Refining Processes

Refining

Processes

2002

www.HydrocarbonProcessing.com

2002 Processes

Refining Process Index Alkylation Alkylation . . . . . . . . . . . . . . . 86, 86, 88, 89, 89, 90 Alkyl lkylat at ion—feed ion—feed preparat ion . . . . . . . . 90 Aromat ics ics extraction extraction . . . . . . . . . . . . . . . 91 Aromat ics ics extractive extractive distil distillation lation . . . . . . 91 Aromat ics ics recovery recovery . . . . . . . . . . . . . . . . 92 Benzene reduction . . . . . . . . . . . . . . . . . 92 Cata lytic lytic cracki cracking ng . . . . . . . . . . . . . . . . . . 94 Cata lytic lytic dewa xing xing . . . . . . . . . . . . . . 94, 94, 95 Cata lytic lytic reforming . . . . . . . . . . . . . 95, 95, 96 Cata lytic SOx removal . . . . . . . . . . . . . . . 97 Coking Coking . . . . . . . . . . . . . . . . . . . . . . . . 97, 97, 98 Crude Crude distillation distillation . . . . . . . . . . . . . . 99, 99, 100 100 Dearomatization— middle distil distillate late . . . . . . . . . . . . . . . 100 100 Deasphalting . . . . . . . . . . . . . . . . . . . . 101 101 Deep cata lytic lytic cracki cracking ng . . . . . . . . . . . . 102 102 Deep thermal conver conversi sion on . . . . . . . . . . 102 102 Desulfurizat ion . . . . . . . . . . . . . . . . . . . 103 Dew axing/w ax de oiling oiling . . . . . . . . . . . . 104 104 Diesel Diesel desulfurizat desulfurizat ion . . . . . . . . . . . . . 104 104 Diesel Diesel hydrotrea tment . . . . . . . . . . . . . 105 105 Electrical lectrical desa lting . . . . . . . . . . . . . . . . 105 Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . 106 106 Ethers-MTBE . . . . . . . . . . . . . . . . . . . . . 108 Fluid ca ta lytic cracking cracking . . . . . . . . . . 108, 108, 110, 110, 111, 111, 112 Gas treating—H 2S removal removal . . . . . . . . . 112 112 Ga sification sification . . . . . . . . . . . . . . . . . . . . . . 113

Gasoline Gasoline de sulfurization sulfurization . . . . . . . . . . . 113 113 Gasoline Gasoline desulfurizat desulfurizat ion, ultra-deep ultra-deep . . . . . . . . . . . . . . . . . . . . 114 114 H2S and SWS SWS gas conversion conversion . . . . . . . . 114 114 Hydrocracki Hydrocracking ng . . . . . . . . . . . 115, 115, 116 116,, 117 117 Hydrocrack Hydrocracking, ing, residue residue . . . . . . . . . . . . 118 118 Hydrocracking/ hydrotreating—V hydrotreating—VGO GO . . . . . . . . . . . 118 118 Hydrocracking (mild)/ VGO hydrotrea ting . . . . . . . . . . . . . 119 119 Hydrodearomat Hydrodearomat ization . . . . . . . . . . . . 119 119 Hydrode sulfuriza sulfuriza tion . . . . . . . . . . 120, 120, 121 121 Hydrodesulfurization, ultra-low-s ultra-low-sulfur ulfur diesel diesel . . . . . . . . . . 121 121 Hydrodesulfurization— pretreatment pretreatment . . . . . . . . . . . . . . . . . 122 122 Hydrodesulfurization—UD Hydrodesulfurization—UDHDS HDS . . . . . . 122 122 Hydrofinishi Hydrofinishing/ ng/hydrotrea hydrotrea ting . . . . . . . 123 123 Hydrog Hydrog en . . . . . . . . . . . . . . . . . . . . . . . 123 123 Hydrog Hydrog ena tion . . . . . . . . . . . . . . . . . . . 124 124 Hydrotre at ing . . . . 124, 124, 125, 125, 126, 126, 127, 127, 128 128 Hydrotreating—aromatic saturat ion . . . . . . . . . . . . . . . . . . . . 128 128 Hydrotreating—catalytic dew axing . . . . . . . . . . . . . . . . . . . . . 129 129 Hydrotrea Hydrotrea ting—resi ting—residd . . . . . . . . . . . . . . 129 129 Isomeriza tion . . . . . . . . . . . . 130, 130, 131, 131, 132 132 Isoocta ne /isoo isoo ctene . . . . . . . . . . . 132, 132, 133 133

