CN104507572B - Co转化催化剂、co转化反应装置及气化气的精制方法 - Google Patents
Co转化催化剂、co转化反应装置及气化气的精制方法 Download PDFInfo
- Publication number
- CN104507572B CN104507572B CN201280074990.2A CN201280074990A CN104507572B CN 104507572 B CN104507572 B CN 104507572B CN 201280074990 A CN201280074990 A CN 201280074990A CN 104507572 B CN104507572 B CN 104507572B
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- Prior art keywords
- gas
- catalyst
- gasification
- reforming catalysts
- conversion
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002407 reforming Methods 0.000 title claims abstract description 35
- 238000000746 purification Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 7
- 230000008569 process Effects 0.000 title claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 130
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 130
- 239000003426 co-catalyst Substances 0.000 claims abstract description 28
- 239000004615 ingredient Substances 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000470 constituent Substances 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 93
- 238000002309 gasification Methods 0.000 claims description 64
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000002817 coal dust Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000005200 wet scrubbing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 abstract description 14
- 239000011734 sodium Substances 0.000 abstract description 12
- 239000011777 magnesium Substances 0.000 abstract description 10
- 229910052700 potassium Inorganic materials 0.000 abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052791 calcium Inorganic materials 0.000 abstract description 6
- 239000011591 potassium Substances 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 39
- 208000012839 conversion disease Diseases 0.000 description 37
