CN110684008B - Method and device for synthesizing 3, 4-methylenedioxymandelic acid by emulsification process - Google Patents
Method and device for synthesizing 3, 4-methylenedioxymandelic acid by emulsification process Download PDFInfo
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- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
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- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
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Abstract
The invention discloses a method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process, which is characterized in that gas is introduced into a reaction system in the processes of preparing mixed acid and emulsification synthesis to generate a large amount of bubbles in the reaction system, so that the surface area of reactants is increased, the contact area between the reactants is increased, and the conversion rate and the yield of the reaction can be improved. And in the reaction process, sponge is added, a plurality of small reaction systems can be formed in the emulsification reactor, the problem that the byproduct, namely the erhu acid, is generated by further reaction of the piper nigrum ring and the product due to nonuniform heat transfer and possibly overhigh local reaction temperature is solved, and meanwhile, the viscous product is dispersed into blocks, and the sponge is used as a carrier to increase the fluidity, so that the selectivity and the yield of the reaction are improved. The invention also discloses a device for synthesizing the 3, 4-methylenedioxymandelic acid by the emulsification process, which can efficiently complete the technological process for synthesizing the 3, 4-methylenedioxymandelic acid by the emulsification process.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a method and a device for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process.
Background
3, 4-methylenedioxymandelic acid is an intermediate in the synthesis of piperonal. Piperonal is widely used in perfumes, spices, cherry and vanilla flavors. The perfume has long fragrance retention time, is used as a blending agent and a fixing agent, is a safe perfume accepted by American Association for the manufacture of spice extracts, and is widely applied to indoor fragrances, soap essences, food essences and tobacco essences. It can also be used in chemical and biological pharmacy. Is one of special commodities for which the country enforces export licenses.
The traditional synthesis method of 3, 4-methylenedioxymandelic acid is a method of synthesizing piperonyl-acetal and glyoxylic acid under acidic conditions, and the influence of reaction factors such as reaction temperature, reaction time, molar ratio of glyoxylic acid to piperonyl-acetal is studied by single Shaojun and the like (single Shaojun, dommer. 3, 4-methylenedioxymandelic acid synthesis study [ J ] Anhui chemical industry, 2007, 2. In the research of a silver nitrate method for synthesizing medicinal jasminaldehyde [ J ]. In the research of a synthesis method of the heliotropin, similar preparation of 3, 4-methylenedioxymandelic acid is adopted in the research of the synthesis method of the heliotropin (Wangshuai, li dazao, wangsheng. King Hengchang. Air catalytic oxidation synthesis heliotropin [ J ]. Applied chemical industry, 2009, 4. Wujuan investigated the influence of factors such as reaction temperature, catalyst concentration, raw material ratios and reaction time, and explored the mechanism of action and possible reaction history of sulfuric acid catalysts (wujuan, wuxian, king england. Synthesis and characterization of heliotropin intermediate 3, 4-methylenedioxymandelic acid [ J ] chemical research and application, 2009, 21.
The above prior art has the following disadvantages;
the product 3, 4-methylenedioxymandelic acid has large viscosity, poor fluidity and low mass transfer efficiency in the synthesis process, and moreover, piperonyl and glyoxylic acid are not mutually soluble and the contact area between the two phases is small, so that the reaction is insufficient, the yield is low, the heat transfer is not uniform, and the phenomena of poor selectivity and more byproducts of the reaction are easy to occur
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method and a device for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process.
The invention is realized by the following technical scheme:
a method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process is characterized by comprising the following steps:
step 4, adding 3, 4-methylenedioxymandelic acid into the solution after the step 3 is finished, wherein the ratio of the added 3, 4-methylenedioxymandelic acid to the mass of the water in the step 1 is 3, 4-methylenedioxymandelic acid: water =0.1 to 1:1;
step 6, repeating the step 5 for multiple times, wherein the interval between every two times is 3-10 min, and the ratio of the total amount of the added piperonyl butoxide to the mass of the water in the step 1 is piperonyl butoxide: water =10 to 15:1;
step 7, adding the film-rotating sponge into the solution obtained after the step 6, and stirring at a constant temperature of 0-10 ℃, at a stirring speed of 400-600 rpm for 20-40 min;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total amount of the stop solution to the water mass in the step 1 is the stop solution: water =15 to 30:1, terminating the reaction to obtain a product;
the processes of the step 1 to the step 7 also comprise a process of blowing gas into the solution, wherein the gas blowing amount per minute is 7 to 20 times of the volume of the mixture in the step 1.
