CN103319383A - Preparation method of p-methylsulfonylbenzoic acid - Google Patents
Preparation method of p-methylsulfonylbenzoic acid Download PDFInfo
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Abstract
The invention relates to a preparation method of p-methylsulfonylbenzoic acid. The method provided by the invention mainly comprises the following steps: (1) fusing; (2) preheating; (3) chemical oxidation; (4) solid-liquid separation; (5) neutralization for salt formation; (6) solid-liquid separation; (7) adsorption for removal of impurities; (8) solid-liquid separation; (9) acidification and crystallization; (10) solid-liquid separation; (11) washing; (12) dewatering and drying for obtaining a product p-methylsulfonylbenzoic acid; and (13) electrochemical oxidation. The preparation method provided by the invention is simple, has advantages of reasonable technology, low production cost, high product purity and safe process, is convenient to realize large-scale industrialization, and is a clean production technology which is used for preparing p-methylsulfonylbenzoic acid and accords with green chemical development requirements.
Description
Technical field
The present invention relates to a kind of preparation method to thiamphenicol benzoic acid, particularly a kind of to be that the direct chemical oxidation of raw material prepares the method to thiamphenicol benzoic acid to methylsulfonyl toluene, belong to the fine chemical technology field.
Background technology
Main raw material of the present invention is the powder of white crystals shape under the normal temperature for being a kind of aromatics to methylsulfonyl toluene, and molecular formula is C
8H
10O
2S, 88 ℃～89 ℃ of melting ranges, 312 ℃ of boiling points, density is 1.154g/cm
3, be dissolved in organic solvents such as alcohol, ether, be slightly soluble in water.
Product of the present invention is to thiamphenicol benzoic acid; another name is to methylsulfonyl toluene, to the carboxyl lauseto neu, to methyl sulfonylbenzoic acid and 4-methyl sulfonylbenzoic acid etc. to carboxyl; English 4-methylsulphonylbenzoic acid by name; 4-(methylsulfonyl) benzoic acid; P-methylsufonyl benzoic acid; 4-(methylsulfonyl) benzoate, 4-Methanesulfonyl-benzoic acid etc., molecular formula is C
8H
7O
4S, molecular weight 199.2.To being white crystal under the thiamphenicol benzoic acid normal temperature, be slightly soluble in water, be dissolved in organic solvents such as ethanol, density is 1.392g/cm
3, fusing point is 276 ℃～276 ℃, boiling point is 432.4 ℃.
Be the raw material of synthetic medicine and agricultural chemicals to thiamphenicol benzoic acid, be mainly used in the intermediate of synthetic herbicide, antiseptic-germicide and bleach activator etc.
Existing preparation technology to thiamphenicol benzoic acid is being that raw material obtains through chemical oxidation to methylsulfonyl toluene, and oxygenant commonly used is air, nitric acid etc.Present industrial main technique technology is nitric acid oxidation method, and mainly there is following problem in this technology:
(1) level of response is wayward, and the selectivity of process, transformation efficiency and yield are low.
(2) reaction product complexity, the separation and purification difficulty, quality product is low;
(3) safe reliability is poor, and is seriously polluted.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the process for cleanly preparing to thiamphenicol benzoic acid that a kind of technology is reasonable, the preparation method is simple, production cost is low, product purity is high, process is safe is provided.
The technical scheme that realizes above-mentioned purpose is: a kind of preparation method to thiamphenicol benzoic acid is being that raw material carries out the selective oxidation preparation to the method for thiamphenicol benzoic acid to methylsulfonyl toluene, and its step is as follows:
(1) fusion: in fusion apparatus, raw material is warmed up to 90 ℃～150 ℃ to methylsulfonyl toluene, makes that to be in the solid-state fusion to methylsulfonyl toluene under the room temperature be liquid material;
(2) preheating: in preliminary heating device, add aqueous sulfuric acid and oxygenant potassium bichromate, and heat to 90 ℃～120 ℃;
(3) chemical oxidation: in liquid-liquid-liquid heterogeneous reaction device, through the reactant of fusion methylsulfonyl toluene and previous step being carried out liquid-liquid through the potassium bichromate aqueous sulfuric acid of preheating mixes, potassium bichromate will be oxidized to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid the methylsulfonyl methylbenzene selective, along with the raising to the methylsulfonyl toluene conversion, generate to thiamphenicol benzoic acid and to the methylsulfonyl phenyl aldehyde crystallization separate out, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in the solid-liquid separating device, the material that previous step is obtained carries out solid-liquid to be separated, and solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) in and salify: the solid-phase material that neutralizing agent and previous step are obtained mixes, the reaction to thiamphenicol benzoic acid and neutralizing agent in the material generates the water-soluble solution of thiamphenicol benzoic acid salt is entered liquid phase, and solid phase is unreacted raw material to methylsulfonyl toluene and intermediate product to the methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in the solid-liquid separating device, the material that previous step is obtained carries out the solid-liquid separation, and mother liquor enters next step, and solid-phase material enters in the fusion apparatus of the first step, recycles as reaction raw materials;
