CN107805183A - The method that one kettle way catalytic hydrogenation prepares 1,4 cyclohexanedimethanols - Google Patents
The method that one kettle way catalytic hydrogenation prepares 1,4 cyclohexanedimethanols Download PDFInfo
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- CN107805183A CN107805183A CN201710917236.5A CN201710917236A CN107805183A CN 107805183 A CN107805183 A CN 107805183A CN 201710917236 A CN201710917236 A CN 201710917236A CN 107805183 A CN107805183 A CN 107805183A
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- nickel
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- catalytic hydrogenation
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 18
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical class OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 title description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 7
- 238000002161 passivation Methods 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000009938 salting Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 239000011777 magnesium Substances 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- 230000003647 oxidation Effects 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 abstract description 54
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 7
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 6
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 4
- OSFGNZOUZOPXBL-UHFFFAOYSA-N nitric acid;trihydrate Chemical class O.O.O.O[N+]([O-])=O OSFGNZOUZOPXBL-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical class OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- AIACXWOETVLBIA-UHFFFAOYSA-N dimethyl cyclohexane-1,2-dicarboxylate Chemical class COC(=O)C1CCCCC1C(=O)OC AIACXWOETVLBIA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical class O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- -1 terephthalic acid ester Chemical class 0.000 description 1
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C07C29/147—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
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
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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
- B01J23/70—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
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to heterogeneous catalysis technology field, particularly discloses a kind of method that one kettle way catalytic hydrogenation prepares Isosorbide-5-Nitrae cyclohexanedimethanol.The method that the one kettle way catalytic hydrogenation prepares Isosorbide-5-Nitrae cyclohexanedimethanol, it is characterized in that：Nickel-containing catalyst is activated under hydrogen atmosphere, is subsequently placed in air and is passivated, obtains activation passivation nickel-containing catalyst；Cu-contained catalyst and activation passivation nickel-containing catalyst are mixed, is placed in the mixed liquor of dimethyl terephthalate (DMT) and alcohols solvent, hydrogenation reaction is carried out in hydrogenation reaction kettle；By reaction product through being separated, distilling, purifying, product is obtained.The step of this invention simplifies substep Hydrogenation for Isosorbide-5-Nitrae cyclohexanedimethanol, the preparation method of Isosorbide-5-Nitrae cyclohexanedimethanol is set to have obtained simply, being convenient for；Hydrogenation catalyst preparation is simple, cost is cheap, and catalytic hydrogenation step is terse.
Description
（One）Technical field
The present invention relates to heterogeneous catalysis technology field, more particularly to a kind of one kettle way catalytic hydrogenation prepares 1,4-CHDM
Method.
（Two）Background technology
1,4-CHDM is new polyester monocase, can produce poly- PCT with copolymerization such as terephthalic acid (TPA), ethylene glycol
（Terephthalic acid (TPA) 1,4- cyclohexane dicarboxylates）, the new polyester such as PETG/PCTG.CHDM structure has symmetry, contains ring
Hexane ring, its resin produced and final finished all have good heat endurance, are mainly used in electric field and automobile
Industry.The 1,4 cyclohexane dimethanol of world's year consumption at present（CHDM）About 100,000 tons or so.
CHDM industrialized production mainly uses two-step method, i.e. terephthalic acid (TPA) or terephthalate as raw material,
The effect of the noble metal catalysts such as ruthenium, palladium is lower to occur benzene ring hydrogenation, obtains Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic or Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic
Ester, then ester group hydrogenation is carried out under the catalyst actions such as ruthenium, palladium, copper, obtain product 1,4-CHDM.Phenyl ring adds at present
Hydrogen is in the majority with noble metal catalyst research, is catalyzed as patent CN01110643.3 discloses one kind by main active component of Metal Palladium
The method that agent catalytic hydrogenation dimethyl terephthalate (DMT) prepares 1,4 dimethyl hexahydrophthalates.Ester group hydrogenation in noble metal with
Copper-based catalysts have research, are urged as patent CN200510028606.7 discloses one kind using metal rubidium and tin as main active component
Agent catalytic hydrogenation Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic prepares the method for preparing catalyst of 1,4-CHDM, patent
CN201110134923.2 is disclosed a kind of be catalyzed with copper-based catalysts and prepares 1,4- hexamethylenes two by dimethyl terephthalate (DMT)
Methanol intermediate product DMCD Hydrogenations for 1,4 cyclohexane dimethanol method.
