CN110540496A - Preparation method of 3,5-dihydroxybenzoic acid - Google Patents
Preparation method of 3,5-dihydroxybenzoic acid Download PDFInfo
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- CN110540496A CN110540496A CN201910917791.7A CN201910917791A CN110540496A CN 110540496 A CN110540496 A CN 110540496A CN 201910917791 A CN201910917791 A CN 201910917791A CN 110540496 A CN110540496 A CN 110540496A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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Abstract
The invention discloses a preparation method of 3,5-dihydroxy benzoic acid, belonging to the technical field of chemical industry. Firstly, carrying out sulfonation reaction on benzoic acid and fuming sulfuric acid to obtain a sulfonated substance; then carrying out hydrolysis reaction on the sulfonated substance, transferring the hydrolysis reaction product into an acid precipitation kettle, centrifuging the reaction product, washing a filter cake obtained after centrifugation with a proper amount of methanol, reducing the pressure of a mother solution to-0.08 MPa, cooling to 60 ℃, adding methanol, centrifuging a methanol mixed solution, washing the filter cake with methanol, combining the methanol mother solutions, recovering the methanol to 80-90 ℃, reducing the pressure for half an hour, adding purified water, heating to reflux to full solution, cooling to below 10 ℃, transferring the product into a crystallization kettle, reacting for 1 hour to obtain a reactant, and centrifuging the reactant to obtain the 3,5-dihydroxybenzoic acid. The method has the advantages of simple reaction flow and reaction device, simple and convenient operation, higher product yield and contribution to industrial popularization.
Description
The technical field is as follows:
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of 3,5-dihydroxy benzoic acid.
background art:
3,5-dihydroxy benzoic acid (3, 5-dihydrobenzoic acid) is an important fine chemical intermediate, and can be used for synthesizing medical products, polyester compounds and pesticides, for example, 3,5-dihydroxy benzoic acid is an important raw material for producing resveratrol. Resveratrol is widely concerned because of its biological and pharmacological activities such as anti-tumor, anti-mutation, anti-inflammatory, anti-oxidation, estrogen regulation and the like, which are beneficial to human health, and resveratrol (3,5, 4' -trihydroxy stilbene) is a naturally occurring stilbene compound as an antitoxin from seed plants, has a special health care function for human health, has high popularization and comprehensive utilization value, and is very important at home and abroad. Wherein, the 3,5-dihydroxy benzoic acid is a key raw material for synthesizing the resveratrol, so the method also attracts attention to the optimization of the synthesis and preparation of the 3,5-dihydroxy benzoic acid, and particularly relates to the aspects of environmental protection and the like.
At present, the synthesis path of 3,5-dihydroxy benzoic acid is more, and a plurality of documents are reported, such as a plant extraction method for extracting resveratrol from plants by adopting an ultrasonic auxiliary technology, a biological system expression method for producing resveratrol and the like. Wherein the plant extraction method has low yield and complex process flow; the treatment device prepared by adopting the biological system expression method at present has strict requirements and higher production cost. Therefore, the 3,5-dihydroxybenzoic acid is synthesized by adopting benzoic acid and fuming sulfuric acid as raw materials and adopting a chemical method, the method is simple and easy to control, the production cost is low, no obvious harmful byproducts such as hazardous wastes and the like are generated, the method is a good synthesis process path, and the flow control production methods such as synthesis and preparation processes and the like can be greatly popularized.
the invention content is as follows:
the invention provides a preparation method of 3,5-dihydroxy benzoic acid to overcome the defects in the prior art. The preparation method of the 3,5-dihydroxy benzoic acid provided by the invention comprises the following specific steps:
(1) Firstly, performing sulfonation reaction, placing benzoic acid and fuming sulfuric acid with the mass concentration of 50% in a reaction kettle, wherein the mass ratio of the benzoic acid to the fuming sulfuric acid is 1-2: 1, reacting for 6 hours at 120 ℃, cooling to 40-50 ℃ after the reaction, adding reactants into a common reaction kettle containing 5000L of saturated salt water, cooling to 10 ℃, centrifuging to obtain a damp product, pulping once with the saturated salt water, centrifuging again, and drying the obtained damp product to obtain a sulfonated product.
