CN101146894A - 脱硫剂以及使用该脱硫剂的脱硫方法 - Google Patents
脱硫剂以及使用该脱硫剂的脱硫方法 Download PDFInfo
- Publication number
- CN101146894A CN101146894A CNA2006800095170A CN200680009517A CN101146894A CN 101146894 A CN101146894 A CN 101146894A CN A2006800095170 A CNA2006800095170 A CN A2006800095170A CN 200680009517 A CN200680009517 A CN 200680009517A CN 101146894 A CN101146894 A CN 101146894A
- Authority
- CN
- China
- Prior art keywords
- sweetening agent
- nickel
- fuel cell
- quality
- hydrogen
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 45
- 230000023556 desulfurization Effects 0.000 title claims abstract description 40
- 230000003009 desulfurizing effect Effects 0.000 title abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000000446 fuel Substances 0.000 claims abstract description 62
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 57
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 56
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 56
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 238000000629 steam reforming Methods 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 235000003599 food sweetener Nutrition 0.000 claims description 128
- 239000003765 sweetening agent Substances 0.000 claims description 128
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 34
- 239000005864 Sulphur Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 27
- 239000003350 kerosene Substances 0.000 claims description 24
- -1 sulphur compound Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 229960001866 silicon dioxide Drugs 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 239000003345 natural gas Substances 0.000 claims description 7
- 235000009508 confectionery Nutrition 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 4
- 239000003637 basic solution Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims description 2
- 238000002407 reforming Methods 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000002453 autothermal reforming Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- 229920001296 polysiloxane Polymers 0.000 description 12
- 235000019353 potassium silicate Nutrition 0.000 description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 10
