CN115626869B - Method for preparing 3-hydroxy propanal by hydration of acrolein - Google Patents
Method for preparing 3-hydroxy propanal by hydration of acrolein Download PDFInfo
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- CN115626869B CN115626869B CN202211336777.6A CN202211336777A CN115626869B CN 115626869 B CN115626869 B CN 115626869B CN 202211336777 A CN202211336777 A CN 202211336777A CN 115626869 B CN115626869 B CN 115626869B
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- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 46
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000036571 hydration Effects 0.000 title claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 27
- 239000003929 acidic solution Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 12
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 8
- 229940035437 1,3-propanediol Drugs 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 9
- 239000007805 chemical reaction reactant Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 4
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- 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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/86—Use of additives, e.g. for stabilisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing 3-hydroxy-propanal by hydration of acrolein. The method comprises the following steps: the method comprises the steps of carrying out hydration reaction on reaction raw materials comprising acrolein, a catalyst and a solvent in a fixed bed reactor to obtain a product system comprising 3-hydroxy propanal, wherein the solvent is a mixed solvent of an organic solvent and water, and the catalyst is an acidic solution modified molecular sieve. In the method for preparing the 3-hydroxy-propanal by hydration of the acrolein, the concentration of the acrolein in a unit volume of solution is improved by adopting the mixed solvent of the organic solvent and the water, the water consumption is reduced, the overall yield of the 3-hydroxy-propanal is improved, the difficulty of subsequent separation of products is reduced, and the energy is saved and the consumption is reduced. Meanwhile, the improvement of the concentration of the acrolein in the reaction raw materials accelerates the hydration reaction rate and reduces the production cost. In addition, under the catalysis of the molecular sieve modified by the acid solution, the conversion rate (more than or equal to 50%) and the selectivity (more than or equal to 87%) of the acrolein can be improved.
Description
Technical Field
The invention relates to the technical field of preparation of 3-hydroxy-propanal, in particular to a method for preparing 3-hydroxy-propanal by hydration of acrolein.
Background
1, 3-propanediol (1, 3-PDO) is colorless, odorless, transparent viscous liquid with hygroscopicity, has excellent moisture-preserving property and antibacterial property, low biotoxicity and high low-temperature stability, is an important organic chemical raw material, can be directly used as an antifreezing agent, is widely applied to fields of cosmetics, printing ink, printing and dyeing, coating, lubricant and the like, can be used for synthesizing medicines and organic synthesis intermediates, but has the most main application field of being used as a polymerized monomer for synthesizing polyester material-polytrimethylene terephthalate (PTT), so that PTT molecules have a Z-shaped spring-shaped structure and unique physical and chemical properties, and therefore, PTT fibers have good performances of softness, easy coloration and the like, have good rebound resilience and anti-pollution performance like nylon, and have good application prospects in fields of carpets, engineering plastics, clothing fabrics and the like.
The current industrial synthesis method of 1,3-PDO mainly comprises the following steps: an ethylene oxide hydroformylation method, an acrolein hydration hydrogenation method and a microbial fermentation method. The reaction of the ethylene oxide hydroformylation method is carried out at high temperature and high pressure, the technical difficulty is high, particularly the requirements on catalysts in the reaction are very strict, the main cobalt catalytic system and the rhodium catalytic system for catalysis are developed at present, the structures of the two catalytic systems are complex, transition metals are required to be used as catalytic substrates, the production cost is high, the manufacturing process is harsh, the stability is poor, and in addition, phosphine ligands used by the catalysts are extremely toxic; and the raw material ethylene oxide is inflammable and explosive. The strain selection in the microbial fermentation reaction is strict, the experimental conditions are complex, the fermentation strength is low, and the production cost is high.
