobutane required 1.2 bbl / bbl butylene feed
capacities up to 10,000 bpsd.
Alkylate quality 97 RON / 94 MON
Continued 
Rvp, psi 3
Alkylation, sulfuric acid, continued Economic advantages: Better economy of scale—Reactor system is sim-
ple and easily expandable with 10,000 bpsd single train capacities easily
Technical advantages: achievable
• Autorefridgeration is thermodynamically more efficient, allows Reference: Lerner, H., “Exxon sulfuric acid alkylation technology,” Hand-
lower reactor temperatures, which favor better product quality, and book of Petroleum Refining Processes, Second Ed., R. A. Meyers, Ed.,
lowers energy usage. pp. 1.3–1.14.
• Staged reactor results in a high average isobutane concentration,
which favors high product quality. Licensor: ExxonMobil Research & Engineering Co.
• Low space velocity results in high product quality and reduced
ester formation eliminating corrosion problems in fractionation equip-
ment. click here to e-mail for more information
• Low reactor operating pressure translates into high reliability for
the mechanical seals for the mixers, which operate in the vapor phase.
Alkylation—HF
Application: UOP HF Alkylation improves gasoline quality by adding
clean-burning, mid-boiling-range isoparaffins and reducing gasoline
pool vapor pressure and olefin content by conversion of C3 – C5 olefin Cooling
water
components to alkylate.
Description: The alkylation reaction catalytically combines C3 – C5 olefins Saturate
with isobutane to produce motor-fuel alkylate. Alkylation takes place in feed
Olefin feed
the presence of HF catalyst under conditions selected to maximize alkyl-
ate yield and quality.
UOP offers two configurations. Both ensure efficient contacting and Recycle n-C4
i-C4 product
mixing of hydrocarbon feed with the acid catalyst. Our gravity flow de- Propane
product
sign provides good mixing without the need for a catalyst circulation
pump. The forced circulation design reduces acid inventory and reaction Forced circulation design
Alkylate
vessel elevations.
Acid regeneration occurs in the acid regenerator or via a patented
internal-acid-regeneration method. Internal regeneration allows the
refiner to shutdown the acid regenerator, thereby realizing a utility
savings as well as reducing acid consumption and eliminating polymer
disposal.
Feed: Alkylation feedstocks are typically treated to remove sulfur and Efficiency: HF Alkylation remains the most economically viable method
for the production of alkylate. The acid consumption rate for HF Alkyla-
water. In cases where MTBE and TAME raffinates are still being pro-
tion is less than 1/100th the rate for sulfuric alkylation units. And un-
cessed, an oxygenate removal unit (ORU) may be desirable.
like sulfuric alkylation units, HF Alkylation does not require refrigeration
Selective hydrogenation of butylene feedstock is recommended to
equipment to maintain a low reactor temperature.
reduce acid regeneration requirements, catalyst (acid) consumption and
increase alkylate octane by isomerizing 1-butene to 2-butene. Installations: Since 1942, UOP has licensed 216 alkylation units.
Licensor: UOP.

Aromatics Makeup H2
Reactor purge gas
Application: DX process converts ethylbenzene (EB) contained in the C8
aromatics feedstocks to high-purity benzene plus ethane and upgrades Offgas
mixed xylenes to premium grade. The feedstocks can be either pygas C8
or reformer C8 streams. The technology features a proprietary catalyst
with high activity, low ring loss and superior long catalyst cycle length. Light ends
This technology is partnered with Toray Industries, Inc.

Reactor
Description: The technology encompasses two main processing areas:
reactor section and product distillation section. In this process, C8 aro- Deheptanizer
matics feed stream is first mixed with hydrogen. The mixed stream is then
heated against reactor effluent and sent through a process furnace. The Feed
heated mixture is fed into the DX reaction unit, where EB is de-alkylated
at very high conversion and xylenes are isomerized to equilibrium. Reduced EB product
The reactor effluent is cooled and flows to the separator, where the
hydrogen-rich vapor phase is separated from the liquid stream. A small
portion of the vapor phase is purged to control the recycle hydrogen
purity. The recycle hydrogen is then compressed, mixed with makeup • Low ring loss at very high EB conversion
hydrogen and returned to the reactor. • On-specification benzene with traditional distillation
The liquid stream from the separator is pumped to the deheptanizer • Extremely stable catalyst
to remove light hydrocarbons. The liquid stream from the deheptanizer • Low hydrogen consumption
overhead contains benzene and toluene and is sent to distillation sec- • Moderate operating parameters
tion to produce high-purity benzene and toluene products. The liquid • Efficient heat integration scheme reduces energy consumption
stream from the deheptanizer bottoms contains mixed xylenes and a • Turnkey package for high-purity benzene, toluene and PX produc-
small amount of C9+ aromatics. This liquid stream is sent to the PX re- tion available from licensor.
covery section. The mixed xylenes stream is very low in EB due to high
EB conversion in the DX reactor, which debottlenecks the PX recovery Economics: Feedrate (pygas basis): 100 thousand tpy (2,200 bpsd);
unit. erected cost: $10 MM (ISBL, 2007 US Gulf Coast Basis)
Process advantages: Installation: Commercialized technology available for license.

• Simple, low cost fixed-bed reactor design
• Flexible feedstocks and operation Licensor: GTC Technology.
• High EB conversion per pass can be nearly 100wt%
• DX products are isomerized to equilibrium composition of xylene,
which unloads the isomerization unit click here to e-mail for more information
Aromatics
Fuel gas
Application: GT-STDP process technology produces benzene and para- H2
enriched xylenes from toluene disproportionation. The technology fea- Separator
tures a proprietary catalyst with high activity and selectivity toward par-
axylene.
Description: The technology encompasses three main processing areas: Reactor

reactor section, product distillation and paraxylene (PX) recovery. Fresh Heater Stabilizer
toluene and recycled toluene from the product distillation area are mixed
with hydrogen. The hydrogen-to-toluene ratio is about 1 to 1.5. The
mixed stream is heated against reactor effluent and through a process Benzene
furnace. The heated vapor stream flows to the reactor, which produces PX recovery
the benzene and xylenes. The toluene disproportionation reactions are Product
distillation
(>90 wt % PX)
Toluene
mildly exothermic.
Toluene recycle C9+ aromatics
portion of the vapor phase is purged to control recycle hydrogen purity.
The recycle hydrogen is then compressed, mixed with makeup hydrogen • Physically stable catalyst
and returned to the reactor. • Low hydrogen consumption
The liquid stream from the separator is pumped to the stripper to • Moderate operating parameters; catalyst can be used as replace-
remove light hydrocarbons. The liquid stream from the stripper bottoms ment for traditional toluene disproportionation unit or in grassroots de-
contains benzene, toluene, mixed xylenes and a small quantity of C9+ signs
aromatics. This liquid stream is sent to product distillation section to ob- • Efficient heat integration scheme; reduced energy consumption
tain benzene product, toluene for recycle to the reactor, mixed xylenes • Turnkey package for high-purity benzene and paraxylene produc-
to the PX recovery section and C9+ aromatics. The PX in the mixed xy- tion available from licensor.
lenes stream is over 90% purity, which permits low-cost crystallization
technology to be used for the PX purification. Economics: Feed rate 1,000 thousand tpy (22,000 bpsd), erected cost
$25MM (ISBL, 2008 US Gulf Coast Basis)
Advantages:
• Simple, low cost fixed-bed reactor design Installation: GTC markets this technology on a select, regional basis.
• Drop-in catalyst replacement for existing hydroprocessing reactors There are two commercial applications of the GT-STDP process.
• Paraxylene enriched to over 90% in the xylene stream
• On-specification benzene with traditional distillation Licensor: GTC Technology.

Aromatics Recycle plus

Application: GT-TransAlk produces benzene and xylenes from toluene Toluene make-up H2
(optional)
and/or heavy aromatics streams. The technology features a proprietary
catalyst and can accommodate varying ratios of feedstock while main- C9/C10
taining high activity and selectivity.
Charge
Process description: The technology encompasses three main process- Heavy
heater
Offgas
Light HC
ing areas: splitter, reactor and stabilizer sections. The heavy-aromatics aromatics
Feed
stream (C9+ feed) is fed to the splitter. The overhead C9 /C10 aromatic splitter Reactor
Stabilizer
product is the feed to the transalkylation reactor section. The splitter
bottoms are exchanged with other streams for heat recovery before Separator
leaving the system.

C11+
The aromatic product is mixed with toluene and hydrogen, vapor- Aromatics to
ized and fed to the reactor. The reactor gaseous product is primarily product
fractionation
unreacted hydrogen, which is recycled to the reactor. The liquid prod-
uct stream is subsequently stabilized to remove light components. The
resulting aromatics are routed to product fractionation to produce the
final benzene and xylene products.
• Catalyst is resistant to impurities common to this service
The reactor is charged with zeolite catalyst, which exhibits both long
• Moderate operating parameters; catalyst can be used as replace-
life and good flexibility to feed stream variations including substantial
ment to other transalkylation units, or in grass roots designs
C10 aromatics. Depending on feed compositions and light components
• Decreased hydrogen consumption due to low cracking rates
present, the xylene yield can vary from 25% to 32% and C9 conversion
• Significant decrease in energy consumption due to efficient heat
from 53% to 67%.
integration scheme.
Process advantages:
• Simple, low cost fixed-bed reactor design; drop in replacement for
Economics: Feedrate 1,000 thousand tpy (22,000 bpsd); erected cost
$18 MM (ISBL, 2007 US Gulf Coast Basis).
other catalysts
• Very high selectivity; benzene purity is 99.9% without extraction Installation: Two commercial licenses.
• Physically stable catalyst
• Flexible to handle up to 90+% C9+ components in feed with high Licensor: GTC Technology.
conversion

Aromatics extractive distillation

Nonaromatics
Application: Recovery of high-purity aromatics from reformate, pyrolysis
Extractive
gasoline or coke oven light oil using extractive distillation. distillation
column
Description: In Uhde’s proprietary extractive distillation (ED) Morphylane
process, a single-compound solvent, N-Formylmorpholine (NFM), alters the
vapor pressure of the components being separated. The vapor pressure of Aromatics
fraction
the aromatics is lowered more than that of the less soluble nonaromatics.
Aromatics
Nonaromatics vapors leave the top of the ED column with some solv
ent, which is recovered in a small column that can either be mounted on Stripper
column
the main column or installed separately.
Bottom product of the ED column is fed to the stripper to separate
pure aromatics from the solvent. After intensive heat exchange, the lean
Solvent+aromatics
solvent is recycled to the ED column. NFM perfectly satisfies the neces-
Solvent
sary solvent properties needed for this process including high selectivity,
thermal stability and a suitable boiling point.
Uhde’s new single-column morphylane extractive distillation process
uses a single-column configuration, which integrates the ED column and
the stripper column of the conventional design. It represents a superior
Reformate feedstock with low-aromatics content (20 wt%):
process option in terms of investment and operating cost.
Benzene
Economics: Quality
Benzene 10 wt ppm NA*
Pygas feedstock:
Production yield Benzene Benzene/toluene Consumption
Steam 320 kg/t ED feed
Benzene 99.95% 99.95%
Toluene – 99.98% *Maximum content of nonaromatics **Including benzene/toluene splitter
Quality
Benzene 30 wt ppm NA* 80 wt ppm NA* Installation: More than 55 Morphylane plants (total capacity of more
Toluene – 600 wt ppm NA* than 11 MMtpy). The first single-column Morphylane unit went
Consumption onstream in 2004.
Steam 475 kg/t ED feed 680 kg/t ED feed**
References: Diehl, T., B. Kolbe and H. Gehrke, “Uhde Morphylane Ex-
tractive Distillation—Where do we stand?” ERTC Petrochemical Confer-
ence, October 3–5, 2005, Prague.
Continued 
Aromatics extractive distillation, continued
Emmrich, G., U. Ranke and H. Gehrke, “Working with an extractive dis-
tillation process,” Petroleum Technology Quarterly, Summer 2001, p. 125.
Licensor: Uhde GmbH.

Aromatics recovery
Application: GT-BTX is an aromatics recovery technology that uses ex-
tractive distillation to remove benzene, toluene, and xylene (BTX) from
refinery or petrochemical aromatics streams such as catalytic reformate Raffinate
Lean solvent
or pyrolysis gasoline. With lower capital and operating costs, simplicity of
Aromatics to
operation, and range of feedstock and solvent performance, extractive Extractive
downstream
distillation
distillation is superior to conventional liquid-liquid extraction processes. Hydrocarbon column (EDC) Solvent
fractionation
feed
Flexibility of design allows use for grassroots aromatics recovery units, recovery
column
debottlenecking or expansion of conventional extraction systems.
Description: Hydrocarbon feed is preheated with hot circulating solvent

and fed at a midpoint into the extractive distillation column (EDC). Lean
solvent is fed at an upper point to selectively extract the aromatics into Aromatics-rich solvent
the column bottoms in a vapor/liquid distillation operation. The non-

aromatic hydrocarbons exit the top of the column and pass through a
condenser. A portion of the overhead stream is returned to the top of
the column as reflux to wash out any entrained solvent. The balance of • Energy integration options to further reduce operating costs
the overhead stream is raffinate product and does not require further • Higher product purity and aromatic recovery
treatment. • Recovers aromatics from full-range BTX feedstock
Rich solvent from the bottom of the EDC is routed to the solvent- • Distillation-based operation provides better control and simplified
recovery column (SRC), where the aromatics are stripped overhead. operation
Stripping steam from a closed-loop water circuit facilitates hydrocarbon • Proprietary formulation of commercially available solvent exhibits
stripping. The SRC is operated under a vacuum to reduce the boiling high selectivity and capacity
point at the base of the column. • Low solvent circulation rates
Lean solvent from the bottom of the SRC is passed through heat • Insignificant fouling due to elimination of liquid-liquid contactors
exchange before returning to the EDC. A small portion of the lean cir- • Fewer hydrocarbon emission sources for environmental benefits.
culating solvent is processed in a solvent regeneration step to remove
heavy decomposition products. Economics: New unit
The SRC overhead mixed aromatics product is routed to the purifi- Feedrate 12,000 bdp reformate or pygas
cation section, where it is fractionated to produce chemical-grade ben- ISBL capital cost $15 MM
zene, toluene and xylenes. Installations: Twenty-two.
Process advantages: Licensor: GTC Technology.
• Lower capital cost compared to conventional liquid-liquid extrac-
tion or other extractive distillation systems click here to e-mail for more information
Benzene saturation Offgas

Offgas
Application: GTC Technology’s GT-BenZap is a benzene saturation tech-
nology that allows refiners to achieve the upcoming benzene limit re-
quired by EPA’s regulations under Mobile Sources Air Toxics Phase 2 C5-
(MSAT2). Benzene saturation is applied when the logistics of benzene

recovery and production are unfavorable, or where the economy of scale
for benzene production is not sufficient. Full-range
C6- rich with Stabilizer
reformate
benzene
Description: GT-BenZap process features a reliable traditional design Reformate
paired with a proven nickel-based catalyst. The process consists of splitter
H2
hydrotreating a narrow-cut C6 fraction, which is separated from the
full-range reformate to saturate the benzene component into cyclo- Low-benzene gasoline
C7+
hexane. The reformate is first fed to a reformate splitter where the C6 blend stock
heart cut is separated as a side-draw fraction, while the C7+ cut and
the C5– light fraction are removed as bottom and top products of the
column.
The C6 olefins present in the C6 cut are also hydrogenated to par- Process advantages:
affins, while the C5– olefins removed at the top of the splitter are • Simple and reliable technology; low operating costs
not, thus preserving the octane number. The hydrogenated C6 frac- • An economical alternative to platinum-based systems
tion from the reactor outlet is sent to a stabilizer column where the • Ability to reduce the benzene in the reformate stream by over
remaining hydrogen and lights are removed overhead. The C5– cut, 99.9%
produced from the splitter overhead, is recombined with the hydroge- • Minimized impact to hydrogen balance and octane loss.
nated C6 cut within the GT-BenZap process in a unique manner that
reduces energy consumption and capital equipment cost. The light Installation: Technology available for license.
reformate is mixed with the C7+ cut from the splitter column and to-
gether form the full-range reformate, which is low in benzene. GTC Licensor: GTC Technology.
also offers a modular construction option and the possibility to reuse
existing equipment.

Paraxylene
High-purity PX PX recovery section
Application: CrystPX is a modern suspension crystallization technology production section
PX wash
for production of paraxylene (PX). The process can be applied in a single- Primary
centrifuge
stage for concentrated PX feedstock or in two stages for equilibrium
xylenes feed. The technology has fewer pieces of equipment, simplified
(Cake)
flow schemes and a more reliable operation compared to traditional
crystallization methods. Secondary
centrifuge
(Slurry)
(Slurry) PX lean filtrate
Description: Suspension crystallization of PX in the xylene isomer mix- PX melt
ture is used to produce PX crystals. The technology uses an optimized PX rich feed (Cake)
arrangement of equipment to obtain the required recovery and product
purity. Washing the PX crystal with the final product in a high efficiency Feed PX product
drum
pusher-centrifuge system produces the PX product.
When PX content in the feed is enriched above equilibrium, such
as streams originating from selective toluene conversion processes, the
proprietary crystallization process technology is even more economical
to produce high-purity PX product at high recoveries. The process tech-
nology takes advantage of recent advances in crystallization techniques • Operation is flexible to meet market requirements for PX purity
and improvements in equipment to create this cost-effective method for • System is easily amenable to future requirement for incremental
paraxylene recovery and purification. capacity increases
The design uses only crystallizers and centrifuges in the primary op- • Feed concentration of PX is used efficiently through an innovative
eration. This simplicity of equipment promotes low maintenance costs, flow scheme
easy incremental expansions and controlled flexibility. High-purity PX is • Technology is flexible to process a range of feed concentrations
produced in the front section of the process at warm temperatures, tak- (20–95 wt.% PX) using a single or multistage system
ing advantage of the high concentration of PX already in the feed. At • The aromatics complex using CrystPX technology is cost competi-
the back end of the process, high PX recovery is obtained by operating tive with adsorption-based systems for PX recovery.
the crystallizers at colder temperatures. This scheme minimizes recycling
excessive amounts of filtrate, thus reducing total energy requirements. Economics: For 400 thousand tpy capacity from concentrated feed:
CrystPX Other crystallization
Process advantages: technologies
• High PX purity and recovery ISBL Investment Cost $35 MM $45 MM
• Crystallization equipment is simple, easy to procure and opera- Paraxylene recovery 95% 95%
tionally trouble free Electricity consumption 50 kwh/ ton PX 80 kwh/ ton PX
• Compact design requires small plot size and lowest capital invest- Operation mode Continuous Batch
ment
Continued 
Paraxylene, continued
Installation: Two commercial licenses.
Licensor: CrystPX is a proprietary process technology marketed and li-
censed by GTC Technology Inc., in alliance with Lyondell.

Styrene recovery
Application: GT-Styrene is an extractive distillation (ED) process that di- C8 aromatics
rectly recovers styrene from the raw pyrolysis gasoline derived from the
Finishing
steam cracking of naphtha, gasoils and natural gas liquids (NGLs). The treatment
99.9+ wt%
produced styrene is high purity and suitable for polymerization at a very H2 Solvent
Styrene
attractive cost compared to conventional styrene production routes. If product
desired, the mixed xylenes can also be extracted from the pygas, up- Pygas C8 cut PA
grading their value as a chemical feedstock. The process is economically hydrogenation
attractive for pygas feeds containing more than 15,000 tpy styrene.
Description: Raw pyrolysis gasoline is prefractionated into a heartcut

Heavies
C8 stream. The resulting styrene concentrate is fed to an ED column
Feed Extractive Solvent Styrene
and mixed with a selective solvent, which extracts the styrene to the pretreatment distillation recovery finishing
tower bottoms. The rich solvent mixture is routed to a solvent recovery
column SRC), which recycles the lean solvent back to the ED column
and recovers the styrene overhead. A final purification step produces a
99.9% styrene product containing less than 50-ppm phenyl acetylene.
The ED column overhead can be further processed to recover a high-
Economics: Basis: 25,000 tpy styrene capacity
quality mixed-xylene stream. A typical world-scale cracker can produce
Typical USGC capital cost $25 million
approximately 25,000 tpy styrene and 75,000 tpy mixed xylenes from
Styrene value in pygas $800/ton
pyrolysis gasoline.
Styrene product sales value $1,400/ton
Process advantages: Net processing $160/ton
• Produces polymer-grade styrene at 99.9% purity Gross margin $11 million/yr
• Allows the recovery of isomer-quality mixed xylenes for paraxylene Pretax ROI 44%
production
Installation: Two commercial licenses.
• Upgrades pygas stream components to chemical value
• Debottlenecks pygas hydrotreater and extends cycle length Licensor: GTC Technology.
• Reduces hydrogen consumed in hydrotreating
• Optimized solvent system and design provide economical operat-
ing costs

Xylene isomerization Makeup H2

Reactor purge gas
Application: GT-IsomPX is GTC’s xylene isomerization technology. It is
available in two versions: EB isomerization type and EB dealkylation type. Offgas
Both versions gain high ethylbenzene (EB) conversion rates while pro-
ducing equilibrium mixed xylenes. Catalysts that exhibit superior physi-
Light ends
cal activity and stability are the key to this technology. The technology
and catalysts are used commercially in several applications.
Reactor
Description: For an EB dealkylation type of isomerization, the technolo-
Deheptanizer
gy encompasses two main processing areas: reactor section and product
distillation section. In this process, paraxylene (PX)-depleted feed stream
is first mixed with hydrogen. The mixed stream is then heated against Feed
reactor effluent and through a process furnace. The heated mixture is

fed into isomerization reaction unit, where m-xylene,o-xylene and PX Deheptanizer bottom
are isomerized to equilibrium and EB is de-alkylated to benzene.
portion of the vapor phase is purged to control recycle hydrogen purity. • Low H2/HC ratio, high WHSV and low xylenes loss
The recycle hydrogen is then compressed, mixed with makeup hydrogen • Long cycle length
and returned to the reactor. • Efficient heat integration scheme reduces energy consumption
The liquid stream from the separator is pumped to the deheptanizer • Turnkey package for high-purity benzene, toluene and PX produc-
to remove light hydrocarbons. The liquid stream from the deheptanizer tion available from licensor.
overhead contains benzene and toluene and is sent to the distillation
section to produce high-purity benzene and toluene products. The liquid Economics: Feedrate: 4,000 thousand tpy (88,000 bpsd); erected cost:
stream from the deheptanizer bottoms contains mixed xylenes and a $29 MM (ISBL, 2007 US Gulf Coast Basis).
small amount of C9+ aromatics. This liquid stream is returned to the PX
recovery section. Installation: Technology available for license.
Process advantages: Licensor: GTC Technology.

• PX in xylenes reaches thermodynamic equilibrium after reaction
• With the EB-dealkylation catalyst, the byproduct benzene is pro-
duced at high purity by simple distillation.

Biodiesel
Application: Consumption of primary energy has risen substantially in
recent years, and greenhouse gases (GHG) emissions have increased by Reactor 1 Reactor 2
a substantial amount. To counter this trend, there is a global strong em-
phasis on regenerative energy such as biofuels to effectively reduce or Oil Transesterification Biodiesel
avoid such emissions.
Description: The Lurgi biodiesel process is centered on the transesterifi- Glycerin

cross-flow Wash
cation of different raw materials to methyl ester using methanol in the Methanol (patented) column
presence of a catalyst. In principle, most edible oils and fats — both veg- Methanol
Closed washwater loop
etable and animal sources— can be transesterified if suitably prepared. Catalyst recovery
Transesterification is based on the chemical reaction of triglycerides Glycerin water

evaporation
with methanol to methyl ester and glycerine in the presence of an alka- Glycerin water Crude glycerin
line catalyst. The reaction occurs in two mixer-settler units. The actual
conversion occurs in the mixers. The separation of methyl ester as the
light phase and glycerine water as the heavy phase occurs in the settlers
due to the insolubility of both products and the difference in density.
Byproduct components are removed from the methyl ester in the down-
stream washing stage, which operates in a counter-current mode. After
a final drying step under vacuum, the biodiesel is ready for use.
Any residual methanol contained in the glycerine water is removed Methanol, kg 96
in a rectification column. In this unit operation, the methanol has a puri- Catalyst (Na-methylate 100%), kg 5
ty, which is suitable for recycling back to process. For further refinement Hydrochloric acid (37%), kg 10
of the glycerine water, optional steps are available such as chemical Caustic soda (50%), kg 1.5
treatment, evaporation, distillation and bleaching to either deliver crude Nitrogen, Nm3 1
glycerine at approximately 80% concentration or pharmaceutical-grade Installation: Lurgi has been building biodiesel plants for 20 years. Only in
glycerine at >99.7% purity. the last five years, Lurgi has contracted more than 40 plants for the pro-
Economics: The (approximate) consumption figures—without glycerine duction of biodiesel with capacities ranging from 30,000 to 250,000 tpy.
distillation and bleaching—stated below are valid for the production of Licensors: Lurgi GmbH.
one ton of rapeseed methyl ester at continuous operation and nominal
capacity.
Steam, kg 320
3
Water, cooling (t = 10°C), m 25
Electrical energy, kWh 12 click here to e-mail for more information
Biodiesel Esterification Transesterification

reactor reactor
Application: The RHT- Biodiesel process is optimized to produce biodiesel Triglycerides
from palm oil, rape-seed oil, vegetable and animal products that contain LP
fatty acids with even number of carbon atom (12 to 22). The lack of Methanol
sulfur in the biodiesel enables complying with many international fuel Biodiesel
Biodiesel product
specifications. Purification
Mixer
The biodiesel is comparable to petroleum-based diesel. Triglycerides Gravity
Water wash
are reacted with methanol, ethanol or higher alcohols to yield biodiesel separator
MeOH/water for recovery
within the acceptable boiling range. Methanol is most commonly used Water
for the biodiesel production since it is the most cost-effective of alco-
hols, and it can provide better economics for the biodiesel producers.
Purification
Biodiesel is produced by reacting vegetable oils and animal fats (triglyc-
Glycerine product
erides) with methanol in the presence of highly alkaline heterogeneous
Esterification Transesterification
catalyst at moderate pressure and temperature. Pretreatment may be reactor reactors Wash solvent
required if the vegetable oil has a high free-fatty acids content to Triglycerides
optimize methyl esters yield. If free fatty acids are present in the LP
Residual glycerine/wash solvent
feed, first step is esterfication of the free-fatty acid with metha- Methanol
nol. However if the free-fatty acids concentrations are low, then Biodiesel Biodiesel product
this step can be deleted. Mixer
The triglycerides and methanol are converted by transesterfication Gravity
Water wash
separator
reaction to yield methyl esters of the oils and fats, and glycerine is pro- MeOH/water for recovery
Water
duced as a byproduct. The glycerine is separated from the methyl esters
(biodiesel) by phase separation via gravity settling. The methyl esters and
glycerine are purified to meet the product specifications. Purification
Glycerine product
Description: In the simplified process flow diagram (1), the feed—veg-
etable oil or animal fats—is pumped from storage and is mixed with
methanol in the required molar ratio vegetable/methanol at moderate
operating pressure. The feed is heated to the reaction temperature and
the heated feed is sent to the transesterfication reactor, where 3 moles
is sent to esterification reactor. Free-fatty acids are pretreated if the con-
of methanol react with the triglyceride to produce 3 moles of methyl
centration exceeds 3% percent of the feed. The reactor contains an acid
ester oil (biodiesel) and one mole of glycerine. The transesterfication re-
catalyst for this reaction and can remove 99.9 % of free-fatty acids from
actor uses a highly alkaline heterogeneous catalyst and provides essen-
the vegetable oils. (Note: the pretreatment is only required when the
tially 100% conversion. The transesterification reactor effluent is sent
feed contains free-fatty acids; otherwise, this step can be omitted.
The effluent from the first reactor (if free-fatty acids are present) or Continued 
Biodiesel, continued Economics: The normal utilities for continuous biodiesel unit based on
heterogeneous catalyst for tph of biodiesel capacity are listed. This does
not include the glycerine purification utilities. The capital cost for the
to gravity separator/settler. The biodiesel product is taken from the top
ISBL Biodiesel plant on Gulf coast site basis based on 1Q 2006 is pro-
of the separator, and is water washed. The washed biodiesel product is
vided below.
taken from the top of the drum. Water washing removes excess metha-
nol from the reaction products, which is recovered by normal distillation; CAPEX ISBL plant : USD/ton Biodiesel 235–265
the pure methanol is recycled back to the reactor. The bottoms from the Steam, lb/h 368
separator/settler are sent to the purification unit to remove impurities Water, cooling gpm 64
and residual methanol, which is recycled back. Pure glycerine product is Power, kWh 9
sent to storage.
Fig. 2 is an alternate flow scheme; a spare transesterification reactor Licensor: Refining Hydrocarbon Technologies LLC.
is added to remove glycerine from the reactor to sustain reaction rates.
Once the reaction rates are reduced the reactor is switched and washed
with hot solvent to remove residual glycerine and biodiesel. This extra click here to e-mail for more information
reactor patented mode of operation provides higher reactions rates and
onstream capability while enhancing yield and productivity. Glycerine
purity can exceed 99.8% after distillation.
Reaction chemistry: Transesterification reactions:

Triglycerides + 3 Methanol ➞ Methyl Ester of the oil (biodiesel) + Glycerol
Comparision of the Diesel/Biodiesel Properties
Fuel Property Diesel Biodiesel
Fuel standard ASTM D 975 ASTM P S 121
Fuel composition C10 – C21 HC C12 – C22 FAME
Lower heating value, Btu/gal 131 117
Kinemetic Vis @ 40°C 1.3– 4.1 1.9– 6
SG at 60°F 0.85 0.88
Water, wppm 161 500
Carbon 87 77
Hydrogen 13 12
Oxygen 0 11
Sulfur, wppm 15–500 0
Bp, °F 380– 650 370–340
Flash Pt, °F 140–175 210–140
Green diesel
Feed Makeup hydrogen
Application: The UOP/Eni Ecofining process for the production of green
diesel fuel is UOP’s solution to meeting the increasing demand for a sus-
tainable high-quality renewable diesel using conventional hydroprocess- Reactor
ing technology already widely used in refineries. system Acid gas CO2
scrubber
Description: The Ecofining process deoxygenates and then hydroge- Green propane and light ends
nates triglycerides and/or free fatty-acid feedstocks such as vegetable
oils and animal fats. The resulting paraffins are then isomerized to create Separator
a high-quality hydrocarbon known as green diesel. If desired, the Ecofin- Green naphtha product
ing process can also be designed to produce a slipstream of a paraffinic
Green jet product
green jet fuel stream in addition to the green diesel product. Water
A thermochemical process, the Ecofining process produces green
diesel fuel that is indistinguishable from traditional diesel fuel. It can be
used as a direct replacement fuel or as a valuable blendstock to enhance Jet option
the quality of the existing diesel pool. Blending of high-quality green Green
diesel
diesel will allow the use of lower quality diesel range refinery product product
streams, ultimately reducing the cost of biofuel compliance and increas- Green diesel product
ing the overall diesel pool.

Designed for feedstock flexibility, the Ecofining process works with
a wide range of pretreated biofeedstocks—from vegetable oils and ani-
mal fats to second generation, non-food-based options such as jatropha energy sources in existing or new petroleum refineries worldwide. The
and algal oils. Ecofining process is an extension of UOP’s leading portfolio of hydropro-
The diesel yield and hydrogen consumption vary slightly according cessing and isomerization technologies.
to the feed-stock source and the required product cloud point. The hy-
drogen consumption may also vary between different feeds. Installation: ENI has announced construction of the first Ecofining unit,
with startup due in 2010. A second unit was licensed in early 2008 amid
Experience: UOP introduced Ecofining in early 2007 as the first com- significant market interest.
mercial offering from its Renewable Energy & Chemicals business group
dedicated to introducing new technology for processing renewable Licensor: UOP.

Deep catalytic cracking

Application: Selective conversion of gasoil and paraffinic residual feed-
stocks.
Products: C2–C5 olefins, aromatic-rich, high-octane gasoline and dis-

tillate.
Description: Deep catalytic cracking (DCC) is a fluidized process for se-

lectively cracking a wide variety of feedstocks to light olefins. Propylene
yields over 24 wt% are achievable with paraffinic feeds. DCC uses a
conventional traditional reactor/regenerator unit design with a catalyst
that has physical properties similar to traditional FCC catalyst. The DCC
unit may be operated in two operational modes: maximum propylene
(Type I) or maximum iso-olefins (Type II).
Each operational mode utilizes unique catalyst as well as reaction
conditions. Maximum propylene DCC uses both riser and bed crack-
ing at relatively severe reactor conditions while Type II DCC uses only
riser cracking like a modern fluid catalytic cracking (FCC) unit at milder
conditions.
The overall flow scheme of DCC is very similar to that of a con-
ventional FCC. However, innovations in the areas of catalyst devel-
opment, process variable selection and severity and gas plant design
enables the DCC to produce significantly more olefins than FCC in a DCC rather than steam cracking for propylene production is a direct
maximum-olefins mode of operation. consequence of relative cost differences between DCC heavy feeds
This technology is quite suitable for revamps as well as grassroots and steam cracker’s light feeds. Additional capital and operating cost-
applications. Feed enters the unit through proprietary feed nozzles, savings are achieved by the integration of the DCC unit and the adja-
as shown in the schematic. Integrating DCC technology into existing cent steam cracker.
refineries as either a grassroots or revamp application can offer an at-
tractive opportunity to produce large quantities of light olefins. Products (wt% of fresh feed) DCC Type I DCC Type II FCC
In a market requiring both propylene and ethylene, use of both Ethylene 6.1 2.3 0.9
thermal and catalytic processes is essential, due to the fundamental Propylene 20.5 14.3 6.8
differences in the reaction mechanisms involved. The combination of Butylene 14.3 14.6 11.0
thermal and catalytic cracking mechanisms is the only way to increase in which iC4 = 5.4 6.1 3.3
total olefins from light and heavy feedstocks while meeting the need Amylene — 9.8 8.5
for increased propylene to ethylene ratio. A benefit associated with in which iC5 = — 6.5 4.3
Deep catalytic cracking, continued
Installation: A total of 15 DCC units have been licensed.
Reference: Dharia, D., et al., “Increase light olefins production,” Hydro-
carbon Processing, April 2004, pp. 61– 66.
Licensor: Shaw and Research Institute of Petroleum Processing, Sinopec.


Application: Conversion of gas oils and residues to light olefins, high-
octane gasoline, and distillates using the compact, self supporting Or-
thoflow converter.
Description: Feed enters through the proprietary ATOMAX-2 feed injec-

tion system. Reaction vapors pass through a right angle turn and are
quickly separated from the catalyst in a positive pressure closed-cyclone
system. Closed cyclones minimize dry-gas make and increase gasoline
yield. Spent catalyst flows through a stripper equipped with Dynaflux
baffles to the regenerator where countercurrent flow of catalyst and air
contacting is carried out.
Catalyst flow from the regenerator to the external vertical riser is
controlled by riser outlet temperature, which regulates the regenerated
catalyst slide valve. A plug valve located in the regenerator bottom head
controls the level in the stripper by regulating the catalyst flow from the
spent catalyst standpipe.
Either partial or complete CO combustion may be used in the regen-
erator. Flue gas flows to an external plenum and then to the flue-gas
system. A Cyclofines Third Stage Separator may be used to remove par-
ticulates from the flue gas for protection of a power recovery expander
and/or compliance with particulate emissions standards. References: “Maximizing flexibility for FCC’s designed to maximize
propylene,” 2008 NPRA Annual Meeting, March 9–11, 2008, San Diego.
Economics: The converter is a one-piece modularized unit that combines
“Optimize FCC Flue-Gas Emission Control—Part 2,” Hydrocarbon
the disengager, stripper and regenerator vessels into a single structure.
Processing, Vol. 81, No. 10, October 2002, pp. 85–91.
This unique design minimizes the cost of construction, and also reduces
“New developments in FCC feed injection and stripping technolo-
the amount of field mechanical work and required plot space.
gies,” NPRA Annual Meeting, March 2000.
Installations: More than 150 grassroots units have been designed, re-
Licensors: KBR and ExxonMobil
sulting in a total of over 4 million bpsd fresh feed, with 12 of the latest
units since 1990.


Application: Selective and high conversion of a wide range of feedstocks
into high-value products. Feedstocks include virgin or hydrotreated

gasoils that may also include lube oil extract, coker gasoil and resid.

Products: High-octane gasoline, light olefins and distillate. Flexibility in
unit operation allows for maximizing the most desirable product.

Description: The Lummus process incorporates an advanced reaction
system, high-efficiency catalyst stripper and a mechanically robust,
single-stage fast fluidized bed regenerator. Oil is injected into the
base of the riser via proprietary Micro-Jet feed injection nozzles (1).

Catalyst and oil vapor flow upwards through a short-contact time,
all-vertical riser (2) where raw oil feedstock is cracked under opti-
mum conditions.
Reaction products exiting the riser are separated from the spent
catalyst in a patented, direct-coupled cyclone system (3). Product va-
pors are routed directly to fractionation, thereby eliminating nonselec- to energy recovery/flue gas treating. The hot regenerated catalyst
tive post-riser cracking reactions and maintaining the optimum product is withdrawn via an external withdrawal well (10). The well allows
yield slate. Spent catalyst containing only minute quantities of hydro- independent optimization of catalyst density in the regenerated cata-
carbon is discharged from the diplegs of the direct-coupled cyclones lyst standpipe, maximizes slide valve (11) pressure drop and ensures
into the cyclone containment vessel (4). The catalyst flows down into stable catalyst flow back to the riser feed injection zone.
the stripper containing proprietary modular grid (MG) baffles (5). The catalyst formulation can be tailored to maximize the most
Trace hydrocarbons entrained with spent catalyst are removed in desired product.
the MG stripper using stripping steam. The MG stripper efficiently
removes hydrocarbons at low steam rate. The net stripper vapors are
Economics:
routed to the fractionator via specially designed vents in the direct- Investment (basis: 30,000 bpsd including reaction/regeneration
coupled cyclones. Catalyst from the stripper flows down the spent- system and product recovery. Excluding offsites, power recovery
catalyst standpipe and through the slide valve (6). The spent catalyst and flue gas scrubbing US Gulf Coast 2006.)
is then transported in dilute phase to the center of the regenerator $/bpsd (typical) 2,400–3,500
(8) through a unique square-bend-spent catalyst transfer line (7). This Utilities, typical per bbl fresh feed:
arrangement provides the lowest overall unit elevation. Catalyst is Electricity, kWh 0.8–1.0
regenerated by efficient contacting with air for complete combus- Steam, 600 psig (produced) 50–200
tion of coke. For resid-containing feeds, a catalyst cooler is integrat- Maintenance, % of investment per year 2–3
ed with the regenerator. The resulting flue gas exits via cyclones (9)
Continued 
Fluid catalytic cracking, continued
Installation: Seventeen grassroots units licensed. Thirty-three units re-
vamped, with five revamps in design stage.
Licensor: Lummus Technology, a CB&I company.


Application: Selective conversion of gas oil feedstocks.
Products: High-octane gasoline, distillate and C3 – C4 olefins.
Description: Catalytic and selective cracking in a short-contact-time riser
where oil feed is effectively dispersed and vaporized through a proprietary
feed-injection system. Operation is carried out at a temperature consistent
with targeted yields. The riser temperature profile can be optimized with
the proprietary mixed temperature control (MTC) system.
Reaction products exit the riser-reactor through a high-efficiency,
close-coupled, proprietary riser termination device RSS (riser separator
stripper). Spent catalyst is pre-stripped followed by an advanced high-
efficiency packed stripper prior to regeneration. The reaction prod-
uct vapor may be quenched to give the lowest possible dry gas and
maximum gasoline yield. Final recovery of catalyst particles occurs in
cyclones before the product vapor is transferred to the fractionation
section.
Catalyst regeneration is carried out in a single regenerator equipped
with proprietary air and catalyst distribution systems, and may be oper-
ated for either full or partial CO combustion. Heat removal for heavier
feedstocks may be accomplished by using reliable dense-phase catalyst Available options include power recovery, waste-heat recovery,
cooler, which has been commercially proven in over 56 units. As an flue-gas treatment and slurry filtration. Revamps incorporating pro-
alternative to catalyst cooling, this unit can easily be retrofitted to a prietary feed injection and riser termination devices and vapor quench
two-regenerator system (R2R) in the event that a future resid operation result in substantial improvements in capacity, yields and feedstock
is desired. flexibility within the mechanical limits of the existing unit.
The converter vessels use a cold-wall design that results in mini-
mum capital investment and maximum mechanical reliability and safe- Installation: Shaw and Axens have licensed 34 grassroots FCC units and
ty. Reliable operation is ensured through the use of advanced fluidi- performed more than 160 revamp projects.
zation technology combined with a proprietary reaction system. Unit
Reference: Meyers, R., Handbook of Petroleum Refining Process, Third Ed.
design is tailored to the refiner’s needs and can include wide turndown
flexibility. Licensor: Shaw and Axens.


Application: To convert heavy distillates and residues into high-value Shell FCC design Shell MILOS-FCC design
products, including selective propylene production when required, us- To fractionator To fractionator
ing the Shell fluid catalytic cracking (FCC) process. Close Close To fractionator
coupled coupled MILOS
cyclones cyclones catalyst
Description: In this process, Shell’s high-performance feed nozzle sys- separator
tem feeds hydrocarbons to a short contact-time riser. This design en- Staged
sures good mixing and rapid vaporization into the hot catalyst stream. Catalyst stripping
circulation
Staged
Cracking selectivity is enhanced by the feed nozzles and proprietary stripping
enhancement MILOS
technology riser
riser-internals, which reduce catalyst back mixing while reducing overall Riser Riser reactor
Advanced
riser pressure drop. internals spent cat internals
Riser termination design incorporates reliable close-couple cyclones inlet device
High High
that provide rapid catalyst/hydrocarbon separation. It minimizes post- performance
feed nozzles
Cold-wall performance
feed nozzles
Cold-wall
construction construction
riser cracking and maximizes desired product yields, with no slurry clean
up required. Stripping begins in the staged stripper, equipped with high-
capacity baffle structure.
A single-stage partial or full-burn regenerator delivers excellent per-
formance at low cost. Proprietary internals are used at the catalyst inlet with improved quality and more propylene from FCC units. The key ele-
to disperse catalyst, and the catalyst outlet to provide significant catalyst ment of MILOS is a separate riser to produce the additional propylene,
circulation enhancement. Catalyst coolers can be added for more feed- with its own optimal process conditions, while the existing FCC riser is
stock flexibility. used for “normal” cracking or for enhanced light cycle oil (LCO) make.
Cyclone-systems in the reactor and regenerator use a proprietary This process option has a wide flexibility with respect to products, ranging
design, thus providing reliability, efficiency and robustness. Flue gas from the normal product slate to maximized propylene or diesel, which
cleanup can be incorporated with Shell’s third-stage separator. can be achieved through operational measures.
Shell Global Solutions FCC technologies are proven reliability champi-
ons due to simplicity of components and incorporation of Shell’s extensive Installation: Over 30 grassroots units designed/licensed, including 7 to
operating experience. The latest addition to the Shell Global Solutions handle residue feeds, and over 30 units revamped.
FCC technology is the MILOS process (Middle Distillate and Lower Olefins
Selective process). With this technology, refiners can produce more diesel Supplier: Shell Global Solutions International B.V.


Application: Selectively convert gas oils and residue feedstocks into
Reactor
higher value products using the UOP FCC process, the UOP Resid FCC
(RFCC) and the UOP PetroFCC process.
Regenerator
Products: Light olefins (for alkylation, polymerization, etherification or
petrochemicals), LPG, high-octane gasoline, distillates and fuel oils.
Recycled catalyst standpipe
Description: UOP’s process uses a side-by-side reactor/regenerator con-
figuration and a patented pre-acceleration zone to condition the regen-
erated catalyst. Modern Optimix feed distributors inject the feed into
the riser, which terminates in a vortex separation system (VSS). A high-
efficiency stripper then separates the remaining hydrocarbons from the
catalyst, which is then reactivated in a combustor-style regenerator. With
RxCat technology, a portion of the catalyst that is pre-stripped by the
riser termination device can be recycled back to the riser via a standpipe
and the MxR chamber. MxR chamber
The reactor zone features a short-contact-time riser, state-of the-

art riser termination device for quick separation of catalyst and vapor,
perature to sustain the same kinetic combustion rate. RxCat technology
with high hydrocarbon containment (VSS/VDS technology) and RxCat
has been licensed for use in four units, two of which are currently in
technology, wherein a portion of the pre-stripped (carbonized) catalyst
construction. The first unit to incorporate RxCat technology has been
from the riser termination device is blended with the hotter regenerated
operating successfully since the second quarter of 2005.
catalyst in a proprietary mixing chamber (MxR) for delivery to the riser.
The combustor-style regenerator burns coke in a fast-fluidized envi-
Unlike other approaches to increasing the catalyst-to-oil ratio, this
ronment completely to CO2 with very low levels of CO. The circulation
technology does not affect the total heat balance and, therefore, does
of hot catalyst from the upper section to the combustor provides added
not increase coke yield. The reactor temperature can be lowered to re-
control over the burn-zone temperature and kinetics and enhances ra-
duce thermal cracking with no negative impact on conversion, thus im-
dial mixing. Catalyst coolers can be added to new and existing units to
proving product selectivity. The ability to vary the carbonized/regener-
reduce catalyst temperature and increase unit flexibility for commercial
ated catalyst ratio provides considerable flexibility to handle changes in
operations of feeds up to 6 wt% Conradson carbon. A recent study of
feedstock quality and shortens the time for operating adjustments by
eight different combustor-style regenerators and 15 bubbling-bed re-
enabling rapid switches between gasoline, olefins or distillate operat-
generators clearly demonstrated that at a given excess oxygen level, less
ing modes. Since coke yield can be decreased at constant conversion,
NOx is emitted from the combustor-style regenerators than other avail-
capacity and reaction severity can be increased, and CO2 emissions re-
able technologies.
duced. Furthermore, because the catalyst delivered to the regenerator
has a higher coke content, it requires less excess oxygen at a given tem- Continued 
Fluid catalytic cracking, continued increased conversion, higher selectivity for desired products, the ability
to operate at high catalyst flux and increased capacity, and lower steam
consumption. One application of AF trays resulted in a 0.04 wt% reduc-
For heavier residue feeds, the two-stage regenerator is used. In the
tion in coke, a 14°F (8°C) drop in the regenerator temperature, and a
first stage, upper zone, the bulk of the carbon is burned from the cata-
2.3 LV% boost in conversion. Another FCC unit utilizes these trays to
lyst, forming a mixture of CO and CO2. Catalyst is transferred to the
handle a high catalyst flux rate of over 2-M lb/ft2 min. The installation
second stage, lower zone, where the remaining coke is burned in com-
of AF grids in a small unit increased conversion and gasoline yield by 3.0
plete combustion, producing low levels of carbon on regenerated cata-
LV% and 2.8 LV% respectively, paying back the investment in less than
lyst. A catalyst cooler is located between the stages. This configuration
three months. UOP’s stripper technology has been implemented in more
maximizes oxygen use, requires only one train of cyclones and one flue
than 36 FCC units with a combined on-stream capacity exceeding 1MM
gas stream, which avoids costly multiple flue gas systems and creates a
bpsd.
hydraulically-simple. The two stage regenerator system has processed
feeds up to 8.5 wt% Conradson carbon. Installation: All of UOP’s technology and equipment are commercially
PetroFCC is a customized application using mechanical features such proven for both process performance and mechanical reliability. UOP
as RxCAT technology for recontacting carbonized catalyst, high sever- has been an active designer and licensor of FCC technology since the
ity processing conditions and selected catalyst and additives to produce early 1940s and has licensed more than 225 FCC, Resid FCC and MSCC
high yields of propylene, light olefins and aromatics for petrochemical process units. More than 150 of these units are operating worldwide. In
applications. addition to applying our technology and skills to new units, UOP is also
UOP’s Advanced Fluidization (AF) spent catalyst stripper internals extensively involved in the revamping of existing units. During the past
provide a family of options (trays, grids and packing) all with state of the 15 years, UOP’s FCC Engineering department has undertaken 40 to 60
art efficiency. Often the optimal selection is dependent on the unique revamp projects or studies per year.
configuration of the unit, site constructability and inspection issues.
Within residence constraints, the new designs can save about 10 feet in Licensor: UOP.
length compared to 1990s units of the same capacity and diameter. The
benefits provided by the AF internals include reduced coke, lower re-
generator temperature, higher catalyst circulation, lower dry gas make, click here to e-mail for more information
Fluid catalytic cracking for maximum

olefins

Application: The Indmax FCC (I-FCC) process cracks a wide range of
feedstocks into light olefins. Feedstocks include virgin or hydrotreated
gasoil that may include lube oil extract, coker gasoil and resid.

Products: Light olefins (principally propylene, but also ethylene and
butylenes), high-octane gasoline, blending components, and distillate.

Flexibility of unit operation allows for maximizing propylene, propylene
plus ethylene, or propylene plus gasoline.
Catalyst: The Indmax catalyst is a unique, proprietary, multi-component,

multi-functional catalyst formulation that promotes selective component
cracking to provide very high conversion and yield of light olefins. It is

highly metals-tolerant and produces low delta coke and dry gas – prop-
erties that are particularly important when processing residue to make
light olefins.
down into the stripper containing proprietary modular grid (MG)
Description: The I-FCC unit is designed for and operated at Indmax
baffles (5).
process conditions: riser reactor temperature from 560°C to 600°C,
Trace hydrocarbons entrained with spent catalyst are removed
catalyst-to-oil ratio from 12 to 20, and lower hydrocarbon partial
in the MG stripper using stripping steam. The MG stripper efficient-
pressure compared to conventional FCC operations. The I-FCC pro-
ly removes hydrocarbons at low steam rate. The net stripper vapors
cess incorporates an advanced reaction system, high-efficiency cata-
are routed to the fractionator via specially designed vents in the
lyst stripper and a mechanically robust, single-stage fast fluidized bed
direct-coupled cyclones. Catalyst from the stripper flows down the
regenerator. Oil is injected into the base of the riser via proprietary
spent-catalyst standpipe and through the slide valve (6). The spent
Micro-Jet feed injection nozzles (1). Catalyst and oil vapor flow up-
catalyst is then transported in dilute phase to the center of the re-
wards through a short-contact time, all-vertical riser (2) where raw oil
generator (8) through a unique square-bend-spent catalyst transfer
feedstock is cracked under optimum conditions.
line (7). This arrangement provides the lowest overall unit elevation.
Reaction products exiting the riser are separated from the spent
Catalyst is regenerated by efficient contacting with air for complete
catalyst in a patented, direct-coupled cyclone system (3). Product
combustion of coke. For resid-containing feeds, the optional cata-
vapors are routed directly to fractionation, thereby eliminating non-
lyst cooler is integrated with the regenerator. The resulting flue gas
selective, post-riser cracking and maintaining the optimum prod-
exits via cyclones (9) to energy recovery/flue gas treating. The hot
uct yield slate. Spent catalyst containing only minute quantities of
regenerated catalyst is withdrawn via an external withdrawal well
hydrocarbon is discharged from the diplegs of the direct-coupled
cyclones into the cyclone containment vessel (4). The catalyst flows Continued 
Fluid catalytic cracking for maximum olefins, continued Installation: Two grassroots units licensed. One demonstration-scale unit
is commercially operating.
(10). The well allows independent optimization of catalyst density Licensor: Lummus Technology, a CB&I company.
in the regenerated catalyst standpipe, maximizes slide valve (11)
pressure drop and ensures stable catalyst flow back to the riser feed
injection zone. click here to e-mail for more information
Economics:
Investment (basis: 30,000 bpsd including reaction/regeneration
system and product recovery. Excluding offsites, power recovery
and flue gas scrubbing US Gulf Coast 2006.)
$/bpsd (typical) 3,000 – 4,000
Fluid catalytic cracking, high olefin

Application: MAXOFIN FCC offers refiners greater returns by maximizing
propylene yields from FCC feedstocks. Over 20 wt% propylene yield can
be produced from gasoils by combining the effects of enhanced ZSM-5
catalysts and proprietary hardware.
Description: This dual-riser design uses independent riser reaction con-

ditions (cat/oil and temperatures) for heavy and light feedstocks. C4–C6
nonaromatic naphtha cuts can be recycled to the light hydrocarbon riser.
In addition to processing light naphtha, the recycle riser can also accept
coker and light-straight-run naphthas from the refinery. Both risers can
operate at 100% gas oil/resid if market conditions dictate the need for
petroleum products instead of petrochemicals.
The recycle riser is an external, cold wall riser similar to the primary
riser. Products produced from both risers merge in the disengager vessel
and travel as a common stream to the main fractionator.
Yields: The following yields were produced from a pilot plant using a
hydrocracked gasoil feedstock:
Yields, wt% Run A Run B Run C Run D
Ethylene 3.2 3.9 6.4 8.2
Propylene 16.0 18.7 19.1 21.5 Reference: “Maximizing Flexibility for FCC’s Designed to Maximize
C5+ gasoline 37.9 28.8 26.2 25.0 Propylene,” NPRA 2008 Annual Meeting, March 9–11, 2008, San Diego.
“Future refinery—FCC’s role in refinery/petrochemical integration,”
Economics: Investment and operating costs are only slightly higher than NPRA 2001 Annual Meeting, March 2001.
a conventional FCC with a single riser.
Licensors: KBR and ExxonMobil.
Installation: All elements of MAXOFIN FCC technology have been prov-
en. Propylene yield was dependent upon constraints in the downstream
gas plant and not the converter section.

