CN114133325A - Method for producing potassium sorbate by liquid-liquid neutralization reaction continuous cooling crystallization - Google Patents
Method for producing potassium sorbate by liquid-liquid neutralization reaction continuous cooling crystallization Download PDFInfo
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- CN114133325A CN114133325A CN202111613422.2A CN202111613422A CN114133325A CN 114133325 A CN114133325 A CN 114133325A CN 202111613422 A CN202111613422 A CN 202111613422A CN 114133325 A CN114133325 A CN 114133325A
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- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 title claims abstract description 145
- 239000004302 potassium sorbate Substances 0.000 title claims abstract description 145
- 235000010241 potassium sorbate Nutrition 0.000 title claims abstract description 145
- 229940069338 potassium sorbate Drugs 0.000 title claims abstract description 145
- 238000002425 crystallisation Methods 0.000 title claims abstract description 93
- 230000008025 crystallization Effects 0.000 title claims abstract description 93
- 238000006386 neutralization reaction Methods 0.000 title claims abstract description 61
- 238000001816 cooling Methods 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000004334 sorbic acid Substances 0.000 claims abstract description 67
- 235000010199 sorbic acid Nutrition 0.000 claims abstract description 67
- 229940075582 sorbic acid Drugs 0.000 claims abstract description 67
- 239000000243 solution Substances 0.000 claims abstract description 62
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000012046 mixed solvent Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- 239000012452 mother liquor Substances 0.000 claims description 25
- 238000005086 pumping Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 10
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000013361 beverage Nutrition 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 15
- 238000002834 transmittance Methods 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 238000000926 separation method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- 239000002910 solid waste Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000011549 crystallization solution Substances 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization, belonging to the field of chemical industry. The invention dissolves sorbic acid in a mixed solvent to obtain a sorbic acid solution, the sorbic acid solution and a potassium hydroxide or potassium carbonate aqueous solution are respectively pumped into a neutralization reactor to carry out neutralization reaction to obtain a potassium sorbate solution, then the potassium sorbate solution is pumped into a two-stage crystallization reactor to carry out continuous cooling crystallization, and finally the crystallized wet potassium sorbate is dried to obtain a finished potassium sorbate product, wherein the mixed solvent is a mixed solvent composed of one or two of ethanol or acetone and water, and the concentration of the ethanol or/and the acetone is 10-80%. The invention dissolves sorbic acid in the solution to carry out liquid-liquid reaction with the potassium hydroxide solution, the mixture is more uniform and the reaction is easy to control, and the potassium sorbate crystals in the obtained potassium sorbate finished product are regular particles, the content is more than or equal to 99.8 percent, and the transmittance is more than or equal to 98.5 percent.
Description
Technical Field
The invention relates to a method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization, belonging to the field of chemical industry.
Background
Potassium sorbate is one of several preservatives approved by the world health organization additive committee. Two double bonds in the potassium sorbate are combined with sulfydryl in a microbial enzyme system, so that the microbial enzyme system can be damaged, the propagation of microbes is inhibited, and the purpose of corrosion prevention is achieved. Potassium sorbate is widely used in the fields of food, beverage, medicine, cosmetics and the like because of its good bacteriostatic effect and safety.
The main preparation method of potassium sorbate in the current industrial production comprises the following steps: performing neutralization reaction on the crude sorbic acid and a potassium carbonate or potassium hydroxide solution to obtain a potassium sorbate solution, adding activated carbon to remove impurities such as pigment in the potassium sorbate solution, filtering and separating the activated carbon to obtain a potassium sorbate liquid, drying the potassium sorbate liquid in a high-speed centrifugal spraying mode to obtain potassium sorbate powder, and granulating, drying and screening to obtain the potassium sorbate product.
Patent publication CN101402557A reports a process for preparing potassium sorbate, in which a mixture of sorbic acid hydrolysate and tar is directly reacted with potassium carbonate to remove decoking step without using ethanol, and in the later stage, the potassium sorbate solution is subjected to activated carbon to remove pigment and tar, and then to nano-filtration process to further remove pigment and tar, and in the later stage, the potassium sorbate solution is dried by high-speed centrifugal spraying to obtain potassium sorbate powder, and then granulated by a granulator to obtain columnar potassium sorbate particles, and the transmittance of the finished potassium sorbate product reaches 98.5%. However, the process uses activated carbon for decolorization, generates a large amount of solid waste, and the nano-filtration process has high cost and is not suitable for industrial production.
