CN115806467A - Process for preparing 1, 3-propanediol - Google Patents
Process for preparing 1, 3-propanediol Download PDFInfo
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- CN115806467A CN115806467A CN202111075132.7A CN202111075132A CN115806467A CN 115806467 A CN115806467 A CN 115806467A CN 202111075132 A CN202111075132 A CN 202111075132A CN 115806467 A CN115806467 A CN 115806467A
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- China
- Prior art keywords
- catalyst
- acrolein
- propanediol
- acetoxy
- acetoxypropionaldehyde
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 52
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 title claims abstract description 44
- 229940035437 1,3-propanediol Drugs 0.000 title claims abstract description 44
- 229920000166 polytrimethylene carbonate Polymers 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- PRSPLAWXBFRHKV-UHFFFAOYSA-N 3-oxopropyl acetate Chemical compound CC(=O)OCCC=O PRSPLAWXBFRHKV-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 49
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 26
- DOUBAFNWVFAWEC-UHFFFAOYSA-N 3-hydroxypropyl acetate Chemical compound CC(=O)OCCCO DOUBAFNWVFAWEC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 80
- 238000002360 preparation method Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- 239000003112 inhibitor Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 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 description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-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 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- 239000000203 mixture Substances 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- 229960000583 acetic acid Drugs 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000010813 internal standard method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- -1 polytrimethylene terephthalate Polymers 0.000 description 4
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- WTEICVOERQQONI-UHFFFAOYSA-N [C].C1CO1 Chemical compound [C].C1CO1 WTEICVOERQQONI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention particularly relates to a method for preparing 1, 3-propylene glycol. A process for preparing 1, 3-propanediol is disclosed. The method comprises the following steps: (1) In the presence of a solvent and a ruthenium catalyst, carrying out hydrogenation reaction on 3-acetoxy propionaldehyde to obtain 3-acetoxy propanol; (2) hydrolyzing the 3-acetoxy propanol; wherein the ruthenium catalyst comprises a carrier and an active component ruthenium loaded on the carrier. The method of the invention can improve the yield of the 1, 3-propanediol.
Description
Technical Field
The invention relates to a method for preparing 1, 3-propylene glycol.
Background
1, 3-propanediol (1, 3-PDO) is a main raw material for producing polytrimethylene terephthalate (PTT) and is also a raw material for synthesizing a plasticizer, a detergent, a preservative and an emulsifier. In particular, the PTT fiber with excellent performance has the performance of polyethylene terephthalate (PET), has good rebound resilience and pollution resistance of nylon, and is widely applied to the fields of carpets, engineering plastics, clothing fabrics and the like. The industrial production of 1, 3-propanediol worldwide has been low and expensive for a long time, which has hindered the development of the polytrimethylene terephthalate industry.
The current global production of 1,3-PDO is basically monopolized by Degussa, U.S. Shell and DuPont, germany. Three companies each employ a different technical route. The Degussa company uses the acrolein hydrohydrogenation process, the Shell company uses the ethylene oxide carbonylation process, and both companies are "petrochemical routes". DuPont company adopts its own innovative bioengineering method. Because only DuPont uses the fermentation method of transgenic engineering bacteria to produce 1, 3-propanediol in the world at present, duPont strictly protects the related technology and process through patent application, and forms a high technical monopoly.
The technical route of the existing acrolein hydration hydrogenation method is as follows: 3-hydroxypropanal (3-HPA) is prepared by hydration of acrolein using an inorganic acid as a catalyst, but has a low yield and poor selectivity, accompanied by occurrence of side reactions. In order to solve the problems, degussa company adopts weak acid ion exchange resin as a catalyst to improve the selectivity of 3-HPA, and the conversion rate and selectivity of acrolein hydration can be greatly improved. The Degussa company and the Hoechst company have successively studied and developed an inorganic supported acid catalyst.
The ethylene oxide carbon-based method has large equipment investment and high technical difficulty, and particularly, the preparation of the catalyst is difficult.
The intermediate products of both ethylene oxide carbonylation process and acrolein hydration and hydrogenation process are 3-hydroxy-propionaldehyde, which has unstable chemical property and is easy to produce aldol condensation reaction. And the pressure of the synthesis gas used for the carbonylation of the ethylene oxide is very high and is more than 10 MPa.