Fluid catalytic cracking, residual

Application: Conversion of low-value residual feeds and deasphalted oils
from heavy crudes to high-valued light olefins, gasoline and distillates.
Description: The converter is a one-piece modularized unit that efficiently

combines KBR’s proven Orthoflow features with ExxonMobil’s advanced
reaction design features. The regenerator is a single vessel that operates
in partial or complete CO combustion with a dense phase catalyst cooler
depending on the coke-forming tendencies of the feedstock.
The regenerator operates with a counter current flow of air and
catalyst featuring a (1) spent catalyst distributor that evenly distributes
the catalyst over the regenerator bed; and a (2) proprietary baffle that
limits back-mixing between the upper and lower portions of the bed,
effectively achieving a staged combustion in a single regenerator. The
counter-current regeneration also reduces NOx emissions compared to
other types of regenerators.
Economics:
Investment: (basis 50,000 BPSD fresh feed including converter, main
fractionator, vapor recovery unit, C3 splitter, and amine treating (no
power recovery), battery limit, direct material and labor, 2008 Gulf
Coast), $/bbl- 4900 to 5400.
Reference: “Holding the key,” Hydrocarbon Engineering, March 2008.
Utilities, typical per bbl fresh feed
Niccum, P. K. et al., “Optimize FCC Flue-Gas Emission Control—
Electricity, kWh 0.7–1.0
Part 2,” Hydrocarbon Processing, Vol. 81, No. 10, October 2002, pp.
Steam, 600 psig, produced, lb 40–200
85–91.
Maintenance: % of plant replacement cost/y 3
“New developments in FCC feed injection and stripping technolo-
Installation: Since 1990, KBR has designed more than a dozen FCC units, gies,” 2000 NPRA Annual Meeting, March 2000.
including those that process resid and have revamped more than 160
Licensors: KBR and ExxonMobil.
FCC units worldwide

Fluid catalytic cracking—pretreatment Recycle gas

compressor
Application: Topsøe’s FCC pretreatment technology is designed to treat Makeup
hydrogen
a wide variety of feedstocks ranging from gasoils through heavy-vacu-
um gas oils and coker streams to resids. This pretreatment process can Absorber
Furnace
maximize FCC unit performance. Lean amine
Objectives: The processing objectives range from deep desulfurization Reactor

for meeting gasoline-sulfur specifications from the FCC products, to de-
Rich amine
nitrogenation and metals removal, thus maximizing FCC catalyst activ-
ity. Additional objectives can include Conradson carbon reduction and Fresh feed
H2 rich gas
saturation of polyaromatics to maximize gasoline yields.
START
Products to
Description: The Topsøe FCC Pretreatment technology combines under- High-pressure FCC or fractionation
separator
standing of kinetics, high-activity catalysts, state-of-the-art internals and
Low-pressure
engineering skills. The unit can be designed to meet specific process- separator
ing objectives in a cost-effective manner by utilizing the combination of
processing severity and catalyst activity.
Topsøe has experience in revamping moderate- to low-pressure
units for deep desulfurization. Such efforts enable refiners to directly Operating conditions: Typical operating pressures range from 60 to 125
blend gasoline produced from the FCC and meet future low-sulfur (less bar (900 to 1,800 psi), and temperatures from 300°C to 430°C (575°F
than 15 ppm) gasoline specifications. to 800°F).
An additional option is Topsøe’s Aroshift process that maximizes the References: Andonov, G., S. Petrov, D. Stratiev and P. Zeuthen, “MCHC
conversion of polyaromatics which can be equilibrium limited at high mode vs. HDS mode in an FCC unit in relation to Euro IV fuels specifica-
operating temperatures. The Aroshift process increases the FCC conver- tions,” 10th ERTC, Vienna, November 2005.
sion, and the yield of gasoline and C3 /C4 olefins, while reducing the Patel R., H. Moore and B. Hamari, “FCC hydrotreater revamp for low-
amount of light- and heavy-cycle oil. Furthermore, the quality of the sulfur gasoline,” NPRA Annual Meeting, San Antonio, March 2004.
FCC gasoline is improved. Patel, R., P. Zeuthen and M. Schaldemose, “Advanced FCC feed pre-
Topsøe has a wide variety of catalysts for FCC pretreatment service. The treatment technology and catalysts improves FCC profitability,” NPRA
catalyst types cover TK-558 BRIM, a CoMo catalyst with high desulfurization Annual Meeting, San Antonio, March 2002.
activity, and TK-559 BRIM, a NiMo catalyst with hydrodesulfurization and
high hydrodenitrogenation activity. Topsøe offers a wide range of engi- Installations: Four units in the US.
neering scopes from full scoping studies, reactor design packages and Licensor: Haldor Topsøe A/S.
process design packages to engineering design packages.


Application: Selective conversion of gasoil and heavy residual feed-
stocks.
Products: High-octane gasoline, distillate and C3– C4 olefins.

Description: For residue cracking the process is known as R2R (reactor–2
regenerators). Catalytic and selective cracking occurs in a short-contact-
time riser where oil feed is effectively dispersed and vaporized through a
proprietary feed-injection system. Operation is carried out at a tempera-
ture consistent with targeted yields. The riser temperature profile can be
optimized with the proprietary mixed temperature control (MTC) system.
Reaction products exit the riser-reactor through a high-efficiency,
close-coupled, proprietary riser termination device RSS (riser separator
stripper). Spent catalyst is pre-stripped followed by an advanced high-
efficiency packed stripper prior to regeneration. The reaction product
vapor may be quenched to give the lowest dry gas and maximum gaso- Reliable operation is ensured through the use of advanced fluidiza-
line yield. Final recovery of catalyst particles occurs in cyclones before tion technology combined with a proprietary reaction system. Unit design
the product vapor is transferred to the fractionation section. is tailored to refiner’s needs and can include wide turndown flexibility.
Catalyst regeneration is carried out in two independent stages Available options include power recovery, wasteheat recovery, flue-
equipped with proprietary air and catalyst distribution systems resulting gas treatment and slurry filtration.
in fully regenerated catalyst with minimum hydrothermal deactivation, Existing gasoil units can be easily retrofitted to this technology. Re-
plus superior metals tolerance relative to single-stage systems. These vamps incorporating proprietary feed injection and riser termination de-
benefits are derived by operating the first-stage regenerator in a partial vices and vapor quench result in substantial improvements in capacity,
burn mode, the second-stage regenerator in a full-combustion mode yields and feedstock flexibility within the mechanical limits of the exist-
and both regenerators in parallel with respect to air and flue gas flows. ing unit.
The resulting system is capable of processing feeds up to about
6 wt% ConC without additional catalyst cooling means, with less air, Installation: Shaw and Axens have licensed 34 grassroots FCC units and
lower catalyst deactivation and smaller regenerators than a single-stage performed more than 160 revamp projects.
regenerator design. Reference: Meyers, R., Handbook of Petroleum Refining Process, Third Ed.
Heat removal for heavier feedstocks (above 6 CCR) may be accom-
plished by using a reliable dense-phase catalyst cooler, which has been Licensor: Shaw and Axens.
commercially proven in over 56 units.
The converter vessels use a cold-wall design that results in minimum
capital investment and maximum mechanical reliability and safety. click here to e-mail for more information
Resid cracking
Application: Selective conversion of heavy feedstocks into petrochemi-
cal products
Products: C3 – C4 olefins, in particular propylene; high-octane gasoline,

aromatics
Description: Based on the R2R resid fluid catalytic cracking (RFCC) pro-
cess using a riser and a double regenerator for gasoline production, this
new petrochemical version is oriented toward light olefins, particularly
propylene, and aromatics. The process is characterized by the utilization
of two independent risers. The main riser cracks the resid feed under con-
ditions to optimize fuels production; the second PetroRiser riser is oper-
ated to selectively crack specific recycle streams to maximize propylene
production.
The RFCC applies a short contact-time riser, proprietary injection sys-
tem and severe cracking conditions for bottoms conversion. The tempera-
ture and catalyst circulation rates are higher than those used for a conven-
tional gasoline mode operation. The main riser temperature profile can
be optimized with a mixed temperature control (MTC) system. Reaction
products are then rapidly separated from the catalyst through a high-
efficiency riser termination device (RS2).
regenerator configuration and even higher contents with the addition of
Recycle feed is re-cracked in the PetroRiser under conditions, which
a catalyst cooler.
are substantially more severe than in the main riser. A precise selection of
The recycle feeds that can be used in the PetroRiser are light and
recycle cuts combined with adapted commercial FCC catalysts and addi-
medium FCC gasoline as well as olefin streams coming from a butenes
tives lead to high propylene yields with moderate dry-gas production.
oligomerization unit. This last option is of particular interesting under
Both the main riser and PetroRiser are equipped with a rapid sepa-
market conditions that favor propylene over C4 olefins.
ration system, and the deactivated catalysts are collected in to a single
The reaction and regeneration sections use a cold-wall design that re-
packed stripper, which enhances steam stripping efficiency of the cata-
sults in minimum capital investment and maximum mechanical reliability
lyst. Catalyst regeneration is carried out in two, independent stages to
and safety. Units are tailored to fit the market needs (feedstock and prod-
minimize permanent hydrothermal activity loss. The first stage is operated
uct slate) and can include a wide range of turndown flexibility. Available
in a mild partial-combustion mode that removes produced moisture and
options include power recovery, waste-heat recovery, flue-gas treatment
limits catalyst deactivation, while the second stage finishes the combus-
and slurry filtration and light olefins recovery and purification.
tion at higher temperature to fully restore catalyst activity. The R2R system
is able to process residue feed containing high metals and CCR using this Continued 
Resid cracking, continued Reference: “Fine-tune FCC operations for changing fuels market,” Hy-
drocarbon Processing, September 2005.
Installation: PetroRiser technology is available for revamp of all RFCC Licensor: Axens and Shaw.
and FCC units. Axens and the Shaw Group have licensed more than 40
FCC units and performed more than 100 revamp projects since the alli-
ance was created. click here to e-mail for more information
Catalytic reforming
Application: Upgrade various types of naphtha to produce high-octane
reformate, BTX and LPG.
Feed
Description: Two different designs are offered. One design is conventional
where the catalyst is regenerated in place at the end of each cycle. Oper- START
4
ating normally in a pressure range of 12 to 25 kg /cm2 (170 to 350 psig) 2 3
and with low pressure drop in the hydrogen loop, the product is 90 to 100 1
RONC. With their higher selectivity, trimetallic catalysts RG582 and RG682
make an excellent catalyst replacement for semi-regenerative reformers.
The second, the advanced Octanizing process, uses continuous cata-
lyst regeneration allowing operating pressures as low as 3.5 kg /cm2 (50
psig). This is made possible by smooth-flowing moving bed reactors (1–3) Reformate
which use a highly stable and selective catalyst suitable for continuous
regeneration (4). Main features of Axens’ regenerative technology are:
• S ide-by-side reactor arrangement, which is very easy to erect and
consequently leads to low investment cost.
Installation: Of 140 units licensed, 88 units are designed with continu-
• T he RegenC-2 catalyst regeneration system featuring the dry burn
ous regeneration technology capability.
loop, completely restores the catalyst activity while maintaining its
specific area for more than 600 cycles. Reference: “Fixed Bed Reformer Revamp Solutions for Gasoline Pool
Finally, with the new CR 601 (gasoline mode) and AR 701 (aromatics Improvement,” Petroleum Technology Quarterly, Summer 2000.
production) catalysts specifically developed for ultra-low operating pres- “Increase reformer performance through catalytic solutions,” Sev-
sure and the very effective catalyst regeneration system, refiners operat- enth ERTC, November 2002, Paris.
ing Octanizing or Aromizing processes can obtain the highest hydrogen, “Squeezing the most out of fixed-bed reactors,” Hart Show Special,
C5+ and aromatics yields over the entire catalyst life. NPRA 2003 Annual.
“Octanizing reformer options to optimize existing assets,” NPRA
Yields: Typical for a 90°C to 170°C (176°F to 338°F) cut from light Ara-
Annual Meeting, March 15–17, 2005, San Francisco.
bian feedstock: Conventional Octanizing/Aromizing
“Octanizing reformer options,” Petroleum Technology Quarterly,
Oper. press., kg /cm2 10 –15 3 –7
Spring, 2006.
Yield, wt% of feed:
Boitiaux, J. P., et al., “New developments accelerating catalyst re-
Hydrogen 2.8 3 – 4
search,” Hydrocarbon Processing, September 2006, pp. 33–40.
C5+ 83 88 – 95
RONC 100 100 –105 Licensor: Axens.
MONC 89 89 – 92
Catalytic reforming
Application: The UOP CCR Platforming process is used throughout the Stacked
world in the petroleum and petrochemical industries. It produces feed reactor Net H2
rich gas
Naphtha feed
for an aromatics complex or a high-octane gasoline blending product from treating Net gas
CCR Fuel gas
and a significant amount of hydrogen. regenerator
Combined
compressor
Recovery
feed section
Description: Hydrotreated naphtha feed is combined with recycle hy- exchanger
drogen gas and heat exchanged against reactor effluent. The combined
feed is then raised to reaction temperature in the charge heater and sent Light ends
Separator
to the reactor section. Stabilizer
Radial-flow reactors are arranged in a vertical stack. The predomi-
Regenerated
nant reactions are endothermic; so an interheater is used between each catalyst
Fired heaters
reactor to reheat the charge to reaction temperature. The effluent from
Spent
the last reactor is heat exchanged against combined feed, cooled and catalyst Aromatic
rich reformate
split into vapor and liquid products in a separator. The vapor phase is
hydrogen-rich. A portion of the gas is compressed and recycled back to
the reactors. The net hydrogen-rich gas is compressed and charged to-
gether with the separator liquid phase to the product recovery section.
This section is engineered to provide optimum performance.
Catalyst flows vertically by gravity down the reactor stack. Over
time, coke builds up on the catalyst at reaction conditions. Partially de- bpd of capacity) with another 50 in various stages of design, construc-
activated catalyst is continually withdrawn from the bottom of the reaction and commissioning.
tor stack and transferred to the CCR regenerator.
Efficiency/product quality: Commercial onstream efficiencies of more
Installation: UOP commercialized the CCR Platforming process in 1971 than 97% are routinely achieved in CCR Platforming units.
and now has commissioned more than 210 units (more than 4.7 million
Licensor: UOP.

Coking %SZHBT
736 $$
Application: Upgrade residues to lighter hydrocarbon fractions using the
Selective Yield Delayed Coking (SYDEC) process.

Description: Charge is fed directly to the fractionator (1) where it com- /BQIUIB
bines with recycle and is pumped to the coker heater. The mixture is
heated to coking temperature, causing partial vaporization and mild
cracking. The vapor-liquid mix enters a coke drum (2 or 3) for further 4UFBN
cracking. Drum overhead enters the fractionator (1) to be separated into -JHIUHBTPJM
gas, naphtha, and light and heavy gas oils. Gas and naphtha enter the
vapor recovery unit (VRU)(4). There are at least two coking drums, one
)FBWZHBTPJM
coking while the other is decoked using high-pressure water jets. The 'FFE
coking unit also includes a coke handling, coke cutting, water recovery
45"35
and blowdown system. Vent gas from the blowdown system is recov-
ered in the VRU.
Operating conditions: Typical ranges are: Utilities, typical per bbl feed:
Heater outlet temperature, ºF 900 – 950 Fuel, 103 Btu 120
Coke drum pressure, psig 15 – 100 Electricity, kWh 3
Recycle ratio, equiv. fresh feed 0 – 1.0 Steam (exported), lb 35
Increased coking temperature decreases coke production; increases Water, cooling, gal 36
liquid yield and gas oil end point. Increasing pressure and/or recycle ra-
tio increases gas and coke make, decreases liquid yield and gas oil end Installations: Currently, 52 delayed cokers are installed worldwide with
point. a total installed capacity over 2.5 million bpsd
Yields: References: Handbook of Petroleum Refining Processes, Third Ed., Mc-

Operation: Graw-Hill, pp. 12.33 –12.89.
Products, wt% Max dist. Anode coke Needle coke “Delayed coking revamps,” Hydrocarbon Processing, September 2004.
Gas 8.7 8.4 9.8 “Residue upgrading with SYDEC Delayed Coking: Benefits & Eco-
Naphtha 14.0 21.6 8.4 nomics,” AIChE Spring National Meeting, April 23–27, 2006, Orlando.
Gas oil 48.3 43.8 41.6 “Upgrade refinery residuals into value-added products,” Hydrocar-
Coke 29.3 26.2 40.2 bon Processing, June 2006.
Economics: Licensor: Foster Wheeler USA Corp./UOP.

Investment (basis 65,000 –10,000 bpsd)
2Q 2005 US Gulf), $ per bpsd 6,700 –13,600 click here to e-mail for more information
Coking Vapors to recovery

Fuel gas
Application: The coking process involves cracking of heavy residual oils LPG
into more valuable gasoil, distillate, naphtha and LPG products. Coke Blowdown VRU
Naphtha
is also produced. Normal feeds include vacuum bottoms, atmospheric Slop oil to
coker feed Water
bottoms, asphaltenes from ROSE and other types of solvent deasphalt-
Water
ing units, bitumen and other heavy oils, thermal and pyrolsis tars, de-
Makeup
cant oils, visbreaker and thermal tars. water Hydraulic
decoking
Description: Delayed coking is a semi-batch thermal cracking process.
The process is comprised of coker heaters, coke drums, fractionation, Light GO
vapor recovery unit, hydraulic decoking, coke handling and blowdown HGO
systems. Feed is normally routed via coker fractionator to remove light Steam
fractions. Feed plus recycle from the fractionator are brought to coking Steam BFW
temperature in a specially designed heater and then sent to the coke Coke
handling
BFW
drum. The feed cracks into lighter fractions and coke in the coke drum. Crushed coke
Cracked material exiting from the overhead is quenched and sent to the Resid feed
fractionator.
After the coke level in the drum has reached the maximum accepted
level, the feed is directed to the second drum. The drum with coke is
cooled, then cut with high-pressure water jets and removed to coke
handling area. The drum is then heated and put back in service when Process development:
the second drum fills up with coke. KBR operates a large one bpd coker pilot plant at its Technology Center
in Houston. The pilot plant is used for process development and for run-
Process applications: KBR has designed and delivered significant pilot-
ning coker pilot tests for clients.
plant work on coking of asphaltenes obtained from bitumen and other
heavy oils. Experience: KBR has provided process technology for more than 15 cok-
Comparison of coke produced from vacuum resid and asphaltenes: ers. The most recent design is for a bitumen vacuum resid coker, which
Basis: Refinery Feed: 200,000 bpsd is expected startup in 2008.
Arab Heavy Maya Licensor: KBR.

VTB Asphaltene VTB Asphaltene
Coker Feed
Mbpsd 49.7 26.5 63.6 49.1
wt.% CCR 23.8 38 31.2 38
Coke make, Mtd 2.7 2.1 4.4 4 click here to e-mail for more information
Coking
Application: Conversion of atmospheric and vacuum residues, hydro- 'VFMHBT
treated and hydrocracked resids, asphalt, pyrolysis tar, decant oil, visbro-
$$-1(
ken or coal tar pitch, solvent-refined and Athabasca bitumen.
$PLFSOBQIUIB
Description: Feedstock is introduced (after heat exchange) to the bot-
tom of the coker fractionator (1) where it mixes with condensed recycle.
The mixture is pumped to one of two coke drums (3) through the coker 4UN
heater (2) where the desired coking temperature is achieved. Steam or 4UN #'8
boiler feedwater is injected into the heater tubes to prevent coking in -JHIUHBTPJM
the furnace tubes. Coke drum overhead vapors flow to the fractionator
#'8
(1) where they are separated into an overhead stream containing the
)FBWZHBTPJM
wet gas, LPG and naphtha and two gasoil sidestreams.
The overhead stream is sent to a vapor recovery unit (4) where the 'SFTIGFFE
individual light product streams are separated. The coke that forms in 45"35
4UN
one of at least two (parallel connected) drums is then removed using
high-pressure water. The plant also includes a blow-down system for
recovery of all vent gas and slop streams, coke handling and a water
recovery system.
Operating conditions: Products, wt%

Heater outlet temperature, °F 900 –950 Gas + LPG 7.9 9.0 9.2
Coke drum pressure, psig 15 –90 Naphtha 12.6 11.1 12.5
Recycle ratio, vol/vol feed, % 0 –100 Gas oils 50.8 44.0 46.0
Coke 28.7 35.9 32.5
Yields:
Vacuum residue of Economics:
Middle East hydrotreated Athabasca Investment (basis: 20,000 bpsd straight-run vacuum residue feed,
Feedstock vac. residue bottoms bitumen US Gulf Coast 2008, fuel-grade coke, includes vapor recovery), US$
Gravity, °API 7.4 1.3 2.5 per bpsd (typical) 8,000
Sulfur, wt% 4.2 2.3 5.7
Conradson
carbon, wt% 20.0 27.6 23.0
Continued 
Coking, continued Installation: More than 60 units.
Reference: Sieli, G. M., A. Faegh and S. Shimoda, “The impact of de-
Economics (continued): layed coker operating conditions on refinery operations,” ERTC Coking
Utilities, typical/bbl of feed: & Gasification Conference, April 16–18, 2007.
Fuel, 103 Btu 123
Electricity, kWh 3.6 Licensor: Lummus Technology, a CB&I company.
Steam (exported), lb 1
Water, cooling, gal 58
Boiler feedwater, lbs 38
Condensate (exported), lbs 24
Coking, fluid
Reactor products
Application: ExxonMobil’s Research & Engineering (EMRE’s) continuous to fractionator
thermal conversion process with fluidized bed reactor to convert heavy
Flue gas to CO boiler
hydrocarbons (vacuum residuum, extra heavy oil or bitumen) to lighter
liquid products and fuel-grade coke. Attractive when markets available START 1
for fuel-grade fluid coke, or if planned applications include present or 3

future addition of a fluid bed boiler for cogeneration of steam and pow- 2
Net coke
er as this combination has both heat integration as well as SOx removal
benefits. Air
blower
Products: Liquid products produced are similar in yields and quality to Air
Cold Hot
delayed coking. These products are upgraded through conventional coke coke
hydrotreating, hydrocracking or in a fluid catalytic cracker (FCC). Fluid
coke is used as a solid fuel, with particular advantages in cement kilns
or fluid bed boilers.
the coke is burned with air to supply process heat requirements, elimi-
Description: A fluid coking unit is similar in operation to an FCC unit but nating the need for an external fuel supply. The rest of the coke is with-
operates on much more difficult vacuum resid feeds. Instead of cata- drawn from the burner and either sold as a product or burned in a fluid
lyst, fluid coke particles are circulated between the burner and reactor bed boiler in cogen projects.
to transfer process heat. Feed, typically 1,050°F+ vacuum resid from
the bottom of the vacuum pipestill, is pumped without the need for a Yields: Typical vacuum resid (~26 wt% Concarbon, 4.6 wt% sulfur, 125
preheat furnace directly to the scrubber (1) on the top of the reactor Ni+V):
(2). The scrubber (1) has several functions: i) to further heat the feed by Component yield wt% wt%
direct heat exchange with reactor effluent vapors, ii) to separate coke Fuel gas (C2 –) 6.7
particles for return to the fluid bed reactor and iii) to recycle the higher LPG, (C3 / C4 ) 4.4
boiling reactor effluent hydrocarbons (typically at 975+°F, but this can Total C4– 11.1
be adjusted to meet downstream gas oil processing requirements) back Naphtha (C5-430°F) 15.3
to the reactor with fresh feed. Distillate (430°F – 650°F) 11.0
Specially designed nozzles in the reactor (2) produce droplets of Gas oil (650°F – 975 °F) 32.2
feed, which interact with the circulating coke particles. Gas and liquid Total C5+ Liquids 58.6
thermal conversion products are removed from the top of the scrubber Product coke 24.8
and a layer of coke is added to the circulating particles. Heat for the Consumed for process heat 5.5
thermal cracking reactions is supplied by burning a fraction of the coke Total reactor coke 30.3
in the fluid bed burner (3). Hot coke circulates between the burner (3) Total: 100 100
and reactor (2), and cold coke returns to the burner (3). About 20% of
Continued 
• Internally heat integrated, minimal use of fuel gas, and lower coke
Coking, fluid, continued production than delayed coking.
• Combination of fluid coking and fluid-bed boilers for COGEN has
Competitive advantages: heat integration and SOx removal synergies.
• Continuous fluid bed process, coke conveyed pneumatically and
contained in fluid solids and product silos. Licensor: ExxonMobil Research and Engineering Co.
• Process very heavy feeds from tar sands bitumen to Venezuelan
heavy crudes.
Asphaltene pelletization
Application: The AQUAFORM unit is designed for pelletizing heavy hy- Proprietary
drocarbons including asphaltenes from ROSE solvent deasphalting pro- high-capacity
feed distributor
cess.
Pelletizer
vessel
Description: AQUAFORM has been designed for easy integration with Surge
drum
the KBR ROSE solvent deasphalting unit. Asphaltenes from the ROSE Cooling water
Trim heat
asphaltene product drum are pumped through an exchanger to the exchanger Pellets and
Hot liquid water
AQUAFORM pelletizing vessel. A rotating head inside the vessel pro- asphaltene
duces small droplets of asphaltene, which are quenched in a water bath. Cooling
Feed pump
The pellets are removed on screen separators and then transferred to water pump
storage using conveyer systems. The water is filtered, cooled and re- Screen for Water dump
Solid pellets Conveyor belt dewatering Solids Fin fan
turned to the pelletizing vessel. to storage for pellet drying filter or water
transportation
The unit is constructed of carbon steel metallurgy and operates at cooler
moderate temperatures and at near atmospheric pressure. An asphaltene

pelletizing vessel is designed for up to 1,000 tpd of asphaltene feed. Pel-
let size can be controlled by adjusting key operating conditions.
are suitable for use in cement plants and steel mills. The higher heating
Properties of pellets: The pellets have ~ 30% higher heating value than
value of the pellets as compared to coke can help in the debottlenecking
petroleum coke. The crush strength is high thus allowing for storage
of cement and steel mills. The pellets can be melted again after trans-
in silos.
portation for gasification and cracking in cokers.
Process applications: The asphaltene pellets can be stored at ambient
conditions and can be transported using bulk transporters. The pellets
Licensor: KBR.

Deasphalting
Application: Prepare quality feed for FCC units and hydrocrackers from
vacuum residue, and blending stocks for lube oil and asphalt manufac-
turing.
Products: Deasphalted oil (DAO) for catalytic cracking and hydrocracking 7BDVVN )PUPJM

%"0
feedstocks, resins for specification asphalts, and pitch for specification SFTJEVF TFQBSBUPS
DIBSHF &YUSBDUPS
asphalts and residue fuels.
1JUDI
Description: Feed and light paraffinic solvent are mixed and then TUSJQQFS
charged to the extractor (1). The DAO and pitch phases, both containing
solvents, exit the extractor. The DAO and solvent mixture is separated %"0
under supercritical conditions (2). Both the pitch and DAO products are
)PUPJM TUSJQQFS
stripped of entrained solvent (3,4). A second extraction stage is utililized
if resins are to be produced.
1JUDI %"0
Operating conditions: Typical ranges are:

Solvent various blends of C3– C7 hydrocarbons includ-
ing light naphthas
Pressure, psig 300 – 600
Temp., °F 120 – 450 Visc., SSU@210ºF 165 540
Solvent to oil ratio: 4/1 to 13/1 Ni/V, wppm 0.25/0.37 4.5/10.3
Pitch
Yields:
Softening point, R&B, ºF 149 240
Feed, type Lube oil Cracking stock
Penetration@77ºF 12 0
Gravity, ºAPI 6.6 6.5
Sulfur, wt% 4.9 3.0 Economics:
CCR, wt% 20.1 21.8 Investment (basis: 40,000 –2,000 bpsd)
Visc, SSU@210ºF 7,300 8,720 2Q 2005, US Gulf, $/bpsd 2,000 – 8,000
Ni/V, wppm 29/100 46/125 Utilities, typical per bbl feed:
DAO Fuel, 103 Btu (hot oil) 56 – 100
Yield, vol.% of feed 30 65 Electricity, kWh 1.9 – 2.0
Gravity, ºAPI 20.3 15.1 Steam, 150 psig, lb 6 – 9
Sulfur, wt% 2.7 2.2 Water, cooling (25ºF rise), gal 10
CCR, wt% 1.4 6.2
Continued 
“When Solvent Deasphalting is the Most Appropriate Technology
Deasphalting, continued for Upgrading Residue,” International Downstream Technology Confer-
ence, February 15 –16, 2006, London.
Installations: Over 50 units installed; this also includes both UOP and
Foster Wheeler units originally licensed separately before merging the Licensor: Foster Wheeler USA Corp./UOP.
technologies in 1996.
References: Handbook of Petroleum Refining Processes, Third Ed., Mc- click here to e-mail for more information
Graw Hill, 2003, pp. 10.37–10.61.
Deasphalting
E-2
Application: KBR’s ROSE (Residuum Oil Supercritical Extraction) solvent
deasphalting technology is used to extract maximum volumes of FCCU,
P-1
or hydrocracker/hydrotreater feedstocks from atmospheric and vacuum E-1 E-4
resids, and in some special cases from whole crude oils. The extracted
deasphalted oil (DAO) yields can be adjusted to optimize integration
with downstream units. The ROSE DAO has “order of magnitude” lower
E-3
heptane insolubles content as well as lower metals and conradson car-
Residuum E-6
bon than from other solvent deasphalting processes. This lower hep-
V-1
V-2
V-3
T-1
T-2
T-3
START
tane insolubles content allows refiners to achieve longer run lengths in M-1 S-1
hydrotreating and hydrocracking units and reduced catalyst usage in Hot
FCC units. Moderate operating temperatures almost alleviates the need oil
Oils
Hot
for 317SS metallurgy when processing high acid crude oils. oil P-2
ROSE is also useful in production and upgrading of heavy oils. The Asphaltenes Resins
process is also used for debottlenecking of existing vacuum distillation

units and cokers.
Products: Lube blendstocks, synthetic crude, FCCU feed, hydrocracker internals. These high-efficiency, high-capacity internals offer superior
feed, coker feed, resins and asphaltenes. product yield and quality while minimizing vessel size and capital invest-
ment. These internals can also be used to debottleneck and improve
Description: Resid is charged through a mixer (M-1), where it is mixed
operations of existing solvent deasphalting units.
with solvent before entering the asphaltene separator (V-1), which uses
special internals to achieve maximum benefit of counter current solvent Yields: The solvent composition and operating conditions are adjusted
flow. The solvent extracts primarily non-asphaltenic, paraffinic deas- to provide the highest product quality and yields required for down-
phalted oil. The asphaltene-rich stream leaves from the bottom of the stream processing or to meet finished product specifications. Solvents
separator. The extracted oils and solvent flow overhead (V-1) through range from propane through hexane and almost always are streams pro-
heat exchangers (E-1, E-4, E-6) so that the solvent reaches conditions duced in refineries.
where it exists as a supercritical fluid in which the oil is virtually insoluble.
Recovered solvent leaves the separator top (V-3) to be cooled by heat Economics:
exchange (E-4, E-1) and a cooler (E-2). The only solvent vaporized is a Investment: (Basis: 30,000 bpsd, US Gulf Coast), $1,850 per bpsd
small amount dissolved in fractions withdrawn in the separators. This Utilities, typical per bbl feed:
solvent is recovered in the product strippers. Fuel absorbed, 103 Btu 80–110
Alternately an intermediate resin rich product can be produced in Electricity, kWh 2.0
V2 and T2 as shown in the attached figure. Steam, 150-psig, lb 12
V-1, V-2 and V-3 are equipped with high-performance ROSEMAX Continued 
Deasphalting, continued Reference: Patel, V., R. Iqbal and O. Eng, “To vacuum or not to vacuum,”
Hydrocarbon Engineering, June 2007.
Iqbal, R., A. Khan, O. Eng and R. Floyd, “Unlocking current refinery
Installation: KBR has licensed 48 units with a combined capacity of over constraints,” PTQ, Summer 2008.
900,000 bpd. More than 25 units are operating with several more ex-
pected to startup within the next two years. Licensor: KBR.

Desulfurization C5-
Desulfurized/de-aromatized
Application: GT-BTX PluS accomplishes desulfurization of FCC gasoline olefin-rich gasoline
GT-BTX PluS
with no octane loss and decreased hydrogen consumption by using a
Feed fractionation
proprietary solvent in an extractive-distillation system. This process also
Full-range
recovers valuable aromatics compounds, which can be used as petro- FCC naphtha Aromatics/
chemical feedstock. sulfur-rich H2 H 2S
extract Benzene
Toluene
Description: The optimum feed is the mid fraction of FCC gasoline Xylenes
C9+
from 70°C to 150°C. This material is fed to the GT-BTX PluS unit, HDS
Aromatics
fractionation
which extracts the sulfur and aromatics from the hydrocarbon stream.
The sulfur-containing aromatic components are processed in a conven-
tional hydrotreater to convert the sulfur into hydrogen sulfide (H2S).
Because the portion of gasoline being hydrotreated is reduced in vol-
Process advantages:
ume and free of olefins, hydrogen consumption and operating costs
• Eliminates FCC gasoline sulfur species to meet a pool gasoline
are greatly reduced. In contrast, conventional desulfurization schemes
target of 10 ppm sulfur.
must process the majority of the gasoline through hydrotreating units
• Rejects olefins from being hydrotreated in the HDS unit to prevent
to remove sulfur, which inevitably results in olefin saturation, octane
loss of octane rating and to reduce hydrogen consumption.
downgrade and yield loss.
• Fewer components (only the heavy-most fraction and the aromatic
FCC gasoline is fed to the extractive distillation column (EDC). In
concentrate from the ED unit) are sent to hydrodesulfurization, resulting
a vapor-liquid operation, the solvent extracts the sulfur compounds
in a smaller HDS unit and less yield loss.
into the bottoms of the column along with the aromatic components,
• Purified benzene and other aromatics can be produced from the
while rejecting the olefins and non-aromatics into the overhead as
aromatic-rich extract stream after hydrotreating.
raffinate. Nearly all of the non-aromatics, including olefins, are effec-
• Olefin-rich raffinate stream (from the ED unit) can be directed to
tively separated into the raffinate stream. The raffinate stream can be
an aromatization unit to produce additional BTX or recycled to the FCC
optionally caustic washed before routing to the gasoline pool or to an
unit to increase the light olefin production.
aromatization unit to further increase benzene, toluene and xylene
(BTX) production. Economics: Feedrate 1,000 thousand tpy (22,000 bpsd); erected cost
Rich solvent, containing aromatics and sulfur compounds, is routed (including Fractionation and Hydrotreating) $30 MM (ISBL, 2007 US
to the solvent recovery column (SRC), where the hydrocarbons and sul- Gulf Coast Basis).
fur species are separated and lean solvent is recovered in columns bot-
toms. The SRC overhead is hydrotreated by conventional means and Installation: Technology available for license.
either used as desulfurized gasoline or directed to an aromatics plant.
Lean solvent from the SRC bottoms is recycled back to the EDC.
Licensor: GTC Technology.

Diesel upgrading
Application: Topsøe’s Diesel Upgrading process can be applied for im- Hydrogen makeup
Recycle gas
provement of a variety of diesel properties, including reduction of diesel compressor
specific gravity, reduction of T90 and T95 distillation (Back-end-shift),
reduction of aromatics, and improvements of cetane, cold-flow prop- Furnace Upgrading
reactor Lean amine
erties, (pour point, clouds point, viscosity and CFPP) and diesel color Treating Absorber
reactor
reduction (poly shift). Feeds can range from blends of straight-run and
cracked gas oils up to heavy distillates, including light vacuum gasoil. Rich amine
Description: Topsøe’s Diesel Upgrading process is a combination of treating

H2-rich
and upgrading. The technology combines state-of-the-art reactor internals, Fresh feed gas
engineering expertise in quality design, high-activity treating catalyst and High-pressure
Product
fractionation
proprietary diesel upgrading catalyst. Every unit is individually designed to separator
improve the diesel property that requires upgrading. This is done by se- Low-pressure
separator
lecting the optimum processing parameters, including unit pressure and
LHSV and determining the appropriate Topsøe high-activity catalysts and
plant lay-out. The process is suitable for new units or revamps of existing
hydrotreating units.
In the reactor system, the treating section uses Topsøe’s high-activ-
ity CoMo or NiMo catalyst, such as TK-575 BRIM or TK-576 BRIM, to References: Patel, R., “How are refiners meeting the ultra-low-sulfur
remove feed impurities such as sulfur and nitrogen. These compounds diesel challenge?” NPRA Annual Meeting, San Antonio, March 2003.
limit the downstream upgrading catalyst performance, and the purified Fuente, E., P. Christensen, and M. Johansen, “Options for meeting
stream is treated in the downstream upgrading reactor. Reactor catalyst EU year 2005 fuels specifications,” 4th ERTC, November 1999.
used in the application is dependent on the specific diesel property that
requires upgrading. Reactor section is followed by separation and strip- Installations: A total of 16 units; six in Asia-Pacific region, one in the
ping/fractionation where final products are produced. Middle East, two in Europe and seven HDS/HDA units (see Hydrodearo-
Like the conventional Topsøe hydrotreating process, the diesel up- matization).
grading process uses Topsøe’s graded-bed loading and high-efficiency
patented reactor internals to provide optimal reactor performance and Licensor: Haldor Topsøe A/S.
catalyst utilization. Topsøe’s high-efficiency internals are effective for a
wide range of liquid loading. Topsøe’s graded-bed technology and the
use of shape-optimized inert topping material and catalyst minimize
the pressure drop build-up, thereby reducing catalyst skimming require-
ments and ensuring long catalyst cycle lengths.
Diesel—ultra-low-sulfur diesel (ULSD)

Application: Topsøe ULSD process is designed to produce ultra-low-sulfur Makeup hydrogen Recycle gas
compressor
diesel (ULSD) (5–50 wppm S) from cracked and straight-run distillates.
By selecting the proper catalyst and operating conditions, the process
can be designed to produce 5 wppm S diesel at low reactor pressures
Furnace
(<500 psig) or at higher reactor pressure when products with improved Absorber Lean amine
density, cetane, and polyaromatics are required.
Reactor
Description: Topsøe ULSD process is a hydrotreating process that com-

Rich amine
bines Topsøe’s understanding of deep-desulfurization kinetics, high-ac-
tivity catalyst, state-of-the-art reactor internal, and engineering exper- H2 rich gas
Fresh feed
tise in the design of new and revamped ULSD units. The ULSD process
can be applied over a very wide range of reactor pressures. START
Product to
Our highest activity BRIM catalyst is specifically formulated with High-pressure fractionation
separator
high-desulfurization activity and stability at low reactor pressure (~ 500
Low-pressure separator
psig) to produce 5 wppm diesel. This catalyst is suitable for revamping
existing low-pressure hydrotreaters or in new units when minimizing
hydrogen consumption.
The highest activity BRIM catalyst is suitable at higher pressure when
secondary objectives such as cetane improvement and density reduction
are required. Topsøe offers a wide range of engineering deliverables to Sarup, B., M. Johansen, L. Skyum and B. Cooper, “ULSD Production
meet the needs of the refiners. Our offerings include process scoping in Practice,” 9th ERTC, Prague, November 2004.
study, reactor design package, process design package, or engineering Hoekstra, G., V. Pradhan, K. Knudsen, P. Christensen, I. Vasalos and
design package. S. Vousvoukis, “ULSD: Ensuring the unit makes on-spec. product,” NPRA
Annual Meeting, Salt Lake City, March 2006.
Installation: Topsøe has licensed more than 50 ULSD hydrotreaters of
which more than 40 units are designed for less than 10 wppm sulfur in Licensor: Haldor Topsøe A/S.
the diesel. Our reactor internals are installed in more than 60 ULSD units.
References:
Low, G., J. Townsend and T. Shooter, “Systematic approach for the
revamp of a low-pressure hydrotreater to produce 10-ppm, sulfur-free
diesel at BP Conyton Refinery,” 7th ERTC, Paris, November 2002.

Gasoline desulfurization, ultra-deep Sour fuel gas

Hydrogen
Application: ExxonMobil’s Research & Engineering’s (EMRE’s) SCANfin-
ing technology reduces sulfur in FCC gasoline to levels as low as <10
Preheater
wppm by selective hydrotreating to maximize octane retention with the SCANfining 1,
SCANfining 2,
SCANfining technology. Feed Product
or SCANfining with
stripper
ZEROMER reaction
Description: The feed is mixed with hydrogen, heated with reactor efflu- section
ent exchange and passed through a pretreat reactor for diolefin satura- Pretreat
reactor
tion. After further heat exchange with reactor effluent and preheat using Low-sulfur naphtha
a utility, the hydrocarbon/hydrogen mixture enters the main reaction sec-
tion which features ExxonMobil Research and Engineering Co. (EMRE)
proprietary selective catalyst systems. In this section of the plant, sulfur
is removed in the form of H2S under tailored process conditions, which
strongly favor hydrodesulfurization while minimizing olefin saturation.
The feed may be full-range, intermediate or heavy FCC-naphtha
fraction. Other sulfur-containing streams such as light-coker naphtha, Chemicals & Refinery Services LLC to provide EXOMER technology to
steam cracker or light straight-run naphthas can also be processed with refiners.
FCC naphthas. SCANfining technology can be retrofitted to existing
units such as naphtha or diesel hydrotreaters and reformers. SCANfining Yields: Yield of C5 + liquid product is typically over 100 LV%.
technology also features ExxonMobil’s proprietary reactor internals such
Installation: Thirty-seven units under design, construction or operation
as Automatic Bed Bypass Technology for onstream mitigation of reactor
having combined capacity of over 1.1 million bpsd.
plugging/pressure drop buildup.
For high-sulfur feeds and/or very low-sulfur product, with low levels References: Sapre, A.V., et al., “Case History: Desulfurization of FCC
of product mercaptans variations in the plant design from SCANfining I naphtha,” Hydrocarbon Processing, February 2004.
Process to the SCANfining II Process for greater HDS selectivity, or addi- Ellis, E. S., et al., “Meeting the Low Sulfur Mogas Challenge,” World
tion of a ZEROMER process step for mercaptan conversion, or addition Refining Association Third European Fuels Conference, March 2002.
of an EXOMER process unit for mercaptan extraction.
EMRE has an alliance with Kellogg Brown & Root (KBR) to pro- Licensor: ExxonMobil Research and Engineering Co.
vide SCANfining technology to refiners and an alliance with Merichem

Hydrogenation/hydrodesulfurization Low pressure splitter H2 recycle/vent

Hydrocarbons reformate1
Application: The smart configuration can be applied for selective hydroge- Light hydrocarbons
LP
nation/hydroisomerization, aromatic saturation and hydrodesulfurization (A)
Hydrogen
(HDS) of gasoline, kerosine and diesel/distillate desulfurization. In addi- recycle2
tion, this process can be used for the selective hydrogenation of acety- H2
Hydrogenation
lene, MAPD, C3 /C4 /C5 /C6 /C7 and LCN, hydro-isomerization, benzene reactor
saturation and hydrodesulfurization of gasoline, kerosine and diesel/dis-
tillate. Multiple catalyst types provide the best performance and lower
cost with optimum configuration. The RHT process operates the dis- 1 Hydrocarbons from refinery/petrochemical
and other units
tillation and reaction units at optimum conditions and integrates the 2 If recycle is required for excess hydrogen
Heavy hydrocarbons
stabilizer with the main distillation column thereby reducing CAPEX and
SHU Gasoline HDS Compressor
OPEX. By taking multiple draws off from distillation column, it is possible reactor stripper 5 reactor H2 recycle/vent
to obtain the highest conversion, high selectivity with low operating FCC naphtha Mixer
L cat naphtha
costs. The processes apply optimum catalyst and conditions to obtain
(B)
the best results. The process is optimized for energy consumption via H2
Mid cut
H2 Recycle
Compressor
Vent
heat integration to provide low CAPEX and OPEX. Recycle H2 naphtha

Makeup
Description: Flash H2
drum
RHT-Hydrogenation: In the RHT- Hydrogenation process (flow dia-
gram A), the hydrocarbon feed is sent to the distillation column where
Flash
the feed is treated and taken as a side draw or multiple draw offs. The drum
feed can be treated in an optimum way for catalyst/reactor utilization.
Additional liquid is needed to dilute the feed and to maintain reaction H2 to furnace
Furnace
temperature. The feed is mixed with sufficient hydrogen to maintain the
required for reaction before entering the reactor. The side draw is mixed
with liquid from the heat sink and is heated to the reactor temperature.
The reactor effluent is sent back to the distillation column to remove draws allows heat sink and highest conversions and selectivity required
light ends/hydrogen at top, and the product is taken as side draw after for the process/olefins or saturation. The process uses lower pressure
the pasteurization section. The bottom product does not require further than conventional processes and can work in single phase or two phase
treatment except in the isomerization option. reactor operation.
The process uses metal catalyst used for hydrogenation. Most com- RHT-HDS: FCC Gasoline: The RHT- HDS process (flow diagram B)
monly used catalysts are Pt/Pd, Pd/Ag, Pd, Ni, Ni/Mo, and Co/Mo on can be used for FCC gasoline. Processing scheme for straight-run naph-
silica or alumina base. (Catalysts such as zeolite/Pt can be used aromatic tha, heavy gasoil and diesel is similar to conventional schemes. The FCC
saturation). The process can be optimized for multiple or single cata-
lyst to provide best catalyst utilization and lower cost. The multiple side Continued 
Mo. RHT processes do not use any internals. Additionally, if the capacity
Hydrogenation/hydrodesulfurization, continued must be increased for future processes with special internals become a
bottleneck and one has to install complete additional train, which is very
gasoline is mixed with hydrogen and is heated to moderate tempera- expensive.
ture. The feed is sent to the selective hydrogenation reactor to remove RHT-HDS: Gasoil/diesel: RHT has a configuration to desulfurize the
diolefins to prevent the formation of gums and polymers and coking crude and vacuum unit pumparound and main fractionators side draws
on the HDS catalyst. The reactor operates in two phases or single phase at the location with staggered pressures so that hydrogen can be spilled
down-flow reaction mode. Reactor effluent is sent to the splitter where into lower pressure unit, gasoil, diesel/kerosine/naphtha in that order.
light cut naphtha (LCN) is taken as side-draw overhead and heavy cut The flow schemes are similar to conventional processes with reactor
naphtha (HCN) is taken from the bottom and medium cut naphtha internals designed to meet high-distribution efficiency. The catalyst is
(MCN) is taken as side draw. The LCN is almost sulfur-free and contains same as mentioned above earlier, e.g., Co/Mo, Ni/W, Ni/Mo. Zeolite/Pt
less than 3 to 5 wppm mercaptans and other sulfur compounds. DMS is catalyst and Ni is used for light cycle oil (LCO) aromatic saturation and
essentially eliminated or minimized. ring opening.
The HCN is taken from bottom of the splitter and is mixed with hy-
drogen required for HDS and is heated to the desulfurization temperature Economics: 1Q 2006 Gulf coast Basis;
in the furnace. The feed is fed to the HDS reactor in down-flow mode. RHT-Hydrogenation:
The HDS occurs in the catalyst zone at high temperatures to support CAPEX (ISBL facility only), $/bbl 517
high desulfurization rates HCN, which contains the maximum sulfur lev- Utilities and catalyst, $/bbl 0.25
el and is the most refractory. The MCN is also mixed with hydrogen and RHT-HDS:
heated to the reactor temperature and is sent the HDS reactor around Capex (ISBL facility only), $/bbl 980
the middle of reactor. The space velocity for HCN and MCN depends on Utilities and catalyst, $/bbl 1.26
the total sulfur concentration in both streams and the sulfur-containing
species. Another consideration for the catalyst quantity is based on the Product properties: Hydrogenation stream meets the diolefin specifica-
product specifications required. The reactor effluent is sent to stabilizer, tion as required with high selectivity. For HDS, the product sulfur speci-
where residual sulfur is driven from the MCN and HCN product and is fications are met below 10 wppm.
taken as the bottom product from stabilizer.
The catalyst used for first reactor for selective hydrogenations are Pt/ Installation: Technology is ready for commercialization.
Pd, Pd, Ni, Ni//W or Ni/Mo depending upon the feed and operating con- Licensor: Refining Hydrocarbon Technologies LLC.
ditions selected. Catalyst required for HDS include Co/ Mo, Ni/W or Ni/

Crude distillation
Flash gas
Application: Separates and recovers the relatively lighter fractions (e.g., 6
Light naphtha
naphtha, kerosine, diesel and cracking stock) from a fresh crude oil charge.
Heavy naphtha
The vacuum flasher processes the crude distillation bottoms to produce
7 Kerosine
an increased yield of liquid distillates and a heavy residual material.
5 8 Diesel
4
Description: The charge is preheated (1), desalted (2) and directed to a 3 9
Cracker feed
preheat train (3) where it recovers heat from product and reflux streams. 10
To vac. system
The typical crude fired heater (4) inlet temperature is on the order of
2
550 ° F, while the outlet temperature is on the order of 675°F to 725°F. Lt. vac. gas oil
Heater effluent then enters a crude distillation column (5) where light Stm. Stm. Hvy. vac.
1 12
naphtha is drawn off the tower overhead (6); heavy naphtha, kerosine, gas oil
Crude 11
diesel and cracking stock are sidestream drawoffs. External reflux for Vac. gas oil
Stm. (cracker feed)
the tower is provided by pumparound streams (7–10). The atmospheric START
residue is charged to a fired heater (11) where the typical outlet tem- Asphalt
perature is on the order of 725 ° F to 775°F.
From the heater outlet, the stream is fed into a vacuum tower
(12), where the distillate is condensed in two sections and withdrawn
as two sidestreams. The two sidestreams are combined to form crack- Economics:
ing feedstock. An asphalt base stock is pumped from the bottom of Investment ( basis: 100,000–50,000 bpsd,
the tower. Two circulating reflux streams serve as heat removal media 2nd Q, 2005, US Gulf ), $ per bpsd 1,600 – 2,000
for the tower. Utility requirements, typical per bbl fresh feed
Yields: Typical for Merey crude oil: Steam, lb 24
3
Fuel (liberated), 10 Btu ( 80 – 120 )
Crude unit products wt% °API Pour, °F
Power, kWh 0.6
Overhead & naphtha 6.2 58.0 —
Water, cooling, gal 300 – 400
Kerosine 4.5 41.4 – 85
Diesel 18.0 30.0 – 10 Installation: Foster Wheeler has designed and constructed crude units
Gas oil 3.9 24.0 20 having a total crude capacity in excess of 15 MMbpsd.
Lt. vac. gas oil 2.6 23.4 35 Reference: Encyclopedia of Chemical Processing and Design, Marcel-
Hvy. vac. gas oil 10.9 19.5 85 Dekker, 1997, pp. 230 – 249.
Vac. bottoms 53.9 5.8 (120)*
Total 100.0 8.7 85 Licensor: Foster Wheeler USA Corp.
*Softening point, °F
Note: Crude unit feed is 2.19 wt% sulfur. Vacuum unit feed is 2.91 wt% sulfur. click here to e-mail for more information
Crude distillation FG
Application: The Shell Bulk CDU is a highly integrated concept. It sepa-

rates the crude in long residue, middle distillates and a naphtha minus Rec NHT
LPG
fraction. Compared with stand-alone units, the total integration of a
crude distillation unit (CDU), hydrodesulfurization unit (HDS), high vac- Tops
H
uum unit (HVU) and a visbreaker (VBU) results in a 50% reduction in C HDS D
Kero
equipment count and significantly lowered operating costs. A promi- Crude
D
U
F
nent feature embedded in this design is the Shell deepflash HVU tech- Naphtha
Vac LGO
nology. This technology can also be provided in cost-effective process HGO
VGO
designs for both feedprep and lube oil HVUs as stand-alone units. For H Kero
LR V WD
each application, tailor-made designs can be produced. U HCU GO
Storage Bleed
Description: The basic concept of the bulk CDU is the separation of the VBU
Flash column
VBU
naphtha minus and the long residue from the middle distillate fraction, Residue
which is routed to a bulk HDS. After desulfurization in the HDS unit,
final product separation of the bulk middle distillate stream from the
CDU occurs in the HDS fractionator (HDF), which consists of a main at-
mospheric fractionator with side strippers.
The long residue is routed hot to a feedprep HVU, which recov- Economics: Due to the incorporation of Shell high capacity internals
ers the waxy distillate fraction from long residue as the feedstock for a and the deeply integrated designs, a CAPEX reduction in the order of
cat-cracker or hydrocracker unit (HCU). Typical flashzone conditions are 30% can be achieved. Investment costs are dependent on the required
415°C and 24 mbara. The Shell design features a deentrainment sec- configuration and process objectives.
tion, empty spray sections to obtain a lower flashzone pressure, and a Installation: Over 100 Shell CDUs have been designed and operated
vacuum gasoil (VGO) recovery section to recover up to 10 wt% as auto- since the early 1900s. Additionally, a total of some 50 HVU units have
motive diesel. The Shell furnace design prevents excessive cracking and been built while a similar number has been debottlenecked, including
enables a five-year run length between decoke. many third-party designs of feedprep and lube oil HVUs.
Yields: Typical for Arabian light crude Licensor: Shell Global Solutions International B.V.
Products wt, %
Gas C1–C4 0.7
Gasoline C5 –150°C 15.2
Kerosine 150°C –250°C 17.4
Gasoil (GO) 250°C –350°C 18.3
VGO 350°C –370°C 3.6
Waxy distillate (WD) 370°C –575°C 28.8
Residue 575°C+ 16.0
Crude distillation
LPG
Application: The D2000 process is progressive distillation to minimize the Feed
total energy consumption required to separate crude oils or condensates START Light naphtha
into hydrocarbon cuts, which number and properties are optimized to fit 4 Medium naphtha
with sophisticated refining schemes and future regulations. This process is
applied normally for new topping units or new integrated topping/vacu- Heavy naphtha
um units but the concept can be used for debottlenecking purpose. One or two kerosine cut
Stm.
1
Products: This process is particularly suitable when more than two 2 3
Two kerosine cut
naphtha cuts are to be produced. Typically the process is optimized to 5
Vacuum gas oil
produce three naphtha cuts or more, one or two kerosine cuts, two at-
mospheric gas oil cuts, one vacuum gas oil cut, two vacuum distillates 6 Distillate
cuts, and one vacuum residue. Distillate for FCC
Vacuum
Description: The crude is preheated and desalted (1). It is fed to a first residue
dry reboiled pre-flash tower (2) and then to a wet pre-flash tower (3).
The overhead products of the two pre-flash towers are then fraction-
ated as required in a gas plant and rectification towers (4).
The topped crude typically reduced by 2/3 of the total naphtha cut is
then heated in a conventional heater and conventional topping column
(5). If necessary the reduced crude is fractionated in one deep vacuum Utility requirements, typical per bbl of crude feed:
column designed for a sharp fractionation between vacuum gas oil, two Fuel fired, 103 btu 50–65
vacuum distillates (6) and a vacuum residue, which could be also a road Power, kWh 0.9–1.2
bitumen. Steam 65 psig, lb 0–5
Extensive use of pinch technology minimizes heat supplied by heat- Water cooling, (15°C rise) gal 50–100
ers and heat removed by air and water coolers. Total primary energy consumption:
This process is particularly suitable for large crude capacity from for Arabian Light or Russian Export Blend: 1.25 tons of fuel
150,000 to 250,000 bpsd. per 100 tons of Crude
It is also available for condensates and light crudes progressive distil- for Arabian Heavy 1.15 tons of fuel
lation with a slightly adapted scheme. per 100 tons of Crude
Economics: Installation: Technip has designed and constructed one crude unit and
Investment (basis 230,000 bpsd including atmospheric and one condensate unit with the D2000 concept. The latest revamp proj-
vacuum distillation, gas plant and rectification tower) $750 to
$950 per bpsd (US Gulf Coast 2000).
Continued 
Crude distillation, continued
ect currently in operation shows an increase of capacity of the existing
crude unit of 30% without heater addition.
Licensor: TOTAL and Technip.