There is researcher to have studied terephthalic acid (TPA) or terephthalic acid ester one-step method hydrogenation, such as patent
CN201210007690.4 discloses a kind of method for preparing catalyst using ruthenium, platinum, tin as main active component and application, two
One kettle way obtains CHDM under step different condition.In its disclosed catalyst composition, noble ruthenium, palladium content minimum 5%, catalysis
Agent cost is higher.Patent CN201610226957.7 discloses a kind of for benzene ring hydrogenation and the bifunctional catalyst of carbonyl reduction
And its prepare and apply, CHDM is obtained by two step differential responses condition one kettle ways in fixed bed, it is main in its disclosed method
Component nickel oxide is wanted to need to reduce at relatively high temperatures, and another key component cupric oxide needs to reduce at a lower temperature, compared with
Reduction can cause the agglomeration of copper particle in catalyst at high temperature, cause catalyst life poor.
（Three）The content of the invention
The present invention is in order to make up the deficiencies in the prior art, there is provided a kind of step is simple, cost is cheap, product yield is high one pot
The method that method catalytic hydrogenation prepares 1,4 cyclohexane dimethanol.
The present invention is achieved through the following technical solutions：
A kind of method that one kettle way catalytic hydrogenation prepares 1,4-CHDM, comprises the following steps：
（1）By nickel-containing catalyst at 300-800 DEG C, room temperature is cooled to after activating 2-8h under hydrogen atmosphere, is placed in air
Passivation, obtains activation-passivation nickel-containing catalyst；
（2）Cu-contained catalyst and activation-passivation nickel-containing catalyst are mixed, are placed in dimethyl terephthalate (DMT) and alcohols solvent
In mixed liquor, hydrogenation reaction is carried out in hydrogenation reaction kettle；
（3）By reaction product through being separated, distilling, purifying, product is obtained.
The present invention is with dimethyl terephthalate (DMT)（DMT）For raw material, Isosorbide-5-Nitrae-ring is prepared using one kettle way two-step catalyzing hydrogenation
Hexane dimethanol（CHDM）, the catalyst of conventional each step hydrogenation reaction is required for being activated, and the method that the present invention uses is
The catalyst of second step hydrogenation is together added in reaction with the first step hydrogenation catalyst after activated, it is anti-in first step hydrogenation
Second step hydrogenation catalyst should be activated simultaneously, and second step hydrogenation reaction is carried out by changing reaction condition.
The present invention more excellent technical scheme be：
Step（1）In, nickel-containing catalyst is that mass ratio is 50-90%：10-50% nickel oxide and the mixture of auxiliary agent, auxiliary agent are
One or more in magnesia, aluminum oxide, manganese oxide, chrome green, tin oxide, lanthanum sesquioxide.
Step（1）In, after nickel-containing catalyst activation cooling, it is placed in content 0.1-5% air and is passivated 10-100min.
Step（2）In, Cu-contained catalyst is that mass ratio is 10-80%：20-90% cupric oxide and the mixture of auxiliary agent, are helped
Agent is the one or more in magnesia, aluminum oxide, manganese oxide, chrome green, zinc oxide and tin oxide.
Step（2）In, hydrogenation reaction is carried out in two steps, and first step reaction temperature is 200-400 DEG C, mixing speed 200-
1000r/min, pressure 2-10MPa, reaction time 2-10h；After end, it is anti-that temperature rises to 200-400 DEG C of beginning second step
Should, mixing speed 200-1000r/min, pressure 2-10MPa, the reaction time are 2-10 hours.
Step（1）In, the preparation method of nickel-containing catalyst comprises the following steps：1. by soluble nickel salt and form auxiliary agent
Salt is configured to mixing salt solution, and nickel salt mass concentration is 2-10%, and the salt mass concentration for forming auxiliary agent is 1-5%；2. configure
The isometric sodium carbonate of ratio and the mixed ammonium/alkali solutions of sodium hydroxide, wherein, the mass concentration of sodium hydroxide is nickel salt and builder salts
1.5-2 times of class concentration, sodium carbonate mass concentration are the 10-50% of sodium hydroxide；3. by volume mixture salting liquid volume 30-
After 150% deionized water is heated to 50-90 DEG C, mixing salt solution and mixed ammonium/alkali solutions, rate of addition 0.2- is added dropwise
5mL/min, mixing speed 50-300r/min；4. after being added dropwise, identical mixing speed 4-24h is maintained at 50-90 DEG C；
5. obtained turbid solution filtering, the solid filtered out are dried 5-24h at 50-200 DEG C, ground after drying；6. after grinding
Solid powder is placed in Muffle furnace at 400-800 DEG C and is calcined, and obtains nickel-containing catalyst.
