JP2004504478A - Use of hydrogen to regenerate metal oxide hydrogen sulfide sorbents - Google Patents
Use of hydrogen to regenerate metal oxide hydrogen sulfide sorbents Download PDFInfo
- Publication number
- JP2004504478A JP2004504478A JP2002514251A JP2002514251A JP2004504478A JP 2004504478 A JP2004504478 A JP 2004504478A JP 2002514251 A JP2002514251 A JP 2002514251A JP 2002514251 A JP2002514251 A JP 2002514251A JP 2004504478 A JP2004504478 A JP 2004504478A
- Authority
- JP
- Japan
- Prior art keywords
- sorbent
- hydrogen sulfide
- hydrogen
- regenerating
- regeneration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002594 sorbent Substances 0.000 title claims abstract description 223
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims description 66
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 45
- 239000001257 hydrogen Substances 0.000 title claims description 45
- 229910044991 metal oxide Inorganic materials 0.000 title abstract description 9
- -1 metal oxide hydrogen sulfide Chemical class 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 89
- 238000011069 regeneration method Methods 0.000 claims abstract description 63
- 230000008929 regeneration Effects 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 29
- 230000023556 desulfurization Effects 0.000 claims abstract description 29
- 230000001172 regenerating effect Effects 0.000 claims abstract description 19
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 67
- 239000003054 catalyst Substances 0.000 claims description 55
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 51
- 229910052717 sulfur Inorganic materials 0.000 claims description 51
- 239000011593 sulfur Substances 0.000 claims description 51
- 230000008569 process Effects 0.000 claims description 40
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011246 composite particle Substances 0.000 claims description 2
- 230000001629 suppression Effects 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 claims 2
- 239000003085 diluting agent Substances 0.000 claims 2
- 229910052721 tungsten Inorganic materials 0.000 claims 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 239000003701 inert diluent Substances 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 claims 1
- 150000002739 metals Chemical group 0.000 abstract description 11
- 150000004706 metal oxides Chemical class 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 19
- 230000000694 effects Effects 0.000 description 17
- 229910052593 corundum Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910020630 Co Ni Inorganic materials 0.000 description 3
- 229910002440 Co–Ni Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 3
- 229910001603 clinoptilolite Inorganic materials 0.000 description 3
- 230000001010 compromised effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910020706 Co—Re Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000012993 chemical processing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
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- 230000000149 penetrating effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 101100025412 Arabidopsis thaliana XI-A gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020637 Co-Cu Inorganic materials 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical group 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/56—Use in the form of a bed
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Abstract
水素ガスを用いて金属酸化物脱硫収着剤を再生するための方法。収着剤は、事実上、単一金属又は多金属のものであってよく、好ましくはＮｉ及び／又はＣｏを含んで成る。望ましくは、二次金属を取込んで再生効率及び／又は能力を増大させることができる。その他の添加剤が炭化水素の分解を抑制する。A method for regenerating a metal oxide desulfurization sorbent using hydrogen gas. The sorbent may be monometallic or polymetallic in nature, and preferably comprises Ni and / or Co. Desirably, secondary metals can be incorporated to increase regeneration efficiency and / or capacity. Other additives suppress the decomposition of hydrocarbons.
Description
【０００１】
関連出願に対する相互参照
本出願は、仮出願第６０／０２４，７３７号の利益を主張する米国特許５，９２５，２３９号として１９９９年７月２０日に発行された１９９７年８月２２日付の米国出願第０８／９１８，６４１号の一部継続出願である、１９９９年６月７日付けの米国出願第０９／３２６，８２７号の一部継続出願である。
【０００２】
発明の分野
本発明は、水素ガスを使用して金属酸化物硫化水素収着剤を再生するための方法に関する。収着剤は、一元又は多元金属収着剤でありうる。
【０００３】
発明の背景
供給原料から硫黄を除去することは、精製及び石油化学工業の基本的プロセスである。供給原料から硫黄を除去するための１つの方法は、水素化脱硫である。水素化脱硫は、硫化水素を形成するべく、かなり厳しい温度及び圧力で、Ｐｔ、Ｐｄのような貴金属又は非貴金属硫化物、特にＣｏ／Ｍｏ又はＮｉ／Ｍｏを担持した触媒で水素と供給原料の硫黄を反応させることに関している。水素化脱硫触媒は、硫化水素の存在によって性能が阻害される。脱硫で生成された硫化水素を除去するために収着剤を使用すれば、水素化脱硫方法全体の有効性が改善される。
【０００４】
硫化水素収着剤の性能は、さまざまな物性によって左右される。硫化の熱力学及び反応速度は、予め定められたＨ２Ｓレベルで突破（ブレークスルー）する前の全硫黄容量が決定されることから、明らかに重要である。その他の重要な収着剤特性には、長時間の使用における安定性及び再生可能性、再生に必要な運転条件及び下流の硫黄回収方法の選択を大きく決定する再生オフガスの組成が含まれる。
【０００５】
任意の硫化水素収着剤の使用に関する１つの実際的な制限は、収着剤を再生する能力にある。最も見込みがあり広く研究されている収着剤の酸化亜鉛は、硫化については非常に高い平衡定数を有するが、硫化水素用収着剤として使用後に酸化亜鉛を再生することは困難である。従って、かかる収着剤の範囲及び利用可能性は、処理されている硫黄のレベル、必要とされる反応器の容積特性及び使用済み収着剤の除去及び廃棄に関する問題に関連した経済的制約によって制限される。これらの制約は、硫化水素収着剤が収着剤再生手段によって可能となる多重サイクル作業の能力をもっていれば緩和される。
