CN117945871A - Preparation method of 1, 3-cyclohexanedione sodium salt aqueous solution - Google Patents
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- CN117945871A CN117945871A CN202410188509.7A CN202410188509A CN117945871A CN 117945871 A CN117945871 A CN 117945871A CN 202410188509 A CN202410188509 A CN 202410188509A CN 117945871 A CN117945871 A CN 117945871A
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- KYIBHFNJISEQRB-UHFFFAOYSA-N cyclohexane-1,3-dione;sodium Chemical compound [Na].O=C1CCCC(=O)C1 KYIBHFNJISEQRB-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 22
- 159000000000 sodium salts Chemical class 0.000 claims description 38
- 239000010409 thin film Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 239000008213 purified water Substances 0.000 claims description 8
- 230000001276 controlling effect Effects 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 9
- 239000012535 impurity Substances 0.000 abstract description 14
- 238000001704 evaporation Methods 0.000 abstract description 12
- 230000008020 evaporation Effects 0.000 abstract description 12
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 14
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- MGTZCLMLSSAXLD-UHFFFAOYSA-N 5-oxohexanoic acid Chemical compound CC(=O)CCCC(O)=O MGTZCLMLSSAXLD-UHFFFAOYSA-N 0.000 description 7
- 230000020477 pH reduction Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- AVVPOKSKJSJVIX-UHFFFAOYSA-N methyl 5-oxohexanoate Chemical compound COC(=O)CCCC(C)=O AVVPOKSKJSJVIX-UHFFFAOYSA-N 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- -1 material monomers Chemical class 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 206010020772 Hypertension Diseases 0.000 description 1
- 239000005578 Mesotrione Substances 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003474 anti-emetic effect Effects 0.000 description 1
- 239000002111 antiemetic agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- NPAKNKYSJIDKMW-UHFFFAOYSA-N carvedilol Chemical compound COC1=CC=CC=C1OCCNCC(O)COC1=CC=CC2=NC3=CC=C[CH]C3=C12 NPAKNKYSJIDKMW-UHFFFAOYSA-N 0.000 description 1
- 229960004195 carvedilol Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- IXAWUFIHYPMJRK-UHFFFAOYSA-M sodium;5-oxohexanoate Chemical compound [Na+].CC(=O)CCCC([O-])=O IXAWUFIHYPMJRK-UHFFFAOYSA-M 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 1, 3-cyclohexanedione sodium salt aqueous solution, which belongs to the technical field of chemical synthesis, and specifically relates to a preparation method of 1, 3-cyclohexanedione sodium salt aqueous solution, wherein 1, 3-cyclohexanedione sodium salt reaction solution is used as a starting material, and high-purity 1, 3-cyclohexanedione sodium salt aqueous solution is obtained after primary flash evaporation dealcoholization, neutralization and secondary flash evaporation dehydration; the high-efficiency flash evaporation process provided by the invention avoids side reactions such as cyclohexanedione hydrolysis and polymerization caused by long time, high temperature and large alkalinity in the common distillation process, simultaneously rapidly recovers the organic solvent, and is suitable for industrial production, and the 1, 3-cyclohexanedione sodium salt aqueous solution prepared by the process has high purity, less impurities, high efficiency, simple and convenient operation and low energy consumption.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of 1, 3-cyclohexanedione sodium salt aqueous solution.
Background
The 1, 3-cyclohexanedione can be used for synthesizing specific medicines of carvedilol and an antiemetic of anthradansienone for protecting cardiac and cerebral vessels and treating hypertension, and is also an intermediate of herbicide mesotrione and cyclosulfamide. Meanwhile, the 3-cyclohexanedione is an important fine chemical product and can be used for synthesizing various organic compounds such as material monomers, curing agents, solvents and the like.
The 1, 3-cyclohexanedione sodium salt aqueous solution is used as a key intermediate for preparing 1, 3-cyclohexanedione, is sensitive to temperature and alkalinity, is unstable at higher temperature and higher alkalinity, and is easy to generate impurities such as 5-oxo-hexanoic acid, dimers and the like, thereby influencing the reaction yield.