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000274 adsorptive effect Effects 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical group 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 239000010742 number 1 fuel oil Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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Abstract
本发明提供可以高效地将烃原料和/或含氧烃原料中的硫成分除去至极低浓度、且寿命长、有利于工业的脱硫剂;以及将使用该脱硫剂进行脱硫处理的烃原料和/或含氧烃原料进行水蒸气重整、部分氧化重整或自热重整处理,制造燃料电池用氢的方法;以及使用由该方法制造的氢的燃料电池系统。本发明涉及除去烃原料和/或含氧烃原料中的硫化合物的脱硫剂,该脱硫剂含有镍或者镍和铜、以及硅,堆积密度为0.95-2.0g/cm3,孔容积为0.10-0.40ml/g,微孔表面积为100-250m2/g,且外表面积为100m2/g或以下;还涉及使用上述脱硫剂的燃料电池用氢的制造方法;以及使用由该方法制造的氢的燃料电池系统。
Description
技术领域
本发明涉及脱硫剂、该脱硫剂的制造方法、使用该脱硫剂进行的脱硫方法、燃料电池用氢的制造方法以及使用该氢的燃料电池系统。具体地说,涉及可以高效地除去烃原料和/或含氧烃原料中的硫成分至极低浓度、且寿命长的脱硫剂;该脱硫剂的制造方法;将使用该脱硫剂进行脱硫处理的烃原料和/或含氧烃原料进行重整处理,制造燃料电池用氢的方法;以及使用由该方法制造的氢的燃料电池系统。
背景技术
近年来,由于环境问题使新能源技术受到重视,作为该新能源技术之一,燃料电池日益引人瞩目。该燃料电池是通过使氢与氧发生电化学反应,将化学能转变为电能的装置,具有能源利用效率高的特征,作为民用、工业用或汽车用等,其实用化技术研究得到积极发展。已知该燃料电池根据所使用的电解质的种类不同而分为磷酸型、熔融碳酸盐型、固体氧化物型、固体高分子型等类型。另一方面,作为氢源,目前正在研究以甲醇、甲烷为主体的液化天然气、以该天然气为主要成分的城市供气、以天然气为原料的合成液体燃料、以及石油系的石脑油或煤油等烃油的应用。
将燃料电池应用于民用或汽车用等时,上述烃油在常温常压下为液体状,保管和操作方便,并且特别是对于石油系的燃料,加油站或零售商店等供应系统完备,因此适合作为氢源使用。但是,上述烃油与甲醇或天然气体系燃料相比,硫的含量较多。使用该烃油制造氢时,通常采用在重整催化剂的存在下将该烃油进行水蒸气重整或部分氧化重整处理的方法等。上述重整处理中,上述重整催化剂因烃油中的硫成分而中毒,因此从催化剂寿命角度考虑,必须对该烃油实施脱硫处理,使硫成分含量长时间内降低至0.2质量ppm或以下。
另外,在汽车上直接装载氢时,从安全角度考虑,需要研究在氢中添加添味剂,使由存在于原料油中的硫化合物形成的添味剂保持极低浓度,这也同样很重要。
目前已对石油系烃的脱硫方法进行了很多研究,例如已知有使用Co-Mo/氧化铝或Ni-Mo/氧化铝等氢化脱硫催化剂和ZnO等硫化氢吸附剂,在常压-5MPa.G的压力下、在200-400℃的温度下进行氢化脱硫的方法。该方法是在苛刻的条件下进行氢化脱硫、将硫成分制成硫化氢加以除去的方法,作为小规模的分散型燃料电池用,考虑到安全、环境问题、与高压气体使用规定等相关法规的关系,不优选。即,为了应用于燃料电池,人们希望可在低于1MPa.G的条件下长时间地对燃料进行脱硫的脱硫剂。
作为在温和的条件下吸附除去燃料油中的硫成分的脱硫剂,有人提出镍系的吸附剂(例如参照专利文献1-12)。还有人提出了将其改良的镍-铜系的吸附剂(例如参照专利文献11或13)。
但是,从脱硫剂的寿命角度考虑,上述以往公开的技术并未达到实际应用水平。特别是对于上述镍-铜系的吸附剂,由于堆积密度低,因此只得增大脱硫器的大小,难以实际应用,同时,用常规大小的脱硫器不足以有效地进行脱硫。
专利文献1:日本特公平6-65602号公报
专利文献2:日本特公平7-115842号公报
专利文献3:日本特开平1-188405号公报
专利文献4:日本特公平7-115843号公报
专利文献5:日本特开平2-275701号公报
专利文献6:日本特开平2-204301号公报
专利文献7:日本特开平5-70780号公报
专利文献8:日本特开平6-80972号公报
专利文献9:日本特开平6-91173号公报
专利文献10:日本特开平6-228570号公报
专利文献11:日本特开2001-279259号公报
专利文献12:日本特开2001-342465号公报
专利文献13:日本特开平6-315628号公报
发明内容
本发明针对上述状况,其目的在于提供:可高效除去烃原料和/或含氧烃原料中的硫成分至极低浓度、且寿命长、有利于工业化的脱硫剂;对使用该脱硫剂进行脱硫处理的烃原料和/或含氧烃原料进行水蒸气重整、部分氧化重整或自热重整处理、制造燃料电池用氢的方法;以及使用通过该方法制造的氢的燃料电池系统。其目的特别在于提供:在配备小型、紧凑式脱硫器的燃料电池系统中,可高效地除去硫至低浓度的脱硫剂、以及使用该脱硫剂的脱硫方法。