Isoo Isoo ctene /Isoocta ne /ETBE . . . . . . . . . 133 133 Low -tempe rature NO x r e d uc uc t io io n . . . . 134 LPG recovery . . . . . . . . . . . . . . . . . . . . . 134 134 Lube hyd roprocessi roprocessing ng . . . . . . . . . . . . . 135 135 Lube treat ing . . . . . . . . . . . . 135, 135, 136 136,, 137 137 NO x aba tement . . . . . . . . . . . . . . . . . . 137 137 Olefins . . . . . . . . . . . . . . . . . . . . . . . . . . 138 138 Olefins recovery recovery . . . . . . . . . . . . . . . . . . 139 139 Oligomerization Oligomerization o f C 3C4 cuts . . . . . . . . 139 139 Oligomeri Oligomerization— zation—poly polynaphtha naphtha . . . . . 140 140 Prereformi Prereforming ng w ith feed ultrapurific ultrapurificat at ion . . . . . . . . . . . . . . . 140 140 Resid Resid cata lytic lytic cracki cracking ng . . . . . . . . . . . . 142 142 Residue Residue hyd roprocessing roprocessing . . . . . . . . . . . 142 142 SO 2 removal . . . . . . . . . . . . . . . . . . . . . 143 143 Sour gas treatment . . . . . . . . . . . . . . . 143 143 Spent acid recovery recovery . . . . . . . . . . . . . . . 144 144 Sulfur Sulfur deg assing assing . . . . . . . . . . . . . . . . . . 144 144 Therma l ga soil process . . . . . . . . . . . . . 145 145 Treating . . . . . . . . . . . . . . . . . . . . . . . . 145 145 Vacuum d istil istillation lation . . . . . . . . . . . . . . . 146 146 Visbrea isbrea king king . . . . . . . . . . . . . . . . . . 146, 146, 147 147 Wet scrubbing scrubbing system system . . . . . . . . . . . . . 147 147 Wet -chem istry istry NOx reduction reduction . . . . . . . 148 148 White oil and w ax hydrotrea ting . . . . . . . . . . . . . . . . . 148 148

Licens Lic ensor or Ind ex ABB ABB Lumm Lumm us Globa l Inc. Inc. . . . . . . . . .86, 97, 97, 108, 127, 128, 130 ABB ABB Lumm Lumm us Glob al B.V. B.V. . . .102, 145, 145, 146 146 Aker Kvaerner Kvaerner . . . . . . . . . . . . . . . . . . . 133 133 Akzo Nobel Catalysts B.V. . . . .86, 122, 129 Axens Axens . . . . . . . . . . . . . . . . . . . . . 90, 90, 92, 95, 95, 105, 106, 111, 114, 115, 118, 129, 130, 139, 140, 142 Axens Axens NA . . . . . . . . . . . . . . . . . . 90, 90, 92, 95, 95, 105, 106, 114, 115, 118, 129, 130, 139, 140 BARC BARCO O . . . . . . . . . . . . . . . . . . . . . . . . . . 94 BASF BASF . . . . . . . . . . . . . . . . . . . . . . . . . . . 148 Bechte l Corp. Corp. . . . . . . . . . . . . . 98, 104, 104, 135 135 Belco Techn olo g ies Corp. . . . . . . . . . . . . 134, 134, 143, 143, 147, 147, 148 148 Black &Vea &Vea tch Pritchard, Inc. . . . 134, 134, 144 144 BOC Group, Inc. Inc. . . . . . . . . . . . . . . . . . . 134 134 Cansolv Techno log ies Inc. Inc. . . . . . . . . . . 148 CDTECH CDTECH . . . . . . . . . 106, 124, 131, 133, 133, 146 Chevron Lummus Glob al LLC LLC . . . . 115, 115, 116 116 Chicago Chicago Bridg Bridg e &Iron Co. . . . 96, 96, 105, 105, 125 125 Conoco Inc. . . . . . . . . . . . . . . . . . . . . . . . 98

Cono coPh illips illips Co., Co., Fuels Techn olo g y Divisi Division on . . . . . . . . . . . 88, 88, 104, 104, 113, 113, 131 131 Criteri Criterion on Cata lyst lyst a nd Techno log ies Co. Co. . . . . . . . . . . . 127, 127, 128 128 Davy Process Techno logy . . . . . . . . . . . 140 140 Enge lhard Corp. . . . . . . . . . . . . . . . . . . 100 100 ExxonMo xxonMo bil Resea Resea rch &Eng &Eng ineering Co. . . . . 86, 94, 94, 110, 110, 112, 120, 120, 136, 136, 137 137 Fina Resea Resea rch rch S.A. S.A. . . . . . . . . . . . . . . . . 129 129 Fortum Oil and Gas OY . . . . . . . . . 86, 86, 132 132 Fost er Wheele r . . . . . 98, 99, 99, 101, 101, 123, 123, 147 147 GTC GTC Techn olo g y Inc. . . . . . . . . . . . . 92, 103 103 Hald or Top Top søe A/S . . . . . . . . . . . 88, 95, 95, 97, 114, 119, 121, 125, 143, 144 Howe -Baker Engineers, Engineers, Ltd. Ltd. . 96, 96, 105, 105, 125 125 IFP Gro up Techno Techno log ies . . . . . . . . 111, 111, 142 142 JGC . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 126 Kellogg Kellogg Brown &Root, Inc. . 101, 101, 110 110,, 132 132 Linde BOC Proce ss Plan ts, LL LLC . . 126, 139 Lyond ell Chem Chem ical ical Co. . . . . . . . . . 131, 131, 133 133 Merichem Chemicals &Refinery Services Services LL LLC . . . . . . . . . . . . . . . . . . . 145 Process Dyna mics . . . . . . . . . . . . . . . . . 126 126

