CN112427038A - Preparation method of catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde - Google Patents
Preparation method of catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde Download PDFInfo
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- CN112427038A CN112427038A CN202011242686.7A CN202011242686A CN112427038A CN 112427038 A CN112427038 A CN 112427038A CN 202011242686 A CN202011242686 A CN 202011242686A CN 112427038 A CN112427038 A CN 112427038A
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- neopentyl glycol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 title claims abstract description 32
- JJMOMMLADQPZNY-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanal Chemical compound OCC(C)(C)C=O JJMOMMLADQPZNY-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 22
- 239000012266 salt solution Substances 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Chemical class 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 229910052726 zirconium Chemical class 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical class [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 3
- 150000007529 inorganic bases Chemical class 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 17
- 239000006227 byproduct Substances 0.000 abstract description 7
- 229940117969 neopentyl glycol Drugs 0.000 description 31
- 239000012065 filter cake Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 229910001868 water Inorganic materials 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 10
- 238000002242 deionisation method Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 6
- -1 neopentyl glycol acetal compounds Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 5
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 5
- RKLJSBNBBHBEOT-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropanoyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)C(=O)OC(=O)C(C)(C)CO RKLJSBNBBHBEOT-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- JVGJTPDCCWPUHQ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol 3-hydroxy-2,2-dimethylpropanal Chemical compound OCC(C)(C)CO.OCC(C)(C)C=O JVGJTPDCCWPUHQ-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910008159 Zr(SO4)2 Inorganic materials 0.000 description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229910052927 chalcanthite Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- HNWHVVWRJAXEEC-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 2-methylpropanoate Chemical compound CC(C)C(=O)OCC(C)(C)CO HNWHVVWRJAXEEC-UHFFFAOYSA-N 0.000 description 1
- SZCWBURCISJFEZ-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)COC(=O)C(C)(C)CO SZCWBURCISJFEZ-UHFFFAOYSA-N 0.000 description 1
- 229910016341 Al2O3 ZrO2 Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical class [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/83—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 rare earths or actinides
-
- 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
-
- 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- C07C29/147—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 carboxylic acids or derivatives thereof
- C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a preparation method of a catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde, which comprises the following steps of (1) dissolving inorganic salts of copper, cobalt, cerium, aluminum and zirconium in deionized water to prepare a mixed salt solution; carrying out neutralization and precipitation on the mixed salt solution and the inorganic alkali solution in a cocurrent flow mode under stirring; (2) aging, filtering and washing the aging liquid after the neutralization and precipitation to be neutral under stirring, and then drying to obtain a catalyst precursor; (3) and roasting and molding the catalyst precursor to obtain the molded catalyst. The method is simple, mild in process condition, low in price, excellent in low-temperature performance, good in stability, few in by-products and high in conversion efficiency.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method of a catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde.
Background
Neopentyl glycol has good reactivity and wide application, and is mainly used for producing polyester resin for powder coating and saturated polyester resin (accounting for about 70 percent of neopentyl glycol consumption) for coil steel, unsaturated polyester resin and alkyd resin chemical products at present, and is also involved in the production of polyurethane resin, foamed plastic, medical intermediates and other products.
The industrial production of neopentyl glycol generally employs two methods, namely a disproportionation method in which isobutyraldehyde and an aqueous formaldehyde solution are subjected to an aldol condensation reaction using a strong basic catalyst to produce hydroxypivalaldehyde, and the hydroxypivalaldehyde is further reacted with an excess of formaldehyde to produce neopentyl glycol, and a condensation hydrogenation method. However, a large amount of formate is generated in the process of producing neopentyl glycol by using the technology, the product quality is influenced, and the product is harmful to the environment, and the technology is gradually replaced by a condensation hydrogenation method at present. The condensation hydrogenation method is characterized in that organic amine is used as a catalyst to catalyze formaldehyde and isobutyraldehyde to carry out aldol condensation, and the generated hydroxypivalaldehyde is further catalyzed and hydrogenated to obtain neopentyl glycol.