- 239000003245 coal Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 10
- 238000010248 power generation Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- TVAATYMJWZHIQJ-UHFFFAOYSA-N molybdenum;tetrahydrate Chemical compound O.O.O.O.[Mo] TVAATYMJWZHIQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
-
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J23/8872—Alkali or alkaline earth metals
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- B01J23/8906—Iron and noble metals
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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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J23/8946—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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Abstract
本发明的CO转化催化剂是对气体中的一氧化碳(CO)进行改质的CO转化催化剂,包含以下而成:以钼(Mo)或铁(Fe)中的任意一种为主成分、且以镍(Ni)或钌(Ru)中的任意一种为副成分的活性成分;以钙(Ca)、钾(K)、钠(Na)、磷(P)和镁(Mg)中的任意一种为成分的助催化剂成分;以及担载所述活性成分和助催化剂成分的包含钛(Ti)、锆(Zr)和铈(Ce)中的任意一种或两种以上的氧化物的载体。
Description
技术领域
本发明涉及将气化气中的CO转化为CO2的CO转化催化剂、CO转化反应装置及气化气的精制方法。
背景技术
煤的有效利用作为在近年来的能源问题上的强有力的手段之一受到关注。
另一方面,为了将煤转换为附加值高的能量媒质,需要煤气化技术、气体精制技术等尖端技术。
已提出了使用该气化气进行发电的煤气化复合发电系统(专利文献1)。
该煤气化复合发电(Integrated coal.Gasification Combined Cycle:IGCC)是指将煤在高温高压的气化炉内转换成可燃性气体并以其气化气为燃料利用燃气涡轮和蒸汽涡轮进行复合发电的系统。
例如存在于煤气化气(生成气体)中的烃化合物大部分是一氧化碳(CO),二氧化碳(CO2)、烃(CH4、CnHm)仅为几个百分点。其结果是,为了回收CO2,需要将生成气体中存在的CO转换为CO2,提出了添加水蒸气(H2O)并且使用转化催化剂,通过下述反应转换为CO2(专利文献2)。
迄今为止,根据对于化工领域中的转化反应的认识,通过充分提高CO转化反应器入口的水蒸气添加比例(H2O/CO),促进上述(1)的反应的基础上,能够得到希望的CO→CO2转换率。
现有技术文献
专利文献
专利文献1:日本特开2004-331701号公报
专利文献2:日本特开2011-157486号公报
发明内容
发明所要解决的课题
例如作为CO转化催化剂,通常使用Co-Mo/Al2O3系催化剂,由于在高温域(例如350℃以上)发挥活性,因此担心C析出。
因此,作为对C析出的应对措施,需要添加过剩的水蒸气量(水蒸气(H2O)/CO≥3)。
另一方面,具备CO2回收设备的IGCC成套设备是发电成套设备,需要在顾及环境(CO2排出量的降低)的同时,把重点放在成套设备发电效率上。