The equation for the preparation of 1, 3-propanediol by the acrolein hydrohydrogenation process is as follows:
in the prior art, the reaction condition for preparing 3-hydroxy-propanal by hydration of acrolein in the first step is mild and easy to operate, but water in the prior art is used as a raw material and a solvent, the saturated solubility of acrolein in water is 20%, the solubility is low, the highest reaction concentration is 20%, the conversion rate of hydration reaction is generally 50% in order to control the impurity content in the reaction process, and the concentration of 3-HPA in the aqueous solution is less than or equal to 10%; in the second step of hydrogenation reaction, a two-stage hydrogenation method is generally adopted, the hydrogenation conversion rate and the 1,3-PDO selectivity are close to 100%, the concentration of 1,3-PDO in the generated hydrogenation liquid is only about 10%, 9-10 t of water is required to be separated every 1t of PDO is produced, the separated energy consumption can reach 8-10 t of steam/t of product, the separation energy consumption and the cost are high, a large amount of coal or natural gas resources are consumed, and the development trend of green low-carbon cleaning at present is not met.
At present, the catalyst for preparing 3-HPA by hydration of acrolein has various kinds, and mainly comprises inorganic mineral acid, zeolite molecular sieve, inorganic and organic acid-base buffer solution and various ion exchange resins. If they are in the form of their catalytic action in the reaction, they can be classified into homogeneous catalysis and heterogeneous catalysis. The problem of difficult separation of the product when using mineral acids or buffer solutions of homogeneous catalysts is difficult to solve, and such catalysts are difficult to obtain for large-scale applications. The acidic cation resin has the advantages of simple operation, high conversion rate, long residence time, increased side reaction and low 3-HPA selectivity. Because of its unique spatial structure, zeolite molecular sieves have high selectivity but very low conversion compared to inorganic acids and acidic resins. Therefore, if the zeolite molecular sieve can greatly improve the conversion rate of the acrolein while maintaining high selectivity, the competitiveness of the acrolein hydration hydrogenation method for preparing the 1,3-PDO can be greatly improved.
Disclosure of Invention
The invention mainly aims to provide a method for preparing 3-hydroxy-propanal by hydration of acrolein, which aims to solve the problems of low raw material conversion rate and product selectivity and high energy consumption for post-treatment separation in the preparation method of 3-hydroxy-propanal in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a process for producing 3-hydroxypropanal by hydration of acrolein, the process comprising: the method comprises the steps of carrying out hydration reaction on reaction raw materials comprising acrolein, a catalyst and a solvent in a fixed bed reactor to obtain a product system comprising 3-hydroxy propanal, wherein the solvent is a mixed solvent of an organic solvent and water, and the catalyst is an acidic solution modified molecular sieve.
Further, the mass concentration of the acrolein in the reaction raw material solution is 50 to 71wt%.
Further, the mass ratio of the water to the organic solvent is 1-5:1, preferably the organic solvent is selected from any one or more of methanol, ethanol, 1, 3-propanediol, acetonitrile, tetrahydrofuran, 1, 4-dioxane and N, N-dimethylformamide, and preferably the organic solvent is selected from any one or more of ethanol, tetrahydrofuran, 1, 3-propanediol and 1, 4-dioxane.
Further, the reaction raw materials further comprise 100-2000 ppm of polymerization inhibitor, preferably any one or more of hydroquinone, p-hydroxyanisole and phenothiazine.
Further, the preparation method of the acidic solution modified molecular sieve comprises the following steps: step S1, carrying out reflux reaction on a molecular sieve and an acidic solution to obtain a treated molecular sieve; and S2, calcining the treated molecular sieve to obtain the molecular sieve modified by the acid solution.
Further, the mass ratio of the molecular sieve to the acidic solution is 1:2-1:20, and the molecular sieve is preferably selected from any one or more of a Y-type molecular sieve, a ZSM-5 molecular sieve and a beta-type molecular sieve.
Further, the concentration of the acidic solution is 0.1 to 5.0mol/L, and the acidic solution is preferably selected from any one or more of ammonium nitrate, citric acid, sulfuric acid, phosphotungstic acid, oxalic acid, tartaric acid and phosphoric acid.
Further, the temperature of the reflux reaction is 10 to 100 ℃, and the reflux reaction time is preferably 0.5 to 24 hours.
Further, the calcination temperature is 300 to 600 ℃, and the calcination time is preferably 1 to 24 hours.
Further, in the hydration reaction, the space velocity of the reaction raw material entering the fixed bed reactor is 0.1 to 2.0h -1 The ratio of height to diameter of the catalyst to be charged is preferably 15 to 100:1, the temperature of the hydration reaction is preferably 60 to 100 ℃, and the pressure of the hydration reaction is preferably 0.2 to 5MPa.