PDVSA-IN PDVSA-INT TEVEP EVEP . . . . . . . . . . . . . . . . . . .121 Research Research Institute Institute of Petroleum Processi Processing ng . . . . . . . . . . . . . . . . . . . . 102 102 Shell Glob al Solutions Inte rnat iona l B.V. B.V. . . . . . . . 99, 102 102,, 111, 111, 113, 116, 127, 128, 135, 142, 145, 146 SK Corp . . . . . . . . . . . . . . . . . . . . . 122, 122, 137 137 Snamproge tti SpA . . . . . . . . . . . . 106, 106, 133 133 Stone &Webster Inc. Inc. . . . . . . 102, 102, 111 111,, 142 142 Strat co, Inc. Inc. . . . . . . . . . . . . . . . . . . . . . . . 89 Synetix . . . . . . . . . . . . . . . . . . . . . . . . . .140 Technip-Coflexip echnip-Coflexip . . . . . . . . . . . . . . . . . 100 100 TOTAL OTAL FINA FINA ELF ELF . . . . . . . . . . . . . . . . . . 100 Udhe Edeleanu Gmb H . . . . 108, 108, 123 123,, 136, 136, 146, 148 Udhe Gm bH . . . . . . . . . . . . . . . . . . 91, 91, 138 138 UniPure Corp. . . . . . . . . . . . . . . . . . . . . 103 103 UOP LLC LLC . . . . . . . . . . . . . . . . . . . 89, 90, 90, 94, 96, 98, 101, 112, 117, 121, 127, 128, 132, 147 VEBA OEL OEL Gmb H . . . . . . . . . . . . . . . . . 117 117 Washington G roup Inte rnat iona l . . . . . . . . . . 100, 100, 122, 122, 137 137 H Y D R O C A R B O N P RO RO C E SS SS I NG

NOVEMBER NOVEMBER 2002

I 85

2002 Processes

Refining Process Index Alkylation Alkylation . . . . . . . . . . . . . . . 86, 86, 88, 89, 89, 90 Alkyl lkylat at ion—feed ion—feed preparat ion . . . . . . . . 90 Aromat ics ics extraction extraction . . . . . . . . . . . . . . . 91 Aromat ics ics extractive extractive distil distillation lation . . . . . . 91 Aromat ics ics recovery recovery . . . . . . . . . . . . . . . . 92 Benzene reduction . . . . . . . . . . . . . . . . . 92 Cata lytic lytic cracki cracking ng . . . . . . . . . . . . . . . . . . 94 Cata lytic lytic dewa xing xing . . . . . . . . . . . . . . 94, 94, 95 Cata lytic lytic reforming . . . . . . . . . . . . . 95, 95, 96 Cata lytic SOx removal . . . . . . . . . . . . . . . 97 Coking Coking . . . . . . . . . . . . . . . . . . . . . . . . 97, 97, 98 Crude Crude distillation distillation . . . . . . . . . . . . . . 99, 99, 100 100 Dearomatization— middle distil distillate late . . . . . . . . . . . . . . . 100 100 Deasphalting . . . . . . . . . . . . . . . . . . . . 101 101 Deep cata lytic lytic cracki cracking ng . . . . . . . . . . . . 102 102 Deep thermal conver conversi sion on . . . . . . . . . . 102 102 Desulfurizat ion . . . . . . . . . . . . . . . . . . . 103 Dew axing/w ax de oiling oiling . . . . . . . . . . . . 104 104 Diesel Diesel desulfurizat desulfurizat ion . . . . . . . . . . . . . 104 104 Diesel Diesel hydrotrea tment . . . . . . . . . . . . . 105 105 Electrical lectrical desa lting . . . . . . . . . . . . . . . . 105 Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . 106 106 Ethers-MTBE . . . . . . . . . . . . . . . . . . . . . 108 Fluid ca ta lytic cracking cracking . . . . . . . . . . 108, 108, 110, 110, 111, 111, 112 Gas treating—H 2S removal removal . . . . . . . . . 112 112 Ga sification sification . . . . . . . . . . . . . . . . . . . . . . 113

Gasoline Gasoline de sulfurization sulfurization . . . . . . . . . . . 113 113 Gasoline Gasoline desulfurizat desulfurizat ion, ultra-deep ultra-deep . . . . . . . . . . . . . . . . . . . . 114 114 H2S and SWS SWS gas conversion conversion . . . . . . . . 114 114 Hydrocracki Hydrocracking ng . . . . . . . . . . . 115, 115, 116 116,, 117 117 Hydrocrack Hydrocracking, ing, residue residue . . . . . . . . . . . . 118 118 Hydrocracking/ hydrotreating—V hydrotreating—VGO GO . . . . . . . . . . . 118 118 Hydrocracking (mild)/ VGO hydrotrea ting . . . . . . . . . . . . . 119 119 Hydrodearomat Hydrodearomat ization . . . . . . . . . . . . 119 119 Hydrode sulfuriza sulfuriza tion . . . . . . . . . . 120, 120, 121 121 Hydrodesulfurization, ultra-low-s ultra-low-sulfur ulfur diesel diesel . . . . . . . . . . 121 121 Hydrodesulfurization— pretreatment pretreatment . . . . . . . . . . . . . . . . . 122 122 Hydrodesulfurization—UD Hydrodesulfurization—UDHDS HDS . . . . . . 122 122 Hydrofinishi Hydrofinishing/ ng/hydrotrea hydrotrea ting . . . . . . . 123 123 Hydrog Hydrog en . . . . . . . . . . . . . . . . . . . . . . . 123 123 Hydrog Hydrog ena tion . . . . . . . . . . . . . . . . . . . 124 124 Hydrotre at ing . . . . 124, 124, 125, 125, 126, 126, 127, 127, 128 128 Hydrotreating—aromatic saturat ion . . . . . . . . . . . . . . . . . . . . 128 128 Hydrotreating—catalytic dew axing . . . . . . . . . . . . . . . . . . . . . 129 129 Hydrotrea Hydrotrea ting—resi ting—residd . . . . . . . . . . . . . . 129 129 Isomeriza tion . . . . . . . . . . . . 130, 130, 131, 131, 132 132 Isoocta ne /isoo isoo ctene . . . . . . . . . . . 132, 132, 133 133

