CN114956995A - Preparation method of acetate - Google Patents
Preparation method of acetate Download PDFInfo
- Publication number
- CN114956995A CN114956995A CN202110212129.9A CN202110212129A CN114956995A CN 114956995 A CN114956995 A CN 114956995A CN 202110212129 A CN202110212129 A CN 202110212129A CN 114956995 A CN114956995 A CN 114956995A
- Authority
- CN
- China
- Prior art keywords
- acid
- alcohol
- acetic acid
- reaction
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 165
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000012074 organic phase Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 42
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000002808 molecular sieve Substances 0.000 claims description 32
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 23
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 20
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000001087 glyceryl triacetate Substances 0.000 claims description 10
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 229960002622 triacetin Drugs 0.000 claims description 10
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940116423 propylene glycol diacetate Drugs 0.000 claims description 8
- 150000001206 Neodymium Chemical class 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical group [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims 2
- 229920006395 saturated elastomer Polymers 0.000 claims 2
- 235000019439 ethyl acetate Nutrition 0.000 claims 1
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 abstract description 29
- 230000032050 esterification Effects 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004334 oxygen containing inorganic group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The application relates to the field of preparation of acetate, and particularly discloses a preparation method of acetate, which comprises the following steps: uniformly stirring acetic acid, alcohol and a water-carrying agent; adding the supported heteropolyacid catalyst in batches while stirring, heating for reaction to finally obtain a mixed solution, separating the mixed solution, washing an organic phase, carrying out vacuum distillation on the washed organic phase, and collecting the required fraction. The method has the advantages that the reaction of acetic acid and alcohol is catalyzed by utilizing the self-made supported heteropolyacid catalyst, so that the esterification rate of the acetic acid and the alcohol is high, and the supported polyacid catalyst can be repeatedly used.
Description
Technical Field
The application relates to the field of preparation of acetate, and more particularly relates to a preparation method of acetate.
Background
The esterification reaction is a common chemical reaction, namely the reaction of alcohol and carboxylic acid or oxygen-containing inorganic acid to generate ester and water, and the product such as organic carboxylic ester is an important fine chemical product and has a wide market at home and abroad.
The esterification reaction is divided into two types of reactions of carboxylic acid and alcohol, inorganic oxyacid and inorganic strong acid, the esterification reaction of carboxylic acid and alcohol is reversible and is generally very slow, so the common catalyst is used for catalyzing the reaction, and the typical esterification reaction is the reaction of ethanol and acetic acid to generate ethyl acetate with aromatic odor, which is a raw material for manufacturing dyes and medicines. However, so far, catalysts such as concentrated sulfuric acid, phosphoric acid, p-toluenesulfonic acid and the like are commonly used for catalyzing esterification of alcohol and acid in synthesis of organic carboxylic ester, and although the catalysts have high catalytic activity and are cheap and easily available, the method has the defects of serious corrosion to equipment, more side reactions, low catalytic efficiency and incapability of recycling, so that the method is not in accordance with the development concept of green environmental protection.
Disclosure of Invention
In order to solve the problem that the existing catalyst does not accord with the green environmental protection development concept, the application provides a preparation method of acetate.
A preparation method of acetate comprises the following steps:
s1: stirring acetic acid and alcohol for 5-15 min under the condition of 20-50 r/min; adding a supported heteropolyacid catalyst in batches while stirring, wherein the weight ratio of acetic acid, alcohol and the supported heteropolyacid catalyst is (0.8-3): 1: (0.03-0.05);
s2: heating and reacting the product obtained in the step S1 at the temperature of 120-140 ℃ for 20-50 min;
s3: washing a reaction product of S2, and separating to obtain an organic phase;
s4: the organic phase washed in S3 was vacuum distilled to collect the desired fraction.
By adopting the technical scheme, compared with the original esterification reaction catalyzed by concentrated sulfuric acid, phosphoric acid and the like serving as catalysts, the supported heteropolyacid catalyst used in the method catalyzes the reaction of acetic acid and alcohol, so that the contact area of the acetic acid and the alcohol in the reaction with the catalyst is increased, the reaction esterification rate of the acetic acid and the alcohol is improved, the supported polyacid catalyst can be repeatedly used, the reaction of the acetic acid and the alcohol is catalyzed repeatedly, and the method is green and environment-friendly.