The catalyst for preparing neopentyl glycol by hydrogenating hydroxypivalaldehyde is one of the main difficulties of industrialization of a condensation hydrogenation method, and at present, hydroxypivalaldehyde hydrogenation catalysts mainly comprise noble metals, nickel-based catalysts and copper-based catalysts. Noble metal catalysts have good activity, good selectivity and low activation temperature, but are expensive and not suitable for industrial application. The nickel-based catalyst is represented by Raney nickel, and has the advantages of poor stability, high cost, complex preparation and post-treatment and less industrial application. The copper-based catalyst has low price and good catalytic performance, and becomes the most widely used catalyst in the industry at present.
In the production process of preparing hydroxypivalaldehyde by condensing formaldehyde and isobutyraldehyde and in the process of separating unreacted raw materials from liquid-phase products after reaction, neopentyl glycol acetal compounds (mainly neopentyl glycol formal and neopentyl glycol hydroxypivalaldehyde) are inevitably generated, and hydroxypivalyl hydroxypivalate is also easily generated in the condensation process. CN103351277B adopts two-stage hydrogenation process to prepare neopentyl glycol, and the first stage catalyst is CuO, MnO and Al2O3And/or ZrO2CdO and/or ZnO, In2O3、CeO2Or Nd2O3The second-stage hydrogenation catalyst is CuO, MnO, ZnO and ZrO2And/or TiO2、Y2O3、In2O3By adopting the method, the neopentyl glycol acetal compound generated in the NPG prepared by the hydrogenation process can be converted into NPG by more than 98%, and the HPHP can be converted into NPG by more than 97%. But the reaction temperature of the hydrogenation catalyst adopted in the two-stage hydrogenation process is higher than that of the conventional copper-based catalyst.
In the hydrogenation process, when the hydrogenation temperature is higher, a sharp increase of the amount of by-products, particularly neopentyl glycol-monoisobutyrate, can occur, which not only reduces the selectivity of neopentyl glycol and consequently the yield of neopentyl glycol, but also makes it difficult to separate neopentyl glycol from neopentyl glycol in a neopentyl glycol refining unit, and reduces the quality of the neopentyl glycol product. Therefore, the hydrogenation catalyst needs to show good catalytic performance at a lower reaction temperature.
Therefore, a catalyst which is low in cost, excellent in low-temperature performance, good in stability, less in by-products and capable of converting hydroxypivalyl hydroxypivalate and neopentyl glycol acetal compounds into neopentyl glycol is required in industrial production.
Disclosure of Invention
The invention aims to solve the technical problems and provides a preparation method of a catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde, which has the advantages of simple method, mild process conditions, low price, excellent low-temperature performance, good stability, few byproducts and high conversion efficiency.
The technical scheme comprises the following steps:
(1) dissolving inorganic salts of copper, cobalt, cerium, aluminum and zirconium in deionized water to prepare a mixed salt solution; neutralizing and precipitating the mixed salt solution and the inorganic alkali solution in a cocurrent mode under stirring;
(2) aging, filtering and washing the aging liquid after the neutralization and precipitation to be neutral under stirring, and then drying to obtain a catalyst precursor;
(3) roasting and molding the catalyst precursor to obtain a molded catalyst, wherein the catalyst comprises the following components in percentage by weight: 10-45 wt% of CuO and Co3O4:1~10wt%,CeO2:1~10wt%, Al2O3:20~50wt%,ZrO210 to 40 wt%, the total being 100%. Preferably CuO: 20 to 40 wt%, Co3O4: 3~8wt%,CeO2:2~6wt%,Al2O3:20~50wt%,ZrO210 to 40 wt%, the total being 100%. In the step 1), the inorganic salt may be at least one of nitrate, sulfate or chloride.