Isoo Isoo ctene /Isoocta ne /ETBE . . . . . . . . . 133 133 Low -tempe rature NO x r e d uc uc t io io n . . . . 134 LPG recovery . . . . . . . . . . . . . . . . . . . . . 134 134 Lube hyd roprocessi roprocessing ng . . . . . . . . . . . . . 135 135 Lube treat ing . . . . . . . . . . . . 135, 135, 136 136,, 137 137 NO x aba tement . . . . . . . . . . . . . . . . . . 137 137 Olefins . . . . . . . . . . . . . . . . . . . . . . . . . . 138 138 Olefins recovery recovery . . . . . . . . . . . . . . . . . . 139 139 Oligomerization Oligomerization o f C 3C4 cuts . . . . . . . . 139 139 Oligomeri Oligomerization— zation—poly polynaphtha naphtha . . . . . 140 140 Prereformi Prereforming ng w ith feed ultrapurific ultrapurificat at ion . . . . . . . . . . . . . . . 140 140 Resid Resid cata lytic lytic cracki cracking ng . . . . . . . . . . . . 142 142 Residue Residue hyd roprocessing roprocessing . . . . . . . . . . . 142 142 SO 2 removal . . . . . . . . . . . . . . . . . . . . . 143 143 Sour gas treatment . . . . . . . . . . . . . . . 143 143 Spent acid recovery recovery . . . . . . . . . . . . . . . 144 144 Sulfur Sulfur deg assing assing . . . . . . . . . . . . . . . . . . 144 144 Therma l ga soil process . . . . . . . . . . . . . 145 145 Treating . . . . . . . . . . . . . . . . . . . . . . . . 145 145 Vacuum d istil istillation lation . . . . . . . . . . . . . . . 146 146 Visbrea isbrea king king . . . . . . . . . . . . . . . . . . 146, 146, 147 147 Wet scrubbing scrubbing system system . . . . . . . . . . . . . 147 147 Wet -chem istry istry NOx reduction reduction . . . . . . . 148 148 White oil and w ax hydrotrea ting . . . . . . . . . . . . . . . . . 148 148

Licens Lic ensor or Ind ex ABB ABB Lumm Lumm us Globa l Inc. Inc. . . . . . . . . .86, 97, 97, 108, 127, 128, 130 ABB ABB Lumm Lumm us Glob al B.V. B.V. . . .102, 145, 145, 146 146 Aker Kvaerner Kvaerner . . . . . . . . . . . . . . . . . . . 133 133 Akzo Nobel Catalysts B.V. . . . .86, 122, 129 Axens Axens . . . . . . . . . . . . . . . . . . . . . 90, 90, 92, 95, 95, 105, 106, 111, 114, 115, 118, 129, 130, 139, 140, 142 Axens Axens NA . . . . . . . . . . . . . . . . . . 90, 90, 92, 95, 95, 105, 106, 114, 115, 118, 129, 130, 139, 140 BARC BARCO O . . . . . . . . . . . . . . . . . . . . . . . . . . 94 BASF BASF . . . . . . . . . . . . . . . . . . . . . . . . . . . 148 Bechte l Corp. Corp. . . . . . . . . . . . . . 98, 104, 104, 135 135 Belco Techn olo g ies Corp. . . . . . . . . . . . . 134, 134, 143, 143, 147, 147, 148 148 Black &Vea &Vea tch Pritchard, Inc. . . . 134, 134, 144 144 BOC Group, Inc. Inc. . . . . . . . . . . . . . . . . . . 134 134 Cansolv Techno log ies Inc. Inc. . . . . . . . . . . 148 CDTECH CDTECH . . . . . . . . . 106, 124, 131, 133, 133, 146 Chevron Lummus Glob al LLC LLC . . . . 115, 115, 116 116 Chicago Chicago Bridg Bridg e &Iron Co. . . . 96, 96, 105, 105, 125 125 Conoco Inc. . . . . . . . . . . . . . . . . . . . . . . . 98

Cono coPh illips illips Co., Co., Fuels Techn olo g y Divisi Division on . . . . . . . . . . . 88, 88, 104, 104, 113, 113, 131 131 Criteri Criterion on Cata lyst lyst a nd Techno log ies Co. Co. . . . . . . . . . . . 127, 127, 128 128 Davy Process Techno logy . . . . . . . . . . . 140 140 Enge lhard Corp. . . . . . . . . . . . . . . . . . . 100 100 ExxonMo xxonMo bil Resea Resea rch &Eng &Eng ineering Co. . . . . 86, 94, 94, 110, 110, 112, 120, 120, 136, 136, 137 137 Fina Resea Resea rch rch S.A. S.A. . . . . . . . . . . . . . . . . 129 129 Fortum Oil and Gas OY . . . . . . . . . 86, 86, 132 132 Fost er Wheele r . . . . . 98, 99, 99, 101, 101, 123, 123, 147 147 GTC GTC Techn olo g y Inc. . . . . . . . . . . . . 92, 103 103 Hald or Top Top søe A/S . . . . . . . . . . . 88, 95, 95, 97, 114, 119, 121, 125, 143, 144 Howe -Baker Engineers, Engineers, Ltd. Ltd. . 96, 96, 105, 105, 125 125 IFP Gro up Techno Techno log ies . . . . . . . . 111, 111, 142 142 JGC . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 126 Kellogg Kellogg Brown &Root, Inc. . 101, 101, 110 110,, 132 132 Linde BOC Proce ss Plan ts, LL LLC . . 126, 139 Lyond ell Chem Chem ical ical Co. . . . . . . . . . 131, 131, 133 133 Merichem Chemicals &Refinery Services Services LL LLC . . . . . . . . . . . . . . . . . . . 145 Process Dyna mics . . . . . . . . . . . . . . . . . 126 126

