Segment 3

Petrochemical Processes

PROCESS INDEX Methanol 297, 298, 299, 300

Methylamines 300
Acetic acid 271 Mixed xylenes 301
Acrylonitrile 271 Octenes 302
Alkylbenzene, linear 272 Olefins 303, 304
Alpha olefins, linear 272 Paraffin, normal 304
Ammonia 273, 274 Paraxylene 305, 306
Phenol 307
Ammonia, KBR purifier 275 Phthalic anhydride 307
Aniline 275 Polyalkylene terephthalates—PET, PBT, PTT, PEN 308
Aromatics extraction 276 Polycaproamide 308
Aromatics extractive distillation 276 Polyesters (polyethylene terephthalate) 309
Benzene 277 Polyethylene 309, 310, 311, 312
Bisphenol-A 277 Polyethylene, HDPE 313
BTX aromatics 278, 279 Polyethylene, LDPE 313
Butadiene extraction 280 Polypropylene 314, 315, 316, 317
Butanediol, 1,4- 280, 281 Polystyrene 318
Butene-1 281 Propylene 319, 320, 321
Butyraldehyde, n and i 282 Propylene—Methanol fo propylene (MTP) 321
Caprolactam 282 PVC (suspension) 322
Cumene 283, 284 Styrene 323, 324
Cyclohexane 284 Terephthalic acid 324, 325
Dimethyl terephthalate 285 Urea-formaldehyde 325
Dimethylformamide 285 VCM removal 326
EDC via oxygen lean oxychlorination 286 m-Xylene 326
Ethanolamines 286 Xylene isomerization 327
Ethyl acetate 287
Ethylbenzene 287, 288
Ethylene 289, 290, 291, 292 LICENSOR INDEX
Ethylene feed pretreatment—mercury, arsenic
and lead removal 293 ABB Lummus Global 277, 278, 283, 287, 288, 289,
Ethylene glycol 293, 294 297, 318, 319, 323
Ethylene oxide 295, 296 Axens 272, 278, 281, 284, 293, 301, 302, 305, 319, 327
Formaldehyde 296 Axens NA 272, 281, 284, 293, 301, 302, 305, 319, 327
Maleic anhydride 297 Basell Polyolefins 309, 313, 314

269
270 SEGMENT 3. PETROCHEMICAL PROCESSES

BASF AG 307 Lurgi Oel Gas Chemie GmbH. 281, 298, 307, 320, 321,
Borealis A/S 310, 315 324, 325
BP 310, 316 Mitsubishi Chemical Corp. 277
BP Chemicals 281, 318 Mitsui Chemicals, Inc. 312, 317
CDTECH 283, 287 Niro Process Technology B.V. 306, 326
Chevron Phillips Chemical Co., LP 311 Novolen Technology Holdings C.V. 314
Chisso Corp. 316, 322, 326 Research Institute of Petroleum Processing, Sinopec 304
Chiyoda Corp. 271 Scientific Design Co., Inc. 294, 295
Davy Process Technology 280, 282, 285, 286, 287, 297 Shell International Chemicals B.V. 294, 296
Dow Chemical Co. 282, 293, 295, 317 SNAICO Engineering S.p.A. 282
ExxonMobil Chemical Co. 301, 305, 311, 327 SNIA BPD S.p.A. 282
Fina Technology Co. 324 Stone and Webster, Inc. 290, 304
GTC Technology Inc. 278, 285, 323 Synetix 297
Haldor Topsøe A/S 273, 296, 299, 300 Technip-Coflexip 291, 292
Hydro 303 Uhde GmbH 274, 276, 286, 298, 302, 303, 322
INVENTA-FISCHER 308, 309, 325 Union Carbide Corp. 293, 295
Kellogg Brown & Root, Inc. 271, 274, 275, 280, 289, Univation Technologies 312
304, 320 UOP LLC 272, 279, 283, 288, 292, 303, 306, 321
Linde AG 273, 290 Vin Tec GmbH 286, 322
Lonza S.p.A. 297 Washington Group International, Inc. 284, 288, 306,
324, 326
 SEGMENTS. PETROCHEMICAL PROCESSES 271