Vacuum distillation
Application: Process to produce vacuum distillates that are suitable for Vacuum tower Side strippers To vacuum system
lubricating oil production by downstream units, and as feedstocks to Vacuum gasoil
FCC and hydrocracker units.
Feed: Atmospheric bottoms from crude oils (atmospheric residue) or Heater
hydrocracker bottoms. Stm
Product: Vacuum distillates of precisely defined viscosities and flash points Low visc.
Stm
(for lube production) and low metals content (for FCC and hydrocracker Medium visc.
units) as well as vacuum residue with specified softening point, penetra- BFW High visc.
tion and flash point. Metals cut
Description: Feed is preheated in a heat-exchanger train and fed to the Vacuum resid.
fired heater. The heater outlet temperature is controlled to produce the

Feed
required quality of vacuum distillates and residue. Structured packings
are typically used as tower internals to achieve low flashzone pressure
and, hence, to maximize distillate yields. Circulating reflux streams en-
able maximum heat recovery and reduced column diameter.
A wash section immediately above the flash zone ensures that the
metals content in the lowest side draw is minimized. Heavy distillate Installation: Numerous installations using the Uhde (Edeleanu) propri
from the wash trays is recycled to the heater inlet or withdrawn as met- etary technology are in operation worldwide. The most recent reference
als cut. is a 86,000-bpd unit for a German refinery, which was commissioned
When processing naphthenic residues, a neutralization section may in 2004; the unit produces vacuum distillates as feedstock for FCC and
be added to the fractionator. hydrocracker units.
Utility requirements (typical, North Sea Crude), units per m³ of feed: Licensor: Uhde GmbH.
Electricity, kWh 5
Steam, MP, kg 15
Steam production, LP, kg 60
Fuel oil, kg 7
Water, cooling, m³ 3

Ethers
Raffinate C4
Application: The Snamprogetti Etherification Technology allows to pro-
duce high-octane oxygenates compounds such as methyl tert-butyl ether
(MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), tert- 1 2
amyl ethyl ether (TAEE) and etherified light cracked naphtha (ELCN).
4
Feed: C4 streams from steam cracker, fluid catalytic cracking unit (FCCU)
3
and isobutane dehydrogenation units, with isobutene contents ranging C4 feed
from 15 wt% to 50 wt%, C5 and light cracked naphtha (LCN–FCC light
gasoline 35°C–100°C) from FCC Units.
Alcohol 5
Description: A typical MTBE/ETBE unit using FCC cut is based on a sin-

Ether
gle-stage scheme with a tubular (1) and an adiabatic (2) reactor. The
front-end reactor uses the proprietary water cooled tubular reactor
(WCTR). The WCTR is a very flexible reactor and can treat all C4 cuts
on a once-through basis. It is the optimal solution for the etherification
reaction since it enables an optimal temperature profile with the best
compromise between kinetic and thermodynamic.
The reactor effluent is sent to the first column (3) where the prod- Utilities: (Referred to a feedstock at 20 wt% isobutylene concentrate—
uct is recovered as bottom stream while the residual C4 are sent to the light cracked naphtha).
washing column (4) to separate the alcohol. The water/alcohol leaving Steam 0.8 ÷ 0.9 t/t Ether
the column is sent to alcohol-recovery column (5), to recycle both alco- Water, cooling 53 ÷ 62 m³/t Ether
hol and water. Power 8.4 ÷ 9.2 kWh/ t Ether
This scheme will provide a total isobutene conversion up to 95 wt%.
Installation: Over 25 units including MTBE, ETBE, TAME and TAEE have
With the double-stage scheme, it is possible to reach more than 99
been licensed by Snamprogetti.
wt%.
The industrial experience has proven that this plant with the WCTR, Licensor: Snamprogetti, a company of Saipem.
can be easily switched from ETBE to MTBE production, and vice ver-
sa, without stopping the plant and any reduction in feedrates. Process
schemes are similar for production of heavier ethers starting from C5 or
LCN streams.

Ethers, ETBE
Application: The CDEtbe catalytic distillation technology processes C4 Boiling point
reactor
Catalytic
distillation
Ethanol
extraction
Ethanol
recovery
streams from steam cracker, refining and isobutane dehydrogenation Fresh ethanol Recycle ethanol
units to produce ETBE. Mixed C4s
Catalytic C4 raffinate
Ethanol
Description: ETBE is formed by the catalytic etherification of isobutylene and C4s
with ethanol. The patented CDEtbe process is based on a two-step re-
actor design, consisting of a fixed bed reactor followed by final con-
version in a catalytic distillation column. The process utilizes an acidic
ion exchange resin catalyst in both its fixed bed reactor and proprietary
catalytic distillation structures. Water
The unique catalytic distillation column combines reaction and

fractionation in a single unit operation. It allows a high conversion of ETBE
isobutylene to be achieved simply and economically. By using distillation
to separate the product from the reactants, the equilibrium limitation
is exceeded and higher conversion of isobutylene is achieved. The ETBE
produced has a very low ethanol content that does not require addi-
tional downstream processing. CDTECH’s boiling point reactor offers:
• Simple and effective control
Product: The produced ETBE can be blended as a high quality bio-fuel. • Elimination of hot spots
• Long catalyst life
Process advantages: • High flexibility
• Low capital cost
CDTECH’s catalytic distillation offers:
• Elimination of catalyst attrition
• Improved kinetics
• Most effective heat removal technique
• High conversion (beyond fixed bed-equilibrium limit)
• Elimination of cooling water requirement.
• Low utilities Installation: CDTECH converted the first MTBE unit to produce ETBE in
• Long catalyst life with sustained high conversion 2002, and continues to work with numerous licensors to retrofit other
• Reduced plot space. existing MTBE units to produce ETBE.
Licensor: CDTECH

Ethers—ETBE
Application: The Uhde (Edeleanu) ETBE process combines ethanol and
isobutene to produce the high-octane oxygenate ethyl tertiary butyl ETBE Debutanizer Water Ethanol/water
reactor wash separation
ether (ETBE). BB raffinate
Feeds: C4 cuts from steam cracker and FCC units with isobutene con-
tents ranging from 12% to 30%.
Ethanol/water
Products: ETBE and other tertiary alkyl ethers are primarily used in gas- azeotrope
oline blending as an octane enhancer to improve hydrocarbon com-
bustion efficiency. Moreover, blending of ETBE to the gasoline pool will
C4 feedstock
lower vapor pressure (Rvp).
Ethanol
Description: The Uhde (Edeleanu) technology features a two-stage re-
actor system of which the first reactor is operated in the recycle mode. ETBE product
With this method, a slight expansion of the catalyst bed is achieved that
ensures very uniform concentration profiles in the reactor and, most
important, avoids hot spot formation. Undesired side reactions, such as
the formation of di-ethyl ether (DEE), are minimized.
The reactor inlet temperature ranges from 50°C at start-of-run to
about 65°C at end-of-run conditions. One important feature of the two- Utility requirements: (C4 feed containing 21% isobutene; per metric
stage system is that the catalyst can be replaced in each reactor sepa- ton of ETBE):
rately, without shutting down the ETBE unit. Steam, LP, kg 110
The catalyst used in this process is a cation-exchange resin and is available Steam, MP, kg 1,000
from several manufacturers. Isobutene conversions of 94% are typical for Electricity, kWh 35
FCC feedstocks. Higher conversions are attainable when processing steam- Water, cooling, m3 24
cracker C4 cuts that contain isobutene concentrations of about 25%.
ETBE is recovered as the bottoms product of the distillation unit. The Installation: The Uhde (Edeleanu) proprietary ETBE process has been
ethanol-rich C4 distillate is sent to the ethanol recovery section. Water is successfully applied in three refineries, converting existing MTBE units.
used to extract excess ethanol and recycle it back to process. At the top Two other MTBE plants are in the conversion stage.
of the ethanol / water separation column, an ethanol / water azeotrope is Licensor: Uhde GmbH.
recycled to the reactor section. The isobutene-depleted C4 stream may
be sent to a raffinate stripper or to a molsieve-based unit to remove
oxygenates such as DEE, ETBE, ethanol and tert- butanol.
Ethers—MTBE
Application: To process C4 streams from steam cracker, refinery and isobu- Fresh
wash
Boiling point
reactor
Catalytic
distillation
Methanol
extraction
Methanol
recovery
tane dehydrogenation units to produce methyl tertiary butyl ether (MTBE). Fresh methanol Recycle methanol
C4 raffinate
Description: MTBE is formed by the catalytic etherification of isobutylene
Methanol
with methanol. The patented CDMtbe process is based on a two-step and C4s
reactor design, consisting of a boiling point fixed-bed reactor followed
Water
by final conversion in a catalytic distillation column. The process uses
an acidic ion-exchange resin catalyst in both its fixed-bed reactor and
proprietary catalytic distillation structures.
The unique catalytic distillation column combines reaction and Mixed C4s Water
fractionation in a single unit operation. It allows a high conversion of
isobutylene to be achieved simply and economically. By using distillation MTBE
Water and
to separate the product from the reactants, the equilibrium limitation is contaminants
exceeded and higher conversion of isobutylene is achieved.
Products: MTBE synthesis is a highly selective process for removal of

isobutylene. It can be used for pretreatment to produce high-purity butene-1
CDTECH’s boiling point reactor offers:
or for recovery to make high-purity isobutylene via MTBE decomposition.
Process advantages: CDTECH’s catalytic distillation offers: • Elimination of hot spots
• Improved kinetics • Long catalyst life
• High conversion (beyond fixed bed-equilibrium limit) • High flexibility
• Low capital cost • Low capital cost
• Low utilities • Elimination of catalyst attrition
• Long catalyst life with sustained high conversion • Most effective heat removal technique
• Reduced plot space • Elimination of cooling water requirement.
Installations: With more than 20 years of experience and a total of 117

licensed ethers units, 88 units are MTBE, with 36 still in operation.
Licensor: CDTECH.

Ethers—MTBE
MTBE reactor Debutanizer Water Methanol/water
Application: The Uhde (Edeleanu) MTBE process combines methanol wash separation
BB raffinate
and isobutene to produce the high-octane oxygenate—methyl tertiary
butyl ether (MTBE).
Feeds: C4-cuts from steam cracker and FCC units with isobutene con-
tents range from 12% to 30%.
Products: MTBE and other tertiary alkyl ethers are primarily used in gas-
oline blending as an octane enhancer to improve hydrocarbon combus- C4 feedstock
tion efficiency.
Methanol
Description: The technology features a two-stage reactor system of
MTBE product
which the first reactor is operated in the recycle mode. With this meth-
od, a slight expansion of the catalyst bed is achieved which ensures very
uniform concentration profiles within the reactor and, most important,
avoids hot spot formation. Undesired side reactions, such as the forma-
tion of dimethyl ether (DME), are minimized.
when the raffinate-stream from the MTBE unit will be used to produce
The reactor inlet temperature ranges from 45°C at start-of-run to
a high-purity butene-1 product.
about 60°C at end-of-run conditions. One important factor of the two-
For a C4 cut containing 22% isobutene, the isobutene conversion
stage system is that the catalyst may be replaced in each reactor sepa-
may exceed 98% at a selectivity for MTBE of 99.5%.
rately, without shutting down the MTBE unit.
The catalyst used in this process is a cation-exchange resin and is Utility requirements, (C4 feed containing 21% isobutene; per metric ton
available from several catalyst manufacturers. Isobutene conversions of of MTBE):
97% are typical for FCC feedstocks. Higher conversions are attainable Steam, MP, kg 100
when processing steam-cracker C4 cuts that contain isobutene concen- Electricity, kWh 35
trations of 25%. Water, cooling, m3 15
MTBE is recovered as the bottoms product of the distillation unit. Steam, LP, kg 900
The methanol-rich C4 distillate is sent to the methanol-recovery section.
Water is used to extract excess methanol and recycle it back to process. Installation: The Uhde (Edeleanu) proprietary MTBE process has been
The isobutene-depleted C4 stream may be sent to a raffinate stripper successfully applied in five refineries. The accumulated licensed capacity
or to a molsieve-based unit to remove other oxygenates such as DME, exceeds 1 MMtpy.
MTBE, methanol and tert-butanol.
Very high isobutene conversion, in excess of 99%, can be achieved Licensor: Uhde GmbH.
through a debutanizer column with structured packings containing ad-
ditional catalyst. This reactive distillation technique is particularly suited click here to e-mail for more information
Olefin etherification
Application: New processing methods improve etherification of C4– C7
reactive olefins including light catalytic naphtha (LCN) with alcohol (e.g., Water Wash column
trayed or packed
1st
reactor
Fractionator Condenser Finishing
reactor
Alcohol
extraction
Alcohol recovery
column
methanol and ethanol). The processes, RHT-MixedEthers, RHT-MTBE, Alcohol MeOH C4 or C5
RHT-ETBE, RHT-TAME and RHT-TAEE, use unique concepts to achieve the or ETOH raffinate OSBL
Water
Alcohol recycle LPS
maximum conversion without applying cumbersome catalyst in the col- C4 or C5/C7
purge
CW CW
umn. The processing economics provide improvements over other avail-
7
able ether technologies currently available. The technology suite can Wash water 2
3
CW
Alcohol
1 CW recycle
be applied to ethyl tertiary butyl ether (ETBE) production in which wet C4 feed or to reactor
C5-C7* 5 6
ethanol can be used in place of dry ethanol. The drier can be eliminated,
4
which is approximately half the cost for an etherification unit. The RHT Water
MPS C4 or C5
raffinate** LP
ethers processes can provide the highest conversion with unique mul-
MTBE/ETBE or mixed
tiple equilibrium stages. ether product Alcohol Water makeup
* No recycle reactor required. **only C5s

Description: The feed is water washed to remove basic compounds
that are poisons for the resin catalyst of the etherification reaction. The
C4 ethers—methyl tertiary butyl ether (MTBE)/ETBE), C5 – tertiary amyl
methyl ether (TAME/ tertiary amyl ethyl ether (TAEE) and C6 /C7 ethers
are made in this process separately. The reaction is difficult; heavier
ethers conversion of the reactive olefins are equilibrium conversion of separate the ether and heavy hydrocarbons from C4 or C5 hydrocarbons,
about 97% for MTBE and 70% for TAME and much lower for C6 /C7 which are taken as overhead. Single or multiple draw offs are taken from
ethers are expected. the fractionation column. In the fractionation column, unreacted olefins
Higher alcohols have similar effects (azeotrope hydrocarbon/alcohol (C4 or C5) are sent to the finishing reactor (5). This stream normally does
relationship decreases when using methanol over ethanol). The equilib- not require alcohol, since azeotrope levels are available. But, some ad-
rium conversions and azeotrope effects for higher ethers are lower, as is ditional alcohol is added for the equilibrium-stage reaction. Depending
expected. After the hydrocarbon feed is washed, it is mixed with alcohol on the liquid withdrawn (number of side draws), the conversion can be
with reactive olefin ratio control with alcohol. enhanced to a higher level than via other conventional or unconven-
The feed mixture is heated to reaction temperature (and mixed with tional processes.
recycle stream (for MTBE/ETBE only) and is sent to the first reactor (1), By installing multiple reactors, it is possible to extinct the olefins
where equilibrium conversion is done in the presence of sulfonated resin within the raffinate. The cost of side draws and reactors can achieve
catalyst, e.g. Amberlyst 15 or 35 or equivalent from other vendors. pay-off in 6 to 18 months by the higher catalyst cost as compared to
Major vaporization is detrimental to this reaction. Vapor-phase re- other processes. This process could provide 97– 99.9% isobutene con-
active olefins are not available for reaction. Additionally at higher tem- version in C4 feed (depending on the configuration) and 95 – 98+% of
peratures, there is slight thermal degradation of the catalyst occurs. The isoamylenes in C5 stream.
reactor effluent is sent to fractionator (debutanizer or depentanizer) to Continued 
catalyst. Distillation is done at optimum conditions. Much lower steam
Olefin etherification, continued consumption for alcohol recovery. For example, the C5 feed case requires
less alcohol with RHT configuration (azeotropic alcohol is not required)
The ether product is taken from the bottom, cooled and sent to the
and lowers lower steam consumption.
storage. The raffinate is washed in extractor column (6) with and is sent
to the OSBL. The water/alcohol mixture is sent to alcohol recovery col- Economics:
umn (7) where the alcohol is recovered and recycled as feed. CAPEX ISBL, MM USD (US Gulf Coast 1Q06,
For ETBE and TAEE, ethanol dehydration is required for most of the 1,000-bpd ether product) 9.1
processes, whereas for RHT process, wet ethanol can be used providing Utilities Basis 1,000 bpd ether
maximum conversions. If need be, the TBA specification can be met by Power kWh 45.0
optimum design with additional equipment providing high ETBE yield 3
Water, cooling m / h 250
and conversion. Cost of ethanol dehydration is much more than the Steam MP, Kg / h 6,000
present configuration for the RHT wet-ethanol process. Basis: FCC Feed (about 15–20% isobutylene in C4 mixed stream)
The total capital cost /economics is lower with conventional catalyst
usage, compared to other technologies, which use complicated struc- Commercial units: Technology is ready for commercialization.
ture, require installing a manway (cumbersome) and require frequently
catalyst changes outs. Licensor: Refining Hydrocarbon Technologies LLC.
The RHT ether processes can provide maximum conversion as com-
pared to other technologies with better economics. No complicated or
proprietary internals for the column including single source expensive
TAEE, from refinery C5 feeds

Application: To process C5 streams from refinery units to produce ter- Fresh
wash
Boiling point
reactor
Catalytic
distillation
Ethanol
extraction
Ethanol
recovery
tiary amyl ethyl ether (TAEE). Fresh ethanol Recycle Ethanol
C5 raffinate
Description: TAEE is formed by the catalytic etherification of isoamylene
Ethanol
with ethanol. The patented CDTaee process is based on a two-step reac- and C5s
tor design, consisting of a boiling point fixed-bed reactor followed by
Water
final conversion in a catalytic distillation column. The process uses an
acidic ion-exchange resin catalyst in both its fixed-bed reactor and pro-
prietary catalytic distillation structures.
The unique catalytic distillation column combines reaction and frac- Mixed C5s Water
tionation in a single unit operation. It allows a high conversion of isoam-
ylene (exceeding fixed-bed equilibrium limitations) to be achieved simply TAEE
Water and
and economically. By using distillation to separate the product from the contaminants
reactants, the equilibrium limitation is exceeded and higher conversion
of isoamylene is achieved. Catalytic distillation also takes advantage of
the improved kinetics through increased temperature without penaliz-
ing equilibrium conversion.
Installation: With 20 years of experience, CDTECH has 120 licensed
ethers units.
• Elimination of hot spots Licensor: CDTECH.
• High flexibility

TAME, from refinery and

steamcracker C5 feeds
TAME
Application: The CD-Isotame process combines skeletal isomerization
and etherification steps to maximize the production of tertiary amyl C5 olefin
Selective C5 raffinate 1
Lights
methyl ether (TAME) from refinery and steam-cracker C5 streams. Hydrogen hydrogenation
and CDTAME
ISOMPLUS
Description: TAME is formed by the catalytic etherification of reactive Optional

Extract Isomerate
isoamylenes with methanol. Skeletal isomerization increases TAME pro- Fresh methanol recycle C5 raffinate
duction from an olefinic C5 stream by converting normal amylenes to Recycle
isoamylenes. The combination significantly reduces olefin content while
also increasing octane. Methanol
Extract
CDTAME
This process provides the minimum capital cost at about 80% C5 recovery Methanol
olefin reduction. The olefinic C5 stream is fed to a selective hydroge-

nation step where dienes are converted to olefins. Removal of dienes
reduces color and gum formation in the TAME product. In addition, un-
reactive 3 methyl 1-butene (3MB1) is converted to reactive isoamylene
via hydroisomerization, thus increasing the TAME yield.
The primary TAME product is made in the first CDTame unit where • High selectivity of isomerization (> 90%)
greater than 90% conversion of isoamylene is achieved. Raffinate 1 • Isomerization of 3MB1 to reactive isoamylene
from this unit is fed to a skeletal isomerization unit (ISOMPLUS) where • Improved C5 raffinate as gasoline feedstock due to reduced, color,
n-pentenes are converted to isoamylenes at high yield and selectivity. gum formation and olefin content
The vapor-phase reaction takes place over a robust catalyst with long • Increased TAME production
cycles between regenerations. • Increased gasoline pool octane
The isomerate is then fed to a second CDTame unit where additional • Decreased gasoline pool Rvp and olefins
TAME is produced at greater than 95% conversion of isoamylenes. Even • Low capital and operating cost
higher conversion of normal pentenes to TAME can be achieved by an • Superior economics and performance over C5 alkylation
optional raffinate 2 recycle to the skeletal isomerization unit. A purge • High-quality TAME product without objectionable odor or color.
stream removes the saturated C5s from the recycle stream. A common Installation: Out of the 120 licensed ethers units, approximately half of
methanol recovery unit serves both CDTame units. the units use the TAME technology.
Process advantages include: Licensor: CDTECH.
• Selective hydrogenation of diolefins at minimum capital cost
• High conversion of isoamylenes (> 95%)
• High conversion of normal pentenes (> 70%)
TAME, from refinery C5 feeds

Fresh Boiling point Catalytic Methanol Methanol
Application: To process C5 streams from refinery units to produce ter- wash reactor distillation extraction recovery
Fresh methanol Recycle methanol
tiary amyl methyl ether (TAME).
C5 raffinate
Description: TAME is formed by the catalytic etherification of isoamylene Methanol

and C5s
with methanol. The patented CDTame process is based on a two-step
reactor design, consisting of a boiling point fixed-bed reactor followed Water
by final conversion in a catalytic distillation column. The process utilizes
an acidic ion-exchange resin catalyst in both its fixed-bed reactor and
proprietary catalytic distillation structures.
Mixed C5s Water
The unique catalytic distillation column combines reaction and
fractionation in a single unit operation. It allows a high conversion
TAME
of isoamylene (exceeding fixed-bed equilibrium limitations) to be Water and
contaminants
achieved simply and economically. By using distillation also to separate
the product from the reactants, the equilibrium limitation is exceeded
and higher conversion of isoamylene is achieved. Catalytic distillation
also takes advantage of the improved kinetics through increased tem-
perature without penalizing equilibrium conversion. Advanced process Installation: Out of the 120 licensed ethers units, approximately half of
control maximizes catalyst life and activity to provide high sustained units use the TAME technology.
TAME production.
Licensor: CDTECH.
• Elimination of hot spots
• High flexibility

Gasification Low heating

value coke gas
Application: ExxonMobil’s Reserach & Engineering’s (EMRE’s) continuous Tertiary cyclones
fluid-bed coking with integrated steam gasification technology to con- Reactor products Steam
to fractionator generation
vert heavy hydrocarbons (vacuum residuum, extra heavy oil or bitumen) 5
to lighter liquid products and a clean burning fuel gas, Flexigas, with 5 Direct
minimum coke production. Attractive when coking for complete resid contact
1 cooler
conversion with low or no fuel oil production is preferred and when START
Sour
outlets for fuel coke are limited or not economic, and especially when water
2 Coke
low-cost clean fuel gas is needed or where natural gas is high cost. 3 4 fines
Products: Liquid product yields are similar to delayed coking and are
upgraded to transportation fuels in the refinery by hydrotreating, Steam
hydrocracking, fluid catalytic cracker (FCC), or other processes. A large Hot Air
Cold blower
quantity of clean fuel gas is produced, which can be burned in a variety coke coke
of grassroots or revamp furnaces and boilers in the refinery or in nearby Air
power plants with low SOx and NOx emissions.
Description: FLEXICOKING has essentially the same feed system and

used for recovery of V. Partial gasification with coke withdrawal can also
fluid bed reactor (1) and scrubber (2) sections as FLUID COKING, and
be used to provide additional process flexibility for increased capacity or
also has the same process flexibility to directly process vacuum tower
to make fuel grade coke if attractive markets are available.
bottoms without the need for a preheat furnace. It can also handle very
heavy feeds, and can adjust recycle cut point depending upon gasoil Reactor yields: Typical 1,050°F+ cut point vacuum resid (~26 wt% Con-
product quality requirements. A steam /air gasification fluid bed reactor radson carbon, 4.6 wt% sulfur, 125 wppm Ni + V)
(4) is added to convert coke produced in the reactor to a CO and H2-rich Component yield wt% wt%
fuel gas, diluted by N2. Fuel gas (C2 –) 6.7
The heater vessel (3) serves as a fluid solids heat exchanger to pro- LPG, (C3 / C4) 4.4
vide process heat for reactions in the heater and gasifier and to initially Total C4– 11.1
cool and clean Flexigas from the gasifier. Flexigas overhead from the Naphtha (C5-430°F) 15.3
heater (3) is cooled and cleaned in several steps (5) to remove fines and Distillate (430°F – 650°F) 11.0
is then treated with FLEXSORB hindered amine to reduce H2S to as low Gas oil (650°F – 975°F) 32.2
10 wppm if needed. Typically 95 wt%–97 wt% of the coke generated in Total C5+ liquids 58.6
the reactor is gasified to produce process heat and Flexigas, depending Net product coke 1.7
upon the amount of nickel (Ni) and vanadium (V) in the feed, A small Gasified coke 28.6
amount of purge or net product coke is withdrawn from the heater (3) Total reactor coke 30.3
and fines removal system (5), which can be burned in cement kilns or Total: 100 100 Continued 
• Environmental advantages with lower SOx, NOx, and particulates
Gasification, continued emissions than conventional delayed coking processes
• Much lower investment and more reliable than delayed coking
Fuel gas production: Steam and air gasification of coke produced in the plus partial oxidation or direct gasification of solids or heavy feeds. Par-
reactor generates a large fuel gas stream that is rich in CO / H2, which ticularly attractive for SAGD tar sands upgrading with large fuel require-
can be used as fuel. Fuel gas production consistent with the above yields ments.
for a 31,000 bpd FLEXICOKING Unit is:
Flexigas production: 1,580 MBtu / hr [460 MW (th)] Reference: Kamienski, P. W. , S. Massenzio and M. de Wit, “Coking
Flexigas heating value: 128 Btu / SCF without the coke,” Hydrocarbon Engineering, March 2008.
H2S content: 10 wppm Kamienski, P. W. , S. Massenzio and M. de Wit, “FLEXICOKING: Inte-
grated Coking and Gasification Technology,” ERTC Coking and gasifica-
Competitive advantages: tion Conference, Rome, April 21–22, 2008.
• Integrated coking and gasification technology that yields the same
valuable liquid products as other coking processes but produces clean Licensor: ExxonMobil Research and Engineering Co.
fuel gas instead of high-sulfur coke.
• Fluid bed process with coke transferred pneumatically and con-
tained within fluid solids reactors and product silos.
Gasification
Liquid wastes
Application: To produce high-value products (hydrogen, fuel gas, chemi- (optional) CO2
cal synthesis gas (CO + H2) and steam) from the lowest value residual BFW
Fuel gas
Steam
streams (resid, tar or coke), using GE’s Gasification Process. Tar
Sour
shift
Sulfur is removed as hydrogen sulfide (H2S), and metals are removed Oxygen Hydrogen
in a filter cake, for further processing. If desired, up to 90% of the Gas
separation
carbon in the feed can be recovered as a purified carbon dioxide (CO2) Acid gas
Gasifier & (to SRU)
stream. syngas Soot
scrubber
Typically, 80%–90% of the energy in the feed is recovered in prod- cooler Blowdown to SWS
uct and export steam streams. The fuel gas produced is well-suited for
combustion turbines. Filter cake
Soot water
Filtration processing
(optional)
Description: Heavy feed is mixed with steam and/or hot soot water and Ni/V ash
fed with oxygen to the gasifier, at pressures ranging from 400 psig to
1,250 psig and temperatures ranging from 2,300°F to 2,700°F, which
breaks down hydrocarbons into syngas (CO and H2 ) and minimal soot
and ash.
The cooled syngas is water-scrubbed to remove soot and ash. The CO2, tons /bbl 0.5 0.5
moisturized gas passes through a water-shift reactor; carbon monoxide Fuel gas, 106 Btu 0.8 0.8
(CO) reacts with steam producing additional hydrogen and CO2. This al- Steam SH HP, export, lb 500 600
lows the adjustment of the H2 / CO ratio in the syngas to values greater
than 1. The dry syngas is then separated into various components us- Utilities, typical per bbl feed
ing conventional methods (physical and/or chemical solvents, pressure Steam Sat’d LP, cons, lb 0 100
swing adsorption, etc.) Heat can be recovered as HP steam (up to 2,000 Power, kWh 12 12
psig) from syngas cooling and water-shift reaction. Oxygen, tons 0.2 0.2
Water, cooling, gal 1,800 1,400
Economics:
Yields: *Economics based on 2004 data.
Feed Maya crude Oil sands
Installation: As of July 1, 2008, 63 units using GE’s Gasification process
Type SDA Tar Visbr Tar
are operating worldwide; 13 in refinery applications, producing hydro-
API – 4.4 0
gen, turbine fuel gas and syngas for chemicals manufacturing.
Sulfur, wt% 7 7
Ni + V, ppm 1,200 600 Licensor: GE Energy.
Products, typical per bbl feed
Hydrogen, Mscf 14 14 click here to e-mail for more information
Gasification
Application: The Shell Gasification Process (SGP) converts heavy refinery Oil
residual liquid hydrocarbon streams with high-sulfur and metals content Process Syngas
steam Steam
into a clean synthesis gas (syngas) and marketable metal oxides. Sulfur (S)
is removed by normal gas treating processes and sold as elemental S. Oxygen Scrubber
The process converts residual streams with virtually zero value as Boiler
BFW Bleed to SWS
fuel-blending components into marketable, clean gas and byproducts.
This gas can be used to generate power in gas turbines and for making
hydrogen (H2) by the well-known shift and pressure swing adsorption
(PSA) technology. It is one of the few environmentally acceptable solu- Reactor Effluent Filtercake Ni/V ash
boiler work up
tions for residual hydrocarbon streams.
Soot quench Filtration
Products: Synthesis gas (CO + H2), sulfur and metal oxides.
Description: Liquid hydrocarbon feedstock (from very light such as natu-
ral gas to very heavy such as vacuum flashed cracked residue (VFCR) and
ashphalt) is fed into a reactor, and gasified with pure O2 and steam. The
net reaction is exothermic and produces a gas primarily containing car-
bon monoxide (CO) and H2. Depending on the final syngas application, Installation: Over the past 40 years, more than 150 SGP units have been
operating pressures, ranging from atmospheric up to 65 bar, can easily installed that convert residue feedstock into synthesis gas for chemical
be accommodated. applications. The Shell Pernis refinery near Rotterdam, The Netherlands,
SGP uses refractory-lined reactors that are fitted with a gasification uses the SGP process in a close refinery integration. This highly com-
burner and syngas effluent cooler, designed to produce high-pressure plex refinery depends on the SGP process for its H2 supply. Recently, ENI
steam—over 100 bar (about 2.5 tons per ton feedstock). Gases leaving refinery in Sannazzaro, Italy, has been successfully started-up. Similar
the steam generator are at a temperature approaching the steam tem- projects are underway in Canada and China.
perature; thus, further heat recovery occurs in an economizer. The Shell middle distillate synthesis plant in Bintulu, Malaysia, uses
Soot (unconverted carbon) and ash are removed from the raw gas SGP to convert 100 million scfd of natural gas into synthesis gas that is
by a two-stage waterwash. After the final scrubbing, the gas is virtually used for petrochemical applications.
particulate-free; it is then routed to a selective-acid-gas-removal system. A related process—the Shell Coal Gasification Process (SCGP)—gas-
Net water from the scrubber section is routed to the soot ash removal ifies solids such as coal or petroleum coke. The reactor is different, but
unit (SARU) to filter out soot and ash from the slurry. By controlled oxi- main process layout and work-up are similar. The Demkolec Power plant
dation of the filtercake, ash components are recovered as marketable at Buggenum, The Netherlands, produces 250 mega watts based on the
oxides—principally vanadium pentoxide. The (clean) filtrate is returned SCGP process. In total, over 20 licenses are in different phases of project
to the scrubber. execution using SCGP.
Continued 
Gasification, continued Zuideveld, P. and J. Wolff,“New methods upgrade refinery residu-
als into lighter products,” Hydrocarbon Processing, February 2006, pp.
73–79.
Reference: “Shell Gasification Process,” Conference Defining the Fu-
“Shell Gasification Technology—Optimal disposal solution for refin-
ture, Bahrain, June 1–2, 2004.
eries heavy ends,” ERTC Gasification Conference, Paris, 2007.
“Shell Gasification Process for Upgrading Gdansk Refinery,” The
“Shell Gasification Technology: Generating Profit from the Bottom
6th European Gasification Conference IChemE, Brighton, May 10–12,
of the Barrel,” NPRA, Annual Meeting, San Diego, March 9–11,2008.
2004.
“Shell Gasification Technology—Part of refinery upgrading strate-
“Overview of Shell Global Solutions Worldwide Gasification Devel-
gies,” ERTC Gasification Conference, Rome, April 21–23,2008.
opments,” 2003 Gasification Technologies Conference, San Francisco,
Oct. 12–15, 2003. Licensor: Shell Global Solutions International B.V.

Gasification—PDQ Feed dust Cyclone filter

Application: The PRENFLO (PRessurized ENtrained-FLOw) direct quench Steam
Steam
(PDQ) is an optimized design of the proven PSG gasification process for PRENFLO drum
Lock hopper gasifier Boiler feed water
all types of solid feedstock as petcoke, solid refinery residues, coal and
biomass for chemical applications (ammonia,methanol, hydrogen, syn- Feed bin
Raw gas
fuel.) Oxygen
Scrubber
Description: First, the feed dust is prepared in the feed preparation unit.
Approximately 80% of the dust is smaller than 0.1 mm and has a water
content of approximately 1 wt%–2 wt% in the case of hard coals, and Direct
quench Wash water
approximately 8 wt%–10 wt% for lignite.
Slurry
This feed dust is gasified in the PRENFLO gasifier using oxygen and filtration
steam as the gasification agent. The gasification temperature is higher Slag crusher/ Filter cake
than ash-melting temperature, which allows feedstocks containing ash collector Waste water
to be removed as slag. The cooled-type gasifier is equipped with mul- Slag lock
hopper
tiple, horizontally arranged burners. Slag
The raw gas produced, which contains mainly carbon monoxide and
hydrogen, is quenched with water in a direct quench in the gasifier ves-
sel and then cleaned in a scrubber.
Economics: Typical raw gas composition:

CO + H2 > 85 vol%
Main process data:
CO2 6–8 vol%
Gasification pressure: 40 bar and higher
CH4 < 0.1 vol%
Gasification temperature: > 2,000°C
Gas temperature at outlet of gasifier/quench: 200°C–250°C Installation: The PRENFLO PDQ process is under development for indus-
Carbon conversion: > 99% trial-scale applications

Gasification—PSG Boiler feed water Steam
Application: The PRENFLO (PRessurized ENtrained-FLOw) process can be Steam

used to gasify all types of solid feedstocks (petcoke, solid refinery resi- Feed
Cyclone
filter
drum
dues, coal and biomass). dust
Description: First, the feed dust is prepared in the feed preparation unit. Lock Filter
hopper
Approximately 80% of the dust is smaller than 0.1 mm and has a water Fly
ash
content of approximately 1wt%-2 wt% in the case of hard coals, and Feed bin lock
Scrubber
PRENFLO
approximately 8wt%-10 wt% for lignite. gasifier hopper Fly
Raw gas
Oxygen ash
This feed dust is then gasified in the PRENFLO gasifier using oxygen feed
bin
and steam as gasification agents. The gasification temperature is higher
Wash water
than the ash-melting temperature, which allows the feedstock contain-
Slag crusher/
ing ash to be removed as slag. The cooled-type gasifier is equipped with collector Waste heat boiler
Fly ash
multiple, horizontally arranged burners.
Slag lock
In the PRENFLO process with steam generation (PSG), the raw gas hopper
produced, which contains mainly carbon monoxide and hydrogen, is Slag
cooled in the waste-heat boiler and generates steam. The gas is de-
dusted in a candle filter and further treated in a scrubber unit.
Economics: Ultimate Coal Petcoke Mixture Raw gas analysis

Main process data analysis CO2, vol% 2.9
• Gasification pressure: > 40 bar C, wt% 36.3 82.2 59.2 CO, vol% 59.9
• Gasification temperature: > 2,000°C H, wt% 2.5 3.1 2.8 H2, vol% 21.7
• Gas temperature at outlet of gasifier: 1,350°C–1,600°C N, wt% 0.8 1.9 1.4 N2 + Ar, vol% 14.4*
• Carbon conversion: > 99% O, wt% 6.6 – 3.3 CH4, vol% <0.1
Typical raw gas composition: S, wt% 0.9 5.5 3.2 H2S + COS, vol% 1.1
• CO + H2 > 85 vol.% Ash, wt% 41.1 0.3 20.7 Total, vol%: 100.0
Water, wt% 11.8 7.0 9.4 LHV, dry, MJ/m3n 10.16
• CO2 2– 4 vol.%
• CH4 < 0.1 vol.% Total, wt% 100.0 100.0 100.0
LHV, MJ/kg 13.1 32.6 23.1
Reference: PRENFLO technology has been successfully commercialized
in the world’s largest solid-feedstock based IGCC 300 MWe net power
plant in Puertollano, Spain.

Multipurpose gasification
Feedstock MP-steam
Quench
Application: Production of synthesis gas, essentially H2 and CO, from C.W. water
O2/steam
a wide range of gaseous to extra heavy liquid hydrocarbons, as well as
Venturi
emulsions and slurries. Recent new applications are in (chemical) waste scrubber
1
gasification. The main advantage over comparable processes is its ex- Reactor 2 3 4
treme feedstock flexibility in the quench mode. A boiler mode for high- MP- C.W.
boiler
est efficiency is also available. Quench
water C.W.
Description: Continuous noncatalytic partial oxidation process. The BFW

Quench Raw gas
quench mode is shown above: hydrocarbon feedstock, moderator (H2O,
CO2 or N2) and oxidant (pure or diluted O2, air) are fed through a special 6
burner into the reactor (1), a refractory-lined pressure vessel. Operating Metals ash Alternative route to raw gas shift
conditions are automatically controlled. Hot gas leaves the reactor at the recovery system MARS
(soot slurry treatment) 5
bottom, passing the quench where water is injected to lower the tem- Slurry
collector
perature near the saturation temperature. Quench water washes out
Metals/ash Waste water
most particulates as unconverted carbon (soot) and ash.
Further cleaning occurs in a venturi scrubber (2) from where the gas
passes to a medium-pressure steam boiler (3) for heat recovery and to
the final cooler (4) before further processing. In hydrogen production,
the hot, wet gas from the venturi is passed directly to a raw gas shift for highest feedstock flexibility. At low-salt contents, the boiler mode can
conversion. The soot/ash slurry from the process contains virtually all recover heat as high-pressure steam, raising overall efficiency.
metals and ashes from the feedstock. It is withdrawn via a slurry col-
lector (5) and processed in the metals ash recovery system (MARS) (6). Economics: Characteristic consumption and production rates per ton of
There, soot/ash is filtered from the slurry and incinerated under con- heavy residue feedstock: 1 to 1.1 t O2 (100%), export 0.5 t MP steam
trolled conditions, yielding a saleable metal/ash product. Filtered water (quench) to 2.2 t HP steam (boiler mode), 2.2 t raw syngas (dry) equiv. to
is returned for quenching. Excess water is stripped and sent to conven- 2,600 Nm3 H2 + CO. Cold gas efficiency is 82% to 85%. In boiler mode,
tional wastewater treatment. thermal efficiencies including HP steam generated are about 95% based
on feedstock HHV. This makes the process attractive for syngas produc-
Operating conditions: Actual gasification temperatures of 1,200°C to tion and for an IGCC power plant. A highly integrated and efficient
1,500°C, pressures from atmospheric to 70 bar (or higher, if economically power complex will be in the range of $1,200/kW total invested cost.
justified). Feedstock and oxidant preheat possible in a wide range from
100°C to 600°C, depending on type of feed. Product yields and composi- Installations: A large-scale industrial plant operates in Germany, demon-
tion vary with moderator rate and type of feed. Water quench is selected strating full feedstock and product flexibility by feeding to a methanol
Continued 
Multipurpose gasification, continued
and IGCC complex. Another plant gasifies residue asphalt, producing
syngas for an ammonia plant.
Reference: Liebner, W. and C. Erdmann, “MPG—Lurgi Multipurpose

Gasification—Recent Applications and Experiences,” World Petroleum
Congress 2000, Calgary, Canada, June 2000.
Licensor: Lurgi GmbH.

Hydroconversion—VGO and DAO

Application: An ebullated-bed process H-OilDC is used for hydrocon- Recycle hydrogen Recycle hydrogen
Amine
version (hydrocracking and hydrotreating) of heavy vacuum gasoil and compressor absorber
Fixed-bed
DAO having high Conradson carbon residue and metal contents and Makeup hydrogen
HDS
low asphaltene content. It is best suited for high severity operations and Fuel gas
applications requiring long run lengths. VGO feed Ebullated High
reactor pressure
START Naphtha S=
Description: The flow diagram includes integrated mid-distillate hydro- separator <2 wppm
treating for an ultra-low-sulfur-diesel product. The typical battery limits Stabilizer
scheme includes oil- and hydrogen-fired heaters, an advanced design Oil feed Diesel S=
hot high-pressure separator and ebullating pump recycle system, a re- heater <50 wppm
cycle gas scrubber and product separation and fractionation. Gas-oil
stripper
Catalyst in the reactor is replaced periodically without shutdown FCC feed S=
Ebullating 1,000-1,500 wppm
and, for cases of feeds with low metal contents, the catalyst can be re- Hydrogen pump
generated onsite to reduce catalyst consumption. heater
Various catalysts are available as a function of the feedstock and

the required objectives. An H-OilDC unit can operate for four-year run
lengths at constant catalyst activity with conversion in the 20-80% range
in once-through mode and to more than 95% in recycle mode with up
Economics: Basis—2008 US Gulf Coast
to 99% hydrodesulfurization.
Investment in $ per bpsd 2,800 – 4,500
Operating conditions: Utilities, per bbl of feed
Temperature, °F 750– 820 Fuel, 103 Btu 60
Hydrogen partial pressure, psi 600 –1,500 Power, kWh 3
LHSV, hr –1 0.5 –3.0 Catalyst makeup, lb 0.01– 0.3
Conversion, wt% 20 –80 in once-through mode
Installation: The H-OilDC process has two references, one in operation
Example: VGO + DAO feed: a blend of heavy VGO and C5 DAO con- and one under construction, with a total cumulative capacity of 139,900
taining close to 100 ppm metals is processed at 80% conversion at an bpsd. This technology has been commercially demonstrated based on
overall desulfurization rate of over 96%. the ebullated bed reactor making a total of 11 references for residue
and VGO hydroconversion.
Licensor: Axens.

Hydrocracking
Fuel gas
Application: Upgrade vacuum gas oil alone or blended with various
feedstocks (light-cycle oil, deasphalted oil, visbreaker or coker gasoil). H2 makeup
Products: Jet fuel, diesel, very-low-sulfur fuel oil, extra-quality FCC Heavy
naphtha
feed with limited or no FCC gasoline post-treatment or high VI lube
Jet fuel
base stocks. 5
1 2 3 4
Diesel
Description: This process uses a refining catalyst usually followed by
an amorphous and/or zeolite-type hydrocracking catalyst. Main features Wild naphtha
of this process are:
• High tolerance toward feedstock nitrogen
• High selectivity toward middle distillates Feed
• High activity of the zeolite, allowing for 3–4 year cycle lengths and START
Low-sulfur VGO
products with low aromatics content until end of cycle.
Three different process arrangements are available: single-step/
once-through; single-step/total conversion with liquid recycle; and two-
step hydrocracking. The process consists of: reaction section (1, 2), gas
separator (3), stripper (4) and product fractionator (5). Installation: More than 67 references, cumulative capacity exceeding
2.7 million bpsd, conversions up to 99%.
Product quality: Typical for HVGO (50/50 Arabian light/heavy):
Feed, Jet Licensor: Axens.
HVGO fuel Diesel
Sp. gr. 0.932 0.800 0.826
TBP cut point, °C 405– 565 140 –225 225 –360
Sulfur, ppm 31,700 <10 <10
Nitrogen, ppm 853 <5 <5
Metals, ppm <2 – –
Cetane index – – 62
Flash pt., °C –  40 125
Smoke pt., mm, EOR – 26–28 –
Aromatics, vol%, EOR – < 12 <8
Viscosity @ 38°C, cSt 110 – 5.3
PAH, wt%, EOR <2
Hydrocracking
Application: Convert naphthas, AGO, VGO, DAO, cracked oils from FCC 8
units, delayed cokers and visbreakers, and intermediate products from
residue hydroprocessing units using the Chevron Lummus Global ISO- 1 4
CRACKING Process. H2S
5
Products: Lighter, high-quality, more valuable products: LPG, gasoline, Light naphtha
catalytic reformer feed, jet fuel, kerosene, diesel and feeds for FCC, eth- Hydrogen-
FG, LPG
Water rich gas to
ylene cracker or lube oil units. recovery naphtha Heavy
naphtha
Description: A broad range of both amorphous/zeolite and zeolitic 2
Jet/kerosine
catalysts, including noble-metal zeolitic catalysts, are used to tailor the 3 7
ISOCRACKING Process exactly to the refiner’s objectives. In general, Sour Diesel
water 6
the process involves a staged reactor system with an initial stage of START
hydrotreating and partially hydrocracking the feed, and a subsequent Makeup hydrogen
stage continuing the conversion or product upgrade process in a more R UCO to
lubes FCC or
favorable environment. ethylene unit
Feeds can be introduced in between stages using Chevron Lummus
Global patented split-feed injection technology, or effluent flow paths can
be arranged to best utilize hydrogen and minimize quench-gas requirements
using proprietary SSRS (single-stage reaction sequenced) technology. Yields: Typical from various feeds:
Most modern large-capacity flow schemes involving heavy sour gas Feed VGO VGO VGO VGO
oils require two reactors (1, 4) and one high-pressure separation system Gravity, API 24.1 24.1 24.1 21.3
(2) with an optional recycle gas scrubber (5) and one recycle-gas com- TBP range, °F 700–1,100 700–1,100 700–1,100 700–1,100
pressor (8). The low-pressure separators (3), product stripper (6) and Nitrogen, wppm 2,500 2,500 2,500 900
fractionator (7) provide the flexibility to fractionate products either in Sulfur, wt % 1.9 1.9 1.9 2.5
between reaction stages or at the tail-end, depending on desired prod- Mode Max. Diesel Max. Jet Max. Mid- Max. Mid-
uct slate and selectivity requirements. Distillate Distillate
Single-stage options are used in once-through mode typically for + Lubes
mild hydrocracking or when a significant quantity of unconverted oil is Yields, vol %
required for FCC, lubes, or ethylene units. The single-stage recycle op- Naphtha 22.8 30.8 14.0 18
tion is used for lower capacity units when economical. The reactors use Jet/kerosine – 79.7 22.0 50
patented internals technology called ISOMIX for near-flawless mixing Diesel 85.5 – 73.0 35
and redistribution. UCO – – – 10
Continued 
Hydrocracking, continued Installation: More than 80 units worldwide with over two million-bpsd
total capacity.
Feed VGO VGO VGO VGO Reference: Dahlberg, A., U. Mukherjee and C. W. Olsen, “Consider us-
Product quality ing integrated hydroprocessing methods for processing clean fuels,” Hy-
Kerosine smoke, mm 29–32 29–32 29–32 drocarbon Processing, September 2007, pp. 111–120.
Diesel cetane number 58–64 58–64 58–64 Mukherjee, U., J. Mayer and B. Srinivasan, “Hydroprocessing Inno-
UCO BMCI 6–8 vation—Some Recent Applications, Petroleum Technology Quarterly,
UCO Waxy V.I. 143–145 Summer 2004.
UCO Dewaxed V.I. 131–133 Bridge, A. G. and U. Mukherjee, “ISOCRACKING—Hydrocracking
for Superior Fuels and Lubes Production,” Handbook of Petroleum Re-
Economics: ISBL total installed cost of 50,000-bpsd unit at 100% con- fining Processes, McGraw Hill, Third Edition.
version to middle distillates using Middle Eastern VGO feed (USGC, 2007
basis): $300 million. Licensor: Chevron Lummus Global LLC.
Process fuel (absorbed), MMBtu/hr 180
Electricity, MW 10
CW, gpm 2,500 click here to e-mail for more information
Steam (export at 150 psig), M lb/hr 22
Hydrocracking
Makeup hydrogen
Application: The IsoTherming process provides refiners an economical
means to upgrade gasoil, heavy gasoil, coker gasoils, deasphalted oil
and FCC cycle oils. GO/DAO
feed
Products: Low-sulfur, low-nitrogen FCC feed, low-sulfur gasoline-ker-
To FG treating
osine type products, and low-nitrogen fuels and/or downstream feed-
stocks.
Light naphtha
Description: This process uses a novel approach to introduce hydrogen in
Heavy naphtha
excess of reaction requirements into the reactor. It enables much higher Kerosine
To FG treating
space velocities than conventional hydrocracking reactors. The IsoTherm-
ing process eliminates problems associated with flow mal-distribution, ULSD diesel
gas-liquid mass transfer and catalyst wetting. The process eliminates the
FCC feed
need for some of the equipment in conventional hydrotreating thereby
lowering cost.
Fresh feed, after heat exchange, is combined with recycle product
and hydrogen in a mixer internal to the reactor. The liquid feed with
soluble hydrogen is fed to IsoTherming reactor/bed one where partial Economics: Revamp investment is estimated to be half that of con-
desulfurization, removal of metals or mild hydrocracking occurs. The ventional hydrocracking due to the primary advantages offered by Iso-
stream is combined with additional hydrogen in a second mixer and fed Therming, which include:
to the second IsoTherming reactor/bed where further mild hydrocracking • Elimination of a recycle gas compressor, high-pressure flash drum
takes place. The treated oil from the second IsoTherming bed may then and separator, condenser and amine scrubber.
be fed to additional IsoTherming beds to achieve the desired level of • Smaller volume(s) of catalyst required for a given feed basis.
conversion. At this time the technology is recommended for maximum
Installation: Three units are licensed for mild hydrocracking of heavy oils
feed conversion of approximately 65%.
with startups scheduled in 4Q08, 1Q09.
Treated oil is recycled back to the inlet of reactor one. This recycle
stream delivers more hydrogen to the reactors and also acts as a heat Licensor: DuPont
sink; thus, a nearly isothermal reactor operation is achieved.