Step（2）In, the preparation method of Cu-contained catalyst comprises the following steps：1. by soluble copper salt and form auxiliary agent
Salt is configured to mixing salt solution, and mantoquita mass concentration is 1-10%, and the salt mass concentration for forming auxiliary agent is 1-20%；2. configure
The isometric sodium carbonate of ratio and the mixed ammonium/alkali solutions of sodium hydroxide or aqueous sodium carbonate, wherein, the mass concentration of sodium hydroxide
For 1.5-3 times of mantoquita and auxiliary agent salt density, sodium carbonate mass concentration is the 10-50% of sodium hydroxide, or, sodium carbonate
In solution, the mass concentration of ammonium carbonate is 3-4 times of mantoquita and auxiliary agent salt density；3. by volume mixture salting liquid volume 30-
After 150% deionized water is heated to 50-90 DEG C, mixing salt solution and mixed ammonium/alkali solutions or aqueous sodium carbonate is added dropwise, drips
Acceleration is 0.2-5mL/min, mixing speed 50-300r/min；4. after being added dropwise, at 50-90 DEG C remaining identical stirs
Mix speed 4-24h；5. obtained turbid solution filtering, the solid filtered out are dried 5-24h at 50-200 DEG C, ground after drying；
It is calcined 6. the solid powder after grinding is placed in Muffle furnace at 400-800 DEG C, obtains Cu-contained catalyst.
The step of this invention simplifies substep Hydrogenation for 1,4-CHDM, make the system of 1,4-CHDM
Preparation Method has obtained simply, being convenient for；Hydrogenation catalyst preparation is simple, cost is cheap, and catalytic hydrogenation step is terse, and 1,
The yield of 4- cyclohexanedimethanols is more than 90%.
（Four）Embodiment
Embodiment 1：
The water nickel nitrates of 14g six, 4.3g magnesium nitrate hexahydrates and the water aluminum nitrates of 2.5g nine are weighed respectively, is configured to the 100mL aqueous solution, are claimed
6.4g sodium hydroxides and 7g natrium carbonicum calcinatums are taken, is configured to the 100mL aqueous solution, takes 80mL deionized waters to be heated to 60 DEG C.Then
Salting liquid and aqueous slkali are added dropwise in deionized water altogether with 2mL/min speed, and keeping temperature is constant with 200r/min's
Stirring.After dripping, keeping temperature is constant and stirring continues to react 6h.By gained reacting liquid filtering, the solid of filtering gained
16h is dried at 110 DEG C, is then ground to powder.A certain amount of solid powder is taken at 110 DEG C and 500 DEG C, in atmosphere of hydrogen
Reduction activation 4h, the nitrogen inerting 1h containing 5% air is passed through after being down to room temperature.
Weigh 7.4g nitrate trihydrates copper, 8.5g magnesium nitrate hexahydrates, the water aluminum nitrates of 12.4g nine and be configured to the 100mL aqueous solution, claim
Take 6.4g sodium hydroxides, 7.0g natrium carbonicum calcinatums to be configured to the 100mL aqueous solution, take 80mL deionized waters to be heated to 60 DEG C.Then
Salting liquid and aqueous slkali are added dropwise in deionized water altogether with 2mL/min speed, and keeping temperature is constant with 200r/min's
Stirring.After dripping, keeping temperature is constant and stirring continues to react 6h.By gained reacting liquid filtering, the solid of filtering gained
16h is dried at 110 DEG C, is then ground to powder.
The dimethyl terephthalate (DMT) methanol solution 42g of the 4.01g containing dimethyl terephthalate (DMT) is prepared, adds 0.4003g
Nickel-containing catalyst and 0.8005g copper-based catalysts are activated-have been passivated, under 200 DEG C, Hydrogen Vapor Pressure 4MPa, 700r/min stirring
Hydrogenation reaction 4h.Then temperature rises to 240 DEG C, and Hydrogen Vapor Pressure is adjusted to 8MPa, reacts 4h under 700r/min stirrings.
After reaction night is cooled into room temperature, centrifuges, be separated by filtration catalyst, retort solution, Isosorbide-5-Nitrae-hexamethylene is obtained after purification
Alkane dimethanol product, yield 92%.
