CN107771100A - 含铜氢化催化剂的制备和用途 - Google Patents
含铜氢化催化剂的制备和用途 Download PDFInfo
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- CN107771100A CN107771100A CN201680033096.9A CN201680033096A CN107771100A CN 107771100 A CN107771100 A CN 107771100A CN 201680033096 A CN201680033096 A CN 201680033096A CN 107771100 A CN107771100 A CN 107771100A
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- silicate
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- mantoquita
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 title description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 14
- 229910052802 copper Inorganic materials 0.000 title description 14
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 62
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000007787 solid Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 45
- 238000001556 precipitation Methods 0.000 claims abstract description 45
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims description 41
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 claims description 27
- 238000007493 shaping process Methods 0.000 claims description 21
- 235000012241 calcium silicate Nutrition 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 16
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 15
- 239000000378 calcium silicate Substances 0.000 claims description 15
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 15
- 229960003340 calcium silicate Drugs 0.000 claims description 15
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- -1 silicate Compound Chemical class 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 abstract description 7
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- 239000000377 silicon dioxide Substances 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 150000001879 copper Chemical class 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
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- 235000010755 mineral Nutrition 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
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- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- 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
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- 150000002576 ketones Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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- 238000001354 calcination Methods 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 238000009938 salting Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003756 stirring 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
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- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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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
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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
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
- C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
- C07C33/22—Benzylalcohol; phenethyl alcohol
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/72—Copper
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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Abstract
本发明涉及一种制备催化剂的方法,其包含:将含有铜盐的溶液与含有硅酸盐的组合物混合,从而产生沉淀的固体;以及使所沉淀的固体经受150到500℃范围内的温度。另外,本发明涉及一种能利用所述方法获得的含铜催化剂。再另外,本发明涉及一种使用这类含铜催化剂的氢化方法,更具体地说,使甲基苯基酮氢化成甲基苯基甲醇的方法。
Description
技术领域
本发明涉及一种制备含铜催化剂、更具体地说含铜氢化催化剂的方法;能利用所述方法获得的含铜催化剂;以及使用这类含铜催化剂的氢化方法,更具体地说,使甲基苯基酮氢化成甲基苯基甲醇的方法。
背景技术
已知含铜催化剂用于所有类型的工艺中,更具体地说,氢化工艺中。
举例而言,EP0714877A2公开了一种通过苯乙酮氢化来生产α-苯乙醇的方法,其使用含有至少一种碱土金属碳酸盐和/或至少一种碱金属化合物的铜基催化剂。所述苯乙酮相当于甲基苯基酮(MPK);且所述α-苯乙醇相当于甲基苯基甲醇(MPC;1-苯乙醇)。
本发明的一个目标是提供一种制备含铜催化剂的方法,其中如此获得的催化剂可以用于氢化方法中,例如使甲基苯基酮发生氢化、从而产生相对较高的转化率和/或选择性的方法。
发明内容
已惊人地发现,具有高度活性和选择性的含铜氢化催化剂可以利用包含以下的方法制备:
将含有铜盐的溶液与含有硅酸盐的组合物混合,产生沉淀的固体;以及
使所沉淀的固体经受150到500℃范围内的温度。
