CN104761450A - Preparation method of ethyl propionate - Google Patents
Preparation method of ethyl propionate Download PDFInfo
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- CN104761450A CN104761450A CN201510126543.2A CN201510126543A CN104761450A CN 104761450 A CN104761450 A CN 104761450A CN 201510126543 A CN201510126543 A CN 201510126543A CN 104761450 A CN104761450 A CN 104761450A
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- exchange resin
- propionic acid
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- acid
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- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 102
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 55
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 55
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 51
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 51
- 238000005886 esterification reaction Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims description 47
- 229920005989 resin Polymers 0.000 claims description 47
- 238000000605 extraction Methods 0.000 claims description 40
- 230000032050 esterification Effects 0.000 claims description 37
- 230000002378 acidificating effect Effects 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 48
- 239000000126 substance Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 19
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 19
- 229940017219 methyl propionate Drugs 0.000 description 19
- 150000002148 esters Chemical class 0.000 description 18
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000009736 wetting Methods 0.000 description 13
- 238000004364 calculation method Methods 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011831 acidic ionic liquid Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl imidazolium cation Chemical compound 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- GEMITLJMEMBDKW-UHFFFAOYSA-N hydrogen sulfate;1h-imidazol-3-ium Chemical compound C1=CNC=N1.OS(O)(=O)=O GEMITLJMEMBDKW-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000007518 monoprotic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JAELLLITIZHOGQ-UHFFFAOYSA-N tert-butyl propanoate Chemical compound CCC(=O)OC(C)(C)C JAELLLITIZHOGQ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed is a preparation method of ethyl propionate. The invention relates to preparation of propionate from propionic acid and monohydric alcohol in the presence of a catalyst of a gel-type strong-acid ion exchange resin through an esterification reaction. The gel-type strong-acid ion exchange resin is a hydrogen-form styrene-stilbene copolymer containing sulfonate groups, and has a bore diameter less than 8nm. The invention belongs to the technical field of organic matter preparation. According to the invention, the catalyst is adopted for effectively absorbing impurities, so that the product purity is improved. The catalyst is good in catalytic effect and low in corrosivity, and is easy to separate from the product.
Description
The application is the applying date is on December 20th, 2012, and application number is 201210557811.2, and denomination of invention is the divisional application of " preparation method of propionic ester ".
Technical field
The present invention relates to a kind of method being raw material production propionic ester with propionic acid and monohydroxy-alcohol, belong to organic preparing technical field.
Background technology
The most basic industrial chemicals with methyl propionate, ethyl propionate, n propyl propionate and the isopropyl propionate etc. that propionic acid and monohydroxy-alcohol obtain for raw material, can be used as organism solvent to use, and be widely used in the preparation of spices and the preparation of other organic compound.At present, some special industries, such as battery industry, increase day by day to the demand of this type of propionic ester, simultaneously high to the requirement of its purity, and its purity of general requirement reaches more than 99.5%, requires that higher needs reaches more than 99.8%.
Methyl propionate is obtained by propionic acid and methanol esterification, and ethyl propionate is obtained by propionic acid and ethyl esterification, and n propyl propionate is obtained by propionic acid and n-propyl alcohol esterification, and isopropyl propionate is obtained by propionic acid and Virahol esterification.Its conventional preparation method is by propionic acid and monohydroxy-alcohol mixing, direct esterification under the catalysis of sulfuric acid, through rectifying, and obtained finished product.Although this preparation method is with low cost, because sulfuric acid is that strong acid has very strong oxidisability and dehydration property, cause side reaction in reaction many, be unfavorable for preparing highly purified propionic ester.In addition, this preparation method is comparatively serious to the corrosion of production unit; Contaminative is high, and environmental protection pressure is large.At present, a lot of people is just being devoted to find the new catalyst that can substitute sulfuric acid.
Chinese patent literature CN102336661A(application number is: the preparation method 201110205756.6) disclosing a kind of methyl propionate, under the effect of acidic ionic liquid catalysts, make propionic acid and methyl alcohol send out should propionic acid synthesized methyl esters, and wherein the cationic moiety of acidic ionic liquid catalysts is selected from alkyl imidazolium cation, pyridines positively charged ion, quaternaries cation and season phosphonium salt cationoid.Chinese patent literature CN102320962A(application number is: a kind of method 201110200706.9) disclosing catalytic synthesis of methyl propionate, selects the ionic liquid of pyridine hydrosulfate, imidazole bisulfate, pyridine p-toluenesulfonic acid, imidazoles tosic acid, imidazoles hydrophosphate or tosic acid to be catalyzer.Although these two kinds of methods can reduce the corrodibility to equipment, acidic ionic liquid catalysts and product extremely difficulty are separated, and can affect the purity of product, practicality is not good enough.