Optionally, the alcohol is any one of glycerol, propylene glycol and phenethyl alcohol, and the weight ratio of glycerol to acetic acid is 1: (2.5-3); the weight ratio of propylene glycol to acetic acid is 1: (2.0-2.5); the weight ratio of the phenethyl alcohol to the acetic acid is 1: (0.8 to 1).
By adopting the technical scheme, the esterification reaction of glycerol, propylene glycol, phenethyl alcohol and acetic acid is three common esterification reactions, and the supported heteropolyacid is used as a catalyst in the three esterification reactions, so that the wide applicability of the supported heteropolyacid catalyst in the catalytic esterification reaction is proved.
Optionally, in the step S3, a saturated saline solution is added to the mixed solution for washing, and then liquid separation is performed, where the weight ratio of the saturated saline solution to the mixed solution is (1-2): 1.
by adopting the technical scheme, as the acetate is a low-polarity organic matter, is easy to dissolve in an organic solvent and is not easy to dissolve in water, the saturated saline solution increases the ionic strength of water to ensure that the acetate is more difficult to dissolve, namely, the solubility of the acetate in the water is reduced, and meanwhile, the saturated saline solution is used for washing and removing unreacted raw materials, part of reaction impurities and the like, so that the purity of the acetate after final liquid separation is higher, and the saline solution is convenient to prepare and low in cost, and therefore, the acetate is washed by the saturated saline solution.
Optionally, when the alcohol is glycerol, the step S4 is to perform reduced pressure distillation under a pressure of 1.2kPa, and collect a fraction with a temperature of 132 to 139 ℃ to obtain triacetin; when the alcohol is propylene glycol, distilling under reduced pressure of 1.2kPa in the step S4, and collecting a fraction with the temperature of 105-110 ℃ to prepare propylene glycol diacetate; and when the alcohol is phenethyl alcohol, distilling under reduced pressure of 1.2kPa in the step S4, and collecting fractions at the temperature of 80-83 ℃ to prepare phenethyl acetate.
By adopting the technical scheme, the esters prepared by the reaction of different alcohols and acetic acid adopt different reduced pressure distillation temperatures, so that the finally collected different esters have higher purity.
Optionally, in step S2, rectification is performed while the system is heated for reaction, so as to remove water generated by the reaction and return the acetic acid fraction to the system.
By adopting the technical scheme, as the reaction raw material acetic acid and the water generated by the reaction are continuously gasified and evaporated under the heating condition of 120-140 ℃, the acetic acid and the water are condensed and separated by adopting a rectification mode, the obtained water is discharged, and the acetic acid fraction is returned to the system, so that the water generated in the reaction system is continuously taken away circularly, the balance of the reaction is changed, the reaction is moved to the esterification direction, and the reaction conversion rate is increased.
Optionally, the preparation method of the supported polyacid catalyst comprises the following steps:
(1): dispersing and dissolving neodymium salt, potassium salt, copper salt and a USY molecular sieve in water, stirring for 6-8 hours under the condition of 100-130 r/min, then adding heteropoly acid, and continuously stirring for 5-6 hours under the condition of 100-120 r/min to obtain a colloid system, wherein the weight ratio of the neodymium salt, the potassium salt, the copper salt, the heteropoly acid, the USY molecular sieve to the water is (1-2): (1-2): (1-2): (3-5): 5: (3-4);
(2): drying the colloid system at 70-90 ℃ for 1-2 h, and then roasting at 200-400 ℃ for 2-4 h to obtain the supported heteropolyacid catalyst.
By adopting the technical scheme, the isomerization performance of the cracking catalyst is improved by utilizing the metal ion modified molecular sieve, so that the number of B acid centers of the original USY molecular sieve is increased, the strength of the B acid centers is increased, and the catalytic efficiency is higher when the reaction of acetic acid and alcohol is catalyzed; and then adding the heteropoly acid, wherein the heteropoly acid can generate a pseudo liquid phase system with a non-aqueous medium polar solvent, has strong acidity and shows good catalytic activity for various esterification reactions, and the specific surface area of the heteropoly acid can be increased by loading the heteropoly acid on a USY molecular sieve, so that the catalytic activity can be improved, and the catalyst is easy to separate and recover.
Optionally, before the step (1), the USY molecular sieve is treated in advance as follows:
(0): immersing the USY molecular sieve in an acid solution, stirring for 0.5-1.5 h at the temperature of 80-90 ℃, filtering, washing with water, drying for 1-1.5 h at the temperature of 100-120 ℃, roasting for 3-5 h at the temperature of 400-600 ℃, wherein the weight ratio of the USY molecular sieve to the acid solution is 1: (3-10).
