Refining Processes

(1)

2002

www.HydrocarbonProcessing.comwww.HydrocarbonProcessing.com

R

Re

ef

fi

in

ni

in

ng

g

R

e

f

i

n

i

n

g

Processes

(2)

H Y D

H Y D R O CR O C A R B O NA R B O N P RP ROO C E SC E SS IS IN GN G NOVEMNOVEMBER 200BER 20022 II8585

R

e

f

i

n

i

n

g

Processes

2002

Process Index

Lic

Licens

ensor

or

Ind

ex

Al

Alkylation kylation . . . .. . . 8686, 88, 8, 88, 89, 909, 90 A

Alklkylylatat ion—ion—feed feed preparatpreparat ion ion . . . .. . . 9090 A

Aromatromat icics exs extraction traction . . . .. 9191 A

Aromatromat icics exs extractive distractive distiltillation lation . . . .. . . 9191 A

Aromatromat icics rs recovery ecovery . . . .. . 9292 Benzene reduction

Benzene reduction . . . .. . . 9292 Cata

Cata lylytic ctic crackiracking ng . . . .. . . 9494 Cata

Cata lylytic dewatic dewa xixing ng . . . .. . . 9494, 95, 95 Cata

Cata lylytic tic reforming reforming . . . .. . 9595, 96, 96 Cata

Cata lytic lytic SOSOxxremoval . . . 97removal . . . 97

Coki

Coking ng . . . .. . . 9797, 98, 98 Cr

Crude ude distildistillation lation . . . .. . . 9999, 10, 1000 Dearomatization—

Dearomatization— middle dis

middle distiltillate late . . . .. 101000 Deasphalting

Deasphalting . . . .. . 101011 Deep cata

Deep cata lytilytic cc crackiracking ng . . . .. . . . 101022 Deep thermal c

Deep thermal converonversision on . . . .. . . 101022 Desulfurizat

Desulfurizat ion . . . ion . . . .. . 103103 Dew

Dew axing/axing/ww ax deax de oiloiling ing . . . .. . . 101044 Di

Diesel esel desulfuridesulfurizatzat ion ion . . . .. . . 101044 Di

Diesel esel hydrotreahydrotrea tment tment . . . .. . . 101055 E

Electrilectrical desacal desa lting lting . . . .. . 105105 E

Ethers thers . . . .. . . . 101066 Ethers-MT

Ethers-MTBE BE . . . .. . . 108108 F

Fluid caluid ca tata lyticlytic cracki

cracking ng . . . . . . .. . . . 108108, 110, 110, 111, 111, 112, 112 Gas treating—H

Gas treating—H22S rS removal emoval . . . .. . 111122

Ga

Ga sisification fication . . . .. 113113

Gasoli

Gasoline dene de sulsulfurization furization . . . .. . . . 111133 Gasoli

Gasoline ne desulfuridesulfurizatzat ion,ion,

ultra-ultra-deep deep . . . .. . . 111144 H

H22S and SWS and SWS gas conversS gas conversion ion . . . .. . . 111144

Hydroc

Hydrocrackiracking ng . . . .. . . 11115, 15, 11616, 11, 1177 Hydr

Hydrocrackocracking, resing, residue idue . . . .. . . 111188 Hydrocracking/ Hydrocracking/ hydrotr hydrotreating—Veating—VGO GO . . . .. . . . 111188 Hydrocracking (mild)/ Hydrocracking (mild)/ V

VGO hydrotreaGO hydrotrea ting ting . . . .. . . 111199 Hy

Hydrodearomatdrodearomat iization zation . . . .. . 111199 Hydrode

Hydrode sulsulfurizafuriza tion tion . . . .. . 120120, 12, 1211 Hydrodesulfurization,

Hydrodesulfurization,

ultra-ultra-low-slow-sulfur diulfur diesel esel . . . .. . . 121211 Hydrodesulfurization— Hydrodesulfurization— pretr pretreatment eatment . . . .. . . 121222 Hydrodesul Hydrodesulfurization—UDfurization—UDHDS . . . HDS . . . .. 121222 Hydrofini

Hydrofinishishing/ng/hydrotreahydrotrea ting ting . . . .. 121233 Hydr

Hydrogog en en . . . .. . 121233 Hydr

Hydrogog enaena tion tion . . . .. . . . 121244 Hydrotre

Hydrotre atat ing ing . . . .. . . . 12124, 124, 125, 125, 126, 126, 127, 127, 1288 Hydrotreating—aromatic

Hydrotreating—aromatic saturat

saturat ion ion . . . .. . . 121288 Hydrotreating—catalytic

Hydrotreating—catalytic dew

dew axing . . . axing . . . .. . . 121299 Hydr

Hydrotreaotrea ting—rting—resiesid d . . . .. . . 121299 IIsomerizasomeriza tion tion . . . .. . . . 130130, 13, 131, 11, 13232 IIsooctasoocta nene //isisoooo ctene ctene . . . .. . . . 13132, 12, 13333

Is

Isoooo ctenectene //IIsooctasoocta nene //EETTBE BE . . . .. 131333 L

Lowow --tempetempe rature rature NNOOxxr e d ur e d uc t ic t io n o n . . . .. 113344

L

LPG recovery PG recovery . . . .. . . 131344 L

Lube hydube hyd roprocesroprocessising ng . . . .. . . 131355 L

Lube ube treattreat ing ing . . . .. . . 13135, 15, 13636, 13, 1377 NO

NOxxabaaba tement tement . . . .. . . . 131377

Olefins . . . . Olefins . . . 131388 Olefins r

Olefins recovery ecovery . . . .. . . . 131399 Ol

Oligomerization oigomerization o f Cf C33CC44cuts . . . .cuts . . . 131399

Ol

Oligomeriigomerization—zation—polypolynaphtha naphtha . . . . .. . . 141400 Prer

Prereformieforming ng ww iith th feedfeed ultrapuri

ultrapurificficatat ion ion . . . .. . . 141400 Res

Resid cataid cata lylytic ctic crackiracking ng . . . .. . . 141422 Res

Residue hydidue hyd roprocessiroprocessing ng . . . .. . . . 141422 SO

SO22removal removal . . . .. . . 141433

SSour gas treatment our gas treatment . . . .. . . . 141433 Spent acid rec

Spent acid recovery overy . . . .. . . 141444 Sul

Sulfur degfur deg assassing ing . . . .. . . 141444 T

Thermaherma l gal ga soil soil process . . . .process . . . 141455 T

Treating reating . . . .. . . 141455 V

Vacuum dacuum d isistiltillation lation . . . .. . . 141466 V

Visisbreabrea kiking ng . . . .. . . 146146, 14, 1477 W

Wet scret scrubbing ubbing sysystem stem . . . .. . . 141477 W

Wetet --chemchem isistry try NONOxxreducreduction tion . . . .. . . 141488

W

White oil hite oil and and ww axax hydrotrea

hydrotrea ting ting . . . .. . . 141488

AB

ABB LB Lummumm us Globaus Globa l Il Inc. nc. . . . . . .86, 9. . .86, 97,7, 108, 127, 128, 130 108, 127, 128, 130 AB

ABB LB Lummumm us Globus Glob al B.Val B.V. . . . .102, 14. . .102, 145, 145, 1466 A

Aker Kker Kvaerner vaerner . . . .. . . . 131333 Akzo Nobel Catalysts B.V. . . . .86, 122, 129 Akzo Nobel Catalysts B.V. . . . .86, 122, 129 Ax Axens ens . . . .. . . 9090, 92, 9, 92, 95,5, 105, 106, 111, 114, 115, 105, 106, 111, 114, 115, 118, 129, 130, 139, 140, 142 118, 129, 130, 139, 140, 142 Ax Axens NA . . ens NA . . . . . . . . . . . .. 9090, 92, 9, 92, 95,5, 105, 106, 114, 115, 118, 105, 106, 114, 115, 118, 129, 130, 139, 140 129, 130, 139, 140 BA BARCRCO O . . . .. . . . 9494 BA BASF SF . . . .. . . 148148 Bechte

Bechte l Cl Corp. orp. . . . .. . . 98, 98, 10104, 14, 13535 Belco T

Belco Technechn oloolo gg iesies Corp.

Corp. . . . .. . . 134134, 14, 143, 143, 147, 147, 1488 Black &V

Black &Veaea tch Pritchard, Inc. tch Pritchard, Inc. . . .. . . 13134, 14, 14444 BOC

BOC Group, IncGroup, Inc. . . . . .. . . 131344 Cansolv T

Cansolv Technoechno loglog ies ies IncInc. . . . . .. . . 148148 CDT

CDTECH . . . ECH . . . . .. . 106, 124, 131, 13106, 124, 131, 133, 1463, 146 Chevron Lummus Glob

Chevron Lummus Glob al LLal LLC . . . C . . . .. 11115, 115, 1166 Chi

Chicago cago BriBridgdg e &Iron Co. e &Iron Co. . . .. . . 9696, 10, 105, 15, 12525 Conoco Inc.