Hydrocracking
Application: Topsøe’s hydrocracking process can be used to convert Hydrogen makeup
Recycle gas
straight run vacuum gas oils and heavy cracked gasoils to high quality compressor
“sulfur-free” naphtha, kerosene, diesel, and FCC feed, meeting current
Hydrocracking
and future regulatory requirements. In addition, high VI lube stocks and Furnace reactor
petrochemical feedstock can be produced to increase the refinery’s prof- Pre-
treating
itability. reactor
Process gas
Product: By proper selection of operating conditions, process configura-
tion, and catalysts, the Topsøe hydrocracking process can be designed H2-rich
gas Naphtha
for high conversion to produce high smoke point kerosine and high Product
Fresh feed
cetane diesel. The process can also be designed for lower conversion/ fractionator Middle
High-pressure distillate
upgrade mode to produce low sulfur FCC feed with the optimum hy- separator
drogen uptake or high VI (>145) lube stock. The FCC gasoline produced
Low-pressure
from a Topsøe hydrocracking unit does not require post-treatment for separator
Lube stock
sulfur removal.
Description: Topsøe’s hydrocracking process uses well proven co-current

downflow fixed bed reactors with state - of - the - art reactor internals and
catalysts. The process uses recycle hydrogen and can be configured in
partial conversion once-through feed mode or with recycle of partially Installations: One operating licensed hydrocracking unit. Topsøe hydro-
converted oil to obtain 100% conversion to diesel and lighter prod- cracking catalysts have been supplied to eight hydrocrackers.
ucts. Topsøe’s zeolitic and amorphous hydrocracking catalysts have been
proven in several commercial hydrocrackers. Licensor: Haldor Topsøe A/S.
Operating conditions: Typical operating pressure and temperatures
range from 55 to 170 bar (800 to 2500 psig) and 340 to 420°C (645 to
780°F).

Hydrocracking
Fresh gas
Application: To convert heavy vacuum gasoil (VGO) and other low-cost
cracked and extracted feedstocks into high-value, high-quality products,
Recycle gas
such as low-sulfur diesel, jet fuel, high-octane light gasoline and reform- Process gas
er feed via the Shell Hydrocracking Process. Unconverted or recycle oil Recycle
compressor
are prime feeds for secondary processing in fluid catalytic cracking units Quench gas
2 Light naphtha
(FCCUs), lube base oil plants and ethylene crackers. CHP
separator Heavy naphtha
Description: Heavy feed hydrocarbons are preheated with reactor efflu- 3
HHP Kerosine
ent (1). Fresh hydrogen is combined with recycle gas from the cold high- separator
pressure separator, preheated with reactor effluent, and then heated in 1 Diesel
HLP
a single-phase furnace. Reactants pass via trickle flow through multi-bed separator CLP
separator Fractionator
reactor(s) containing proprietary pre-treat, cracking and post-treat cata-
FCC/lube
lysts (2). Interbed ultra-flat quench internals and high-dispersion nozzle Feed oil/ethylene
trays combine excellent quench, mixing and liquid flow distribution at
the top of each catalyst bed while helps maximize reactor volume utiliza-
tion. After cooling by feed streams, reactor effluent enters a separator
system. Hot effluent is routed to fractionation (3).
Installation: Over 30 new and revamp designs installed or under design.
Two-stage, series flow and single-stage unit design configurations
Revamps have been implemented in own or other licensors’ designs
are available, capable of converting a wide range of heavy feedstocks,
usually to debottleneck and increase feed heaviness.
especially heavy coker gasoils and deasphalted oils directly into clean fu-
els. The catalyst systems are carefully tailored for maximum yield of the Supplier: Shell Global Solutions International B.V.
desired product slate at an optimum catalyst cycle length.

Hydrocracking
Application: Convert a wide variety of feedstocks into lower-molecular- Makeup hydrogen
weight products using the UOP Unicracking process. Wash
water
Feed: Feedstocks include atmospheric gasoil, vacuum gasoil, FCC/RCC cycle
oil, coker gasoil, deasphalted oil and naphtha for production of LPG. 1
Products: Processing objectives include production of gasoline, jet fuel, 2

4 Flash gas
diesel fuel, lube stocks, ethylene-plant feedstock, high-quality FCC feed-
stock and LPG.
5
Description: Feed and hydrogen are contacted with catalysts, which in- Fresh feed To fractionator
duce desulfurization, denitrogenation and hydrocracking. Catalysts are
START 3
based upon both amorphous and molecular-sieve containing supports. Sour water
Process objectives and feedstock properties determine catalyst selection
Recycle oil To fractionator
and process flow scheme for a specific unit. Product from the reactor
section is condensed, separated from hydrogen-rich gas and fraction-
ated into desired products. Unconverted oil is recycled or used as lube
stock, FCC feedstock or ethylene-plant feedstock.
Yields: Example: 30,000 bpsd typical vacuum gasoil feed Economics:
FCC cycle Vacuum Fluid coker Utilities, typical per bbl feed:
Feed type oil blend gasoil gasoil Fuel, 103 Btu 70–130
Gravity, °API 27.8 22.3 8.4 Electricity, kWh 7–10
Boiling, 10%, °F 481 690 640 Installation: Selected for 190 commercial units, including several converted
End pt., °F 674 1,015 1,100 from competing technologies. Total capacity exceeds 4.4 million bpsd.
Sulfur, wt% 0.54 2.4 4.57
Nitrogen, wt% 0.024 0.15 0.269 Licensor: UOP.
Yields, vol% of feed with principal product of diesel
Butanes 3.0
Light gasoline 6.6
Heavy naphtha 11.2
Distillate 92.3
H2 consump., scf/bbl 1,550
Hydrocracking, moderate pressure Hydrogen

Application: Convert a wide variety of feedstocks including vacuum
deep-cut gas oil, coker gas oils, de-asphalted oil (DAO), and FCC cy-
cle oils into high-quality, low-sulfur fuels using ExxonMobil Research Recycle Lean amine
and Engineering Company’s (EMRE) moderate pressure hydrocracking compressor
(MPHC) process. Absorber
HVGO
Naphtha
Products: Products include a wide range of high-quality, low-sulfur dis- DAO
HCGO Rich Kerosine
tillates and blending stocks including LPG, high-octane gasoline, high- amine
quality reformer naphtha. Unconverted bottoms product from the MPHC Heater LPG/naphtha Diesel
unit is very low in sulfur and is an excellent feedstock for fluid catalytic Reactor LTS Fractionator
cracking (FCC), lube-oil basestock production, steam cracking and low- HTS
sulfur fuel oil.
FCC feed LSGO
Description: The process uses a multiple catalyst system in multi-bed Stripper
reactor(s) that incorporates proprietary advanced quench and redistri-
bution internals (Spider Vortex). Heavy hydrocarbons and recycle gas
are preheated and contact the catalyst in the trickle-phase fixed-bed
reactor(s). Reactor effluent is flashed in high- and low-temperature
separators. An amine scrubber removes H2S from the recycle gas be-
fore it gets compressed and re-circulated back to the unit. An opti- Yields:
mized, low cost stripper/fractionator arrangement is used for product Naphtha, wt% 4 10 10
recovery. Kero/jet, wt% 6 10 10
When higher-quality distillates are required, the addition of a low- Diesel, wt% 22 26 27
cost, highly integrated distillate post-treating unit (PTU) can be incor- LSGO (FCC feed), wt% 65 50 50
porated in the design to meet or exceed high-pressure hydrocracking H2 consumption, wt% 1.0 –1.5 1.3 –1.8 1.5 – 2.0
product quality at lower capital cost and hydrogen consumption
Product quality:
Operating conditions and yields: Typical operating conditions on a Mid- Kero sulfur, wppm 20 – 200 20 – 200 20 – 200
dle East VGO for a once-through MPHC operation are shown: Kero smoke Pt, mm 13 – 18 15 – 20 17 – 22
Diesel sulfur, wppm 30 – 500 30 – 300 30 – 200
Operation conditions: Diesel cetane no. 45 – 50 47 – 52 50 – 55
Configuration MPHC MPHC MPHC Utilities, per bbl of feed:
Nominal conversion, % 35 50 50
H2 pressure, psig 800 800 1,250
Continued 
EMRE’s MPHC process is equally amenable to revamp or grassroots
Hydrocracking, moderate pressure continued applications. EMRE has an alliance with Kellogg Brown & Root (KBR) to
provide MPHC technology to refiners.
Electric power, kW 4.1 7.2
Fuel (absorbed), Btu 67,100 69,600 Installation: Four operating units; two in construction.
Steam, MP (export), lb (15.9) (21.1)
Water, cooling, gal 101 178 Licensor: ExxonMobil Research and Engineering Co.
Wash water, gal 1.5 2.2
Lean amine, gal 36.1 36.1
Hydrocracking, resid
Application: Desulfurization, demetalization, CCR reduction and hydro-
cracking of atmospheric and vacuum resids using the LC-FINING Pro- Makeup hydrogen
cess.
Recycle H2
LC-FINING Steam
Products: Full range of high-quality distillates. Residual products can reactor 1 6
be used as fuel oil, synthetic crude or feedstock for a resid FCC, coker, 2
visbreaker or solvent deasphalter.
5
3
Description: Fresh hydrocarbon liquid feed is mixed with hydrogen and
Hydrocarbon
reacted within an expanded catalyst bed (1) maintained in turbulence by feed
liquid upflow to achieve efficient isothermal operation. Product quality is START 4
maintained constant and at a high level by intermittent catalyst addition
and withdrawal. Reactor products flow to a high-pressure separator (2), Products
low-pressure separator (3) and product fractionator (4). Recycle hydro-
gen is separated (5) and purified (6).
Process features include onstream catalyst addition and withdrawal.
Recovering and purifying the recycled H2 at low pressure rather than at high
pressure can reduce capital cost and allows design at lower gas rates.
Operating conditions:
Reactor temperature, °F 725 – 840
Atm. resid Vac. resid
Reactor pressure, psig 1,400 – 3,500 Feed
Gravity, °API 12.40 4.73 4.73 4.73
H2 partial pressure, psig 1,000 – 2,700
Sulfur, wt % 3.90 4.97 4.97 4.97
LSHV 0.1 to 0.6
Ni / V, ppmw 18 /65 39 /142 39 /142 39 /142
Conversion, % 40 – 97+ Conversion, vol% 45 60 75 95
Desulfurization, % 60 – 90 (1,022°F+)
Demetalization, % 50 – 98 Products, vol%
CCR reduction, % 35 – 80 C4 1.11 2.35 3.57 5.53
C5–350°F 6.89 12.60 18.25 23.86
Yields: For Arabian heavy/Arabian light blends: 350 –700°F (650°F) (15.24) 30.62 42.65 64.81
700 (650°F) –1,022°F (55.27) 21.46 19.32 11.92
1,022°F+ 25.33 40.00 25.00 5.0
C5+, °API / wt% S 23.70 / 0.54 22.5 / 0.71 26.6 / 0.66 33.3 / 0.33
Continued 
Hydrocracking, resid, continued Installation: Six LC-FINING units are in operation, and three LC-FINING
Units are in engineering.
Economics: Reference: Gupta, A., “Chevron Lummus Global Ebullated Bed Bottom-
Investment, estimated (US Gulf Coast, 2007) of-theBarrel Hydroconversion (LC-FINING) Process,” Handbook of Petro-
Size, bpsd fresh feed 92,000 49,000 leum Refining Prcesses, McGraw Hill, Third Edition.
$/bpsd typical fresh feed 4,000 6,000 7,000 8,000 “LC-FINING Options for Heavy Oil Upgrading,” NPRA Annual Meet-
Utilities, per bbl fresh feed ing, March 9–11, 2008, San Diego, Paper AM-08-33.
Fuel fired, 103 Btu 56.1 62.8 69.8 88.6
Electricity, kWh 8.4 13.9 16.5 22.9 Licensor: Chevron Lummus Global LLC.
Steam (export), lb 35.5 69.2 97.0 97.7
Water, cooling, gal. 64.2 163 164 248
Hydrocracking—residue Makeup H2
Application: H-OilRC is an ebullated-bed process for hydrocracking at- Air

Acid gas
Sour
cooler gas
mospheric or vacuum residue. It is the ideal solution for feedstocks hav- Inter stage removal and
separator HPU
ing high metal, CCR and asphaltene contents. The process can have two (optional)
V/L
different objectives: at high conversion, to produce stable products; or, separator
Sour water
at moderate conversion, to produce a synthetic crude oil. Heater V/L
separator Sour gas
Description: The flow diagram illustrates a typical H-OilRC unit that in-
Fractionation Naphtha
cludes oil and hydrogen fired heaters, an optional inter stage separa- and
tor, an internal recycle cup providing feed to the ebullating pump, high stabilization
pressure separators, recycle gas scrubber and product separation and Mid distillate
fractionation (not required for synthetic crude oil production).

Vacuum gasoil
Catalyst is replaced periodically in the reactor, without shutdown. H-oil
reactor
Different catalysts are available as a function of the feedstock and Resid feed V/L Vacuum
separator tower
the required objectives. An H-OilRC unit can operate for three-year run
Heater Vacuum bottoms recycle (optional) Vacuum residue
lengths at constant catalyst activity with conversion in the 50 – 80%
range and hydrodesulfurization as high as 85%.
Operating conditions: Economics: Basis 2008 US Gulf Coast

Temperature, °F 770– 820 Investment in $ per bpsd 5,100 – 7,400
Hydrogen partial pressure, psi 1,600 –1,950 Utilities, per bbl of feed
LHSV, hr –1 0.25– 0.6 Fuel, 103 Btu 70
Conversion, wt% 50 – 80 Power, kWh 11
Catalyst makeup, lb 0.2– 0.8
Examples: Ural VR feed: a 540°C+ cut from Ural crude is processed at
66% conversion to obtain a stable fuel oil containing less than 1%wt Installation: There are nine H-OilRC units, seven in operation and two un-
sulfur, 25% diesel and 30% VGO. The diesel cut is further hydrotreated der design, with a total capacity of 336,500 bpsd. Two additional refer-
to meet ULSD specifications using an integrated Prime-D unit. Arab Me- ences for H-OilDC, the ebullated bed technology for VGO and DAO, add
dium VR feed: a vacuum residue from a blend 70% Arab Light-30% another 139,900 bpsd.
Arab Heavy containing 5.5wt% sulfur is processed at above 75% con-
version to obtain a stable fuel oil with 2wt% sulfur. Reference: “Resid hydrocracker produces low-sulfur diesel from difficult
feed,” Hydrocarbon Processing, May 2006.
Licensor: Axens.

Hydrodearomatization
.BLFVQIZESPHFO 3FDZDMFHBT
Application: Topsøe’s two-stage hydrodesulfurization hydrodearomati- DPNQSFTTPS
"NJOF
zation (HDS/HDA) process is designed to produce low-aromatics distil- )%4 TDSVCCFS
)%4 TFQBSBUPS
late products. This process enables refiners to meet the new, stringent %JFTFM
TUSJQQFS
GFFE 8BTI
standards for environmentally friendly fuels. XBUFS 0WFSIFBE
WBQPS
Products: Ultra-low sulfur, ultra-low nitrogen, low-aromatics diesel, ker- 'JSTU )%4
TUBHF SFBDUPS )%4
osine and solvents (ultra-low aromatics). TUSJQQFS 4PVS
XBUFS 8BUFS
Description: The process consists of four sections: initial hydrotreating,
intermediate stripping, final hydrotreating and product stripping. The 8JME
initial hydrotreating step, or the “first stage” of the two-stage reaction )%" 1SPEVDU OBQIUIB
4FDPOE SFBDUPS EJFTFM
process, is similar to conventional Topsøe hydrotreating, using a Topsøe TUBHF TUSJQQFS 4UFBN
high-activity base metal catalyst such as TK-575 BRIM to perform deep %JFTFMQSPEVDU
desulfurization and deep denitrification of the distillate feed. Liquid ef- )%"
TFQBSBUPS
fluent from this first stage is sent to an intermediate stripping section, in %JFTFMDPPMFS
which H2S and ammonia are removed using steam or recycle hydrogen.
Stripped distillate is sent to the final hydrotreating reactor, or the “second
stage.” In this reactor, distillate feed undergoes saturation of aromatics
using a Topsøe noble metal catalyst, either TK-907/TK-911 or TK-915, a
high-activity dearomatization catalyst. Finally, the desulfurized, dearoma- Operating conditions: Typical operating pressures range from 20 to 60
tized distillate product is steam stripped in the product stripping column barg (300 to 900 psig), and typical operating temperatures range from
to remove H2S, dissolved gases and a small amount of naphtha formed. 320°C to 400°C (600°F to 750°F) in the first stage reactor, and from
Like the conventional Topsøe hydrotreating process, the HDS/HDA 260°C to 330°C (500°F to 625°F) in the second stage reactor. An ex-
process uses Topsøe’s graded bed loading and high-efficiency patented ample of the Topsøe HDS/HDA treatment of a heavy straight-run gas oil
reactor internals to provide optimum reactor performance and catalyst feed is shown below:
use leading to the longest possible catalyst cycle lengths. Topsøe’s high Feed Product
efficiency internals have a low sensitivity to unlevelness and are designed Specific gravity 0.86 0.83
to ensure the most effective mixing of liquid and vapor streams and max- Sulfur, ppmw 3,000 1
imum utilization of catalyst. These internals are effective at high liquid Nitrogen, ppmw 400 <1
loadings, thereby enabling high turndown ratios. Topsøe’s graded-bed Total aromatics, wt% 30 <10
technology and the use of shape-optimized inert topping and catalysts Cetane index, D-976 49 57
minimize the build-up of pressure drop, thereby enabling longer catalyst
cycle length.
Continued 
Hydrodearomatization, continued
References: Cooper, Hannerup and Søgaard-Andersen, “Reduction of
aromatics in diesel,” Oil and Gas, September 1994.
de la Fuente, E., P. Christensen, and M. Johansen, “Options for meet-
ing EU year 2005 fuel specifications,” 4th ERTC, Paris, November 1999.
Installation: A total of seven units.

Licensor: Haldor Topsøe A/S.

Hydrofinishing
Application: Deeply saturate single- and multiple-ring aromatics in base-
oil feedstocks. The product will have very low-aromatics content, very Makeup hydrogen Process gas
high-oxidation stability and high thermal stability.
Description: ISOFINISHING catalysts hydrogenate aromatics at relative-
ly low reaction temperatures. They are especially effective in complete
polyaromatics saturation—a reaction that is normally equilibrium limited. 1
Typical feedstocks are the effluent from a dewaxing reactor, effluent from
hydrated feeds or solvent-dewaxed feedstocks. The products are highly
stabilized base-oil, technical-grade white oil or food-grade white oil. Light ends
As shown in the simplified flow diagram, feedstocks are mixed with Fresh dewaxed
2
4
recycle hydrogen and fresh makeup hydrogen, heated and charged to a feed 3
reactor containing ISOFINISHING Catalyst (1). Effluent from the finishing START
reactor is flashed in high-pressure and low-pressure separators (2, 3). Base oil product
A very small amount of light products are recovered in a fractionation
system (4).
Yields: For a typical feedstock, such as dewaxing reactor effluent, the
yield can be >99%. The chemical-hydrogen consumption is usually very
low, less than ~10 Nm3/m3 oil.
Installation: Twenty-nine units are in various stages of operation, con-
Economics: struction or design.
Investment: For a stand-alone ISOFINISHING Unit, the ISBL capital is
about 3,000 –5,000 $/bpsd, depending on the pressure
Reference: NPRA Annual Meeting, March 2004, San Antonio, Paper
AM-04-68.
level and size.
Utilities: Typical per bbl feed: Licensor: Chevron Lummus Global LLC.
Power, kW 2.6
Fuel, kcal 3.4 x 103

Hydrogen
Recycle H2 Process steam
Application: Production of high-purity hydrogen (H2) from hydrocarbon Compressor Feed
(HC) feedstocks, using the steam reforming process. HC feedstock, ROG pumping pretreatment Pre-reformer
(optional) Export
Makeup fuel
steam
Feedstocks: Ranging from natural gas, LPG to naphtha as well as poten- Steam
system
Combustion air
tial refinery offgases (ROG). Several modern hydrogen plants designed Fuel system
by TECHNIP have multiple feedstock flexibility. Steam

PG boiler
Reformer Steam Dosing
Description: The generic flowsheet consists of feed pre-treatment, Steam BFW
BFW preparation
system
pre-reforming (optional), steam-HC reforming, shift conversion and APH coils Purge gas to
(Opt.) Process
Shift fuel system
hydrogen purification by pressure swing adsorption (PSA). However, it coils
conversion
Process
Shock condensate
is often tailored to satisfy specific requirements. coils
Cooling
Feed pre-treatment normally involves preheating to 350°C to Stack train
PSA
400°C and catalytic removal of sulfur, chlorine and other contaminants Air To steam DMW Recycle H2
detrimental to downstream catalysts. The treated feed gas mixed with system
BFW to steam
process steam is sent to the fired steam reformer (or adiabatic pre- system Hydrogen product
reformer upstream when applied) after necessary superheating.
The net reforming reaction is strongly endothermic. Heat is sup-
plied externally by combustion of PSA purge gas, supplemented by
make-up fuel in multiple burners in a top-fired reformer. Reforming depending upon the feedstock, plant capacity, optimization criteria
severity is optimized for each specific case mainly in terms of S/C ratio and steam export conditions. Recent advances include gas turbine in-
and outlet temperature. The reformer effluent is essentially an equi- tegration for steam-power synergy, environmental performance and
librium mixture and is cooled though HP-steam generation in the PG recuperative reforming for capacity retrofit.
boiler before going for shift conversion, where a major portion of car-
bon monoxide (CO) further converts to hydrogen. Installation: TECHNIP, maintaining a leading market share, has designed
The process condensate resulting from heat recovery and cooling over 250 hydrogen plants worldwide covering a wide range of capaci-
is separated and generally re-utilized in the steam system after neces- ties ranging from 12 to 520 tpd (5–220 MMscfd). Most of these instal-
sary treatment. The entire steam generation is usually on natural circu- lations are for refinery application with basic features for high reliability
lation, which adds to high reliability. The cooled process gas flows to (99.5%+ excluding forced outage) and optimized cost.
the PSA unit that provides high-purity hydrogen product (typically < 10
ppmv total carbon oxides and in some cases <1ppmv CO). Licensor: TECHNIP
Typical specific energy consumptions based on feed + fuel – export
steam range between 3 to 3.5 Gcal/KNm3 (330 to 370 Btu/scf) LHV,

Hydrogen
Steam reformer
Application: Production of hydrogen for refinery applications and petro- Fuel Steam
chemical and other industrial uses. drum
Desulfuri- 3 HT shift
Feed: Natural gas, refinery offgases, LPG, naphtha or mixtures thereof zation
2
or any other feedstocks. 1
4
CW
Product: High-purity hydrogen (typically >99.9%), CO, CO2, HP steam

and/or electricity may be produced as separate creditable byproduct. Gas cooler
Description: The plant generally comprises four process units. The feed is Steam export
desulfurized, mixed with steam and converted to synthesis gas in steam Feed PSA
Hydrogen
reformer over a nickel containing catalyst at 20 – 40 bar pressure and Combustion air 5
outlet temperatures of typically 860°C– 890°C for hydrogen production. BFW
The synthesis gas is further treated in the adiabatic carbon monoxide
(CO) shift and the pressure swing adsorption unit to obtain high-purity
hydrogen. Process options include feed evaporation, adiabatic feed pre-
reforming and/or HT/LT shift to process, e.g., heavier feeds and/or opti-
mize feed/fuel consumption and steam production.
Uhde’s design enables maximizing process heat recovery and op- Recent developments include the reduction of CO2-emissions while
timizing energy efficiency with operational safety and reliability. The using removed CO2 for sequestration or enhanced oil recovery (EOR).
Uhde’s steam reformer features a well-proven top-fired design with Economics: Depending on the individual plant concept, the typical con-
tubes made of centrifugally cast alloy steel and a unique proprietary sumption figure for natural gas based plants (feed + fuel – steam) may
“cold” outlet manifold system for enhanced reliability. AA special fea- be as low as 3.05 Gcal /1,000 Nm3 (324 MMBtu/ MMscf).
ture further speciality is Uhde’s bi-sectional steam system for the envi-
ronment-friendly full recovery of process condensate and production of Installation: Uhde is currently executing several designs for hydrogen
contaminant-free high-pressure export steam (3) with a proven process plants. These include a 150,000 Nm³/134 MMscfd plant for Shell in
gas cooler design. Canada and a 91,000 Nm³/h/81 MMscfd plant for Bayernoil in Germa-
The Uhde steam reformer concept also includes a modularized ny. In addition, Uhde is building a multi-feedstock hydrogen plant for
shop-tested convection bank to maximize plant quality and minimize an Italian refiner and a naphtha and natural- gas fed plant for Neste Oil
construction risks. Uhde usually offers tailor-made designs based on ei- OYJ of Finland. Uhde has also successfully started up Europe’s largest
ther their own or the customer’s design standards. The hydrogen plant hydrogen plant for Neste Oil OYJ with a capacity of 155,000 Nm³/h
is often fully integrated into the refinery, particularly with respect to (139 MMscfd). This plant features, among others, a unit to reduce CO2
steam production and use of refinery waste gases. Uhde has extensive emissions.
experience and expertise in the construction of highly reliable reform-
ers with hydrogen capacities of up to 220,000 Nm3/ h (197 MMscfd). Continued 
Michel, M., “Design and Engineering Experience with Large-Scale
Hydrogen, continued Hydrogen Plants,” Oil Gas European Magazine, Vol. 30 (2004) No. 2 in:
Erdöl Erdgas Kohle Vol. 120 (2004) No. 6, pp. OG 85–88.
References: Ruthardt, K. and M. Smith, “Reliability and availability,” Hy-
drocarbon Engineering, February 2008. Licensor: Uhde GmbH.
Ruthardt, K., K. R. Radtke and J. Larsen, “Hydrogen trends,” Hydro-
carbon Engineering, November 2005, pp. 41– 45.
Hydrogen (steam reforming) Fuel Feed Export
Application: Hydrogen production from natural gas, refinery gas, associ-

ated gas, naphtha, LPG or any mixture of these. Appropriate purity prod- Desulfurization
uct (up to 99.999%) can be used in refinery upgrade processes, chemi- Process steam
cal production and metallurgy (direct reduction). Possible byproducts are Pre-reforming
(optional)
export steam or electricity, depending on cost and/or efficiency optimi-
zation targets. Heat recovery
Steam reforming
Description: The hydrocarbon feedstock is admixed with some recycle

hydrogen and preheated to 350°C –380°C. Sulfur components are to- Shift conversion Demineralized
water
tally converted to H2S at CoMo catalyst and then adsorbed on zinc oxide Flue gas
by conversion to ZnS. The desulfurized feed is mixed with process steam Pressure swing
adsorption
at an optimized steam/carbon ratio.
The desulfurized feed is mixed with process steam at an optimized
steam/carbon ratio, superheated to 500°C– 650°C and fed to the Lurgi Hydrogen
Reformer. The feed/steam mixture passing the reformer tubes is convert-
ed at 800°C –900°C by presence of a nickel catalyst to a reformed gas
containing H2, CO2, CO, CH4 and undecomposed steam. The reformed
gas is cooled to approximately 330°C in a reformed gas boiler. PSA unit, where pure hydrogen is separated from the shift-gas stream.
The Lurgi Reformer is a top-fired reformer with a low number of Offgas is used as fuel for steam reforming.
burners and low heat losses, almost uniform wall temperature over the Recovered waste heat from the reformed and flue gases generates
entire heated tube length and low NOx formation by very accurate fuel steam, which is used as process steam with the excess exported to bat-
and combustion air equipartition to the burners. tery limits.
An adiabatic pre-reformer operating at an inlet temperature of Turndown rates of 30% or even less are achievable. The control
400°C–500°C (dependent on feedstock) may be inserted upstream of concept allows fully automatic operation with load changes up to 3%
the feed superheater as a process option. Feedgas is partly converted to of full capacity/minute.
H2, CO and CO2 with high-activity catalyst; all hydrocarbons are totally Economics: Consumption figures based on light natural gas feedstock/1
converted to methane. The pre-reformer limits steam export to maxi- millon scfd of H2:
mize heat recovery from the process and increases feedstock flexibility. Feed + fuel, million scfd 0.4
The CO in the reformed gas is shift-converted with an iron-chromi- Demineralized water, t 1.25
um catalyst, increasing hydrogen yield and reducing CO content to be- Water, cooling, m3 3.0
low 3 vol.%. The shift gas is cooled to 40°C and any process condensate Electricity, kWh 19
is separated and recycled to the process. The gas is then routed to the Export steam, t 0.7 Continued 
Hydrogen (steam reform), continued
Installations: More than 125 gas reforming plants, 33 being hydrogen
plants, with single-train capacities ranging from 1 million scfd to 200
million scfd.
Licensor: Lurgi GmbH.

Hydrogen—HTCR and HTCR twin

plants
S-removal Prereformer HTCR Twin reformer Shift PSA
Application: Produce hydrogen from hydrocarbon feedstocks such as:
natural gas, LPG, naphtha, refinery offgases, etc., using the Haldor Top-
søe Convective Reformer (HTCR). Plant capacities range from approxi-
mately 5,000 Nm3/ h to 25,000+ Nm3/ h (5 MM scfd to 25+ MMscfd) and Steam
H2
hydrogen purity from about 99.5 – 99.999+%. This is achieved without
3x
any steam export.
Description: The HTCR-based hydrogen plant can be tailor-made to suit

the customer’s needs with respect to feedstock flexibility. A typical plant Feed Combustion air
comprises feedstock desulfurization, pre-reforming, HTCR reforming, Flue gas

Offgas
shift reaction and pressure swing adsorption (PSA) purification to obtain
Fuel
product-grade hydrogen. PSA offgases are used as fuel in the HTCR. Ex-
cess heat in the plant is efficiently used for process heating and process
steam generation.
A unique feature of the HTCR is the high thermal efficiency. Product
gas and flue gas are cooled by providing heat to the reforming reac-
tion to about 600°C (1,100°F). The high thermal efficiency is utilized
to design energy-efficient hydrogen plants without the need for steam ity and safety. Fully automated operation, startup and shutdown allow
export. In larger plants, the reforming section consists of two HTCR re- minimum operator attendance. A net energy efficiency of about 3.4
formers operating in parallel. Gcal / 1,000 Nm3 hydrogen (361 MMBtu /scf H2) is achieved depending
on size and feedstock.
Economics: HTCR-based hydrogen plants provide the customer with
a low-investment cost and low operating expenses for hydrogen pro- Installations: Twenty-eight licensed units.
duction. The plant is supplied as a skid-mounted unit providing a short
installation time. These plants provide high operating flexibility, reliabil- Licensor: Haldor Topsøe A/S.

Hydrogen—HTER-p
Application: Topsøe’s proprietary and patented HTER-p (Haldor Top-
Prereformer Tubular reformer HTER-p
søe Exchange Reformer— parallel installation) technology is a revamp
option for production increase in a steam-reforming-based hydrogen Process
plant. The technology allows hydrogen capacity increases of more than steam
25%. This option is especially advantageous because the significant ca-

pacity expansion is possible with minimal impact on the existing tubular
reformer, which usually is the plant bottleneck.
Description: The HTER-p is installed in parallel with the tubular steam Desulfurized feed
methane reformer (SMR) and fed independently with desulfurized To CO shift
feed taken upstream the reformer section. This enables individual ad- converter
To stack
justment of feedrate and steam- and process steam-to-carbon ratio to
obtain the desired conversion. The hydrocarbon feed is reformed over
a catalyst bed installed in the HTER-p. Process effluent from the SMR Fuel
is transferred to the HTER-p and mixed internally with the product gas
from the HTER-p catalyst. The process gas supplies the required heat
for the reforming reaction in the tubes of the HTER-p. Thus, no addi-
tional firing is required for the reforming reactions in the HTER-p.
Economics: An HTER-p offers a compact and cost-effective hydrogen References: Dybkjær, I., and S. W. Madsen, “Novel Revamp Solutions
capacity expansion. The investment cost is as low as 60% of that for a for Increased Hydrogen Demands,” Eighth European Refining Technol-
new hydrogen plant. Energy consumption increases only slightly. For a ogy Conference, November 17–19, 2003, London, UK
25% capacity increase, the net energy consumption is 3.13 Gcal / 1,000
Nm3 H 2 (333 MM Btu / scf H 2 ). Licensor: Haldor Topsøe A/S.

Hydrogen—Methanol-to-Shift
Application: Topsøe’s proprietary Methanol-to-Shift technology is a re-
Large methanol
vamp option for hydrogen production increase for a reforming-based storage tank Methanol
day tank
hydrogen plant. This technology can raise hydrogen production ca- Methanol
evaporation
pacity by more than 25%. The capacity expansion is flexible and can Steam
Steam export
be changed in very short time; the technology is suitable for capacity

peak shaving and offers the refiner higher feedstock and product slate
flexibility. Gas from prereformer Tubular
CO shift
methanol
reformer cracking
Description: Additional hydrogen is produced by reforming of methanol
over Topsøe’s novel dual-function catalyst—LK-510. When installed in the
Waste heat
existing CO shift converter and fed simultaneously with methanol and re- recovery and
purification
formed gas, the LK-510 catalyst promotes both the conversion of CO with
To stack
steam to H2 and CO2 and the reforming of methanol to H2 and CO2.
Methanol from a day tank is pumped to a steam-heated evaporator Fuel gas and
combustion air
and fed as vapor to the existing CO shift converter, now loaded with
the LK-510 catalyst. In most cases, it will be necessary to revamp the
PSA unit for the additional capacity and to check the equipment down-
stream of the CO shift converter and modify as required.
Economics: The Methanol-to-Shift revamp technology is a low-invest- References: Dybkjær, I., and S. W. Madsen, “Novel Revamp Solutions
ment option for hydrogen capacity increase and is rapid to install. The for Increased Hydrogen Demands,” Eighth European Refining Technol-
total investment cost is less than 40% of that of a new hydrogen plant. ogy Conference, November 17–19, 2003, London, UK.
Methanol consumption is approximately 0.54 kg / Nm3 hydrogen (0.03
lb/scf H2 ). Licensor: Haldor Topsøe A/S.

Hydrogen—recovery
Application: To recover and purify hydrogen or to reject hydrogen from
Nonpermeate product
refinery, petrochemical or gas processing streams using a PRISM mem-
brane. Refinery streams include hydrotreating or hydrocracking purge,
catalytic reformer offgas, fluid catalytic cracker offgas or fuel gas. Pet-
rochemical process streams include ammonia synthesis purge, methanol Feed gas
1
synthesis purge or ethylene offgas. Synthesis gas includes those gener-
2 3
ated from steam reforming or partial oxidation. Additional
H2 product
Product: Typical hydrogen (H2) product purity is 90% – 98% and, in
some cases, 99.9%. Product purity is dependent upon feed purity, avail- Optional
able differential partial pressure and desired H2 recovery level. Typical H2
Hydrogen product
recovery is 80–95% or more.
The hydrocarbon-rich nonpermeate product is returned at nearly
the same pressure as the feed gas for use as fuel gas, or in the case of
synthesis gas applications, as a carbon monoxide (CO) enriched feed to
oxo-alcohol, organic acid, or Fisher-Tropsch synthesis.
Membrane systems consist of a pre-assembled skid unit with pres-
Description: Typical PRISM membrane systems consist of a pretreatment sure vessels, interconnecting piping, and instrumentation and are fac-
(1) section to remove entrained liquids and preheat feed before gas en- tory tested for ease of installation and commissioning.
ters the membrane separators (2). Various membrane separator con-
figurations are possible to optimize purity and recovery, and operating Economics: Economic benefits are derived from high-product recoveries
and capital costs such as adding a second stage membrane separator and purities, from high reliability and low capital cost. Additional ben-
(3). Pretreatment options include water scrubbing to recover ammonia efits include relative ease of operation with minimal maintenance. Also,
from ammonia synthesis purge stream. systems are expandable and adaptable to changing requirements.
Membrane separators are compact bundles of hollow fibers contained in
Installations: Over 400 PRISM H2 membrane systems have been com-
a coded pressure vessel. The pressurized feed enters the vessel and flows on
missioned or are in design. These systems include over 80 systems in re-
the outside of the fibers (shell side). Hydrogen selectively permeates through
finery applications, 210 in ammonia synthesis purge and 50 in synthesis
the membrane to the inside of the hollow fibers (tube side), which is at lower
gas applications.
pressure. PRISM membrane separators’ key benefits include resistance to wa-
ter exposure, particulates and low feed to nonpermeate pressure drop. Licensor: Air Products and Chemicals, Inc.

Hydrogen—steam methane
reforming (SMR) S-removal Pre-
reformer
Radiant wall
reformer
CO shift
reactor
PSA
Steam export
Application: Production of hydrogen from hydrocarbon feedstocks such
as: natural gas, LPG, butane, naphtha, refinery offgases, etc., using the
Haldor Topsøe radiant-wall Steam Methane Reformer (SMR). Plant ca-
pacities range from 5,000 Nm3/h to more than 200,000 Nm3/h hydro-
gen (200+ MMscfd H2) and hydrogen purity of up to 99.999+%.
Description: The Haldor Topsøe SMR-based hydrogen plant is tailor-made Feed H2

to suit the customer’s needs with respect to economics, feedstock flex- Flue gas
ibility and steam export. In a typical Topsøe SMR-based hydrogen plant,
a mix of hydrocarbon feedstocks or a single feedstock stream is first de-
sulfurized. Subsequently, process steam is added, and the mixture is fed Combustion air
to a prereformer. Further reforming is carried out in the Haldor Topsøe BFW
radiant wall SMR. The process gas is reacted in a medium-temperature Fuel gas
CO shift reactor and purified by pressure swing absorption (PSA) to ob-

tain product-grade hydrogen. PSA offgases are used as fuel in the SMR.
Excess heat in the plant is efficiently used for process heating and steam
generation.
The Haldor Topsøe radiant wall SMR operates at high outlet temper-
References: Rostrup-Nielsen, J. R. and T. Rostrup-Nielsen, “Large scale
atures up to 950°C (1,740°F). The Topsøe reforming catalysts allow op-
hydrogen production,” CatTech, Vol. 6, no. 4, 2002.
eration at low steam-to-carbon ratio. Advanced Steam Reforming uses
Dybkjær, I., and S. W. Madsen, “Advanced reforming technologies
both high outlet temperature and low steam-to-carbon ratio, which are
for hydrogen production,” Hydrocarbon Engineering, December/Janu-
necessary for high-energy efficiency and low hydrogen production cost.
ary 1997/1998.
The Advanced Steam Reforming design is in operation in many indus-
Gøl, J.N., and I. Dybkjær, “Options for hydrogen production,” HTI
trial plants throughout the world.
Quarterly: Summer 1995.
Economics: The Advanced Steam Reforming conditions described can Licensor: Haldor Topsøe A/S.
achieve a net energy efficiency as low as 2.96 Gcal /1,000 Nm3 hydrogen
using natural gas feed (315 MM Btu/scf H2).
Installations: More than 100 units.

Hydrogen—steam reforming
Application: Manufacture hydrogen for hydrotreating, hydrocracking or
other refinery or chemical use.
)ZESPDBSCPOGFFE
4UFBN
Feedstock: Light saturated hydrocarbons: refinery gas or natural gas,
4UFBN
LPG or light naphtha.

Products: Typical purity 99.99%; pressure 300 psig, with steam or CO2
as byproducts.
Description: Hydrogen is produced by steam reforming of hydrocarbons 4UFBN

with purification by pressure swing adsorption (PSA). Feed is heated (1) 1SPEVDUIZESPHFO

and then hydrogenated (2) over a cobalt-molybdenum catalyst bed fol-
lowed by purification (3) with zinc oxide to remove sulfur. The purified 1VSHFHBT
feed is mixed with steam and preheated further, then reformed over 'VFMHBT
nickel catalyst in the tubes of the reforming furnace (1).
Foster Wheeler’s Terrace Wall reformer combines high efficiency with
ease of operation and reliability. Depending on size or site requirements,
Foster Wheeler can also provide a down-fired furnace. Combustion air
preheat can be used to reduce fuel consumption and steam export. Air Steam
Pre-reforming can be used upstream of the reformer if a mixture preheat generation
of naphtha and light feeds will be used, or if steam export must be Natural gas, feed + fuel, MMBtu/hr 780 885
minimized. The syngas from the reformer is cooled by generating steam, Export steam at 600 psig/700ºF, lb/hr 35,000 130,000
then reacted in the shift converter (4) where CO reacts with steam to Boiler feedwater, lb/hr 70,000 170,000
form additional H2 and CO2. Electricity, kW 670 170
In the PSA section (5), impurities are removed by solid adsorbent, Water, cooling, 18ºF rise, gpm 350 350
and the adsorbent beds are regenerated by depressurizing. Purge gas Installations: Over 100 plants, ranging from less than 1 MMscfd to 95
from the PSA section, containing CO2, CH4, CO and some H2, is used as MMscfd in a single train, with numerous multi-train installations.
fuel in the reforming furnace. Heat recovery from reformer flue gas may
be via combustion air preheat or additional steam generation. Variations Reference: Handbook of Petroleum Refining Processes, Third Ed., Mc-
include a scrubbing system to recover CO2. Graw-Hill, 2003, pp 6.3–6.33.
Economics: Licensor: Foster Wheeler USA Corp.

Investment: 10 –100 MMscfd, First Q 2005, USGC $10 – 60 million
Utilities, 50 MMscfd plant:
Prereforming with feed

ultra purification Steam
Application: Ultra-desulfurization and adiabatic-steam reforming of hy-
drocarbon feed from refinery offgas or natural gas through LPG to naph-
tha feeds as a prereforming step in the route to hydrogen production.
Description: Sulfur components contained in the hydrocarbon feed are Preheat Preheat
converted to H 2 S in the HDS vessel and then fed to two desulfurization
vessels in series. Each vessel contains two catalyst types—the first for
bulk sulfur removal and the second for ultrapurification down to sulfur Product
levels of less than 1 ppb. gas
The two-desulfurization vessels are arranged in series in such a way HDS vessel Lead Lag CRG
that either may be located in the lead position allowing online change desulfurization desulfurization prereformer
vessel vessel
out of the catalysts. The novel interchanger between the two vessels Hydrocarbon feed
allows for the lead and lag vessels to work under different optimized
conditions for the duties that require two catalyst types. This arrange-
ment may be retrofitted to existing units.
Desulfurized feed is then fed to a fixed bed of nickel-based catalyst
that converts the hydrocarbon feed, in the presence of steam, to a prod-
uct stream containing only methane together with H 2, CO, CO 2 and Installation: CRG process technology covers 40 years of experience with
unreacted steam which is suitable for further processing in a conven- over 150 plants built and operated. Ongoing development of the cata-
tional fired reformer. The CRG prereformer enables capital cost savings lyst has lead to almost 50 such units since 1990.
in primary reforming due to reductions in the radiant box heat load. It
also allows high-activity gas-reforming catalyst to be used. The ability to Catalyst: The CRG catalyst is manufactured under license by Johnson
increase preheat temperatures and transfer radiant duty to the convec- Matthey Catalysts.
tion section of the primary reformer can minimize involuntary steam
production. Licensor: The process and CRG catalyst are licensed by Davy Process
Technology.
Operating conditions: The desulfurization section typically operates be-
tween 170 ° C and 420 ° C and the CRG prereformer will operate over a
wide range of temperatures from 250 ° C to 650 ° C and at pressures up
to 75 bara.