In the above technical solution, in step 1, the water: 50wt% aqueous glyoxylic acid =1: 15-17, and stirring at a constant temperature of-28 to-23 ℃ and a stirring speed of 380 to 420rpm.
In the above technical scheme, in the step 4, the ratio of the amount of the 3, 4-methylenedioxymandelic acid added to the mass of the water is 3, 4-methylenedioxymandelic acid: water =0.4 to 1:1.
in the technical scheme, in the step 5, the emulsifying speed is 12-15 Kr/min, pepper rings are added dropwise during emulsification, the adding amount per minute is 0.5-1 time of the mass of the water, and the emulsifying time is 5-10 min.
In the above technical scheme, in the step 6, the step 5 is repeated for 3-8 times, the interval between each time is 3-10 min, and the ratio of the total amount of added piperonyl butoxide to the mass of water is piperonyl butoxide: water =10 to 12:1.
in the above technical scheme, in the step 7, the added film-transferring sponge is 0.8-1.2 cm in volume 3 The total amount of the added particles is 0.5 to 1.2 times of the volume of the solution obtained at the end of the step 6.
In the above technical solution, in the step 8, the added stop solution is water, and the ratio of the total amount of the stop solution added to the water in the step 1 is the stop solution: water =15 to 25:1.
in the technical scheme, the method comprises the following steps:
and 4, adding 3, 4-methylenedioxymandelic acid into the solution after the step 3 is completed, wherein the mass ratio of the added 3, 4-methylenedioxymandelic acid to the water in the step 1 is 3, 4-methylenedioxymandelic acid: water =0.1 to 0.4:1;
step 6, repeating the step 5 for multiple times, wherein the interval between every two times is 3-10 min, and the mass ratio of the total amount of the added piperonyl butoxide to the water in the step 1 is piperonyl butoxide: water =10 to 12:1;
step 7, adding the film-rotating sponge into the solution obtained after the step 6, and stirring at a constant temperature of 0-10 ℃, at a stirring speed of 400-600 rpm for 20-40 min;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total amount of the stop solution to the water mass in the step 1 is the stop solution: water =20 to 25:1, terminating the reaction to obtain a product;
the processes of the step 1 to the step 7 also comprise a process of blowing gas into the solution, wherein the gas blowing amount per minute is 7 to 15 times of the volume of the mixture.
In the technical scheme, the air blowing medium adopted in the air blowing process is nitrogen.
The utility model provides a device of synthetic 3, 4-methylenedioxybenzene glycolic acid of emulsification process, includes jacketed distributor stirred tank, sulphuric acid metering tank, jacketed distributor stirred tank, pepper ring metering tank, the constant temperature tank, filtration equipment, the charge pump, the gas holder, the filtrate groove, sulphuric acid metering tank export links to each other with jacketed distributor stirred tank pipeline, constant temperature tank circulation liquid export adopts the pipe connection respectively jacket inlet and the jacket inlet of jacketed distributor stirred tank, constant temperature tank circulation liquid entry adopts the pipe connection respectively jacket outlet and the jacket outlet of jacketed distributor stirred tank, the export of jacketed distributor stirred tank links to each other with the inlet pipeline of charge pump, the export of pepper ring metering tank links to each other with jacketed distributor emulsified tank pipeline, jacketed distributor emulsified tank export with the feed inlet pipe connection of filtration equipment, the export of gas holder adopts the pipe connection respectively jacket distributor stirred tank's gas distribution pipe entry with the jacket distributor emulsified tank's gas inlet, the filtration distributor emulsified tank exports filter tank entry is connected.
In the technical scheme, flow meters are arranged at outlet pipes of the sulfuric acid metering tank and the pepper ring metering tank.
In the technical scheme, the jacket inlet pipe of the jacketed distributor stirring kettle and the jacket inlet pipe of the jacketed distributor emulsifying kettle are both provided with liquid flow meters.
In the technical scheme, gas flow meters are arranged on the gas distribution pipe inlet pipe of the jacketed distributor stirring kettle and the gas distribution pipe inlet pipe of the jacketed distributor emulsifying kettle.
In the technical scheme, the emulsifying device and the wall scraping stirring device are arranged on the jacket type distributor emulsifying kettle.
In the technical scheme, the jacketed distributor emulsifying kettle is provided with 2 sets of emulsifying devices and wall scraping stirring devices.