Conoco Inc. . . . .. . 9898

Cono

Cono coPhcoPh illillips Cips Co., Fuels To., Fuels Technechn oloolo gg yy Divi

Divisision on . . . .. . . 8888, 104, 104, 11, 113, 133, 1311 Cr

Criteriiterion on CataCata lylyst ast a ndnd T

Technoechno loglog ies Cies Co. o. . . . . . . .. 12127, 127, 1288 Davy Process T

Davy Process Technoechno logy logy . . . .. . . 141400 E

Engenge lhard Corp. lhard Corp. . . . .. . . 101000 E

ExxxxonMoonMo bil Rbil Reseaesea rch &Erch &Engng ineeringineering Co.

Co. . . . .. . . . 86, 9486, 94, 110, 110, 112, 1, 112, 120, 120, 136, 1336, 1377 F

Fina Resina Reseaea rcrch S.Ah S.A. . . . . .. . . 121299 F

Fortum Oil ortum Oil and and Gas OY Gas OY . . . .. . 8686, 13, 1322 F

Fostost er Wheeleer Wheele r . . . . .r . . . 98, 998, 99, 109, 101, 121, 123, 143, 1477 GT

GTC TC Technechn oloolo gg y Inc. . . y Inc. . . . . . . . .. . . 92, 1092, 1033 Hald

Hald or Tor Topop søe A/søe A/S . . S . . . . . . . . .. . . . 88, 9588, 95, 97,, 97, 114, 119, 121, 125, 143, 144 114, 119, 121, 125, 143, 144 Howe

Howe --Baker EBaker Engineers, Lngineers, Ltd. td. .. 9696, 10, 105, 15, 12525 IIFFP GroP Gro up Tup Technoechno loglog ies ies . . . . .. . 11111, 141, 1422 JGC

JGC . . . .. . . 121266 Kel

Kellogg logg Brown Brown &Root, Inc. .&Root, Inc. . 10101, 11, 11010, 13, 1322 L

Linde BOC inde BOC ProceProce ss ss PlanPlan ts, Lts, LLLC C . . .. 126, 126, 139139 L

Lyondyond ell Cell Chemhem icical Co. al Co. . . . .. 13131, 11, 13333 Merichem Chemicals &Refinery

Merichem Chemicals &Refinery Servic

Services Les LLLC C . . . .. . . 145145 Process

Process DynaDyna mics mics . . . .. . . 121266

PDVSA-PDVSA-ININTTEVEVEP . . EP . . . . . . . . . . . . . . . . . . .121. .121 Res

Research Insearch Institute titute of of PetroleumPetroleum Proces

Processising ng . . . .. . . 101022 Shell

Shell GlobGlob al Solutionsal Solutions

IIntente rnatrnat ionaiona l B.Vl B.V. . . . . . .. . . . 99, 199, 10202, 111, 111,, 113, 116, 127, 128, 113, 116, 127, 128, 135, 142, 145, 146 135, 142, 145, 146 SK SK Corp Corp . . . .. . . 122122, 13, 1377 Snamproge

Snamproge tti SpA tti SpA . . . .. . . . 10106, 16, 13333 Stone

Stone &Webster I&Webster Inc. nc. . . . .. . . 10102, 12, 11111, 14, 1422 Strat

Strat co, Incco, Inc. . . . . . .. . . 8989 Synetix

Synetix . . . .140. . . .140 T

Technip-echnip-Coflexip Coflexip . . . .. . . 101000 T

TOTOTAL AL FIFINA NA ELELF F . . . . . . . . . . . . . . . . . .. . . 100100 Udhe Edeleanu Gmb Udhe Edeleanu Gmb H H . . . .. . . . 10108, 18, 12323, 13, 136,6, 146, 148 146, 148 Udhe Gm Udhe Gm bH bH . . . .. . . 9191, 13, 1388 UniPure Corp. UniPure Corp. . . . .. . . 101033 UOP LL UOP LLC C . . . .. . . 89, 989, 90, 94,0, 94, 96, 98, 101, 112, 117, 96, 98, 101, 112, 117, 121, 127, 128, 132, 147 121, 127, 128, 132, 147 V VEEBA OEBA OEL L GmbGmb H H . . . .. . . 111177 W

Washington Gashington G rouproup

(3)

H Y D

H Y D R O CR O C A R B O NA R B O N P RP ROO C E SC E SS IS IN GN G NOVEMNOVEMBER 200BER 20022 II8585

R

e

f

i

n

i

n

g

Processes

2002

Process Index

Lic

Licens

ensor

or

Ind

ex

Al

Alkylation kylation . . . .. . . 8686, 88, 8, 88, 89, 909, 90 A

Alklkylylatat ion—ion—feed feed preparatpreparat ion ion . . . .. . . 9090 A

Aromatromat icics exs extraction traction . . . .. 9191 A

Aromatromat icics exs extractive distractive distiltillation lation . . . .. . . 9191 A

Aromatromat icics rs recovery ecovery . . . .. . 9292 Benzene reduction

Benzene reduction . . . .. . . 9292 Cata

Cata lylytic ctic crackiracking ng . . . .. . . 9494 Cata

Cata lylytic dewatic dewa xixing ng . . . .. . . 9494, 95, 95 Cata

Cata lylytic tic reforming reforming . . . .. . 9595, 96, 96 Cata

Cata lytic lytic SOSOxxremoval . . . 97removal . . . 97

Coki

Coking ng . . . .. . . 9797, 98, 98 Cr

Crude ude distildistillation lation . . . .. . . 9999, 10, 1000 Dearomatization—

Dearomatization— middle dis

middle distiltillate late . . . .. 101000 Deasphalting

Deasphalting . . . .. . 101011 Deep cata

Deep cata lytilytic cc crackiracking ng . . . .. . . . 101022 Deep thermal c

Deep thermal converonversision on . . . .. . . 101022 Desulfurizat

Desulfurizat ion . . . ion . . . .. . 103103 Dew

Dew axing/axing/ww ax deax de oiloiling ing . . . .. . . 101044 Di

Diesel esel desulfuridesulfurizatzat ion ion . . . .. . . 101044 Di

Diesel esel hydrotreahydrotrea tment tment . . . .. . . 101055 E

Electrilectrical desacal desa lting lting . . . .. . 105105 E

Ethers thers . . . .. . . . 101066 Ethers-MT

Ethers-MTBE BE . . . .. . . 108108 F

Fluid caluid ca tata lyticlytic cracki

cracking ng . . . . . . .. . . . 108108, 110, 110, 111, 111, 112, 112 Gas treating—H

Gas treating—H22S rS removal emoval . . . .. . 111122

Ga

Ga sisification fication . . . .. 113113

Gasoli

Gasoline dene de sulsulfurization furization . . . .. . . . 111133 Gasoli

Gasoline ne desulfuridesulfurizatzat ion,ion,

ultra-ultra-deep deep . . . .. . . 111144 H

H22S and SWS and SWS gas conversS gas conversion ion . . . .. . . 111144

Hydroc

Hydrocrackiracking ng . . . .. . . 11115, 15, 11616, 11, 1177 Hydr

Hydrocrackocracking, resing, residue idue . . . .. . . 111188 Hydrocracking/ Hydrocracking/ hydrotr hydrotreating—Veating—VGO GO . . . .. . . . 111188 Hydrocracking (mild)/ Hydrocracking (mild)/ V

VGO hydrotreaGO hydrotrea ting ting . . . .. . . 111199 Hy

Hydrodearomatdrodearomat iization zation . . . .. . 111199 Hydrode

Hydrode sulsulfurizafuriza tion tion . . . .. . 120120, 12, 1211 Hydrodesulfurization,

Hydrodesulfurization,

ultra-ultra-low-slow-sulfur diulfur diesel esel . . . .. . . 121211 Hydrodesulfurization— Hydrodesulfurization— pretr pretreatment eatment . . . .. . . 121222 Hydrodesul Hydrodesulfurization—UDfurization—UDHDS . . . HDS . . . .. 121222 Hydrofini

Hydrofinishishing/ng/hydrotreahydrotrea ting ting . . . .. 121233 Hydr

Hydrogog en en . . . .. . 121233 Hydr

Hydrogog enaena tion tion . . . .. . . . 121244 Hydrotre

Hydrotre atat ing ing . . . .. . . . 12124, 124, 125, 125, 126, 126, 127, 127, 1288 Hydrotreating—aromatic

Hydrotreating—aromatic saturat

saturat ion ion . . . .. . . 121288 Hydrotreating—catalytic

Hydrotreating—catalytic dew

dew axing . . . axing . . . .. . . 121299 Hydr

Hydrotreaotrea ting—rting—resiesid d . . . .. . . 121299 IIsomerizasomeriza tion tion . . . .. . . . 130130, 13, 131, 11, 13232 IIsooctasoocta nene //isisoooo ctene ctene . . . .. . . . 13132, 12, 13333

Is

Isoooo ctenectene //IIsooctasoocta nene //EETTBE BE . . . .. 131333 L

Lowow --tempetempe rature rature NNOOxxr e d ur e d uc t ic t io n o n . . . .. 113344