Embodiment 2：
The water nickel nitrates of 12.8g six, 4.76g lanthanum nitrate hexahydrates and the water aluminum nitrates of 4.12g nine are weighed respectively, and it is water-soluble to be configured to 100mL
Liquid, 4.22g sodium hydroxides and 4.6g natrium carbonicum calcinatums are weighed, be configured to the 100mL aqueous solution, take 80mL deionized waters to be heated to 60
℃.Then salting liquid and aqueous slkali are added dropwise in deionized water altogether with 2.1mL/min speed, and keeping temperature it is constant and
200r/min stirring.After dripping, keeping temperature is constant and stirring continues to react 4h.By gained reacting liquid filtering, filtering
The solid of gained dries 16h at 110 DEG C, is then ground to powder.Take a certain amount of solid powder at 110 DEG C and 500 DEG C,
Reduction activation 4h in atmosphere of hydrogen, the nitrogen inerting 1h containing 5% air is passed through after being down to room temperature.
Weigh 9.7g nitrate trihydrates copper, 9.55g zinc nitrate hexahydrates, the water aluminum nitrates of 7.5g nine and be configured to the 100mL aqueous solution, claim
Take 5.12g sodium hydroxides, 4.24g natrium carbonicum calcinatums to be configured to the 100mL aqueous solution, take 100mL deionized waters to be heated to 60 DEG C.So
Salting liquid and aqueous slkali are added dropwise in deionized water altogether with 1.9mL/min speed afterwards, and keeping temperature is constant and 200r/
Min stirring.After dripping, keeping temperature is constant and stirring continues to react 6h.By gained reacting liquid filtering, filtering gained
Solid dries 16h at 110 DEG C, is then ground to powder.
The dimethyl terephthalate (DMT) methanol solution 42g of the 4.05g containing dimethyl terephthalate (DMT) is prepared, adds 0.4005g
Nickel-containing catalyst and 0.8002g copper-based catalysts are activated-have been passivated, under 200 DEG C, Hydrogen Vapor Pressure 4MPa, 700r/min stirring
Hydrogenation reaction 4h.Then temperature rises to 240 DEG C, and Hydrogen Vapor Pressure is adjusted to 8MPa, reacts 4h under 700r/min stirrings.
After reaction night is cooled into room temperature, centrifuges, be separated by filtration catalyst, retort solution, Isosorbide-5-Nitrae-hexamethylene is obtained after purification
Alkane dimethanol product, yield 91.5%.
Embodiment 3：
The water nickel nitrates of 29.05g six and the water aluminum nitrates of 18.75g nine are weighed respectively, are configured to the 100mL aqueous solution, are weighed 9.6g hydrogen-oxygens
Change sodium and 10.6g natrium carbonicum calcinatums, be configured to the 100mL aqueous solution, take 100mL deionized waters to be heated to 70 DEG C.Then with 2mL/
Salting liquid and aqueous slkali are added dropwise in deionized water by min speed altogether, and keeping temperature is constant and 200 r/min stirring.
After dripping, keeping temperature is constant and stirring continues to react 16h.By gained reacting liquid filtering, the solid of filtering gained in 110
16h is dried at DEG C, is then ground to powder.A certain amount of solid powder is taken to be reduced at 110 DEG C and 500 DEG C, in atmosphere of hydrogen
4h is activated, the nitrogen inerting 1h containing 5% air is passed through after being down to room temperature.
Weigh 11.6g nitrate trihydrates copper and 8.2g magnesium nitrate hexahydrates are configured to the 100mL aqueous solution, weigh 3.2g hydroxides
Sodium, 4.3g natrium carbonicum calcinatums are configured to the 100mL aqueous solution, take 120mL deionized waters to be heated to 60 DEG C.Then with 1.8mL/min
Speed salting liquid and aqueous slkali are added dropwise in deionized water altogether, and keeping temperature is constant and 200r/min stirring.It is added dropwise
After complete, keeping temperature is constant and stirring continues to react 6h.By gained reacting liquid filtering, the solid of filtering gained at 110 DEG C
16h is dried, is then ground to powder.
The dimethyl terephthalate (DMT) methanol solution 42.5g of the 4.06g containing dimethyl terephthalate (DMT) is prepared, is added
0.4004g has activated-has been passivated nickel-containing catalyst and 0.8003g copper-based catalysts, in 200 DEG C, Hydrogen Vapor Pressure 4MPa, 700r/min
The lower hydrogenation reaction 4h of stirring.Then temperature rises to 240 DEG C, and Hydrogen Vapor Pressure is adjusted to 8MPa, reacts 4h under 700r/min stirrings.