Pressure swing adsorption—rapid Centralized cPSA

cycle in H2 plant
Applications: Proper management of hydrogen molecules within the LPG Natural gas
Refinery gas
H2 to
process
H2
refineries and chemical plants is becoming increasingly important due Propane
plant
PSA units
Virgin Butane
to the introduction of stringent product sulfur specifications. Hydro- naphtha Cat Gasoline
gen recovery/purification from fuel gas and hydrogen containing offgas HDT reformer
Atmospheric
Crude oil
streams in refining and chemical processes offers many potential ben-
pipestill
Jet fuel Jet fuel
HDT Hydro-
efits, including product uplift, reduced H2 costs, avoided H2 plant expan- cracker
sion and emission reductions. Diesel
HDT Diesel
Rapid-cycle pressure swing adsorption (RCPSA) technology offers a
more-compact, less-expensive and more-energy-efficient solution for H2
Vacuum
pipestill
FCC CAT
recovery compared to conventional PSA (cPSA) technology. This technol- CAT naphtha
feed HDT
ogy has been jointly developed by ExxonMobil Research and Engineer- HDT
ing Co. (EMRE) and QuestAir Technologies. The RCPSA unit for hydro- Distributed RCPSA
in process loops
gen recovery/purification is marketed as the QuestAir H-6200.
Some of the potential applications of RCPSA are:
H2 recovery/purification from:
• Fuel gas
• Recycle gas loop in hydrotreater Multi-bed RCPSA systems can be efficiently packaged in an inte-
• Naphtha reformer hydrogen offgas grated, modular rotating bed design. The net result is that large PSA
• Hydrocracker offgas and purges systems made up of multiple vessels of beaded adsorbent, complex pro-
• Steam cracker offgas. cess piping and multiple switching valves can be replaced with integrat-
ed modular skid-mounted QuestAir H-6200 plants that are a fraction
Description: RCPSA technology overcomes the inherent disadvantages
of the required footprint of a cPSA of equivalent capacity. In addition,
of cPSA, namely, slow cycle speeds, relatively large adsorbent beads and
the RCPSA’s modular skid mounted design reduces installation time and
complex networks of individual switching valves. RCPSA uses two novel
cost. In the high feed pressure (p > 500 psig) applications, RCPSA can
proprietary technologies: structured adsorbents—replacing convention-
be stably operated without a tail-gas compressor resulting in further
al beaded cPSA adsorbents—and integrated rotary valves—replacing
reduction of total installed cost in comparison to cPSA. Flexible prod-
solenoid-actuated valves used in cPSA. Structured adsorbents provide
uct purity, enhanced recovery and better control of RCPSA can result in
mass transfer coefficients that are up to 100 times higher than beaded
capital and operating cost savings. The modular skid mounted design of
adsorbents used in cPSA; thus, significantly increasing the productivity
the RCPSA makes it possible for refiners to manage H2 molecules closer
of a unit volume of adsorbent bed. The multi-port rotary valves are used
to the processing units as needed, a new paradigm for distributed H2
for rapid and efficient switching of gases between adsorbent beds, ef-
recovery technology for refineries and chemical plants.
fectively capturing the increased capacity of the structured adsorbent.
Continued 
Typical N2 consumption in normal start-up operation: 0.12 nm3/h
Pressure swing adsorption, rapid cycle, continued per H-6200 module
Instrument air consumption: 1.5 Nm3h estimated for operation per
Installation: The first commercial QuestAir H- 6200 unit was started-up H-6200 module
at an ExxonMobil Refinery in 2007. It is installed in the diesel hydrotreater Power: 480 – 600V 3ph, 50 or 60 Hz to suit local requirements, con-
recycle loop to increase H2 purity that results in product uplift and mini- sumption: 37 kw/module
mizes valuable H2 loss from the hydrotreating unit.
References: “PSA technology hits the fast lane,” Chemical Processing,
Yields: Available upon request. August 2003.
“Recovery costs less,” Hydrocarbon Engineering, November 2007.
Utilities: Compact RCPSA technology results in significantly less inert gas ”Rapid Cycle Pressure Swing Adsorption (RCPSA), A new, low-cost
consumption in operation or in purging. Furthermore, since the switch- commercialized H2 recovery process” NPRA Annual Meeting, March
ing valve function is controlled through an electric motor, instrument air 9–11, 2008, San Diego.
is only required for the operation of each module’s product control valve
and automated isolation valves. Licensor: ExxonMobil Research and Engineering Co., and QuestAir
Technologies Inc.
Nitrogen consumption: Estimated inert purge gas requirement: 40.4
nm3
Hydrogenation Hydrogen recycle

Application: The CDHydro process is used to selectively hydrogenate diole-
CW
fins in the top section of a hydrocarbon distillation column. Additional ap- Offgas
plications—including mercaptan removal, hydroisomerization and hydro-
genation of olefins and aromatics are also available.
Description: The patented CDHydro process combines fractionation 2

Hydrogen
with hydrogenation. Proprietary devices containing catalyst are installed 1
in the fractionation column’s top section (1). Hydrogen is introduced FCC C4+
beneath the catalyst zone. Fractionation carries light components into MP steam Reflux Treated FCC C4s
the catalyst zone where the reaction with hydrogen occurs. Fraction-
ation also sends heavy materials to the bottom. This prevents foulants FCC C5+ gasoline
and heavy catalyst poisons in the feed from contacting the catalyst. In Depentanizer
addition, clean hydrogenated reflux continuously washes the catalyst
zone. These factors combine to give a long catalyst life. Additionally,
mercaptans can react with diolefins to make heavy, thermally-stable sul-
fides. The sulfides are fractionated to the bottoms product. This can
eliminate the need for a separate mercaptan removal step. The distillate Economics: Fixed-bed hydrogenation requires a distillation column fol-
product is ideal feedstock for alkylation or etherification processes. lowed by a fixed-bed hydrogenation unit. The CDHydro process elimi-
The heat of reaction evaporates liquid, and the resulting vapor is nates the fixed-bed unit by incorporating catalyst in the column. When
condensed in the overhead condenser (2) to provide additional reflux. a new distillation column is used, capital cost of the column is only 5%
The natural temperature profile in the fractionation column results in a to 20% more than for a standard column depending on the CDHydro
virtually isothermal catalyst bed rather than the temperature increase application. Elimination of the fixed-bed reactor and stripper can reduce
typical of conventional reactors. capital cost by as much as 50%.
The CDHydro process can operate at much lower pressure than Installation: There are 50 CDHydro units are commercially licensed for
conventional processes. Pressures for the CDHydro process are typically C4, C5, C6, LCN and benzene hydrogenation applications. Twenty units
set by the fractionation requirements. Additionally, the elimination of a have been in operation for more than five years and total commer-
separate hydrogenation reactor and hydrogen stripper offers significant cial operating time now exceeds 100 years for CDHydro technologies.
capital cost reduction relative to conventional technologies. Eleven units are currently in engineering / construction.
Feeding the CDHydro process with reformate and light-straight run
for benzene saturation provides the refiner with increased flexibility to Licensor: CDTECH.
produce low-benzene gasoline. Isomerization of the resulting C5 / C6
overhead stream provides higher octane and yield due to reduced ben-
zene and C7 + content compared to typical isomerization feedstocks. click here to e-mail for more information
Hydrogenation, selective for

MTBE/ETBE C4 raffinates MTBE/ETBE debutainzer
CW Offgas
Application: To achieve selective hydrogenation of butadiene to n-butenes

in a catalytic distillation column.
Overhead
drum
Description: The C4 CDHydro catalytic distillation technology processes
C4 streams from refineries or steam crackers within an methyl tertiary Hydrogen
Treated C4s
butyl ether (MTBE)/ethyl tertiary butyl ether (ETBE) debutanizer to pro- Reflux
raffinate
duce a raffinate with a high butylenes content that is essentially butadi- C4s with MTBE/ETBE
and methanol/ethanol
ene-free. After methanol recovery, the treated C4 raffinate can be used
for butene-1 production or alkylation feed. LP steam
Selective hydrogenation increases butenes available for alkylation
or isomerization, reduces acid consumption in alkylation units, and MTBE/ETBE
greatly improves the quality of HF alkylate. The process uses commer-
cially available catalyst in its proprietary catalytic distillation structures
(CDModules).
The C4 stream is combined with hydrogen in the MTBE/ETBE
debutanizer. Treated C4 raffinate is taken overhead. The washing action • Sulfur tolerant catalyst
of the reflux minimizes oligomer formation, flushing heavy compounds • Essentially mercaptan-sulfur-free distillate product
from the catalyst and promoting long catalyst life. Excess hydrogen and • Flexible butene-1/butene-2 ratio
lights are vented from the overhead drum. The catalyst is sulfur tolerant. • Retrofit to existing C4 columns
Feed sulfur compounds react with diolefins to form heavy compounds • All carbon steel construction.
that exit in the tower bottoms with the MTBE/ETBE product. The distil- Economics: Capital costs are considerably lower than conventional hy-
late product is essentually mercaptan-sulfur free. drotreaters since the single column design eliminates costs associated
Process advantages include: with fixed-bed systems. The C4 CDHydro process would typically be in-
• Low capital cost stalled in a conventional or catalytic MTBE/ETBE debutanizer, either as a
• Low catalyst requirements retrofit or in a new column.
• Low operating cost Installation: There are 50 total commercially licensed CDHydro units,
• High product yield (low saturation to paraffins) 11 of which are currently in design or construction.
• No polymer recycle across catalyst
• Use of reaction heat Licensor: CDTECH.


refinery C4 feeds CW Offgas
Application: To process C4 streams from refineries to produce a stream Overhead

with high butylenes content that is essentially butadiene-free, suitable drum
for methyl tertiary butyl ether (MTBE) production, butene-1 production Low-pressure
hydrogen Treated C4s
or alkylation feed.
C 4+ Reflux
Description: The patented C4 CDHydro process achieves selective hy-
drogenation of butadiene to n-butenes in a catalytic distillation column.
Selective hydrogenation increases butenes available for alkylation or LP steam
isomerization, reduces acid consumption in alkylation units, and greatly
improves the quality of HF alkylate. The process uses commercially avail- C5+
able catalyst in proprietary catalytic distillation structures.
The unique catalytic distillation column combines reaction and frac-
tionation in a single unit operation. This constant pressure boiling system
assures precise temperature control in the catalyst zone. Low reaction
temperature and isothermal operation enhance selectivity and minimize Process advantages include:
yield losses to paraffins. Isomerization of butene-1 to butene-2 can be • Low operating pressure
maximized to improve HF alkylate quality or minimized for increased • Low operating cost
butene-1 recovery. • High product yield (low paraffin make)
Refinery C4 streams are combined with hydrogen in the catalytic • No polymer recycle across catalyst
column. Treated C4 products are taken overhead. The washing action • No sweetening required
of the reflux minimizes oligomer formation, flushing heavy compounds • Essentially mercaptan sulfur-free distillate product
from the catalyst and promoting long catalyst life. Excess hydrogen and • Flexible butene-1/butene-2 ratio
lights are vented from the overhead drum. The catalyst will react acidic • Retrofit to existing C4 columns
sulfur compounds with diolefins to form heavy compounds which exit • All carbon steel construction
in the tower bottoms. The distillate product is essentially mercaptan- • Isomerization option
sulfur-free. • No hydrogen compressor.
Economics: Capital costs are considerably lower than conventional hy- Installation: There are 50 total commercially licensed CDHydro units,
drotreaters since the single column design eliminates costs associated 11 of which are in design or under construction.
with fixed-bed systems. Additionally, the ability to remove acidic sulfur Licensor: CDTECH.
compounds eliminates the need for sweetening. The C4 CDHydro pro-
cess would typically be installed in a debutanizer, either as a retrofit or
in a new column.
Hydrogenation—benzene in reformate Hydrogen recycle

Application: The CDHydro catalytic distillation technology processes re- Benzene-toluene CW
formate streams from refineries to reduce benzene to levels required by splitter Offgas
low-benzene gasoline specifications.
Overhead
Description: The patented CDHydro process achieves hydrogenation of drum
benzene to cyclohexane in a catalytic distillation column. Hydrogenation
reduces benzene in the gasoline pool. The process uses commercially Low-pressure
hydrogen
available catalyst in proprietary catalytic distillation structures.
Reflux Treated C6s
C5 – C9 reformate
Selective hydrogenation: Reformate and hydrogen are fed to the catalytic
distillation column. Hydrogenation of benzene to cyclohexane can exceed MP steam
99%. Benzene conversion can easily be limited to lower levels through con-
trol of hydrogen addition. Washing action of the reflux minimizes oligomer Low benzene
formation, flushes heavy compounds from the catalyst and promotes long C7+ reformate
catalyst life. Treated C6 product is taken as overhead. Excess hydrogen and

lights are recycled and vented from the overhead drum. The C7+ product is
taken as bottom with essentially full recovery of heavy aromatics.
The unique catalytic distillation column combines reaction and frac- • Simple operation
tionation in a single unit operation. This constant-pressure boiling sys- • Low operating pressure
tem assures precise temperature control in the catalyst zone. Low reac- • Low operating cost
tion temperature and isothermal operation enhance safety. • Low capital cost
• Low benzene in reformate
Economics: Capital costs are considerably lower than conventional hy-
• All carbon steel construction
drotreaters since the single-column design eliminates costs associated
• No hydrogen compressor
with fixed-bed systems and operates at low enough pressure to avoid
• Isothermal operation
the need for a hydrogen compressor. The CDHydro process would typi-
• Reduced plot area.
cally be installed in a benzene-toluene splitter, either as a retrofit or in a
new column. Installation: There are six operational units, the oldest in operation since
1995.
Advantages:
• Lower capital cost Licensor: CDTECH.
• High conversion


refinery C5 feeds CW Offgas
Application: To process C5 streams from refineries to produce a stream Overhead

with high isoamylenes content that is essentially free of diolefins. The drum
treated C5 stream is suitable for tertiary amyl methyl ether (TAME) pro- Low-pressure
hydrogen Treated C5s
duction or alkylation feed.
Light cat naphtha Reflux
Description: The patented C5 CDHydro process achieves selective hydro-
genates diolefins to amylenes in a catalytic distillation column. Selective
hydrogenation is a required pretreatment step for TAME production and LP steam
C5 alkylation, improving product quality in both, and reducing acid con-
sumption in the latter. C6+
The process uses commercially available catalyst in proprietary cata-
lytic distillation structures. The unique catalytic distillation column com-
bines reaction and fractionation in a single unit operation. This constant
pressure boiling system assures precise temperature control in the cata-
lyst zone. Low reaction temperature and isothermal operation enhance Process advantages include:
selectivity and minimize yield losses to paraffins. Non-reactive 3-methyl • Low operating pressure
butene-1 is isomerized to reactive 2-methyl butene-2, which increas- • Low operating cost
es potential TAME production. Pentene-1 is isomerized to pentene-2, • High product yield (low paraffin make)
which improves octane number. • No polymer recycle across catalyst
Refinery C5 streams are combined with hydrogen in the catalytic • No sweetening required
column. Treated C5 products are taken overhead. The washing action • Essentially mercaptan sulfur-free distillate product
of the reflux minimizes oligomer formation, flushing heavy compounds • Flexible butene-1/butene-2 ratio
from the catalyst and promoting long catalyst life. The catalyst will react • Retrofit to existing C4 columns
acidic sulfur compounds with diolefins to form heavy compounds, which • All carbon steel construction
exit in the tower bottoms. The distillate product is essentially mercaptan- • Isomerization option
sulfur-free. • No hydrogen compressor.
Economics: Capital costs are considerably lower than conventional hy- Installation: There are 50 total commercially licensed CDHydro units,
drotreaters since the single column design eliminates costs associated 11 of which are currently in design or construction.
with fixed-bed systems. Additionally, the ability to remove acidic sulfur
compounds eliminates the need for sweetening. The C5 CDHydro pro- Licensor: CDTECH.
cess would typically be installed in a depentanizer, either as a retrofit or
in a new column.
Hydroprocessing—resid
Makeup H2
Application: The UOP SRC Uniflex process is a high-conversion residue
hydroprocessing process for the production of gasoil conversion unit
HHPS
feedstocks, distillates and naphtha. The normal feedstock to a SRC Uni- CHPS
flex Process Unit is vacuum residue, although atmospheric residue and Slurry
other streams (SDA pitch) can be processed. Recycle
reactor
C4-
H2
Description: The feed is heated to the desired temperature by separate Naphtha Vacuum
heating from the bulk of the recycle gas, which is heated to an elevated column LVGO
temperature above the desired mix temperature. Small particulate cata- Diesel HVGO
lyst is added continuously in the feed just before the feed heater. The
recycle gas is heated in its own heater then the feed plus the recycle
Pitch
gas are mixed in the bottom zone of the reactor. Product and catalyst Catalyst Stripper/
product
leave the top of the reactor, are then immediately quenched then flow Vacuum fractionator
HVGO recycle
to the hot high-pressure separator (HHPS) and to further fractionation. residue
feed
The vapor stream from the CHPS is recycled back to the reactor after
combining with make-up hydrogen. HVGO is typically recycled to almost
extinction.
Economics: The SRC Uniflex Process will result in very high refinery mar-
gins due to the high conversion to distillates and naphtha’s.
Experience: One has been in operation at the PetroCanada Montreal

Refinery.
Licensor: UOP.

Hydroprocessing, ULSD
Recycle
Application: A versatile family of ExxonMobil Research and Engineering compressor
Co. (EMRE) process technologies and catalysts are used to meet all cur- ULSD
Lean amine
rent and possible future premium diesel requirements. reactor
ULSD HDS—Ultra-deep hydrodesulfurization process to produce Wash water Absorber
distillate products with sulfur levels below 10 wppm. Heater
HDHC—Heavy-distillate mild-hydrocracking process for the reduc- Cold
Rich amine
tion of T90 and T95 boiling points, and high-level density reduction. separator Fuel gas
Sour
MAXSAT—High-activity aromatics saturation process for the selec- water Product
tive reduction of polyaromatics under low pressure and temperature Hot stripper
separator
conditions. Gas oil feed
CPI—Diesel cloud point improvement by selective normal paraffin Naphtha
hydrocracking (MDDW) or by paraffin isomerization dewaxing (MIDW).
Charge pump
Description: EMRE units combine the technologies listed above in Hydrogen Steam
low-cost integrated designs to achieve the necessary product uplift at Makeup
compressor Low-sulfur diesel
minimum investment and operating cost. For ultra-low-sulfur-diesel
hydrodesulfurization (ULSD HDS), a single-stage single-reactor process
can be designed. A small cetane improvement, together with the reduc-
tion of polyaromatics to less than 11 wt.% or as low as 5 wt.%, can be
economically achieved with proper specification of catalyst, hydrogen offer either paraffin isomerization dewaxing (MIDW) or selective normal
partial pressure, space velocity and the installation of high-performance paraffin cracking-based dewaxing technologies (MDDW). These can be
Spider Vortex internals. closely integrated with ULSD HDS and other functions to achieve the full
The addition of heavy-diesel hydrocracking (HDHC) function to the HDS upgrading requirements.
reactor can achieve T95 boiling point reduction together with higher levels The EMRE ULSD technologies are equally amenable to revamp or
of density and aromatics reduction and greater cetane improvement. grassroots applications. EMRE has an alliance with Kellogg Brown &
When feedstock aromatics are very high, or very low aromatics in Root (KBR) to provide these technologies to refiners.
the product are desired, a second-stage aromatics saturation (MAXSAT)
system is specified to avoid very high design pressures required for a Installation: Nineteen distillate upgrading units have applied the EMRE
single-step base-metal hydrotreating catalyst system. When the distil- ULSD technologies. Twelve of these applications are revamps.
late product must also meet stringent fluidity specifications, EMRE can
Licensor: ExxonMobil Research and Engineering Co.

Hydrotreating
LCN
Application: The CDHydro and CDHDS processes are used to selectively
desulfurize FCC gasoline with minimum octane loss.
CDHydro MCN
Products: Ultra-low-sulfur FCC gasoline with maximum retention of Hydrogen
olefins and octane. FCC C5 + gasoline
Description: The light, mid and heavy cat naphthas (LCN, MCN, HCN)
CDHDS
are treated separately, under optimal conditions for each. The full- MCN/HCN
range FCC gasoline sulfur reduction begins with fractionation of the
light naphtha overhead in a CDHydro column. Mercaptan sulfur re-
Hydrogen
acts quantitatively with excess diolefins to produce heavier sulfur com-
pounds, and the remaining diolefins are partially saturated to olefins HCN
by reaction with hydrogen. Bottoms from the CDHydro column, con-
taining the reacted mercaptans, are fed to the CDHDS column where
the MCN and HCN are catalytically desulfurized in two separate zones.
HDS conditions are optimized for each fraction to achieve the desired
catalytic distillation is increased significantly beyond typical fixed-bed
sulfur reduction with minimal olefin saturation. Olefins are concentrat-
life. The CDHydro/CDHDS units can operate throughout an FCC turn-
ed at the top of the column, where conditions are mild, while sulfur
around cycle up to six years without requiring a shutdown to regenerate
is concentrated at the bottom where the conditions result in very high
or to replace catalyst. Typical fixed-bed processes will require a mid FCC
levels of HDS.
shutdown to regenerate/replace catalyst, requiring higher capital cost
No cracking reactions occur at the mild conditions, so that yield
for feed, storage, pumping and additional feed capacity.
losses are easily minimized with vent-gas recovery. The three product
streams are stabilized together or separately, as desired, resulting in Economics: The estimated ISBL capital cost for a 50,000-bpd CDHydro/
product streams appropriate for their subsequent use. The two columns CDHDS unit with 95% desulfurization is $40 million (2005 US Gulf
are heat integrated to minimize energy requirements. Typical reformer Coast).
hydrogen is used in both columns without makeup compression. The
sulfur reduction achieved will allow the blending of gasoline that meets Installation: There are 38 CDHydro/CDHDS desulfurization units com-
current and future regulations. mercially licensed to treat FCC gasoline, of which 12 are currently in en-
Catalytic distillation essentially eliminates catalyst fouling because gineering/construction. Total licensed capacity exceeds 1.3 million bpd.
the fractionation removes heavy-coke precursors from the catalyst zone
before coke can form and foul the catalyst pores. Thus, catalyst life in Licensor: CDTECH.

Hydrotreating Makeup H2 gas

HP purge gas
Application: Hydrotreating of light and middle distillates and various gas
oils, including cracked feedstocks (coker naphtha, coker LGO and HGO, Lean amine
visbreaker gas oil, and LCO) using the ISOTREATING Process for deep
desulfurization, denitrification and aromatics saturation and to produce Wash 3
low-sulfur naphtha, jet fuel, ultra-low sulfur diesel (ULSD), or improved- 1 water
Light ends
quality FCC feed. A
and naphtha
Rich amine
2
A B
Description: Feedstock is mixed with hydrogen-rich treat gas, heated H2 and
light ends
and reacted over high-activity hydrogenation catalyst (1). Several CoMo 2 5
and NiMo catalysts are available for use in the ISOTREATING Process. One 4
or multiple beds of catalyst(s), together with Chevron Lummus Global’s Feed B
advanced high-efficiency reactor internals for reactant distribution and Product
interbed quenching, are used. 4 Sour water

Stripping
Reactor effluent is cooled and flashed (2) producing hydrogen-rich steam
recycle gas, which, after H2S removal by amine (3), is partially used as
quench gas while the rest is combined with makeup hydrogen gas to
form the required treat gas. An intermediate pressure level flash (4) can to produce ULSD (<10 wppm sulfur). Chemical-hydrogen consumption
be used to recover some additional hydrogen-rich gas from the liquid ranges from 450 –900+ scf/bbl feed.
effluent prior to the flashed liquids being stripped or fractionated (5) to
remove light ends, H2S and naphtha-boiling range material, and/or to Economics: Investment will vary depending on feedstock character-
fractionate the higher boiling range materials into separate products. istics and product requirements. For a 40,000–45,000-bpsd unit for
ULSD, the ISBL investment cost (US Gulf Coast 2007) is $2,000–$3,000/
Operating conditions: Typical reactor operating conditions can range bspd.
from 600 –2,300 psig and 500 –780°F, 350 –2,000 psia hydrogen partial
pressure, and 0.6-3 hr –1 LHSV, all depending on feedstock(s) and prod- Installation: Currently, there are more than 50 units operating based on
uct quality objective(s). ISOTREATING technology and an additional 17 units in various stages of
engineering.
Yields: Depends on feedstock(s) characteristics and product require-
ments. Desired product recovery is maximized based on required flash Licensor: Chevron Lummus Global LLC.
point and/or specific fractionation specification. Reactor liquid product
(350°F plus TBP material) is maximized through efficient hydrogenation
with minimum lighter liquid product and gas production. Reactor liq-
uid product (350°F plus) yield can vary between 98 vol% from straight-
run gas oil feed to >104 vol% from predominantly cracked feedstock click here to e-mail for more information
Hydrotreating
Recycle
Application: The IsoTherming process provides refiners an economical Makeup hydrogen compressor Not required
Purge gas
means to produce ultra-low-sulfur diesel (ULSD), low-sulfur and low- for grassroots
Heater projects
nitrogen feedstocks and other very low-sulfur hydrocarbon products. In Amine
treating
addition, IsoTherming can also be used for feed upgrading in a mild-to Heater
partial-conversion hydrocracking mode in conjunction with or in lieu of IsoTherming Fuel gas
reactor Grassroots
conventional hydrotreating. only
Feed Trickle-bed Separator
Products: ULSD, low-sulfur FCC feed, low-sulfur gasoline-kerosine type reactor
Naphtha
products. Recycle
Cold
pump
separator
Description: This process uses a novel approach to introduce dissolved
hydrogen in excess of reaction requirements into the reactor. This ap- Hot
separator
proach allows operation at higher space velocities than conventional Grassroots
Legend:
trickle-bed reactors. The IsoTherming process eliminates problems asso- Existing equipment
only
Stripper
ciated with flow mal-distribution, gas-liquid mass transfer and catalyst New equipment
wetting. The process obviates the need for some equipment in conven- Product diesel
tional hydrotreating thereby lowering cost.

The technology can be installed as a pre-treat unit ahead of an exist-
ing hydrotreater reactor or a new stand-alone process unit. Fresh feed,
after heat exchange, is combined with recycled product and hydrogen in Operating conditions: Typical diesel IsoTherming revamp conditions are:
a mixer internal to the reactor. The liquid feed with soluble hydrogen is Treated product
fed to IsoTherming reactor/bed one where partial desulfurization occurs. IsoTherming from existing
The stream is combined with additional hydrogen in a second mixer and Diesel pre-treat conventional
fed to the second IsoTherming reactor/bed where further desulfurization feed reactor reactor
takes place. LCO, vol% 42
Treated oil is recycled back to the inlet of reactor one. This recycle SR, vol% 58
stream delivers more hydrogen to the reactors and also acts as a heat Sulfur, ppm 4,300 451 7
sink; thus, a nearly isothermal reactor operation is achieved. Nitrogen, ppm 415 49 0
The treated oil from the second IsoTherming reactor/bed may then H2 Consumption, scf/bbl 305 245
be fed to additional IsoTherming reactors/beds and/or a trickle-bed –1
LHSV, Hr * 4 2.1
hydrotreating reactor (revamp case only) acting in the polishing mode to Reactor DT 24 30
produce an ultra-low-sulfur product. Reactor Pressure, psig 900 750
* Based on fresh feedrate without recycle
Continued 
Hydrotreating, continued
Economics: Revamp investment (basis 15,000–20,000 bpsd, 1Q2008,
US Gulf Coast) $500/bpsd diesel.
Installation: Six units have been licensed for ULSD; two units licensed for
mild hydrocracking; and one unit for gasoil desulfurization.
Licensor: DuPont.

Hydrotreating Recycle gas

compressor
Application: Topsøe hydrotreating technology has a wide range of ap- Makeup
hydrogen
plications, including the purification of naphtha, distillates and residue,
as well as the deep desulfurization and color improvement of diesel fuel Absorber
Furnace Lean amine
and pretreatment of FCC and hydrocracker feedstocks.
Products: Ultra-low-sulfur diesel fuel, and clean feedstocks for FCC and Reactor
hydrocracker units.
Rich amine
Description: Topsøe’s hydrotreating process design incorporates our in- Fresh feed H2 rich gas
dustrially proven high-activity TK catalysts with optimized graded-bed
loading and high-performance, patented reactor internals. The combi- START
Products to
nation of these features and custom design of grassroots and revamp High-pressure fractionation
separator
hydrotreating units result in process solutions that meet the refiner’s Low-pressure
objectives in the most economic way. separator
In the Topsøe hydrotreater, feed is mixed with hydrogen, heated
and partially evaporated in a feed/effluent exchanger before it enters
the reactor. In the reactor, Topsøe’s high-efficiency internals have a
low sensitivity to unlevelness and are designed to ensure the most Operating conditions: Typical operating pressures range from 20 to 80
effective mixing of liquid and vapor streams and the maximum utili- barg (300 to 1,200 psig), and typical operating temperatures range from
zation of the catalyst volume. These internals are effective at a high 320°C to 400°C (600°F to 750°F).
range of liquid loadings, thereby enabling high turndown ratios. Top-
References: Cooper, B. H. and K. G. Knudsen, “Production of ULSD: Cat-
søe’s graded-bed technology and the use of shape-optimized inert
alyst, kinetics and reactor design,” World Petroleum Congress, 2002.
topping and catalysts minimize the build-up of pressure drop, there-
Patel, R. and K. G. Knudsen, “How are refiners meeting the ul-
by enabling longer catalyst cycle length. The hydrotreating catalysts
tra-low-sulfur diesel challenge,” NPRA Annual Meeting, San Antonio,
themselves are of the Topsøe TK series, and have proven their high
March 2003.
activities and outstanding performance in numerous operating units
Topsøe, H., K. Knudsen, L. Skyum and B. Cooper, “ULSD with BRIM
throughout the world. The reactor effluent is cooled in the feed-ef-
catalyst technology,” NPRA Annual Meeting, San Francisco, March 2005.
fluent exchanger, and the gas and liquid are separated. The hydro-
gen gas is sent to an amine wash for removal of hydrogen sulfide Installation: More than 60 Topsøe hydrotreating units for the various ap-
and is then recycled to the reactor. Cold hydrogen recycle is used as plications above are in operation or in the design phase.
quench gas between the catalyst beds, if required. The liquid product
is steam stripped in a product stripper column to remove hydrogen Licensor: Haldor Topsøe A/S.
sulfide, dissolved gases and light ends.
Hydrotreating
Application: RCD Unionfining process reduces the sulfur, nitrogen, Con- Guard Main reactors (2-4)
radson carbon, asphaltene and organometallic contents of heavier resi- Resid charge
reactor
due-derived feedstocks to allow them to be used as either specification

START
fuel oils or as feedstocks for downstream processing units such as hydro- HHPS
crackers, fluidized catalytic crackers, resid catalytic crackers and cokers.
Recycle
Makeup gas comp.
Feed: Feedstocks range from solvent-derived materials to atmospheric hydrogen
and vacuum residues. Gas
Recycle
gas heater Fuel gas
Description: The process uses a fixed-bed catalytic system that operates at Naphtha
moderate temperatures and moderate to high hydrogen partial pressures. Lean amine
Distillate
Typically, moderate levels of hydrogen are consumed with minimal pro-
duction of light gaseous and liquid products. However, adjustments can Rich amine Treated
atm. resid
be made to the unit’s operating conditions, flowscheme configuration or Amine Cold high Cold low Hot low
scrubber press. sep. press. flash press. flash Fractionator
catalysts to increase conversion to distillate and lighter products.
Fresh feed is combined with makeup hydrogen and recycled gas,
and then heated by exchange and fired heaters before entering the
unit’s reactor section. Simple downflow reactors incorporating a graded
bed catalyst system designed to accomplish the desired reactions while
minimizing side reactions and pressure drop buildup are used. Reactor
effluent flows to a series of separators to recover recycle gas and liquid Economics:
products. The hydrogen-rich recycle gas is scrubbed to remove H2S and Utilities, typical per barrel of fresh feed (20,000 bpsd basis)
recycled to the reactors while finished products are recovered in the Fuel, MMBtu/hr 46
fractionation section. Fractionation facilities may be designed to simply Electricity, kWh 5,100
recover a full-boiling range product or to recover individual fractions of Steam, HP, lb / hr 8,900
the hydrotreated product. Steam, LP, lb / hr 1,500
Installation: Twenty-eight licensed units with a combined licensed ca-

pacity of approximately one million bpsd. Commercial applications have
included processing of atmospheric and vacuum residues and solvent-
derived feedstocks.
Licensor: UOP.

Hydrotreating
Application: Hydrodesulfurization, hydrodenitrogenation and hydro- Light components
genation of petroleum and chemical feedstocks using the UOP Union-
Makeup
fining processes. hydrogen
Products: Ultra-low-sulfur diesel fuel; feed for catalytic reforming, 3

1
FCC pretreat; upgrading distillates (higher cetane, lower aromatics);
desulfurization, denitrogenation and demetallization of vacuum and at-
mospheric gas oils, coker gas oils and chemical feedstocks. Product
Feed
Description: Feed and hydrogen-rich gas are mixed, heated and contact- START 2
ed with regenerable catalyst (1). Reactor effluent is cooled and separated
(2). Hydrogen-rich gas is recycled or used elsewhere. Liquid is stripped
(3) to remove light components and remaining hydrogen sulfide, or frac-
tionated for splitting into multiple products.
Operating conditions: Operating conditions depend on feedstock and

desired level of impurities removal. Pressures range from 500 to 2,000 Distillate, vol% 97.2 97.6 98.0 100.3
psi. Temperatures and space velocities are determined by process objec- Gravity, °API 24.0 26.9 27.8 38.6
tives. Boiling range, °F 400+ 325/660 300+ 310 +
Sulfur, wt% 0.025 0.001 0.002 0.001
Yields: H2 consump., scf/bbl 700 350 620 310
Purpose FCC feed Desulf. Desulf. Desulf.
Feed, source VGO + Coker AGO VGO VGO + LCO Economics:
Gravity, °API 17.0 25.7 24.3 36.6 Utilities, typical per bbl feed:
Boiling range, °F 400/1,000 310/660 540/1,085 390/690 Fuel, 103 Btu 40–100
Sulfur, wt% 1.37 1.40 3 0.1 Electricity, kWh 0.5–1.5
Nitrogen, ppmw 6,050 400 1,670 280
Installation: Several hundred units installed.
Bromine number — 26 — 3.9
Naphtha, vol% 4.8 4.2 3.9 2.0 Licensor: UOP.
Gravity, °API 45.0 50.0 54.0 55
Boiling range, °F 180/400 C4/325 C4/356 C5/310
Sulfur, ppmw 50 <2 <2 <5
Nitrogen, ppmw 30 <1 <2 <2
Hydrotreating, diesel
Application: Produce ultra-low-sulfur diesel (ULSD) and high-cetane and 3 Offgas
improved-color diesel fuel from a wide range of middle distillates feeds
2 Additional
including large amount of cracked stock (such as LCO, light coker/vis- catalyst
breaker gasoils or MHC-GO, AR/VRDS GO) using Axens’ Prime-D Toolbox volume
of proven state-of-the-art technology (including high activity/stability HR 7
Series catalysts and high-performances EquiFlow internals) and services.

4
Low-sulfur
Description: In the basic process, as shown in the diagram, feed and 1 5 product
hydrogen are heated in the feed-reactor effluent exchanger (1) and fur- 6
nace (2) and enter the reaction section (3), with possible added volume
Feed H2 recycle Amine New amine
for revamp cases. The reaction effluent is cooled by the exchanger (1) absorber absorber
and air cooler (4) and separated in the separator (5). The hydrogen- PSA purified
hydrogen
rich gas phase is treated in an existing or new amine absorber for H2S H2S
removal (6) and recycled to the reactor. The liquid phase is sent to the
stripper (7) where small amounts of gas and naphtha are removed and
high-quality product diesel is recovered.
Whether the need is for a new unit or for maximum reuse of exist-
ing diesel HDS units, the Prime-D Hydrotreating Toolbox of solutions • Application of Advanced Process Control for dependable opera-
meets the challenge. Process objectives ranging from low-sulfur, ultra- tion and longer catalyst life.
low-sulfur, low-aromatics, and/or high-cetane number are met with • Sound engineering design based on years of R&D, process design
minimum cost by: and technical service feedback to ensure the right application of the
• Selection of the proper combination of catalyst from HR Series and right technology for new and revamp projects.
ACT grading materials for maximized cycle length and performance. HR Whatever the diesel quality goals—ULSD, high cetane or low aro-
626 catalyst covers the range of ULSD requirements with highly active matics—Prime-D’s Hydrotreating Toolbox approach will attain your goals
and stable catalysts. HR 626 CoMo exhibits high desulfurization rates at in a cost-effective manner.
low to medium pressures; HR 538/HR 548 NiMo have higher hydrogena-
tion activities at higher pressures. Installation: Over 200 middle distillate hydrotreaters have been licensed
• Use of proven, high-performance reactor internals, EquiFlow, that or revamped. They include 85 low- and ultra-low-sulfur diesel units, as
allow near-perfect gas and liquid distribution and outstanding radial well as a number of cetane boosting units equipped with Equiflow
temperature profiles (implemented in over 100 units). internals and loaded with HR series catalysts.
• Loading catalyst in the reactor(s) with the Catapac dense loading
technique for up to 20% more reactor capacity. Over 15,000 tons of References: “Getting Total Performance with Hydrotreating,” Petroleum
catalyst have been loaded quickly, easily and safely in recent years using Technology Quarterly, Spring 2002.
the Catapac technique. Continued 
Hydrotreating, diesel, continued “Squeezing the most from hydrotreaters,” Hydrocarbon Asia, April/
May 2004.
“Upgrade hydrocracked resid through integrated hydrotreating,”
“Premium Performance Hydrotreating with Axens HR 400 Series Hydrocarbon Processing, September 2008.
Hydrotreating Catalysts,” NPRA Annual Meeting, March 2002, San
Antonio. Licensor: Axens.
“The Hydrotreating Toolbox Approach,” Hart’s European Fuel News,
May 29, 2002.
Hydrotreating, pyrolysis gasoline

Application: GTC Technology, in alliance with technology partners, of- 1st Stage HDT
Makeup H2
2nd Stage HDT
fers an optimized technology for two-stage pyrolysis gasoline (pygas) Reactor purge gas
hydrotreatment in cases where di-olefins, olefins and styrene in the raw H2
Offgas Offgas
pygas feed are saturated. The technology is simple and easy to imple- Feed
ment into existing plant requirements. The process is applied to the C5+
C5
fraction of raw pyrolysis gasoline.
Fractionation
Description: The hydrotreating unit consists of three sections: Stabilizer Stabilizer
• First stage hydrotreating section saturates di-olefins to olefins
• Second stage hydrotreating section saturates olefins and desulfur-
izes the pygas C6-C8
C9+ product
• Fractionation section stabilizes the hydrotreated streams and re-
covers the C6 – C8 heart cut for further processing for aromatics extrac- Gasoline
tion and the C9+ cut.
Raw pygas is first sent to the first stage hydrotreating section. The
pygas feed stream along with hydrogen is preheated by the recycle
liquid stream to the desired temperature and sent to the first stage In the second stage hydrotreating section, the C6 – C8 heart cut com-
hydrotreating (HDT) reactor where most diolefins in the feed are selec- bined with a recycle vapor stream and makeup hydrogen is preheated
tively saturated into olefins only—preserving the octane value of the in the second stage feed/effluent heat exchanger before being heated
hydrotreated stream. further to the desirable reaction temperature by a charge heater. The
The reactor effluent is sent to the first stage product separator. Part feed mixture passes through the fixed catalyst beds in the second stage
of the liquid from the bottom of the product separator is recycled back HDT reactor where olefin species are saturated and sulfur species are
to the front section of the first stage hydrogenator to control reactor converted to hydrogen sulfide (H2S).
temperature rise. Excess hydrogen and light hydrocarbons are removed The reactor effluent is then cooled in the second stage feed/efflu-
at the top of the separator and sent to the recycle gas compressor. The ent heat exchanger and subsequently in an after-cooler before being
separator liquid is fed to a first stage stabilizer column. In the receiver, routed to a second stage product separator. In the product separator,
H2 and light hydrocarbons are separated and drawn as a vapor product, the unreacted hydrogen and other light components are separated from
which is sent as offgas to the battery limit (B.L.). The liquid from the the hydrotreated liquid products and recycled to the HDT reactor using
receiver is fully returned as reflux to the column. The liquid stream from a recycle gas compressor. A small vapor stream is purged as offgas to
the stabilizer bottoms is C5 + gasoline fraction and can be sent to the control impurities level in the recycle gas.
gasoline pool. To produce benzene, toluene and xylene (BTX), this C5+ The hydrotreated liquid stream is fed to the second stage stabilizer
stream is sent to a fractionation section to obtain a C6 – C8 heat cut, column. The column vapors are partially condensed in the overhead
which will be further hydrotreated to saturate mono-olefins in the sec-
ond stage hydrotreating section. Continued 
• Catalyst exhibits high activity, stability, mechanical strength and
Hydrotreating, pyrolysis gasoline, continued poison resistance
• Aromatics saturation in second stage reactor is less than 1%
condenser and sent to an overhead receiver. In the receiver, H2 and light • Efficient heat integration scheme reduces energy consumption
hydrocarbons are separated and drawn as a vapor product, which is • Turnkey package for high-purity benzene, toluene and paraxylene
sent as offgas to the BL. The liquid from the receiver is fully returned as production available from licensor.
reflux to the column. The bottoms product from the stabilizer, which is
the hydrotreated C6 – C8 cut is cooled further and sent to BL for further Economics: Feedrate 500 thousand tpy (11,000 bpsd); erected cost
processing for aromatics extraction. $26MM (ISBL, 2007 US Gulf Coast Basis).
Process advantages: Installation: Commercialized technology available for license.

Process advantages:
• Flexibility in prefractionator cut point and a proprietary vaporizer Licensor: GTC Technology.
allows control of polymerization potential in the hydrotreaters
• Reactor operates at high liquid content with mixed phases to mini-
mize polymer byproduct plugging
• Optimized recycle scheme minimizes hydrocarbon vaporization
and thereby extends reactor run length
Hydrotreating/desulfurization
Application: The UOP SelectFining process is a gasoline desulfurization Recycle gas
technology developed to produce ultra-low-sulfur gasoline by removing Makeup H2
more than 99% of the sulfur present in olefinic naphtha while: Di-olefin reactor Main
reactor
• Minimizing octane loss
• Maximizing liquid yield
Light ends
• Minimizing H2 consumption
• Eliminating recombination sulfur.
Heater
Description: The SelectFining process can hydrotreat full boiling-range
(FBR) olefinic naphtha or, when used in conjunction with a naphtha split-
ter, any fraction of FBR naphtha.
The configuration of a single-stage SelectFining unit processing
FBR olefinic naphtha (Fig. 1) is very similar to that of a conventional Feed
Product
hydrotreater. The operating conditions of the SelectFining process are
similar to those of conventional hydrotreating: it enables refiners to re-
use existing idle hydroprocessing equipment.
Since FBR olefinic naphtha can contain highly reactive di-olefins
(which may polymerize and foul equipment and catalyst beds), the Se- port (with optimized acidity) and non-noble metal promoters to achieve
lectFining unit may include a separate reactor for di-olefin stabilization. the optimal combination of desulfurization, olefin retention and operat-
Incoming naphtha is mixed with a small stream of heated hydrogen-rich ing stability.
recycle gas and directed to this reactor. The “stabilized” naphtha is then In addition to processing FBR naphtha, the SelectFining technology
heated to final reaction conditions and processed in the unit’s main reac- can also be used in an integrated gasoline upgrading configuration that
tor over SelectFining catalyst. includes naphtha splitting, Merox extraction technology for mercaptan
Effluent from the main reactor is washed, cooled and separated into removal and ISAL hydroconversion technology for octane recovery.
liquid and gaseous fractions. Recovered gases are scrubbed (for H2S re-
moval) and recycled to the unit’s reactor section, while recovered liquids Economics: A SelectFining unit can preserve olefins while desulfur-
are debutanized (for Rvp control) and sent to gasoline blending. izing FBR naphtha from a fluid catalytic cracking unit. When produc-
ing a 50-wppm sulfur product (~98% HDS), the additional olefin re-
Process chemistry: While the principal reactions that occur in a tention provided by the single-stage SelectFining unit corresponds to a
hydrotreater involve conversion of sulfur and nitrogen components, 2.5 (R+M)/2 octane advantage relative to conventional hydrotreating.
conventional hydrotreaters also promote other reactions, including This advantage increases to 3.5 (R+M)/2 when a two-stage unit is used.
olefin saturation, reducing the feed’s octane. UOP’s S 200 SelectFining Based upon an octane value of $0.50 per octane-bbl, hydrogen cost of
catalyst was developed to effectively hydrotreat the olefinic naphtha
while minimizing olefin saturation. It uses an amorphous alumina sup- Continued 
Hydrotreating/desulfurization, continued and more than 240 Merox units (for naphtha service) in operation. The
first commercial SelectFining unit has been operating successfully since
$6 per 1,000 SCFB and 20,000 BPSD naphtha throughput, the resulting 2006.
savings in processing costs can range from $8 to $12 million per year
Licensor: UOP in cooperation with PDVSA-INTEVEP.
depending upon the SelectFining process flowscheme applied.
Installation: UOP’s experience in hydroprocessing and gasoline click here to e-mail for more information
desulfurization is extensive with approximately 200 Unionfining units
Hydrotreating—RDS/VRDS/UFR/OCR
Makeup hydrogen To gas recovery
Application: Hydrotreat atmospheric and vacuum residuum feedstocks
to reduce sulfur, metals, nitrogen, carbon residue and asphaltene con-
Reactors
tents. The process converts residuum into lighter products while im- Unstabilized
Recycle gas H2S naphtha
proving the quality of unconverted bottoms for more economic down-
scrubbing
stream use.
Product
Cold HP stripper
Products: Residuum FCC feedstock, coker feedstock, SDA feedstock or separator Diesel
H 2O
low-sulfur fuel oil. VGO product, if separated, is suitable for further up- Steam
grading by FCC units or hydrocrackers for gasoline/mid-distillate manu- Product
Sour water
facture. Mid-distillate material can be directly blended into low-sulfur
diesel or further hydrotreated into ultra-low-sulfur diesel (ULSD). Fresh feed
The process integrates well with residuum FCC units to minimize Hot HP LP
Filter separator separator
catalyst consumption, improve yields and reduce sulfur content of FCC
products. RDS/VRDS also can be used to substantially improve the yields
of downstream cokers and SDA units.
Description: Oil feed and hydrogen are charged to the reactors in a suited to revamp existing RDS/VRDS units for additional throughput or
once-through operation. The catalyst combination can be varied signifi- heavier feedstock.
cantly according to feedstock properties to meet the required product
Installation: Over 26 RDS/VRDS units are in operation. Six units have ex-
qualities. Product separation is done by the hot separator, cold separator
tensive experience with VR feedstocks. Sixteen units prepare feedstock
and fractionator. Recycle hydrogen passes through an H2S absorber.
for RFCC units. Four OCR units and two UFR unit are in operation, with
A wide range of AR, VR and DAO feedstocks can be processed. Ex-
another six in engineering. Total current operating capacity is about 1.1
isting units have processed feedstocks with viscosities as high as 6,000
million bpsd
cSt at 100°C and feed-metals contents of 500 ppm.
Onstream Catalyst Replacement (OCR) reactor technology has been References: Reynolds, “Resid Hydroprocessing With Chevron Technol-
commercialized to improve catalyst utilization and increase run length ogy,” JPI, Tokyo, Japan, Fall 1998.
with high-metals, heavy feedstocks. This technology allows spent cata- Reynolds and Brossard, “RDS/VRDS Hydrotreating Broadens Appli-
lyst to be removed from one or more reactors and replaced with fresh cation of RFCC,” HTI Quarterly, Winter 1995/96.
while the reactors continue to operate normally. The novel use of up- Reynolds, et al., “VRDS for conversion to middle distillate,” NPRA
flow reactors in OCR provides greatly increased tolerance of feed solids Annual Meetng, March 1998, Paper AM-98-23.
while maintaining low-pressure drop.
A related technology called UFR (upflow reactor) uses a multibed Licensor: Chevron Lummus Global LLC.
upflow reactor for minimum pressure drop in cases where onstream
catalyst replacement is not necessary. OCR and UFR are particularly well click here to e-mail for more information
Hydrotreating—resid
Feed
Application: Upgrade and/or convert atmospheric and vacuum residues
using the Hyvahl fixed-bed process.
Products: Low-sulfur fuels (0.3% to 1.0% sulfur) and RFCC feeds (re-
moval of metals, sulfur and nitrogen, reduction of carbon residue). Thirty HDM-HDS
percent to 50% conversion of the 565°C+ fraction into distillates. reaction
section
Description: Residue feed and hydrogen, heated in a feed/effluent ex-

changer and furnace, enter a reactor section—typically comprising of a
guard-reactor section (PRS), main HDM and HDS reactors.
Product
The guard reactors are onstream at the same time in series, and they
protect downstream reactors by removing or converting sediment, met- Guard reactors
als and asphaltenes. For heavy feeds, they are permutable in operation
(PRS technology) and allow catalyst reloading during the run. Permuta-
tion frequency is adjusted according to feed-metals content and process
objectives. Regular catalyst changeout allows a high and constant pro- References: Plain, C., D. Guillaume and E. Benazzi, “Residue desulphu-
tection of downstream reactors. risation and conversion,” Petroleum Technology Quarterly, Summer
Following the guard reactors, the HDM section carries out the re- 2006.
maining demetallization and conversion functions. With most of the Plain, C., D. Guillaume and E. Benazzi, “Better margins with cheaper
contaminants removed, the residue is sent to the HDS section where the crudes,” ERTC 2005 Show Daily.
sulfur level is reduced to the design specification. “Option for Resid Conversion,” BBTC, Oct. 8–9, 2002, Istanbul.
The PRS technology associated with the high stability of the HDS “Maintaining on-spec products with residue hydroprocessing,”
catalytic system leads to cycle runs exceeding a year even when process- 2000 NPRA Annual Meeting, March 26–28, 2000, San Antonio.
ing VR-type feeds to produce ultra-low-sulfur fuel oil.
Licensor: Axens.
Yields: Typical HDS and HDM rates are above 90%. Net production of
12% to 25% of diesel + naphtha.
Installation: In addition to three units in operation, four more were li-

censed in 2005 / 07. Total installed capacity will reach 370,000 bpsd.
Two units will be operating on AR and VR feed, five on VR alone.

Isomerization
Application: C5 /C6 paraffin-rich hydrocarbon streams are isomerized to
produce high RON and MON product suitable for addition to the gaso-
line pool. CW
Offgas
Description: Several variations of the C5 / C6 isomerization process are C5/C6 feed
available. The choice can be a once-through reaction for an inexpensive-
but-limited octane boost, or, for substantial octane improvement and as START
1
an alternate (in addition) to the conventional DIH recycle option, the Ip- Isomerate
2 3
sorb Isom scheme shown to recycle the normal paraffins for their com-
plete conversion. The Hexorb Isom configuration achieves a complete
normal paraffin conversion plus substantial conversion of low (75) oc-
Hydrogen
tane methyl pentanes gives the maximum octane results. With the most
active isomerization catalyst (chlorinated alumina), particularly with the Recycle
Albemarle /Axens jointly developed ATIS2L catalyst, the isomerization
performance varies from 84 to 92: once-through isomerization -84,
isomerization with DIH recycle -88, Ipsorb -90, Hexorb-92.
Operating conditions: The Ipsorb Isom process uses a deisopentanizer

(1) to separate the isopentane from the reactor feed. A small amount of Installation: Of 35 licenses issued for C5 / C6 isomerization plants, 14
hydrogen is also added to reactor (2) feed. The isomerization reaction units are operating including one Ipsorb unit.
proceeds at moderate temperature producing an equilibrium mixture of
Reference: Axens /Albemarle, “Advanced solutions for paraffin
normal and isoparaffins. The catalyst has a long service life. The reactor
isomerization,” NPRA Annual Meeting, March 2004, San Antonio.
products are separated into isomerate product and normal paraffins in
“Paraffins isomerizatioin options,” Petroleum Technology Quarterly,
the Ipsorb molecular sieve separation section (3) which features a novel
Q2, 2005.
vapor phase PSA technique. This enables the product to consist entirely
of branched isomers. Licensor: Axens.

Isomerization
2
Application: Convert normal olefins to isoolefins.
C4s to MTBE unit
Description:
C4 olefin skeletal isomerization (IsomPlus)
A zeolite-based catalyst especially developed for this process pro- 3
vides near equilibrium conversion of normal butenes to isobutylene at 4 5
high selectivity and long process cycle times. A simple process scheme
and moderate process conditions result in low capital and operating
costs. Hydrocarbon feed containing n-butenes, such as C4 raffinate, can C5+
be processed without steam or other diluents, nor the addition of cata-
MTBE unit raffinate
lyst activation agents to promote the reaction. Near-equilibrium con-
version levels up to 44% of the contained n-butenes are achieved at
greater than 90% selectivity to isobutylene. During the process cycle,
coke gradually builds up on the catalyst, reducing the isomerization ac-
tivity. At the end of the process cycle, the feed is switched to a fresh
catalyst bed, and the spent catalyst bed is regenerated by oxidizing the Total installed cost: Feedrate, Mbpd ISBL cost, $MM
coke with an air/nitrogen mixture. The butene isomerate is suitable for 10 8
making high purity isobutylene product. 15 11
30 20
C5 olefin skeletal isomerization (IsomPlus) Utility consumption: per barrel of feed (assuming an electric-motor-
A zeolite-based catalyst especially developed for this process pro- driven compressor) are:
vides near-equilibrium conversion of normal pentenes to isoamylene at Power, kWh 3.2
high selectivity and long process cycle times. Hydrocarbon feeds con- Fuel gas, MMBtu 0.44
taining n-pentenes, such as C5 raffinate, are processed in the skeletal Steam, MP, MMBtu 0.002
isomerization reactor without steam or other diluents, nor the addition Water, cooling, MMBtu 0.051
of catalyst activation agents to promote the reaction. Near-equilibrium Nitrogen, scf 57–250
conversion levels up to 72% of the contained normal pentenes are ob-
served at greater than 95% selectivity to isoamylenes. Installation: Two plants are in operation. Two licensed units are in vari-
ous stages of design.
Economics: The IsomPlus process offers the advantages of low capital
investment and operating costs coupled with a high yield of isobutylene Licensor: CDTECH and Lyondell Chemical Co.
or isoamylene. Also, the small quantity of heavy byproducts formed can
easily be blended into the gasoline pool. Capital costs (equipment, labor
and detailed engineering) for three different plant sizes are: click here to e-mail for more information
Isomerization Makeup hydrogen

Preheater
Application: For more refiners, the issue of benzene in the gasoline pool (for startup only)
is one of managing benzene production from the catalytic reformer. The
Light ends
two primary strategies to accomplish this goal include the minimization to FG
of benzene and benzene precursors in the catalytic reformer feed, or
Stabilizer
elimination of the benzene from the reformate after it is formed. The
UOP BenSat process can be applied in either of these strategies. The Reactor
process can operate in stand-along mode or in conjunction with C5 – C6
isomerization such as the UOP Penex-Plus process configuration.
Description: The UOP BenSat process was developed as a low-cost Feed/effluent

stand-alone option to treat C5 – C6 feedstocks that are high in benzene. exchanger
Benzene is saturated to C6 naphthenes. The catalyst used in this process Product
is highly selective for benzene saturation to C6 naphthenes.

Makeup hydrogen is provided in an amount slightly above the stoi- Feed
chiometric level required for benzene saturation. The heat of reaction
associated with benzene saturation is carefully managed to control tem-
perature rise across the reactor. Use of a relatively high space velocity in hydrogen consumption is minimized and is near the stoichiometric level
the reactor contributes to the unit’s cost-effectiveness. of three moles of hydrogen per mole of benzene saturated. The BenSat
process saturates benzene without an increase in Rvp.
Feed: Typical feeds include hydrotreated light straight-run (LSR) naphtha
or light reformate streams. The Ben Sat process is designed to handle 30 Installation: The first BenSat unit was started in 1994. Since then 13 ad-
vol% or more benzene in the feed. Sulfur suppresses activity, as expect- ditional units have been commissioned either as a stand-alone unit or
ed for any noble-metal-based catalyst. However, the suppression effect integrated with the Penex process in a Penex-Plus configuration. Several
is fully reversible by subsequent processing with clean feedstocks. additional units are in design and construction.
Yields: For feeds with 5–10 vol% benzene, the C5+ volumetric product Licensor: UOP.
yields are 101–106% of the feed. Because of high catalyst selectivity,

Isomerization Makeup gas
Application: The UOP Par-Isom process is an innovative application us-

ing high-performance nonchlorided-alumina catalysts for light-naphtha Offgas
isomerization. The process uses PI-242 catalyst, which approaches the
activity of chlorided alumina catalysts without requiring organic chloride
injection. The catalyst is regenerable and is sulfur and water tolerant.
Stabilizer
Description: The fresh C5 / C6 feed is combined with make-up and recy-
Rx
cle hydrogen which is directed to a heat exchanger, where the reactants
Product
are heated to reaction temperature. The heated combined feed is then separator
sent to the reactor. Either one or two reactors can be used in series, de-
pending on the specific application.
The reactor effluent is cooled and sent to a product separator where
the recycle hydrogen is separated from the other products. Recovered Reactor feed
recycle hydrogen is directed to the recycle compressor and back to the
reaction section. Liquid product is sent to a stabilizer column where light Isomerate
ends and any dissolved hydrogen are removed. The stabilized isomerate
product can be sent directly to gasoline blending.
Feed: Typical feed sources for the Par-Isom process include hydrotreated
light straight-run naphtha, light natural gasoline or condensate and light Installation: The first commercial Par-Isom process unit was placed in
raffinate from benzene extraction units. operation in 1996. There are currently 13 units in operation. The first
Water and oxygenates at concentrations of typical hydrotreated commercial application of PI-242 catalyst was in 2003. There are several
naphtha are not detrimental, although free water in the feedstock must units in operation with PI-242 catalyst successsfully meeting all perfor-
be avoided. Sulfur suppresses activity, as expected, for any noble-metal mance expectations.
based catalyst. However, the suppression effect is fully reversible by sub-
sequent processing with clean feedstocks. Licensor: UOP.
Yield: Typical product C5+ yields are 97 wt% of the fresh feed. The
product octane is 81 to 87, depending on the flow configuration and
feedstock qualities.