L

LPG recovery PG recovery . . . .. . . 131344 L

Lube hydube hyd roprocesroprocessising ng . . . .. . . 131355 L

Lube ube treattreat ing ing . . . .. . . 13135, 15, 13636, 13, 1377 NO

NOxxabaaba tement tement . . . .. . . . 131377

Olefins . . . . Olefins . . . 131388 Olefins r

Olefins recovery ecovery . . . .. . . . 131399 Ol

Oligomerization oigomerization o f Cf C33CC44cuts . . . .cuts . . . 131399

Ol

Oligomeriigomerization—zation—polypolynaphtha naphtha . . . . .. . . 141400 Prer

Prereformieforming ng ww iith th feedfeed ultrapuri

ultrapurificficatat ion ion . . . .. . . 141400 Res

Resid cataid cata lylytic ctic crackiracking ng . . . .. . . 141422 Res

Residue hydidue hyd roprocessiroprocessing ng . . . .. . . . 141422 SO

SO22removal removal . . . .. . . 141433

SSour gas treatment our gas treatment . . . .. . . . 141433 Spent acid rec

Spent acid recovery overy . . . .. . . 141444 Sul

Sulfur degfur deg assassing ing . . . .. . . 141444 T

Thermaherma l gal ga soil soil process . . . .process . . . 141455 T

Treating reating . . . .. . . 141455 V

Vacuum dacuum d isistiltillation lation . . . .. . . 141466 V

Visisbreabrea kiking ng . . . .. . . 146146, 14, 1477 W

Wet scret scrubbing ubbing sysystem stem . . . .. . . 141477 W

Wetet --chemchem isistry try NONOxxreducreduction tion . . . .. . . 141488

W

White oil hite oil and and ww axax hydrotrea

hydrotrea ting ting . . . .. . . 141488

AB

ABB LB Lummumm us Globaus Globa l Il Inc. nc. . . . . . .86, 9. . .86, 97,7, 108, 127, 128, 130 108, 127, 128, 130 AB

ABB LB Lummumm us Globus Glob al B.Val B.V. . . . .102, 14. . .102, 145, 145, 1466 A

Aker Kker Kvaerner vaerner . . . .. . . . 131333 Akzo Nobel Catalysts B.V. . . . .86, 122, 129 Akzo Nobel Catalysts B.V. . . . .86, 122, 129 Ax Axens ens . . . .. . . 9090, 92, 9, 92, 95,5, 105, 106, 111, 114, 115, 105, 106, 111, 114, 115, 118, 129, 130, 139, 140, 142 118, 129, 130, 139, 140, 142 Ax Axens NA . . ens NA . . . . . . . . . . . .. 9090, 92, 9, 92, 95,5, 105, 106, 114, 115, 118, 105, 106, 114, 115, 118, 129, 130, 139, 140 129, 130, 139, 140 BA BARCRCO O . . . .. . . . 9494 BA BASF SF . . . .. . . 148148 Bechte

Bechte l Cl Corp. orp. . . . .. . . 98, 98, 10104, 14, 13535 Belco T

Belco Technechn oloolo gg iesies Corp.

Corp. . . . .. . . 134134, 14, 143, 143, 147, 147, 1488 Black &V

Black &Veaea tch Pritchard, Inc. tch Pritchard, Inc. . . .. . . 13134, 14, 14444 BOC

BOC Group, IncGroup, Inc. . . . . .. . . 131344 Cansolv T

Cansolv Technoechno loglog ies ies IncInc. . . . . .. . . 148148 CDT

CDTECH . . . ECH . . . . .. . 106, 124, 131, 13106, 124, 131, 133, 1463, 146 Chevron Lummus Glob

Chevron Lummus Glob al LLal LLC . . . C . . . .. 11115, 115, 1166 Chi

Chicago cago BriBridgdg e &Iron Co. e &Iron Co. . . .. . . 9696, 10, 105, 15, 12525 Conoco Inc.

Conoco Inc. . . . .. . 9898

Cono

Cono coPhcoPh illillips Cips Co., Fuels To., Fuels Technechn oloolo gg yy Divi

Divisision on . . . .. . . 8888, 104, 104, 11, 113, 133, 1311 Cr

Criteriiterion on CataCata lylyst ast a ndnd T

Technoechno loglog ies Cies Co. o. . . . . . . .. 12127, 127, 1288 Davy Process T

Davy Process Technoechno logy logy . . . .. . . 141400 E

Engenge lhard Corp. lhard Corp. . . . .. . . 101000 E

ExxxxonMoonMo bil Rbil Reseaesea rch &Erch &Engng ineeringineering Co.

Co. . . . .. . . . 86, 9486, 94, 110, 110, 112, 1, 112, 120, 120, 136, 1336, 1377 F

Fina Resina Reseaea rcrch S.Ah S.A. . . . . .. . . 121299 F

Fortum Oil ortum Oil and and Gas OY Gas OY . . . .. . 8686, 13, 1322 F

Fostost er Wheeleer Wheele r . . . . .r . . . 98, 998, 99, 109, 101, 121, 123, 143, 1477 GT

GTC TC Technechn oloolo gg y Inc. . . y Inc. . . . . . . . .. . . 92, 1092, 1033 Hald

Hald or Tor Topop søe A/søe A/S . . S . . . . . . . . .. . . . 88, 9588, 95, 97,, 97, 114, 119, 121, 125, 143, 144 114, 119, 121, 125, 143, 144 Howe

Howe --Baker EBaker Engineers, Lngineers, Ltd. td. .. 9696, 10, 105, 15, 12525 IIFFP GroP Gro up Tup Technoechno loglog ies ies . . . . .. . 11111, 141, 1422 JGC

JGC . . . .. . . 121266 Kel

Kellogg logg Brown Brown &Root, Inc. .&Root, Inc. . 10101, 11, 11010, 13, 1322 L

Linde BOC inde BOC ProceProce ss ss PlanPlan ts, Lts, LLLC C . . .. 126, 126, 139139 L

Lyondyond ell Cell Chemhem icical Co. al Co. . . . .. 13131, 11, 13333 Merichem Chemicals &Refinery

Merichem Chemicals &Refinery Servic

Services Les LLLC C . . . .. . . 145145 Process

Process DynaDyna mics mics . . . .. . . 121266

PDVSA-PDVSA-ININTTEVEVEP . . EP . . . . . . . . . . . . . . . . . . .121. .121 Res

Research Insearch Institute titute of of PetroleumPetroleum Proces

Processising ng . . . .. . . 101022 Shell

Shell GlobGlob al Solutionsal Solutions

IIntente rnatrnat ionaiona l B.Vl B.V. . . . . . .. . . . 99, 199, 10202, 111, 111,, 113, 116, 127, 128, 113, 116, 127, 128, 135, 142, 145, 146 135, 142, 145, 146 SK SK Corp Corp . . . .. . . 122122, 13, 1377 Snamproge

Snamproge tti SpA tti SpA . . . .. . . . 10106, 16, 13333 Stone

Stone &Webster I&Webster Inc. nc. . . . .. . . 10102, 12, 11111, 14, 1422 Strat

Strat co, Incco, Inc. . . . . . .. . . 8989 Synetix

Synetix . . . .140. . . .140 T

Technip-echnip-Coflexip Coflexip . . . .. . . 101000 T

TOTOTAL AL FIFINA NA ELELF F . . . . . . . . . . . . . . . . . .. . . 100100 Udhe Edeleanu Gmb Udhe Edeleanu Gmb H H . . . .. . . . 10108, 18, 12323, 13, 136,6, 146, 148 146, 148 Udhe Gm Udhe Gm bH bH . . . .. . . 9191, 13, 1388 UniPure Corp. UniPure Corp. . . . .. . . 101033 UOP LL UOP LLC C . . . .. . . 89, 989, 90, 94,0, 94, 96, 98, 101, 112, 117, 96, 98, 101, 112, 117, 121, 127, 128, 132, 147 121, 127, 128, 132, 147 V VEEBA OEBA OEL L GmbGmb H H . . . .. . . 111177 W

Washington Gashington G rouproup

(4)

Alkylation

Application:

Application: The AlkyClean process converts light olefins into The AlkyClean process converts light olefins into alky- alky-late by reacting the olefins with isobutane over a true solid acid catalyst. late by reacting the olefins with isobutane over a true solid acid catalyst. Alk

AlkyCleyCleanan’’s us uniqunique ce catalatalyst, yst, reareactoctor dr desigesign an and nd procprocess ess schscheme eme allallows ows opeoper- r-ation at low external isobutene to

ation at low external isobutene to olefin ratios while maintaining excel-olefin ratios while maintaining excel-lent product quality.

lent product quality. Products:

Products: Alkylate Alkylate is is a a high-octane, low-Rvp high-octane, low-Rvp gasoline gasoline componentcomponent used for blending in all

used for blending in all grades of gasoline.grades of gasoline. Description:

Description: The light olefin feed is combined with the isobuteneThe light olefin feed is combined with the isobutene make-up and recycle and sent to the alkylation reactors which convert the make-up and recycle and sent to the alkylation reactors which convert the olefins into alkylate using a solid

olefins into alkylate using a solid acid catalyst (1). The AlkyClean pro-acid catalyst (1). The AlkyClean pro-cess uses a true

cess uses a true solid acid catalyst to produce alkylate eliminating the safety solid acid catalyst to produce alkylate eliminating the safety and environmental hazards associated with liquid acid technologies. and environmental hazards associated with liquid acid technologies. Simultaneously

