CN115010687B - Demulsifier, preparation method thereof and extraction process of vanillin - Google Patents

Demulsifier, preparation method thereof and extraction process of vanillin Download PDF

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CN115010687B
CN115010687B CN202210670317.0A CN202210670317A CN115010687B CN 115010687 B CN115010687 B CN 115010687B CN 202210670317 A CN202210670317 A CN 202210670317A CN 115010687 B CN115010687 B CN 115010687B
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acid
aldehyde
mass ratio
vanillin
bromo
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CN115010687A (en
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丁大康
李玮华
马德森
边新建
范立耸
刘振峰
李俊平
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • 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
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

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Abstract

The invention discloses a demulsifier, a preparation method thereof and an extraction process of vanillin, wherein the demulsifier has the following structural formula: Wherein R represents hydrogen or C1-C6 alkyl, decarboxylation and extraction are carried out in one reactor, oxidation reaction liquid, extractant and acid liquid are respectively and continuously added from different positions of the reactor, and continuous decarboxylation and extraction are completed in the reactor, so that the method has the advantages of simple process flow, low energy consumption and the like.

Description

Demulsifier, preparation method thereof and extraction process of vanillin
Technical Field
The invention belongs to the field of vanillin synthesis, and particularly relates to a demulsifier, a preparation method thereof and an extraction process of vanillin.
Background
Vanillin, also known as vanillin, is an organic compound extracted from the plant Vanilla, the Rutaceae family, under the chemical name 3-methoxy-4-hydroxybenzaldehyde. As a common food flavoring agent, the flavoring agent is widely applied to the fields of chocolate, milk powder, cake, ice cream, toothpaste, perfume and the like.
At present, a process route of guaiacol and glyoxylate is mainly adopted for synthesizing vanillin, and the route comprises the steps of condensation, oxidation, decarboxylation extraction and the like, wherein the decarboxylation reaction is to carry out decarboxylation reaction on 3-methoxy-4-hydroxy-phenylketoacid generated by the previous step of oxidation under the action of Lewis acid, so that vanillin is generated and carbon dioxide is released. The solubility of vanillin in water at normal temperature is only 1%, and a large amount of vanillin is generated to be separated out from the reaction liquid, and an extractant is needed to be added for collection. The existing decarboxylation process is divided into decarboxylation and extraction, namely, the decarboxylation reaction liquid is conveyed to an extraction device, and the process is an intermittent process, and has two outstanding problems; firstly, the vanillin separated out by decarboxylation is easy to solidify into solid, and the risk of blocking a pipeline exists; secondly, a large number of emulsion layers can appear in the process of extracting the organic solvent, which causes great trouble for subsequent separation.
The decarboxylation reaction temperature is normal temperature, in order to solve the problem of the decarboxylation reaction, the patent CN102010310A increases the decarboxylation reaction temperature to 60-65 ℃, and the risk of separating out vanillin into solid can be effectively reduced, but the vanillin is a heat-sensitive substance, and the high temperature can lead to lower decarboxylation reaction yield. The patent CN102190567A provides a process for eliminating an emulsion layer of a decarboxylation extract, the emulsion layer is centrifugally separated, and an organic phase, an insoluble copper salt and a water phase in the emulsion layer can be completely separated by adopting a mode of combining a decanter centrifuge and a tubular centrifuge, but the invention introduces more movable equipment, increases the investment of the device and has complex operation. The patent CN102276434A adds the vanillin separated out from the decarboxylated liquid into a washing kettle, and washes the vanillin with clear water for multiple times, and the washed vanillin is melted and then enters an extraction procedure, so that the vanillin is prevented from separating out, impurities can be washed away in advance, the occurrence of an emulsion layer is reduced, more waste water is caused by excessive washing, and the energy consumption is higher.
Disclosure of Invention
The invention provides an improvement on the process for preparing vanillin by condensing, oxidizing, decarboxylating and extracting guaiacol and glyoxylic acid, and aims to solve the defects of the prior invention, and the invention provides a demulsifier and a preparation method thereof, which are used for extracting vanillin decarboxylation reaction liquid, can effectively avoid the emulsification phenomenon in the extraction process and improve the separation efficiency; the invention also provides an extraction process of vanillin.
In order to solve the above problems, the present invention provides a demulsifier, which has the structural formula:
wherein R represents hydrogen or C1-C6 alkyl.