By adopting the technical scheme, the USY molecular sieve has smaller aperture, and non-framework aluminum can be formed in the preparation process of the molecular sieve, and can block the pore channel of the molecular sieve, so that the catalytic performance of the molecular sieve is influenced, most of the non-framework aluminum and part of the framework aluminum can be removed by adopting acid treatment, secondary mesopores can be generated, the solid carrying capacity of metal ions and heteropoly acid on the molecular sieve is increased, the acidity is enhanced, and the catalytic performance of the esterification reaction is improved.
Optionally, the heteropoly acid is phosphotungstic acid.
By adopting the technical scheme, the crystal strength of the phosphotungstic acid is stronger than that of other heteropoly acids, the acidity of the phosphotungstic acid is stronger than that of most heteropoly acids, and the phosphotungstic acid is poor in reduction activity by hydrogen, so that the phosphotungstic acid is immobilized on the USY molecular sieve, and the catalytic efficiency of the supported heteropoly acid catalyst along with the esterification reaction is higher.
Optionally, neodymium nitrate is used as the neodymium salt, potassium nitrate is used as the potassium salt, and copper nitrate is used as the copper salt.
By adopting the technical scheme, the three metal salts are all nitrates, so that the reaction between different acid salts is avoided, the three metal salts are more stable to the increase of the number and the strength of the B acid centers on the USY molecular sieve, and the formed supported heteropoly acid catalyst is more stable in self performance and more stable in catalysis of esterification reaction.
Optionally, the acid solution is any one of 0.5-2 mol/L oxalic acid, 0.5-2 mol/L citric acid and 0.5-2 mol/L tartaric acid.
By adopting the technical scheme, when the acid concentration is insufficient, the size of the formed pore channel is small, and phosphotungstic acid cannot fully enter the pore channel, so that the activity of the catalyst is not high; when the acid concentration is too high, the excessive framework aluminum can be removed by the acid, so that the framework structure of the molecular sieve collapses, and the specific surface area is reduced, therefore, the addition of a proper amount of acid enables the modification effect of the acid on the USY molecular sieve to be optimal, and finally the catalytic effect of the supported polyacid catalyst on the esterification reaction to be better.
In summary, the present application has the following beneficial effects:
1. the reaction of acetic acid and alcohol is catalyzed by the supported heteropolyacid catalyst, so that the contact area of the acetic acid and the alcohol in the reaction with the catalyst is increased, the reaction esterification rate of the acetic acid and the alcohol is high, and the supported polyacid catalyst can be repeatedly used;
2. the isomerization performance of the cracking catalyst is improved by modifying the molecular sieve through metal ions, so that the number of B acid centers of the original USY molecular sieve is increased, the strength of the B acid centers is increased, and the catalytic efficiency is higher when the reaction of acetic acid and alcohol is catalyzed;
3. the acidity of the catalyst can be increased by loading the heteropoly acid on the USY molecular sieve, and the specific surface area of the heteropoly acid is increased, so that the number of B acid centers on the USY molecular sieve is increased, the catalytic activity is improved, and the catalyst is easy to separate and recycle.
Detailed Description
The present application will be described in further detail with reference to examples.
In the following examples and comparative examples, the sources of the raw materials are as follows:
acetic acid, glycerol, propylene glycol, and phenethyl alcohol were purchased from Shanghai Michelin Biotech, Inc.; oxalic acid, sulfuric acid, citric acid, tartaric acid, potassium nitrate, and copper nitrate were purchased from Shanghai Mulberry well chemical Co., Ltd; phosphotungstic acid and USY molecular sieves were purchased from Shanghai Allan Biotechnology Ltd.