Chinese patent literature CN101560152B(application number is: a kind of method 200910027313.5) disclosing synthesizing propionate.The method is propionic acid and alkene synthesizing propionate under the effect of macropore strong acid ion-exchange resin catalyst, and wherein macropore strong acid ion-exchange resin catalyst is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group.A kind of raw material that this synthetic method adopts is propionic acid, and another kind of raw material is alkene (propylene or iso-butylene), and the product of synthesis is isopropyl propionate or propanoic acid tert-butyl ester, so reaction does not generate water, is different from the reaction that propionic acid and monoprotic acid esterification generate propionic ester.In addition, macroporous type strong-acid ion exchange resin uses as an acidic catalyst, although reaction conversion ratio is high, selectivity is high, and easy and product separation helps not quite the purity improving propionic ester.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind ofly passes through adopted catalyzer absorption reaction impurity effectively, improves product purity, and catalyst is effective, corrodibility is low, easily and the preparation method of the propionic ester of product separation.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of propionic ester, esterification is there is and generates propionic ester in propionic acid and monohydroxy-alcohol under the effect of gel-type strongly acidic ion-exchange resin catalyst, described gel-type strong-acid ion exchange resin is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and the aperture of resin is less than 8nm.
In order to solve the problems of the technologies described above, present invention also offers a kind of preparation method of propionic ester, esterification is there is and generates propionic ester in propionic acid and monohydroxy-alcohol under the effect of gel-type strongly acidic ion-exchange resin catalyst, described monohydroxy-alcohol is methyl alcohol, described propionic ester is methyl propionate, described gel-type strong-acid ion exchange resin is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and the aperture of resin is less than 8nm.。The method is for the preparation of highly purified methyl propionate.
In order to solve the problems of the technologies described above, present invention also offers a kind of preparation method of propionic ester, esterification is there is and generates propionic ester in propionic acid and monohydroxy-alcohol under the effect of gel-type strongly acidic ion-exchange resin catalyst, described monohydroxy-alcohol is ethanol, described propionic ester is ethyl propionate, described gel-type strong-acid ion exchange resin is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and the aperture of resin is less than 8nm.The method is for the preparation of highly purified ethyl propionate.
In order to solve the problems of the technologies described above, present invention also offers a kind of preparation method of propionic ester, esterification is there is and generates propionic ester in propionic acid and monohydroxy-alcohol under the effect of gel-type strongly acidic ion-exchange resin catalyst, described monohydroxy-alcohol is n-propyl alcohol, described propionic ester is n propyl propionate, described gel-type strong-acid ion exchange resin is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and the aperture of resin is less than 8nm.The method is for the preparation of highly purified n propyl propionate.
In order to solve the problems of the technologies described above, present invention also offers a kind of preparation method of propionic ester, esterification is there is and generates propionic ester in propionic acid and monohydroxy-alcohol under the effect of gel-type strongly acidic ion-exchange resin catalyst, described monohydroxy-alcohol is Virahol, described propionic ester is isopropyl propionate, described gel-type strong-acid ion exchange resin is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and the aperture of resin is less than 8nm.The method is for the preparation of highly purified isopropyl propionate.
In order to make the better effects if of gel-type strong-acid ion exchange resin adsorbing contaminant, improve the transformation efficiency of esterification and the yield of propionic ester, the one of technique scheme is preferably: above-mentioned gel-type strong-acid ion exchange resin is Dowex 50W × 2 hydrogen form resin, Dowex 50W × 4 hydrogen form resin or Dowex 50W × 8 hydrogen form resin simultaneously.
In order to the quality of the speed of reaction and product that ensure esterification, the one of technique scheme preferably: before esterification, in reactor, add propionic acid and account for the gel-type strongly acidic ion-exchange resin catalyst of propionic acid quality 2% to 20%.
In order to improve the speed of reaction of esterification, further ensure the quality of product, the one of technique scheme is preferably: during esterification, temperature in reactor is 90 DEG C to 120 DEG C, stirring velocity is 600rpm/min to 1000rpm/min, in reactor, add the mixed solution of propionic acid and monohydroxy-alcohol continuously with the speed of 1.0L/min to 1.5L/min, in described mixed solution, the mol ratio of propionic acid and monohydroxy-alcohol is 1:1 to 2:1.
In order to effectively promote the ester content of finished product, the one of technique scheme is preferably: carry out rectifying after esterification, in order to the propionic ester in separation and Extraction vapor of mixture liquid, during rectifying, in vapor of mixture liquid, add extraction agent, the mass ratio of extraction agent and azeotropic mixed solution is 1:5 to 1:25.
In order to improve rectification effect, thus promote the ester content of finished product better, the one of technique scheme is preferably: above-mentioned extraction agent is ethylene glycol.
The present invention has positive effect: the preparation method of propionic ester of the present invention adopts gel-type strong-acid ion exchange resin as catalyzer, the aperture of this resin is at below 8nm, wetting back aperture is at below 5nm, compare the aperture of macroporous type strong-acid ion exchange resin 20nm to 500nm, the gel-type strong-acid ion exchange resin adopting very low pore size in the esterification reaction can the impurity effectively in absorption reaction thing and the impurity in product, is conducive to the purity promoting product.Being measured by stratographic analysis compares known to the ester content in propionic ester finished product, even if the macroporous type strong-acid ion exchange resin adopting aperture less is as catalyzer (as: Amberlyst 15, mean pore size is 29nm), ester content in propionic ester finished product is than adopting low by about 0.5% as catalyzer of gel-type strong-acid ion exchange resin.In addition, the yield of propionic ester is also than adopting low as catalyzer of gel-type strong-acid ion exchange resin.If the macroporous type strong-acid ion exchange resin adopting aperture larger is as catalyzer, the difference of ester content and yield will be more obvious.The method is applicable to low cost and produces the propionic esters such as methyl propionate, ethyl propionate, n propyl propionate and isopropyl propionate on a large scale, has high economic worth.In addition, adopt gel-type strong-acid ion exchange resin as catalyzer, reaction conversion ratio is high, and selectivity is high, and by product is few.Because gel-type strong-acid ion exchange resin is solid granular, just can be separated with product catalyzer easily by simple strainer filtering device, catalyzer can reuse, economic environmental protection.
Embodiment
(embodiment 1 methyl propionate)
The concrete steps of the preparation method of the propionic ester of the present embodiment are as follows:
(1) before esterification, to capacity be 1000L distillation column reactor still in, drop into the propionic acid (chemical pure) of 400kg and the gel-type strongly acidic ion-exchange resin catalyst of 20kg.Described gel-type strongly acidic ion-exchange resin catalyst is the granular size that DOW Chemical is produced is the Dowex 50W × 2 hydrogen form resin of 200mesh to 400mesh, this resin is solid granular, main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and degree of crosslinking is 2%.After wetting, the aperture of this resin is 2nm to 4nm.
(2) reacting by heating still, controlled by temperature in the kettle at 103 DEG C to 108 DEG C, stir continuously the material in reactor, mixing speed is 800rpm/min.The mixed solution dropping into propionic acid (chemical pure) and methyl alcohol (chemical pure) with the speed of 1.2L/min in reactor continuously carries out esterification, and wherein the molar mass of propionic acid and methyl alcohol is than being 6:5.
(3) esterification reaction product after filtration is left standstill in water trap, from water trap bottom part from water outlet, isolate the vapor of mixture liquid of methyl propionate and methyl alcohol from water trap top.In vapor of mixture liquid, add extraction agent, described extraction agent is ethylene glycol, and the mass ratio of extraction agent and azeotropic mixed solution is 1:10.The plate number of rectifying tower is 16, and the tower top temperature of rectifying tower controlled at 79.2 DEG C to 80.3 DEG C, control reflux ratio is 4:1, from overhead extraction methyl propionate finished product.
The ester content that stratographic analysis measures in methyl propionate finished product is 99.8%, and acid number is 0.82mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of methyl propionate is 98.60%.
(embodiment 2 methyl propionate)
The concrete steps of the preparation method of the propionic ester of the present embodiment are as follows:
(1) before esterification, to capacity be 1000L distillation column reactor still in, drop into the propionic acid (chemical pure) of 300kg and the gel-type strongly acidic ion-exchange resin catalyst of 30kg.Described gel-type strongly acidic ion-exchange resin catalyst is the granular size that DOW Chemical is produced is the Dowex 50W × 4 hydrogen form resin of 200mesh to 400mesh, this resin is solid granular, main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and degree of crosslinking is 4%.After wetting, the aperture of this resin is 2nm to 4nm.
(2) reacting by heating still, controlled by temperature in the kettle at 103 DEG C to 108 DEG C, stir continuously the material in reactor, mixing speed is 800rpm/min.The mixed solution dropping into propionic acid (chemical pure) and methyl alcohol (chemical pure) with the speed of 1.5L/min in reactor continuously carries out esterification, and wherein the molar mass of propionic acid and methyl alcohol is than being 5:4.
(3) esterification reaction product after filtration is left standstill in water trap, from water trap bottom part from water outlet, isolate the vapor of mixture liquid of methyl propionate and methyl alcohol from water trap top.In vapor of mixture liquid, add extraction agent, described extraction agent is ethylene glycol, and the mass ratio of extraction agent and azeotropic mixed solution is 1:12.The plate number of rectifying tower is 16, and the tower top temperature of rectifying tower controlled at 79.2 DEG C to 80.3 DEG C, control reflux ratio is 3:1, from overhead extraction methyl propionate finished product.
The ester content that stratographic analysis measures in methyl propionate finished product is 99.7%, and acid number is 0.88mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of methyl propionate is 97.28%.
(comparative example 1 methyl propionate)
The rest part of the preparation method of the propionic ester of the present embodiment is identical with embodiment 1, be without part: catalyzer adopts macroporous type strongly acidic ion-exchange resin catalyst, described macroporous type strongly acidic ion-exchange resin catalyst is Amberlyst 15 resin that DOW Chemical is produced, this resin is solid granular, and main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group.After wetting, the mean pore size of this resin is 29nm.
The ester content that stratographic analysis measures in the methyl propionate finished product adopting this preparation method to obtain is 99.2%, and acid number is 0.97mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of methyl propionate is 92.61%.
(embodiment 3 ethyl propionate)
The concrete steps of the preparation method of the propionic ester of the present embodiment are as follows:
(1) before esterification, to capacity be 1000L distillation column reactor still in, drop into the propionic acid (chemical pure) of 400kg and the gel-type strongly acidic ion-exchange resin catalyst of 20kg.Described gel-type strongly acidic ion-exchange resin catalyst is the granular size that DOW Chemical is produced is the Dowex 50W × 2 hydrogen form resin of 100mesh to 200mesh, this resin is solid granular, main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and degree of crosslinking is 2%.After wetting, the aperture of this resin is 2nm to 4nm.
(2) reacting by heating still, controlled by temperature in the kettle at 107 DEG C to 110 DEG C, stir continuously the material in reactor, mixing speed is 800rpm/min.The mixed solution dropping into propionic acid (chemical pure) and ethanol (chemical pure) with the speed of 1.2L/min in reactor continuously carries out esterification, and wherein the molar mass of propionic acid and ethanol is than being 6:5.
(3) esterification reaction product after filtration is left standstill in water trap, from water trap bottom part from water outlet, isolate the vapor of mixture liquid of ethyl propionate and ethanol from water trap top.In vapor of mixture liquid, add extraction agent, described extraction agent is ethylene glycol, and the mass ratio of extraction agent and azeotropic mixed solution is 1:10.The plate number of rectifying tower is 16, and the tower top temperature of rectifying tower controlled at 89.5 DEG C to 99.7 DEG C, control reflux ratio is 4:1, from overhead extraction ethyl propionate finished product.
The ester content that stratographic analysis measures in ethyl propionate finished product is 99.9%, and acid number is 0.81mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of ethyl propionate is 99.13%.
(embodiment 4 ethyl propionate)
The concrete steps of the preparation method of the propionic ester of the present embodiment are as follows:
(1) before esterification, to capacity be 1000L distillation column reactor still in, drop into the propionic acid (chemical pure) of 300kg and the gel-type strongly acidic ion-exchange resin catalyst of 10kg.Described gel-type strongly acidic ion-exchange resin catalyst is the granular size that DOW Chemical is produced is the Dowex 50W × 8 hydrogen form resin of 200mesh to 400mesh, this resin is solid granular, main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and degree of crosslinking is 8%.After wetting, the aperture of this resin is 2nm to 4nm.
(2) reacting by heating still, controlled by temperature in the kettle at 107 DEG C to 110 DEG C, stir continuously the material in reactor, mixing speed is 800rpm/min.The mixed solution dropping into propionic acid (chemical pure) and ethanol (chemical pure) with the speed of 1.5L/min in reactor continuously carries out esterification, and wherein the molar mass of propionic acid and ethanol is than being 5:4.
(3) esterification reaction product after filtration is left standstill in water trap, from water trap bottom part from water outlet, isolate the vapor of mixture liquid of ethyl propionate and ethanol from water trap top.In vapor of mixture liquid, add extraction agent, described extraction agent is ethylene glycol, and the mass ratio of extraction agent and azeotropic mixed solution is 1:15.The plate number of rectifying tower is 16, and the tower top temperature of rectifying tower controlled at 89.5 DEG C to 99.7 DEG C, control reflux ratio is 5:1, from overhead extraction ethyl propionate finished product.
The ester content that stratographic analysis measures in ethyl propionate finished product is 99.7%, and acid number is 0.86mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of ethyl propionate is 97.52%.
(comparative example 2 ethyl propionate)
The rest part of the preparation method of the propionic ester of the present embodiment is identical with embodiment 3, be without part: catalyzer adopts macroporous type strongly acidic ion-exchange resin catalyst, described macroporous type strongly acidic ion-exchange resin catalyst is Amberlyst 15 resin that DOW Chemical is produced, this resin is solid granular, and main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group.After wetting, the mean pore size of this resin is 29nm.
The ester content that stratographic analysis measures in the ethyl propionate finished product adopting this preparation method to obtain is 99.3%, and acid number is 0.95mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of ethyl propionate is 93.16%.
(embodiment 5 n propyl propionate)
The concrete steps of the preparation method of the propionic ester of the present embodiment are as follows:
(1) before esterification, to capacity be 1000L distillation column reactor still in, drop into the propionic acid (chemical pure) of 400kg and the gel-type strongly acidic ion-exchange resin catalyst of 20kg.Described gel-type strongly acidic ion-exchange resin catalyst is the granular size that DOW Chemical is produced is the Dowex 50W × 2 hydrogen form resin of 200mesh to 400mesh, this resin is solid granular, main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and degree of crosslinking is 2%.After wetting, the aperture of this resin is 2nm to 4nm.
(2) reacting by heating still, controlled by temperature in the kettle at 108 DEG C to 113 DEG C, stir continuously the material in reactor, mixing speed is 800rpm/min.The mixed solution dropping into propionic acid (chemical pure) and n-propyl alcohol (chemical pure) with the speed of 1.2L/min in reactor continuously carries out esterification, and wherein the molar mass of propionic acid and n-propyl alcohol is than being 6:5.
(3) esterification reaction product after filtration is left standstill in water trap, from water trap bottom part from water outlet, isolate the vapor of mixture liquid of n propyl propionate and n-propyl alcohol from water trap top.In vapor of mixture liquid, add extraction agent, described extraction agent is ethylene glycol, and the mass ratio of extraction agent and azeotropic mixed solution is 1:5.The plate number of rectifying tower is 16, and the tower top temperature of rectifying tower controlled at 121.5 DEG C to 124.5 DEG C, control reflux ratio is 3:1, from overhead extraction n propyl propionate finished product.
The ester content that stratographic analysis measures in n propyl propionate finished product is 99.8%, and acid number is 0.88mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of n propyl propionate is 97.36%.
(embodiment 6 n propyl propionate)
The concrete steps of the preparation method of the propionic ester of the present embodiment are as follows:
(1) before esterification, to capacity be 1000L distillation column reactor still in, drop into the propionic acid (chemical pure) of 300kg and the gel-type strongly acidic ion-exchange resin catalyst of 10kg.Described gel-type strongly acidic ion-exchange resin catalyst is the granular size that DOW Chemical is produced is the Dowex 50W × 4 hydrogen form resin of 200mesh to 400mesh, this resin is solid granular, main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and degree of crosslinking is 4%.After wetting, the aperture of this resin is 2nm to 4nm.
(2) reacting by heating still, controlled by temperature in the kettle at 108 DEG C to 113 DEG C, stir continuously the material in reactor, mixing speed is 800rpm/min.The mixed solution dropping into propionic acid (chemical pure) and n-propyl alcohol (chemical pure) with the speed of 1.5L/min in reactor continuously carries out esterification, and wherein the molar mass of propionic acid and n-propyl alcohol is than being 5:4.
(3) esterification reaction product after filtration is left standstill in water trap, from water trap bottom part from water outlet, isolate the vapor of mixture liquid of n propyl propionate and n-propyl alcohol from water trap top.In vapor of mixture liquid, add extraction agent, described extraction agent is ethylene glycol, and the mass ratio of extraction agent and azeotropic mixed solution is 1:10.The plate number of rectifying tower is 16, and the tower top temperature of rectifying tower controlled at 121.5 DEG C to 124.5 DEG C, control reflux ratio is 3:1, from overhead extraction n propyl propionate finished product.
The ester content that stratographic analysis measures in n propyl propionate finished product is 99.7%, and acid number is 0.91mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of n propyl propionate is 96.21%.
(comparative example 3 n propyl propionate)
The rest part of the preparation method of the propionic ester of the present embodiment is identical with embodiment 5, be without part: catalyzer adopts macroporous type strongly acidic ion-exchange resin catalyst, described macroporous type strongly acidic ion-exchange resin catalyst is Amberlyst 15 resin that DOW Chemical is produced, this resin is solid granular, and main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group.After wetting, the mean pore size of this resin is 29nm.
The ester content that stratographic analysis measures in the n propyl propionate finished product adopting this preparation method to obtain is 99.2%, and acid number is 0.93mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of n propyl propionate is 91.29%.
(embodiment 7 isopropyl propionate)
The concrete steps of the preparation method of the propionic ester of the present embodiment are as follows:
(1) before esterification, to capacity be 1000L distillation column reactor still in, drop into the propionic acid (chemical pure) of 400kg and the gel-type strongly acidic ion-exchange resin catalyst of 20kg.Described gel-type strongly acidic ion-exchange resin catalyst is the granular size that DOW Chemical is produced is the Dowex 50W × 4 hydrogen form resin of 200mesh to 400mesh, this resin is solid granular, main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and degree of crosslinking is 2%.After wetting, the aperture of this resin is 2nm to 4nm.
(2) reacting by heating still, controlled by temperature in the kettle at 108 DEG C to 113 DEG C, stir continuously the material in reactor, mixing speed is 800rpm/min.The mixed solution dropping into propionic acid (chemical pure) and Virahol (chemical pure) with the speed of 1.2L/min in reactor continuously carries out esterification, and wherein the molar mass of propionic acid and Virahol is than being 7:5.
(3) esterification reaction product after filtration is left standstill in water trap, from water trap bottom part from water outlet, isolate the vapor of mixture liquid of isopropyl propionate and Virahol from water trap top.In vapor of mixture liquid, add extraction agent, described extraction agent is ethylene glycol, and the mass ratio of extraction agent and azeotropic mixed solution is 1:10.The plate number of rectifying tower is 16, and the tower top temperature of rectifying tower controlled at 121.5 DEG C to 124.5 DEG C, control reflux ratio is 4:1, from overhead extraction isopropyl propionate finished product.
The ester content that stratographic analysis measures in isopropyl propionate finished product is 99.8%, and acid number is 0.89mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of isopropyl propionate is 97.12%.
(embodiment 8 isopropyl propionate)
The concrete steps of the preparation method of the propionic ester of the present embodiment are as follows:
(1) before esterification, to capacity be 1000L distillation column reactor still in, drop into the propionic acid (chemical pure) of 300kg and the gel-type strongly acidic ion-exchange resin catalyst of 9kg.Described gel-type strongly acidic ion-exchange resin catalyst is the granular size that DOW Chemical is produced is the Dowex 50W × 8 hydrogen form resin of 100mesh to 200mesh, this resin is solid granular, main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and degree of crosslinking is 8%.After wetting, the aperture of this resin is 2nm to 4nm.
(2) reacting by heating still, controlled by temperature in the kettle at 108 DEG C to 113 DEG C, stir continuously the material in reactor, mixing speed is 800rpm/min.The mixed solution dropping into propionic acid (chemical pure) and Virahol (chemical pure) with the speed of 1.5L/min in reactor continuously carries out esterification, and wherein the molar mass of propionic acid and Virahol is than being 6:5.
(3) esterification reaction product after filtration is left standstill in water trap, from water trap bottom part from water outlet, isolate the vapor of mixture liquid of isopropyl propionate and Virahol from water trap top.In vapor of mixture liquid, add extraction agent, described extraction agent is ethylene glycol, and the mass ratio of extraction agent and azeotropic mixed solution is 1:5.The plate number of rectifying tower is 16, and the tower top temperature of rectifying tower controlled at 121.5 DEG C to 124.5 DEG C, control reflux ratio is 4:1, from overhead extraction isopropyl propionate finished product.
The ester content that stratographic analysis measures in isopropyl propionate finished product is 99.7%, and acid number is 0.92mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of isopropyl propionate is 96.53%.
(comparative example 4 isopropyl propionate)
The rest part of the preparation method of the propionic ester of the present embodiment is identical with embodiment 5, be without part: catalyzer adopts macroporous type strongly acidic ion-exchange resin catalyst, described macroporous type strongly acidic ion-exchange resin catalyst is Amberlyst 15 resin that DOW Chemical is produced, this resin is solid granular, and main component is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group.After wetting, the mean pore size of this resin is 29nm.
The ester content that stratographic analysis measures in the isopropyl propionate finished product adopting this preparation method to obtain is 99.4%, and acid number is 0.89mgKOH/g.Can obtain according to the concentration of reactant and product and Mass Calculation, the yield of isopropyl propionate is 93.77%.
Claims (2)
1. the preparation method of an ethyl propionate, it is characterized in that: propionic acid and ethanol esterification occur under the effect of gel-type strongly acidic ion-exchange resin catalyst and generates ethyl propionate, described gel-type strong-acid ion exchange resin is the vinylbenzene-styrene copolymer of Hydrogen band sulfonate group, and the aperture of resin is 2nm to 4nm; Before esterification, in reactor, add propionic acid and the gel-type strongly acidic ion-exchange resin catalyst accounting for propionic acid quality 2% to 20%; During esterification, temperature in reactor is 90 DEG C to 120 DEG C, stirring velocity is 600rpm/min to 1000rpm/min, adds the mixed solution of propionic acid and ethanol with the speed of 1.0L/min to 1.5L/min in reactor continuously, and in described mixed solution, the mol ratio of propionic acid and ethanol is 1:1 to 2:1; Carry out rectifying after esterification, in order to the ethyl propionate in separation and Extraction vapor of mixture liquid, during rectifying, in vapor of mixture liquid, add extraction agent, the mass ratio of extraction agent and azeotropic mixed solution is 1:5 to 1:25;
Described gel-type strong-acid ion exchange resin is Dowex 50W × 2 hydrogen form resins;
Described extraction agent is ethylene glycol.
2. the ethyl propionate made of a preparation method as claimed in claim 1.
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| CN1197791A (en) * | 1997-04-28 | 1998-11-04 | 国营吴江香料厂 | Ethyl propionate producing technology |
| CN101560152A (en) * | 2009-05-27 | 2009-10-21 | 南京工业大学 | Method for synthesizing propionate |
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| US4528395A (en) * | 1983-08-15 | 1985-07-09 | American Cyanamid Co. | Process for esterifying 3,5-di-tert-butyl-4-hydroxybenzoic acid |
| DE19732578C2 (en) * | 1997-07-29 | 2000-08-24 | Aventis Res & Tech Gmbh & Co | Use of sulfonated aromatic polyether ketone cation exchangers and sulfonated polyphenylene sulfide cation exchangers as catalysts |
| JP4160087B2 (en) * | 2006-07-11 | 2008-10-01 | 株式会社日本触媒 | Method for producing acrylic ester |
| US20080167485A1 (en) * | 2007-01-09 | 2008-07-10 | Rajiv Manohar Banavali | Method for heterogeneous acid catalysis |
| US20110065943A1 (en) * | 2009-09-16 | 2011-03-17 | Rajiv Manohar Banavali | Method for selective esterification of free fatty acids in triglycerides |
| CN102320962B (en) * | 2011-07-18 | 2013-10-02 | 旭阳化学技术研究院有限公司 | Method for catalytic synthesis of methyl propionate |
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| CN1197791A (en) * | 1997-04-28 | 1998-11-04 | 国营吴江香料厂 | Ethyl propionate producing technology |
| CN101560152A (en) * | 2009-05-27 | 2009-10-21 | 南京工业大学 | Method for synthesizing propionate |
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| CN102976939B (en) | 2015-03-25 |
| CN104788311A (en) | 2015-07-22 |
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