CN116444358A - Recovery treatment process of cinnamaldehyde production wastewater - Google Patents
Recovery treatment process of cinnamaldehyde production wastewater Download PDFInfo
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- CN116444358A CN116444358A CN202310273975.0A CN202310273975A CN116444358A CN 116444358 A CN116444358 A CN 116444358A CN 202310273975 A CN202310273975 A CN 202310273975A CN 116444358 A CN116444358 A CN 116444358A
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- acetaldehyde
- cinnamaldehyde
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- production wastewater
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- 239000002351 wastewater Substances 0.000 title claims abstract description 96
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 62
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229940117916 cinnamic aldehyde Drugs 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 58
- 230000008569 process Effects 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 238000011084 recovery Methods 0.000 title claims abstract description 32
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 70
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000012071 phase Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 36
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 235000021190 leftovers Nutrition 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000007790 solid phase Substances 0.000 claims abstract description 19
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 18
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 18
- 239000002699 waste material Substances 0.000 claims abstract description 18
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 230000020477 pH reduction Effects 0.000 claims abstract description 15
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 13
- 239000008346 aqueous phase Substances 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012044 organic layer Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000004537 pulping Methods 0.000 claims description 12
- IATNQCGERGDVDN-UHFFFAOYSA-N 5-phenylpent-2-enoic acid Chemical compound OC(=O)C=CCCC1=CC=CC=C1 IATNQCGERGDVDN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 238000004042 decolorization Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 6
- YKZQOAOGXBOKCS-UHFFFAOYSA-N acetaldehyde;benzaldehyde Chemical compound CC=O.O=CC1=CC=CC=C1 YKZQOAOGXBOKCS-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 4
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 23
- 239000002585 base Substances 0.000 description 14
- 238000004811 liquid chromatography Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 229920002521 macromolecule Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000012691 depolymerization reaction Methods 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LSFCNJZMBBDBJT-UHFFFAOYSA-N 3-phenylprop-2-enal Chemical compound O=CC=CC1=CC=CC=C1.O=CC=CC1=CC=CC=C1 LSFCNJZMBBDBJT-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 239000005956 Metaldehyde Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229940112822 chewing gum Drugs 0.000 description 1
- 235000015218 chewing gum Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- GKKDCARASOJPNG-UHFFFAOYSA-N metaldehyde Chemical compound CC1OC(C)OC(C)OC(C)O1 GKKDCARASOJPNG-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
- C07C45/84—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by azeotropic distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
Abstract
The invention discloses a recovery treatment process of cinnamaldehyde production wastewater. The process comprises the following steps: cooling and filtering the cinnamaldehyde production wastewater to obtain a first water phase and a first solid phase; performing azeotropic distillation on the first aqueous phase to separate an azeotrope of acetaldehyde, benzaldehyde and water, thereby obtaining wastewater containing the poly-acetaldehyde; adding acid into the wastewater containing the poly-acetaldehyde for acidolysis reaction, then distilling to recover the acetaldehyde, and filtering the mixture left by distillation to obtain de-acetaldehyde wastewater and leftovers; dissolving the first solid phase by adopting a first organic solvent, then adding alkali to perform a first neutralization reaction, separating liquid after the reaction is completed, and then performing first acidification on the inorganic layer to obtain benzoic acid and concentrating the organic layer to obtain leftovers. The invention realizes the comprehensive utilization of useful components in the wastewater, reduces the emission and the treatment intensity of the final waste, changes waste into valuables, comprehensively utilizes resources, obviously improves the economic benefit and greatly improves the market competitiveness of cinnamaldehyde projects.
Description
Technical Field
The invention relates to the technical field of treatment of wastewater from cinnamaldehyde production, in particular to a recovery treatment process of wastewater from cinnamaldehyde production.
Background
Cinnamaldehyde (3-phenyl-2-propenal), english name: the cinnamaldehyde is an important chemical raw material and is also a widely used synthetic spice for food, and can be used for preparing food preservatives, seasonings, oral care products, chewing gum and essence for candies.
At present, most of the industrial cinnamaldehyde is synthesized by taking benzaldehyde and acetaldehyde as raw materials through condensation reaction under the condition of a catalyst. After the condensation reaction is finished, the target product cinnamaldehyde is obtained by distillation and rectification after liquid separation. In the process, the obtained water phase contains a large amount of byproducts such as unconverted benzaldehyde, a small amount of cinnamaldehyde, and poly-acetaldehyde. Directly used as wastewater, has high COD concentration of more than 4 ten thousand due to a plurality of organic species and complex content, and has high wastewater treatment difficulty. If the wastewater enters the sewage treatment system through pretreatment, larger impact is caused on the sewage treatment system, so that the sewage treatment system collapses, and the wastewater treatment does not reach the standard. Meanwhile, the waste water contains a plurality of useful raw materials, products and byproducts, which are directly treated as waste materials, thereby greatly improving the production cost.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a recovery treatment process for cinnamaldehyde production wastewater, which solves the technical problems of difficult treatment and poor economic benefit of the cinnamaldehyde production wastewater in the prior art.