换言之,作为供给至转化反应器并用于水蒸气添加比例(H2O/CO)的水蒸气添加源,例如使用来自于HRSG(废热回收锅炉)的抽气中压蒸气,然而,降低抽气水蒸气量在实现成套设备效率提高方面是重要的要素,因此,从提高发电效率的观点出发,要求尽可能减少来自于HRSG(废热回收锅炉)的抽气水蒸气量。
因此,迫切期望即使将水蒸气的供给量从水蒸气(H2O)/CO=3大幅降低至水蒸气(H2O)/CO=1左右时仍能够实现对C析出的耐久性的提高、并且能够长期而稳定地进行CO转化的CO转化催化剂的出现。
本发明鉴于上述问题,课题在于提供即使水蒸气量少时催化剂劣化的程度也不激烈并能够稳定且高效地进行CO转化反应的CO转化催化剂、CO转化反应装置及气化气的精制方法。
用于解决课题的方法
用于解决上述课题的本发明的第一发明的CO转化催化剂的特征在于,其是对气体中的一氧化碳(CO)进行改质的CO转化催化剂,包含:以钼(Mo)或铁(Fe)中的任意一种为主成分、且以镍(Ni)或钌(Ru)中的任意一种为副成分的活性成分;以钙(Ca)、钾(K)、钠(Na)、磷(P)和镁(Mg)中的任意一种为成分的助催化剂成分;以及担载所述活性成分和助催化剂成分的包含钛(Ti)、锆(Zr)和铈(Ce)中的任意一种或两种以上的氧化物的载体。
第二发明的CO转化催化剂的特征在于,在第一发明中,上述活性成分的主成分的担载量为0.1~25重量%,副成分的担载量为0.01~10重量%,并且助催化剂成分的担载量为0.1~2.0重量%。
第三发明的CO转化反应装置的特征在于,将第一或第二发明的CO转化催化剂填充于反应塔内而成。
第四发明的气化气的精制方法的特征在于,利用过滤器除去由气化炉得到的气化气中的煤尘后,利用湿式洗气装置进一步净化CO转化反应后的气化气,接着,除去气化气中的二氧化碳及硫化氢,使用第一或第二发明的CO转化催化剂,进行将气化气中的CO转化为CO2的CO转化反应,从而得到精制气体。
发明效果
本发明的CO转化催化剂起到如下效果,通过添加助催化剂,初期氧量变少,即使在低水蒸气量的情况下,耐久试验后的CO转化率的降低也少,能够良好地维持CO转化反应。
附图说明
图1是具备填充有本实施例的CO转化催化剂的CO转化反应装置的气化气精制系统的示意图。
图2是与试验催化剂2的对耐久试验的初期CO转化率(%)和经过100小时后的CO转化率(%)进行比较的图表。
图3是表示煤气化发电成套设备的一例的图。
具体实施方式
以下,参照附图对本发明进行详细说明。需要说明的是,本发明不限定于下述实施例。另外,在下述实施例中的构成要素中,包含本领域技术人员容易想到的内容、实质上相同的内容、所谓等同的范围的内容。此外,下述实施例中公开的构成要素可以适当组合。
实施例
对于基于本发明的实施例的CO转化催化剂及使用其的CO转化反应装置,参照附图进行说明。图1是具备填充有本实施例的CO转化催化剂的CO转化反应装置的气化气精制系统的示意图。
如图1所示,气化气精制系统10具备:将作为燃料F的煤进行气化的气化炉11;除去作为生成气体的气化气12中的煤尘的过滤器13;除去通过过滤器13后的气化气12中的卤素的湿式洗气装置14;包括吸收除去热交换后的气化气12中的CO2及H2S的吸收塔15A和进行再生的再生塔15B,并且在再生塔15B侧具备再生过热器16的气体精制装置15;提高气化气12的温度的第一热交换器17及第二热交换器18;具备将温度上升至例如300℃的气化气12中的CO转化为CO2而成为精制气体22的CO转化催化剂19的CO转化反应装置20。需要说明的是,图1中的符号21表示水蒸气。
在气化炉11中,使作为燃料F的煤与空气、氧等气化剂接触,通过燃烧、气化而生成气化气12。气化炉11中生成的气化气12以一氧化碳(CO)、氢(H2)、二氧化碳(CO2)为主成分,还微量地含有煤中微量包含的元素(例如卤素化合物、汞(Hg)等重金属)、煤气化时的未燃化合物(例如酚、蒽等多环芳香族,氰,氨等)等。
气化炉11中生成的气化气12从气化炉11导入至过滤器13。导入至过滤器13的气化气12除去了气化气12中的煤尘。需要说明的是,除过滤器13以外,还可以使用旋风、电集尘装置(EP:Electrostatic Precipitator)等。
对于气化气12而言,在过滤器13中除去煤尘后,通过气体精制装置15进行气体精制,随后通过第一及第二热交换器17、18使气化气12的温度上升。
