CN110862370B - Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by enhancing emulsification - Google Patents
Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by enhancing emulsification Download PDFInfo
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- CN110862370B CN110862370B CN201810984094.9A CN201810984094A CN110862370B CN 110862370 B CN110862370 B CN 110862370B CN 201810984094 A CN201810984094 A CN 201810984094A CN 110862370 B CN110862370 B CN 110862370B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
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Abstract
The invention discloses a method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid, which 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 number 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. By utilizing the homogenization of the emulsification process, the piperonyl is uniformly dispersed in the glyoxylic acid in the form of tiny liquid drops, so that the contact efficiency between reactants can be improved, and the purity and yield of the product can be improved. The product is used as an emulsifying agent, so that a stable emulsifying system can be formed without introducing substances outside the reaction system, and the product separation process is simpler and easier. In the reaction process, the emulsified solution is dispersed into fine liquid drops by adopting the loop reactor with the Venturi ejector and the circulating suspension bed reactor to form a micro reaction system, so that the heat and mass transfer efficiency is improved, and the problem of byproducts caused by uneven heat transfer is solved.
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 enhancing 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 enhancing emulsification to synthesize 3, 4-methylenedioxy-benzilic acid.
The invention is realized by the following technical scheme:
a method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by enhancing 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 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 the 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;
step 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, uniformly mixing the solution after the step 6 by a loop reactor with a Venturi ejector, and then entering a suspension bed reactor for continuous reaction, wherein the temperature in the suspension bed reactor is 0-10 ℃, an external circulation loop of the loop reactor with the Venturi ejector is provided with a heat exchanger, the temperature of a solution outlet of the heat exchanger is-30-20 ℃, the diameter of bubbles in the loop reactor is 0.01-0.07 mm, the gas flow in the Venturi ejector is 100-200 times/min of the volume of the mixture in the step 1, and the mixing reaction time in the suspension bed reactor is 3-10 min;
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 the step 1 to the step 6 also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 7 to 20 times of the volume of the mixture in the step 1.
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 is 3, 4-methylenedioxy-mandelic acid: water=0.1 to 0.4:1.
in the technical scheme, in the step 5, the emulsifying speed is 10-12 Kr/min, the pepper ring is added dropwise at the same time during emulsifying, the adding amount per minute is 0.5-0.8 times of the water mass, and the emulsifying time is 5-10 min.
In the above technical scheme, step 6, step 5 is repeated 3-8 times, each time is separated by 3-10 min, and the ratio of the total amount of the added piper ring to the water mass is piper ring: water=10 to 12:1.
in the above technical solution, in step 7, the heat exchange medium in the heat exchanger is ethylene glycol.
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.
in the technical scheme, the method comprises the following steps of:
step 1, mixing the following components in percentage by mass: 50wt% glyoxylate aqueous solution = 1: stirring the mixture at a constant temperature of 14-16, wherein the constant temperature stirring temperature is minus 30 ℃ to minus 25 ℃ and the stirring speed is 400rpm;
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 0.03-0.07 times of the mass of the mixture, and the mass ratio of the total 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 a temperature of-30 ℃ to-20 ℃;
step 3, continuously stirring for 20-30 min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 30 ℃ to minus 25 ℃;
step 4, adding 3, 4-methylenedioxy-phenylglyoxylic acid into the solution after the completion of the step 3, wherein the mass ratio of the added 3, 4-methylenedioxy-phenylglyoxylic acid to the water in the step 1 is 3, 4-methylenedioxy-phenylglyoxylic acid: water=0.3 to 0.4:1, a step of;
step 5, emulsifying the solution after the step 4, wherein the emulsifying speed is 11-12 Kr/min, simultaneously dropwise adding a piper ring in the emulsifying process, wherein the dropwise adding amount per minute is 0.5-0.6 time of the water mass in the step 1, and the emulsifying time is 3-5 min;
step 6, repeating the step 5 for a plurality of times, wherein the interval between each time is 3-10 min, and the mass ratio of the total amount of the added piper nigrum to the water in the step 1 is that the piper nigrum: water=10 to 11:1, a step of;
step 7, uniformly mixing the solution after the step 6 by a loop reactor with a Venturi ejector, then entering a suspension bed reactor for continuous reaction, wherein the temperature in the suspension bed reactor is 0-5 ℃, an external circulation loop of the loop reactor with the Venturi ejector is provided with a heat exchanger, the temperature of the solution outlet of the heat exchanger is-25-20 ℃, the diameter of bubbles in the loop reactor is 0.03-0.05 mm, the gas flow rate in the Venturi ejector is 100-150 times/min of the volume of the mixture in the step 1, and the mixing reaction time in the suspension bed reactor is 4-8 min;
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 20:1, terminating the reaction to obtain a product;
the process of step 1 to step 6 also comprises the process of blowing air into the solution, and the air blowing amount per minute is 12-20 times of the volume of the mixture in step 1.