According to the technical scheme, in the method for preparing the 3-hydroxy-propanal by hydration of the acrolein, the concentration of the acrolein in a unit volume of solution is improved by adopting the mixed solvent of the organic solvent and the water, the water consumption is reduced, the overall yield of the 3-hydroxy-propanal is improved, the difficulty of subsequent separation of products is reduced, and the energy is saved and the consumption is reduced. Meanwhile, the improvement of the concentration of the acrolein in the reaction raw materials accelerates the hydration reaction rate and reduces the production cost. In addition, under the catalysis of the molecular sieve modified by the acid solution, the conversion rate (more than or equal to 50%) and the selectivity (more than or equal to 87%) of the acrolein can be improved.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed in the background art of the present application, the preparation method of 3-hydroxy-propanal in the prior art has the problems of low raw material conversion rate and product selectivity and high energy consumption for post-treatment separation, and in order to solve the problems, the present application provides a method for preparing 3-hydroxy-propanal by hydration of acrolein.
In one exemplary embodiment of the present application, a process for the hydration of acrolein to 3-hydroxypropionaldehyde is provided, the process comprising: the method comprises the steps of carrying out hydration reaction on reaction raw materials comprising acrolein, a catalyst and a solvent in a fixed bed reactor to obtain a product system comprising 3-hydroxy propanal, wherein the solvent is a mixed solvent of an organic solvent and water, and the catalyst is an acidic solution modified molecular sieve.
In the method for preparing the 3-hydroxy-propanal by hydration of the acrolein, the concentration of the acrolein in a unit volume of solution is improved by adopting the mixed solvent of the organic solvent and the water, the water consumption is reduced, the overall yield of the 3-hydroxy-propanal is improved, the difficulty of subsequent separation of products is reduced, and the energy is saved and the consumption is reduced. Meanwhile, the improvement of the concentration of the acrolein in the reaction raw materials accelerates the hydration reaction rate and reduces the production cost. In addition, under the catalysis of the molecular sieve modified by the acid solution, the conversion rate (more than or equal to 50%) and the selectivity (more than or equal to 87%) of the acrolein can be improved.
The mass concentration of the acrolein in the reaction raw material solution is preferably 50-71 wt%, so that the reaction concentration of the acrolein is increased, the water consumption in the hydration reaction is ensured, and the yield of the 3-hydroxy-propionaldehyde and lower treatment energy consumption are both achieved.
In one embodiment of the present application, the mass ratio of the water to the organic solvent is 1-5:1, preferably the organic solvent is selected from any one or more of methanol, ethanol, 1, 3-propanediol, acetonitrile, tetrahydrofuran, 1, 4-dioxane and N, N-dimethylformamide, and preferably the organic solvent is selected from any one or more of ethanol, tetrahydrofuran, 1, 3-propanediol and 1, 4-dioxane.
The preferable types of the organic solvents and the volume ratio of the organic solvents to the water are favorable for improving the mass concentration of the acrolein in the mixed solvent, so that the reaction concentration of the acrolein is improved, the water consumption in the hydration reaction is ensured, the yield of the 3-hydroxy-propionaldehyde is finally improved, and the energy consumption for post-treatment of the product is reduced.
Preferably, the reaction raw materials further comprise 100-2000 ppm of polymerization inhibitor, preferably the polymerization inhibitor is selected from any one or more of hydroquinone, p-hydroxyanisole and phenothiazine, so that the occurrence probability of polymerizable side reactions such as acrolein and the like is reduced.
In one embodiment of the present application, the method for preparing the acidic solution modified molecular sieve includes: step S1, carrying out reflux reaction on a molecular sieve and an acidic solution to obtain a treated molecular sieve; and S2, calcining the treated molecular sieve to obtain the molecular sieve modified by the acid solution.
The acidity of the molecular sieve and the size of the pores can be changed through acid solution and calcination treatment, so that the molecular sieve is more suitable for catalyzing the hydration reaction.