Supported heteropolyacid catalyst
Preparation example 1
(0): immersing 20kg of USY molecular sieve in 60L of 0.5mol/L tartaric acid solution, stirring for 0.5h at 90 ℃, filtering and washing with water, drying for 1h at 120 ℃, and roasting for 3h at 600 ℃;
(1): dispersing and dissolving 2kg of neodymium nitrate, 4kg of potassium nitrate, 2kg of copper nitrate and 10kg of USY molecular sieve obtained in the step (0) in 12L of water, stirring for 6h under the condition of 130r/min, then adding 10kg of phosphotungstic acid, and continuously stirring for 6h under the condition of 100r/min to obtain a colloid system;
(2): drying the colloid system at 70 ℃ for 2h, and then roasting at 200 ℃ for 4h to obtain a supported heteropoly acid catalyst;
preparation example 2
(0): immersing 20kg of USY molecular sieve in 100L of 2mol/L citric acid solution, stirring for 1.5h at 80 ℃, filtering, washing with water, drying for 1.5h at 100 ℃, and roasting for 5h at 400 ℃;
(1): dispersing and dissolving 4kg of neodymium nitrate, 2kg of potassium nitrate, 4kg of copper nitrate and 10kg of USY molecular sieve obtained in the step (0) in 16L of water, stirring for 8h under the condition of 100r/min, then adding 10kg of phosphotungstic acid, and continuously stirring for 5h under the condition of 120r/min to obtain a colloid system;
(2): drying the colloid system at 90 ℃ for 1h, and then roasting at 400 ℃ for 2h to obtain the supported heteropolyacid catalyst.
Preparation example 3
(0): immersing 20kg of USY molecular sieve in 80L of 1mol/L oxalic acid solution, stirring for 1h at 85 ℃, filtering, washing with water, drying for 1.2h at 110 ℃, and roasting for 4h at 500 ℃;
(1): dispersing and dissolving 3kg of neodymium nitrate, 3kg of potassium nitrate, 3kg of copper nitrate and 10kg of USY molecular sieve obtained in the step (0) in 14L of water, stirring for 7h under the condition of 115r/min, then adding 10kg of phosphotungstic acid, and continuously stirring for 5.5h under the condition of 110r/min to obtain a colloid system;
(2): drying the colloid system at 80 ℃ for 1.5h, and then roasting at 300 ℃ for 3h to obtain the supported heteropolyacid catalyst.
Example 1
A method for preparing acetate, comprising the following steps:
s1: stirring 25kg of acetic acid and 10kg of glycerol for 15min under the condition of 20 r/min; 0.3kg of the supported heteropolyacid catalyst of preparation example 1 was added in portions while stirring;
s2: heating the product obtained in the step S1 at 120 ℃ for 50min, rectifying to remove water generated in the reaction, and returning acetic acid fraction to the system;
s3: adding 18kg of saturated saline solution to the reaction product of S2, washing and separating out an organic phase;
s4: and distilling the organic phase washed in the S3 under reduced pressure at 1.2kPa, and collecting the fraction at 132-139 ℃ to prepare the glyceryl triacetate.
Example 2
A method for preparing acetate comprises the following steps:
s1: stirring 30kg of acetic acid and 10kg of glycerol for 5min at the speed of 50 r/min; while stirring, 0.5kg of the supported heteropolyacid catalyst of preparation example 2 was added in portions;
s2: heating the product obtained in the step S1 at 140 ℃ for 20min, rectifying to remove water generated in the reaction, and returning acetic acid fraction to the system;
s3: adding 10kg of saturated saline solution into the reaction product of S2, washing and separating out an organic phase;
s4: and distilling the organic phase washed in the S3 under reduced pressure at 1.2kPa, and collecting the fraction at 132-139 ℃ to prepare the glyceryl triacetate.
Example 3
A method for preparing acetate comprises the following steps:
s1: stirring 28kg of acetic acid and 10kg of glycerol for 10min at the speed of 35 r/min; while stirring, 0.4kg of the supported heteropolyacid catalyst of preparation example 3 was added in portions;
s2: heating the product obtained in the step S1 at 130 ℃ for 35min, rectifying to remove water generated in the reaction, and returning the acetic acid fraction to the system;
s3: adding 14kg of saturated saline solution into the reaction product of S2, washing and separating out an organic phase;
s4: and distilling the organic phase washed in the S3 under reduced pressure at 1.2kPa, and collecting the fraction at 132-139 ℃ to prepare the glyceryl triacetate.
Example 4
A method for preparing acetate comprises the following steps:
s1: stirring 20kg of acetic acid and 10kg of propylene glycol for 15min at the speed of 20 r/min; while stirring, 0.3kg of the supported heteropolyacid catalyst of preparation example 1 was added in portions;
s2: heating the product obtained in the step S1 at 120 ℃ for 50min, rectifying to remove water generated in the reaction, and returning acetic acid fraction to the system;
s3: adding 20kg of saturated saline solution to the reaction product of S2, washing and separating out an organic phase;
s4: and distilling the organic phase washed in the S3 under reduced pressure of 1.2kPa, and collecting the fraction at 105-110 ℃ to obtain the propylene glycol diacetate.
