JP5535990B2 - シフト触媒、ガス精製方法及び設備 - Google Patents
シフト触媒、ガス精製方法及び設備 Download PDFInfo
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- JP5535990B2 JP5535990B2 JP2011143998A JP2011143998A JP5535990B2 JP 5535990 B2 JP5535990 B2 JP 5535990B2 JP 2011143998 A JP2011143998 A JP 2011143998A JP 2011143998 A JP2011143998 A JP 2011143998A JP 5535990 B2 JP5535990 B2 JP 5535990B2
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- 239000003054 catalyst Substances 0.000 title claims description 178
- 238000000746 purification Methods 0.000 title description 37
- 238000000034 method Methods 0.000 title description 33
- 238000006243 chemical reaction Methods 0.000 claims description 120
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 39
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000003796 beauty Effects 0.000 claims 1
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 116
- 238000012360 testing method Methods 0.000 description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 230000000694 effects Effects 0.000 description 25
- 238000002309 gasification Methods 0.000 description 20
- 239000003245 coal Substances 0.000 description 19
- 238000010521 absorption reaction Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 238000011084 recovery Methods 0.000 description 15
- 241000196324 Embryophyta Species 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 12
- 238000010248 power generation Methods 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- -1 ammonium heptamolybdate tetrahydrate Chemical class 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005486 sulfidation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910017518 Cu Zn Inorganic materials 0.000 description 3
- 229910017752 Cu-Zn Inorganic materials 0.000 description 3
- 229910017943 Cu—Zn Inorganic materials 0.000 description 3
- 102100027373 Melanin-concentrating hormone receptor 2 Human genes 0.000 description 3
- 101710089759 Melanin-concentrating hormone receptor 2 Proteins 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 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 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910017060 Fe Cr Inorganic materials 0.000 description 2
- 229910002544 Fe-Cr Inorganic materials 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- 102000005717 Myeloma Proteins Human genes 0.000 description 1
- 108010045503 Myeloma Proteins Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 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
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Description
Claims (4)
- COとH2SとCOSとを含むガス中のCOSをH 2 Oと反応させてCO 2 とH 2 Sへ転換するCOS転化反応と、前記ガス中のCOをH2Oと反応させてCO2とH2へ転換するCOシフト反応とを促進させるシフト触媒であって、
Ni、Mo、及びTiO 2 を含み、
Moの金属モル数MaとNiの金属モル数Mbとのモル比Mb/Maは、0.25〜0.5の範囲にあることを特徴とするシフト触媒。 - 請求項1記載のシフト触媒において、Al2O3 及びZrO2の中から選ばれる1種以上の無機酸化物を含むシフト触媒。
- 請求項1記載のシフト触媒において、
Moの金属モル数MaとTiO2中のTiの金属モル数Mcとのモル比Ma/Mcは、0.025〜0.5の範囲にあるシフト触媒。 - 請求項1から3のいずれか1項記載のシフト触媒において、
比表面積が100m2/g以上、及び平均細孔直径が10nm以下であるシフト触媒。
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JP5762386B2 (ja) * | 2012-11-28 | 2015-08-12 | 株式会社日立製作所 | シフト触媒、石炭ガス化プラントのガス精製方法及びガス精製設備 |
JP5968465B2 (ja) * | 2012-12-28 | 2016-08-10 | 三菱重工業株式会社 | Coシフト触媒、coシフト反応装置及びガス化ガスの精製方法 |
JP6025603B2 (ja) | 2013-02-21 | 2016-11-16 | 三菱重工業株式会社 | Coシフト反応装置及びcoシフト変換方法 |
EP2962754B1 (en) * | 2013-02-27 | 2021-04-07 | Mitsubishi Heavy Industries Engineering, Ltd. | Method of producing co shift catalyst |
US10774278B2 (en) | 2013-02-27 | 2020-09-15 | Mitsubishi Heavy Industries Engineering, Ltd. | CO shift catalyst, CO shift reaction apparatus, and method for purifying gasified gas |
SG11201807943UA (en) | 2016-03-23 | 2018-10-30 | Shell Int Research | High metals content hydrolysis catalyst for catalytic reduction of sulfur in a gas stream |
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NL175835B (nl) * | 1973-04-17 | 1984-08-01 | Shell Int Research | Werkwijze ter bereiding van een waterstofrijk gas uit een koolmonoxyde-bevattend gas met behulp van een nikkel en/of kobalt en molybdeen bevattende katalysator. |
DE4424695A1 (de) * | 1993-07-14 | 1995-01-19 | Cabot Corp | Neue Katalysatoren und Behandlung von Gasen mit denselben |
WO2005113124A1 (en) * | 2004-04-22 | 2005-12-01 | Fluor Technologies Corporation | Cos-claus configurations and methods |
US20070072949A1 (en) * | 2005-09-28 | 2007-03-29 | General Electric Company | Methods and apparatus for hydrogen gas production |
JP2012522089A (ja) * | 2009-03-30 | 2012-09-20 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | 精製合成ガス流を生成する方法 |
CN102378648B (zh) * | 2009-04-10 | 2014-07-02 | 三菱重工业株式会社 | Co变换催化剂、co变换反应装置及气化气体的精制方法 |
US8828339B2 (en) * | 2010-02-24 | 2014-09-09 | Mitsubishi Heavy Industries, Ltd. | CO shift catalyst, CO shift reactor, and method for purifying gasified gas |
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