相应地,本发明涉及一种制备催化剂的方法,所述方法包含上述步骤。
在本发明方法的另一个实施例中,继上述步骤之后为:
将经热处理的沉淀固体与含有成形助剂的悬浮液混合;
使如此获得的混合物成形,从而产生成形体;以及
使所述成形体经受150到500℃范围内的温度。
另外,本发明涉及一种能利用所述方法获得的含铜催化剂。
再另外,本发明涉及一种使用所述含铜催化剂的氢化方法,更具体地说,使甲基苯基酮氢化成甲基苯基甲醇的方法。
具体实施方式
因此,本发明的催化剂制备方法包含以下步骤:
将含有铜盐的溶液与含有硅酸盐的组合物混合,产生沉淀的固体;以及
使所沉淀的固体经受150到500℃范围内的温度,从而产生经热处理的沉淀固体。
虽然本发明的方法被描述为“包含”、“含有”或“包括”一个或多个不同所述步骤,但是其也可以“基本上由所述一或多个不同所述步骤组成”或“由所述一或多个不同所述步骤组成”。这同样适用于“包含”、“含有”或“包括”一种或多种不同所述组分的组合物、气流等。
在本发明中,含有铜盐的溶液优选水溶液。另外,所述溶液中的铜盐可以是任何铜盐。铜盐可以是铜的硝酸盐、硫酸盐、氯化物或有机酸盐。铜盐优选硝酸铜或铜的有机酸盐,最优选硝酸铜。适合的铜有机酸盐是乙酸铜。
本发明方法所能获得的催化剂中的铜含量按氧化铜(II)(CuO)形式计算,按催化剂总重量计,优选40到95wt.%,更优选50到80wt.%。
在本发明中,含有硅酸盐的组合物可以包含含有硅酸盐的溶液和/或含有硅酸盐的悬浮液。也就是说,含有硅酸盐的组合物可以包含含有硅酸盐的溶液;或含有硅酸盐的悬浮液;或含有硅酸盐的溶液和含有硅酸盐的悬浮液。在本发明中,含有硅酸盐的组合物优选水性组合物,也就是说,水溶液和/或悬浮液。在本发明中,含有硅酸盐的溶液优选水溶液。另外,所述组合物(也就是说,溶液和/或悬浮液)中的硅酸盐可以是任何硅酸盐。优选的是,硅酸盐包含碱金属硅酸盐,优选钠硅酸盐;和/或碱土金属硅酸盐,优选钙硅酸盐。更优选的是,硅酸盐包含碱金属硅酸盐,优选钠硅酸盐。在硅酸盐包含碱金属硅酸盐的情况下,含有硅酸盐的组合物优选包含含有硅酸盐的溶液。在硅酸盐包含碱土金属硅酸盐的情况下,含有硅酸盐的组合物优选包含含有硅酸盐的悬浮液。
最优选的是,硅酸盐包含碱金属硅酸盐,优选钠硅酸盐,并且另外,将所沉淀的固体(通过将含有铜盐的溶液与含有硅酸盐的组合物(也就是说,溶液和/或悬浮液)混合所产生)与碱土金属硅酸盐(优选钙硅酸盐)混合,随后使如此获得的混合物经受150到500℃范围内的温度。
在本发明中,碱土金属硅酸盐,优选钙硅酸盐:
可以在含有铜盐的溶液与含有硅酸盐的组合物混合之前和/或期间,与含有铜盐的溶液和/或含有硅酸盐的组合物混合;和/或
可以与所沉淀的固体(含有铜盐的溶液与含有硅酸盐的组合物混合所产生)混合,随后使如此获得的混合物经受150到500℃范围内的温度;和/或
可以与经热处理的所沉淀固体(使所沉淀的固体经受150到500℃范围内的温度所产生)混合,其条件是使如此获得的混合物经受150到500℃范围内的温度。
也就是说,在本发明中,可以按照一种或多种上述方式添加碱土金属硅酸盐。碱土金属硅酸盐优选通过与所沉淀的固体(通过将含有铜盐的溶液与含有硅酸盐的组合物混合所产生)混合、随后使如此获得的混合物经受150到500℃范围内的温度来添加。另外,碱土金属硅酸盐可以作为含有碱土金属硅酸盐的悬浮液(优选水性悬浮液)添加。另外,优选的是,与含铜盐溶液混合的含硅酸盐组合物中的硅酸盐包含碱金属硅酸盐,优选钠硅酸盐。
优选的是,在悬浮液(例如水性悬浮液)使用钙硅酸盐的任一前述情况下,这类悬浮液的pH是7或更高,更优选7到9。在此pH下,有利的是,通过将含有钙硅酸盐的悬浮液与包含例如氢氧化钠和/或碳酸钠的碱性溶液混合,基本上不会形成碳酸钙。由于碳酸盐在酸性环境中形成二氧化碳,因此最终催化剂中优选不含有碳酸钙。这不利于催化剂稳定性。
在本发明中,沉淀优选在碱存在下进行。这可以如下实现:将碱添加到含铜盐溶液和含硅酸盐组合物(也就是说,溶液和/或悬浮液)的混合物中,或添加到含硅酸盐组合物(也就是说,溶液和/或悬浮液)中,随后与含铜盐溶液混合。另外,所述碱可以包含选自由以下组成的群组的一种或多种碱:氢氧化钠、碳酸钠、碳酸氢钠、氢氧化钾、碳酸钾和碳酸氢钾。优选使用碳酸钠,或氢氧化钠与碳酸钠的混合物。
碱量优选使得基本上所有的铜盐都沉淀。这可以通过使用在分散液(或浆液)中使pH达到7或更大或7.5或更大或8或更大的碱量来实现,所述分散液(或浆液)是通过将含铜盐溶液与含硅酸盐组合物(也就是说,溶液和/或悬浮液)混合所产生。优选的是,在沉淀步骤中,将包含铜和硅酸盐且任选地包含碱的合并混合物(例如溶液和/或悬浮液)加热,例如在50到95℃下(优选70到95℃)加热。