【０００６】
スピネル及びゼオライトベースの材料は、再生可能な硫化水素収着剤である。これらの材料は、プロセス温度が好ましくは約７５〜１２５℃に制限されているガス流から硫化水素を除去するのに特に適しているが、これらの材料は、従来の水素化脱硫技術で使用される高温での硫化水素の捕捉用としては効率の低いものである。
【０００７】
クリノプティロライト分子ふるいも同じく再生可能である。ただし、クリノプティロライト分子ふるいが標準的に処理される温度は、同様に比較的低いものである。クリノプティロライト分子ふるいは、約９０℃〜約２６０℃の温度でＣ４〜Ｃ１２の原料流から硫化水素を除去するために使用される。使用済みクリプティロライト分子ふるいは、約１５０℃〜約３７０℃の温度でパージガスと共に再生される。
【０００８】
現在、高温ガス流の処理に使用されている再生可能な固体収着剤は、一般的に金属酸化物をベースにしており、約６００℃よりも往々にして高い温度の酸化条件下で再生される。酸化雰囲気を用いたこれらの収着剤の再生には、可燃性有機物質及び水素の初期置換が必要であり、これはコストが高いばかりでなく、特にこのような高温では危険でもある。
【０００９】
当該技術分野においては、なおも、さまざまな硫化水素収着剤材料を再生しうる方法に対するニーズが存在している。
【００１０】
発明の概要
本発明は、第１サイクル容量をもつ硫化水素収着剤を再生するための方法において、再生用濃度の水素を含むガスに対し、水素が使用済み硫化水素収着剤を再生し、かくして第１サイクル容量と実質的に同じ再生された容量をもつ再生収着剤を生成するのに有効な条件下で、使用済み硫化水素収着剤を暴露する工程を含む方法を提供する。
【００１１】
発明の詳細な説明
本発明は、固体硫化水素収着剤を再生するために、酸化雰囲気の代りに還元雰囲気を使用する。還元雰囲気は、好ましくは、単独で又は不活性ガス好ましくは窒素と組み合せた水素ガスを含む。
【００１２】
本発明の再生可能な収着剤は、好ましくは、Ｆｅ、Ｎｉ、Ｃｏ又はＣｕから選択された少なくとも一種の金属の酸化物である。好ましい実施形態では、金属は、Ｎｉ、Ｃｏ、及びそれらの組み合せから成る群から選択される。適切な担持された金属及び金属酸化物ベースの再生可能な硫化水素収着剤の例としては、５Ｃｏ／Ａｌ２Ｏ３；１０Ｃｏ／ＳｉＯ２；２０Ｃｏ／ＴｉＯ２；２０Ｃｏ／ＺｒＯ２；５Ｎｉ／Ａｌ２Ｏ３；１０Ｎｉ／ＳｉＯ２；２０Ｎｉ／ＺｒＯ２；５Ｃｕ／Ａｌ２Ｏ３；１０Ｃｕ／ＳｉＯ２；２０Ｃｕ／ＺｒＯ２；５Ｆｅ／Ａｌ２Ｏ３；１０Ｆｅ／ＳｉＯ２；２０Ｆｅ／ＮｉＺｒＯ２；５Ｃｏ−５Ｃｕ／Ａｌ２Ｏ３；１０Ｃｏ−１０Ｃｕ／ＳｉＯ２；１０Ｎｉ−５Ｃｕ／ＳｉＯ２；２０Ｎｉ−２Ｃｕ／ＺｒＯ２；１０Ｃｏ−２Ｐｔ／Ａｌ２Ｏ３；１０Ｃｏ−５Ｐｄ／ＳｉＯ２；１０Ｃｏ−１Ｓｎ／Ａｌ２Ｏ３；２０Ｎｉ−４Ｓｎ／ＳｉＯ２が含まれるが、必ずしもこれらに制限されるわけではない。ここで、数字は、収着剤の合計重量に基づく金属の重量％を意味する。
【００１３】
収着剤は、ラネー金属、重質塊状金属（ｐｏｎｄｅｒｏｕｓ ｍｅｔａｌｓ）、リッケ金属及び金属スポンジを含めた、細分割されたスケルトン金属を内包する（ただし必ずしもこれらに制限されるわけではない）バルク金属として、又はバルク金属酸化物として利用可能である。
【００１４】
収着剤は、例えば表面積、細孔容積及び／又は細孔径を増大させるために無機担体材料上に担持されうる。適切な担体材料は、アルミナ、シリカ、ジルコニア、炭素、炭化ケイ素、珪藻土、アモルファス及び結晶質シリカ−アルミナ、シリカ−マグネシア、アルミノホスフェート、ボリア、チタニア及びそれらの組み合せを含む（ただし、必ずしもこれらに制限されるわけではない）無機酸化物担体材料である。好ましい担体材料には、アルミナ、ジルコニア及びシリカが含まれる。金属又は金属酸化物は、当該技術分野において既知の従来の技術によりこれらの担体上に担持され得る。かかる技術には、初期湿潤による含浸、余剰の含浸媒質からの吸着、及びイオン交換が含まれる。好ましい実施形態においては、再生可能な収着剤は、金属ハロゲン化物、酸化物、水酸化物、炭酸塩、硝酸塩、亜硝酸塩、硫酸塩、亜硫酸塩、カルボン酸塩などの水溶液を用いた従来の含浸技術によって調製される。金属又は金属酸化物の担持は、１サイクルあたりに吸着すべき硫黄の量、サイクル回数及び再生プロセス条件及び機器（ハードウェア）に伴って変動し得る。金属担持は、再生可能な収着剤の合計重量に基づいて約２重量％〜約８０重量％、好ましくは約３重量％〜約６０重量％、より好ましくは約５重量％〜約５０重量％の範囲内にある。
【００１５】
担体上への含浸後、収着剤は一般的に乾燥され、カ焼され、還元される。これらの作業は、所望により、ｅｘ ｓｉｔｕでもｉｎ ｓｉｔｕでも行なうことができる。再生可能な収着剤は、単一の金属又は２種以上の金属を含むことができる。いくつかの金属の組み合せは、個々の金属の使用に比べて改善された容量、再生可能性及び作業性を提供する。二元及び多元金属収着剤については、類似した範囲が各々の成分にあてはまる。ただし担持は、一種の金属の担持がもう一種の金属の担持よりも大きいか小さく、平衡又は非平衡のいずれであってもよい。
【００１６】
金属収着剤、特にＮｉ及びＣｏベースの収着剤の再生は、収着剤をその初期活性状態に回復させるのに必要とされる還元反応の触媒として作用する再生増加作用物質を収着剤中に内在することで容易になる。かかる作用物質には、元素周期表の第ＶＩＩＩ族の貴金属、好ましくはＩｒ、Ｐｔ、Ｐｄ及びＲｈから成る群から選択される貴金属が含まれるが、必ずしもこれに制限されるわけではない。これら金属のうち一種を約０．０１重量％〜約１０重量％添加すれば、再生周期を減少させ、及び／又は再生温度を低下させることにより、収着剤の再生可能性にとって有利に作用する。Ｃｏ−Ｎｉ二元金属収着剤も同様に、対応するＮｉのみの収着剤に比べより完全な再生を受ける。
【００１７】
硫化水素収着剤としての活性に加えて、Ｆｅ、Ｃｏ又はＮｉは同様に、水素化分解活性金属でもある。その水素化分解活性が抑制されないかぎり、これらの金属は、処理されつつある炭化水素流の水素化分解をひき起こし、価値の低い軽質ガスの生成につながる可能性がある。収着剤金属の水素化分解活性は、Ｃｕ、Ａｇ、Ａｕ、Ｓｎ及びＰｂといった元素周期表の第ＩＢ族又は第ＩＶＡ族から選択された金属、特にＣｕを約１重量％〜約１０重量％（収着剤の重量に基づく）、好ましくは約１．５重量％〜約７重量％、そして最も好ましくは約２重量％〜約６重量％取込むことによって抑制され得る。本書で言及している元素の周期表は、「メルク インデックス（Ｍｅｒｃｈ Ｉｎｄｅｘ）」、第１２版、Ｍｅｒｋ ＆ Ｃｏ．， １９９６年発行、の内側カバーページに記されている。元素周期表の第ＶＩＡ族から選択された単数又は複数の元素を少量、好ましくは約０．０１重量％〜約１重量％取込むことによって、水素化分解を抑制することもできる。
【００１８】
従って、収着剤は、約１５分〜約１５時間又は硫黄のブレークスルーが検出されるまで、約２００℃〜約４００℃の温度で未使用の収着剤を希釈硫化水素に暴露するといった従来の方法により予め硫化することができる。予備硫化された収着剤の硫黄レベルは、収着剤の合計重量に基づいて約０．０１〜約１．０重量％、好ましくは約０．０２〜約０．７重量％、さらに好ましくは約０．０２〜約０．５重量％となる。代わりに収着剤好ましくは未使用の収着剤を、含浸条件下で約１〜約１０％の硫酸の希釈水溶液に暴露することによって、硫黄が取込まれる。
【００１９】
望ましくは、収着剤金属と同時に又はそれ以後に、収着剤内に再生増加剤及び水素化分解抑制剤を取込むこともできる。含浸など従来の方法を利用することができる。
【００２０】
還元性環境による収着剤の再生は、一般に、水素化脱硫（ＨＤＳ）反応に利用される温度よりも、さらに厳しい温度を必要とする。一般的な再生温度は、約１００℃〜約７００℃、好ましくは約２５０℃〜約６００℃であり、最も好ましくは約２７５℃〜約５５０℃の範囲内にある。再生プロセスは、生成物の品質改善に関する意図された目標と一貫性があり、かつ共通又は逐次的な反応器アセンブリのいずれかにおいて本発明が組合わされている任意の下流プロセスと一貫性ある温度及び圧力範囲全体にわたって運転可能である。ポンドあたり毎時約１０〜約２０００標準立方フィート（ＳＣＦ／ｈｒ／ｌｂ）、好ましくは約２０〜約１５０ＳＣＦ／ｈｒ／ｌｂ、より好ましくは約１００〜約１０００ＳＣＦ／ｈｒ／ｌｂの収着剤というＨ２ガス速度で、運転圧力は、約０〜約３０００ｐｓｉａ、好ましくは約５０〜約１０００ｐｓｉａの範囲内でありうる。
【００２１】
本発明の再生プロセスには水素が好ましく、精製又は化学処理環境において、往々にしてそうであるように、その他の活性がないガス、すなわち不活性ガスと混和された形又は純粋な形で供給され得る。水素流は、実質的に硫黄を含まないことが好ましく、これは従来の技術により達成できる。再生流は、約５０％〜約１００％の水素、好ましくは約７０〜約１００％、より好ましくは約８０〜約１００％の水素を含有することになり、残余部分は活性又は飽和軽質炭化水素ガスである。
【００２２】
再生可能な硫化水素収着剤に望まれる特性は、硫化水素吸収容量、再生可能性、そして吸着−再生シーケンスの多重サイクル全体にわたる両方の長所の保持である。収着剤の容量及び再生可能性が共に１００％に近づくことが好ましいが、このレベルが、有効で再生可能な収着剤にとって必要条件ではないことがわかる。全体的プロセスの目的にかなった合理的な再生頻度を可能にする容量及び再生性があれば、許容でき適切である。この条件を念頭に置くと、「再生される有効容量」は、第１サイクル容量の約５〜約１００重量％、好ましくは約１０〜約１００重量％、最も好ましくは約２０〜約１００重量％である。「第１サイクル容量」とは、新鮮な又は「未使用の」収着剤材料の収着剤硫化水素容量を意味する。
【００２３】
好ましい一実施形態においては、収着剤は、留出物及びナフサの水素化脱硫（ＨＤＳ）プロセス、好ましくは、本明細書に全て参考として内包されている米国特許５，９２５，２３９号、５，９２８，４９８及び５，９３５，４２０号で記述されているプロセスで使用される。典型的な水素化脱硫条件には、約４０℃〜約５００℃（１０４〜９３０°Ｆ）、好ましくは約２００℃〜約４５０℃（３９０〜８４０°Ｆ）、より好ましくは約２２５℃〜約４００℃（４３７〜７５０°Ｆ）の温度が含まれる。運転圧力には、約５０〜約１０，０００ＳＣＦ／Ｂ、好ましくは約１００〜約７５００ＳＣＦ／Ｂ、より好ましくは約５００〜約５０００ＳＣＦ／Ｂのガス速度で、約５０〜約３０００ｐｓｉｇ、好ましくは約５０〜約１２００ｐｓｉｇ、より好ましくは約１００〜約８００ｐｓｉｇが含まれる。液空間時速は、約０．１〜約１００Ｖ／Ｖ／Ｈｒ、好ましくは約０．３〜約４０Ｖ／Ｖ／Ｈｒ、より好ましくは約０．５〜約３０Ｖ／Ｖ／Ｈｒの範囲にわたり変動しうる。液空間速度は、時間あたり触媒１体積あたりの供給原料体積（Ｖ／Ｖ／Ｈｒ）に基づいている。
【００２４】