Disclosure of Invention
The invention aims to overcome the problems of difficult preservation and difficult synthesis of 3-hydroxypropionaldehyde serving as a raw material in the prior art, and provides a method for preparing 1, 3-propanediol, which takes 3-acetoxypropionaldehyde as a raw material to prepare the 1, 3-propanediol under mild conditions.
In order to achieve the above object, the present invention provides a method for preparing 1, 3-propanediol, comprising the steps of:
(1) In the presence of a solvent and a ruthenium catalyst, carrying out hydrogenation reaction on 3-acetoxy propionaldehyde to obtain 3-acetoxy propanol;
(2) Hydrolyzing 3-acetoxy propanol;
wherein the ruthenium catalyst comprises a carrier and an active component ruthenium loaded on the carrier.
The invention adopts 3-acetoxy propionaldehyde which has stable performance and is easy to store as a raw material, and selects a proper catalyst to prepare the 1, 3-propylene glycol under mild conditions. The hydrogenation catalyst is a solid phase, namely a heterogeneous catalyst, and is easy to separate a product from the catalyst. Particularly, the method can obviously improve the yield of the 1, 3-propylene glycol.
Particularly preferably, the method for preparing the 3-acetoxy propionaldehyde does not need to add combustible gas, so that the occurrence of accidents can be reduced, meanwhile, the raw materials adopted by the method are easy to obtain, and a catalyst and a solvent are not needed, so that the problems of difficult preparation of the catalyst and high energy consumption for recovering the solvent are solved, and the production cost of the 3-acetoxy propionaldehyde can be reduced.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the pressures mentioned are gauge pressures.
The invention provides a method for preparing 1, 3-propanediol, which comprises the following steps:
(1) In the presence of a solvent and a ruthenium catalyst, carrying out hydrogenation reaction on 3-acetoxy propionaldehyde to obtain 3-acetoxy propanol;
(2) Hydrolyzing 3-acetoxy propanol;
wherein the ruthenium catalyst comprises a carrier and an active component ruthenium loaded on the carrier.
According to the present invention, the kind of the solvent is not particularly limited, and preferably, the solvent is a polar solvent, and more preferably at least one of methanol, ethanol, propanol, butanol, N-dimethylformamide, and tetrahydrofuran.
According to the invention, the amount of the solvent and the 3-acetoxypropionaldehyde can be selected in a wide range, and preferably, the mass ratio of the solvent to the 3-acetoxypropionaldehyde is 20-50:1, preferably 30 to 40:1.
according to the invention, the amount of the ruthenium catalyst and the 3-acetoxypropionaldehyde can be selected within a wide range, and preferably, the weight ratio of the ruthenium catalyst to the 3-acetoxypropionaldehyde is 0.01-10:1, more preferably 0.1 to 8:1.
according to the present invention, the hydrogenation reaction conditions may be those commonly used in the art, and preferably, the hydrogenation reaction conditions include: the temperature is 0-300 ℃, more preferably 80-250 ℃; the pressure of the hydrogen is from 0.1 to 10MPa, more preferably from 0.5 to 8MPa.
According to the present invention, preferably, the hydrolysis is carried out by reacting 3-acetoxypropanol with water at 0-100 ℃ in the presence of a hydrolysis catalyst; more preferably, the hydrolysis is performed by mixing a hydrolysis catalyst with water to prepare an aqueous solution, and reacting the aqueous solution of the hydrolysis catalyst with 3-acetoxypropanol at 0-100 ℃.
According to the present invention, the type of the hydrolysis catalyst is not particularly limited, and the hydrolysis catalyst is preferably an alkali containing an alkali metal, and more preferably at least one of sodium hydroxide, lithium hydroxide and potassium hydroxide.
According to the invention, preferably, the weight ratio of the hydrolysis catalyst to the 3-acetoxypropanol is from 0.01 to 1:1, preferably 0.1 to 0.8:1.
according to the invention, preferably, the weight ratio of the hydrolysis catalyst to water is between 0.1 and 10:1, preferably 0.3 to 8:1.
according to the present invention, preferably, the support comprises at least one of carbon, silica, alumina and MOFs materials, preferably at least one of carbon, alumina and MOFs materials.
According to the present invention, preferably, the content of the active component ruthenium in the ruthenium catalyst is 1 to 10wt%, preferably 3 to 5wt%.