本发明人为实现上述目的进行了各种深入研究,结果发现:含有镍或者镍和铜、以及硅,堆积密度、孔容积和微孔表面积在特定范围,且外表面积在特定值或以下的脱硫剂可以解决上述问题。本发明基于该认识完成。
即,本发明提供以下的脱硫剂、脱硫方法、燃料电池用氢的制造方法以及燃料电池系统。
1.脱硫剂,该脱硫剂除去烃原料和/或含氧烃原料中的硫化合物,其特征在于:含有镍或者镍和铜、以及硅,堆积密度为0.95-2.0g/cm3,孔容积为0.10-0.40ml/g,微孔表面积为100-250m2/g,且外表面积为100m2/g或以下。
2.上述1的脱硫剂,其中,镍的含量在40-90质量%的范围。
3.上述1或2的脱硫剂,其中,铜的含量在0.01-40质量%的范围。
4.上述1-3中任一项的脱硫剂,其中,硅的含量换算成SiO2(二氧化硅)为50质量%或以下。
5.上述1-4中任一项的脱硫剂,其中,烃原料和/或含氧烃原料选自煤油、轻油、液化石油气(LPG)、石脑油、汽油、天然气和二甲醚的至少一种。
6.脱硫剂的制造方法,其中将含有镍或者镍和铜的酸性溶液或酸性水性分散液与含有硅的碱性溶液混合,瞬间形成沉淀而得到堆积密度为0.95-2.0g/cm3,孔容积为0.10-0.40ml/g,微孔表面积为100-250m2/g,外表面积为100m2/g或以下的脱硫剂。
7.上述6的脱硫剂的制造方法,其中,酸性溶液或酸性水性分散液与碱性溶液的混合、以及沉淀的形成是在内径为3-100mm的反应管内进行。
8.脱硫方法,其特征在于:使用上述1-5中任一项的脱硫剂,在-40至300℃范围的温度下进行烃原料和/或含氧烃原料的脱硫。
9.燃料电池用氢的制造方法,其特征在于:使用上述1-5中任一项的脱硫剂,对烃原料和/或含氧烃原料进行脱硫,然后进行重整。
10.上述9的燃料电池用氢的制造方法,其中,重整为水蒸气重整、部分氧化重整或自热重整。
11.上述9或10的燃料电池用氢的制造方法,其中,用于重整的催化剂为钌系催化剂或镍系催化剂。
12.上述11的燃料电池用氢的制造方法,其中,用于重整的催化剂的载体成分含有选自氧化锰、氧化铈、以及氧化锆的至少一种。
13.燃料电池系统,其特征在于:使用通过上述9-12中任一项的方法制造的氢。
发明效果
本发明的脱硫剂中,吸附硫的有效的微细孔多,微细孔以外的细孔少,因此单位容积的硫化合物吸附能力提高,可以将脱硫剂制成小型紧凑化。根据本发明,可以提供可以将烃原料和/或含氧烃原料中的硫成分高效除去至极低浓度、且寿命长的脱硫剂;该脱硫剂的制造方法;以及将使用该脱硫剂进行脱硫处理的烃原料和/或含氧烃原料进行重整处理,制造燃料电池用氢的方法。特别是在配备小型、紧凑式脱硫器的燃料电池系统中,可以高效地将硫除去至低浓度。
附图简述
图1是表示本发明的燃料电池系统的一个例子的概略流程图。
符号的说明
1: 气化器
2: 燃料电池系统
20:氢制造系统
21:燃料罐
23:脱硫器
31:重整器
32:CO转化器
33:CO选择性氧化炉
34:燃料电池组
34A:负极
34B:正极
34C:高分子电解质
36: 气水分离器
37: 排热回收装置
37A:热交换器
37B:热交换器
37C:冷却器
实施发明的最佳方式
本发明的脱硫剂是将烃原料和/或含氧烃原料中的硫化合物除去的脱硫剂,含有镍或者镍和铜、以及硅,堆积密度为0.95-2.0g/cm3,孔容积为0.10-0.40ml/g,微孔表面积为100-250m2/g,且外表面积为100m2/g或以下。
本发明的脱硫剂中,镍通过吸附硫或与硫反应,形成硫化物,起到除去硫的作用。镍成分通常有氧化镍、将其还原得到的金属镍、以及其它碳酸镍、硝酸镍、氯化镍、硫酸镍、乙酸镍等,本发明的脱硫剂中,优选其中镍成分的60质量%或以上为金属镍。金属镍为60质量%或以上,则脱硫剂表面的活性点数多,可得到特别高的脱硫性能。
镍(Ni)的含量相对于脱硫剂总量优选为40-90质量%范围,更优选60-85质量%的范围,进一步优选65-85质量%的范围。镍含量在50质量%或以上,则可得到高的脱硫活性;为90质量%或以下,则通过确保后述载体的含量,使脱硫剂的表面积充分,脱硫性能不会降低。
本发明的脱硫剂中,根据需要使用的铜可以提高镍的分散性,同时抑制填塞现象,起到促进硫的吸附的作用。铜(Cu)的含量相对于脱硫剂总量优选为0.01-40质量%,更优选0.01-35质量%,进一步优选0.01-30质量%。铜的含量为0.01-40质量%,则不会抑制上述镍的效果,可以使作为脱硫剂的功能提高。
本发明的脱硫剂中,Ni和Cu的总量相对于脱硫剂总量优选为50-90质量%的范围。总量在该范围内,则脱硫所必需的活性点数足够,可得到所希望的脱硫性能。
本发明的脱硫剂中,如果含有硅(二氧化硅),则不仅脱硫剂的成型变得容易,也形成对脱硫有效的细孔结构。即,二氧化硅作为载体成分,在提高镍和铜的分散性的同时还具有形成后述的微孔的作用。本发明的脱硫剂中,硅的含量相对于脱硫剂总量优选换算成SiO2为50质量%或以下,更优选10-40质量%。硅含量在50质量%或以下,则可确保对脱硫有效的镍量或者镍和铜量。本发明中,还可以少量混合钴、铁、锰和铬等其它金属成分。
本发明的脱硫剂要求堆积密度为0.95-2.0g/cm3,优选1.1-1.8g/cm3。这里,堆积密度是指将脱硫剂以一定的方法填充到体积已知的容器中,将该脱硫剂的质量用包括颗粒间空隙的体积除所得的值。堆积密度为0.95 g/cm3或以上,则单位容积的硫化合物吸附能力提高,因此可以将脱硫器制成小型、紧凑化。2.0 g/cm3是堆积密度的通常的上限。