PDVSA-IN PDVSA-INT TEVEP EVEP . . . . . . . . . . . . . . . . . . .121 Research Research Institute Institute of Petroleum Processi Processing ng . . . . . . . . . . . . . . . . . . . . 102 102 Shell Glob al Solutions Inte rnat iona l B.V. B.V. . . . . . . . 99, 102 102,, 111, 111, 113, 116, 127, 128, 135, 142, 145, 146 SK Corp . . . . . . . . . . . . . . . . . . . . . 122, 122, 137 137 Snamproge tti SpA . . . . . . . . . . . . 106, 106, 133 133 Stone &Webster Inc. Inc. . . . . . . 102, 102, 111 111,, 142 142 Strat co, Inc. Inc. . . . . . . . . . . . . . . . . . . . . . . . 89 Synetix . . . . . . . . . . . . . . . . . . . . . . . . . .140 Technip-Coflexip echnip-Coflexip . . . . . . . . . . . . . . . . . 100 100 TOTAL OTAL FINA FINA ELF ELF . . . . . . . . . . . . . . . . . . 100 Udhe Edeleanu Gmb H . . . . 108, 108, 123 123,, 136, 136, 146, 148 Udhe Gm bH . . . . . . . . . . . . . . . . . . 91, 91, 138 138 UniPure Corp. . . . . . . . . . . . . . . . . . . . . 103 103 UOP LLC LLC . . . . . . . . . . . . . . . . . . . 89, 90, 90, 94, 96, 98, 101, 112, 117, 121, 127, 128, 132, 147 VEBA OEL OEL Gmb H . . . . . . . . . . . . . . . . . 117 117 Washington G roup Inte rnat iona l . . . . . . . . . . 100, 100, 122, 122, 137 137 H Y D R O C A R B O N P RO RO C E SS SS I NG

NOVEMBER NOVEMBER 2002

I 85

Refining P roc roces ess ses 20 20 0 2 Propane product Isobutane Reactor system (1)

Olefin feed

Hydrogen Product distillation (3)

Isobutane feed

Recycle isobutane

Refrigerant

n-Butane Alkylate product

Hydrogen

3

2

Catalyst regeneration (2)

1

4 5

Olefin feed START

Recycle acid

Butane product

 

Makeup isobutane

6

Alkylate product

Alkylation

Alkylation

Application: The AlkyClean process converts light olefins into alkylate by reacting the olefins with isobutane over a true solid acid catalyst.  AlkyCle  Alk yClean an’’s uniqu uniquee catal catalyst, yst, reacto reactorr desig design n and and process process scheme scheme allows allows operoperation at low external isobutene to olefin ratios while maintaining excellent product quality.

Application: Combines propylene, butylene and pentylene with isobutane, in the presence of sulfuric acid a cid catalyst, to form a high-octane, mogas component. Products: A h highly ighly isoparaffinic, isoparaffinic, low Rvp, high-octane high-octane gasoline gasoline blendblendstock is produced from the alkylation process. Description: Olefin feed and recycled isobutane are introduced into the stirred, autorefrigerated reactor (1). Mixers provide intimate contact between the reactants and the acid catalyst. Reaction heat is removed from the reactor by the highly efficient autorefrigeration method. The hydrocarbons that are vaporized from the reactor, and that provide cooling to the 40°F level, are routed to the refrigeration compressor (2) where they  are compressed, condensed and returned to the reactor. A depropanizer (3), which is fed by a slipstream from the refrigeration section, is designed to remove any propane introduced to the plant with the feeds. The reactor 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 deisobutanizer deisobutanizer (5) along with makeup isobutane. The isobutane-rich overhead is recycled to the reactor. The bottoms are then sent to a debutanizer (6) to produce a low Rvp alkylate product with an FBP less than 400°F. Major features of the reactor are: • Use of the autorefrigeration method of cooling is thermodynamically efficient. It also allows lower temperatures, which are favorable for producing high product quality with low power requirements. requirements. • Use of a staged reactor system results in a high average isobutane concentration, which favors high product quality. • Use of low space velocity in the reactor design results in i n high product quality and eliminates any corrosion problems in the fractionation section associated with the formation of esters. • Use of low reactor operating pressure means high reliability for the mechanical seals for the mixers. • Use of simple reactor internals translates to low cost. Yields:

Products:  Alkylate is a high-octane, low-Rvp gasoline component used for blending in all grades of gasoline. Description: The light olefin feed is combined with the isobutene make-up and recycle and sent to the alkylation reactors which convert the olefins into alkylate using a solid acid catalyst (1). The AlkyClean process uses a true solid acid catalyst to produce alkylate eliminating the safety  and environmental hazards associated with liquid acid technologies. Simultaneously, Simultaneously, reactors are undergoing a mild liquid-phase liquid- phase regeneration using isobutene and hydrogen and, periodically, a reactor undergoes a  higher temperature vapor phase hydrogen strip (2). The reactor and mild regeneration effluent is sent to the product-fractionation section,  which produces propane, n-butane and alkylate, while also recycling  isobutene and recovering hydrogen used in regeneration for reuse in other refinery hydroprocessing units (3). AlkyClean does not produce any  acid soluble oils (ASO) or require post treatment of the reactor effluent or final products. Product: The C 5+ alkylate has a RON of 93–98 depending on processing conditions and feed composition. Economics: sis 10 10, 000 --b b p sd sd U ni n it ) $/b p sd sd Investment (b a si O p e r a t in g co st , $/g a l

3, 10 100 0. 47

Fortum’s Porvoo, Finland RefinInstallation: Demonstration unit at Fortum’s ery. Reference: “The Process: A new solid acid catalyst gasoline alkylation technology,” NPRA 2002 Annual Meeting, March 17–19, 2002.

