CN116283568A - Preparation method of sorbate - Google Patents
Preparation method of sorbate Download PDFInfo
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- CN116283568A CN116283568A CN202111576052.XA CN202111576052A CN116283568A CN 116283568 A CN116283568 A CN 116283568A CN 202111576052 A CN202111576052 A CN 202111576052A CN 116283568 A CN116283568 A CN 116283568A
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- sorbate
- sorbic acid
- ionic liquid
- alcohol
- catalyst
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- 229940075554 sorbate Drugs 0.000 title claims abstract description 69
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000004334 sorbic acid Substances 0.000 claims abstract description 75
- 229940075582 sorbic acid Drugs 0.000 claims abstract description 75
- 235000010199 sorbic acid Nutrition 0.000 claims abstract description 75
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002608 ionic liquid Substances 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 238000004821 distillation Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- -1 sorbate ester Chemical class 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 12
- ZYWVUGXNGJVBAL-UHFFFAOYSA-N propan-1-amine;sulfuric acid Chemical compound CCCN.OS(O)(=O)=O ZYWVUGXNGJVBAL-UHFFFAOYSA-N 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 210000004196 psta Anatomy 0.000 claims description 6
- JTTWNTXHFYNETH-UHFFFAOYSA-N propyl 4-methylbenzenesulfonate Chemical compound CCCOS(=O)(=O)C1=CC=C(C)C=C1 JTTWNTXHFYNETH-UHFFFAOYSA-N 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- OIALIKXMLIAOSN-UHFFFAOYSA-N 2-Propylpyridine Chemical compound CCCC1=CC=CC=N1 OIALIKXMLIAOSN-UHFFFAOYSA-N 0.000 claims description 3
- QHMHDXVZSKJPRC-UHFFFAOYSA-N hydrogen sulfate 3-methyl-2-propyl-1H-imidazol-3-ium Chemical compound OS([O-])(=O)=O.CCCc1[nH]cc[n+]1C QHMHDXVZSKJPRC-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- LYCYHYFONCRQGV-UHFFFAOYSA-N methanesulfonic acid;propan-1-amine Chemical compound CCC[NH3+].CS([O-])(=O)=O LYCYHYFONCRQGV-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 9
- 239000010815 organic waste Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000000638 solvent extraction Methods 0.000 abstract description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 8
- KWKVAGQCDSHWFK-VNKDHWASSA-N Methyl sorbate Chemical compound COC(=O)\C=C\C=C\C KWKVAGQCDSHWFK-VNKDHWASSA-N 0.000 description 7
- 239000001375 methyl (2E,4E)-hexa-2,4-dienoate Substances 0.000 description 7
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 235000014443 Pyrus communis Nutrition 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- SCVZKPKDMFXESQ-VSAQMIDASA-N butyl (2e,4e)-hexa-2,4-dienoate Chemical compound CCCCOC(=O)\C=C\C=C\C SCVZKPKDMFXESQ-VSAQMIDASA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- OZZYKXXGCOLLLO-TWTPFVCWSA-N ethyl (2e,4e)-hexa-2,4-dienoate Chemical compound CCOC(=O)\C=C\C=C\C OZZYKXXGCOLLLO-TWTPFVCWSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 150000003397 sorbic acid derivatives Chemical class 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
-
- 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
-
- 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
-
- 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
In order to solve the problems that organic waste liquid and alkaline waste water are generated when sorbic acid and a catalyst are separated after sorbic acid esterification reaction and the yield of sorbate is low in the prior art, the invention provides a preparation method of sorbate, and the method comprises the steps of separating alcohol through distillation after the reaction of sorbic acid, alcohol and an ionic liquid catalyst, cooling the liquid, crystallizing and separating out the catalyst and sorbic acid, carrying out solid-liquid separation, and collecting sorbate from upper liquid through reduced pressure distillation; the crystallized sorbic acid and the ionic liquid catalyst can be continuously subjected to esterification reaction. According to the preparation method, sorbic acid and the ionic liquid catalyst are recycled, so that the utilization rate is improved, and meanwhile, the waste is avoided through alkali liquor neutralization, and the generation of alkaline wastewater is reduced; the sorbate is separated in a reduced pressure distillation mode, organic solvent extraction is not needed, and the generation of organic waste liquid is avoided.
Description
Technical Field
The invention belongs to the technical field of sorbic acid product preparation, and particularly relates to a preparation method of sorbate.
Background
The sorbate is a sorbic acid derivative, has good antibacterial activity, can be used for food additives, is mainly prepared by an acid catalysis direct esterification method at present, and is required to separate and remove unreacted sorbic acid and a catalyst by an organic solvent extraction and alkali liquor neutralization method due to incomplete sorbic acid reaction, so that the purpose of separation and purification is achieved.
The research of an ionic liquid catalyst as a green catalyst in esterification reaction is a hot topic at present, the ionic liquid catalyst is used as a catalyst in the esterification reaction of sorbic acid and alcohol, the sorbic acid reaction is incomplete, and sorbic acid and the ionic liquid catalyst are separated to generate waste liquid; at present, no research on recycling sorbic acid and ionic liquid catalysts and improving the yield of sorbate exists.
In view of the technical problems, the method for preparing the sorbate through the continuous esterification and the combined reduced pressure distillation has the advantages of high yield, almost no wastewater generation and accordance with the concept of green chemistry.
Disclosure of Invention
Aiming at the problems of low sorbate yield caused by separation of sorbic acid and catalyst to produce organic waste liquid and alkaline waste water after esterification reaction in the prior art, the invention provides a preparation method of sorbate.
The invention provides a preparation method of sorbate, which comprises the following steps:
the preparation method of the sorbate comprises the following steps:
a: adding sorbic acid, alcohol and ionic liquid catalyst into a reaction container, stirring at normal temperature, and heating to react after the reactants are completely dissolved;
b: distilling the liquid after the reaction in the step A, and recovering the fraction of unreacted alcohol;
c: cooling the residual liquid after distillation in the step B, crystallizing and separating out sorbic acid and the ionic liquid catalyst, and then separating crystals; distilling the obtained liquid under reduced pressure, and collecting the fraction of the finished product of sorbate;
d: and (3) recycling the sorbic acid and the ionic liquid catalyst which are crystallized and separated out in the step (C) to the step (A) to further react with newly added alcohol, sorbic acid and the ionic liquid catalyst.
Preferably, the cooling temperature of the residual liquid in the step C is 6-14 ℃.
Preferably, the cooling temperature of the remaining liquid in the step C is 8-10 ℃.
Preferably, in the step A, the mass ratio of the pear acid to the alcohol to the ionic liquid catalyst is 1: (1-5): (0.01-0.05).
Preferably, in the step A, the mass ratio of the pear acid to the alcohol to the ionic liquid catalyst is 1: (2-5): (0.01-0.03).
Preferably, the reaction temperature in the step A is 50-100 ℃, and the reaction time is 4-12 h.
Preferably, the reaction temperature in the step A is 60-80 ℃, and the reaction time is 6-10 h.
Preferably, in the step C, the distillation is performed under reduced pressure, the distillation pressure is between minus 0.08Mpa and minus 0.1Mpa, and the distillation temperature is between 40 ℃ and 80 ℃.
Preferably, the ionic liquid catalyst comprises at least one of triethylsulfonic acid propyl p-toluenesulfonate ([ NEt3PS ] pSTA), triethylsulfonic acid propyl ammonium bisulfate ([ NEt3PS ] HSO 4), triethylsulfonic acid propyl ammonium methanesulfonate ([ NEt3PS ] MSA), 1-sulfonic acid propyl-3-methylimidazole bisulfate ([ MIMPS ] HSO 4), 1-sulfonic acid propyl-3-methylimidazole p-toluenesulfonate ([ MIMPS ] pSTA), 1-sulfonic acid propyl-3-methylimidazole methanesulfonate ([ MIMPS ] MSA), N-sulfonic acid propyl pyridine bisulfate (PyPS ] HSO 4), N-sulfonic acid propyl pyridine p-toluenesulfonate ([ PyPS ] pTSA), N-sulfonic acid propyl pyridine methanesulfonate ([ PyPS ] MSA).
Preferably, the alcohol is a saturated aliphatic hydrocarbon alcohol having 1 to 4 carbon atoms.
The invention has the beneficial effects that:
1. the unreacted sorbic acid crystals are kept at the bottom of the container, so that the waste of the unreacted sorbic acid crystals is avoided by neutralizing with alkali liquor, the sorbic acid is recycled, the utilization rate of the sorbic acid is greatly improved, and the production cost is reduced; meanwhile, the production of alkaline wastewater is reduced, and the national energy conservation and emission reduction policies are met.
2. The sorbate is separated in a reduced pressure distillation mode, organic solvent extraction is not needed, the method for collecting the product is simple, the yield is increased, the cost is saved, and the generation of organic waste liquid is avoided.
3. The ionic liquid catalyst is crystallized in a liquid cooling mode and is kept at the bottom of the container, so that the separation step of the ionic liquid catalyst and sorbate is reduced, and the process time is saved; the ionic liquid catalyst can be reused, continuous production is realized, and production efficiency is improved.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In one aspect, the invention provides a method for preparing sorbate, comprising the following steps:
a: adding sorbic acid, alcohol and an ionic liquid catalyst into a reaction container, stirring at normal temperature, and heating to react after the reactants are completely dissolved;
b: distilling the liquid after the reaction in the step A to recover a fraction of unreacted alcohol;
c: cooling the residual liquid after distillation in the step B, crystallizing and separating out sorbic acid and the ionic liquid catalyst, and then separating crystals; distilling the obtained liquid under reduced pressure, and collecting the fraction of the finished product of sorbate;
d: and (3) recycling the sorbic acid and the ionic liquid catalyst which are crystallized and separated out in the step (C) to the step (A) to further react with newly added alcohol, sorbic acid and the ionic liquid catalyst.
The alcohol is recycled after being separated and dried by distillation; the utilization rate of alcohol is improved. The sorbic acid and the ionic liquid catalyst are kept at the bottom of the container through cooling crystallization; the unreacted sorbic acid crystals are kept at the bottom of the container, so that the waste of the unreacted sorbic acid crystals is avoided by neutralizing with alkali liquor, the sorbic acid is recycled, the utilization rate of the sorbic acid is greatly improved, and the production cost is reduced; meanwhile, the production of alkaline wastewater is reduced, and the national energy conservation and emission reduction policies are met. The ionic liquid catalyst is crystallized in a cooling mode and is kept at the bottom of the container, so that the separation step of the ionic liquid catalyst and sorbate is reduced, and the process time is saved; the ionic liquid catalyst can be reused, continuous production is realized, and production efficiency is improved. The sorbate is separated in a reduced pressure distillation mode, organic solvent extraction is not needed, the method for collecting the product is simple, the cost is saved, and the generation of organic waste liquid is avoided; the purity of the finished product of the sorbate obtained by the collection in a reduced pressure distillation mode can reach more than 98.5 percent, and the purity of the finished product of the sorbate is improved.
In some embodiments, the vessel in step a of the method for preparing sorbate is a reaction vessel having a reflux condenser, and the reflux condenser is fed with a cooling fluid to cool the liquid in the vessel.
In some embodiments, the cooling temperature of the remaining liquid in step C of the method of preparing sorbate is 6-14 ℃.
The residual liquid is cooled, and sorbic acid and the ionic liquid catalyst are crystallized, so that the purpose of separating from sorbate is achieved, the separation method is simple, alkaline waste liquid and organic waste liquid are not generated, the green production is realized, and the national energy conservation and emission reduction policies are met. The cooling temperature range is obtained according to the phase equilibrium relation of sorbic acid, the ionic liquid catalyst and the sorbate, if the temperature range is lower than the temperature range, the effective crystallization proportion of the sorbic acid and the ionic liquid catalyst is reduced, and if the temperature range is higher than the temperature range, the sorbate product is crystallized and separated out, so that the separation cost of the sorbate is increased.
In some preferred embodiments, the cooling temperature of the remaining liquid in step C of the method of preparing sorbate is 8-10deg.C.
The preferred temperature of liquid cooling crystallization is 8-10 ℃, and the crystallization proportion of sorbic acid and ionic liquid catalyst is higher in the temperature range.
In some embodiments, the mass ratio of the sorbic acid, the alcohol and the ionic liquid catalyst in the step A of the preparation method of the sorbate is 1: (1-5): (0.01-0.05).
In the esterification reaction, in order to make sorbic acid react as completely as possible, the content of alcohol is generally higher than that of sorbic acid, and in some embodiments, the content of alcohol is 1-5 times that of sorbic acid, and the content of alcohol in the reactant is high and reacts with sorbic acid as much as possible to generate sorbate. The ionic liquid catalyst only plays a role in catalysis, so that the reaction rate of sorbic acid and alcohol is accelerated, and the content of the ionic liquid catalyst is 1% -5% of the content of sorbic acid; the ionic liquid catalyst has high cost, the ionic liquid catalyst in the preparation method can be recycled, and only the ionic liquid catalyst with 1-5% of sorbic acid content can achieve a better catalytic effect, and meanwhile, the ionic liquid catalyst can be recycled, so that the cost is reduced.
In some preferred embodiments, the mass ratio of the sorbic acid, the alcohol and the ionic liquid catalyst in the step A of the preparation method of the sorbate is 1: (2-5): (0.01-0.03).
In some embodiments, the reaction temperature in step a of the method for preparing sorbate is 50 ℃ to 100 ℃ and the reaction time is 4h to 12h.
In some preferred embodiments, the reaction temperature in step A of the method for preparing sorbate is 60-80 ℃, and the reaction time is 6-10 h.
The sorbic acid and the alcohol are required to be heated in the reaction, the container can be heated in a heating device such as an oil bath pot, or can be directly heated, and different heating modes can be selected according to actual conditions. Heating to promote esterification of sorbic acid and alcohol, and improving production efficiency. The preferable reaction temperature and reaction time promote the reaction of sorbic acid and alcohol, improve the reaction rate and increase the yield of the sorbate product.
In some preferred embodiments, the sorbate is prepared by distillation under reduced pressure in step C, at a distillation pressure of-0.08 MPa to-0.1 MPa, and at a distillation temperature of 40-80deg.C.
In the step C, the upper layer liquid is subjected to reduced pressure distillation, and sorbate is separated out to obtain sorbate products; the pressure and the distillation temperature of reduced pressure distillation are in a preferable range according to the precipitation amounts of the sorbate at different pressures and temperatures, and in the temperature and pressure range, the amount of the sorbate precipitated is more, the yield of the sorbate is higher, the purity of the sorbate finished product reaches more than 98.5 percent, and the production efficiency is effectively improved.
In some preferred embodiments, the ionic liquid catalyst comprises at least one of triethylsulfonic acid propyl p-toluenesulfonate ([ NEt3PS ] pSTA), triethylsulfonic acid propyl ammonium bisulfate ([ NEt3PS ] HSO 4), triethylsulfonic acid propyl ammonium methanesulfonate ([ NEt3PS ] MSA), 1-sulfonic acid propyl-3-methylimidazole bisulfate ([ MIMPS ] HSO 4), 1-sulfonic acid propyl-3-methylimidazole p-toluenesulfonate ([ MIMPS ] pSTA), 1-sulfonic acid propyl-3-methylimidazole methanesulfonate ([ MIMPS ] MSA), N-sulfonic acid propyl pyridine bisulfate (PyPS ] HSO 4), N-sulfonic acid propyl pyridine p-toluenesulfonate ([ PyPS ] pTSA), N-sulfonic acid propyl pyridine methanesulfonate ([ PyPS ] MSA).
In some preferred embodiments, the alcohol is a saturated aliphatic hydrocarbon alcohol having 1 to 4 carbon atoms. Specifically, the saturated aliphatic hydrocarbon alcohol having 1 to 4 carbon atoms includes methanol, ethanol, propanol, butanol, 1, 2-ethylene glycol, propylene glycol, 1, 3-butanediol, glycerol, butanetriol, and the like.
The invention is further illustrated by the following examples.
Example 1
112g of sorbic acid is put into a 1000mL three-neck flask provided with a serpentine condenser, 460g of methanol is poured into the three-neck flask, 2g of triethylsulfonic acid propyl ammonium bisulfate catalyst is added, the three-neck flask is magnetically stirred and dissolved, and the three-neck flask is heated in an oil bath for reflux reaction for 12 hours, and the heating temperature is 75 ℃. Methanol is distilled and collected, and the collected methanol is dried for recycling. After methanol is removed, adding condensed water into a condensing tube of a three-neck flask, cooling the rest liquid in the flask to 8 ℃, crystallizing and separating out sorbic acid and triethylsulfonic acid propyl ammonium bisulfate catalyst, pouring the upper liquid into the single-neck flask, and collecting 90.7g of finished product of methyl sorbate through reduced pressure distillation; wherein the pressure in reduced pressure distillation is-0.1 Mpa, and the distillation temperature is 55deg.C. The three-necked flask crystals remained.
112g of sorbic acid and 460g of methanol are continuously put into a three-neck flask, the steps are repeated, and 110.3g of finished product of methyl sorbate is collected.
The yields of sorbate were calculated as: 79.76%.
Wherein, the calculation formula of the yield of the sorbate is as follows: (actual sorbate product mass/theoretical sorbate product mass). Times.100%, the following examples 2 to 4 and comparative example 1 were calculated in the same manner as in example 1.
Example 2
112g of sorbic acid is put into a 1000mL three-neck flask provided with a serpentine condenser, 460g of methanol is poured into the three-neck flask, 2g of 1-sulfopropyl-3-methylimidazole bisulfate catalyst is added, the catalyst is magnetically stirred and dissolved, the reflux reaction is carried out by heating in an oil bath for 12 hours, and the heating temperature is 75 ℃. Methanol is distilled and collected, and the collected methanol is dried for recycling. After methanol is removed, adding condensed water into a condensing tube of a three-neck flask, cooling the rest liquid in the flask to 10 ℃, crystallizing and separating out sorbic acid and 1-sulfopropyl-3-methylimidazole bisulfate catalyst, pouring the upper liquid into the single-neck flask, distilling under reduced pressure, and collecting 89.4g of finished product of methyl sorbate; wherein the pressure in reduced pressure distillation is-0.1 Mpa, and the distillation temperature is 55deg.C. The three-necked flask crystals remained.
To the three-necked flask, 112g of sorbic acid and 460g of methanol were continuously charged, the above steps were repeated, and 109.6g of a finished product of methyl sorbate was collected.
The yields of sorbate were calculated as: 78.97%.
Example 3
112g of sorbic acid is put into a 1000mL three-neck flask provided with a serpentine condenser, 460g of ethanol is poured into the three-neck flask, 2g of triethylsulfonic acid propyl p-toluenesulfonate catalyst is added, magnetic stirring is carried out for dissolution, oil bath heating reflux reaction is carried out for 12 hours, and the heating temperature is 75 ℃. Ethanol is distilled, and ethanol is collected, and the collected ethanol is dried for recycling. After ethanol is removed, adding condensed water into a condensing tube of a three-neck flask, cooling the residual liquid in the flask to 14 ℃, crystallizing and separating out sorbic acid and a triethylsulfonic acid propyl p-toluenesulfonate catalyst, pouring the upper liquid into the single-neck flask, and collecting 89.4g of finished product of ethyl sorbate through reduced pressure distillation; wherein the pressure in reduced pressure distillation is-0.1 Mpa, and the distillation temperature is 55deg.C. The three-necked flask crystals remained.
112g of sorbic acid and 460g of ethanol are continuously put into a three-neck flask, the steps are repeated, and 108.0g of finished product of ethyl sorbate is collected.
The yields of sorbate were calculated as: 78.33%.
Example 4
112g of sorbic acid is put into a 1000mL three-neck flask provided with a serpentine condenser, 460g of butanol is poured, 2g of triethylsulfonic acid propyl ammonium bisulfate catalyst is added, magnetic stirring is carried out for dissolution, and oil bath heating reflux reaction is carried out for 12 hours, and the heating temperature is 75 ℃. Butanol is distilled and collected, and the collected butanol is dried for recycling. After butanol is removed, adding condensed water into a condensing tube of a three-neck flask, cooling the rest liquid in the flask to 6 ℃, crystallizing and separating out sorbic acid and triethylsulfonic acid propyl ammonium bisulfate catalyst, pouring the upper liquid into the single-neck flask, and collecting 86.9g of butyl sorbate finished product through reduced pressure distillation; wherein the pressure in reduced pressure distillation is-0.1 Mpa, and the distillation temperature is 55deg.C. The three-necked flask crystals remained.
112g of sorbic acid and 460g of butanol are continuously put into a three-neck flask, the steps are repeated, and 106.5g of finished butyl sorbate is collected.
The yields of sorbate were calculated as: 76.75%.
Comparative example 1
112g of sorbic acid is put into a 1000mL three-neck flask provided with a serpentine condenser, 460g of methanol is poured into the three-neck flask, 2g of triethylsulfonic acid propyl ammonium bisulfate catalyst is added, the three-neck flask is magnetically stirred and dissolved, and the three-neck flask is heated in an oil bath for reflux reaction for 12 hours, and the heating temperature is 75 ℃. Methanol is distilled and collected, and the collected methanol is dried for recycling. After methanol is removed, adding condensed water into a condensing tube of a three-neck flask, cooling the residual liquid in the flask to 16 ℃, crystallizing and separating out sorbic acid and triethylsulfonic acid propyl ammonium bisulfate catalyst, pouring the upper liquid into the single-neck flask, and collecting 90.7g of finished product of methyl sorbate through reduced pressure distillation; wherein the pressure in reduced pressure distillation is-0.1 Mpa, and the distillation temperature is 55deg.C. The three-necked flask crystals remained.
To the three-necked flask, 112g of sorbic acid and 460g of methanol were continuously charged, the above steps were repeated, and 55.2g of a finished product of methyl sorbate was collected.
The yields of sorbate were calculated as: 59.90%.
Comparative example 2
112g of sorbic acid is put into a 1000mL three-neck flask provided with a serpentine condenser, 512g of methanol and 2g of concentrated sulfuric acid are poured into the three-neck flask as catalysts, the catalyst is magnetically stirred and dissolved, and the heating temperature is 70 ℃ after heating reflux reaction for 10 hours in an oil bath. Methanol is distilled and collected, methanol is removed, the reaction solution is poured into a separating funnel, 500mL of diethyl ether is added, an diethyl ether layer is washed with 0.1mol/L of sodium bicarbonate solution until the diethyl ether layer is neutral, the diethyl ether layer is collected, diethyl ether is removed by reduced pressure distillation, and a methyl sorbate product is obtained.
As can be seen from comparison of examples 1 to 4 with comparative example 1, after the reaction of alcohol, sorbic acid and ionic liquid catalyst is completed, the residual liquid after the reaction is cooled, the cooling temperature is not in the range of 6-14 ℃, and when the recovered sorbic acid and ionic liquid catalyst are subjected to cyclic reaction, the yield of sorbate products obtained by reduced pressure distillation is low; mainly because the residual liquid after the reaction is cooled, when the cooling temperature is not within the range of 6-14 ℃, the recovered sorbic acid and the ionic liquid catalyst contain other impurities, and the reaction rate is influenced, so that the yield of the sorbate product is reduced. The residual liquid after the reaction in examples 1-4 is cooled to a temperature ranging from 8 ℃ to 10 ℃, and the yield of the prepared sorbate product is higher; different types of alcohol and ionic liquid catalysts have small influence on the reaction rate, and basically do not influence the yield of sorbate.
In comparative example 2, concentrated sulfuric acid is used as a catalyst, the sorbate obtained in the reaction is separated by adopting an ether organic solution, the residual sorbic acid and the concentrated sulfuric acid catalyst are removed by using alkaline liquid, organic waste liquid and alkaline waste liquid are generated, the residual sorbic acid in the reaction cannot be recycled, and the production cost is increased.
Compared with comparative examples 1 and 2, the preparation methods of the sorbate in examples 1 to 4 can realize the repeated use of sorbic acid and ionic liquid catalysts, and the yield of the sorbate is not reduced, namely, no organic waste liquid and alkaline waste liquid are generated, continuous production is realized, and the production efficiency is improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the sorbate is characterized by comprising the following steps of:
a: adding sorbic acid, alcohol and ionic liquid catalyst into a reaction container, stirring at normal temperature, and heating to react after the reactants are completely dissolved;
b: distilling the liquid after the reaction in the step A to recover a fraction of unreacted alcohol;
c: cooling the residual liquid after distillation in the step B, crystallizing and separating out sorbic acid and the ionic liquid catalyst, and then separating crystals; distilling the obtained liquid under reduced pressure, and collecting the fraction of the finished product of sorbate;
d: and (3) recycling the sorbic acid and the ionic liquid catalyst which are crystallized and separated out in the step (C) to the step (A) to further react with newly added alcohol, sorbic acid and the ionic liquid catalyst.
2. The method for producing sorbate ester according to claim 1, wherein the cooling temperature of the remaining liquid in the step C is 6 ℃ to 14 ℃.
3. The method for producing sorbate ester according to claim 2, characterized in that the cooling temperature of the remaining liquid in step C is 8 ℃ to 10 ℃.
4. The method for preparing sorbate ester according to claim 1, wherein the mass ratio of the sorbic acid, the alcohol and the ionic liquid catalyst in the step a is 1: (1-5): (0.01-0.05).
5. The method for preparing sorbate ester according to claim 4, wherein the mass ratio of the sorbic acid, the alcohol and the ionic liquid catalyst in the step a is 1: (2-5): (0.01-0.03).
6. The method for preparing sorbate ester according to claim 1, wherein the reaction temperature in the step a is 50-100 ℃ and the reaction time is 4-12 h.
7. The method for producing sorbate ester according to claim 6, wherein the reaction temperature in the step a is 60 ℃ to 80 ℃ and the reaction time is 6h to 10h.
8. The method for producing sorbate ester according to claim 1, wherein the distillation is performed under reduced pressure in the step C, the distillation pressure is-0.08 Mpa to-0.1 Mpa, and the distillation temperature is 40 ℃ to 80 ℃.
9. The method for preparing sorbate according to claim 1, wherein the ionic liquid catalyst comprises at least one of triethylsulfonic acid propyl p-toluenesulfonate ([ NEt3PS ] pSTA), triethylsulfonic acid propyl ammonium bisulfate ([ NEt3PS ] HSO 4), triethylsulfonic acid propyl ammonium methanesulfonate ([ NEt3PS ] MSA), 1-sulfonic acid propyl-3-methylimidazole bisulfate ([ MIMPS ] HSO 4), 1-sulfonic acid propyl-3-methylimidazole p-toluenesulfonate ([ MIMPS ] pSTA), 1-sulfonic acid propyl-3-methylimidazole methanesulfonate ([ MIMPS ] MSA), N-sulfonic acid propyl pyridine bisulfate (PyPS ] HSO 4), N-sulfonic acid propyl pyridine p-toluenesulfonate ([ PyPS ] pTSA), N-sulfonic acid propyl pyridine methanesulfonate ([ PyPS ] MSA).
10. The method for producing sorbate ester according to claim 1, wherein the alcohol is a saturated aliphatic hydrocarbon alcohol having 1 to 4 carbon atoms.
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