The invention also provides a preparation method of the demulsifier, which comprises the following steps:
(1) Sulfonation reaction is carried out on the 4-bromo-2-hydroxybenzaldehyde compound and sulfuric acid to obtain a 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound;
(2) And (3) dropwise adding butyl lithium into the 2-bromo-5-aldehyde-4-hydroxy benzenesulfonic acid compound, and then reacting with triethylamine to generate the 2- (diethylamino) -5-aldehyde-4-hydroxy benzenesulfonic acid compound.
(3) Reacting 2- (diethylamino) -5-aldehyde-4-hydroxy benzene sulfonic acid compound with acetic anhydride under the action of a catalyst to obtain the demulsifier.
Wherein the structural formula of the 4-bromo-2-hydroxybenzaldehyde compound is as follows: R represents hydrogen or C1-C6 alkyl.
The structural formula of the 2-bromo-5-aldehyde-4-hydroxy benzenesulfonic acid compound is as follows: R represents hydrogen or C1-C6 alkyl.
The structural formula of the 2- (diethylamino) -5-aldehyde-4-hydroxy benzenesulfonic acid compound is as follows: wherein R represents hydrogen or C1-C6 alkyl.
The synthetic route of the demulsifier is shown as follows:
The step (1) of the present invention may be performed at normal temperature and pressure.
Step (1) of the present invention may be performed in a solvent a comprising at least one of water, acetone, DMF, DMAC and DMSO, preferably DMF or water.
In the step (1), the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to the solvent A is 1 (3-10), preferably 1 (5-8).
The sulfuric acid in the step (1) is derived from fuming sulfuric acid or 98% concentrated sulfuric acid.
In the step (1), the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to sulfuric acid is 1 (1.5-4), preferably 1 (2-3).
The reaction time of the step (1) is 1 to 8 hours, preferably 3 to 5 hours.
Step (2) of the present invention may be carried out in a solvent B comprising one or more of toluene, ethylbenzene, tetrahydrofuran, DMF and diethyl ether, preferably toluene or tetrahydrofuran.
In the step (2), the mass ratio of the 2-bromo-5-aldehyde-4-hydroxy benzene sulfonic acid compound to the solvent B is 1 (3-10), preferably 1 (5-8).
The mass ratio of the 2-bromo-5-aldehyde-4-hydroxy benzenesulfonic acid compound to the butyllithium in the step (2) is (2-4): 1, preferably (2.5 to 3): 1, a step of; the mass ratio of the triethylamine to the 2-bromo-5-aldehyde-4-hydroxy benzenesulfonic acid compound is (1-4): 1, preferably (2 to 3): 1.
The reaction condition in the step (2) is anhydrous and anaerobic.
In the step (2), the initial reaction stage is the butyl lithium dropwise adding stage, the reaction temperature is-100-0 ℃, the acetone is used for bathing, and after the butyl lithium dropwise adding is finished, triethylamine is added, the temperature is slowly raised to the room temperature, and the reaction is continued.
The reaction time of the step (2) is 3-8 h, and the preferable reaction time is 4-6 h.
The post-treatment mode of the step (2) is as follows: adding deionized water to quench unreacted butyl lithium, and adding a solvent to extract to obtain a crude product, wherein the preferred extraction solvent is n-hexane or petroleum ether.
The solvent selected in the step (3) is DMF, and the mass ratio of DMF to 2- (diethylamino) -5-aldehyde-4-hydroxy benzene sulfonic acid compound is (3-15): 1, preferably (5 to 10): 1.
The catalyst in the step (3) is one or more of sodium acetate, calcium acetate and potassium acetate, and the mass ratio of the 2- (diethylamino) -5-aldehyde-4-hydroxy benzenesulfonic acid compound to the catalyst is (10-50): 1, preferably (20 to 30): 1.
The mass ratio of acetic anhydride to 2- (diethylamino) -5-aldehyde-4-hydroxy benzenesulfonic acid in the step (3) is (4-10): 1, preferably (5 to 8): 1.
The reaction temperature in the step (3) is 100-200 ℃, preferably 120-140 ℃.
The reaction time in the step (3) is 0.1 to 2 hours, preferably 0.5 to 1 hour.
An extraction process of vanillin, wherein the demulsifier is added in the extraction process.
In the vanillin extraction process, the solution to be extracted is a reaction solution obtained after mandelic acid oxidation and decarboxylation. And extracting vanillin in the reaction liquid by using an extracting agent, wherein a demulsifier is added in the reaction liquid.
Preferably, the mass ratio of the demulsifier to the added amount of the mandelic acid oxidation reaction liquid is 0.01-0.05.
A process for extracting vanillin includes such steps as continuously adding the oxidizing reaction liquid of mandelic acid, acid liquid, demulsifier and extractant to reactor, feeding the oxidizing reaction liquid of mandelic acid to reactor, feeding the extractant to reactor, and extracting the oxidizing reaction liquid of mandelic acid.
Preferably, the feed rate ratio of the extractant to the mandelic acid oxidation reaction liquid is 1: 3-1: 10.
In the invention, decarboxylation and extraction can be combined into a whole, the extractant and the mandelic acid oxidation reaction liquid can be continuously injected into a reactor, the acid liquor and the 3-methoxy-4-hydroxy-phenylketoacid in the mandelic acid oxidation reaction liquid undergo decarboxylation reaction, and the generated vanillin is recovered by the extractant, so that continuous decarboxylation and continuous extraction can be realized in one reactor.
The reactor can be selected from a reaction kettle with stirring, a plate type extraction tower, a rotary disk extraction tower, a Qu Ni extraction tower and the like, and is preferably a rotary disk extraction tower. The uppermost end of the reactor is provided with an exhaust hole, and the reactor can be in the shape of a cylinder with a thin middle and thick two ends for better standing layering.
The mandelic acid oxidation reaction liquid is an intermediate reaction liquid for synthesizing vanillin, is a reaction liquid obtained by oxidizing 3-methoxy-4-hydroxy mandelic acid serving as a raw material, and mainly comprises 70-90wt% of water, 5-15wt% of 3-methoxy-4-hydroxy phenylketoacid and 5-8wt% of sodium sulfate. The extractant is selected from one or more of toluene, ethyl acetate, butyl acetate, n-hexane, anisole, methyl isobutyl ketone and acetophenone, and the preferred extractant is methyl isobutyl ketone or toluene.
The demulsifier and the acid liquor are fed from the upper part of the reactor, and can be mixed first and then are continuously added from the top of the reactor, wherein the acid liquor adopts one or more of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, the concentration is 5-30%, and the mass ratio of the acid liquor to the reaction liquid is 1:10 to 20.
The invention has the beneficial effects that:
The invention provides a novel demulsifier 6-sulfonic group-7- (diethylamino) benzopyrone for extraction, which takes coumarin as a main body and has a similar main body structure with impurities in vanillin, so that the same post-treatment process is convenient for the later stage, and the introduction of sulfonic groups and quaternary ammonium groups respectively enhances the solubility and demulsification capability of the material in water, and better realizes the separation of extractant and vanillin reaction liquid.
The invention also provides an extraction process of vanillin, and the demulsifier can integrate decarboxylation and extraction into one reactor, so that continuous operation can be performed, the operation is simple, the process flow is optimized, and the problems of complex operation, vanillin precipitation and the like in the conventional intermittent decarboxylation and intermittent extraction are avoided.
Drawings
FIG. 1 is a schematic diagram of a continuous decarboxylation and extraction reaction process of the present invention.
Detailed Description
The following examples will further illustrate the method provided by the present invention, but the invention is not limited to the examples listed and should include any other known modifications within the scope of the claimed invention.
The raw material sources are as follows:
4-bromo-2-hydroxybenzaldehyde, shanghai Meilin Biochemical technologies Co., ltd;
4-bromo-2-hydroxy-6-methylbenzaldehyde, shanghai Xinyuan medical science and technology Co.
Example 1
40G of 4-bromo-2-hydroxybenzaldehyde and 140gDMF g of concentrated sulfuric acid (98%) are injected into a three-mouth bottle, then 64g of concentrated sulfuric acid is slowly added dropwise, the reaction is continued for 1.5h after the dropwise addition, and the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid is obtained through separation and purification. Into a anhydrous and anaerobic glass bottle, 40g of 2-bromo-5-aldehyde-4-hydroxy benzenesulfonic acid and 125g of toluene are injected, 20g of butyllithium (1 mol/L) is slowly added dropwise into the reaction system at the temperature of minus 78 ℃, 40g of triethylamine is then added, the reaction is continued for 4 hours after the temperature is raised to the room temperature, and the 2- (diethylamino) -5-aldehyde-4-hydroxy benzenesulfonic acid is obtained after separation and purification. 40g of 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid, 160g of acetic anhydride and 4g of sodium acetate were dissolved in DMF and reacted at 120℃for 40min to give the extraction modifier 6-sulfo-7- (diethylamino) benzopyrone.
Referring to FIG. 1, the reaction liquid (water 85wt%, 3-methoxy-4-hydroxy-benzoic acid 9wt%, sodium sulfate 6 wt%) after oxidation of 3-methoxy-4-hydroxy-mandelic acid was continuously fed at 1kg/h from the upper end of the rotary disk extraction column, toluene was continuously fed at 0.33kg/h from the bottom of the rotary disk extraction column, 6-sulfonic acid-7- (diethylamino) benzopyrone as an extraction modifier and a mixed solution of dilute sulfuric acid (the mass of the extraction modifier and 30wt% of dilute sulfuric acid was fed at 5:95) was continuously fed at 200g/h from the top of the rotary disk extraction column, decarboxylation and extraction took place in the rotary disk extraction column, exhaust gas generated by decarboxylation was discharged from the exhaust hole at the top, vanillin generated by the reaction was extracted by toluene and discharged from the top of the rotary disk extraction column, and rectification separation was carried out. No significant emulsification was found throughout the decarboxylation and extraction process, with the water-oil interface zone (not fully separated zone) accounting for about 2% of the total carousel extraction column volume.
Example 2
60G of 4-bromo-2-hydroxy-6-methylbenzaldehyde and 480gDMAC g of concentrated sulfuric acid (98%) are injected into a three-necked flask, then 180g of concentrated sulfuric acid is slowly added dropwise, the reaction is continued for 3 hours after the dropwise addition, and 2-bromo-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid is obtained through separation and purification. Into a anhydrous and anaerobic glass bottle, 40g of 2-bromo-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid and 120g of tetrahydrofuran are injected, 17g of butyllithium (1 mol/L) is slowly dripped into a reaction system at the temperature of minus 78 ℃, 80g of triethylamine is then added, the reaction is continued for 6 hours after the temperature is raised to the room temperature, and the 2- (diethylamino) -4-hydroxy-5-aldehyde-6-ethylbenzenesulfonic acid is obtained after separation and purification. 40g of 2- (diethylamino) -4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid, 360g of acetic anhydride and 2g of calcium acetate are dissolved in DMF and reacted at 160 ℃ for 30min to obtain an extraction modifier 5-methyl-6-sulfonic acid-7- (diethylamino) benzopyrone.
The reaction liquid (85 wt% of water, 9wt% of 3-methoxy-4-hydroxy-phenylketoacid and 6wt% of sodium sulfate) obtained after the oxidation of 3-methoxy-4-hydroxy-mandelic acid is continuously added from the upper end of a rotary disk extraction tower at a rate of 1kg/h, methyl isobutyl ketone is continuously added from the bottom of the disk extraction tower at a rate of 0.2kg/h, 5-methyl-6-sulfonic-7- (diethylamino) benzopyrone is used as an extraction modifier and a mixed solution of dilute acid (the mass ratio of the extraction modifier to 30wt% of dilute sulfuric acid is 1:9) is continuously added into the rotary disk extraction tower from the top at a rate of 200g/h, decarboxylation and extraction occur in the rotary disk extraction tower, waste gas generated by decarboxylation is discharged from an exhaust hole at the top, vanillin generated by the reaction is extracted by methyl isobutyl ketone and is discharged from the top of the rotary disk extraction tower, and rectification separation is performed. No significant emulsification was found throughout the decarboxylation and extraction process, with the water-oil interface zone (not fully separated zone) accounting for about 2% of the total carousel extraction column volume.
Example 3
40G of 4-bromo-2-hydroxy-6-methylbenzaldehyde and 150g of water are injected into a three-necked flask, 65g of concentrated sulfuric acid (98%) is slowly added dropwise, the reaction is continued for 5 hours after the dropwise addition, and the 2-bromo-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid is obtained through separation and purification. 40g of 2-bromo-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid and 160gDMF g of butyllithium (1 mol/L) are injected into an anhydrous and anaerobic glass bottle, 10g of butyllithium (1 mol/L) is slowly dripped into a reaction system at the temperature of minus 78 ℃, 100g of triethylamine is then added, the reaction is continued for 3.5h after the temperature is raised to the room temperature, and the 2- (diethylamino) -4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid is obtained after separation and purification. 40g of 2- (diethylamino) -4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid, 160g of acetic anhydride and 1g of potassium acetate are dissolved in DMF and reacted at 110 ℃ for 20min to obtain an extraction modifier 5-methyl-6-sulfonic acid-7- (diethylamino) benzopyrone.
The reaction liquid (85 wt% of water, 9wt% of 3-methoxy-4-hydroxy-benzoic acid and 6wt% of sodium sulfate) obtained after the oxidation of 3-methoxy-4-hydroxy-mandelic acid is continuously added from the upper end of a rotary disk extraction tower at a rate of 1kg/h, butyl acetate is continuously added from the bottom of the rotary disk extraction tower at a rate of 0.15kg/h, 5-methyl-6-sulfonic-7- (diethylamino) benzopyrone is used as an extraction modifier and a mixed liquid of dilute acid (the mass ratio of the extraction modifier to 30wt% of dilute sulfuric acid is 15:85) is continuously added into the rotary disk extraction tower from the top at a rate of 300g/h, decarboxylation and extraction occur in the rotary disk extraction tower, waste gas generated by decarboxylation is discharged from a vent hole at the top, vanillin generated by the reaction is extracted by butyl acetate and discharged from the top of the rotary disk extraction tower for rectification separation. No significant emulsification was found throughout the decarboxylation and extraction process, with the water-oil interface zone (not fully separated zone) accounting for about 2% of the total carousel extraction column volume.
Example 4
40G of 4-bromo-2-hydroxy-6-methylbenzaldehyde and 200gDMF g of concentrated sulfuric acid (98%) are injected into a three-necked flask, then 120g of concentrated sulfuric acid is slowly added dropwise, the reaction is continued for 2.8h after the dropwise addition is finished, and the 2-bromo-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid is obtained through separation and purification. 42g of 2-bromo-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid and 120g of tetrahydrofuran are injected into an anhydrous and anaerobic glass bottle, 16g of butyllithium (1 mol/L) is slowly dripped into a reaction system at the temperature of minus 78 ℃, 90g of triethylamine is then added, the reaction is continued for 5 hours after the temperature is raised to the room temperature, and the 2- (diethylamino) -4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid is obtained after separation and purification. 40g of 2- (diethylamino) -4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid, 200g of acetic anhydride and 1.8g of calcium acetate were dissolved in DMF and reacted at 180℃for 30min to give an extraction modifier 5-methyl-6-sulfonic acid-7- (diethylamino) benzopyrone.
The reaction liquid (85 wt% of water, 9wt% of 3-methoxy-4-hydroxy-phenylketoacid and 6wt% of sodium sulfate) obtained after the oxidation of 3-methoxy-4-hydroxy-mandelic acid is continuously added from the upper end of a rotary disk extraction tower at a rate of 1kg/h, methyl isobutyl ketone is continuously added from the bottom of the disk extraction tower at a rate of 0.2kg/h, 5-methyl-6-sulfonic-7- (diethylamino) benzopyrone is used as an extraction modifier and a mixed solution of dilute acid (the mass ratio of the extraction modifier to 30wt% of dilute sulfuric acid is 1:9) is continuously added into the rotary disk extraction tower from the top at a rate of 200g/h, decarboxylation and extraction occur in the rotary disk extraction tower, waste gas generated by decarboxylation is discharged from an exhaust hole at the top, vanillin generated by the reaction is extracted by methyl isobutyl ketone and is discharged from the top of the rotary disk extraction tower, and rectification separation is performed. No significant emulsification was found throughout the decarboxylation and extraction process, with the water-oil interface zone (not fully separated zone) accounting for about 2% of the total carousel extraction column volume.
Comparative example 1
The reaction liquid (85 wt% of water, 9wt% of 3-methoxy-4-hydroxy phenylketoacid and 6wt% of sodium sulfate) obtained after the oxidation of 3-methoxy-4-hydroxy mandelic acid is continuously added from the upper end of a rotary disk extraction tower at the rate of 1kg/h, methyl isobutyl ketone is continuously added from the bottom of the plate extraction tower at the rate of 0.2kg/h, 30% dilute acid solution is continuously added into the rotary disk extraction tower from the top at the rate of 200g/h, decarboxylation and extraction occur in the rotary disk extraction tower, waste gas generated by decarboxylation is discharged from an exhaust hole at the top, vanillin generated by the reaction is extracted by methyl isobutyl ketone, and is discharged from the top of the rotary disk extraction tower for rectification separation. The whole extraction process found significant emulsification, with the water-oil interface zone (not fully separated zone) accounting for about 20% of the total carousel extraction column volume.

Claims (46)

1. The demulsifier is characterized by having the structural formula:
wherein R represents hydrogen or C1-C6 alkyl.
2. A method of preparing the demulsifier of claim 1, comprising the steps of:
(1) Sulfonation reaction is carried out on the 4-bromo-2-hydroxybenzaldehyde compound and sulfuric acid to obtain a 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound;
(2) Dripping butyl lithium into the 2-bromo-5-aldehyde-4-hydroxy benzenesulfonic acid compound, and then reacting with triethylamine to generate 2- (diethylamino) -5-aldehyde-4-hydroxy benzenesulfonic acid compound;
(3) Reacting 2- (diethylamino) -5-aldehyde-4-hydroxy benzene sulfonic acid compound with acetic anhydride under the action of a catalyst to obtain the demulsifier.
3. The preparation method according to claim 2, wherein the structural formula of the 4-bromo-2-hydroxybenzaldehyde compound is: r represents hydrogen or C1-C6 alkyl;
The structural formula of the 2-bromo-5-aldehyde-4-hydroxy benzenesulfonic acid compound is as follows: r represents hydrogen or C1-C6 alkyl;
The structural formula of the 2- (diethylamino) -5-aldehyde-4-hydroxy benzenesulfonic acid compound is as follows: wherein R represents hydrogen or C1-C6 alkyl.
4. A method of preparation according to claim 2 or 3, wherein step (1) is carried out in a solvent a comprising at least one of water, acetone, DMF, DMAC and DMSO.
5. The process of claim 4, wherein solvent A is DMF or water.
6. The process according to claim 4, wherein in the step (1), the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to the solvent A is 1 (3 to 10).
7. The process according to claim 6, wherein in the step (1), the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to the solvent A is 1 (5 to 8).
8. The method according to claim 2, wherein the sulfuric acid in the step (1) is selected from fuming sulfuric acid or 98% concentrated sulfuric acid.
9. The method according to claim 2, wherein the reaction time in the step (1) is 1 to 8 hours.
10. The method according to claim 9, wherein the reaction time in the step (1) is 3 to 5 hours.
11. The process according to claim 2, wherein in the step (1), the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to sulfuric acid is 1 (1.5 to 4).
12. The process according to claim 11, wherein in the step (1), the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to sulfuric acid is 1 (2 to 3).
13. The method of claim 2, wherein step (2) is performed in a solvent B comprising one or more of toluene, ethylbenzene, tetrahydrofuran, DMF, and diethyl ether.
14. The preparation method according to claim 13, wherein the solvent B is toluene or tetrahydrofuran.
15. The preparation method according to claim 13, wherein in the step (2), the mass ratio of the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound to the solvent B is 1 (3-10).
16. The preparation method according to claim 15, wherein in the step (2), the mass ratio of the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound to the solvent B is 1 (5-8).
17. The preparation method according to claim 2, wherein the mass ratio of the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound to butyllithium in the step (2) is (2-4): 1.
18. The method according to claim 17, wherein the mass ratio of the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound to butyllithium in the step (2) is (2.5 to 3): 1.
19. The preparation method according to claim 2, wherein the mass ratio of triethylamine to 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound is (1-4): 1.
20. The preparation method according to claim 19, wherein the mass ratio of triethylamine to 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound is (2-3): 1.
21. The method according to claim 2, wherein the reaction conditions in the step (2) are anhydrous, anaerobic conditions.
22. The preparation method according to claim 2, wherein the initial reaction stage in the step (2) is a butyl lithium dropwise adding stage, the reaction temperature is-100 ℃ to 0 ℃, the acetone is used for bathing, and triethylamine is added after the butyl lithium dropwise adding is completed, and the reaction is continued after the triethylamine is slowly heated to room temperature.
23. The method according to claim 2, wherein the reaction time in the step (2) is 3 to 8 hours.
24. The process of claim 23, wherein the reaction time in step (2) is 4 to 6 hours.
25. The method according to claim 2, wherein the post-treatment in step (2) is as follows: adding deionized water to quench unreacted butyl lithium, and adding a solvent to extract to obtain a crude product.
26. The process of claim 25, wherein the extraction solvent is n-hexane or petroleum ether.
27. The preparation method of claim 2, wherein the solvent selected in the step (3) is DMF, and the mass ratio of DMF to 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid compound is (3-15): 1.
28. The preparation method of claim 27, wherein the mass ratio of DMF to 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid compound is (5-10): 1.
29. The preparation method of claim 2, wherein the catalyst in the step (3) is one or more of sodium acetate, calcium acetate and potassium acetate, and the mass ratio of the 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid compound to the catalyst is (10-50): 1.
30. The preparation method of claim 29, wherein the mass ratio of the 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid compound to the catalyst is (20-30): 1.
31. The preparation method according to claim 2, wherein the mass ratio of acetic anhydride to 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid in the step (3) is (4-10): 1.
32. The preparation method according to claim 31, wherein the mass ratio of acetic anhydride to 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid in the step (3) is (5-8): 1.
33. The method according to claim 2, wherein the reaction temperature in the step (3) is 100 to 200 ℃.
34. The process of claim 33, wherein the reaction temperature in step (3) is 120-140 ℃.
35. The method according to claim 2, wherein the reaction time in the step (3) is 0.1 to 2 hours.
36. The method of claim 35, wherein the reaction time in step (3) is 0.5 to 1 hour.
37. An extraction process of vanillin, wherein the demulsifier of claim 1 or the demulsifier prepared by the preparation method of any one of claims 2 to 36 is added to the extraction process;
In the vanillin extraction process, the solution to be extracted is a reaction solution obtained after mandelic acid oxidation and decarboxylation.
38. The process for extracting vanillin according to claim 37, wherein the vanillin in the reaction liquid is extracted by an extractant, and a demulsifier is added in the reaction liquid.
39. The extraction process of vanillin according to claim 37, wherein the mass ratio of the demulsifier to the mandelic acid oxidation reaction liquid is 0.01-0.05.
40. The extraction process of vanillin according to claim 37, wherein the mandelic acid oxidation reaction solution, the acid solution, the demulsifier and the extractant are continuously added into the reactor, the mandelic acid oxidation reaction solution is fed from the upper part of the reactor, the extractant is fed from the lower end of the reactor, and the extractant and the mandelic acid oxidation reaction solution are discharged from the upper part of the reactor after being contacted and extracted in the reactor.
41. The extraction process of vanillin of claim 40, wherein the feed rate ratio of extractant to mandelic acid oxidation reaction liquid is 1: 3-1: 10.
42. According to the extraction process of vanillin of claim 40, the decarboxylation and the extraction of the mandelic acid oxidation reaction liquid are combined, the extractant and the mandelic acid oxidation reaction liquid are continuously injected into the reactor, the acid liquor and the 3-methoxy-4-hydroxyphenylketo acid in the mandelic acid oxidation reaction liquid undergo decarboxylation reaction, the generated vanillin is recovered by the extractant, and continuous decarboxylation and continuous extraction are realized in one reactor.
43. The extraction process of vanillin according to claim 40, wherein the mandelic acid oxidation reaction solution is an intermediate reaction solution for synthesizing vanillin, is a reaction solution obtained by oxidizing 3-methoxy-4-hydroxy mandelic acid as a raw material, and mainly comprises 70-90wt% of water, 5-15wt% of 3-methoxy-4-hydroxy-phenylketoacid and 5-8wt% of sodium sulfate.
44. According to the extraction process of vanillin of claim 40, the demulsifier and the acid liquor are fed from the upper part of the reactor, and can be mixed first and then are continuously added from the top of the reactor, wherein the acid liquor adopts one or more of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, the concentration is 5% -30%, and the mass ratio of the acid liquor to the reaction solution is 1:10 to 20.
45. The process for extracting vanillin according to any of claims 37-44, wherein the extractant is selected from one or more of toluene, ethyl acetate, butyl acetate, n-hexane, anisole, methyl isobutyl ketone, acetophenone.
46. The extraction process of claim 45, wherein the extractant is methyl isobutyl ketone or toluene.
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