CN111450836A - Method for synthesizing p-hydroxybenzyl alcohol - Google Patents
Method for synthesizing p-hydroxybenzyl alcohol Download PDFInfo
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- CN111450836A CN111450836A CN202010282714.1A CN202010282714A CN111450836A CN 111450836 A CN111450836 A CN 111450836A CN 202010282714 A CN202010282714 A CN 202010282714A CN 111450836 A CN111450836 A CN 111450836A
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- hydroxybenzyl alcohol
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- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- -1 p-hydroxybenzyl aldehyde Chemical class 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 4
- 239000010439 graphite Substances 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 165
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 76
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 33
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 33
- 238000000926 separation method Methods 0.000 description 30
- 239000007795 chemical reaction product Substances 0.000 description 29
- 238000004817 gas chromatography Methods 0.000 description 28
- 238000003756 stirring Methods 0.000 description 23
- 229910052698 phosphorus Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 241000305491 Gastrodia elata Species 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000006909 anti-apoptosis Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 210000001130 astrocyte Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000000971 hippocampal effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010805 inorganic waste Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000002569 neuron Anatomy 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
Classifications
-
- 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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/83—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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/043—Noble metals
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
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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
- C07C29/14—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
Abstract
The invention discloses a method for synthesizing p-hydroxybenzyl alcohol, p-hydroxybenzyl aldehyde and hydrogen are synthesized into p-hydroxybenzyl alcohol in one step under the action of a catalyst; the catalyst comprises a carrier, an active component, an auxiliary agent and a functional element P, wherein the carrier is SiO2、Al2O3Active carbon, diatomite, molecular sieve, graphite, carbon nano tube and titanium oxideOr one or more of zirconia, the active component is one or more of Fe, Co, Ni, Cu, Au, Ag, Pt, Pd, Ir and Rh, the auxiliary agent is one or more of Ca, Ce, L a, Mo, Zr and Zn, the active component is 1-50 wt%, the auxiliary agent is 0.01-15 wt% and the functional element P is 0-15 wt%.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for synthesizing p-hydroxybenzyl alcohol.
Background
P-hydroxybenzyl alcohol (molecular formula: C7H8O2) is named as follows: 4-hydroxybenzyl alcohol is an important medical intermediate, and is mainly used for synthesizing medicines and spices. The p-hydroxybenzyl alcohol is also one of the effective components of the gastrodia elata and is a main metabolite of the gastrodia elata in a human body. It has been found that p-hydroxybenzyl alcohol has various biological protection functions of antioxidation, anti-inflammation, anti-cytotoxicity, anti-apoptosis, etc., and can reduce the death of hippocampal neuronal cells, and reduce the activation degree of astrocytes, etc. At present, the preparation process of the p-hydroxybenzyl alcohol mainly comprises two processes: the first method is to extract rhizoma gastrodiae by using an organic solvent, which consumes a large amount of solvent, and has low efficiency and high cost; the second method is to synthesize p-hydroxybenzyl alcohol by using reducing reagents such as sodium borohydride and potassium borohydride by a chemical reduction method, and a large amount of inorganic waste is generated in the production process, so that the environment is polluted, and the large-scale production is not facilitated.
The hydrogen is used as a reducing agent, and the aldehyde is reduced in the presence of a catalyst to prepare the alcohol, so that the prepared product has high purity, and the only byproduct is water, thereby conforming to the current green and environment-friendly concept. At present, the industrial research on the catalytic reduction synthesis of the p-hydroxybenzaldehyde into the p-hydroxybenzaldehyde is less at home and abroad, and the key for solving the current problems is how to research the process for synthesizing the p-hydroxybenzaldehyde into the p-hydroxybenzaldehyde through the catalytic hydrogenation with high activity, high selectivity, high stability and low price.
Disclosure of Invention
The present invention aims at providing a method for synthesizing p-hydroxybenzyl alcohol to solve the defects of the prior art.