Acetic acid AeryIonitriIe

Application: To produce acetic acid using the process, ACETICA. Application: A process to produce high-purity acrylonitrileand high-
Methanol and carbon monoxide (CO) are reacted with the carbonylation purity hydrogen cyanide from propylene, ammonia and air. Recovery of
reaction using a heterogeneous Rd catalyst. byproduct acetonitrile is optional.
Description: Fresh methanol is split into two streams and is contacted Description: Propylene, ammonia, and air are fed to a fluidized bed
with reactor o@as in the high-pressureabsorber (7) and light gases in the reactor to produce acrylonitrile (ACRN) using DuPont’s proprietary
low-pressure absorber (8). The methanol, exiting the absorbers, are catalyst system. Other useful products from the reaction are hydrogen
recombined and mixed with the recyde liquid from the recyde-surge drum cyanide (HCN) and acetonitrile (ACE). The reaction i s highly exother-
(6).This stream is charged to a unique bubble-column reactor (1). mic and heat is recovered from the reactor by producing high-pressure
Carbon monoxide is compressed and sparged into the reactor riser. steam. The reactor effluent is quenched and neutralized with a sulfuric
The reactor has no mechanical moving parts, and is free from leak- solution to remove the excess ammonia.
agelmaintenance problems. The ACETICA Catalyst is an immobilized Rd- The product gas from the quench is absorbed with water to recover the
complex catalyst on solid support; it offers higher activity and operates ACRN, HCN, and ACE. The aqueous solution of ACRN, HCN, and
under less water condition in the system due to heterogeneous system. ACE is then fractionated and purified into high-quality products. The
Result: the system is much less corrosivity. products’ recovery and purification is a highly efficient and low-energy con-
Reactor effluent liquid is withdrawn and flash-vaporized in Flash Col- sumption process. This ACRN technology minimizes the amount of
umn (2) to remove the net acetic acid product and reject the C O dis- aqueous effluent, a major consideration for all acrylonitrile producers.
solved in the liquid. The crude acetic acid is sent to the dehydration tower This ACRN technology is based on a high-activity, high-throughput
(3) to remove the remaining water and any residual organic materials. catalyst. The propykne conversion is 99% with a selectivity of 85% to use-
Dried acetic acid is routed to the finishing column (4), where heavy ful products ofACRN, HCN, and ACE. The DuPont catalystis a mechan-
byproducts are removed in the bottom draw off.The finished acetic-acid ically superior catalyst, resulting in a low catalyst loss. DuPont has devel-
product is treated to remove color bodies. oped a Catalyst Bed Management Program (CBMP) to maintain the
Vapor streams from the flash vessel and dehydration column over- properties of the catalyst bed inside the reactor at optimal performance
head are combined and contacted with methanol in the low-pressure throughout the operation. The catalyst properties, the CBMP and pro-
absorber. Unconverted CO, methane, acetaldehyde, other light byprod- prietary reactor internals provide an optimal performance of the ACRN
ucts exiting in the vapor outlets of the high- and low-pressureabsorbers reactor, resulting in high yields.
and heavy byproducts from the finishing column are sent to the inciner- With over 30 years of operating experience, DuPont has developed
ator (9) and flue-gas scrubber (10). know-how to increase the onstream factor of the plant. This know-how
indudes the effective use of inhibitors to reduce the formation of cyanide
Economics:The Gulf Coast ISBL cost is estimated as US$94.1 mil- and nitrile polymers and effective application of an antifoulant system
lion for a 200,000-mtpy: to increase onstream time for equipment.
Feed and utility consumption: Commercial plants: DuPont Chemical Solution Enterprise, Beau-
Methanol, mumt 0.539
CO,mt/mt 0.517 mont, Texas (200,000 mtpy).
Power ( K OSupply 0 WG), kWh/mt 129 Licensor: Kellogg Brown & Root, Inc.
Water, cooling, m3/mt 137
Steam QIOOpsig, mVmt 1.7
Commercial plant: Contract for license and preparation of basic
design package has been signed for a Chinese d e n t on September 2002.
Reference: “The ChiyoddUOP ACETICA process for the produc-
tion of acetic acid,” 8th Annual Saudi-JapaneseSymposium on Catalysts
in Petroleum Refining and Petrochemicals, KFWM-RI, Dhahran, Saudi
Arabia, Nov. 29-30, 1998.
Elsevier, “Recent advances in process and catalysts for the production
of acetic acid,”Applied Catalysr:Indwtrial Catabtic Processes, Vol. 221,l-2,
2001, p. 253.
Licensor: Chiyoda Corp.
 272 SEGMENT 3. PETROCHEMICAL PROCESSES