At present, two processes for synthesizing 1, 3-cyclohexanedione are mainly available, namely, a condensation method for synthesizing 1, 3-cyclohexanedione by cyclizing gamma-acetyl butyrate by taking sodium alkoxide as a condensing agent amide and the like as a reaction medium and condensing alpha, beta-unsaturated carboxylic acid ester and ketone. Another reduction method is to synthesize 1, 3-cyclohexanedione by using resorcinol as the starting material through reactions such as alkalization, hydrogenation reduction or hydrogen transfer reduction, acidification, rearrangement and the like. However, both of these processes inevitably undergo the critical steps of preparing an aqueous solution of 1, 3-cyclohexanedione sodium salt.
Patent CN113336629a reports that, using acetylacetone and methyl acrylate as raw materials, after michael addition reaction and claisen cyclization and basic deacetylation reaction, concentrating under reduced pressure to remove solvent, adding water to prepare 1, 3-cyclohexanedione sodium salt aqueous solution, acidifying, centrifuging, pulping, filtering, and drying to obtain the product 1, 3-cyclohexanedione. The patent CN116606198A prepares a metal alkoxide solution by using a metal source and a first alcohol, prepares a 5-oxo-caproic acid ester solution by using 5-oxo-caproic acid, a second alcohol and an acid catalyst, carries out condensation reaction on the metal alkoxide, the 5-oxo-caproic acid ester and an alcohol solvent to obtain a 1, 3-cyclohexanedione sodium salt condensation reaction liquid, and sequentially carries out desolvation, acidification and cooling crystallization on the condensation reaction liquid to obtain a 1, 3-cyclohexanedione product. The patent CN106083545A is prepared by transferring salt forming liquid prepared by taking resorcinol and sodium hydroxide as raw materials into a hydrogenation kettle, introducing hydrogen, preparing 1, 3-cyclohexanedione sodium salt aqueous solution under the conditions of high temperature and high pressure of 1.2-1.5MPa and 95-105 ℃, and preparing the 1, 3-cyclohexanedione after acidification, centrifugation and drying. The patent CN1680247A is neutralized to form salt by using resorcinol and inorganic strong base, and is subjected to hydrogenation reduction under the catalysis of a catalyst at the temperature of 50-150 ℃ under the pressure of 0.5-3MPa to prepare a 1, 3-cyclohexanedione sodium salt aqueous solution, and the 1, 3-cyclohexanedione is prepared after acidification and rearrangement.
In the process of preparing the 1, 3-cyclohexanedione sodium salt aqueous solution, the alkali is too strong due to the excessive addition of condensing agents such as inorganic alkali, the temperature is higher, and the like, so that more 1, 3-cyclohexanedione sodium salt is hydrolyzed into 5-oxohexanoic acid sodium salt, 5-oxohexanoic acid impurities are further generated in the subsequent acidification process, and the impurities are difficult to remove; meanwhile, in the concentration and solvent removal process, the result of higher concentration of 1, 3-cyclohexanedione sodium salt is easy to cause more dimer impurities under the conditions of high temperature, high pressure and the like, wherein the structures of the dimer impurities and the 5-oxo-hexanoic acid impurities are as follows:
This poses a great challenge in preparing a product of high purity.
Disclosure of Invention
The invention aims to solve the problem of impurity increase caused by high temperature, high pressure, long time, high concentration and the like in the conventional synthesis process, and provides a preparation method of 1, 3-cyclohexanedione sodium salt aqueous solution.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
a method for preparing 1, 3-cyclohexanedione sodium salt aqueous solution, comprising the following steps:
1) Pumping the 1, 3-cyclohexanedione sodium salt reaction solution into a thin film evaporator, heating, controlling the vacuum degree, and desolventizing to obtain a concentrated solution;
2) Adding the concentrated solution obtained in the step 1) into purified water, stirring and dissolving, and regulating the pH of a system to 10-13 by using acid to obtain a mixed solution;
3) Pumping the mixture obtained in the step 3) into a thin film evaporator, heating, controlling the vacuum degree, and continuously desolventizing to obtain a1, 3-cyclohexanedione sodium salt aqueous solution.
And in the step 1), heating to 30-120 ℃.
And in the step 1), the vacuum degree is controlled to be 50-700 mbar.
The speed of pumping the 1, 3-cyclohexanedione sodium salt reaction liquid into the thin film evaporator in the step 1) is 30-200 g/min.
The mass of the concentrated solution in the step 1) is 10-70% of that of the 1, 3-cyclohexanedione sodium salt reaction solution.
In the step 2), the mass ratio of the purified water to the sodium salt in the 1, 3-cyclohexanedione sodium salt reaction solution is 3-10: 1.
The acid in the step 2) is sulfuric acid or hydrochloric acid.
And in the step 3), heating to 30-90 ℃.
And 3) controlling the vacuum degree to be 10-500 mbar in the step 3).
The speed of pumping the mixture into the thin film evaporator in the step 3) is 30-200 g/min.
Compared with the prior art, the invention has the following advantages:
According to the preparation method of the 1, 3-cyclohexanedione sodium salt aqueous solution, the primary flash evaporation desolventizing, the pH adjustment, the alkalinity reduction and the flash evaporation secondary desolventizing are carried out on the 1, 3-cyclohexanedione sodium salt reaction solution, so that the phenomenon of impurity increase caused by too strong alkalinity, higher temperature and other reasons due to excessive addition of condensing agents such as inorganic alkali in the conventional process is avoided, the preparation rate is improved, and the possibility of impurity increase caused by unstable system due to long-time operation is avoided; meanwhile, in the concentration and solvent removal process, the production of dimer impurities is avoided by controlling the concentration of the concentrated solution.
The 1, 3-cyclohexanedione sodium salt aqueous solution prepared by the method has few impurities, the liquid phase purity is up to more than 99%, the quality of the 1, 3-cyclohexanedione product obtained by acidification and crystallization is high, and the yield of the 1, 3-cyclohexanedione is further improved; and the solvent obtained in the post-treatment high-efficiency flash evaporation process can be recovered, so that the production cost is greatly reduced, the production period is shortened, and the production energy consumption is reduced.
The post-treatment method of the 1, 3-cyclohexanedione sodium salt reaction solution has the advantages of high efficiency, high yield, high liquid phase purity of the obtained sodium salt aqueous solution, simple operation, mild process, low production cost, environment friendliness and suitability for industrial production.
Detailed Description
The foregoing is further elaborated by the following description of embodiments of the present invention, which are given by way of example only, and should not be construed as limiting the scope of the present invention. All techniques implemented based on the above description of the invention are within the scope of the invention.
Example 1 preparation of 1, 3-cyclohexanedione sodium salt reaction solution:
Methyl 5-oxo-hexanoate is used as a raw material, sodium methoxide is used as a condensing agent, and methanol is used as a solvent to prepare a1, 3-cyclohexanedione sodium salt alcohol solution, wherein the sodium salt content is 20%.
Preparation of 1, 3-cyclohexanedione sodium salt aqueous solution:
Setting the vacuum degree of a thin film evaporator to be 500mbar, adding 3600g purified water into a receiving bottle at the water bath temperature of 60 ℃, stirring, injecting 6000g of 1, 3-cyclohexanedione sodium salt alcohol solution into the thin film evaporator at the feeding speed of 100g/min by using a peristaltic pump, rapidly removing methanol from the reaction liquid, separating out sodium salt, and directly dropping the obtained slurry into the receiving bottle containing water, stirring and dissolving. After 1h, 3600g of methanol solvent was recovered by flash evaporation to obtain an aqueous solution of 1, 3-cyclohexanedione sodium salt with a part of methanol, the pH of the system was adjusted to 11.2 using 31% hydrochloric acid, the water bath temperature of the thin film evaporator was set at 70℃and the vacuum was controlled at 100mbar, and the solution was again fed to the thin film evaporator at a feed rate of 100g/min and stopped after 1h to obtain an aqueous solution of sodium salt with a 1, 3-cyclohexanedione sodium salt content of 30%. The liquid phase purity of the 1, 3-cyclohexanedione sodium salt aqueous solution detected by HPLC was 99.3% in accordance with the liquid phase purity of the sodium salt reaction solution before desolvation. And the sodium salt yield of the 1, 3-cyclohexanedione sodium salt aqueous solution prepared by the modes of primary flash evaporation desolventizing, pH adjustment, alkalinity reduction and flash evaporation secondary desolventizing is identical with the sodium salt yield in the reaction liquid, and is 96.8%, and the hydrolysis and polymerization impurities of the 1, 3-cyclohexanedione are not increased.
Example 2 preparation of 1, 3-cyclohexanedione sodium salt reaction solution:
Methyl 5-oxo-hexanoate is used as a raw material, sodium methoxide is used as a condensing agent, and methanol is used as a solvent to prepare a1, 3-cyclohexanedione sodium salt alcohol solution, wherein the sodium salt content is 20%.
Preparation of 1, 3-cyclohexanedione sodium salt aqueous solution:
Setting the vacuum degree of a thin film evaporator to 300mbar, adding 7200g purified water into a receiving bottle at the water bath temperature of 50 ℃, stirring, injecting 6000g 1, 3-cyclohexanedione sodium salt alcohol solution into the thin film evaporator by using a peristaltic pump at the feeding speed of 200g/min, rapidly removing methanol from the reaction liquid, separating out sodium salt, and directly dropping the obtained slurry into the receiving bottle containing water, stirring and dissolving. After 30min, 3200g of methanol solvent was recovered by flash evaporation to obtain an aqueous solution of 1, 3-cyclohexanedione sodium salt with a part of methanol, the pH of the system was adjusted to 12.5 by using 31% hydrochloric acid, the water bath temperature of the thin film evaporator was set at 80℃and the vacuum was controlled at 200mbar, and the solution was again injected into the thin film evaporator at a feed rate of 200g/min and stopped after 50min to obtain an aqueous solution of sodium salt with a content of 28% of 1, 3-cyclohexanedione sodium salt. The liquid phase purity of the sodium salt aqueous solution detected by HPLC is consistent with that of the sodium salt alcohol reaction liquid, and is 99.2%, and the sodium salt yield of the 1, 3-cyclohexanedione sodium salt aqueous solution prepared by the process is consistent with that of the sodium salt in the reaction liquid, which is obtained through a liquid phase external standard test, and the hydrolysis and polymerization impurities of cyclohexanedione are not increased.
Example 3 preparation of 1, 3-cyclohexanedione sodium salt reaction solution:
methyl 5-oxo-hexanoate is used as a raw material, sodium methoxide is used as a condensing agent, and DMF is used as a solvent to prepare a1, 3-cyclohexanedione sodium salt reaction solution, wherein the sodium salt content is 30%.
Preparation of 1, 3-cyclohexanedione sodium salt aqueous solution:
setting the vacuum degree of a thin film evaporator to 80mbar, adding 6000g purified water into a receiving bottle at the water bath temperature of 80 ℃, stirring, injecting 3000g 1, 3-cyclohexanedione sodium salt reaction liquid into the thin film evaporator by using a peristaltic pump at the feeding speed of 50g/min, rapidly removing DMF from the reaction liquid, directly dropping sodium salt concentrated feed liquid into the receiving bottle containing water, and uniformly stirring. After 1h 1700g of DMF solvent was recovered by flash evaporation to give an aqueous solution of 1, 3-cyclohexanedione sodium salt with some DMF, the pH of the system was adjusted to 13.0 using 31% hydrochloric acid, the water bath temperature of the thin film evaporator was set to 90℃and the vacuum was controlled to 100mbar, and the solution was re-injected into the thin film evaporator at a feed rate of 70g/min and stopped after 133min to give an aqueous solution of sodium salt with a sodium salt content of 31%. The purity of the liquid phase of the sodium salt aqueous solution detected by HPLC is consistent with that of the liquid phase of the sodium salt reaction solution, and is 99.7 percent. The yield of the sodium salt aqueous solution obtained by calculation is 98.5% according to the content of sodium salt in the liquid phase external standard reaction solution and the sodium salt aqueous solution after desolventizing, and the yield of the sodium salt aqueous solution is not increased with that of the reaction solution before desolventizing.
Example 4 preparation of 1, 3-cyclohexanedione sodium salt reaction solution:
methyl 5-oxo-hexanoate is used as a raw material, sodium methoxide is used as a condensing agent, and DMAC is used as a solvent to prepare a1, 3-cyclohexanedione sodium salt reaction solution, wherein the sodium salt content is 30%.
Preparation of 1, 3-cyclohexanedione sodium salt aqueous solution:
Setting the vacuum degree of a thin film evaporator to 50mbar, adding 5000g of purified water into a receiving bottle at the water bath temperature of 85 ℃, stirring, injecting 3000g of 1, 3-cyclohexanedione sodium salt reaction liquid into the thin film evaporator by using a peristaltic pump at the feeding speed of 30g/min, rapidly removing DMAC from the reaction liquid, directly dropping sodium salt concentrated feed liquid into the receiving bottle containing water, and uniformly stirring. After 100min, 1800g of DMAC solvent was recovered by flash evaporation to obtain an aqueous solution of 1, 3-cyclohexanedione sodium salt with a portion of DMAC, the pH of the system was adjusted to 12.5 using sulfuric acid, the water bath temperature of the thin film evaporator was set at 90℃and the vacuum was controlled at 50mbar, and the solution was again injected into the thin film evaporator at a feed rate of 60g/min, and after 2h, it was stopped to obtain an aqueous solution of sodium salt having a sodium salt content of 30%. The purity of the liquid phase of the sodium salt aqueous solution detected by HPLC is consistent with that of the liquid phase of the sodium salt reaction solution, and is 99.75 percent. The yield of the sodium salt aqueous solution obtained by calculation is 98.0% according to the content of sodium salt in the liquid phase external standard reaction solution and the sodium salt aqueous solution after desolventizing, and the yield of the sodium salt aqueous solution is not increased with that of the reaction solution before desolventizing.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and various modifications or variations may be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.
Claims (10)
1. A method for preparing 1, 3-cyclohexanedione sodium salt aqueous solution, which is characterized in that: the method comprises the following steps:
1) Pumping the 1, 3-cyclohexanedione sodium salt reaction solution into a thin film evaporator, heating, controlling the vacuum degree, and desolventizing to obtain a concentrated solution;
2) Adding the concentrated solution obtained in the step 1) into purified water, stirring and dissolving, and regulating the pH of a system to 10-13 by using acid to obtain a mixed solution;
3) Pumping the mixture obtained in the step 3) into a thin film evaporator, heating, controlling the vacuum degree, and continuously desolventizing to obtain a1, 3-cyclohexanedione sodium salt aqueous solution.
2. A process for the preparation of an aqueous 1, 3-cyclohexanedione sodium salt solution according to claim 1, characterized in that: and in the step 1), heating to 30-120 ℃.
3. A process for the preparation of an aqueous 1, 3-cyclohexanedione sodium salt solution according to claim 1, characterized in that: and in the step 1), the vacuum degree is controlled to be 50-700 mbar.
4. A process for the preparation of an aqueous 1, 3-cyclohexanedione sodium salt solution according to claim 1, characterized in that: the speed of pumping the 1, 3-cyclohexanedione sodium salt reaction liquid into the thin film evaporator in the step 1) is 30-200 g/min.
5. A process for the preparation of an aqueous 1, 3-cyclohexanedione sodium salt solution according to claim 1, characterized in that: the mass of the concentrated solution in the step 1) is 10-70% of that of the 1, 3-cyclohexanedione sodium salt reaction solution.
6. A process for the preparation of an aqueous 1, 3-cyclohexanedione sodium salt solution according to claim 1, characterized in that: in the step 2), the mass ratio of the purified water to the sodium salt in the 1, 3-cyclohexanedione sodium salt reaction solution is 3-10: 1.
7. A process for the preparation of an aqueous 1, 3-cyclohexanedione sodium salt solution according to claim 1, characterized in that: the acid in the step 2) is sulfuric acid or hydrochloric acid.
8. A process for the preparation of an aqueous 1, 3-cyclohexanedione sodium salt solution according to claim 1, characterized in that: and in the step 3), heating to 30-90 ℃.
9. A process for the preparation of an aqueous 1, 3-cyclohexanedione sodium salt solution according to claim 1, characterized in that: and 3) controlling the vacuum degree to be 10-500 mbar in the step 3).
10. A process for the preparation of an aqueous 1, 3-cyclohexanedione sodium salt solution according to claim 1, characterized in that: the speed of pumping the mixture into the thin film evaporator in the step 3) is 30-200 g/min.
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