In the step 1), the inorganic alkali in the inorganic alkali solution is at least one of ammonia water, sodium carbonate, sodium bicarbonate or ammonium bicarbonate.
In the step 1), the temperature is controlled to be 50-90 ℃ and the pH value is 7.0-9.5, and the preferable precipitation temperature is 60-80 ℃ and the pH value is 7.5-9.0.
In the aging step of the step 2), the aging temperature is controlled to be 50-90 ℃, the aging time is 1-6 hours, more preferably 60-80 ℃, and the aging time is 2-4 hours.
In the drying step of the step 2), the drying temperature is controlled to be 70-120 ℃ for 4-24 h,
in the roasting step in the step 3), the roasting temperature is controlled to be 300-600 ℃, the roasting time is 1-8 hours, and more preferably, the roasting temperature is 400-500 ℃, and the roasting time is 3-6 hours.
In view of the problems in the background art, the inventors have made the following improvements:
(1) the invention takes Co and Ce as auxiliary agents on the basis of a copper-based catalyst, and Co exists in the catalyst2+Ionic form, can migrate to Al2O3In the lattice defect of (2), the catalyst is preferentially oxidized in the catalytic hydrogenation process, so that the Cu crystal phase is stabilized, and the activity and the stability of the catalyst are improved; ce can promote the dispersion of Cu on the carrier, form smaller Cu crystals, and expose more active centers of Cu, thereby improving the hydrogenation activity of the catalyst.
The CuO content of the catalyst product is 10-45 wt%, the CuO content is too low, the hydrogenation active sites in the catalyst are few, the catalytic performance is poor, the CuO content is too high, and large Cu grains are easily formed, so that the catalytic performance is influenced. Co3O41 to 10 wt% of CeO2The content is 1-10 wt%, the promotion effect is limited when the content of the auxiliary agent is too low, and the catalyst active sites can be covered when the content of the auxiliary agent is too high, so that the activity of the catalyst is reduced.
(2) With Al2O3-ZrO2Is a carrier, wherein ZrO2In presence of H2Overflow phenomenon, H2Overflow to ZrO after Cu commercial adsorption2Surface, ZrO2Surface hydroxyls accelerate the hydrogen flooding process, flooded H2The reduction of CuO can be promoted, so that Cu always keeps an atomic state with catalytic activity in the hydrogenation process, and the stability of the catalyst is improved; at the same time, Cu and ZrO2Can generate electron transfer between the two, which is beneficial to improving the performance of the catalyst.
In the promotion of Co and Ce as additives and ZrO as carrier2Under the combined action of the promoting effect, the catalyst has very good hydrogenation catalyst performance, and can convert neopentyl glycol hydroxypivalate and neopentyl glycol acetal compounds into neopentyl glycol. In addition, the hydrogenation reaction of the raw material and the reaction for producing the by-product are competitive reactions, and the catalyst has good hydrogenation performance and canMore raw materials are converted into neopentyl glycol, the conversion efficiency is high, and meanwhile, the byproducts are reduced.
Has the advantages that:
the catalyst has the advantages of simple method, mild process conditions, low raw material cost and operation cost, short preparation period, excellent low-temperature performance (the catalytic reaction temperature is as low as 90 ℃), good stability, few byproducts and high conversion efficiency, and is particularly suitable for being used as a catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde.
Drawings
FIG. 1 is a graph of stability test data for the catalyst prepared in example 9.