In the above technical scheme, the air-blowing medium adopted in the air-blowing process is nitrogen.
The device for enhancing the emulsification synthesis of 3, 4-methylenedioxy-phenylglycolic acid comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor emulsified tank, a jacketed distributor product stirred tank, a loop reactor with a Venturi ejector, a circulating suspension bed reactor, a pepper ring metering tank, a constant temperature tank, a filtering device, a charging pump, a gas storage tank and a filtrate tank, wherein the sulfuric acid metering tank outlet is connected with a pipeline of the jacketed distributor stirred tank, the constant temperature tank circulating liquid outlet is respectively connected with the jacket inlet of the jacketed distributor stirred tank, the heat exchange medium inlet of a heat exchanger and the jacket inlet of the jacketed distributor product stirred tank, the constant temperature tank circulating liquid inlet is respectively connected with the jacket outlet of the jacketed distributor stirred tank, the heat exchange medium outlet of the heat exchanger and the jacket outlet of the jacketed distributor product stirred tank, the outlet of the jacketed distributor stirred tank is connected with the inlet pipeline of the Venturi ejector, the outlet of the pumped circulation bed reactor is connected with the inlet of the venturi distributor stirred tank, the outlet of the liquid phase distributor stirred tank is connected with the inlet of the venturi distributor stirred tank, and the inlet of the circulating reactor is connected with the inlet of the venturi ejector stirred tank, and the inlet of the circulating bed reactor is connected with the inlet of the circulating bed reactor, and the circulating bed reactor is connected with the circulating bed reactor, 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 filtering equipment, and the liquid phase outlet of the filtering equipment is connected with the inlet of the filtrate tank.
In the above technical scheme, the loop reactor with venturi ejector includes venturi ejector, high-pressure reaction kettle, return circuit circulating pump and heat exchanger, wherein venturi ejector sets up upper portion in the high-pressure reaction kettle, high-pressure reaction kettle lower part is provided with material export and circulation export, circulation export with the entry linkage of return circuit circulating pump, the exit linkage of return circuit circulating pump the material entry of heat exchanger, the material exit linkage of heat exchanger the material entry at high-pressure reaction kettle top.
In the technical scheme, the outlet pipes of the sulfuric acid metering tank and the pepper ring metering tank are respectively provided with a flowmeter.
In the technical scheme, the sulfuric acid metering tank is arranged above the stirring kettle of the jacketed distributor, and the pepper ring metering tank is arranged above the emulsifying kettle of the jacketed distributor.
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, the heat exchange medium inlet pipe of the heat exchanger and the jacket inlet pipe of the jacket type distributor product stirring kettle.
In the technical scheme, 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 are respectively provided with a gas flowmeter.
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 above technical solution, the filtering device may be a 2-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 enhancing 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. In the reaction process, the emulsified solution is dispersed into fine liquid drops by adopting the loop reactor with the Venturi ejector and the circulating suspension bed reactor to form countless tiny reaction systems, and the reaction systems react independently, so that the heat and mass transfer efficiency is improved, and the problem of byproducts caused by uneven heat transfer is solved.
