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1、Ultra Low Sulfur Gasoline via Commercially Proven Catalytic Distillation Gasoline Desulfurization Requirements - Pool sulfur specification - Europe European Union 50 ppm max - 2005 10 ppm max - available 2005 - standard 2008 - US, Canada 30 ppm avg - 2002 to 2008 - Future 15 -10 -5 ppm? - 2005+ - Mx
2、ico 300 / 500 ppm max (150 avg) - 2004 80 ppm max (30 avg) - 2006 / 2008 Modern Refinery Requirements Maximize refinery margin Minimize refinery downtime/shutdown costs Minimum FCC turnaround cycle 5 years Avoid any FCC downstream shutdowns - Choose FCC gasoline HDS technology wisely FCC Gasoline Fe
3、ed Composition 0 2000 4000 6000 8000 10000 12000 50100150200250 Temperature, C Sulfur, ppm 0 10 20 30 40 Olefins, % SulfurOlefins FCC C5+ GASOLINE Optimized FCC Gasoline HDS LCN Mild HDSMild HDS MediumMedium HDSHDS SevereSevere HDSHDS MCN HCN MCN/HCN Conventional FCC LCN Treating Fractionate LCN fro
4、m FCC Gasoline Selective Hydrogenation TREATED LCN HYDROGEN Hydrogen Compression FCC C5+ GASOLINE MCN/HCN FRESH CAUSTIC Mercaptan Removal SPENT CAUSTIC Caustic wash for mercaptan removal - 90% effective Selective hydrogenation of dienes for alky/ethers Compression of makeup hydrogen LCN Vent Gas CW
5、Steam Hydrogen Bottoms Treated Distillate Hydrocarbon Feed CDHydroProcess Hydrogenation/Distillation Add Hydrogen Feed Replace trays with structured distillation packing containing catalyst Vent excess Hydrogen Catalyst Section Drawing LCN LCN RSH Dienes Hydrogen Wire Mesh Catalyst Reflux Sulfides C
6、atalytic Distillation RSH + Diene Sulfide Selective Hydrogenation FCC C5+ GASOLINE FRESH CAUSTIC TREATED LCN HYDROGEN MCN/HCN Mercaptan Removal Hydrogen Compression SPENT CAUSTIC Improved LCN Treating Replace upper section with CDHydro (5-7 barg) HYDROGEN Eliminate fresh caustic and caustic wash - 9
7、9.5% HDS Heavy sulfur to bottom Off GasCW Hydrogen Desulfurized FCC C7+ Gasoline CDHDS FCC C7+ Gasoline Light olefins to top Min octane loss Low H2 consumption Low sulfur bottoms product good for gasoline or diesel No yield loss due to cracking No makeup compressor No mid-cycle shutdown for catalyst
8、 regen No feed storage required MCN HCN CD Optimized FCC Gasoline HDS Hydrogen CDHDS Hydrogen FCC C5+ GASOLINE LCN MCN/HCN CDHydro ShellMartinez, CaliforniaDepentanizer LCN CDHydroSeptember-95 PennzoilShrevesport, LouisianaDepentanizer LCN CDHydroApril-97 ShellPort Arthur, Texas Dehexanizer HCN CDHD
9、SMay-00 Irving OilSt. John, New Brunswick, Can. Dehexanizer LCN CDHydroNovember-00 Irving OilSt. John, New Brunswick, Can. Splitter HCN CDHDSNovember-00 Veba OelGelsenkirchen, Germany Dehexanizer LCN CDHydroOctober-00 ChevronTexacoPembroke, UK Dehexanizer LCN CDHydroJanuary-00 ChevronTexacoPembroke,
10、 UK Splitter HCN CDHDSJanuary-00 PetroChinaNanchong, China Dehexanizer LCN CDHydroJanuary-00 Motiva Port Arthur, Texas Dehexanizer LCN CDHydroFebruary-03 Motiva Port Arthur, Texas Splitter HCN CDHDSFebruary-03 HellenicAspropyrgos, GreeceDehexanizer LCN CDHydroSeptember-03 MotivaConvent, LouisianaDeh
11、exanizer LCN CDHydroOctober-03 MotivaConvent, LouisianaSplitter HCN CDHDSOctober-03 ValeroTexas City, TexasDehexanizer LCN CDHydroNovember-03 ValeroTexas City, TexasSplitter HCN CDHDSNovember-03 EquilonPuget Sound, WADehexanizer LCN CDHydroNovember-03 EquilonPuget Sound, WASplitter HCN CDHDSNovember
12、-03 MotivaNorco, LouisianaDehexanizer LCN CDHydroJanuary-04 MotivaNorco, LouisianaSplitter HCN CDHDSJanuary-04 CDTECH FCC Gasoline Desulfurization Operating Experience 21 Units with greater than 45 years total operation Why does CDTECH have less octane loss for a given olefin reduction? CDHDS Select
13、ivity Comparison MCN/HCN Feed 0 0.2 0.4 0.6 0.8 1 200250300350400450500 Temperature, F Conversion, Fraction Sulfur reductionOlefin reduction Olefin saturation is higher for heavy olefins Conventional Fixed Bed Reactor Selectivity Comparison 0.00% 20.00% 40.00% 60.00% 80.00% 100.00% 20025030035040045