Detailed Description
Example 1
15.19g of Cu (NO)3)2·3H2O、1.81g Co(NO3)2·6H2O、5.04g Ce(NO3)3·6H2O、 183.96g Al(NO3)3·9H2O、60.97g Zr(NO3)4·5H2Dissolving O in 1000ml of deionized water; preparing a sodium bicarbonate aqueous solution with the concentration of 1.5 mol/L; placing 5000ml of three-neck flask in a 70 ℃ water bath, dripping the salt solution and the alkali solution into the three-neck flask in a cocurrent flow manner by using a dropping funnel, stirring by using a stirring paddle in the dripping process, controlling the pH value of the reaction to be 8.5-9.0, stopping dripping the alkali solution after the dripping of the salt solution is finished, and stirring and aging for 2 hours at 70 ℃. Filtering the aged solution to obtain a blue solid, washing by deionization, filtering again, measuring the pH value of the filtrate by using pH test paper, stopping washing when the pH value shows neutral, and drying the obtained filter cake in an oven at 100 ℃ for 14 hours; then the dried filter cake is roasted for 3 hours at 500 ℃ to obtain the product with 10 wt% of CuO and Co3O4Content 1% CeO2Content 4% of Al2O3Content 50% ZrO2Catalyst in an amount of 35 wt%.
Example 2
26.79g of CuCl2·2H2O、4.04g CoCl2、3.58g CeCl3、52.31g AlCl3、28.37g ZrCl4Dissolved in 1000ml of deionized water; preparing 2mol/L ammonium bicarbonate aqueous solution; placing 5000ml of three-neck flask in a water bath at 75 ℃, dropwise adding a salt solution and an alkali solution into the three-neck flask in a cocurrent flow manner by using a dropping funnel, stirring by using a stirring paddle in the dropwise adding process, controlling the reaction pH to be 7.0-7.5, stopping dropwise adding the ammonia water after the dropwise adding of the salt solution is finished, and stirring and aging for 3 hours at 75 ℃. Filtering the aged solution to obtain a blue solid, washing by deionization, filtering again, measuring the pH value of the filtrate by using pH test paper, stopping washing when the pH value shows neutral, and drying the obtained filter cake in an oven at 70 ℃ for 24 hours; then the dried filter cake is roasted for 2h at 400 ℃ to obtain the product with 25 wt% of CuO and Co3O4Content 5% CeO25% of Al2O3Content of 35% ZrO2Catalyst in an amount of 30 wt%.
Example 3
30.37g of Cu (NO)3)2·3H2O、10.88g Co(NO3)2·6H2O、1.26g Ce(NO3)3·6H2O、 121.41g Al(NO3)3·9H2O、69.68g Zr(NO3)4·5H2Dissolving O in 1000ml of deionized water; preparing a sodium carbonate aqueous solution with the concentration of 1 mol/L; placing 5000ml of three-neck flask in a water bath at 50 ℃, dropwise adding a salt solution and an alkali solution into the three-neck flask in a cocurrent flow manner by using a dropping funnel, stirring by using a stirring paddle in the dropwise adding process, controlling the pH value of the reaction to be 8.0-8.5, stopping dropwise adding the alkali solution, and stirring and aging for 6 hours at 50 ℃. Filtering the aged solution to obtain a blue solid, washing by deionization, filtering again, measuring the pH value of the filtrate by using pH test paper, stopping washing when the pH value shows neutral, and drying the obtained filter cake in an oven at 110 ℃ for 10 hours; then roasting the dried filter cake for 8 hours at 300 ℃ to obtain the product with the CuO content of 20 wt% and the Co content of3O4Content 6% CeO21% of Al2O3Content 33% ZrO2Catalyst in an amount of 40 wt%.
Example 4
53.16g of CuSO4·5H2O、9.07g CoSO4·H2O、12.61g Ce2(SO4)3、147.17g Al2(SO4)3·18H2O、17.42g Zr(SO4)2·4H2Dissolving O in 1000ml of deionized water; using 25% ammonia water as alkali solution; placing 5000ml of three-neck flask in a water bath at 65 ℃, dropwise adding a salt solution and an alkali solution into the three-neck flask in a parallel flow manner by using a dropping funnel, stirring by using a stirring paddle in the dropwise adding process, controlling the pH value of the reaction to be 7.5-8.0, stopping dropwise adding ammonia water after the dropwise adding of the salt solution is finished, and stirring and aging for 4 hours at 65 ℃. Filtering the aged solution to obtain a blue solid, washing by deionization, filtering again, measuring the pH value of the filtrate by using pH test paper, stopping washing when the pH value shows neutral, and drying the obtained filter cake in an oven at 80 ℃ for 20 hours; then roasting the dried filter cake at 400 ℃ for 6h to obtain the product with the CuO content of 35 wt% and the Co content of3O4Content 5% CeO210% of Al2O340% by weight of ZrO2Catalyst in an amount of 10 wt%.