本发明的脱硫剂要求孔容积为0.10-0.40ml/g,优选0.15-0.40ml/g。孔容积为0.40ml/g或以下,则脱硫剂的密度增大,单位容积的硫化合物吸附能力提高。孔容积为0.10ml/g或以上,则有效的细孔数充分增大,脱硫能力提高。
本发明的脱硫剂还要求微孔表面积为100-250m2/g、外表面积为100 m2/g或以下。优选微孔表面积为120-240 m2/g、外表面积为90m2/g或以下。进一步优选外表面积为80 m2/g或以下。微孔表面积为100m2/g或以上,则被担载的镍的分散性提高,脱硫有效果。
硫化合物强烈吸附于微孔中,但是在微孔以外的地方吸附弱。本发明的脱硫剂中,微孔表面积大,无效的外表面积为100m2/g或以下,较小,因此可以有效地进行脱硫。即,外表面积为100m2/g或以下,则脱硫剂的密度增大,因此单位容积的硫化合物吸附能力提高。
本发明的脱硫剂中,微孔表面积/外表面积为1或以上,由此,可以实现吸附能力的提高和长寿命,还可以使脱硫器制成小型、紧凑化。微孔表面积/外表面积优选为1.2或以上,进一步优选为1.5或以上。
获得具有上述特性的脱硫剂的方法没有特别限定,可通过含浸法、共沉淀法、混炼法等实现。其中,从可以简便地制造堆积密度为0.95g/cm3或以上的脱硫剂的角度考虑,最优选共沉淀法。
以下对共沉淀法进行详细说明。本发明的共沉淀法中,首先制造含有作为必需成分的镍源和根据需要的铜源的酸性水溶液或酸性水性分散液、以及含有硅源的碱性水溶液。
以往的共沉淀法中,是将上述制造的酸性水溶液或水性分散液以及碱性水溶液分别加温至50-90℃左右,将两者混合,再保持50-90℃左右的温度,终止反应,但是该方法无法增大孔容积,且无法提高堆积密度,最多只能达到0.9 g/cm3左右。另外,与有效的微孔表面积相比,外表面积增大。
与此相对,本发明中,通过将上述酸性水溶液或水性分散液和碱性水溶液两者同时供给反应管内,在反应管内瞬间形成沉淀。通过使用这样的方法(以下称为“瞬间沉淀法”),可以获得具有上述特性的脱硫剂。这里,所使用的反应管可以是直管也可以是弯管,优选内径在3-100 mm的范围。也可以使用静态混合器。
将上述酸性水溶液或水性分散液和碱性水溶液两者同时导入小的接收器中、瞬间形成沉淀的方法也与上述方法同样有效。该方法中,将生成的沉淀物或溶液残留在接收器中,添加的酸性水溶液或水性分散液和碱性水溶液被它们稀释,无法瞬间形成沉淀,无法获得堆积密度高的脱硫剂。因此,要连续地排出生成的沉淀物或溶液,使其不会残留在接收器中,或者使用足够小的容器,这是非常重要的。
本发明的脱硫剂的成型方法可使用通常使用的成型方法,优选使用挤出成型、旋转制粒或通过干燥物的粗粉碎或破碎进行的成型方法。考虑提高脱硫剂的堆积密度时,压缩成型法有效,但是脱硫反应中有效的细孔破裂,微孔表面积和孔容积可能降低。微孔表面积和孔容积降低,则作为活性点的镍等金属的分散度丧失,另外,硫化合物的吸附点减少,使脱硫性能受损。
以下,对制造本发明优选的脱硫剂之一的在二氧化硅载体上担载镍-铜而成的堆积密度为0.95g/cm3或以上的脱硫剂的制造方法进行具体说明。
首先,制造含有镍源和铜源的酸性水溶液或酸性水性分散液、含有硅源的碱性水溶液。酸性水溶液或酸性水性分散液中使用的镍源例如有氯化镍、硝酸镍、硫酸镍、乙酸镍、碳酸镍和它们的水合物等。铜源例如有氯化铜、硝酸铜、硫酸铜、乙酸铜及它们的水合物等。
碱性水溶液中使用的硅源只要是可溶于碱水溶液、通过烧结形成二氧化硅即可,没有特别限定,例如有原硅酸、偏硅酸以及它们的钠盐或钾盐、水玻璃等。另外,该碱性水溶液中还可以根据需要含有碱金属的碳酸盐或氢氧化物等无机盐。
接着,使用上述酸性水溶液或酸性水性分散液和碱性水溶液,将上述瞬间沉淀法中生成的沉淀物充分洗涤,然后进行固液分离,或者在将生成的沉淀物固液分离后进行充分洗涤,接着,按照公知的方法,在80-150℃左右的温度下对该沉淀物进行干燥处理。将上述所得干燥处理物优选在200-400℃范围的温度中进行烧结,得到在形成了微细孔的二氧化硅载体上担载有金属成分的脱硫剂。
本发明的脱硫剂优选具有0.15 mmol/g或以上的氢吸附量。该氢吸附量为0.15 mmol/g或以上,则脱硫所必需的活性点数足够,可得到高的脱硫性能。
进一步对上述方法所得的脱硫剂进行还原处理,控制金属镍的量和氢吸附量,这可适当采用本领域中通常使用的方法。该还原处理是在燃料电池用氢的制造中,在即将进行该脱硫处理步骤之前进行、或者在脱硫剂制造步骤结束后进行。在脱硫剂制造后进行还原时,优选进行稳定化处理,即使用空气、稀释氧、二氧化碳等对脱硫剂的最表面进行氧化处理。使用该经稳定化处理的脱硫剂时,在填充到脱硫反应器中后,必须再次进行还原处理。进行还原处理后,可以用惰性气体、脱硫煤油进行密封。
使用本发明的脱硫剂进行脱硫的烃原料和/或含氧烃原料没有特别限定,例如有煤油、轻油、液化石油气(LPG)、石脑油、汽油、天然气、二甲醚等,或者是它们的混合物。其中,作为适合本发明的脱硫剂的优选原料,优选为煤油和液化石油气(LPG),特别是在煤油中,优选硫成分含量为80质量ppm或以下的JIS1号煤油。该JIS1号煤油可通过将原油常压蒸馏、将所得的粗煤油进行脱硫获得。该粗煤油通常硫成分较多,无法直接作为JIS1号煤油使用,必须降低硫成分。降低该硫成分的方法优选通过通常工业化实施的加氢精制法进行脱硫处理。这种情况下,脱硫催化剂通常使用将镍、钴、钼、钨等过渡金属以适当比例混合,将所得物以金属、氧化物、硫化物等形式担载在以氧化铝作为主要成分的载体上的材料。反应条件例如采用反应温度250-400℃,压力2-10MPa·G、氢/油摩尔比2-10,液空速(LHSV)1-5h-1等条件。