(7) adsorption-edulcoration: previous step obtain to the thiamphenicol benzoic acid salts solution in add sorbent material and carry out the adsorption-edulcoration operation, the material after adsorption-edulcoration is handled enters next step;
(8) solid-liquid separates: in the solid-liquid separating device, the material that previous step is obtained carries out solid-liquid to be separated, and mother liquor enters next step, and solid phase obtains sorbent material and gets back to previous step and recycle after manipulation of regeneration;
(9) acidizing crystal: add mineral acid in the mother liquor that previous step obtains, regulate pH value to 2～6, the crystallization to thiamphenicol benzoic acid that obtains is separated out, and material enters next step;
(10) solid-liquid separates: in the solid-liquid separating device, the material that previous step is obtained carries out the solid-liquid separation, solid-phase material enters next step, and the liquid phase material that contains inorganic salt is used for second preparation that goes on foot the potassium bichromate aqueous sulfuric acid and recycles after further handling;
(11) washing: the solid-phase material that previous step obtains is washed removal of impurities, and solid phase enters next step, and washing water recycle after treatment;
(12) dehydrate: previous step is carried out dehydration operation through what wash to the thiamphenicol benzoic acid solid-phase material, and the solid after the dehydration is dry under 100 ℃～180 ℃, obtains product to thiamphenicol benzoic acid;
(13) electrochemical oxidation: in the electrochemical oxidation reactions device, the liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), the Cr (VI) that regeneration obtains enters second oxygenant that goes on foot as oxidizing reaction and recycles.
Further, in the described second step pre-heating step, the concentration of oxygenant potassium bichromate is 0.5mol/L～3.0mol/L, and the concentration of sulfuric acid is 0.1mol/L～8.0mol/L.
Further, in described the 3rd step liquid-liquid oxidation reaction, be 1: 1.1～1.8 to the mol ratio of methylsulfonyl toluene and oxygenant potassium bichromate, service temperature is 90 ℃～150 ℃.
Further, the reactor of described the 3rd step chemical oxidation is any one in stirred-tank reactor or the static mixing reactor.
Further, in the 5th step and in the salify step, described neutralizing agent is the aqueous solution of any one or arbitrary combination in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, the potassium hydroxide, the concentration of neutralizing agent is 0.1mol/L～6.0mol/L, consumption be in and the pH value that is adjusted to system in the salification process be 8～10, service temperature is 20 ℃～60 ℃.
Further, in described the 7th step adsorption-edulcoration step, sorbent material is the mixture of any one or any two kinds or any three kinds of components in molecular sieve or activated carbon or the diatomite, consumption is 1%～5% of liquor capacity, the service temperature of adsorption-edulcoration is 20 ℃～60 ℃, and the pounds per square inch absolute (psia) of operation is 0.1MPa～0.6MPa.
Further, in described the 9th step acidizing crystal step, mineral acid is any one in sulfuric acid or the hydrochloric acid, and service temperature is 20 ℃～80 ℃.
Further, the 4th step, the 6th step, the 8th step and described solid-liquid separating device of the tenth step are any one in decanter type or filtering type or centrifugal or the vane-type solid-liquid separating device.
Further, the electrochemical reactor in described the tenth step is plate electrochemical reactor or three-dimensional electrochemical reactor, and anolyte compartment and the cathode compartment of reactor are isolated by barrier film, barrier film preferred cationic film.In the electrochemical oxidation system, the concentration of sulfuric acid is 0.5mol/L～4.0mol/L, and service temperature is 20 ℃～60 ℃, and actuating current density is 500A/m
2～2000A/m
2
Realize that the main technique equipment that the present invention needs is: liquid-liquid-liquid heterogeneous reaction device, electrochemical reactor, fusion apparatus, preliminary heating device, solid-liquid separating device, washing plant, crystallizer, drying plant etc.
The equation of chemical reaction involved in the present invention is:
(1) oxidation of methylsulfonyl methylbenzene selective is generated thiamphenicol benzoic acid:
(2) Cr (III) electrochemistry oxygen turns to Cr (VI):
(3) to the salt-forming reaction of thiamphenicol benzoic acid and neutralizing agent (be example with yellow soda ash):
(4) to the acidification reaction of thiamphenicol benzoic acid salt:
Adopt principle and the advantage of technique scheme to be:
(1) utilization is to the characteristics of methylsulfonyl toluene easy oxidation under acidic conditions, and the oxidisability by acidity and the temperature of reaction of regulation and control reactive system are regulated potassium bichromate realizes the selective oxidation to methylsulfonyl toluene, thereby obtains the thiamphenicol benzoic acid product.
(2) having selected potassium bichromate is oxygenant, and the Cr (III) that oxidizing reaction generates is renewable by electrochemical oxidation to be Cr (VI), has realized recycling of oxygenant, has reduced pollution, has reduced cost.
(3) being that raw material carries out selective oxidation preparation in the thiamphenicol benzoic acid process to methylsulfonyl toluene, can generate intermediate product to the methylsulfonyl phenyl aldehyde, therefore, in the reaction product except containing the thiamphenicol benzoic acid, also contain unreacted raw material to methylsulfonyl toluene and by product to the methylsulfonyl phenyl aldehyde, so need carry out separation and purification to this mixture.That the art of this patent is utilized is less to thiamphenicol benzoic acid solubleness in water, with easy salify and the salt that the generates characteristic soluble in water of alkali metal compound (alkali, alkalimetal oxide or alkaline carbonate), to be converted into thiamphenicol benzoic acid salt thiamphenicol benzoic acid, be dissolved in liquid phase, thereby with solid phase methylsulfonyl toluene is reached the methylsulfonyl phenyl aldehyde separated.Recycling is insoluble in the characteristic of water to what thiamphenicol benzoic acid salt and acid neutralization generated to thiamphenicol benzoic acid, will separate out the thiamphenicol benzoic acid crystallization by acidizing crystal, thereby make thiamphenicol benzoic acid.Also make simultaneously raw material that methylsulfonyl toluene and intermediate product are reclaimed use to the methylsulfonyl phenyl aldehyde.
Technology of the present invention is reasonable, and the preparation method is simple, and production cost is low, the product purity height, and process safety is convenient to realize heavy industrialization, is a kind of process for cleanly preparing that meets the green chemical industry demand for development.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Embodiment one
Main technique equipment: stirred-tank reactor, plate electrochemical reactor, decanter type solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, crystallizer, drying plant etc.
As shown in Figure 1, a kind of preparation method to thiamphenicol benzoic acid is being that raw material carries out selective oxidation preparation to the method for thiamphenicol benzoic acid to methylsulfonyl toluene, and its step is as follows:
(1) fusion: in stirring tank, will be warmed up to 90 ℃ to methylsulfonyl toluene, and make that to be in the solid-state fusion to methylsulfonyl toluene under the room temperature be liquid material;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 90 ℃, the concentration of potassium bichromate is 0.5mol/L in the system, the concentration of sulfuric acid is 0.1mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyl toluene with raw material;
(3) chemical oxidation: in stirred-tank reactor, the aqueous sulfuric acid of previous step through the potassium bichromate of preheating mixed methylsulfonyl toluene with the liquid reaction raw material of process fusion, mol ratio to methylsulfonyl toluene and oxygenant potassium bichromate is 1:1.1, service temperature is 90 ℃, potassium bichromate will be oxidized to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid the methylsulfonyl methylbenzene selective, along with the raising to the methylsulfonyl toluene conversion, generate to thiamphenicol benzoic acid and to the methylsulfonyl phenyl aldehyde crystallization separate out, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in decanter type solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and solid-phase material enters next step, and liquid phase material entered for the 13 step and carries out electrochemical oxidation regeneration;
(5) in and salify: in stirring tank, compound concentration is that the 0.1mol/L aqueous sodium carbonate is as neutralizing agent, the solid-phase material that neutralizing agent and previous step are obtained mixes, service temperature is 20 ℃, the pH value that is neutralized to system is 8, the reaction to thiamphenicol benzoic acid and neutralizing agent in the solid-phase material generates the water-soluble solution of thiamphenicol benzoic acid salt is entered liquid phase, and solid phase is unreacted raw material to methylsulfonyl toluene and intermediate product to the methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in decanter type solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, and mother liquor enters next step, and solid-phase material enters in the fusion apparatus of the first step, recycles as reaction raw materials;
(7) adsorption-edulcoration: previous step obtain to the thiamphenicol benzoic acid salts solution in add the sorbent molecule sieve, the consumption of sorbent material is 1% of liquor capacity, the service temperature of adsorption-edulcoration is 20 ℃, and the pounds per square inch absolute (psia) of operation is 0.1MPa, and the material after adsorption-edulcoration is handled enters next step;
(8) solid-liquid separates: in decanter type solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and mother liquor enters next step, and solid phase obtains sorbent material and gets back to previous step and recycle after manipulation of regeneration;
(9) acidizing crystal: add sulfuric acid in the mother liquor that previous step obtains, service temperature is 20 ℃, regulates pH value to 2, and the crystallization to thiamphenicol benzoic acid that obtains is separated out, and material enters next step;
(10) solid-liquid separates: in decanter type solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, solid-phase material enters next step, and the liquid phase material that contains inorganic salt is used for second preparation that goes on foot the potassium bichromate aqueous sulfuric acid and recycles after further handling;
(11) washing: the solid-phase material that previous step obtains is washed removal of impurities, and solid phase enters next step, and washing water recycle after treatment;
(12) dehydrate: previous step is carried out dehydration operation through what wash to the thiamphenicol benzoic acid solid-phase material, and the solid after the dehydration is dry under 100 ℃, obtains product to thiamphenicol benzoic acid;
(13) electrochemical oxidation: in the plate electrochemical reactor of positively charged ion barrier film, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 0.5mol/L, service temperature is 20 ℃, and actuating current density is 500A/m
2, the Cr (VI) that regeneration obtains enters second oxygenant that goes on foot as oxidizing reaction and recycles.
Embodiment two
Main technique equipment: static mixing reactor, three-dimensional electrochemical reactor, filtering type solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, crystallizer, drying plant etc.
Step is as follows:
(1) fusion: in the falling film type fusion apparatus, will be warmed up to 150 ℃ to methylsulfonyl toluene, and make that to be in the solid-state fusion to methylsulfonyl toluene under the room temperature be liquid material;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 ℃, the concentration of potassium bichromate is 3.0mol/L in the system, the concentration of sulfuric acid is 8.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyl toluene with raw material;
(3) chemical oxidation: in static mixing reactor, the aqueous sulfuric acid of previous step through the potassium bichromate of preheating mixed methylsulfonyl toluene with the liquid reaction raw material of process fusion, mol ratio to methylsulfonyl toluene and oxygenant potassium bichromate is 1: 1.8, service temperature is 150 ℃, potassium bichromate will be oxidized to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid the methylsulfonyl methylbenzene selective, along with the raising to the methylsulfonyl toluene conversion, generate to thiamphenicol benzoic acid and to the methylsulfonyl phenyl aldehyde crystallization separate out, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in filtering type solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and solid-phase material enters next step, and liquid phase material entered for the 13 step and carries out electrochemical oxidation regeneration;
(5) in and salify: in stirring tank, compound concentration is that the 6.0mol/L wet chemical is as neutralizing agent, the solid-phase material that neutralizing agent and previous step are obtained mixes, service temperature is 60 ℃, the pH value that is neutralized to system is 10, the reaction to thiamphenicol benzoic acid and neutralizing agent in the solid-phase material generates the water-soluble solution of thiamphenicol benzoic acid salt is entered liquid phase, and solid phase is unreacted raw material to methylsulfonyl toluene and intermediate product to the methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in filtering type solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, and mother liquor enters next step, and solid-phase material enters in the fusion apparatus of the first step, recycles as reaction raw materials;
(7) adsorption-edulcoration: previous step obtain to the thiamphenicol benzoic acid salts solution in add sorbent material diatomite, the sorbent material consumption is 5% of liquor capacity, the service temperature of adsorption-edulcoration is 60 ℃, and the pounds per square inch absolute (psia) of operation is 0.6MPa, and the material after adsorption-edulcoration is handled enters next step;
(8) solid-liquid separates: in filtering type solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and mother liquor enters next step, and solid phase obtains sorbent material and gets back to previous step and recycle after manipulation of regeneration;
(9) acidizing crystal: add hydrochloric acid in the mother liquor that previous step obtains, service temperature is 80 ℃, regulates pH value to 6, and the crystallization to thiamphenicol benzoic acid that obtains is separated out, and material enters next step;
(10) solid-liquid separates: in filtering type solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, solid-phase material enters next step, and the liquid phase material that contains inorganic salt is used for second preparation that goes on foot the potassium bichromate aqueous sulfuric acid and recycles after further handling;
(11) washing: the solid-phase material that previous step obtains is washed removal of impurities, and solid phase enters next step, and washing water recycle after treatment;
(12) dehydrate: previous step is carried out dehydration operation through what wash to the thiamphenicol benzoic acid solid-phase material, and the solid after the dehydration is dry under 180 ℃, obtains product to thiamphenicol benzoic acid;
(13) electrochemical oxidation: in positively charged ion barrier film three-dimensional electrochemical reactor, the liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 4.0mol/L, and 60 ℃ of service temperatures, actuating current density are 2000A/m
2, the Cr (VI) that regeneration obtains enters second oxygenant that goes on foot as oxidizing reaction and recycles.
Embodiment three
Main technique equipment: static mixing reactor, plate electrochemical reactor, centrifugal solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, crystallizer, drying plant etc.
Step is as follows:
(1) fusion: in stirring tank, will be warmed up to 120 ℃ to methylsulfonyl toluene, and make that to be in the solid-state fusion to methylsulfonyl toluene under the room temperature be liquid material;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 100 ℃, the concentration of potassium bichromate is 2.0mol/L in the system, the concentration of sulfuric acid is 4.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyl toluene with raw material;
(3) chemical oxidation: in static mixing reactor, the aqueous sulfuric acid of previous step through the potassium bichromate of preheating mixed methylsulfonyl toluene with the liquid reaction raw material of process fusion, mol ratio to methylsulfonyl toluene and oxygenant potassium bichromate is 1:1.6, service temperature is 120 ℃, potassium bichromate will be oxidized to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid the methylsulfonyl methylbenzene selective, along with the raising to the methylsulfonyl toluene conversion, generate to thiamphenicol benzoic acid and to the methylsulfonyl phenyl aldehyde crystallization separate out, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in centrifugal solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) in and salify: in stirring tank, compound concentration is that the 3.0mol/L aqueous sodium hydroxide solution is as neutralizing agent, the solid-phase material that neutralizing agent and previous step are obtained mixes, service temperature is 60 ℃, the pH value that is neutralized to system is 10, the reaction to methylsulfonyl toluic acid and neutralizing agent in the solid-phase material generates methylsulfonyl toluene hydrochlorate is entered liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyl toluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in centrifugal solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, and mother liquor enters next step, and solid-phase material enters in the fusion apparatus of the first step, recycles as reaction raw materials;
(7) adsorption-edulcoration: previous step obtain to the thiamphenicol benzoic acid salts solution in add activated carbon of sorbent, the sorbent material consumption is 2% of liquor capacity, the service temperature of adsorption-edulcoration is 40 ℃, and the pounds per square inch absolute (psia) of operation is 0.3MPa, and the material after adsorption-edulcoration is handled enters next step;
(8) solid-liquid separates: in centrifugal solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and mother liquor enters next step, and solid phase obtains sorbent material and gets back to previous step and recycle after manipulation of regeneration;
(9) acidizing crystal: add hydrochloric acid in the mother liquor that previous step obtains, service temperature is 60 ℃, regulates pH value to 4, and the crystallization to thiamphenicol benzoic acid that obtains is separated out, and material enters next step;
(10) solid-liquid separates: in centrifugal solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, solid-phase material enters next step, and the liquid phase material that contains inorganic salt is used for second preparation that goes on foot the potassium bichromate aqueous sulfuric acid and recycles after further handling;
(11) washing: the solid-phase material that previous step obtains is washed removal of impurities, and solid phase enters next step, and washing water recycle after treatment;
(12) dehydrate: previous step is carried out dehydration operation through what wash to the thiamphenicol benzoic acid solid-phase material, and the solid after the dehydration is dry under 120 ℃, obtains product to thiamphenicol benzoic acid;
(13) electrochemical oxidation: in the plate electrochemical reactor of cationic membrane barrier film, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 2.0mol/L, service temperature is 50 ℃, actuating current density 1000A/m
2, the Cr (VI) that regeneration obtains enters second oxygenant that goes on foot as oxidizing reaction and recycles.
Embodiment four
Main technique equipment: stirred-tank reactor, three-dimensional electrochemical reactor, vane-type solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, crystallizer, drying plant etc.
Step is as follows:
(1) fusion: in the falling film type fusion apparatus, will be warmed up to 120 ℃ to methylsulfonyl toluene, and make that to be in the solid-state fusion to methylsulfonyl toluene under the room temperature be liquid material;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 ℃, the concentration of potassium bichromate is 2.0mol/L in the system, the concentration of sulfuric acid is 4.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyl toluene with raw material;
(3) chemical oxidation: in stirred-tank reactor, the aqueous sulfuric acid of previous step through the potassium bichromate of preheating mixed methylsulfonyl toluene with the liquid reaction raw material of process fusion, mol ratio to methylsulfonyl toluene and oxygenant potassium bichromate is 1: 1.1, service temperature is 120 ℃, potassium bichromate will be oxidized to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid the methylsulfonyl methylbenzene selective, along with the raising to the methylsulfonyl toluene conversion, generate to thiamphenicol benzoic acid and to the methylsulfonyl phenyl aldehyde crystallization separate out, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in vane-type solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and solid-phase material enters next step, and liquid phase material entered for the 13 step and carries out electrochemical oxidation regeneration;
(5) in and salify: in stirring tank, compound concentration is that 1.0mol/L saleratus and 1.0mol/L potassium hydroxide aqueous solution are as neutralizing agent, the solid-phase material that neutralizing agent and previous step are obtained mixes, service temperature is 50 ℃, the pH value that is neutralized to system is 10, methylsulfonyl toluic acid and neutralizing agent reaction are generated methylsulfonyl toluene hydrochlorate in the solid-phase material, the water-soluble solution of methylsulfonyl toluene hydrochlorate is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyl toluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in vane-type solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, and mother liquor enters next step, and solid-phase material enters in the fusion apparatus of the first step, recycles as reaction raw materials;
(7) adsorption-edulcoration: previous step obtain to the thiamphenicol benzoic acid salts solution in add the activated carbon of liquor capacity 1% and 1% diatomite as sorbent material, the service temperature of adsorption-edulcoration is 40 ℃, the pounds per square inch absolute (psia) of operation is 0.2MPa, and the material after adsorption-edulcoration is handled enters next step;
(8) solid-liquid separates: in vane-type solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and mother liquor enters next step, and solid phase obtains sorbent material and gets back to previous step and recycle after manipulation of regeneration;
(9) acidizing crystal: in the mother liquor that previous step obtains, add any one mineral acid in sulfuric acid, hydrochloric acid or the acetic acid,, service temperature is 500 ℃, regulates pH value to 4, and the crystallization to thiamphenicol benzoic acid that obtains is separated out, and material enters next step;
(10) solid-liquid separates: in vane-type solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, solid-phase material enters next step, and the liquid phase material that contains inorganic salt is used for second preparation that goes on foot the potassium bichromate aqueous sulfuric acid and recycles after further handling;
(11) washing: the solid-phase material that previous step obtains is washed removal of impurities, and solid phase enters next step, and washing water recycle after treatment;
(12) dehydrate: previous step is carried out dehydration operation through what wash to the thiamphenicol benzoic acid solid-phase material, and the solid after the dehydration is dry under 120 ℃, obtains product to thiamphenicol benzoic acid;
(13) electrochemical oxidation: in positively charged ion barrier film three-dimensional electrochemical reactor, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 4.0mol/L, and service temperature is 60 ℃, and actuating current density is 150A/m
2, the Cr (VI) that regeneration obtains enters second oxygenant that goes on foot as oxidizing reaction and recycles.
Embodiment five
Main technique equipment: stirred-tank reactor, three-dimensional electrochemical reactor, decanter type solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, crystallizer, drying plant etc.
Step is as follows:
(1) fusion: in stirring tank formula fusion apparatus, will be warmed up to 150 ℃ to methylsulfonyl toluene, and make that to be in the solid-state fusion to methylsulfonyl toluene under the room temperature be liquid material;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 ℃, the concentration of potassium bichromate is 3.0mol/L in the system, the concentration of sulfuric acid is 8.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyl toluene with raw material;
(3) chemical oxidation: in stirred-tank reactor, the aqueous sulfuric acid of previous step through the potassium bichromate of preheating mixed methylsulfonyl toluene with the liquid reaction raw material of process fusion, mol ratio to methylsulfonyl toluene and oxygenant potassium bichromate is 1: 1.40, service temperature is 120 ℃, potassium bichromate will be oxidized to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid the methylsulfonyl methylbenzene selective, along with the raising to the methylsulfonyl toluene conversion, generate to thiamphenicol benzoic acid and to the methylsulfonyl phenyl aldehyde crystallization separate out, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in decanter type solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and solid-phase material enters next step, and liquid phase material entered for the 13 step and carries out electrochemical oxidation regeneration;
(5) in and salify: in stirring tank, the compound concentration total concn is that the aqueous solution that waits sodium bicarbonate that mole mixes and salt of wormwood of 6.0mol/L is as neutralizing agent, the solid-phase material that neutralizing agent and previous step are obtained mixes, service temperature is 40 ℃, the pH value that is neutralized to system is 8, the reaction to thiamphenicol benzoic acid and neutralizing agent in the material generates the water-soluble solution of thiamphenicol benzoic acid salt is entered liquid phase, and solid phase is unreacted raw material to methylsulfonyl toluene and intermediate product to the methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in decanter type solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, and mother liquor enters next step, and solid-phase material enters in the fusion apparatus of the first step, recycles as reaction raw materials;
(7) adsorption-edulcoration: previous step obtain to the thiamphenicol benzoic acid salts solution in add liquor capacity 1% molecular sieve, 1% activated carbon and 1% diatomite as sorbent material, the service temperature of adsorption-edulcoration is 60 ℃, the pounds per square inch absolute (psia) of operation is 0.6MPa, and the material after adsorption-edulcoration is handled enters next step;
(8) solid-liquid separates: in decanter type solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and mother liquor enters next step, and solid phase obtains sorbent material and gets back to previous step and recycle after manipulation of regeneration;
(9) acidizing crystal: add sulfuric acid in the mother liquor that previous step obtains, service temperature is 200 ℃, regulates pH value to 4, and the crystallization to thiamphenicol benzoic acid that obtains is separated out, and material enters next step;
(10) solid-liquid separates: in decanter type solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, solid-phase material enters next step, and the liquid phase material that contains inorganic salt is used for second preparation that goes on foot the potassium bichromate aqueous sulfuric acid and recycles after further handling;
(11) washing: the solid-phase material that previous step obtains is washed removal of impurities, and solid phase enters next step, and washing water recycle after treatment;
(12) dehydrate: previous step is carried out dehydration operation through what wash to the thiamphenicol benzoic acid solid-phase material, and the solid after the dehydration is dry under 140 ℃, obtains product to thiamphenicol benzoic acid;
(13) electrochemical oxidation: in positively charged ion barrier film three-dimensional electrochemical reactor, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 2.0mol/L, service temperature is 60 ℃, and actuating current density is 1000A/m
2, the Cr (VI) that regeneration obtains enters second oxygenant that goes on foot as oxidizing reaction and recycles.
Embodiment six
Main technique equipment: static mixing reactor, three-dimensional electrochemical reactor, centrifugal solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, crystallizer, drying plant etc.
Step is as follows:
(1) fusion: in the falling film type fusion apparatus, will be warmed up to 120 ℃ to methylsulfonyl toluene, and make that to be in the solid-state fusion to methylsulfonyl toluene under the room temperature be liquid material;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 ℃, the concentration of potassium bichromate is 1.0mol/L in the system, the concentration of sulfuric acid is 2.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyl toluene with raw material;
(3) chemical oxidation: in static mixing reactor, the aqueous sulfuric acid of previous step through the potassium bichromate of preheating mixed methylsulfonyl toluene with the liquid reaction raw material of process fusion, mol ratio to methylsulfonyl toluene and oxygenant potassium bichromate is 1: 1.6, service temperature is 100 ℃, potassium bichromate will be oxidized to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid the methylsulfonyl methylbenzene selective, along with the raising to the methylsulfonyl toluene conversion, generate to thiamphenicol benzoic acid and to the methylsulfonyl phenyl aldehyde crystallization separate out, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in centrifugal solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and solid-phase material enters next step, and liquid phase material entered for the 13 step and carries out electrochemical oxidation regeneration;
(5) in and salify: in stirring tank, with yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, mole such as potassium hydroxide mixes, preparing then and obtaining total concn is that the 6.0mol/L neutralizing agent aqueous solution is as neutralizing agent, the solid-phase material that neutralizing agent and previous step are obtained mixes, service temperature is 50 ℃, the pH value that is neutralized to system is 10, methylsulfonyl toluic acid and neutralizing agent reaction are generated methylsulfonyl toluene hydrochlorate in the solid-phase material, the water-soluble solution of methylsulfonyl toluene hydrochlorate is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyl toluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in centrifugal solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, and mother liquor enters next step, and solid-phase material enters in the fusion apparatus of the first step, recycles as reaction raw materials;
(7) adsorption-edulcoration: previous step obtain to the thiamphenicol benzoic acid salts solution in add the diatomite of liquor capacity 2% as sorbent material, the service temperature of adsorption-edulcoration is 30 ℃, the pounds per square inch absolute (psia) of operation is 0.2MPa, and the material after adsorption-edulcoration is handled enters next step;
(8) solid-liquid separates: in centrifugal solid-liquid separator, the material that previous step is obtained carries out solid-liquid to be separated, and mother liquor enters next step, and solid phase obtains sorbent material and gets back to previous step and recycle after manipulation of regeneration;
(9) acidizing crystal: add sulfuric acid in the mother liquor that previous step obtains, service temperature is 60 ℃, regulates pH value to 5, and the crystallization to thiamphenicol benzoic acid that obtains is separated out, and material enters next step;
(10) solid-liquid separates: in centrifugal solid-liquid separator, the material that previous step is obtained carries out the solid-liquid separation, solid-phase material enters next step, and the liquid phase material that contains inorganic salt is used for second preparation that goes on foot the potassium bichromate aqueous sulfuric acid and recycles after further handling;
(11) washing: the solid-phase material that previous step obtains is washed removal of impurities, and solid phase enters next step, and washing water recycle after treatment;
(12) dehydrate: previous step is carried out dehydration operation through what wash to the thiamphenicol benzoic acid solid-phase material, and the solid after the dehydration is dry under 120 ℃, obtains product to thiamphenicol benzoic acid;
(13) electrochemical oxidation: isolate in the three-dimensional electrochemical reactor at positively charged ion, the liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 3.0mol/L, and service temperature is 60 ℃, and actuating current density is 1800A/m
2, the Cr (VI) that regeneration obtains enters second oxygenant that goes on foot as oxidizing reaction and recycles.
Except the various embodiments described above, embodiment of the present invention also have a lot, and the technical scheme that all employings are equal to or equivalence is replaced is all within protection scope of the present invention.
Claims (9)
1. preparation method to thiamphenicol benzoic acid is being that raw material carries out the selective oxidation preparation to the method for thiamphenicol benzoic acid to methylsulfonyl toluene, it is characterized in that described step is as follows:
(1) fusion: in fusion apparatus, raw material is warmed up to 90 ℃～150 ℃ to methylsulfonyl toluene, makes that to be in the solid-state fusion to methylsulfonyl toluene under the room temperature be liquid material;
(2) preheating: in preliminary heating device, add aqueous sulfuric acid and oxygenant potassium bichromate, and heat to 90 ℃～120 ℃;
(3) chemical oxidation: in liquid-liquid-liquid heterogeneous reaction device, through the reactant of fusion methylsulfonyl toluene and previous step being carried out liquid-liquid through the potassium bichromate aqueous sulfuric acid of preheating mixes, potassium bichromate will be oxidized to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid the methylsulfonyl methylbenzene selective, along with the raising to the methylsulfonyl toluene conversion, generate to thiamphenicol benzoic acid and to the methylsulfonyl phenyl aldehyde crystallization separate out, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in the solid-liquid separating device, the material that previous step is obtained carries out solid-liquid to be separated, and solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) in and salify: the solid-phase material that neutralizing agent and previous step are obtained mixes, the reaction to thiamphenicol benzoic acid and neutralizing agent in the material generates the water-soluble solution of thiamphenicol benzoic acid salt is entered liquid phase, and solid phase is unreacted raw material to methylsulfonyl toluene and intermediate product to the methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in the solid-liquid separating device, the material that previous step is obtained carries out the solid-liquid separation, and mother liquor enters next step, and solid-phase material enters in the fusion apparatus of the first step, recycles as reaction raw materials;
(7) adsorption-edulcoration: previous step obtain to the thiamphenicol benzoic acid salts solution in add sorbent material and carry out the adsorption-edulcoration operation, the material after adsorption-edulcoration is handled enters next step;
(8) solid-liquid separates: in the solid-liquid separating device, the material that previous step is obtained carries out solid-liquid to be separated, and mother liquor enters next step, and solid phase obtains sorbent material and gets back to previous step and recycle after manipulation of regeneration;
(9) acidizing crystal: add mineral acid in the mother liquor that previous step obtains, regulate pH value to 2～6, the crystallization to thiamphenicol benzoic acid that obtains is separated out, and material enters next step;
(10) solid-liquid separates: in the solid-liquid separating device, the material that previous step is obtained carries out the solid-liquid separation, solid-phase material enters next step, and the liquid phase material that contains inorganic salt is used for second preparation that goes on foot the potassium bichromate aqueous sulfuric acid and recycles after further handling;
(11) washing: the solid-phase material that previous step obtains is washed removal of impurities, and solid phase enters next step, and washing water recycle after treatment;
(12) dehydrate: previous step is carried out dehydration operation through what wash to the thiamphenicol benzoic acid solid-phase material, and the solid after the dehydration is dry under 100 ℃～180 ℃, obtains product to thiamphenicol benzoic acid;
(13) electrochemical oxidation: in the electrochemical oxidation reactions device, the liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), the Cr (VI) that regeneration obtains enters second oxygenant that goes on foot as oxidizing reaction and recycles.
2. according to the described preparation method to thiamphenicol benzoic acid of claim 1, it is characterized in that: in described (2) the step pre-heating step, the concentration of oxygenant potassium bichromate is 0.5mol/L～3.0mol/L, and the concentration of sulfuric acid is 0.1mol/L～8.0mol/L.
3. according to the described preparation method to thiamphenicol benzoic acid of claim 1, it is characterized in that: in described (3) step liquid-liquid oxidation reaction, be 1: 1.1～1.8 to the mol ratio of methylsulfonyl toluene and oxygenant potassium bichromate, service temperature is 90 ℃～150 ℃.
4. according to the described preparation method to thiamphenicol benzoic acid of claim 1, it is characterized in that: the reactor of described (3) step chemical oxidation is any one in stirred-tank reactor or the static mixing reactor.
5. according to the described preparation method to thiamphenicol benzoic acid of claim 1, it is characterized in that: in (5) step and in the salify step, described neutralizing agent is the aqueous solution of any one or arbitrary combination in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, the potassium hydroxide, the concentration of neutralizing agent is 0.1mol/L～6.0mol/L, consumption be in and the pH value that is adjusted to system in the salification process be 8～10, service temperature is 20 ℃～60 ℃.
6. according to the described preparation method to thiamphenicol benzoic acid of claim 1, it is characterized in that: in described (7) the step adsorption-edulcoration step, sorbent material is the mixture of any one or any two kinds or any three kinds of components in molecular sieve or activated carbon or the diatomite, consumption is 1%～5% of liquor capacity, the service temperature of adsorption-edulcoration is 20 ℃～60 ℃, and the pounds per square inch absolute (psia) of operation is 0.1MPa～0.6MPa.
7. according to the described preparation method to thiamphenicol benzoic acid of claim 1, it is characterized in that: in described (9) the step acidizing crystal step, mineral acid is any one in sulfuric acid or the hydrochloric acid, and service temperature is 20 ℃～80 ℃.
8. according to the described preparation method to thiamphenicol benzoic acid of claim 1, it is characterized in that: (4) step, (6) step, (8) step and described solid-liquid separating device of (10) step are any one in decanter type or filtering type or centrifugal or the vane-type solid-liquid separating device.
9. according to the described preparation method to thiamphenicol benzoic acid of claim 1, it is characterized in that: the electrochemical reactor in described (10) step is plate electrochemical reactor or three-dimensional electrochemical reactor, anolyte compartment and the cathode compartment of reactor are isolated by barrier film, barrier film preferred cationic film.In the electrochemical oxidation system, the concentration of sulfuric acid is 0.5mol/L～4.0mol/L, and service temperature is 20 ℃～60 ℃, and actuating current density is 500A/m
2～2000A/m
2
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| CN104805466B (en) * | 2015-04-09 | 2017-12-19 | 嘉兴学院 | A kind of indirect electrooxidation prepares method of the adjacent nitro to thiamphenicol benzoic acid |
| CN108299258A (en) * | 2018-02-26 | 2018-07-20 | 青岛科技大学 | A kind of synthetic method to thiamphenicol benzoic acid |
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| CN104805466B (en) * | 2015-04-09 | 2017-12-19 | 嘉兴学院 | A kind of indirect electrooxidation prepares method of the adjacent nitro to thiamphenicol benzoic acid |
| CN108299258A (en) * | 2018-02-26 | 2018-07-20 | 青岛科技大学 | A kind of synthetic method to thiamphenicol benzoic acid |
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