The invention provides a recovery treatment process of cinnamaldehyde production wastewater, which comprises the following steps:
cooling and filtering the cinnamaldehyde production wastewater to obtain a first water phase and a first solid phase;
performing azeotropic distillation on the first aqueous phase to separate an azeotrope of acetaldehyde, benzaldehyde and water, thereby obtaining wastewater containing the poly-acetaldehyde;
adding acid into the wastewater containing the poly-acetaldehyde for acidolysis reaction, then distilling to recover acetaldehyde, and filtering the mixture left by distillation to obtain de-acetaldehyde wastewater and leftovers;
dissolving the first solid phase by adopting a first organic solvent, adding alkali to perform a first neutralization reaction, separating liquid after the reaction is completed, performing first acidification on an inorganic layer to obtain benzoic acid, and concentrating an organic layer to obtain leftovers.
Compared with the prior art, the invention has the beneficial effects that:
the invention realizes the comprehensive utilization of useful components in the wastewater, reduces the emission and the treatment intensity of the final waste, changes waste into valuables, comprehensively utilizes resources, obviously improves the economic benefit and greatly improves the market competitiveness of cinnamaldehyde projects.
Drawings
FIG. 1 is a process flow diagram of an embodiment of a recovery treatment process for cinnamaldehyde production wastewater provided by the invention;
fig. 2 is a process flow chart of another embodiment of a recovery treatment process of cinnamaldehyde production wastewater provided by the invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. 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.
Referring to fig. 1, the invention provides a recovery treatment process of cinnamaldehyde production wastewater, which comprises the following steps:
s1, cooling and filtering the cinnamaldehyde production wastewater to obtain a first water phase and a first solid phase. In the step, the inventor finds that the cinnamaldehyde production wastewater contains unreacted complete materials benzaldehyde and acetaldehyde according to the analysis of the components of the cinnamaldehyde production wastewater, firstly, the materials are designed and considered to be recycled, and the materials reenter a synthesis reaction system, so that the utilization rate of the whole raw materials is improved. Firstly, cooling the cinnamaldehyde production wastewater, wherein high molecular weight organic matters, benzoic acid and other solubilities are reduced along with the reduction of temperature, the high molecular weight organic matters, the benzoic acid and other solubilities are separated out, and the first solid phase obtained after filtration contains benzoic acid, organic macromolecules and polymers.
S2, performing azeotropic distillation on the first aqueous phase to separate azeotrope of acetaldehyde, benzaldehyde and water, thereby obtaining wastewater containing poly-acetaldehyde (such as paraldehyde, metaldehyde and the like). In this step, distilled water containing acetaldehyde and benzaldehyde is returned to the cinnamaldehyde condensation step.
S3, adding acid into the wastewater containing the poly-acetaldehyde for acidolysis reaction, then distilling to recover the acetaldehyde, and filtering the mixture left by distillation to obtain the wastewater and the leftovers of de-acetaldehyde. In the step, the polymeric acetaldehyde is depolymerized by adding acid and distilled to recover acetaldehyde, the distilled mixture is filtered to obtain the de-acetaldehyde wastewater, the de-acetaldehyde wastewater has small impact on a sewage treatment system, and the de-acetaldehyde wastewater can enter the sewage treatment system for biochemical treatment after micro-electrolysis and Fenton treatment and can be directly discharged.
S4, dissolving the first solid phase by adopting a first organic solvent, then adding alkali to perform a first neutralization reaction, separating liquid after the reaction is completed, and then performing first acidification on an inorganic layer to obtain benzoic acid and concentrating an organic layer to obtain leftovers.
The inventor finds that though the conditions of cinnamaldehyde synthesis reaction and product separation post-treatment are different in each batch, the main organic component content of the generated wastewater is different, but the components of the wastewater are basically benzaldehyde, acetaldehyde, cinnamaldehyde, polymeric acetaldehyde, benzoic acid, other organic polymers and the like, the components are various, and the wastewater is partially soluble in water and partially slightly soluble in water. If separated alone, the cost is too high. Therefore, the design of an efficient treatment process, the comprehensive utilization of useful components in the wastewater, the reduction of emission and the reduction of the treatment intensity of the final waste are key to the whole cinnamaldehyde production. The inventor develops a treatment process for comprehensively utilizing the cinnamaldehyde wastewater through long-term research and practice, thereby changing waste into valuables, comprehensively utilizing resources and greatly improving the market competitiveness of the cinnamaldehyde project. The present invention has been proposed.
In the embodiment, in the step S1, in the cooling treatment process, the temperature of the wastewater from cinnamaldehyde production is reduced to-5-0 ℃. In some embodiments of the invention, the cinnamaldehyde production wastewater is subjected to cooling treatment by means of ice bath cooling.
In this embodiment, in step S2, the azeotropic distillation is carried out at a temperature of 50 to 70℃and preferably 55 to 65 ℃.
In the embodiment, in the step S3, during the acidolysis reaction, the first acid is concentrated sulfuric acid with the mass fraction of 90-98%, and the dosage ratio of the wastewater containing the polyacetaldehyde to the concentrated sulfuric acid is 1kg: (0.01-0.03) mL; the acidolysis reaction temperature is 55-80 ℃, preferably 55-70 ℃, and the acidolysis reaction time is 4-6h; in the distillation, the distillation temperature is 50-80deg.C, preferably 55-75deg.C.
In this embodiment, in step S4, the first organic solvent is at least one of ethyl acetate, methyl tert-butyl ether, diisopropyl ether, methanol, ethanol, and dichloromethane, preferably ethyl acetate; the dosage ratio of the first solid phase to the first organic solvent is 0.8-2kg:1L; in the first neutralization reaction, the type of the first base used in the present invention is not limited, and may be selected according to the actual conditions by those skilled in the art, and may be, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, and ammonia. In some embodiments of the invention, the first base is sodium hydroxide. In some more specific embodiments of the invention, the first base is added to the system in the form of an aqueous solution, the mass concentration of the first base solution is 10% -30%, and the dosage ratio of the first solid phase to the first base solution is 1kg: (0.1-0.3) mL; the temperature of the first neutralization reaction is 50-60 ℃, and the time of the first neutralization reaction is 4-6h; in the first acidification process, the final pH value is adjusted to 3-4 to obtain benzoic acid, if the pH value is too high, the cost of the hydrochloric acid is excessively increased, and if the pH value is too low, the hydrochloric acid cannot be completely converted into the benzoic acid; the invention does not limit the type and concentration of the first acid solution used in the acidification process, and the person skilled in the art can select according to practical conditions, for example, the acid can be inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and the like; in some embodiments of the invention, the first acid solution is hydrochloric acid, and the mass fraction of hydrochloric acid is 15% -20%.
Referring to fig. 2, in the present invention, the recovery treatment process of the above-mentioned cinnamaldehyde production wastewater further includes the following steps:
s5, dissolving the leftovers by using a second organic solvent, adding alkali to perform a second neutralization reaction, adding activated carbon into the neutralization solution to perform adsorption decolorization, removing the activated carbon, and separating the solution to obtain a first oil phase and a second water phase. In the step, carboxylic acid in the leftovers is converted into water-soluble salt by acid-base neutralization reaction, so that the water solubility of the carboxylic acid is increased, and the phenomenon of membrane blockage is obviously reduced; then removing ions and pigments in the solution through activated carbon adsorption and decolorization; and removing the polymer dissolved in the ethyl acetate in the cinnamaldehyde waste solution through separating liquid.
S6, removing the second organic solvent from the first oil phase, adding an alcohol solvent, pulping, filtering to obtain filter residues and filtrate, and removing the alcohol solvent from the filtrate to obtain oily liquid, wherein the filter residues are benzaldehyde acetaldehyde polymers. In the step, a small amount of carboxylic acid substances also exist in the first oil phase, and the carboxylic acid substances in the first oil phase can be dissolved into the alcohol solvent by adopting a pulping mode of removing the second organic solvent and the alcohol solvent, so that the carboxylic acid substances are separated from benzaldehyde acetaldehyde polymer, and the recovery rate of carboxylic acid is improved.
S7, adding acid into the second water phase and the oily liquid to carry out second acidification, then adopting a third organic solvent to extract the acidification liquid to obtain a second oil phase and a third water phase, carrying out desolventizing treatment on the second oil phase, and then cooling and crystallizing to obtain the 5-phenylpent-2-enoic acid. In the step, the main component of the oily liquid is carboxylic acid substances, the carboxylic acid substances are combined with a second water phase, water-soluble carboxylate is converted into carboxylic acid through acidification, and finally, the 5-phenylpent-2-enoic acid with the purity of more than or equal to 98% is obtained through extraction by a third organic solvent, drying and dewatering, removal of the third organic solvent, reduced pressure distillation and cooling crystallization; the third aqueous phase can be used for neutralization after desalting treatment.
In this embodiment, in step S5, before the leftovers are fully dissolved in the second organic solvent, the relative content of carboxylic acid in the cinnamaldehyde waste sample can be detected by a liquid chromatography method, so that the recovery rate of carboxylic acid can be conveniently tested later. In order to enhance the dissolution effect, the cinnamaldehyde waste is sufficiently dissolved in the form of powder with a second organic solvent. Further, the cinnamaldehyde waste powder is obtained by sufficiently grinding the cinnamaldehyde waste. The second organic solvent is at least one of ethyl acetate, methyl tertiary butyl ether, diisopropyl ether, methanol, ethanol and dichloromethane, preferably ethyl acetate; the dosage ratio of the offal to the second organic solvent is 1g: (3-8) mL. If the concentration of the waste is too high, the system is sticky, and the reactivity is reduced; if the concentration of the waste is too low, the solvent consumption and the treatment times are increased, and the treatment cost is increased. In the second neutralization reaction, the present invention is not limited to the type of the second base used, and those skilled in the art can choose the second base according to the actual situation, and for example, the second base may be an inorganic base such as sodium hydroxide, potassium hydroxide, and ammonia water. In some embodiments of the invention, the second base is sodium hydroxide. The invention adopts sodium hydroxide as the second alkali, has small addition amount and saves cost. In some more specific embodiments of the invention, the second base is added to the system in the form of an aqueous solution, the mass concentration of the second base solution being from 10% to 20%; the dosage ratio of the offal to the second alkali solution is 1g: (1-3) mL. If the amount of the second base added is too small, the carboxylic acid reaction is incomplete, the yield is lowered, and if the amount of the second base added is too large, the treatment cost is increased. In the adsorption decoloring process, the addition amount of the activated carbon is 20% -30% of the mass of the cinnamaldehyde waste; the decolorization temperature is 30-60deg.C, preferably 30-50deg.C, and the decolorization time is 20-100min, preferably 80-90min. The inventor finds that if the neutralization solution is directly subjected to liquid separation in the experimental process, the viscosity of the neutralization solution is too high to carry out subsequent liquid separation operation; and, the inventors have screened for different decolorization temperatures and decolorization times, and found that carboxylic acid crystals have the highest purity (. Gtoreq.99%) within this temperature and time range. Too high a temperature, too fast volatilization of the second organic solvent, too low a temperature or too short a heat preservation time, insufficient adsorption of impurities. After the liquid separation process is finished, the organic layer obtained by liquid separation can be extracted by water, and the inorganic layer is combined to improve the recovery rate of the 5-phenylpent-2-enoic acid.
In this embodiment, in step S6, the alcohol solvent may be methanol, ethanol, or the like. In the pulping process, in order to improve the recovery rate of carboxylic acid, the obtained filter residue can be added with ethanol again for repeated pulping, and the filtrate obtained in each pulping process is combined. In some embodiments of the invention, the ratio of the amount of the offal to the alcohol solvent is 1g: (3-10) mL, and the pulping time is 4-6h each time.
In the embodiment, in the step S7, in the second acidification process, the final pH is adjusted to 2-3 to obtain 5-phenylpent-2-enoic acid, if the pH is too high, the cost of the hydrochloric acid is excessively increased, and if the pH is too low, the carboxylate cannot be completely converted into carboxylic acid; the invention does not limit the type and concentration of the acid solution used in the acidification process, and the acid solution can be selected by a person skilled in the art according to actual conditions, and can be inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and the like; in some embodiments of the invention, the acid solution is hydrochloric acid, the mass fraction of which is 15% -20%; the third organic solvent is ethyl acetate, methyl tert-butyl ether, diisopropyl ether, methanol, ethanol, dichloromethane, etc., preferably ethyl acetate; the volume ratio of the acidizing fluid to the third organic solvent is 1: (0.2-2), and the temperature of the cooling crystallization is-5-0 ℃.
In the invention, the second organic solvent, the alcohol solvent and the third organic solvent are removed by reduced pressure distillation. Further, the temperature of the reduced pressure distillation is 30 to 60 ℃, preferably 30 to 55 ℃.
Example 1
(1) Filtering 15kg of cinnamaldehyde production wastewater after ice bath cooling treatment to obtain 14kg of water phase and 1kg of solid phase, detecting the relative content of benzaldehyde and acetaldehyde in the water phase through liquid chromatography, and testing the total content to be about 25%;
(2) Performing azeotropic distillation on the water phase in the step (1) at 65 ℃ to obtain 3kg of aqueous solution containing benzaldehyde and acetaldehyde;
(3) Adding 200mL of concentrated sulfuric acid with the mass concentration of 90% into the wastewater containing the polymeric acetaldehyde by azeotropic distillation in the step (2), carrying out reflux depolymerization reaction at 60 ℃, distilling the reaction solution at 65 ℃ after 5 hours to obtain 1.1kg of aqueous solution of the polymeric acetaldehyde, filtering the mixture left by distillation to obtain 0.26kg of macromolecular polymer (leftovers), carrying out micro-electrolysis, feton treatment and biochemical treatment on the water phase left by filtration in sequence to finally obtain 11kg of wastewater capable of being discharged, carrying out liquid chromatography on the wastewater capable of being discharged again to detect the total content of the benzaldehyde and the acetaldehyde, wherein the result shows that the total content of the benzaldehyde and the acetaldehyde is about 9.5%, and the recovery rate of the benzaldehyde and the acetaldehyde is 1- (11 x 9.5%)/(14 x 25%) +/-100% = 70%;
(4) 1L of ethyl acetate is added into the solid phase in the step (1) to be fully dissolved to form a homogeneous solution, then 200mL of sodium hydroxide with mass concentration of 20% is added to be neutralized at 50 ℃ for 4 hours, the solution is separated after the reaction is completed, then 0.15kg of macromolecular polymer (leftovers) is obtained by concentrating an organic layer, and 250mL of hydrochloric acid with mass concentration of 20% is added into the inorganic layer obtained by separating the solution to adjust pH=3-4, so that 0.64kg of benzoic acid is finally obtained. The overall utilization of the wastewater was = (3+0.64+1.1+0.15+0.26)/15×100% = 34%.
Repeating the process for a plurality of times, wherein the recovery rate of benzaldehyde and acetaldehyde in the wastewater is 70-75%, the overall utilization rate of the wastewater is 30-35%, and the reduction amount of the wastewater is 25-30%.
Example 2
(1) Filtering 15kg of cinnamaldehyde production wastewater after ice bath cooling treatment to obtain 14kg of water phase and 1kg of solid phase, detecting the relative content of benzaldehyde and acetaldehyde in the water phase through liquid chromatography, and testing the total content to be about 25%;
(2) Carrying out azeotropic distillation on the water phase in the step (1) at 55 ℃ to obtain 4kg of aqueous solution containing benzaldehyde and acetaldehyde;
(3) Adding 200mL of concentrated sulfuric acid with the mass concentration of 90% into the wastewater containing the polymeric acetaldehyde which is subjected to azeotropic distillation in the step (2), carrying out reflux depolymerization reaction at 60 ℃, distilling the reaction solution at 75 ℃ after 5 hours to obtain 1kg of aqueous solution of the polymeric acetaldehyde, filtering the mixture which is left after distillation to obtain 0.16kg of macromolecular polymer (leftover), carrying out micro-electrolysis, feton treatment and biochemical treatment on the water phase which is left after filtration in sequence to finally obtain 9kg of wastewater which can be discharged, and carrying out liquid chromatography on the wastewater which can be discharged again to detect the total content of the benzaldehyde and the acetaldehyde, wherein the result shows that the total content of the benzaldehyde and the acetaldehyde accounts for 9.7%, and the recovery rate of the benzaldehyde and the acetaldehyde is 1- (9.7%)/(14.25%) +/-100% = 75%;
(4) 1L of ethyl acetate is added into the solid phase in the step (1) to be fully dissolved to form a homogeneous solution, then 200mL of sodium hydroxide with mass concentration of 20% is added to be neutralized at 50 ℃ for 4 hours, the solution is separated after the reaction is completed, then 0.2kg of macromolecular polymer (leftovers) is obtained by concentrating an organic layer, and 250mL of hydrochloric acid solution with mass concentration of 20% is added into the inorganic layer obtained by separating the solution to adjust pH=3-4, and finally 0.60kg of benzoic acid is obtained. The overall utilization of the wastewater= (4+0.6+1+0.2+0.16)/15×100% = 40%.
Repeating the process for a plurality of times, wherein the recovery rate of benzaldehyde and acetaldehyde in the wastewater is 75-80%, the overall utilization rate of the wastewater is 38-43%, and the reduction amount of the wastewater is 40-45%.
Example 3
(1) Filtering 15kg of cinnamaldehyde production wastewater after ice bath cooling treatment to obtain 14kg of water phase and 1kg of solid phase, detecting the relative content of benzaldehyde and acetaldehyde in the water phase through liquid chromatography, and testing the total content to be about 25%;
(2) Carrying out azeotropic distillation on the water phase in the step (1) at 55 ℃ to obtain 4kg of aqueous solution containing benzaldehyde and acetaldehyde;
(3) Adding 200mL of concentrated sulfuric acid with the mass concentration of 90% into the wastewater containing the polymeric acetaldehyde by azeotropic distillation in the step (2), carrying out reflux depolymerization reaction at 60 ℃, distilling the reaction solution at 55 ℃ after 5 hours to obtain 0.8kg of aqueous solution of the polymeric acetaldehyde, filtering the mixture left by distillation to obtain 0.4kg of macromolecular polymer (leftovers), carrying out micro-electrolysis, feton treatment and biochemical treatment on the water phase left by filtration in sequence to finally obtain 10kg of wastewater capable of being discharged, and carrying out liquid chromatography again on the wastewater capable of being discharged to detect the total content of the benzaldehyde and the acetaldehyde by the wastewater with the wastewater reduction of = (15-10)/15 x 100% = 33%, wherein the result shows that the total content of the benzaldehyde and the acetaldehyde accounts for 8.5%, and the recovery rate of the benzaldehyde and the acetaldehyde is 1- (10 x 8.5%)/(14 x 25%) = 76%;
(4) 1L of ethyl acetate is added into the solid phase in the step (1) to be fully dissolved to form a homogeneous solution, then 200mL of sodium hydroxide with mass concentration of 20% is added to be neutralized at 50 ℃ for 4 hours, the solution is separated after the reaction is completed, then 0.2kg of macromolecular polymer (leftovers) is obtained by concentrating an organic layer, and 250mL of hydrochloric acid with mass concentration of 20% is added into the inorganic layer obtained by separating the solution to adjust pH=3-4, so that 0.62kg of benzoic acid is finally obtained. The overall utilization rate of the wastewater is= (4+0.62+0.8+0.2+0.4)/15 x 100% = 40% repeated flow, the recovery rate of benzaldehyde and acetaldehyde in the wastewater is 75% -80%, the overall utilization rate of the wastewater is 38% -43%, and the reduction amount of the wastewater is 30% -35%.
Example 4
(1) Taking the offcut sample obtained in the embodiment, detecting the type and the relative content of carboxylic acid in the sample by a liquid chromatography method, wherein the test result shows that the type of carboxylic acid contained in the cinnamaldehyde waste is 5-phenylpentan-2-enoic acid, and the content is about 35%;
(2) Taking 200g of leftovers, fully dissolving the leftovers by using 1L of ethyl acetate, then adding 400mL of sodium hydroxide solution with mass concentration of 20%, fully stirring, adding 60g of active carbon, carrying out heat preservation, adsorption and decoloration for 90min at 50 ℃, filtering to remove the active carbon, and separating to obtain an oil phase and a water phase;
(3) Distilling the oil phase in the step (2) at 50 ℃ under reduced pressure to remove ethyl acetate, adding 1L of ethanol, pulping for 4 hours, filtering to obtain first filter residue and first filtrate, and recovering 960mL of ethyl acetate in the stage; taking the first filter residue, adding 1L of ethanol again, pulping, and filtering to obtain 130g of second filter residue (benzaldehyde acetaldehyde polymer) and second filtrate, wherein the macromolecule removal rate is=65%; combining the first filtrate and the second filtrate, and desolventizing to obtain 10g of oily liquid, wherein 1900mL of ethanol is recovered at the stage;
(4) Combining the aqueous phase in (2) with the oily liquid in (3), adding 400mL of hydrochloric acid solution with mass concentration of 20% to adjust pH=2-3, and then adding 300mL of ethyl acetate for extraction to obtain an oil phase and an aqueous phase; drying the oil phase for dewatering, distilling under reduced pressure to obtain pale yellow oily liquid, and finally cooling at 0 ℃ to separate out 60g of white crystal 5-phenylpent-2-enoic acid, wherein the carboxylic acid yield is 30%, and 290mL of ethyl acetate is recovered at the stage; the aqueous phase produced by this process can be used for neutralization after desalting treatment.
The process is repeated for a plurality of times, the carboxylic acid yield=30-35%, and the macromolecule removal rate is 60-65%.
Example 5
(1) Taking the offcut sample obtained in the embodiment, detecting the type and the relative content of carboxylic acid in the sample by a liquid chromatography method, wherein the test result shows that the type of carboxylic acid contained in the cinnamaldehyde waste is 5-phenylpentan-2-enoic acid, and the content is about 35%;
(2) Taking 200g of leftovers, fully dissolving the leftovers by using 1L of dichloromethane, then adding 400mL of sodium hydroxide solution with mass concentration of 20%, fully stirring, adding 60g of active carbon, carrying out heat preservation, adsorption and decolorization for 90min at 30 ℃, filtering to remove the active carbon, and separating to obtain an oil phase and a water phase;
(3) Distilling the oil phase in the step (2) at 50 ℃ under reduced pressure to remove dichloromethane, adding 1L of ethanol, pulping for 4 hours, filtering to obtain first filter residue and first filtrate, and recovering 900mL of dichloromethane in the stage; taking the first filter residue, adding 1L of ethanol again, pulping, and filtering to obtain 125g of second filter residue (benzaldehyde acetaldehyde polymer) and second filtrate, wherein the macromolecule removal rate is=62.5%; combining the first filtrate and the second filtrate, and desolventizing to obtain 10g of oily liquid, wherein 1900mL of ethanol is recovered at the stage;
(4) Combining the aqueous phase in (2) with the oily liquid in (3), adding 400mL of hydrochloric acid solution with mass concentration of 20% to adjust pH=2-3, and then adding 300mL of ethyl acetate for extraction to obtain an oil phase and an aqueous phase; drying the oil phase for dewatering, distilling under reduced pressure to obtain pale yellow oily liquid, and finally cooling at 0 ℃ to separate out 38g of white crystal 5-phenylpent-2-enoic acid, wherein the carboxylic acid yield is 19%, and 290mL of ethyl acetate is recovered at the stage; the aqueous phase produced by this process can be used for neutralization after desalting treatment.
Repeated procedures, the yield of carboxylic acid is 15-20%, the macromolecule removal rate is 60-65%, and the method has the defects that the yield is low when dichloromethane is used, the solvent is high in volatility, cannot be recycled for multiple times, is high in price, is not friendly to the environment, is high in toxicity and the like.
In summary, the invention also has the following beneficial effects:
(1) The recovery rate of benzaldehyde and acetaldehyde in the wastewater is more than or equal to 70 percent
Benzaldehyde and acetaldehyde in the wastewater are initial materials of cinnamaldehyde, recovery of the materials has a critical effect on the production cost of the cinnamaldehyde, and the recovery rate of the benzaldehyde and the acetaldehyde exceeds 70% through optimization in the wastewater treatment and recovery and reuse process, so that the production cost of the cinnamaldehyde is greatly reduced.
(2) The integral utilization rate of the wastewater is more than or equal to 30 percent
The waste water has more components and more complex components, but the benzaldehyde and the acetaldehyde, the benzoic acid and the 5-phenylpentenoic acid extracted from the leftovers are treated by the process, the benzaldehyde and the acetaldehyde can be directly used as starting materials of cinnamaldehyde, the benzoic acid is used as a byproduct, and products such as the 5-phenylpentenoic acid extracted from the leftovers have higher added value. Overall, the waste water utilization rate exceeds 30% through comprehensive evaluation of the energy consumption and the cost of the process.
(3) The removal rate of benzoic acid and macromolecules in the wastewater is more than or equal to 60 percent
The benzoic acid can be effectively separated through retreating the distilled and rectified wastewater, and the macromolecular polymer is recovered as solid waste, and the removal rate of the benzoic acid and the macromolecular polymer exceeds 60% through one process, so that the COD of the wastewater is greatly reduced, and the pressure of wastewater treatment is reduced.
(4) The waste water reduction is more than or equal to 25 percent
When the benzaldehyde and the acetaldehyde are condensed to synthesize the cinnamaldehyde, water is used as a solvent, the amount of the reactant with the water consumption being approximately 20 times, if the reactant is directly used as waste water treatment pressure is very high, the fact that useful materials and products are contained in the reactant, particularly the benzaldehyde and the acetaldehyde form an azeotropic system with water in the distillation recovery process, and meanwhile, the obtained aqueous solution of the acetaldehyde in the process of recovering the acetaldehyde can be directly recycled, and the waste water amount can be reduced by at least 25% in comprehensive consideration.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. The recovery treatment process of the cinnamaldehyde production wastewater is characterized by comprising the following steps of:
cooling and filtering the cinnamaldehyde production wastewater to obtain a first water phase and a first solid phase;
performing azeotropic distillation on the first aqueous phase to separate an azeotrope of acetaldehyde, benzaldehyde and water, thereby obtaining wastewater containing the poly-acetaldehyde;
adding acid into the wastewater containing the poly-acetaldehyde for acidolysis reaction, then distilling to recover the acetaldehyde, and filtering the mixture left by distillation to obtain de-acetaldehyde wastewater and leftovers;
and dissolving the first solid phase by adopting a first organic solvent, adding alkali to perform a first neutralization reaction, separating liquid after the reaction is completed, and performing first acidification on an inorganic layer to obtain benzoic acid and concentrating an organic layer to obtain leftovers.
2. The recovery treatment process of cinnamaldehyde production wastewater according to claim 1, wherein in the cooling treatment process, the cinnamaldehyde production wastewater is cooled to-5-0 ℃; in the azeotropic distillation process, the temperature of the azeotropic distillation is 50-70 ℃.
3. The recovery treatment process of cinnamaldehyde production wastewater according to claim 1, wherein in the acidolysis reaction process, the first acid is concentrated sulfuric acid with the mass fraction of 90-98%, and the dosage ratio of the wastewater containing the polyacetaldehyde to the concentrated sulfuric acid is 1kg: (0.01-0.03) mL; the acidolysis reaction temperature is 55-80 ℃, and the acidolysis reaction time is 4-6h; in the distillation process, the temperature of the distillation is 50-80 ℃.
4. The recycling process of cinnamaldehyde production wastewater according to claim 1, wherein the first organic solvent is at least one of ethyl acetate, methyl tertiary butyl ether, diisopropyl ether, methanol, ethanol and dichloromethane; the dosage ratio of the first solid phase to the first organic solvent is 0.8-2kg:1L; in the first acidification process, the final pH is adjusted to 3-4.
5. The recycling process of cinnamaldehyde production wastewater according to claim 1, wherein in the first neutralization reaction process, the first alkali is at least one of sodium hydroxide, potassium hydroxide and ammonia water; the first alkali is added into the system in the form of an aqueous solution, the mass concentration of the first alkali solution is 10% -30%, and the dosage ratio of the first solid phase to the first alkali solution is 1kg: (0.1-0.3) mL; the temperature of the first neutralization reaction is 50-60 ℃, and the time of the first neutralization reaction is 4-6h.
6. The recovery processing process of cinnamaldehyde production wastewater according to claim 1, wherein the recovery processing process of cinnamaldehyde production wastewater further comprises the steps of:
dissolving the leftovers with a second organic solvent, adding alkali to perform a second neutralization reaction, adding activated carbon into the neutralization solution to perform adsorption decolorization, removing the activated carbon, and separating the solution to obtain a first oil phase and a second water phase;
removing the second organic solvent from the first oil phase, adding an alcohol solvent, pulping, filtering to obtain filter residues and filtrate, and removing the alcohol solvent from the filtrate to obtain oily liquid, wherein the filter residues are benzaldehyde acetaldehyde polymers;
adding acid into the second water phase and oily liquid to carry out second acidification, then adopting a third organic solvent to extract the acidification liquid to obtain a second oil phase and a third water phase, carrying out desolventizing treatment on the second oil phase, and then cooling and crystallizing to obtain the 5-phenylpent-2-enoic acid.
7. The recycling process of cinnamaldehyde production wastewater according to claim 6, wherein the second organic solvent is at least one of ethyl acetate, methyl tertiary butyl ether, diisopropyl ether, methanol, ethanol and dichloromethane; the dosage ratio of the offal to the second organic solvent is 1g: (3-8) mL; in the second neutralization reaction process, the second alkali is at least one of sodium hydroxide, potassium hydroxide and ammonia water; the second alkali is added into the system in the form of an aqueous solution, and the mass concentration of the second alkali solution is 10% -20%; the dosage ratio of the offal to the second alkali solution is 1g: (1-3) mL; in the adsorption decoloring process, the addition amount of the activated carbon is 20% -30% of the mass of the cinnamaldehyde waste; the decoloring temperature is 30-60 ℃ and the decoloring time is 20-100min.
8. The recovery processing process of cinnamaldehyde production wastewater according to claim 6, wherein the alcohol solvent is at least one of methanol and ethanol; the dosage ratio of the leftovers to the alcohol solvent is 1g: (3-10) mL, and the pulping time is 4-6h each time.
9. The recycling process of cinnamaldehyde production wastewater according to claim 6, wherein the final pH is adjusted to 2-3 during the second acidification process; the third organic solvent is at least one of ethyl acetate, methyl tertiary butyl ether, diisopropyl ether, methanol, ethanol and methylene dichloride; the volume ratio of the acidizing fluid to the third organic solvent is 1: (0.2-2), wherein the temperature of the cooling crystallization is-5-0 ℃.
10. The recovery processing process of cinnamaldehyde production wastewater according to claim 6, wherein the second organic solvent, the alcohol solvent and the third organic solvent are removed by vacuum distillation.
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