接着,通过水蒸气供给装置(水蒸气供给单元)供给水蒸气21后,导入至具有CO转化催化剂19的CO转化反应装置20。通过该CO转化反应装置20,对气化气12中的一氧化碳(CO)进行改质,在CO转化催化剂19的作用下转化为二氧化碳(CO2)。
本发明的CO转化催化剂19是对气体中的一氧化碳(CO)进行改质的CO转化催化剂,由以下构成:作为以钼(Mo)或铁(Fe)的任意一种为主成分、且以镍(Ni)或钌(Ru)的任意一种为副成分的活性成分;钙(Ca)、钾(K)、钠(Na)、磷(P)和镁(Mg)中的任意一种为成分的助催化剂成分;以及担载所述活性成分和助催化剂成分的钛(Ti)、锆(Zr)和铈(Ce)的氧化物中的任意一种或两种以上的载体。
作为上述载体,优选为TiO2、ZrO2、CeO2的氧化物。
另外,也可以作为这些的复合氧化物(例如TiO2-SiO2、TiO2-ZrO2、TiO2-Al2O3、ZrO2-Al2O3、TiO2-CeO2、TiO2-La2O3等)。
在本发明中,为了抑制使碳析出进行的催化剂上的酸点的活性,通过添加以碱金属为代表的第三成分的助催化剂成分,即使在低水蒸气量的情况下,也能抑制碳析出,减轻活性的降低程度。
其结果是,使用本发明的CO转化催化剂时,即使在降低水蒸气量(例如从水蒸气(H2O)/CO=3大幅降低至水蒸气(H2O)/CO=1左右)的情况下,由于通过中和等来抑制酸点的活性,因此碳(C)析出被抑制,不会覆盖活性成分。其结果是,即使经过长期、以低水蒸气量进行CO转化反应,因为碳析出被抑制,所以CO转化反应效率没有大幅降低,能够进行良好的CO转化反应。
在此,作为主成分(第一成分)的钼(Mo)或铁(Fe)的担载量优选为0.1~25重量%,更优选为7~20重量%,作为副成分(第二成分)的镍(Ni)或钌(Ru)的担载量优选为0.01~10重量%,更优选为2~10重量%。
另外,作为助催化剂(第三成分),可以列举例如钙(Ca)、钾(K)、钠(Na)等碱金属或碱土金属,磷(P)和镁(Mg)中的任意一种。另外,也可以使用钡(Ba)、锶(Sr)等。
需要说明的是,虽然磷(P)不属于碱金属或碱土金属,但具有抑制酸点的作用,因此能够作为助催化剂使用。
在本发明中,通过添加例如钙(Ca)、钾(K)、钠(Na)、磷(P)和镁(Mg)中的任意一种,使初期的酸点减少(参照后述的试验例)。
其结果是,虽然初期的CO转化率与未添加助催化剂的现有催化剂相比有些降低,但是例如100小时耐久试验后的CO转化率高于现有催化剂。
作为其理由被推测为,通过添加助催化剂(第三成分)使催化剂所具有的初期酸量降低,由此能够降低碳(C)析出量。
可见,根据本发明的CO转化催化剂,在将气化炉11中气化的气化气12中的CO转化为CO2时,从水蒸气(H2O)/CO=3大幅降低至水蒸气(H2O)/CO=1左右时,碳的析出被抑制,能够长期稳定地进行CO转化。另外,通过使供给的水蒸气量降低,能够提供高效率的气体精制工艺。
[试验例]
以下,对展示本发明的效果的试验例进行说明。
1)试验催化剂1的制法
将石原产业制氧化钛(TiO2(“MC-90”商品名))100g放入瓷皿中,添加溶解于150ml水中的硝酸镍六水合物(NN)和钼酸铵四水合物(MA),以使相对于最终得到的全粉末量,作为主活性成分(第一成分)担载有MoO314重量%、作为副活性成分(第二成分)担载有NiO4重量%,作为助催化剂(第三成分)担载有Ca0.5重量%,然后,在瓷皿上进行蒸发干燥固化并含浸。并且,利用干燥器将得到的粉末完全干燥后,通过在500℃实施3小时(升温速度100℃/h)烧成而得到粉末催化剂。
将得到的粉末催化剂利用30吨的加压成形器使粉末固定化后,以粒径达到规定粒径(例如2~4mm)的范围的方式破碎后进行筛分而得到试验催化剂1。
2)试验催化剂2的制法
在试验催化剂1的制造中,作为助催化剂(第三成分),代替Ca而担载钾(K),除此以外,同样地操作而得到试验催化剂2。
3)试验催化剂3的制法
在试验催化剂1的制造中,作为助催化剂(第三成分),代替Ca而担载钠(Na),除此以外,同样地操作而得到试验催化剂3。
4)试验催化剂4的制法
在试验催化剂1的制造中,作为助催化剂(第三成分),代替Ca而担载磷(P),除此以外,同样地操作而得到试验催化剂4。
5)试验催化剂5的制法