Alkylbenzene, linear Alpha olefins, linear

Application: To produce linear alkylbenzene (LAB) from Cl0to CI4 Application: To produce hi&-purity alpha olefins (C4-CIo) suitable
linear paraffins by alkylating benzene with olefins made by the Pacol dehy- as copolymers for LLDPE production and as precursors for plasticizer alco-
drogenation and the DeFine selective hydrogenation processes. The alky- hols and polyalphaolefins using the AlphaSelect process.
lation reaction is carried out over a solid, heterogeneous catalyst in the
Detal process unit. Description: Polymer-grade ethylene is oligomerized in the liquid-
phase reactor (1) with a catalystlsolvent system designed for high activ-
Description: The Pacol reactor (1) dehydrogenates the feed into cor- ity and selectivity. Liquid effluent and spent catalyst are then separated
responding linear olefin. Reactor effluent is separated into gas and liq- (2); the liquid is distilled (3) for recycling unreacted ethylene to the
uid phases in a separator (2). Diolefins in the Pacol separator liquid are reactor, then fractionated (4) into high-purity alpha-olefins. Spent cata-
selectivelyconverted back to mono-olefins in the DeFine reactor (3).Light lyst is treated to remove volatile hydrocarbons and recovered. The table
ends are removed from the reactor effluent in a stripper (4). The olefin- below illustrates the superior purities attainable (wt%) with the Alpha-
paraffin mixture is then alkylated with benzene in the M - b e d Detal reac- Select process:
tor (5). Product from the reactor flows to the fractionationsection (6) for
n-Butene-1 >99
separation and recycle of unreacted benzene to the reactor, and unreacted n-Hexene-1 >98
paraffins are separated (7) and recycled to the Pacol section. A rerun col- n-Octene-1 >96
umn (8) separates the LAB product from the heavy alkylate bottoms n-Decene-1 s92
stream.
An exisiting LAB producer can increase production by using UOP's The process is simple;it operates at mild operating temperatures and pressures
new Pacol catalyst or by adding a PEP unit to remove aromatics and and only carbon steel equipment is required. The catalyst is nontoxic and easily
increase the alkylation reaction efficiency. handled.
The process is nonpolluting. No process waste streams are produced. Yields: Yields are adjustable to meet market requirements and very lit-
The catalysts used are noncorrosive and require no special handling. tle high boiling polymer is produced as illustrated:
Yields: Based on 100 weight parts of LAB, 81 parts of linear paraffins Alpha-olefin product distribution, wtoh
and 34 parts of benzene are charged to process. The LAB product has a
typical Bromine Index of less than 10 and is 99% sulfonable. n-Butene-1 33-43
n-Hexene-1 30-32
Economics: US Gulf Coast battery limits for the production of n-Octene-I 17-2 1
80,000 tpy of LAB: n-Decene-1 9-1 4

Investment, $/tpy 650

Economics:Typical case for a 2002 ISBL investment at a Gulf Coast
vpical utilities consumption, per metric ton of LAB: location producing 65,000 tpy of C&
,, alpha-olefins is:
Catalysts and chemicals, $ 17
Power, kWh 287 Investment, million US$ 36
Water, cooling, m3 12 Raw material
Fuel fired, lo6 kcal 4.2 Ethylene, tons per ton of product 1.15
Commercial plants: Twenty-five LAB complexes based on the Byproducts, tonlton of main products
CI2+olefins 0.1
Pacol process are in operation. Three of these complexes use the Detal Fuel gas 0.03
process. Heavy ends 0.02
Reference:Banerji, A., et al., Growth and Developments in LAB Tech- Utilities cost, US$/ton product 51
nobgies: 30 Years of Innovation andMore to Come, 1993 World Surfac- Catalyst + chemicals, US$/ton product 32
tant Congress, Montreaux, Switzerland, September 1993.
Commercial plants: The AlphaSelect process is strongly backed by
Licensor: UOP LLC. extensive Axens industrial experience in homogeneous catalysis, in par-
ticular, the Alphabutol process for producing butene-l for which there
are 20 units producing 318,000 tpy.
Licensor: h e n s , Axens NA.
 SEGMENTS. PETROCHEMICAL PROCESSES 273