Isomerization
Application: Most of the implemented legislation requires limiting Makeup hydrogen
Gas to scrubbing
benzene concentration in the gasoline pool. This has increased the and fuel
demand for high-performance C5 and C6 naphtha isomerization tech-

Reactors
nology because of its ability to reduce the benzene concentration in Dryer
the gasoline pool while maintaining or increasing the pool octane. The
UOP Penex process has served as the primary isomerization technology Stabilizer
for upgrading C5 / C6 light straight-run naphtha.
Description: UOP’s innovative hydrogen-once-through (HOT) Penex pro-

cess results in subtantial savings in capital equipment and utility costs by
eliminating the need for a product separator or recycle-gas compressor.
The Penex process is a fixed-bed process that uses high-activity chlo- Dryer
ride-promoted catalysts to isomerize C5 / C6 paraffins to higher-octane-

Penex isomerate
branched components. The reaction conditions promote isomerization C5/C6 charge
and minimize hydrocracking.

Typically, two reactors, in series flow, are used to achieve high
onstream efficiency. The catalyst can be replaced in one reactor while
operation continues in the other. The stabilizer separates light gas from
the reactor effluent.
Feed: Penex process can process feeds with high levels of C6 cyclics and
Products: For typical C5 / C6 feeds, equilibrium will limit the product to C7 components. In addition, feeds with substantial levels of benzene
83 to 86 RONC on a single hydrocarbon pass basis. To achieve higher can be processed without the need for a separate saturation section.
octane, UOP offers several schemes in which lower octane components
are separated from the reactor effluent and recycled back to the reac- Installation: UOP is the leading world-wide provider of isomerization tech-
tors. These recycle modes of operation can lead to product octane as nology. More than 140 Penex units are in operation. Capacities range
high as 93 RONC, depending on feed quality. from 1,000 bpsd to more than 25,000 bpsd of fresh feed capacity.
Yields: Licensor: UOP.
Penex process: Octane 86
Penex process/DIH: Octane 90
Penex process/Molex process: Octane 91
DIP/Penex process/DIH: Octane 93

Isomerization
Application: The widely used UOP Butamer process is a high-efficien- (BTUPTDSVCCJOH
BOEGVFM
cy, cost effective means of meeting the demands for the production of
isobutane by isomerizing normal butane (nC4) to isobutane (i C4).
Motor-fuel alkylate is one blending component that has seen a sub-
stantial increase in demand because of its paraffinic, high-octane, low- 3FBDUPS
vapor pressure blending properties. Isobutane is a primary feedstock for
4UBCJMJ[FS
producing motor-fuel alkylate.
%SZFS
Description: UOP’s innovative hydrogen-once-through (HOT) Butamer pro-
cess results in substantial savings in capital equipment and utility costs by
eliminating the need for a product separator or recycle-gas compressor. O#VUBOF
Typically, two reactors, in series flow, are used to achieve high
%SZFS
onstream efficiency. The catalyst can be replaced in one reactor while
operation continues in the other. The stabilizer separates the light gas *TPNFSBUF
.BLFVQIZESPHFO
from the reactor effluent.
A Butamer unit can be integrated with an alkylation unit. In this
application, the Butamer unit feed is a side-cut from an isostripper col-
umn, and the stabilized isomerate is returned to the isostripper column.
Unconverted n-butane is recycled to the Butamer unit, along with n-bu-
tane from the fresh feed. Virtually complete conversion of n-butane to Installation: More than 70 Butamer units have been commissioned, and
isobutane can be achieved. additional units are in design or construction. Butamer unit feed capaci-
Feed: The best feeds for a Butamer unit contain the highest practical ties range from 800 to 35,000+ bpsd (74 to 3,250 tpd).
n-butane content, and only small amounts of isobutane, pentanes and Licensor: UOP.
heavier material. Natural gas liquids (NGL) from a UOP NGL recovery unit
can be processed in a Butamer unit.
Yield: The stabilized isomerate is a near-equilibrium mixture of isobutane
and n-butane with small amounts of heavier material. The light-ends
yield from cracking is less than 1 wt% of the butane feed.

Isooctene/isooctane
Application: Conversion of isobutylene contained in mixed-C4 feeds to C4 raffinate to
alky or dehydro
isooctane (2,2,4 tri-methyl pentane) to produce a high-quality gasoline
blendstock. The full-range of C4 feeds can be processed—from refinery
FCC, olefin-plant raffinate and isobutane dehydrogenation processes. C4 feed/
The NExOCTANE process is specifically developed to minimize conver- isobutylene Isobutylene Isooctene Isooctene
dimerization product recovery
sion costs of existing MTBE units and offers a cost-effective alternative
to MTBE production.
TBA recycle
Products: Isooctene and isooctane can be produced, depending on the Hydrogenation
Isooctane
refiner’s gasoline pool. Flexibility to retain MTBE/ETBE production ca-

pability is also possible for a multipurpose swing plant. Typical product
properties using C4 feed from FCC are:
Hydrogen
Isooctene Isooctane
RONC 101.1 99.1
MONC 85.7 96.3
(R+M)/2 93.4 97.7
Specific gravity 0.73 0.70
not require recirculation of hydrogen. In the refinery, the NExOCTANE
Vapor pressure, psia 1.8 1.8
process fits as a replacement to MTBE production, thus associated refin-
Distillation ASTM D86
ery operations are mostly unaffected.
T50, °F 221 216
T90, °F 238 234 Process efficiency: The NExOCTANE process is optimized to minimize
EP, °F 380 390 revamp costs but can also be designed for flexibility to multiple products
(isooctene, isooctane, MTBE or ETBE) or to maximize product yield. In
Description: In the NExOCTANE process, reuse of existing equipment fact, >99% conversion of isobutylene with a selectivity of over 91% to
from the MTBE unit is maximized. The process consists of three sections.
isooctene can be achieved.
First, isobutylene is dimerized to isooctene in the reaction section. The
dimerization reaction occurs in the liquid phase over a proprietary acidic Economics: Investment cost for revamps depend on the existing MTBE
ion-exchange resin catalyst, and it uses simple liquid-phase fixed-bed plant design, capacity and feedstock composition.
reactors. The isooctene product is recovered in a distillation system that
Utilities, typical per bbl isooctene product
generally can utilize the existing fractionation equipment. Recovered
Steam, 150-psig, lb 700
isooctene product can be further hydrogenated to produce isooctane. A
Electricity, kWh 2.0
highly efficient trickle-bed hydrogenation technology is offered with the 3
Water, cooling, ft 150
NExOCTANE process. This compact and cost-effective technology does
Continued 
Isooctene/isooctane, continued Reference: Hunszinger et al. “Case History: Converting an MTBE Unit to
Isooctane Operation,” Hydrocarbon Processing, September 2003, pp.
57–62.
Installation: The NExOCTANE process has been in commercial operation Halinen et al., “Economic Evaluation of Production and Blending of
since 2002. Current installed production capacity is over 37,000 bpd in Iso-octene and Iso-octane Produced by Isobutylene Dimerization,” 2005
both refinery and dehydrogenation applications. Recent projects include NPRA Annual Meeting. March 13–15, 2005, AM-05-28, San Francisco.
MTBE unit conversions at Valero’s Corpus Christi refinery and the BP
Carson refinery. Licensor: KBR and Neste Jacobs OY.

Isooctene/isooctane Water wash Mixer 1st Debutanizer Finishing Isooctene

column reactor reactor column C raffinate
Application: New processes, RHT-isooctene and RHT-isooctane, can be 5 4
used to revamp existing MTBE units to isooctene/isooctane production. 3 12 Selectivator

LP recycle IPA
Feeds include C4 iso-olefin feed from FCC, steam crackers, thermal Water wash H2
crackers or on-purpose iso-butylene from dehydrogenation units. The 7
2 9
13
processes uses a unique configuration for dimerization. A new selectiva- 10 11
tor is used, together with a dual-bed catalyst. 8
4
C4 feed (1)
The configuration is capable of revamping conventional or reactive
1
distillation MTBE units. The process provides higher conversion, better 14
Isooctene
Water to treatment (1) 1
selectivity, conventional catalyst, and a new selectivator supports with to 3% propylene in feed
product
longer catalyst life with a dual catalyst application. Mixer 1st reactor KO drum Isooctene
6
Isooctene CW stripper
The process is designed to apply a hydrogenation unit to convert 5 Vent
7
isooctene into isooctane, if desired, by utilizing a dual-catalyst system, 6 11
in the first and finishing reactors. The process operates at lower pressure H2 1 6
and provides lower costs for the hydrogenation unit. Finishing
reactor 4
Description: The feed is water washed to remove any basic compounds 9
that can poison the catalyst system. Most applications will be directed 3
toward isooctene production. However as olefin specifications are re- Hydrogen
10
Isooctene product
6
quired, the isooctene can be hydrogenated to isooctane, which is an
excellent gasoline blending stock.
The RHT isooctene process has a unique configuration; it is flexible
and can provide low per pass conversion through dilution, using a new provides the dilution, and reactor effluent is fed to the column at mul-
selectivator. The dual catalyst system also provides multiple advantages. tiple locations. Recycling does not increase column size due to the
The isobutylene conversion is 97–99 %, with better selectivity and yield unique configuration of the process. The isooctene is taken from the
together with enhanced catalyst life. The product is over 91% C8 olefins, debutanizer column bottom and is sent to OSBL after cooling or as is
and 5 – 9% C12 olefins, with very small amount of C16 olefins. sent to hydrogenation unit. The C4s are taken as overhead stream and
The feed after water wash, is mixed with recycle stream, which sent to OSBL or alkylation unit. Isooctene/product, octane (R+M)/2 is
provides the dilution (also some unreacted isobutylene) and is mixed expected to be about 105.
with a small amount of hydrogen. The feed is sent to the dual-bed re- If isooctane is to be produced the debutanizer bottom, isooctene
actor for isooctene reaction in which most of isobutylene is converted product is sent to hydrogenation unit. The isooctene is pumped to the
to isooctene and codimer. The residual conversion is done with single- required pressure (which is much lower than conventional processes),
resin catalyst via a side reactor. The feed to the side reactor is taken as mixed with recycle stream and hydrogen and is heated to the reaction
a side draw from the column and does contain unreacted isobutylene,
selectivator, normal olefins and non-reactive C4s. The recycle stream Continued 
Isooctene/Isooctane, continued Economics:
Isooctene Isooctane1
temperature before sending it the first hydrogenation reactor. This reac- CAPEX ISBL, MM USD
tor uses a nickel (Ni) or palladium (Pd) catalyst. (US Gulf Coast 1Q 06, 1,000 bpd) 8.15 5.5
If feed is coming directly from the isooctene unit, only a start-up Utilities basis 1,000-bpd isooctene/isooctane
heater is required. The reactor effluent is flashed, and the vent is sent Power, kWh 65 105
to OSBL. The liquid stream is recycled to the reactor after cooling (to Water, cooling, m /h 3 154 243
remove heat of reaction) and a portion is forwarded to the finishing Steam, HP, kg/h 3,870 4,650
reactor—which also applies a Ni or Pd catalyst (preferably Pd catalyst) — Basis: FCC feed (about 15 –20% isobutelene in C4 mixed stream)
and residual hydrogenation to isooctane reaction occurs. The isooctane 1These utilities are for isooctene / isooctane cumulative.
product, octane (R+M)/2 is >98.
The reaction occurs in liquid phase or two phase (preferably two Installation: Technology is ready for commercial application.
phases), which results in lower pressure option. The olefins in isooctene
product are hydrogenated to over 99%. The finishing reactor effluent is Licensor: Refining Hydrocarbon Technologies LLC.
sent to isooctane stripper, which removes all light ends, and the product
is stabilized and can be stored easily. click here to e-mail for more information
Isooctene/isooctane
Application: The Snamprogetti dimerization/hydrogenation technology
is used to produce isooctene/isooctane—high-octane compounds (rich Oxygenate feed 5 Oxygenate
to reactors
in C8 ) for gasoline blending. 6
2
Feed: C4 streams from steam cracker, fluid catalytic cracking (FCC) and
3
isobutane dehydrogenation units with isobutene contents ranging from C4 raffinate
15 wt% to 50 wt %. Oxygenate
to reactors
1
Products: Isooctene and Isooctane streams contain at least 85 wt% of
C8s with less than 5,000 ppm of oligomers higher than C12s. C4 feed
4
Description. Depending on conversion and investment requirements
various options are available to reach isobutene conversion ranging from
Isooctane
85 wt% to 99 wt%. Isooctene
7
Oxygenates, such as methanol, methyl tertiary butyl ether (MTBE)
and/or tert-butyl alcohol (TBA), are used as “selectivator” to improve se-
lectivity of the dimerization reaction while avoiding formation of heavier
oligomers. tion (Dimer8 process) the plant configuration can be optionally modified
A high conversion level of isobutene (99 wt%) can be reached with with the introduction of a catalytic distillation (CD Column), to have an
a double-stage configuration where, in both stages, water cooled tubu- alternative scheme particularly suitable for revamping of refinery MTBE
lar reactors (WCTR), (1) and (2), are used for the isobutene dimerization units.
to maintain an optimal temperature control inside the catalytic bed.
The reactors effluents are sent to two fractionation columns (3) and
Utilities: (Referred to a feedstock from isobutane dehydrogenation at
50% wt isobutylene concentrate)
(5) to separate the residual C4 from the mixture oxygenate-dimers. At
Steam 1 t / t isooctene
the end, the oxygenates are recovered from raffinate C4 (6) and from
Water, cooling 65 m³/ t isoocetene
dimers (column 4) and then recycled to reactors.
Power 15 kWh / t isooctene
The isooctene product, collected as bottom of column (4), can be
sent to storage or fed to the hydrogenation unit (7) to produce the satu- Installation: Five industrial tests have been carried out with different
rate hydrocarbon stream—isooctane. feedstock, and two units have been licensed by Snamprogetti.
Due to a joint development agreement between Snamprogetti and
Catalytic Distillation Technologies (CDTech) for the isobutene dimeriza- Licensor: Snamprogetti, a company of Saipem.

Isooctene/isooctane, conversion
of refinery MTBE units Feed
wash
Primary
reactor
Catalytic
distillation
Oxygenate
recovery
column column
Makeup oxygenate C4 raffinate
Application: The Dimer8 process uses a fixed-bed reactor followed by Oxygenate
recycle
catalytic distillation to achieve final isobutene conversion at high dim-
er selectivity. The Dimer8 process is the most attractive technology for
converting a refinery-based methyl tertiary butyl ether (MTBE) unit to Water
isooctene/isooctane production.
Description: The selective dimerization of isobutenes over acidic ion-

C4 feed
exchange resin produces isooctene or di-isobutylene (DIB). Oxygenates Isooctene
such as methanol, MTBE, water or tert-butyl-alcohol (TBA) are used Offgas

Wastewater
as selectivators for the dimerization reaction, to prevent formation of H2 feed Olefin Isooctane
heavier oligomers. The Dimer8 process uses a fixed-bed reactor followed saturation unit
by catalytic distillation to achieve final isobutene conversion at high di-
mer selectivity.
The primary fixed-bed reactor can utilize a boiling point reactor or a
water-cooled tubular reactor (WCTR) design depending on the finished
product and operational requirements of the refiner. Either reactor can Process advantages include:
be used to achieve high isobutylene conversion with excellent dimmer • E asy implementation, minimum revamp changes, low capital cost,
selectivity. short schedule
The unique catalytic distillation (CD) column combines reaction and • 90+% isobutylene conversion
distillation in a single unit operation. Continuous removal of heavier • 80+% C8 selectivity
dimer product from the reaction zone enables further conversion of • High flexibility
isobutene without loss of dimer selectivity. The use of CD eliminates the • Simple control
need for any downstream reaction/fractionation system to achieve such • High octane/low Rvp blend stock
performance. • Low utilities.
Isooctene can be used as a gasoline blendstock due to its excellent
characteristics. Should olefin restrictions require a paraffinic product, the Licensor: Jointly licensed CDTECH and Snamprogetti.
isooctene product can be saturated to isooctane in a trickle-bed hydro-
genation reactor. Hydrogenation uses a base or noble metal catalyst
depending on the feed contamination level.

Hydrofinishing/hydrotreating
Application: Process to produce finished lube-base oils and special oils. Reactor
Stm
Reactor Stripper Vent gas
Feeds: Dewaxed solvent or hydrogen-refined lube stocks or raw vacuum feed heater to heater
distillates for lubricating oils ranging from spindle oil to machine oil and Stm
bright stock.
HP separator
Products: Finished lube oils (base grades or intermediate lube oils) and To fuel
Drier
gas (H2S
special oils with specified color, thermal and oxidation stability. Makeup Recycle absorption)
gas comp. gas comp. Stm
Description: Feedstock is fed together with make-up and recycle hydro-
gen over a fixed-bed catalyst at moderate temperature and pressure.
The treated oil is separated from unreacted hydrogen, which is recycled. Makeup LP separator Sour water
Very high yields product are obtained. hydrogen
Slop oil
For lube-oil hydrofinishing, the catalytic hydrogenation process is
operated at medium hydrogen pressure, moderate temperature and low Feed
Oil product
hydrogen consumption. The catalyst is easily regenerated with steam
and air.
Operating pressures for hydrogen-finishing processes range from
25 to 80 bar. The higher-pressure range enables greater flexibility with
regard to base-stock source and product qualities. Oil color and thermal
stability depend on treating severity. Hydrogen consumption depends Installation: Numerous installations using the Uhde (Edeleanu) propri-
on the feed stock and desired product quality. etary technology are in operation worldwide. The most recent reference
is a complete lube-oil production facility licensed to the state of Turk-
Utility requirements (typical, Middle East crude), units per m3 of feed: menistan.
Electricity, kWh 15
Steam, MP, kg 25 Licensor: Uhde GmbH.
Steam, LP, kg 45
Fuel oil, kg 3
Water, cooling, m3 10

Lube extraction
Application: Bechtel’s MP Refining process is a solvent-extraction pro-
2
cess that uses N-methyl-2-pyrrolidone (NMP) as the solvent to selec- Feed 3 4
tively remove the undesirable components of low-quality lubrication oil,
START 5
which are naturally present in crude oil distillate and residual stocks. 1
The unit produces paraffinic or naphthenic raffinates suitable for further
processing into lube-base stocks. This process selectively removes aro- Stm. Water
matics and compounds containing heteroatoms (e.g., oxygen, nitrogen Stm.
and sulfur).
Refined oil
Products: A raffinate that may be dewaxed to produce a high-qual- Extract
ity lube-base oil, characterized by high viscosity index, good thermal
and oxidation stability, light color and excellent additive response. The
byproduct extracts, being high in aromatic content, can be used, in
some cases, for carbon black feedstocks, rubber extender oils and other
nonlube applications where this feature is desirable. Economics:
Description: The distillate or residual feedstock and solvent are contact- Investment (Basis: 10,000-bpsd feedrate
ed in the extraction tower (1) at controlled temperatures and flowrates capacity, 2008 US Gulf Coast), $/bpsd 6,000
required for optimum countercurrent, liquid-liquid extraction of the Utilities, typical per bbl feed:
feedstock. The extract stream, containing the bulk of the solvent, exits Fuel, 103 Btu (absorbed) 100
the bottom of the extraction tower. It is routed to a recovery section Electricity, kWh 2
to remove solvent contained in this stream. Solvent is separated from Steam, lb 5
the extract oil by multiple-effect evaporation (2) at various pressures, Water, cooling (25°F rise), gal 600
followed by vacuum flashing and steam stripping (3) under vacuum. Installation: This process is being used in 15 licensed units to produce high-
The raffinate stream exits the overhead of the extraction tower and is quality lubricating oils. Of this number, eight are units converted from phe-
routed to a recovery section to remove the NMP solvent contained in nol or furfural, with another three units under license for conversion.
this stream by flashing and steam stripping (4) under vacuum.
Overhead vapors from the steam strippers are condensed and com- Licensor: Bechtel Corp.
bined with solvent condensate from the recovery sections and are dis-
tilled at low pressure to remove water from the solvent (5). Solvent is
recovered in a single tower because NMP does not form an azeotrope
with water, as does furfural. The water is drained to the oily-water sew-
er. The solvent is cooled and recycled to the extraction section.
Continued 
Lube extraction
Application: Bechtel’s Furfural Refining process is a solvent-extraction
process that uses furfural as the solvent to selectively remove undesir-
2
able components of low lubrication oil quality, which are naturally pres- Feed 3 4
ent in crude oil distillate and residual stocks. This process selectively re-
START 5 6
moves aromatics and compounds containing heteroatoms (e.g., oxygen, 1
nitrogen and sulfur). The unit produces paraffinic raffinates suitable for Stm.
further processing into lube base stocks. Stm.
Stm.
Products: A raffinate that may be dewaxed to produce a high-qual- Water
ity lube-base oil, characterized by high viscosity index, good thermal Refined oil
and oxidation stability, light color and excellent additive response. The
Extract
byproduct extracts, being high in aromatic content, can be used, in
some cases, for carbon black feedstocks, rubber extender oils and other
nonlube applications where this feature is desirable.
Description: The distillate or residual feedstock and solvent are contact-

ed in the extraction tower (1) at controlled temperatures and flowrates
required for optimum countercurrent, liquid-liquid extraction of the
feedstock. The extract stream, containing the bulk of the solvent, exits Economics:
the bottom of the extraction tower. It is routed to a recovery section to Investment (Basis: 10,000-bpsd feed rate capacity,
remove solvent contained in this stream. Solvent is separated from the 2008 US Gulf Coast), $/ bpsd 6,200
extract oil by multiple-effect evaporation (2) at various pressures, fol- Utilities, typical per bbl feed:
lowed by vacuum flashing and steam stripping (3) under vacuum. The Fuel, 103 Btu (absorbed) 120
raffinate stream exits the overhead of the extraction tower and is routed Electricity, kWh 2
to a recovery section to remove the furfural solvent contained in this Steam, lb 5
stream by flashing and steam stripping (4) under vacuum. Water, cooling (25°F rise), gal 650
The solvent is cooled and recycled to the extraction section. Over-
Installation: For almost 60 years, this process has been or is being used
head vapors from the steam strippers are condensed and combined with
in over 100 licensed units to produce high-quality lubricating oils.
the solvent condensate from the recovery sections and are distilled at
low pressure to remove water from the solvent. Furfural forms an azeo- Licensor: Bechtel Corp.
trope with water and requires two fractionators. One fractionator (5)
separates the furfural from the azeotrope, and the second (6) separates
water from the azeotrope. The water drains to the oily-water sewer. The
solvent is cooled and recycled to the extraction section. click here to e-mail for more information
Lube hydrotreating
Application: The Bechtel Hy-Finishing process is a specialized hydrotreating
technology to remove impurities and improve the quality of paraffinic
Offgas
and naphthenic lubricating base oils. In the normal configuration, the
hydrogen finishing unit is located in the processing scheme between the
1
solvent extraction and solvent dewaxing units for a lube plant operating
3
on an approved lube crude. In this application, the unit operates under
mild hydrotreating conditions to improve color and stability, to reduce Feed
sulfur, nitrogen, oxygen and aromatics, and to remove metals. START
Unstable naphtha
Another application is Hy-Starting, which is a more severe hydro- 2
treating process (higher pressure and lower space velocity) and upgrades
H2
distillates from lower-quality crudes. This unit is usually placed before 4 5
solvent extraction in the processing sequence to upgrade distillate qual-
ity and, thus, improve extraction yields at the same raffinate quality. Wax product
Description: Hydrocarbon feed is mixed with hydrogen (recycle plus

makeup), preheated, and charged to a fixed-bed hydrotreating reac-
tor (1). Reactor effluent is cooled in exchange with the mixed feed-hy-
drogen stream. Gas-liquid separation of the effluent occurs first in the
hot separator (2) then in the cold separator (3). The hydrocarbon liquid
stream from each of the two separators is sent to the product stripper (4)
to remove the remaining gas and unstabilized distillate from the lube-oil
product. The product is then dried in a vacuum flash (5). Gas from the
cold separator is amine-scrubbed (6) to remove H2S before compression
in the recycle hydrogen compressor (7).
Economics:
Investment (Basis 7,000-bpsd feedrate capacity,
2008 US Gulf Coast), $/bpsd 7,700
Utilities, typical per bbl feed:
Fuel, 103 Btu (absorbed) 20
Electricity, kWh 5
Steam, lb 15
Water, cooling (25°F rise), gal 400
Licensor: Bechtel Corp.
Lube hydrotreating
Application: Hy-Raff is a new process to hydrotreat raffinates from an Makeup H2
extraction unit of a solvent-based lube oil plant for upgrading standard
Group I lube-base oils to produce Group II base oils. Sulfur is reduced to
below 0.03 wt% and saturates are increased to greater than 90 wt%. 7
The integration of this process into an existing base oil plant allows 1
the operator to cost-effectively upgrade base-oil products to the new
6 Amine
specifications rather than scrapping the existing plant and building an
Feed
expensive new hydrocracker-based plant. 3
START
The product from the Hy-Raff unit is a lube-base oil of sufficient
quality to meet Group II specifications. The color of the finished prod- 2 Unstable naphtha
uct is significantly improved over standard-base oils. Middle distillate
byproducts are of sufficient quality for blending into diesel. 4 5
Stm.
Description: Raffinate feed is mixed with hydrogen (recycle plus make- Lube oil
up), preheated, and charged to a fixed-bed hydrotreating reactor (1).
The reactor effluent is cooled in exchange with the mixed feed-hydrogen
stream. Gas-liquid separation of the effluent occurs first in the hot sepa-
rator (2) then in the cold separator (3). The hydrocarbon liquid stream
from each of the two separators is sent to the product stripper (4) to
remove the remaining gas and unstabilized distillate from the lube-oil
product, and product is dried in a vacuum flash (5). Gas from the cold
separator is amine-scrubbed (6) for removal of H2S before compression
in the recycle-hydrogen compressor (7).
Economics:
2008 U.S. Gulf Coast), $/bpsd 10,700
Utilitiies, typical per bbl feed:
Electricity, kWh 5
Steam, lb 15
Water, cooling (25°F rise), gal 200
Licensor: Bechtel Corp. click here to e-mail for more information


Water, gasoline
Application: The Revivoil process can be used to produce high yields of Light ends
premium quality lube bases from spent motor oils. Requiring neither Gas oil
Hydrotreated gas oil
acid nor clay treatment steps, the process can eliminate environmental Water and
lights removal TDA
and logistical problems of waste handling and disposal associated with column
conventional re-refining schemes.
Base
Hydrofinishing oils
Description: Spent oil is distilled in an atmospheric flash distillation Spent oil
column to remove water and gasoline and then sent to the Thermal
Deasphalting (TDA) vacuum column for recovery of gas oil overhead Hydrogen
DAO
and oil bases as side streams. The energy-efficient TDA column features
excellent performance with no plugging and no moving parts. Metals (Optional)
Asphalt
and metalloids concentrate in the residue, which is sent to an optional Selectopropane
Selectopropane unit for brightstock and asphalt recovery. This scheme
is different from those for which the entire vacuum column feed goes
through a deasphalting step; Revivoil’s energy savings are significant,
and the overall lube oil base recovery is maximized. The results are sub-
stantial improvements in selectivity, quality and yields. Health & safety and environment: The high-pressure process is in line
The final, but very important step for base oil quality is a specific with future European specifications concerning carcinogenic PNA com-
hydrofinishing process that reduces or removes remaining metals and pounds in the final product at a level inferior to 5 wppm (less than 1
metalloids, Conradson Carbon, organic acids, and compounds contain- wt% PCA - IP346 method).
ing chlorine, sulfur and nitrogen. Color, UV and thermal stability are
restored and polynuclear aromatics are reduced to values far below the Economics: The process can be installed stepwise or entirely. A simpler
latest health thresholds. Viscosity index remains equal to or better than scheme consists of the atmospheric flash, TDA and hydrofinishing unit
the original feed. For metal removal (> 96%) and refining-purification and enables 70%– 80% recovery of lube oil bases. The Selectopropane
duty, the multicomponent catalyst system is the industry’s best. unit can be added at a later stage, to bring the oil recovery to the 95%
level on dry basis. For two plants of equal capacity, payout times before
Product quality: The oil bases are premium products; all lube oil base taxes are two years in both cases.
specifications are met by Revivoil processing from Group 1 through
Installation: Ten units have been licensed using all or part of the Revivoil
Group 2 of the API basestocks definitions. Besides, a diesel can be ob-
Technology.
tained, in compliance with the EURO 5 requirements (low sulfur).
Licensor: Axens and Viscolube SpA.

Lube treating
Application: Process to produce lube oil raffinates with high viscosity Raffinate
flasher
index from vacuum distillates and deasphalted oil. stripper
Raffinate
Extraction mix buffer
Feeds: Vacuum distillate lube cuts and deasphalted oils. tower Stm Raffinate
Products: Lube oil raffinates of high viscosity indices. The raffinates con- Extract
flasher
Extract
tain substantially all of the desirable lubricating oil components present Extract flash
stripper
in the feedstock. The extract contains a concentrate of aromatics that mix system
settler
may be utilized as rubber oil or cracker feed. Stm
Extract
Description: This liquid-liquid extraction process uses furfural or N-

Stm Furfural Solvent
methyl pyrrolidone (NMP) as the selective solvent to remove aromat- Feed stripper drying
deaerator system
ics and other impurities present in the distillates and deasphalted oils. buffer Water
stripper
The solvents have a high solvent power for those components that are
Stm
unstable to oxygen as well as for other undesirable materials includ- Feed
Decanter Stm
ing color bodies, resins, carbon-forming constituents and sulfur com- Sewer
pounds. In the extraction tower, the feed oil is introduced below the top
at a predetermined temperature. The raffinate phase leaves at the top
of the tower, and the extract, which contains the bulk of the furfural, is
withdrawn from the bottom. The extract phase is cooled and a so-called
“pseudo raffinate“ may be sent back to the extraction tower. Multi- Installation: Numerous installations using the Uhde (Edeleanu) propri-
stage solvent recovery systems for raffinate and extract solutions secure etary technology are in operation worldwide. The most recent is a com-
energy efficient operation. plete lube-oil production facility licensed to the state of Turkmenistan.
Utility requirements (typical, Middle East crude), units per m3 of feed: Licensor: Uhde GmbH.
Electricity, kWh 10
Steam, MP, kg 10
Steam, LP, kg 35
Fuel oil, kg 20
Water, cooling, m3 20


Water, gasoline
Application: The Revivoil process can be used to produce high yields of
Light ends
premium quality lube bases from spent motor oils. Requiring neither Gas oil
acid nor clay treatment steps, the process can eliminate environmental Water and Hydrotreated gas oil
lights removal
and logistical problems of waste handling and disposal associated with TDA
column
conventional re-refining schemes.
Base
Hydrofinishing
Description: Spent oil is distilled in an atmospheric flash distillation oils
Spent oil
column to remove water and gasoline and then sent to the Thermal
Deasphalting (TDA) vacuum column for recovery of gas oil overhead Hydrogen
and oil bases as side streams. The energy-efficient TDA column features DAO
excellent performance with no plugging and no moving parts. Metals

(Optional)
and metalloids concentrate in the residue, which is sent to an optional Asphalt
Selectopropane
Selectopropane unit for brightstock and asphalt recovery. This scheme
is different from those for which the entire vacuum column feed goes
through a deasphalting step; Revivoil’s energy savings are significant,
and the overall lube oil base recovery is maximized. The results are sub-
stantial improvements in selectivity, quality and yields. Health & safety and environment: The high-pressure process is in line
The final, but very important step for base oil quality is a specific with future European specifications concerning carcinogenic PNA com-
hydrofinishing process that reduces or removes remaining metals and pounds in the final product at a level inferior to 5 wppm (less than 1
metalloids, Conradson Carbon, organic acids, and compounds con- wt% PCA—IP346 method).
taining chlorine, sulfur and nitrogen. Color, UV and thermal stability
are restored and polynuclear aromatics are reduced to values far be- Economics: The process can be installed stepwise or entirely. A simpler
low the latest health thresholds. Viscosity index remains equal to or scheme consists of the atmospheric flash, TDA and hydrofinishing unit
better than the original feed. For metal removal (> 96%) and refining- and enables 70%-80% recovery of lube oil bases. The Selectopropane
purification duty, the multicomponent catalyst system is the industry’s unit can be added at a later stage, to bring the oil recovery to the 95%
best. level on dry basis. For two plants of equal capacity, payout times before
taxes are two years in both cases.
Product quality: The oil bases are premium products; all lube oil base
specifications are met by Revivoil processing from Group 1 through Installation: Ten units have been licensed using all or part of the Revivoil
Group 2 of the API basestocks definitions. Besides, a diesel can be ob- Technology.
tained, in compliance with the EURO 5 requirements (low sulfur). Licensor: Axens and Viscolube SpA.

Butene-1 recovery
Application: The Snamprogetti butene-1 recovery technology allows ex-
tracting a C4 cut as a very high-purity butene-1 stream that is suitable as Light ends
a comonomer for polyethylene production.
Feed: Olefinic C4 streams from steam cracker or fluid catalytic cracking

(FCC) unit can be used as feedstock for the recovery of butene-1.
C4 feed
1 2
Description: The Snamprogetti process for butene-1 is based on propri-
etary binary interaction parameters that are specifically optimized after
experimental work to minimize investment cost and utilities consump-
tion. The plant is a super-fractionation unit composed of two fraction-
ation towers provided with traditional trays. Heavy ends Butene-1
Depending on the C4 feed composition, Snamprogetti offers differ-

ent possible processing schemes. In a typical configuration, the C4 feed
is sent to the first column (1) where the heavy hydrocarbons (mainly
n-butane and butenes-2) are removed as bottom stream. In the second
column (2), the butene-1 is recovered at the bottom and the light-ends
(mainly isobutane) are removed as overhead stream. Installation: Four units have been licensed by Snamprogetti.
This plant covers a wide range of product specifications including
Licensor: Snamprogetti, a company of Saipem.
the more challenging level of butene-1 purities (99.3 wt%–99.6 wt%).
Utilities:
Steam 4 t / t 1-butene
Water, cooling 110 m³/ t 1-butene
Power 43 kWh / t 1-butene

Isobutylene, from MTBE

decomposition
Application: To decompose commercial-grade methyl tertiary butyl ether Methanol
MTBE Methanol
(MTBE) feed to high-purity isobutylene and commercial-grade methanol. recovery
Isobutylene purity of greater than 99.9% is achievable. Lights Methanol/
Washwater
MTBE/water
Description: By utilizing the CDIB technology, commercial MTBE feed- Fuel
MTBE Pre- MTBE Product
stock is first fractionated to remove light ends and heavies. The high- fractionation
Reaction
MTBE purification
purity MTBE is then fed to the decomposition reactor where MTBE is isobutylene High-purity
methanol isobutylene
converted to isobutylene and methanol. The decomposition reaction Heavies
takes place in vapor phase and is performed with high selectivity. Heat MTBE
of reaction is supplied by medium-pressure steam. The methanol is ex-
tracted from the reactor effluent in a water wash. The aqueous stream
is fractionated to recover the wash water and MTBE for recycle, and to
produce high-quality methanol. The water-washed reactor effluent is
fractionated to remove heavies (including MTBE for recycle) and light
ends, leaving a high-purity (>99.9%) isobutylene product.
• High isobutylene selectivity
Economics: The CDIB technology can be provided in a stand-alone unit • High flexibility
or can be coupled with a CDMtbe unit to provide a very efficient inte- • Low capital cost
grated unit. Capital and operating costs are reduced when compared • High purity isobutylene
to separate units. Isobutylene product purification can be simplified by • No corrosion problems
providing recycle to the MTBE unit. CDIB methanol recovery can be sim- • Significant operating experience.
plified by combining it with MTBE unit methanol recovery in common
equipment. Installation: There are three operational units at present; two are in op-
eration since 1987 and 1989.
Process advantages include:
• Simple and effective control Licensor: CDTECH.
• High MTBE conversion

Isobutylene, high-purity Light ends
Application: The Snamprogetti methyl tertiary butyl ether (MTBE) crack-

Ether
ing technology allows producing high-purity isobutylene, which can be
used as monomer for elastomers (polyIsobutylene, butyl rubber), and/ MTBE feed
3 4
or as intermediate for the production of chemicals (MMA, tertiary-butyl
phenols, tertiary-butyl amines, etc.)
Feed: MTBE can be used as the feedstock in the plant; in case of high level 1
2 High-purity
of impurities, a purification section can be added before the reactor. MeOH isobutene
Description: The MTBE cracking technology is based on proprietary cat-

alyst and reactor that carry out the reaction with excellent flexibility, mild 5
conditions as well as without corrosion and environmental problems.
With Snamprogetti consolidated technology, it is possible to reach
the desired isobutylene purity and production with only one tubular re-
actor (1) filled with a proprietary catalyst characterized for the right bal-
ance between acidity and activity.
The reaction effluent, mainly consisting of isobutylene, methanol
and unconverted MTBE, is sent to a counter-current washing tower (2) Utilities:
to separate out methanol and then to two fractionation towers to sepa- Steam 5 t / t isobutylene
rate isobutylene from unconverted MTBE, which is recycled to the reac- Water, cooling 186 m³/t isobutylene
tor (3) and from lights compounds (4). The produced isobutylene has a Power 17.4 kWh / t isobutylene
product purity of 99.9+ wt%.
Installation: Four units have been licensed by Snamprogetti.
The methanol/water solution leaving the washing tower is fed to the
alcohol recovery section (5) where high-quality methanol is recovered. Licensor: Snamprogetti, a company of Saipem.

Olefins recovery
Application: Recover high-purity hydrogen (H2) and C2+ liquid products
from refinery offgases using cryogenics.

Description: Cryogenic separation of refinery offgases and purges con-
taining 10%– 80%
H2 and 15% – 40% hydrocarbon liquids such as eth- 3FmOFSZ
PGGHBTTFT
ylene, ethane, propylene, propane and butanes. Refinery offgases are
optionally compressed and then pretreated (1) to remove sulfur, carbon
dioxide ( CO2 ), H2 O and other trace impurities. Treated feed is partially
condensed in an integrated multi-passage exchanger system (2) against
returning products and refrigerant.

Separated liquids are sent to a demethanizer (3) for stabilization 4/(PS $QSPEVDU
while hydrogen is concentrated (4) to 90% – 95%+ purity by further GVFM $
cooling. Methane, other impurities, and unrecovered products are sent $
)JHIQVSJUZ
$
to fuel or optionally split into a synthetic natural gas (SNG) product and IZESPHFO
low-Btu fuel. Refrigeration is provided by a closed-loop system (5). Mixed
C2+ liquids from the demethanizer can be further fractionated (6) into
finished petrochemical feeds and products such as ethane, ethylene,
propane and propylene.
Installations: Five operating refinery offgas cryogenic systems processing
Operating conditions: Feed capacities from 10 to 150+ million scfd. Feed
FCC offgas, cat reformer offgas, hydrotreater purge gas, coker offgas
pressures as low as 150 psig. Ethylene recoveries are greater than 95%,
and refinery fuel gas. Several process and refrigeration schemes used
with higher recoveries of ethane and heavier components. Hydrogen
since 1987 with the most recent plant startup in 2001.
recoveries are better than 95% recovery.
Reference: US Patents 6,266,977 and 6,560,989.
Economics: Hydrogen is economically co-produced with liquid hydro-
Trautmann, S. R. and R. A. Davis, “Refinery offgases—alternative
carbon products, especially ethylene and propylene, whose high value
sources for ethylene recovery and integration,” AIChE Spring Meeting,
can subsidize the capital investment. High hydrocarbon liquid products
New Orleans, March 14, 2002, Paper 102d.
recovery is achieved without the cost for feed compression and subse-
quent feed expansion to fuel pressure. Power consumption is a function Licensor: Air Products and Chemicals Inc.
of hydrocarbon quantities in the feed and feed pressure. High-purity
hydrogen is produced without the investment for a “back-end” PSA
system. Project costs can have less than a two-year simple payback.

Olefins—butenes extractive distillation

Application: Separation of pure C4 olefins from olefinic/paraffinic C4 mix- C4 paraffins
tures via extractive distillation using a selective solvent. BUTENEX is the
Uhde technology to separate light olefins from various C4 feedstocks,
which include ethylene cracker and FCC sources.
Description: In the extractive distillation (ED) process, a single-com- C4 olefins

Extractive
pound solvent, N-Formylmorpholine (NFM), or NFM in a mixture with C4 distillation Stripper
fraction
further morpholine derivatives, alters the vapor pressure of the com- column column
ponents being separated. The vapor pressure of the olefins is lowered
more than that of the less soluble paraffins. Paraffinic vapors leave the
top of the ED column, and solvent with olefins leaves the bottom of the
ED column.
The bottom product of the ED column is fed to the stripper to Solvent + olefins
Solvent
separate pure olefins (mixtures) from the solvent. After intensive heat
exchange, the lean solvent is recycled to the ED column. The solvent,
which can be either NFM or a mixture including NFM, perfectly satisfies
the solvent properties needed for this process, including high selectivity,
thermal stability and a suitable boiling point.
Economics: Installation: Two commercial plants for the recovery of n - butenes have
Consumption per metric ton of FCC C4 fraction feedstock: been installed since 1998.
Steam, t / t 0.5 – 0.8
Water, cooling ( DT = 10°C ), m3/ t 15.0 Licensor: Uhde GmbH.
Electric power, kWh/t 25.0
Product purity:
n - Butene content 99.+ wt.– % min.
Solvent content 1 wt.– ppm max.

Olefins—dehydrogenation of light
paraffins to olefins HP steam
Air
Application: The Uhde STeam Active Reforming (STAR) process produces Fuel gas
Feed
(a) propylene as feedstock for polypropylene, propylene oxide, cumene, preheater Raw gas
compression
Star Fuel gas
acrylonitrile or other propylene derivatives, and (b) butylenes as feed- reformer
stock for methyl tertiary butyl ether (MTBE), alkylate, isooctane, polybu-
tylenes or other butylene derivatives. O2/air
Oxy Heat Gas
Feed: Liquefied petroleum gas (LPG) from gas fields, gas condensate reactor recovery separation
fields and refineries.

Hydrocarbon feed
Olefin
product
Product: Propylene (polymer- or chemical-grade); isobutylene; n-butylenes; Boiler feed water
Fractionation
Process condensate
high-purity hydrogen (H2) may also be produced as a byproduct.
Process steam Hydrocarbon
recycle
Description: The fresh paraffin feedstock is combined with paraffin re-
cycle and internally generated steam. After preheating, the feed is sent
to the reaction section. This section consists of an externally fired tubular
fixed-bed reactor (Uhde reformer) connected in series with an adiabat-
ic fixed-bed oxyreactor (secondary reformer type). In the reformer, the Apart from light-ends, which are internally used as fuel gas, the
endothermic dehydrogenation reaction takes place over a proprietary, olefin is the only product. High-purity H2 may optionally be recovered
noble metal catalyst. from light-ends in the gas separation section.
In the adiabatic oxyreactor, part of the hydrogen from the intermediate
product leaving the reformer is selectively converted with added oxygen Economics: Typical specific consumption figures (for polymer-grade
or air, thereby forming steam. This is followed by further dehydrogenation propylene production) are shown (per metric ton of propylene product,
over the same noble-metal catalyst. Exothermic selective H2 conversion including production of oxygen and all steam required):
in the oxyreactor increases olefin product space-time yield and supplies Propane, kg/metric ton 1,200
heat for further endothermic dehydrogenation. The reaction takes place Fuel gas, GJ/metric ton 6.4
3
Circul. cooling water, m /metric ton 170
at temperatures between 500°C and 600°C and at 4 – 6 bar.
The Uhde reformer is top-fired and has a proprietary “cold” out- Electrical energy, kWh/metric ton 100
let manifold system to enhance reliability. Heat recovery utilizes process Installation: Two commercial plants using the STAR process for dehy-
heat for high-pressure steam generation, feed preheat and for heat re- drogenation of isobutene to isobutylene have been commissioned (in
quired in the fractionation section. the US and Argentina). A STAR process oxydehydrogenation plant for
After cooling and condensate separation, the product is subse- the production of 350,000 tpy propylene will go on-stream in Egypt in
quently compressed, light-ends are separated and the olefin product is
separated from unconverted paraffins in the fractionation section. Continued 
Heinritz-Adrian, M., “STAR process – Advanced propane dehydro-
Olefins, continued genation for on-purpose propylene production,” CMT 5th Middle East
Olefins & Polyolefins Conference, Dubai, November 2007.
2009. More than 60 Uhde reformers and 25 Uhde secondary reformers
Wenzel, S., “STAR process—Uhde´s oxydehydrogenation technol-
have been constructed worldwide.
ogy,“ 9th International Petrochemicals & Gas Conference and Exhibi-
References: Heinritz-Adrian, M., S. Wenzel and F. Youssef, “Advanced tion, London, 2007.
propane dehydrogenation,” Petroleum Technology Quarterly, Spring
2008, pp. 83–91.