Example 5
60.75g of Cu (NO)3)2·3H2O、10.88g Co(NO3)2·6H2O、5.04g Ce(NO3)3·6H2O、 91.98g Al(NO3)3·9H2O、43.55g Zr(NO3)4·5H2Dissolving O in 1000ml of deionized water; preparing a sodium carbonate aqueous solution with the concentration of 1 mol/L; placing 5000ml of three-neck flask in a water bath at 75 ℃, dropwise adding a salt solution and an alkali solution into the three-neck flask in a cocurrent flow manner by using a dropping funnel, stirring by using a stirring paddle in the dropwise adding process, stopping dropwise adding the alkali solution after the dropwise adding of the salt solution is finished under the condition that the reaction pH is controlled to be 8.0-8.5, and stirring and aging for 2 hours at 75 ℃. Filtering the aged solution to obtain a blue solid, washing by deionization, filtering again, measuring the pH value of the filtrate by using pH test paper, stopping washing when the pH value shows neutral, and drying the obtained filter cake in an oven at 120 ℃ for 4 hours; then roasting the dried filter cake for 8 hours at 300 ℃ to obtain the product with the CuO content of 40 wt% and the Co content of3O4Content 6% CeO2Content 4% of Al2O3Content 25% ZrO2Catalyst in an amount of 25 wt%.
Example 6
32.15g of CuCl2·2H2O、4.04g CoCl2、3.58g CeCl3、32.69g AlCl3、33.10g ZrCl4Dissolving in 1000ml deionized water; preparing a sodium bicarbonate aqueous solution with the concentration of 1.5 mol/L; placing 5000ml of three-neck flask in a water bath at 90 ℃, dropwise adding a salt solution and an alkali solution into the three-neck flask in a cocurrent flow manner by using a dropping funnel, stirring by using a stirring paddle in the dropwise adding process, controlling the reaction pH to be 8.0-8.5, stopping dropwise adding the alkali solution, and stirring and aging for 1h at 90 ℃. Filtering the aged solution to obtain a blue solid, washing by deionization, filtering again, measuring the pH value of the filtrate by using pH test paper, stopping washing when the pH value shows neutral, and drying the obtained filter cake in an oven at 110 ℃ for 10 hours; then the dried filter cake is roasted for 1h at 600 ℃ to obtain the product with the CuO content of 30 wt% and the Co content3O4Content 5% CeO25% of Al2O3Content 25% ZrO2Catalyst in an amount of 35 wt%.
Example 7
68.34g of CuSO4·5H2O、18.13g CoSO4·H2O、3.78g Ce2(SO4)3、73.58g Al2(SO4)3·18H2O、38.33g Zr(SO4)2·4H2Dissolving O in 1000ml of deionized water; 2mol/L ammonium bicarbonate aqueous solution; placing 5000ml of three-neck flask in a 70 ℃ water bath, dripping a salt solution and an alkali solution into the three-neck flask in a parallel flow manner by using a dropping funnel, stirring by using a stirring paddle in the dripping process, controlling the pH value of the reaction to be 8.5-9.0, stopping dripping ammonia water after the salt solution is dripped, and stirring and aging for 3 hours at 70 ℃. Filtering the aged solution to obtain a blue solid, washing by deionization, filtering again, measuring the pH value of the filtrate by using pH test paper, stopping washing when the pH value shows neutral, and drying the obtained filter cake in an oven at 100 ℃ for 14 hours; then the dried filter cake is roasted for 8 hours at 350 ℃ to obtain the product with the CuO content of 45 wt% and the Co content3O410% of CeO2Content 3% of Al2O3Content 20% ZrO2Catalyst in an amount of 22 wt%.