The invention adopts the following technical scheme:
a method for synthesizing p-hydroxybenzyl alcohol is characterized in that p-hydroxybenzyl alcohol and hydrogen are synthesized into the p-hydroxybenzyl alcohol in one step under the action of a supported high-dispersion heterogeneous catalyst;
the load type high-dispersion heterogeneous catalyst comprises a carrier, an active component, an auxiliary agent and a functional element P, wherein the carrier is SiO2、Al2O3The catalyst comprises one or more of active carbon, diatomite, a molecular sieve, graphite, a carbon nano tube, titanium oxide or zirconium oxide, wherein the active component is one or more of Fe, Co, Ni, Cu, Au, Ag, Pt, Pd, Ir and Rh, the auxiliary agent is one or more of Ca, Ce, L a, Mo, Zr and Zn, the mass of the active component is 1-50% of the mass of the catalyst, the mass of the auxiliary agent is 0.01-15% of the mass of the catalyst, the mass of the functional element P is 0-15% of the mass of the catalyst, and the balance is a carrier.
Furthermore, the mass of the active component in the supported high-dispersion heterogeneous catalyst is 10-25% of the mass of the catalyst, the mass of the auxiliary agent is 0.1-5% of the mass of the catalyst, the mass of the functional element P is 0.01-10% of the mass of the catalyst, and the balance is the carrier.
Further, the supported high-dispersion heterogeneous catalyst is prepared by the following steps:
(1) dissolving the active component soluble salt and the auxiliary agent precursor soluble salt in the formula ratio in deionized water to obtain a salt solution;
(2) adding the carriers in the formula amount into the salt solution obtained in the step (1), and uniformly mixing to obtain a mixed solution;
(3) drying the mixed solution obtained in the step (2) at the temperature of 30-40 ℃ for 5-48 h;
(4) drying the product obtained in the step (3) for 10-30 h at 110-130 ℃;
(5) roasting the product obtained in the step (4) for 2-38 hours at the temperature of 300-1000 ℃;
(6) mixing the product obtained in the step (5) with (NH) in formula amount4)2HPO4Or NaH2PO2Mechanically mixing, and roasting at 500-800 deg.C for 5-20 hr in inert gas atmosphere to obtainTo the supported highly dispersed heterogeneous catalyst.
Further, the prepared supported high-dispersion heterogeneous catalyst needs hydrogen to be reduced before use, the reduction temperature is 100-800 ℃, the reduction time is 2-10 h, and the gas space velocity is 500-2000 h-1。
Further, the reduction temperature is 350-650 ℃, and the air space velocity is 800-1500 h-1。
Furthermore, a solvent is used or not used in the one-step synthesis of the p-hydroxybenzyl alcohol, the mass concentration of the p-hydroxybenzyl aldehyde serving as a reaction raw material is 1-100%, and the solvent is one or more of methanol, ethanol, propanol, N-butanol, N-dimethylformamide, N-dimethylacetamide, ethyl acetate, butanone, N-heptane, N-hexane, N-pentane, cyclohexane, cyclopentane, isooctane, benzene, toluene, xylene, tetrahydrofuran, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloroethane or pyridine.
Furthermore, the mass concentration of the p-hydroxybenzaldehyde serving as the reaction raw material is 5-30%.
Further, the reaction temperature of the one-step synthesis of the p-hydroxybenzyl alcohol is 10-180 ℃, the reaction pressure is 0.5-7 MPa, and the reaction time is 30-900 min.
Further, the reaction temperature is 20-120 ℃, the reaction pressure is 1-5 MPa, and the reaction time is 60-600 min.
Further, the p-hydroxybenzyl alcohol is further synthesized and then is sequentially subjected to separation, distillation or rectification post-treatment to obtain the p-hydroxybenzyl alcohol.
The invention has the beneficial effects that:
the invention can obtain high conversion rate of p-hydroxybenzaldehyde and high selectivity of p-hydroxybenzyl alcohol under mild conditions, has simple reaction process, good product quality and easy separation, and is suitable for industrial production. The supported high-dispersion heterogeneous catalyst is adopted to replace the traditional reducing reagent to prepare the p-hydroxybenzyl alcohol by the reduction of the p-hydroxybenzaldehyde, the high catalytic activity (99.8%) and the high selectivity (98.7%) are shown, and the method is in line with the current green chemical development route. Meanwhile, the catalyst has long service life, and is stable after being recycled for 6 times.
Detailed Description
The present invention will be further explained with reference to examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
A process for synthesizing p-hydroxy-benzaldehyde features that under the action of load-type high-dispersity heterogeneous catalyst, p-hydroxy-benzaldehyde and hydrogen are used to synthesize p-hydroxy-benzyl alcohol in one step.