在试验催化剂4的制造中,作为助催化剂(第三成分),使磷(P)的担载量变更为0.1重量%,除此以外,同样地操作而得到试验催化剂5。
6)试验催化剂6的制法
在试验催化剂4的制造中,作为助催化剂(第三成分),使磷(P)的担载量变更为0.3重量%,除此以外,同样地操作而得到试验催化剂6。
7)试验催化剂7的制法
在试验催化剂4的制造中,作为助催化剂(第三成分),使磷(P)的担载量变更为1.0重量%,除此以外,同样地操作而得到试验催化剂7。
8)试验催化剂8的制法
在试验催化剂4的制造中,作为助催化剂(第三成分),使磷(P)的担载量变更为2.0重量%,除此以外,同样地操作而得到试验催化剂8。
9)比较催化剂的制法
在试验催化剂1的制造中,不添加助催化剂(第三成分),除此以外,同样地操作而得到比较催化剂。
催化剂的评价按下述方式进行。
评价试验是向内径14mm的管型反应管中填充3.3cc催化剂,通过流通式微型反应器装置评价催化剂活性。
初期的催化剂活性的比较是求出催化剂层入口、出口的气体流量变化的CO转化率。
初期及耐久后的活性评价条件为如下条件。
气体组成为H2/CO/CO2=30/50/20摩尔%、H2S=700ppm、S/CO=1.0,以0.9MPa、温度250℃、SV=6000h-1的条件进行试验。
CO转化率由下述式(I)求出。
CO转化率(%)=(1-(催化剂层出口CO气体流速(mol/小时))/(催化剂层入口CO气体流速(mol/小时)))×100···(I)
另外,耐久(加速)试验为如下条件。
气体组成为H2/CO/CO2=30/50/20摩尔%、H2S=700ppm、S/CO=0.1,以0.9MPa、温度450℃、SV=2000h-1的条件进行试验。
该催化剂的组成的一览表及试验的结果示于表1中。
【表1】
如表1所示,本试验例的催化剂1至8确认了,通过添加助催化剂,初期氧量变少,即使在低水蒸气量的情况下,100小时的耐久试验后的CO转化率的降低少,能良好地维持CO转化反应。
任一催化剂的CO转化率的劣化比例均为90%~96%而良好,没有大幅的降低。
特别是,试验催化剂2、4~6的催化剂的初期氧量也少,100小时耐久试验后的CO转化率的降低极小。
相对于此,比较例的比较催化剂的CO转化率大幅降低(劣化比例75%)。
图2是与试验催化剂2的对耐久试验的初期CO转化率(%)和经过100小时后的CO转化率(%)进行比较的图表。
由图2可以明确,试验催化剂2添加K作为助催化剂,因此初期的氧量小到0.11mmol/g。需要说明的是,虽然CO转化率比比较催化剂1(73.2%)小(69.3%),但是在耐久试验中碳析出少,因此经过100小时后的CO转化率(%)与比较催化剂1的结果(54.9%)相比,为64.8%,其劣化比例小(94%)。
由此判断,本试验的CO转化催化剂由于添加Ca、K、P等助催化剂成分作为第三成分,因此能够减小初期氧量,碳(C)析出的发生量少,因此耐久性优异,能够长期稳定地维持CO转化反应。
<煤气化发电成套设备>
对于具备本实施例的CO转化反应装置20的煤气化发电成套设备,参照附图进行说明。图3是表示煤气化发电成套设备的一例的图。如图3所示,煤气化发电成套设备50具有:气化炉11、过滤器13、COS转化装置51、CO转化反应装置20、气体精制装置(H2S/CO2回收装置)15和复合发电设备52。
向气化炉11供给作为燃料F的煤和来自于气化空气压缩机53的空气54,使煤在气化炉11中气化,得到作为生成气体的气化气12。另外,在气化炉11中,将空气54利用空气分离装置55分离为氮(N2)和氧(O2),将N2、O2适当供给于气化炉11内。在煤气化发电成套设备50中,将由气化炉11得到的气化气12供给至过滤器13,除尘后供给至COS转化装置51,将气化气12中所含的COS转化为H2S。
随后,将含有H2S的气化气12供给至CO转化反应装置20,并且将水蒸气21供给至CO转化反应装置20内,在CO转化反应装置20内发生将气化气12中的CO转化为CO2的CO转化反应。
在该CO转化反应装置20中使用本发明的CO转化催化剂,因此即使按照上述大幅降低水蒸气量,也能够长期高效地生成改质气体。
在CO转化反应装置20中将气化气12中的CO转化为CO2后,将得到的改质气体供给至作为气体精制装置15的H2S/CO2回收装置,在H2S/CO2回收装置中除去改质气体中的CO2及H2S。