Refinery offgas—purification
and olefins recovery ROG from
refinery
Amine wash
DeOxo feed/
effluent cross
DeOxo
steam
DeOxo
reactor
exchanger heater
Application: Purification and recovery of olefins from FCC, RFCC and
DCC offgas.
Reactor effluent Dry feed
cooler drum
Products: Hydrogen, methane, ethylene and LPG.
Treated ROG to
ethylene plant Arsine RSH/COS Dryer/mercury
Description: Refinery offgas (ROG) streams from fluid catalytic cracker removal bed removal beds removal beds
(FCC) units, deep catalytic cracking (DCC) units, catalytic pyrolysis pro-
cess (CPP) units and coker units are normally used as fuel gas in refiner-
ies. Most FCC type units recover their propylene separately. But the ROG ROG from
refinery DeOxo feed/ DeOxo
Amine Caustic DeOxo
steam (typically C2 and lighter) may, in certain cases, also contain a por- wash wash
effluent cross
exchanger
steam
heater
reactor
tion of propylene. However, these streams contain significant amounts
of olefins (ethylene and propylene), which can be economically recov- Reactor effluent Dry feed Dryer/mercury
ered. In fact, many such streams can be recovered with project payout cooler drum removal beds
Fuel gas
times of less than one year. As FCC type units use more zeolitic type
RSH/COS
catalysts, the respective proportion of both propylene and ethylene will Dilute or
removal beds
polymer-grade
increase. ethylene plant Arsine/ Cold box/expander
Offgas-recovery units can be integrated with existing olefins units polishing bed compressor
or, if the flows are large enough, stand-alone units may be feasible.
ROG recovery units can be broken down into sections including feed
contaminant removal, ethylene recovery and propylene recovery. Feed
contaminants including acid gases, O2, NOx, arsine, mercury, ammonia, box, followed by a demethanizer, a deethanizer; and for PGE and C2
nitrites, COS, acetylenes and water must be removed. The ROG feed- splitter.
stock pretreatment is critical since many of the trace components in the Removal of contaminants including acid gases, COS, RSH, NO2, NH3,
ROG streams can impact the ultimate product purity, downstream cata- HCN, H2O, AsH3 and Hg is achieved by established processing methods,
lyst performance and operational safety. depending on the concentrations in the ROG feed. The difficult con-
The ethylene recovery section can be a stand-alone unit where ei- taminants to remove in the ROG are the O2 and NOx, which are typically
ther dilute ethylene or polymer-grade ethylene (PGE) is produced; or a removed by hydrogenation to H2O and NH3 (DeOxo unit). Commercially
unit where partially recovered streams suitable for integration into an available hydrogenation catalysts cause significant loss of ethylene to
ethylene plant recovery section are produced. ethane. BASF together with Shaw have developed a copper-based De-
Integration of treated ROG into an ethylene plant involves com- Oxo catalyst (R3-81), which in sulfided form is capable of complete hy-
pression and treatment /removal of contaminants. If an ethylene prod- drogenation of the O2 and NOx.
uct is required (dilute ethylene or PGE), an additional section is needed
that cryogenically separates hydrogen, nitrogen and methane in a cold Continued 
comes from the superior selectivity of the special catalyst— allowing
Refinery offgas—purification and olefins recovery, deep removal of O2 and NOx, with negligible ethylene loss.
continued
Installation: Three such latest DeOxo units are currently operating. Sev-
DeOxo reactor. The DeOxo Reactor, in which the sulfided-copper cata- eral units are under construction, and many units are under design.
lyst (R3-81) is used, serves a dual function. By removing the O2, NOx and
acetylene, it provides necessary purification of olefins but is also vital Licensor: Shaw.
toward the safety of the process. Without it, the formation of explosive
deposits in and around the downstream cold box can become an issue.
An additional, economic benefit of the Shaw Stone & Webster solution, click here to e-mail for more information
Oxygen enrichment for Claus units Liquid oxygen tank

Claus plant process
Application: Increase the capacity of Claus plants and decompose haz- Vaporizer control system
ardous materials such as ammonia

Controller
Description: As “clean fuels” regulations become effective, refiners

must recover more sulfur in their Claus plants. As a byproduct of deep Measuring and
control unit
1 Steam
desulfurization, ammonia is generated and typically must be decom- FLOWTRAIN
posed in the Claus plant. To upgrade the sulfur recovery units (SRUs) 2 4 Process gas
accordingly, oxygen enrichment is an effcient and low-cost option. to catalytic
Air reactors
Oxygen enrichment can increase sulfur capacity substantially and is Onsite ASU
capable of decomposing ammonia from sour-water stripper gas very 3
efficiently.
Oxygen addition can be done in three levels, depending on the Oxygen pipeline
Acid gas plus sour
water stripper gas
BFW
required capacity increase:

1 Alternative oxygen sources
1. Up to approximately 28% oxygen. Oxygen is simply added to 2 FLOWTRAIN with all required safety features
3 Oxygen injection and mixing device
the Claus furnace air. This can raise sulfur capacity by up to 35%. 4 Claus reaction furnace with burner for air and/or oxygen enriched operation
2. Up to approximately 40% oxygen. The burner of the Claus fur-
nace must be replaced. Up to 50% additional sulfur capacity can be
achieved by this method.
3. Beyond 40% oxygen. The temperature in the Claus furnace is
elevated so high that the product gas must be recycled to maintain for a short and highly turbulent flame, which ensures good approach
temperature control. This process is expensive and, therefore, rarely toward equilibrium for Claus operation and for the decomposition of
applied. ammonia.
Oxygen sources can be liquid oxygen tanks, onsite ASUs or pipe-
Economics: As oxygen enrichment provides substantial additional
line supply. Oxygen consumption in Claus plants fluctuates widely in
Claus capacity, it is a low-cost alternative to building an additional Claus
most cases; thus, tanks are the best choice due to ease of operation,
plant. It can save investment, manpower and maintenance. Installed
flexibility and economy. For oxygen addition into the CS air duct, a
cost for oxygen enrichment per level 1 is typically below $250,000.
number of safety rules must be observed. The oxygen metering device
For level 2, the investment costs range from $200,000 to $500,000
FLOWTRAIN contains all of the necessary safety features, including
and depend on the size of the Claus plant. Operating costs are varied
flow control, low-temperature and low-pressure alarm and switch-off,
and depend on the duration of oxygen usage. Typically, annual costs
and safe standby operation. All features are connected to the Claus
of oxygen enrichment are estimated as 10% to 40% of the operating
plants’ process control system.
cost for a Claus plant, providing the same additional sulfur capacity.
An effcient mixing device ensures even oxygen distribution in the
Due to improved ammonia destruction maintenance work, as cleaning
Claus air. A proprietary Claus burner was developed especially for ap-
plication for air- and oxygen-enriched operations. This burner provides Continued 
Oxygen enrichment for Claus units, continued Reference: Reinhardt, H. J. and P. M. Heisel, “Increasing the capacity of
Claus plants with oxygen,” Reports on Science and Technology, No. 61
(1999), p. 2.
of heat exchanger tubes from ammonium salts and the respective cor-
rosion become substantially less. Contributor: Linde AG, Division Gas and Engineering.
Installations: Over 10, plus numerous test installations to quantify the

effects of capacity increase and ammonia decomposition. click here to e-mail for more information
Oxygen enrichment for FCC units Liquid oxygen tank

Offgas
Vaporizer
Application: Increase the throughput capacity by up to 50% and/or con- Crack gas
Steam
version in FCC units; process heavier feeds; overcome blower limita- 7
tions, also temporarily. 2 Steam
5
Gasoline
Description: “Clean fuels” regulations are being implemented. Plus, the 1 8

Gas oil
3 6
demand for transport fuels continually shifts toward more kerosine and
Residue
diesel. The reason is that the regulations and the change in demand are Onsite ASU Air
totally independent developments. But both contribute to the require- 9
4
ment of more flexibility in fluid catalytic cracking units (FCCUs). Conse-
quently, FCCUs require more flexibility to treat a wider range of feeds, Oxygen pipeline Vacuum gasoil
especially heavier feeds, and increasing throughput capacity. Both goals Cycle oil
can be achieved via oxygen enrichment in the FCC regeneration. 1 Alternative oxygen sources 5 FCC reactor
2 Process control system for FCC unit 6 Regenerator
In the FCC reactor, long-chain hydrocarbons are cleaved into shorter 3 FLOWTRAIN for dosing oxygen with all 7 Steam boiler
required safety features 8 Fractionator
chains in a fluidized-bed reactor at 450 –550°C. This reaction produces 4 Oxygen injection and mixing device 9 Cycle oil separator
coke as a byproduct that deposits on the catalyst. To remove the coke
from the catalyst, it is burned off at 650 –750°C in the regenerator. The
regenerated catalyst is returned to the reactor.
Oxygen enrichment, typically up to 27 vol% oxygen, intensifies cata- products, such as naphtha. Likewise, lower value products increased
lyst regeneration and can substantially raise throughput capacity and/or only 5%, as fuel gas. The net profit increased substantially. Installed cost
conversion of the FCC unit. Oxygen sources can be liquid oxygen tanks, for oxygen enrichment is typically below $250,000.
onsite ASUs or pipeline supply. Oxygen consumption in FCC units fluctu- Operating costs will depend on the cost for oxygen and the duration
ates widely in most cases; thus, tanks are the best choice with respect to of oxygen enrichment. Economical oxygen usage can be calculated on
ease of operation, flexibility and economy. a case-by-case basis and should include increased yields of higher-value
For oxygen addition into the CS air duct, a number of safety rules products and optional usage of lower-value feeds.
must be observed. The oxygen metering device FLOWTRAIN contains all
necessary safety features, including flow control, low-temperature and Installations: Currently, four units are in operation, plus test installations
low-pressure alarm and switch-off, and safe standby operation. All of to quantify the effects of higher capacity and conversion levels.
these features are connected to the FCC units’ process control system.
Reference: Heisel, M. P., C. Morén, A. Reichhold, A. Krause, A. Berlanga,
An efficient mixing device ensures even oxygen distribution in the air
“Cracking with Oxygen,” Linde Technology 1, 2004.
feed to the FCC regeneration.
Contributor: Linde AG, Division Gas and Engineering.
Economics: Oxygen enrichment in FCC regeneration is economically
favorable in many plants. For example, one refinery increased through-
put by 15%. The net improvement was a 26% increase in higher-value click here to e-mail for more information
Carboxylic acid recovery

Application: The GT-CAR recovery process combines GTC’s liquid-liquid Acids-containing
First-stage
distillation
extraction technology with distillation to recover and concentrate car- water stream removes
water Water
boxylic acids from wastewater. Using a high-boiling solvent enables the
Acid-rich solvent
process to attain the lowest energy use of any commercially available stream Dehydrator
Recovered
acids
process with minimal capital costs. The recovered acids have sufficient
purity to be sold as glacial grade or recycled back to the process. The Liquid-liquid
extractor
Solvent
stripper
biological oxygen demand (BOD) of the resulting wastewater stream is High-selectivity
greatly reduced. The process is economical for any aqueous stream gen- solvent removes
Second-stage
acids from the
erated in the production of dimethyl terephthalate (DMT), acetic acid, water by liquid distillation
extraction to recover acids
pulp/paper, furfural and other processes. Lean solvent
and regenerate
To wastewater the solvent
treatment <0.2%
Process description: Acid-containing aqueous stream is fed to an ex- acids content
traction column, which operates using a proprietary, phosphine oxide-

based solvent, highly selective to carboxylic acids. The acid-rich solvent
stream is carried overhead from the extraction column for regeneration.
In the two-stage regeneration step, surplus water is removed (dehydra-
• Use of high-boiling solvent yields high-acetic recovery and
tion) and the acids are recovered by acid stripping. The solvent is routed
substantial energy savings
back to the extraction column for reuse. Final processing of the concen-
• Solvent is easily separated from water, giving a solvent-free
trated acids is determined on a plant-by-plant basis. The treated waste-
(< 20 ppm) wastewater exit stream
water stream, containing acid levels on the order of < 2,000 ppm, exits
• Acetic acid product purity allows for recycle or resale
the system to the plant’s wastewater treatment area.
• High acid recovery provides environmental benefits, unloading the
Advantages: biological treatment system
• Up to 98% of the acids can be recovered
Installation: Two licensed units.
• Acid concentrations as low as 0.5%+ can be economically
recovered Licensor: GTC Technology.
• Low capital investment results in typical ROI up to 40%
• Modular systems approach enables minimal disruption
of plant operation and shorter project schedule

Dimethyl terephthalate Low acids

recovery
Application: Modifications to the traditional process for manufacturing ATM
dimethyl terephthalate (DMT) can significantly improve results includ- MeOH recycle MeOH
PX
ing capacity increase, yield improvements, reduced energy consumption recovery WW
DMT
and upgrade of byproduct quality for increased commercial value. Crystallization
The technology is flexible and may be implemented in increments. WW
GTC can optimize the design or configuration to maximize use of exist- PX
Methy p-toluate
ing equipment. MPT to oxidation
MeOH Pure DMT
Air
Description: The common method for the production of DMT from par- Catalyst To filtrate recovery
axylene (PX) and methanol consists of four major steps: oxidation, es- Residue and isomer removal
terification, distillation and crystallization. A mixture of PX and PT-ester

is oxidized with air in the presence of a heavy metal catalyst. All useful Residue
organics are recovered from the offgas and recycled to the system. The PX recycle treatment
acid mixture resulting from the oxidation is esterified with methanol Catalyst recovery/recycle Residue removal
Methyl benzoate
removal
(MeOH) to produce a mixture of esters. The crude ester mixture is dis- Residue recycle
tilled to remove all the heavy boilers and residue produced; the lighter
esters are recycled to the oxidation section. The raw DMT is then sent
to the crystallization section to remove DMT isomers, residual acids and
aromatic aldehydes. This purification produces DMT that meets world- • Lower energy consumption/ton DMT produced
market specifications and is preferred in some polyester applications. • Flexible application for revamp projects
Byproducts are recovered for sale or burned for fuel value and usable • Accumulated technical expertise available through engineering
intermediate materials are recycled. packages and follow-up services
The GTC process improvements enhance the traditional process in
Oxidation section
each of the four sections through changes in process configurations
• Improved oxidation reduces side reactions and more effectively
and operating conditions, alteration of separation schemes, revision of
uses reaction volume, resulting in lower PX consumption.
recovery arrangements, increase in the value of byproducts and reduc-
• New and more efficient scheme for the catalyst recovery in the
tion in the total recycles in the plant. The upgrade options may be imple-
plant helps reduce residue formation.
mented individually, combined or through a series of revamps over a
• Improved recovery of PX and removal of methyl benzoate: Prod-
period of time.
uct is upgraded to food or perfume grade.
Process advantages: • Carboxylic acid recovery: Recovery of formic and acetic acid as
• Reduction in use of raw materials (p-xylene and methanol) byproducts, upgrading value and reducing load in biotreatment unit.
• Higher specific throughput
Continued 
• Improved methanol recovery and handling system reduces plant
Dimethyl terephthlate, continued losses.
• Improved isomer removal system helps reduce DMT losses.
Distillation section
• Improved distillation scheme increases purity of DMT to crystalliza- Esterification
tion and reduces plant recycles. • Improved reactor design gives higher throughputs and improved
• Improved residue treatment can increase the yields of the plant by methanol usage.
recovering valuable materials.
Installation: Five licensed units.
Crystallization Licensor: GTC Technology.
• Typical double-crystallization scheme is simplified to increase
throughputs and minimize equipment.
• New single-stage crystallization offers a low-cost alternative in re- click here to e-mail for more information
vamps.
Reactor internals efficiently remove fouling materials yet take up virtually no valuable re-
actor volume
Application: A suite of proprietary reactor internals that offer uniform • Robust design—Nuts and bolts are not used for any fixing. We of-
gas and liquid distribution to increase catalyst utilization and efficiently fer global manufacturing options, and units are designed to withstand
quench highly exothermic hydroprocessing catalytic reactions. The state- tilting and fouling.
of-the-art reactor internals take up less space, thus enabling high reac- Business value: The HD tray results in improved liquid and thermal dis-
tor volume utilization while helping maximize catalyst run length. The tribution, so ensuring maximum use of the catalyst bed. Refiners may
designs are simple and robust and allow easy access to the reactor and double their cycle lengths as a result of using the new tray. These longer
efficient maintenance and catalyst change-out activities. cycle lengths are due to the slower catalyst deactivation; the lower inlet
Description: Shell Global Solutions’ high-dispersion (HD) trays help to temperatures required to produce high-specification products; and the
optimize catalyst utilization by achieving highly uniform vapor–liquid better thermal distribution that the HD trays offer. The anti-fouling trays
distribution and excellent thermal distribution. Each tray nozzle is cus- have resulted in increases in cycle length of up to 200%.
tomized so that gas flow momentum is used to disperse the liquid into a Installation: All Shell Global Solutions’ internals have been commercially
mist of small droplets. This operating concept differentiates the technol- proven through more than 230 hydroprocessing applications.
ogy from conventional downcomers or bubble caps because the nozzles A South Korean refiner was experiencing hot spots in the catalyst
fully and uniformly wet the entire catalyst surface and make efficient use beds of its lube-oil hydrotreater. Shell Global Solutions and its affiliate
of the top part of the catalyst bed. Criterion Catalysts & Technologies worked together to resolve the prob-
Our reactor internals system also includes the following technology: lem. HD trays were applied in combination with UFQ interbed internals
• Top-bed scale-catching trays to trap fouling material and prevent to improve quenching and mixing between the catalyst beds. As a re-
it from entering the catalyst beds sult, catalyst utilization improved significantly, and helped to facilitate a
• Ultra-flat quench (UFQ) interbed internals for uniform process and longer cycle and more severe operation.
quench mixing at the interbeds Shell Global Solutions and Criterion Catalysts & Technologies tai-
• Catalyst support grids lored a system for JSC Naftan refinery when it converted a hydrotreating
• Compact bottom baskets to help maximize the catalyst volume in reactor for use as a mild hydrocracker. The system incorporated state-
the bottom domes. of-the-art internals and new-generation pre-treatment and cracking
Performance data: catalysts. The revamped unit was able to achieve conversion of the
• Activity—Shell Global Solutions’ reactor internals can produce 370°C+ vacuum gasoil fraction at levels up to 50% higher than the
30% –50% activity gains through improved catalyst utilization and extra design target.
volume for loading catalyst. Licensor: Shell Global Solutions International B.V.
• Efficiency—HD trays can help to utilize nearly 100% of the cata-
lyst inventory.
• Operating window—HD trays offer high flexibility of feedrate:
typically +50% to –70% for liquid as well as gas.
• Anti-fouling capacity—Shell Global Solutions’ top-bed filters can click here to e-mail for more information
Sulfur processing
Application: The D’GAASS Sulfur Degassing Process removes dissolved
H2S and H2Sx from produced liquid sulfur. Undegassed sulfur can create Air+H2S
odor problems and poses toxic and explosive hazards during the storage
and transport of liquid sulfur.
Description: Degasification is accomplished in a pressurized vertical ves-

Sulfur Degassing
sel where undegassed sulfur is efficiently contacted with pressurized degassing contactor
Sulfur
process air (instrument or clean utility air). The contactor vessel may be rundowns pump
from SRU Air
located at any convenient location. The undegassed sulfur is pumped to
the vessel and intimately contacted with air across special fixed vessel
internals. Degassed
sulfur
Operation at elevated pressure and a controlled temperature ac- Sulfur
celerates the oxidation of H2S and polysulfides (H2Sx ) to sulfur. The de- pit
gassed sulfur can be sent to storage or directly to loading without ad-
ditional pumping. Operation at elevated pressure allows the overhead
vapor stream to be routed to the traditional incinerator location, or to
the SRU main burner or TGTU line burner—thus eliminating the degas-
sing unit as an SO2 emission source.
Nasato, E. and T. A. Allison, “Sulfur degasification—The D’GAASS
Economics: D’GAASS achieves 10 ppmw combined H2S/H2Sx in product process,” Laurance Reid Gas Conditioning Conference, Norman, Okla-
sulfur without using catalyst. Elevated pressure results in the following homa, March, 1998.
benefits: low capital investment, very small footprint, low operating cost Fenderson, S., “Continued development of the D’GAASS sulfur de-
and low air requirement. Operation is simple, requiring minimal opera- gasification process,” Brimstone Sulfur Recovery Symposium, Canmore,
tor and maintenance time. No chemicals, catalysts, etc., are required. Alberta, May 2001.
Installations: Over 65 licensed units with total capacity over 35,000 long Licensor: Goar, Allison & Associates, Inc., an Air Products Company.
ton per day (LTPD).
Reference: US Patent 5,632,967.

Sulfur recovery
Application: The COPE Oxygen Enrichment Process allows existing Claus Motive steam
HPS Recycle gas
sulfur recovery/tail gas cleanup units to increase capacity and recov Acid gas feed RH1 HPS
ery, can provide redundant sulfur processing capacity, and can improve W.H. LPS
Oxygen boiler LPS
combustion performance of units processing lean acid gas. 1 RF 2 R1
Claus
Description: The sulfur processing capacity of typical Claus sulfur re Air
BFW
C1 reactor
C2
covery units can be increased to more than 200% of the base capacity Air blower
BFW SL
SL
through partial to complete replacement of combustion air with pure HPS RH2
BFW
oxygen (O2). SRU capacity is typically limited by hydraulic pressure drop. RH3 HPS
LPS
As O2 replaces combustion air, the quantity of inert nitrogen is reduced LPS
allowing additional acid gas to be processed. 3 R2 To tail gas cleanup
R3 4 R3
The process can be implemented in two stages. As the O2 enrich
C3
ment level increases, the combustion temperature (1) increases. COPE C4
Phase I, which does not use a recycle stream, can often achieve 50% BFW SL
BFW SL
capacity increase through O2 enrichment to the maximum reaction fur
nace refractory temperature limit of 2,700ºF – 2,800ºF. Higher O2 enrich
ment levels are possible with COPE Phase II which uses an internal pro
cess recycle stream to moderate the combustion temperature allowing
enrichment up to 100% O2.
ings of up to 25%, and redundant capacity at 15% of base capital cost.
Flow through the remainder of the SRU (2, 3, and 4) and the tail
Operating costs are a function of O2 cost, reduced incinerator fuel, and
gas cleanup unit is greatly reduced. Ammonia and hydrocarbon acid
reduced operating and maintenance labor costs.
gas impurity destruction and thermal stage conversion are improved at
the higher O2 enriched combustion temperatures. Overall SRU sulfur Installations: Thirty-two COPE trains at 19 locations.
recovery is typically increased by 0.5% to 1%. A single proprietary COPE
burner handles acid gas, recycle gas, air and O2. Reference: US Patents 4,552,747 and 6,508,998.
Sala, L., W. P. Ferrell and P. Morris, “The COPE process—Increase
Operating conditions: Combustion pressure is from 6 psig to 12 psig; sulfur recovery capacity to meet changing needs,” European Fuels Week
combustion temperature is up to 2,800ºF. Oxygen concentration is from Conference, Giardini Naxos, Taormina, Italy, April 2000.
21% to 100%. Nasato, E. and T. A. Allison, “COPE Ejector—Proven technology,”
Sulphur 2002, Vienna, Austria, October 2002.
Economics: Expanded SRU and tail gas unit retrofit sulfur processing
capacity at capital cost of 15% – 25% of new plant cost. New plant sav Licensor: Goar, Allison & Associates, Inc., an Air Products Company.

Sulfur recovery Acid gas LP steam MP steam

plus MP steam LP steam LP steam Fuel Air
Application: Sulfur recovery from typical Claus gas rich in hydrogen sul- SWS gas
fide (H2S) from industrial gases, and sour-water stripper (SWS) gas. V01A
2A
Description: DEGsulf is an improved Claus process plus tail-gas treat- 5
ment that allows sulfur recovery rates of 99.8+% with just two cata- 1 6
E03 D03B
lytic reactors. Downstream of the Claus furnace and waste-heat boiler D03A
R01A 3A R01B 3B
(1) are two catalytic reactors (3A / B) integrating the Claus step and F01/ E01
D01 F02
a sub-dewpoint tail-gas treatment. Its main feature is the use of in- V01B
E02 4
D02
ternally cooled reactors, which control the reaction temperatures by 2B
special welded plate-heat exchangers in the catalyst beds. The first bed
(3A) operates at high temperatures, the second bed (3B) below the
sulfur dew point. This reactor adsorbs sulfur and must be regenerated LP BFW
Plant air MP BFW LP BFW
eventually, which is done by switching the cool second reactor to the supply supply
7
position of the hot first reactor and vice versa. The use of proprietary Sulfur
4-way valves (2A / B) makes the switch-over between adsorption and
regeneration simple and reliable. The produced sulfur is recovered in
the sulfur condenser (4) and collected in the sulfur pit (7). Prior to en-
Economics: Capital cost depends on the amount of feed gas and on
tering the 2nd reactor the process gas is reheated (5). The desulfurized
the required sulfur recovery rate. Products are bright yellow sulfur and
gas is incinerated (6).
steam. Utility consumptions are very low, as in a conventional Claus
Conventional Claus catalysts are applied. They ensure up to 99.85%
process.
sulfur recovery. In no-operating mode, there are no dead pipes. This
avoids the related problems of corrosion and sulfur plugging. Installation: More than 10 units have been built, both 1-reactor and
Typical feed gas is Claus gas rich in H2S. DEGsulf is capable of han- 2-reactor plants.
dling wide fluctuations of feed gas flows and compositions. Turn-down
ratios up to 6/1 have been realized. Sulfur recovery rates up to 99.8+% Reference: Kunkel, J. and M. Heisel, “Clinsulf-SDP makes its debut,”
were observed. The process operates fully automatic, including the SULPHUR, no.243.
switch-over.
Licensor: Worley Parsons.

Treating—phenolic caustic CO2
Application: ECOMERICAT treating systems removes phenols from phe-

Sweetened hydrocarbon
nolic caustics by neutralization in conjunction with solvent washing us- Untreated hydrocarbon
ing a FIBER-FILM Contactor.
Description: An ECOMERICAT system contacts the spent caustic with a

slipstream of sweetened gasoline containing CO2 whereby neutralizing
Oxidation air
the spent caustic, springing the phenols, absorbing the phenols into
Mericat Ecomericat
the sweetened gasoline yielding neutral brine with minimal phenolic
content.
Fresh caustic (batch)
Competitive advantages: Catalyst in
Batch
• Minimizes spent caustic disposal cost

Low phenols
• Reduces the phenol content of spent caustic and increases the content neutralized
phenol content of sweetened gasoline thus adding value brine to storage
• Operates over a wide pH range Phenolic caustic Phenolic

caustic
• Simple to operate
• No corrosion problems due to the buffering effect of CO2.
Installation: Two installation worldwide.

Licensor: Merichem Chemicals & Refinery Services LLC, Process Technol-
ogy Division.

Treating—Pressure swing adsorption

Application: Pressure swing adsorption (PSA) process selectively adsorb-
ing impurities from product streams. The impurities are adsorbed in a Product Co-current Repressurization
fixed-bed adsorber at high pressure and desorbed by “swinging” the depressurization Purge
adsorber from the feed to the tail gas pressure and by using a high-
purity purge. Typically, the desired component is not adsorbed and is 1 2 3 4 5
recovered at high purity.
Description: A PSA system operates as a batch process. However, mul-

tiple adsorbers operating in a staggered sequence are used to produce
constant feed, product and tail gas flows.
Step 1: Adsorption. The feed gas enters an adsorber at a high pres-
Offgas
sure, impurities are adsorbed and high-purity product is produced. Flow
Feed gas Counter-current
is normally in the upwardly direction. When an adsorber has reached depressurization
its adsorption capacity, it is taken offline, and the feed automatically
switched to a fresh adsorber.
Step 2: Co-current depressurization. To recover the product trapped
in the adsorbent void spaces, the adsorber is co-currently (in the direc-
tion of feed flow) depressurized. The product gas withdrawn is used
internally to repressurize and purge other adsorbers.
Step 3: Counter-current depressurization. At the end of the co-cur- UOP’s Polybed PSA system offers:
rent depressurization step, the adsorbent is partially regenerated by • High reliability (greater than 99.8% onstream time)
counter-currently depressurizing the adsorber to the tail-gas pressure, • Minimal manpower requirements due to automatic operation
and thereby rejecting the impurities. • Reduced equipment costs and enhanced performance based on
Step 4: Purge. The adsorbent is purged with a high-purity stream high performance adsorbents and advanced PSA cycles
(taken from another adsorber on the cocurrent depressurization step) at • Lower operating and equipment costs for downstream process
a constant pressure to further regenerate the bed. units
Step 5: Repressurization. The repressurization gas is provided from • Flexibility to process more than one feedstock
the co-current depressurization step and a slipstream from the product. • Modular construction for improved delivery times and low instal-
When the adsorber has reached the adsorption pressure, the cycle has lation costs
been completed. The vessel is ready for the next adsorption cycle. • Minimal feed pretreatment and utility requirements
• Adsorbents last for the life of the mechanical equipment (more
than 30 years).
Continued 
Treating—pressure swing adsorption, continued 1,000 psig (7 to 70 kg/cm2g) with concentrations of the desired com-
ponent typically in the range of 30 to 98+ mole%. System capacities
range from less than 1 to more than 350 MMscfd (less than 1,100 to
Installation: Since commercialization in 1966, UOP has provided over
more than 390,000 Nm3/hr). UOP provides unit and complex integration
800 PSA systems in more than 60 countries in the refining, petrochemi-
development support to ensure the PSA system meets the end-user’s
cal, steel and power-generation industries. The Polybed PSA System has
processing objectives and worldwide service and technical support after
demonstrated exceptional economic value in many applications, such
startup.
as hydrogen recovery from steam methane reforming, refinery offgas,
monomer recovery in polyolefin plants, hydrogen extraction from gasifi- Licensor: UOP.
cation syngas, helium purification for industrial gas use, adjustment of
synthesis gas for ammonia production, methane purification for petro-
chemicals productions, and H2/CO ratio adjustment for syngas used in click here to e-mail for more information
oxo-alcohols production. Feed conditions typically range from 100 to
Treating— spent caustic deep

neutralization Fuel gas or nitrogen Offgas to sulfur plant
Application: MERICON systems neutralize spent caustics containing sul- Fresh caustic
fides, mercaptans, naphthenic acids, and phenols.
Description: A MERICON system neutralizes spent caustic with acid to

a low pH. The sprung acid oils are separated from the acidic brine. The Neutralized
brine to WWTP
resulting acid gases (H2S and mercaptans) flow to a sulfur plant. The
sprung acid oils are returned to the refinery for processing. The acid-
Acid oils to storage
ic brine is further stripped with fuel gas to remove traces of H2S and
mercaptans. Finally, the acidic brine is mixed with caustic to return it to
Sulfuric acid
a neutral pH for final disposal.
Spent caustic feed Acid brine
Competitive advantages:
• Minimal operator attention and 100 % onstream factor between
turnarounds
• Minimal capital investment
• Maximum COD reduction
• Non-odorous neutralized brine product
• Recovery of valuable hydrocarbons.
Reference: Petroleum Technology Quarterly, Spring 2001, p. 55.
Installation: Twenty-five installations worldwide. Licensor: Merichem Chemicals & Refinery Services LLC, Process Technol-
ogy Division.

Gas treating—H2S removal Treated gas
Application: ExxonMobil’s Research & Engineering (EMRE’s) FLEXSORB

SE and SE Plus removes H2S selectively, or remove a group of acidic im- Lean amine
purities (H2S, CO2, COS, CS2 and mercaptans) from a variety of streams, 1 Acid gas
depending on the solvent used. FLEXSORB SE technology has been used Feed gas to Claus
in refineries, natural gas production facilities and petrochemical opera-
tions. Rich amine
FLEXSORB SE or SE Plus solvent is used on: hydrogenated Claus plant
tail gas to give H2S, ranging down to H2S <10 ppmv; pipeline natural 2
gas to give H2S <0.25 gr/100 scf; or FLEXICOKING low-Btu fuel gas. The
resulting acid gas byproduct stream is rich in H2S.
Hybrid FLEXSORB SE solvent is used to selectively remove H2S, as
well as organic sulfur impurities commonly found in natural gas.
Description: A typical amine system flow scheme is used. The feed gas
contacts the treating solvent in the absorber (1). The resulting rich-sol-
vent bottom stream is heated and sent to the regenerator (2). Regen- Reference: Garrison, J., et al., “Keyspan Energy Canada Rimbey acid gas
erator heat is supplied by any suitable heat source. Lean solvent from enrichment with FLEXSORB SE Plus technology,” 2002 Laurance Reid
the regenerator is sent through rich/lean solvent exchangers and coolers Gas Conditioning Conference, Norman, Oklahoma.
before returning to the absorber. Adams-Smith, J., et al., Chevron USA Production Company, “Carter
FLEXSORB SE solvent is an aqueous solution of a hindered amine. Creek Gas Plant FLEXSORB tail gas treating unit,” 2002 GPA Annual
FLEXSORB SE Plus solvent is an enhanced aqueous solution, which has Meeting, Dallas.
improved H2S regenerability yielding <10 vppm H2S in the treated gas. Connock, L., et al., “High recovery tail gas treating,” Sulphur, No.
Hybrid FLEXSORB SE solvent is a hybrid solution containing FLEXSORB SE 296, November/ December 2004.
amine, a physical solvent and water. Fedich, R., et al., “Selective H2S Removal,” Hydrocarbon Engineer-
ing, May 2004.
Economics: Lower investment and energy requirements based primarily
Fedich, R. B., et al., “Solvent changeover benefits,” Hydrocarbon
on requiring 30% to 50% lower solution circulation rates, compared to
Engineering, Vol. 10, No. 5, May 2005.
other selective solvents.
“Gas Processes 2006,” Hydrocarbon Processing, January 2006.
Installations: Total gases treated by FLEXSORB solvents are about 2 bil- Fedich,R, et al., “Selective cleanups,” Hydrocarbon Engineering,
lion scfd and the total sulfur recovery is about 900 long tpd. February 2008.
FLEXSORB SE—31 plants operating, three in design
FLEXSORB SE Plus—19 plants operating, nine in design
Hybrid FLEXSORB SE—two plants operating, three in design click here to e-mail for more information
Over 60 plants operating or in design.
H2S removal Sweet gas

Application: ELIMINATOR technology consisting of a full line of ELIMI-
NATOR products removes hydrogen sulfide (H2S) and light mercaptans
from a variety of process gas streams in a safe, efficient, environmentally
friendly and easy to operate manner.
Absorber
Inlet
Description: The ELIMINATOR technology is extremely versatile, and its Sour gas knockout
performance is not sensitive to operating pressure. In properly designed pot
systems, H2S concentrations of less than 1 ppm can easily be achieved

on a continuous basis. Drains
A number of different treatment methodologies may be used to Spent scavenger

treat sour gas streams.
• Line injection—ELIMINATOR can be sprayed directly into a gas
stream with removal of the spent product in a downstream knockout
pot.
• Sparge tower—Sour gas is bubbled up through a static volume of Economics: Operating costs are very favorable for removing less than
ELIMINATOR. A lead-lag vessel arrangement can be installed to allow for 250 kg /d of H2S.
the removal of spent solution and the addition of fresh solution without
shutting down. This arrangement also results in the optimum utilization Installation: Fifteen units in operation.
of the solution. Licensor: Merichem Chemicals & Refinery Services LLC, Gas Technology
• Packed tower—Sour gas is contacted with circulating solution of Products Division.
ELIMINATOR in a counter, packed-bed scrubber.
Products: A full line of ELIMINATOR products can treat any type of gas
streams.

H2S removal Sweet gas
Application: LO-CAT removes H2S from gas streams and produces el-
Spent air Sulfur filter
emental sulfur. LO-CAT units are in service treating refinery fuel gas,
hydrodesulfurization offgas, sour-water-stripper gas, amine acid gas, Fe3+
claus tail gas and sulfur tank vent gas. Sulfur capacities are typically less Filtrate
2
than 25 ltpd down to several pounds per day. Key benefits of operation 1
are high (99.9%) H2S removal efficiency, and flexible operation, with vir- Oxidizer
tually 100% turndown capability of H2S composition and total gas flow.
Sour gas
Sulfur is recovered as a slurry, filter cake or high-purity molten sulfur.
The sulfur cake is increasingly being used in agriculture, but can also be Fe2+
deposited in a nonhazardous landfill.
Absorber
Air blower
Description: The conventional configuration is used to process combus-
tible gas and product gas streams. Sour gas contacts the dilute, propri-
etary, iron chelate catalyst solution in an absorber (1), where the H2S is
absorbed and oxidized to solid sulfur. Sweet gas leaves the absorber for Operating conditions: Operating pressures range from vacuum condi-
use by the refinery. The reduced catalyst solution returns to the oxidizer tions to 1,000 psi. Operating temperatures range from 40°F to 140°F.
(2), where sparged air reoxidizes the catalyst solution. The catalyst solu- Hydrogen sulfide concentrations range from a few ppm to 100%. Sul-
tion is returned to the absorber. Continuous regeneration of the catalyst fur loadings range from a few pounds per day to 25+ tons per day. No
solution allows for very low chemical operating costs. restrictions on type of gas to be treated; however, some contaminants,
In the patented autocirculation configuration, the absorber (1) and such as SO2, may increase operating costs.
oxidizer (2) are combined in one vessel, but separated internally by baf-
fles. Sparging of the sour gas and regeneration air into the specially Installations: Presently, 180 licensed units are in operation with four
designed baffle system creates a series of “gas lift” pumps, eliminating units under construction.
the external circulation pumps. This configuration is ideally suited for
treating amine acid gas and sour-water-stripper gas streams. Reference: Nagl, G., W. Rouleau and J. Watson,, “Consider optimized
In both configurations, sulfur is concentrated in the oxidizer cone Iron-Redox processes to remove sulfur,” Hydrocarbon Processing, Janu-
and sent to a sulfur filter, which can produce filter cake as high as 85% ary 2003, pp. 53–57.
sulfur. If desired, the filter cake can be further washed and melted to Licensor: Merichem Chemicals & Refinery Services LLC, Gas Technology
produce pure molten sulfur. Products Division.

H2S removal
Applications: Sulfur-Rite is a solid-bed scavenger for removal of H2S from
aerobic and anaerobic gas streams. Suitable applications are generally
sulfur loads below 200 lb/d sulfur, and/or remote refinery locations. Sul-
fur vents, loading and unloading facilities, or backup insurance for other H2O inject
refinery sulfur-removal systems are examples.

Inlet
The spent media is nonpyrophoric, and is suitable for disposition in knockout
Sour gas pot
nonhazardous landfills.
Sweet gas
Description: Single-bed (shown) or dual “lead-lag” configurations are
Drains
possible. Sour gas is saturated prior to entering media bed. Gas enters
vessel top, flows over media where H2S is removed and reacted. Sweet
gas exits the bottom of vessel. In the single-vessel configuration, when
the H2S level exceeds the level allowed, the vessel must be bypassed,
media removed through the lower manway, fresh media installed and
vessel returned to service.
For continuous operation, a dual “lead-lag” configuration is desir- Operating conditions: Gas streams up to 400°F can be treated. Gas
able. The two vessels operate in series, with one vessel in the lead posi- streams should be at least 50% water saturated.
tion, the other in the lag position. When the H2S level at the outlet of
the lead vessel equals the inlet H2S level (the media is completely spent), Installations: Sixteen units installed.
the gas flow is changed and the vessels reverse rolls, so that the “lag”
Licensor: Merichem Chemicals & Refinery Services LLC, Gas Technology
vessel becomes the “lead” vessel. The vessel with the spent media is
Products Division.
bypassed. The media is replaced, and the vessel with fresh media is re-
turned to service in the “lag” position.

Treating
7
Application: The AMMEX process integrates sour water stripping and 5 E
sour gas scrubbing in a single simple process. It can be used without
supplemental ammonia (NH3) to remove some of the hydrogen sulfide
(H2S) from a gas stream, for instance to unload an existing amine unit. 4 C
X
8
Adding a substoichiometric amount of NH3 allows AMMEX to reduce B
H2S in the scrubbed gas to low concentration, eliminating the need for P
a separate amine system for gas treating. AMMEX is especially attractive 6 P D
when the sour water stripper gas is converted to ammonium thiosulfate
2 X
in ThioSolv’s SWAATS process.
A
Description: ThioSolv developed this process by modeling in PRO/II 8.1 1 S

using electrolyte thermo. Water in contact with refining process gases T
readily dissolves essentially all of the NH3 from the gas. The NH3 solu- 3 X P
tion, in turn, dissolves roughly equimolar amounts of H2S, which is typi-

9
cally present in excess. The molar ratio of H2S/NH3 in the feed to the sour
water stripper is therefore typically about 1. Because the vapor pressure
of H2S over water increases faster with temperature than the vapor pres-
sure of NH3, the ratio of H2S/NH3 in the sour water stripper reflux liquid
is about 1/3. When liquid from the reflux drum is cooled, excess NH3 in is added to the second contacting zone B. The refinery sour water (8)
solution allows the liquid to absorb more H2S from a gas stream. feeds the stripper conventionally, with the net stripped water (9) leaving
Sour feed gas (1) is fed to a first contact zone A, where it is scrubbed the system. Net H2S and NH3 leave the reflux drum C as sour water strip-
with a stream of cooled liquid (2) from the reflux drum C of a sour-water per gas (7). Heat for stripping is provided by LP steam S.
stripper D (SWS). The high ratio of NH3 to H2S in the liquid allows it to The SWS acid gas may be fed to a conventional sulfur recovery pro-
dissolve H2S from the gas. Rich liquid (3) from the bottom of the first cess, but more favorably would be converted to ammonium thiosulfate
contact zone is preheated by exchange (X) and combined with the par- (ATS) fertilizer in ThioSolv’s SWAATS process.
tially-condensed stream from the SWS condenser E. Heat removal from
the condenser is modulated to control the temperature of the combined Economics: AMMEX is highly energy efficient. Most of the H2S is re-
stream to the reflux drum. The gas leaving the first contact zone, con- moved from the feed gas by the circulation from the reflux drum, using
taining some NH3 stripped from the recycle liquid and some H2S, enters latent heat of condensation that would normally be rejected to atmo-
a second contacting zone B, where it is washed with cooled, recycled sphere to reheat the rich liquid and flash out excess H2S. Circulation of
sour water (4), which dissolves some H2S and essentially all of the NH3 the reflux liquid costs only pump power and some cooling water. The
from the gas, carrying it into the first zone A. If the intent is to reduce recycle rate of stripped water required to remove NH3 from the gas in
the H2S concentration in the scrubbed gas to meet a specification, rath- the second contactor adds only a relatively small load to the sour water
er than simply to remove most of the H2S, a small amount of NH3 (6) Continued 
cle of 14 gpm of stripped sour water for washing. By contrast, scrubbing
Treating, continued the fuel gas with MDEA would require six times as much circulation.
The sour water stripper gas produced can be converted to ATS in a
stripper. Because the amount of H2S in the gas entering the second zone SWAATS unit at negligible operating cost.
B is small compared to the amount in the feed gas, the moles of NH3
addition required to reduce the H2S concentration to <100 ppm is less Installation: None. Patent pending.
than the total moles of H2S captured.
Licensor: ThioSolv, LLC.
Example: A refinery makes 10 tpd of sulfur as H2S, 90% in sour fuel gas
and 10% in sour water. Sour fuel gas containing 6% H2S and 0.6% CO2
can be treated to <20 ppm H2S using 4.6 tpd of NH3 addition and recy- click here to e-mail for more information
Treating—gases Untreated gas

Treated gas
Application: AMINEX and THIOLEX systems extract COS and H2S from Fresh caustic or lean amine
from regeneration unit
gases with amine or caustic solution using FIBER-FILM Contactor tech-
nology.
Description: In an AMINEX system, the amine phase flows along the fi-
bers of the FIBER-FILM Contactor as it preferentially wets the fibers. The
gas phase flows through the Contactor parallel to the amine-wetted
fibers as the COS and H2S is extracted into the amine. The two phases
disengage in the separator vessel with the rich amine flowing to the
amine regeneration unit and the treated gas flowing to its final use.
Similarly, a THIOLEX system employs the same process utilizing caus-
tic and caustic/amine solutions to preferentially wet the fibers as the
COS and H2S is extracted into the caustic phase. The rich caustic flows
to sulfidic caustic storage and the treated gas flows to its final use. Spent caustic to disposal or
rich amine to regeneration unit
Competitive advantages: FIBER-FILM Contactor technology requires
smaller processing vessels thus saving valuable plant space and reducing
capital expenditures.
Installation: Four installations worldwide in THIOLEX service.

Reference: Hydrocarbon Processing, Vol. 63, No. 4, April 1984, P. 87.
ogy Division.

Treating—sour water stripper gas AAG Claus reactors Sulfur

and condensers
Application: The sour water ammonia to ammonium thiosulfate
(SWAATS) process diverts sour water stripper gas (SWSG) from the
Claus
Claus to convert the ammonia (NH3 ) and hydrogen sulfide (H2S) to thermal reactor Tail
gas
ammonium thiosulfate (ATS) solution, thus freeing up Claus capacity Incinerator
and improving operability. SWAATS also can treat Claus tail gas to low
Burner X
emissions at low cost. For plants producing small amounts of sulfur,
SWAATS can be designed to capture all of the refinery H2S. The cost of Rx
supplemental ammonia (0.54 ton NH3 / ton sulfur) is justified by having X
SWSG
only one unit that can process both SWSG and amine-acid gas (AAG) WHB
with low emission rates.
High chemical selectivity of the process enables it to economically
SWAATS SWAATS ATS
remove H2S or SO2 from gas mixtures including carbon dioxide. The reactor absorber
process has been recognized by EPA as best available control technology
(BACT) for control of sulfur oxide (SO2) emissions.
Description: Ammonia and a stoichiometric amount of H2S are selec-

tively absorbed from SWSG. The reject H2S and Claus tail gas, if desired,
ing NH3 from the Claus feed also greatly improves Claus operability
are selectively oxidized to convert all sulfur species to SO2, which is then
and extends the service life of the catalyst. With SWAATS, the SWSG
scrubbed from the combustion gas in a low pressure drop system to
ammonia is an asset; the value of the process increases as higher
yield a vent gas with very low SOx concentration and no reduced sulfur
severity hydrotreating for ultra-low-sulfur diesel production increases
requiring incineration:
denitrification to over 90%, greatly increasing ammonia production.
6NH3 + 4SO2 + 2H2S + H2O 3(NH4)2S 2O3(ATS) CAPEX for SWAATS to process SWSG and Claus tail gas is about a
quarter of the CAPEX for construction of an equivalent amount of new
SWAATS may be controlled to import or export H2S to balance on Claus and tail-gas treating capacity. SWAATS OPEX is typically negative
the NH3 available in the SWSG, or supplemental NH3 may be added to due to credit for export of MP steam, substantially lower than the OPEX
capture additional H2S. for oxygen enrichment or for amine-based tail gas treatment. SWAATS
The chemistry and internal circulation rates provide for robust op- consumes no external chemicals or reducing gas. Licensor removes the
eration, resistant to upsets in the feedstreams. They also prevent or re- ATS produced.
verse sulfur precipitation by converting any elemental sulfur in the Claus
tail gas to thiosulfate. Control is based on simple inline analyzers (pH, Installation: The first unit is operating since June 2007, using supple-
combustion gas O2) and requires little attention. mental NH3 to capture all of the refinery sulfur to eliminate need for a
second type of sulfur-recovery unit. Two more SWAATS units have been
Economics: Each ton of SWSG sulfur diverted from Claus to SWAATS licensed and designed as of June ‘08.
frees up Claus capacity for about three tons of AAG sulfur. Remov- Continued 
Treating—sour water stripper gas, continued
Reference: US Patent 6,534,030 and other patents pending.
Berry, R., “Treating hydrogen sulfide: When Claus is not enough,”
Chemical Engineering, Oct. 6, 1980, p. 92.
Anderson, M.C., “Increasing SRU capacity,” Sulphur, September-
October 2007, p. 52.
Licensor: ThioSolv, LLC.

Wet gas scrubbing (WGS), wet gas ATM

scrubbing plus Stack
Application: ExxonMobil’s Research & Engineering’s (EMRE’s) can reduce CO boiler
fluid catalytic cracking unit (FCCU) particulate (catalyst) and sulfur oxides
(SOx) and nitrogen oxide (NOx) emissions to achieve compliance with FCCU
Venturi
scrubbers
environmental regulations—generally NSPS (New Source Performance regenerator
or third
Standards) and consent decrees (in the US). The technology can also be separator
Makeup water Disengaging
adapted for other refinery applications, e.g., coke calciners when flue
drum
gases must be treated to reduce SOx and particulate emissions. Air Oxidation
tank
Description: The WGS process takes dirty gas from FCCUs and simul- Oxidation Caustic
Slurry circulation
blower
taneously removes particulate matter and SOx via direct contact with a pumps
buffered liquid. Particulate removal is accomplished via inertial impaction
of the particulate with the scrubbing liquid. SO2 removal is accomplished
Treated purge
via absorption into and reaction with the buffered scrubbing liquid. SO3
removal is accomplished via a combination of nucleate condensation, Circulation
pump and spare Filter press
absorption and inertial impaction. All of this can be accomplished with Filter feed Dry solids
pump and spare Dry solids dumpster
low-pressure (3-in. of water column) or no pressure drop. This is impor-
tant when aged heat recovery systems are involved.
The liquid purge from the WGS system is further treated in either the
refinery wastewater system or in a segregated system, either of which
will remove solids for landfill disposal and will reduce the chemical oxy- Performance: All WGS facilities are in compliance with their permitted
gen demand (COD) of the stream to meet local discharge requirements. values. Compliance has been achieved for the current consent decree
NOx can be removed by adding an additional particulate limits that can require emission of less than ¼ -lb of particu-
Operation of WGS systems demonstrates: lates /1,000 lb of coke burned. They are also in compliance with consent
• Flexible/”forgiving” performance under a wide range of FCCU op- decree SO2 requirements of 25 vppmd @ 0% O2 and SO3 consent de-
erations/upsets cree emission requirements of less than 10 vppmd. In addition, the WGS
• Service factors equal to or better than FCCUs with runs exceeding has recorded run lengths in excess of 12 years without affecting FCCU
12 years throughput.
• Low/zero pressure drop
• Ability to meet stringent emission regulations, e.g., consent de-
Installation: More than 25 operating plants have over 500 years of op-
erating experience. Several additional units are in various stages of en-
cree requirements.
gineering.
Continued 
Wet gas scrubbing (WGS), wet gas scrubbing plus, Technology owner: ExxonMobil Research and Engineering Co.
continued Licensor: Hamon Research-Cottrell, GN-Hamon, LLC.
Reference: 1991 AIChE Spring National Meeting, Paper No. 62c.
1990 National Petroleum Refiners Association Annual Meeting, Pa- click here to e-mail for more information
per No. AM-90-45, March 1990.
1996 National Petroleum Refiners Association Annual Meeting, Pa-
per No. AM-96-47, March 1996.
Flue gas denitrification

NO, NO2
Application: The Topsøe SCR DeNOx process removes NOx from flue QI
gases through reactions with an ammonia-based reducing agent over From furnace
a specially designed fixed-bed monolithic catalyst. By carefully select-
Compressed air
ing the catalyst parameters, channel size and chemical composition, the
process covers a wide range of operating conditions and flue-gas dust SCR
reactor PI
contents and may be applied to practically all types of refinery units in- FI
cluding furnaces, boilers, crackers and FCC units. PI
Caustic ammonia
Products: The Topsøe SCR DeNOx converts NOx into inert nitrogen and Soot blower
water vapor. The process may be designed for NOx reductions in excess Steam
of 95% and with an ammonia leakage of just a few ppm.
To stack
Description: The reducing agent such as ammonia or urea, aqueous or
Control
pure, is injected into the flue gas stream in stoichiometric proportion to QI QI unit
the amount of NOx in the flue gas, controlled by measurement of flue NH3 NO
gas flow and NOx concentration. The injection takes place in a grid over
the entire cross-section of the flue-gas duct to ensure a uniform distribu-
tion of NOx and ammonia upstream the SCR catalyst vessel.
The process incorporates Topsøe’s well-proven corrugated mono-
lithic DNX catalyst. DNX is manufactured in small units, which may be Installation: More than 50 refinery units use Topsøe SCR DeNOx catalyst
combined into larger modules to match any requirement in terms of and technology. The applications range from low-dust furnaces to high-
vessel dimensions and pressure drop, and in both horizontal and vertical dust FCC units and temperatures up to 500°C (930°F).
vessel configurations.
The DNX catalyst is based on a fiber-reinforced ceramic carrier, which References: Damgaard, L., B. Widroth and M. Schröter: “Control refin-
gives a unique combination of a high strength and a high micro-poros- ery NOx with SCRs,” Hydrocarbon Processing, November 2004.
ity. The high micro-porosity provides a superior resistance to catalyst
poisons and low weight. The fibers add flexibility to the catalyst so that Licensor: Haldor Topsøe A/S.
it can tolerate a wide range of heating and cooling rates.
Operating conditions: Typical operating conditions range from 300°C to

500°C (570–930°F), up to 3 bar (44 psia) and up to 50 g/Nm3 of dust in
the flue gas.

NOx abatement/SNCR
Application: Flue gases are treated with ammonia: ExxonMobil’s Re- Heater load NOx
NH3 flow analyzer
search & Engineering’s (EMRE’s) proprietary selective noncatalytic NOx controller
Pressure
reduction technology—SNCR THERMAL DeNOx (TDN). NOx plus ammo- controller
nia (NH3) are converted to elemental nitrogen and water if temperature
and residence time are appropriate. The technology has been widely
applied since it was first commercialized in 1974. Injectors
Anhydrous NH3
Products: If conditions are appropriate, the flue gas is treated to achieve storage
NOx reductions of 40% to 70%+ with minimal NH3 slip or leakage. NH3 Heater
vaporizer Flow controller
Description: The technology involves the gas-phase reaction of NO with Heater load
NH3 (either aqueous or anhydrous) to produce elemental nitrogen if con-
Fuel
ditions are favorable. Ammonia is injected into the flue gas using steam Carrier supply Combustion air
or air as a carrier gas into a zone where the temperature is 1,600°F
to 2,000°F. This range can be extended down to 1,300°F with a small
amount of hydrogen added to the injected gas. For most applications,
wall injectors are used for simplicity of operation.
McIntyre, A. D., “The THERMAL DeNOx process: Liquid fuels appli-
Yield: Cleaned flue gas with 40% to 70%+ NOx reduction and less than cations,” International Flame Research Foundation’s 11th Topic Oriented
10-ppm NH3 slip. Technical Meeting, Biarritz, France, 1995.
McIntyre, A. D., “Applications of the THERMAL DeNOx process to
Installation: Over 135 applications on all types of fired heaters, boilers FBC boilers,” CIBO 13th Annual Fluidized Bed Conference, Lake Charles,
and incinerators with a wide variety of fuels (gas, oil, coal, coke, wood Louisiana, 1997.
and waste). The technology has also been applied to full and partial-
burn FCCU regenerators. Licensor: ExxonMobil Research and Engineering Co., via an alliance with
Engineers India Ltd. (for India) and Hamon Research-Cottrell (for the rest
Reference: McIntyre, A. D., “Applications of the THERMAL DeNOx pro- of the world).
cess to utility and independent power production boilers,” ASME Joint
International Power Generation Conference, Phoenix, 1994.

Treating—Coker LPG to low total Treated coker LPG
sulfur levels Coker LPG Total sulfur < 2ppm-wt
Application: AMINEX/THIOLEX and REGEN ULS treating processes are

used to remove COS, H2S and mercaptans from LPG streams with high
mercaptans levels and produce treated streams with less than 2 ppm-wt
of total sulfur.
Lean amine or
Description: The removal of COS and H2S can be achieved utilizing an Caustic/MEA
AMINEX treating unit using an amine solution or with a THIOLEX treating Rich amine or
Spent caustic/MEA Solvent
unit using a caustic solution. When using the THIOLEX unit, mercaptan
impurities are removed with a caustic solution, and the caustic is regen- Air
erated to previously unachievable purity levels in the REGEN ULS system. Vent
The combination of THIOLEX/REGEN ULS results in minimal back extrac- Solvent/DSO
tion of disulfide oil (DSO) into the treated product. Thus, the treated
product will meet specifications of less than 2 ppm-wt of total sulfur.
Installations: One under installation.

ogy Division.

Treating— gasoline and LPG Treated hydrocarbon

Application: THIOLEX/REGEN systems extract H2S and mercaptans from
gases and light liquid hydrocarbon streams, including gasolines, with Oxidation air
Offgas
caustic using FIBER-FILM Contactor technology. It can also be used to
hydrolyze and remove COS from LPG and propane. Untreated
Fresh solvent
hydrocarbon
Description: In a THIOLEX system, the caustic phase flows along the
fibers of the FIBER-FILM Contactor as it preferentially wets the fibers.
Hydrocarbon flows through the caustic-wetted fibers where the H2S and
mercaptans are extracted into the caustic phase. The two phases disen-
Spent
gage and the caustic flows to the REGEN where the caustic is regener- caustic
ated using heat, air and catalyst. The disulfide oil formed in this reaction Catalyst
may be removed via gravity separation, FIBER-FILM solvent washing or
a combination of the two. The regenerated caustic flows back to the Fresh caustic
THIOLEX system for continued re-use.
Solvent/DSO
COS is removed from LPG or propane by either employing AMINEX
technology using an amine solution or THIOLEX technology using an
MEA/caustic solution to hydrolyze the COS to H2S and CO2 which are
easily removed by amine or caustic.
Competitive advantages: FIBER-FILM Contactor technology requires References: Oil & Gas Journal, August 12, 1985, p. 78.
smaller processing vessels thus saving valuable plant space and reducing Hydrocarbon Engineering, February 2000.
capital expenditures.
Installation: At present, 373 installations worldwide. ogy Division.

Treating—gasoline desulfurization,
ultra deep To outside
disposal Or Spent treating
solution cleaning
plant
Application: EXOMER extracts recombinant mercaptan sulfur from se- Cleansed treating solution to
wastewater treatment plant
lectively hydrotreated FCC gasoline streams with a proprietary treating
solution. FIBER-FILM Contactor technology is used for mass transfer ef- Spent treating
solution storage Treated FCC naphtha
ficiency to obtain a maximum reduction in total sulfur content. EXOMER
is jointly developed with ExxonMobil Research & Engineering Co.
Hydrotreated FCC naphtha
Rich treating solution
Description: In an EXOMER system, the lean treating solution phase
flows along the fibers of the FIBER-FILM Contactor along with the hy- Mercaptan
extraction
Fresh treating
solution
drocarbon phase, allowing the recombinant mercaptans to be extracted system
into the treating solution in a non-dispersive manner. The two phases Regenerated
treating solution Treating solution
disengage in the separator vessel with the treated hydrocarbon flowing regeneration
system
to storage. Sulfur-rich
Treating solution purge stream
The separated rich treating solution phase is sent to the regenera-
tion unit where sulfur-bearing components are removed. The removed
sulfur is sent to another refinery unit for further processing. The regen-
erated lean treating solution is returned to the EXOMER extraction step
for further use.
Installation: Three installations worldwide.
Economics: EXOMER allows refiners to meet stricter sulfur specifica-
tions while preserving octane by allowing the hydrotreater severity to be Reference: Hydrocarbon Processing, February 2002, p. 45.
reduced. The capital expenditure for a grass roots EXOMER is 35 – 50%
of the cost of incremental hydrotreating capacity. Operating costs per Licensor: Merichem Chemicals & Refinery Services LLC, Process Technol-
barrel are about 60 –70% less than hydrotreating. ogy Division.