Simultaneously, reactors are undergoing a mild liquid-, reactors are undergoing a mild liquid-phase regenerationphase regeneration using isobutene and hydrogen and, periodically, a reactor undergoes a using isobutene and hydrogen and, periodically, a reactor undergoes a higher temperature vapor phase hydrogen strip (2). The reactor and higher temperature vapor phase hydrogen strip (2). The reactor and mild regeneration effluent is sent to

mild regeneration effluent is sent to the product-fractionation section,the product-fractionation section, which

which produces propane, produces propane, n-butane and n-butane and alkylate, while alkylate, while also also recycling recycling isobutene and recovering hydrogen used in regeneration for reuse in isobutene and recovering hydrogen used in regeneration for reuse in other refinery hydroprocessing units (3). AlkyClean does not

other refinery hydroprocessing units (3). AlkyClean does not produce any produce any acid soluble oils (ASO) or require post treatment of the reactor effluent acid soluble oils (ASO) or require post treatment of the reactor effluent or final products.

or final products. Product:

Product: The CThe C₅₅++_{alkylate has a RON of 93–98 depending on pro-}_{alkylate has a RON of 93–98 depending on}

pro-cessing conditions and feed composition. cessing conditions and feed composition. Economics:

Economics:

Investment

Investment((b a sb a siis 1s 100,,00000 -0 -b p sb p sd U nd U niit ) t ) $$//b p sb p sdd 33, 1, 10000 O

Oppee rraa tt iinng g ccoo sstt , , $$//gg aa ll 00..4477

Installation:

Installation: Demonstration unit Demonstration unit at Fortum’at Fortum’s Porvoo, Finland Refin-s Porvoo, Finland Refin-ery.

ery.

Reference:

Reference: “The Process: A new solid acid catalyst gasoline alkylation“The Process: A new solid acid catalyst gasoline alkylation technology,” NPRA 2002 Annual Meeting, March 17–19, 2002. technology,” NPRA 2002 Annual Meeting, March 17–19, 2002. Licensor:

Licensor: ABB Lumm ABB Lummus Global us Global Inc., Akzo Inc., Akzo Nobel Nobel Catalysts aCatalysts and For-nd For-tum Oil and Gas.

tum Oil and Gas.

Reactor Reactor system system (1) (1) Catalyst Catalyst regeneration regeneration (2) (2) Product Product distillation distillation (3) (3) Olefin feed Olefin feed Hydrogen Hydrogen Isobutane Isobutane Isobutane feed Isobutane feed Hydrogen Hydrogen n-Butane n-Butane Alkylate Alkylate product product

Alkylation

Application:

Application: Combines propylene, butylene and pentylene withCombines propylene, butylene and pentylene with isobutane, in the presence of sulfuric a

isobutane, in the presence of sulfuric acid catalyst, to form a high-octane,cid catalyst, to form a high-octane, mogas component.

mogas component. Products:

Products: A h A highly ighly isoparaisoparaffinic, ffinic, low low Rvp, Rvp, high-ohigh-octane ctane gasoligasoline bne blend- lend-stock is produced from

stock is produced from the alkylation process.the alkylation process. Description:

Description: Olefin feed and recycled isobutane are introduced intoOlefin feed and recycled isobutane are introduced into the stirred, autorefrigerated reactor (1). Mixers provide

the stirred, autorefrigerated reactor (1). Mixers provide intimate contactintimate contact between the reactants and the acid catalyst. Reaction heat is

between the reactants and the acid catalyst. Reaction heat is removed fromremoved from the reactor by the highly efficient autorefrigeration method. The the reactor by the highly efficient autorefrigeration method. The hydro-carbons that are vaporized from the reactor, and that provide cooling to carbons that are vaporized from the reactor, and that provide cooling to the 40°F level, are routed to the refrigeration compressor (2) where they the 40°F level, are routed to the refrigeration compressor (2) where they are compressed, condensed and returned to the reactor. A depropanizer are compressed, condensed and returned to the reactor. A depropanizer (3), which is fed by a

(3), which is fed by a slipstream from the refrigeration section, is designedslipstream from the refrigeration section, is designed to remove any propane introduced to the plant with the feeds. The to remove any propane introduced to the plant with the feeds. The reac-tor product is sent to the settler (4), where the hydrocarbons are separated tor product is sent to the settler (4), where the hydrocarbons are separated from the acid that is recycled. The hydrocarbons are then sent to the from the acid that is recycled. The hydrocarbons are then sent to the deisobutanize

deisobutanizer (5) r (5) along with makeup isobutane. The along with makeup isobutane. The isobutane-rich over-isobutane-rich over-head is recycled to the reactor. The bottoms are then sent to

head is recycled to the reactor. The bottoms are then sent to a debutanizera debutanizer (6) to produce a low Rvp alkylate product with an FBP less than 400°F. (6) to produce a low Rvp alkylate product with an FBP less than 400°F.

Major features of the reactor are: Major features of the reactor are:

•• Use of the autorefrigeration method of cooling is Use of the autorefrigeration method of cooling is thermodynami- thermodynami-cally efficient. It also allows lower temperatures, which

cally efficient. It also allows lower temperatures, which are favorable for pro-are favorable for pro-ducing high product

ducing high product quality with low quality with low power requirementspower requirements..

•• Use of a staged reactor system results in a high average isobutane con-Use of a staged reactor system results in a high average isobutane con-centration, which favors high product quality.

centration, which favors high product quality.

•• Use of low space velocity in the reactor design results iUse of low space velocity in the reactor design results in high prod-n high prod-uct quality and eliminates any

uct quality and eliminates any corrosion problems in the fractionationcorrosion problems in the fractionation section associated with the formation of

section associated with the formation of esters.esters.

•• Use of low reactor operating pressure means high reliability for theUse of low reactor operating pressure means high reliability for the mechanical seals for the

mechanical seals for the mixers.mixers.

•• Use of simple reactor internals translates to low cost.Use of simple reactor internals translates to low cost. Yields:

Yields:

A

Allkkyyllaa tt e e yyiiee lldd 11..778 8 bb bb l l CC55++//bbbb l butl but ylene feylene fe eded

IIsobutane (pure) sobutane (pure) requiredrequired 1.1.17 17 bbl/bbl/bbl butylene feedbbl butylene feed A

Allkkyyllaa tt e e qq uuaa lliitt yy 996 6 RROONN//994 4 MMOONN

Economics: Economics:

Utilities,

Utilities,typictypical per al per barrel of barrel of alkylalkylatat e produced:e produced: W

Wa ta te re r, , cco oo olliinng (g (2200° F ° F rriisse )e ), , 11,,00000 0 g a lg a l 22..11 P Poo ww ee rr,,kkWWhh 1100..55 S Stt ee aa mm , , 660 0 ppssiigg , , llbb 220000 H H22SOSO44,,llbb 1199 N Naa OOHH,,110000%%,,llbb 00..11 Installation:

Installation: 115,000-bpd capacity at 11 locations with the sizes115,000-bpd capacity at 11 locations with the sizes ranging from 2,000 to 30,000 bpd. Single reactor/settle trains with ranging from 2,000 to 30,000 bpd. Single reactor/settle trains with capacities up to 9,500 bpsd.

capacities up to 9,500 bpsd. Reference:

Reference: Lerner, H., “Exxon sulfuric acid alkylation technology,”Lerner, H., “Exxon sulfuric acid alkylation technology,”

Handbook of Petroleum Refining Processes,

Handbook of Petroleum Refining Processes,2nd ed., R.2nd ed., R. A. MeyerA. Meyers, Ed., pp.s, Ed., pp. 1.3–1.14.

1.3–1.14. Licensor:

Licensor: ExxonMobil Research & Engineering Co.ExxonMobil Research & Engineering Co.

START START Alkylate Alkylate product product Butane Butane product product Olefin Olefin feed feed Recycle acid

Recycle acid MakeupMakeup isobutane isobutane Propane product Propane product Recycle Recycle isobutane isobutane Refrigerant Refrigerant 11 ₄₄ 5 5 66 33 22 C

Ciirrcclle e 22775 5 oon n RReeaaddeer r SSeerrvviicce e CCaarrdd CCiirrcclle e 22776 6 oon n RReeaaddeer r SSeerrvviicce e CCaarrdd

86

86 IIH Y DH Y D R O CR O C A R B O NA R B O N P RP RO CO C E SE SS IS IN GN G NOVEMNOVEMBER 200BER 20022

Refining

(5)

Alkylation

Application: The Topsøe fixed-bed alkylation (FBA) technology applies a unique fixed-bed reactor system with a liquid superacid catalyst absorbed on a solid support. FBA converts isobutane with propylene, buty-lene and amybuty-lenes to produce branched chain hydrocarbons. As an alter-native, FBA can conveniently be used to alkylate isopentane as a means of disposing isopentane for RVP control purpose.

Products: A high-octane, low-RVP and ultra-low-sulfur blending stock for motor and aviation gasoline.