Example 5
A method for preparing acetate comprises the following steps:
s1: stirring 25kg of acetic acid and 10kg of propylene glycol for 5min at the speed of 50 r/min; while stirring, 0.5kg of the supported heteropolyacid catalyst of preparation example 2 was added in portions;
s2: heating the product obtained from the step S1 at 140 ℃ for 20min, rectifying to remove water generated by the reaction, and returning acetic acid fraction to the system;
s3: adding 13kg of saturated saline solution into the reaction product of S2, washing and separating out an organic phase;
s4: and distilling the organic phase washed in the S3 under reduced pressure at 1.2kPa, and collecting the fraction at 105-110 ℃ to prepare propylene glycol diacetate.
Example 6
A method for preparing acetate comprises the following steps:
s1: stirring 23kg of acetic acid and 10kg of propylene glycol for 10min at the speed of 35 r/min; while stirring, 0.4kg of the supported heteropolyacid catalyst of preparation example 3 was added in portions;
s2: heating the product obtained from the step S1 at 130 ℃ for 35min for reaction, rectifying to remove water generated by the reaction, and returning acetic acid fraction to the system;
s3: adding 16kg of saturated saline solution into the reaction product of S2, washing and separating out an organic phase;
s4: and distilling the organic phase washed in the S3 under reduced pressure at 1.2kPa, and collecting the fraction at 105-110 ℃ to prepare propylene glycol diacetate.
Example 7
A method for preparing acetate comprises the following steps:
s1: stirring 8kg of acetic acid and 10kg of phenethyl alcohol for 15min under the condition of 20 r/min; while stirring, 0.3kg of the supported heteropolyacid catalyst of preparation example 1 was added in portions;
s2: heating the product obtained in the step S1 at 120 ℃ for 50min, rectifying to remove water generated in the reaction, and returning acetic acid fraction to the system;
s3: 10kg of the reaction product of the saturated brine S2 was washed and the organic phase was separated;
s4: and distilling the organic phase washed in the S3 under reduced pressure at 1.2kPa, and collecting fractions at 80-83 ℃ to prepare the phenethyl acetate.
Example 8
A method for preparing acetate comprises the following steps:
s1: stirring 12kg of acetic acid and 10kg of phenethyl alcohol for 5min at the speed of 50 r/min; while stirring, 0.5kg of the supported heteropolyacid catalyst of preparation example 2 was added in portions;
s2: heating the product obtained in the step S1 at 140 ℃ for 20min, rectifying to remove water generated in the reaction, and returning acetic acid fraction to the system;
s3: adding 18kg of saturated saline solution to the reaction product of S2, washing and separating out an organic phase;
s4: and distilling the organic phase washed in the S3 under reduced pressure at 1.2kPa, and collecting fractions at 80-83 ℃ to prepare the phenethyl acetate.
Example 9
A method for preparing acetate comprises the following steps:
s1: stirring 10kg of acetic acid and 10kg of phenethyl alcohol for 10min at the condition of 35 r/min; while stirring, 0.4kg of the supported heteropolyacid catalyst of preparation example 3 was added in portions;
s2: heating the product obtained in the step S1 at 130 ℃ for 35min, rectifying to remove water generated in the reaction, and returning the acetic acid fraction to the system;
s3: adding 14kg of saturated saline solution into the reaction product of S2, washing and separating out an organic phase;
s4: and distilling the organic phase washed in the S3 under reduced pressure at 1.2kPa, and collecting fractions at 80-83 ℃ to prepare the phenethyl acetate.
Example 10
The difference from example 9 is that: in the step of S1, 10kg of the supported heteropolyacid catalyst of preparation example 3 was added in one portion while stirring.
Example 11
The difference from example 9 is that: in the step S1, as the supported heteropolyacid catalyst, a supported heteropolyacid catalyst which had been circulated 5 times in the same manner as in example 9 was used.
Example 12
The difference from example 9 is that: in the step S1, as the supported heteropolyacid catalyst, a supported heteropolyacid catalyst which had been circulated 10 times in the same manner as in example 9 was used.
Example 13
The difference from example 9 is that: in the step S1, as the supported heteropolyacid catalyst, a supported heteropolyacid catalyst which had been circulated 20 times in the same manner as in example 9 was used.