本発明の実施においては、さまざまな収着剤床構成を使用することができる。適切な床構成の例としては、気泡床、並流又は向流モードで運転される固定床、非流動移動床、流動床又は連続撹拌式タンク反応器（「ＣＳＴＲ」）内のＨＤＳ触媒及び収着剤のスラリー、又はスラリー気泡塔が含まれるが、これらに必ずしも制限されるわけではない。流動床は、収着剤の連続的再生が必要とされるプロセスと組み合せた形で有利である。さらに、触媒と収着剤のための分離域を内包する貫通式流動床技術も、収着剤粒子を再生するのに有用である。プロセスは、液相、蒸気相又は混合相条件下で運転し得る。ＨＤＳ触媒及び収着剤が、分離した粒子、ＨＤＳ触媒と収着剤の複合物及び収着剤上に含浸されたＨＤＳ触媒のいずれでもありうる、という点に留意すべきである。ただし、収着剤を還元する間、ＨＤＳが存在するように収着剤とＨＤＳ触媒が配置されれば、ＨＤＳ触媒の望ましくない脱硫が結果としてもたらされる可能性がある。そのような場合、収着剤の還元条件を調整してＨＤＳ触媒の脱硫の影響を和らげること、又はＨＤＳ触媒を再利用するに先立ち再硫化工程に付すこと、又は貴金属ＨＤＳ触媒といった硫化を必要としないＨＤＳ触媒を利用することが望ましい。ＨＤＳ触媒は、硫黄含有炭化水素供給原料と触媒を接触させることによって、再硫化され得る。
【００２５】
固定床構成は、並流及び向流モードのいずれか、すなわち水素含有処理ガスが硫黄含有供給原料と同じ方向又は反対方向でＨＤＳ触媒上に流通している状態で、運転できる。もう１つの実施形態においては、水素含有処理ガスは、「単流式」配置で利用され、従って再循環されない。硫黄含有供給原料、処理ガス及び触媒との接触の増大が望ましい場合、及びＨ２Ｓストリッピングの増大が有利である場合に、向流ＨＤＳ配置が好ましい可能性がある。収着剤の連続的再生が必要とされるプロセスでは、流動床が有利であるかもしれない。さらに、触媒及び収着剤のための分離域を内包する貫通式流動床技術が、収着剤粒子を再生するのに有用であり得る。
【００２６】
当業者であれば、ＨＤＳ触媒及び収着剤の床構成の選択が、特にプロセスが単数又は複数の後続プロセスと一体化されている場合又は、プロセス全体の目標が生成物品質の１側面と他側面との関係における選択性に有利な作用を及ぼす場合に、プロセス全体の目標によって左右されることがわかる。しかしながら、収着剤がＨＤＳ触媒の上流には設置されないことが好ましい。
【００２７】
好ましい実施形態では、新鮮な収着剤が使用されている間、使用済み収着剤の再生が可能に設計された旋回式反応器を伴う積層床構成が使用される。積層床構成では、ＨＤＳ触媒は収着剤上流で吸着剤上に積重ねられるか又は層状化される。積層床は、共通の反応器を占有していてもよいし、ＨＤＳ触媒が、収着剤を収納する反応器の上流で分離型反応器を占有していてもよい。この専用反応器シーケンスは、ＨＤＳ触媒及び収着剤が異なる反応器温度を必要とする場合に好ましい。
【００２８】
もう１つの実施形態では、収着剤及びＨＤＳ触媒は、混合床構成で用いられる。この構成では、ＨＤＳ触媒の粒子は、収着剤の粒子と密に互いに混合されている。積層床及び混合床の両方の構成において、ＨＤＳ触媒粒子及び収着剤粒子は、類似又は同一の形状及びサイズをもち得る。同様に１つの成分の粒子は、第２の成分の粒子と、例えば形状、密度及び／又はサイズ面で異なっていてもよい。異なるサイズをもつ粒子を使用する方法は、例えば、排出又は再加工する時点で床成分の物理的分離が単純である場合に利用できる。
【００２９】
さらにもう１つの実施形態では、２つの成分を配合して、ＨＤＳ触媒及び収着剤の両方又は個々の不連続成分を内包する複合粒子を形成させる。例えば、アルミナＨＤＳ触媒上の細分割された粉状化Ｐｔを再生可能な収着剤と均質に配合させ、混合物を共通の触媒粒子の形に成型する。あるいは、再生可能収着剤を担体内に取り込み、例えばＰｔをアルミナなどの収着剤含有担体上に含浸させることができる。
【００３０】
もう１つの２成分構成では、アルミナ担体にＨＤＳ金属及び収着剤とを共通ベース上に含浸させる。両方の金属とも触媒粒子全体を通して均等に分布させることができ、収着剤及び／又はＨＤＳ成分を、粒子の外側上に優先的に被着させて、リム状又は卵殻状に収着剤又はＨＤＳリッチ域を形成することもできる。
【００３１】
３成分床構成も同じく使用可能である。混合／積層型と呼ばれる１つの実施形態では、単一のＨＤＳ／水素化分解触媒の上流に混合型ＨＤＳ触媒／収着剤床が構成される。積層／積層／積層構成として知られるもう１つの実施形態では、３つの成分が、ＨＤＳ触媒／収着剤／ＨＤＳ触媒といったように、上面から底面まで層状化される。１つの実施形態では、３成分系は、共通の反応器を占有し得る。もう１つの実施形態では、ＨＤＳ触媒／収着剤が混合型又は積層型構成の中の先行反応器を占有し、ＨＤＳ触媒が後続反応器を占有する２反応器列の形で、３成分系を使用できる。この配置は、特に温度などの異なるプロセス条件において２つの反応器区分の運転を可能にし、選択性及び／又は生成物品質といったプロセスパラメータを制御する上での柔軟性を付与する。
【００３２】
床の組成は、構成とは無関係であり、本発明が応用される特定的又は一体型のプロセスに応じて変動し得る。収着剤の容量に制限がある場合、床の組成は、プロセスの予想寿命つまりサイクルと一貫性がなくてはならない。これらのパラメータはそれ自体、加工中の供給原料の硫黄含有量及び望まれる脱硫度に敏感である。これらの理由から、床の組成は、柔軟で可変的であり、１つの利用分野にとって最適な床組成が、代替的な利用分野にも同等の役割を果たすとは限らない可能性もある。一般に、水素化脱硫触媒に対する収着剤の重量比は、約０．０１〜約１０００の範囲内、好ましくは約０．５〜約４０、より好ましくは約０．７〜約３０の範囲内にありうる。３成分構成では、これらの範囲は、混合／積層型配置の混合域、及び積層／積層／積層設計における最初の２つの域にあてはまる。これら２つのアレイの最終域内に存在する水素化脱硫触媒は、一般に、上流域の組み合せ型重量組成と同じかそれ以下の重量比で存在する。
【００３３】
該プロセスは、例えば、燃料、潤滑油及び化学物質などの独立型プロセスとして使用可能である。全プロセスが組合わされていないプロセスに比べて生成物及びプロセス上の利点及び改善を提供するような形で、その他のプロセスと組み合せ及び一体化することが可能である。以下の実施形態は、本発明のプロセスの用途を（制限するのではなく）例示するために内包される。
【００３４】
燃料プロセスに関連するプロセスとしては、ガソリン範囲の原料及び生成物流れの脱硫、留出物流れの脱硫、第２段プロセスへの再循環に先行するＦＣＣ流の脱硫、水素化分解原料の脱硫、選択的開環による多環芳香族変換、芳香族飽和プロセス、水素異性体化、天然、合成及び再循環ガス流及び石化用原油流からの硫黄除去が含まれる。潤滑油の製造に関するプロセスには、次のものが含まれる。水素化分解、穏やかな仕上げ処理を通した製品品質の改善、触媒コストを削減し及び／又は荷重補正係数を拡大することによる白油プロセスの最適化。化学的処理に関係するプロセスには、環境によくないニッケルベースの水素化プロセスの代用、さまざまな分解プロセスによるオレフィン製造、及びオキシ機能化プロセスにより酸素化物を生成する高品質な供給原料の調製、溶剤及び重合体グレードのオレフィン及び芳香族の生成が含まれる。
【００３５】
本発明は、相反する指示のないかぎり、以下の実験条件の使用が例示されるが、これらの例に制限されるわけではない。
【００３６】
一般条件
各収着剤の名目当量の供給原料を用いて、Ｃａｈｎ ＴＧ１２１熱比重分析装置（Ｔｈｅｒｍｏｇｒａｖｉｍｅｔｒｉｃ Ａｎａｌｙｚｅｒ）により、硫化水素収着剤の容量及び水素再生可能性を評価した。候補である収着剤を、最初に４００℃で３時間空気中でカ焼し、分析装置内に設置した。収着剤を、水素中５００℃で１時間加熱し、その後、３２５℃まで冷却し、Ｈ２中に１００ｖｐｐｍのＨ２Ｓを含むガス配合物に２時間暴露し、この間、Ｈ２Ｓの吸着に付随する重量増加を記録した。使用済み収着剤をＨ２中で５００℃まで１時間加熱し、５５０℃まで１時間加熱し、この間、Ｈ２Ｓの放散つまり収着剤の再生が認められた。マルチサイクルテストにおいては、反復的吸着−再生サイクルをシミュレートするべく、このシーケンスを再現した。再生可能性は、Ｘ線回折計に取付けられた環境管理型高温セルを用いた相変化の観察によってさらに確認された。
【００３７】
収着剤は、金属硝酸塩水溶液でのさまざまな担体材料の初期湿潤、含浸によって調製した。押出し成形物を２４時間、１２０℃で真空下において空気乾燥した。流通空気内でのカ焼を小型の触媒前処理ユニット、又はこの機能専用の熱比重測定ユニット中で行なった。両方ともカ焼を３時間４００℃で実施した。例中の全ての収着剤組成は、担体上の公称金属重量％である。
【００３８】
実施例１
この実験では、対照としての酸化亜鉛（非水素再生可能な収着剤）を、Ｆｅ、Ｃｏ、Ｎｉ、及びＣｕ担持収着剤と比較した。
【００３９】
【表１】
再生％は、再生中に収着剤から除去され化学収着された硫黄の百分率を意味する。再生中全く硫黄が放出されない場合、この値はゼロである。再生中の完全な硫黄除去が、１００％の再生に対応する。
【００４１】
結果は、Ｆｅ、Ｃｏ、Ｎｉ及びＣｕが活性な硫化水素収着剤であり、さまざまな程度まで水素により再生されたことを立証している。Ｃｏ及びＮｉは、共通担体上でＦｅ及びＣｕよりもさらに再生可能であった。金属担持（サンプル４及び５）は、容量に影響を及ぼしたが再生可能性には影響を及ぼさなかった。チタニア（サンプル７）は、再生可能性が本発明の限界内にあったものの、担体としては最も好ましくなかった。
【００４２】
実施例ＩＩ
いかなる要因が容量及び再生可能性に対する影響をもつかを見極めるために、実験を行った。
【００４３】
【表２】
サンプル８〜１３は、共通する金属について、容量及び再生％が、担体と無関係であったことを例示している。予想通り、容量は、金属担持の一関数であったが、再生度は合計金属含有量による影響を受けなかった。サンプル１４〜１５及び１６〜１８は、共通担体上のＣｏでは収着剤の硫化水素容量が金属含有量の一関数であるが、水素再生の反応速度が金属担持に敏感でないことを例示している。
【００４５】
【表３】
実施例ＩＩＩ
サンプル５（実施例Ｉ）の硫化水素収着剤を、上述の手順によりマルチサイクル吸着−再生に付した。２０Ｎｉ／ＺｒＯ２収着剤を５回のフルサイクルに付したが、硫化水素容量及び水素再生可能性の有意な損失はなかった。硫黄重量増加及び再生可能性度は、サンプル５の値とほぼ同等であった。
【００４７】
実施例ＩＶ
サンプル１７（実施例ＩＩ）の硫化水素収着剤を、上述の手順によりマルチサイクル吸着−再生に付した。１０Ｃｏ／Ａｌ２Ｏ３収着剤を６回のフルサイクルに付したが、硫化水素容量及び水素再生可能性の有意な損失はなかった。硫黄重量増加及び再生可能性度は、サンプル１７の値と同等であった。
【００４８】
実施例Ｖ
サンプル１７（実施例ＩＩ）の１０Ｃｏ／Ａｌ２Ｏ３収着剤の１．０ｇサンプルを、３０ｇの不活性物質で希釈し、貫通式固定床反応器に投入した。収着剤を５００℃で水素中で１時間還元し、次に３００℃でかつ５０ｍｌ／分のガス流速でＨ２中の１０００ｖｐｐｍのＨ２Ｓ配合物に付した。収着剤床を出た水素流を、収着剤の完全飽和を近似するブレークスルー時間を測定するＨ２Ｓ検出器を用いて、Ｈ２Ｓ含有量を監視した。この要領で、収着剤を３回の全く異なる試験において評価し、これについては以下で要約されている。