使用本发明的脱硫剂对烃原料和/或含氧烃原料进行脱硫的条件可根据该原料的性状适当选择,没有特别限定,通常可在-40至300℃的范围内脱硫。该原料使用烃、例如JIS1号煤油,并以液相的形式在填充了本发明的脱硫剂的脱硫塔中向上或向下流动通过而进行脱硫时,在温度130-230℃左右、压力为常压-1MPa·G左右、液空速(LHSV)为0.1-100 h- 1左右的条件下进行脱硫处理。此时,可以根据需要使少量的氢共存。通过在上述范围内适当选择脱硫条件,可以得到硫成分为0.2质量ppm或以下的烃。
下面,关于本发明燃料电池用氢的制造方法,是将如上所述经脱硫处理的烃和/或含氧烃原料进行水蒸气重整、部分氧化重整或自热重整,更具体地说,是通过与水蒸气重整催化剂、部分氧化重整催化剂或自热重整催化剂接触,来制造燃料电池用氢。
这里所使用的重整催化剂没有特别限定,可以从以往作为烃的重整催化剂而已知的公知材料中适当选择任意的使用。上述重整催化剂例如有在适当的载体上担载镍或锆、或者钌、铑、铂等贵金属所得的。上述担载金属可以是一种,也可以将两种或以上组合。这些催化剂中,优选担载镍的催化剂(以下称为镍系催化剂)、担载钌的催化剂(以下称为钌系催化剂),它们在水蒸气重整处理、部分氧化重整处理或自热重整处理中抑制碳沉淀的效果大。
担载上述重整催化剂的载体优选含有氧化锰、氧化铈、氧化锆等,特别优选含有选自其中至少一种的载体。
为镍系催化剂时,镍的担载量以载体为基准优选为3-60质量%的范围。该担载量在上述范围内,则水蒸气重整催化剂、部分氧化重整催化剂或自热重整催化剂的活性可充分发挥,同时在成本上有利。考虑到催化剂活性和经济性等,更优选的镍担载量是5-50质量%,特别优选10-30质量%的范围。
另外,为钌系催化剂时,钌的担载量以载体为基准优选为0.05-20质量%的范围。钌的担载量在上述范围内,则水蒸气重整催化剂、部分氧化重整催化剂或自热重整催化剂的活性可充分发挥,同时在成本方面有利。考虑催化剂活性和经济性等,更优选的钌的担载量是0.05-15质量%,特别优选0.1-2质量%的范围。
水蒸气重整处理的反应条件中,水蒸气与来自原料的碳的比即蒸汽/碳(mol比)通常在1.5-10的范围内选择。蒸汽/碳(mol比)为1.5或以上,则氢的生成量充分,为10或以下,则过量的水蒸气成为不必要,因此热损失小,可以高效地进行氢的制造。从上述角度考虑,优选蒸汽/碳(mol比)在1.5-5的范围内,进一步优选在2-4的范围内。
优选水蒸气重整催化剂层的入口温度保持在630℃或以下进行水蒸气重整。入口温度在630℃或以下,则不会发生原料的热分解,不容易发生经由碳自由基向催化剂或反应管壁上沉淀碳的问题。从以上角度考虑,进一步优选水蒸气重整催化剂层的入口温度为600℃或以下。催化剂层的出口温度没有特别限定,优选650-800℃的范围。为650℃或以上,则氢的生成量充分,为800℃或以下,则反应装置无需由耐热材料构成,在经济方面优选。
部分氧化重整处理的反应条件中,通常采用压力为常压至5MPa.G,温度400-1100℃,氧(O2)/碳(mol比)为0.2-0.8,液空速(LHSV)为0.1-100 hr-1的条件。
自热重整处理的反应条件中,通常采用压力为常压至5 MPa.G,温度为400-1100℃,蒸汽/碳(mol比)为0.1-10,氧(O2)/碳(mol比)为0.1-1,液空速(LHSV)为0.1-2 hr-1,气空速(GHSV)为1000-100000 hr-1的条件。
上述水蒸气重整、部分氧化重整或自热重整得到的CO会对氢的生成产生不良影响,优选通过反应,将CO转化成CO2除去。这样,根据本发明的方法,可以高效地制造燃料电池用氢。
使用液体原料的燃料电池系统通常由原料供应装置、脱硫装置、重整装置、燃料电池构成,将按照上述本发明的方法制造的氢供给燃料电池。以下,根据图1对本发明的燃料电池系统进行说明。
图1是表示本发明的燃料电池系统的一个例子的概略流程图。图1中,燃料罐21内的燃料经由燃料泵22流入到脱硫器23中。在脱硫器23中进行了脱硫的燃料由水罐经过水泵24与水混合,然后导入到汽化器1中,进行气化,或者在气化后混合,送入重整器31中。重整器31的内部填充有上述重整催化剂,通过上述任意一种重整反应,由送入到重整器31中的燃料混合物(含有水蒸气和烃燃料的混合气体)制造氢。
上述制造的氢通过作为CO除去装置的CO转化器32和CO选择性氧化炉33,使其CO浓度降低至不会对燃料电池组的特性产生影响的程度。按照本发明的方法除去了微量的C2以上烃化合物的氢送入燃料电池组。
燃料电池组34是在负极34A和正极34B之间具备高分子电解质34C的固体高分子型燃料电池组。由上述方法得到的富氢气体、以及由空气鼓风机35送出的空气分别根据需要进行适当的加湿处理(加湿装置未图示),然后分别导入负极侧和正极侧。
此时,在负极侧,氢气成为质子,进行释放电子的反应,在正极侧,氧气得到电子和质子,进行生成水的反应,在两极34A、34B之间产生直流电流。负极使用铂黑、活性碳担载的Pt催化剂或Pt-Ru合金催化剂等,正极使用铂黑、活性碳担载的Pt催化剂等。