Comparative example 1
The difference from example 3 is that: the supported heteropolyacid catalyst was replaced with an equivalent amount of commercially available sulfuric acid.
Comparative example 2
The difference from example 6 is that: the supported heteropolyacid catalyst was replaced with an equivalent amount of commercially available phosphotungstic acid.
Comparative example 3
The difference from example 3 is that: no rectification was performed in the S2 step to remove water produced by the reaction and to return the acetic acid fraction to the system.
Performance test
The esterification rates of triacetin, propylene glycol diacetate and phenethylacetate obtained in examples 1 to 13 and comparative examples 1 to 3 were measured, and the results are shown in the following table 1:
TABLE 1
Esterification ratio (%) | Esterification rate (%) | Esterification rate (%) | |||
Example 1 | 87.0 | Example 7 | 85.6 | Example 13 | 81.4 |
Example 2 | 88.5 | Example 8 | 88.1 | Comparative example 1 | 76.4 |
Example 3 | 89.8 | Example 9 | 89.9 | Comparative example 2 | 63.7 |
Example 4 | 86.2 | Example 10 | 84.3 | Comparative example 3 | 78.5 |
Example 5 | 87.6 | Example 11 | 83.6 | ||
Example 6 | 90.4 | Example 12 | 82.8 |
In combination with examples 1, 2 and 3, it can be seen that, in the preparation process of glyceryl triacetate in example 3, the esterification rate of glyceryl triacetate is finally improved by optimizing the weight parts of the raw materials, and the supported heteropolyacid catalyst prepared in preparation example 3 has the best catalytic effect.
In combination with examples 4, 5 and 6, it can be seen that, in the preparation process of propylene glycol diacetate in example 6, the esterification rate of propylene glycol diacetate is finally improved by optimizing the weight parts of the raw materials, and the supported heteropolyacid catalyst prepared in preparation example 3 has the best catalytic effect.
In combination with examples 7, 8 and 9, it can be seen that, in the preparation process of phenethyl acetate in example 9, the esterification rate of phenethyl acetate is finally improved by optimizing the weight parts of the raw materials, and the supported heteropolyacid catalyst prepared in preparation example 3 has the best catalytic effect.
In combination with examples 10 and 9, it can be seen that in example 10, the supported heteropolyacid catalyst is added in portions, so that the supported heteropolyacid catalyst is used as a reaction catalyst and is fully contacted with acetic acid and phenethyl alcohol, and finally, the esterification rate of phenethyl acetate is improved.
In combination with examples 9, 11, 12 and 13, it can be seen that the supported heteropolyacid catalyst still has a good catalytic effect on the reaction between acetic acid and phenethyl alcohol after being recycled for many times, which proves that the supported heteropolyacid catalyst can be recycled, and is energy-saving and environment-friendly.
In combination with comparative examples 1 and 2 and example 3, it can be seen that the supported heteropolyacid catalyst synthesized by the method is higher in esterification rate when used for catalyzing the reaction of acetic acid and glycerol than when sulfuric acid is used for catalyzing the reaction of acetic acid and glycerol.
By combining comparative example 3 and example 3, it can be seen that the reaction of acetic acid and glycerol can be promoted to be continuously promoted towards the direction of generating glyceryl triacetate by rectifying to remove water, so that the esterification rate of the prepared glyceryl triacetate is high.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A method for preparing acetate, which is characterized by comprising the following steps:
s1: stirring acetic acid and alcohol for 5-15 min under the condition of 20-50 r/min; adding a supported heteropolyacid catalyst in batches while stirring, wherein the weight ratio of acetic acid, alcohol and the supported heteropolyacid catalyst is (0.8-3): 1: (0.03-0.05);
s2: heating the product obtained in the step S1 at the temperature of 120-140 ℃ for reaction for 20-50 min;
s3: washing a reaction product obtained in the step S2, and separating to obtain an organic phase;
s4: the organic phase washed in S3 was vacuum distilled to collect the desired fraction.
2. The process according to claim 1, wherein: the alcohol is any one of glycerol, propylene glycol and phenethyl alcohol, and the weight ratio of the glycerol to the acetic acid is 1: (2.5-3); the weight ratio of propylene glycol to acetic acid is 1: (2.0-2.5); the weight ratio of the phenethyl alcohol to the acetic acid is 1: (0.8-1).