气体精制装置15中精制处理后的精制气体22被供给至复合发电设备52。复合发电设备52具有气体涡轮61、蒸气涡轮62、发电机63和废热回收锅炉(HRSG:Heat RecoverySteam Generator)64。复合发电设备52将精制气体22供给至作为发电单元的气体涡轮61的燃烧器65。另外,气体涡轮61将供给到压缩机66的空气67供给至燃烧器65。气体涡轮61将精制气体22在燃烧器65中燃烧而生成高温、高压的燃烧气体68,通过该燃烧气体68驱动涡轮69。涡轮69与发电机63相连接,通过涡轮69的驱动而使发电机63产生电力。驱动涡轮69后的排气70具有500~600℃的温度,因此送至废热回收锅炉(HRSG:Heat Recovery SteamGenerator)64回收热能。在废热回收锅炉(HRSG)64中,通过排气70的热能而生成蒸气71,通过该蒸气71驱动蒸气涡轮62。蒸气71在蒸气涡轮62中被使用后,从蒸气涡轮62排出,在热交换器72中冷却后,供给至废热回收锅炉64。另外,对于在废热回收锅炉64中回收了热能的排气73而言,用脱硝装置(未图示)等除去排气73中的NOx等之后,经由烟囱74排出到大气中。
可见,对于具备本实施例的CO转化反应装置20的煤气化发电成套设备50而言,即使是使气化炉11中气化后的气化气12在CO转化反应装置20中降低水蒸气量的情况下(水蒸气(H2O)/CO=1左右),在CO转化催化剂中,通过添加助催化剂,减少初期氧量,减少CO转化率的降低,因此能够将气化气12中所含的CO转化为CO2,使改质气体长期稳定地进行CO转化反应。
由此,在CO转化反应中,能够以少量水蒸气来稳定地继续CO转化反应,能够减少从HRSG64抽气的水蒸气量,能够进行提高了煤气化发电成套设备50的能量效率的运转。
需要说明的是,CO转化反应装置20并非限定于设置于COS转化装置51与气体精制装置(H2S/CO2回收装置)15之间(H2S/CO2回收装置的前段侧)的情况,也可以设置于气体精制装置(H2S/CO2回收装置)15的下游侧。
另外,在本实施例中,说明了将从气体精制装置(H2S/CO2回收装置)15排出的精制气体22用作涡轮用气体的情况,为了在CO转化反应装置20中,将气化气12中大量含有的CO转化为CO2,除涡轮用气体以外,还可以使用例如将甲醇、氨等化工品合成的原料气体。
以上,对于本实施例的CO转化反应装置20而言,说明了通过利用气化炉11使煤等燃料F气化而生成的气化气12中的CO转化为CO2的情况,但本发明并不限定于此,能够同样适用于如下的CO转化反应装置,例如用于利用燃料电池等使含有CO的气体转化为CO2的CO转化反应装置等。
符号说明
10 气化气精制系统
11 气化炉
12 气化气
13 过滤器
14 湿式洗气装置
15A 吸收塔
15B 再生塔
15 气体精制装置
19 CO转化催化剂
20 CO转化反应装置
21 水蒸气
22 精制气体
Claims (4)
1.一种CO转化催化剂,其特征在于,是对气体中的一氧化碳CO进行改质的CO转化催化剂,并包含:
以钼Mo为主成分且以钌Ru为副成分的活性成分、或者以Fe为主成分且以镍Ni或钌Ru中的任意一种作为副成分的活性成分;
助催化剂成分磷P;以及
担载所述活性成分和助催化剂成分的包含钛Ti、锆Zr和铈Ce中的任意一种或两种以上的氧化物的载体,
所述磷P即使在水蒸气相对于一氧化碳从3降低至1的情况下也抑制碳的析出。
2.根据权利要求1所述的CO转化催化剂,其特征在于,
所述活性成分的主成分的担载量为0.1~25重量%,副成分的担载量为0.01~10重量%,并且助催化剂成分的担载量为0.1~2.0重量%。
3.一种CO转化反应装置,其特征在于,
将权利要求1或2的CO转化催化剂填充于反应塔内而成。
4.一种气化气的精制方法,其特征在于,
利用过滤器除去由气化炉得到的气化气中的煤尘后,
利用湿式洗气装置进一步净化CO转化反应后的气化气,
接着,除去气化气中的二氧化碳及硫化氢,
使用权利要求1或2的CO转化催化剂,
进行将气化气中的CO转化为CO2的CO转化反应,从而得到精制气体。
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