Preferably, the mass ratio of the molecular sieve to the acidic solution is 1:2-1:20, and preferably, the molecular sieve is selected from any one or more of a Y-type molecular sieve, a ZSM-5 molecular sieve and a beta-type molecular sieve, so that the modification effect of the acidic solution on the molecular sieve is improved, and the molecular sieve catalyst with excellent catalytic performance is obtained.
The concentration of the acidic solution is preferably 0.1-5.0 mol/L, and the acidic solution is preferably any one or more of ammonium nitrate, citric acid, sulfuric acid, phosphotungstic acid, oxalic acid, tartaric acid and phosphoric acid, so that the acidic solution is favorable for adapting the characteristics of the molecular sieve to modify the molecular sieve better.
The temperature of the reflux reaction is preferably 10 to 100 ℃, and the reflux reaction time is preferably 0.5 to 24 hours, so that the acidic solution is sufficiently contacted with the molecular sieve to modify the acidic solution.
The calcination temperature is preferably 300 to 600 ℃, and the calcination time is preferably 1 to 24 hours, so that the acidity, the porosity and the like of the modified molecular sieve obtained after calcination are more suitable for catalyzing the reaction of preparing 3-hydroxy-propionaldehyde by hydration of acrolein.
In order to precisely control the acidity and catalytic activity of the modified molecular sieve, the method preferably further comprises the steps of filtering the treated molecular sieve, washing the molecular sieve with deionized water for a plurality of times until the pH value of the molecular sieve is nearly neutral, drying the molecular sieve, and then calcining the molecular sieve.
In one embodiment of the present application, in the hydration reaction, the space velocity of the reaction raw material entering the fixed bed reactor is 0.1 to 2.0h -1 The ratio of height to diameter of the catalyst to be charged is preferably 15 to 100:1, the temperature of the hydration reaction is preferably 60 to 100 ℃, and the pressure of the hydration reaction is preferably 0.2 to 5MPa.
The hydration reaction conditions are favorable for further improving the efficiency of the hydration reaction, thereby improving the overall yield of the 3-hydroxy-propionaldehyde.
The advantageous effects of the present application will be further described below with reference to examples.
Example 1
30.5g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 =25) to 200mL of an aqueous ammonium nitrate solution having a concentration of 0.2mol/L, inStirring for 5h at 90 ℃ in the reaction kettle, filtering the molecular sieve, and washing to be neutral. The molecular sieve is dried at 120 ℃ overnight for 12 hours and calcined at 500 ℃ for 4 hours to prepare the catalyst ZSM-5-0.2-500, wherein 0.2 represents the concentration of ammonium nitrate and 500 represents the calcining temperature of the catalyst.
500.3g of water and 500.7g of ethanol are mixed to prepare a mixed solution, and 1.1g of hydroquinone and 999.7g of acrolein are added into the aqueous solution of the organic solvent to prepare a reaction raw material, wherein the concentration of the acrolein in the raw material is 49.97%. The reaction starting material was reacted for 0.1h -1 And the catalyst ZSM-5-0.2-500 is filled into a fixed bed reactor, the filling mass is 70.2g, and the height-diameter ratio is 15:1. And (3) carrying out hydration reaction at 60 ℃ and 0.5MPa to obtain the 3-hydroxy-propanal. After 8 hours of reaction, the effluent was collected by cooling and the product composition was analyzed by gas chromatography. The results are shown in Table 1.
Example 2
The difference from example 1 is that 30.4g of NaY molecular sieve was added to 200mL of aqueous citric acid solution having a concentration of 0.2mol/L, stirred at 50℃for 10 hours in a reaction vessel, and the molecular sieve was filtered and washed to neutrality. Drying the molecular sieve at 100 ℃ overnight for 12h, and calcining at 500 ℃ for 4h to obtain the catalyst HY-0.2-500, wherein 0.2 represents the concentration of citric acid, and 500 represents the calcining temperature of the catalyst.
The catalyst in the fixed bed reactor was changed to HY-0.2-500 to finally obtain 3-hydroxypropionaldehyde, and the composition of the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 3
30.2-g H-beta molecular sieve is added into 200mL of nitric acid aqueous solution with concentration of 0.2mol/L, stirred for 24h at 50 ℃ in a reaction kettle, and the molecular sieve is filtered and washed to be neutral. The molecular sieve is dried at 120 ℃ overnight for 12 hours and calcined at 550 ℃ for 4 hours to obtain the catalyst H-beta-0.2-550, wherein 0.2 represents the concentration of ammonium nitrate and 550 represents the calcining temperature of the catalyst.
500.2g of water and 100.1g of 1, 4-dioxane were mixed to prepare an aqueous organic solvent solution, and 0.5g of hydroquinone and 700.4g of acrolein were added to prepare a reaction raw material, wherein the concentration of acrolein in the raw material was 53.85%. The reaction starting material was reacted for 0.1h -1 Introducing into a fixed bed for reactionThe filling mass of the catalyst H-beta-0.2-550 is 70.2g, and the height-diameter ratio is 15:1. And (3) carrying out hydration reaction at 70 ℃ and 0.5MPa to prepare the 3-hydroxy-propanal. After 8 hours of reaction, the effluent was collected by cooling and the product composition was analyzed by gas chromatography. The results are shown in Table 1.
Example 4
30.1-g H-beta molecular sieve is added into 150mL of citric acid aqueous solution with the concentration of 0.2mol/L, stirred for 3h at 60 ℃ in a reaction kettle, and the molecular sieve is filtered and washed to be neutral. The molecular sieve is dried at 120 ℃ overnight for 12H and calcined at 500 ℃ for 4H to obtain the catalyst H-beta-0.2-500, wherein 0.2 represents the concentration of ammonium nitrate and 500 represents the calcining temperature of the catalyst.
400.4g of water and 150.1g of 1, 3-propanediol were mixed to prepare an aqueous organic solvent solution, and 1.1g of hydroquinone and 1000.1g of acrolein were added to prepare a reaction raw material having an acrolein concentration of 64.5%. The reaction starting material was reacted for 0.1h -1 And (3) introducing the catalyst into a fixed bed reactor, wherein the loading mass of the catalyst H-beta-0.2-500 is 70.2g, and the height-diameter ratio is 15:1. And (3) carrying out hydration reaction at 70 ℃ and 0.5MPa to prepare the 3-hydroxy-propanal. After 8 hours of reaction, the effluent was collected by cooling and the product composition was analyzed by gas chromatography. The results are shown in Table 1.
Example 5
The difference from example 1 is that 30.4g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 =25) was added to 150mL of an aqueous solution of tartaric acid at a concentration of 0.1mol/L, stirred in a reaction vessel at 60 ℃ for 12 hours, and the molecular sieve was filtered and washed to neutrality. The molecular sieve is dried at 120 ℃ overnight for 12 hours and calcined at 500 ℃ for 4 hours to prepare the catalyst ZSM-5-0.1-500, wherein 0.1 represents the concentration of ammonium nitrate and 500 represents the calcining temperature of the catalyst.
The catalyst in the fixed bed reactor was changed to ZSM-5-0.1-500 to finally obtain 3-hydroxypropionaldehyde, and the composition of the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 6
500.1g of water and 100.2g of tetrahydrofuran are mixed to prepare an organic solvent aqueous solution, and 1.1g of hydroquinone and 999.8g of acrolein are added to prepare a reaction raw material, wherein the concentration of the acrolein in the raw material is 62.48%. The reaction raw materials are fed into a fixed bed reactor in 0.2h < -1 >, the loading mass of the catalyst ZSM-5-0.2-500 is 70.2g, and the height-diameter ratio is 15:1. And (3) carrying out hydration reaction at 60 ℃ and 1MPa to prepare the 3-hydroxy-propanal. After 8 hours of reaction, the effluent was collected by cooling. The product composition was analyzed by gas chromatography, and the results are shown in Table 1.
Example 7
The difference from example 1 was that 200.1g of water and 200.6g of 1, 4-dioxane were mixed to prepare an aqueous organic solvent solution, and 0.5g of hydroquinone and 500.3g of acrolein were added to prepare a reaction raw material, the concentration of acrolein in the raw material being 55.53%. The reaction starting material was reacted for 0.1h -1 Introducing the catalyst into a fixed bed reactor, wherein the loading mass of the catalyst HY-0.2-500 is 70.2g, and the height-diameter ratio is 15:1. And (3) carrying out hydration reaction at 70 ℃ and 0.5MPa to prepare the 3-hydroxy-propanal. After 8 hours of reaction, the effluent was collected by cooling, and the product composition was analyzed by gas chromatography, and the results are shown in Table 1.
Example 8
The difference from example 1 was that 600.1g of water and 84.4g of ethanol were mixed to prepare an aqueous organic solvent solution, and 0.6g of hydroquinone and 578.7g of acrolein were added to prepare a reaction raw material, the concentration of acrolein in the raw material being 45.81%, and the results are shown in Table 1. Finally, 3-hydroxypropanal was prepared, and the composition of the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 9
The difference from example 1 was that 181.1g of water and 50.2g of tetrahydrofuran were mixed to prepare an aqueous organic solvent solution, and 1.1g of hydroquinone and 559.1g of acrolein were added to prepare a reaction raw material having an acrolein concentration of 70.74% to the aqueous organic solvent solution, and the results are shown in Table 1.
Example 10
The difference from example 1 is that 30.5g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 =25) was added to 40.5mL of an aqueous solution of 1mol/L ammonium nitrate, stirred in a reaction vessel at 90 ℃ for 5 hours, and the molecular sieve was filtered and washed to neutrality. The molecular sieve was dried at 120℃overnight for 12 hours and calcined at 500℃for 4 hours to give a catalyst ZSM-5-0.2-500 in which 0.2 represents the concentration of ammonium nitrate and 500 represents the calcination temperature of the catalyst, and finally 3-hydroxypropionaldehyde was prepared, and the composition of the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 11
The difference from example 1 is that 30.5g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 =25) was added to 500.3mL of an aqueous ammonium nitrate solution having a concentration of 1mol/L, stirred in a reaction vessel at 90 ℃ for 5 hours, and the molecular sieve was filtered and washed to neutrality. The molecular sieve was dried at 120℃overnight for 12 hours and calcined at 500℃for 4 hours to give a catalyst ZSM-5-0.2-500 in which 0.2 represents the concentration of ammonium nitrate and 500 represents the calcination temperature of the catalyst, and finally 3-hydroxypropionaldehyde was prepared, and the composition of the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 12
The difference from example 1 is that the molecular sieve was dried at 120℃overnight for 12 hours and calcined at 300℃for 4 hours to prepare the catalyst ZSM-5-0.2-500, and finally 3-hydroxypropionaldehyde was prepared, and the composition of the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 13
The difference from example 1 is that the reaction starting material is reacted for 0.1h -1 Introducing the catalyst into a fixed bed reactor, wherein the loading mass of the catalyst ZSM-5-0.2-500 is 30.2g, and the height-diameter ratio is 15:1. Hydration reaction was carried out at 60℃and 0.5MPa for 6 hours, and after the reaction, the effluent was collected by cooling to obtain 3-hydroxypropanal, and the composition of the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 14
The difference from example 1 is that the reaction starting material is reacted for 1h -1 And the catalyst ZSM-5-0.2-500 is filled into a fixed bed reactor, the filling mass is 70.2g, and the height-diameter ratio is 15:1. The hydration reaction was carried out at 60℃and 1MPa for 4 hours, and then the effluent was collected by cooling to obtain 3-hydroxypropanal, and the composition of the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 15
Differences from example 1In that the reaction starting material was reacted for 1h -1 And the catalyst ZSM-5-0.2-500 is filled into a fixed bed reactor, the filling mass is 70.2g, and the height-diameter ratio is 100:1. Hydration reaction was carried out at 60℃and 5MPa for 8 hours, and after the reaction, the effluent was collected by cooling to obtain 3-hydroxypropanal, and the composition of the product was analyzed by gas chromatography, and the results are shown in Table 1.
Comparative example 1
The difference from example 1 was that the reaction raw material was prepared by adding 0.3g of hydroquinone and 225.3g of acrolein to 1225.1 water, and the concentration of acrolein in the raw material was 15.5%. The reaction starting material was reacted for 0.1h -1 Is fed into a fixed bed reactor, and the catalyst ZSM-5 (SiO 2 /Al 2 O 3 =25) the loading mass was 70.3g and the aspect ratio was 15:1. And (3) carrying out hydration reaction at 80 ℃ and 0.5MPa to prepare the 3-hydroxy-propanal. After 8 hours of reaction, the effluent was collected by cooling, and the product composition was analyzed by gas chromatography, and the results are shown in Table 1.