使重整器31的燃烧器31A与负极34A一侧连接,可以以多余的氢作为燃料。另外,在与正极34B一侧连接的气水分离器36中,将供给正极34B一侧的空气中的氧与氢结合产生的水与排气分离,水可以用来生成水蒸汽。
燃料电池组34中,伴随着发电会产生热,因此可附设排热回收装置37,回收该热加以有效利用。排热回收装置37具备夺取在反应时产生的热的热交换机37A、用于将用该热交换器37A夺得的热与水进行热交换的热交换器37B、冷却器37C、使冷介质在这些热交换机37A、37B和冷却器37C中循环的泵37D,在热交换器37B中得到的温水可有效利用于其它的设备等中。
实施例
下面通过实施例进一步详细说明本发明,但本发明并不受这些例子的限定。各例中得到的脱硫剂按照下述方法评价。
[评价方法]
(1)堆积密度
将脱硫剂填充到5cm3的量筒中,通过测定其质量计算。
(2)孔容积
作为前处理,对脱硫剂在200℃下进行3小时的真空排气处理,在液氮温度下进行氮的物理吸附测定。使用氮吸附等温线,计算直至100nm孔半径下的容积(相当于相对压力0.990),将其作为脱硫剂的孔容积。
(3)微孔表面积
由通过BET法得到的总表面积减去由t-plot法得到的外表面积,由此求出微孔表面积。总表面积是将N2吸附等温线在相对压力0.01-0.3的范围内、使用BET多点法进行分析计算。在t-plot分析中,为了将相对压力变换成吸附物质的厚度,使用de Bore式。
(4)外表面积
外表面积是通过t-plot法对N2吸附等温线进行分析,由t-plot的高压一侧直线部分的斜率计算外表面积。
(5)煤油的脱硫实验
将15m1各实施例和比较例中制造的脱硫剂填充到内径为17mm的SUS制反应管中。在常压下、在氢气流中升温至120℃,保持30分钟。然后再用1小时升温至300℃,在300℃下保持3小时,使脱硫剂活化。然后将温度降温至200℃,保持该温度。接着在常压下、在液体空速(LHSV)20h-1下将具有表1所示性状的JIS-1号煤油流过反应管。该LHSV20h-1的条件相当于实际燃料电池系统中LHSV的约100倍,是加速寿命试验条件。以经过30小时后的硫浓度来评价脱硫性能。
表1
蒸馏性状(℃) | 初馏点 | 153 |
10%馏出温度 | 176 | |
30%馏出温度 | 194 | |
50%馏出温度 | 209 | |
70%馏出温度 | 224 | |
90%馏出温度 | 249 | |
终点 | 267 | |
硫含量(质量ppm) | 48 |
实施例1
将360.1g硫酸镍六水合物(特级、和光纯药株式会社制造)和85.2g硫酸铜五水合物(特级、和光纯药株式会社制造)溶解于3L加温至80℃的离子交换水中,得到制造液A。将300.0g碳酸钠溶解于3L另外准备的加温至80℃的离子交换水中,加入135.5g水玻璃(JIS-3号、Si浓度29质量%、日本化学工业株式会社制造),得到制造液B。
将制造液A、B的温度分别保持80℃,将两者导入内径为10mm、长度10cm的不锈钢制反应管内,得到沉淀饼。然后使用100L离子交换水进行沉淀饼的洗涤·过滤,用120℃的送风干燥机将产物干燥12小时。使用玛瑙乳钵将所得干燥物进行粉碎,使平均粒径为0.8mm,在350℃下烧结3小时,得到脱硫剂a。
所得脱硫剂a的镍含量(换算为NiO)为60.0质量%,铜含量(换算为CuO)为15.0质量%,硅含量(换算为SiO2)为25.0质量%。镍和铜完全被还原时,镍含量(换算为Ni)相当于56.0质量%,铜含量(换算为Cu)相当于14.0质量%,硅含量(换算为SiO2)相当于30.0质量%。将该脱硫剂a按照上述评价方法进行评价。结果如表2所示。
比较例1
按照与实施例1同样的方法得到制造液A和制造液B.将制造液A、B的温度分别保持80℃,用10分钟向制造液A中滴加制造液B,得到沉淀饼。使用100L离子交换水对沉淀饼进行洗涤·过滤,用120℃送风干燥机将产物干燥12小时。将所得干燥物用玛瑙乳钵粉碎,使平均粒径为0.8mm,然后在350℃下烧结3小时,得到脱硫剂b。
所得脱硫剂b的镍含量(换算为NiO)为60.0质量%,铜含量(换算为CuO)为15.0质量%,硅含量(换算为SiO2)为25.0质量%。将该脱硫剂b按照上述评价方法评价。结果如表2所示。
实施例2
实施例1中,使硫酸镍六水合物的使用量为444.5g,不使用硫酸铜五水合物,且使水玻璃的使用量为108.4g,除此之外与实施例1同样地得到平均粒径为0.8mm的脱硫剂c。
所得脱硫剂c的镍含量(换算为NiO)为80.0质量%,铜含量(换算为CuO)为0质量%,硅含量(换算为SiO2)为20.0质量%。将该脱硫剂c按照上述评价方法评价。结果如表2所示。
实施例3
实施例1中,使硫酸镍六水合物的使用量为438.9g,使硫酸铜五水合物的使用量为5.3g,使水玻璃的使用量为108.4g,除此之外与实施例1同样地得到平均粒径为0.8mm的脱硫剂d。
所得脱硫剂d的镍含量(换算为NiO)为79.0质量%,铜含量(换算为CuO)为1.0质量%,硅含量(换算为SiO2)为20.0质量%。将该脱硫剂d按照上述评价方法评价。结果如表2所示。
实施例4
实施例1中,使硫酸镍六水合物的使用量为438.9g,使硫酸铜五水合物的使用量为10.7g,使水玻璃的使用量为108.4g,除此之外与实施例1同样地得到平均粒径为0.8 mm的脱硫剂e。