5. The invention adopts a loop reactor with a Venturi ejector, wherein the Venturi ejector (instead of a gas distributor or other gas dispersing systems) is a high-performance gas-liquid mixing device, and is a unique intensified mixing structure. It is composed of four parts, turbulent nozzle, air chamber, gas circulation pipeline and pipe. The pumped liquid is sprayed out through the nozzle to form a rapid jet flow, and the gas in the gas carrying chamber is sprayed out, so that the liquid impacts on the pipe wall to form energy consumption. This creates a strong mixing shock zone in which the intense turbulence spreads the foam well. The gas foam generated by the impact is very small, and the gas-liquid ratio reaches more than 0.5 to 2.0. Therefore, the device is an ideal initial foremost dispersing device for the loop reactor to carry out gas-liquid reaction, achieves the initial foremost mass transfer function, and then the gas-liquid two-phase mixture is sprayed into the liquid storage in the high-pressure reaction kettle. The autoclave does not require a baffle plate, and generally has a large aspect ratio compared to a stirred tank reactor, which reduces manufacturing costs and provides substantial savings in the manufacture of loop reactors for high pressures. The two-phase mixture injected by the venturi injector above is injected into the autoclave causing a second vigorous mixing, again achieving good mass transfer performance. The mass transfer is completed by small bubbles in the reaction kettle, the diameter of the small bubbles is between 0.03 and 0.07mm, and the diameter of the small bubbles is larger than that of the bubbles in the Venturi injection gas, because the small bubbles in the Venturi injector are polymerized at the moment.
The external heat exchanger (instead of coil or internal heat exchanger) is not limited in size by the volume of the reaction vessel (reaction vessel) as compared with the conventional internal heat exchanger. The external heat exchanger can work in full heat exchange area, even under the condition of reducing the working volume, such as semi-batch operation or semi-kettle material reaction.
The loop circulation pump (instead of the agitator) achieves a very high working volume output to achieve the high mass transfer efficiency formation requirement. The new circulation pump is capable of delivering a reaction mixture of high solids content (8% by mass) and high air load (30% by volume of gas foam).
Drawings
FIG. 1 is a schematic flow chart of an enhanced emulsification synthesis of 3, 4-methylenedioxy-mandelic acid.
Fig. 2 is a schematic diagram of embodiment 3 of the present invention.
FIG. 3 is a schematic of a loop reactor with venturi ejectors in example 3 of the present invention.
Fig. 4 is a schematic diagram of embodiment 4 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: jacketed distributor product stirred tank, 13: loop reactor with venturi ejector, 14: a circulating suspended bed reactor;
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 flowmeter, 10-4: fourth gas flow meter, 11-1: first liquid flow meter, 11-2: second liquid flow meter, 11-3: third liquid flow meter, 11-4: fourth liquid flow meter, 13-1: high-pressure reaction kettle, 13-2: loop circulation pump, 13-3: heat exchanger, 13-4: a venturi eductor.