The composition of the products of the gas chromatographic analyses of examples 1 to 15 and comparative example 1 above are shown in Table 1.
TABLE 1
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
in the method for preparing the 3-hydroxy-propanal by hydration of the acrolein, the concentration of the acrolein in a unit volume of solution is improved by adopting the mixed solvent of the organic solvent and the water, the water consumption is reduced, the overall yield of the 3-hydroxy-propanal is improved, the difficulty of subsequent separation of products is reduced, and the energy is saved and the consumption is reduced. Meanwhile, the improvement of the concentration of the acrolein in the reaction raw materials accelerates the hydration reaction rate and reduces the production cost. In addition, under the catalysis of the molecular sieve modified by the acid solution, the conversion rate (more than or equal to 50%) and the selectivity (more than or equal to 87%) of the acrolein can be improved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (17)
1. A process for the hydration of acrolein to produce 3-hydroxypropionaldehyde, the process comprising:
the reaction raw materials comprising acrolein, catalyst and solvent are subjected to hydration reaction in a fixed bed reactor to obtain a product system comprising 3-hydroxy-propionaldehyde,
wherein the solvent is a mixed solvent of an organic solvent and water, and the catalyst is an acidic solution modified molecular sieve;
the organic solvent is selected from any one or more of methanol, ethanol, 1, 3-propylene glycol, acetonitrile, tetrahydrofuran, 1, 4-dioxane and N, N-dimethylformamide;
the reaction raw materials also comprise 100-2000 ppm of polymerization inhibitor;
the concentration of the acidic solution is 0.1-5.0 mol/L.
2. The method according to claim 1, wherein the mass concentration of the acrolein in the reaction raw material solution is 50 to 71wt%.
3. The method according to claim 1, wherein the mass ratio of the water to the organic solvent is 1-5:1.
4. The method according to claim 1, wherein the organic solvent is selected from any one or more of ethanol, tetrahydrofuran, 1, 3-propanediol, 1, 4-dioxane.
5. The method according to any one of claims 1 to 4, wherein the polymerization inhibitor is selected from any one or more of hydroquinone, p-hydroxyanisole, phenothiazine.
6. The method according to any one of claims 1 to 4, wherein the acidic solution modified molecular sieve is prepared by a process comprising:
step S1, carrying out reflux reaction on a molecular sieve and an acidic solution to obtain a treated molecular sieve;
and S2, calcining the treated molecular sieve to obtain the molecular sieve modified by the acidic solution.
7. The method of claim 6, wherein the mass ratio of the molecular sieve to the acidic solution is 1:2 to 1:20.
8. The method of claim 6, wherein the molecular sieve is selected from any one or more of a Y-type molecular sieve, a ZSM-5 molecular sieve, and a beta-type molecular sieve.
9. The method of claim 6, wherein the acidic solution is selected from any one or more of ammonium nitrate, citric acid, sulfuric acid, phosphotungstic acid, oxalic acid, tartaric acid, phosphoric acid.
10. The method according to claim 6, wherein the temperature of the reflux reaction is 10 to 100 ℃.
11. The method of claim 6, wherein the reflux reaction time is 0.5 to 24 hours.
12. The method of claim 6, wherein the calcination temperature is 300 to 600 ℃.
13. The method of claim 6, wherein the calcination is for a period of 1 to 24 hours.
14. The process according to any one of claims 1 to 4, wherein in the hydration reaction, the space velocity of the reaction raw material into the fixed bed reactor is 0.1 to 2.0h -1 。
15. The method according to any one of claims 1 to 4, wherein the catalyst is packed in an aspect ratio of 15 to 100:1.
16. The method according to any one of claims 1 to 4, wherein the temperature of the hydration reaction is 60 to 100 ℃.
17. The method according to any one of claims 1 to 4, wherein the hydration reaction is carried out at a pressure of 0.2 to 5MPa.
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