所得脱硫剂e的镍含量(换算为NiO)为78.0质量%,铜含量(换算为CuO)为2.0质量%,硅含量(换算为SiO2)为20.0质量%。将该脱硫剂e按照上述评价方法评价。结果如表2所示。
实施例5
实施例1中,使硫酸镍六水合物的使用量为405.1g,使硫酸铜五水合物的使用量为42.6g,使水玻璃的使用量为108.4g,除此之外与实施例1同样地得到平均粒径为0.8mm的脱硫剂f。
所得脱硫剂f的镍含量(换算为NiO)为72.0质量%,铜含量(换算为CuO)为8.0质量%,硅含量(换算为SiO2)为20.0质量%。将该脱硫剂f按照上述评价方法评价。结果如表2所示。
实施例6
实施例1中,使硫酸镍六水合物的使用量为478.3g,使硫酸铜五水合物的使用量为26.5g,使水玻璃的使用量为54.2g,除此之外与实施例1同样地得到平均粒径为0.8mm的脱硫剂g。
所得脱硫剂g的镍含量(换算为NiO)为85.0质量%,铜含量(换算为CuO)为5.0质量%,硅含量(换算为SiO2)为10.0质量%。将该脱硫剂g按照上述评价方法评价。结果如表2所示。
实施例7
实施例1中,使硫酸镍六水合物的使用量为422.1g,使硫酸铜五水合物的使用量为26.5g,使水玻璃的使用量为108.4g,除此之外与实施例1同样地得到平均粒径为0.8mm的脱硫剂h。
所得脱硫剂h的镍含量(换算为NiO)为75.0质量%,铜含量(换算为CuO)为5.0质量%,硅含量(换算为SiO2)为20.0质量%。将该脱硫剂h按照上述评价方法评价。结果如表2所示。
实施例8
实施例1中,使硫酸镍六水合物的使用量为365.8g,使硫酸铜五水合物的使用量为26.5g,使水玻璃的使用量为162.6g,除此之外与实施例1同样地得到平均粒径为0.8mm的脱硫剂i。
所得脱硫剂i的镍含量(换算为NiO)为65.0质量%,铜含量(换算为CuO)为5.0质量%,硅含量(换算为SiO2)为30.0质量%。将该脱硫剂i按照上述评价方法评价。结果如表2所示。
比较例2
实施例1中,使硫酸镍六水合物的使用量为196.9g,使硫酸铜五水合物的使用量为26.5g,使水玻璃的使用量为325.2g,除此之外与实施例1同样地得到平均粒径为0.8mm的脱硫剂j。
所得脱硫剂j的镍含量(换算为NiO)为35.0质量%,铜含量(换算为CuO)为5.0质量%,硅含量(换算为SiO2)为60.0质量%。将该脱硫剂j按照上述评价方法评价。结果如表2所示。
比较例3
将365.8g硫酸镍六水合物(特级、和光纯药株式会社制造)和26.5g硫酸铜五水合物(特级、和光纯药株式会社制造)溶解于3L加温至80℃的离子交换水中,将10.8g假勃姆石(Cataloid-AP、A12O3计为67质量%、触媒化成工业株式会社制造)与其混合,得到制造液C。将300.0g碳酸钠溶解于3L加温至80℃的离子交换水中,加入140.4g水玻璃(JIS-3号、Si浓度29质量%、日本化学工业株式会社制造),得到制造液D。
实施例1中,使用制造液C、D代替制造液A、B,除此之外,与实施例1同样地得到平均粒径为0.8mm的脱硫剂k。
所得脱硫剂k的镍含量(换算为NiO)为65.0质量%,铜含量(换算为CuO)为5.0质量%,硅铝含量为30.0质量%。将该脱硫剂k按照上述评价方法评价。结果如表2所示。
[表2]
表2-1
脱硫剂 | 堆积密度(g/cm3) | 孔容积(ml/g) | 微孔表面积(m2/g) | 外表面积(m2/g) | 镍含量[换算为Ni0](质量%) | 铜含量换算为cu0](质量%) | |
实施例1 | a | 1.25 | 0.310 | 234 | 75 | 60.0 | 15.0 |
实施例2 | c | 1.62 | 0.265 | 232 | 55 | 80.0 | 0.0 |
实施例3 | d | 1.48 | 0.212 | 227 | 38 | 79.0 | 1.0 |
实施例4 | e | 1.41 | 0.246 | 234 | 45 | 78.0 | 2.0 |
实施例5 | f | 1.28 | 0.251 | 178 | 68 | 72.0 | 8.0 |
实施例6 | g | 1.65 | 0.231 | 183 | 35 | 85.0 | 5.0 |
实施例7 | h | 1.50 | 0.252 | 201 | 61 | 75.0 | 5.0 |
实施例8 | i | 1.35 | 0.271 | 211 | 91 | 65.0 | 5.0 |
比较例1 | b | 0.75 | 0.480 | 181 | 131 | 60.0 | 15.0 |
比较例2 | j | 0.85 | 0.420 | 201 | 107 | 35.0 | 5.0 |
比较例3 | k | 1.12 | 0.381 | 225 | 105 | 65.0 | 5.0 |
[表3]
表2-2
脱硫剂 | 载体含量 | 平均粒径(mm) | 评价条件 | 评价结果 | |||
种类 | (质量%) | 燃料 | LHSV(h-1) | 脱硫性能(质量ppm) | |||
实施例1 | a | 二氧化硅 | 25.0 | 0.8 | 煤油 | 20 | 0.8 |
实施例2 | c | 二氧化硅 | 20.0 | 0.8 | 煤油 | 20 | 1.8 |
