CN110862369B - Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification - Google Patents
Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D317/46—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 condensed with one six-membered ring
- 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
- C07D317/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention provides a method and a device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification. The water reducer is added in the reaction process, and can be directionally adsorbed on the surface of the oil phase liquid drop, so that the surface of the oil phase liquid drop is charged, electrostatic repulsion is generated, the dispersion effect of the water reducer is exerted, and the oil phase is dispersed to increase the fluidity. Meanwhile, the water reducer has a lubricating effect, hydrophilic groups are increased to form a solvated water film, friction is reduced, a pepper ring phase in a viscous stage of a product is more dispersed, the water film is formed to play a role in lubricating, the mass transfer and heat transfer processes of a reaction system are uniform, and the purity and yield of the product are improved. Inert solvent is dripped in the reaction process, so that the conversion rate of the reaction is improved on the basis of increasing the fluidity of the product, and the problem of viscous product is solved. And provides a set of devices for the 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-methylenedioxy-phenylglycolic acid by improved emulsification.
Background
3, 4-methylenedioxy-mandelic acid is an intermediate in the synthesis of piperonal. Piperonal is widely used as a flavoring agent for perfumes, fragrances, cherries and vanilla flavors. The long-lasting fragrance is used as a sum fragrance agent and a fixing fragrance agent, is a safe fragrance approved by American perfume extract manufacturing society, and is widely applied to indoor fragrances, soap fragrances, food fragrances and tobacco fragrances. Can also be used in chemical biopharmaceuticals. Is one of the special commodities for the country to carry out export license.
The conventional synthesis method of 3, 4-methylenedioxy-mandelic acid is a method of synthesizing piperonyl 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 and the like is studied by Shan Shaojun and the like (Shan Shaojun, du Zhenmei. Synthesis research of 3, 4-methylenedioxy-mandelic acid [ J ]. Anhui chemical, 2007,2; 46-47.). Wang Shuai et al (Wang Shuai, li Yaoxian, wang Hengguo. Air catalytic oxidation to heliotropin [ J ]. Applied chemical, 2009, 4:491-493.) and Zhang Kunshui et al (Zhang Kunshui, huanghan, chen Yisheng. Silver nitrate methods for synthesis of medicinal jasmonate [ J ]. Chinese modern pharmaceutical applications. 2008, 2:53-54.) A similar process for preparing 3, 4-methylenedioxy-phenylglycolic acid was also employed in the study of heliotropin synthesis. Hongjuan the influence of factors such as reaction temperature, catalyst concentration, raw material proportion and reaction time is examined, and the action mechanism and possible reaction courses of the sulfuric acid catalyst are discussed (Hongjuan, gao Zhixian, wang Jianguo. Synthesis and characterization of heliotropin intermediate 3, 4-methylenedioxy-benzilic acid [ J ]. Chemical research and application, 2009, 21:396-400.).
The above prior art has the following disadvantages;
because the product 3, 4-methylenedioxy-phenylglycolic acid has high viscosity, poor fluidity in the synthesis process, low mass transfer efficiency, immiscibility between the piperonyl and the glyoxylic acid and small contact area between the two phases, insufficient reaction results in low yield, poor heat transfer non-uniform effect, and easy occurrence of the phenomena of poor selectivity and more byproducts of the reaction
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-methylenedioxy-benzilic acid by improving emulsification.