14、0500 Temperature, F Conversion, Fraction Sulfur reductionOlefin reduction Olefin saturation is higher for light olefins Heavy Olefins Have Less Octane loss RON Linear Olefin - RON Linear Saturate 0 20 40 60 80 100 120 567891011 Carbon Number RON Why is CDTECHs octane loss lower? Answer: Conventional
15、 fixed bed hydrotreaters - Saturate primarily light olefins - Light olefin saturation causes high octane loss CDHDS - Higher saturation of heavy olefins - Less octane to lose in heavy olefins - Lower octane loss at a given olefin reduction Why Does CDTECH Claim Longer Catalyst Life? Conventional fix
16、ed bed hydrotreaters - Olefins form oligomers - Oligomers form coke that fouls catalyst - Catalyst activity reduced - Regenerate or replace catalyst CDHydro/CDHDS - Olefins form oligomers - Oligomers removed by distillation - Catalyst stays clean - Replace catalyst at end of FCC cycle (5 years) - No
17、 mid FCC cycle shutdown required Commercial Catalyst Activity for FCC Gasoline HDS 0365730 Days on Oil Fixed Bed HDS SOR EOR Conventional Fixed Bed Technology Catalyst Activity Tracker for the Motiva, Port Arthur CDHDS Units CDTECH - Confidential 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 3/15/0010/1/004/1
18、9/0111/5/015/24/0212/10/026/28/031/14/048/1/04 Date Observed Rate Const. K pod CDHDS1K pod CDHDS2 Update ! An approach used by others LCN HCN FCC Diene Treater Fixed-bed Wet treatment Wet treatment An approach used by others LCN HCN FCC Diene Treater Fixed-bed Wet treatment Wet treatment CDTECH has
19、lower capital cost Long CDTECH Catalyst Cycle Reduces Capex Conventional Fixed Bed HDS - Feed diene removal required - Mid FCC cycle catalyst regeneration/replacement - Shutdown FCC or store HDS feed CDHydro/CDHDS - No feed diene removal required - No shutdown during FCC cycle - No FCC shutdown - No
20、 additional storage tanks - No additional capex required FCC Gasoline HDS Commercial Status CDHydro - 12 commercial units in operation - 5 years guaranteed catalyst life CDHDS - 7 commercial units in operation - Motiva, Port Arthur (expanded) - Irving Oil, Saint John, NB - ChevronTexaco, Pembroke, U
21、K - Motiva, Convent - SOPUS, Puget Sound - Valero - 5 years guaranteed catalyst life Motiva Port Arthur CDHDS Phase 1 12,000 BPD HCN 90% HDS Phase 2 - Tier II - 30 ppm S - 50,000 BPD FRCN - New CDHydro - Additional CDHDS - Future 10 ppm S capability - Demo 1400 ppm to 8ppm Irving Oil Limited CDHydro
22、/CDHDS Saint John, New Brunswick Canada 58,000 BPD RFCC gasoline November 2000 start up - 1 month to acceptance - 150 ppm pool - 2 years ahead of regulations 2002 - 30 ppm pool - 3 years ahead of regulations Texaco Pembroke, UK 50,000 BPD full range FCC gasoline 1st CDHydro/CDHDS in Europe 1Q02 star
23、t up - UK ULSG supported by tax incentive Equilon/Motiva/Deer Park Refining 7 refineries 275,000 bpd FCC gasoline capacity CDHydro and/or CDHDS Start-up 2002 - 2004 Valero Refining 5(+2) refineries World Fuels Today statement by Valero V.P. - For grassroots units, CDTECH has: - Lowest capital cost -
24、 Lowest octane loss - Lowest hydrogen consumption PetroChina Announcement 05/03/2003 2002 World Oil Industry Top Ten Technology Breakthroughs - 9 upstream technologies - 1 downstream technology - CDTECHs CDHydro/CDHDS FCC gasoline desulfurization Conclusions CDHydro - Lowest sulfur and diolefins in
25、LCN - Eliminates separate mercaptan and diolefin removal units - Boosts octane CDHDS - Lowest olefin loss via HDS - No diene pretreatment required - No regeneration/feed storage required CDHydro/CDHDS - Commercially proven - Most cost effective HDS in FR FCC CN - Long catalyst life via catalytic distillation - Only HDS technology to provide 5 year life - Low capital cost Q&A