3. The process according to claim 1, wherein: and in the step S3, adding saturated salt solution into the mixed solution for washing, and then separating the solution, wherein the weight ratio of the saturated salt solution to the mixed solution is (1-2): 1.
4. the process according to claim 2, wherein: when the alcohol is glycerol, distilling under reduced pressure of 1.2kPa in the step S4, and collecting the fraction with the temperature of 132-139 ℃ to prepare glyceryl triacetate; when the alcohol is propylene glycol, distilling under reduced pressure of 1.2kPa in the step S4, and collecting a fraction with the temperature of 105-110 ℃ to prepare propylene glycol diacetate; and when the alcohol is phenethyl alcohol, distilling under reduced pressure of 1.2kPa in the step S4, and collecting fractions at the temperature of 80-83 ℃ to prepare phenethyl acetate.
5. The process according to claim 1, wherein: in the step S2, rectification is performed while the system is heated for reaction to remove water produced by the reaction and to return the acetic acid fraction to the system.
6. The process according to claim 1, wherein: the preparation method of the supported polyacid catalyst comprises the following steps:
(1): dispersing and dissolving neodymium salt, potassium salt, copper salt and a USY molecular sieve in water, stirring for 6-8 hours under the condition of 100-130 r/min, then adding heteropoly acid, and continuously stirring for 5-6 hours under the condition of 100-120 r/min to obtain a colloid system, wherein the weight ratio of the neodymium salt, the potassium salt, the copper salt, the heteropoly acid, the USY molecular sieve to the water is (1-2): (1-2): (1-2): (3-5): 5: (3-4);
(2): drying the colloid system at 70-90 ℃ for 1-2 h, and then roasting at 200-400 ℃ for 2-4 h to obtain the supported heteropolyacid catalyst.
7. The process according to claim 6, wherein: in step S1, the USY molecular sieve is previously treated as follows:
(0): immersing the USY molecular sieve in an acid solution, stirring for 0.5-1.5 h at the temperature of 80-90 ℃, filtering, washing with water, drying for 1-1.5 h at the temperature of 100-120 ℃, roasting for 3-5 h at the temperature of 400-600 ℃, wherein the weight ratio of the USY molecular sieve to the acid solution is 1: (3-10).
8. The process according to claim 6 for the preparation of acetic esters, characterized in that: the heteropoly acid adopts phosphotungstic acid.
9. The process according to claim 6, wherein: the neodymium salt is neodymium nitrate, the potassium salt is potassium nitrate, and the copper salt is copper nitrate.
10. The process according to claim 7, wherein: the acid solution is any one of 0.5-2 mol/L oxalic acid, 0.5-2 mol/L citric acid and 0.5-2 mol/L tartaric acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110212129.9A CN114956995A (en) | 2021-02-25 | 2021-02-25 | Preparation method of acetate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110212129.9A CN114956995A (en) | 2021-02-25 | 2021-02-25 | Preparation method of acetate |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114956995A true CN114956995A (en) | 2022-08-30 |
Family
ID=82973758
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110212129.9A Pending CN114956995A (en) | 2021-02-25 | 2021-02-25 | Preparation method of acetate |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114956995A (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11286468A (en) * | 1999-02-08 | 1999-10-19 | Showa Denko Kk | Production of lower fatty acid ester |
GB0411895D0 (en) * | 2001-12-27 | 2004-06-30 | Daicel Chem | Catalyst and process for the production of lower fatty acid esters |
CN1583253A (en) * | 2004-06-04 | 2005-02-23 | 南京工业大学 | Preparation and use of heteropolyacid catalyst carried on dealuminized super-stable gamma zeolite |
CN105753691A (en) * | 2016-03-30 | 2016-07-13 | 广西新天德能源有限公司 | Method for utilizing molecular sieve supported catalyst to prepare acetic ether |
CN105820052A (en) * | 2016-03-30 | 2016-08-03 | 广西新天德能源有限公司 | Method for preparing n-butyl acetate from molecular sieve immobilized catalyst |
CN106946698A (en) * | 2017-05-09 | 2017-07-14 | 江苏瑞晨化学有限公司 | A kind of method that utilization macromolecule loading mesoporous catalyst prepares triacetyl glycerine |