The invention is realized by the following technical scheme:
a method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification, which comprises the following steps:
step 1, mixing the following components in percentage by mass: 50wt% glyoxylate aqueous solution = 1: stirring the mixture at a constant temperature of 15-20, wherein the constant temperature stirring temperature is minus 30 ℃ to minus 20 ℃ and the stirring speed is 350 rpm-450 rpm;
step 2, after stirring is started, 98wt% of concentrated sulfuric acid is dropwise added to the mixture, wherein the dropwise adding amount per minute is 0.03-0.1 time of the mass of the mixture, and the ratio of the total 98wt% of concentrated sulfuric acid to the mass of water in the step 1 is 98wt% of concentrated sulfuric acid: water=12 to 15:1, stirring at a temperature of-30 ℃ to-20 ℃;
step 3, continuously stirring for 20-40 min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 30 ℃ to minus 20 ℃;
step 4, adding 3, 4-methylenedioxy-mandelic acid to the solution after completion of step 3, wherein the ratio of the amount of 3, 4-methylenedioxy-mandelic acid added to the water mass in step 1 is 3, 4-methylenedioxy-mandelic acid: water=0.1 to 1:1, a step of;
step 5, emulsifying the solution after the step 4, wherein the emulsifying speed is 10-15 Kr/min, simultaneously dripping piper ring in the emulsifying process, wherein the dripping amount per minute is 0.1-1 times of the water mass in the step 1, and the emulsifying time is 3-10 min;
and 6, repeating the step 5 for a plurality of times, wherein the interval between each time is 3-10 min, and the ratio of the total amount of the added piper nigrum to the water mass in the step 1 is piper nigrum: water=10 to 15:1, a step of;
step 7, stirring the solution after the step 6 at a constant temperature, wherein the stirring temperature is 0-10 ℃, the stirring speed is 400-600 rpm, the stirring time is 20-40 min, and the inert solvent and/or the water reducer are/is added dropwise during the stirring process;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total addition 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 process of step 1 to step 7 also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 7-20 times of the volume of the mixture.
In the above technical scheme, in the step 1, the mass ratio of water is as follows: 50wt% glyoxylate aqueous solution = 1: the mixture of 15 to 17 is stirred at constant temperature, the constant temperature stirring temperature is minus 28 ℃ to minus 23 ℃, and the stirring speed is 380rpm to 420rpm.
In the above technical scheme, in the step 4, the ratio of the amount of 3, 4-methylenedioxy-mandelic acid added to the water mass in the step 1 is 3, 4-methylenedioxy-mandelic acid: water=0.4 to 1:1.
in the technical scheme, in the step 5, the emulsifying speed is 12-15 Kr/min, the pepper ring is added dropwise at the same time during emulsifying, the adding amount per minute is 0.5-1 time of the water mass in the step 1, and the emulsifying time is 5-10 min.
In the above technical scheme, in the step 6, the step 5 is repeated 3-8 times, the interval between each time is 3-10 min, and the ratio of the total amount of the added piper nigrum to the water mass in the step 1 is piper nigrum: water=10 to 12:1, a step of;
in the above technical scheme, in step 7, the inert solvent is one or a combination of any more of dichloromethane, toluene, paraffin oil, naphthenic oil and white oil, the drop amount per minute is 1.5-3 times of the water mass in step 1, and the total mass of the drop inert solvent is 15-30 times of the water mass in step 1.
In the above technical scheme, in the step 7, the water reducer is a polycarboxylic acid high-performance water reducer, and the ratio of the total amount of the polycarboxylic acid high-performance water reducer added to the water mass in the step 1 is the polycarboxylic acid high-performance water reducer: water=0.15 to 0.3:1, a step of;
in the above technical scheme, in the step 7, the inert solvent is added dropwise in the stirring process in a manner that the inert solvent is added dropwise after 10-20 minutes after the start of the step 7, wherein the adding amount of the inert solvent per minute is 1.5-3 times of the water mass in the step 1, and the total adding mass of the inert solvent is 15-30 times of the water mass in the step 1.
In the above technical scheme, in the step 8, the added stop solution is water, and the ratio of the total adding amount of the stop solution to the water mass in the step 1 is the stop solution: water=15 to 25:1.