In the present invention, the ruthenium catalyst can be prepared according to the method of a common hydrogenation catalyst, for example, by using an impregnation method, a precipitation method, an in-situ loading method, and preferably, the ruthenium catalyst is prepared by the following preparation method: mixing the ruthenium metal salt with a carrier, and reducing ruthenium ions into ruthenium atoms by using a reducing agent to be loaded on the carrier. Wherein the reducing agent can be sodium borohydride or hydrogen.
According to the invention, preferably, the 3-acetoxy propionaldehyde is prepared by the following method: in the presence of polymerization inhibitor, acrolein and acetic acid are contacted to react under 0.1-10 MPa.
According to the invention, in order to increase the conversion of acrolein, the reaction is preferably carried out at 0.3 to 2 MPa.
According to the present invention, the kind of the polymerization inhibitor is not particularly limited, and in order to further increase the conversion rate of acrolein, it is preferable that the polymerization inhibitor includes a phenolic polymerization inhibitor and/or a quinone polymerization inhibitor; more preferably, the phenolic polymerization inhibitor comprises at least one of hydroquinone, 2-t-butylhydroquinone, and 2, 5-di-t-butylhydroquinone; more preferably, the quinone type polymerization inhibitor includes benzoquinone and/or methyl hydroquinone.
According to the invention, the molar ratio of the polymerization inhibitor to acrolein can be selected within a wide range, preferably the molar ratio of the polymerization inhibitor to acrolein is between 0 and 1:1, preferably 0.001 to 0.2:1.
according to the invention, preferably, the molar ratio of acrolein to acetic acid is 1:1-10; preferably 1:1-5.
According to the invention, the reaction temperature is preferably between 0 ℃ and 200 ℃, preferably between 25 ℃ and 150 ℃.
According to the invention, the reaction time is preferably between 0.1 and 10h, preferably between 1 and 6h.
According to the present invention, preferably, the reaction takes place under an inert gas atmosphere; the inert gas includes at least one of nitrogen, helium, and argon.
According to the present invention, preferably, the reaction does not require the addition of solvents and catalysts. In the prior art, a solvent is required to be added for synthesizing the 3-acetoxy propionaldehyde, so that the solvent is required to be separated, recycled and reused, and the energy consumption and the cost in the production process are increased; in the prior art, a catalyst is also needed to be added for synthesizing the 3-acetoxy propionaldehyde, the technical difficulty of preparing the catalyst is high, the metal active components are generally expensive, and the production cost of the 3-acetoxy propionaldehyde is further increased.
According to a particularly preferred embodiment of the present invention, the process for the preparation of 3-acetoxypropionaldehyde comprises the steps of:
(1) Polymerization inhibitor hydroquinone and acrolein are mixed according to the ratio of 0.001-0.01:1 to obtain a mixture.
(2) Mixing the mixture of the step (1) and acetic acid according to the ratio of 1:1-2, and then reacting at 100-120 ℃ and 0.3-0.5MPa, wherein the reaction atmosphere is nitrogen.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the raw materials used in the following examples and comparative examples are commercially available.
Room temperature was about 25 ℃ and atmospheric pressure was about 0.1MPa.
Conversion of acrolein = mole of acrolein participating in the reaction ÷ feed mole of acrolein × 100%.
Selectivity to 3-acetoxypropionaldehyde = moles of 3-acetoxypropionaldehyde in the product ÷ moles of acrolein participating in the reaction × 100%.
The yield of 3-acetoxypropionaldehyde = conversion of acrolein x 3-acetoxypropionaldehyde x selectivity x 100%.
Conversion of 3-acetoxypropionaldehyde = moles of 3-acetoxypropionaldehyde participating in the reaction ÷ moles of 3-acetoxypropionaldehyde fed x 100%.
Total yield of 1, 3-propanediol = acrolein x 3-acetoxypropionaldehyde yield x 3-acetoxypropionaldehyde conversion x 100%.
Preparation example 1
This preparation example illustrates the preparation of a Ru/C catalyst
60g of activated carbon dispersed in 200mL of distilled water, 7.8g of RuCl, was weighed 3 ·3H 2 O was dissolved in 100mL of distilled water, and the two solutions were mixed and stirred at room temperature for 1 hour to obtain a mixed solution. 1.5g of sodium borohydride is weighed and dissolved in 100mL of distilled water, then the sodium borohydride solution is dripped into the mixed solution, and the mixed solution is stirred for 1 hour at room temperature after the dripping is finished. And (3) carrying out suction filtration to obtain a black solid, washing the black solid with distilled water until the black solid is neutral, drying the black solid at the temperature of 80 ℃ for 12 hours, and measuring the percentage content of metal ruthenium in the Ru/C catalyst to be 5wt% by element analysis.