Lummus Global Inc., Akzo Nobel Catalysts and and ForLicensor:  ABB Lummus tum Oil and Gas.

Alky la t e y ie ld Isobutane (pure) required Alky la t e q u a lit y

1. 78 b b l C5+ /bb l but ylene fe ed 1.17 1.17 bbl/bbl butylene feed 96 RO N/94 M O N

Economics: typical per barrel of alkylat alkylat e produced: Utilities, typical Wa te t e r,r, co ol o lin g (2 (20° F r ise ),), 1, 000 g a l 2. 1 P o w e r, kWh 10. 5 St e a m , 60 p sig , lb 200 H2SO 4 , lb 19 Na O H , 100%, lb 0. 1

Installation: 115,000-bpd capacity at 11 locations with the sizes ranging from 2,000 to 30,000 bpd. Single reactor/settle trains with capacities up to 9,500 bpsd. Reference: Lerner, H., “Exxon sulfuric acid alkylation technology,” Meyers, Ed., pp. Handbook of Petroleum Refining Processes, 2nd ed., R. A. Meyers, 1.3–1.14. Licensor: ExxonMobil Research & Engineering Co. Circle 275 on Reader Service Card 86

I HYD ROC ARBON

P RO RO C E SS SS I NG

NOVEMBER NOVEMBER 2002

Circle 276 on Reader Service Card

Refining P rocesses 20 0 2

Isobutane recycle

Propane Is ob ut an e

3

Is ob ut an e r ec yc le n-Butane

Propane

1

Olefin feed

Olefin feed

1

3

2

START

2 Motor fuel butane

 

4

Alkylate

Isobutane Alkylate

START

Alkylation

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, butylene and amylenes to produce branched chain hydrocarbons. As an alternative, FBA can conveniently be used to alkylate isopentane as a means of disposing isopentane for RVP control purpose.

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

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 catalyst with the advantages of a fixed-bed reactor system. Olefin and isobutane feedstocks are mixed with a recycle stream of isobutane and charged to the reactor section (1). The olefins are fully converted over a supportedliquid-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 quantitatively 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 activity maintenance is a distinct f eature of the FBA process. Other significant 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 C4 cut C3 –C5 cut Alkylate product RON (C 5+ ) 98 95 93 MON (C 5+ ) 95 92 91

Economics: (Basis: MTBE raffinate, inclusive feed pretreatment and on-site catalyst activity maintenance) Investment (basis: 6,000 bpsd unit), $ per bpsd Utilities, typical per bbl alkylate: Ele ct ricit y, kWh St e a m , MP (150 psig ), lb St e a m , LP (50 psig ), lb Wat er, coo ling (20°F rise), ga l103

Licensor: Haldor Topsøe A/S.

5,600 10 60 200 2.2

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 differential gravity head to effect catalyst circulation through a cooler prior to contacting 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 products. Small amount of dissolved catalyst is removed from the propane product 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 amylene 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-acidalkylation unit or a dimerization plant. ReVAP 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 PropyleneBut ylene but ylene mix

Composition (lv% ) Pro pyle ne Pro pa ne But yle ne i-But a ne n-But a ne i-Pent a ne Alkylate product G ra vit y, API RVP, psi ASTM 10%, ° F ASTM 90%, ° F RONC Per bbl olefin converted i-But a ne co nsum e d , b b l Alkyla t e pro d uce d , b b l

0.8 1.5 47.0 33.8 14.7 2.2

24.6 12.5 30.3 21.8 9.5 1.3

70.1 6–7 185 236 96.0

71.1 6–7 170 253 93.5

1.139 1.780

1.175 1.755

Installation: 107 alkylation units licensed worldwide. Licensor: Fuels Technology Division of ConocoPhillips Co. Circle 277 on Reader Service Card 88

I HYD ROC ARBON

P RO C E SS I NG

NOVEMBER 2002

Circle 278 on Reader Service Card

Refining P rocesses 20 0 2 Propane product

Light ends

5

2

LPG

3

6

1

4

n-Butane product

3 2

Alkylate product

Olefin feed

i- C4 /H 2

4

Olefin feed

Alkylate

i- C4 /H 2

START

1

i-Butane

Isobutane recycle

START

Alkylation

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.

Application: The Alkylene process uses a solid catalyst to react isobutane with light olefins (C 3 to 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 liquid-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.

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 H 2SO4 are charged to the STRATCO Contactor reactor (1). The liquid contents of the Contactor reactor 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 settler (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 Utilities, typical per bbl alkylate: Ele ct ricit y, kWh St e a m , 150 psig , lb Water, cooling (20 o F rise), 10 3 g a l Acid , lb Ca ust ic, lb

3,500 13.5 180 1.85 15 0.1

Installation: Nearly 600,000 bpsd installed capacity.

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 alkylate product is separated from the LPG product. There is no acid soluble 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 C 4 olefin feed)

Investment (b a s is : 6 ,0 00-b p sd u n it ), $ p e r b p sd Operating cost ($/g a l)

6 ,1 00 0.45

Licensor: UOP LLC.