Description: The FBA process combines the benefits of a liquid cat-alyst with the advantages of a fixed-bed reactor system. Olefin and isobu-tane feedstocks are mixed with a recycle stream of isobuisobu-tane and charged to the reactor section (1). The olefins are fully converted over a supported-liquid-phase catalyst confined within a mobile, well-defined catalyst zone. The simple fixed-bed reactor system allows easy monitoring and maintenance of the catalyst zone with no handling of solids.

Traces of dissolved acid in the net reactor effluent are removed quan-titatively in a compact and simple-to-operate effluent treatment unit (2). In the fractionation section (3), the acid-free net reactor effluent is split into propane, isobutane, n-butane and alkylate. The unique reactor concept allows an easy and selective withdrawal of small amounts of passivated acid. The acid catalyst is fully recovered in a compact catalyst activity maintenance unit (4). The integrated, inexpensive, on-site catalyst activ-ity maintenance is a distinct f eature of the FBA process. Other signifi-cant features of FBA include:

• High flexibility (feedstock, operation temperature) • Low operating costs

• Low catalyst consumption. Process perf orm ance:

Olefin feed type

MTBE raffinate FCC C4cut C3 –C5cut

Alkylate product

RON (C₅+ ) 98 95 93 MON (C5+ ) 95 92 91

Economics: (Basis: MTBE raffinate, inclusive feed pretreatment and on-site catalyst activity maintenance)

Investment (basis: 6,000 bpsd unit), $ per bpsd 5,600 Utilities,typical per bbl alkylate:

Ele ct ricit y,kWh 10 St e a m , MP (150 psig ), lb 60 St e a m , LP (50 psig ), lb 200 Wat er, coo ling (20°F rise), ga l103 _2.2

Licensor: Haldor Topsøe A/S.

Propane n-Butane Is ob ut an e Is ob ut an e r ec yc le Olefin feed 1 2 3 4 Alkylate

Alkylation

Application: Convert propylene, amylenes, butylenes and isobutane to the highest quality motor fuel using ReVAP alkylation.

Products: An ultra-low-sulfur, high-octane and low-Rvp blending stock for motor and aviation fuels.

Description: Dry liquid feed containing olefins and isobutane is charged to a combined reactor-settler (1). The reactor uses the principle of differ-ential gravity head to effect catalyst circulation through a cooler prior to con-tacting highly dispersed hydrocarbon in the reactor pipe. The hydrocarbon phase that is produced in the settler is fed to the main fractionator (2), which separates LPG-quality propane, isobutane recycle, n-butane and alkylate ucts. Small amount of dissolved catalyst is removed from the propane prod-uct by a small stripper tower (3). Major process features are:

• Gravity catalyst circulation (no catalyst circulation pumps required) • Low catalyst consumption

• Low operating cost

• Superior alkylate qualities from propylene, isobutylene and amy-lene feedstocks

• Onsite catalyst regeneration

• Environmentally responsible (very low emissions/waste)

• Between 60% and 90% reduction in airborne catalyst release over traditional catalysts

• Can be installed in all licensors’ HF alkylation units.

With the proposed reduction of MTBE in gasoline, ReVAP offers significant advantages over sending the isobutylene to a sulfuric-acid-alkylation unit or a dimerization plant. ReVAP sulfuric-acid-alkylation produces higher octane, lower RVP and endpoint product than a sulfuric-acid-alkylation unit and nearly twice as many octane barrels as can be produced from a dimerization unit.

Yields: Feed t ype

Propylene-But ylene but ylene mix Composition (lv% ) Pro pyle ne 0.8 24.6 Pro pa ne 1.5 12.5 But yle ne 47.0 30.3 i-But a ne 33.8 21.8 n-But a ne 14.7 9.5 i-Pent a ne 2.2 1.3 Alkylate product G ra vit y, API 70.1 71.1 RVP,psi 6–7 6–7 ASTM 10%, ° F 185 170 ASTM 90%, ° F 236 253 RONC 96.0 93.5 Per bbl olefin converted

i-But a ne co nsum e d , b b l 1.139 1.175 Alkyla t e pro d uce d , b b l 1.780 1.755

Installation: 107 alkylation units licensed worldwide. Licensor: Fuels Technology Division of ConocoPhillips Co.

START START Isobutane recycle 1 2 3 Olefin feed Isobutane

Motor fuel butane Alkylate Propane

Circle 277 on Reader Service Card Circle 278 on Reader Service Card

88 IH Y D R O C A R B O N P RO C E SS IN G NOVEMBER 2002

(6)

Alkylation

Application: To combine propylene, butylenes and amylenes with isobutane in the presence of strong sulfuric acid to produce high-octane branched chain hydrocarbons using the Effluent Refrigeration Alkylation process.

Products: Branched chain hydrocarbons for use in high-octane motor fuel and aviation gasoline.

Description: Plants are designed to process a mixture of propylene, butylenes and amylenes. Olefins and isobutane-rich streams along with a recycle stream of H2SO4are charged to the STRATCO Contactor

reac-tor (1). The liquid contents of the Contacreac-tor reacreac-tor are circulated at high velocities and an extremely large amount of interfacial area is exposed between the reacting hydrocarbons and the acid catalyst from the acid set-tler (2). The entire volume of the liquid in the Contactor reactor is maintained at a uniform temperature, less than 1°F between any two points within the reaction mass. Contractor reactor products pass through a flash drum (3) and deisobutanizer (4). The refrigeration section consists of a compressor (5) and depropanizer (6).

The overhead from the deisobutanizer (4) and effluent refrigerant recycle (6) constitutes the total isobutane recycle to the reaction zone. This total quantity of isobutane and all other hydrocarbons is maintained in the liquid phase throughout the Contactor reactor, thereby serving to promote the alkylation reaction. Onsite acid regeneration technology is also available.

Product quality: The total debutanized alkylate has RON of 92 to 96 clear and MON of 90 to 94 clear. When processing straight butylenes, the debutanized total alkylate has RON as high as 98 clear. Endpoint of 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. Economics (basis: butylene feed):

Investment(basis: 10,000-bpsd unit), $ per bpsd 3,500 Utilities,typical per bbl alkylate:

Ele ct ricit y, kWh 13.5 St e a m , 150 psig , lb 180 Water, cooling (20o_{F rise), 10}3_{g a l} _1.85

Acid ,lb 15 Ca ust ic,lb 0.1

Installation: Nearly 600,000 bpsd installed capacity.

Reference:Hydrocarbon Processing,Vol. 64, No. 9, September 1985, pp. 67–71.

Licensor: Stratco, Inc.

START START Olefin feed 6 i-Butane 3 5 1 2 Propane product 4 n-Butane product Alkylate product

Alkylation

Application: The Alkylene process uses a solid catalyst to react isobu-tane with light olefins (C3to C5) to produce a branched-chain paraffinic

fuel. The performance characteristics of this catalyst and novel process design have yielded a technology that is competitive with traditional liq-uid-acid-alkylation processes. Unlike liquid-acid-catalyzed technologies, significant opportunities to continually advance the catalytic activity and selectivity of this exciting new technology are possible. This process meets today’s demand for both improved gasoline formulations and a more “environmentally friendly” light olefin upgrading technology.

Description: Olefin charge is first treated to remove impurities such as diolefins and oxygenates (1). The olefin feed and isobutane recycle are mixed with reactivated catalyst at the bottom of the reactor vessel riser (2). The reactants and catalyst flow up the riser in a cocurrent manner where the alkylation reaction occurs. Upon exiting the riser, the catalyst separates easily from the hydrocarbon effluent liquid by gravity and flows downward into the cold reactivation zone of the reactor. The hydrocarbon effluent flows to the fractionation section (3), where the alky-late product is separated from the LPG product. There is no acid solu-ble oil (ASO) or heavy polymer to dispose of as with liquid acid technology. The catalyst flows slowly down the annulus section of the reactor around the riser as a packed bed. Isobutane saturated with hydrogen is injected to reactivate the catalyst. The reactivated catalyst then flows through standpipes back into the bottom of the riser. The reactivation in this section is nearly complete, but some strongly adsorbed material remains on the catalyst surface. This is removed by processing a small portion of the circulating catalyst in the reactivation vessel (4), where the temperature is elevated for complete reactivation. The reactivated catalyst then flows back to the bottom of the riser.

Product quality: Alkylate has ideal gasoline properties such as: high research and motor octane numbers, low Reid vapor pressure (Rvp), and no aromatics, olefins or sulfur. The alkylate from an Alkylene unit has the particular advantage of lower 50% and 90% distillation temperatures, which is important for new reformulated gasoline specifications.

Economics: (basis: FCC source C4olefin feed)

Investment(b a s is : 6 ,0 00-b p sd u n it ), $ p e r b p sd 6 ,1 00 Operating cost($/g a l) 0.45 Licensor: UOP LLC. Light ends Alkylate LPG 4 2 1 Olefin feed i- C₄ /H₂ i- C₄ /H₂ Isobutane recycle 3

H Y D R O C A R B O N P RO C E SS IN G NOVEMBER 2002 I89

(7)

Alkylation

Application: The UOP Indirect Alkylation (InAlk) process uses solid catalysts to react isobutylene with light olefins (C3to C5) to produce a

high-octane, low-vapor pressure, paraffinic gasoline component similar in quality to traditional motor alkylate.