the utility model provides a device for improving emulsification synthesis 3, 4-methylenedioxy phenylglycolic acid, includes jacket formula distributor stirred tank, sulfuric acid metering tank, jacket formula distributor stirred tank, pepper ring metering tank, constant temperature tank, charging metering tank, filtration equipment, the charge pump, the gas holder, the filtrate tank, sulfuric acid metering tank export links to each other with jacket formula distributor stirred tank pipeline, constant temperature tank circulation liquid outlet adopts the pipe connection respectively jacket entry of jacket formula distributor stirred tank, jacket entry of jacket formula distributor stirred tank and jacket formula distributor stirred tank's jacket entry, constant temperature tank circulation liquid entry adopts the pipe connection respectively jacket export of jacket formula distributor stirred tank, jacket formula distributor stirred tank's jacket export and jacket type distributor stirred tank's jacket export, the export of jacket formula distributor stirred tank links to each other with the inlet pipe of charge pump, the export of pepper ring metering tank links to each other with jacket formula distributor stirred tank pipeline, the export of constant temperature tank circulation liquid links to each other with jacket formula distributor stirred tank pipeline, jacket formula distributor stirred tank's jacket entry, jacket type distributed tank's outlet and gas inlet, the gas inlet of jacket distributor stirred tank inlet, gas inlet of jacket type distributor stirred tank inlet, gas inlet pipe inlet connection respectively.
In the technical scheme, the outlet pipes of the sulfuric acid metering tank, the pepper ring metering tank and the feeding metering tank are all provided with flow meters.
In the technical scheme, the liquid flow meters are arranged on the jacket inlet pipe of the jacket type distributor stirring kettle, the jacket inlet pipe of the jacket type distributor emulsifying kettle and the jacket inlet pipe of the jacket type distributor product stirring kettle.
In the technical scheme, gas flow meters are arranged on the gas distribution pipe inlet pipe of the jacketed distributor stirring kettle, the gas distribution pipe inlet pipe of the jacketed distributor emulsifying kettle and the gas distribution pipe inlet pipe of the jacketed distributor product stirring kettle.
In the technical scheme, the emulsifying device and the wall scraping stirring device are arranged on the jacketed distributor emulsifying kettle.
In the technical scheme, 2 sets of emulsifying devices and wall scraping stirring devices are arranged on the jacketed distributor emulsifying kettle.
In the above technical solution, the filtering device may be a multi-stage filtering device.
In the technical scheme, the temperature detection instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
The invention has the advantages and beneficial effects that:
1. the method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid adopts a method for synthesizing by improving an emulsification process, and the method is characterized in that gas is introduced into a reaction system in the processes of preparing mixed acid and emulsifying synthesis, so that a large amount of bubbles are generated in the reaction system, 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.
2. The invention adopts an emulsification method to synthesize the 3, 4-methylenedioxy-phenylglyoxylic acid, and utilizes the homogenization function of the emulsification process in the synthesis to ensure that the piperonyl is uniformly dispersed in the glyoxylic acid in the form of tiny liquid drops, thereby improving the contact efficiency between reactants and improving the purity and yield of the product.
3. The emulsifier adopted by the invention is 3, 4-methylenedioxy-phenylglycolic acid, and the method uses the product as the emulsifier according to the principle that the 3, 4-methylenedioxy-phenylglycolic acid has both lipophilic and hydrophilic groups, so that a stable emulsifying system can be formed without introducing substances outside a reaction system, and the product separation process is simpler and easier.
4. According to the invention, a water reducer is added in the reaction process, so that the water reducer can be directionally adsorbed on the surfaces of oil phase liquid drops, the surfaces of the oil phase liquid drops are charged, electrostatic repulsion is generated, the dispersion effect of the water reducer is exerted, the oil phase is dispersed, and the fluidity is increased. Meanwhile, the water reducer has a lubricating effect, hydrophilic groups are increased, a solvated water film is formed, friction is reduced, a pepper ring phase in a viscous stage of a product is more dispersed, the lubricating effect is achieved in a water film form, the mass and heat transfer process of a reaction system is uniform, and the purity and yield of the product are improved.
5. In the reaction process, the method of dropwise adding inert solvents such as dichloromethane, toluene, paraffin oil, naphthenic oil, white oil and the like is adopted, and the inert solvents are not involved in the reaction, so that the conversion rate of the reaction is improved on the basis of increasing the fluidity of the product, and the problem of viscous product is solved. Therefore, one of the solvents can be selected during the selection, or a plurality of solvents can be selected for combination, and the reaction is prevented from being influenced by the large amount of dissolved piperonyl in the reaction system by using a dripping mode.