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. The jacketed reactor is connected with a constant temperature tank, the temperature of the constant temperature tank is set to be 5 ℃, and the constant temperature tank is operated to cool for more than half an hour until the temperature of liquid in the jacket reaches 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 enhancing emulsification, which comprises the following steps:
step 1, stirring a mixture of 10g of water and 160g of 50wt% glyoxylate solution at a constant temperature, wherein the constant stirring temperature is-25 ℃, and the stirring speed is 400rpm;
step 2, after stirring is started, 98 weight percent of concentrated sulfuric acid is dropwise added into the mixture, 7g/min of the concentrated sulfuric acid is dropwise added per minute, 140g of the total 98 weight percent of the concentrated sulfuric acid is dropwise added, the stirring temperature is minus 25 ℃, and the stirring speed is 400rpm;
step 3, continuously stirring for 30min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 25 ℃;
step 4, adding 3, 4-methylenedioxy-phenylglycolic acid and benzyl triethyl ammonium chloride into the solution after the completion of the step 3, wherein the amount of the added 3, 4-methylenedioxy-phenylglycolic acid is 4g, and the amount of the added benzyl triethyl ammonium chloride is 8g;
step 5, emulsifying the solution after the step 4, wherein the emulsifying speed is 12Kr/min, and simultaneously dropwise adding piper nigrum rings in the emulsifying process, wherein the dropwise adding amount is 5g per minute, and the emulsifying time is 5min;
step 6, repeating the step 5 for 4 times, wherein the interval between each time is 3min, and adding 100g of total piper nigrum;
step 7, uniformly mixing the solution after the step 6 by a loop reactor with a Venturi ejector, and then entering a suspension bed reactor for continuous reaction, wherein the temperature in the suspension bed reactor is 5 ℃, a heat exchanger is arranged in an external circulation loop of the loop reactor with the Venturi ejector, the temperature of a solution outlet of the heat exchanger is-25 ℃ to-20 ℃, the diameter of bubbles in the loop reactor is 0.03mm, the gas flow rate in the Venturi ejector is 20L/min, and the mixing reaction time in the suspension bed reactor is 5min;
step 8, adding 200ml of water into the solution after the step 7 is finished, and stopping the reaction to obtain a product;
the steps 1-6 also comprise the process of blowing air into the solution, the air blowing amount per minute is 2.5L/min, and the adopted air blowing medium is nitrogen.
The purity of the product is 98.00% and the total yield is 95.20%.
Example 2
A method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by enhancing emulsification, which comprises the following steps:
step 1, stirring a mixture of 10g of water and 200g of 50wt% glyoxylate solution at a constant temperature, wherein the constant temperature stirring temperature is minus 30 ℃, and the stirring speed is 430rpm;
step 2, after stirring is started, 98 weight percent of concentrated sulfuric acid is dropwise added into the mixture, 9g/min of the total amount of 98 weight percent of concentrated sulfuric acid is dropwise added per minute, 150g of the total amount of 98 weight percent of concentrated sulfuric acid is dropwise added, the stirring temperature is minus 28 ℃, and the stirring speed is 430rpm;
step 3, continuously stirring for 30min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 28 ℃;
step 4, adding 3, 4-methylenedioxy-benzilic acid to the solution after the completion of step 3, and adding 9g of 3, 4-methylenedioxy-benzilic acid;
step 5, emulsifying the solution after the step 4, wherein the emulsifying speed is 15Kr/min, simultaneously dripping piper nigrum rings in the emulsifying process, the dripping amount per minute is 5g, and the emulsifying time is 7min;
step 6, repeating the step 5 for 4 times, wherein the interval between each time is 3min, and 140g of total piper nigrum is added;
step 7, uniformly mixing the solution after the step 6 by a loop reactor with a Venturi ejector, and then entering a suspension bed reactor for continuous reaction, wherein the temperature in the suspension bed reactor is 7 ℃, a heat exchanger is arranged in an external circulation loop of the loop reactor with the Venturi ejector, the temperature of the solution outlet of the heat exchanger is-20 ℃, the diameter of bubbles in the loop reactor is 0.03mm, the gas flow rate in the Venturi ejector is 25L/min, and the mixing reaction time in the suspension bed reactor is 4min;
step 8, adding 200ml of water into the solution after the step 7 is finished, and stopping the reaction to obtain a product;
the steps 1-6 also comprise the process of blowing air into the solution, the air blowing amount per minute is 2.5L/min, and the adopted air blowing medium is nitrogen.
The detected purity is 97.53 percent and the total yield is 91.43 percent.