Example 8
37.97g of Cu (NO)3)2·3H2O、10.88g Co(NO3)2·6H2O、12.61g Ce(NO3)3·6H2O、 110.38g Al(NO3)3·9H2O、50.52g Zr(NO3)4·5H2Dissolving O in 1000ml of deionized water; using 25% ammonia water as alkali solution; placing 5000ml of three-neck flask in a 65 ℃ water bath, dripping a salt solution and an alkali solution into the three-neck flask in a cocurrent flow manner by using a dropping funnel, stirring by using a stirring paddle in the dripping process, controlling the reaction pH to be 8.0-8.5, stopping dripping ammonia water after the salt solution is dripped, and stirring and aging for 4 hours at 65 ℃. Filtering the aged solution to obtain a blue solid, washing by deionization, filtering again, measuring the pH value of the filtrate by using pH test paper, stopping washing when the pH value shows neutral, and drying the obtained filter cake in an oven at 110 ℃ for 10 hours; then the dried filter cake is roasted for 5h at 460 ℃ to obtain the product with 25 wt% of CuO and Co3O4Content 6% CeO210% of Al2O3Content 30% ZrO2Catalyst in an amount of 29 wt%.
Example 9
45.56g of Cu (NO)3)2·3H2O、14.50g Co(NO3)2·6H2O、6.31g Ce(NO3)3·6H2O、 117.73g Al(NO3)3·9H2O、43.55g Zr(NO3)4·5H2Dissolving O in 1000ml of deionized water; preparing 1mol/L sodium carbonate aqueous solution; placing 5000ml of three-neck flask in a water bath at 75 ℃, dropwise adding a salt solution and an alkali solution into the three-neck flask in a cocurrent flow manner by using a dropping funnel, stirring by using a stirring paddle in the dropwise adding process, controlling the pH value of the reaction to be 7.5-8.0, stopping dropwise adding ammonia water after the dropwise adding of the salt solution is finished, and stirring and aging for 2 hours at 75 ℃. Filtering the aged solution to obtain a blue solid, washing by deionization, filtering again, measuring the pH value of the filtrate by using pH test paper, stopping washing when the pH value shows neutral, and drying the obtained filter cake in an oven at 110 ℃ for 10 hours; then the dried filter cake is roasted for 6h at 420 ℃ to obtain the CuO content of 30 wt%,Co3O4Content 8% CeO25% of Al2O3Content 32% ZrO2Catalyst in an amount of 25 wt%. The catalyst stability test data are shown in figure 1.
The calcined catalysts of examples 1-9 were each pelletized by a pellet mill to give pelletsThen crushing the mixture into 20-40 mesh particles, filling the particles into a constant temperature section of a fixed bed reactor, and filling the upper end and the lower end of the reactor with 20-40 mesh quartz sand. The catalyst is pure H2Reducing at 300 deg.C for 4-5H under normal pressure, cooling to reaction temperature, and adding H2Raising the pressure to the reaction pressure, pumping in raw material liquid for reaction, wherein the raw material liquid is an aqueous solution of hydroxypivalaldehyde, neopentylglycol, hydroxypivalyl hydroxypivalate, neopentyl glycol formal and neopentyl glycol hydroxypivalaldehyde, and the evaluation data of the catalyst in each example are shown in Table 1.
As can be seen from Table 1, the catalysts prepared in examples 1-9 can effectively perform catalytic hydrogenation on a solution containing hydroxypivalaldehyde to prepare neopentyl glycol, and the catalysts prepared by the invention can effectively convert HPA, HPHP and neopentyl glycol acetal into NPG, wherein the highest conversion rate of HPA is more than 99%, and the highest conversion rate of HPHP and neopentyl glycol acetal is more than 90%. The catalyst of example 9 remained stable in performance over 1000h of operation.