Description: The InAlk process combines two, commercially proven technologies: polymerization and olefin saturation. Isobutylene is reacted with light olefins (C3to C5) in the polymerization reactor (1), the

result-ing mixture is stabilized (2) and the isooctane-rich stream is saturated in the saturation reactor (3). Recycle hydrogen is removed (4) and the product is stripped (5) to remove light-ends.

The InAlk process is more flexible than the traditional alkylation pro-cesses. Using a direct alkylation process, refiners must match the isobutane requirement with olefin availability. The InAlk process does not require isobutane to produce a high-quality product. Additional flexibility comes from being able to revamp existing catalytic condensation and MTBE units easily to the InAlk process.

The flexibility of the InAlk process is in both the polymerization and saturation 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 saturation section and optimized processing condi-tions. Existing MTBE units can be converted to the InAlk process with only minor modifications.

Product quality: High-octane, low Rvp, mid-boiling-range paraf-finic gasoline blending component with no aromatic content, low-sul-fur content and adjustable olefin content.

Economics: (basis: C4feed from FCC unit)

Investment (ba sis: 2,800-bp sd u nit ), $/bp sd

G ra ssro o t s 3,000 Re va m p o f MTBE unit 1,580 Utilities(per bbl alkylate)

Hyd ro g e n,lb 5.2 Po w er,kW 7.5 St e a m ,HP,lb 385 St e a m ,LP,lb 50 Licensor: UOP LLC. 1 2 3 4 5 Olefin feed Raffinate Offgas Alkylate Makeup hydrogen Polymerization reactors Debutanizer column Saturation reactor Product stripper

Alkylation— feed preparat ion

Application: Upgrades alkylation plant feeds with Alkyfining process. Description: Diolefins and acetylenes in the C4(or C3–C4) feed react

selectively with hydrogen in the liquid-phase, fixed-bed reactor under mild temperature and pressure conditions. Butadiene and, if C3s are present,

methylacetylene and propadiene are converted to olefins.

The high isomerization activity of the catalyst transforms 1-butene intocis - andtrans -2-butenes, which affords higher octane-barrel pro-duction.

Good hydrogen distribution and reactor design eliminate channel-ing while enablchannel-ing 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 possible when pure hydrogen is available eliminating the need for a stabilizer. The

process integrates easily with the C3/C4splitter.

Alkyfining performance and impact on HF alkylation product:

The results of an Alkyfining unit t reat ing a n FCC C4HF a

lkyla-tion unit feed containing 0.8% 1,3-butadiene are: But a d ie ne in a lkyla t e, ppm < 10 1-b ut e ne iso me riz a t io n, % 70 But ene s yie ld , % 100.5 RON incre a se in a lkyla t e 2 MON incre a se in a lkyla t e 1 Alkylat e 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 reduces ASO production and HF consumption.

Economics:

Investment: Gra ssroo ts ISBL cost:

For a n HF un it, $/bp sd 430 For a n H₂SO₄unit , $/b psd 210 Annual savings for a 10,000-bpsd alkylat ion unit : HF unit 4.1 m illio n U.S.$ H2SO4unit 5.5 m illio n U.S.$

Installation: Over 80 units are operating with a total installed capac-ity of 700,000 bpsd

Licensor: Axens, Axens NA.

Reactor Stripper Fuel gas

Hydroisomerized C4s to alkylation

Hydrogen C4 feed

(8)

Arom at ics ext ractio n

Application: Simultaneous recovery of benzene, toluene and xylenes (BTX) from reformate or pyrolysis gasoline (pygas) using liquid-liquid extraction.

Description: At the top of extractor operating at 30°C to 50°C and 1 to 3 bar, the solvent, N-Formylmorpholin with 4% to 6% water, is fed as a continuous phase. The feedstock—reformate or pygas—enters sev-eral stages above the base of the column. Due to density differences, the feedstock bubbles upwards, countercurrent to the solvent. Aromatics pass into the solvent, while the nonaromatics move to the top, remain-ing in the light phase. Low-boilremain-ing nonaromatics from the top of the extrac-tive distillation (ED) column enter the base of the extractor as counter-solvent.

Aromatics and solvent from the bottom of the extractor enter the ED, which is operated at reduced pressure due to the boiling-temperature threshold. Additional solvent is fed above the aromatics feed containing small amounts of nonaromatics that move to the top of the column. In the bottom section, as well as in the side rectifier, aromatics and practically water-free solvent are separated.

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.

Economics:

Consumption per ton of feedstock

St e a m (20 b a r), t /t 0.46 Wat er, coo ling (T= 10ºC), m3_/t ₁₂

Ele ct ric po w e r, kWh/t 18 Production yield Be nz ene ,% ~ 100 To luene ,% 99.7 EB, Xyle ne s,% 94.0 Purity Be nz ene , w t % 99.999 To luene , w t % >99.99 EB, Xyle ne s, w t % >99.99

Installation: One Morphylex plant was erected.

Reference: Emmrich, G., F. Ennenbach and U. Ranke, “Krupp Uhde Processes for Aromatics Recover y,” European Petrochemical Technology Conference, June 21–22, 1999, London.

Licensor: Uhde GmbH. Nonaromatics Aromatics Side stripper Light nonaromatics Extractive distillation column Water Water Feed BTX-fraction Extractor Washer Water & solvent

Arom at ics ext ract ive dist illation

Application: Recovery of high-purity aromatics from reformate, pyrolysis gasoline or coke-oven light oil using extractive distillation. Description: In the extractive distillation (ED) process, a single-compound solvent, N-Formylmorpholin (NFM) alters the vapor pres-sure of the components being separated. The vapor prespres-sure of the aro-matics is lowered more than that of the less soluble nonaroaro-matics.

Nonaromatics vapors leave the top of the ED column with some sol-vent, which is recovered in a small column that can either be mounted on the main column or installed separately.

Bottom product of the ED column is fed to the stripper to separate pure aromatics from the solvent. After intensive heat exchange, the lean solvent is recycled to the ED column. NFM perfectly satisfies the neces-sary solvent properties needed for this process including high selectivity, thermal stability and a suitable boiling point.

Economics: Pygas feedstock: Benzene Benzene/toluene Production yield Be nze ne 99.95% 99.95% To lue ne – 99.98% Quality

Be nze ne 30 w t ppm NA* 80 w t ppm NA* To lue ne – 600 w t ppm NA* Consumption

St e a m 475 kg /t ED f ee d 680 kg /t ED f e ed ** Reformate feedstock with low aromatics content (20wt%):

Benzene Quality

Be nze ne 10 w t ppm NA* Consumption

St e a m 320 kg /t ED fe e d

* Maximum content of nonaromatics. * * Including benzene/toluene splitter.

Installation: 45 Morphylane plants (total capacity of more than 6 MMtpa).

Reference:Emmrich, G., F. Ennenbach and U. Ranke, “Krupp Uhde Processes for Aromatics Recovery,” European Petrochemical Technology Conference, June 21–22, 1999, London.

Licensor: Uhde GmbH. Nonaromatics Aromatics Extractive distillation column Stripper column Aromatics fraction Solvent Solvent+aromatics

(9)

Aromatics recovery

Application: GT-BTX is an aromatics recovery process. The technol-ogy uses extractive distillation to remove benzene, toluene and xylene (BTX) from refinery or petrochemical aromatics streams such as catalytic reformate or pyrolysis gasoline. The process is superior to conventional liq-uid-liquid and other extraction processes in terms of lower capital and oper-ating costs, simplicity of operation, range of feedstock and solvent perfor-mance. Flexibility of design allows its use for grassroots aromatics recovery units, debottlenecking or expansion of conventional extraction systems. Description: The technology has several advantages:

• Less equipment required, thus, significantly lower capital cost com-pared to conventional liquid-liquid extraction systems

• Energy integration reduces operating costs • Higher product purity and aromatic recovery

• Recovers aromatics from full-range BTX feedstock without pre-fractionation

• Distillation-based operation provides better control and simplified operation

• Proprietary formulation of commercially available solvents exhibits high selectivity and capacity

• Low solvent circulation rates

• Insignificant fouling due to elimination of liquid-liquid contactors

• Fewer hydrocarbon emission sources for environmental benefits • Flexibility of design options for grassroots plants or expansion of existing liquid-liquid extraction units.

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 column bottoms in a vapor/liquid distillation operation. The nonaromatic hydro-carbons exit the top of the column and pass through a condenser. A por-tion 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-recov-ery column (SRC), where the aromatics are stripped overhead. Stripping steam from a closed-loop water circuit facilitates hydrocarbon removal. The SRC is operated under a vacuum to reduce the boiling point at the base of the column. Lean solvent from the bottom of the SRC is passed through heat exchange before returning to the EDC. A small portion of the lean cir-culating solvent is processed in a solvent-regeneration step to remove heavy decomposition products.