Example 3
The utility model provides a device of reinforcing emulsification synthesis 3, 4-methylenedioxy phenylglycol acid, includes jacket formula distributor stirred tank, sulfuric acid metering tank, jacket formula distributor emulsifying tank, jacket formula distributor product stirred tank has venturi ejector's loop reactor, circulating suspended bed reactor, and the pepper ring metering tank, constant temperature tank, filtration equipment, charge pump, gas holder, filtrate tank, sulfuric acid metering tank export links to each other with jacket formula distributor stirred tank pipeline, sulfuric acid metering tank sets up the top of jacket formula distributor stirred tank, constant temperature tank circulation liquid outlet adopts the pipe connection respectively jacket entry of jacket formula distributor stirred tank, jacket formula distributor emulsifying tank's jacket entry, heat transfer medium entry and the jacket formula distributor product stirred tank of heat exchanger, constant temperature tank circulation liquid entry adopts the pipe connection jacket export of jacket formula distributor stirred tank, jacket formula distributor emulsifying tank's jacket export, the heat transfer medium export of heat transfer medium of heat exchanger and jacket formula distributor product stirred tank, the export of jacket formula distributor stirred tank, the outlet of jacket formula distributor stirred tank pipeline links to each other with jacket formula distributor stirred tank's jacket, jacket formula distributor stirred tank's outlet links to each other with the pipe, jacket formula distributor stirred tank metering tank and jacket meter stirred tank, the jacket is provided with the equal pipe is equipped with the jacket and is equipped with the equal to the pipe of jacket type distributor stirred tank. The loop reactor with the Venturi ejector comprises the Venturi ejector, a high-pressure reaction kettle, a loop circulating pump and a heat exchanger, wherein the Venturi ejector is arranged at the upper part in the high-pressure reaction kettle, a material outlet and a circulating outlet are arranged at the lower part of the high-pressure reaction kettle, the circulating outlet is connected with an inlet of the loop circulating pump, an outlet of the loop circulating pump is connected with a material inlet of the heat exchanger, and a material outlet of the heat exchanger is connected with a material inlet at the top of the high-pressure reaction kettle. The outlet of the jacketed distributor emulsifying kettle is connected with the inlet of the loop circulating pump of the loop reactor with the Venturi ejector, the material outlet arranged at the lower part of the high-pressure reaction kettle of the loop reactor with the Venturi ejector is connected with the inlet pipeline of the circulating suspended bed reactor, the outlet of the circulating suspended bed reactor is connected with the inlet pipeline of the jacketed distributor product stirring kettle, the outlet of the jacketed distributor product stirring kettle is connected with the inlet pipeline of the filtering equipment, the outlet of the air storage tank is respectively connected with the inlet of the gas distribution pipe of the jacketed distributor stirring kettle, the inlet of the gas distribution pipe of the jacketed distributor emulsifying kettle, the inlet of the Venturi ejector of the loop reactor and the inlet of the gas distribution pipe of the jacketed distributor product stirring kettle, the liquid phase outlet of the filtering equipment is connected with the inlet of the filtrate tank, and temperature detection meters are respectively arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
The jacket inlet pipe of the jacket type distributor stirring kettle, the jacket inlet pipe of the jacket type distributor emulsifying kettle, the heat exchange medium inlet pipe of the heat exchanger and the jacket inlet pipe of the jacket type distributor product stirring kettle are all provided with liquid flow meters. The gas flow meters are arranged on the gas inlet pipe of the venturi ejector and the gas inlet pipe of the jacketed distributor product stirring kettle.