CN108772100A (en) * | 2018-05-22 | 2018-11-09 | 广东工业大学 | A kind of heteropolyacid salt solid catalyst and its preparation method and application |
CN112371101A (en) * | 2020-11-17 | 2021-02-19 | 广西壮族自治区林业科学研究院 | Catalyst for catalyzing fatty acid esterification reaction and fatty acid ester green synthesis method |
-
2021
- 2021-02-25 CN CN202110212129.9A patent/CN114956995A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11286468A (en) * | 1999-02-08 | 1999-10-19 | Showa Denko Kk | Production of lower fatty acid ester |
GB0411895D0 (en) * | 2001-12-27 | 2004-06-30 | Daicel Chem | Catalyst and process for the production of lower fatty acid esters |
CN1583253A (en) * | 2004-06-04 | 2005-02-23 | 南京工业大学 | Preparation and use of heteropolyacid catalyst carried on dealuminized super-stable gamma zeolite |
CN105753691A (en) * | 2016-03-30 | 2016-07-13 | 广西新天德能源有限公司 | Method for utilizing molecular sieve supported catalyst to prepare acetic ether |
CN105820052A (en) * | 2016-03-30 | 2016-08-03 | 广西新天德能源有限公司 | Method for preparing n-butyl acetate from molecular sieve immobilized catalyst |
CN106946698A (en) * | 2017-05-09 | 2017-07-14 | 江苏瑞晨化学有限公司 | A kind of method that utilization macromolecule loading mesoporous catalyst prepares triacetyl glycerine |
CN108772100A (en) * | 2018-05-22 | 2018-11-09 | 广东工业大学 | A kind of heteropolyacid salt solid catalyst and its preparation method and application |
CN112371101A (en) * | 2020-11-17 | 2021-02-19 | 广西壮族自治区林业科学研究院 | Catalyst for catalyzing fatty acid esterification reaction and fatty acid ester green synthesis method |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101455976A (en) | Effective catalyst used in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol and production method thereof | |
CN107814939B (en) | Method for synthesizing poly (ethylene glycol methyl phosphonate) by metal oxide catalysis | |
CN112898250B (en) | Preparation method of 2, 5-furandicarboxylic acid | |
UA123868C2 (en) | Process for the preparation of ethylene glycol from sugars | |
CN105130801B (en) | Catalytic synthesis method of n-butyl hydroxyacetate | |
CN107899612A (en) | A kind of more acids ionic-liquid catalysts of functionalization, preparation method and catalyze and synthesize the method for compounding acetic isoborneol ester with it | |
CN114956995A (en) | Preparation method of acetate | |
CN103848739A (en) | Production method of high-purity dimethyl fumarate | |
CN111675612B (en) | Method for preparing 2,3,5-trimethylhydroquinone diester | |
CN108043456A (en) | A kind of polyacid class ionic-liquid catalyst, preparation method and the method for preparing cyclohexanol with its catalysis ethyl cyclohexyl ester hydrolysis | |
EP3173403B1 (en) | Method for preparing n,n'-bis(2-cyanoethyl)-1,2-ethylenediamine by using cation exchange resin as catalyst | |
CN103922930A (en) | Method for preparing n-propyl acetate by using multi-acid intercalated hydrotalcite catalyst | |
CN107722030A (en) | A kind of method for preparing dissident's sugar alcohol | |
CN112898251A (en) | Method for preparing 2, 5-furandicarboxylic acid | |
CN110776419B (en) | Green and clean production process for preparing dibutyl phthalate | |
CN105272825B (en) | Synthesis method of 3-methyl-2-en-4-yn pentanol through acid ionic liquid catalysis | |
CN106083585A (en) | A kind of method that dimethyl carbonate is prepared in indirect alcoholysis | |
CN113788775B (en) | Sulfonic acid functionalized pyrrolidone ionic liquid catalyst, and preparation method and application thereof | |
CN107952479A (en) | A kind of functionalization more acids ionic-liquid catalyst, preparation method and the methods with its catalysis cyclohexene direct esterification | |
JPH06271557A (en) | Production of cis-epoxysuccinic acid salt | |
CN114436844B (en) | Synthesis method of methyl glycolate | |
CN107473933A (en) | A kind of sec-butyl alcohol of catalyst containing ionic liquid | |
CN107032986A (en) | A kind of method that presence of acidic ionic liquid catalyst synthesizes the propanol ether acetate of 2 methoxyl group 1 | |
CN115819188B (en) | Preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol | |
CN115385767B (en) | Preparation method of divinyl aromatic compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |