Hydrocarbon Processing Refining Processes 2000 (2001)

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Refining Processes 2000
process index contributor index key word
Alkylation
Alkylation feed preparation
process
Select a Process
to view Aromatics extraction category/type
Aromatics extracted distillation
Aromatics recovery
Benzene reduction
Benzene saturation
Catalytic cracking
Catalytic dewaxing
Catalytic reforming
Coking
Crude distillation
Deasphalting
Deep catalytic cracking
Deep thermal conversion
Delayed coking
Desulfurization
Dewaxing
Electric desalting
Ethers
Fluid catalytic cracking
GULF PUBLISHING COMPANY Gas oil hydrotreatment
3 Greenway Plaza, 9th Floor, Houston, TX 77046 Gas treating—H2S removal
Phone 713-529-4301, Fax 713-520-4433
E-mail: editorial@hydrocarbonprocessing.com
next
Gasification
Gasoline desulfurization
process
Select a Process
to view Gasoline desulfurization, ultra-deep category/type
Hydrocracking
Hydrocracking, residue
Hydrocracking/hydrotreating—VGO back
Hydrodearomatization
Hydrodesulfurization
Hydrodesulfurization—UDHDS
Hydrogenation
Hydrotreating Hydrotreating—
catalytic dewaxing
Hydrotreating—HDAr
Hydrotreating—HDHDC
Hydrotreating, residue
Iso-octane
Isomerization
Lube hydroprocessing
Lube treating
NOx abatement
Oily waste treatment
GULF PUBLISHING COMPANY Olefins recovery
3 Greenway Plaza, 9th Floor, Houston, TX 77046 Resid catalytic cracking
Phone 713-529-4301, Fax 713-520-4433 next
E-mail: editorial@hydrocarbonprocessing.com Residue hydroprocessing
Thermal gas oil process

Treating
process
Select a Process
to view Visbreaking category/type
back
GULF PUBLISHING COMPANY

3 Greenway Plaza, 9th Floor, Houston, TX 77046
Phone 713-529-4301, Fax 713-520-4433
ABB Lummus Global Inc.

Coking
contributing
Select a Process
to view Fluid catalytic cracking
Hydrocracking
company/licensor
Hydrocracking
Hydrotreating
Isomerization
Thermal gasoil process
Visbreaking
Akzo Nobel Chemicals B.V.
Hydrotreating—catalytic dewaxing
Isomerization
BARCO
Catalytic cracking
Bechtel Corp.
Delayed coking
Dewaxing
Lube treating
BP Corp.
Hydrocracking
CDTECH
Ethers
Hydrogenation
3 Greenway Plaza, 9th Floor, Houston, TX 77046 Hydrotreating
Phone 713-529-4301, Fax 713-520-4433
Iso-octane/iso-octene next
Isomerization
Chevron Research and Technology Co.

Hydrocracking
contributing
Select a Process
to view Hydrotreating company/licensor
Conoco Inc.
Desulfurization
ELF back
Crude distillation
ExxonMobil Research & Engineering Co.
Alkylation
Catalytic dewaxing
Gas treating—H2S removal
Hydrotreating—catalytic dewaxing
Lube treating
NOx abatement
Foster Wheeler USA Corp.
Coking
Crude distillation
Deasphalting
Visbreaking
Fuels Technology Division of Phillips Petroleum Co.
Alkylation
Gasoline desulfurization
Isomerization
3 Greenway Plaza, 9th Floor, Houston, TX 77046 GTC Technology Corp.
Phone 713-529-4301, Fax 713-520-4433
E-mail: editorial@hydrocarbonprocessing.com Aromatics recovery next
Desulfurization
Haldor Topsøe A/S

Hydrodearomatization
contributing
Select a Process
to view Hydrotreating company/licensor
Howe-Baker Engineers, Inc.
Catalytic reforming
Electrical desalting back
Hydrotreating
IFP
Benzene reduction
Catalytic reforming
Gas oil hydrotreatment
Gasoline desulfurization, ultra-deep
Hydrocracking
Hydrocracking/hydrotreating—VGO
Hydrotreating, residue
Isomerization
Resid catalytic cracking
IFP North America
Gasoline desulfurization, ultra-deep
Hydrocracking/hydrotreating—VGO
Imperial Petroleum Recovery Corp.
GULF PUBLISHING COMPANY Kellogg Brown & Root, Inc.
3 Greenway Plaza, 9th Floor, Houston, TX 77046 Deasphalting
Phone 713-529-4301, Fax 713-520-4433
E-mail: editorial@hydrocarbonprocessing.com Fluid catalytic cracking next
Hydrocracking
Kellogg Brown & Root, Inc. continued

contributing
Select a Process
to view Hydrotreating—HDHDC company/licensor
Iso-octane
Isomerization
Krupp Uhde back
Aromatics extractive distillation
Lyondell Chemical Co.
Isomerization
Merichem Co.
Treating
Neste Engineering Oy
Iso-octane
Oxy Research & Development Co.
Hydrocracking
Pro-Quip Corp.
Olefins recovery
Research Institute of Petroleum
Shell Global Solutions International B.V.
Crude distillation
Deep thermal conversion
GULF PUBLISHING COMPANY Fluid catalytic cracking
3 Greenway Plaza, 9th Floor, Houston, TX 77046 Gasification
Phone 713-529-4301, Fax 713-520-4433
E-mail: editorial@hydrocarbonprocessing.com Hydrocracking next
Hydrotreating
Shell Global Solutions International B.V. continued

Lube hydroprocessing
contributing
Select a Process
to view
Residue hydroprocessing
Visbreaking
company/licensor
Shell International Oil Products B.V.
Thermal gasoil process back
SK Corp.
Lube treating
Snamprogetti SpA
Ethers
Iso-octane/iso-octene
Stone & Webster Inc., a Shaw Group Co.
Resid catalytic cracking
Stratco Inc.
Alkylation
TECHNIP
Crude distillation
UOP LLC
Alkylation
Alkylation
Catalytic cracking
GULF PUBLISHING COMPANY Catalytic reforming
3 Greenway Plaza, 9th Floor, Houston, TX 77046 Coking
Phone 713-529-4301, Fax 713-520-4433
E-mail: editorial@hydrocarbonprocessing.com Deasphalting next
UOP LLC continued

Hydrocracking
contributing
Select a Process
to view Hydrodesulfurization
Hydrotreating
company/licensor
Hydrotreating
Isomerization
Visbreaking back
VEBA OEL Technologie und Automatisierung GmbH
Hydrocracking
Washington Group International
Lube treating

3 Greenway Plaza, 9th Floor, Houston, TX 77046
Phone 713-529-4301, Fax 713-520-4433
REFINING PROCESSES 2000
plant with the feeds. The reactor product is sent to the settler (4), where
Propane product the hydrocarbons are separated from the acid that is recycled. The
hydrocarbons are then sent to the deisobutanizer (5) along with
makeup isobutane. The isobutane-rich overhead is recycled to the
reactor. The bottoms are then sent to a debutanizer (6) to produce a
3 low Rvp alkylate product with an FBP less than 400°F.
2 Recycle
Refrigerant isobutane Butane Major features of the reactor are:
product • Use of the autorefrigeration method of cooling is thermodynamically
efficient. It also allows lower temperatures, which are favorable for pro-
ducing high product quality with low power requirements.
1
4 • Use of a staged reactor system results in a high average isobu-
5 6 tane concentration, which favors high product quality.
Olefin • Use of low space velocity in the reactor design results in high prod-
feed uct quality and eliminates any corrosion problems in the fractiona-
tion section associated with the formation of esters.
START
Alkylate • Use of low reactor operating pressure means high reliability for
Recycle acid Makeup product
isobutane the mechanical seals for the mixers.
• Use of simple reactor internals translates to low cost.
Yields:
Alkylate yield 1.78 bbl C 5+/bbl butylene feed
Alkylation Isobutane (pure) required
Alkylate quality
1.17 bbl/bbl butylene feed
96 RON/94 MON
Application: Combines propylene, butylene and pentylene with Economics:
isobutane, in the presence of sulfuric acid catalyst, to form a high- Utilities, typical per barrel of alkylate produced:
octane, mogas component. Water, cooling (20°F rise), 1,000 gal 2.1
Products: A highly isoparaffinic, low Rvp, high-octane gasoline Power, kWh 10.5
Steam, 60 psig, lb 200
blendstock is produced from the alkylation process. H2SO4, lb 19
Description: Olefin feed and recycled isobutane are introduced into NaOH, 100%, lb 0.1
the stirred, autorefrigerated reactor (1). Mixers provide intimate con- Installation: 100,000-bpd capacity at nine locations with the sizes
tact between the reactants and the acid catalyst. Reaction heat is ranging from 2,000 to 30,000 bpd. Single reactor/settle trains with
removed from the reactor by the highly efficient autorefrigeration capacities up to 89,000 bpd.
method. The hydrocarbons that are vaporized from the reactor, and that
provide cooling to the 40°F level, are routed to the refrigeration com- Reference: Lerner, H., “Exxon sulfuric acid alkylation technol-
pressor (2) where they are compressed, condensed and returned to the ogy,” Handbook of Petroleum Refining Processes, 2nd Ed., R. A. Mey-
reactor. A depropanizer (3), which is fed by a slipstream from the refrig- ers, ed., pp. 1.3–1.14.
eration section, is designed to remove any propane introduced to the Licensor: ExxonMobil Research & Engineering Co.
back to main menu Copyright © 2001 by Gulf Publishing Company. All rights reserved.
required)
• Low catalyst consumption
• Low operating cost
Isobutane recycle • Superior alkylate qualities from propylene, isobutylene and
amylene feedstocks
3
• Onsite catalyst regeneration
• Environmentally responsible (very low emissions/waste)
Propane • Between 60%–90% reduction in airborne catalyst release over
Olefin feed 1 traditional catalysts
START
• Can be installed in all licensors’ HF alkylation units.
2 With the proposed reduction of MTBE in gasoline, ReVAP offers
Motor fuel butane significant advantages over sending the isobutylene to a sulfuric-
acid-alkylation unit or a dimerization plant. ReVAP alkylation pro-
duces higher octane, lower RVP and endpoint product than a sulfu-
Isobutane
ric-acid-alkylation unit and nearly twice as many octane barrels as
Alkylate
START can be produced from a dimerization unit.
Yields: Feed type
Butylene Propylene-butylene mix
Composition (lv%)
Propylene 0.8 24.6
Alkylation Propane
Butylene
1.5
47.0
12.5
30.3
Application: Convert propylene, amylenes, butylenes and isobutane i-Butane 33.8 21.8
to the highest quality motor fuel using ReVAP alkylation. n-Butane 14.7 9.5
i-Pentane 2.2 1.3
Products: An ultra-low-sulfur, high-octane and low-RVP blending Alkylate product
stock for motor and aviation fuels. Gravity, API 70.1 71.1
RVP, psi 6–7 6–7
Description: Dry liquid feed containing olefins and isobutane is ASTM 10%, °F 185 170
charged to a combined reactor-settler (1). The reactor uses the prin- ASTM 90%, °F 236 253
ciple of differential gravity head to effect catalyst circulation through RONC 96.0 93.5
a cooler prior to contacting highly dispersed hydrocarbon in the Per bbl olefin converted
reactor pipe. The hydrocarbon phase that is produced in the settler i-Butane consumed, bbl 1.139 1.175
is fed to the main fractionator (2), which separates LPG-quality Alkylate produced, bbl 1.780 1.755
propane, isobutane recycle, n-butane and alkylate products. Small
amount of dissolved catalyst is removed from the propane product Installation: 107 alkylation units licensed worldwide.
by a small stripper tower (3). Major process features are: Licensor: Fuels Technology Division of Phillips Petroleum Co.
• Gravity catalyst circulation (no catalyst circulation pumps
and an extremely large amount of interfacial area is exposed between
Propane the reacting hydrocarbons and the acid catalyst from the acid settler
product (2). The entire volume of the liquid in the Contactor is maintained
5 at a uniform temperature, less than 1°F between any two points
2
within the reaction mass. Reactor products pass through a flash drum
n-Butane (3) and deisobutanizer (4). The refrigeration section consists of a com-
3
6 product pressor (5) and depropanizer (6).
4 The overhead from the deisobutanizer (4) and effluent refrigerant
1
recycle (6) constitutes the total isobutane recycle to the reaction
Alkylate zone. This total quantity of isobutane and all other hydrocarbons is
product maintained in the liquid phase throughout the Contactor, thereby
Olefin feed serving to promote the alkylation reaction. Onsite acid regeneration
START technology is also available.
i-Butane Product quality: The total debutanized alkylate has RON of 92 to

96 clear and MON of 90 to 94 clear. When processing straight
START
butylenes, the debutanized total alkylate has RON as high as 98 clear.
Endpoint of the total alkylate from straight butylene feeds is less than
390°F and less than 420°F for mixed feeds containing amylenes in
most cases.
Alkylation Economics (basis: butylene feed):
Investment (basis: 10,000-bpsd unit), $ per bpsd 3,500
Application: To combine propylene, butylenes and amylenes with Utilities, typical per bbl alkylate:
isobutane in the presence of strong sulfuric acid to produce high- Electricity, kWh 13.5
octane branched chain hydrocarbons using the Effluent Refrigera- Steam, 150 psig, lb 180
tion Alkylation process. Water, cooling (20oF rise), 103 gal 1.85
Products: Branched chain hydrocarbons for use in high-octane Acid, lb 15
motor fuel and aviation gasoline. Caustic, lb 0.1
Description: Plants are designed to process a mixture of propylene, Installation: Nearly 600,000 bpsd installed capacity.
butylenes and amylenes. Olefins and isobutane-rich streams along Reference: Hydrocarbon Processing, Vol. 64, No. 9, September
with a recycle stream of H2SO4 are charged to the Contactor (1). The 1985, pp. 67–71.
liquid contents of the Contactor are circulated at high velocities
Licensor: Stratco, Inc.
Description: Olefin charge is first treated to remove impurities such
Light ends as diolefins and oxygenates (1). The olefin feed and isobutane recy-
cle are mixed with reactivated catalyst at the bottom of the reactor
vessel riser (2). The reactants and catalyst flow up the riser in a cocur-
LPG rent manner where the alkylation reaction occurs. Upon exiting the
i-C4/H2 3 riser, the catalyst separates easily from the hydrocarbon effluent liq-
uid by gravity and flows downward into the cold reactivation zone
of the reactor. The hydrocarbon effluent flows to the fractionation sec-
2 tion (3), where the alkylate product is separated from the LPG prod-
Olefin feed 4 uct. There is no acid soluble oil (ASO) or heavy polymer to dispose
Alkylate of as with liquid acid technology.
The catalyst flows slowly down the annulus section of the reactor
i-C4/H2 around the riser as a packed bed. Isobutane saturated with hydrogen
is injected to reactivate the catalyst. The reactivated catalyst then
1
flows through standpipes back into the bottom of the riser. The reac-
tivation in this section is nearly complete, but some strongly adsorbed
Isobutane recycle
material remains on the catalyst surface. This is removed by process-
ing a small portion of the circulating catalyst in the reactivation ves-
sel (4), where the temperature is elevated for complete reactivation. The
reactivated catalyst then flows back to the bottom of the riser.
Alkylation Product quality: Alkylate has ideal gasoline properties such as: high
Application: The Alkylene process uses a solid catalyst to react isobu- research and motor octane numbers, low Reid vapor pressure (Rvp),
tane with light olefins (C3 to C5) to produce a branched-chain paraf- and no aromatics, olefins or sulfur. The alkylate from an Alkylene
finic fuel. The performance characteristics of this catalyst and novel unit has the particular advantage of lower 50% and 90% distillation
process design have yielded a technology that is competitive with tra- temperatures, which is important for new reformulated gasoline
ditional liquid-acid-alkylation processes. Unlike liquid-acid-cat- specifications.
alyzed technologies, significant opportunities to continually advance Economics: (basis: FCC source C4 olefin feed)
the catalytic activity and selectivity of this exciting new technology Investment (basis: 6,000-bpsd unit), $ per bpsd 4,940
are possible. This process meets today’s demand for both improved Operating cost ($/gal) 0.54
gasoline formulations and a more “environmentally friendly” light
olefin upgrading technology. Licensor: UOP LLC.
stabilized (4) to produce a paraffinic gasoline component
Makeup H2 Offgas The InAlk process is more flexible than the traditional alkyla-
tion processes. Using a direct alkylation process, refiners must match
the isobutane requirement with olefin availability. The InAlk pro-
5 cess does not require a set amount of isobutane to produce a high-
Olefin
feed quality product. Additional flexibility comes from being able to revamp
1 2 4 existing catalytic condensation and MTBE units easily to the InAlk
LPG process.
3 The flexibility of the InAlk process is in both the polymerization
and hydrogenation sections. Both sections have different catalyst
options based on specific operating objectives and site conditions.
This flexibility allows existing catalytic condensation units to revamp
to the InAlk process with the addition of the hydrogenation section
and optimized processing conditions. Existing MTBE units can be
converted to the InAlk process with only minor modifications.
Alkylate Product quality: High octane (99 RON, 94 MON), low Rvp, mid-boil-
ing-range paraffinic gasoline blending component with no aromatic
content, low-sulfur content and adjustable olefin content.
Economics: (basis: C4 feed from FCC unit)
Alkylation Investment (basis: 2,800-bpsd unit), $ / bpsd
Application: The UOP Indirect Alkylation (InAlk) process uses Grassroots 3,000
solid catalysts to react isobutylene with light olefins (C3 to C5) to pro- Revamp of MTBE unit 1,580
duce a high-octane, low-vapor pressure, paraffinic gasoline compo-
Utilities (per bbl InAlkylate)
nent similar in quality to traditional motor alkylate.
Hydrogen, lb 4.3
Description: The InAlk process combines two, commercially proven Power, kW 2.1
technologies: polymerization and olefin saturation. Isobutylene is HP steam, lb 65
reacted with light olefins (C3 to C5) in the polymerization reactor (1). LP steam, lb 33
The resulting mixture of iso-olefins is saturated in the hydrogena-
Licensor: UOP LLC.
tion reactor (2). Recycle hydrogen is removed (3) and the product is
while enabling high turndown ratios. Butene yields are maximized,
hydrogen is completely consumed, and essentially no gaseous byprod-
ucts or heavier compounds are formed. Additional savings are pos-
Fuel gas
sible when pure hydrogen is available eliminating the need for a sta-
bilizer. The process integrates easily with the C 3/C4 splitter.
Alkyfining performance and impact on HF alkylation
product: The table below shows the results of an Alkyfining unit
treating an FCC C4-HF-alkylation unit feed containing 0.8% 1,3-
Reactor Stripper butadiene.
Butadiene in alkylate, ppm < 10
Hydrogen 1-butene isomerization, % 70
Butenes yield, % 100.5
C4 feed RON increase in alkylate 2
Hydroisomerized
MON increase in alkylate 1
C4s to alkylation
START
Alkylate end-point reduction, °C –20
The increases in MON, RON and butenes yield are reflected in a
substantial octane-barrel increase while the lower alkylate end
point results in reductions in ASO production and HF consumption.
Alkylation feed preparation Economics:

Investment: Grassroots ISBL cost:
Application: Upgrades alkylation plant feeds with Alkyfining process.
For an HF unit, $/bpsd 430
Description: Diolefins and acetylenes in the C4 (or C3–C4) feed For an H2SO4 unit, $/bpsd 210
react selectively with hydrogen in the liquid-phase, fixed-bed reac-
tor under mild temperature and pressure conditions. Butadiene Annual savings for a 10,000-bpsd alkylation unit:
and, if C3s are present, methylacetylene and propadiene are converted For an HF unit: U.S.$ 4.1 million
to olefins. For an H2SO4 unit: U.S.$ 5.5 million
The high isomerization activity of the catalyst transforms 1-butene
into cis- and trans-2-butenes, which affords higher octane-barrel Installation: Over 80 units, for a total capacity of 700,000 bpsd.
production.
Good hydrogen distribution and reactor design eliminate channeling Licensor: IFP.
from the top of the extractive distillation (ED) column enter the base
Nonaromatics of the extractor as countersolvent.
Washer
Aromatics and solvent from the bottom of the extractor enter the
Extractive ED, which is operated at reduced pressure due to the boiling-tem-
distillation perature threshold. Additional solvent is fed above the aromatics
Extractor column Water feed containing small amounts of nonaromatics that move to the top
Water &
solvent of the column. In the bottom section as well as in the side rectifier aro-
Feed BTX- matics and practically water-free solvent are separated.
fraction The water is produced as a second subphase in the reflux drum
after azeotropic distillation in the top section of the ED. This water
is then fed to the solvent-recovery stage of the extraction process.
Water Economics:
Side Consumption per ton of feedstock
stripper Aromatics Steam (20 bar), t/t 0.46
Water, cooling (T=10ºC), m3/t 12
Electric power, kWh/t 18
Light nonaromatics Production yield
Benzene, % ~100
Toluene, % 99.7
Aromatics extraction EB, Xylenes,%
Purity
94.0
Application: Simultaneous recovery of benzene, toluene and xylenes Benzene, wt% 99.999
(BTX) from reformate or pyrolysis gasoline (pygas) using liquid-liq- Toluene, wt% >99.99
uid extraction. EB, Xylenes, wt% >99.99
Description: At the top of extractor operating at 30°C to 50°C and Installation: One Morphylane plant was erected.
1 to 3 bar, the solvent, N-Formylmorpholin with 4% to 6% water, is Reference: Emmrich, G., F. Ennenbach, and U. Ranke, “Krupp Uhde
fed as a continuous phase. The feedstock—reformate or pygas— Processes for Aromatics Recovery,” European Petrochemical Tech-
enters several stages above the base of the column. Due to density nology Conference, June 21–22, 1999, London.
differences, the feedstock bubbles upwards, countercurrent to the sol-
vent. Aromatics pass into the solvent, while the nonaromatics move Licensor: Krupp Uhde.
to the top, remaining in the light phase. Low-boiling nonaromatics
mounted on the main column or installed separately.
Extractive Nonaromatics Bottom product of the ED column is fed to the stripper to separate
distillation pure aromatics from the solvent. After intensive heat exchange, the
column lean solvent is recycled to the ED column. NFM perfectly satisfies
the necessary solvent properties needed for this process including
high selectivity, thermal stability and a suitable boiling point.
Aromatics Economics:
fraction Pygas feedstock:
Benzene Benzene/toluene
Aromatics Production yield
Stripper Benzene 99.95% 99.95%
column Toluene – 99.98%
Quality
Benzene 30 wt ppm NA* 80 wt ppm NA*
Toluene – 600 wt ppm NA*
Solvent+aromatics Consumption
Solvent
Steam 475 kg/t ED feed 680 kg/t ED feed**
Reformate feedstock with low aromatics content (20wt%):
Aromatics extractive Quality

Benzene
Benzene 10 wt ppm NA*

distillation Consumption
Steam 320 kg/t ED feed
Application: Recovery of high-purity aromatics from reformate,
*Maximum content of nonaromatics.
pyrolysis gasoline or coke-oven light oil using extractive distillation. **Including benzene/toluene splitter.
Description: In the extractive distillation (ED) process, a single-com- Installation: 45 plants (total capacity of more than 6 MMtpa).
pound solvent, N-Formylmorpholin (NFM) alters the vapor pressure
of the components being separated. The vapor pressure of the aro- Reference: Emmrich, G., F. Ennenbach, and U. Ranke, “Krupp
matics is lowered more than that of the less soluble nonaromatics. Uhde Processes for Aromatics Recovery,” European Petrochemical
Nonaromatics vapors leave the top of the ED column with some Technology Conference, June 21–22, 1999, London.
solvent, which is recovered in a small column that can either be
Licensor: Krupp Uhde.
fractionation
• Distillation-based operation provides better control and sim-
plified operation
• Proprietary formulation of commercially available solvents
Water exhibits high selectivity and capacity
Raffinate
• Low solvent circulation rates
Lean solvent • Insignificant fouling due to elimination of liquid-liquid
Aromatics to
Hydrocarbon Extractive downstream contactors
feed 1 distillation Solvent fractionation • Fewer hydrocarbon emission sources for environmental benefits
column recovery • Flexibility of design options for grassroots plants or expansion
START
column of existing liquid-liquid extraction units.
2
Steam 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 the col-
umn bottoms in a vapor/liquid distillation operation. The nonaromatic
Aromatics-rich solvent 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 the overhead
stream is the raffinate product, requiring no further treatment.
Rich solvent from the bottom of the EDC is routed to the solvent-
Aromatics recovery recovery column (SRC), where the aromatics are stripped overhead.
Stripping steam from a closed-loop water circuit facilitates hydro-
Application: GT-BTX is an aromatics recovery process. The technology carbon removal. The SRC is operated under a vacuum to reduce the
uses extractive distillation to remove benzene, toluene and xylene (BTX) boiling point at the base of the column. Lean solvent from the bottom
from refinery or petrochemical aromatics streams such as catalytic refor- of the SRC is passed through heat exchange before returning to the
mate or pyrolysis gasoline. The process is superior to conventional liquid- EDC. A small portion of the lean circulating solvent is processed in a
liquid extraction processes in terms of lower capital and operating costs, solvent-regeneration step to remove heavy decomposition products.
simplicity of operation, range of feedstock and solvent performance. Flex- The SRC overhead mixed aromatics product is routed to the purifi-
ibility of design allows its use for grassroots aromatics recovery units, debot- cation section, where it is fractionated to produce chemical-grade
tlenecking or expansion of conventional extraction systems. benzene, toluene and xylenes.
Description: The technology has several advantages: Economics: Estimated installed cost for a 15,000-bpd GT-BTX
• Less equipment required, thus, significantly lower capital cost extraction unit processing BT-Reformate feedstock is $12 million (U.S.
compared to conventional liquid-liquid extraction systems Gulf Coast 2000 basis).
• Energy integration reduces operating costs
• Higher product purity and aromatic recovery Installations: Three grassroots applications.
• Recovers aromatics from full-range BTX feedstock without pre- Licensor: GTC Technology Corp.
Above the feed injection tray, a benzene-rich light fraction is with-
drawn and pumped to the hydrogenation reactor outside the column.
Offgas A pump enables the reactor to operate at higher pressure than the
C5/C6 column, thus ensuring increased solubility of hydrogen in the feed.
Splitter A slightly higher-than-chemical stoichiometric ratio of hydrogen to
benzene is added to the feed to ensure that the benzene content of
C5-C9 the resulting gasoline pool is below mandated levels, i.e., below 1.0
vol% for many major markets. The low hydrogen flow minimizes
Reformate H2
losses of gasoline product in the offgas of the column. Benzene con-
Light version to cyclohexane can easily be increased if even lower benzene
reformate content is desired. The reactor effluent, essentially benzene-free, is
returned to the column.
The absence of benzene disrupts the benzene-iso-C7 azeotropes,
thereby ensuring that the latter components leave with the bot-
Heavy toms fraction of the column. This is particularly advantageous when
reformate the light reformate is destined to be isomerized, because iso-C7
paraffins tend to be cracked to C3 and C4 components, thus leading
to a loss of gasoline production.
Economics:
Benzene reduction Investment:
Combined utilities:
Grassroots ISBL cost: 300 $/bpsd
0.17 $/bbl
Application: Benzene reduction from reformate, with the Benfree Hydrogen: Stoichiometric to benzene
process, using integrated reactive distillation. Catalyst: 0.01 $/bbl
Description: Full-range reformate from either a semiregenerative Installation: Eight benzene reduction units have been licensed.
or CCR reformer is fed to the reformate splitter column, shown Reference: “The Domino Interaction of Refinery Processes for
above. The splitter operates as a dehexanizer lifting C 6 and lower- Gasoline Quality Attainment,” NPRA Annual Meeting, March 26–28,
boiling components to the overhead section of the column. Benzene 2000, San Antonio.
is lifted with the light ends, but toluene is not. Since benzene forms
azeotropic mixtures with some C 7 paraffin isomers, these fractions Licensor: IFP.
are also entrained with the light fraction.
Penex process with benzene saturation for high-benzene feedstocks.
Makeup hydrogen Complete benzene saturation is achieved while maintaining the
desired C5 and C6 isomerization reactions for octane upgrading.
Light end to FG Benzene levels in Penex-Plus and BenSat feedstocks range from
a few percent to 30 vol% or more.
Preheater Description: Both the BenSat and Penex-Plus processes use a
(for startup only) noble metal catalyst developed by UOP. The heat of reaction asso-
2 ciated with benzene saturation is carefully managed to control the
3 temperature rise. The BenSat process is preferred when no octane
upgrade is required. The Penex-Plus process is chosen when an
Feed 1 octane increase is required.
effluent The accompanying flow diagram represents the BenSat process.
exchanger Feed is heated (1) against reactor effluent, mixed with makeup
Feed hydrogen and sent to the benzene saturation reactor section (2).
Product Reactor effluent is sent to the stabilizer (3) after heat exchange. Sta-
START bilizer bottoms are sent to gasoline blending and light ends are sent
to fuel gas.
Economics:
Investment (basis: 2nd Quarter 2000, U.S. Gulf Coast)
Benzene saturation Operation BenSat Penex-Plus
Size basis, bpsd 10,000 15,000
Application: Remove benzene from light reformate or light straight- Benzene basis, lv% 20 7
run naphtha streams to meet benzene specifications in the gasoline $ per bpsd 555 795
pool. Benzene is saturated to cyclohexane at high selectivity. This sat-
uration can be achieved either in a stand-alone option or in combi- Installation: The BenSat and Penex-Plus processes were first
nation with isomerization to upgrade the octane. offered for license in 1991. Four Penex-Plus units and three BenSat
The BenSat process is a stand-alone option to treat C5-C6 feedstocks units are in operation.
that are high in benzene. Benzene is completely saturated to cyclo-
Reference: AIChE meeting, New Orleans, Louisiana, April 1992.
hexane in the presence of hydrogen.
The Penex-Plus process integrates the isomerization features of the Licensor: UOP LLC.
initial contact of oil and catalyst occurs without a riser in a very short
residence time followed by a rapid separation of initial reaction
products. Because there is no riser and the catalyst is downflowing,
startup and operability are outstanding.
1 Regenerator The configuration of an MSCC unit has the regenerator (1) at a
higher elevation than the reactor (2). Regenerated catalyst falls down
a standpipe (3), through a shaped opening (4) that creates a falling
curtain of catalyst, and across a well-distributed feed stream. Many
3 products from this initial reaction are quickly separated from the
catalyst. The catalyst then passes into a second higher-temperature
reaction zone (5), where further reaction and stripping occurs. The
higher temperature is achieved through contact with regenerated
2 4 catalyst.
Feed Since a large portion of the reaction product is produced under
MSCC reactor 5 very short time conditions, the reaction mixture maintains good prod-
uct olefinicity and retains hydrogen content in the heavier liquid
products. Additional reaction time is available for the more-difficult-
to-crack species in the second reaction zone/stripper.
Stripped catalyst is airlifted back to the regenerator where coke
deposits are burned, creating clean, hot catalyst to begin the sequence
Catalytic cracking again.
Application: To selectively convert gas oils and residual feedstocks Installations: A new MSCC unit began operation earlier this year,
to higher-value cracked products such as light olefins, gasoline and and a revamped MSCC unit has been in operation since 1994. Two
distillates. additional MSCC facilities are in design and construction.
Description: The Milli-Second Catalytic Cracking (MSCC) process Reference: “Short-Contact-Time FCC,” AIChE 1998 Spring Meet-
uses a fluid catalyst and a novel contacting arrangement to crack ing, New Orleans.
heavier materials into a highly selective yield of light olefins, gaso- Licensor: UOP LLC (in cooperation with BARCO).
line and distillates. A distinguishing feature of the process is that the
hydrotreated stocks. The improved selectivity of MSDW for the
Makeup Purge Fuel ags to LP absorber highly isoparaffinic-lube components, which results in higher lube
H2 yields and VI’s. The process uses multiple catalyst systems with mul-
M/U Water Wild naphtha tiple reactors. Internals are proprietary (the Spider Vortex Quench
wash HP Zone technology is used). Feed and recycle gases are preheated and
Rec stripper Sour water contact the catalyst in a down-flow-fixed-bed reactor. Reactor efflu-
HDW HDT
Rxr
MP steam ent is cooled, and the remaining aromatics are saturated in a post-
Rxr Water Vacuum system treat reactor. The process can be integrated into a lube hydrocracker
wash or lube hydrotreater. Postfractionation is targeted for client needs.
Waxy Water Vac
feed strip. Sour Operating conditions:
LT Oily water
HT sep water Temperatures, °F 550 to 800
sep Hydrogen partial pressures, psig 500 to 2,500
Distillate LHSV 0.4 to 3.0
Conversion depends on feed wax content
MP steam Pour point reduction as needed.
Lube product Vac Yields:
dryer
Light neutral Heavy neutral
Lube yield, wt% 94.5 96.5
C1 to C4, wt% 1.5 1.0
Catalytic dewaxing C5–400°F, wt% 2.7 1.8
400°F–Lube, wt% 1.5 1.0
Application: Use the ExxonMobil Selective Catalytic Dewaxing H2 cons,scf/bbl 100–300 100–300
(MSDW) process to make high VI lube base stock.
Economics: $3,000–5,500 per bpsd installed cost (U. S. Gulf Coast).
Products: High VI/ low-aromatics lube base oils (light neutral
through bright stocks). Byproducts include fuel gas, naphtha and low- Installation: Three units are operating, one under construction
pour diesel. and one being converted.
Description: MSDW is targeted for hydrocracked or severely Licensor: ExxonMobil Research & Engineering Co.
3 to 7 mols/mol of feed. Straight run and/or cracked feeds are typi-
cally hydrotreated, but low-sulfur feeds (<10 ppm) may be reformed
BFW Steam
without hydrotreatment.
Heaters
Operating conditions: 875°F to 1,000°F and 150 to 400 psig reac-
tor conditions.
Reactors Yields: Depend on feed characteristics, product octane and reactor

Hot pressure. The following yields are one example. The feed contains
feed 51.4% paraffins, 41.5% naphthenes and 7.1% aromatics, and boils
from 208°F to 375°F (ASTM D86). Product octane is 99.7 RONC and
START
average reactor pressure is 200 psig.
Component wt% vol%
Net gas Low- H2 2.3 1,150 scf/bbl
CW pressure C1 1.1 —
High- flash C2 1.8 —
pressure —
flash Liquid to stabilizer C3 3.2
iC4 1.6 —
nC4 2.3 —
C5+ 87.1 —
LPG — 3.7
Catalytic reforming Reformate — 83.2
Application: Increase the octane of straight run or cracked naph- Economics:
thas for gasoline production. Utilities, (per bbl feed)
Fuel, 103 Btu release 275
Products: High-octane gasoline and hydrogen-rich gas. Byprod- Electricity, kWh 7.2
ucts may be LPG, fuel gas and steam. Water, cooling (20°F rise), gal 216
Description: Semi-regenerative multibed reforming over platinum Steam produced (175 psig sat), lb 100
or bimetallic catalysts. Hydrogen recycled to reactors at the rate of Licensor: Howe-Baker Engineers, Inc.
• Side-by-side reactor arrangement, which is very easy to erect and
consequently leads to low investment cost.
• The Regen C catalyst regeneration system featuring the dry burn
loop, completely restores the catalyst activity while maintaining its
specific area for more than 600 cycles.
Feed Finally, with the new CR401 (gasoline mode) and AR501 (aromat-
START
ics production) catalysts specifically developed for ultra-low operating
4 5 pressure and the very effective catalyst regeneration system, refiners
2 3 operating Octanizing or Aromizing processes can obtain the highest
1 hydrogen, C5+ and aromatics yields over the entire catalyst life.
Yields: Typical for a 90°C to 170°C (176°F to 338°F) cut from light
Arabian feedstock:
Conventional Octanizing
Oper. press., kg/cm2 10 –15 <5
Yield, wt% of feed
Hydrogen 2.8 3.8
Reformate C 5+ 83 88
RONC 100 102
MONC 89 90.5
Catalytic reforming Economics:

Investment (basis 25,000 bpsd continuous
Octanizing unit, battery limits, erected cost,
Application: Upgrade various types of naphtha to produce high- mid-2000 Gulf Coast), U.S.$ per bpsd 1,700
octane reformate, BTX and LPG. Utilities: typical per bbl feed:
Description: Two different designs are offered. One design is con- Fuel, 103 kcal 65
ventional where the catalyst is regenerated in place at the end of each Electricity, kWh 0.96
cycle. Operating normally in a pressure range of 12 to 25 kg/cm2 (170 Steam, net, HP, kg 12.5
to 350 psig) and with low pressure drop in the hydrogen loop, the prod- Water, boiler feed, m3 0.03
uct is 90 to 100 RONC. With its higher selectivity, trimetallic cata- Installation: Of 104 units licensed, 56 units are designed with con-
lyst RG582 makes an excellent catalyst replacement for semi-regen- tinuous regeneration technology capability.
erative reformers. Reference: “Continuing Innovation In Cat Reforming,” NPRA
The second, the advanced Octanizing process, uses continuous
Annual Meeting, March 15–17, 1998, San Antonio.
catalyst regeneration allowing operating pressures as low as 3.5
“Fixed Bed Reformer Revamp Solutions for Gasoline Pool Improve-
kg/cm2 (50 psig). This is made possible by smooth-flowing moving bed ment,”Petroleum Technology Quarterly, Summer 2000.
reactors (1–4) which use a highly stable and selective catalyst suit-
able for continuous regeneration (5). Main features of IFP’s regen- Licensor: IFP.
erative technology are:
Semiregenerative reforming units also benefit from the latest UOP
Spent catalyst Net gas to fuel catalysts. The R-72 staged loading system provides the highest C5+
yields available. Refiners use UOP engineering and technical service
experience to tune operations, plan the most cost-effective revamps,
and implement a stepwise approach for conversion of semiregenera-
Net gas to tive units to obtain the full benefits of CCR Platforming technology.
2 H2 users
Yields:
1 6 7 Operating mode Semiregen. Continuous
3 Onstream availability, days/yr 330 360
Feedstock, P/N/A LV% 63/25/12 63/25/12
4 To fractionator IBP/EP,°F 200/360 200/360
5 Operating conditions
Reactor pressure, psig 200 50
C5+ octane, RONC 100 100
Charge Catalyst R-72 staged loading R-274
START
Yield information
Hydrogen, scfb 1,270 1,690
C5 +, wt% 85.3 91.6
Economics:
Catalytic reforming Investment (basis: 20,000 bpsd CCR Platforming unit, 50 psig reac-
tor pressure, 100 C 5+ RONC, 2000, U.S. Gulf Coast ISBL):
Application: Upgrade naphtha for use as a gasoline blendstock or $ per bpsd 2,000
feed to a petrochemical complex with the UOP CCR Platforming pro-
cess. The unit is also a reliable, continuous source of high-purity Installation: UOP has licensed more than 800 platforming units; 37
hydrogen. customers operate 2 or more CCR Platformers. Twenty-six refiners
operate 90 of the 163 operating units. Twenty units are designed for
Description: Constant product yields and onstream availability initial semiregenerative operation with the future installation of a
distinguish the CCR Platforming process featuring catalyst transfer CCR regeneration section.
with minimum lifts, no valves closing on catalyst and gravity flow
from reactor to reactor (2,3,4). The CycleMax regenerator (1) provides Operating Design & const.
Total CCR Platforming units 163 41
simplified operation and enhanced performance at a lower cost than
Ultra-low 50 psig units 40 27
other designs. The product recovery section downstream of the sep-
Units at 35,000+ bpsd 29 4
arator (7) is customized to meet site-specific requirements. The R-
Semiregenerative units
270 series catalysts offer the highest C5+ and hydrogen yields while
with a stacked reactor 14 5
also providing the R-230 series attributes of CCR Platforming pro-
cess unit flexibility through reduced coke make. Licensor: UOP LLC.
The overhead stream is sent to a vapor recovery unit (4) where the
Fuel gas individual product streams are separated. The coke that forms in one
of at least two (parallel connected) drums is then removed using high-
C3/C4 LP pressure water. The plant also includes a blow-down system, coke han-
4
Coker naphtha dling and a water recovery system.
3 3
Operating conditions:
Heater outlet temperature, °F 900–950
Stm. Coke drum pressure, psig 15 –90
Stm. 1 BFW Recycle ratio, vol/vol feed, % 0–100
Light gas oil
Yields:
2 BFW Vacuum residue of
Middle East hydrotreated Coal tar
Heavy gas oil Feedstock vac. residue bottoms pitch
Fresh feed Gravity, °API 7.4 1.3 —11.0
Sulfur, wt% 4.2 2.3 0.5
START
Stm. Conradson
carbon, wt% 20.0 27.6 —
Products, wt%
Gas + LPG 7.9 9.0 3.9
Coking Naphtha 12.6 11.1 —
Gas oils 50.8 44.0 31.0
Application: Conversion of vacuum residues (virgin and Coke 28.7 35.9 65.1
hydrotreated), various petroleum tars and coal tar pitch through
delayed coking.
Products: Fuel gas, LPG, naphtha, gas oils and fuel, anode or nee-
dle grade coke (depending on feedstock and operating conditions).
Description: Feedstock is introduced (after heat exchange) to the
bottom of the coker fractionator (1) where it mixes with condensed
recycle. The mixture is pumped through the coker heater (2) where
the desired coking temperature is achieved, to one of two coke drums
(3). Steam or boiler feedwater is injected into the heater tubes to pre-
vent coking in the furnace tubes. Coke drum overhead vapors flow
to the fractionator (1) where they are separated into an overhead
stream containing the wet gas, LPG and naphtha; two gas oil
sidestreams; and the recycle that rejoins the feed.
Economics:
Investment (basis: 20,000 bpsd straight run vacuum residue feed,
U.S. Gulf Coast 2000, fuel-grade coke, includes vapor recovery),
U.S. $ per bpsd (typical) 4,000
Utilities, typical/bbl of feed:
3
Fuel, 10 Btu 145
Electricity, kWh 3.9
Steam (exported), lb 20
Water, cooling, gal 180
Installation: More than 55 units.
Licensor: ABB Lummus Global Inc.
Operating conditions: Typical ranges are:
Heater outlet temperature, °F 900–950
Coke drum pressure, psig 15–100
Recycle ratio, equiv. fresh feed 0.05–1.0
Increased coking temperature decreases coke production; increases
liquid yield and gas oil end point. Increasing pressure and/or recy-
2 3 Naphtha cle ratio increases gas and coke make, decreases liquid yield and gas
oil end point.
Yields:
1 Steam Feed, source Venezuela N. Africa —
Type Vac. resid Vac. resid Decant oil
Light gas oil Gravity, °API 2.6 15.2 40.7
Sulfur, wt% 4.4 0.7 0.5
Feed Concarbon, wt% 23.3 16.7 —
Heavy gas oil Operation Max dist. Anode coke Needle coke
START Products, wt%
Gas 8.7 7.7 9.8
Naphtha 10.0 19.9 8.4
Gas oil 50.3 46.0 41.6
Coking Coke 31.0 26.4 40.2
Economics:
Application: Manufacture petroleum coke and upgrade residues to Investment (basis: 65,000–10,000 bpsd, 4th Q, 1999, U.S. Gulf),
lighter hydrocarbon fractions using the Selective Yield Delayed Cok- $ per bpsd 2,500–4,000
ing (SYDEC) process. Utilities, typical per bbl feed:
Products: Coke, gas, LPG, naphtha and gas oils. Fuel, 103 Btu 120
Electricity, kWh 3.6
Description: Charge is fed directly to the fractionator (1) where it Steam (exported), lb (40)
combines with recycle and is pumped to the coker heater where it is Water, cooling, gal 36
heated to coking temperature, causing partial vaporization and mild
Installation: More than 58,000 tpd of fuel, anode and needle coke.
cracking. The vapor-liquid mix enters a coke drum (2 or 3) for fur-
ther cracking. Drum overhead enters the fractionator (1) to be sep- Reference: Handbook of Petroleum Refining Processes, 2nd Ed., pp.
arated into gas, naphtha, and light and heavy gas oils. There are at 12.25–12.82; Oil & Gas Journal, Feb. 4, 1991, pp. 41–44; Hydrocarbon
least two coking drums, one coking while the other is decoked using Processing, Vol. 71, No. 1, January 1992, pp. 75–84.
high-pressure water jets.
Licensor: Foster Wheeler USA Corp./UOP LLC
. (3). The overhead products of the two pre-flash towers are then
LPG fractionated as required in a gas plant and rectification towers (4).
Feed
Light naphtha The topped crude typically reduced by 2⁄3 of the total naphtha cut
START
is then heated in a conventional heater and conventional topping col-
4 Medium naphtha umn (5). If necessary the reduced crude is fractionated in one deep
vacuum column designed for a sharp fractionation between vacuum
Heavy naphtha gas oil, two vacuum distillates (6) and a vacuum residue, which
could be also a road bitumen.
Stm. One or two kerosine cut
1 Extensive use of pinch technology minimizes heat supplied by
Two kerosine cut heaters and heat removed by air and water coolers.
2 3 This process is particularly suitable for large crude capacity from
5
Vacuum gas oil 150,000 to 250,000 bpsd.
Distillate It is also available for condensates and light crudes progressive
6 distillation with a slightly adapted scheme.
Distillate for FCC Economics:
Investment (basis 230,000 bpsd including atmospheric and
Vacuum residue
vacuum distillation, gas plant and rectification tower) 750 to
950 $ per bpsd (U.S. Gulf Coast 2000).
Utility requirements, typical per bbl of crude feed:
Fuel fired, 103 btu 50–65
Crude distillation Power, kWh
Steam 65 psig, lb
0.9–1.2
0–5
Application: The D2000 process is progressive distillation to min- Water cooling, (15°C rise) gal 50–100
imize the total energy consumption required to separate crude oils Total primary energy consumption:
or condensates into hydrocarbon cuts, which number and properties
are optimized to fit with sophisticated refining schemes and future for Arabian Light or Russian
regulations. This process is applied normally for new topping units Export Blend: 1.25 tons of fuel
per 100 tons of Crude
or new integrated topping / vacuum units but the concept can be used
for debottlenecking purpose. for Arabian Heavy 1.15 tons of fuel
per 100 tons of Crude
Products: This process is particularly suitable when more than two
naphtha cuts are to be produced. Typically the process is optimized Installation: Technip has designed and constructed one crude unit
to produce three naphtha cuts or more, one or two kerosine cuts, two and one condensate unit with the D2000 concept. The latest revamp
atmospheric gas oil cuts, one vacuum gas oil cut, two vacuum dis- project currently in operation shows an increase of capacity of the
tillates cuts, and one vacuum residue. existing crude unit of 30% without heater addition.
Description: The crude is preheated and desalted (1). It is fed to a Licensors: ELF and TECHNIP.
first dry reboiled pre-flash tower (2) and then to a wet pre-flash tower
(11) where the typical outlet temperature is on the order of 750°F to
Flash gas 775°F.
6
Light naphtha
From the heater outlet, the stream is fed into a vacuum tower (12),
where the distillate is condensed in two sections and withdrawn as
Heavy naphtha two sidestreams. The two sidestreams are combined to form crack-
7 Kerosine ing feedstock. An asphalt base stock is pumped from the bottom of
4 5 8 Diesel
the tower. Two circulating reflux streams serve as heat removal
3 9 media for the tower.
Cracker feed
10 Yields: Typical for Merey crude oil:
To vac. system
wt% °API Pour, °F
2
Lt. vac. gas oil Crude unit products
Stm. Stm. Hvy. vac. Overhead & naphtha 6.2 58.0 —
1 12 Kerosine 4.5 41.4 485
gas oil
Crude Vac. gas oil
Diesel 18.0 30.0 410
Stm. (cracker feed)
Gas oil 3.9 24.0 20
START
Lt. vac. gas oil 2.6 23.4 35
Asphalt Hvy. vac. gas oil 10.9 19.5 85
Vac. bottoms 53.9 5.8 (120)*
Total 100.00 8.7 85
Crude distillation *Softening point, °F
Note: Crude unit feed is 2.19 wt% sulfur. Vacuum unit feed is 2.91 wt% sulfur.
Application: Separates and recovers the relatively lighter frac- Economics:

tions from a fresh crude oil charge (e.g., naphtha, kerosine, diesel and Investment (basis: 100,000–50,000 bpsd, 4th Q, 1999, U.S. Gulf),
cracking stock). The vacuum flasher processes the crude distillation $ per bpsd 850–1,050
bottoms to produce an increased yield of liquid distillates and a Utility requirements, typical per bbl fresh feed
heavy residual material. Steam, lb 24
Fuel (liberated), 103 Btu (80–120)
Description: The charge is preheated (1), desalted (2) and directed
Power, kWh 0.6
to a preheat train (3) where it recovers heat from product and reflux Water, cooling, gal 300–400
streams. The typical crude fired heater (4) inlet temperature is on
the order of 550°F, while the outlet temperature is on the order of Installation: Foster Wheeler has designed and constructed crude
675°F to 725°F. Heater effluent then enters a crude distillation col- units having a total crude capacity in excess of 10 MMbpsd.
umn (5) where light naphtha is drawn off the tower overhead (6);
heavy naphtha, kerosine, diesel and cracking stock are sidestream Reference: Encyclopedia of Chemical Processing and Design, Mar-
drawoffs. External reflux for the tower is provided by pumparound cel-Dekker, 1997, pp. 230–249.
streams (7–10). The atmospheric residue is charged to a fired heater Licensor: Foster Wheeler USA Corp.
late fraction which is routed to the HDS. After desulfurization in the
FG HDS unit, final product separation of the bulk middle distillate
stream from the CDU takes place in the HDS fractionator (HDF),
Rec NHT which consists of a main atmospheric fractionator with side strippers.
LPG The long residue is routed hot to a feedprep HVU, which recovers
the waxy distillate fraction from long residue as the feedstock for a
H Tops cat cracker or hydrocracker unit (HCU). Typical flashzone condi-
C HDS D tions are 415°C and 24 mbara. The Shell design features a deen-
D Kero
Crude F trainment section, spray sections to obtain a lower flashzone pres-
U
Vac LGO Naphtha sure, and a VGO recovery section to recover up to 10 wt% of as
VGO HGO automotive diesel. The Shell furnace design prevents excessive
H cracking and enables a 5-year run length between decoke.
LR V WD
HCU Kero
U Yields: Typical for Arabian light crude
Storage GO
VBU
VBU Flash column Bleed Products % wt
Gas C1-C4 0.7
Residue Gasoline C5-150°C 15.2
Kerosine 150-250°C 17.4
Gasoil (GO) 250-350°C 18.3
VGO 350-370°C 3.6
Crude distillation Waxy distillate (WD)
Residue
370-575°C
575°C +
28.8
16.0
Application: The Shell Bulk CDU is a highly integrated concept. It sep-
arates the crude in long residue, waxy distillate, middle distillates Economics: Due to the incorporation of Shell high capacity inter-
and a naphtha minus fraction. Compared with stand-alone units, the nals and the deeply integrated designs, typical bulk crude distillers
overall integration of a crude distillation unit (CDU), hydrodesulfur- are 30% cheaper than alternative designs. Investment costs are
ization unit (HDS), high vacuum unit (HVU) and a visbreaker (VBU) dependent on the required configuration and process objectives.
results in a 50% reduction in equipment count and significantly reduced Installation: Over 100 Shell CDU’s have been designed and oper-
operating costs. A prominent feature embedded in this design is the Shell ated since the beginning of the century. Additionally, a total of some
deepflash HVU technology. This technology can also be provided in cost- 50 HVU units have been built while a similar number has been debot-
effective process designs for both feedprep and lube oil HVU’s as stand- tlenecked, including many third-party designs of feedprep and lube
alone units. For each application, tailor-made designs can be produced. oil HVU’s.
Description: The basic concept of the bulk CDU is the separation Licensor: Shell Global Solutions International B.V.
of the naphtha minus and the long residue from the middle distil-
of C2–C7 hydrocarbons including light naphthas. Pressure, 300 to 600
Deasphalted oil separator Deasphalted oil stripper psig. Temp., 120°F to 450°F. Solvent/oil ratio, 4/1 to 13/1.
Deasphalted oil
Yields:
Feed, type Lube oil Cracking stock
2 4 Stm. Gravity, °API 6.6 6.5
Stm. Sulfur, wt% 4.9 3.0
1 Rams carbon, wt% 20.1 21.8
Extraction Solvent Visc., SSU @ 210°F 7,300 8,720
tower drum Ni/V, ppm 29/100 46/125
DAO Case 1 Case 2
Asphalt Yield, vol% on feed 30 53 65
Stm. flash 5 Gravity, °API 20.3 17.6 15.1
3 drum Sour Sulfur, wt% 2.7 1.9 2.2
water Rams carbon, wt% 1.4 3.5 6.2
Asphalt heater
Feed Visc., SSU @ 210°F 165 307 540
Stm.
START Asphalt Ni/V, ppm 0.25/0.37 1.8/3.4 4.5/10.3
Asphalt
Softening pt, R&B, °F 149 226 240
Penetration @ 77°F 12 0 0
Deasphalting Economics:
Investment (basis: 40,000–2,000 bpsd, 4th Q, 1999, U.S. Gulf),
Application: Prepare quality feed and blending stock using the $ per bpsd 800–3,000
Low-Energy Deasphalting (LEDA) Process. Utilities, typical per bbl feed: Lube oil Cracked
Fuel, 103 Btu 81 56
Products: Bright stocks for lube oil refining, catalytic cracking Electricity, kWh 1.5 1.8
and hydrocracking feed; specification asphalt. Steam, 150 psig, lb 116 11
Description: Residue is extracted with liquid hydrocarbon solvent Water, cooling (25°F rise), gal 15 nil
in a rotating disc contactor (1) where extraction efficiency is main- Installation: 42 units.
tained at all charge rates by varying rotor speed. Deasphalted oil sep-
arator recovers solvent at supercritical conditions (2) and asphalt flash Reference: Handbook of Petroleum Refining Processes, 2nd Ed.,
(3) recovers solvent. Products are steam stripped (4, 5). McGraw-Hill, 1997, pp. 10.15–10.44.
Operating conditions: Typical ranges are: solvent, various blends Licensor: Foster Wheeler USA Corp.
2), yielding an intermediate product (resins) that is stripped of solvent
E-2 (T-2). The overhead is heated (E-4, E-6) so the solvent exists as a super-
critical fluid in which the oil is virtually insoluble. Recovered solvent leaves
the separator top (V-3) to be cooled by heat exchange (E-4, E-1) and a cooler
P-1 E-1 E-4 (E-2). Deasphalted oil from the oil separator (V-3) is stripped (T-3) of dis-
solved solvent. The only solvent vaporized is a small amount dissolved
in fractions withdrawn in the separators. This solvent is recovered in the
product strippers. V-1, V-2 and V-3 are equipped with high-performance
Resid- E-3 ROSEMAX internals. These high-efficiency, high-capacity internals
uum E-6 offer superior product yield and quality while minimizing vessel size and
capital investment. They can also debottleneck and improve operations
V-1
V-2
V-3
T-1
T-2
T-3
START
S-1 of existing solvent deasphalting units.

M-1 The system can be simplified by removing equipment in the outlined
Hot box to make two products. The intermediate fraction can be shifted,
Hot oil Oils into the final oil fraction by adjusting operating conditions. Only one
oil P-2 exchanger (E-6) provides heat to warm the resid charge and the small
Resins
Asphaltenes amount of extraction solvent recovered in the product strippers.
Yields: The extraction solvent composition and operating condi-
tions are adjusted to provide the product quality and yields required
for downstream processing or to meet finished product specifications.
Deasphalting Solvents range from propane through hexane and include blends nor-
mally produced in refineries.
Application: Extract lubricating oil blend stocks and FCCU or hydro-
cracker feedstocks with low metal and Conradson carbon contents from Economics:
atmospheric and vacuum resid using ROSE Supercritical Fluid Tech- Investment (basis: 30,000 bpsd, 4th Q 1998 U.S. Gulf Coast),
nology. Can be used to upgrade existing solvent deasphalters. ROSE $ per bpsd 1,250
may also be used to economically upgrade heavy crude oil. Utilities, typical per bbl feed:
3
Fuel absorbed, 10 Btu 80 –110
Products: Lube blend stocks, FCCU feed, hydrocracker feed, resins Electricity, kWh 2.0
and asphaltenes. Steam, 150-psig, lb 12
Description: Resid is charged through a mixer (M-1), where it is mixed Installation: Nineteen units in operation; combined capacity of
with solvent before entering the asphaltene separator (V-1). Counter- 320,000 bpsd. Additional units are licensed.
current solvent flow extracts lighter components from the resid while
rejecting asphaltenes with a small amount of solvent. Asphaltenes are Reference: Northup, A. H., and H. D. Sloan, “Advances in solvent
then heated and stripped of solvent (T-1). Remaining solvent solution goes deasphalting technology,” 1996 NPRA Annual Meeting, San Antonio.
overhead (V-1) through heat exchange (E-1) and a second separation (V- Licensor: Kellogg Brown & Root, Inc.
of C3–C7 hydrocarbons including light naphthas. Pressure: 300 to 600
psig. Temp.: 120 to 450°F. Solvent-to-oil ratio: 4/1 to 13/1.
Yields:
Feed, type Lube oil Cracking stock
Gravity, °API 6.6 6.5
Vacuum
2 DAO
Sulfur, wt.% 4.9 3.0
residue separator CCR, wt% 20.1 21.8
charge 1 Extractor Visc, SSU@ 210°F 7,300 8,720
NI/V, wppm 29/100 46/125
Pitch
stripper DAO
Yield, vol.% of Feed 30 53 65
Gravity, °API 20.3 17.6 15.1
3 4 DAO Sulfur, wt% 2.7 1.9 2.2
stripper CCR, wt% 1.4 3.5 6.2
Visc., SSU@ 210°F 165 307 540
Ni/V, wppm 0.25/0.37 1.8/3.4 4.5/10.3
Pitch DAO
Pitch
Softening point,
R&B,°F 149 226 240
Deasphalting Penetration@77°F 12 0 0
Application: Prepare quality feed for FCC units and hydrocrackers Economics:
from vacuum residue and blending stocks for lube oil and asphalt Investment (basis: 2,000 –40,000 bpsd
manufacturing. 4th Qtr 2000, U.S. Gulf), $/bpsd 800 – 3,000
Utilities, typical per bbl feed: Lube oil Cracking stock
Products: Deasphalted oil (DAO) for catalytic cracking and hydro- Fuel, 103 Btu 81 56
cracking feedstocks, resins for specification asphalts, and pitch for Electricity, kWh 1.5 1.8
specification asphalts and residue fuels. Steam, 150-psig, lb 116 11
Description: Feed and light paraffinic solvent are mixed then Water, cooling (25°F rise), gal 15 nil
charged to the extractor (1). The DAO and pitch phases, both con- Installations: 50+. This also includes both UOP and Foster Wheeler
taining solvents, exit the extractor. The DAO and solvent mixture is units originally licensed separately before the merging the tech-
separated under supercritical conditions (2). Both the pitch and nologies in 1996.
DAO products are stripped of entrained solvent (3,4). A second
extraction stage is utilized if resins are to be produced. Reference: Handbook of Petroleum Refining Processes, 2nd Ed.,
McGraw Hill, 1997, pp.10.15–10.60.
Operating conditions: Typical ranges are: solvent, various blends
Licensor: UOP LLC.
The overall flow scheme of DCC is very similar to that of a con-
ventional FCC. However, innovations in the areas of catalyst devel-
Product vapors opment, process variable selection and severity and gas plant design
Reactor enables the DCC to produce significantly more olefins than FCC in
a maximum olefins mode of operation.
Flue gas Vapor and catalyst
This technology is quite suitable for revamps as well as grass
distributor
root applications. Integrating DCC technology into existing refiner-
Stripper ies as either a grassroots or revamp application can offer an attrac-
Regenerator tive opportunity to produce large quantities of light olefins. In a mar-
ket requiring both proplylene and ethylene, use of both thermal
Reactor riser and catalytic processes is essential, due to the fundamental differ-
Combustion air ences in the reaction mechanisms involved. The combination of ther-
mal and catalytic cracking mechanisms is the only way to increase
Riser steam total olefins from heavier feeds while meeting the need for a increased
Regen. cat. standpipe propylene to ethylene ratio. The integrated DCC/steam cracking
Feed nozzles (FIT) complex offers significant capital savings over a conventional stand-
alone refinery for propylene production.
Products: DCC Type I DCC Type II FCC
Deep catalytic cracking wt% FF

Ethylene 6.1 2.3 0.9
Application: Selective conversion of gas oil and paraffinic residual Propylene 20.5 14.3 6.8
feedstocks. Butylene 14.3 14.6 11.0
in which IC 4= 5.4 6.1 3.3
Products: C2–C5 olefins, aromatic rich, high octane gasoline and Amylene — 9.8 8.5
distillate. in which IC 5= — 6.5 4.3
Description: DCC is a fluidized process for selectively cracking a wide Installation: There are currently five operating units in China and
variety of feedstocks to light olefins. Propylene yields over 24 wt% are one in Thailand. Several more units are under design in China.
achievable with paraffinic feeds. A traditional reactor/regenerator
unit design uses a catalyst with physical properties similar to tradi- Reference: Chapin, Letzsch and Zaiting, “Petrochemical options from
tional FCC catalyst. The DCC unit may be operated in two operational deep catalytic cracking and the FCCU,” paper AM-98-44, NPRA
modes: maximum propylene (Type I) or maximum iso-olefins (Type II). Annual Meeting , March 1998.
Each operational mode utilizes unique catalyst as well as reaction con-
Licensor: Stone & Webster Inc., a Shaw Group Co., Research Insti-
ditions. Maximum propylene DCC uses both riser and bed cracking at
tute of Petroleum
severe reactor conditions while Type II DDC uses only riser cracking
like a modern FCC unit at milder conditions.
an atmospheric fractionator (3) to produce the desired products like
Gas gas, LPG, naphtha, kerosine and gas oil. The fractionator bottoms
are subsequently routed to a vacuum flasher (4), which recovers addi-
tional gas oil and waxy distillate. The residual liquid coke is routed
Naphtha for further processing depending on the outlet.
Yields: Depend on feed type and product specifications.
3
Feed, vacuum residue Middle East
Stm. Gas oil Viscosity, cSt @ 100°C 770
2 Stm.
Products in % wt. on feed
1 Gas 4.0
Charge Waxy distillate Gasoline ECP 165°C 8.0
Gas oil ECP 350°C 18.1
4 Waxy distillate ECP 520°C 22.5
Residue ECP 520°C + 47.4
Liquid coke
Economics: The investment ranges from 1,300 to 1,600 U.S.$/bbl
installed excl. treating facilities and depending on the capacity and
configuration (basis: 1998)
Deep thermal conversion Utilities, typical per bbl @ 180°C

Fuel, Mcal 26
Application: The Shell Deep Thermal Conversion process closes the Electricity, kWh 0.5
gap between visbreaking and coking. The process yields a maximum Net steam production, kg 20
of distillates by applying deep thermal conversion of the vacuum Water, cooling, m3 0.15
residue feed and by vacuum flashing the cracked residue. High-dis-
tillate yields are obtained, while still producing a stable liquid resid- Installation: To date, four Deep Thermal Conversion units have been
ual product, referred to as liquid coke. The liquid coke, not suitable for licensed. In two cases this involved a revamp of an existing Shell
blending to commercial fuel, is used for speciality products, gasifica- Soaker Visbreaker unit. In addition, two units are planned for
tion and/or combustion, e.g., to generate power and/or hydrogen. revamp, while one grass-roots unit is currently under construction.
Post start-up services and technical services on existing units are
Description: The preheated short residue is charged to the heater available from Shell.
(1) and from there to the soaker (2), where the deep conversion
takes place. The conversion is maximised by controlling the operat- Reference: Visbreaking Technology, Erdöl and Kohle, January 1986.
ing temperature and pressure. The cracked feed is then charged to Licensor: Shell Global Solutions International B.V.
drum temperature decreases. Coke is deposited in the coke drums.
The vapor is routed to the fractionator, where it is condensed and frac-
Fractionator Gas and naphtha tionated into product streams—typically fuel gas, LPG, naphtha, dis-
to gas plant tillate and gas oil.
When one of the pair of coke drums is full of coke, the heater out-
let stream is directed to the other coke drum. The full drum is taken
Distillate offline, cooled with steam and water and opened. The coke is removed
Coke
drums by hydraulic cutting. The empty drum is then closed, warmed-up
Gas oil and made ready to receive feed while the other drum becomes full.
Benefits of Conoco-Bechtel’s delayed coking technology are:
Green coke Feed • Maximum liquid-product yields and minimum coke yield
through low-pressure operation, patented distillate recycle technol-
ogy and zero (patented) or minimum natural recycle operation
Furnace • Maximum flexibility; distillate recycle operation can be used
to adjust the liquid-product slate or can be withdrawn to maximize
unit capacity
• Extended furnace runlengths between decokings
• Ultra-low-cycle-time operation maximizes capacity and asset
utilization
• Higher reliability and maintainability enables higher onstream
Delayed coking time and lowers maintenance costs
• Lower investment cost.
Application: Upgrading of petroleum residues (vacuum residue, bitu-
Economics: For a delayed coker processing 35,000 bpsd of heavy,
men, solvent-deasphalter pitch and fuel oil) to more valuable liquid
high-sulfur vacuum residue, the U.S. Gulf Coast investment cost is
products (LPG, naphtha, distillate and gas oil). Fuel gas and
approximately U.S.$145–160 million.
petroleum coke are also produced.
Installation: Low investment cost and attractive yield structure has
Description: The delayed coking process is a thermal process and
made delayed coking the technology of choice for bottom-of-the-bar-
consists of fired heater(s), coke drums and main fractionator. The
rel upgrading. Numerous delayed coking units are operating in
cracking and coking reactions are initiated in the fired heater under
petroleum refineries worldwide.
controlled time-temperature-pressure conditions. The reactions con-
tinue as the process stream moves to the coke drums. Being highly Licensor: Bechtel Corp., and Conoco Inc.
endothermic, the coking-reaction rate drops dramatically as coke-
washing units to eliminate the sulfur. That method inevitably results
in olefin saturation, octane downgrade and yield loss.
GT-DeSulf has these advantages:
Desufurized/ • Eliminates FCC-gasoline sulfur species to meet a pool gaso-
de-aromatised line target of 20 ppm
olefin-rich gasoline • Preserves more than 90% of the olefins from being hydrotreated
FCC in the HDS unit; and thus, prevents significant octane loss and
gasoline Extractive reduces hydrogen consumption
feed 1 distillation Solvent • Fewer components (only those boiling higher than 210°C and the
column recovery Hydrogenation aromatic concentrate from ED unit) are sent to the HDS unit; conse-
START
column quently, a smaller HDS unit is needed and there is less yield loss
2
Steam • No mercaptan extraction unit is required to treat non-thio-
phene type of sulfurs
Desulfurized • Purified benzene and other aromatics can be produced from
aromatic the aromatic-rich extract stream after hydrotreating
extract • Olefin-rich raffinate stream (from the ED unit) can be recy-
Lean solvent cled to the FCC unit to increase the light olefin production.
FCC gasoline is fed to the extractive distillation column (EDC). In
a vapor-liquid operation, the solvent extracts the sulfur compounds
into the bottoms of the column along with the aromatic components,
Desulfurization while rejecting the olefins and nonaromatics into the overhead as
raffinate. Nearly all of the nonaromatics, including olefins, are effec-
Application: GT-DeSulf addresses overall plant profitability by tively separated into the raffinate stream. The raffinate stream can
desulfurizing the FCC stream with no octane loss and decreased be optionally caustic washed before routing to the gasoline pool, or to
hydrogen consumption by using a proprietary solvent in an extrac- a C 3= producing unit.
tive distillation system. This process also recovers valuable aro- Rich solvent, containing aromatics and sulfur compounds, is
matics compounds. routed to the solvent recovery column, (SRC), where the hydrocarbons
and sulfur species are separated, and lean solvent is recovered in
Description: FCC gasoline, with endpoint up to 210°C, is fed to the columns bottoms. The SRC overhead is hydrotreated by conventional
GT-DeSulf unit, which extracts sulfur and aromatics from the hydro- means and used as desulfurized gasoline, or processed through an
carbon stream. The sulfur and aromatic components are processed aromatics recovery unit. Lean solvent from the SRC bottoms are
in a conventional hydrotreater to convert the sulfur into H2S. Because treated and recycled back to the EDC.
the portion of gasoline being hydrotreated is reduced in volume and
free of olefins, hydrogen consumption and operating costs are greatly Economics: Production cost of $0.50/bbl of feed for desulfurization
reduced. In contrast, conventional desulfurization schemes process and dearomatization.
the majority of the gasoline through hydrotreating and caustic- Licensor: GTC Technology Corp.
controlled manner in scraped surface exchangers (1) and refriger-
ated chillers (2) to form a wax /oil/ solvent slurry. The dewaxed oil prod-
3 4 5 uct is filtered through the primary filter stage (3) and routed to the
dewaxed oil recovery section (6) for separation of solvent from oil. Waxy
Refrigerant stream from the primary stage is filtered again in the repulp filter (4)
to reduce the oil content to approximately 10%. The low-oil content slack
wax is then warmed to melt the low-melting-points waxes (soft wax)
Refrigerant 2 and is filtered in a third stage (5) to separate the hard wax from the
7 8
soft wax. The hard and soft wax products are each routed to solvent
Hard wax recovery sections (7, 8) to strip solvent out of the product streams
(dewaxed oil, hard wax, and soft wax). The recovered solvent is collected,
dried and recycled back to the chilling section.
1 Solvent
6 recovery Water Economics:
Waxy Steam Investment (basis: 7,000 bpsd feedrate
feed Steam or water
capacity, 2000 U.S. Gulf Coast), $ per bpsd 10,500
Soft wax Refrigerant
Dewaxed oil Process steam Utilities, typical per bbl feed:
Fuel, 103 Btu 280
Dewaxing Electricity, kWh
Steam, lb
46
60
Application: To remove waxy components from lubrication base oils Water, cooling (25°F rise), gal 1,500
streams to simultaneously meet desired low-temperature properties Solvent makeup, lb 0.6
for dewaxed oils and produce hard wax as a salable byproduct. Installation: Six in service. One new unit is scheduled for startup
Description: Waxy feedstock (raffinate, distillate or deasphalted oil) in early 2001.
is mixed with a binary solvent system and chilled down in a very closely Licensor : Bechtel Corp.
duce highly intimate contact between the oil and washwater phases.
The electrical desalting process consists of adding process (wash)
Hydrocarbon Electrical Desalted product water to the feedstock, generating an emulsion to assure maximum
feedstock power unit contact and then utilizing a highly efficient AC electrical field to
START
resolve the emulsion. The impurity-laden water phase can then be
easily withdrawn as underflow.
Depending on the characteristics of the hydrocarbon feedstock
Demulsifier Internal being processed, optimum desalting temperatures will be in the
LC
chemical electrodes range of 150°F to 300°F. For unrefined crude feedstocks, the desalter
is located in the crude unit preheat train such that the desired tem-
perature is achieved by heat exchange with the crude unit products
or pumparound reflux. Washwater, usually 3 to 6 vol%, is added
Mixing Effluent upstream and/or downstream of the heat exchanger(s). The combined
Alternate device water streams pass through a mixing device thereby creating a stable
water-in-oil emulsion. Properties of the emulsion are controlled by
Process water adjusting the pressure drop across the mixing device.
The emulsion enters the desalter vessel where it is subjected to a
high voltage electrostatic field. The electrostatic field causes the dis-
persed water droplets to coalesce, agglomerate and settle to the
lower portion of the vessel. The water phase, containing the various
impurities removed from the hydrocarbon feedstock, is continuously
Electrical desalting discharged to the effluent system. A portion of the water stream may
Application: For removal of undesirable impurities such as salt, be recycled back to the desalter to assist in water conservation
water, suspended solids and metallic contaminants from unrefined efforts. Clean, desalted hydrocarbon product flows from the top of the
crude oil, residuums and FCC feedstocks. desalter vessel to subsequent processing facilities.
Desalting and dehydration efficiency of the oil phase is enhanced
Description: Salts such as sodium, calcium and magnesium chlo- by using EDGE (Enhanced Deep-Grid Electrode) technology which
rides are generally contained in the residual water suspended in the creates both high and low intensity AC electrical fields inside the ves-
oil phase of hydrocarbon feedstocks. All feedstocks also contain, as sel. Demulsifying chemicals may be used in small quantities to
mechanical suspensions, such impurities as silt, iron oxides, sand and assist in oil/water separation and to assure low oil contents in the
crystalline salt. These undesirable components can be removed from effluent water.
hydrocarbon feedstocks by dissolving them in washwater or causing Licensor: Howe-Baker Engineers, Inc.
them to be water-wetted. Emulsion formation is the best way to pro-
mal tubular reactor is used, when optimum, to allow maximum
Methanol C4 raffinate temperature control. The equilibrium-converted reactor effluent
Recycle methanol flows to the CD column (2) where the reaction continues. Concurrently,
START
MTBE is separated from unreacted C 4s as the bottom product.
This scheme can provide overall isobutylene conversions up to
Mixed C4s 99.99%. Heat input to the column is reduced due to the heat pro-
START duced in the boiling-point reactor and reaction zone. Over time, the
3 boiling-reactor catalyst loses activity. As the boiling-point reactor
conversion decreases, the CD reaction column recovers lost conver-
4 sion, so that high overall conversion is sustained. CD column overhead
1 is washed in an extraction column (3) with a countercurrent water
stream to extract methanol. The water extract stream is sent to a
methanol recovery column (4) to recycle both methanol and water.
2 C4s ex-FCCU require a well-designed feed waterwash to remove
Water
catalyst poisons for economic catalyst life and MTBE production.
MTBE Conversion: The information below is for 98% isobutylene conversion, typ-
ical for refinery feedstocks. Conversion is slightly less for ETBE than for
MTBE. For TAME and TAEE, isoamylene conversions of 95%+ are achiev-
able. For heavier ethers, conversion to equilibrium limits are achieved.
Ethers Economics: Based on a 1,500-bpsd MTBE unit, (6,460-bpsd C4s ex-

FCCU, 19% vol. isobutylene, 520-bpsd MeOH feeds) located on the
Application: To produce high-octane, low-vapor-pressure oxygenates U.S. Gulf Coast, the inside battery limits investment is:
such as methyl tertiary butyl ether (MTBE), tertiary amyl methyl Investment, $ per bpsd of MTBE product 3,500
ether (TAME) or heavier tertiary ethers for gasoline blending to Typical utility requirements, per bbl of product
reduce olefin content and/or meet oxygen/octane/vapor pressure Electricity, kWh 0.5
specifications. The processes use boiling-point/tubular reactor and Steam, 150-psig, lb 210
catalytic distillation (CD) technologies to react methanol (MeOH) or Steam, 50-psig, lb 35
ethanol with tertiary iso-olefins to produce respective ethers. Water, cooling (30° F rise), gal 1,050
Description: For an MTBE unit, the process can be described as fol- Installation: Over 60 units are in operation using catalytic distil-
lows. Process description is similar for production of heavier ethers. lation to produce MTBE, TAME and ETBE. More than 100 ether proj-
The C4s and methanol are fed to the boiling-point reactor (1)—a fixed- ects have been awarded to CDTECH since the first unit came
bed, downflow adiabatic reactor. In the reactor, the liquid is heated onstream in 1981. Snamprogetti has over 20 operating ether units
to its boiling point by the heat of reaction, and limited vaporization using tubular reactors.
occurs. System pressure is controlled to set the boiling point of the Licensor: CDTECH (CDTECH and Snamprogetti are cooperating
reactor contents and hence, the maximum temperatures. An isother- to further develop and license their ether technologies.)
a patented, direct-coupled cyclone system (3). Product vapors are routed
directly to fractionation, thereby eliminating nonselective, post-riser
Vapor to fractionator cracking and maintaining the optimum product yield slate. Spent cata-
lyst containing only minute quantities of hydrocarbon is discharged from
the diplegs of the direct-coupled cyclones into the cyclone containment ves-
3 2 sel (4). Trace hydrocarbons entrained with spent catalyst are removed in
4 Flue gas the stripper (5) using stripping steam. The net stripper vapors are routed
to the fractionator via specially designed vents in the direct-coupled
cyclones. Catalyst from the stripper flows through the slide valve (6) to
9 the spent catalyst distributor (7) which disperses catalyst evenly across
5 6
the regenerator (8). Catalyst is regenerated by efficient contacting with
air to affect complete combustion of coke. For resid-containing feeds, the
optional catalyst cooler is integrated with the regenerator. The resulting
10 flue gas exits via cyclones (9) to energy recovery/flue gas treating. The hot
Feed 8
7 regenerated catalyst is withdrawn via an external withdrawal well (10).
START The well allows independent optimization of catalyst density in the
1 11 regenerated catalyst slide valve (11) pressure drop and ensures stable cat-
alyst flow back to the riser feed injector zone.
Economics:
Investment, (basis: 30,000 bpsd including reaction/regeneration sys-
Fluid catalytic cracking tem and product recovery. Excluding offsites, power recovery and
flue gas scrubbing. U.S. Gulf Coast 1998)
Application: Selective conversion of a wide range of gas oils into high- $ per bpsd (typical) 2,100–2,800
value products. Typical feedstocks are virgin or hydrotreated gas Utilities, typical per bbl fresh feed:
oils but may also include lube oil extract, coker gas oil and resid. Electricity, kWh 0.8–1.0
Steam, 600 psig (produced) 50–200
Products: High-octane gasoline, light olefins and distillate. Flexi-
Maintenance, % of investment per year 2–3
bility of mode of operation allows for maximizing the most desirable
product. The new Selective Component Cracking (SCC) technology Installation: 13 installations to date and two currently in design as
maximizes propylene production. well as numerous revamps. Twelve applications of the patented
direct-coupled cyclones are in operation, construction or design.
Description: The Lummus process incorporates an advanced reaction
system, high-efficiency catalyst stripper and a mechanically robust, sin- References: Chan, T. Y., and K. M. Sundaram, “Advanced FCCU
gle-stage fast fluidized bed regenerator. Oil is injected into the base of the Technology for Maximum Propylene Production.” AIChE Spring
riser via proprietary Micro-Jet feed injection nozzles (1). Catalyst and oil Meeting, 2nd International Conference in Refinery Processing, Hous-
vapor flow upwards through a short contact time, all-vertical riser (2) ton, March 14–18, 1999.
where the raw oil feedstock is cracked under optimum conditions. Reac-
tion products exiting the riser are separated from the spent catalyst in Licensor: ABB Lummus Global Inc.
gas, through the only expansion joint (2) to the base of the external
vertical riser reactor (3). Feed enters through the proprietary
5 Vapor to fractionator ATOMAX feed injection system. Reaction vapors pass through a
4 patented right-angle turn (4) and a patented closed-cyclone system
(5). Spent catalyst flows through a two-stage stripper (6) to regen-
8 eration (7) where advanced catalyst distribution and air distribution
6 are used. Either partial or complete CO combustion may be used in
3 Flue gas the regenerator, depending on the coke-forming tendency of the
feedstock. The system uses a patented external flue gas plenum
(8), all-vertical solids flow and improved plug valves (9, 10). An
7 advanced dense-phase catalyst cooler (11) is used to optimize prof-
Feed itability when heavier feeds are processed.
11
START
Economics:
2 Investment (basis: 50,000 bpsd fresh feed including converter, frac-
1 10 tionator, vapor recovery and amine treating but not power recov-
9 ery; battery limit, direct material and labor, 1994 U.S. Gulf Coast),
$ per bpsd 1,950–2,150
Utilities, typical per bbl fresh feed
Electricity, kWh 0.7–1.0
Fluid catalytic cracking Steam, 600 psig (produced) lb
Catalyst, makeup, lb
40–200
0.10–0.15
Application: Conversion of gas oils and residues to high-value Maintenance, % of plant replacement cost per yr 3
products using the efficient and flexible Orthoflow Catalytic Crack- Installation: More than 120 resulting in a total of over two and a
ing process. half million bpd fresh feed, with 18 designed in the past 10 years.
Products: Light olefins, high-octane gasoline and distillate. Reference: Oil and Gas Journal, Vol. 88, No. 13, March 26, 1990,
Description: The converter is modularized to efficiently combine Kel- pp. 56–62.
logg’s proven Orthoflow features with Mobil’s advanced design fea- Licensor: Kellogg Brown & Root, Inc.
tures. Regenerated catalyst flows through a lateral (1), fluidized by
vides rapid catalyst/hydrocarbon separation to maximise desired
Shell 2 vessel design Shell external reactor design product yields and a staged stripper achieves low hydrogen in coke
To fractionator External To fractionator without excessive gas or coke formation. A single stage partial burn
cyclones regenerator delivers excellent performance at low cost (full burn can
also be applied). Cat coolers can be added for feedstock flexibil-
Integral Close Pre- ity.Flue gas cleanup is by Shell’s third stage separator and power
TSS coupled stripping recovery can be incorporated if justified.
cyclones reactor There are currently two FCC design configurations. The Shell 2
Advanced Staged cyclone Vessel design is recommended for feeds (including residue) with
spent cat stripping Staged mild coking tendencies, the incorporation of reactor and regenera-
inlet device stripping tor elements within the vessels leads to low capital expenditure. The
Riser Shell External Reactor design is the preferred option for heavy feeds
Counter internals Riser
current Counter with high coking tendencies, delivering improved robustness.The pre-
internals stripping cyclone reduces post riser coke make and the external
regen. current
High regen High preformance reactor design eliminates stagnant areas for coke growth. Cost effec-
preformance nozzles tiveness is achieved through a simple, low-elevation design. The
Coldwall nozzles Coldwall designs have proven to be reliable due to incorporation of Shell’s exten-
construction construction sive operating experience.
Shell can also provide advanced distillation designs, advanced process
control and optimisers as part of an integrated FCC design solution.
Fluid catalytic cracking Installation: Shell has designed and licensed over 30 grassroots units,
Application: The Shell FCC process converts heavy petroleum dis- including seven for residue feed. Shell has revamped over 25 units,
tillates and residues to high-value products. Profitability is increased including the designs of other licensors. Shell has converted eight
by a reliable and robust process, which has flexibility to process heavy existing distillate units to residue operation. A Shell close-coupled
feeds and maximize product upgrading. riser termination system has been designed for 14 units and Shell’s
high performance feed nozzles for nine units. Shell has over 1,000+
Products: Light olefins, LPG, high octane gasoline and distillate. years of own FCC operational experience.
Description: Hydrocarbon is fed to a short contact-time-riser by Reference: “Update on Shell Residue FCC Process and Opera-
Shell’s high performance feed nozzle system, ensuring good mixing tion,” AIChE 1998 Spring Meeting.“Design and Operation of Shell’s
and rapid vaporisation. Proprietary riser internals lower pressure Residue Catalytic Crackers in East Asia,” ARTC 1998 Conference.
drop and reduce back mixing. The riser termination design pro-
Licensor: Shell Global Solutions International B.V.
flows through a rapid preliminary stripping section, followed by a
high-efficiency baffled stripper prior to regeneration.
Vapor products only are quenched using Amoco’s proprietary tech-
Reactor nology to give the lowest possible dry gas and maximum gasoline yield.
Proprietary riser
The hydrocarbons are further cleaned by cyclones before they are
termination device
transferred to fractionation. Catalyst regeneration is carried out in
a single regenerator (3) equipped with proprietary air rings and
Stripper catalyst distribution system, and may be operated for either full or
Regenerator partial CO combustion. Maximum production of more desirable
products can be achieved with the proprietary Mixed Temperature
Control (MTC) system (4). Heat removal for heavier feedstocks may
Reactor riser be accomplished by the use of a reliable dense-phase catalyst cooler
which has been commercially proven in over 24 units and is licensed
exclusively by Stone & Webster/IFP. As an alternative to catalyst cool-
ing, this unit can easily be retrofitted to a two-regenerator system
Regen. cat. Feed nozzles
in the event that a future resid operation is desired.
standpipe The converter vessels use a cold-wall design that results in min-
imum capital investment and maximum mechanical reliability and
safety. Cracking operation makes use of advanced fluidization tech-
nology combined with a proprietary reaction system. Unit design is
Fluid catalytic cracking tailored to the refiner’s needs and can include wide turndown flex-
ibility. Available options include power recovery in addition to waste-
Application: Selective conversion of gas oil feedstocks. heat recovery.
Products: High-octane gasoline, distillate and C3–C4 olefins. Installation: Stone & Webster has licensed 26 full-technology units
and performed more than 100 revamp projects.
Description: Catalytic and selective cracking in a short-contact-time
riser (1) where oil feed is effectively dispersed and vaporized through Reference: Letzsch, W. S., “1999 FCC Technology Advances,” 1999
a proprietary feed injection system. Operation is carried out at a tem- Stone & Webster Eleventh Annual Refining Seminar at NPRA Q&A,
perature consistent with targeted yields. Reaction products exit the Dallas, Oct. 5, 1999.
riser-reactor through a high-efficiency, proprietary riser termination
Licensor: Stone & Webster Inc., a Shaw Group Co./Institut Français
device (2). Spent catalyst that has not been cooled is pre-stripped and
du Pétrole.
effectively contacting catalyst with finely atomized oil droplets. The lift
FCC To fractionation RFCC To fractionation gas conditions the catalyst and passivates active metal sites.
The reactor zone features a short-contact-time riser and a state-
Combustor-style Two-stage
of-the-art riser termination device (4) for quick separation of cata-
regenerator regenerator
Flue gas 4 lyst and vapor, with high hydrocarbon containment (VSS/VDS tech-
4 Flue gas nology). This design offers high gasoline yields and selectivity with
12
Combuster low dry gas yields. Steam is used in an annular stripper (5) to dis-
riser Primary place and remove entrained hydrocarbons from the catalyst. Exist-
1st stage 5
5 air ing units can be revamped to include these features (1–5).
7 9 The combustor-style regenerator (6) burns coke, in a fast-fluidized
Hot-catalyst 11 environment, completely to CO2 with very low levels of CO. The cir-
circulation 2nd culation of hot catalyst (7) from the upper section to the combustor
6
10 Catalyst 3
3 stage cooler provides added control over the burn-zone temperature and kinet-
Feed Feed ics and enhances radial mixing. Catalyst coolers (8) can be added to
8 Catalyst 2
2 transfer line new and existing units to reduce catalyst temperature and increase
Catalyst 1
cooler 1 Secondary
unit flexibility for commercial operations of feeds up to 6 wt% Con-
Air Lift media air Lift media radson carbon.
For heavier resid feeds, the two-stage regenerator is used. In the
first stage, upper zone (9), the bulk of the carbon is burned from the
catalyst, forming a mixture of CO and CO 2. Catalyst is transferred
Fluid catalytic cracking to the second stage, lower zone (10), where the remaining coke is
burned in complete combustion, producing low levels of carbon on
Application: Selectively convert gas oils and resid feedstocks into regenerated catalyst. A catalyst cooler (11) is located between the
higher-value products using the FCC/RFCC/PETROFCC process. stages. This configuration maximizes oxygen use, requires only one
Products: Light olefins (for alkylation, polymerization, etherifica- train of cyclones and one flue gas stream (12), avoids costly multi-
tion or petrochemicals), LPG, high-octane gasoline, distillates and ple flue gas systems and creates a hydraulically-simple and well-cir-
fuel oils. culating layout. The two-stage regenerator system has processed feeds
up to 10 wt% Conradson carbon.
Description: The combustor-style unit is used to process gas oils and PETROFCC is a customized application using mechanical fea-
moderately contaminated resids, while the two-stage unit is used for tures such as RxCAT technology for recontacting carbonized catalyst,
more contaminated resids. high-severity processing conditions and selected catalyst and addi-
In either unit style, the reactor section is similar. A lift media of light tives to produe high yields of propylene, light olefins and aromatics
hydrocarbons, steam or a mixture of both contacts regenerated cata- for petrochemical applications.
lyst at the base of the riser (1). This patented acceleration zone (2), with
Licensor: UOP LLC.
elevated Optimix feed nozzles (3), enhances the yield structure by
meet (avoiding unjustified investment) future sulfur, specific grav-
Offgas ity, cetane and heavy polyaromatics (HPA) specifications when they
4 arrive (ultimately < 5 ppm sulfur and < 1–2% PAH) via stepwise
2 additions. These additions include items such as an additional reac-
tor, different catalysts, changing operating conditions and using
3
two stages as shown in Cases 1– 4 below. For ultra-low sulfur targets
8 proprietary design reactor internals and quench systems are installed.
5 9 Low-sulfur
product Examples of various Prime-D processing options
Drier
1 Case 1: Case 2: Case 3: Case 4:
H 2S Low sulfur Ultra-low sulfur. Improved Full aromatics
Feed year 2000 HDS with cetane hydrogenation
START H2 recycle HDS unit implemented single-stage two-state
Amine ultra- HDS–HDA .HDS–HDA
H2 unit deep HDS
7 6 provisions
Sulfur, ppm 350 < 10 < 10 <5
Specific
gravity < 0.845 < 0.840 < 0.834 < 0.825
Gas oil hydrotreatment PAH content,
wt% 11 < 2 –3 <2 < 1 –2
Application: Produce high-quality diesel fuel via Prime-D technol- Cetane
ogy for deep hydrodesulfurization, ultra-deep hydrodesulfurization, number 51 55 58 58
aromatics reduction and cetane improvement. Pressure P 1.7 x P 2.5 x P 1.7 x P
LHSV, h-1 Base 0.4 x Base 0.25 x Base 0.4 x Base +
Description: In the basic process shown above, feed and hydrogen noble metal
are heated in the feed-furnace effluent exchanger (1) and furnace (2), ISBL
and enter the reactor (3), where sulfur content is reduced using a rel- investment Base 1.65 x Base 2.1 x Base 2.7 x Base
atively inexpensive catalyst. The reactor effluent is cooled by
exchanger (1) and air cooler (4), and separated in the tri-phase sep- Installation: Over 100 middle distillate hydrotreaters have been
arator (5). The hydrogen-rich gas phase is recycled to the amine unit licensed or revamped. They include low-and ultra-low-sulfur (<
for H2S removal and recompression (7), and recycle to the feed- 50ppm), as well as cetane improvement units.
effluent exchanger. The liquid phase is sent to the stripper (8), Reference: “Distillate hydrotreating routes: from deep HDS to cetane
where gas and naphtha are removed. The stripper bottoms flow to number improvement,” IFP Refining Seminar, November 1999.
the drier (9) and then to blending and storage.
Through provisions in the basic design, the refiner will be able to Licensor: IFP.
Products: FLEXSORB produces a clean gas containing as little as
Condenser 10 vppm H2S and an enriched acid gas for treatment in a sulfur recov-
H2S -free treated gas H2S -rich ery process.
Reflux acid gas to
Lean Description: The feed (acid gas) is countercurrently contacted with
drum sulfur
solution recovery lean solvent where H2S is selectively absorbed. The rich solvent is
Rich then regenerated in a reboiled regenerator.
Absorber solution
Economics: FLEXSORB offers 10% to 40% circulation rate and
Sour Regenerator energy requirement savings relative to competing conventional tech-
feed gas Cooler nology. Thus, smaller equipment can be used, and lower space
Reboiler requirements are needed. The process is particularly applicable in
START
Heat Steam retrofit, revamp or expansion scenarios and/or situations where
exchanger space is at a premium. It is not unusual to be able to use FLEXSORB
for a low cost 25% debottleneck of existing facilities. FLEXSORB can
be used for Claus sulfur plant tail-gas cleanup, for natural gas treat-
ing/sweetening and for acid-gas enrichment.
Installation: More than 40 applications of FLEXSORB are in oper-
ation, with several startups within the last year.
References: Chudlinski, G. R., et al., “Commercial Experience
Gas treating—H2S removal with FLEXSORB Absorbent,” AIChE National Meeting, New Orleans,
Application: The FLEXSORB process selectively removes H2S in the April 8, 1986.
presence of CO2 in petroleum refining, natural gas processing, petro- van Son, K. J., et al., “Asgard B process selection for hydrogen
chemicals operations and power generation. This technology uses a sulfide removal and disposal,” Gas Processors Association 78th
proprietary sterically hindered amine solvent in conventional gas- Annual Convention, Nashville, March 1-3, 1999.
treating equipment. Licensor: ExxonMobil Research & Engineering Co.
pure O2 and steam. The net reaction is exothermic and produces a gas
Oil primarily containing CO and H2. Depending on the final syngas appli-
Scrubber cation, operating pressures, ranging from atmospheric up to 65 bar, can
Process Syngas easily be accommodated. SGP uses refractory-lined reactors that are
steam Steam
fitted with both burners and a heat-recovery-steam generator, designed
to produce high-pressure steam—over 100 bar (about 2.5 tons per ton
Oxygen
Boiler BFW feedstock). Gases leaving the steam generator are at a temperature
Bleed to SWS approaching the steam temperature; thus further heat recovery occurrs
in an economizer.
Soot (unconverted carbon) and ash are removed from the raw gas
Ni/V by a two-stage waterwash. After the final scrubbing, the gas is vir-
Reactor Filtercake ash tually particulate-free; it is then routed to a selective-acid-gas-
Effluent removal system. Net water from the scrubber section is routed to the
boiler work up
soot ash removal unit ( SARU ) to filter out soot and ash from the
Filtration slurry. By controlled oxidation of the filtercake, the ash components
Soot
quench are recovered as valuable oxides— principally vanadium pentoxide.
The (clean) filtrate is returned to the scrubber.
A related process—the Shell Coal Gasification Process (SCGP)—
gasifies solids such as coal or petroleum coke. The reactor is differ-
ent, but main process layout and work-up are similar.
Gasification Installation: Over the past 40 years, more than 150 SGP units
have been installed, that convert residue feedstock into synthesis gas
Application: The Shell Gasification Process (SGP) converts the heav- for chemical applications. The latest, flagship installation is in the
iest residual liquid hydrocarbon streams with high-sulfur and metals Shell Pernis refinery near Rotterdam, The Netherlands. This highly
content into a clean synthesis gas and valuable metal oxides. Sulfur (S) is complex refinery depends on the SGP process for its H2 supply. Sim-
removed by normal gas treating processes and sold as elemental S. The ilar projects are underway in India and Italy.
process converts residual streams with virtually zero value as fuel- The Demkolec Power plant at Buggenum, The Netherlands produces
blending components into valuable, clean gas and byproducts. This gas 250 Mwe based on the SCGP process. The Shell middle distillate syn-
can be used to generate power in gas turbines and for making H2 by the thesis plant in Bintulu, Malaysia, uses SGP to convert 100 million scfd
well-known shift and PSA technology. It is one of the few ultimate, envi- of natural gas into synthesis gas used for petrochemical applications.
ronmentally acceptable solutions for residual hydrocarbon streams.
Reference: “Shell Gasification Process,” AIChE Spring National
Products: Synthesis gas (CO+H2), sulfur and metal oxides. Meeting, paper 70b, March 5 –9, 2000. “Shell Pernis Netherlands
Process description: Liquid hydrocarbon feedstock (from very light Refinery Residue Gasification Project,” 1999 Gasification Tech-
such as natural gas to very heavy such as vacuum flashed cracked nologies Conference, San Francisco, Oct. 17–20, 1999.
residue, VFCR and ashphalt ) is fed into a reactor, and gasified with Licensor: Shell Global Solutions International B.V.
Regeneration: The sorbent (catalyst) is continuously withdrawn from
SO2 & CO2 To SRU the reactor and transferred to the regenerator section (2), where the
sulfur is removed as SO 2 and sent to a sulfur-recovery unit. The
Air Fuel gas cleansed sorbent is reconditioned and returned to the reactor. The
Sorber 1 2
rate of sorbent circulation is controlled to help maintain the desired
Regen. Nitrogen sulfur concentration in the product.
Economics:
General operating conditions:
Temperature, °F 650–775
Stabilizer
Hydrogen Charge Recycle Pressure, psig 100–300
heater compressor Space velocity, whsv 4–10
Hydrogen purity, % 70–99
Steam
Total H2 usage, scf/bbl 40–60
Case study premises:
Cat. Desulfurized
gasoline 25,000-bpd feed
product
Product 775-ppm feed sulfur
separator 25-ppm product sulfur (97% removal)
No cat gasoline splitter
Results:
Gasoline desulfurization C5+ yield, vol% of feed
Lights yield, wt% of feed
~ 100
< 0.2
(R+M) Loss
Application: Convert high-sulfur gasoline streams into a low-sul- 2
0.6 (or <0.6)
fur gasoline blendstock using S Zorb sulfur-removal technology.
Capital cost, $/bbl 900
Products: A very-low sulfur blending stock for gasoline motor fuels. Operating cost, ¢/gal* 0.9
Applications for diesel are under development. * Includes utilities, 4% per year maintenance and sorbent costs.
Description: Gasoline from the fluid catalytic cracker unit is com- Installation: First commercial operations in early 2001 at a Texas
bined with a small hydrogen stream and heated. Vaporized gasoline facility. Field license sold to a major U.S. refiner.
is injected into the expanded fluid-bed reactor (1), where the pro-
prietary sorbent removes sulfur from the feed. A disengaging zone Licensor: Fuels Technology Division of Phillips Petroleum Co.
in the reactor removes suspended sorbent from the vapor, which exits
the reactor to be cooled.
split to produce a light cat naphtha (LCN) cut and a heavy cat naph-
LCN to TAME or alky. unit tha (HCN). The LCN stream is mercaptans-free with a low sulfur and
diolefin concentration enabling further processing in an etherifica-
tion or alkylation unit. The HCN then enters the main Prime-G+ sec-
Fuel gas
Splitter tion, where it undergoes in a dual catalyst system a deep HDS with
(optional) very limited olefins saturation and no aromatics losses to produce
an ultra-low sulfur gasoline. Pool sulfur specifications as low as
Prime-G+ Stabilizer less than 10 ppm can be attained with the Prime-G+ process.
Selective dual catalyst Full-range FCC gasoline, Feed Prime-G+
hydro. reactor system Ultra-low 40°C–220°C product
Feed sulfur Sulfur, ppm 2,000 50*
gasoline RON 91 88.8
START
HCN MON 79 78.2
(RON + MON)/2 85 83.5
Hydrogen  (RON + MON)/2 1.5
makeup % HDS 97.5
*  30 ppm pool sulfur after blending.
Economics:
Investment: Grassroots ISBL cost: 600 – 800 $/bpsd
Gasoline desulfurization, Combined utilities: 0.32 $/bbl
ultra-deep Hydrogen:
Catalyst:
0.28 $/bbl
0.03 $/bbl
Application: Ultra-deep desulfurization of FCC gasoline with min- Installation: Thirteen Prime-G+ units have been licensed
imal octane penalty using Prime-G+ process.
Reference: “The Domino Interaction of Refinery Processes for
Description: FCC debutanizer bottoms are fed directly to the first Gasoline Quality Attainment,” NPRA Annual Meeting, March 26–28,
reactor, wherein under mild conditions diolefins are selectively 2000, San Antonio.
hydrogenated, and mercaptans are converted to heavier sulfur
species. The selective hydrogenation reactor effluent is then usually Licensor: IFP and IFP North America.
rather than at high pressure can result in lower capital cost and
High-pressure Low-pressure allows design at lower gas rates.
section section Makeup hydrogen Operating conditions: Typical reactor temp., 725°F to 840°F; reac-
Recycle tor press., 1,400 to 3,500 psig; H2 part. press., 1,000 to 2,700 psig;
LC-Fining Stm. H2 LHSV, 0.1 to 0.6; conversion, 40% to 97+%; desulfurization, 60% to
reactor 1 90%; demetallization, 50% to 98%; CCR reduction, 35% to 80%.
6
2 Yields: For Arabian Heavy/Arabian Light blends:
Feed Atm. resid Vac. resid
Gravity, °API 12.40 4.73 4.73 4.73
3 5 Sulfur, wt% 3.90 4.97 4.97 4.97
Ni/V, ppmw 18/65 39/142 39/142 39/142
Conversion vol%
Hydrocarbon (1,022°F+) 45 60 75 95
feed 4 Products, vol%
START C4 1.11 2.35 3.57 5.53
Products C5–350°F 6.89 12.60 18.25 23.86
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
Hydrocracking C5 +°API/wt%S 23.7/0.54 22.5/0.71 26.6/0.66 33.3/0.33
Economics: Investment,estimated (U.S. Gulf Coast, 2000)
Application: Desulfurization, demetallization, CCR reduction, and hydro- Size, bpsd fresh feed 92,000 49,000
cracking of atmospheric and vacuum resids using the LC-Fining process. $ per bpsd
(typical) fresh feed 2,200 3,500 4,200 5,200
Products: Full range of high quality distillates. Residual products Utilities, per bbl fresh feed
can be used as fuel oil, synthetic crude or feedstock for a resid FCC, 3
Fuel fired, 10 Btu 56.1 62.8 69.8 88.6
coker, visbreaker or solvent deasphalter. Electricity, kWh 8.4 13.9 16.5 22.9
Steam (export), lb 35.5 69.2 97.0 97.7
Description: Fresh hydrocarbon liquid feed is mixed with hydrogen
Water, cooling, gal 64.2 163 164 248
and reacted within an expanded catalyst bed (1) maintained in tur-
bulence by liquid upflow to achieve efficient isothermal operation. Prod- Installation: Four LC-Fining units and three using Oxy Research
uct quality is maintained constant and at a high level by intermittent & Development Co. technology. Another is under construction/design
catalyst addition and withdrawal. Reactor products flow to a high-pres- for Shell Canada. Sizes: 6,000 to 80,000 bpsd.
sure separator (2), low-pressure separator (3) and product fractiona-
tor (4). Recycle hydrogen is separated (5) and purified (6). Licensor: ABB Lummus Global Inc., Oxy Research & Develop-
Process features include on stream catalyst addition and with- ment Co. and BP Corp.
drawal. Recovering and purifying the recycled H2 at low pressure
to provide flexibility to vary the light-to-heavy product ratio and
obtain maximum catalytic efficiency. Single-stage options (both
once-through and recycle) are also used when economical.
Yields: Typical from various feeds:
H 2S Feed Naphtha LCCO VGO VGO
1 Process gas Catalyst stages 1 2 2 2
3 Gravity, °API 72.5 24.6 25.8 21.6
ASTM 10%/EP, °F 154/290 478/632 740/1,050 740/1,100
Wash Light naphtha Sulfur, wt% 0.005 0.6 1.0 2.5
water Nitrogen, ppm 0.1 500 1,000 900
Feed Heavy naphtha
5 6 Yields, vol%
2 — —
START 7 Kerosine Propane 55 3.4
iso-Butane 29 9.1 3.0 2.5
Diesel n-Butane 19 4.5 3.0 2.5
Light naphtha 23 30.0 11.9 7.0
Diesel — — — 50.0
Makeup Product quality
hydrogen Sour water Kerosine smoke pt., mm — — 28 28
Diesel Cetane index — — — 58
Kerosine freeze pt., °F — — 465 475
Diesel pour pt., °F — — — 410
Hydrocracking
Application: Convert naphthas, AGO, VGO and cracked oils from
FCCs, cokers, hydroprocessing plants and SDA plants using the
Chevron ISOCRACKING process.
Products: Lighter, high-quality, more valuable products: LPG, gaso-
line, catalytic reformer feed, jet fuel, kerosine, diesel, lube oils and
feeds for FCC or ethylene plants.
Description: A broad range of both amorphous/zeolite and zeolite
catalysts are used to obtain an exact match with the refiner’s pro-
cess objective. An extensive range of proprietary amorphous/zeolitic
catalysts and various process configurations are used to match the
refiner’s process objectives. Generally, a staged reactor system con-
sists of one reactor (1, 4) and one HP separator (2, 5) per stage
optional recycle scrubber (3), LP separator (6) and fractionator (7)
Heavy naphtha — 78.7 14.2 7.0
Kerosine — — 86.8 48.0
Economics:
Investment (basis: 30,000 bpsd maximum conversion unit,
Mid- East VGO feed, includes only on-plot facilities and first
catalyst charge, 1994 U.S. Gulf Coast), $ per bpsd
2,80
0 Utilities, typical per bbl feed:
Fuel, equiv. fuel oil, gal 1
Electricity, kWh 7
Steam, 150 psig (net produced), lb (50)
Water, cooling, gal 330
Installation: More than 50 units exceeding 750,000 bpsd total capacity.
Licensor: Chevron Research and Technology Co. Available
through Chevron Products Co. (Technology Marketing) and ABB
Lummus Global Inc.
Three different process arrangements are available: single-
Fuel gas Fuel gas step/once-through; single-step/total conversion with liquid recycle;
H2 and two-step hydrocracking. The process consists of: reaction section
makeup (1, 2), gas separator (3), stripper (4) and product fractionator (5).
Light Product quality: Typical for HVGO (50/50 Arabian light/heavy):
gas oil
Feed, Jet
5 HVGO fuel Diesel
1 2 3 4 Sp. gr. 0.932 0.800 0.826
TBP cut point, °C 405 –565 140 –225 225 –360
Diesel Sulfur, ppm 31,700 < 10 < 10
Nitrogen, ppm 853 <5 <5
Wild naphtha Metals, ppm <2 – –
Cetane index – – 62
Feed Flash pt., °C –  40 125
START
Low-sulfur fuel oil Smoke pt., mm, EOR – 26 –28 –
Aromatics, vol%, EOR – < 12 <8
Viscosity @ 38°C, cSt 110 – 5.3
PAH, wt%, EOR <2
Hydrocracking Economics:
Investment (basis: 40,000-bpsd unit, once-through, 90% con-
version, battery limits, erected, engineering fees included,
Application: Upgrade vacuum gas oil alone or blended with various 2000 Gulf Coast), $ per bpsd 2,500 –3,000
feedstocks (light-cycle oil, deasphalted oil, visbreaker or coker-gas oil). Utilities, typical per bbl feed:
Products: Middle distillates, very-low-sulfur fuel oil, extra-quality Fuel oil, kg 5.3
FCC feed or high VI lube base stocks. Electricity, kWh 3 6.9
Water, cooling, m 0.64
Description: This process uses a refining catalyst usually followed Steam, MP balance
by a zeolite-type hydrocracking catalyst. Main features of this pro- Installation: Forty references, cumulative capacity exceeding
cess are: 1,000,000 bpsd, conversion ranging from 20% to 99%.
• High tolerance toward feedstock nitrogen
• High selectivity toward middle distillates Licensor: IFP.
• High activity of the zeolite, allowing for 3–4 year cycle lengths
and products with low aromatics content until end of cycle.
redistribution internals (Spider Vortex Quench Zone Technology). Feed
and recycle gas are preheated and contact the catalyst in the down-
Feed flow fixed-bed reactor (1). Reactor effluent is flashed in high and low
wash H2S temperature separators, (2) and (3). An amine contactor tower (4)
Naphtha scrubs H2S from recycle gas. A simple stripper/fractionator arrange-
4 Fuel ment is shown for product recovery (5) and (6).
1 gas
Kerosine Operating conditions: Typical operating conditions are categorized
Naphtha according to either single-pass or extinction recycle configurations:
3 Diesel
6 Single pass Recycle
Temperature, °F 700–800 700–800
2 5 Pressure, psig 1,000–2,000 1,500–3,000
Yields: Typical operation on Middle East VGO and FCC LCO.
START
Feed Feed AL/AH VGO LCO
Gravity, °API 20.2 19.0
ASTM FBP, °F 1,050 620
Makeup Recycle oil Sulfur, wt% 2.9 1.0
hydrogen Low-sulfur HGO
Nitrogen, ppmw 900 600
Cetane index — 28
Conversion 50% 70% 98% 50%
Hydrocracking Naphtha, vol%
Kerosine, vol%
12.9
14.1
22.6
24.5
17.2
26.9
54.0
—
Diesel, vol% 31.8 32.5 63.6 54.3
Application: Convert a wide variety of feedstocks including vacuum LSGO, vol% 50.0 30 2.2 —
gas oil, coker gas oils and FCC cycle oils into high-quality, low-sul- H2 consumed, scf/bbl 1,080 1,300 1,525 1,730
fur fuels using the MAKFining HDC process. Product Quality
Naphtha, RON 64 63 66 92
Products: A wide range of high-quality, low-sulfur distillate fuels and Diesel cetane index 53 55 61 39
blending stocks including LPG, high-octane gasoline, reformer naphtha, Diesel sulfur, ppmw < 30 < 10 < 10 < 10
jet fuel, kerosine and diesel fuel. Unconverted products from single-pass
operations are excellent feedstocks for fluid catalytic cracking, lube oil Economics:
basestock production, steam cracking and low-sulfur fuel oil. Investment, $ per bpsd 2,000 –4,000
Description: MAKFining HDC technology is a product of an alliance Installation: Four operating units. One unit in design.
between ExxonMobil, Akzo Nobel, Kellogg Brown & Root and Fina
Reference: Paper AM-94-21, NPRA meeting, March 20–22, 1994.
Research S.A. The process uses a multiple catalyst system in multi-
bed reactors that incorporate proprietary advanced quench and Licensor: Kellogg Brown & Root, Inc.
Description: Heavy hydrocarbons are discharged to the reactor
Fresh gas circuit and preheated with reactor effluent (1). Fresh hydrogen is dis-
Recycle gas charged to the reactor circuit and combined with recycle gas from the
cold high-pressure separator. The mixed gas is supplied as quench
370– for reactor interbed cooling with the balance first preheated with reac-
Recycle tor effluent followed by further heating in a single phase furnace. After
Quench gas compressor
mixing with the liquid feed, the reactants pass in trickle flow through
2 CHP the multi-bed reactor(s) which contains proprietary pre-treat, crack-
separator ing and post-treat catalysts (2). Interbed ultra-flat quench internals
3 and high dispersion nozzle trays combine excellent quench, mixing
HHP Fractionator
and liquid flow distribution at the top of each catalyst bed while max-
separator imizing reactor volume utilization. After cooling by incoming feed
1
HLP streams, reactor effluent enters a four-separator system from which
separator CLP hot effluent is routed to the fractionator (3). Wash water is applied
Feed separator via the cold separators in a novel countercurrent configuration to
370+
Bleed scrub the effluent of corrosive salts and avoid equipment corrosion.
START
Two-stage, series flow and single-stage unit design configurations are
all available including the single reactor stacked catalyst bed
which is suitable for capacities up to 10,000 tpd in partial or full con-
version modes. The catalyst system is carefully tailored for the
Hydrocracking desired product slate and cycle run length.
Application: The Shell hydrocracking process converts heavy VGO Installation: Over 20 new distillate and lube oil units including two
and other low-cost cracked and extracted feedstocks to high-value, recent single-reactor high-capacity stacked bed units. Over a dozen
high-quality products. Profitability is maximized by careful choice revamps have been carried out on own and other licensor designs usu-
of process configuration, conditions and catalyst system to match ally to debottleneck and increase feed heaviness.
refiners’ product quality and selectivity requirements. References: “Performance optimisation of trickle bed processes,”
Products: Low-sulfur diesel and jet fuel with excellent combustion European Refining Technology Conference, Berlin, November 1998;
properties, high-octane light gasoline, and high-quality reformer, cat “Design and operation of Shell single reactor hydrocrackers,” 3rd
cracker or lube oil feedstocks. International Petroleum Conference, New Delhi, January 1999.
Licensor: Shell Global Solutions International B.V.
Catalysts are based upon both amorphous and molecular-sieve con-
taining supports. Process objectives determine catalyst selection for
Wash a specific unit. Product from the reactor section is condensed, sep-
water Makeup arated from hydrogen-rich gas and fractionated into desired products.
hydrogen Unconverted oil is recycled or used as lube stock, FCC feedstock or
ethylene-plant feedstock.
1
Yields: Example:
2
4 Flash gas FCC cycle Vacuum Fluid coker
Feed type oil blend gas oil gas oil
Gravity, °API 27.8 22.7 8.4
5 Boiling, 10%, °F 481 690 640
End pt., °F 674 1,015 1,100
Fresh feed To fractionator Sulfur, wt% 0.54 2.4 4.57
START
3 Sour water Nitrogen, wt% 0.024 0.08 0.269
Principal products Gasoline Jet Diesel FCC feed
Recycle oil To fractionator Diesel fuel 94.1 33.8
600°F + gas oil 35.0
H2 consump., scf/bbl 2,150 1,860 1,550 2,500
Hydrocracking
Application: Convert a wide variety of feedstocks into lower-molec-
ular-weight products using the Unicracking process.
Feed: Feedstocks include atmospheric gas oil, vacuum gas oil,
FCC/RCC cycle oil, coker gas oil, deasphalted oil and naphtha for pro-
duction of LPG.
Products: Processing objectives include production of gasoline, jet
fuel, diesel fuel, lube stocks, ethylene-plant feedstock, high-quality
FCC feedstock and LPG.
Description: Feed and hydrogen are contacted with catalysts,
which induce desulfurization, denitrogenation and hydrocracking.
Yields, vol% of feed
Butanes 16.0 6.3 3.8 5.2
Light gasoline 33.0 12.9 7.9 8.8
Heavy naphtha 75.0 11.0 9.4 31.8
Jet fuel 89.0
Economics: Example:
Investment, $ per bpsd capacity 2,000 –4,000
Utilities, typical per bbl feed:
Fuel, 103 Btu 120–150
Electricity, kWh 8 –12
Installation: Selected for 142 commercial units, including several
converted from competing technologies. Total capacity exceeds 2.9
million bpsd.
Licensors: UOP LLC.
toms distillates and straight run distillates (optional), are routed to
Straight run distillates the catalytical fixed-bed reactors of the GPH (4), which operates at
the same pressure as the LPH. GPH pressure is typically above
Vacuum residue Recycle hydrocracking conditions, therefore, GPH mild hydrocracking can also
Additive gas be applied to allow a shift in yield structure to lighter products. Sep-
Offgas aration of syncrude and associated gases is performed in a cold sep-
1 2 4 7 arator system (5). The syncrude after separation is sent to a stabi-
lizer (6) and a fractionation unit. After being washed in a lean oil
scrubber (7), the gases are recycled to the LPH section.
Feed: Feedstock quality ranges covered are:
5 3 to 14
6 Gravity, °API
Syn- Sulfur, wt% 0.7 to 7
3 crude Metals (Ni,V), ppm up to 2,180
Asphaltenes, wt% 2 to 80
Hydrogen Waste water
Yields:
Hydrogenation residue
Naphtha < 180°C, wt% 15–30
Middle distillates, wt% 35–40
Vac. gasoil > 350°C, wt% 15–30
Hydrocracking Product qualities:

Naphtha: Sulfur <5 ppm, Nitrogen <5 ppm
Application: Upgrading of heavy and extra heavy crudes as well as Kerosine: Smoke point >20 mm, Cloud point <50°C
residual oils. Diesel: Sulfur <50 ppm, Cetane no >45
Vac. gasoil: Sulfur <150 ppm, CCR <0.1wt%, Metals <1 ppm
Products: Full-range high quality syncrude.
Economics: Plant capacity 23,000 bpsd.
Description: A hydrogen addition process applying the principles Investment U.S. MM$190 (US Gulf Coast, 1st Q. 1994)
of thermal hydrocracking in liquid-phase hydrogenation reactors Utilities:
(LPH) (1) for primary conversion directly coupled with an integrated Fuel oil, MW 12
catalytical hydrofinishing step (GPH). In the LPH slurry phase Power, MW 17
reactors, residue is converted up to 95% at temperatures between Steam, tph -34
440°C and 500°C. In the hot separator (HS) (2), light distillates are Water, cooling, m3/h 2,000
separated from the unconverted material. By vacuum-flash distil-
lation (3) the HS bottoms distillates are recovered. For further Installation: Two licenses have been granted.
hydrotreating, the HS overheads, together with the recovered HS bot-
Licensor: VEBA OEL Technologie und Automatisierung GmbH.
uum bottoms for recycle.
Purge to Operating conditions: Temperature, 770°F– 840°F; hydrogen par-
Catalyst H2 recovery tial pressure, psi 1,000–2,500; LHSV, 0.1–1.0 hr –1; conversion
30%–90%.
H2
makeup Process performance and yields: From commercial two-stage
2 processing:
Vacuum residue conversion 52 W% 70 W%
Fuel gas Processing objective LSFO Conversion
1 1 Naphtha Feed Ural VR Arab H VR+FCC slurry
3 Middle distillate Gravity, ºAPI 13 3.6
to diesel pool 1,000ºF+, vol% 85 85
START VGO to FCC Sulfur, wt% 2.8 5.2
Performance, yields and product qualities
Catalyst Vacuum bottoms to
Vacuum residue withdrawal
Chem. H2 Cons, scf/bbl 920 1,540
feedstock fuel oil, coker, etc. Naphtha, vol% 7 8
Diesel, vol% 25 33
VGO, vol% 31 38
Residue, vol% 41 25
Diesel sulfur, wppm 400 2,000
Hydrocracking, residue VGO sulfur, wt% 0.18 0.9
Residue sulfur, wt% 0.8 2.0
Application: Catalytic hydrocracking and desulfurization of residua Residue gravity, ºAPI 14 4.0
and heavy oils in an ebullated-bed reactor using the H-Oil process.
Products: Full-range distillates and upgraded residue, trans-
portation fuels, FCC or coker feed, low-sulfur-fuel oil.
Description: A one, two or three stage ebullated-bed (1) reactor sys-
tem. Feed consists of atmospheric or vacuum residue, recycle from
downstream fractionation (3), hydrogen-rich recycle gas and makeup
hydrogen. Combined feed is fed to the bottom of the reactor and
expands the catalyst bed resulting in good mixing, near isothermal
operation and allows for onstream catalyst replacement to maintain
catalyst activity and 3 to 4 year run lengths between turnarounds.
Two-phase reactor effluent is sent to high-pressure separator (2); liq-
uid is sent to fractionation (3) to recover light liquid products and vac-
HDS, wt% 85 83
HDN, wt% 40 38
Economics: Basis 2000 U.S. Gulf Coast Investment—
$ per bpsd 3,000 –
5,000 Utilities—per bbl of feed
Fuel, 103 Btu 40 –100
Power, kWh 9 –15
Water, cooling (20°F rise), gal 100 –200
Catalyst makeup, $ 0.2 –1.5
Installation: Seven units currently in operation.
Licensor: IFP, IFP North America.
shutdown. This ensures the maintenance of constant, optimal cat-
Recycle hydrogen Recycle hydrogen alyst activity and consistent product slate and quality. After high-
Amine pressure recovery of the effluent and recycle gas, the products are
compressor absorber
Fixed-bed separated and stabilized through fractionation. A T-Star unit can oper-
Makeup hydrogen HDS ate for four-year run lengths with conversion in the 20%–60% range
Fuel gas and hydrodesulfurization in the 93%–99% range.
VGO feed T-star
reactor High Naphtha S= Operating conditions:
START
pressure <2 wppm Temperature, °F 750 –820
separator Hydrogen partial pressure, psi 600 –1,500
Stabilizer
LHSV, hr –1 0.5 –3.0
Diesel S=
Oil feed VGO conversion, % 20 –60
<50 wppm
heater Gas-oil Examples: In Case 1, a deep-cut Arab heavy VGO is processed at
stripper FCC feed S= 40 wt% conversion with objectives of mild conversion and preparing
1,000-1,500 wppm specification diesel and FCC unit feed. In Case 2, a VGO blend con-
Hydrogen Ebullating
pump taining 20% coker material is processed at lower conversion to also
heater obtain specification FCC unit feedstock and high-quality diesel.
Economics: Basis 2000 U.S. Gulf Coast
Hydrocracking/ Investment in $ per bpsd

Utilities—per bbl of feed
1,200 –2,500
Fuel, 103 Btu

hydrotreating—VGO Power, kWh
60
3
Catalyst makeup, $ 0.05 –0.20
Application: The T-Star Process is an ebullated-bed process for the
hydrotreatment/hydrocracking of vacuum gas oils. The T-Star Pro- Installation: The T-Star process is commercially demonstrated
cess is best suited for difficult feedstocks (coker VGO, DAO), high- based on the ebullated-bed reactor. IFP has licensed more than 1.3
severity operations and applications requiring a long run length. MMbpsd of capacity in gas oil, VGO and residue. IFP has seven com-
mercially operating ebullated-bed units and one is under construc-
Description: A T-Star process flow diagram, which includes inte-
tion that will process a variety of VGO feedstocks.
grated mid-distillate hydrotreating, is shown above. The typical T-
Star battery limits include oil/hydrogen fired heaters, an advanced Reference: “A Novel Approach to Attain New Fuel Specifications,”
hot high-pressure design for product separation and for providing recy- Petroleum Technology Quarterly, Winter 1999/2000.
cle to the ebullating pump, recycle gas scrubbing and product sep-
aration. Catalyst is replaced periodically from the reactor, without Licensor: IFP, IFP North America.
is sent to the final hydrotreating reactor, or the “second stage.” In this reac-
Makeup hydrogen Recycle gas Amine tor, distillate feed undergoes saturation of aromatics using a Topsøe noble
compressor scrubber metal catalyst, either TK-907/ TK-908 or TK-915, a newly developed high-
HDS activity dearomatization catalyst. Finally, the desulfurized, dearomatized
Diesel
stripper Wash distillate product is steam stripped in the product stripping column to remove
HDS separator
feed Overhead
water vapor H2S, dissolved gases and a small amount of naphtha formed.
First HDS Like the conventional Topsøe hydrotreating process, the HDS/HDA pro-
HDS cess uses Topsøe’s graded bed loading and high-efficiency patented reactor
stage reactor stripper internals to provide optimum reactor performance and catalyst use lead-
Sour
water Water ing to the longest possible catalyst cycle lengths. Topsøe’s high efficiency
internals have a low sensitivity to unlevelness and are designed to ensure the
Wild most effective mixing of liquid and vapor streams and maximum utiliza-
HDA Product naphtha tion of catalyst. These internals are effective at high of liquid loadings,
Second diesel thereby enabling high turndown ratios. Topsøe’s graded-bed technology and
reactor Steam
stage stripper the use of shape-optimized inert topping and catalysts minimize the build-
Diesel product up of pressure drop, thereby enabling longer catalyst cycle length.
HDA
separator Operating conditions: Typical operating pressures range from 20
Diesel cooler to 60 barg (300 to 900 psig), and typical operating temperatures range
from 320°C to 400°C (600°F to 750°F) in the first stage reactor, and
from 260°C to 330°C (500°F to 625°F) in the second stage reactor. The
Hydrodearomatization Topsøe HDS/HDA treatment of a heavy straight-run gas oil feed
yielded these product specifications:
Application: Topsøe’s two-stage hydrodesulfurization hydrodearom- Feed Product
atization (HDS / HDA) process is designed to produce low-aromatics Specific gravity 0.86 0.83
distillate products. This process enables refiners to meet the new, Sulfur, ppmw 3,000 1
stringent standards for environmentally friendly fuels. Nitrogen, ppmw 400 <1
Total aromatics, wt% 30 <10
Products: Ultra-low sulfur, ultra-low nitrogen, low-aromatics diesel,
Cetane index, D-976 49 57
kerosine and solvents (ultra-low aromatics).
References: Cooper, Hannerup and Søgaard-Andersen, “Reduc-
Description: The process consists of four sections: initial hydrotreating, tion of Aromatics in Diesel,” Oil and Gas, September 1994
intermediate stripping, final hydrotreating and product stripping. The Søgaard-Andersen, Cooper and Hannerup, “Topsøe’s Process for
initial hydrotreating step, or the “first stage” of the two-stage reaction pro- Improving Diesel Quality,” NPRA Annual Meeting, 1992.
cess, is similar to conventional Topsøe hydrotreating, using a Topsøe high- de la Fuente, E., P. Christensen, and M. Johansen, “Options for
activity base metal catalyst such as TK-573 to perform deep desulfuriza- meeting EU year 2005 fuel specifications.”
tion and deep denitrification of the distillate feed. Liquid effluent from this
first stage is sent to an intermediate stripping section, in which H2S and Installation: A total of four, two in Europe and two in North America.
ammonia are removed using steam or recycle hydrogen. Stripped distillate Licensor: Haldor Topsøe A/S.
mixed with hydrogen-rich recycle gas and processed across fixed cat-
Fresh feed alyst beds at moderate temperatures and pressures. Following heat
exchange and separation, the reactor effluent is stabilized. The sim-
ilarity of an ISAL unit to a conventional naphtha hydrotreating
unit makes implementation both simple and straightforward. The
technology can be applied to idle reforming and hydrotreating units.
Light ends Product quality: The unit operation can be adjusted to optimize var-
1
ious desulfurization, octane and yield combinations.
Wash water
Hydro- ISAL
4 Property Feed treater Case A Case B Case C
API° 47.3 48.1 48.7 48.5 48.5
2 Sulfur, wppm 2,160 25 25 25 <5
3
Olefins vol% 27.6 <1 <1 <1 <1
Hydrogen makeup C5 + vol% 100.1 99.7 98.0 97
Low-sulfur R+M/2 octane
Sour water naphtha change -8.9 -1.5 0 0
Economics: The capital and operating costs of an ISAL unit are only
slightly higher than those of a typical naphtha hydrotreating unit.
Hydrodesulfurization With this process, refiners benefit from a higher-octane product
with minimal additional operating cost. A payback period of less than
Application: The ISAL process enables refiners to meet the world’s one year is expected on the small incremental investment for ISAL
most stringent specifications for gasoline sulfur and olefin content. over that for conventional hydrotreating.
This low-pressure, fixed-bed hydroprocessing technology desulfur- Installations: The first ISAL process unit is a reload of an existing
izes gasoline-range feedstocks and selectively reconfigures lower hydrotreater for a U.S. Gulf Coast refinery that started operation in
octane components to control product octane. September 2000. As of October 2000, two revamp applications and
Description: The flow scheme of the ISAL process is very similar two new units are in the engineering phase.
to that of a conventional hydrotreating process. The naphtha feed is Licensor: UOP LLC (in cooperation with PDVSA-INTEVEP).
A small cetane and API gravity uplift together with the reduction of
Water wash Recycle polyaromatics to less than 11 wt% or as low as 5 wt% can be eco-
compressor Fuel nomically achieved.
Lean amine gas
UDHDS Description: MAKFining technology is offered through the global
reactor Absorber hydroprocessing alliance between ExxonMobil Research and Engi-
neering, Akzo Nobel Chemicals, Kellogg Brown & Root and Fina
Rich amine Research S.A. MAKFining PDT units combine a family of technolo-
Heater gies in low-cost integrated designs to achieve the necessary product
Cold
Hot separator
Sour water uplift. The first step for any PDT unit is ultra-deep HDS. A single-
separator stage, single-reactor process incorporates proprietary high-perfor-
Naphtha
mance-distribution and advanced-quench internals. Feed and com-
bined recycle and makeup gas are preheated and contact the catalyst
Steam
Distillate in a downflow-concurrent-fixed-bed reactor. The reactor effluent is
Product
feed Charge stripper flashed in a high- and a low-pressure separator. An amine absorber
pump Hydrogen tower is used to remove H2S from the recycle gas. In the example
Makeup Low-sulfur shown, a steam stripper is used for final product recovery. The
compressor diesel MAKFining UDHDS technology is equally applicable to revamp
and grassroots applications.
Economics: Investment (basis: 25,000 to 35,000 bpsd, 1st quarter
Hydrodesulfurization— 2000 U.S. Gulf Coast)
New unit, $ per bpsd 1,000 to 1,800
UDHDS Installation: Thirty-six distillate-upgrading units have applied the
Application: A versatile family of MAKFining Premium Distillates MAKFining Premium Distillates Technologies. Eleven of these appli-
Technologies (PDT) is used to meet all current and possible future cations are revamps.
premium diesel upgrading requirements. Ultra-deep hydrodesulfu- Reference: “MAKFining—Premium Distillates Technology: The
rization (UDHDS) process can produce distillate products with sul- Future of Distillate Upgrading,” Paper AM-00-18, NPRA Annual
fur levels below 10 wppm from a wide range of distillate feedstocks. Meeting, March 2000, San Antonio.
Products: High volume yield of ultra-low-sulfur distillate is produced. Licensor: Akzo Nobel and Kellogg Brown & Root, Inc.
catalyst life. Additionally, mercaptans can react with diolefins to make
Hydrogen recycle heavy, thermally-stable sulfides. The sulfides are fractionated to the
bottoms product. This can eliminate the need for a separate mer-
CW Off gas captan removal step. The distillate product is ideal feedstock for alky-
lation or etherification processes.
The heat of reaction evaporates liquid, and the resulting vapor
is condensed in the overhead condenser (2) to provide additional
reflux. The natural temperature profile in the fractionation column
2 results in a virtually isothermal catalyst bed rather than the tem-
Hydrogen perature increase typical of conventional reactors.
1
The CDHydro process can operate at much lower pressure than
FCC C4+ conventional processes. Pressures for CDHydro are typically set by
Reflux Treated FCC C4s
MP the fractionation requirements. Additionally, the elimination of a
steam separate hydrogenation reactor and hydrogen stripper offer signifi-
FCC C5+ gasoline cant capital cost reduction relative to conventional technologies.
Feeding CDHydro with reformate and light-straight run for ben-
Depentanizer zene saturation provides the refiner with increased flexibility to pro-
duce RFG. Isomerization of the resulting C5/C6 overhead stream pro-
vides higher octane and yield due to reduced benzene and C7+ content
compared to typical isomerization feedstocks.
Hydrogenation Economics: Fixed-bed hydrogenation requires a distillation column
Application: CDHydro is used to selectively hydrogenate diolefins followed by a fixed-bed hydrogenation unit. CDHydro eliminates the
in the top section of a hydrocarbon distillation column. Additional fixed-bed unit by incorporating catalyst in the column. When a new
applications—including mercaptan removal, hydroisomerization distillation column is used, capital cost of the column is only 5% to
and hydrogenation of olefins and aromatics are also available. 20% more than for a standard column depending on the CDHydro
application. Elimination of the fixed-bed reactor and stripper can
Description: The patented process CDHydro combines fractionation reduce capital cost by as much as 50%.
with hydrogenation. Proprietary devices containing catalyst are
installed in the fractionation column’s top section (1). Hydrogen is Installation: Fourteen CDHydro units are in commercial operation
introduced beneath the catalyst zone. Fractionation carries light for C4, C5, C6 and benzene hydrogenation applications. Three units
components into the catalyst zone where the reaction with hydrogen have been in operation for more than five years and total commer-
occurs. Fractionation also sends heavy materials to the bottom. This cial operating time now exceeds 50 years for CDHydro technologies.
prevents foulants and heavy catalyst poisons in the feed from con- Twelve additional units are currently in engineering/construction.
tacting the catalyst. In addition, clean hydrogenated reflux contin- Licensor: CDTECH.
uously washes the catalyst zone. These factors combine to give a long
ment can be added as required. The process combines ABB Lummus
Global’s cocurrent and/or patented countercurrent reactor technology with
Vapor/liquid special SynCat catalysts from Criterion Catalyst Co. LP. It incorporates
Firststage separation/recycle design and operations experience from Shell Global Solutions, to max-
reactor imize reactor performance by using advanced reactor internals.
Interstage Second stage
stripper reactor A single-stage or integrated two-stage reactor system provides
various process configuration options and revamp opportunities. In a
two-stage reactor system, the feed, makeup and recycle gas are heated
and fed to a first-stage cocurrent reactor. Effluent from the first stage
is stripped to remove impurities and light ends before being sent to the
H2 second-stage countercurrent reactor. When a countercurrent reactor
rich gas is used, fresh makeup hydrogen can be introduced at the bottom of
the catalyst bed to achieve optimum reaction conditions.
Operating conditions: Typical operating conditions range from 500–1,000
psig and 600°F–750°F. Feedstocks range from straight-run gas oils to feed
Product to blends containing up to 70% cracked feedstocks that have been com-
Feed oil stripping
mercially processed. For example, the SynShift upgrading of a feed blend
containing 72% LCO and LCGO gave these performance figures:
Feed blend Product
Gravity, °API 25 33.1
Hydrotreating Sulfur, wt% (wppm)
Nitrogen, wppm
1.52
631
(2)
<1
Aromatics, vol% 64.7 34.3
Application: Hydroprocessing of middle distillates, including cracked Cetane index 34.2 43.7
materials (coker/visbreaker gas oils and LCO) using SynTechnology, max- Liquid yield on feed, vol% 107.5
imizes distillate yield while producing ultra-low-sulfur diesel with improved
cetane and API gain, reduced aromatics, T95 reduction and cold-flow Economics: SynTechnology encompasses a family of low-to-moderate
improvement through selective ring opening, saturation and/or isomer- pressure processes. Investment cost will be greatly dependent on feed
ization. Various process configurations are available for revamps and new quality and hydroprocessing objectives. For a 30,000 to 35,000-bpsd
unit design to stage investments to meet changing diesel specifications. unit, the typical ISBL investment cost in U.S.$/bpsd (U.S. Gulf
Coast 2000) are:
Products: Maximum yield of improved quality distillate while min- Revamp existing unit 450 –950
imizing fuel gas and naphtha. Diesel properties include less than 10- New unit for deep HDS 1,100 –1,200
ppm sulfur, with aromatics content (total and/or PNA), cetane, den- New unit for cetane improvement and HDA 1,500 –1,600
sity and T95 dependent on product objectives and feedstock. Installation: SynTechnology has been selected for more than 30 units,
Description: SynTechnology includes SynHDS for ultra-deep desul- with half of the projects being revamps. Seven units are in operation.
furization and SynShift/SynSat for cetane improvement, aromatics sat- Licensor: ABB Lummus Global, Inc., on behalf of the SynAlliance,
uration and density/ T95 reduction. SynFlow for cold flow improve- which includes Criterion Catalyst Co. LP, and Shell Global Solutions.
two separate zones. HDS conditions are optimized for each fraction
to achieve the desired sulfur reduction with minimal olefin satura-
LCN tion. Olefins are concentrated at the top of the column, where con-
ditions are mild, while sulfur is concentrated at the bottom where
the conditions result in very high levels of HDS.
CDHydro MCN No cracking reactions occur at the mild conditions, so that yield
Hydrogen losses are easily minimized with vent-gas recovery. The three prod-
uct streams are stabilized together or separately, as desired, result-
ing in product streams appropriate for their subsequent use. The
FCC C5+ gasoline two columns are heat integrated to minimize energy requirements.
MCN/HCN
CDHDS Typical reformer hydrogen is used in both columns without makeup
compression. Optimal integration with hydrogen generation and
sour-gas treating facilities at some sites may result in the inclusion
Hydrogen of hydrogen recycle and vent-gas treating within the process. The
sulfur reduction achieved will allow the blending of gasoline that
HCN meets current and future regulations.
Catalytic distillation essentially eliminates catalyst fouling
because the fractionation removes heavy-coke precursors from the
catalyst zone before coke can form and foul the catalyst pores. Thus,
catalyst life in catalytic distillation is increased significantly beyond
Hydrotreating typical fixed-bed life. The CDHydro/CDHDS units can operate
throughout an FCC turnaround cycle up to five years without requir-
Application: CDHydro and CDHDS are used to selectively desul- ing a shutdown to regenerate or to replace catalyst.
furize FCC gasoline with minimum octane loss.
Economics: The estimated ISBL capital cost for a 35,000 bpd
Products: Ultra-low-sulfur FCC gasoline with maximum retention CDHydro/CDHDS unit with 92% desulfurization is $25 million (2000
of olefins and octane. U.S. Gulf Coast). Direct operating costs—including utilities, catalyst,
hydrogen and octane replacement—are estimated at $0.03/gas of full-
Description: The light, mid and heavy cat naphthas (LCN, MCN, range FCC gasoline.
HCN) are treated separately, under optimal conditions for each.
The full-range FCC gasoline sulfur reduction begins with fraction- Installation: Three CDHydro units are in operation treating FCC
ation of the light naphtha overhead in a CDHydro column. Mercaptan gasoline and twelve more units are currently in engineering/con-
sulfur reacts quantitatively with excess diolefins to product heavier struction. Two CDHDS units are in operation with six additional units
sulfur compounds, and the remaining diolefins are partially saturated currently in engineering/construction.
to olefins by reaction with hydrogen. Bottoms from the CDHydro col-
Licensor: CDTECH.
umn, containing the reacted mercaptans, are fed to the CDHDS
column where the MCN and HCN are catalytically desulfurized in
The process integrates well with residuum FCC units to minimize
Makeup catalyst consumption and improve yields and with delayed coking,
hydrogen which minimizes quantity and improves coke quality. Processing dea-
sphalted oil in a VRDS unit achieves high conversion to distillate
Wash 5 H 2S products.
water Process gas
Description: Oil feed and hydrogen are charged to the reactor (1)
Unstabilized in a once-through operation. Product separation is done by the hot
naphtha high-pressure separator (2), cold high-pressure separator (3) and frac-
3 tionator (4). Recycle hydrogen passes through an H2S absorber (5).
1
Middle A wide range of feedstocks can be processed. Existing units have
4 distillate processed feeds with viscosities as high as 6,000 cSt at 100°C and met-
als contents as high as 500 ppm.
2 Sour VGO Onstream catalyst replacement (OCR) technology allows spent cat-
Fresh feed water alyst to be removed from one or more reactors and replaced with fresh
Hydrotreated catalyst while all reactors operate normally. This allows very heavy
START resid product feedstocks to be processed with long run lengths (one year or more).
Installation: 22 RDS/VRDS hydrotreaters are operating, including
a 96,000-bpsd unit. Six VRDS units are operating including a 30,000-
bpsd unit. Eleven RDS units pretreat residuum charged to RFCC
Hydrotreating units. Three RDS units, one of which is a 50,000-bpsd unit, receive
demetallized residuum from OCR reactors. Two new RDS units and
Application: Hydrotreat atmospheric or vacuum residuum feedstocks one revamp unit using Up Flow Reactor (UFR) technology are in engi-
to reduce sulfur, nitrogen, metals, asphaltene and carbon residue con- neering or under construction. Total current capacity is 894,000
tents. To convert residuum into lighter products while reducing the bpsd. Future additional RDS capacity is 148,000 bpsd.
viscosity of the unconverted bottoms using the RDS/VRDS hydrotreat-
ing process. Reference: Reynolds, “Resid Hydroprocessing with Chevron Tech-
nology,” JPI, Tokyo, Japan, October 19, 1998. Reynolds and Brossard,
Products: Residuum FCC unit feedstock, coker feedstock or low-sul- “RDS/VRDS Hydrotreating Broadens Application of RFCC,” HTI
fur fuel oil. VGO product, if recovered, is suitable for further upgrad- Quarterly, Winter 1995/96.
ing in FCC units or hydrocrackers for gasoline/mid-distillate man-
ufacture. Mid-distillate products are suitable for blending into diesel Licensor: Chevron Research and Technology Co. Available through:
product. Chevron Products Co. (Technology Marketing)
In the Topsøe hydrotreater, feed is mixed with hydrogen, heated
and partially evaporated in a feed/effluent exchanger before it enters
Makeup the reactor. In the reactor, Topsøe’s high-efficiency internals have a
hydrogen Absorber
low sensitivity to unlevelness and are designed to ensure the most
Lean DEA effective mixing of liquid and vapor streams and the maximum uti-
Furnace lization of the catalyst volume. These internals are effective at a high
range of liquid loadings, thereby enabling high turndown ratios. Top-
søe’s graded-bed technology and the use of shape-optimized inert
Reactor topping and catalysts minimize the build-up of pressure drop, thereby
Rich DEA
enabling longer catalyst cycle length. The hydrotreating catalysts
themselves are of the Topsøe TK series, and have proven their high
Fresh feed H2 rich gas activities and outstanding performance in numerous operating units
throughout the world. The reactor effluent is cooled in the feed-efflu-
START
ent exchanger, and the gas and liquid are separated. The hydrogen gas
High-pressure Product is sent to an amine wash for removal of hydrogen sulfide and is then
separator recycled to the reactor. Cold hydrogen recycle is used as quench gas
Low-pressure separator between the catalyst beds, if required. The liquid product is steam
stripped in a product stripper column to remove hydrogen sulfide,
dissolved gases and light ends.
Hydrotreating Operation conditions: Typical operating pressures range from 20

to 80 barg (300 to 1,200 psig), and typical operating temperatures
Application: Topsøe hydrotreating technology has a wide range of range from 320°C to 400°C (600°F to 750°F).
applications, including the purification of naphtha, distillates and References: Bingham, Muller, Christensen and Moyse, “Perfor-
residue, as well as the deep desulfurization and color improvement mance Focused Reactor Design to Maximize Benefits of High Activ-
of diesel fuel and pretreatment of FCC and hydrocracker feedstocks. ity Hydrotreating Catalysts,” European Refining Technology Con-
Products: Ultra-low-sulfur diesel fuel, and clean feedstocks for ference, 1997.
FCC and hydrocracker units. Cooper, “Meeting the Challenge for Middle Distillates: Scientific
and Industrial Aspects,” Petrotech, 1997.
Description: Topsøe’s hydrotreating process design incorporates our de la Fuente, E., P. Christensen, and M. Johansen, “Options for
industrially proven high-activity TK catalysts with optimized graded- meeting EU year 2005 fuel specifications.”
bed loading and high-performance, patented reactor internals. The
combination of these features and custom design of hydrotreating Installation: More than 30 Topsøe hydrotreating units for the var-
units result in process solutions that meet the refiner’s objectives in ious applications above are in operation or in the design phase.
the most economic way. Licensor: Haldor Topsøe A/ S.
Description: Single or multibed catalytic treatment of hydrocarbon
liquids in the presence of hydrogen converts organic sulfur to hydro-
Fired gen sulfide and organic nitrogen to ammonia. Naphtha treating
heater normally occurs in the vapor phase, and heavier oils usually oper-
ate in mixed-phase. Multiple beds may be placed in a single reactor
1 shell for purposes of redistribution and/or interbed quenching for heat
Liquid removal. Hydrogen-rich gas is usually recycled to the reactor(s) (1)
feed Feed/effluent to maintain adequate hyrogen-to-feed ratio. Depending on the sul-
START exchangers fur level in the feed, H2S may be scrubbed from the recycle gas. Prod-
Makeup uct stripping is done with either a reboiler or with steam. Catalysts
Hydrogen makeup compressor are cobalt-molybdenum, nickel-molybdenum, nickel-tungsten or a
Recycle compressor
combination of the three.
Flash gas to fuel High- Operating conditions: 550°F to 750°F and 400 to 1,500 psig reac-
pressure tor conditions.
Low-pressure
Liquid to stripper flash flash Yields: Depend on feed characteristics and product specifications.
Recovery of desired product almost always exceeds 98.5 wt% and usu-
ally exceeds 99%.
Economics:
Hydrotreating Utilities, (per bbl feed)
Fuel, 103 Btu release
Naphtha
48
Diesel
59.5
Application: Reduction of the sulfur, nitrogen, and metals content Electricity, kWh 0.65 1.60
of naphthas, kerosines, diesel or gas oil streams. Water, cooling (20°F rise), gal 35 42
Products: Low-sulfur products for sale or additional processing. Licensor: Howe-Baker Engineers, Inc.
Operating conditions: Operating conditions depend on feedstock
and desired level of impurities removal. Pressures range from 500
to 2,000 psi. Temperatures and space velocities are determined by
Light components process objectives.
Makeup Yields:
hydrogen Purpose FCC feed Desulf. Desulf. Desulf.
Feed, source VGO + Coker AGO VGO DSL
1 3 Gravity, °API 17.0 25.7 24.3 30.1
Boiling range, °F 400/1,000 310/660 700/1,000 350/700
Sulfur, wt% 1.37 1.40 2.3 0.7
Product Nitrogen, ppmw 6,050 400 830 660
Feed Bromine number — 26 — —
Naphtha, vol% 4.8 4.2 2.6 3.3
START 2 Gravity, °API 45.0 50.0 54.0 60
Boiling range, °F 180/400 C4/325 C4/356 C5/325
Sulfur, ppmw 50 5 40 5
Nitrogen, ppmw 30 1 30 0.5
Distillate, vol% 97.2 97.6 98.0 99.4
Gravity, °API 24.0 26.9 27.8 35.2
Boiling range, °F 400+ 325/660 356+ 325+
Hydrotreating Sulfur, wt% 0.025 0.05 0.20 0.005
H2 consump.,
Application: Hydrodesulfurization, hydrodenitrogenation and hydro- scf/bbl 700 350 290 780
genation of petroleum and chemical feedstocks using the Unionfin-
ing and MQD Unionfining processes. Economics:
Investment, $ per bpsd 1,200–2,000
Products: Low-sulfur diesel fuel; feed for catalytic reforming, FCC Utilities, typical per bbl feed:
pretreat; upgrading distillates (higher cetane, lower aromatics); Fuel, 103 Btu 40 –100
desulfurization, denitrogenation and demetallization of vacuum and Electricity, kWh 0.5 –1.5
atmospheric gas oils, coker gas oils and chemical feedstocks.
Installation: Several hundred units installed.
Description: Feed and hydrogen-rich gas are mixed, heated and con-
tacted with regenerable catalyst (1). Reactor effluent is cooled and Reference: Baron, K., et al., Ketjen Catalyst Symposium, Am-
separated (2). Hydrogen-rich gas is recycled or used elsewhere. Liq- sterdam, the Netherlands, May 27–30, 1984.
uid is stripped (3) to remove light components and remaining hydro-
gen sulfide, or fractionated for splitting into multiple products. Licensor: UOP LLC.
with minimal production of light gaseous and liquid products. How-
Resid Guard Main reactors (2-4) ever, adjustments can be made to the unit’s operating conditions,
charge reactor flowscheme configuration or catalysts to increase conversion to dis-
tillate and lighter products.
START Fresh feed is combined with makeup hydrogen and recycled gas,
HHPS and then heated by exchange and fired heaters before entering the
Recycle unit’s reactor section. Simple downflow reactors incorporating a
Makeup gas comp. graded bed catalyst system designed to accomplish the desired reac-
hydrogen tions while minimizing side reactions and pressure drop buildup are
Gas used. Reactor effluent flows to a series of separators to recover recy-
Recycle
gas heater Fuel gas Naphtha cle gas and liquid products. The hydrogen-rich recycle gas is scrubbed
to remove H2S and recycled to the reactors while finished products
Lean amine Distillate are recovered in the fractionation section. Fractionation facilities may
Treated be designed to simply recover a full-boiling range product or to
Rich amine recover individual fractions of the hydrotreated product.
atm. resid
Amine Cold high Cold low Hot low Economics:
scrubber press. sep. press. flash press. flash Fractionator Investment (basis: 15,000 to 20,000 bpsd, 2nd quarter 2000, U.S.
Gulf Coast)
$ per bpsd 2,000–3,500
Hydrotreating Utilities, typical per barrel of fresh feed (20,000 bpsd basis)
Fuel 46 MMBtu/hr
Application: RCD Unionfining reduces the sulfur, nitrogen, Con- Electricity 5,100 kWh
radson carbon, asphaltene and organometallic contents of heavier Steam 8,900 lb/hr (HP)
residue-derived feedstocks to allow them to be used as either spec- 1,500 lb/hr (LP)
ification fuel oils or as feedstocks for downstream processing units Installation: Twenty-five licensed units with a combined licensed
such as hydrocrackers, fluidized catalytic crackers, resid catalytic capacity of approximately 830,000 bpsd. Commercial applications
crackers and cokers. have included processing of atmospheric and vacuum residues and
Feed: Feedstocks range from solvent-derived materials to atmo- solvent-derived feedstocks.
spheric and vacuum residues. Reference: Thompson, G. J., “UOP RCD Unionfining Process,”
Description: The process uses a fixed-bed catalytic system that oper- Robert A. Meyers, ed., Handbook of Petroleum Refining Processes, 2nd
ates at moderate temperatures and moderate to high hydrogen par- ed., New York, McGraw-Hill, 1996.
tial pressures. Typically, moderate levels of hydrogen are consumed Licensor: UOP LLC.
or pour point product quality diesel can be achieved with the CFI and
Water wash Recycle MIDW processes. The MIDW products will be of higher diesel qual-
compressor Fuel ity than the CFI distillates.
Lean amine gas
CFI/ Description: MAKFining technology is offered through the global
MIDW hydroprocessing alliance between ExxonMobil Research and Engi-
reactor Absorber
neering, Akzo Nobel Chemicals, Kellogg Brown & Root and Fina
Rich amine Research S.A.. MAKFining PDT units combine a family of tech-
Heater nologies in low-cost-integrated designs to achieve necessary product
Cold
Hot separator
Sour water uplift. The first step for any PDT unit is ultra-deep HDS. When the
separator distillate product must also meet stringent fluidity specifications,
Naphtha
MAKFining can offer either paraffin isomerization dewaxing (MIDW)
Steam or selective normal paraffin cracking based dewaxing technologies
Distillate (CFI). These can be closely integrated with HDS and other functions
Product
feed Charge stripper to achieve the full upgrading requirements. Isomerization dewaxing
pump Hydrogen is generally a higher cost process, but delivers higher yields and higher
Makeup Low-sulfur total product quality (density, aromatics and cetane improvement)
compressor diesel at the same level of cloud-point reduction. The isomerization dewax-
ing process can be a single- or two-stage process, depending on the
level of heteroatoms in the feed. The selective paraffin hydrocrack-
Hydrotreating— ing process uses a single-stage design. The MAKFining Premium Dis-
tillates Technologies are equally applicable to revamp and grassroots
applications.
catalytic dewaxing Economics: Investment (basis:15,000 to 25,000 bpsd, 1st quarter
Application: A versatile family of MAKFining Premium Distillates 2000 U.S. Gulf Cost)
Technologies (PDT) is used to meet all current and possible future Grassroots unit, $ per bpsd 1,000 to 2,000
premium diesel upgrading requirements. The addition of selective
paraffin isomerization dewaxing (MIDW) or selective normal paraf- Installation: Thirty-six distillate upgrading units have applied the
fin hydrocracking (CFI) function to the hydrodesulfurization (HDS) MAKFining Premium Distillates Technologies. Eleven of these appli-
reactor will improve the diesel product cold flow properties for a wide cations are revamps.
range of waxy distillate feedstocks. Reference: “MAKFining—Premium Distillates Technology; The
Products: Ultra-low-sulfur distillate is produced with small amounts Future of Distillate Upgrading,” Paper AM-00-18, NPRA Annual
of lighter products. The MIDW process is more distillate selective than Meeting, March 2000, San Antonio.
the CFI process, resulting in higher yield of distillate. Low-cloud point, Licensor: Akzo Nobel and ExxonMobil Research & Engineering Co.
Description: MAKFining technology is offered through the global
Water wash Lean amine Fuel
Absorber hydroprocessing alliance between ExxonMobil Research and Engi-
UDHDS gas neering, Akzo Nobel Chemicals, Kellogg Brown & Root and Fina
Interstage Product
spider stripper Rich stripper Research S.A. MAKFining PDT units combine a family of technolo-
vortex amine gies in low-cost integrated designs to achieve necessary product
reactor uplift. The first step for any PDT unit is ultra-deep hydrodesulfur-
Sour water ization (UDHDS). Fresh feed and combined recycle and makeup
Heater
gas are preheated and contact the HDS catalyst in a downflow-con-
current-fixed-bed reactor. Effluent from the HDS reactor is hot
Naphtha stripped, and liquid is processed in a small second-stage HDAr sys-
HDAr tem to reduce polyaromatics or total aromatics to any low level
Recycle
spider Steam desired. The gas fraction is flashed in a cold high-pressure separa-
vortex compressor
Distillate tor. The hydrogen-rich gas is treated in an amine absorber tower to
feed reactor
remove H2S and used in the second stage HDAr reactor. The per-
formance and size of both stages are optimized to minimize capital
Hydrogen cost. In the above example, a stream stripper is used for final prod-
Makeup Low-aromatics
diesel uct recovery. The MAKFining Spider Vortex quench and redistribu-
compressor tion technology is key to reducing reactor volume and enhancing the
unit’s operability and reliability. The MAKFining Premium Distil-
lates Technologies are equally applicable to revamp and grassroots
Hydrotreating—HDAr applications.
Application: A versatile family of MAKFining Premium Distillates Economics: Investment (basis: 20,000 to 25,000 bpsd, 1st quarter
Technologies (PDT) is used to meet all current and possible future 2000 U.S. Gulf Coast)
premium diesel upgrading requirements. When feedstock aromatics Grassroots unit, $ per bpsd 1,000 to 2,000
are very high, or very low aromatics (<10 wt%) in the product are Installation: Thirty-six distillate-upgrading units have applied the
desired, a second-stage hydrodearomatization (HDAr) system can MAKFining Premium Distillates Technologies. Eleven of these appli-
reduce costs and avoid very high-design pressures, which would cations are revamps.
otherwise be required for a single-step-base-metal hydrotreating
catalyst system. Reference: "MAKFining—Premium Distillates Technology: The
Future of Distillate Upgrading," Paper AM-00-18, NPRA Annual
Products: Very high volume yield of ultra-low-sulfur distillate is pro- Meeting, March 2000, San Antonio.
duced with very low polynuclear and total aromatics content. Cetane
and density improvements of the diesel product can be achieved, Licensor: Kellogg Brown & Root, Inc.
depending on the feed quality and processing objectives.
Description: MAKFining technology is offered through the global
Recycle
Water wash compressor hydroprocessing alliance between ExxonMobil Research and Engi-
Fuel neering, Akzo Nobel Chemicals, Kellogg Brown & Root and Fina
Lean amine gas Research S.A. MAKFining PDT units combine a family of technolo-
HDHDC
spider gies in low-cost integrated designs to realize necessary product
vortex Absorber uplift. The first step for any PDT unit is ultra-deep HDS (UDHDS).
reactor Rich amine The addition of heavy diesel hydrocracking (HDHDC) function to the
Heater UDHDS unit can achieve T95 boiling point reduction together with
Hot separator higher levels of density, aromatics reduction, and greater cetane
Cold Sour water improvement. Product quality upgrades are accomplished with con-
separator Naphtha siderably lower hydrogen consumption in comparison to an aro-
matics saturation process. The MAKFining Spider Vortex quench and
Steam redistribution technology is key to the implementation of HDHDC
Distillate Product in a single-stage process configuration. Feed and combined recycle
feed Charge stripper
Hydrogen and makeup gas are preheated and contact the catalyst in a down-
pump flow-concurrent-fixed-bed reactor. The reactor effluent is flashed in
Makeup Low-aromatics
diesel a high- and a low-pressure separator. An amine absorber tower is used
compressor
to remove H2S from the recycle gas. In the above example, a steam
stripper is used for final product recovery. The MAKFining Pre-
mium Distillates Technologies are equally applicable to revamp and
Hydrotreating—HDHDC grassroots applications.
Economics: Investment (basis: 25,000 to 35,000 bpsd, 1st quarter
Application: A versatile family of MAKFining Premium Distillates
2000 U.S. Gulf Coast)
Technologies (PDT) is used to meet all current and possible future pre- Grassroots Unit, $ per bpsd 1,100 to 2,000
mium diesel upgrading requirements. The addition of heavy-diesel
hydrocracking (HDHDC) function to an hydrodesulfurization (HDS) Installation: Thirty-six distillate-upgrading units have applied the
reactor system will reduce diesel sulfur, nitrogen, ASTM D-86 95% boil- MAKFining Premium Distillates Technologies. Eleven of these appli-
ing point (T95) and polynuclear aromatics, as well as improve diesel prod- cations are revamps.
uct density and cetane for a wide range of distillate feedstocks.
Reference: "MAKFining—Premium Distillates Technology: The
Products: High volume yield of ultra-low-sulfur distillate is produced Future of Distillate Upgrading," Paper AM-00-18, NPRA Annual
along with some naphtha and fuel gas. The distillate product qual- Meeting, March 2000, San Antonio.
ity achieved depends on feed and processing objectives, but large
reduction in T95, density and polynuclear aromatics—along with Licensor: Kellogg Brown & Root, Inc.
improved cetane—are possible.
The guard reactors are onstream at the same time in series and
HDM demetallization, conversion HDS desulfurization, refining protect the downstream reactors by removing or converting sediment,
metals and asphaltenes. For heavy feeds, they are permutable in oper-
Permutable guard ation (PRS technology) and allow catalyst reloading during the run.
reactors Permutation frequency is adjusted according to feed metals con-
tent and process objectives. Regular catalyst changeout allows high
To gas and constant protection of downstream reactors.
1 1 treatment Following the guard reactors, the main HDM reactors carry out the
a b 2 3 4 5 remaining demetallization and conversion functions. With most of
the contaminants removed, the residue is sent to the HDS reactors
where the sulfur level is reduced to the design specification.
Yields: Typical HDS and HDM rates are above 90%. Net production
of 12% to 25% of diesel + naphtha.
Feed
Economics:
START To fractionation
Investments (basis: 40,000-bpsd VR, 1999 Gulf Coast)
Hydrogen section U.S. $ per bpsd 4,500 –5,500
Utilities (per bbl feed)
Fuel, Gcal 3
Power, kWhr 10
Hydrotreating, residue MP steam production, kg
HP steam consumption, kg
25
10
Application: Upgrade or convert atmospheric and vacuum residues Water, cooling, m3 1.1
using the Hyvahl process.
Installation: A 20,000-tpy plant at Solaize, France. Two units are
Products: Low-sulfur fuels—0.3% to 1.0% sulfur—and RFCC feeds in operation (one on atmospheric residue feed, the other on vacuum
(removal of metals, sulfur and nitrogen, reduction of carbon residue). residue), with a total capacity of 80,000 bpsd.
30% to 50% conversion of the 550°C+ fraction into distillates.
Reference: “Maintaining On-spec Products with Residue Hydropro-
Description: Residue feed and hydrogen, heated in a feed/effluent cessing,” NPRA Annual Meeting, March 26–28, 2000, San Antonio.
exchangers and furnace, enter a reactor section typically comprising
guard reactor section, main HDM and HDS reactors. Licensor: IFP.
Iso-octene Iso-octane
RONC 101–103 99–100
C4 raffinate to MONC 85–87 96–99
alky or dehydro Specific gravity 0.701–0.704 0.726–0.729
Vapor pressure, psia 1.8 1.8
ASTM EP, °F 380–390 370–380
C4 feed/
isobutylene Iso-octene Description: In the NExOCTANE process, reuse of existing equipment
Isobutylene Iso-octene
dimerization product recovery from the MTBE unit is maximized. The process consists of three sec-
tions. First, isobutylene is dimerized to iso-octene in the reaction sec-
tion. The dimerization reaction occurs in the liquid phase over an
TBA recycle Iso-octane acidic ion-exchange resin catalyst, and it uses simple liquid-phase-fixed-
Hydrogenation bed reactors. The iso-octene product is recovered in a distillation sys-
tem, for which generally the existing fractionation equipment can be
reused. The recovered iso-octene product can be further hydrogenated
to produce iso-octane. A highly efficient trickle-bed hydrogenation
Hydrogen technology is offered with the NExOCTANE process. This compact and
cost-effective technology does not require recirculation of hydrogen. In
the refinery, the NExOCTANE process fits as a replacement to MTBE
production, thus associated refinery operations are mostly unaffected.
Iso-octane Economics: Investment cost for revamps depend on the existing
MTBE plant design, capacity and feedstock composition. Typical
Application: Conversion of isobutylene contained in mixed-C4 utility requirements per bbl product:
feeds to iso-octane (2,2,4 tri-methyl pentane) to produce a high-qual-
ity gasoline blendstock. The full range of MTBE plant feeds can be Steam, 150-psig, lb 700
processed—from refinery FCC, olefin-plant raffinate and isobu- Electricity, kWh 2.3
tane dehydrogenation processes. The NExOCTANE process is specif- Water, cooling, ft3 1.2
ically developed to minimize conversion costs of existing MTBE Installations: Currently, several licenses for this emerging technology
units and offers a cost-effective alternative to MTBE production. have been signed and are under design. The first commercial oper-
Products: Iso-octene and iso-octane can be produced, depending on ation is anticipated for startup in the first half of 2001.
the refiner’s gasoline pool. Typical product properties are: Licensor: Kellogg Brown & Root, Inc., and Neste Engineering Oy
(Fortum Group).
Description: Depending on conversion and investment require-
C4 raffinate ments, various options are available. A typical one-stage reaction pro-
MeOH recovery cess, which can provide isobutylene conversion of up to 85%, is as fol-
lows. The C4 feed is mixed with a recycle stream containing
Iso-octene product oxygenates (such as TBA and MTBE), used as “selectivator” and
heated before entering the reactor. The reactor (1) is a water-cooled-
tubular reactor (WCTR) (or, if available, a boiling-point reactor
Hydrogen could be used for lower conversion requirements in a revamp). The
2 3 heat of reaction is removed by circulating water through the shell of
1 the WCTR. There is no product recycle. The reactor effluent flows,
Makeup along with the selectivator, to the debutanizer (2), where iso-octene
methanol Hydrogenation is separated from the unreacted C4s. Unreacted C4s are taken as col-
umn overhead, while iso-octene, TBA and MTBE are removed as the
Makeup water bottom product together with C5 hydrocarbons, if any. The subsequent
Iso-octane bottom product is fed to the iso-octene purification column (3). The
C4 feed Selectivator recycle product bottom product is iso-octene. It can be sent to storage or fed to the
“hydrogenation unit” to produce saturated hydrocarbon—iso-octane.
A two-stage reaction process can also be designed, which allows for
conversion up to 99%. In this case, a second reaction stage is pro-
vided either as a fixed-bed or catalytic distillation (CD) system.
Iso-octane / iso-octene Economics:
Application: Manufacture of high-octane, low-vapor pressure, Investment (basis grassroots iso-octene unit, charging FCC C4s)
“MTBE-free” iso-octene and/or iso-octane for gasoline blending. 5,000–7,000 U.S. $ per bpsd
Coproduction of MTBE and iso-octene/iso-octane can be produced in Investment for retrofitting an existing MTBE unit to iso-octene
the desired ratio. production
2,000– 2,500 U.S. $ per bpsd
Feed: Hydrocarbon streams containing reactive tertiary olefins Utilities, per bbl of iso-octene:
such as: FCC C4s, steam-cracker C4s or isobutane dehydrogenation Steam, 103 lb 0.2–0.3
product. Water, cooling, gal 1,500–2,000
Power, kWh 0.6–1.0
Products: Iso-octene or iso-octane stream containing at least 85%
of C8s, with less than 5,000 ppm oligomers higher than C12s. Licensors: Snamprogetti SpA and CDTECH.
duces a stabilized isomerate with an 84 to 85 RONC. Corresponding
yield is in excess of 99.5 vol% on feed. Optionally to achieve higher
Dryers Reactor Stabilizer Scrubber product octane, optimized separation/recycle facilities are incorpo-
Makeup
hydrogen Fuel gas rated into the process. In one such configuration, a deisohexanizer
is used to produce 88 RONC isomerate.
Description: The Lummus process uses Akzo Nobel’s high-activity
Circulating
chlorided-alumina catalyst that allows operation at low temperatures,
caustic which maximizes conversion and selectivity while minimizing cat-
1 1 2 3 4 alyst requirements. Excellent stability at low hydrogen flowrates elim-
inates the need for hydrogen recycle compression, further reducing
investment cost.
Spent caustic As depicted above, the C5/C6 feed and makeup hydrogen streams
C5/C6 feed are dried over molecular sieves (1), combined, heated to reaction tem-
C5/C6 isomerate perature in feed/effluent exchangers followed by a trim heater and
START sent to the fixed-bed reaction zone (2). Reactor product, which
approaches equilibrium conversion levels, is directed to the product
stabilizer (3). Stabilizer overhead, containing light hydrocarbons
and excess hydrogen, is directed to fuel gas via a caustic scrubber (4).
Stabilized bottoms is sent to isomerate product storage in single pass
Isomerization operation or optionally to separation facilities in recycle operation.
Application: To efficiently upgrade the octane number of C5/C6 Economics:
refinery streams by conversion of normal paraffins to their higher Investment estimated (basis ISBL, U.S. Gulf Coast 2000)
octane isomers. Typical feedstocks include light straight-run naph- $/bpsd (typical) 700–1,500
tha, light reformate and light hydrocrackate. In addition to paraffin
isomerization, the technology also achieves benzene saturation with Installation: Three units have been licensed and designed. Approx-
subsequent octane upgrading of resulting cyclohexane. imately a dozen of these units use the Akzo Nobel catalyst.
Products: The Lummus C5/C6 isomerization process typically pro- Licensor: ABB Lummus Global Inc. and Akzo Nobel Chemicals b.v.
ization activity. At the end of the process cycle, the feed is switched to
a fresh catalyst bed, and the spent catalyst bed is regenerated by oxi-
2 dizing the coke with an air/nitrogen mixture. The butene isomerate is
C4s to MTBE unit suitable for making high purity isobutylene product.
C5 olefin skeletal isomerization (IsomPlus)
A zeolite-based catalyst especially developed for this process pro-
vides near-equilibrium conversion of normal pentenes to isoamylene
3 at high selectivity and long process cycle times. Hydrocarbon feeds
containing n-pentenes, such as C5 raffinate, are processed in the
4 5 skeletal isomerization reactor without steam or other diluents, nor
the addition of catalyst activation agents to promote the reaction.
Near-equilibrium conversion levels up to 72% of the contained normal
C5+ pentenes are observed at greater than 95% selectivity to isoamylenes.
MTBE unit raffinate Economics: The Lyondell isomerization process offers the advan-
tages of low capital investment and operating costs coupled with a
high yield of isobutylene. Also, the small quantity of heavy byprod-
ucts formed can easily be blended into the gasoline pool. Capital costs
(equipment, labor and detailed engineering) for three different plant
sizes are:
Isomerization Total installed cost: Feedrate, Mbpd ISBL cost, $MM
10 8
Application: Convert normal olefins to iso-olefins. 15 11
30 30
Description: Utility costs: per barrel of feed (assuming an electric-motor-
C4 olefin skeletal isomerization (IsomPlus) driven compressor) are:
A zeolite-based catalyst especially developed for this process pro- Power, kWh 3.2
vides near equilibrium conversion of normal butenes to isobutylene at Fuel gas, MMBtu 0.44
high selectivity and long process cycle times. A simple process scheme Steam, MP, MMBtu 0.002
and moderate process conditions result in low capital and operating Water, cooling, MMBtu 0.051
costs. Hydrocarbon feed containing n-butenes, such as C4 raffinate, can Nitrogen, scf 57–250
be processed without steam or other diluents, nor the addition of cat-
Installation: One plant is in operation. Three licensed units are in
alyst activation agents to promote the reaction. Near-equilibrium
various stages of design.
conversion levels up to 44% of the contained n-butenes are achieved
at greater than 90% selectivity to isobutylene. During the process Licensor: CDTECH and Lyondell Chemical Co.
cycle, coke gradually builds up on the catalyst, reducing the isomer-
for typical cat cracker streams, requires no recycle or cooling. Hydro-
gen is added downstream of the olefin feed pump on ratio control and
Light-ends the feed mixture is preheated by exchange with the fractionator
Overhead Vent
separator bottoms and/or low-pressure steam. The feed then flows downward
condenser
over a fixed bed of commercial catalyst.
The reaction is liquid-phase, at a pressure just above the bubble
point of the hydrocarbon/hydrogen mixture. The rise in reactor tem-
Reactor perature is a function of the quantity of butadiene in the feed and
feed Drain the amount of butene saturation that occurs.
Hydrogen The Hydrisom process can also be configured using a proprietary
heater
Reflux pump catalyst to upgrade streams containing diolefins up to 50% or more,
e.g., steam cracker C4 steams, producing olefin-rich streams for use
Olefin Reboiler as chemical, etherification and/or alkylation feedstocks.
START Reactor Installation of a Phillips Hydrisom unit upstream of an etherifi-
cation and/or alkylation unit can result in a very quick payout of the
Olefin investment due to:
HF alkylation or etherification unit feed • Improved etherification unit operations
feed pump
• Increased ether production
• Increased alkylate octane number
• Increased alkylate yield
Isomerization • Reduced chemical and HF acid costs
• Reduced ASO handling
Application: Hydrisom is Phillips Petroleum Co.’s selective diolefin • Reduced alkylation unit utilities
hydrogenation process, with specific isomerization of butene-1 to • Upgraded steam cracker or other high diolefin streams (30% to
butene-2 and 3-methyl-butene-1 to 2-methyl-butene-1 and 2-methyl- 50%) for further processing.
butene-2. The Hydrisom process uses a liquid-phase reaction over a
Installation: Ten units licensed worldwide, including an installation
commercially available catalyst in a fixed-bed reactor.
at Phillips Refinery, Sweeny, Texas.
Description: The Hydrisom process is a once-through reaction and,
Licensor: Fuels Technology Division of Phillips Petroleum Co.
Chlorinated
Zeolite alumina
Process configuration catalyst catalyst
Once-through 80 83
Deisopentanizer and once-through 82 84
CW Off gas Deisohexanizer and recycle 86 88
C5/C6 feed Normal recycle-Ipsorb 88 90
Normal and deisohex. recycle-Hexorb 92 92
START
1 Operating conditions: The Ipsorb Isom process uses a deisopen-

Isomerate
2 3 tanizer (1) to separate the isopentane from the reactor feed. A small
amount of hydrogen is also added to reactor (2) feed. The isomerization
reaction proceeds at moderate temperature producing an equilibrium
mixture of normal and isoparaffins. The catalyst has a long service
Hydrogen
life owing to its regenerability. The reactor products are separated
into isomerate product and normal paraffins in the Ipsorb molecu-
Recycle lar sieve separation section (3) which features a novel vapor phase
PSA technique. This enables the product to consist entirely of
branched isomers.
Economics: (basis: Ipsorb “A” Isomerization unit with a 5,000-bpsd
Isomerization 70 RONC feed needing a 20 point octane boost):
Investment*, million U.S.$ 13
Application: C5/C6 paraffin-rich hydrocarbon streams are isomer-
Utilities:
ized to produce high RON and MON product suitable for addition to HP steam, tph 1.0
the gasoline pool. MP steam, tph 8.5
Description: Several variations of the C5/C6 isomerization process are LP steam, tph 6.8
available. With either a zeolite or chlorinated alumina catalyst, the Power, kWh/h 310
choice can be a once-through reaction for an inexpensive-but-limited Cooling water, m3/h 100
octane boost, or, for substantial octane improvement, the Ipsorb Isom * Mid-2000, Gulf coast, excluding cost of noble metals
scheme shown above to recycle the normal paraffins for their complete
conversion. The Hexorb Isom configuration achieves a complete nor- Installation: Of 21 licenses issued for C5/C6 isomerization plants,
mal paraffin conversion plus substantial conversion of low (75) octane 10 units are operating including one Ibsorb unit.
methyl pentanes gives the maximum octane results. The product Licensor: IFP.
octanes from five process schemes for treating a light naphtha feed (70
RON) containing a 50/50 mixture of C5/C6 paraffins are:
Products: The CKS ISOM process provides an upgrade of 10 to 18
Makeup octane numbers, depending on the feed and product recovery flow
hydrogen Recycle hydrogen scheme. The flow scheme is tailored to achieve the refiner’s required
C4- to fuel gas octane improvement at minimum capital investment and operating cost.
Description: The CKS ISOM process is based on Süd Chemie’s
Recycle HYSOPAR catalyst, which is sulfur and water tolerant and fully
Isomerization gas regenerable. Feed hydrotreating and drying (unless free water is pre-
reactor compressor sent) are not required. Less expensive regenerable caustic scrubbing
Debutanizer can be used for feed sulfur levels above 100 ppm. In the once-
Naphtha Feed heater through configuration depicted above, the C 5/C 6 feed and makeup
feed hydrogen are heated against reactor effluent and in a feed preheater
Reactor Isomerate and then fed to the reactor. The reactor product, at near-equilibrium
effluent product conversion level, is fed to a stabilizer. The stabilizer overhead, con-
separator taining excess hydrogen, is compressed and recycled to the reactor.
The stabilizer bottoms are sent to a debutanizer where the C4¯
overhead goes to fuel gas and bottoms are sent to the gasoline
blending pool. For greater octane uplift, the bottoms can be sepa-
rated to recycle unconverted n-pentane, n-hexane and methyl pen-
tanes to reactor.
Isomerization Economics: Indicative capital cost for once-through unit (basis
ISBL, U.S. Gulf Coast) $/bpsd: 500 –700
Application: To upgrade the octane number of refinery streams rich
in C 5/C 6 normal paraffins, such as light-straight run (LSR) naph- Installation: One isomerization unit is in commercial operation.
tha, light hydrocrackate, raffinate from aromatics extraction and nat- HYSOPAR catalyst is in service in 12 other units worldwide.
ural gas condensate. Feedstocks may contain up to 100-ppm sulfur
on continuous basis and up to 200-ppm-sulfur for short periods of time. Licensor: Kellogg Brown & Root, Inc.
fractionation in a deisohexanizer column or a combination of fraction-
Makeup hydrogen Gas to scrubbing ation and selective adsorption. The Par-Isom process is a lower cost iso-
and fuel merization option. It provides a 1–2 lower octane-number product
with regenerable catalyst. Dryers are not required, recycle hydrogen
is needed. The metal oxide catalyst is an ideal replacement for zeolitic
1 catalyst. This process is a cost-effective revamp option.
2 2
Description: Hydrogen recycle is not required for the Penex process,
and high conversion is achieved at low temperature with negligible
yield loss. A fired heater is not required. The flow diagram represents
3 the Hydrogen-Once-Through (HOT) Penex process. A two reactor in
series flow configuration is normally used with the total required cat-
alyst being equally distributed between the two vessels. This allows
the catalyst to be fully utilized.
1 Feed and makeup hydrogen are dried (1) over adsorbent and
C5/C6 charge then mixed. The mixture is heated against reactor effluent and sent
START
Penex isomerate to the reactors (2). Reactor effluent passes directly to the stabilizer
(3) after heat exchange. Stabilizer bottoms are sent to gasoline
blending in a once-through operation or to separation (adsorption or
fractionation) in a recycle operation. The light ends are sent to a caus-
Isomerization tic-scrubber column and then to fuel.
Economics: The typical estimated erected costs for 2Q1998 ISBL, U.S.
Application: Paraffin isomerization technology for light naphtha Gulf Coast for a 10,000 bpsd unit are:
offers a wide variety of processing options that allow refiners to tai-
lor performance to their specific needs. Applications include octane Flowscheme EEC, $MM
enhancement and benzene reduction. The Penex process is specifi- Penex 8.5
cally designed for continuous catalytic isomerization of pentanes, hex- Penex/Molex 23.4
anes and mixtures of the two. The reactions take place in a hydro- Penex/DIH 15.5
gen atmosphere, over a fixed catalyst bed, and at operating conditions
Installation: UOP is the world’s leading licensor in C 5/C6 isomer-
that promote isomerization and minimize hydrocracking.
ization technology. The first Penex unit was placed on stream in 1958.
Products: A typical C5/C6 light naphtha feedstock can be upgraded to Over 180 UOP C5/C6 isomerization units have been commissioned as
82-84 RONC in hydrocarbon once-through operation. This can be of June 2000. Another 27 units are in various stages of design and
increased to about 87-93 RONC by recycling unconverted normal pen- construction.
tane, normal hexane and/or methylpentanes. Some systems for sepa-
rating the components for recycle are: vapor phase adsorptive separa- Reference: Hydrocarbon Technology International, 1991, p. 73.
tion (IsoSiv process), liquid phase adsorptive separation (Molex process), Licensor: UOP LLC
cessing depends upon the feedstock and the objectives of debottle-
necking (min. capital expenditure or max. capacity increase).
Vacuum Solvent Hydrotreating When the Shell process is used to debottleneck a lube oil plant, it
distillation extraction & redistillation Dewaxing
125 neutral is necessary to construct two new unit: a hydrotreating/redistillation
Atmospheric unit and an additional dewaxing unit (the existing dewaxing unit usu-
residue 250 neutral ally has insufficient spare capacity). There is normally no need to con-
struct additional vacuum distillation/deasphalting/solvent extraction
500 neutral units. However, some modifications will be required to the existing vac-
uum distillation and solvent extraction units.
Yields: Depend upon the grade of base oil and the crude origin of the
Extracts feedstock. Shell Hybrid gives a significantly higher yield of base oil
Bright stock crude and the yield is much less sensitive to feedstock origin than
Deasphalting
with solvent extraction process.
Base oils obtained via the Shell Hybrid process are lighter in color
and have lower Conradson carbon residue contents than their sol-
Asphalt Tops Waxes/LPG vent extracted counterparts and can more advantageously be used
in a number of special applications. Moreover, the low-sulfur, low-
pour-point gas oil byproducts from the hydrotreating unit can have
enhanced value in special markets, while the quantity of low-value
byproducts (e.g. extracts) is substantially reduced.
Lube hydroprocessing Economics: The following table compares the economics of debot-
Application: The Hybrid base oil manufacturing process is an opti- tlenecking a 300 ktpy solvent extraction complex to 500 ktpy with
mized combination of solvent extraction and one-stage hydropro- the economics of a new 200 ktpy solvent extraction complex.
cessing. It is particularly suited to the revamping/debottlenecking of Solvent extraction Hybrid debottlenecking
existing solvent extraction lube oil plants; capacity increases as 200 ktpy grass-roots (from 300 to 500 ktpy)
great as 60% can be achieved. Solvent extraction also liensed by Shell.
Capital charge 36% of total 24-36% of solvex total
Feed: Derived from a wider range of crudes than can be used with Fixed costs 20% of total 7-9% of solvex total
solvent extraction. Yields and capacity are less sensitive to feedstock Variable costs 8% of total 8% of solvex total
than when the solvent extraction process is applied. Hydrocarbon cost 36% of total 11% of solvex total
Total 100% of total 50-64% of solvex total
Description: Two separate upgrading units are used; solvent extrac-
tion and one-stage hydroprocessing. Individual waxy distillate Installation: The process has been commercially applied in Shell’s Gee-
streams are either mildly solvent-extracted and then hydropro- long refinery since 1980. Pertamina is applying the Shell Hybrid
cessed or are solvent extracted at normal severity. Deasphalted oil technology to debottleneck its Cilacap refinery—the successful start
is either mildly solvent extracted and then hydroprocessed or is occurred in the second half of 1998.
only hydroprocessed. The choice of solvent extraction and hydropro- Licensor: Shell Global Solutions International B.V
Description: The distillate or residual feedstock and solvent are
contacted in the extraction tower (1) at controlled temperatures and
flowrates required for optimum counter-current, liquid-liquid extrac-
2 tion of the feedstock. The extract stream, containing the bulk of the
Feed 3 4 solvent, exits the bottom of the extraction tower. It is routed to a recov-
ery solvent to remove contained in this stream. Solvent is separated
START 5 from the extract oil by multiple-effect evaporation (2) at various pres-
1
sures, followed by vacuum flashing and steam stripping (3) under vac-
uum. The raffinate stream exits the overhead of the extraction tower
Stm. Water and is routed to a recovery section for removal of the NMP solvent con-
Stm. tained in this stream by vacuum flashing and steam stripping (4) under
vacuum.
Refined oil
Overhead vapors from the steam strippers are condensed and
combined with solvent condensate from the recovery sections and are
Extract distilled at low pressure to remove water from the solvent (5). Sol-
vent is recovered in a single tower because NMP does not form an
azeotrope with water. The water is drained to the oily-water sewer.
The solvent is cooled and recycled to the extraction section.
Economics:
Lube treating Investment: (basis 10,000 bpsd,
Application: MP Refining is a solvent extraction process that uses N- 2000 U.S. Gulf Coast) $ per bpsd 2,500
methyl-2-pyrrolidone (NMP) as the solvent to selectively remove the
undesirable components of low lubricating oil quality naturally present Utilities, typical per bbl feed:
in crude oil distillate and residual stocks. The unit produces paraffinic Fuel, absorbed, 103 Btu 130
or naphthenic raffinates suitable for further processing into lube base Electricity, kWh 0.8
stocks. The process selectively removes aromatics and compounds con- Steam, barrels 8.1
taining heteroatoms (e.g., oxygen, nitrogen, sulfur). Water, cooling (25°F), gal 550
Products: A raffinate that may be dewaxed to produce a high- Installation: This process has been used in 13 licensed units to pro-
quality lube base oil, characterized by high viscosity index, good ther- duce high-quality lubricating oils. Presently, two new units that
mal and oxidation stability, light color and excellent additive response. will refine used oil are in the design stage. Of this number, eight are
The byproduct extracts, being high in aromatic content, can be used units converted from phenol or furfural, with another two units
in some cases for carbon black feedstocks, rubber extender oils and being planned for conversion from phenol.
other nonlube applications where this feature is desirable.
Licensor : Bechtel Corp
ucts, lower-oil-content waxes can be produced by the use of additional
Dichill Scraped Cold-wash solvent dewaxing and/or “warm-up deoiling” stages.
crystallizer(s) surface
Waxy feed chillers Dewaxing filters Description: DILCHILL is a novel dewaxing technology in which
1 or 2 stages wax crystals are formed by cooling waxy oil stocks, which have been
Warm-up
START
Wax slurry deoiling heater diluted with ketone solvents, in a proprietary crystallizer tower
Precoolers that has a number of mixing stages. This nucleation environment pro-
Fresh solvent vides crystals that filter more quickly and retain less oil. This tech-
Cold-wash Refrigeration nology has the following advantages over conventional incremental-
solvent system dilution dewaxing in scraped surface exchanges: less filter area is
required, less washing of the filter cake to achieve the same oil-in-
Deoiling filters wax content is required, refrigeration duty is lower, and scraped sur-
(2 stages) face chillers which means that unit maintenance costs are lower. No
wax recrystallization is required for deoiling.
Solvent Solvent Solvent Solvent Warm waxy feed is cooled in prechillers before it enters the
recovery recovery recovery
DILCHILL crystallizer tower. Cold solvents is then added in the
crystallizer tower under highly agitated conditions. Most of the crys-
Dewaxed oil Dewaxed wax “Foots oil” tallization occurs in the crystallizer tower. The slurry of wax/oil/ketone
is then further cooled in scraped surface chillers and the slurry is
then filtered in rotary vacuum filters. Flashing and stripping of prod-
Lube treating ucts recover solvent. Additional filtration stages can be added to
recover additional oil or produce low-oil-content waxes.
Application: Lube raffinates from extraction are dewaxed to pro- Economics: Depend on the slate of stocks to be dewaxed, the tar-
vide basestocks having low pour points (as low as –35°C). Basestocks get pour points and the target oil-in-wax content.
range from light stocks (60N) to higher viscosity grades (600N and
Bright Stock). Byproduct waxes can also be upgraded for use in Utilities: Depend on the slate of stocks to be dewaxed, pour point
food applications. targets and the required oil-in-wax content.
Feeds: DILCHILL dewaxing can be used for a wide range of stocks Installation: The first application of DILCHILL dewaxing was the
that boil above 550°F, from 60N up through Bright Stock. In addi- conversion of an Exxon affiliate unit on the U.S. Gulf Coast in 1972.
tion to raffinates from extraction, DILCHILL dewaxing can be Since that time, ten other applications have been constructed. These
applied to hydrocracked stocks and to other stocks from raffinate applications include both grassroots units and conversions of incre-
hydroconversion processes. mental dilution plants. Six applications use “warm-up deoiling”.
Processes: Lube basestocks having low pour points. Although Licensor: ExxonMobil Research & Engineering Co.
slack waxes containing 2–10 vol% residual oil are the typical byprod-
operation. Excess distillates are sent back to the hydrocracker.
Excess distillates Since the withdrawn UCO can usually be replaced with an equal
Lights to amount of additional fresh vacuum distillate feed, the hydrocracker
refinery fuels production is maintained. The hydrocracking and catalytic
dewaxing steps are not included in the Yukong UCO Lube Process,
Intermediate but are readily available from others.
storage
Properties:
Yukong
Unconverted oil (UCO) Catalytic Lube Solvent Lube UCO Lube
START
dewaxing products Test item Test method refining hydrocracking Process
Distillation
Viscosity @ 100°C, cSt ASTM D 445 5.2 5.1 6.0
Viscosity index ASTM D 2270 97 99 130
Pour point, °C ASTM D 97 -12 -12 -12
Hydrogen CCS vis @ -20°C, cP ASTM D 2602 2,100 2,000 1,440
Flash point, °C ASTM D 92 218 220 234
NOACK volatility, wt% DIN 51581 17.0 16.6 7.8
Lube treating Aromatics, wt%