Example 4
The utility model provides a device of reinforcing emulsification synthesis 3, 4-methylenedioxy phenylglycol acid, includes jacket formula distributor stirred tank, sulfuric acid metering tank, jacket formula distributor emulsifying tank, jacket formula distributor product stirred tank has venturi ejector's loop reactor, circulating suspended bed reactor, and the pepper ring metering tank, constant temperature tank, filtration equipment, charge pump, gas holder, filtrate tank, sulfuric acid metering tank export links to each other with jacket formula distributor stirred tank pipeline, sulfuric acid metering tank sets up the top of jacket formula distributor stirred tank, constant temperature tank circulation liquid outlet adopts the pipe connection respectively jacket entry of jacket formula distributor stirred tank, jacket formula distributor emulsifying tank's jacket entry, heat transfer medium entry and the jacket formula distributor product stirred tank of heat exchanger, constant temperature tank circulation liquid entry adopts the pipe connection jacket export of jacket formula distributor stirred tank, jacket formula distributor emulsifying tank's jacket export, the heat transfer medium export of heat transfer medium of heat exchanger and jacket formula distributor product stirred tank, the export of jacket formula distributor stirred tank, the outlet of jacket formula distributor stirred tank pipeline links to each other with jacket formula distributor stirred tank's jacket, jacket formula distributor stirred tank's outlet links to each other with the pipe, jacket formula distributor stirred tank metering tank and jacket meter stirred tank, the jacket is provided with the equal pipe is equipped with the jacket and is equipped with the equal to the pipe of jacket type distributor stirred tank. The loop reactor with the Venturi ejector comprises the Venturi ejector, a high-pressure reaction kettle, a loop circulating pump and a heat exchanger, wherein the Venturi ejector is arranged at the upper part in the high-pressure reaction kettle, a material outlet and a circulating outlet are arranged at the lower part of the high-pressure reaction kettle, the circulating outlet is connected with an inlet of the loop circulating pump, an outlet of the loop circulating pump is connected with a material inlet of the heat exchanger, and a material outlet of the heat exchanger is connected with a material inlet at the top of the high-pressure reaction kettle. The outlet of the circulating suspended bed reactor is connected with the inlet pipeline of the jacketed distributor product stirring kettle, the outlet of the jacketed distributor product stirring kettle is connected with the inlet pipeline of the primary filtering equipment, the discharge port of the primary filtering equipment is connected with the inlet pipeline of the secondary filtering equipment, the outlet of the air storage tank is respectively connected with the gas distribution pipe inlet of the jacketed distributor stirring kettle, the gas inlet of the venturi sprayer of the loop reactor and the gas distribution pipe inlet of the jacketed distributor product stirring kettle, the liquid phase outlet of the secondary filtering equipment is connected with the inlet of the filtrate tank, and temperature detection meters are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
The jacket inlet pipe of the jacket type distributor stirring kettle, the jacket inlet pipe of the jacket type distributor emulsifying kettle, the heat exchange medium inlet pipe of the heat exchanger and the jacket inlet pipe of the jacket type distributor product stirring kettle are all provided with liquid flow meters. The gas flow meters are arranged on the gas inlet pipe of the venturi ejector and the gas inlet pipe of the jacketed distributor product stirring 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 enhancing 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 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 the 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-phenylglyoxylic acid into the solution after the completion of the step 3, wherein the mass ratio of the added 3, 4-methylenedioxy-phenylglyoxylic acid to the water in the step 1 is 3, 4-methylenedioxy-phenylglyoxylic 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;
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, uniformly mixing the solution after the step 6 by a loop reactor with a Venturi ejector, and then entering a suspension bed reactor for continuous reaction, wherein the temperature in the suspension bed reactor is 0-10 ℃, an external circulation loop of the loop reactor with the Venturi ejector is provided with a heat exchanger, the temperature of a solution outlet of the heat exchanger is-30-20 ℃, the diameter of bubbles in the loop reactor is 0.01-0.07 mm, the gas flow in the Venturi ejector is 100-200 times/min of the volume of the mixture in the step 1, and the mixing reaction time in the suspension bed reactor is 3-10 min;
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, wherein the added termination liquid is water;
the process of the step 1 to the step 6 also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 7 to 20 times of the volume of the mixture in the step 1.
2. The method for enhancing emulsification synthesis of 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in step 1, the mass ratio is water: 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.