【００４９】
【表４】
収着剤Ｃｏ含有量をＣｏ９Ｓ８へ換算する硫黄計算値は、３．０重量％であった。上記表中のデータは、固定床構成でのＴＧＡの結果を確認し、収着剤容量の再現可能な効率の良い利用を表わしている。
【００５１】
実施例ＶＩ
収着剤が、各々不活性物質で希釈された１０Ｃｏ／Ａｌ２Ｏ３を含有する、不活性物質により分離された３つの独立した域で構成した点を除いて、実施例Ｖの手順に従った。硫化水素のブレークスルーは、２９．３時間目にこの床で発生し、これは単一収着剤域の場合の約３倍に相当する。各域を分離し、硫黄を分析した。上部、中央及び底部域での硫黄値は、それぞれ３．１、３．３及び３．３重量％であった。これらの値は、収着剤のきわめて効率の高い運転を反映している。
【００５２】
実施例ＶＩＩ
３域収着剤床を用いて、実施例ＶＩに記述された通りの手順をくり返した。２７時間目にＨ２Ｓのブレークスルーが検出された後、収着剤床を、４５０℃で３時間、５００℃で３時間そして最後に５５０℃で１０時間、水素を用いて５００ｍｌ／分で再生した。３つの収着剤域を分離し、硫黄を分析した。上部、中央及び底部域での硫黄値は、それぞれ０．２、０．２及び０．２重量％であった。これらの硫黄値は、約９５％の再生効率レベルでの全収着剤床の水素再生を立証している。
【００５３】
実施例ＶＩＩＩ
実施例ＶＩＩＩの手順を、単一収着剤域を用いてくり返した。Ｈ２Ｓのブレークスルーが検出された後、床を水素で再生した。収着剤を次に３００℃まで冷却し、Ｈ２流中の希釈Ｈ２Ｓに暴露した。吸着−再生サイクルを４サイクルくり返し、その終結時点で収着剤を最後に硫化した。結果は、下表に要約されている。
【００５４】
【表５】
ブレークスルー時間は、Ｈ２Ｓに対する各暴露後に収着剤の再生が成功し、効率の良いことを表わしている。１サイクルあたりの再生が完全に起こらなければ、後続する各サイクルでのブレークスルー時間に著しい減少が予想されることになる。収着剤の硫黄含有量は、マルチサイクルの使用後でも硫黄容量が損われないことを例示した。
【００５６】
実施例ＩＸ
サンプル１７（実施例ＩＩ）の１０Ｃｏ／Ａｌ２Ｏ３を、前述の通り、Ｈ２内の希釈Ｈ２Ｓに付した。Ｈ２Ｓブレークスルーが検出された後、以下の表に示す通り、Ｈ２処理速度、温度及び時間を変動させて収着剤を再生した。結果は、再生周期がこれらのプロセス変数の一関数であり、特定された再生効率に達するのに必要とされる再生周期及び／又は再生度を維持するように選択できることを表わしている。
【００５７】
【表６】
実施例Ｘ
収着剤中の金属の組み合せが、達成される再生に対して影響をもつか否かを見極めるために、実験を行なった。結果は、下表に示されている。
【００５９】
【表７】
サンプル１９〜２１は、合計金属担持が等価であるもののＣｏ対Ｎｉの比率が変動しているＣｏ−Ｎｉベースの収着剤セットが、硫黄容量及び再生効率を共有していたことを示している。硫黄容量は、一金属収着剤により予測されたものと合致していたが、Ｃｏ−Ｎｉ二元金属収着剤は、予想外に、対応するＮｉのみの収着剤に比べてより完全に再生された。
【００６１】
サンプル２２〜２４は、Ｃｏ−Ｒｅ収着剤が適正な硫黄容量を有し、これは、Ｒｅ担持の増加に従って下落しており、一定の時間内での硫黄摂取を制限したＨ２Ｓとの反応速度（図示せず）の低下に起因することを例示している。Ｃｏ−Ｒｅ収着剤は、データが示す通り、水素を用いて容易に再生可能であった。
【００６２】
サンプル２５〜２７は、Ｐｔの存在下で硫黄摂取速度が遅くなったにもかかわらず、第ＶＩＩＩ族貴金属の取込みがＣｏの硫黄容量を損うことがなかったことを実証している。これらの二元金属収着剤の水素再生は、新鮮な収着剤容量を基本的に定量的に回収するに伴って、容易に起こった。
【００６３】
実施例ＸＩ
さまざまな二元金属収着剤の１．０ｇサンプルを３０ｇの不活性物質で希釈し、貫通式固定床反応器に投入した。収着剤を５００℃で水素により１時間還元し、その後、３００℃かつ５０ｍｌ／分のガス流速でＨ２中、１０００ｖｐｐｍのＨ２Ｓの配合に付した。収着剤床から出る水素流を、収着剤の完全な飽和を近似するブレークスルー時間を測定するＨ２Ｓ検出器を用いて、Ｈ２Ｓ含有量を監視した。
【００６４】
Ｈ２Ｓの初期ブレークスルーが検出された後、４５０℃で３時間、５００℃で３時間、そして最後に５５０℃で３時間の温度−時間プログラムを用いて、３００ｍｌ／分で流れるＨ２中で収着剤床を再生した。この吸着−再生シーケンスをくり返して、２〜３回の完全なサイクルをシミュレートした。２回目の再生後に、収着剤の残留硫黄含有量を分析により測定した。結果は、下表に示されている。
【００６５】
【表８】
第２及び第３サイクルの収着剤についてのブレークスルー時間は、新鮮な収着剤のブレークスルー周期の特徴であり、これらの二元金属収着剤で水素再生がうまくいくことを表わしている。水素再生されないと、マルチサイクル収着剤でのブレークスルー周期は、著しく減少することになる。再生された収着剤の硫黄含有量は、再生速度が残りの収着剤に比べ緩慢であるＮｉ−Ｃｕ／ＺｒＯ２を除き、全てのケースで、６０％を超える再生度が達成されたことを実証している。
【００６７】
実施例ＸＩＩ
サンプル１３（実施例ＩＩ）のＣｏ／Ａｌ２Ｏ３収着剤を、メタンへの水素化分解に反映される収着剤の水素化分解活性を測定するため、ヘプタン分解試験に付した。同じＣｏ／Ａｌ２Ｏ３収着剤に希硫酸を含浸させて０．０５重量％の硫黄を収着剤中に導入した。
【００６８】
５０ｍＬの脱イオン水で濃硫酸１ｍＬを希釈することによって、硫酸原液を調製した。９．０ｍＬの脱イオン水に溶解した０．５ｍＬの硫酸原液の溶液を、以前に調製した１０％のＣｏ／Ａｌ２Ｏ３収着剤１０ｇに撹拌しながら、滴下、添加した。収着剤を一晩放置し、３時間、４００℃の空気中でカ焼するため反応器に投入した。材料を１４〜３５メッシュまで転換した。分析：Ｃｏ９．９１；Ｓ、０．０５５（重量％）。
【００６９】
メタンへの水素化分解に反映される収着剤の水素化分解活性を測定するため、硫化された収着剤をヘプタン分解に付した。同じＣｏ／Ａｌ２Ｏ３収着剤も希硫酸を含浸させて、収着剤内に０．２５重量％の硫黄を導入した。硫化された収着剤をヘプタン分解試験に付して、メタンへの水素化分解に反映される収着剤の水素化分解活性を測定した。結果は下表に示されている。
【００７０】
【表９】
実施例ＩＩ、ＩＶ及びＶは、担持されたＣｏ収着剤が硫化水素捕獲の高い活性を示し、高い硫化水素容量をもち、マルチサイクル水素再生後に容量保持能力をもつことを例示している。サンプル３２は、この収着剤が軽質ガスへと供給原料を水素化分解するのにきわめて活性であることを示している。サンプル３３及び３４は、この水素化分解活性が、低レベルの硫黄の存在により大幅に減少し、無くなることを実証している。
【００７２】
実施例ＸＩＩＩ
実施例ＩＩの手順を、サンプル３３及び３４の硫黄含有Ｃｏ／Ａｌ２Ｏ３収着剤を用いてくり返した。収着剤の硫化水素捕獲容量は、実施例ＩＩ中のサンプル１３に等しく、硫化水素の捕獲収着剤の親和性は、低レベルの硫黄が存在しても損われなかったことを表わしている。
【００７３】
実施例ＸＩＶ
１０Ｃｏ−１０Ｃｕ／ＳｉＯ２収着剤を合成した。１２．３ｇのＣｏ（ＮＯ３）２（６Ｈ２Ｏ）及び９．６ｇのＣｕ（ＮＯ３）２（３Ｈ２Ｏ）を脱イオン水５０ｍＬ中に溶解した溶液を撹拌しながら、小型蒸発皿に入った２５ｇのＳｉＯ２押出し成形物に滴下した。混合物を乾燥するまで室温に放置し、次に１２０℃で真空下で２４時間乾燥させた。収着剤を小型の触媒前処理ユニットに投入し、４００℃で空気中で３時間カ焼した。収着剤を、試験用の１４〜３５メッシュの粒子へと転換した。分析：Ｃｏ，８．２３重量％；Ｃｕ，８．１２重量％。使用中のマルチサイクル容量及び再生可能性はＴＧＡによって実証された。
【００７４】
実施例ＸＶ
メタンへの水素化分解に反映される収着剤の水素化分解活性を測定するため、以下の収着剤をヘプタン分解試験に付した。サンプル１３のＣｏ／Ａｌ２Ｏ３収着剤（実施例ＩＩ）；サンプル５のＮｉ／ＺｒＯ２収着剤（実施例Ｉ）；サンプル１１のＣｏ／ＺｒＯ２収着剤（実施例ＩＩ）；及びサンプル２８のＣｕ／ＺｒＯ２収着剤（実施例ＸＩ）；サンプル３０のＣｏ−Ｃｕ／ＺｒＯ２収着剤（実施例ＸＩ）及び１０Ｃｏ−１０Ｃｕ／ＳｉＯ２収着剤（サンプル３５）。結果は、下表に示されている。
【００７５】
【表１０】
以上により、単一金属収着剤の水素化分解活性がきわめて高いと結論付けられる。この水素化分解活性は、水素化分解減速剤を添加することで有効に抑制される。単一金属の相似物に比べ二元金属触媒では（サンプル２８、３０）、水素での処理により再生される能力及び硫黄容量のいずれも脅かされない。
【００７７】
実施例ＸＶＩ
例えば収着剤に貴金属を添加することによって、水素再生を増大できるか否かを見極めるために、実験を行なった。結果は、下表に表わされている。
【００７８】
【表１１】
サンプル１２は、Ｃｏが１０％支持された硫化水素収着剤に標準的な硫黄容量を示している。水素処理（５００℃で１時間）により完全に再生されないように意図的に選択された条件で、コバルト収着剤が吸着された硫化水素の４７％を失い、すなわち４７％が再生される。Ｐｄの添加（サンプル２６、３６〜３８）は、硫黄容量に対しいかなる影響ももたなかったが、Ｐｄの存在は明らかに、共通の条件下での水素再生を容易にした。再生度は、約２重量％のＰｄレベルまでＰｄの増加と共に増大した。
【００８０】
サンプル２７、３９、４０は、水素再生速度を促進するのにＰｄよりも有効であるＰｔが存在する場合、類似の傾向を例示している。Ｐｔ２重量％での硫黄容量の見かけの損失は、硫黄ピックアップの反応速度の低下に大きく起因している。
【００８１】
ＰｔとＰｄが同量の重量％担持であるが、異なる原子担持で存在するサンプル４１は、１重量％で存在する場合に、いずれかの金属単独よりも容易に再生され、二種の貴金属間の相乗効果を表わしている。
【００８２】
このデータは、飽和度の高い硫化水素収着剤の水素再生が、元素周期表第ＶＩＩＩ族の単数、又は複数の貴金属の存在によって促進されることを例示している。この促進効果は、再生周期を短縮するため、再生温度を低下させるため、又はその両方のために使用できる。[0001]
Cross reference to related application
This application claims the benefit of US application Ser. No. 08/918, Aug. 22, 1997, issued Jul. 20, 1999 as US Pat. No. 5,925,239, which claims the benefit of provisional application No. 60 / 024,737. No. 09 / 326,827, filed Jun. 7, 1999, which is a continuation-in-part application of US Pat.