Sulfur content, wt%
ASTM D 2549 27.7
ANTEC 0.58
3.5
0.03
1.0
0.00
Application: Unconverted oil from a fuels hydrocracker is used to Economics: Investment (Basis: 5,000 bpd of lube base oils exclud-
produce higher quality lube base stocks at lower investment and oper- ing fuels hydrocracker, 1998 U.S. Gulf Coast) $80 million.
ating costs than either solvent refining or lube oil hydrocracking uti-
lizing the Yukong UCO Lube Process. Installations: 3,500 bpd of VHVI lube base oils at SK Corporation’s
Ulsan refinery.
Description: The oils manufactured by the Yukong UCO Lube Pro-
cess have many desirable properties as lube base stocks over those References: Andre, J. P., S. H. Kwong and S. K. Hahn, “Yukong’s
produced by conventional solvent-refining or lube hydrocracking new lube base oil plant,” Hydrocarbon Engineering, November 1997.
processes. “An economical route to high quality lubricants,” Am-96-38, NPRA.
Unconverted oil from the existing fractionator in a fuels hydroc- Licensor: Washington Group International, Petroleum and
racker is processed and separated into grades having the desired vis- Chemicals Technology Center, under exclusive arrangement with
cosity, which are then cooled and sent to intermediate storage. The SK Corporation.
various grades of base oil are then catalytically dewaxed in blocked
leakage.
Heater load NOx Description: The technology involves the gas-phase reaction of NO
NH3 flow analyzer with NH3 (either aqueous or anhydrous) to produce elemental nitro-
Pressure controller gen if conditions are favorable. Ammonia is injected into the flue gas
controller using steam or air as a carrier gas into a zone where the temperature
is 1,600°F to 2,000°F. This range can be extended down to 1,300°F with
a small amount of hydrogen added to the injected gas. For most
Anhydrous NH3 Injectors applications, wall injectors are used for simplicity of operation.
storage Yield: Cleaned flue gas with 40% to 70%+ NO x reduction and less
NH3 Heater than 10-ppm NH3 slip.
Flow controller
vaporizer Economics: Considerably less costly than catalytic systems but rel-
Heater load atively variable depending on scale and site specifics. Third-party
studies have estimated the all-in cost at about 600 U.S.$/ton of NOx
Fuel removed.
Carrier supply Combustion air Installation: Over 135 applications on all types of fired heaters, boil-
ers and incinerators with a wide variety of fuels (gas, oil, coal, coke,
wood and waste).
NOx abatement Reference: McIntyre, A. D., “Applications of the THERMAL DeNOx
process to utility and independent power production boilers,” ASME
Application: Flue gases are treated with ammonia via ExxonMo- Joint International Power Generation Conference, Phoenix, 1994.
bil’s proprietary selective noncatalytic NO x reduction technology— McIntyre, A. D., “The THERMAL DeNO x process: Liquid fuels
Thermal DeNOx. NOx plus ammonia (NH3) are converted to ele- applications,” International Flame Research Foundation’s 11th Topic
mental nitrogen and water if temperature and residence time are Oriented Technical Meeting, Biarritz, France, 1995.
appropriate. The technology has been widely applied since it was first McIntyre, A. D., “Applications of the THERMAL DeNOx process
commercialized in 1974. to FBC boilers,” CIBO 13th Annual Fluidized Bed Conference, Lake
Products: If conditions are appropriate, the flue gas is treated to Charles, Louisiana, 1997.
achieve NOx reductions of 40% to 70%+ with minimal NH 3 slip or Licensor: ExxonMobil Research & Engineering Co.
oil plus solids) and a solids stream. MST is most readily applied to
sludges/emulsions that are less than 5% to 10% solids and have an
Emulsion breaking Emulsion separation oil-to-water ratio between 4 to 1 and 1 to 4.
system system
Wave guide Description: Sludge is fed from a holding tank at a temperature of
Oil 80°F to 150°F. Radio frequency microwave energy is applied to the emul-
Water sion to preferentially heat the water, facilitating separation by creat-
Either Solids ing differences in surface tension and viscosity of the constituent
Microwave Centrifuge phases. The destabilized emulsion typically exits the unit at a tem-
applicator perature between 180°F and 200°F. The emulsion can then be sepa-
Auto rated via centrifuging or gravity separation. Typically, the oil is recov-
Microwave Settling tank 2
power unit tuner ered and further processed, the water is sent to wastewater treatment
Pumps
Oil Oil and the solids are treated further or landfilled. Single units can be
Water Water designed for up to 4,000 bpd of feed. Higher rates can be handled by
Emulsion placing several units in parallel. The units are compact and can be skid
Solids Solids
Incoming receiving tank or trailer mounted. They are simple to operate (with remote monitoring
Settling tank Settling tank and checking during operator rounds) and require low maintenance.
emulsion 1 2
Economics: MST units are typically leased at fees of 1 to 2 U.S.$/bbl
of sludge treated. Leasee pays for site prep and utilities. The major
utility is electric power and is less than 100 watts/bpd of sludge.
Oily waste treatment Installation: MST is in commercial operation at ExxonMobil’s Tor-
Application: Oily sludges/emulsions are treated with microwave rance, California, refinery.
energy to preferentially heat the water and destabilize the emulsion.
Microwave separation technology (MST) enables more rapid sepa- Reference: Albinson, K. R., C. H. Hsai, T. R. Melli, and G. L. Wool-
ration of the emulsion into its three constituent phases via cen- ery, “Microwave Separation Technology (MST),” AIChE Spring Meet-
trifuging or gravity separation. ing, Atlanta, 2000.
Products: Destabilized emulsion that can typically be separated into Licensor: Imperial Petroleum Recovery Corp./ExxonMobil Research
an oil-rich phase (1% to 5% BS&W), a water-rich phase (1% to 2% & Engineering Co.
sources are first dehydrated by molecular sieve (1). The expander/com-
Residue gas pressor (2a) compresses the gas stream, which is then cooled by
to fuel heat exchange with internal process streams (3). Depending on the
Expander C3 richness of the feed gas, supplemental refrigeration (4) may be used
Inlet heat to further cool the gas stream prior to primary vapor/liquid separa-
2b
3 exchanger tion (5). Light gases are fed to a turboexpander (2b) where the pres-
sure is reduced resulting in a low discharge temperature. The
expander discharge is fed to the bottom of the LEFC (6). The HEFC
HEFC (7) overhead is cooled and fed to the top of the LEFC. The recovered
2a Expander 7
6 propylene and heavier liquid stream exit the bottom of the HEFC (7).
compressor C3 5 Process advantages include:
Condensate • Low capital cost
1 Cold LEFC • High propylene recovery (up to 99%)
separator Stm. • Low energy usage
Inlet gas
from • Small footprint—can be modularized
dehydration • Simple to operate
Liquid product • Wide range of turndown capability.
Economics: Typically, the payback time for plant investment is one
to two years.
Olefins recovery Installation: Sixteen plants operating in U.S. refineries, with two
under construction. The first plant was installed in 1984.
Application: Pro-Quip’s Cryo-Plus process recovers propylene and
heavier components from refinery offgas streams. Typical applica- References: Buck, L., “Separating Hydrocarbon Gases,” U.S. Patent
tions are on cat crackers, cokers or reformers downstream of the exist- No. 4,617,039, Oct. 14, 1986.
ing gas-recovery systems. Incremental valuable hydrocarbons that Key, R., and Z. Malik, “Technology advances improve liquid recov-
are currently being lost to the refinery fuel system can now be eco- ery from refinery offgases,” NPRA Annual Meeting, San Antonio,
nomically recovered. paper AM-00-06, March 26–28, 2000.
Description: Refinery offgases from cat crackers, cokers or other Licensor: Pro-Quip Corp, a subsidiary of Linde A.G.
yield. The hydrocarbons are further cleaned by cyclones before they are
Number 2 flue gas transferred to fractionation. Regeneration in two stages (3, 4) with pro-
Second-stage prietary air rings and catalyst distribution systems results in very clean
regenerator catalyst with a minimum of hydrothermal deactivation, plus superior
metals tolerance relative to single-stage regenerator systems. These ben-
Product vapors
efits are derived by operating the first-stage regenerator in a partial-
Withdrawal well Riser termination device burn mode, the second-stage regenerator in a full combustion mode and
4
both regenerators in parallel with respect to air and flue gas flows. This,
Air ring 2 Vapor quench in turn, results in lower air requirements and two smaller regenera-
Number 1 flue gas Reactor tor vessels compared to one large regenerator vessel.
Stripper Maximum production of more desirable products can be achieved with
First-stage regenerator 1 Reactor riser the proprietary Mixed Temperature Control (MTC) system (5). Heat
removal for heavier feedstocks (above 6 CCR) is accomplished by the
5 MTC system use of a reliable dense-phase catalyst cooler which has been com-
Air ring
3 Gas oil or resid. feed mercially proven and is licensed exclusively by Stone & Webster/IFP.
Lift air START
The converter vessels use a cold-wall design that results in minimum
capital investment and maximum mechanical reliability and safety.
Cracking operation makes use of advanced fluidization technology
combined with a proprietary reaction system. Unit design is tailored
Resid catalytic cracking to refiner’s needs and can include wide turndown flexibility. Available
options include power recovery in addition to waste-heat recovery.
Application: Selective conversion of gas oil and heavy residual
feedstocks. Existing gas oil units can be easily retrofitted to this technology.
Revamps incorporating proprietary feed injection and riser termi-
Products: High-octane gasoline, distillate and C3–C4 olefins. nation devices and vapor quench result in substantial improve-
Description: Catalytic and selective cracking occurs in a short-con- ments in capacity, yields and feedstock flexibility within the mechan-
tact-time riser (1) where oil feed is effectively dispersed and vaporized ical limits of the existing unit.
through a proprietary feed injection system. Operation is carried out Installation: Stone & Webster has licensed 26 full-technology units
at a temperature consistent with targeted yields. Reaction products and performed more than 100 revamp projects.
exit the riser-reactor through a high-efficiency, proprietary riser ter-
mination device; (2) spent catalyst that has not been cooled is pre- Reference: Letzsch, W. S., “Commercial performance of the latest
stripped and flows through a rapid preliminary stripping section, fol- FCC technology advances,” paper AM-00-07, NPRA Annual Meeting,
lowed by a high-efficiency baffled stripper prior to regeneration. March 2000.
Only the vapor products are quenched using Amoco’s proprietary Licensor: Stone & Webster Inc., a Shaw Group Co., and Institut
quench technology to give the lowest dry gas and maximum gasoline Français du Pétrole
the synthetic vacuum gasoil into distillates, can be efficiently inte-
Fresh gas grated into the unit. A wide range of residue feeds, like atmospheric
or vacuum residues and deasphalted oils, can be processed using Shell
residue hydroprocessing technologies.
Operating conditions:
Cat. Cat. Cat. Quench gas to reactors Reactor pressures: 100 –200 bar
1,450 –3,000 psi
Reactor temperatures: 370 –420°C
700 –790°F
HHPS CHPS
Yields: Typical yields for an SR HYCON unit on Kuwait feed:
SR with
CLPS Feedstock (95% 520C+) integrated HCU
HLPS Yields: [%wof] [%wof]
Gases C1 – C4 3 5
Cat. Cat. Cat. C5 – 165°C
START
Feed To fractionator Naphtha 4 18
HDM section HCON section Kero + gasoil 165 – 370°C 20 43
VGO 370 – 580°C 41 4
Residue 580°C+ 29 29
H2 cons. 2 3
Residue hydroprocessing Economics: Investment costs for the various options depend strongly
on feed properties and process objectives of the residue hydroprocessing
Application: Produces maximum distillates and low-sulfur fuel oil,
unit. Investment costs for a typical new single string 5,000 tpsd SR-
or low-sulfur LR-CCU feedstock, with very tight sulfur, vanadium and
Hycon unit will range from 200–300 MM US $, the higher figure
CCR specifications, using moving bed “bunker” and fixed-bed tech-
includes an integrated hydrocracker.
nologies. Bunker units are available as a retrofit option to existing
fixed-bed residue HDS units. Installation: There is one unit with both bunker reactors and fixed-
bed reactors, operating on short residue (vacuum residue) at 4,300 tpd
Description: At limited feed metal contents, the process typically or 27 kbpsd capacity, and two all-fixed bed units of 7,700 and 7,000 tpd
uses all fixed-bed reactors. With increasing feed metal content, one (48 and 44 kbpsd resp.), the latter one in one single string. Commer-
or more moving-bed “bunker” reactors are added up-front of the cial experiences range from low-sulfur atmospheric residues to high-
fixed-bed reactors to ensure a fixed-bed catalyst life of at least one metal, high-sulfur vacuum residues with over 300 ppmw metals.
year. A steady state is developed by continuous catalyst addition and
withdrawal: the catalyst aging is fully compensated by catalyst Reference: Scheffer, B., et al, “The Shell Residue Hydroconversion
replacement, at typically 0.5 to 2 vol% of inventory per day. Process: Development and Achievements,” The European Refining
An all bunker option, which eliminates the need for catalyst Technology Conference, London, November 1997.
change-out, is also available. A hydrocracking reactor, which converts Licensor: Shell Global Solutions International B.V.
trolled by the operating temperature and pressure. The soaker efflu-
ent is routed to a cyclone (3). The cyclone overheads are charged to
Gas an atmospheric fractionator (4) to produce the desired products
Naptha including a light waxy distillate. The cyclone and fractionator bot-
toms are routed to a vacuum flasher (6), where waxy distillate is recov-
ered. The combined waxy distillates are fully converted in the dis-
4 Steam Gasoil tillate heater (5) at elevated pressure.
Yields: Depend on feed type and product specifications.
Feed atmospheric residue Middle East
Waxy Viscosity, cSt @ 100°C 31
3 5 distillate Products in % wt. on feed
6 Gas 6.4
2 Steam Gasoline ECP 165°C 12.9
Gasoil ECP 350°C 38.6
Vacuum flashed Residue ECP 520°C+ 42.1
Charge 1
cracked residue Viscosity 165°C plus, cSt @100°C 7.7
Economics: The investment amounts to 1,400–1,600 U.S.$/bbl
installed excluding treating facilities and depending on capacity
and configuration (basis: 1998)
Thermal gasoil process Utilities, typical per bbl @ 180°C:
Application: The Shell Thermal Gasoil process is a combined Fuel, Mcal 34
residue and waxy distillate conversion unit. The process is an attrac- Electricity, kWh 0.8
tive low-cost conversion option for hydroskimming refineries in Net steam production, kg 29
gasoil-driven markets or for complex refineries with constrained Water, cooling, m3 0.17
waxy distillate conversion capacity. The typical feedstock is atmo-
Installation: Eight Shell thermal gasoil units have been built and
spheric residue, which eliminates the need for an upstream vacuum
are in operation. Post startup services and technical services on
flasher. This process features Shell Soaker Visbreaking technology
existing units are available from Shell.
for residue conversion and an integrated recycle heater system for
the conversion of waxy distillate. Reference: “Thermal Conversion Technology in Modern Power
Description: The preheated atmospheric (or vacuum) residue is Integrated Refinery Schemes,” 1999 NPRA Annual Meeting.
charged to the visbreaker heater (1) and from there to the soaker (2). Licensor: Shell International Oil Products B.V., and ABB Lummus
The conversion takes place in both the heater and soaker and is con- Global B.V
• Low capital cost
Air • Small sized equipment and low space requirement
Catalyst in (batch) • Low pressure drop
Jet fuel • Can be retrofitted into existing systems or skid mounted for easy
system installation
Re-
START
4 5 • Low guaranteed aqueous carryover.

cycle
Recycle Recycle AQUAFINING FIBER-FILM Technology uses water to remove
amines and caustic contaminants from hydrocarbon streams.
1 THIOLEX FIBER-FILM Technology removes H2S, COS and mer-
LC LC 3 Jet fuel captans from gas, LPGs, butanes and gasolines with caustic.
LC 2
AMINEX FIBER-FILM Technology removes H2S, COS and CO 2
from gas, LPGs and butanes with amines.
THIOLEX coupled with REGEN Technology, a caustic regeneration
process, is used for mercaptan extraction with minimal caustic con-
M Water in sumption. One or more stages of caustic extraction are used to remove
Caustic out M
mercaptans from gas, LPGs, butanes and gasolines. The catalyst con-
Water out taining caustic solution then is sent to a tower for regeneration with
Caustic in
air. The disulfides formed are either gravity separated and/or solvent
extracted. The regenerated solution is then reused in the extraction unit.
MERICAT FIBER-FILM Technology uses a catalyst-containing
Treating caustic solution and air to oxidize mercaptans to disulfides in
gasolines.
Application: Treating gas, LPGs, butanes, gasolines, kerosines MERICAT II FIBER-FILM Technology sweetens kerosine/jet fuel
and diesels with caustic, amines, water and acid using FIBER-FILM by combining Mericat with a catalyst impregnated carbon bed.
technology. NAPFINING FIBER-FILM Technology uses caustic to reduce the
acidity of kerosines/jet fuel and heavier middle distillates.
Description: A proprietary FIBER-FILM Contactor is used in aque-
CHLOREX FIBER-FILM Technology uses dilute caustic to remove
ous treating processes to achieve intimate, co-current contacting
HCl and NH4Cl from reformer gas and liquid products.
between the hydrocarbon feed and aqueous solution. The FIBER- ESTEREX FIBER-FILM Technology uses sulfuric acid to remove
FILM Contactor is comprised of a bundle of long, continuous, small neutral and acidic esters from alkylation reactor effluent streams.
diameter fibers contained in a cylinder. The aqueous solution coats MERICON oxidizes and/or neutralizes spent caustics containing
the surface of the fibers while the hydrocarbon stream flows as a con- sulfides, mercaptans, naphthenic acids and phenols.
tinuous phase through the fiber bundle, coming into intimate con-
tact with the solution adhering to the fiber surface. The large inter- Installation: Approximately 500 installations treating 5.0 million
facial area created by the contactor greatly enhances mass transfer bpsd and 21 MMscfd in 37 countries.
without dispersion of one phase into the other as is necessary for typ-
ical conventional mixing systems. Process advantages include: Licensor: Merichem Co.
Operating conditions: Typical ranges are:
Gas Heater outlet temperature, °F 850–910
Quenched temperature, °F 710–800
An increase in heater outlet temperature will result in an increase
in overall severity.
Yields:
Gasoline Feed, source Light Arabian Light Arabian
Reduced 1 2 Type Atm. resid Vac. resid
crude charge Gravity, °API 15.9 7.1
Sulfur, wt% 3.0 4.0
START Steam Concarbon, wt% 8.5 20.3
Viscosity, CKS @ 130°F 150 30,000
Gas oil CKS @ 210°F 25 900
Products, wt%
Tar Gas 3.1 2.4
Naphtha (C5–330°F) 7.9 6.0
Gas oil (330–600°F) 14.5 15.5(1)
Visbroken resid (600°F+) 74.5 76.1(2)
(1) 330–662°F cut for Light Arabian vacuum residue
Visbreaking (2) 662°F+ cut for Light Arabian vacuum residue
Economics:
Application: Manufacture incremental gas and distillate products
Investment (basis: 40,000 –10,000 bpsd, 4th Q, 1999, U.S. Gulf),
and simultaneously reduce fuel oil viscosity and pour point. Also, $ per bpsd 785 –1,650
reduce the amount of cutter stock required to dilute the resid to meet Utilities, typical per bbl feed:
the fuel oil specifications. Foster Wheeler/UOP offer “coil” type vis- Fuel, MMBtu 0.1195
breaking process. Power, kW/bpsd 0.0358
Products: Gas, naphtha, gas oil, visbroken resid (tar). MP steam, lb 6.4
Water, cooling, gal 71.0
Description: In a “coil” type operation, charge is fed to the visbreaker
heater (1) where it is heated to a high temperature, causing partial Installation: Over 50 units worldwide.
vaporization and mild cracking. The heater outlet stream is quenched Reference: Handbook of Petroleum Refining Processes, 2nd Ed.,
with gas oil or fractionator bottoms to stop the cracking reaction. The McGraw-Hill, 1997, pp. 12.83–12.97.
vapor-liquid mixture enters the fractionator (2) to be separated into
gas, naphtha, gas oil and visbroken resid (tar). Licensor: Foster Wheeler USA Corp./UOP LLC.
version level and/or unit capacity. The cracked feed is then charged
Gas to an atmospheric fractionator (3) to produce the desired products like
gas, LPG, naphtha, kerosine, gas oil, waxy distillates and cracked
residue. If a vacuum flasher is installed, additional gas oil and waxy
distillates are recovered from the cracked residue.
3 Naphtha Yields: Vary with feed type and product specifications.
Feed, vacuum residue Middle East
Steam Gas oil Viscosity, cSt @100°C 770
2 Products, wt%
Residue
charge Steam Vacuum system Gas 2.3
Gasoline, 165°C EP 4.7
START Vacuum gas oil Gas oil, 350°C EP 14.0
1
Visbroken residue Waxy distillate, 520°C EP 20.0
4 Residue, 520°C+ 59.0
Viscosity, 165°C plus, cSt @100°C 97
Cutter stock
Economics:
The investment amounts to 1,000 to 1,400 U.S.$/bbl installed
excluding treating facilities and depending on capacity and the
presence of a vacuum flasher (basis: 1998).
Visbreaking Utilities, typical consumption per bbl feed @180°C:
Application:The Shell Soaker Visbreaking process is most suitable Fuel, 103 kcal 16
to reduce the viscosity of vacuum (and atmospheric) residues in Electricity, kWh 0.5
(semi) complex refineries. The products are primarily distillates Net steam production, kg 18
and stable fuel oil. The total fuel oil production is reduced by decreas- Water, cooling, m3 0.1
ing the quantity of cutter stock required. Optionally, a Shell vacuum Installation: 70 Shell Soaker Visbreakers have been built or are cur-
flasher may be installed to recover additional gas oil and waxy dis- rently under construction. Post startup services and technical ser-
tillates as cat cracker or hydrocracker feed from the cracked residue. vices for existing units are available from Shell.
The Shell Soaker Visbreaking technology has also proven to be a very
cost-effective revamp option for existing units. Reference: Visbreaking Technology, Erdöl und Kohle, January
1986.
Description: The preheated vacuum residue is charged to the vis-
breaker heater (1) and from there to the soaker (2). The conversion Licensor: Shell Global Solutions International B.V. and ABB Lum-
takes place in both the heater and the soaker. The operating tem- mus Global B.V.
perature and pressure are controlled such as to reach the desired con-

Hydrocarbon Processing Refining Processes 2000 (2001)

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Hydrocarbon Processing Refining Processes 2000 (2001)

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Hydrocarbon Processing ®

Thermal gas oil process

GULF PUBLISHING COMPANY

ABB Lummus Global Inc.

Chevron Research and Technology Co.

Haldor Topsøe A/S

Kellogg Brown & Root, Inc. continued

Shell Global Solutions International B.V. continued

UOP LLC continued

GULF PUBLISHING COMPANY

i-Butane Product quality: The total debutanized alkylate has RON of 92 to

Alkylation feed preparation Economics:

Aromatics extractive Quality

Benzene 10 wt ppm NA*

Reactors Yields: Depend on feed characteristics, product octane and reactor

Catalytic reforming Economics:

Application: Separates and recovers the relatively lighter frac- Economics:

S-1 of existing solvent deasphalting units.

Deep catalytic cracking wt% FF

Deep thermal conversion Utilities, typical per bbl @ 180°C

Ethers Economics: Based on a 1,500-bpsd MTBE unit, (6,460-bpsd C4s ex-

Hydrocracking Product qualities:

Hydrocracking/ Investment in $ per bpsd

Fuel, 103 Btu

Hydrotreating Operation conditions: Typical operating pressures range from 20

1 Operating conditions: The Ipsorb Isom process uses a deisopen-

Lube treating Aromatics, wt%

4 5 • Low guaranteed aqueous carryover.

Visbreaking (2) 662°F+ cut for Light Arabian vacuum residue

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