实施例3 | d | 二氧化硅 | 20.0 | 0.8 | 煤油 | 20 | 0.8 |
实施例4 | e | 二氧化硅 | 20.0 | 0.8 | 煤油 | 20 | 0.5 |
实施例 5 | f | 二氧化硅 | 20.0 | 0.8 | 煤油 | 20 | 0.6 |
实施例6 | g | 二氧化硅 | 10.0 | 0.8 | 煤油 | 20 | 0.5 |
实施例7 | h | 二氧化硅 | 20.0 | 0.8 | 煤油 | 20 | 0.4 |
实施例8 | i | 二氧化硅 | 30.0 | 0.8 | 煤油 | 20 | 1.0 |
比较例1 | b | 二氧化硅 | 25.0 | 0.8 | 煤油 | 20 | 29.5 |
比较例2 | j | 二氧化硅 | 60.0 | 0.8 | 煤油 | 20 | 18.5 |
比较例3 | k | 硅铝 | 30.0 | 0.8 | 煤油 | 20 | 7.4 |
产业实用性
本发明的脱硫剂可以高效除去烃原料和/或含氧烃原料中的硫成分至极低浓度,以较少量的容积即具有足够的脱硫性能,因此在应用于由原料供应装置、脱硫装置、重整装置、燃料电池构成的通常的燃料电池系统的脱硫装置时,可以使该脱硫装置紧凑化。本发明的脱硫剂寿命长,因此长时间仍可使重整装置的催化剂保持高活性状态,可高效地制造燃料电池用氢。
Claims (13)
1.脱硫剂,用于除去烃原料和/或含氧烃原料中的硫化合物,其特征在于:含有镍或镍和铜,以及硅,堆积密度为0.95-2.0g/cm3,孔容积为0.10-0.40ml/g,微孔表面积为100-250m2/g,且外表面积为100m2/g或以下。
2.权利要求1的脱硫剂,其中,镍的含量在40-90质量%的范围。
3.权利要求1或2的脱硫剂,其中,铜的含量在0.01-40质量%的范围。
4.权利要求1-3中任一项的脱硫剂,其中,硅的含量换算成SiO2(二氧化硅)为50质量%或以下。
5.权利要求1-4中任一项的脱硫剂,其中,烃原料和/或含氧烃原料选自煤油、轻油、液化石油气(LPG)、石脑油、汽油、天然气和二甲醚的至少一种。
6.脱硫剂的制造方法,其中将含有镍或者镍和铜的酸性溶液或酸性水性分散液与含有硅的碱性溶液混合,瞬间形成沉淀而制造堆积密度为0.95-2.0g/cm3,孔容积为0.10-0.40ml/g,微孔表面积为100-250m2/g,外表面积为100m2/g或以下的脱硫剂。
7.权利要求6的脱硫剂的制造方法,其中,酸性溶液或酸性水性分散液与碱性溶液的混合、以及沉淀的形成在内径为3-100mm的反应管内进行。
8.脱硫方法,其特征在于:使用权利要求1-5中任一项的脱硫剂,在-40至300℃范围的温度下进行烃原料和/或含氧烃原料的脱硫。
9.燃料电池用氢的制造方法,其特征在于:使用权利要求1-5中任一项的脱硫剂,对烃原料和/或含氧烃原料进行脱硫,然后进行重整。
10.权利要求9的燃料电池用氢的制造方法,其中,重整为水蒸气重整、部分氧化重整或自热重整。
11.权利要求9或10的燃料电池用氢的制造方法,其中,用于重整的催化剂为钌系催化剂或镍系催化剂。
12.权利要求11的燃料电池用氢的制造方法,其中,用于重整的催化剂的载体成分含有选自氧化锰、氧化铈、以及氧化锆的至少一种。
13.燃料电池系统,其特征在于:使用通过权利要求9-12中任一项的方法制造的氢。
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PCT/JP2006/305560 WO2006101079A1 (ja) | 2005-03-24 | 2006-03-20 | 脱硫剤及びこれを用いた脱硫方法 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101559925A (zh) * | 2008-03-28 | 2009-10-21 | Ifp公司 | 用热集成脱硫装置制造氢的方法 |
CN102365348A (zh) * | 2009-03-31 | 2012-02-29 | 吉坤日矿日石能源株式会社 | 烃用脱硫剂前体及其制备方法、烃用脱硫剂煅烧前体及其制备方法、烃用脱硫剂及其制备方法、烃的脱硫方法以及燃料电池体系 |
CN103920454A (zh) * | 2014-04-29 | 2014-07-16 | 哈尔滨理工大学 | 一种常温脱除硫系恶臭物质的复合铜基脱硫剂及其制备方法 |
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CN101146894B (zh) | 2012-12-19 |
EP1878781A4 (en) | 2009-07-01 |
KR20070115991A (ko) | 2007-12-06 |
CA2601124A1 (en) | 2006-09-28 |
JPWO2006101079A1 (ja) | 2008-09-04 |
EP1878781A1 (en) | 2008-01-16 |
US20090075131A1 (en) | 2009-03-19 |
CA2601124C (en) | 2013-12-17 |
WO2006101079A1 (ja) | 2006-09-28 |
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