product

Ammonia Ammonia
Application: To produce ammonia from a variety of hydrocarbon feed- Application: The Linde ammonia concept (LAC) produces ammo-
st& ranging from natural gas to heavy naphtha using Topsoe’s low-energy nia from light hydrocarbons. The process is a simplified route to ammo-
ammonia technology. nia, consisting of a modern hydrogen plant, standard nitrogen unit and
a high-efficiency ammonia synthesis loop.
Description: Natural gas or another hydrocarbon feedstock is com-
pressed (if required), desulfurized, mixed with steam and then converted Description:Hydrocarbon feed is preheated and desulfurized (1).
into synthesis gas. The reforming section comprises a prereformer (optional, Process steam, generated from process condensate in the isothermal shift
but gives particular benefits when the feedstock is higher hydrocarbons or reactor ( 5 ) is added to give a steam ratio of about 2.7; reformer feed is
naphtha), a fired tubular reformer, and a secondary reformer, where pro- further preheated (2). Reformer (3) operates with an exit temperature
cess air is added. The amount of air is adjusted to obtain an H2/Nz ratio of 850°C.
of 3.0 as required by the ammonia synthesis reaction. The tubular steam Reformed gas is cooled to the shift inlet temperature of 250°C by
reformer is Topsoe’s proprietary side-wall-fired design. After the reform- generating steam (4).The C O shift reaction takes place in a single stage
ing section, the synthesis gas undergoes high- and low-temperature shift in the tube-cooled isothermal shift reactor (5), where process steam is
conversion, carbon dioxide removal and methanation. generated from condensate. No process condensate effluent from the
Synthesis gas is compressed to the synthesis pressure, typically ranging LAC plant is generated, thus eliminating a condensate treatment system.
from 140 to 220 kglcm’g and converted into ammonia in a synthesis After hrther heat recovery, final cooling and condensate separation (6),
loop using radial flow synthesis converters, either the two-bed S-200, the the gas is sent to the pressure swing adsorption (PSA) unit (7). Loaded
three-bed S-300, or the S-250 concept using an S-200 converter followed adsorbers are regenerated isothermally using a controlled sequence of
by a boiler or steam superheater, and a one-bed S-50 converter. Ammo- depressurization and purging steps.
nia product is condensed and separated by refrigeration. This process lay- Nitrogen is produced by the low-temperature air separation in a cold box
out is flexible, and each ammonia plant will be optimized for the local (10).Air is filtered, compressed and pursed before being supplied to the cold
conditions by adjustment of various process parameters. Topsoe supplies box. Pure nitrogen product is further compressed and mixed with the hydro-
all catalysts used in the catalytic process steps for ammonia production. gen to give a pure ammonia synthesis gas. The synthesis gas is compressed
Features, such as the inclusion of a prereformer, installation of a ring- to ammonia-synthesispressure by the syngas compressor (1 I), which also
type burner with nozzles for the secondary reformer and upgrading to recycles unconverted gas through the ammonia loop. Pure syngas elimi-
an S-300 ammonia converter, are all features that can be applied for exist- nates the loop purge and associatedpurge gas treatment system.
ing ammonia plants. These features will ease maintenance and improve The ammonia loop is based on the Ammonia Casale axial-radial three-
plant efficiency. bed converter with internal heat exchangers (13), giving a high conversion.
Heat from the ammonia synthesis reaction is used to generate H P steam
Commercial plants: More than 60 plants use the Topsoe process (14),preheat feed gas (12) and the gas is then cooled and refrigerated to
concept. Since 1990, 50% of the new ammonia production capacity has separate ammonia product ( 1 5). Unconverted gas is recycled to the syn-
been based on the Topsoe technology. Capacities of the plants con- gas compressor (1 1) and ammonia product chilled to -33°C (16) for
structed within the last decade range from 650 mtpd up to 2,050 mtpd storage. Utility units in the LAC plant are the power-generation system
being the worlds largest ammonia plant. Design of new plants with (17), which provides power for the plant from H P superheated steam,
even higher capacities are available. BFW purification unit (18) and the refrigeration unit (19).
Licensor: Haldor Topsoe A / S . Economics: Simplification over conventional processes gives impor-
tant savings such as: investment, catalyst-replacement costs, mainte-
nance costs, etc. Total feed requirement (process feed plus fuel) is approx-
imately 7 GcaVmetric ton (mt) ammonia (25.2 MMBtdshort ton)
depending on plant design and location.
Commercial plants:The first complete LAC plant, for 1,350-mtd
ammonia, has been built for GSFC in India. Two other LAC plants, for
230- and 600-mtd ammonia, are under construction in Australia. There
are extensive reference lists for Linde hydrogen and nitrogen plants and
Ammonia Casale synthesis systems.
References: “A Combination of Proven Technologies,” Nitrogen,
March-April 1994.
Licensor: Linde AG.
274 SEGMENT 3. PETROCHEMICAL PROCESSES