The SRC overhead mixed aromatics product is routed to the purifi-cation section, where it is fractionated to produce chemical-grade ben-zene, toluene and xylenes.

Economics: Estimated installed cost for a 15,000-bpd GT-BTX extraction unit processing BT-Reformate feedstock is $12 million (U.S. Gulf Coast 2002 basis).

Installations: Three grassroots applications. Licensor: GTC Technology Inc.

START Lean solvent Aromatics-rich solvent Aromatics to downstream fractionation Steam Water Raffinate Solvent recovery column Extractive distillation column 1 2 Hydrocarbon feed

Benzene reduction

Application: Benzene reduction from reformate, with the Benfree pro-cess, using integrated reactive distillation.

Description: Full-range reformate from either a semiregenerative or CCR reformer is fed to the reformate splitter column, shown above. The splitter operates as a dehexanizer lifting C6and lower-boiling components

to the overhead section of the column. Benzene is lifted with the light ends, but toluene is not. Since benzene forms azeotropic mixtures with some C7 paraffin isomers, these fractions are also entrained with the light

fraction.

Above the feed injection tray, a benzene-rich light fraction is wi th-drawn and pumped to the hydrogenation reactor outside the column. A pump enables the reactor to operate at higher pressure than the column, thus ensuring increased solubility of hydrogen in the feed.

A slightly higher-than-chemical stoichiometric ratio of hydrogen to benzene is added to the feed to ensure that the benzene content of the resulting gasoline pool is below mandated levels, i.e., below 1.0 vol% for many major markets. The low hydrogen flow minimizes losses of gasoline product in the offgas of the column. Benzene conversion to cyclohexane can easily be increased if even lower benzene content is desired. The reac-tor effluent, essentially benzene-free, is returned to the column.

The absence of benzene disrupts the benzene-iso-C 7azeotropes,

thereby ensuring that the latter components leave with the bottoms frac-tion of the column. This is particularly advantageous when the light refor-mate is destined to be isomerized, because iso-C₇paraffins tend to be cracked to C3and C4components, thus leading to a loss of gasoline

pro-duction. Economics:

Investment,G ra ssro o t s ISBL co st , $/b psd : 300 Combined utilit ies,$/b b l 0.17 Hydrogen Stoichiometric to benzene Catalyst,$/b b l 0.01

Installation: Eighteen benzene reduction units have been licensed. Licensor: Axens, Axens NA.

. C₅-C₉ Reformate H2 Splitter Offgas Heavy reformate Light reformate C5 /C6

(10)

Cat alyt ic cracking

Application: To selectively convert gas oils and residual feedstocks to higher-value cracked products such as light olefins, gasoline and distillates. Description: The Milli-Second Catalytic Cracking (MSCC) process uses a fluid catalyst and a novel contacting arrangement to crack heav-ier materials into a highly selective yield of light olefins, gasoline and dis-tillates. A distinguishing feature of the process is that the 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 out-standing.

The configuration of an MSCC unit has the regenerator (1) at a higher elevation than the reactor (2). Regenerated catalyst falls down a stand-pipe (3), through a shaped opening (4) that creates a falling curtain of catalyst, and across a well-distributed feed stream. The products from this initial reaction are quickly separated from the catalyst. The catalyst then passes into a second reaction zone (5), where further reaction and stripping occurs. This second zone can be operated at a higher temperature, which is achieved through contact with regenerated catalyst.

Since a large portion of the reaction product is produced under very short time conditions, the reaction mixture maintains good product 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 again. Installations: A new MSCC unit began operation earlier this year. Four MSCC units are currently in operation.

Reference: “Short-Contact-Time FCC,” AIChE 1998 Spring Meet-ing, New Orleans.

Licensor: UOP LLC (in cooperation with BARCO).

Feed MSCC reactor Regenerator 3 4 2 1 5

Cat alytic dew axing

Application: Use the ExxonMobil Selective Catalytic Dewaxing (MSDW) process to make high VI lube base stock.

Products: High VI/low-aromatics lube base oils (light neutral through bright stocks). Byproducts include fuel gas, naphtha and low-pour diesel. Description: MSDW is targeted for hydrocracked or severely hydrotreated stocks. The improved selectivity of MSDW for the highly isoparaffinic-lube components, which results in higher lube yields and VI’s. The process uses multiple catalyst systems with multiple reactors. Inter-nals are proprietary (the Spider Vortex Quench Zone technology is used). Feed and recycle gases are preheated and contact the catalyst in a down-flow-fixed-bed reactor. Reactor effluent is cooled, and the remain-ing aromatics are saturated in a post-treat reactor. The process can be inte-grated into a lube hydrocracker or lube hydrotreater. Postfractionation is targeted for client needs.

Operating conditi ons:

Tempera tures , °F 550 to 800 Hydrogen partial pressures, psig 500 to 2,500 LHSV 0.4 to 3.0

Conversion depends on feed wax content Pour point reduction as needed.

Yields:

Light neut ral Heavy neut ral Lub e yie ld , w t % 94.5 96.5 C1t o C4,w t % 1.5 1.0

C₅– 400° F,w t % 2.7 1.8 400° F–Lub e, w t % 1.5 1.0 H2co ns, scf /b b l 100–300 100–300

Economics: $3,000–5,500 per bpsd installed cost (U. S. Gulf Coast). Installation: Three units are operating, one under construction and one being converted.

Licensor: ExxonMobil Research & Engineering Co.

Lube product HDT Rxr HDW Rxr Purge MP steam Oily water LT sep HT sep Water

Fuel ags to LP absorber Wild naphtha Sour water Sour water Distillate Vacuum system Makeup H2 MP steam Vac dryer Vac strip. Water wash Water wash M/ U Rec HP stripper Waxy feed

(11)

Cat alytic dew axing

Application: Catalytic dewaxing process improves the cold flow properties (pour point, CFPP) of distillate fuels so that deeper cuts can be made at the crude unit. Thus, middle-distillate fuel production can be increased. The waxy n-paraffins are selectively cracked to produce a very high yield of distillate with some fuel gas, LPG and naphtha. Description: The heart of the dewaxing process is the zeolitic cata-lyst, which operates at typical distillate hydrotreating conditions. This fea-ture allows low-cost revamp for existing hydrotreaters into a HDS/DW unit by adding reactor volume. The dewaxing step requires a very small increase in hydrogen consumption; thus, the incremental operating cost is low. Since the dewaxing catalyst is tolerant of sulfur and nitrogen components in the feed, it can be located upstream of the HDS catalyst. The run length for the dewaxing catalyst can be designed to match the HDS catalyst.

Economics: The cost of a new HDS/DW is estimated at 1,000-2,000 $/bbl depending primarily on hydrotreating requirements.

Installation: One unit is operating, and one ultra-low-sulfur/dewax-ing unit is under design.

Hydrogen m akeup Fresh feed Dewaxing reactor Hydrotreating reactor H2-rich gas Absorber Lean amine HP separator LP separator Product stripper Diesel Wild naphtha Offgas Rich amine Furnace

Catalytic reforming

Application: Upgrade various types of naphtha to produce high-octane reformate, BTX and LPG.

Description: Two different designs are offered. One design is conven-tional where the catalyst is regenerated in place at the end of each cycle. Oper-ating normally in a pressure range of 12 to 25 kg/cm2 (170 to 350 psig) and with low pressure drop in the hydrogen loop, the product is 90 to 100 RONC. With its higher selectivity, trimetallic catalyst RG582 and RG682 make an excellent catalyst replacement for semi-regenerative reformers.

The second, the advanced Octanizing process, uses continuous cata-lyst regeneration allowing operating pressures as low as 3.5 kg/cm2₍₅₀

psig). This is made possible by smooth-flowing moving bed reactors (1– 3) which use a highly stable and selective catalyst suitable for continuous regeneration (4). Main features of Axens’s regenerative technology are:

• Side-by-side reactor arrangement, which is very easy to erect and con-sequently 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.

Finally, with the new CR401 (gasoline mode) and AR501 (aromatics production) catalysts specifically developed for ultra-low operating pres-sure and the very effective catalyst regeneration system, refiners operating Octanizing or Aromizing processes can obtain the highest 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:

Co nven tional Oct an izing Ope r. press., kg /cm2 _10–15 _<5 Yield, w t% of f eed Hyd ro g e n 2.8 3.8 C5+ 83 88 RONC 100 102 MONC 89 90.5 Economics:

Investment(basis 25,000 bpsd cont inuous octa nizing u nit, ba tt ery limits, erecte d cost, mid-2002 Gulf Coa st), U.S.$ per b psd 1,800 Utilities:typical per b bl feed:

Fue l, 103_{kca l} ₆₅

Ele ct ricit y, kWh 0.96 St e a m , ne t , HP, kg 12.5 Wat er, boiler feed , m3 _0.03

Installation: Of 110 units licensed, 60 units are designed with con-tinuous regeneration technology capability.

Reference: “Continuing Innovation In Cat Reforming,” NPRA Annual Meeting, March 15–17, 1998, San Antonio.

“Fixed Bed Reformer Revamp Solutions for Gasoline Pool Improve-ment,”Petroleum Technology Quarterly,Summer 2000.