[0002]
Field of the invention
The present invention relates to a method for regenerating a metal oxide hydrogen sulfide sorbent using hydrogen gas. The sorbent can be a single or multi-metal sorbent.
[0003]
Background of the Invention
Removing sulfur from feedstocks is a fundamental process in the refining and petrochemical industries. One method for removing sulfur from feedstocks is hydrodesulfurization. Hydrodesulphurization involves the formation of hydrogen sulphide at fairly severe temperatures and pressures with a catalyst supporting noble or non-noble metal sulphides such as Pt, Pd, especially Co / Mo or Ni / Mo. It is concerned with reacting sulfur. The performance of the hydrodesulfurization catalyst is hindered by the presence of hydrogen sulfide. The use of a sorbent to remove the hydrogen sulfide produced in the desulfurization improves the overall effectiveness of the hydrodesulfurization process.
[0004]
The performance of hydrogen sulfide sorbents depends on various physical properties. The thermodynamics and reaction rate of sulfidation are determined by a predetermined H2This is clearly important because it determines the total sulfur capacity before breaking through at the S level. Other important sorbent properties include stability and renewability over long periods of use, the composition of the regeneration offgas which largely determines the operating conditions required for regeneration and the choice of downstream sulfur recovery methods.
[0005]
One practical limitation on the use of any hydrogen sulfide sorbent is the ability to regenerate the sorbent. The most promising and widely studied sorbent, zinc oxide, has a very high equilibrium constant for sulfidation, but it is difficult to regenerate zinc oxide after use as a sorbent for hydrogen sulfide. Thus, the extent and availability of such sorbents is limited by the level of sulfur being treated, the required volumetric properties of the reactor and the economic constraints associated with the problem of removal and disposal of used sorbents. Limited. These constraints are alleviated if the hydrogen sulfide sorbent has the capability of multi-cycle operation enabled by the sorbent regeneration means.
[0006]
Spinel and zeolite based materials are renewable hydrogen sulfide sorbents. Although these materials are particularly suitable for removing hydrogen sulfide from gas streams where the process temperature is preferably limited to about 75-125 ° C, these materials are used in conventional hydrodesulfurization techniques. It has low efficiency for capturing hydrogen sulfide at very high temperatures.
[0007]
Clinoptilolite molecular sieves are also renewable. However, the temperatures at which clinoptilolite molecular sieves are typically treated are also relatively low. Clinoptilolite molecular sieves can be used at temperatures from about 90 ° C to about 260 ° C.4~ C12Used to remove hydrogen sulphide from feed streams. The used cryptorillolite molecular sieve is regenerated with a purge gas at a temperature from about 150C to about 370C.
[0008]
Currently, renewable solid sorbents used for the treatment of hot gas streams are generally based on metal oxides and are regenerated under oxidizing conditions at temperatures often higher than about 600 ° C. You. Regeneration of these sorbents using an oxidizing atmosphere requires initial replacement of flammable organics and hydrogen, which is not only costly, but also dangerous, especially at such high temperatures.
[0009]
There is still a need in the art for a method that can regenerate various hydrogen sulfide sorbent materials.
[0010]
Summary of the Invention
The present invention provides a method for regenerating a hydrogen sulfide sorbent having a first cycle capacity, wherein the hydrogen regenerates the used hydrogen sulfide sorbent against a gas containing hydrogen at a regenerating concentration; A method comprising exposing a used hydrogen sulfide sorbent under conditions effective to produce a regenerated sorbent having a regenerated capacity substantially the same as the cycle capacity.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention uses a reducing atmosphere instead of an oxidizing atmosphere to regenerate the solid hydrogen sulfide sorbent. The reducing atmosphere preferably comprises hydrogen gas alone or in combination with an inert gas, preferably nitrogen.
[0012]
The renewable sorbent of the present invention is preferably an oxide of at least one metal selected from Fe, Ni, Co or Cu. In a preferred embodiment, the metal is selected from the group consisting of Ni, Co, and combinations thereof. Examples of suitable supported metal and metal oxide based renewable hydrogen sulfide sorbents include 5Co / Al2O310Co / SiO2; 20Co / TiO220Co / ZrO25Ni / Al2O310Ni / SiO2; 20Ni / ZrO2; 5Cu / Al2O310Cu / SiO2; 20Cu / ZrO25Fe / Al2O310Fe / SiO2; 20Fe / NiZrO25Co-5Cu / Al2O310Co-10Cu / SiO210Ni-5Cu / SiO220Ni-2Cu / ZrO210Co-2Pt / Al2O310Co-5Pd / SiO210Co-1Sn / Al2O320Ni-4Sn / SiO2, But is not necessarily limited to these. Here, the numbers refer to the weight percent of metal based on the total weight of the sorbent.
[0013]
The sorbent is a bulk metal that includes (but is not necessarily limited to) subdivided skeleton metals, including Raney metals, heavy metals (Rickemetals), Ricke metals and metal sponges. Or as a bulk metal oxide.
[0014]
The sorbent can be supported on an inorganic support material, for example, to increase surface area, pore volume and / or pore size. Suitable support materials include, but are not necessarily limited to, alumina, silica, zirconia, carbon, silicon carbide, diatomaceous earth, amorphous and crystalline silica-alumina, silica-magnesia, aluminophosphate, boria, titania and combinations thereof. (Not necessarily) inorganic oxide carrier material. Preferred support materials include alumina, zirconia and silica. Metals or metal oxides can be supported on these supports by conventional techniques known in the art. Such techniques include impregnation by incipient wetness, adsorption from excess impregnating medium, and ion exchange. In a preferred embodiment, the renewable sorbent is a metal halide, oxide, hydroxide, carbonate, nitrate, nitrite, sulfate, sulfite, carboxylate, or other conventional aqueous solution. Prepared by impregnation technique. Metal or metal oxide loading can vary with the amount of sulfur to be adsorbed per cycle, the number of cycles and regeneration process conditions and equipment (hardware). The metal loading is from about 2% to about 80%, preferably from about 3% to about 60%, more preferably from about 5% to about 50% by weight based on the total weight of the renewable sorbent. Within the range.
[0015]
After impregnation on the support, the sorbent is generally dried, calcined and reduced. These operations can be performed ex @ situ or in @ situ as desired. Renewable sorbents can include a single metal or more than one metal. Some metal combinations offer improved capacity, reproducibility and workability compared to the use of individual metals. For binary and multimetal sorbents, similar ranges apply to each component. However, the loading of one metal is larger or smaller than that of another metal, and may be either equilibrium or non-equilibrium.
[0016]
Regeneration of metal sorbents, especially Ni- and Co-based sorbents, involves a regeneration-enhancing agent that acts as a catalyst for the reduction reactions required to restore the sorbent to its initial active state Being inside makes it easier. Such agents include, but are not necessarily limited to, noble metals of Group VIII of the Periodic Table of the Elements, preferably selected from the group consisting of Ir, Pt, Pd, and Rh. The addition of about 0.01% to about 10% by weight of one of these metals has a beneficial effect on the reproducibility of the sorbent by reducing the regeneration cycle and / or reducing the regeneration temperature. . Co-Ni binary metal sorbents likewise undergo more complete regeneration than the corresponding Ni-only sorbents.
[0017]
In addition to its activity as a hydrogen sulfide sorbent, Fe, Co or Ni is also a hydrocracking active metal. Unless their hydrocracking activity is suppressed, these metals can cause hydrocracking of the hydrocarbon stream being treated, leading to the production of low value light gases. The hydrocracking activity of the sorbent metal is from about 1% to about 10% by weight of a metal selected from Group IB or IVA of the Periodic Table of the Elements, such as Cu, Ag, Au, Sn and Pb, especially Cu. (Based on the weight of the sorbent), preferably from about 1.5% to about 7%, and most preferably from about 2% to about 6% by weight. The periodic table of the elements referred to in this document can be found in "Merck Index", 12th edition, Merk & Co. , @ 1996, published on the inner cover page. Hydrogenolysis can also be suppressed by incorporating a small amount of one or more elements from Group VIA of the Periodic Table of the Elements, preferably from about 0.01% to about 1% by weight.
[0018]
Thus, the sorbent is conventionally exposed to fresh sorbent at a temperature of about 200 ° C. to about 400 ° C. to dilute hydrogen sulfide for about 15 minutes to about 15 hours or until a sulfur breakthrough is detected. Can be preliminarily sulfided. The sulfur level of the presulfurized sorbent is from about 0.01 to about 1.0%, preferably from about 0.02 to about 0.7%, more preferably from about 0.01 to about 1.0% by weight based on the total weight of the sorbent. It is about 0.02 to about 0.5% by weight. Alternatively, sulfur is incorporated by exposing the sorbent, preferably a fresh sorbent, to a dilute aqueous solution of about 1 to about 10% sulfuric acid under impregnating conditions.