通过将含铜盐溶液与含硅酸盐组合物(也就是说,溶液和/或悬浮液)混合所产生的分散液(或浆液)中的包含铜和硅酸盐的沉淀固体能够通过过滤而自其中回收。所分离的固体可以用水洗涤,优选无碱金属的去离子水,例如以便去除基本上所有的碱金属离子。
所述沉淀固体(任选地与如上文所述的碱土金属硅酸盐混合)可以在干燥之后,例如在80到160℃(100到140℃适宜)范围内的温度下干燥之后,经受150到500℃、优选200到400℃范围内的温度。这类热处理优选在含有氧气的气体(如空气)存在下进行。后者热处理也可以称为煅烧。最后,可以将所得固体催化剂磨碎。
在另一个实施例中,本发明的催化剂制备方法包含以下步骤:
将含铜盐溶液与含硅酸盐组合物(也就是说,溶液和/或悬浮液)混合,从而产生沉淀的固体;
使所沉淀的固体经受150到500℃范围内的温度,从而产生经热处理的沉淀固体;
将经热处理的沉淀固体与含有成形助剂的悬浮液混合;
使如此获得的混合物成形,从而产生成形体;以及
使所述成形体经受150到500℃范围内的温度。
上述另一个第二实施例中的前两个步骤与如上文所述的第一实施例的步骤相同。因此,第一实施例的以上描述也适用于第二(另一个)实施例中的这前两个步骤。举例来说,硅酸盐优选包含碱金属硅酸盐,优选钠硅酸盐;和/或碱土金属硅酸盐,优选钙硅酸盐。更优选的是,硅酸盐包含碱金属硅酸盐,优选钠硅酸盐。
在上述另一个实施例中,将可以是粉末的经热处理的沉淀固体与含有成形助剂的悬浮液混合。含有成形助剂的悬浮液优选水性悬浮液。成形助剂的性质并非关键。因此,成形助剂可以是生产含有催化剂的成形体所常用的任一种成形助剂。可以用于本发明中的成形助剂实例包括二氧化硅、石墨、氧化铝等等。在本发明中,宜使用二氧化硅作为成形助剂。含有所述成形助剂(例如二氧化硅)的悬浮液可以是溶胶,优选含有平均尺寸在1到100nm、更优选5到60nm、最优选5到30nm范围内的成形助剂(例如二氧化硅)颗粒。所述悬浮液可以具有任何pH。举例来说,pH可以低于7(酸性)。然而,也可以应用铵稳定性(碱性)悬浮液。
接着使通过经热处理的沉淀固体与含有成形助剂的悬浮液混合而获得的混合物成形。所得成形体可以具有任何形式。举例来说,所述混合物可以成形为薄片形式。另外,可以应用任何成形方法,如挤出。
所述成形体可以在干燥之后,例如在80到160℃(100到140℃适宜)范围内的温度下干燥之后,经受150到500℃、优选200到400℃范围内的温度。这类热处理优选在含有氧气的气体(如空气)存在下进行。后者热处理也可以称为煅烧。所得经热处理的成形体宜用作固定床反应器中的催化剂。
在上述另一个实施例中,优选的是,首先在150到500℃范围内的温度下热处理之后,添加碱土金属硅酸盐,优选钙硅酸盐,随后使成形体经受150到500℃范围内的温度。举例来说,这类碱土金属硅酸盐可以在成形步骤之前或在成形步骤期间添加。然而,优选的是,此碱土金属硅酸盐是在与含有成形助剂(例如二氧化硅)的悬浮液混合之前或期间(优选混合之前),与经热处理的沉淀固体混合。
在如上文所述第一热处理之后添加此碱土金属硅酸盐的情况下,第一(沉淀)步骤中所用的硅酸盐优选包含碱金属硅酸盐,优选钠硅酸盐,和/或碱土金属硅酸盐,优选钙硅酸盐。在此情况下,所述硅酸盐更优选包含所述碱金属硅酸盐。
在本发明的上述另一个实施例中,碱土金属硅酸盐,优选钙硅酸盐:
可以在含有铜盐的溶液与含有硅酸盐的组合物混合之前和/或期间,与含有铜盐的溶液和/或含有硅酸盐的组合物混合;和/或
可以与所沉淀的固体(含有铜盐的溶液与含有硅酸盐的组合物混合所产生)混合,随后使如此获得的混合物经受150到500℃范围内的温度;和/或
可以在使通过将经热处理的沉淀固体与含有二氧化硅的悬浮液混合而获得的混合物成形之前,与经热处理的沉淀固体混合,所述经热处理的沉淀固体是所沉淀的固体经受150到500℃范围内的温度而产生,优选在经热处理的沉淀固体与含有二氧化硅的悬浮液混合之前和/或期间产生。