After reaction night is cooled into room temperature, centrifuges, be separated by filtration catalyst, retort solution, Isosorbide-5-Nitrae-hexamethylene is obtained after purification
Alkane dimethanol product, yield 91%.
Embodiment 4：
The water nickel nitrates of 25.6g six and the water aluminum nitrates of 16.5g nine are weighed respectively, are configured to the 120mL aqueous solution, are weighed 8.5g hydroxides
Sodium and 9.3g natrium carbonicum calcinatums, are configured to the 130mL aqueous solution, take 120mL deionized waters to be heated to 60 DEG C.Then with 2.2mL/
Salting liquid and aqueous slkali are added dropwise in deionized water by min speed altogether, and keeping temperature is constant and 200r/min stirring.Drop
After adding, mixed liquor is placed in water heating kettle, the hydro-thermal reaction 16h at 120 DEG C.Filtered after hydro-thermal reaction is down into room temperature,
The solid for filtering gained dries 16h at 110 DEG C, is then ground to powder.A certain amount of solid powder is taken in 110 DEG C and 500
At DEG C, reduction activation 4h in atmosphere of hydrogen, be passed through the nitrogen inerting 1h containing 5% air after being down to room temperature.
Weigh 9.65g nitrate trihydrates copper and the water chromic nitrates of 15.9g nine are configured to the 100mL aqueous solution, it is anhydrous to weigh 11.66g
Sodium carbonate is configured to the 100mL aqueous solution, takes 100mL deionized waters to be heated to 60 DEG C.Then it is with 1.8mL/min speed that salt is molten
Liquid and aqueous slkali are added dropwise in deionized water altogether, and keeping temperature is constant and 200r/min stirring.After dripping, keeping temperature
Constant and stirring continues to react 4h.By gained reacting liquid filtering, the solid of filtering gained is dried 16h, Ran Houyan at 110 DEG C
Clay into power.
The dimethyl terephthalate (DMT) methanol solution 42g of the 4.01g containing dimethyl terephthalate (DMT) is prepared, adds 0.4003g
Nickel-containing catalyst and 0.8002g copper-based catalysts are activated-have been passivated, under 200 DEG C, Hydrogen Vapor Pressure 4MPa, 700r/min stirring
Hydrogenation reaction 4h.Then temperature rises to 240 DEG C, and Hydrogen Vapor Pressure is adjusted to 8MPa, reacts 4h under 700r/min stirrings.
After reaction night is cooled into room temperature, centrifuges, be separated by filtration catalyst, retort solution, Isosorbide-5-Nitrae-hexamethylene is obtained after purification
Alkane dimethanol product, yield 91.5%.
Claims (7)
1. a kind of method that one kettle way catalytic hydrogenation prepares 1,4-CHDM, it is characterized in that, comprise the following steps：（1）
By nickel-containing catalyst at 300-800 DEG C, room temperature is cooled to after activating 2-8h under hydrogen atmosphere, is placed in air and is passivated, obtain
To activation-passivation nickel-containing catalyst；（2）Cu-contained catalyst and activation-passivation nickel-containing catalyst are mixed, are placed in terephthalic acid (TPA)
In the mixed liquor of dimethyl ester and alcohols solvent, hydrogenation reaction is carried out in hydrogenation reaction kettle；（3）By reaction product through be separated,
Distillation, purification, obtain product.
2. the method that one kettle way catalytic hydrogenation according to claim 1 prepares 1,4-CHDM, it is characterised in that：
Step（1）In, nickel-containing catalyst is that mass ratio is 50-90%：10-50% nickel oxide and the mixture of auxiliary agent, auxiliary agent are oxidation
One or more in magnesium, aluminum oxide, manganese oxide, chrome green, tin oxide, lanthanum sesquioxide.
3. the method that one kettle way catalytic hydrogenation according to claim 1 prepares 1,4-CHDM, it is characterised in that：
Step（1）In, after nickel-containing catalyst activation cooling, it is placed in content 0.1-5% air and is passivated 10-100min.
4. the method that one kettle way catalytic hydrogenation according to claim 1 prepares 1,4-CHDM, it is characterised in that：
Step（2）In, Cu-contained catalyst is that mass ratio is 10-80%：20-90% cupric oxide and the mixture of auxiliary agent, auxiliary agent are oxidation
One or more in magnesium, aluminum oxide, manganese oxide, chrome green, zinc oxide and tin oxide.