[0019]
Desirably, the regeneration enhancer and hydrocracking inhibitor can be incorporated into the sorbent at the same time as or after the sorbent metal. Conventional methods such as impregnation can be used.
[0020]
Regeneration of the sorbent with a reducing environment generally requires more severe temperatures than those utilized in hydrodesulfurization (HDS) reactions. Typical regeneration temperatures are from about 100C to about 700C, preferably from about 250C to about 600C, and most preferably in the range of from about 275C to about 550C. The regeneration process is temperature and temperature consistent with the intended goals for product quality improvement and consistent with any downstream process in which the present invention is combined in either a common or sequential reactor assembly. Operable over the entire pressure range. About 10 to about 2000 standard cubic feet per pound per hour (SCF / hr / lb), preferably about 20 to about 150 SCF / hr / lb, more preferably about 100 to about 1000 SCF / hr / lb of sorbent.2At gas rates, operating pressures can range from about 0 to about 3000 psia, preferably from about 50 to about 1000 psia.
[0021]
Hydrogen is preferred for the regeneration process of the present invention and is supplied in a purified or chemical processing environment, as is often the case, in a form mixed with or pure in other inert gases, i.e., inert gases. obtain. Preferably, the hydrogen stream is substantially free of sulfur, which can be achieved by conventional techniques. The regeneration stream will contain about 50% to about 100% hydrogen, preferably about 70% to about 100%, more preferably about 80% to about 100% hydrogen, with the balance being active or saturated light hydrocarbons Gas.
[0022]
The desired properties of a renewable hydrogen sulfide sorbent are hydrogen sulfide absorption capacity, renewability, and retention of both advantages over multiple cycles of the adsorption-regeneration sequence. While it is preferred that both the capacity and renewability of the sorbent approach 100%, it can be seen that this level is not a requirement for an effective and renewable sorbent. Any capacity and reproducibility that allows a reasonable frequency of reproduction for the purpose of the overall process is acceptable and appropriate. With this condition in mind, "effective reclaimed volume" is about 5% to about 100%, preferably about 10% to about 100%, most preferably about 20% to about 100% by weight of the first cycle volume. It is. "First cycle capacity" means the sorbent hydrogen sulfide capacity of fresh or "virgin" sorbent material.
[0023]
In one preferred embodiment, the sorbent is a distillate and naphtha hydrodesulfurization (HDS) process, preferably US Pat. No. 5,925,239,5, incorporated herein by reference in its entirety. , 928,498 and 5,935,420. Typical hydrodesulfurization conditions include about 40C to about 500C (104 to 930F), preferably about 200C to about 450C (390 to 840F), and more preferably about 225C to about 225C. A temperature of 400 ° C (437-750 ° F) is included. Operating pressures range from about 50 to about 3000 psig, preferably from about 50 to about 3000 SCF / B, preferably from about 100 to about 7500 SCF / B, more preferably from about 500 to about 5000 SCF / B. To about 1200 psig, more preferably from about 100 to about 800 psig. The liquid hourly space velocity varies over a range from about 0.1 to about 100 V / V / Hr, preferably from about 0.3 to about 40 V / V / Hr, more preferably from about 0.5 to about 30 V / V / Hr. sell. The liquid hourly space velocity is based on the volume of feedstock per volume of catalyst per hour (V / V / Hr).
[0024]
Various sorbent bed configurations can be used in the practice of the present invention. Examples of suitable bed configurations include a bubble bed, a fixed bed operated in co-current or counter-current mode, a non-fluidized moving bed, a fluidized bed or a HDS catalyst in a continuously stirred tank reactor ("CSTR"). Includes, but is not necessarily limited to, a slurry of the adhesive, or a slurry bubble column. Fluidized beds are advantageous in combination with processes where continuous regeneration of the sorbent is required. In addition, penetrating fluidized bed technology that includes a separation zone for catalyst and sorbent is also useful for regenerating sorbent particles. The process may operate under liquid, vapor or mixed phase conditions. It should be noted that the HDS catalyst and sorbent can be any of discrete particles, a composite of HDS catalyst and sorbent, and an HDS catalyst impregnated on the sorbent. However, if the sorbent and HDS catalyst are arranged such that HDS is present during the reduction of the sorbent, undesirable desulfurization of the HDS catalyst may result. In such a case, it is necessary to adjust the reducing conditions of the sorbent to reduce the effect of the desulfurization of the HDS catalyst, or to subject the HDS catalyst to a resulfurization step before reusing the HDS catalyst, or to require sulfidation such as a noble metal HDS catalyst. It is desirable to use a non-HDS catalyst. The HDS catalyst can be resulfurized by contacting the catalyst with a sulfur-containing hydrocarbon feed.
[0025]
The fixed bed configuration can be operated in either co-current or counter-current mode, ie, with the hydrogen-containing treat gas flowing over the HDS catalyst in the same or opposite direction as the sulfur-containing feed. In another embodiment, the hydrogen-containing process gas is utilized in a "single-flow" arrangement and is therefore not recycled. If increased contact with sulfur-containing feedstock, process gas and catalyst is desired, and H2A counter-current HDS arrangement may be preferred where increased S-stripping is advantageous. In processes where continuous regeneration of the sorbent is required, a fluidized bed may be advantageous. Further, a penetrating fluidized bed technique that includes a separation zone for the catalyst and sorbent may be useful for regenerating sorbent particles.
[0026]
One of ordinary skill in the art will appreciate that the choice of HDS catalyst and sorbent bed configuration can be crucial, especially if the process is integrated with one or more subsequent processes, or that the goal of the overall process is one aspect of product quality and other aspects. It can be seen that the effect on the selectivity in relation to the aspects depends on the goals of the overall process. However, it is preferred that the sorbent is not located upstream of the HDS catalyst.
[0027]
In a preferred embodiment, a stacked bed configuration with a swirl reactor designed to allow the regeneration of the used sorbent while fresh sorbent is being used is used. In a stacked bed configuration, the HDS catalyst is stacked or stratified on the adsorbent upstream of the sorbent. The stacked beds may occupy a common reactor, or the HDS catalyst may occupy a separate reactor upstream of the reactor containing the sorbent. This dedicated reactor sequence is preferred when the HDS catalyst and sorbent require different reactor temperatures.
[0028]
In another embodiment, the sorbent and HDS catalyst are used in a mixed bed configuration. In this configuration, the HDS catalyst particles are intimately mixed with the sorbent particles. In both stacked bed and mixed bed configurations, the HDS catalyst particles and the sorbent particles may have similar or identical shapes and sizes. Similarly, particles of one component may differ from particles of a second component, for example, in shape, density, and / or size. Methods using particles of different sizes can be used, for example, when the physical separation of bed components is simple at the time of discharge or reprocessing.
[0029]
In yet another embodiment, the two components are blended to form composite particles containing both the HDS catalyst and the sorbent or individual discrete components. For example, finely divided powdered Pt on an alumina HDS catalyst is homogeneously blended with a regenerable sorbent and the mixture is shaped into common catalyst particles. Alternatively, a renewable sorbent can be incorporated into the support and, for example, Pt can be impregnated on a sorbent-containing support such as alumina.
[0030]
In another two-component configuration, the alumina support is impregnated with HDS metal and a sorbent on a common base. Both metals can be evenly distributed throughout the catalyst particles, and the sorbent and / or HDS components are preferentially deposited on the outside of the particles to provide a rim or eggshell sorbent or HDS component. A rich region can also be formed.
[0031]
A three component bed configuration can be used as well. In one embodiment, called mixed / stacked, a mixed HDS catalyst / sorbent bed is configured upstream of a single HDS / hydrocracking catalyst. In another embodiment, known as a stack / stack / stack configuration, the three components are layered from top to bottom, such as HDS catalyst / sorbent / HDS catalyst. In one embodiment, a ternary system may occupy a common reactor. In another embodiment, a three component system in which the HDS catalyst / sorbent occupies a leading reactor in a mixed or stacked configuration and the HDS catalyst occupies a trailing reactor in a two reactor row. Can be used. This arrangement allows operation of the two reactor sections, especially at different process conditions such as temperature, and provides flexibility in controlling process parameters such as selectivity and / or product quality.
[0032]
The composition of the bed is independent of the configuration and may vary depending on the particular or integrated process to which the invention is applied. If the capacity of the sorbent is limited, the bed composition must be consistent with the expected life or cycle of the process. These parameters are themselves sensitive to the sulfur content of the feedstock being processed and the degree of desulfurization desired. For these reasons, the composition of the floor is flexible and variable, and the optimal floor composition for one application may not play an equivalent role in alternative applications. Generally, the weight ratio of sorbent to hydrodesulfurization catalyst will range from about 0.01 to about 1000, preferably from about 0.5 to about 40, more preferably from about 0.7 to about 30. It is possible. In a three component configuration, these ranges apply to the mixing zone of the mixed / stacked configuration and the first two zones in the stacked / stacked / stacked design. The hydrodesulfurization catalyst present in the final zone of these two arrays is generally present in a weight ratio equal to or less than the combined weight composition of the upstream zone.
[0033]
The process can be used, for example, as a stand-alone process for fuels, lubricants and chemicals. All processes can be combined and integrated with other processes in such a way as to provide product and process advantages and improvements over uncombined processes. The following embodiments are included to illustrate (but not limit) the use of the process of the present invention.
[0034]
Processes associated with the fuel process include desulfurization of gasoline range feed and product streams, desulfurization of distillate streams, desulfurization of FCC streams prior to recycle to the second stage process, desulfurization of hydrocracked feeds, Includes polycyclic aromatic conversion by selective ring opening, aromatic saturation processes, hydroisomerization, removal of sulfur from natural, synthetic and recycled gas streams and petroleum crude oil streams. Processes for the production of lubricating oils include: Optimization of white oil process by hydrocracking, improving product quality through mild finishing, reducing catalyst costs and / or increasing load correction factors. The processes involved in chemical processing include the substitution of unfriendly nickel-based hydrogenation processes, the production of olefins by various cracking processes, and the preparation of high quality feedstocks that produce oxygenates through oxy-functionalization processes, Includes the production of solvents and polymer grade olefins and aromatics.
[0035]
The present invention is exemplified by, but not limited to, the following experimental conditions, unless otherwise indicated.