也就是说,在本发明的上述另一个实施例中,碱土金属硅酸盐可以按照一种或多种上述方式添加。优选的是,碱土金属硅酸盐是通过与经热处理的沉淀固体混合来添加,所述经热处理的沉淀固体是由所沉淀的固体经受150到500℃范围内的温度而产生,随后使通过将经热处理的沉淀固体与含有成形助剂的悬浮液混合而获得的混合物成形,所述经热处理的沉淀固体优选在经热处理的沉淀固体与含有成形助剂的悬浮液混合之前和/或期间产生。另外,碱土金属硅酸盐可以作为含有碱土金属硅酸盐的悬浮液(优选水性悬浮液)添加。另外,优选的是,与含铜盐溶液混合的含硅酸盐组合物中的硅酸盐包含碱金属硅酸盐,优选钠硅酸盐。另外,本发明涉及一种含铜催化剂,其能利用如上文所述的任一种方法获得。再另外,本发明涉及能利用如上文所述的任一种方法获得的含铜催化剂用于氢化方法中的用途。因此,本发明还涉及一种使甲基苯基酮氢化成1-苯乙醇的方法,其中所述氢化是在能利用如上文所述的任一种方法获得的含铜催化剂存在下进行。
本发明进一步通过以下实例来说明。
另外,在此公开了可以使用碱土金属硅酸盐(优选钙硅酸盐)作为催化剂载体或作为若干种催化剂的载体或催化剂组分,所述催化剂含有一种或多种过渡金属,诸如铂(Pt)、银(Ag)、金(Au)、镍(Ni)、铜(Cu)、钴(Co)、钒(V)、钼(Mo)、钨(W)和/或铼(Re),包括这些金属的氧化物。这些催化剂可以利用浸渍或共沉淀来产生。所得催化剂可以应用于任何用途,例如如上文已述的氢化,而且可以用于氧化(例如环己醇氧化)或脱氢。再另外,其可以用于去除硫化氢(H2S)和/或汞(Hg)。在去除Hg的后一种情况下,催化剂优选首先硫化后再使用。
实例1
将9149g孔雀石(其是含有式Cu2CO3(OH)2碱式碳酸铜的矿物质)溶解于硝酸溶液中。所述硝酸溶液含有27.5l水和15.1l HNO3且具有693.2g HNO3/l的浓度。所得溶液含有硝酸铜(Cu(NO3)2)。
通过将3494g氢氧化钠(NaOH)和4630g碳酸钠(Na2CO3)溶解于47.5l水中来制备碱性溶液。摩尔比NaOH:Na2CO3是1.9:1。将碱性溶液的浓度调节到170g NaOH+Na2CO3/l。接着向碱性溶液中添加1.3l含有水玻璃(其是式Na2SiO3的硅酸钠)的溶液。所得碱性溶液含有307.7g SiO2/l和103.95g NaOH/l,且接着加热到80℃。
将含有硝酸铜的溶液添加到经加热的碱性溶液中,同时剧烈搅拌所得浆液。沉淀期间的温度维持在80℃。在浆液的pH 8.3-8.5下,沉淀在约2小时内结束。接着在所述pH和所述温度下且在搅拌的同时,再进行老化60分钟。接着过滤浆液。所得滤饼用去离子水洗涤,直到滤饼的一小部分在800℃下退火所产生的残余物中的Na2O含量低于0.3wt.%为止。接着,将滤饼在空气中、在120℃下干燥8小时且随后在空气中、在300℃下煅烧2小时。接着将所得材料研磨成粒度<1.0mm的催化剂粉末。
将638g所述催化剂粉末与16g粘合剂混合。
接着将325ml二氧化硅水性溶胶悬浮液(1540)缓慢添加到如此获得的混合物中,同时混合(捏合)。如所述悬浮液中所含的水是去矿物质水。所述二氧化硅溶胶悬浮液含有500g SiO2/l且具有低于7的pH。捏合持续10分钟且接着通过将所捏合的混合物挤出成挤出物来使其成形,所述挤出物具有1.6mm的尺寸和TL形状。接着,将挤出物在空气中、在120℃下干燥8小时且随后在空气中、在300℃下煅烧2小时。
实例2
重复实例1的程序,但其中将催化剂粉末与16g(如实例1)混合且还与53.2g硅灰石混合。硅灰石是含有式CaSiO3硅酸钙的矿物质。
比较实例
碳酸铜(CuCO3)在250kg/h流量的空气流中、在315℃下加以热处理,从而产生氧化铜(CuO)粉末。所述粉末具有93wt.%的“灼烧残渣”(ROI;在800℃下进行2小时)和30m2/g的BET表面积。
将1.5kg所述氧化铜粉末与0.057kg(其是粘合剂)、0.113kg硅灰石(其是含有式CaSiO3硅酸钙的矿物质)和0.193kg50(其是二氧化硅)混合。
接着将1.007l二氧化硅水性溶胶悬浮液(1540)缓慢添加到如此获得的混合物中,同时混合(捏合)。如所述悬浮液中所含的水是去矿物质水。所述二氧化硅溶胶悬浮液含有500g SiO2/l且具有低于7的pH。捏合持续10分钟且接着通过将所捏合的混合物挤出成挤出物来使其成形,所述挤出物具有1.6mm的尺寸和TL形状。接着,将挤出物在空气中、在120℃下干燥8小时且随后在空气中、在300℃下煅烧2小时。
氢化实验
如实例1和2中以及比较实例中所制备的催化剂在氢化实验(更具体地说,甲基苯基酮(MPK;苯乙酮)氢化成甲基苯基甲醇(MPC;1-苯乙醇))中加以测试。