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

Circle 279 on Reader Service Card

Circle 280 on Reader Service Card H Y D R O C A R B O N P RO C E SS I NG

NOVEMBER 2002

I 89

Refining P rocesses 20 0 2 Polymerization Debutanizer reactors column

Olefin feed

 

Saturation reactor

Product stripper

Offgas Reactor

Raffinate

1 3

2

4

Fuel gas

Stripper

5 Hydrogen

Hydroisomerized C4 s to alkylation

C4  feed Alkylate Makeup hydrogen

Alkylation

Alkylation— feed preparat ion

Application: The UOP Indirect Alkylation (InAlk) process uses solid catalysts to react isobutylene with light olefins (C 3 to C5) to produce a  high-octane, low-vapor pressure, paraffinic gasoline component similar in quality to traditional motor alkylate.

Application: Upgrades alkylation plant feeds with Alkyfining process.

Description: The InAlk process combines two, commercially proven technologies: polymerization and olefin saturation. Isobutylene is reacted  with light olefins (C3 to C5 ) in the polymerization reactor (1), the resulting 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 processes. 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 conditions. Existing MTBE units can be converted to the InAlk process with only minor modifications. Product quality: High-octane, low Rvp, mid-boiling-range paraffinic gasoline blending component with no aromatic content, low-sulfur content and adjustable olefin content. Economics: (basis: C4 feed from FCC unit)

Investment (ba sis: 2,800-bp sd u nit ), $/bp sd G ra ssro o t s Re va m p o f MTBE unit Utilities (per bbl alkylate) Hyd ro g e n, lb Po w er, kW St e a m , HP, lb St e a m , LP, lb

Licensor: UOP LLC.

3,000 1,580 5.2 7.5 385 50

Description: Diolefins and acetylenes in the C 4 (or C3 –C 4 ) feed react selectively with hydrogen in the liquid-phase, fixed-bed reactor under mild temperature and pressure conditions. Butadiene and, if C 3 s are present, methylacetylene and propadiene are converted to olefins. The high isomerization activity of the catalyst transforms 1-butene into cis - and trans -2-butenes, which affords higher octane-barrel production. Good hydrogen distribution and reactor design eliminate channeling while enabling high turndown ratios. Butene yields are maximized, hydrogen is completely consumed, and essentially, no gaseous byproducts 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 C 3 /C4 splitter. Alkyfining performance and impact on HF alkylation product: The results of an Alkyfining unit t reat ing a n FCC C4 HF a lkylation 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 For a n H 2SO 4 unit , $/b psd

430 210

Annual savings for a 10,000-bpsd alkylat ion unit : HF unit 4.1 m illio n U.S.$ H2SO 4 unit 5.5 m illio n U.S.$

Installation: Over 80 units are operating with a total installed capacity of 700,000 bpsd Licensor: Axens, Axens NA.

Circle 281 on Reader Service Card 90

I HYD ROC ARBON

P RO C E SS I NG

NOVEMBER 2002

Circle 282 on Reader Service Card

Refining P rocesses 20 0 2 Nonaromatics

Washer

Extractor

Water & solvent

Extractive distillation column

Nonaromatics

Extractive distillation column

Water

Aromatics fraction

Feed BTXfraction

Side stripper

Aromatics Stripper column

Water Aromatics

Light nonaromatics

Solvent

Solvent+aromatics

Arom at ics ext ractio n

Arom at ics ext ract ive dist illation

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

Application: Recovery of high-purity aromatics from reformate, pyrolysis gasoline or coke-oven light oil using extractive distillation.

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 several 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, remaining in the light phase. Low-boiling nonaromatics from the top of the extractive distillation (ED) column enter the base of the extractor as countersolvent.  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 Wat er, coo ling (T= 10ºC), m 3/t Ele ct ric po w e r, kWh/t Production yield Be nz ene , % To luene , % EB, Xyle ne s,% Purity Be nz ene , w t % To luene , w t % EB, Xyle ne s, w t %

0.46 12 18 ~ 100 99.7 94.0 99.999 >99.99 >99.99

Description: In the extractive distillation (ED) process, a singlecompound solvent, N-Formylmorpholin (NFM) alters the vapor pressure of the components being separated. The vapor pressure of the aromatics is lowered more than that of the less soluble nonaromatics. Nonaromatics vapors leave the top of the ED column with some solvent, 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 f ed 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 necessary solvent properties needed for this process including high selectivity, thermal stability and a suitable boiling point. Economics: Pygas feedstock: Production yield Be nze ne To lue ne Quality Be nze ne To lue ne Consumption St e a m

Benzene

Benzene/toluene

99.95% –

99.95% 99.98%

30 w t ppm NA* –

80 w t ppm NA* 600 w t ppm NA*

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 f e e d * Maximum content of nonaromatics. * * Including benzene/toluene splitter.

Installation: One Morphylex plant was erected.

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

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

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.

Licensor: Uhde GmbH.

Circle 283 on Reader Service Card

Circle 284 on Reader Service Card H Y D R O C A R B O N P RO C E SS I NG

NOVEMBER 2002

I 91

Refining P rocesses 20 0 2

Offgas

C5 /C 6 Water

Hydrocarbon feed START

1

Splitter

Raffinate

Lean solvent

Extractive distillation column

Solvent recovery column

Aromatics to downstream fractionation

C5 -C 9 Reformate

H2 Light reformate

2 Steam

Heavy reformate

Aromatics-rich solvent

Aromatics recovery

Benzene reduction

Application: GT-BTX is an aromatics recovery process. The technology 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 liquid-liquid and other extraction processes in terms of lower capital and operating costs, simplicity of operation, range of feedstock and solvent performance. 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 compared 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 prefractionation • 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 hydrocarbons exit the top of the column and pass through a condenser. A portion of the overhead stream is returned to the top of the column as reflux  to wash out any entrained solvent. The balance of the overhead stream is the raffinate product, requiring no further treatment. Rich solvent from the bottom of the EDC is routed to the solvent-recovery 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 circulating solvent is processed in a solvent-regeneration step to remove heavy  decomposition products. The SRC overhead mixed aromatics product is routed to the purification section, where it is fractionated to produce chemical-grade benzene, 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.