Drawings
FIG. 1 is a schematic flow chart of an improved emulsion synthesis of 3, 4-methylenedioxy-mandelic acid.
Fig. 2 is a schematic diagram of embodiment 4 of the present invention.
Fig. 3 is a schematic diagram of embodiment 5 of the present invention.
Wherein:
1: jacket formula distributor stirred tank, 2: sulfuric acid metering tank, 3: jacket type distributor emulsifying kettle, 4: pepper ring metering tank, 5: constant temperature tank, 6: filtration device, 7: feed pump, 8: gas holder, 9: a filtrate tank; 12: a jacketed distributor product stirred tank; 13: a feeding metering tank;
6-1: primary filtration equipment, 6-2: secondary filtration device, 10-1: first gas flow meter, 10-2: second gas flowmeter, 10-3: third gas flow meter, 11-1: first liquid flow meter, 11-2: second liquid flow meter, 11-3: a third liquid flow meter.
Other relevant drawings may be made by those of ordinary skill in the art from the above figures without undue burden.
Detailed Description
In order to make the person skilled in the art better understand the solution of the present invention, the following describes the solution of the present invention with reference to specific embodiments.
Comparative example
1. 100g of piper ring, 10g of water, 160g of 50% glyoxylate and 140g of 98% concentrated sulfuric acid are weighed.
2. 10g of water and 160g of 50% glyoxylate aqueous solution were charged into a jacketed reactor.
3. Connecting the jacketed reactor with a constant temperature tank, setting the temperature of the constant temperature tank to 5 ℃, and operating the constant temperature tank to cool for more than half an hour
The temperature of the liquid in the jacket reached 5 ℃.
4. The electric stirrer is connected, and the plastic stirring blade is used for stirring the liquid in the jacketed reactor, and the rotating speed is 400r/min
5. 140g of concentrated sulfuric acid is dropwise added at a constant speed by using a constant pressure funnel, the speed is controlled at 7g/min, and stirring is continued for 30min after the addition.
Obtaining the mixed acid.
6. The mixed acid accounting for 70 percent of the total mass of the mixed acid is removed from the jacketed reactor and refrigerated at 5 ℃.
7. 30g of piper nigrum was added dropwise at a constant speed to the jacketed reactor with a constant pressure funnel, the speed being controlled at 3g/min. After the completion of the dropwise addition, stirring was continued for 30 minutes.
8. 70% of the mixed acid removed in step 6 (dropping time: 1 h) and 70g of piper-ring (dropping time: 0.5 h) were dropped into the jacketed reactor at a constant speed by means of a constant pressure funnel.
9. After the dripping is finished, the speed of the stirring equipment is regulated to 500r/min, and the stirring reaction is continued for 35min
10. 200mL of water was added to the jacketed reactor to terminate the reaction.
11. Filtering with 1L filter flask to obtain solid, weighing, drying, and detecting by liquid chromatography.
12. The yield was 71.42%, purity 68.54% and total yield 44.64%.
Example 1
A method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification, which comprises the following steps:
s1, stirring a mixture of 10g of water and 160g of 50wt% glyoxylate solution at a constant temperature, wherein the constant temperature stirring temperature is-25 ℃, and the stirring speed is 400rpm;
s2, after stirring is started, 98wt% of concentrated sulfuric acid is dropwise added to the mixture, 7g/min of the concentrated sulfuric acid is dropwise added per minute, 140g of the total 98wt% of the concentrated sulfuric acid is dropwise added, the stirring temperature is minus 25 ℃, and the stirring speed is 400rpm;
s3, continuously stirring for 30min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is-25 ℃;
s4, adding 3, 4-methylenedioxy-phenylglycol into the solution after the completion of S3, wherein 4g of 3, 4-methylenedioxy-phenylglycol is added;
s5, emulsifying the solution after the step S4, wherein the emulsifying speed is 12Kr/min, simultaneously dripping piper nigrum rings in the emulsifying process, the dripping amount per minute is 5g, and the emulsifying time is 5min;
s6, repeating the step S5 for 4 times, wherein the interval between every two times is 3min, and adding 100g of total piper nigrum;
and S7, stirring the solution after the completion of the step S6 at a constant temperature, wherein the stirring temperature is 5 ℃, the stirring speed is 500rpm, the stirring time is 30min, and after 15 minutes from the start of stirring, dropwise adding toluene or methylene dichloride, wherein the dropwise adding amount per minute is 20g/min, and the total mass of the dropwise adding toluene or methylene dichloride is 200g. The method comprises the steps of carrying out a first treatment on the surface of the
S8, adding 200ml of water into the solution after the step S7, and stopping the reaction to obtain a product;
the S1-S7 process also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 2.5L/min, and the adopted air blowing medium is nitrogen.