Preparation example 2
This preparation example is illustrative of Ru/Al 2 O 3 Preparation of the catalyst
Weighing 60gAl 2 O 3 Dispersed in 200mL of distilled water after 4 hours of calcination at 350 ℃,4.7g of RuCl 3 ·3H 2 O was dissolved in 100mL of distilled water, and the two solutions were mixed together, stirred at room temperature for 3 hours, and allowed to stand for 7 hours to obtain a mixed solution. 0.9g of sodium borohydride is weighed and dissolved in 100mL of distilled water, then the sodium borohydride solution is added into the mixed solution dropwise, and the mixed solution is stirred for 1 hour at room temperature after the dropwise addition. Filtering to obtain white solid, washing with distilled water to neutrality, oven drying at 80 deg.C for 12 hr, and analyzing element to obtain Ru/Al 2 O 3 The percentage of metallic ruthenium in the catalyst was 3wt%.
Preparation example 3
This preparation example is intended to illustrate the preparation of a Ru/ZIF-8 catalyst
60g of ZIF-8 was weighed out and dispersed in 200mL of distilled water, 7.8g of RuCl 3 ·3H 2 O was dissolved in 100mL of distilled water, and the mixture was stirred at room temperature for 3 hours and then allowed to stand for 7 hours. Filtering to obtain white solid, and washing with distilled water until no Cl is formed - And drying for 6-12 hours at 110 ℃. The obtained white powder is reduced for 3 to 7 hours at the temperature of 120 ℃ under the normal pressure of hydrogen, and the percentage content of the metal ruthenium in the Ru/ZIF-8 catalyst is 3 weight percent through elemental analysis.
Example 1
This example illustrates the preparation of 1, 3-propanediol
(1) Preparation of 3-acetoxypropionaldehyde:
A. polymerization inhibitor (hydroquinone) and acrolein were mixed according to a ratio of 0.001:1 to obtain a mixture.
B. In a 100mL autoclave, the mixture of step A (in which the number of moles of acrolein is 0.18 mol) and 10.714g of glacial acetic acid (0.18 mol) were added as starting materials for the reaction, and the autoclave was sealed. Replacing with nitrogen for three times, heating to the reaction temperature of 150 ℃, setting the nitrogen pressure to be 1MPa, and starting to react for 4 hours. After the reaction, the temperature of the reaction kettle was reduced to room temperature and the pressure was reduced to 0.1MPa, the reaction kettle was opened, the composition of the reaction product was analyzed by gas chromatography, the amount was determined by internal standard method (the internal standard was ethyl propionate), and the conversion of acrolein and the selectivity of 3-acetoxypropionaldehyde were calculated, and the results are shown in table 1. Then, the reaction product is subjected to reduced pressure distillation to obtain 3-acetoxy propionaldehyde for later use.
(2) In a 100mL autoclave, 1.16g (0.01 mol) of 3-acetoxypropionaldehyde, 1g of Ru/C and 39g of methanol were charged, and the autoclave was sealed. Replacing with nitrogen for three times, replacing with hydrogen for three times, heating to the reaction temperature of 100 ℃, setting the hydrogen pressure to be 3MPa, and reacting for 4 hours. The reaction kettle is cooled to room temperature, the pressure is reduced to atmospheric pressure, nitrogen is replaced for three times, the reaction kettle is opened, the composition of a reaction product is analyzed by gas chromatography, the internal standard method (the internal standard substance is ethyl propionate) is used for quantification, the conversion rate of the 3-acetoxy propionaldehyde is calculated, the result is shown in table 1, and the 3-acetoxy propanol is obtained after reduced pressure distillation, separation and purification.
(3) 11.6g (0.1 mol) of 3-acetoxypropanol, 15g 30wt% of NaOH aqueous solution was added, the mixture was heated at 100 ℃ and refluxed for 10 hours, after the reaction was completed, the mixture was extracted three times with 100mL of ethyl acetate, and the 1, 3-propanediol was obtained by distillation under reduced pressure, and the total yield of 1, 3-propanediol is shown in Table 1.
Example 2
This example illustrates the preparation of 1, 3-propanediol
(1) Preparation of 3-acetoxypropionaldehyde:
A. polymerization inhibitor (hydroquinone) and acrolein were mixed according to a ratio of 0.01:1 to obtain a mixture.
B. In a 100mL autoclave, the mixture of step A (in which the number of moles of acrolein is 0.18 mol) and 10.714g of glacial acetic acid (0.18 mol) were added as starting materials for the reaction, and the autoclave was sealed. The mixture is replaced by nitrogen for three times, the temperature is increased to 120 ℃, the nitrogen pressure is set to 0.5MPa, and the reaction is started for 4 hours. After the reaction, the temperature of the reaction kettle was reduced to room temperature and the pressure was reduced to 0.1MPa, the reaction kettle was opened, the composition of the reaction product was analyzed by gas chromatography, the amount was determined by internal standard method (the internal standard was ethyl propionate), and the conversion of acrolein and the selectivity of 3-acetoxypropionaldehyde were calculated, and the results are shown in table 1. Then the reaction product is decompressed and distilled to obtain the 3-acetoxy propionaldehyde for standby.
(2) At a height of 100mL1.16g (0.01 mol) of 3-acetoxypropionaldehyde and 2g of Ru/Al were added to a autoclave 2 O 3 39g of methanol, and sealing the reaction kettle. Replacing with nitrogen for three times, replacing with hydrogen for three times, heating to the reaction temperature of 80 ℃, setting the hydrogen pressure to be 5MPa, and reacting for 4 hours. Reducing the temperature of the reaction kettle to room temperature, reducing the pressure to atmospheric pressure, replacing nitrogen for three times, opening the reaction kettle, analyzing the composition of a reaction product by using gas chromatography, quantifying by an internal standard method, calculating the conversion rate of the 3-acetoxy propionaldehyde, and obtaining the 3-acetoxy propanol after reduced pressure distillation, separation and purification, wherein the result is shown in table 1.
(3) 11.6g (0.1 mol) of 3-acetoxypropanol, 1.5g of an aqueous solution of 30wt% NaOH was added, the mixture was heated at 100 ℃ and refluxed for 10 hours, and after the completion of the reaction, the mixture was extracted three times with 100mL of ethyl acetate and distilled under reduced pressure to obtain 1, 3-propanediol, and the total yield of 1, 3-propanediol was as shown in Table 1.
Example 3
This example illustrates a process for the preparation of 1, 3-propanediol
(1) Preparation of 3-acetoxypropionaldehyde:
A. polymerization inhibitor (hydroquinone) and acrolein were mixed according to a ratio of 0.1:1 to obtain a mixture.
B. In a 100mL autoclave, the mixture of step A in which the number of moles of acrolein was 0.18mol and 10.714g of glacial acetic acid (0.18 mol) were charged as starting materials for the reaction, and the autoclave was sealed. The mixture is replaced by nitrogen for three times, the temperature is increased to 100 ℃, the nitrogen pressure is set to be 0.3MPa, and the reaction is started for 4 hours. After the reaction, the temperature of the reaction vessel was decreased to room temperature and the pressure was decreased to 0.1MPa, the reaction vessel was opened, the composition of the reaction product was analyzed by gas chromatography, the amount was determined by internal standard method (the internal standard was ethyl propionate), and the conversion of acrolein and the selectivity of 3-acetoxypropionaldehyde were calculated, and the results are shown in table 1. Then the reaction product is decompressed and distilled to obtain the 3-acetoxy propionaldehyde for standby.
(2) 1.16g (0.01 mol) of 3-acetoxypropionaldehyde, 2g of Ru/ZIF-8 and 39g of methanol were added to a 100mL autoclave, and the autoclave was sealed. Replacing with nitrogen for three times, replacing with hydrogen for three times, heating to the reaction temperature of 200 ℃, setting the hydrogen pressure to be 3MPa, and reacting for 4 hours. And (3) reducing the temperature of the reaction kettle to room temperature, reducing the pressure to the atmospheric pressure, replacing with nitrogen for three times, opening the reaction kettle, analyzing the composition of a reaction product by using gas chromatography, quantifying by using an internal standard method, calculating the conversion rate of the 3-acetoxy propionaldehyde, and obtaining the 3-acetoxy propanol after reduced pressure distillation, separation and purification, wherein the result is shown in table 1.
(3) 11.6g (0.1 mol) of 3-acetoxypropanol, 15g 30wt% KOH aqueous solution was added, heated at 100 ℃ and refluxed for 10 hours, after the reaction was completed, 100mL ethyl acetate was used for extraction three times, and distillation under reduced pressure was carried out to obtain 1, 3-propanediol, the total yield of 1, 3-propanediol being shown in Table 1.
Example 4
This example is a process for the preparation of illustrative 1, 3-propanediol
1, 3-propanediol was prepared by the method of example 1, except that iron trichloride was used as the polymerization inhibitor.
The conversion of acrolein, the selectivity and conversion of 3-acetoxypropionaldehyde, and the overall yield of 1, 3-propanediol are shown in Table 1.
Example 5
This example illustrates the preparation of 1, 3-propanediol
The preparation of 1, 3-propanediol was carried out according to the method of example 1, except that in step (1), the molar ratio of (hydroquinone) to acrolein was 5:1.
the conversion of acrolein, the selectivity and conversion of 3-acetoxypropionaldehyde, and the overall yield of 1, 3-propanediol are shown in Table 1.
Example 6
This example illustrates the preparation of 1, 3-propanediol
Preparation of 1, 3-propanediol was carried out in the same manner as in example 1, except that in step (1), the reaction temperature was 50 ℃ and the pressure was 1MPa, and the nitrogen reaction atmosphere was replaced with the air reaction atmosphere.
The conversion of acrolein, the selectivity and conversion of 3-acetoxypropionaldehyde, and the overall yield of 1, 3-propanediol are shown in Table 1.
Example 7
This example illustrates a process for the preparation of 1, 3-propanediol
The preparation of 1, 3-propanediol was carried out as in example 1, except that the Ru/C catalyst used was prepared by the following method:
60g of activated carbon are weighed out and dispersed in 200mL of distilled water, 5.7g of Ru (OH) 2 Dissolved in 100mL of distilled water, and the two solutions were mixed and stirred at room temperature for 1 hour to obtain a mixed solution. Standing overnight, filtering, washing with distilled water, drying at 80 deg.C for 12 hr, and analyzing element to obtain Ru/C catalyst with ruthenium content of 5wt%.
The conversion of acrolein, the selectivity and conversion of 3-acetoxypropionaldehyde, and the overall yield of 1, 3-propanediol are shown in Table 1.
Example 8
This example illustrates the preparation of 1, 3-propanediol
1, 3-propanediol was prepared according to the method of example 1 except that 3-acetoxypropionaldehyde was prepared in a manner different from that of example 1, and the preparation of 3-acetoxypropionaldehyde was carried out according to the method reported in the literature (Journal of the Chemical Society Perkin Transmission: organic and biological Chemistry (1972-1999), (8), 2315-2322, 1988). The method specifically comprises the following steps: using sodium acetate as a catalyst, 56g of acrolein (1 mol), 120g of glacial acetic acid (2 mol), 8.2g of sodium acetate (0.1 mol) were reacted at room temperature for 16 hours. The acetic acid was removed by distillation under reduced pressure, the remaining organic was precipitated as a white solid by adding 100mL of diethyl ether, filtered, and the organic phase was distilled under reduced pressure to give 50.2g of 3-acetoxypropionaldehyde as a product, with a yield of 38.6%.
The conversion of acrolein, the yield of 3-acetoxypropionaldehyde, and the total yield of 1, 3-propanediol are shown in Table 1.
Example 9
This example illustrates a process for the preparation of 1, 3-propanediol
1, 3-propanediol was prepared according to the method of example 1, except that 3-acetoxypropionaldehyde was prepared according to the method reported in reference (Tetrahedron 67 (2011) 1654-1664) in contrast to example 1. The method specifically comprises the following steps: an ion exchange resin is used as a catalyst, acrolein (0.8 mol), glacial acetic acid (0.82 mol) and 200mL of ion exchange resin IRA-420 are added, and the reaction is carried out for 48h at room temperature. Ethyl acetate (300 mL) was added and the mixture was extractedIon exchange resin, organic layer using saturated NaHCO 3 (200 mL), washed with saturated brine (100 mL) and anhydrous Na 2 SO 4 Drying and distillation under reduced pressure gave 15g of the product 3-acetoxypropionaldehyde in 16% yield.
