JP2013541414A - 硫黄耐性触媒担体材料 - Google Patents
硫黄耐性触媒担体材料 Download PDFInfo
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- JP2013541414A JP2013541414A JP2013532879A JP2013532879A JP2013541414A JP 2013541414 A JP2013541414 A JP 2013541414A JP 2013532879 A JP2013532879 A JP 2013532879A JP 2013532879 A JP2013532879 A JP 2013532879A JP 2013541414 A JP2013541414 A JP 2013541414A
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- zirconium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000000463 material Substances 0.000 title claims abstract description 77
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 39
- 239000011593 sulfur Substances 0.000 title claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 25
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 22
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000010304 firing Methods 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001694 spray drying Methods 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- ZFQCFWRSIBGRFL-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;zirconium(4+) Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZFQCFWRSIBGRFL-UHFFFAOYSA-B 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 208000021017 Weight Gain Diseases 0.000 description 7
- 230000000607 poisoning effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 230000004584 weight gain Effects 0.000 description 7
- 235000019786 weight gain Nutrition 0.000 description 7
- 231100000572 poisoning Toxicity 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- MHCAFGMQMCSRGH-UHFFFAOYSA-N aluminum;hydrate Chemical compound O.[Al] MHCAFGMQMCSRGH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/613—10-100 m2/g
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- B01J35/615—100-500 m2/g
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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Abstract
Description
Claims (14)
- 担体材料が硫黄含有不純物に曝露される用途において使用するための触媒担体材料であって、
所定サイズの表面及び孔を有する無機酸化物基材と、
表面と相互作用するように構成され、前記基材の孔によって受け入れられるようなサイズをしたジルコニウム層と
を含む、上記触媒担体材料。 - ジルコニウム層が、ジルコニウム金属、ジルコニウム酸化物、又はこれらの混合物である、請求項1に記載の触媒担体材料。
- 前記基材の表面が、約20から400m2/gの範囲内のBET表面積として与えられるサイズを有する、請求項1又は2に記載の触媒担体材料。
- 無機酸化物基材が、酸化アルミニウム、酸化ケイ素、酸化チタン、及びケイ酸アルミニウムの群から選択されるものである、請求項1から3までに記載の触媒担体材料。
- ジルコニウム層が、約1重量%から30重量%の間の範囲の量で触媒担体材料中に存在する、請求項1から4までに記載の触媒担体材料。
- 粉末、ビーズ、又はペレットの形状を有する、請求項1から5までに記載の触媒担体材料。
- 前記基材の孔が、約0.1cc/gから2cc/gの範囲内の孔体積によって示されるサイズを有する、請求項1から6までに記載の触媒担体材料。
- 触媒及び請求項1から7までに記載の触媒担体材料を含む、硫黄含有不純物の存在に曝される反応を触媒するのに使用するための担持触媒系。
- 触媒が、遷移金属、遷移金属酸化物、アルカリ土類金属酸化物、希土類酸化物、及びこれらの混合物の群から選択されるものである、請求項8に記載の担持触媒系。
- 触媒が、約0.1から10重量%の範囲の量で組み込まれる、請求項8又は9に記載の担持触媒系。
- 硫黄含有不純物の存在に曝露される担持触媒系において使用するための触媒担体材料を調製する方法であって、
所定サイズの表面及び孔を有する無機酸化物基材を提供するステップと、
ジルコニウム化合物を提供するステップと、
前記基材の表面及び孔の少なくとも一部にジルコニウム化合物の層を施すことによって、コートされた基材を形成するステップと、
コートされた基材を所定温度で焼成するステップと
を含み、コートされた基材を焼成するステップにより、ジルコニウム化合物が、ジルコニウム金属、ジルコニウム酸化物、又はこれらの混合物から選択されるものに変換される、上記方法。 - ジルコニウム化合物の層を前記基材に施すステップが、含浸、共沈、及び噴霧乾燥(SD)から選択される一種を使用する、請求項11に記載の方法。
- ジルコニウム化合物を提供するステップが、酢酸ジルコニウム、クエン酸ジルコニウム、及びシュウ酸ジルコニウムの群から選択される一種を使用する、請求項11又は12に記載の方法。
- コートされた基材を焼成するステップが、500から1200℃の範囲内の温度を使用する、請求項11から13までに記載の方法。
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US20130252807A1 (en) | 2013-09-26 |
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US10065177B2 (en) | 2018-09-04 |
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