The purity was 88.60% by detection and the total yield was 83.06%.
Example two
A method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification, which comprises the following steps:
s1, stirring a mixture of 10g of water and 160g of 50wt% glyoxylate solution at a constant temperature, wherein the constant temperature stirring temperature is-25 ℃, and the stirring speed is 400rpm;
s2, after stirring is started, 98wt% of concentrated sulfuric acid is dropwise added to the mixture, 7g/min of the concentrated sulfuric acid is dropwise added per minute, 140g of the total 98wt% of the concentrated sulfuric acid is dropwise added, the stirring temperature is minus 25 ℃, and the stirring speed is 400rpm;
s3, continuously stirring for 30min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is-25 ℃;
s4, adding 3, 4-methylenedioxy-phenylglycol into the solution after the completion of S3, wherein 4g of 3, 4-methylenedioxy-phenylglycol is added;
s5, emulsifying the solution after the step S4, wherein the emulsifying speed is 12Kr/min, simultaneously dripping piper nigrum rings in the emulsifying process, the dripping amount per minute is 5g, and the emulsifying time is 5min;
s6, repeating the step S5 for 4 times, wherein the interval between every two times is 3min, and adding 100g of total piper nigrum;
s7, stirring the solution after the step S6 at a constant temperature, wherein the stirring temperature is 5 ℃, the stirring speed is 500rpm, the stirring time is 30min, and the total mass of the dropwise adding liquid antifreezing polycarboxylic acid high-performance water reducer PCE-AF-L-JG/T223-2017 is 3g when stirring starts;
s8, adding 200ml of water into the solution after the step S7, and stopping the reaction to obtain a product;
the S1-S7 process also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 2.5L/min, and the adopted air blowing medium is nitrogen.
The detected purity is 91.50 percent and the total yield is 85.78 percent.
Example III
A method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification, which comprises the following steps:
s1, stirring a mixture of 10g of water and 160g of 50wt% glyoxylate solution at a constant temperature, wherein the constant temperature stirring temperature is-25 ℃, and the stirring speed is 400rpm;
s2, after stirring is started, 98wt% of concentrated sulfuric acid is dropwise added to the mixture, 7g/min of the concentrated sulfuric acid is dropwise added per minute, 140g of the total 98wt% of the concentrated sulfuric acid is dropwise added, the stirring temperature is minus 25 ℃, and the stirring speed is 400rpm;
s3, continuously stirring for 30min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is-25 ℃;
s4, adding 3, 4-methylenedioxy-phenylglycol into the solution after the completion of S3, wherein 4g of 3, 4-methylenedioxy-phenylglycol is added;
s5, emulsifying the solution after the step S4, wherein the emulsifying speed is 12Kr/min, simultaneously dripping piper nigrum rings in the emulsifying process, the dripping amount per minute is 5g, and the emulsifying time is 5min;
s6, repeating the step S5 for 4 times, wherein the interval between every two times is 3min, and adding 100g of total piper nigrum;
s7, stirring the solution after the step S6 at a constant temperature, wherein the stirring temperature is 5 ℃, the stirring speed is 500rpm, the stirring time is 30min, the total mass of the liquid anti-freezing type polycarboxylic acid high-performance water reducer PCE-AF-L-JG/T223-2017 is dropwise added at the beginning of stirring, toluene or methylene dichloride is dropwise added at the beginning of stirring for 15 min, the dropwise adding amount per minute is 20g/min, and the total mass of the toluene or methylene dichloride is dropwise added at the beginning of stirring is 200g;
s8, adding 200ml of water into the solution after the step S7, and stopping the reaction to obtain a product;
the S1-S7 process also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 2.5L/min, and the adopted air blowing medium is nitrogen.
The purity of the product is 97.60% and the total yield is 91.50%.
Example IV
The device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification comprises a jacketed distributor stirring kettle, a sulfuric acid metering tank, a jacketed distributor emulsifying kettle, a jacketed distributor product stirring kettle, a pepper ring metering tank, a constant temperature tank, a feeding metering tank, a filtering device, a feeding pump, a gas storage tank and a filtrate tank, wherein the outlet of the sulfuric acid metering tank is connected with a pipeline of the jacketed distributor stirring kettle, the outlet of the sulfuric acid metering tank is provided with a flowmeter, the outlet of the constant temperature tank is respectively connected with the inlet of the jacket of the jacketed distributor stirring kettle, the inlet of the jacket of the jacketed distributor emulsifying kettle and the inlet of the jacket of the jacketed distributor product stirring kettle by pipelines, the inlet of the constant temperature tank is respectively connected with the outlet of the jacket of the jacketed distributor stirring kettle, the outlet of the jacket distributor emulsifying kettle and the outlet of the jacket distributor product stirring kettle by pipelines, the outlet of the jacketed distributor stirring kettle is connected with an inlet pipeline of a feeding pump, the outlet of the pepper ring metering tank is connected with a jacketed distributor emulsifying kettle pipeline, the outlet of the feeding metering tank is connected with a jacketed distributor product stirring kettle pipeline, the outlet pipe of the feeding metering tank and the outlet pipe of the pepper ring metering tank are both provided with flow meters, the outlet of the jacketed distributor emulsifying kettle is connected with an inlet pipeline of the jacketed distributor product stirring kettle, the outlet of the jacketed distributor product stirring kettle is connected with a feed inlet pipeline of the filtering equipment, the outlet of the air storage tank is respectively connected with a gas distribution pipe inlet of the jacketed distributor stirring kettle, a gas distribution pipe inlet of the jacketed distributor emulsifying kettle and a gas distribution pipe inlet of the jacketed distributor product stirring kettle by pipelines, and the liquid phase outlet of the filtering equipment is connected with the inlet of the filtrate tank. The jacket inlet pipe of the jacket type distributor stirring kettle, the jacket inlet pipe of the jacket type distributor emulsifying kettle and the jacket inlet pipe of the jacket type distributor product stirring kettle are respectively provided with a liquid flowmeter. Gas flow meters are arranged on the gas distribution pipe inlet pipe of the jacketed distributor stirring kettle, the gas distribution pipe inlet pipe of the jacketed distributor emulsifying kettle and the gas distribution pipe inlet pipe of the jacketed distributor product stirring kettle. And 2 sets of emulsifying devices and wall scraping stirring devices are arranged on the jacketed distributor emulsifying kettle. And temperature detection instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
Example five
An improved device for emulsifying and synthesizing 3, 4-methylenedioxy-phenylglycolic acid comprises a jacketed distributor stirring kettle, a sulfuric acid metering tank, a jacketed distributor emulsifying kettle, a jacketed distributor product stirring kettle, a pepper ring metering tank, a constant temperature tank, a feeding metering tank, two-stage filtering equipment, a feeding pump, a gas storage tank and a filtrate tank, wherein the outlet of the sulfuric acid metering tank is connected with a pipeline of the jacketed distributor stirring kettle, the outlet of the sulfuric acid metering tank is provided with a flowmeter, the outlet of the constant temperature tank is respectively connected with the inlet of the jacket of the jacketed distributor stirring kettle, the inlet of the jacket of the jacketed distributor emulsifying kettle and the inlet of the jacket of the jacketed distributor product stirring kettle by adopting pipelines, the inlet of the constant temperature tank is respectively connected with the outlet of the jacket of the jacketed distributor stirring kettle, the outlet of the jacket distributor emulsifying kettle and the outlet of the jacket distributor product stirring kettle, the outlet of the jacketed distributor stirring kettle is connected with an inlet pipeline of a feeding pump, the outlet of the pepper ring metering tank is connected with a jacketed distributor emulsifying kettle pipeline, the outlet of the feeding metering