The conversion of acrolein, the yield of 3-acetoxypropionaldehyde, and the total yield of 1, 3-propanediol are shown in Table 1.
Example 10
This example illustrates a process for the preparation of 1, 3-propanediol
1, 3-propanediol was produced in the same manner as in example 1, except that in the step (1), no polymerization inhibitor was added and the nitrogen pressure during the reaction was set to 0.1MPa.
The conversion of acrolein, the selectivity for 3-acetoxypropionaldehyde, and the overall yield of 1, 3-propanediol are shown in Table 1.
Comparative example 1
1, 3-propanediol was prepared according to the method of example 1, except that the Ru/C catalyst was replaced with a Pd/C catalyst, which was purchased from Inokay, having a palladium metal content of 10wt%.
TABLE 1
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A process for the preparation of 1, 3-propanediol comprising the steps of:
(1) In the presence of a solvent and a ruthenium catalyst, carrying out hydrogenation reaction on 3-acetoxy propionaldehyde to obtain 3-acetoxy propanol;
(2) Hydrolyzing 3-acetoxy propanol;
wherein the ruthenium catalyst comprises a carrier and an active component ruthenium loaded on the carrier.
2. The method according to claim 1, wherein the solvent is a polar solvent, preferably at least one of methanol, ethanol, propanol, butanol, N-dimethylformamide and tetrahydrofuran;
and/or the mass ratio of the solvent to the 3-acetoxy propionaldehyde is 20-50:1, preferably 30 to 40:1.
3. the process according to claim 1 or 2, wherein the weight ratio of the ruthenium catalyst to 3-acetoxypropionaldehyde is from 0.01 to 10:1, preferably 0.1 to 8:1, more preferably 0.5 to 2:1.
4. the process of any one of claims 1-3, wherein the hydrogenation conditions comprise: the temperature is 0-300 ℃, preferably 80-250 ℃; the pressure of the hydrogen is 0.1 to 10MPa, preferably 0.5 to 8MPa.
5. The method according to any one of claims 1 to 4, wherein the hydrolysis is carried out by reacting 3-acetoxypropanol with water at 0-100 ℃ in the presence of a hydrolysis catalyst;
preferably, the hydrolysis catalyst is an alkali containing alkali metal, more preferably at least one of sodium hydroxide, lithium hydroxide and potassium hydroxide;
preferably, the weight ratio of the hydrolysis catalyst to the 3-acetoxypropanol is from 0.01 to 1:1, preferably 0.1 to 0.8:1;
preferably, the weight ratio of the hydrolysis catalyst to water is from 0.1 to 10:1, preferably 0.3 to 8:1.
6. the method according to any of claims 1-5, wherein the support comprises at least one of carbon, silica, alumina and MOFs materials, preferably at least one of carbon, alumina and MOFs materials.
7. A process as claimed in any one of claims 1 to 6, wherein the ruthenium catalyst has an active component ruthenium content of from 1 to 10% by weight, preferably from 3 to 5% by weight.
8. The process of any one of claims 1-7, wherein the 3-acetoxypropionaldehyde is prepared by the following process: in the presence of polymerization inhibitor, acrolein and acetic acid are contacted to react under 0.1-10 MPa.
9. The method of claim 8, wherein the polymerization inhibitor comprises a phenolic polymerization inhibitor and/or a quinone polymerization inhibitor.
10. A process according to claim 8 or 9, wherein the molar ratio of polymerization inhibitor to acrolein is from 0 to 1:1, preferably 0.001 to 0.2:1;
and/or the molar ratio of acrolein to acetic acid is 1:1-10; preferably 1:1-5.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3769331A (en) * | 1970-11-21 | 1973-10-30 | Hoechst Ag | Process for the preparation of acetates of 1,3-propanediol |
| CN102372603A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3769331A (en) * | 1970-11-21 | 1973-10-30 | Hoechst Ag | Process for the preparation of acetates of 1,3-propanediol |
| GB1360663A (en) * | 1970-11-21 | 1974-07-17 | Hoechst Ag | Acetates of 1,3-propanediol |
| CN102372603A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol |
Non-Patent Citations (1)
| Title |
|---|
| 姚其正: "《药物合成反应》", 30 September 2012, 中国医药科技出版社, pages: 403 * |
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