Patent publication CN103351294A describes a new process for granulating potassium sorbate, in which dry powder after spray drying is mixed with potassium sorbate solution to increase binding power and obtain good granulation effect. In the patent, the potassium sorbate solution is directly atomized and dried by a spray dryer, impurities in the aqueous solution still remain in the potassium sorbate powder, and the product quality is not high.
The patent publication CN112479865A provides a preparation method of high-purity feed additive potassium sorbate, potassium hydroxide and sorbic acid are subjected to neutralization reaction to obtain a potassium sorbate primary solution, activated carbon is decolored for 4-6 times to obtain a high-purity potassium sorbate solution, and then spray drying and granulation are carried out to obtain a finished product potassium sorbate. The process is complicated to operate and can generate a large amount of solid wastes.
The existing potassium sorbate preparation process is to carry out solid-liquid reaction on solid sorbic acid and a potassium hydroxide solution, so that the problems of nonuniform reaction, high local concentration, easy generation of more byproducts and the like exist, activated carbon is adopted for decoloration in the later period, a large amount of solid wastes are generated in the decoloration process of the activated carbon, the post-treatment cost is increased, and finally spray drying is adopted for drying, so that impurities in an aqueous solution cannot be effectively removed, and the quality of the potassium sorbate is finally influenced.
Disclosure of Invention
The invention aims to provide a method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization, which solves the problems of uneven neutralization reaction, more byproducts, more solid wastes, low product quality and the like easily generated in the existing potassium sorbate production process. According to the invention, ethanol or acetone is used as a good solvent of sorbic acid to obtain a sorbic acid solution, and the sorbic acid solution and a potassium hydroxide solution or a potassium carbonate solution are subjected to liquid-liquid neutralization reaction, compared with the traditional solid-liquid neutralization reaction, the reaction of the invention is easy to control, the reactants are mixed more uniformly, the obtained potassium sorbate solution can be obtained directly by a continuous cooling crystallization mode, the quality of potassium sorbate products is greatly improved, activated carbon is not required for decolorization, a large amount of solid waste is reduced, and the method has a good industrial prospect.
In order to achieve the above object, the present invention provides a method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization, the method comprising: dissolving sorbic acid in a mixed solvent to obtain a sorbic acid solution, respectively pumping the sorbic acid solution and a potassium hydroxide aqueous solution or a potassium carbonate aqueous solution into a neutralization reactor for neutralization reaction to obtain a potassium sorbate solution, then pumping the potassium sorbate solution into a two-stage crystallization reactor for continuous cooling crystallization, and finally drying wet potassium sorbate obtained by separating crystallized potassium sorbate crystal liquid to obtain a finished potassium sorbate product, wherein the mixed solvent is a mixed solvent composed of one or two of ethanol or acetone and water, and the concentration of ethanol or/and acetone in the mixed solvent is 10-90% (v/v).
Furthermore, the method is realized by adopting a continuous production method.
Further, the mass concentration of the sorbic acid solution is 10-60%.
Further, the process of dissolving sorbic acid in the mixed solvent is carried out at 30-80 ℃.
Further, the temperature of the neutralization reaction is 40-80 ℃, the pH value is 9-11, and the reaction residence time is 0.5-5 h.
Further, the concentration of the potassium hydroxide aqueous solution is 5-30 wt%, and the concentration of the potassium carbonate aqueous solution is 5-30 wt%.
Furthermore, the molar ratio of the sorbic acid to the potassium hydroxide or the potassium carbonate is 1: 0.9-1.3.
Furthermore, the flow rates of the sorbic acid solution and the potassium hydroxide aqueous solution (or potassium carbonate aqueous solution) are respectively 3-15 mL/min and 3-15 mL/min.
Furthermore, in the continuous cooling crystallization process, the crystallization temperature of the primary crystallizer is controlled to be 45-60 ℃, the crystallization residence time is 0.5-3h, the crystallization temperature of the secondary crystallizer is controlled to be 10-30 ℃, and the crystallization residence time is 0.5-5 h.
Further, the system pressure for cooling crystallization is preferably normal pressure.
Further, the crystallizer is a kettle type crystallizer or a tubular type crystallizer.
Further, after the reaction is finished, recovering the solvent from the mother liquor which accounts for 5-30% of the total mass of the mother liquor at normal pressure, directly burning the kettle liquid after the solvent is recovered, and returning the recovered solvent and the rest of the mother liquor to a sorbic acid dissolving process for sorbic acid dissolution to prepare a sorbic acid solution; wherein the mother liquor is obtained after crystallization and crystal precipitation.
Furthermore, the potassium sorbate crystals in the potassium sorbate finished product are regular particles, the content is more than or equal to 99.8%, the transmittance is more than or equal to 98.5%, the proportion below 80 meshes is less than 1%, and the proportion above 30 meshes is less than 5%.
The invention also provides application of the method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization in the fields of food, beverages, medicines, cosmetics, chemical industry and the like.
The method for producing the potassium sorbate by the liquid-liquid neutralization reaction and the continuous cooling crystallization has the following beneficial effects:
1) according to the invention, sorbic acid is dissolved in a solvent to carry out liquid-liquid reaction with a potassium hydroxide solution or a potassium carbonate solution, so that the reaction system can be uniformly mixed, the reaction is more controllable, a continuous crystallizer is used for continuous crystallization, the generation of crystal scale and solid waste in the crystallizer are avoided, the content of potassium sorbate in a wet product obtained by crystallization is high, the product quality is high, and the drying energy consumption is reduced.
2) The solvent is recovered after partial elimination of the mother liquor, and the impurities generated in the reaction can be removed from the eliminated mother liquor in the elimination process, so that the impurities are not excessively accumulated, and therefore, compared with the prior art, the method can remove the decolorization process, remove the use of activated carbon, reduce the cost of raw materials and reduce the generation of solid waste;
3) the invention adopts a continuous crystallization process, impurities can be well separated in the crystallization process, the potassium sorbate is in a better crystal form, the content of potassium sorbate in a wet product is higher, the amount of dried water and residual solvent is less, the drying energy consumption and the retention time of materials at high temperature are greatly reduced, the product quality and the product drying capacity are further improved, the potassium sorbate crystals in the obtained potassium sorbate finished product are in regular particles, the content is more than or equal to 99.8 percent, the transmittance is more than or equal to 98.5 percent, the proportion of more than 30 meshes is less than 5 percent, the proportion of 30-80 meshes is more than 94 percent, and the proportion of less than 80 meshes is less than 1 percent.
Drawings
FIG. 1 is a schematic flow chart of a method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization.
Figure 2 pictures of potassium sorbate cylinders produced using the pelletizer in example 1.
FIG. 3 is a picture of granular potassium sorbate obtained by crystallization in example 1.
Detailed Description
The invention provides a method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization, which comprises the following steps: dissolving sorbic acid in a mixed solvent to obtain a sorbic acid solution, respectively pumping the sorbic acid solution and a potassium hydroxide aqueous solution or a potassium carbonate solution into a neutralization reactor for neutralization reaction to obtain a potassium sorbate solution, then pumping the potassium sorbate solution into a two-stage crystallization reactor for continuous cooling crystallization, finally drying damp potassium sorbate obtained after separation of crystallized potassium sorbate crystal liquid to obtain a potassium sorbate finished product, the mixed solvent is a mixed solvent consisting of one or two of ethanol or acetone and water, the concentration of the ethanol or/and the acetone is 10-90% (v/v), potassium sorbate crystals in the obtained potassium sorbate finished product are in regular particles, the content of the potassium sorbate crystals is more than or equal to 99.8%, the transmittance of the potassium sorbate crystals is more than or equal to 98.5%, the ratio of the potassium sorbate crystals to 30-80 meshes is less than 5%, the ratio of the potassium sorbate crystals to 30-80 meshes is more than 94%, and the ratio of the potassium sorbate crystals to 80 meshes is less than 1%.
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
The test method comprises the following steps:
the method for measuring the content of the potassium sorbate comprises the following steps: 0.2g of dry potassium sorbate is weighed to an accuracy of 0.0002g and placed in a 250mL iodometric vial containing 48mL of glacial acetic acid and 2mL of acetic anhydride and warmed to bring it into solution. After cooling to room temperature, 2 drops of crystal violet indicator solution were added and titrated with perchloric acid standard titration solution (C ═ 0.1mol/L) to the end point of the solution changing from violet to blue-green, the volume of perchloric acid standard titration solution required was V1. At the same time of the measurement, the same steps as in the measurement were carried out, and the volume of perchloric acid standard titration solution required for the blank test was V2 for the same amount of the actual solution to which the sample was added.
The mass fraction W1 of potassium sorbate (on a dry basis) (V1-V2)/1000 x 0.1 x 150.2/m x 100%, m being the mass of the sample.
The transmittance test method comprises the following steps: a5.0 g sample (to the nearest 0.01g) of potassium sorbate was weighed out and dissolved in 20mL of distilled water, and the transmittance was measured at 430nm using distilled water as a reference solution.
The particle size test method comprises the following steps: 100g (to the nearest 0.01g) of potassium sorbate sample is taken and sieved by sieves with different mesh numbers, and the particle size is 100% of the mass/total mass of the particle size.
Example 1
(1) Weighing 100g of sorbic acid and 550g of 60% alcohol-content water solution, continuously mixing and dissolving at 50 ℃, wherein the mass concentration of the sorbic acid after dissolution is 15.4%; then respectively pumping the sorbic acid solution and 500g of 10.1 wt% potassium hydroxide aqueous solution into a neutralization reactor for continuous neutralization reaction at the temperature of 70 ℃ for 3 hours at the flow rates of 6.6mL/min and 3.3mL/min, wherein the pH value is controlled to be kept at 10.5;
(2) then pumping the obtained potassium sorbate neutralization solution into a two-stage continuous kettle type crystallizer according to the flow of 9.9mL/min for continuous cooling crystallization, wherein the pressure of a crystallization system is normal pressure, the crystallization temperature of a primary crystallizer is controlled at 45 ℃, the crystallization residence time is 3 hours, the crystallization temperature of a secondary crystallizer is controlled at 13 ℃, and the crystallization residence time is 4 hours; separating the separated potassium sorbate crystal liquid, and drying the separated wet potassium sorbate to obtain the finished potassium sorbate product.
The determination shows that the finished product potassium sorbate is in regular particles (see fig. 2 and fig. 3), the potassium sorbate content is 99.83%, the transmittance is 98.7%, the proportion of potassium sorbate below 80 meshes is 0.3%, and the proportion of potassium sorbate above 30 meshes is 4.6%, finally, the mother liquor which accounts for 18% of the total mass of the mother liquor in the mother liquor obtained after crystallization and separation is subjected to solvent recovery under normal pressure, the recovered solvent and the rest of the mother liquor are returned to the sorbic acid dissolving process for sorbic acid dissolution, so that a sorbic acid solution is prepared, and the production process is circulated.
Example 2
(1) Continuously mixing and dissolving 100g of sorbic acid and 170g of 60% acetone aqueous solution at 70 ℃, wherein the mass concentration of the dissolved sorbic acid is 37%; continuously feeding the obtained sorbic acid dissolved solution and 270g of 18.7 wt% potassium hydroxide aqueous solution into a neutralization reactor for continuous neutralization reaction at the temperature of 80 ℃ for 1h at the flow rate of 5.5mL/min and 5.5mL/min, and controlling the pH value to be 10.5;
(2) and (2) pumping the potassium sorbate neutralization solution obtained in the step (1) into a two-stage continuous kettle type crystallizer according to the flow of 11mL/min for continuous cooling crystallization, wherein the pressure of a crystallization system is normal pressure, the crystallization temperature of the primary crystallizer is controlled at 50 ℃, the crystallization residence time is 1.5h, the crystallization temperature of the secondary crystallizer is controlled at 22 ℃, the crystallization residence time is 2.5h, continuously separating the separated potassium sorbate crystallization solution, and drying the wet potassium sorbate obtained by separation to obtain a potassium sorbate finished product.
Through determination, the finished product potassium sorbate is in regular particles, the content of potassium sorbate is 99.85%, the transmittance is 98.6%, the proportion of potassium sorbate below 80 meshes is 0.5%, the proportion of potassium sorbate above 30 meshes is 3.2%, finally, the mother liquor which accounts for 22% of the total mass of the mother liquor in the mother liquor obtained by separation after crystallization is subjected to solvent recovery under normal pressure, the recovered solvent and the rest of the mother liquor are returned to a sorbic acid dissolving process for sorbic acid dissolution, so that a sorbic acid solution is prepared, and the production process is circulated.
Example 3
(1) Continuously mixing and dissolving 100g of sorbic acid and 270g of 45% acetone aqueous solution at 70 ℃, wherein the mass concentration of the dissolved sorbic acid is 27%; respectively pumping 27% sorbic acid solution and 200g of 25.3 wt% potassium hydroxide aqueous solution into a neutralization reactor according to the flow rates of 7.3mL/min and 3.5mL/min to perform continuous neutralization reaction, wherein the temperature of the neutralization reaction is controlled at 80 ℃, the retention time is 2 hours, and the pH value of the neutralization reaction is maintained at 10;
(2) pumping the potassium sorbate neutralized liquid obtained in the step (1) into a two-stage continuous tubular crystallizer according to the flow of 10.8mL/min for continuous cooling crystallization, wherein the pressure of a crystallization system is normal pressure, the crystallization temperature of the first-stage crystallizer is controlled at 47 ℃, the crystallization residence time is 3 hours, the crystallization temperature of the second-stage crystallizer is controlled at 19 ℃, and the crystallization residence time is 4.5 hours; and continuously separating the precipitated potassium sorbate crystal liquid, and drying the wet potassium sorbate product obtained by separation to obtain a finished potassium sorbate product.
Through determination, the finished product potassium sorbate is in regular particles, the content of potassium sorbate is 99.82%, the transmittance is 98.5%, the proportion of potassium sorbate below 80 meshes is 0.1%, the proportion of potassium sorbate above 30 meshes is 2.5%, finally, the mother liquor which accounts for 20% of the total mass of the mother liquor in the mother liquor obtained by separation after crystallization is subjected to solvent recovery under normal pressure, the recovered solvent and the rest of the mother liquor are returned to a sorbic acid dissolving process for sorbic acid dissolution, so that a sorbic acid solution is prepared, and the production process is circulated.
Example 4
(1) Continuously mixing 100g sorbic acid and 400g 70% alcohol concentration water solution at 50 deg.C for dissolving, wherein the mass concentration of the dissolved sorbic acid is 20%; respectively pumping the sorbic acid solution with the mass concentration of 20 percent and 500g of 10.1 weight percent potassium hydroxide aqueous solution into a neutralization reactor according to the flow rates of 5mL/min and 5mL/min to carry out continuous neutralization reaction, controlling the reaction temperature at 65 ℃, keeping the reaction time for 3.5h, and maintaining the pH value at 10 during the neutralization reaction;
(2) then, pumping the potassium sorbate neutralization solution in the step (1) into a two-stage continuous kettle type crystallizer according to the flow of 10mL/min for continuous cooling crystallization, wherein the pressure of a crystallization system is normal pressure, the crystallization temperature of the primary crystallizer is controlled at 58 ℃, the crystallization residence time is 1.5h, the crystallization temperature of the secondary crystallizer is controlled at 22 ℃, and the crystallization residence time is 3.5 h; and continuously separating the precipitated potassium sorbate crystal liquid, and drying the wet potassium sorbate product obtained by separation to obtain a finished potassium sorbate product.
Through determination, the finished product potassium sorbate is in regular particles, the content of potassium sorbate is 99.82%, the transmittance is 98.7%, the proportion of potassium sorbate below 80 meshes is 0.41%, the proportion of potassium sorbate above 30 meshes is 2.9%, finally, the mother liquor which accounts for 25% of the total mass of the mother liquor in the mother liquor obtained by separation after crystallization is subjected to solvent recovery under normal pressure, the recovered solvent and the rest of the mother liquor are returned to a sorbic acid dissolving process for sorbic acid dissolution, so that a sorbic acid solution is prepared, and the production process is circulated.
Example 5
(1) Continuously mixing 100g of sorbic acid and 400g of 70% alcohol concentration water solution at 60 ℃ for dissolution, wherein the mass concentration of the dissolved sorbic acid is 20%; respectively pumping a sorbic acid solution with the mass concentration of 20 percent and a potassium hydroxide aqueous solution with the concentration of 250g and the concentration of 20.2 percent by weight into a neutralization reactor according to the flow rates of 6.6mL/min and 3.3g/min to carry out continuous neutralization reaction, controlling the reaction temperature at 75 ℃, keeping the reaction time for 1h, and maintaining the pH value at 10 during the neutralization reaction;
(2) then, pumping the potassium sorbate neutralization solution in the step (1) into a two-stage continuous kettle type crystallizer according to the flow of 9.9mL/min for continuous cooling crystallization, wherein the pressure of a crystallization system is normal pressure, the crystallization temperature of the first-stage crystallizer is controlled at 45 ℃, the crystallization residence time is 0.5h, the crystallization temperature of the second-stage crystallizer is controlled at 10 ℃, and the crystallization residence time is 0.5 h; and continuously separating the precipitated potassium sorbate crystal liquid, and drying the wet potassium sorbate obtained by separation to obtain a potassium sorbate finished product, wherein the finished potassium sorbate is in a regular particle shape, the content of the potassium sorbate is 99.8%, the transmittance is 98.6%, the content of the potassium sorbate above 30 meshes is 4.1%, the content of the potassium sorbate below 30-80 meshes is 95.2%, and the content of the potassium sorbate below 80 meshes is 0.7%.
When the concentration of ethanol or/and acetone in the mixed solvent is 10-90% (v/v), according to the method of the embodiment 1-5, the potassium sorbate crystals in the prepared potassium sorbate finished product are in regular particles, the content is more than or equal to 99.8%, the transmittance is more than or equal to 98.5%, the proportion below 80 meshes is less than 1%, and the proportion above 30 meshes is less than 5%.
Comparative example 1
(1) Continuously mixing 10g of sorbic acid and 1020g of water at 80 ℃ for dissolution, wherein the mass concentration of the dissolved sorbic acid is 0.97%; respectively pumping 0.97% sorbic acid solution and 500g 1% potassium hydroxide solution into a neutralization reactor according to the flow rates of 6.6mL/min and 3.3g/min to perform continuous neutralization reaction, controlling the reaction temperature at 70 ℃, keeping the reaction time for 3 hours, and maintaining the pH value at 10.5 during the neutralization reaction;
(2) then, pumping the potassium sorbate neutralization solution in the step (1) into a two-stage continuous kettle type crystallizer according to the flow of 9.9mL/min for continuous cooling crystallization, wherein the pressure of a crystallization system is normal pressure, the crystallization temperature of the primary crystallizer is controlled at 45 ℃, the crystallization residence time is 3 hours, the crystallization temperature of the secondary crystallizer is controlled at 13 ℃, and the crystallization residence time is 4 hours; no potassium sorbate is separated out.
Comparative example 2
(1) Continuously mixing 100g sorbic acid and 400g 70% alcohol concentration water solution at 50 deg.C for dissolving, wherein the mass concentration of the dissolved sorbic acid is 20%; respectively pumping the sorbic acid solution with the mass concentration of 20 percent and 500g of 10.1 percent potassium hydroxide aqueous solution into a neutralization reactor according to the flow rates of 5mL/min and 5mL/min to carry out continuous neutralization reaction, controlling the reaction temperature at 65 ℃, keeping the reaction time for 3.5h, and maintaining the pH value at 10 during the neutralization reaction;
(2) then, pumping the potassium sorbate neutralization solution obtained in the step (1) into a two-stage continuous kettle type crystallizer according to the flow of 10mL/min for continuous cooling crystallization, wherein the pressure of a crystallization system is normal pressure, the crystallization temperature of the primary crystallizer is controlled at 40 ℃, the crystallization residence time is 0.5h, the crystallization temperature of the secondary crystallizer is controlled at 10 ℃, and the crystallization residence time is 20 min; and continuously separating the precipitated potassium sorbate crystal liquid, and drying the wet potassium sorbate obtained by separation to obtain a potassium sorbate finished product, wherein the finished potassium sorbate is in a regular particle shape, the content of the potassium sorbate is 98.3%, the transmittance is 96.2%, the content of the potassium sorbate above 30 meshes is 3.8%, the content of the potassium sorbate below 80 meshes is 89.8%, and the content of the potassium sorbate below 80 meshes is 6.4%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization is characterized by comprising the following steps: dissolving sorbic acid in a mixed solvent to obtain a sorbic acid solution, respectively pumping the sorbic acid solution and a potassium hydroxide aqueous solution or a potassium carbonate aqueous solution into a neutralization reactor for neutralization reaction to obtain a potassium sorbate solution, then pumping the potassium sorbate solution into a two-stage crystallization reactor for continuous cooling crystallization, and finally drying wet potassium sorbate obtained by separating crystallized potassium sorbate crystal liquid to obtain a finished potassium sorbate product, wherein the mixed solvent is a mixed solvent composed of one or two of ethanol or acetone and water, and the concentration of ethanol or/and acetone in the mixed solvent is 10-90% (v/v).
2. The method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization according to claim 1, wherein the sorbic acid solution has a mass concentration of 10-60%.
3. The method for producing potassium sorbate through liquid-liquid neutralization reaction and continuous cooling crystallization according to claim 2, wherein the process of dissolving sorbic acid in the mixed solvent is performed at 30-80 ℃.
4. The method for producing potassium sorbate by continuous cooling crystallization through liquid-liquid neutralization reaction according to any one of claims 1 to 3, wherein the temperature of the neutralization reaction is 40-80 ℃, the pH value is 9-11, and the reaction residence time is 0.5-5 h.
5. The method for producing potassium sorbate by continuous cooling crystallization through liquid-liquid neutralization reaction according to any one of claims 1 to 4, wherein the concentration of the aqueous potassium hydroxide solution is 5 to 30 wt%, and the concentration of the aqueous potassium carbonate solution is 5 to 30 wt%.
6. The method for producing the potassium sorbate by the liquid-liquid neutralization reaction and the continuous cooling crystallization according to any one of claims 1 to 5, wherein the flow rate of the sorbic acid solution is 3 to 15mL/min, and the flow rate of the potassium hydroxide aqueous solution or the potassium carbonate aqueous solution is 3 to 15 mL/min.
7. The method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization according to any one of claims 1 to 6, wherein in the continuous cooling crystallization process, the crystallization temperature of the primary crystallizer is controlled to be 45-60 ℃, the crystallization residence time is 0.5-3h, the crystallization temperature of the secondary crystallizer is controlled to be 10-30 ℃, and the crystallization residence time is 0.5-5 h.
8. The method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization according to claim 7, wherein the system pressure for cooling crystallization is normal pressure.
9. The method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization according to any one of claims 1 to 8, wherein after the reaction, a solvent is recovered from the mother liquor, which accounts for 5 to 30% of the total mass of the mother liquor, at normal pressure, and the recovered solvent and the rest of the mother liquor are returned to a sorbic acid dissolution process for sorbic acid dissolution, thereby producing a sorbic acid solution.
10. The method for producing potassium sorbate by liquid-liquid neutralization reaction and continuous cooling crystallization according to any one of claims 1 to 9, which is applied to the fields of food, beverages, medicines, cosmetics and chemical industry.
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| CN209392773U (en) * | 2018-12-27 | 2019-09-17 | 南京师范大学 | Multistage continuous alternating temperature crystallization and filtering integral device |
| WO2020087517A1 (en) * | 2018-11-02 | 2020-05-07 | 南通奥凯生物技术开发有限公司 | Method for preparing potassium sorbate with membrane chemical reactor |
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| FR1205366A (en) * | 1957-04-06 | 1960-02-02 | Hoechst Ag | Process for preparing stable sodium sorbate |
| CN103044239A (en) * | 2012-12-17 | 2013-04-17 | 日照金禾博源生化有限公司 | Production method of sodium citrate |
| CN105669439A (en) * | 2016-03-24 | 2016-06-15 | 广西新天德能源有限公司 | Method using ceramic membrane reactor to prepare potassium sorbate |
| WO2020087517A1 (en) * | 2018-11-02 | 2020-05-07 | 南通奥凯生物技术开发有限公司 | Method for preparing potassium sorbate with membrane chemical reactor |
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