Treating— gasoline sweetening
Untreated gasoline Sweetened gasoline
Application: MERICAT systems oxidize mercaptans to disulfides by react-
ing mercaptans with air and caustic in the presence of catalyst using
FIBER-FILM Contactor technology.
Description: In a MERICAT system, the caustic phase flows along the fi-
Oxidation air
bers of the FIBER-FILM Contactor as it preferentially wets the fibers. Prior
to entering the FIBER-FILM Contactor the gasoline phase mixes with air
through a proprietary air sparger. The gasoline then flows through the
caustic-wetted fibers in the Contactor where the mercaptans are ex- Catalyst
tracted and converted to disulfides in the caustic phase. The disulfides Spent caustic
are immediately absorbed back into the gasoline phase. The two phases
disengage and the caustic is recycled back to the FIBER-FILM Contactor
until spent.
Fresh caustic
Competitive advantages: FIBER-FILM Contactor technology uses smaller
processing vessels while guaranteeing the sodium content of the prod-
uct. This saves valuable plant space and reduces capital expenditure.
Installation: At present, 144 installations worldwide.

ogy Division.

Treating—jet fuel/kerosine
Application: NAPFINING / MERICAT II / AQUAFINING systems eliminate Air Catalyst in (batch)
naphthenic acids and mercaptans from kerosine to meet acid number Untreated
and mercaptan jet fuel specifications. Caustic, air and catalyst are used jet fuel
along with FIBER-FILM Contactor technology and an upflow catalyst im- START
pregnated carbon bed saturated with caustic.
Description: In the NAPFINING system, the caustic phase flows along

the fibers of the FIBER-FILM Contactor as it preferentially wets the fi- Treated
jet fuel
bers. The kerosine phase simultaneously flows through the caustic-wet-
ted fibers where naphthenic acids react with the caustic phase to form
sodium naphthenate. The two phases disengage and the naphthenic
acid-free kerosine flows to the MERICAT II where the mercaptans react
Water in
with caustic, air, and catalyst in the FIBER-FILM Contactor to form disul-
Caustic out Caustic in
fides. The two phases disengage again and the kerosine flows upwards Water out
through a catalyst impregnated carbon bed where the remaining heavy
mercaptans are converted to disulfides.
An AQUAFINING system is then used to water wash the kerosine
downstream of the MERICAT II vessel to remove sodium. Salt driers and
clay filters are used downstream of the water wash to remove water,
surfactants and particulates to ensure a completely clean product. Installation: 199 installations worldwide.
Competitive advantages: FIBER-FILM Contactor technology requires References: Hydrocarbon Technology International, 1993.
smaller processing vessels thus saving valuable plant space and reduc- Petroleum Technology Quarterly, Winter 1996/97.
ing capital expenditure. Onstream factor is 100% whereas electrostatic
precipitators and downflow fixed-bed reactors onstream factors are un-
ogy Division.
predictable.

Treating—kerosine and heavy naphtha

sweetening Untreated kerosine Treated kerosine
Application: MERICAT II treating unit oxidizes mercaptan sulfur to disul-

fides to reduce product odor. The streams treated are jet fuel, kerosine, Air in
natural gasoline and selectively hydrotreated FCC gasolines.
Description: A MERICAT II system consists of two treaters. The FIBER- Catalyst in

FILM Contactor section removes hydrogen sulfide and naphthenic acids
while converting some mercaptans to disulfides with air, oxidation cata-
lyst and caustic solution. The partially treated hydrocarbon exits the FI-
BER-FILM Contactor and passes upflow through a catalyst-impregnated
carbon bed saturated with caustic to convert the remaining high-boiling Fresh caustic
mercaptans to disulfides. Spent caustic
Competitive advantages:
• Minimal caustic and catalyst consumption
• Operating simplicity
• Minimal capital investment
• Recausticizing of the carbon bed without interruption of treating.
The FIBER-FILM section keeps organic acids from entering the carbon
Installation: Thirty-nine installations worldwide.
bed. This conserves caustic and avoids fouling of the bed with sodium
naphthenate soaps. Competitive downflow reactors need frequent car- Reference: Hydrocarbon Technology International, 1993.
bon bed hot water washings to remove these soaps whereas MERICAT
II does not require hot water washes. Licensor: Merichem Chemicals & Refinery Services LLC, Process Technol-
The MERICAT II onstream factor is 100% while competitive systems ogy Division.
requiring periodic cleaning have unpredictable onstream factors.

Treating—propane
Application: AMINEX treating system extracts H2S and COS from pro-
pane with an amine solution using FIBER-FILM Contactor technology. Untreated LPG Treated LPG
Description: In an AMINEX system, the amine phase flows along the fi-
bers of the FIBER-FILM Contactor as it preferentially wets the fibers. The
propane phase flows through the amine-wetted fibers as the H2S and
COS are extracted into the amine phase. The two phases disengage in
the separator vessel with the rich amine flowing to the amine regenera-
tion unit and the treated propane flowing to storage.
Competitive advantages: FIBER-FILM Contactor technology requires

smaller processing vessels thus saving valuable plant space and reducing
capital expenditure.
Rich amine to regenerator Lean amine from regenerator
Installation: Twenty-six installations worldwide.

Reference: Hydrocarbon Processing, Vol. 63, No. 4, April 1984, p. 87.
ogy Division.

Treating—reformer products
Application: CHLOREX treating system removes inorganic chloride com-
Untreated reformate Treated reformate
pounds from liquid and gas reformer products using a FIBER-FILM Con-
tactor and an alkaline water treating solution. Recycle
Description: The CHLOREX system uses an alkaline water solution to

extract chloride impurities contained in the reformate stabilizer feed or
the stabilizer overhead product. CHLOREX can also be used to remove
Separator
chlorides from reformer offgas. Fresh caustic and fresh process water are
added to the system to maintain the proper pH of the recycle solution.
Competitive advantages: CHLOREX produces an easily handled waste Spent alkaline water
when compared to disposal of sacrificial solid bed absorbents.
Fresh water
Installation: Four installations worldwide. Fresh caustic

ogy Division.

Flue gas desulfurization—SNOX

Application: The SNOX process treats boiler flue gases from the com-
bustion of high-sulfur fuels, such as heavy residual oil and petroleum Cleaned gas
coke. The SNOX process is a combination of the Topsøe WSA process
Boiler
and the Topsøe SCR DeNOx process. The process removes SO2, SO3 and Blower SCR DeNOx
Petcoke Air and SO2 reactor
NOx as well as dust. The sulfur is recovered in the form of concentrated
commercial-grade sulfuric acid. The SNOX process is distinctly different WSA
from most other flue gas desulfurization processes in that its economy Flue gas condenser
increases with increasing sulfur content in the flue gas.
Filter
Description: Dust is removed from the flue gas by means of an electro-
static precipitator or a bag filter. The flue gas is preheated in a gas/gas Flue gas Heat
Support
blower exchanger NH3
heat exchanger. Thereafter, it is further heated to approximately 400°C Air
heat
and ammonia is added, before it enters the reactor, where two different preheater Acid cooler
Product acid
catalysts are installed. The first catalyst makes the NOx react with ammo-
nia to form N2 and water vapor, and the second catalyst makes the SO2
react with oxygen to form SO3. The second catalyst also removes any
dust traces remaining. During the cooling in the gas/gas heat exchanger,
most of the SO3 reacts with water vapor to form sulfuric acid vapor. The
sulfuric acid vapor is condensed via further cooling in the WSA con-
denser, which is a heat exchanger with vertical glass tubes. • High degree of heat efficiency
Concentrated commercial-grade sulfuric acid is collected in the • Modest utility consumption
bottom of the WSA condenser and is cooled and pumped to storage. • Attractive operating economy
Cleaned flue gas leaves the WSA condenser at 100°C and can be sent • Simple, reliable and flexible process.
to the stack without further treatment. The WSA condenser is cooled by
Installation: Six SNOX units have been contracted for cleaning of a total
atmospheric air. The cooling air can be used as preheated combustion
of more than five million Nm3/ h of flue gas. Additionally, 65 WSA plants
air in the boiler. This process can achieve up to 98% sulfur removal and
have been contracted. These are similar to SNOX plants, only smaller,
about 96% NOx removal.
and some without NOx removal, for other applications than flue gas
Other features of the SNOX process are:
cleaning.
• No absorbent is applied
• No waste products are produced. Besides dust removed from the Licensor: Haldor Topsøe A/S.
flue gas, the only products are cleaned flue gas and concentrated
commercial-grade sulfuric acid.

NOx reduction, low-temperature

Application: The LoTOx low-temperature oxidation process removes NOx
from flue gases in conjunction with BELCO’s EDV wet scrubbing system. EDV scrubber stack
Ozone is a very selective oxidizing agent; it converts relatively insoluble
NO and NO2 to higher, more soluble nitrogen oxides. These oxides are
easily captured in a wet scrubber that is controlling sulfur compounds EDV quench Reagent
and/or particulates simultaneously.
Purge
Description: In the LoTOx process, ozone is added to oxidize insoluble
NO and NO2 to highly oxidized, highly soluble species of NOx that can
be effectively removed by a variety of wet or semi-dry scrubbers. Ozone, LoTOx
injection
a highly effective oxidizing agent, is produced onsite and on demand
by passing oxygen through an ozone generator—an electric corona de-
vice with no moving parts. The rapid reaction rate of ozone with NOx
results in high selectivity for NOx over other components within the gas
stream.
Thus, the NOx in the gas phase is converted to soluble ionic com- Installation: The technology has been developed and commercialized
pounds in the aqueous phase; the reaction is driven to completion, thus over several years, winning the prestigious 2001 Kirkpatrick Chemical
removing NOx with no secondary gaseous pollutants. The ozone is con- Engineering Technology Award. Currently, there are 11 commercial ap-
sumed by the process or destroyed within the system scrubber. All sys- plications, including boilers and 5 FCC units. Many other EDV scrubbers
tem components are proven, well-understood technologies with a his- have been designed for future LoTOx application. Pilot-scale demonstra-
tory of safe and reliable performance. tions have been completed on coal- and petroleum-coke fired boilers, as
well as refinery FCC units.
Operating conditions: Ozone injection typically occurs in the flue-gas
stream upstream of the scrubber, near atmospheric pressure and at Reference: Confuorto, et al., “LoTOx technology demonstration at Mar-
temperatures up to roughly 150°C. For higher-temperature streams, the athon Ashland Petroleum LLC’s refinery at Texas City, Texas,” NPRA An-
ozone is injected after a quench section of the scrubber, at adiabatic nual Meeting, March 2004, San Antonio.
saturation, typically 60°C to 75°C. High-particulate saturated gas and
sulfur loading (SOx or TRS) do not cause problems. Licensor: Belco Technologies Corp.
Economics: The costs for NOx control using this technology are espe-
cially low when used as a part of a multi-pollutant control scenario.
Sulfurous and particulate-laden streams can be treated attractively as no
pretreatment is required by the LoTOx system.
SO2 removal, regenerative

Application: Regenerative scrubbing system to recover SO2 from flue gas Reclaimed SO2
containing high SO2 levels such as gas from FCC regenerator or inciner-
Condenser
ated SRU tail gas and other high SO2 applications. The LABSORB process Cleaned
gas
is a low pressure drop system and is able to operate under varying condi- Quench column
pre-scrubber Stripper
tions and not sensitive to variations in the upstream processes. Absorber
Vapor/
liquid
Products: The product from the LABSORB process is a concentrated SO2 separator
stream consisting of approximately 90% SO2 and 10% moisture. This LP
steam
stream can be sent to the front of the SRU to be mixed with H2S and Buffer
makeup
form sulfur, or it can be concentrated for other marketable uses. Flue gas Heat
exch.
Description: Hot dirty flue gas is cooled in a flue-gas cooler or waste- Buffer tank
Condensate
heat recovery boiler prior to entering the systems. Steam produced can
be used in the LABSORB plant. The gas is then quenched to adiabatic Oxidation
product removal
Particulates
saturation (typically 50°C–75°C) in a quencher/pre-scrubber; it proceeds
to the absorption tower where the SO2 is removed from the gas. The
tower incorporates multiple internal and re-circulation stages to ensure
sufficient absorption.
A safe, chemically stable and regenerable buffer solution is con-
tacted with the SO2-rich gas for absorption. The rich solution is then Installation: One SRU tail-gas system and two FCCU scrubbing systems.
piped to a LABSORB buffer regeneration section where the solution is
regenerated for re-use in the scrubber. Regeneration is achieved using Reference: Confuorto, Weaver and Pedersen, “LABSORB regenerative
low-pressure steam and conventional equipment such as strippers, con- scrubbing operating history, design and economics,” Sulfur 2000, San
densers and heat exchangers. Francisco, October 2000.
Confuorto, Eagleson and Pedersen, “LABSORB, A regenerable wet
Economics: This process is very attractive at higher SO2 concentrations scrubbing process for controlling SO2 emissions,” Petrotech-2001, New
or when liquid or solid effluents are not allowed. The system’s buffer Delhi, January 2001.
loss is very low, contributing to a very low operating cost. Additionally,
when utilizing LABSORB as an SRU tail-gas treater, many components Licensor: Belco Technologies Corp.
normally associated with the SCOT process are not required; thus saving
considerable capital.

Sour gas treatment

Application: The WSA process (Wet gas Sulfuric Acid) treats all types of
sulfur-containing gases such as amine and Rectisol regenerator offgas, Blower
Stack gas
SWS gas and Claus plant tail gas in refineries, gas treatment plants, Combustion air
petrochemicals and coke chemicals plants. The WSA process can also be SO2
applied for SOx removal and regeneration of spent sulfuric acid. H2S gas converter Blower
Air
Sulfur, in any form, is efficiently recovered as concentrated commer- Interbed
Incinerator
cial-quality sulfuric acid. cooler WSA
Interbed condenser
cooler
Description: Feed gas is combusted and cooled to approximately
Gas
420°C in a waste heat boiler. The gas then enters the SO2 converter cooler
containing one or several beds of SO2 oxidation catalyst to convert Steam
system Acid cooler
SO2 to SO3. The gas is cooled in a gas cooler whereby SO3 hydrates to
H2SO4 (gas), which is finally condensed as concentrated sulfuric acid Superheated Product acid
(typically 98% w/w). steam
The WSA condenser is cooled by ambient air, and heated air may
be used as combustion air in the incinerator for increased thermal effi-
ciency. The heat released by incineration and SO2 oxidation is recovered
as steam. The process operates without removing water from the gas.
Therefore, the number of equipment items is minimized, and no liquid
waste is formed. Cleaned process gas leaving the WSA condenser is sent • Efficient heat recovery ensuring economical operation
to stack without further treatment. • Simple and fully automated operation adapting to variations in
The WSA process is characterized by: feed gas flow and composition.
• More than 99% recovery of sulfur as commercial-grade
sulfuric acid Installation: More than 70 units worldwide.
• No generation of waste solids or wastewater Licensor: Haldor Topsøe A/S.
• No consumption of absorbents or auxiliary chemicals

Spent acid regeneration

Application: The WSA process (Wet gas Sulfuric Acid) treats spent sul- Stack gas
furic acid from alkylation as well as other types of waste sulfuric acid
in the petrochemical and chemicals industry. Amine regenerator offgas Dust
and /or refinery gas may be used as auxiliary fuel. The regenerated acid Spent acid removal SO2
DENOX converter
+ fuel Air
will contain min. 98% H 2 SO 4 and can be recycled directly to the alkyla-
tion process. Incinerator
The WSA process is also applied for conversion of H 2S and removal WSA
condenser
of SOx. Export steam
Heat exchange system
Description: Spent acid is decomposed to SO2 and water vapor in an

incinerator using amine regenerator offgas or refinery gas as fuel. The Cooler
SO 2 containing flue gas is cooled in a waste-heat boiler and solid matter
Acid
originating from the acid feed is separated in an electrostatic precipita-
tor. By adding preheated air, the process gas temperature and oxygen
content are adjusted before the catalytic converter converting SO2 to
SO3. The gas is cooled in the gas cooler whereby SO3 is hydrated to
H 2SO4 (gas), which is finally condensed as 98% sulfuric acid.
The WSA condenser is cooled by ambient air. The heated air may be The WSA process is characterized by:
used as combustion air in the burner for increased thermal efficiency. The • No generation of waste solids or wastewater
heat released by incineration and SO 2 oxidation is recovered as steam. • No consumption of absorbents or auxiliary chemicals
The process operates without removing water from the gas. There- • Efficient heat recovery ensuring economical operation
fore, the number of equipment items is minimized and no liquid waste • Simple and fully automated operation adapting to variations in
is formed. This is especially important in spent acid regeneration where feed flow and composition.
SO 3 formed by the acid decomposition will otherwise be lost with the
Installation: More than 70 WSA units worldwide, including 10 for spent
wastewater.
acid regeneration.
Licensor: Haldor Topsøe A/S.

Wet scrubbing system, EDV

Application: EDV Technology is a low pressure drop scrubbing system, Cleaned gas
to scrub particulate matter (including PM2.5), SO2 and SO3 from flue Stack
gases. It is especially well suited where the application requires high reli-
ability, flexibility and the ability to operate for 4 – 7 years continuously Droplet
separators
without maintenance shutdowns. The EDV technology is highly suited Reagent addition
for FCCU regenerator flue-gas applications. Filtering
modules
Products: The effluents from the process will vary based on the re-
Absorber
agent selected for use with the scrubber. In the case where a sodium-
based reagent is used, the product will be a solution of sodium salts. Flue gas
Quench
Similarly, a magnesium-based reagent will result in magnesium salts.
Slipstream to purge treatment unit
A lime/limestone-based system will produce a gypsum waste. The EDV
technology can also be used with the LABSORB buffer thus making Recirculation
pumps
the system regenerative. The product, in that case, would be a usable
condensed SO 2 stream.
Description: The flue gas enters the spray tower through the quench
section where it is immediately quenched to saturation temperature.
It proceeds to the absorber section for particulate and SO2 reduction. Economics: The EDV wet scrubbing system has been extremely suc-
The spray tower is an open tower with multiple levels of BELCO-G- cessful in the incineration and refining industries due to the very high
Nozzles. These nonplugging and abrasion-resistant nozzles remove scrubbing capabilities, very reliable operation and reasonable price.
particulates by impacting on the water/reagent curtains. At the same Installation: More than 200 applications worldwide on various pro-
time, these curtains also reduce SO 2 and SO 3 emissions. The BELCO- cesses including more than 60 FCCU applications, heater applications,
G-Nozzles are designed not to produce mist; thus a conventional mist SRU tailgas unit, fluidized coker application and coal-fired boilers.
eliminator is not required.
Upon leaving the absorber section, the saturated gases are direct- Reference: Confuorto and Weaver, “Flue gas scrubbing of FCCU re-
ed to the EDV filtering modules to remove the fine particulates and ad- generator flue gas—performance, reliability, and flexibility—a case his-
ditional SO3. The filtering module is designed to cause condensation of tory,” Hydrocarbon Engineering, 1999.
the saturated gas onto the fine particles and onto the acid mist, thus Eagleson and Dharia, “Controlling FCCU emissions,” 11th Refin-
allowing it to be collected by the BELCO-F-Nozzle located at the top. ing Technology Meeting, HPCL, Hyderabad, 2000.
To ensure droplet-free stack, the flue gas enters a droplet separa-
tor. This is an open design that contains fixed-spin vanes that induce a Licensor: Belco Technologies Corp.
cyclonic flow of the gas. As the gases spiral down the droplet separa-
tor, the centrifugal forces drive any free droplets to the wall, separat- click here to e-mail for more information
ing them from the gas stream.
Deep thermal conversion

Gas
Application: The Shell Deep Thermal Conversion process closes the gap
between visbreaking and coking. The process yields a maximum of distil- Naphtha
lates by applying deep thermal conversion of the vacuum residue feed
and by vacuum flashing the cracked residue. High-distillate yields are
obtained, while still producing a stable liquid residual product, referred 4
to as liquid coke. The liquid coke, not suitable for blending to commer- Steam LGO
cial fuel, is used for speciality products, gasification and/or combustion,

e.g., to generate power and/or hydrogen. HGO
3
Description: The preheated short residue is charged to the heater (1) Steam
2
and from there to the soaker (2), where the deep conversion takes place. 5
Vacuum flashed
The conversion is maximized by controlling the operating temperature cracked residue
1
and pressure. The soaker effluent is routed to a cyclone (3). The cyclone Feed
overheads are charged to an atmospheric fractionator (4) to produce the

desired products like gas, LPG, naphtha, kero and gasoil. The cyclone
and fractionator bottoms are subsequently routed to a vacuum flasher
(5), which recovers additional gasoil and waxy distillate. The residual liq-
Utilities, typical consumption/production for a 25,000-bpd unit,
uid coke is routed for further processing depending on the outlet.
dependent on configuration and a site’s marginal econmic values for
Yields: Depend on feed type and product specifications. steam and fuel:
Fuel as fuel oil equivalent, bpd 417
Feed, vacuum residue Middle East Power, MW 1.2
Viscosity, cSt @100°C 615 Net steam production (18 bar), tpd 370
Products in % wt. on feed
Gas 3.8 Installation: To date, six Shell Deep Thermal Conversion units have been
Gasoline, ECP 165°C 8.2 licensed. In four cases, this has involved revamping an existing Shell
Gas oil, ECP 350°C 19 Soaker Visbreaker unit. Post startup services and technical services for
Waxy distillate, ECP 520°C 22.8 existing units are available from Shell Global Solutions.
Residue ECP 520°C+ 46.2
Reference: Hydrocarbon Engineering, September 2003.
Economics: The typical investment for a 25,000-bpd unit will be about
$1,900 to $2,300/bbl installed, excluding treating facilities. (Basis: West- Licensor: Shell Global Solutions International B.V. and ABB Lummus
ern Europe, 2004.). Global B.V.


Application: The Akzo Nobel/Quadrise emulsion residue enhancement
process converts highly viscous, low-value, uncut residues from vacuum
unit operations to an emulsion fuel for onward sale to third parties. Re- 1
Distillates (cutter-stock recovery)
finers benefit from term contract offtake of residue and release of HFO
cutter-stock back to the refinery, for higher value realization. Quadrise
typically purchases the residue at a price higher than its intrinsic value,
and assume responsibility for the emulsion fuel sales.
Enhancements include moving to deeper vacuum unit cuts and in-
creasing visbreaker severity or visbreaker vacuum flasher recovery to in-
Residue Emulsion fuel
crease yields of lighter products. Enhancements are achieved without START
2
the normal penalty of increased cutter-stock addition to the resulting
heavier residues. A combination of modifying process conditions and
Process water + surfactants
processing heavier, cheaper, crude oils leads to significantly lower quality
residues in terms of density, CCR and viscosity. The technology handles
these low-quality residues and produces a transportable emulsion fuel
with a viscosity of 200 –1,000cSt at 50°C.
Economics: Margin improvement to the refinery varies according to its
Description: Residues from a vacuum unit, visbreaker, visbreaker vacuum configuration, crude supply and location but typically lies in the range of
flasher or solvent de-asphalter (1) are taken from the refiners run-down $0.25–$1.5/bbl of crude input.
system after process heat has been extracted, but prior to cutter stock
addition. The residue stream is processed to a 70:30 oil-in-water emul- Installed cost: $3000/bbl of residue (USGC 2008) for a unit of 4,000 bbl
sion in a proprietary skid-mounted package (2) supplied by Quadrise un- residue feed. Units are modular; installed system lead-time is typically
der license from Akzo Nobel. Various commercial options are available 12 months.
including licence; BOO/BOOT by Quadrise or JV with refiner.
Utilities: typical per barrel of feed (detail available on request)
Operating conditions: The residue temperature is adjusted to give a vis- Water, cooling Dependent on feedstock temperature
cosity of around 300cSt for supply to the emulsification process. The Process water 0.30–0.45 bbl
maximum supply temperatures are 190°C (standard unit) and 260°C Power <1kWh
(high-temperature unit). The emulsion fuel run-down temperature to Chemicals Dependent on feedstock.
conventional HFO storage tanks is less than 65°C.
Installation: One unit currently operating for emulsion fuel production.
Residue viscosities of up to 100,000cSt (standard unit) and
60,000,000cSt (high-temperature unit) measured at 100°C can be han- Licensor: Akzo Nobel through Quadrise Fuels International.
dled, without impacting the quality of the emulsion fuel. The standard
unit operates at less than 10 bars. click here to e-mail for more information
Heavy oil upgrading

Application: Process designed for upgrading heavy oils including the Diluent return
Athabasca bitumen into a easily transportable synthetic crude oil. S Naphtha

p hydrotreater
Heavy oil D e Synthetic
Description: This process uses various proven and established refining R
U
c
Diesel crude
i
technologies. V a hydrotreater
l
Bitumen with diluent is brought to the upgrader. The diluent is re- R GO
U hydrotreater
covered in the diluent recovery unit (DRU) and returned to the produc- F
C
tion site. The bottom of the DRU is sent to a high deasphalted oil lift ROSE*
C
ROSE solvent deasphalting unit. The DAO is then sent to a special pur-
pose Fluid Catalytic Cracking Unit (FCCU). The FCCU operates at low
Aquaform
conversion, normally between 30% and 60% and uses low cost low
Gasifier
Steam+power
activity catalyst.
Pellets
The metals in DAO are rejected with the spent catalyst. The carbon *Residuum oil supercritical extraction
(CCR) is burnt in regenerator to produce steam. The FCCU products

can be blended into synthetic crude oil. Alternately the products can be
hydrotreated to produce low-sulfur synthetic crude oil. Steam produced
in the FCCU is used within the complex. The asphaltenes from ROSE The synthetic crude oil of following composition can be produced by the
unit can be pelletized using KBR’s AQUAFORM pelletizing technology above scheme:
for ease of transportation to end users. Alternately the asphaltenes can C5-350°F: 15–30 vol.%
be gasified to produce hydrogen, steam and power for bitumen produc- Distillate: 40–65 vol.%
tion and upgrading. Gas oil: 20–30 vol.%
Applications: This scheme can be used for upgrading of bitumen and Economics: KBR estimates that the above scheme will have several per-
other heavy and very heavy oils. cent higher rate of return on investment when compared with tradi-
KBR has performed extensive pilot plant testing to confirm the vi- tional heavy oil upgrading schemes.
ability of the scheme. Given below are pilot test results for KBR’s ROSE
portion of the scheme. Reference: “KBR KLEEN Upgrading Process, ” Conrad Conference, Feb.
23, 2005, Calgary, Alberta.
ROSE pilot results:
Feed: Athabasca Bitumen Licensor: KBR.
Feed Solvents DAO yield, vol.% CCR in DAO, wt.%
Full nC4 to C6 70–82 7–10
ATB C3 to nC5 40–87 1–9
VTB iC4 to nC5 17–65 5–14 click here to e-mail for more information
Hydroprocessing—heavy oil
and residue
Naphtha
Genoil Diesel
Feed hydro-
conversion Gasoil
Acid gas Sulfur Sulfur
Application: Conversion of heavy petroleum residues or crude oil into unit Offgas
recovery
lighter and higher value materials. Vacuum
residue
Hydrogen
Products: Low-sulfur content naphtha, diesel and gasoil
Description: The Genoil Upgrader consists of the proprietary Genoil hy-
Air Acid gas Hydrogen
droconversion unit (GHU) and an integrated gasification and combined separation
O2 Gasification Syngas removal recovery
cycle (IGCC) section. By integrating with gasification and balancing pitch
conversion with hydrogen and utility demands, the GHU and the overall
upgrader becomes a truly bottomless, self-sufficient facility that is suit-
able to be added into an existing refining complex or as a merchant Fuel gas
Steam
Combined
upgrader near a remote oil field. cycle Power
Based on a fixed-bed hydrogenation technology and using special
mixing devices to ensure full catalysts utilization and higher efficiency,
the GHU converts the heavy petroleum feed into lighter products such as
naphtha, diesel and low-sulfur gasoil that can be used as fuel-oil blend • Acid-gas removal unit (AGR)
or FCCU feed. The unconverted portion will be removed as vacuum resi- • Hydrogen recovery unit (HRU)
due (VR) and fed to the IGCC units. In comparison to the traditional resi- • Combined-cycle unit (CCU.)
due treating processes such as visbreaking and delayed coking, the GHU The GHU is similar to normal hydrotreating units consisting sections
offers a significantly higher conversion to valuable petroleum products. such as: feed preparation and preheat, reactions, effluent cooling and
The IGCC will use partial oxidation and gasification technologies to separation, gas recycle and product fractionation. The reactor section
convert the VR into hydrogen, fuel gas and power. The hydrogen will be consists of a series of four reactor beds: guard, hydrodemetalization
recovered and fed to the GHU to support the hydrogenation reactions, (HDM), hydrodesulfurization (HDS) and hydrodenitrogenation (HDN).
whereas fuel gas, steam and power are used to run the overall Genoil The syngas unit converts the VR under a partial oxidation processing
upgrader. condition in the gasifier to produce syngas, which is a mixture of H2, CO
and CO2. The sulfur and nitrogen content in the residue will be con-
Process: In general, the Genoil upgrader consists of these processing verted to H2S, NH3 and HCN. After purification and cooling, the syngas
units (see diagram): will be sent to the AGR unit.
• Genoil hydroconversion unit (GHU) The ASU uses refrigeration and distillation to separate oxygen from
• Syngas unit (SGU) ambient air. The oxygen product stream consisting over 95% oxygen is
• Air separation unit (ASU) fed to the gasifier in the SGU as combustion air.
Continued 
Hydroprocessing—heavy oil and residue, continued Yields: Product yields depend on the quality of feed. For a typical AR
feed, the liquid yields are: 3% Naphtha, 26% Diesel and 57% Gasoil, all
based on the mass of crude feed.
The AGR performs these operations: Remove the H2S from the
syngas, GHU offgas and sour condensate using MDEA absorption tech- Installation: At present, there is no commercial Genoil Upgrader in op-
nology; Convert CO into more H2 using high temperature shift and re- eration. A feasibility study has been completed for the installation of a
move CO2 from sweetened gas using DGA absorption technology. 19,500-bpd unit in the ZJSH Refinery in Hebei, China. Commissioning of
The HRU recovers H2 using pressure swing adsorption (PSA) tech- the unit is scheduled on the first quarter of 2010.
nology. The sulfur recovery unit (SRU) uses a three-stage Claus Unit fol-
lowed by an amine tail gas recovery plant to recover over 99.5% of the Reference: “Is bottomless-barrel refining possible?” Hydrocarbon Pro-
sulfur in the AGR offgas. cessing, September 2007, pp.81–92.
The CCU consists of gas turbine generator (GTG), heat-recovery Oilsands Review, October 2007 and March 2007.
steam generator (HRSG). Part of the steam produced will be used in the “Opportunity Crudes 2008,” HP Company.
Upgrader and the reminder is sent to a steam turbine generator (STG) to
produce more electrical power.
Licensor: Genoil Inc.
Performance: 85+% HDS, 50+%HDN, 8 –12 API increase, 50% pitch

conversion (to balance conversion and utilities requirement)
Thermal gasoil
Application: The Shell Thermal Gasoil process is a combined residue and Gas
waxy distillate conversion unit. The process is an attractive low-cost con-
version option for hydroskimming refineries in gasoil-driven markets or Naphtha
for complex refineries with constrained waxy distillate conversion capac-
Steam
ity. The typical feedstock is atmospheric residue, which eliminates the 4
Gasoil
need for an upstream vacuum flasher. This process features Shell Soaker
Visbreaking technology for residue conversion and an integrated recycle
heater system for the conversion of waxy distillate.
Waxy
3 5 distillate
Description: The preheated atmospheric (or vacuum) residue is charged
to the visbreaker heater (1) and from there to the soaker (2). The con- Steam 6
2
version takes place in both the heater and soaker and is controlled by
the operating temperature and pressure. The soaker effluent is routed 1 Vacuum flashed
Charge
to a cyclone (3). The cyclone overheads are charged to an atmospheric cracked residue
fractionator (4) to produce the desired products including a light waxy

distillate. The cyclone and fractionator bottoms are routed to a vacuum
flasher (6), where waxy distillate is recovered. The combined waxy distil-
lates are fully converted in the distillate heater (5) at elevated pressure.
Yields: Depend on feed type and product specifications. Utilities, typical consumption/production for a 25,000-bpd unit,
Feed atmospheric residue Middle East dependent on configuration and a site’s marginal economic values for
Viscosity, cSt @ 100°C 31 steam and fuel:
Products, % wt. Fuel as fuel oil equivalent, bpd 675
Gas 6.4 Power, MW 1.7
Gasoline, ECP 165°C 12.9 Net steam production (18 bar), tpd 370
Gasoil, ECP 350°C 38.6 Installation: To date, 12 Shell Thermal Gasoil units have been built. Post
Residue, ECP 520°C+ 42.1 startup services and technical services for existing units are available
Economics: The typical investment for a 25,000-bpd unit will be about from Shell Global Solutions..
$2,400 to $3,000/bbl installed, excluding treating facilities. (Basis: West- Licensor: Shell Global Solutions International B.V., and ABB Lummus
ern Euope, 2004.) Global B.V.

Visbreaking
Application: Manufacture incremental gas and distillate products and simul- (BT
taneously reduce fuel oil viscosity and pour point. Also, reduce the amount
of cutter stock required to dilute the resid to meet the fuel oil specifications.
Foster Wheeler/UOP offer both “coil” and “soaker” type visbreaking pro-
cesses. The following information pertains to the “coil” process.
(BTPMJOF
Products: Gas, naphtha, gas oil, visbroken resid (tar). 3FEVDFE
DSVEFDIBSHF 4UFBN
Description: In a “coil” type operation, charge is fed to the visbreaker 45"35
heater (1) where it is heated to a high temperature, causing partial va-
porization and mild cracking. The heater outlet stream is quenched with (BTPJM
gas oil or fractionator bottoms to stop the cracking reaction. The va-
por-liquid mixture enters the fractionator (2) to be separated into gas, 5BS
naphtha, gas oil and visbroken resid (tar). The tar may also be vacuum
flashed for recovery of visbroken vacuum gas oil.
Operating conditions: Typical ranges are:

Heater outlet temperature, ºF 850 – 910
Quenched temperature, ºF 710 – 800
An increase in heater outlet temperature will result in an increase in Economics:
overall severity, further viscosity reduction and an increase in conversion. Investment (basis: 40,000 – 10,000 bpsd, 2Q 2005, US Gulf),
$ per bpsd 1,800 – 3,500
Yields: Utilities, typical per bbl feed:
Feed, source Light Arabian Light Arabian Fuel, MMBtu 0.1195
Type Atm. Resid Vac. Resid Power, kW/bpsd 0.0358
Gravity, ºAPI 15.9 7.1 Steam, MP, lb 6.4
Sulfur, wt% 3.0 4.0 Water, cooling, gal 71.0
Concarbon, wt% 8.5 20.3
Installation: Over 50 units worldwide.
Viscosity, CKS @130ºF 150 30,000
CKS @ 210ºF 25 900 Reference: Handbook of Petroleum Refining Processes, Third Ed., Mc-
Products, wt% Graw-Hill, 2003, pp. 12.91 – 12.105.
Gas 3.1 2.4
Licensor: Foster Wheeler USA Corp./UOP.
Naphtha (C5 – 330 ºF) 7.9 6.0
Gas oil 14.5 15.5
Visbroken resid 74.5 (600ºF+) 76.1 (662ºF+) click here to e-mail for more information
Visbreaking
Gas
Application: The Shell Soaker Visbreaking process is most suitable to re-
duce the viscosity of vacuum (and atmospheric) residues in (semi) complex
refineries. The products are primarily distillates and stable fuel oil. The to-
tal fuel oil production is reduced by decreasing the quantity of cutter stock 3 Naphtha
required. Optionally, a Shell vacuum flasher may be installed to recover
additional gas oil and waxy distillates as cat cracker or hydrocracker feed Steam
Steam Gas oil
2
from the cracked residue. The Shell Soaker Visbreaking technology has
Vacuum system
also proven to be a very cost-effective revamp option for existing units. Residue charge
START Vacuum gas oil

Description: The preheated vacuum residue is charged to the visbreaker 1
Visbroken residue
heater (1) and from there to the soaker (2). The conversion takes place 4
in both the heater and the soaker. The operating temperature and pres-
sure are controlled such as to reach the desired conversion level and/ Cutter stock
or unit capacity. The cracked feed is then charged to an atmospheric

fractionator (3) to produce the desired products like gas, LPG, naph-
tha, kerosine, gas oil, waxy distillates and cracked residue. If a vacuum
flasher is installed, additional gas oil and waxy distillates are recovered bpd unit, dependent on configuration and a site’s marginal economic
from the cracked residue. values for steam and fuel:
Yields: Vary with feed type and product specifications. Fuel as fuel oil equivalent, bpd 400
Power, MW 1.2
Feed, vacuum residue Middle East Net steam production (18 bar), tpd 370
Viscosity, cSt @100°C 615
Products, wt% Installation: More than 70 Shell Soaker Visbreakers have been built. Post
Gas 2.2 startup services and technical services for existing units are available from
Gasoline, 165°C EP 4.8 Shell Global Solutions.
Gas oil, 350°C EP 13.6
Licensor: Shell Global Solutions International B.V. and ABB Lummus
Waxy distillate, 520°C EP 23.4
Global B.V.
Residue, 520°C+ 56
Economics: The typical investment for a 25,000-bpd unit will be about

$1,200 to $1,500/bbl installed, excluding treating facilities. (Basis: West-
ern Europe, 2004.)
Utilities, typical consumption consumption/production for a 25,000-
Catalytic dewaxing
Purge Fuel gas to LP absorber
Application: Use ExxonMobil’s Research & Engineering’s (EMRE’s) Se- Makeup H2
lective Catalytic Dewaxing (MSDW) process to make high VI lube base Water Wild naphtha
M/U wash
stock. HP
Sour water
stripper
HDW HDT Rec
Products: High VI / low-aromatics lube base oils (light neutral through Rxr Rxr
MP steam
Water Vacuum system
bright stocks). Byproducts include fuel gas, naphtha and low-pour die- wash
sel. Water Vac
strip. Sour
Waxy feed
LT Oily water
Description: ExxonMobil’s Research & Engineering’s (EMRE’s) MSDW is HT sep water
targeted for hydrocracked or severely hydrotreated stocks. The improved sep
selectivity of MSDW for the highly isoparaffinic-lube components results Distillate
in higher lube yields and VIs. The process uses multiple catalyst sys-
MP steam
tems with multiple reactors. Internals are proprietary (the Spider Vortex Vac
Lube product
Quench Zone technology is used). Feed and recycle gases are preheated dryer
and contact the catalyst in a down-flow-fixed-bed reactor.
Reactor effluent is cooled, and the remaining aromatics are satu-
rated in a post-treat reactor. The process can be integrated into a lube
hydrocracker or lube hydrotreater. Post-fractionation is targeted for cli- Yields:
ent needs. Light neutral Heavy neutral
Lube yield, wt% 94.5 96.5
Operating conditions: C1 – C4, wt% 1.5 1.0
Temperatures, ° F 550 – 800 C5 – 400°F, wt% 2.7 1.8
Hydrogen partial pressures, psig 500 – 2,500 400°F – Lube, wt% 1.5 1.0
LHSV 0.4 – 3.0 H2 cons, scf / bbl 100 – 300 100 – 300
Conversion depends on feed wax content
Pour point reduction as needed. Installation: Eight units are operating and four are in design.

Dewaxing
Application: Bechtel’s Dewaxing process is used to remove waxy com-
ponents from lubrication base-oil streams to simultaneously meet de- 3 4
sired low-temperature properties for dewaxed oils and produce slack
Refrigerant
wax as a byproduct.
Description: Waxy feedstock (raffinate, distillate or deasphalted oil) is 2

Refrigerant
mixed with a binary-solvent system and chilled in a very closely controlled 6
manner in scraped-surface double-pipe exchangers (1) and refrigerated
chillers (2) to form a wax/oil/solvent slurry.
The slurry is filtered through the primary filter stage (3) and dewaxed
oil mixture is routed to the dewaxed oil recovery section (5) to separate Solvent
1 7 recovery
solvent from oil. Prior to solvent recovery, the primary filtrate is used to 5
Water
cool the feed/solvent mixture (1). Wax from the primary stage is slurried Steam
with cold solvent and filtered again in the repulp filter (4) to reduce the Waxy feed Slack wax Dewaxed Steam Refrigerant
oil Water Process stream
oil content to approximately 10%.
The repulp filtrate is reused as dilution solvent in the feed chilling
train. The wax mixture is routed to a solvent-recovery section (6) to re-
move solvent from the product streams (hard wax and soft wax). The
recovered solvent is collected, dried (7) and recycled back to the chilling
and filtration sections.
Economics:
Investment (Basis: 7,000-bpsd feedrate
capacity, 2008 US Gulf Coast), $/bpsd 17,000
Utilities, typical per bbl feed:
Electricity, kWh 15
Steam, lb 35
Water, cooling (25°F rise), gal 1,100
Installation: Over 100 have been licensed and built.

Licensor: Bechtel Corp.
Dewaxing
Makeup hydrogen Process gas
Application: Selectively convert feedstock’s waxy molecules by isomeriza-
tion in the presence of ISODEWAXING Catalysts. The high-quality prod-
ucts can meet stringent cold flow properties and viscosity index (VI) re- Naphtha
quirements for Group II or Group III baseoils.
5
Jet
1 2
Description: ISODEWAXING Catalysts are very special catalysts that con- Diesel
vert feedstocks with waxy molecules (containing long, paraffinic chains)
into two or three main branch isomers that have low-pour points. The
product also has low aromatics content. Typical feeds are: raffinates, Light base oil
3
slack wax, foots oil, hydrotreated VGO, hydrotreated DAO and uncon- 6 Medium
Fresh feed base oil
verted oil from hydrocracking. 4
As shown in the simplified flow diagram, waxy feedstocks are mixed Heavy base oil
with recycle hydrogen and fresh makeup hydrogen, heated and charged
to a reactor containing ISODEWAXING Catalyst (1). The effluent will
have a much lower pour point and, depending on the operating severity,
the aromatics content is reduced by 50– 80% in the dewaxing reactor.
In a typical configuration, the effluent from a dewaxing reactor is Utilities: Typical per bbl feed:
cooled down and sent to a finishing reactor (2) where the remaining Power, kWh 3.3
single ring and multiple ring aromatics are further saturated by the ISO- Fuel , kcal 13.4 x 103
FINISHING Catalysts. The effluent is flashed in high-pressure and low- Steam, superheated, required, kg 5.3
pressure separators (3, 4). Small amounts of light products are recovered Steam, saturated, produced, kg 2.4
in a fractionation system (5). Water, cooling, kg 192
Chemical-hydrogen consumption, Nm3/m3 oil 30~50
Yields: The base oil yields strongly depend on the feedstocks. For a typi-
cal low wax content feedstock, the base oil yield can be 90–95%. Higher Installation: More than 14 units are in operation and 7 units are in vari-
wax feed will have a little lower base oil yield. ous stages of design or construction.
Economics: Reference: NPRA Annual Meeting, March 2005, San Francisco, Paper
Investment: This is a moderate investment process; for a typical size AM-05-39.
ISODEWAXING/ISOFINISHING Unit, the capital for ISBL
is about $8,000/bpsd. Licensor: Chevron Lummus Global LLC.

Dewaxing/wax deoiling
Application: Bechtel’s Dewaxing/Wax Fractionation processes are used
to remove waxy components from lubrication base-oil streams to si- 3 4 5
multaneously meet desired low-temperature properties for dewaxed oils Refrigerant
and produce hard wax as a premium byproduct.
Description: Bechtel’s two-stage solvent dewaxing process can be ex- Refrigerant 2

panded to simultaneously produce hard wax by adding a third deoiling 7 8
stage using the Wax Fractionation process. Waxy feedstock (raffinate,
distillate or deasphalted oil) is mixed with a binary-solvent system and Hard wax
chilled in a very closely controlled manner in scraped-surface double-

pipe exchangers (1) and refrigerated chillers (2) to form a wax/oil/solvent Solvent
1 9 recovery
slurry. 6
Steam Water
The slurry is filtered through the primary filter stage (3) and dewaxed
oil mixture is routed to the dewaxed oil recovery section (6) to separate Waxy feed Dewaxed Steam Refrigerant
Soft wax oil Water Process stream
solvent from oil. Prior to solvent recovery, the primary filtrate is used to
cool the feed/solvent mixture (1).
Wax from the primary stage is slurried with cold solvent and filtered
again in the repulp filter (4) to reduce the oil content to approximately
10%. The repulp filtrate is reused as dilution solvent in the feed chilling
train. The low-oil content slack wax is warmed by mixing with warm Utilities, typical per bbl feed:
solvent to melt the low-melting-point waxes (soft wax) and is filtered in Fuel, 103 Btu (absorbed) 230
a third stage filtration (5) to separate the hard wax from the soft wax. Electricity, kWh 25
The hard and soft wax mixtures are each routed to solvent recovery sec- Steam, lb 25
tions (7,8) to remove solvent from the product streams (hard wax and Water, cooling (25°F rise), gal 1,500
soft wax). The recovered solvent is collected, dried (9) and recycled back
to the chilling and filtration sections. Installation: Seven in service.
Economics: Licensor: Bechtel Corp.

Investment (Basis: 7,000-bpsd feedrate
capacity, 2008 US Gulf Coast), $/bpsd 20,000

Slack wax deoiling

Application: Process to produce high-melting and low-oil containing Wash solvent from
To refrigeration unit
hard wax products for a wide range of applications. solvent recovery

Refrigeration Gas holder
Feeds: Different types of slack waxes from lube dewaxing units, includ- From heat
unit
ing macrocrystalline (paraffinic) and microcrystalline wax (from residual exchangers Scraped
oil). Oil contents typically range from 5–25 wt%. Feed
exchangers
Feed/ Rotating Rotating

Products: Wax products with an oil content of less than 0.5 wt%, except filtrate vacuum vacuum
exchangers filter 1 filter 2
for the microcrystalline paraffins, which may have a somewhat higher Stm To Feed Feed
oil content. The deoiled wax can be processed further to produce high- refrigeration vessel vessel
unit 1 2 Hard wax/solvent
quality, food-grade wax. mix to solvent
recovery
Description: Warm slack wax is dissolved in a mixture of solvents and
Initial
cooled by heat exchange with cold main filtrate. Cold wash filtrate dilution Soft wax/solvent mix
is added to the mixture, which is chilled to filtration temperature in to solvent recovery
scraped-type coolers. Crystallized wax is separated from the solution in

a rotary drum filter (stage 1). The main filtrate is pumped to the soft-wax
solvent recovery section. Oil is removed from the wax cake in the filter
by thorough washing with chilled solvent.
The wax cake of the first filter stage consists mainly of hard wax and Utility requirements (slack wax feed containing 20 wt% oil, per metric
solvent but still contains some oil and soft wax. Therefore, it is blown off ton of feed):
the filter surface and is again mixed with solvent and repulped in an agi-
tated vessel. From there the slurry is fed to the filter stage 2 and the wax Steam, LP, kg 1,500
cake is washed again with oil-free solvent. The solvent containing hard Water, cooling, m3 120
wax is pumped to a solvent recovery system. The filtrate streams of filter Electricity, kWh 250
stage 2 are returned to the process, the main filtrate as initial dilution to
the crystallization section, and the wash filtrate as repulp solvent. Installation: Wax deoiling units have been added to existing solvent de-
The solvent recovery sections serve to separate solvent from the waxing units in several lube refineries. The most recent reference in-
hard wax respectively from the soft wax. These sections yield oil-free cludes the revamp of a dewaxing unit into two-stage wax deoiling; this
hard wax and soft wax (or foots oil). unit went onstream in 2005.

Wax hydrotreating
Application: Hydrogen finishing technology has largely replaced clay
treatment of low-oil-content waxes to produce food- and medicinal-
Offgas
grade product specifications (color, UV absorbency and sulfur) in new
units. Advantages include lower operating costs, elimination of environ-
1
mental concerns regarding clay disposal and regeneration, and higher
3
net wax product yields.
Bechtel has been offering for license the Wax Hy-Finishing process. Feed
Bechtel now is marketing a line of modular, standard hydrogen finish- START
Unstable naphtha
ing units for wax treatment. Standard sizes are 500, 1,000, 2,000 and 2
3,000-bpsd feedrate.
H2
The core of the unit is standardized; however, individual modules are 4 5
modified as needed for specific client needs. This unit will be fabricated
to industry standards in a shop environment and delivered to the plant Wax product
site as an essentially complete unit. Cost and schedule reductions of at
least 20% over conventional stick-built units are expected. The standard
licensor’s process guarantees and contractor’s performance guarantees
(hydraulic and mechanical) come with the modules.
Description: Hard-wax feed is mixed with hydrogen (recycle plus make-

up), preheated, and charged to a fixed-bed hydrotreating reactor (1). Utilitiies, typical per bbl feed:
The reactor effluent is cooled in exchange with the mixed feed-hydrogen Fuel, 103 Btu (absorbed) 30
stream. Gas-liquid separation of the effluent occurs first in the hot sepa- Electricity, kWh 5
rator (2) then in the cold separator (3). The hydrocarbon liquid stream Steam, lb 25
from each of the two separators is sent to the product stripper (4) to Water, cooling (25°F rise), gal 300
remove the remaining gas and unstabilized distillate from the wax prod-
uct, and the product is dried in a vacuum flash (5). Gas from the cold Licensor: Bechtel Corp.
separator is either compressed and recycled to the reactor or purged
from the unit if the design is for once-through hydrogen.
Economics:
2008 US Gulf Coast), $/bpsd 11,000

White oil and wax hydrotreating

Makeup hydrogen Purge
Application: Process to produce white oils and waxes.
Tailgas
Feeds: Nonrefined as well as solvent- or hydrogen-refined naphthenic or Reactor Oil Reactor
Purge
paraffinic vacuum distillates or deoiled waxes. H2 stripper H2

recycle recycle
Products: Technical- and medical-grade white oils and waxes for plasti-
cizer, textile, cosmetic, pharmaceutical and food industries. Products are
in accordance with the US Food and Drug Administration (FDA) regula-
Stm
tions and the German Pharmacopoeia (DAB 8 and DAB 9) specifications. Food or
medicinal-
grade
Description: This catalytic hydrotreating process uses two reactors. Hydro- white oil
gen and feed are heated upstream of the first reaction zone (containing a
Feed Stripped oil
special presulfided NiMo/alumina catalyst) and are separated downstream
First stage Second stage Technical grade white
of the reactors into the main product and byproducts (hydrogen sulfide oil or fully-refined wax
Technical white oil Food or medicinal-
and light hydrocarbons). A stripping column permits adjusting product or fully refined wax grade white oil
specifications for technical-grade white oil or feed to the second hydro-
genation stage.
When hydrotreating waxes, however, medical quality is obtained
in the one-stage process. In the second reactor, the feed is passed
over a highly active hydrogenation catalyst to achieve a very low level
of aromatics, especially of polynuclear compounds. This scheme per-
Installation: Four installations use the Uhde (Edeleanu) proprietary tech-
nology, one of which has the largest capacity worldwide.
mits each stage to operate independently and to produce technical- or
medical-grade white oils separately. Yields after the first stage range Licensor: Uhde GmbH.
from 85% to 99% depending on feedstock. Yields from the second
hydrogenation step are nearly 100%. When treating waxes, the yield
is approximately 98%.
Utility requirements (typical, Middle East Crude), units per m3 of feed:

1st stage for 2nd stage for Food-grade
techn. white oil med. white oil wax
Electricity, kWh 197 130 70
Steam, LP, kg 665 495 140
Water, cooling, m3 48 20 7
Hydrogen, kg 10.0 2.6 1.6

Atmospheric Distillation Process - Fundamental Concepts - No Appendexes

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