tank is connected with a jacketed distributor product stirring kettle pipeline, the outlet pipe of the feeding metering tank and the outlet pipe of the pepper ring metering tank are both provided with flow meters, the outlet of the jacketed distributor emulsifying kettle is connected with an inlet pipeline of the jacketed distributor product stirring kettle, the outlet of the jacketed distributor product stirring kettle is connected with a feed inlet pipeline of a primary filter device, the discharge port of the primary filter device is connected with a feed inlet pipeline of a secondary filter device, and the outlet of the air storage tank is respectively connected with the inlet of a gas distribution pipe of the jacketed distributor stirring kettle by pipelines, the gas distribution pipe inlet of the jacketed distributor emulsifying kettle and the gas distribution pipe inlet of the jacketed distributor product stirring kettle are connected with the liquid phase outlet of the secondary filtering device, and the liquid phase outlet of the secondary filtering device is connected with the filtrate tank inlet. The jacket inlet pipe of the jacket type distributor stirring kettle, the jacket inlet pipe of the jacket type distributor emulsifying kettle and the jacket inlet pipe of the jacket type distributor product stirring kettle are respectively provided with a liquid flowmeter. Gas flow meters are arranged on the gas distribution pipe inlet pipe of the jacketed distributor stirring kettle, the gas distribution pipe inlet pipe of the jacketed distributor emulsifying kettle and the gas distribution pipe inlet pipe of the jacketed distributor product stirring kettle. And 2 sets of emulsifying devices and wall scraping stirring devices are arranged on the jacketed distributor emulsifying kettle. And temperature detection instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
The primary filter equipment and the secondary filter equipment adopt filter media with different precision, the pore diameter of the filter media adopted on the primary filter equipment is larger, products with larger granularity in a product system can be filtered out, filtrate enters the secondary filter equipment, the pore diameter of the filter media adopted by the secondary filter equipment is smaller, 3, 4-methylenedioxy-phenylglycolic acid which is a final product with smaller granularity can be filtered out, and the product recovery is more sufficient.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. A method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification, which is characterized by comprising the following steps:
step 1, mixing the following components in percentage by mass: 50wt% glyoxylate aqueous solution = 1: stirring the mixture of 15-20 at a constant temperature, wherein the constant temperature is-30 ℃ to-20 ℃, and the stirring speed is 350 rpm-450 rpm;
step 2, after stirring is started, 98wt% of concentrated sulfuric acid is dropwise added to the mixture, wherein the dropwise adding amount per minute is 0.03-0.1 time of the mass of the mixture, and the ratio of the total 98wt% of concentrated sulfuric acid to the mass of water in the step 1 is 98wt% of concentrated sulfuric acid: water=12 to 15:1, stirring at the temperature of minus 30 ℃ to minus 20 ℃;
step 3, continuously stirring for 20-40 min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is-30 ℃ to-20 ℃;
step 4, adding 3, 4-methylenedioxy-mandelic acid to the solution after completion of step 3, wherein the ratio of the amount of 3, 4-methylenedioxy-mandelic acid added to the water mass in step 1 is 3, 4-methylenedioxy-mandelic acid: water=0.1 to 1:1, a step of;
step 5, emulsifying the solution obtained in the step 4 at the speed of 10-15 Kr/min, and simultaneously dripping piper nigrum in the amount which is 0.1-1 times of the water in the step 1 per minute for 3-10 min;
step 6, repeating the step 5 for more than two times, wherein the interval between each two times is 3-10 min, and the ratio of the total amount of the added piper nigrum to the water mass in the step 1 is piper nigrum: water=10 to 15:1, a step of;
step 7, stirring the solution after the step 6 at a constant temperature, wherein the stirring temperature is 0-10 ℃, the stirring speed is 400-600 rpm, the stirring time is 20-40 min, and the inert solvent and/or the water reducer are/is dropwise added in the stirring process;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total addition 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 added stop solution is water;
the process of the steps 1-7 also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 7-20 times of the volume of the mixture.