In the above technical solution, the filtering device is a multi-stage filtering device.
In the above technical solution, the filtering device is a 2-stage filtering device.
In the technical scheme, the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle are both provided with temperature detecting instruments.
The invention has the advantages and beneficial effects that:
1. the method for synthesizing the 3, 4-methylenedioxymandelic acid adopts the emulsification process for synthesis, and the method leads gas to be introduced into a reaction system in the processes of preparing mixed acid and emulsification synthesis, so that a large amount of bubbles are generated in the reaction system, the surface area of reactants is increased, the contact area among the reactants is increased, and the conversion rate and the yield of the reaction can be improved.
2. The invention adopts an emulsification method to synthesize the 3, 4-methylenedioxymandelic acid, and utilizes the homogenization effect of the emulsification process in the synthesis process to uniformly disperse the piperonyl in the glyoxylic acid by tiny droplets, thereby improving the contact efficiency between reactants and improving the purity and the yield of the product.
3. The emulsifier adopted by the invention is 3, 4-methylenedioxymandelic acid, and the method takes the product as the emulsifier according to the principle that the 3, 4-methylenedioxymandelic acid has both lipophilic group and hydrophilic group, so that a stable emulsion system can be formed, and substances outside the reaction system are not introduced, and the product separation process is simpler and easier.
4. The invention adds sponge in the reaction process, can form a plurality of small reaction systems in the emulsification reactor, solves the problems of uneven heat transfer, the local reaction temperature may be too high, which causes the problem that the piperonyl cycloxapride reacts with the product further to generate the byproduct, namely, the erhu acid, and at the same time, the viscous product is dispersed into blocks, and the sponge is used as a carrier to increase the fluidity, thereby improving the selectivity and the yield of the reaction.
Drawings
FIG. 1 is a schematic diagram of a process for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process.
Fig. 2 is a schematic diagram of embodiment 3 of the present invention.
Fig. 3 is a schematic diagram of embodiment 4 of the present invention.
Wherein:
1: jacketed distributor stirred tank, 2: sulfuric acid metering tank, 3: jacketed distributor emulsifying kettle, 4: pepper ring metering tank, 5: thermostatic bath, 6: filtration apparatus, 7: charge pump, 8: gas storage tank, 9: a filtrate tank;
6-1: primary filtering equipment, 6-2: secondary filtration device, 10-1: first gas flow meter, 10-2: second gas flow meter, 11-1: first liquid flow meter, 11-2: a second liquid flow meter.
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Comparative example
1. 100g of piperonyl butoxide, 10g of water, 160g of 50% glyoxylic acid aqueous solution, and 140g of 98% concentrated sulfuric acid were weighed.
2. To a jacketed reactor were added 10g of water and 160g of 50% aqueous glyoxylic acid.
3. Connecting the jacket reactor with a constant temperature bath, setting the temperature of the constant temperature bath to be 5 ℃, operating the constant temperature bath to cool for more than half an hour until the temperature of liquid in the jacket reaches 5 ℃.
4. Connecting an electric stirrer, and stirring the liquid in the jacket reactor by using a plastic stirring blade at the rotating speed of 400r/min
5. Dropwise adding 140g of concentrated sulfuric acid at a constant speed of 7g/min by using a constant-pressure funnel, and continuously stirring for 30min after dropwise adding.
Obtaining the mixed acid.
6. And (3) removing the mixed acid accounting for 70 percent of the total mass of the mixed acid out of the jacketed reactor, and refrigerating the mixed acid in an environment at 5 ℃.
7. 30g of piperonyl butoxide is dropwise added into the jacketed reactor at a constant speed of 3g/min by using a constant-pressure funnel. After the dropwise addition, stirring was continued for 30min.
8. Dropwise adding 70% of the mixed acid removed in the step 6 (the adding time is 1 h) and 70g of piperonyl (the adding time is 0.5 h) into a jacketed reactor at a constant speed by using a constant-pressure funnel.
9. After the dropwise addition, the speed of the stirring equipment is adjusted to 500r/min, and the stirring reaction is continued for 35min
10. The reaction was terminated by adding 200mL of water to the jacketed reactor.
11. Suction filtration was performed using a 1L suction flask to obtain a solid, which was weighed, dried and checked by liquid chromatography.