[0036]
General conditions
Using a nominal equivalent of feed for each sorbent, the capacity and hydrogen regenerability of the hydrogen sulfide sorbent were evaluated by a Cahn @ TG121 thermal density analyzer (Thermogravimetric @ Analyzer). The candidate sorbent was first calcined in air at 400 ° C. for 3 hours and placed in the analyzer. The sorbent is heated in hydrogen at 500 ° C. for 1 hour, then cooled to 325 ° C.2100 vppm H in2Exposure to a gas formulation containing S for 2 hours, during which time H2The weight increase associated with the adsorption of S was recorded. H used spent sorbent2In 500 ° C. for 1 hour, and then to 550 ° C. for 1 hour, during which time H2Emission of S, that is, regeneration of the sorbent was observed. In a multi-cycle test, this sequence was reproduced to simulate a repeated adsorption-regeneration cycle. Reproducibility was further confirmed by observing the phase change using an environmentally controlled high temperature cell attached to the X-ray diffractometer.
[0037]
Sorbents were prepared by incipient wetness and impregnation of various carrier materials with aqueous metal nitrate. The extrudate was air dried for 24 hours at 120 ° C. under vacuum. Calcination in flowing air was carried out in a small catalyst pretreatment unit or a thermal density measurement unit dedicated to this function. Both were calcined at 400 ° C. for 3 hours. All sorbent compositions in the examples are nominal metal weight percent on the carrier.
[0038]
Example 1
In this experiment, zinc oxide (a non-hydrogen regenerable sorbent) as a control was compared to Fe, Co, Ni, and Cu supported sorbents.
[0039]
[Table 1]
% Regeneration means the percentage of sulfur that was removed from the sorbent during regeneration and chemisorbed. This value is zero if no sulfur is released during regeneration. Complete sulfur removal during regeneration corresponds to 100% regeneration.
[0041]
The results demonstrate that Fe, Co, Ni and Cu are active hydrogen sulfide sorbents and have been regenerated by hydrogen to varying degrees. Co and Ni were more reproducible than Fe and Cu on the common support. Metal loading (Samples 4 and 5) affected capacity but not reproducibility. Titania (Sample 7) was the least preferred carrier, although reproducibility was within the limits of the present invention.
[0042]
Example II
Experiments were performed to determine what factors had an effect on capacity and reproducibility.
[0043]
[Table 2]
Samples 8-13 illustrate that for common metals, capacity and% regeneration were independent of the support. As expected, capacity was a function of metal loading, but regeneration was not affected by total metal content. Samples 14-15 and 16-18 illustrate that for Co on a common support, the hydrogen sulfide capacity of the sorbent is a function of the metal content, but the rate of hydrogen regeneration is not sensitive to metal loading. I have.
[0045]
[Table 3]
Example III
The hydrogen sulfide sorbent of Sample 5 (Example I) was subjected to multi-cycle adsorption-regeneration according to the procedure described above. 20Ni / ZrO2The sorbent was subjected to 5 full cycles and there was no significant loss of hydrogen sulfide capacity and hydrogen renewability. The increase in sulfur weight and the degree of reproducibility were almost equal to those of Sample 5.
[0047]
Example IV
The hydrogen sulfide sorbent of Sample 17 (Example II) was subjected to multi-cycle adsorption-regeneration according to the procedure described above. 10Co / Al2O3The sorbent was subjected to six full cycles and there was no significant loss of hydrogen sulfide capacity and hydrogen renewability. The increase in sulfur weight and the degree of reproducibility were equivalent to those of Sample 17.
[0048]
Example V
10Co / Al of sample 17 (Example II)2O3A 1.0 g sample of the sorbent was diluted with 30 g of inert material and charged to a through-bed fixed bed reactor. The sorbent is reduced in hydrogen at 500 ° C. for 1 hour and then H 2 at 300 ° C. and a gas flow rate of 50 ml / min.21000 vppm H in2Applied to the S formulation. The hydrogen flow exiting the sorbent bed is measured by measuring the breakthrough time which approximates full saturation of the sorbent by H2Using an S detector, H2The S content was monitored. In this manner, the sorbent was evaluated in three completely different tests, which are summarized below.
[0049]
[Table 4]
The sorbent Co content is changed to Co9S8The calculated sulfur value was 3.0% by weight. The data in the table above confirms the results of TGA in a fixed bed configuration and demonstrates the reproducible and efficient use of sorbent volume.
[0051]
Example VI
The sorbent is 10 Co / Al, each diluted with an inert material2O3The procedure of Example V was followed except that it consisted of three independent zones separated by an inert material containing Hydrogen sulfide breakthrough occurs in this bed at 29.3 hours, which is about three times that of the single sorbent zone. Each zone was separated and analyzed for sulfur. The sulfur values in the top, middle and bottom areas were 3.1, 3.3 and 3.3% by weight, respectively. These values reflect the very efficient operation of the sorbent.
[0052]
Example VII
The procedure as described in Example VI was repeated using a three zone sorbent bed. H at the 27th hour2After an S breakthrough was detected, the sorbent bed was regenerated with hydrogen at 500 ml / min for 3 hours at 450 ° C., 3 hours at 500 ° C. and finally at 550 ° C. for 10 hours. The three sorbent zones were separated and analyzed for sulfur. The sulfur values in the top, middle and bottom areas were 0.2, 0.2 and 0.2% by weight, respectively. These sulfur values demonstrate hydrogen regeneration of the entire sorbent bed at a regeneration efficiency level of about 95%.
[0053]
Example VIII
The procedure of Example VIII was repeated using a single sorbent zone. H2After an S breakthrough was detected, the bed was regenerated with hydrogen. The sorbent is then cooled to 300.degree.2Dilution H in the flow2Exposure to S. The adsorption-regeneration cycle was repeated four times, at the end of which the sorbent was finally sulfurized. The results are summarized in the table below.
[0054]
[Table 5]
The breakthrough time is H2Regeneration of the sorbent was successful after each exposure to S, indicating efficiency. If regeneration per cycle did not occur completely, a significant decrease in breakthrough time in each subsequent cycle would be expected. The sulfur content of the sorbent illustrated that the sulfur capacity was not compromised even after use of the multicycle.
[0056]
Example IX
10Co / Al of sample 17 (Example II)2O3As described above2Dilution H in2S is attached. H2After an S breakthrough is detected, as shown in the table below,2The sorbent was regenerated with varying processing speed, temperature and time. The results show that the regeneration period is a function of these process variables and can be selected to maintain the regeneration period and / or regeneration required to reach the specified regeneration efficiency.
[0057]
[Table 6]
Example X
Experiments were performed to determine if the combination of metals in the sorbent had an effect on the regeneration achieved. The results are shown in the table below.
[0059]
[Table 7]
Samples 19-21 show that Co-Ni based sorbent sets with equivalent total metal loading but varying Co to Ni ratios shared sulfur capacity and regeneration efficiency. . Although the sulfur capacity was consistent with that predicted by the monometal sorbent, the Co-Ni binary metal sorbent was unexpectedly more completely compared to the corresponding Ni-only sorbent. Played.
[0061]
Samples 22-24 show that the Co-Re sorbent had the proper sulfur capacity, which decreased with increasing Re loading, limiting the sulfur uptake within a certain amount of time to H.2This exemplifies that it is caused by a decrease in the reaction rate (not shown) with S. The Co-Re sorbent was easily reproducible with hydrogen, as shown by the data.
[0062]
Samples 25-27 demonstrate that incorporation of Group VIII noble metals did not impair the sulfur capacity of Co, despite the reduced rate of sulfur uptake in the presence of Pt. Hydrogen regeneration of these binary metal sorbents occurred easily, with essentially quantitative recovery of fresh sorbent volume.
[0063]
Example XI
A 1.0 g sample of the various binary metal sorbents was diluted with 30 g of inert material and charged to a through-bed fixed bed reactor. The sorbent is reduced with hydrogen at 500 ° C. for 1 hour and then H 2 at 300 ° C. and a gas flow rate of 50 ml / min.2Medium, 1000 vppm H2S was added. The hydrogen flow exiting the sorbent bed is measured by measuring the breakthrough time which approximates full saturation of the sorbent by H2Using an S detector, H2The S content was monitored.
[0064]
H2After an initial breakthrough of S is detected, H flowing at 300 ml / min using a temperature-time program of 3 hours at 450 ° C., 3 hours at 500 ° C., and finally 3 hours at 550 ° C.2The sorbent bed was regenerated in. This adsorption-regeneration sequence was repeated to simulate a few complete cycles. After the second regeneration, the residual sulfur content of the sorbent was determined analytically. The results are shown in the table below.
[0065]
[Table 8]
The breakthrough times for the second and third cycle sorbents are characteristic of the breakthrough period of the fresh sorbent and indicate that hydrogen regeneration is successful with these binary metal sorbents. . Without hydrogen regeneration, breakthrough periods with multi-cycle sorbents would be significantly reduced. The sulfur content of the regenerated sorbent is lower than that of Ni-Cu / ZrO, where the regeneration rate is slower than the remaining2Except for all cases, it has been demonstrated that over 60% regeneration was achieved.
[0067]
Example XII
Co / Al of sample 13 (Example II)2O3The sorbent was subjected to a heptane cracking test to determine the hydrocracking activity of the sorbent as reflected in hydrocracking to methane. Same Co / Al2O3The sorbent was impregnated with dilute sulfuric acid to introduce 0.05% by weight sulfur into the sorbent.
[0068]
A sulfuric acid stock solution was prepared by diluting 1 mL of concentrated sulfuric acid with 50 mL of deionized water. A solution of 0.5 mL of the stock sulfuric acid solution in 9.0 mL of deionized water was combined with the previously prepared 10% Co / Al2O3The solution was added dropwise to 10 g of the sorbent while stirring. The sorbent was left overnight and charged to the reactor for calcining in air at 400 ° C. for 3 hours. The material was converted to 14-35 mesh. Analysis: Co 9.91; S, 0.055 (% by weight).
[0069]
To measure the hydrocracking activity of the sorbent as reflected in the hydrocracking to methane, the sulfided sorbent was subjected to heptane cracking. Same Co / Al2O3The sorbent was also impregnated with dilute sulfuric acid to introduce 0.25% by weight sulfur into the sorbent. The sulfurized sorbent was subjected to a heptane cracking test to determine the hydrocracking activity of the sorbent as reflected in the hydrocracking to methane. The results are shown in the table below.
[0070]
[Table 9]
Examples II, IV and V illustrate that the supported Co sorbents exhibit high hydrogen sulfide capture activity, have high hydrogen sulfide capacity, and have capacity retention after multi-cycle hydrogen regeneration. Sample 32 shows that the sorbent is very active in hydrocracking the feedstock to light gas. Samples 33 and 34 demonstrate that this hydrocracking activity is significantly reduced and eliminated by the presence of low levels of sulfur.