“Increase reformer performance through catalytic solutions,” ERTC 2002, Paris.

Licensor: Axens, Axens NA.

START Feed 2 3 4 1 Reformate

(12)

Catalytic reforming

Application: Increase the octane of straight-run or cracked naphthas for gasoline production.

Products: High-octane gasoline and hydrogen-rich gas. Byproducts may be LPG, fuel gas and steam.

Description: Semi-regenerative multibed reforming over platinum or bimetallic catalysts. Hydrogen recycled to reactors at the rate of 3 to 7 mols/mol of feed. Straight-run and/or cracked feeds are typically hydrotreated, but low-sulfur feeds (<10 ppm) may be reformed without hydrotreatment.

Operating conditions: 875°F to 1,000°F and 150 to 400 psig reac-tor conditions.

Yields: Depend on feed characteristics, product octane and reactor pres-sure. The following yields are one example. The feed contains 51.4% paraf-fins, 41.5% naphthenes and 7.1% aromatics, and boils from 208°F to 375°F (ASTM D86). Product octane is 99.7 RONC and average reac-tor pressure is 200 psig.

Component w t % vol% H2 2.3 1,150 scf /b b l C1 1.1 — C2 1.8 — C3 3.2 — iC4 1.6 — nC4 2.3 — C₅+ 87.1 — LPG — 3.7 Re f o rm a t e — 83.2 Economics:

Utilities, (per bb l feed )

Fuel, 103_{Bt u}_{rele a se} ₂₇₅

Elect ricit y,kWh 7.2 Wa t e r, co o ling (20° F rise ), g a l 216 St e a m pro d uce d (175 psig sa t ), lb 100

Licensor: Howe-Baker Engineers, Ltd., a subsidiary of Chicago Bridge & Iron Co.

START Reactors Heaters Net gas High-pressure flash Low-pressure flash CW Liquid to stabilizer Steam BFW Hot feed

Catalytic reforming

Application: Upgrade naphtha for use as a gasoline blendstock or feed to a petrochemical complex with the UOP CCR Platforming process. The unit is also a reliable, continuous source of high-purity hydrogen. Description: Constant product yields and onstream availability dis-tinguish the CCR Platforming process featuring catalyst transfer with min-imum lifts, no valves closing on catalyst and gravity flow from reactor to reactor (2,3,4). The CycleMax regenerator (1) provides simplified oper-ation and enhanced performance at a lower cost than other designs. The product recovery section downstream of the separator (7) is customized to meet site-specific requirements. The R-270 series catalysts offer the high-est C₅+ _{and hydrogen yields while also providing the R-230 series}

attributes of CCR Platforming process unit flexibility through reduced coke make.

Semiregenerative reforming units also benefit from the latest UOP catalysts. R-86 catalyst provides the high stability with excellent yields at low cost. 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 semiregenerative units to obtain the full benefits of CCR Platforming technology.

Yields:

Operat ing mode Sem iregen. Cont inuous Onst re a m a va ila b ilit y, d a ys/yr 330 360 Fee d st o ck, P/N/A LV% 63/25/12 63/25/12 IBP/EP,° F 200/360 200/360 Operating conditions

Re a ct o r pre ssure , psig 200 50 C5+ o ct a ne , RONC 100 100 Ca t a lyst R-86 R-274 Yield information Hyd ro g en, scf b 1,270 1,690 C5+,w t % 84.8 91.6 Economics:

Investment (basis: 20,000 bpsd CCR Platforming unit, 50 psig reactor pressure, 100 C5+ RONC, 2002, U.S. Gu lf Co a st ISBL):

$ per b psd 2,100

Installation: UOP has licensed more than 800 platforming units; 37 customers have selected CCR platforming for two or more catalytic reforming units. Twenty-nine refiners operate 100 of the 173 operating units. Twenty units are designed for initial semiregenerative operation with the future installation of a CCR regeneration section.

Operating Design & const. To t a l CCR Pla t f o rm ing unit s 173 47 Ult ra -lo w 50 psig unit s 44 31 Unit s a t 35,000+ b psd 29 5 Semiregenerat ive units

w it h a st a cked re a ct o r 14 5 Licensor: UOP LLC. START Charge Spent catalyst To fractionator Net gas to H2 users

Net gas to fuel

5 4

3 2

1 6 7

(13)

Cat alyt ic SO

_x

removal

Application: The Wet gas Sulfuric Acid (WSA) process catalytically removes more than 99% + of sulfurous compounds from moist acid gases without prior drying and recovers concentrated sulfuric acid.

WSA combined with selective catalytic reduction, the SNOX pro-cess, efficiently removes nitrogen oxides (up to 95%) and sulfur oxides from flue gases and offgases. The main applications in refineries are H2S gases,

onsite regeneration of alkylation acid (spent acid recovery (SAR)), FCC regenerator offgases (example below), and boiler offgases, especially flue gases from petroleum coke and heavy residual oil fired boilers.

Description: Flue gas from the FCC regenerator is cooled to 430°F (220°C) in the waste-heat boiler. By means of an electrostatic precipita-tor, catalyst and coke particulates are reduced to less than 0.18 lb/MMscf. The flue gas is heated to approximately 770°F (410°C) before entering the SO2 reactor. In the SO2 reactor, SO2 is oxided to SO3, and all

remaining particulates are deposited in the catalyst panels. The reactor consists of several parallel catalyst panels, which can be individually cleaned and reloaded without interrupting plant operation.

After the SO2converter, the gas is cooled to near the acid dew point.

In the last step, concentrated sulfuric acid is condensed, and flue gas is cooled in the WSA condenser. Hot cooling air from the condenser may be used for preheating of boiler feedwater or as preheated air for the FCC regenerator/CO boiler.

All equipment, except the condenser, is made of carbon steel or low alloy steel. The WSA process has few moving parts, low maintenance costs and high onstream availability. The process can be applied to new or revamp installations.

The WSA process is characterized by:

• 99% or more of the flue gas sulfur is recovered as commercial grade concentrated sulfuric acid

• Particulates are essentially completely removed

• No waste solids or wastewater is produced. No absorbents or aux-iliary chemicals are used

• Operating costs decrease with increasing sulfur content in flue gas • Process is fully automated, contains few moving parts and does not use a circulation of slurries or solids

• Simple operation allows wide flexibility in operating loads. Installation: More than 40 units worldwide.

Blower Dust filter Heat exchanger Support heat Offgas FCCU Oil Products Oil feed Lift air CO boiler Acid pump Acid cooler Product acid SO2 converter Hot air Stack gas

Blower Air WSA condenser

Coking

Application: Conversion of vacuum residues (virgin and hydrotreated), various petroleum tars and coal tar pitch through delayed coking. Products: Fuel gas, LPG, naphtha, gas oils and fuel, anode or needle grade coke (depending on feedstock and operating conditions). Description: Feedstock is introduced (after heat exchange) to the bot-tom of the coker fractionator (1) where it mixes with condensed recycle. The mixture is pumped through the coker heater (2) where the desired cok-ing temperature is achieved, to one of two coke drums (3). Steam or boiler feedwater is injected into the heater tubes to prevent coking in the fur nace tubes. Coke drum overhead vapors flow to the fractionator (1) where they are separated into an overhead stream containing the wet gas, LPG and naph-tha; two gas oil sidestreams; and the recycle that rejoins the feed.

The overhead stream is sent to a vapor recovery unit (4) where the individual product streams are separated. The coke that forms in one of at least two (parallel connected) drums is then removed using high-pres-sure water. The plant also includes a blow-down system, coke handling and a water recovery system.

Operating conditi ons:

He a t er o ut le t t e m pera t ure, ° F 900–950 Co ke d rum pre ssure, psig 15–90 Re cycle ra t io , vo l/vo l f e e d , % 0–100

Yields:

Vacuum residue of

M i dd le Ea st h yd ro tre at ed Co al t ar Feedst ock vac. residue bot t oms pit ch G ra vit y, ° API 7.4 1.3 211.0 Sulf ur,w t % 4.2 2.3 0.5 Conradson ca rb o n, w t % 20.0 27.6 — Products, wt% G a s+ LPG 7.9 9.0 3.9 Na pht ha 12.6 11.1 — G a so ils 50.8 44.0 31.0 Co ke 28.7 35.9 65.1 Economics:

Investment (basis: 20,000 bpsd straight-run vacuum residue feed , U.S. Gulf Coast 2002, fuel-gra de coke, includes vapor recov-ery), U.S. $ pe r b psd (t ypica l) 4,000

Utilities,typical/bb l of fee d:

Fue l, 103_{Bt u} ₁₄₅

Ele ct ricit y, kWh 3.9 St e a m (e xpo rt e d ), lb 20 Wa t er, co o ling , g a l 180

Installation: More than 55 units.

Reference: Mallik, Ram, Gary and Hamilton, “Delayed coker design considerations and project execution,” NPRA 2002 Annual Meeting, March 17–19, 2002.

Licensor: ABB Lummus Global Inc.

START 1 4 Fuel gas C₃ /C₄ LP Coker naphtha 2

Light gas oil Heavy gas oil BFW Stm. Stm. Stm. BFW Fresh feed 3 3