12. The detection result shows that the yield is 71.42%, the purity is 68.54%, and the total yield is 44.64%.
Example 1
A method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process comprises the following steps:
step 4, adding 3, 4-methylenedioxymandelic acid into the solution after the step 3 is completed, and adding 4g of 3, 4-methylenedioxymandelic acid;
step 6, repeating the step 5 for 4 times, wherein the interval between every two times is 3min, and adding 100g of total amount of the piperonyl butoxide;
step 7, adding 400 pieces of 1cm × 1cm × 1cm membrane-transferring sponge (brand western blot, production lot number G6002, product number 151837) into the solution obtained after the step 6 is finished, and stirring at a constant temperature of 5 ℃, at a stirring speed of 500rpm, for 30min;
step 8, adding 200ml of water into the solution after the step 7 is finished, and stopping the reaction to obtain a product;
the processes of the step 1 to the step 7 also comprise a process of blowing gas into the solution, wherein the gas blowing amount per minute is 2.5L/min, and the adopted gas blowing medium is nitrogen.
The purity is 98.48 percent and the total yield is 92.32 percent.
Example 2
A method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process comprises the following steps:
step 4, adding 3, 4-methylenedioxymandelic acid into the solution after the step 3 is completed, and adding 8g of 3, 4-methylenedioxymandelic acid;
step 6, repeating the step 5 for 4 times, wherein the interval between every two times is 3min, and adding 150g of total amount of piperonyl butoxide;
step 7, adding 600 pieces of 1cm multiplied by 1cm membrane-transferring sponge (brand western blot, production lot number G6002, commodity number 151837) into the solution after the step 6 is finished, and stirring at a constant temperature of 5 ℃, a stirring speed of 500rpm and a stirring time of 30min;
step 8, adding 250ml of water into the solution after the step 7 is finished, and stopping the reaction to obtain a product;
the processes of the step 1 to the step 7 also comprise a process of blowing gas into the solution, wherein the gas blowing amount per minute is 2.5L/min, and the adopted gas blowing medium is nitrogen.
The purity is 98.37 percent and the total yield is 92.23 percent.
Example 3
A device for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process comprises a jacketed distributor stirring kettle, a sulfuric acid metering tank, a jacketed distributor emulsifying kettle, a pepper ring metering tank, a thermostatic tank, a filtering device, a feeding pump, a gas storage tank and a filtrate tank, wherein an outlet of the sulfuric acid metering tank is connected with a jacketed distributor stirring kettle pipeline, a circulating liquid outlet of the thermostatic tank is respectively connected with a jacket inlet of the jacketed distributor stirring kettle and a jacket inlet of the jacketed distributor emulsifying kettle by pipelines, and liquid flow meters are respectively arranged on a jacket inlet pipe of the jacketed distributor stirring kettle and a jacket inlet pipe of the jacketed distributor emulsifying kettle. Constant temperature bath circulation liquid entry adopts the pipe connection respectively the clamp cover export of clamp sleeve type distributor stirred tank and the clamp cover export of clamp sleeve type distributor emulsification cauldron, the export of clamp sleeve type distributor stirred tank links to each other with the inlet pipeline of charge pump, the export of pepper ring metering tank links to each other with clamp sleeve type distributor emulsification cauldron pipeline, the export of clamp sleeve type distributor emulsification cauldron with filtration equipment's feed inlet pipe connection, the export of gas holder adopts the pipe connection respectively clamp sleeve type distributor stirred tank's gas distribution pipe entry with clamp sleeve type distributor emulsification cauldron's gas distribution pipe entry all is provided with the gas flowmeter on clamp sleeve type distributor stirred tank's gas distribution pipe inlet tube and clamp sleeve type distributor emulsification cauldron's the gas distribution pipe inlet tube, filtration equipment liquid phase exit linkage the filter tank entry. Outlet pipes of the sulfuric acid metering tank and the pepper ring metering tank are provided with flowmeters, temperature detecting instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle respectively, and 2 emulsifying devices and a wall scraping stirring device are arranged on the jacketed distributor emulsifying kettle.
In the implementation of the method for synthesizing 3, 4-methylenedioxymandelic acid by the emulsification process, 2 sets of emulsification devices and wall scraping stirring devices on the jacketed distributor emulsification kettle are started in step 5 and step 6. And 7, closing the 2 sets of emulsifying devices on the jacketed distributor emulsifying kettle, and keeping the wall scraping stirring device in an open state.