5. the method that one kettle way catalytic hydrogenation according to claim 1 prepares 1,4-CHDM, it is characterised in that：
Step（2）In, hydrogenation reaction is carried out in two steps, and first step reaction temperature is 200-400 DEG C, mixing speed 200-1000r/
Min, pressure 2-10MPa, reaction time 2-10h；After end, temperature rises to 200-400 DEG C and starts second step reaction, stirring
Speed is 200-1000r/min, and pressure 2-10MPa, the reaction time is 2-10 hours.
6. the method that one kettle way catalytic hydrogenation according to claim 1 or 2 prepares 1,4-CHDM, its feature exist
In：Step（1）In, the preparation method of nickel-containing catalyst comprises the following steps：1. by soluble nickel salt and the salt of formation auxiliary agent
Mixing salt solution is configured to, nickel salt mass concentration is 2-10%, and the salt mass concentration for forming auxiliary agent is 1-5%；2. the bodies such as configuration
The sodium carbonate of product ratio and the mixed ammonium/alkali solutions of sodium hydroxide, wherein, the mass concentration of sodium hydroxide is dense for nickel salt and auxiliary agent salt
1.5-2 times of degree, sodium carbonate mass concentration are the 10-50% of sodium hydroxide；3. by volume mixture salting liquid volume 30-150%'s
After deionized water is heated to 50-90 DEG C, mixing salt solution and mixed ammonium/alkali solutions are added dropwise, rate of addition 0.2-5mL/min,
Mixing speed is 50-300r/min；4. after being added dropwise, identical mixing speed 4-24h is maintained at 50-90 DEG C；5. obtain
Turbid solution filters, and the solid filtered out dries 5-24h at 50-200 DEG C, is ground after drying；6. by the solid powder after grinding
It is placed in Muffle furnace at 400-800 DEG C and is calcined, obtains nickel-containing catalyst.
7. the method that the one kettle way catalytic hydrogenation according to claim 1 or 4 prepares 1,4-CHDM, its feature exist
In：Step（2）In, the preparation method of Cu-contained catalyst comprises the following steps：1. by soluble copper salt and the salt of formation auxiliary agent
Mixing salt solution is configured to, mantoquita mass concentration is 1-10%, and the salt mass concentration for forming auxiliary agent is 1-20%；2. the bodies such as configuration
The sodium carbonate of product ratio and the mixed ammonium/alkali solutions or aqueous sodium carbonate of sodium hydroxide, wherein, the mass concentration of sodium hydroxide is copper
1.5-3 times of salt and auxiliary agent salt density, sodium carbonate mass concentration are the 10-50% of sodium hydroxide, or, aqueous sodium carbonate
In, the mass concentration of ammonium carbonate is 3-4 times of mantoquita and auxiliary agent salt density；3. by volume mixture salting liquid volume 30-150%
Deionized water be heated to 50-90 DEG C after, be added dropwise mixing salt solution and mixed ammonium/alkali solutions or aqueous sodium carbonate, speed be added dropwise
Spend for 0.2-5mL/min, mixing speed 50-300r/min；4. after being added dropwise, identical stirring speed is maintained at 50-90 DEG C
Spend 4-24h；5. obtained turbid solution filtering, the solid filtered out are dried 5-24h at 50-200 DEG C, ground after drying；6. will
Solid powder after grinding is placed in Muffle furnace at 400-800 DEG C and is calcined, and obtains Cu-contained catalyst.
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| CN113248346A (en) * | 2021-05-26 | 2021-08-13 | 华东师范大学 | Preparation method of 1, 4-cyclohexanedimethanol |
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| CN102658146A (en) * | 2012-03-30 | 2012-09-12 | 中国科学院山西煤炭化学研究所 | Catalyst for production of cyclohexylcarboxylate by phenylcarboxylate hydrogenation and its preparation method and use |
| CN105688915A (en) * | 2016-04-13 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Dual-function catalyst for hydrogenating benzene rings and reducing carbonyl, preparation of dual-function catalyst and application thereof |
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| CN1398841A (en) * | 2001-04-13 | 2003-02-26 | 中国石化集团天津石油化工公司 | Catalyst for hydrogenating 1,4-dimethyl hexahydroterephthalate to produce 1,4-dimethyl cyclohexanol and its prepn process |
| CN102658146A (en) * | 2012-03-30 | 2012-09-12 | 中国科学院山西煤炭化学研究所 | Catalyst for production of cyclohexylcarboxylate by phenylcarboxylate hydrogenation and its preparation method and use |
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| CN113248346A (en) * | 2021-05-26 | 2021-08-13 | 华东师范大学 | Preparation method of 1, 4-cyclohexanedimethanol |
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