3. The method for enhancing the emulsion synthesis of 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in said step 4, the ratio of the amount of 3, 4-methylenedioxy-mandelic acid added to the water mass is 3, 4-methylenedioxy-mandelic acid: water=0.1 to 0.4:1.
4. the method for synthesizing 3, 4-methylenedioxy-mandelic acid by enhancing emulsification according to claim 1, wherein in the step 5, the emulsification speed is 10-12 Kr/min, the pepper rings are added dropwise at the same time during emulsification, the adding amount per minute is 0.5-0.8 times of the water mass, and the emulsification time is 5-10 min.
5. The method for synthesizing 3, 4-methylenedioxy-mandelic acid by enhanced emulsification according to claim 1, wherein in the step 6, the step 5 is repeated 3 to 8 times at intervals of 3 to 10 minutes each time, and the ratio of the total amount of added piper ring to the water mass is piper ring: water=10 to 12:1.
6. the method for enhancing emulsification 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 amount of the stop solution added to the water mass in the step 1 is the stop solution: water=15 to 25:1.
7. the method for enhanced emulsification synthesis of 3, 4-methylenedioxy-mandelic acid according to claim 1, characterized by 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 14-16, wherein the constant temperature stirring temperature is minus 30 ℃ to minus 25 ℃ and the stirring speed is 400rpm;
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 0.03-0.07 times of the mass of the mixture, and the mass ratio of the total 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 a temperature of-30 ℃ to-20 ℃;
step 3, continuously stirring for 20-30 min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 30 ℃ to minus 25 ℃;
step 4, adding 3, 4-methylenedioxy-phenylglyoxylic acid into the solution after the completion of the step 3, wherein the mass ratio of the added 3, 4-methylenedioxy-phenylglyoxylic acid to the water in the step 1 is 3, 4-methylenedioxy-phenylglyoxylic acid: water=0.3 to 0.4:1, a step of;
step 5, emulsifying the solution after the step 4, wherein the emulsifying speed is 11-12 Kr/min, simultaneously dropwise adding a piper ring in the emulsifying process, wherein the dropwise adding amount per minute is 0.5-0.6 time of the water mass in the step 1, and the emulsifying time is 3-5 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 mass ratio of the total amount of the added piper nigrum to the water in the step 1 is that the piper nigrum: water=10 to 11:1, a step of;
step 7, uniformly mixing the solution after the step 6 by a loop reactor with a Venturi ejector, then entering a suspension bed reactor for continuous reaction, wherein the temperature in the suspension bed reactor is 0-5 ℃, an external circulation loop of the loop reactor with the Venturi ejector is provided with a heat exchanger, the temperature of the solution outlet of the heat exchanger is-25-20 ℃, the diameter of bubbles in the loop reactor is 0.03-0.05 mm, the gas flow rate in the Venturi ejector is 100-150 times/min of the volume of the mixture in the step 1, and the mixing reaction time in the suspension bed reactor is 4-8 min;
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 20:1, terminating the reaction to obtain a product, wherein the added termination liquid is water;
the process of step 1 to step 6 also comprises the process of blowing air into the solution, and the air blowing amount per minute is 12-20 times of the volume of the mixture in step 1.
8. The method for synthesizing 3, 4-methylenedioxy-mandelic acid by enhanced emulsification according to any one of claims 1 to 7, wherein the aeration medium used in the aeration process is nitrogen.