The load type high-dispersion heterogeneous catalyst comprises a carrier, an active component, an auxiliary agent and a functional element P, wherein the carrier is SiO2、Al2O3The catalyst comprises one or more of active carbon, diatomite, a molecular sieve, graphite, a carbon nano tube, titanium oxide or zirconium oxide, wherein the active component is one or more of Fe, Co, Ni, Cu, Au, Ag, Pt, Pd, Ir and Rh, the auxiliary agent is one or more of Ca, Ce, L a, Mo, Zr and Zn, the mass of the active component is 1-50% of the mass of the catalyst, the mass of the auxiliary agent is 0.01-15% of the mass of the catalyst, the mass of the functional element P is 0-15% of the mass of the catalyst, and the balance is a carrier, preferably, the mass of the active component is 10-25% of the mass of the catalyst, the mass of the auxiliary agent is 0.1-5% of the mass of the catalyst, the mass of the functional element P is 0.01-10% of the mass of the catalyst, and the balance is the carrier.
The supported high-dispersion heterogeneous catalyst is prepared by the following steps:
(1) dissolving the active component soluble salt and the auxiliary agent precursor soluble salt in the formula ratio in deionized water to obtain a salt solution;
(2) adding the carriers in the formula amount into the salt solution obtained in the step (1), and uniformly mixing to obtain a mixed solution;
(3) drying the mixed solution obtained in the step (2) at the temperature of 30-40 ℃ for 5-48 h;
(4) drying the product obtained in the step (3) for 10-30 h at 110-130 ℃;
(5) roasting the product obtained in the step (4) for 2-38 hours at the temperature of 300-1000 ℃;
(6) mixing the product obtained in the step (5) with (NH) in formula amount4)2HPO4Or NaH2PO2Mechanically mixing, and roasting for 5-20 h at 500-800 ℃ in an inert gas atmosphere to obtain the supported high-dispersion heterogeneous catalyst.
The prepared supported high-dispersion heterogeneous catalyst needs hydrogen to be reduced before use, the reduction temperature is 100-800 ℃, the preferred reduction time is 350-650 ℃, the reduction time is 2-10 h, and the gas space velocity is 500-2000 h-1Preferably 800 to 1500h-1。
The method comprises the steps of using a solvent or not using the solvent in one-step synthesis of p-hydroxybenzyl alcohol, wherein the mass concentration of p-hydroxybenzyl aldehyde serving as a reaction raw material is 1-100%, preferably 5-30%, and the solvent is one or more of methanol, ethanol, propanol, N-butanol, N-dimethylformamide, N-dimethylacetamide, ethyl acetate, butanone, N-heptane, N-hexane, N-pentane, cyclohexane, cyclopentane, isooctane, benzene, toluene, xylene, tetrahydrofuran, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloroethane or pyridine.
The one-step synthesis reaction temperature of the p-hydroxybenzyl alcohol is 10-180 ℃, and the preferable temperature is 20-120 ℃; the reaction pressure is 0.5-7 MPa, preferably 1-5 MPa; the reaction time is 30-900 min, preferably 60-600 min.
After one-step synthesis, the p-hydroxybenzyl alcohol is sequentially subjected to separation, distillation or rectification post-treatment to obtain the p-hydroxybenzyl alcohol.
Example 1
(1) 2.7 part of (NO) 2.7gNi3)2·6H2O and 1.1g (NH)4)6Mo7O24·4H2O is dissolved in 16g of deionized water;
(2) taking 8.3g of SiO2Adding the mixture into the salt solution obtained in the step (1), and uniformly mixing to obtain a mixed solution;
(3) drying the mixed solution in the step (2) at 35 ℃ for 24 hours;
(4) drying the product obtained in the step (3) at 120 ℃ for 10 hours;
(5) roasting the product obtained in the step (4) for 2 hours at 350 ℃;
(6)、mixing the product obtained in the step (5) with 0.3g of (NH)4)2HPO4Mechanically mixing, and roasting at 800 deg.C for 10 hr in nitrogen atmosphere to obtain catalyst 5.7% Ni-6.3% Mo-0.7% P/SiO2。
Before the catalyst is used, hydrogen is needed for reduction, the reduction temperature is 500 ℃, the reduction time is 6h, and the gas space velocity is 900h-1。
Changing the kinds and the amounts of soluble salt of the active component of the catalyst and soluble salt of the precursor of the auxiliary agent, the carrier, and (NH)4)2HPO4Or NaH2PO2In amounts such that the catalysts used in the other examples below can be prepared.
Example 2
The reaction was carried out in a 50m L autoclave, to which 15ml of methanol, 1.0g of P-hydroxybenzaldehyde and 5% of Ni-1% of Mo-0.5% of P/SiO were added20.4g of catalyst, 1.0MPa of hydrogen gas is filled in, magnetons are put in a reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 30 ℃, and then the separation and rectification post-treatment are carried out. The reaction product was analyzed by gas chromatography, and the conversion of p-tolualdehyde was 13.9% and the selectivity to p-methylbenzyl alcohol was 67.9%.
Example 3
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 10 percent of Ni-1 percent of Mo-0.5 percent of P/SiO are added20.4g of catalyst, 1.0MPa of hydrogen gas is filled in, magnetons are put in a reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 35 ℃, and then the separation and rectification post-treatment are carried out. The reaction product was analyzed by gas chromatography, and the conversion of p-tolualdehyde was 87.9% and the selectivity to p-methylbenzyl alcohol was 93.7%.
Example 4
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 20 percent of Ni-2 percent of Mo-0.5 percent of P/SiO are added20.4g of catalyst, 1.0MPa of hydrogen gas is filled in, magnetons are put in a reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 40 ℃, and then the separation and rectification post-treatment are carried out. The reaction product is analyzed by gas chromatography, and the conversion rate of p-tolualdehyde is98.8 percent and the selectivity of the p-methyl benzyl alcohol is 96.7 percent.
Example 5
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 20 percent of Ni-2 percent of Mo-0.5 percent of P/SiO are added20.4g of catalyst, 1.0MPa of hydrogen gas is filled in, magnetons are put in a reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 50 ℃, and then the separation and rectification post-treatment are carried out. The reaction product was analyzed by gas chromatography, and the conversion of p-tolualdehyde was 99.9% and the selectivity to p-methylbenzyl alcohol was 91.8%.
Example 6
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 10 percent of Cu-1 percent of L a-0.5 percent of P/gamma Al are added2O30.4g of catalyst, 1.0MPa of hydrogen gas is filled in, magnetons are put in a reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 60 ℃, and then the separation and rectification post-treatment are carried out. The reaction product was analyzed by gas chromatography, and the conversion of p-tolualdehyde was 99.9% and the selectivity to p-methylbenzyl alcohol was 87.4%.
Example 7
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 10 percent of Cu-1 percent of L a-0.5 percent of P/gamma Al are added2O30.4g of catalyst, 1.0MPa of hydrogen gas is filled in, magnetons are put in a reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 60 ℃, and then the separation and rectification post-treatment are carried out. The reaction product was analyzed by gas chromatography, and the conversion of p-tolualdehyde was 99.9% and the selectivity to p-methylbenzyl alcohol was 77.3%.
Example 8
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 15 percent of Cu is added, 0.5 percent of L a is added, and 0.5 percent of P/gamma Al is added2O30.4g of catalyst, 1.0MPa of hydrogen gas is filled in, magnetons are put in a reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 70 ℃, and then the separation and rectification post-treatment are carried out. The reaction product is analyzed by gas chromatography, the conversion rate of p-tolualdehyde is 99.9 percent, and the selectivity of p-methylbenzyl alcohol is52.7％。
Example 9
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 25 percent of Cu-0.5 percent of L a-0.5 percent of P/gamma Al are added2O30.1g of catalyst, charging 1.0MPa hydrogen, placing magnetons in a reaction kettle, stirring by using a magnetic stirrer, reacting for 120min at 40 ℃, and then carrying out separation and rectification post-treatment. The reaction product was analyzed by gas chromatography, and the conversion of p-tolualdehyde was 68.9%, and the selectivity to p-methylbenzyl alcohol was 77.2%.
Example 10
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 5 percent of Cu-0.5 percent of L a-0.5 percent of P/gamma Al are added2O30.2g of catalyst, charging 1.0MPa hydrogen, placing magnetons in a reaction kettle, stirring by using a magnetic stirrer, reacting for 120min at 40 ℃, and then carrying out separation and rectification post-treatment. The reaction product was analyzed by gas chromatography, and the conversion of p-tolualdehyde was 75.3% and the selectivity to p-methylbenzyl alcohol was 85.1%.
Example 11
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 5% of Cu is added, 0.5% of L a is added, 0.5% of P/diatomite catalyst is added, 1.0MPa of hydrogen is charged, magnetons are placed into the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 91.4%, and the selectivity of P-methylbenzyl alcohol is 91.5%.
Example 12
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 10% of Cu-1% of L a-0.5% of P/diatomite catalyst is added into the kettle, 1.0MPa of hydrogen is charged into the kettle, magnetons are placed into the reaction kettle and stirred by a magnetic stirrer, the reaction is carried out for 120min at the temperature of 40 ℃, and then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, so that the conversion rate of P-tolualdehyde is 98.7%, and the selectivity of P-methylbenzyl alcohol is 94.5%.
Example 13
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 10% of Cu-2% of L a-0.5% of P/diatomite catalyst is added into the kettle, 1.0MPa of hydrogen is charged into the kettle, magnetons are placed into the reaction kettle and stirred by a magnetic stirrer, the reaction is carried out for 120min at the temperature of 40 ℃, and then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, so that the conversion rate of P-tolualdehyde is 99.7%, and the selectivity of P-methylbenzyl alcohol is 73.5%.
Example 14
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 15% of Cu-2% of L a-0.5% of P/diatomite catalyst is added into the kettle, 0.5MPa of hydrogen is charged into the kettle, magnetons are placed into the reaction kettle and stirred by a magnetic stirrer, the reaction is carried out for 120min at the temperature of 40 ℃, and then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, so that the conversion rate of P-tolualdehyde is 84.6%, and the selectivity of P-methylbenzyl alcohol is 71.9%.
Example 15
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 20% of Cu-2% of L a-0.5% of P/diatomite catalyst is added into the kettle, 1.5MPa of hydrogen is charged into the kettle, magnetons are placed into the reaction kettle and stirred by a magnetic stirrer, the reaction is carried out for 120min at the temperature of 40 ℃, and then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, so that the conversion rate of P-tolualdehyde is 87.6%, and the selectivity of P-methylbenzyl alcohol is 82.3%.
Example 16
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 20% of Cu-3% of L a-0.5% of P/diatomite catalyst is added into the kettle, 0.4g of hydrogen with 2.0MPa is filled into the kettle, magnetons are placed into the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 40 ℃, and then separation and rectification post-treatment are carried out, the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 99.8%, and the selectivity of P-methylbenzyl alcohol is 98.7%.
Example 17
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 20% of Cu-3% of L a-0.5% of P/MCM-41 catalyst is added into the kettle, 3.0MPa of hydrogen is filled into the kettle, magnetons are put into the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 98.9%, and the selectivity of P-methylbenzyl alcohol is 91.6%.
Example 18
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 0.4g of 10% Rh-3% Zr-0.5% P/MCM-41 catalyst is added, 4.0MPa hydrogen is charged, magnetons are placed in the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 98.4%, and the selectivity of P-methylbenzyl alcohol is 88.1%.
Example 19
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 0.4g of 15% Rh-1% Zr-0.5% P/MCM-41 catalyst is added, 4.0MPa hydrogen is charged, magnetons are placed in the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 99.1%, and the selectivity of P-methylbenzyl alcohol is 87.6%.
Example 20
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 0.4g of 5% Rh-2% Zr-0.5% P/MCM-41 catalyst is added, 2.0MPa hydrogen is charged, magnetons are placed in the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 60min at the temperature of 40 ℃, and then separation and rectification post-treatment are carried out, the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 87.3%, and the selectivity of P-methylbenzyl alcohol is 84.6%.
Example 21
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 0.4g of 5% Fe-2% Zr-0.5% P/active carbon catalyst is added, 2.0MPa hydrogen is charged, magnetons are placed in the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 200min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 97.3%, and the selectivity of P-methylbenzyl alcohol is 95.7%.
Example 22
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 0.4g of 10% Fe-2% Zr-0.5% P/activated carbon catalyst is added, 2.0MPa hydrogen is charged, magnetons are placed in the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 300min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 98.5%, and the selectivity of P-methylbenzyl alcohol is 94.6%.
Example 23
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 0.4g of 20% Fe-4% Zr-0.5% P/activated carbon catalyst is added, 2.0MPa hydrogen is charged, magnetons are placed in the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 300min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 98.5%, and the selectivity of P-methylbenzyl alcohol is 94.6%.
Example 24
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 0.4g of 30% Fe-3% Zr-0.5% P/activated carbon catalyst is added, 2.0MPa hydrogen is charged, magnetons are placed in the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 400min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 98.7%, and the selectivity of P-methylbenzyl alcohol is 91.4%.
Example 25
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 5% of Fe-1% of Ca and 0.5% of P/active carbon catalyst are added in 0.4g, 2.0MPa of hydrogen is charged in the kettle, magnetons are put in the reaction kettle and stirred by a magnetic stirrer, the reaction is carried out for 500min at 40 ℃, and then the reaction product is separated and rectified for post-treatment, and the gas chromatography analysis of the reaction product shows that the conversion rate of P-tolualdehyde is 98.2% and the selectivity of P-methylbenzyl alcohol is 87.3%.
Example 26
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 0.4g of 10% Fe-1% Ca-0.5% P/activated carbon catalyst is added, 2.0MPa hydrogen is filled, magnetons are placed into the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 500min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 98.4%, and the selectivity of P-methylbenzyl alcohol is 82.7%.
Example 27
The reaction is carried out in a 50m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added in the kettle, 15% of Fe-2% of Ca and 0.5% of P/activated carbon catalyst are added in the kettle, 2.0MPa of hydrogen is charged in the kettle, magnetons are placed in the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 600min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 98.9%, and the selectivity of P-methylbenzyl alcohol is 81.3%.
Example 28
The reaction is carried out in a 100m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 20% of Fe-3% of Ca and 0.5% of P/activated carbon catalyst are added into the kettle, 2.0MPa of hydrogen is charged into the kettle, magnetons are placed into the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 99.1%, and the selectivity of P-methylbenzyl alcohol is 97.3%.
Example 29
The reaction is carried out in a 30m L high-pressure reaction kettle, 15ml of methanol and 1.0g of P-hydroxybenzaldehyde are added into the kettle, 20% Ir-1% Ca-0.5% P/active carbon catalyst 0.4g is added, 2.0MPa hydrogen is filled, magnetons are placed into the reaction kettle, a magnetic stirrer is used for stirring, the reaction is carried out for 120min at the temperature of 40 ℃, then separation and rectification post-treatment are carried out, and the reaction product is analyzed by gas chromatography, the conversion rate of P-tolualdehyde is 97.4%, and the selectivity of P-methylbenzyl alcohol is 95.7%.
Example 30
The catalyst reacted in example 29 was centrifuged in a centrifuge and dried in a vacuum oven at 110 ℃.
The reaction materials, reaction process and analysis procedure were the same as in example 29, except that the conversion of p-tolualdehyde was 97.1% and the selectivity of p-methylbenzyl alcohol was 94.4%.
Example 31
The catalyst reacted in example 30 was centrifuged by a centrifuge and dried in a vacuum oven at 110 ℃.
The reaction materials, reaction process and analysis procedure were the same as in example 29, except that the conversion of p-tolualdehyde was 96.5% and the selectivity of p-methylbenzyl alcohol was 93.8%.
Example 32
The catalyst reacted in example 31 was centrifuged in a centrifuge and dried in a vacuum oven at 110 ℃.
The reaction materials, reaction process and analysis procedure were the same as in example 29, except that the conversion of p-tolualdehyde was 95.9% and the selectivity of p-methylbenzyl alcohol was 93.2%.
Example 33
The catalyst reacted in example 32 was centrifuged by a centrifuge and dried in a vacuum oven at 110 ℃.
The reaction materials, reaction process and analysis procedure were the same as in example 29, except that the conversion of p-tolualdehyde was 95.1% and the selectivity for p-methylbenzyl alcohol was 92.9%.
Example 34
The catalyst reacted in example 33 was centrifuged and separated by a centrifuge and dried in a vacuum oven at 110 ℃.
The reaction materials, reaction process and analysis procedure were the same as in example 29, except that the conversion of p-tolualdehyde was 94.9% and the selectivity of p-methylbenzyl alcohol was 93.1%.
Claims (10)
1. A method for synthesizing p-hydroxybenzyl alcohol is characterized in that p-hydroxybenzyl alcohol and hydrogen are synthesized into the p-hydroxybenzyl alcohol in one step under the action of a supported high-dispersion heterogeneous catalyst;
the load type high-dispersion heterogeneous catalyst comprises a carrier, an active component, an auxiliary agent and a functional element P, wherein the carrier is SiO2、Al2O3The catalyst comprises one or more of active carbon, diatomite, a molecular sieve, graphite, a carbon nano tube, titanium oxide or zirconium oxide, wherein the active component is one or more of Fe, Co, Ni, Cu, Au, Ag, Pt, Pd, Ir and Rh, the auxiliary agent is one or more of Ca, Ce, L a, Mo, Zr and Zn, the mass of the active component is 1-50% of the mass of the catalyst, the mass of the auxiliary agent is 0.01-15% of the mass of the catalyst, the mass of the functional element P is 0-15% of the mass of the catalyst, and the balance is a carrier.
2. The method for synthesizing P-hydroxybenzyl alcohol according to claim 1, characterized in that the mass of the active component in the supported high-dispersion heterogeneous catalyst is 10-25% of the mass of the catalyst, the mass of the auxiliary agent is 0.1-5% of the mass of the catalyst, the mass of the functional element P is 0.01-10% of the mass of the catalyst, and the balance is the carrier.
3. The process for the synthesis of p-hydroxybenzyl alcohols according to claim 1 or 2, characterized in that the supported highly dispersed heterogeneous catalyst is prepared by the following steps:
(1) dissolving the active component soluble salt and the auxiliary agent precursor soluble salt in the formula ratio in deionized water to obtain a salt solution;
(2) adding the carriers in the formula amount into the salt solution obtained in the step (1), and uniformly mixing to obtain a mixed solution;
(3) drying the mixed solution obtained in the step (2) at the temperature of 30-40 ℃ for 5-48 h;
(4) drying the product obtained in the step (3) for 10-30 h at 110-130 ℃;
(5) roasting the product obtained in the step (4) for 2-38 hours at the temperature of 300-1000 ℃;
(6) mixing the product obtained in the step (5) with (NH) in formula amount4)2HPO4Or NaH2PO2Mechanically mixing, and roasting at 500-800 ℃ in an inert gas atmosphere for 5-20 h to obtainThe supported highly dispersed heterogeneous catalyst.
4. The method for synthesizing p-hydroxybenzyl alcohol according to claim 3, wherein the prepared supported high-dispersion heterogeneous catalyst needs hydrogen reduction before use, the reduction temperature is 100-800 ℃, the reduction time is 2-10 h, and the gas space velocity is 500-2000 h-1。
5. The method for synthesizing p-hydroxybenzyl alcohol according to claim 4, wherein the reduction temperature is 350-650 ℃, and the gas space velocity is 800-1500 h-1。
6. The method for synthesizing p-hydroxybenzyl alcohol according to claim 1 or 2, characterized in that the p-hydroxybenzyl alcohol is synthesized in one step with or without solvent, the mass concentration of p-hydroxybenzyl alcohol is 1% -100%, and the solvent is one or more of methanol, ethanol, propanol, N-butanol, N-dimethylformamide, N-dimethylacetamide, ethyl acetate, butanone, N-heptane, N-hexane, N-pentane, cyclohexane, cyclopentane, isooctane, benzene, toluene, xylene, tetrahydrofuran, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloroethane or pyridine.
7. The method for synthesizing p-hydroxybenzyl alcohol according to claim 6, wherein the mass concentration of p-hydroxybenzaldehyde as a raw material is 5-30%.
8. The method for synthesizing p-hydroxybenzyl alcohol according to claim 1 or 2, wherein the one-step synthesis reaction temperature of p-hydroxybenzyl alcohol is 10-180 ℃, the reaction pressure is 0.5-7 MPa, and the reaction time is 30-900 min.
9. The method for synthesizing p-hydroxybenzyl alcohol according to claim 8, wherein the reaction temperature is 20-120 ℃, the reaction pressure is 1-5 MPa, and the reaction time is 60-600 min.
10. The method for synthesizing p-hydroxybenzyl alcohol according to claim 1 or 2, characterized in that the p-hydroxybenzyl alcohol is obtained after one-step synthesis by separating, distilling or rectifying the post-treatment.
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