2. The method for improving the emulsification synthesis of 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in the step 1, the mass ratio is as follows: 50wt% glyoxylate aqueous solution = 1: and (3) stirring the mixture at a constant temperature of 15-17, wherein the constant temperature stirring temperature is minus 28 ℃ to minus 23 ℃, and the stirring speed is 380 rpm-420 rpm.
3. The method for improved emulsification synthesis of 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein the ratio of the amount of 3, 4-methylenedioxy-mandelic acid added to the water mass in step 1 in step 4 is 3, 4-methylenedioxy-mandelic acid: water=0.4 to 1:1.
4. the method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification according to claim 1, wherein in the step 5, the emulsification speed is 12-15 Kr/min, the pepper rings are added dropwise at the same time during emulsification, the adding amount per minute is 0.5-1 time of the water mass in the step 1, and the emulsification time is 5-10 min.
5. The method for synthesizing 3, 4-methylenedioxy-mandelic acid by improved emulsification according to claim 1, wherein in the step 6, the step 5 is repeated 3 to 8 times, each time is separated by 3 to 10 minutes, and the ratio of the total amount of the added piper ring to the water mass in the step 1 is the piper ring: water=10 to 12:1.
6. the method for synthesizing 3, 4-methylenedioxy-mandelic acid by improved emulsification according to claim 1, wherein in the step 7, the inert solvent is dichloromethane, toluene, paraffin oil, naphthenic oil and white oil, the drop amount per minute is 1.5-3 times of the water mass in the step 1, and the total mass of the drop inert solvent is 15-30 times of the water mass in the step 1.
7. The method for improving the emulsification synthesis of 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in the step 7, the water reducing agent is a polycarboxylic acid type high performance water reducing agent, and the ratio of the total amount of the polycarboxylic acid type high performance water reducing agent added to the water mass in the step 1 is the polycarboxylic acid type high performance water reducing agent: water=0.15 to 0.3:1.
8. the method for synthesizing 3, 4-methylenedioxy-mandelic acid by improved emulsification according to claim 1, wherein in the step 7, the inert solvent is added dropwise in a manner that the inert solvent is added dropwise 10 to 20 minutes after the start of the step 7, the amount of the inert solvent added dropwise per minute is 1.5 to 3 times the water mass in the step 1, and the total mass of the inert solvent added dropwise is 15 to 30 times the water mass in the step 1.
9. The method for improving the emulsion synthesis of 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in the step 8, the added stop solution is water, and the ratio of the total added stop solution to the water in the step 1 is the stop solution: water=15 to 25:1.
10. the device for improving the emulsification synthesis of the 3, 4-methylenedioxy-phenylglycolic acid comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor stirred tank, a pepper ring metering tank, a constant temperature tank, a charging metering tank, a filtering device, a charging pump, a gas storage tank and a filtrate tank, wherein the outlet of the sulfuric acid metering tank is connected with a jacketed distributor stirred tank pipeline, the outlet of a circulating liquid of the constant temperature tank is respectively connected with the jacketed inlet of the jacketed distributor stirred tank, the jacketed inlet of the jacketed distributor stirred tank and the jacketed inlet of the jacketed distributor stirred tank, the inlet of the constant temperature tank circulating liquid is respectively connected with the jacketed outlet of the jacketed distributor stirred tank, the jacketed outlet of the jacketed distributor stirred tank and the jacketed outlet of the jacketed distributor stirred tank, the outlet of the jacketed distributor stirred tank is connected with an inlet pipeline of the charging pump, the outlet of the pepper ring metering tank is connected with the jacketed distributor stirred tank pipeline, the outlet of the jacketed distributor stirred tank is connected with the inlet of the gas storage tank, and the inlet of the gas inlet of the jacketed distributor stirred tank is connected with the gas inlet of the gas inlet distributor stirred tank;
the filtration device is a multi-stage filtration device;
and temperature detection instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
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