执行所述氢化实验之前,按照以下方式将催化剂活化。将25cm3催化剂放置于具有2英寸直径的管式反应器中。在第一步骤中,催化剂在具有150v/vh的GHSV(气体每小时空间速度)的含氮气气流中、在120℃下干燥24小时。接着将反应器按3K/min的速率加热到150℃。接着将氮气流的GHSV调节到500v/vh且向所述气流中添加氢气,氢气的初始量为0.2vol.%,借此控制放热还原反应。温度逐步提高到200℃。同时,使氢气比例逐步地进一步增加(且氮气比例减少)到100vol.%氢气。当无进一步的放热反应发生时,催化剂还原过程结束。
接着将温度降低到80℃,在此温度下,除馈送含有氢气的气流之外,还通过将含有50.0wt.%MPK、25.0wt.%乙苯、24.7wt.%MPC和0.3wt.%苯乙烯的含MPK液体馈送到反应器中(滴流模式)来进行氢化实验。反应压力是25巴。液体馈料的LHSV(液体每小时空间速度)是1.2v/vh。气液比率是200:1v/v。
每一种催化剂所得的转化率和选择性展示于下表中。
催化剂得自 | 转化率 | 选择性 |
实例1 | 95% | 99% |
实例2 | 96% | 99% |
比较实例 | 88% | 99% |
根据上表中的结果,似乎有利的是,相较于比较实例中所得的催化剂,在使用根据本发明所得的催化剂(实例1和2)的情况下,实现实质上更高的转化率,同时选择性保持相同。
Claims (14)
1.一种制备催化剂的方法,包含:
将含有铜盐的溶液与含有硅酸盐的组合物混合,产生沉淀的固体;以及
使所述沉淀固体经受150到500℃范围内的温度。
2.根据权利要求1所述的方法,其中所述硅酸盐包含碱金属硅酸盐,优选钠硅酸盐;和/或碱土金属硅酸盐,优选钙硅酸盐。
3.根据权利要求2所述的方法,其中所述硅酸盐包含碱金属硅酸盐,优选钠硅酸盐,且其中使所述沉淀固体与碱土金属硅酸盐、优选钙硅酸盐混合。
4.根据前述权利要求任一项所述的方法,其中碱土金属硅酸盐,优选钙硅酸盐:
是在所述含有铜盐的溶液与所述含有硅酸盐的组合物混合之前和/或期间,与所述含有铜盐的溶液和/或所述含有硅酸盐的组合物混合;和/或
与所述沉淀固体混合,所述沉淀固体是由所述含有铜盐的溶液与所述含有硅酸盐的组合物混合而产生,随后使如此获得的混合物经受150到500℃范围内的温度;和/或
与由所述沉淀固体经受150到500℃范围内的温度所产生的经热处理的所述沉淀固体混合,其条件是使如此获得的混合物经受150到500℃范围内的温度。
5.根据权利要求4所述的方法,其中与所述含有铜盐的溶液混合的所述含有硅酸盐的组合物中的硅酸盐包含碱金属硅酸盐,优选钠硅酸盐。
6.一种制备催化剂的方法,包含:
将含有铜盐的溶液与含有硅酸盐的组合物混合,产生沉淀的固体;
使所述沉淀固体经受150到500℃范围内的温度,从而产生经热处理的沉淀固体;
将所述经热处理的沉淀固体与含有成形助剂的悬浮液混合;
使如此获得的混合物成形,从而产生成形体;以及
使所述成形体经受150到500℃范围内的温度。
7.根据权利要求6所述的方法,其中所述硅酸盐包含碱金属硅酸盐,优选钠硅酸盐;和/或碱土金属硅酸盐,优选钙硅酸盐。
8.根据权利要求7所述的方法,其中所述硅酸盐包含碱金属硅酸盐,优选钠硅酸盐。
9.根据权利要求5到8中任一项所述的方法,其中所述经热处理的沉淀固体是在与所述含有成形助剂的悬浮液混合之前或期间、优选之前,与碱土金属硅酸盐、优选钙硅酸盐混合。
10.根据权利要求5到9中任一项所述的方法,其中碱土金属硅酸盐,优选钙硅酸盐:
是在所述含有铜盐的溶液与所述含有硅酸盐的组合物混合之前和/或期间,与所述含有铜盐的溶液和/或所述含有硅酸盐的组合物混合;和/或
与所述沉淀固体混合,所述沉淀固体是由所述含有铜盐的溶液与所述含有硅酸盐的组合物混合而产生,随后使如此获得的混合物经受150到500℃范围内的温度;和/或
是在使通过将所述经热处理的沉淀固体与所述含有成形助剂的悬浮液混合而获得的混合物成形之前,与所述经热处理的沉淀固体混合,所述经热处理的沉淀固体是所述沉淀固体经受150到500℃范围内的温度而产生,优选在所述经热处理的沉淀固体与所述含有成形助剂的悬浮液混合之前和/或期间产生。
11.根据权利要求10所述的方法,其中与所述含有铜盐的溶液混合的所述含有硅酸盐的组合物中的硅酸盐包含碱金属硅酸盐,优选钠硅酸盐。
12.一种含铜催化剂,能利用根据权利要求1到11中任一项所述的方法获得。
13.一种能利用根据权利要求1到11中任一项所述的方法获得的含铜催化剂用于氢化工艺中的用途。
14.一种使甲基苯基酮氢化成1-苯乙醇的方法,其中所述氢化是在能利用根据权利要求1到11中任一项所述的方法获得的含铜催化剂存在下进行。
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