Claims (8)
1. A preparation method of a catalyst for preparing neopentyl glycol by hydrogenating hydroxypivalaldehyde is characterized by comprising the following steps of:
(1) dissolving inorganic salts of copper, cobalt, cerium, aluminum and zirconium in deionized water to prepare a mixed salt solution; carrying out neutralization and precipitation on the mixed salt solution and the inorganic alkali solution in a cocurrent flow mode under stirring;
(2) aging, filtering and washing the aging liquid after the neutralization and precipitation to be neutral under stirring, and then drying to obtain a catalyst precursor;
(3) roasting and molding the catalyst precursor to obtain a molded catalyst, wherein the catalyst comprises the following components in percentage by weight: 10-45 wt% of CuO and Co3O4:1~10wt%,CeO2:1~10wt%,Al2O3:20~50wt%,ZrO210 to 40 wt%, the total being 100%.
2. The method of claim 1, wherein in step 1), the inorganic salt is selected from at least one of nitrate, sulfate, and chloride.
3. The method of preparing the catalyst according to claim 1, wherein in the step 1), the inorganic base in the inorganic base solution is at least one of ammonia water, sodium carbonate, sodium bicarbonate or ammonium bicarbonate.
4. The method for preparing a catalyst according to any one of claims 1 to 3, wherein in the neutralization and precipitation step of step 1), the temperature is controlled to be 50 to 90 ℃ and the pH is controlled to be 7.0 to 9.5.
5. The method for preparing the catalyst according to claim 1, wherein in the aging step of the step 2), the aging temperature is controlled to be 50-90 ℃ and the aging time is 1-6 h.
6. The method for preparing the catalyst according to claim 1, wherein in the drying step of the step 2), the drying temperature is controlled to be 70-120 ℃ for 4-24 h.
7. The method for preparing the catalyst according to claim 1, wherein in the calcination step in the step 3), the calcination temperature is controlled to be 300-600 ℃ and the calcination time is controlled to be 1-8 h.
8. The method for preparing a catalyst according to claim 1, wherein the concentration of the inorganic base solution in the step 3) is 1 to 2 mol/L.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103420790A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for ethanol preparation through oxygen-containing C2 compound hydrogenation |
CN105664956A (en) * | 2016-01-07 | 2016-06-15 | 上海华谊(集团)公司 | Catalyst for preparing neopentyl glycol through hydrogenation of hydroxyl pivalaldehyde and preparing method thereof, and method |
WO2018035421A1 (en) * | 2016-08-18 | 2018-02-22 | The University Of Chicago | Metal oxide-supported earth-abundant metal catalysts for highly efficient organic transformations |
CN109603837A (en) * | 2019-01-18 | 2019-04-12 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the Cu/Ce/Co catalyst for furfural liquid-phase hydrogenatin |
-
2020
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103420790A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for ethanol preparation through oxygen-containing C2 compound hydrogenation |
CN105664956A (en) * | 2016-01-07 | 2016-06-15 | 上海华谊(集团)公司 | Catalyst for preparing neopentyl glycol through hydrogenation of hydroxyl pivalaldehyde and preparing method thereof, and method |
WO2018035421A1 (en) * | 2016-08-18 | 2018-02-22 | The University Of Chicago | Metal oxide-supported earth-abundant metal catalysts for highly efficient organic transformations |
CN109603837A (en) * | 2019-01-18 | 2019-04-12 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the Cu/Ce/Co catalyst for furfural liquid-phase hydrogenatin |
Non-Patent Citations (1)
Title |
---|
N.-A.M. DERAZ: "Surface and catalytic properties of Co3O4-doped CuO–Al2O3 catalysts", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115487814B (en) * | 2021-06-18 | 2024-03-26 | 中国石油化工股份有限公司 | Dual-function catalyst, preparation method and application thereof, and method for preparing glycol from carbohydrate raw material |
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