(2) carrying out hydrolysis reaction, adding water into a stainless steel reaction kettle, adding caustic soda flakes, heating to 280-300 ℃, adding the sulfonated substance obtained in the step (1) into the stainless steel reaction kettle, reacting at the temperature of 280-300 ℃ for half an hour, cooling to 100 ℃ to obtain a reaction product, adding water until the reaction product is completely dissolved, and transferring the completely dissolved reaction product into an acid precipitation kettle; adjusting the pH value of a reaction product after complete dissolution in the acidification kettle to be a weakly alkaline reaction product by using dilute sulfuric acid, then centrifuging the reaction product, washing a filter cake obtained after centrifugation by using a proper amount of methanol, decompressing the mother liquor to-0.08 MPa, cooling to 60 ℃, adding methanol, centrifuging a methanol mixed solution, washing the filter cake by using methanol, combining the methanol mother liquor, recovering the methanol to 80-90 ℃, decompressing for half an hour, adding purified water, heating and refluxing to complete dissolution, and cooling to below 10 ℃ to obtain a product after complete dissolution.
(3) transferring the product obtained after the step into a crystallization kettle, reacting in the crystallization kettle for 1 hour to obtain a reactant, centrifuging the reactant, washing the centrifuged product with ice water once, and drying the washed damp product to obtain the 3,5-dihydroxybenzoic acid, wherein the washing water can be used repeatedly.
The stainless steel reaction kettle in the step (2) comprises two stainless steel reaction kettles which are alternately used, a frame type stirrer is arranged in each stainless steel reaction kettle, and the height from the bottom of each frame type stirrer to the bottom of each stainless steel reaction kettle is 1-2 cm, so that salt and alkali deposited at the bottom can be smoothly and uniformly stirred; the stainless steel reaction kettle is connected with a heat-conducting oil steam furnace, and heat-conducting oil at 350 ℃ is adopted.
Part of the heat source of the stainless steel reaction kettle can be used for connecting the distillation crystallization kettle 12 so as to distill the industrial methanol; a stainless steel reaction kettle is required to be provided with a 7.5KW motor and a matched speed reducer; the flange in the stainless steel reaction kettle is provided with a glass piece, and the glass piece is attached to the bottom as short as possible.
The reaction kettle in the step (1) is provided with a heat conducting oil steam furnace, and heat conducting oil at 350 ℃ is adopted to ensure high conversion rate of sulfonation reaction.
the pulping water in the step (1) can be used for the next time, and after the number of times of use is large, a proper amount of caustic soda flakes can be added for neutralization.
The sulfonated substance obtained in the step (1) of the invention has the purity of more than or equal to 95 percent by HPLC determination, the water content of less than or equal to 4 percent and the filtration state of less than or equal to 0.25 percent, and is qualified.
In the step (1), 50% oleum is adopted to reduce the discharge amount of acidic wastewater.
the acid mother liquor of the sulfonated product in the step (1) of the invention after centrifugation needs a polypropylene storage tank with the length of 20m3 for temporary storage and treatment.
The purity of the sample is measured by HPLC when the sample is cooled to 100 ℃ in the step (2) of the invention: sulfonate (0.2%, transition state (0.5%, content: 88-95%).
In the step (3), the acid precipitation tank 11 is required to be provided with a glass liquid level meter for detecting the pH value neutralized by dilute sulfuric acid.
In the invention, because the sulfonated product and the alkaline hydrolysis product are separated from the aqueous solution, the product contains most of water, and the separation of the sulfonated product and the alkaline hydrolysis product is preferably carried out by adopting a bubbling plate-and-frame filter press, most of water can be extruded out by bubbling, so that the dry materials can be obtained without drying in a box-type furnace, and can directly enter the next feeding or crystallization.
The invention has the following technical characteristics:
1. The whole reaction process is simple, the used reaction device is simple, the operation is simple and convenient, the product yield is high, the industrial popularization is facilitated, and the factory production has the maximum benefit.
2. The raw materials needed by the invention are cheap and easy to obtain, the used raw materials, namely the benzoic acid and the sulfuric acid, are industrialized raw materials which can be produced in a large scale, and the methanol solvent used in the invention can be recycled, so that the cost is saved, and the economic requirement is met.
Description of the drawings:
FIG. 1 is a schematic view of the process equipment for step (1) of the process of the present invention;
FIG. 2 is a schematic view of the process equipment in step (2) of the method of the present invention;
FIG. 3 is a schematic view of the process equipment in step (3) of the method of the present invention.
In the figure: 1 a: a first tail gas absorption device; 1 b: a second tail gas absorption device; 2: blue glaze enamel reaction kettle; 3: a graphite condenser; 4 a: a first common reaction vessel; 4 b: a second common reaction kettle; 5 a: a first glass condenser; 5 b: a second glass condenser; 5 c: a third glass condenser; 5 d: a fourth glass condenser; 5 e: a fifth glass condenser; 6a, a first bubbling filter press; 6b, a second bubbling filter press; 7: a centrifuge; 8 a: a first stainless steel reaction kettle; 8 b: a second stainless steel reaction kettle; 9 a: a first stainless steel condenser; 9 b: a second stainless steel condenser; 10 a: a first dilute sulphuric acid high-position dripping tank; 10 b: a second dilute sulphuric acid high-position dropping groove; 11 a: a first acid precipitation kettle; 11 b: a second acid precipitation kettle; 12: a crystallization kettle; 13: a methanol recovery kettle.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following specific examples.
Example 1: the preparation steps of the 3,5-dihydroxy benzoic acid are as follows:
(1) and (2) performing sulfonation reaction, namely putting benzoic acid and 50 wt% fuming sulfuric acid (the mass ratio of the benzoic acid to the fuming sulfuric acid is 3:2) into a 2000L blue glaze enamel reaction kettle 2, reacting for 6 hours at 120 ℃, cooling to 40-50 ℃ after the reaction, respectively dripping reactants into a 5000L first common reaction kettle 4a containing saturated salt water and a 5000L second common reaction kettle 4b, cooling to 10 ℃, and centrifuging. Obtaining the damp product. Pulping with saturated saline solution, centrifuging again to obtain damp product, and oven drying to obtain sulfonated substance.
(2) And then carrying out hydrolysis reaction, respectively adding water into 1000L of a first stainless steel reaction kettle 8a and a second stainless steel reaction kettle 8b, adding caustic soda flakes, heating to 280-300 ℃, and adding the sulfonated substances in batches at the temperature of not lower than 260 ℃. Reacting for half an hour at 280-300 ℃, and cooling to about 100 ℃. Adding water to the mixture until the mixture is completely dissolved, then respectively transferring the mixture into a first acid precipitation kettle 11a and a second acid precipitation kettle 11b of 2000L, and adjusting the pH value of a dilute sulfuric acid to be alkalescent; centrifuging, washing filter cake with proper amount of methanol, and decompressing mother liquid water to 100 deg.c/0.08 MPa. Cooling to 60 deg.C, adding methanol (washing methanol is also added); centrifuging, washing a filter cake with methanol, combining methanol mother liquor, recovering the methanol to 80-90 ℃, and then decompressing for half an hour. Adding purified water, heating to reflux to full dissolution, and cooling to below 10 deg.C to obtain the product after full dissolution.
(3) transferring the product obtained in the step (2) after complete dissolution into a 2000L crystallization kettle 12, reacting in the crystallization kettle 12 for 1 hour, centrifuging, washing with ice water once, reusing the washing water to obtain a damp product, and drying to obtain the 3,5-dihydroxy benzoic acid. The detection proves that the product purity is 95 percent and the yield is 85 percent.
example 2: when the sulfonation reaction is carried out in the step (1) under the same reaction conditions as in example 1, benzoic acid and 50 wt% of oleum (the mass ratio of benzoic acid to oleum is 1:1) are subjected to subsequent test methods and procedures without change, and the obtained product, namely 3,5-dihydroxybenzoic acid, has the purity of 96% and the yield of 88% through detection.
Example 3: when the sulfonation reaction is carried out in the step (1) under the same reaction conditions as in example 1, benzoic acid and 50 wt% fuming sulfuric acid (mass ratio is 2:1) are used, the subsequent test method and flow are not changed, and the obtained product 3,5-dihydroxybenzoic acid has the purity of 95% and the yield of 87% through detection.
The use of these examples is merely to illustrate the invention and is not intended to limit the scope of the invention. Further, it is also understood that various changes, modifications and/or alterations of the present invention may be made by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the scope of the present invention.
Claims (3)
1. A preparation method of 3,5-dihydroxy benzoic acid is characterized by comprising the following steps:
(1) Firstly, performing sulfonation reaction, putting benzoic acid and fuming sulfuric acid with the mass concentration of 50% into a reaction kettle, wherein the mass ratio of the benzoic acid to the fuming sulfuric acid is 1-2: 1, reacting for 6 hours at 120 ℃, cooling to 40-50 ℃ after the reaction, adding reactants into a common reaction kettle containing saturated salt water, cooling to 10 ℃, centrifuging to obtain a damp product, pulping once with the saturated salt water, centrifuging again, and drying the obtained damp product to obtain a sulfonated product;
(2) performing hydrolysis reaction, adding water into a stainless steel reaction kettle, adding caustic soda flakes, heating to 280-300 ℃, adding the sulfonate obtained in the step (1) into the stainless steel reaction kettle, reacting for half an hour at the temperature of 280-300 ℃, cooling to 100 ℃ to obtain a reaction product, adding water until the reaction product is completely dissolved, then transferring the fully dissolved reaction product into an acid separation kettle, adjusting the pH value of the fully dissolved reaction product in the acid separation kettle to be a weakly alkaline reaction product by using dilute sulfuric acid, then centrifuging the reaction product, washing a filter cake obtained after centrifugation by using a proper amount of methanol, decompressing mother liquor to-0.08 MPa, cooling to 60 ℃, adding methanol, centrifuging the methanol mixed solution, washing a filter cake with methanol, combining methanol mother liquor, recovering the methanol to 80-90 ℃, reducing the pressure for half an hour, adding purified water, heating and refluxing to be completely dissolved, and cooling to be below 10 ℃ to obtain a completely dissolved product;
(3) Transferring the product obtained in the step into a crystallization kettle, reacting in the crystallization kettle for 1 hour to obtain a reactant, centrifuging the reactant, washing the centrifuged product with ice water once, and drying the washed damp product to obtain the 3,5-dihydroxy benzoic acid.
2. The preparation method of 3,5-dihydroxybenzoic acid according to claim 1, characterized in that said stainless steel reaction kettle in step (2) comprises two stainless steel reaction kettles used alternately, a frame-type stirrer is arranged in said stainless steel reaction kettle, and the height of the bottom of said frame-type stirrer from the bottom of said stainless steel reaction kettle is 1-2 cm, so as to ensure that the salt and alkali deposited at the bottom can be stirred uniformly; the stainless steel reaction kettle is connected with a heat-conducting oil steam furnace, and heat-conducting oil at 350 ℃ is adopted.
3. The method for preparing 3,5-dihydroxybenzoic acid according to claim 1, characterized in that said reaction kettle in step (1) is equipped with a single heat-conducting oil steam furnace, and heat-conducting oil at 350 ℃ is used to ensure high conversion rate of sulfonation reaction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329253A (en) * | 2011-03-22 | 2012-01-25 | 江苏中丹集团股份有限公司 | Reaction apparatus for resorcinol neutralization reaction section and reaction technology thereof |
| CN108417804A (en) * | 2018-03-14 | 2018-08-17 | 成都新柯力化工科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method of high storage stability |
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- 2019-09-26 CN CN201910917791.7A patent/CN110540496A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329253A (en) * | 2011-03-22 | 2012-01-25 | 江苏中丹集团股份有限公司 | Reaction apparatus for resorcinol neutralization reaction section and reaction technology thereof |
| CN108417804A (en) * | 2018-03-14 | 2018-08-17 | 成都新柯力化工科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method of high storage stability |
Non-Patent Citations (2)
| Title |
|---|
| D.E.WINKLER ET AL.: "Some Observations on the Pechmann Reaction", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| 徐宝峰: "2-芳基苯并咪唑还原水解制备3,5-二甲氧基苯甲醛", 《精细石油化工》 * |
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Application publication date: 20191206 |