9. The device for enhancing the emulsification synthesis of 3, 4-methylenedioxy-phenylglycolic acid comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor stirred tank, a loop reactor with a Venturi ejector, a circulating suspension bed reactor, a pepper ring metering tank, a constant temperature 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 pipeline of the jacketed distributor stirred tank, the outlet of the constant temperature tank is respectively connected with the inlet of the jacketed distributor stirred tank by adopting a pipeline, the inlet of the jacket of the jacketed distributor stirred tank, the inlet of a heat exchange medium of a heat exchanger and the inlet of the jacket distributor stirred tank are respectively connected with the outlet of the jacket distributor stirred tank, the outlet of the heat exchange medium of the heat exchanger and the outlet of the jacket distributor stirred tank are respectively connected with the inlet pipeline of the Venturi distributor stirred tank, the outlet of the venturi distributor stirred tank is connected with the inlet of the venturi distributor stirred tank, the outlet of the venturi distributor stirred tank is connected with the inlet of the circulating reactor, the inlet of the venturi distributor stirred tank is connected with the inlet of the product stirred tank, the outlet of the venturi distributor stirred tank is connected with the inlet of the circulating reactor, the outlet of the gas storage tank is connected with the gas distribution pipe inlet of the jacketed distributor stirring kettle, the gas distribution pipe inlet of the jacketed distributor emulsifying kettle and the gas distribution pipe inlet of the jacketed distributor product stirring kettle through pipelines respectively, and the liquid phase outlet of the filtering equipment is connected with the filtrate tank inlet;
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.
10. The apparatus for enhanced emulsification synthesis of 3, 4-methylenedioxy-benzene glycolic acid according to claim 9, wherein the loop reactor having a venturi ejector comprises a venturi ejector, a high pressure reaction vessel, a loop circulation pump and a heat exchanger, wherein the venturi ejector is provided at an upper portion inside the high pressure reaction vessel, a material outlet and a circulation outlet are provided at a lower portion of the high pressure reaction vessel, the circulation outlet is connected to an inlet of the loop circulation pump, an outlet of the loop circulation pump is connected to a material inlet of the heat exchanger, and a material outlet of the heat exchanger is connected to a material inlet at a top portion of the high pressure reaction vessel.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4190583A (en) * | 1977-12-07 | 1980-02-26 | Haarmann & Reimer Gmbh | Process for the preparation of 3,4-methylenedioxymandelic acid |
| JP2001206883A (en) * | 1999-11-16 | 2001-07-31 | Ube Ind Ltd | Method for producing 3,4-methylenedioxymandelic acid |
| JP2002114774A (en) * | 2000-10-04 | 2002-04-16 | Ube Ind Ltd | Method of producing 3,4-methylene-dioxymandelic acid |
| CN104193719A (en) * | 2014-09-12 | 2014-12-10 | 太原理工大学 | Preparation method for 3,4-methylene dioxy mandelic acid |
| CN105693688A (en) * | 2016-04-01 | 2016-06-22 | 衢州信步化工科技有限公司 | Reaction treatment method of heliotropin intermediate 3,4-dioxymethylene mandelic acid |
-
2018
- 2018-08-28 CN CN201810984094.9A patent/CN110862370B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4190583A (en) * | 1977-12-07 | 1980-02-26 | Haarmann & Reimer Gmbh | Process for the preparation of 3,4-methylenedioxymandelic acid |
| JP2001206883A (en) * | 1999-11-16 | 2001-07-31 | Ube Ind Ltd | Method for producing 3,4-methylenedioxymandelic acid |
| JP2002114774A (en) * | 2000-10-04 | 2002-04-16 | Ube Ind Ltd | Method of producing 3,4-methylene-dioxymandelic acid |
| CN104193719A (en) * | 2014-09-12 | 2014-12-10 | 太原理工大学 | Preparation method for 3,4-methylene dioxy mandelic acid |
| CN105693688A (en) * | 2016-04-01 | 2016-06-22 | 衢州信步化工科技有限公司 | Reaction treatment method of heliotropin intermediate 3,4-dioxymethylene mandelic acid |
Non-Patent Citations (1)
| Title |
|---|
| 王帅 ; 李耀先 ; 王恒国 ; 张朝群 ; 王维 ; 孙磊 ; 徐淑飞 ; 李延春 ; 杨清彪 ; .空气催化氧化合成洋茉莉醛.应用化工.2009,(第04期),第491-493页. * |
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