Application: Benzene reduction from reformate, with the Benfree process, using integrated reactive distillation.

Circle 286 on Reader Service Card

Circle 287 on Reader Service Card

92

I HYD ROC ARBON

P RO C E SS I NG

NOVEMBER 2002

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 C 6 and 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 C 7 paraffin isomers, these fractions are also entrained with the light fraction.  Above the feed injection tray, a benzene-rich light fraction is wi thdrawn 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 reactor effluent, essentially benzene-free, is returned to the column. The absence of benzene disrupts the benzene-iso-C 7 azeotropes, thereby ensuring that the latter components leave with the bottoms fraction of the column. This is particularly advantageous when the light reformate is destined to be isomerized, because iso-C 7 paraffins tend to be cracked to C 3 and C4 components, thus leading to a loss of gasoline production. Economics: 300 Investment, G ra ssro o t s ISBL co st , $/b psd : Combined utilit ies, $/b b l 0.17 Stoichiometric to benzene Hydrogen 0.01 Catalyst, $/b b l

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

.

Refining P rocesses 20 0 2 Makeup H2

Regenerator

1

Water wash

M/ U HDW Rxr

3

Feed MSCC reactor

2

Fuel ags to LP absorber

Purge

HDT Rxr

Waxy feed

Rec Water wash LT HT sep sep

4

Water

Wild naphtha HP Sour water stripper MP steam Vacuum system Vac strip.

Sour water

Oily water

Distillate

5

MP steam Lube product

Vac dryer

Cat alyt ic cracking

Cat alytic dew axing

Application: To selectively convert gas oils and residual feedstocks to higher-value cracked products such as light olefins, gasoline and distillates.

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

Description: The Milli-Second Catalytic Cracking (MSCC) process uses a fluid catalyst and a novel contacting arrangement to crack heavier materials into a highly selective yield of light olefins, gasoline and distillates. 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 outstanding. The configuration of an MSCC unit has the regenerator (1) at a higher elevation than the reactor (2). Regenerated catalyst falls down a standpipe (3), through a shaped opening (4) that creates a falling curtain of  catalyst, and across a well-distributed feed stream. 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.

Products: High VI/low-aromatics lube base oils (light neutral through bright stocks). Byproducts include fuel gas, naphtha and low-pour diesel.

Installations: A new MSCC unit began operation earlier this year. Four MSCC units are currently in operation.

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. Internals 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 remaining aromatics are saturated in a post-treat reactor. The process can be integrated into a lube hydrocracker or lube hydrotreater. Postfractionation is targeted for client needs. Operating conditi ons: Tempera tures , ° F Hydrogen partial pressures, psig LHSV

550 to 800 500 to 2,500 0.4 to 3.0

Conversion depends on feed wax content Pour point reduction as needed. Yields: Lub e yie ld , w t % C1 t o C4 , w t % C5 – 400° F, w t % 400° F–Lub e, w t % H 2 co ns, scf /b b l

Light neut ral 94.5 1.5 2.7 1.5 100–300

Heavy neut ral 96.5 1.0 1.8 1.0 100–300

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

Economics: $3,000–5,500 per bpsd installed cost (U. S. Gulf Coast).

Licensor: UOP LLC (in cooperation with BARCO).

Installation: Three units are operating, one under construction and one being converted. Licensor: ExxonMobil Research & Engineering Co.

Circle 288 on Reader Service Card 94

I HYD ROC ARBON

P RO C E SS I NG

NOVEMBER 2002

Circle 289 on Reader Service Card

Refining P rocesses 20 0 2 Hydrogen m akeup

Furnace Dewaxing reactor

Hydrotreating reactor

Absorber Lean amine

Offgas

Feed START

Rich amine

1

4

3

2

H2 -rich gas

Fresh feed HP separator

Wild naphtha LP separator   Product stripper

 

Reformate

Diesel

Cat alytic dew axing

Catalytic reforming

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.

Application: Upgrade various types of naphtha to produce high-octane reformate, BTX and LPG. Description: Two different designs are offered. One design is conventional where the catalyst is regenerated in place at the end of each cycle. Operating 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 catalyst regeneration allowing operating pressures as low as 3.5 kg/cm 2 (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 consequently leads to low investment cost. • The Regen C catalyst regeneration system featuring the dry burn loop, completely restores the catalyst activity while maintaining its specific area for more than 600 cycles. Finally, with the new CR401 (gasoline mode) and AR501 (aromatics production) catalysts specifically developed for ultra-low operating pressure and the very effective catalyst regeneration system, refiners operating  Octanizing or Aromizing processes can obtain the highest hydrogen, C 5+ 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:

Description: The heart of the dewaxing process is the zeolitic catalyst, which operates at typical distillate hydrotreating conditions. This feature 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/dewaxing unit is under design. Licensor: Haldor Topsøe A/S.

Ope r. press., kg /cm 2 Yield, w t% of f eed Hyd ro g e n C5 + RONC MONC

Co nven tional 10–15

Oct an izing