Example 4
A device for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process comprises a jacketed distributor stirring kettle, a sulfuric acid metering tank, a jacketed distributor emulsifying kettle, a pepper ring metering tank, a thermostatic tank, a filtering device, a feeding pump, a gas storage tank and a filter liquid tank, wherein an outlet of the sulfuric acid metering tank is connected with a jacket distributor stirring kettle pipeline, a circulating liquid outlet of the thermostatic tank is respectively connected with a jacket inlet of the jacketed distributor stirring kettle and a jacket inlet of the jacketed distributor emulsifying kettle by pipelines, and liquid flow meters are respectively arranged on a jacket inlet pipe of the jacketed distributor stirring kettle and a jacket inlet pipe of the jacketed distributor emulsifying kettle. Constant temperature groove circulation liquid entry adopts the pipe connection respectively the clamp cover export of clamp sleeve formula distributor stirred tank and the clamp cover export of clamp sleeve formula distributor emulsion cauldron, the export of clamp sleeve formula distributor stirred tank links to each other with the inlet pipeline of charge pump, the export of pepper ring metering tank links to each other with clamp sleeve formula distributor emulsion cauldron pipeline, clamp sleeve formula distributor emulsion cauldron export and one-level filtration equipment's feed inlet pipe connection, one-level filtration equipment's discharge gate links to each other with second grade filtration equipment's feed inlet pipeline, the export of gas holder adopts the pipe connection respectively clamp sleeve formula distributor stirred tank's gas distribution pipe entry with clamp sleeve formula distributor emulsion cauldron's gas distribution pipe entry, all be provided with gas flowmeter on clamp sleeve formula distributor stirred tank's gas distribution pipe inlet tube and clamp sleeve formula distributor emulsion cauldron's the gas distribution pipe inlet tube, second grade filtration equipment liquid phase exit linkage the filter tank entry. And outlet pipes of the sulfuric acid metering tank and the pepper ring metering tank are provided with flow meters, and temperature detection instruments are respectively arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle. And the jacketed distributor emulsifying kettle is provided with 2 sets of emulsifying devices and a wall scraping stirring device.
In the implementation of the method for synthesizing 3, 4-methylenedioxymandelic acid by the emulsification process, 2 sets of emulsification devices and wall scraping stirring devices on the jacketed distributor emulsification kettle are started in step 5 and step 6. And 7, closing the 2 sets of emulsifying devices on the jacketed distributor emulsifying kettle, and keeping the wall scraping stirring device in an open state.
The primary filtering equipment and the secondary filtering equipment adopt filtering media with different precisions, the filtering media adopted on the primary filtering equipment have larger pore sizes, so that the rotary membrane sponge with larger particle sizes in a product system can be filtered out, the filtrate enters the secondary filtering equipment, and the secondary filtering equipment adopts the filtering media with smaller pore sizes, so that the final product 3, 4-methylenedioxymandelic acid can be filtered out.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (9)
1. A method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process is characterized by comprising the following steps:
step 1, mixing water in a mass ratio: 50wt% aqueous glyoxylic acid =1: stirring the mixture of 15 to 20 at constant temperature, wherein the constant temperature stirring temperature is-30 to-20 ℃, and the stirring speed is 350 to 450rpm;
step 2, after stirring, dripping 98wt% of concentrated sulfuric acid into the mixture, wherein the dripping amount per minute is 0.03-0.1 time of the mass of the mixture, and the ratio of the total mass of the 98wt% of concentrated sulfuric acid to the mass of the water in the step 1 is 98wt% of concentrated sulfuric acid: water =12 to 15:1, stirring at-30 to-20 ℃;
step 3, after all the 98wt% concentrated sulfuric acid is dripped, continuously stirring for 20-40 min at the stirring temperature of minus 30-minus 20 ℃;
step 4, adding 3, 4-methylenedioxymandelic acid into the solution after the step 3 is finished, wherein the ratio of the added 3, 4-methylenedioxymandelic acid to the mass of the water in the step 1 is 3, 4-methylenedioxymandelic acid: water =0.1 to 1:1;
step 5, emulsifying the solution obtained in the step 4 at the emulsifying speed of 10-15 Kr/min, dripping pepper rings at the same time during the emulsification, wherein the dripping amount per minute is 0.1-1 time of the mass of the water obtained in the step 1, and the emulsifying time is 3-10 min;
step 6, repeating the step 5 for multiple times, wherein the interval between every two times is 3-10 min, and the ratio of the total amount of the added piperonyl butoxide to the mass of the water in the step 1 is: water =10 to 15:1;
step 7, adding the film-rotating sponge into the solution obtained after the step 6, and stirring at a constant temperature of 0-10 ℃, at a stirring speed of 400-600 rpm for 20-40 min;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total amount of the stop solution added to the water in the step 1 is the stop solution: water =15 to 30:1, terminating the reaction to obtain a product; the stop solution is water;
the processes of the step 1 to the step 7 also comprise a process of blowing gas into the solution, wherein the gas blowing amount per minute is 7 to 20 times of the volume of the mixture in the step 1.