W \L J

Ammonia Amm6i a, KAAPplus

Application: To produce ammonia from natural gas, LNG, LPG or Application: To produce ammonia from hydrocarbon feedstocks
naphtha. Other hydrocarbons-coal, oil, resides or methanol pure gas- using a high-pressure heat exchange-based steam reforming process inte-
are possible feedstocks with an adapted front-end. The process uses con- grated with a low-pressure advanced ammonia synthesis process.
ventional steam reforming synthesis gas generation (front-end) and a
medium-pressure ammonia synthesis loop. It is optimized with respect
Description:The key steps in the KAAPpbs process are reforming
to low energy consumption and maximum reliability. The largest single- using the KBR reforming exchanger system (KRES), cryogenic purifi-
train plant built by Uhde has a nameplate capacity of 1,800 metric tons cation of the synthesis gas and low-pressure ammonia synthesis using
per day (mtpd) and an energy consumption of 6.65 Gcal per metric ton KAAP catalyst.
Following sulfur removal (l), the feed is mixed with steam, heated,
(mt) of ammonia. Since a revamp, it is operating beyond 2,000 mtpd.
and split into two streams. One stream flows to the autothermal reformer
Description: The feedstock (natural gas as an example) is desulfur- (ATR) (2) and the other to the tube side of the reforming exchanger (3),
ized, mixed with steam and converted into synthesis gas over nickel cat- which operates in parallel with the ATR. Both convert the hydrocarbon
alyst at approximately 40 bar and 800°C to 850°C in the primary feed into raw synthesis gas using conventional nickel catalyst. In the ATR,
reformer. The Uhde steam reformer is a top-fired reformer with tubes made feed is partially combusted with excess air to supply the heat needed to
of centrifugal high alloy steel and a proprietary “cold outlet manifold sys- reform the remaining hydrocarbon feed. The hot autothermal reformer
tem, which enhances reliability. effluent is fed to the shell side of the KRES reforming exchanger, where
In the secondary reformer, process air is admitted to the syngas via a spe- it combines with the reformed gas exiting the catalyst-packed tubes. The
cial nozzle system that provides a perfect mixture of air and gas. Subse- combined stream flows across the shell side of the reforming exchanger
quent high-pressure steam generation and superheatingguarantee maximum where it supplies heat to the reforming reaction inside the tubes.
process heat usage to achieve an optimized energy efficient process. Shell-side effluent from the reforming exchanger is cooled in a waste
CO is converted to CO, in the HT and LT shift over standard catalysts. heat boiler, where high-pressure steam is generated, and then flows to
CO, is removed in a scrubbing unit, which is normally either the BASF- the C O shift converters containing two catalyst types: one (4) is a high-
aMDEA or the UOP-Benfield process. Remaining carbonoxides are recon- temperature catalyst and the other (5) is a low-temperature catalyst. Shift
verted to methane in the catalytic methanation to trace ppm levels. reactor effluent is cooled, condensed water separated (6) and then routed
The ammonia synthesis loop uses two ammonia converters with three to the gas purification section. COzis removed from synthesis gas using
catalytic beds. Waste heat is used for steam generation downstream the sec- a wet CO, scrubbing system such as hot potassium carbonate or MDEA
ond and third bed. Waste-heat steam generators with integrated boiler (methyl diethanolamine) (7).
feedwater preheater are supplied with a special cooled tube sheet to min- After COz removal, final purification includes methanation (8), gas dry-
imize skin temperatures and material stresses. The converters themselves ing (9), and cryogenic purification (10). The resulting pure synthesis gas
have radial catalyst beds with standard small grain iron catalyst. The radial is compressed in a single-case compressor and mixed with a recycle stream
flow concept minimizes pressure drop in the synthesis loop and allows (1 1). The gas mixture is fed to the KAAP ammonia converter (12), which
maximum ammonia conversion rates. uses a ruthenium-based, high-activity ammonia synthesis catalyst. It pro-
Liquid ammonia is separated by condensation from the synthesis loop vides high conversion at the relatively low pressure of 90 bar with a small
and is either subcooled and routed to storage, or conveyed at moderate tem- catalyst volume. Effluent vapors are cooled by ammonia refrigeration
perature to subsequent consumers. (13) and unreacted gases are recycled. Anhydrous liquid ammonia is con-
Ammonia flash and purge gases are treated in a scrubbing system and densed and separated (14) from the effluent.
a hydrogen recovery unit (not shown), and the remains are used as fuel. Energy consumption of KBR‘s KAAPplw process is less than 25 MM
Btu (LHV)/short-ton. Elimination of the primary reformer combined
Commercial plants: Fourteen ammonia plants were commissioned with low-pressure synthesis provides a capital cost savings of about 10%
between 1990 and 2000, with capacities ranging from 500 mtpd to over conventional processes.
1,800 mtpd.
Commercial plants: Over 200 large-scale, single-train ammonia
Licensor: Uhde GmbH. plants of KBR design are onstream or have been contracted worldwide.
The KAAPph advanced ammonia technology provides a low-cost, low-
energy design for ammonia plants, minimizes environmental impact,
reduces maintenance and operating requirements and provides enhanced
reliability. Two plants use KRES technology and 17 plants use Purifier
technology. Three 1,850-mtpd grassroots KAAP plants in Trinidad are
in full operation, and a fourth is under construction.
Licensor: Kellogg Brown & Root, Inc.
 SEGMENTS. PETROCHEMICAL PROCESSES 275