[0072]
Example XIII
The procedure of Example II was repeated using the sulfur-containing Co / Al2O3Repeated using sorbent. The hydrogen sulfide capture capacity of the sorbent was equal to sample 13 in Example II, indicating that the affinity of the hydrogen sulfide capture sorbent was not compromised in the presence of low levels of sulfur. .
[0073]
Example XIV
10Co-10Cu / SiO2A sorbent was synthesized. 12.3 g of Co (NO3)2(6H2O) and 9.6 g of Cu (NO3)2(3H2O) in 50 mL of deionized water while stirring a solution of 25 g of SiO in a small evaporating dish.2It was dropped on the extruded product. The mixture was left at room temperature until dry, then dried at 120 ° C. under vacuum for 24 hours. The sorbent was charged into a small catalyst pretreatment unit and calcined at 400 ° C. in air for 3 hours. The sorbent was converted to 14-35 mesh particles for testing. Analysis: Co, 8.23 wt%; Cu, 8.12 wt%. The multi-cycle capacity and reproducibility in use has been demonstrated by TGA.
[0074]
Example XV
The following sorbents were subjected to a heptane cracking test to measure the hydrocracking activity of the sorbents as reflected in the hydrocracking to methane. Sample 13 Co / Al2O3Sorbent (Example II); Ni / ZrO of sample 52Sorbent (Example I); Co / ZrO of sample 112Sorbent (Example II); and Cu / ZrO of sample 282Sorbent (Example XI); Co-Cu / ZrO of sample 302Sorbent (Example XI) and 10Co-10Cu / SiO2Sorbent (sample 35). The results are shown in the table below.
[0075]
[Table 10]
From the above, it can be concluded that the hydrocracking activity of the single metal sorbent is extremely high. This hydrocracking activity can be effectively suppressed by adding a hydrocracking moderator. With bimetallic catalysts (samples 28, 30) compared to single metal analogs, neither the ability to be regenerated by treatment with hydrogen nor the sulfur capacity is compromised.
[0077]
Example XVI
Experiments were performed to determine if, for example, adding a noble metal to the sorbent could increase hydrogen regeneration. The results are shown in the table below.
[0078]
[Table 11]
Sample 12 shows the standard sulfur capacity for a 10% Co supported hydrogen sulfide sorbent. Under conditions intentionally selected so as not to be completely regenerated by hydrogen treatment (500 ° C. for 1 hour), the cobalt sorbent loses 47% of the adsorbed hydrogen sulfide, ie 47% is regenerated. The addition of Pd (samples 26, 36-38) had no effect on sulfur capacity, but the presence of Pd clearly facilitated hydrogen regeneration under common conditions. The degree of regeneration increased with increasing Pd to a Pd level of about 2% by weight.
[0080]
Samples 27, 39, and 40 illustrate a similar trend when there is Pt that is more effective than Pd in promoting hydrogen regeneration rates. The apparent loss of sulfur capacity at 2 wt% Pt is largely due to the reduced reaction rate of the sulfur pickup.
[0081]
Sample 41, in which Pt and Pd are loaded in the same amount by weight but different atoms are loaded, is easier to regenerate than either metal alone when present at 1% by weight, and between two noble metals Represents a synergistic effect.
[0082]
The data illustrates that hydrogen regeneration of highly saturated hydrogen sulfide sorbents is facilitated by the presence of one or more noble metals of Group VIII of the Periodic Table of the Elements. This accelerating effect can be used to shorten the regeneration cycle, lower the regeneration temperature, or both.
Claims (31)
Ｆｅ、Ｎｉ、Ｃｏ又はＣｕの中から選択された少なくとも一種の金属の酸化物を含有する有効量の収着剤を有し、硫化水素吸収の第１サイクル容量を規定する硫黄レベルを有する使用済み硫化水素収着剤を与える工程と、
水素にとって再生された収着剤を生成するのに有効な条件下で、前記使用済み硫化水素収着剤を再生用濃度の水素を含むガスに暴露し、前記使用済み硫化水素収着剤を再生する工程とを含むことを特徴とする方法。A method for regenerating a hydrogen sulfide sorbent,
Spent having an effective amount of sorbent containing an oxide of at least one metal selected from Fe, Ni, Co or Cu and having a sulfur level that defines the first cycle capacity of hydrogen sulfide absorption Providing a hydrogen sulfide sorbent;
Exposing the used hydrogen sulfide sorbent to a gas containing a regenerating concentration of hydrogen under conditions effective to produce a regenerated sorbent for hydrogen to regenerate the used hydrogen sulfide sorbent Performing the steps of:
（ｉ） Ｃｕ、Ａｇ、Ａｕ、Ｓｎ及びＰｂの少なくとも一種であり、抑制量は約１重量％〜約１０重量％の範囲内にあるか、又は
（ｉｉ） 少なくとも一種の第ＶＩＡ族元素であり、抑制量が約０．０１重量％〜約２重量％の範囲内にあることを特徴とする、請求項１０に記載の硫化水素収着剤の再生方法。The hydrocracking inhibitor,
(I) at least one of Cu, Ag, Au, Sn and Pb, wherein the amount of suppression is in the range of about 1% to about 10% by weight; or (ii) at least one group VIA element. The method for regenerating a hydrogen sulfide sorbent according to claim 10, wherein the amount of suppression is in the range of about 0.01% to about 2% by weight.
（ｉ） Ｍｏ、Ｗ、Ｆｅ、Ｃｏ、Ｎｉ、Ｐｔ、Ｐｄ、Ｉｒ及びＲｈの少なくとも一種を含有する水素化脱硫触媒と、
（ｉｉ） Ｆｅ、Ｃｏ、Ｎｉ又はＣｕから選択された少なくとも一種の収着剤金属を含有する硫化水素収着剤であって、硫化水素吸収の第１サイクル容量を規定するレベルの硫黄を含む硫化水素収着剤とから構成され、
かかる接触が、少なくとも一種の脱硫生成物及び使用済み硫化水素収着剤を生成する工程と、次いで
（ｂ） 水素が前記使用済み硫化水素収着剤を再生し、再生済み収着剤を生成するのに有効な条件下で、前記使用済み硫化水素収着剤を、再生濃度の水素を含むガスに暴露する工程とを含むことを特徴とする脱硫方法。(A) contacting a catalytically effective amount of a catalyst system with a sulfur-containing hydrocarbon under catalytic hydrodesulfurization conditions;
(I) a hydrodesulfurization catalyst containing at least one of Mo, W, Fe, Co, Ni, Pt, Pd, Ir and Rh;
(Ii) a hydrogen sulfide sorbent comprising at least one sorbent metal selected from Fe, Co, Ni or Cu, wherein the sulfide comprises a level of sulfur defining a first cycle capacity of hydrogen sulfide absorption; And a hydrogen sorbent,
Such contacting produces at least one desulfurization product and a spent hydrogen sulfide sorbent; and (b) hydrogen regenerates the spent hydrogen sulfide sorbent to produce a regenerated sorbent. Exposing the used hydrogen sulfide sorbent to a gas containing a regenerated concentration of hydrogen under conditions effective for:
（ｉ） Ｃｕ、Ａｇ、Ａｕ、Ｓｎ及びＰｂの少なくとも一種であり、抑制量は約１重量％〜約１０重量％の範囲内にあるか、又は
（ｉｉ） 少なくとも一種の第ＶＩＡ族元素であり、抑制量が約０．０１重量％〜約２重量％の範囲内にあることを特徴とする、請求項２０に記載の脱硫方法。The hydrocracking inhibitor,
(I) at least one of Cu, Ag, Au, Sn and Pb, wherein the amount of suppression is in the range of about 1% to about 10% by weight; or (ii) at least one group VIA element. 21. The desulfurization method of claim 20, wherein the amount of inhibition is in the range of about 0.01% to about 2% by weight.
（ｉｉ） 向流モード、
のうちの１つで運転される固定床法であり、
接触水素化脱硫条件が、約４０℃〜約５００℃の温度と、約１００ｐｓｉｇ〜約３０００ｐｓｉｇの圧力と、約５０〜約１０，０００ＳＣＦ／Ｂの処理ガス速度と、約０．１〜約１００Ｖ／Ｖ／時の空間速度とを含むことを特徴とする、請求項３０に記載の脱硫方法。(I) co-current and (ii) counter-current modes,
A fixed bed method operated on one of the following,
The catalytic hydrodesulfurization conditions include a temperature of about 40 ° C. to about 500 ° C., a pressure of about 100 psig to about 3000 psig, a process gas rate of about 50 to about 10,000 SCF / B, and about 0.1 to about 100 V / 31. The desulfurization method according to claim 30, comprising a space velocity of V / hr.
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| PCT/US2001/022734 WO2002008361A1 (en) | 2000-07-21 | 2001-07-19 | The use of hydrogen to regenerate metal oxide hydrogen sulfide sorbents |
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| US7074324B2 (en) * | 2002-06-05 | 2006-07-11 | Exxonmobil Research And Engineering Company | Process to remove sulfur contaminants from hydrocarbon streams |
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| US5439583A (en) * | 1984-10-31 | 1995-08-08 | Chevron Research And Technology Company | Sulfur removal systems for protection of reforming crystals |
| US4729889A (en) * | 1985-03-29 | 1988-03-08 | California Institute Of Technology | High temperature regenerative H2 S sorbents |
| US4690806A (en) * | 1986-05-01 | 1987-09-01 | Exxon Research And Engineering Company | Removal of sulfur from process streams |
| US5045175A (en) * | 1989-12-28 | 1991-09-03 | Uop | Separation system for C4 hydrotreater effluent having reduced hydrocarbon loss |
| GB9421705D0 (en) * | 1994-10-27 | 1994-12-14 | Ici Plc | Purification process |
| US5935420A (en) * | 1996-08-23 | 1999-08-10 | Exxon Research And Engineering Co. | Desulfurization process for refractory organosulfur heterocycles |
| US5928498A (en) * | 1996-08-23 | 1999-07-27 | Exxon Research And Engineering Co. | Desulfurization and ring opening of petroleum streams |
| US5925239A (en) * | 1996-08-23 | 1999-07-20 | Exxon Research And Engineering Co. | Desulfurization and aromatic saturation of feedstreams containing refractory organosulfur heterocycles and aromatics |
| US6274533B1 (en) * | 1999-12-14 | 2001-08-14 | Phillips Petroleum Company | Desulfurization process and novel bimetallic sorbent systems for same |
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| EP1322728A1 (en) | 2003-07-02 |
| WO2002008361A1 (en) | 2002-01-31 |
| CA2416236A1 (en) | 2002-01-31 |
| AU2001273566A1 (en) | 2002-02-05 |
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| Benzothiophene | FIG. I |