2. The method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process according to claim 1, wherein in the step 1, the mass ratio of water: 50wt% aqueous glyoxylic acid =1: 15-17, stirring at a constant temperature of-28 to-23 ℃ and at a stirring speed of 380 to 420rpm.
3. The method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process according to claim 1, wherein in the step 4, the ratio of the amount of the 3, 4-methylenedioxymandelic acid added to the mass of the water is 3, 4-methylenedioxymandelic acid: water =0.4 to 1:1.
4. the method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process according to claim 1, wherein in the step 5, the emulsification speed is 12-15 Kr/min, pepper rings are added dropwise during emulsification, the addition amount per minute is 0.5-1 time of the mass of the water, and the emulsification time is 5-10 min.
5. The method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process according to claim 1, wherein in the step 6, the step 5 is repeated 3-8 times, each time is separated by 3-10 min, and the ratio of the total amount of added piperonyl to the mass of water is piperonyl: water =10 to 12:1.
6. the method for synthesizing 3, 4-methylenedioxymandelic acid by using emulsification process according to claim 1, wherein in step 7, the rotating membrane sponge is added to a volume of 0.8-1.2 cm 3 The total amount of the added particles is 0.5 to 1.2 times of the volume of the solution obtained at the end of the step 6.
7. The method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsion process according to claim 1, wherein the stop solution added in step 8 is water, and the ratio of the total amount of the stop solution added to the mass of the water in step 1 is stop solution: water =15 to 25:1.
8. the method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsion process according to claim 1, which comprises the following steps:
step 1, mixing water in a mass ratio: 50wt% glyoxylic acid aqueous solution =1: stirring the mixture of 14 to 16 at constant temperature, wherein the constant temperature stirring temperature is-25 ℃ to-23 ℃, and the stirring speed is 400 to 420rpm;
step 2, after stirring, dripping 98wt% of concentrated sulfuric acid into the mixture, wherein the dripping amount per minute is 0.03-0.07 time of the mass of the mixture, and the mass ratio of the total mass of the 98wt% of concentrated sulfuric acid to the water in the step 1 is 98wt% of concentrated sulfuric acid: water =12 to 14:1, stirring at-25 to-23 ℃;
step 3, after all the 98wt% concentrated sulfuric acid is dripped, continuously stirring for 20-30 min at the stirring temperature of minus 25-minus 23 ℃;
and 4, adding 3, 4-methylenedioxymandelic acid into the solution after the step 3 is completed, wherein the mass ratio of the added 3, 4-methylenedioxymandelic acid to the water in the step 1 is 3, 4-methylenedioxymandelic acid: water =0.1 to 0.4:1;
step 5, emulsifying the solution obtained in the step 4 at an emulsifying speed of 12Kr/min, and simultaneously dripping pepper rings at a dripping amount of 0.3-0.5 time of the mass of the water obtained in the step 1 per minute for 3-5 min;
step 6, repeating the step 5 for multiple times, wherein the interval between each time of the step 5 and each time of the step is 3-10 min, and the mass ratio of the total amount of the added piperonyl butoxide to the water in the step 1 is piperonyl butoxide: water =10 to 12:1;
step 7, adding a film-rotating sponge into the solution obtained after the step 6, and stirring at a constant temperature of 0-10 ℃ at a stirring speed of 400-600 rpm for 20-40 min;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total amount of the stop solution added to the water in the step 1 is the stop solution: water =20 to 25:1, terminating the reaction to obtain a product; the stop solution is water;
the processes of the step 1 to the step 7 also comprise a process of blowing gas into the solution, wherein the gas blowing amount per minute is 7 to 15 times of the volume of the mixture.
9. The method for synthesizing 3, 4-methylenedioxymandelic acid by an emulsification process according to any one of claims 1 to 8, wherein the air-blowing medium used in the air-blowing process is nitrogen.
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| CN201810725064.6A Active CN110684008B (en) | 2018-07-04 | 2018-07-04 | Method and device for synthesizing 3, 4-methylenedioxymandelic acid by emulsification process |
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