Dehydration
Aniline
purification
MNB

Ammonia, KBR purifier Aniline

Application: To produce ammonia from hydrocarbon feedstocks Application: A process for the production of high-qualityaniline from
and air. benzene and nitric acid.
Description: The key features of the KBR Purifier Process are mild Description:Aniline is produced by the nitration of benzene with nitric
primary reforming, secondary reforming with excess air, cryogenic purifi- acid to mononitrobenzene (MNB) which is subsequentlyhydrogenated
cation of syngas, and synthesis of ammonia over magnetite catalyst in a to aniline. In the DuPont/KBR process, benzene is nitrated with mixed
horizontal converter. acid (nitric and sulhric) at high efficiency to produce mononitrobenzene
Desulfurized feed is reacted with steam in the primary reformer (1) with (MNB) in the unique dehydrating nitration (DHN) system. The DHN
exit temperature at about 700°C. Primary reformer effluent is reacted system uses an inert gas to remove the water of nitration from the reac-
with excess air in the secondary reformer (2) with exit at about 900°C. The tion mixture, thus eliminating the energy-intensiveand high-cost sulfu-
air compressor is normally a gas-driven turbine (3). Turbine exhaust is ric acid concentration system.
fed to the primary reformer and used as preheated combustion air. An As the inert gas passes through the system, it becomes humidified,
alternative to the above described conventional reforming is to use KBR’s removing the water of reaction from the reaction mixture. Most of the
reforming exchanger system (KRES), as described in KBR‘s KAAPplw. energy required for the gas humidification comes from the heat of nitra-
Secondary reformer exit gas is cooled by generating high-pressure tion. The wet gas is condensed and the inert gas is recycled to the nitra-
steam (4).The shift reaction is carried out in two catalytic steps-high- tor. The condensed organic phase is recycled to the nitrator while the
temperature ( 5 ) and low-temperatureshift (6).Carbon dioxide removal aqueous phase is sent to effluent treatment. The reaction mixture is phase
(7) uses licensed processes. Following CO, removal, residual carbon oxides separated and the sulfuric acid is returned to the nitrator.
are converted to methane in the methanator (8). Methanator effluent is The crude MNB is washed to remove residual acid and the impurities
cooled, and water is separated (9) before the raw gas is dried (10). formed during the nitration reaction. The product is then distilled and
Dried synthesis gas flows to the cryogenic purifier (1 I), where it is residual benzene is recovered and recycled. Purified MNB is fed, together
cooled by feed/effluent heat exchange and fed to a rectifier. The syngas is with hydrogen, into a liquid phase plug-flow hydrogenation reactor that
purified in the rectifier column, producing a column overhead that is contains a DuPonr proprietary catalyst. The supported noble metal cat-
essentially a 7525 ratio of hydrogen and nitrogen. The column bottoms alyst has a high selectivityand the MNB conversion per pass is 100%.
is a waste gas that contains unconverted methane from the reforming The reaction conditionsare o p t i m i i to achieve essentiallyquantitative
section, excess nitrogen and argon. Both overhead and bottoms are reheated yields and the reactor effluent is MNB-free. The reactor product is sent to
in the feedleffluent exchanger. The waste gas stream is used to regenerate a dehydration column to remove the water of reaction followed by a
the dryers and then is burned as fuel in the primary reformer. A small, purification column to produce high-quality aniline product.
low-speed expander provides the net refrigeration.
The purified syngas is compressed in the syngas compressor (12), Commercial plants: DuPont produces aniline using this technol-
mixed with the loop-cycle stream and fed to the converter (13). Con- ogy for the merchant market with a total production capacity of 160,000
verter effluent is cooled and then chilled by ammonia refrigeration. tpy at a plant located in Beaumont, Texas. In addition, DuPont’s aniline
Ammonia product is separated (14) from unreacted syngas. Unreacted technology has been licensed to two companiesin the last eight years with
syngas is recycled back to the syngas compressor.A small purge is scrubbed a total aniline capacity of 150,000 tpy.
with water (15) and recycled to the dryers. Licensor: Kellogg Brown & Root, Inc.
Commercial plants:Over 200 single-train plants of KBR design have
been contracted worldwide. Seventeen of these plants use the KBR Puri-
fier process.
Licensor:Kellogg Brown & Root, Inc.
276 SEGMENT 3. PETROCHEMICAL PROCESSES

Nonaromatics

Aromatics extraction Aromatics extractive distiI lation

Application: Simultaneousrecovery of benzene, toluene and xylenes Application: Recovery of high-purity aromatics from reformate,
(BTX) from reformate or pyrolysis gasoline (pygas) using liquid-liquid pyrolysis gasoline or coke-oven light oil using extractive distillation.
extraction.
Description: In the extractive distillation (ED) process, a single-
Description: At the top of extractor operating at 30°C to 50°C and compound solvent, N-Formylmorpholin (NFM) alters the vapor pres-
1 to 3 bar, the solvent, N-Formylmorpholin with 4% to 6% water, is fed sure of the components being separated. The vapor pressure of the aro-
as a continuous phase. The feedstock-reformate or pygas-enters sev- matics is lowered more than that of the less-soluble nonaromatics.
eral stages above the base of the column. Due to density differences, the Nonaromatics vapors leave the top of the ED column with some sol-
feedstock bubbles upwards, countercurrent to the solvent. Aromatics vent, which is recovered in a small column that can either be mounted on
pass into the solvent, while the nonaromatics move to the top, remain- the main column or installed separately.
ing in the light phase. Low-boiling nonaromatics from the top of the extrac- Bottom product of the ED column is fed to the stripper to separate
tive distillation (ED) column enter the base of the extractor as counter- pure aromatics from the solvent. After intensive heat exchange, the lean
solvent. solvent is recycled to the ED column. NFM perfectly satisfies the neces-
Aromatics and solvent from the bottom of the extractor enter the ED, sary solvent properties needed for this process including high selectivity,
which is operated at reduced pressure due to the boiling-temperature thermal stability and a suitable boiling point.
threshold. Additional solvent is fed above the aromatics feed containing
small amounts of nonaromaticsthat move to the top of the column. In the Economics:
bottom section, as well as in the side rectifier, aromatics and practically Pygas feedstock:
water-free solvent are separated. Benzene Benzeneltoluene
The water is produced as a second subphase in the reflux drum after Production yield
azeotropic distillation in the top section of the ED. This water is then Benzene 99.95% 99.95%
fed to the solvent-recoverystage of the extraction process. Toluene - 99.98%
Economics: Quality
Consumption per ton of feedstock Benzene 30 wt ppm NA* 80 wt pprn NA*
Toluene - 600 wt ppm NA*
Steam (20 bar), t/t 0.46
Water, cooling (T=lO°C), m3/t 12 Consumption
Electric power, kWh/t 18 Steam 475 kg/t ED feed 680 kg/t ED feed**
Production yield Reformate feedstock with low aromatics content (2Owt0/o):
Benzene, ?h -100 Benzene
Toluene, % 99.7
EB, Xylenes.% 94.0 Quality
Benzene 10 wt pprn NA*
Purity
Consumption
Benzene, wt% 99.999
Steam 320 kg/t ED feed
Toluene, wt% >99.99
EB, Xylenes, wt% >99.99 *Maximum content of nonaromatics
**Including benzeneitoluenesplitter
Commercial plants: One Morphylex plant was erected.
Commercial plants: 45 Morphylane plants (total capacity of more
Reference: Emmrich, G., F. Ennenbach and U. Ranke, “Krupp Uhde than 6 MMtpy).
Processes for Aromatics Recovery,” European PetrochemicalTechnology
Conference,June 21-22,1999, London. Reference: Emmrich, G., F. Ennenbach and U. Ranke, “Krupp Uhde
Processes for Aromatics Recovery,”European PetrochemicalTechnology
Licensor: Uhde GmbH. Conference,June 21-22, 1999, London.
Licensor: Uhde GmbH.
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SEGMENTS. PETROCHEMICAL PROCESSES 277

Benzene Bisphenol-A
Application: To produce high-purity benzene and heavier aromatics Application: The Mitsubishi BPA process uses ion-exchange resin cat-
from toluene and heavier aromatics using the Detol process. alysts to react phenol and acetone to produce high-quality Bisphenol-A
(BPA).
Description: Feed and hydrogen are heated and passed over the cat-
alyst (1). Benzene and unconverted toluene and/or xylene and heavier aro- Description: Phenol and acetone are reacted in a BPA synthesis reac-
matics are condensed (2) and stabilized (3). tor (I), which is packed with the proprietary cation-exchange resin-base
To meet acid wash color specifications, stabilizer bottoms are passed catalyst (named “4PET”). This catalyst has a higher acetone conversion,
through a fixed-bed clay treater, then distilled (4)to produce the desired higher BPA selectivity and longer life than conventional catalysts. Unre-
specification benzene. The cryogenic purification of recycle hydrogen to acted acetone, water and some phenol are separated from the reactor efflu-
reduce the make-up hydrogen requirement is optional (6). ent by distillations (2, 3, 4). Acetone is recycled to the BPA reactor (1);
Unconverted toluene and/or xylenes and heavier aromatics are recycled. water is purged as waste. Phenol is mixed with fresh phenol and purified
by distillation (5). The stream, which contains BPA, phenol and other
Yields: Aromatic yield is 99.0 mol% of fresh toluene or heavier aromatic impurities are fed to the crystallizer (6),where phenol-BPA adduct crys-
charge. Typical yields for production of benzene and xylenes are: tal grows. Separated adduct crystals are washed with purified phenol in
Type production Benzene Xylene a solid-liquid separator (7).
Crystals are then melted and sent to the prilling tower (8),where
Feed. wt% spherical prills are produced as the final products. Solidified BPA is con-
Nonaromatics 3.2 2.3 veyed to storage and shipping facilities.
Benzene - 11.3
Toluene 47.3 0.7 The mother liquor is recycled back to the BPA reactor from solid-liq-
CB aromatics 49.5 0.3 uid separator (7). Part of the mother liquor is fed to the purge-recoverysys-
C9+ aromatics - 85.4 tem where impurities are partially decomposed and recombined to form
Products, wt% of feed
BPA. Undesired impurities are condensed and discharged as tarry mate-
Benzene* 75.7 36.9 rials. The optimal purge ratio from the mother liquor controls product
CB aromatics** - 37.7 quality while minimizing raw material unit consumption.
* 5 45°C minimum freeze point
* * 1,000 ppm nonaromatics maximum
Product quality: Typical values for BPA prills:
BPA purity, wt% 99.9-99.98
Economics: Basis of ISBL US Gulf Coast: Freezing point, “C 156.7-1 56.8
Estimated investment, Blbpsd 6,700 Melt color 8175°C. [APHA] 5-1 0
Free phenol, wtppm 5-20
Typical utility requirements, per bbl feed: 2.4-BPA isomer, wtppm 50-1 50
Electricity, kWh 5.8
Fuel, MMBtu 0.31 * Commercial plants: In 2001, Mitsubishi Chemical Corp. (MCC)
Water, cooling, gal 450 acquired from Chiyoda Corp., all intellectual property for BPA technology,
Steam, Ib 14.4 including licensing rights. MCC is improving this process and has developed
* No credit taken for vent gas streams a new catalyst-4PET-which enhances the performance of this process.
MCC’s first BPA plant at Kashima, Japan, started up in 1998 with
Commercial plants: Twelve plants with capacities ranging from about 70,000-tpy (70-Mtpy) capacity. In 2000, the unit was revamped to 100
12 million to 100 million gal/y have been licensed. Mtpy by incorporating the improved process. In 2002, MCC’s second
Licensor: ABB Lummus Global. BPA plant at Kurosaki, Japan, started up with 100-Mtpy capacity and
uses 4PET catalyst. In addition to these plants, two additional plants are
operating, and one plant is now under construction:
Capacity,
Company Mtpy Startup
Shin Nippon Bisphenol (Japan) 95 1991
Taiwan Prosperity Chemical Corp. (Taiwan) 25 1995
Mitsubishi Chemical Corp. (Japan) 100 1998
Mitsubishi Chemical Corp. (Japan) 100 2002
Blue Star Chemical Cleaning Corp. (China) 25 (2003)
Licensor: Mitsubishi Chemical Corp.