CN110862369A - Method and device for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification - Google Patents
Method and device for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification Download PDFInfo
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- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
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- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
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Abstract
The invention provides a method and a device for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification, wherein the method takes a product as an emulsifier according to the principle that the 3, 4-methylenedioxymandelic acid has both lipophilic group and hydrophilic group, so that the separation process of the product is simpler and easier. The water reducing agent is added in the reaction process, and can be adsorbed on the surface of oil phase liquid drops in an oriented mode, so that the surface of the oil phase liquid drops is charged, electrostatic repulsion is generated, the dispersion effect of the water reducing agent is exerted, and the oil phase is dispersed to increase the fluidity. Meanwhile, the water reducing agent has a lubricating effect, increases hydrophilic groups to form a solvation water film, reduces friction force, enables pepper ring phases in a product thickening stage to be more dispersed, forms a water film form to play a lubricating effect, homogenizes the mass and heat transfer process of a reaction system, and improves the purity and yield of the product. And an 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 viscosity of the product is solved. And provides a set of device 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-methylenedioxymandelic acid by improved emulsification.
Background
3, 4-methylenedioxymandelic acid is an intermediate in the synthesis of piperonal. Piperonal is widely used in perfumes, spices, cherry and vanilla flavors. The perfume has long fragrance retention time, is used as a blending agent and a fixing agent, is a safe perfume accepted by American Association for the manufacture of spice extracts, and is widely applied to indoor fragrances, soap essences, food essences and tobacco essences. It can also be used in chemical and biological pharmacy. Is one of special commodities for which the country enforces export licenses.
The traditional synthesis method of 3, 4-methylenedioxymandelic acid is a method of synthesizing piperonyl-acetal and glyoxylic acid under acidic conditions, and the influence of reaction factors such as reaction temperature, reaction time, molar ratio of glyoxylic acid to piperonyl-acetal is studied by Shaoxing army and the like (the study on synthesis of 3, 4-methylenedioxymandelic acid by Shaoxing army, Doismen chemical industry, 2007, 2; 46-47.). Wangshuai et al (Wangshuai, Li dazao, Wangsheng. King Hengchang. air catalytic oxidation synthesis heliotropin [ J ]. applied chemical industry, 2009, 4: 491 + 493.) and Zhang Kun water (Zhang Kun water, Huanghan, Chenyi. pharmaceutical jasmal synthesis) when researching the synthesis method of heliotropin, similar preparation of 3, 4-methylenedioxymandelic acid is adopted. Ximidago considers the influence of factors such as reaction temperature, catalyst concentration, raw material ratio and reaction time, and discusses the mechanism of action and possible reaction process of sulfuric acid catalyst (ximidago, wuxian, king england. helional intermediate 3, 4-methylenedioxymandelic acid synthesis and characterization [ J ] chemical research and application, 2009, 21: 396-400 ].
The above prior art has the following disadvantages;
the product 3, 4-methylenedioxymandelic acid has high viscosity, poor fluidity and low mass transfer efficiency in the synthesis process, and the piperonyl and glyoxylic acid are not mutually soluble and the contact area between the two phases is small, so that the reaction is insufficient, the yield is low, the heat transfer effect is not uniform, and the phenomena of poor selectivity and more byproducts of the reaction are easy to occur
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method and a device for improving emulsion synthesis of 3, 4-methylenedioxymandelic acid, which can improve the mixing efficiency of two phases in a reaction system, improve the reaction speed, shorten the reaction time, improve the reaction yield and reduce the amount of wastewater generated in the reaction process.
The invention is realized by the following technical scheme:
a method for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification comprises the following steps:
step 1, mixing water in a mass ratio: 50 wt% glyoxylic acid aqueous solution ═ 1: stirring the mixture of 15-20 at constant temperature, wherein the constant temperature stirring temperature is-30 ℃ to-20 ℃, and the stirring speed is 350rpm to 450 rpm;
step 3, after all the 98 wt% concentrated sulfuric acid is dripped, continuously stirring for 20-40 min at the stirring temperature of minus 30-minus 20 ℃;
and 4, adding 3, 4-methylenedioxymandelic acid into the solution after the step 3 is finished, wherein the ratio of the added 3, 4-methylenedioxymandelic acid to the water mass in the step 1 is 3, 4-methylenedioxymandelic acid: water is 0.1-1: 1;
step 5, emulsifying the solution obtained in the step 4 at an emulsifying speed of 10-15 Kr/min, dripping pepper rings at the same time during emulsification, wherein the dripping amount per minute is 0.1-1 time of the mass of the water obtained in the step 1, and the emulsifying time is 3-10 min;
and 6, repeating the step 5 for multiple times at intervals of 3-10 min, wherein the ratio of the total amount of added piperonyl butoxide to the mass of the water in the step 1 is piperonyl butoxide: water is 10-15: 1;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total amount of the stop solution to the water mass in the step 1 is the stop solution: 15-30% of water: 1, terminating the reaction to obtain a product;
and the processes of the step 1 to the step 7 also comprise a process of blowing gas into the solution, wherein the gas blowing amount per minute is 7-20 times of the volume of the mixture.
In the above technical scheme, in the step 1, the mass ratio of water: 50 wt% glyoxylic acid aqueous solution ═ 1: 15-17, stirring at a constant temperature of-28 to-23 ℃ and at a stirring speed of 380 to 420 rpm.
In the technical scheme, in the step 4, the ratio of the amount of the 3, 4-methylenedioxymandelic acid added to the mass of the water in the step 1 is 3, 4-methylenedioxymandelic acid: water is 0.4-1: 1.
in the technical scheme, in the step 5, the emulsifying speed is 12-15 Kr/min, pepper rings are added dropwise simultaneously during emulsification, the adding amount per minute is 0.5-1 time of the mass of the water 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 for 3-8 times, the interval between each time is 3-10 min, and the ratio of the total amount of added piperonyl pepper to the water mass in the step 1 is piperonyl pepper: water is 10-12: 1;
in the above technical scheme, in the step 7, the inert solvent is one or a combination of any more of dichloromethane, toluene, paraffin oil, naphthenic oil and white oil, the dropping amount per minute is 1.5-3 times of the mass of the water in the step 1, and the total mass of the dropped inert solvent is 15-30 times of the mass of the water in the step 1.
In the above technical scheme, in the step 7, the water reducing agent is a polycarboxylic acid-based high-performance water reducing agent, and the ratio of the total amount of the polycarboxylic acid-based high-performance water reducing agent added to the water in the step 1 to the mass of the water is polycarboxylic acid-based high-performance water reducing agent: water is 0.15 to 0.3: 1;
in the technical scheme, in the step 7, the inert solvent is dropwise added in the stirring process, the inert solvent is dropwise added after 10-20 minutes from the beginning of the step 7, the dropwise adding amount per minute is 1.5-3 times of the mass of the water in the step 1, and the total mass of the dropwise added inert solvent is 15-30 times of the mass of the water in the step 1.
In the above technical solution, in the step 8, the added stop solution is water, and the ratio of the total amount of the stop solution added to the water in the step 1 is the stop solution: 15-25% of water: 1.
an improved device for synthesizing 3, 4-methylenedioxymandelic acid by emulsification comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor emulsified tank, a jacketed distributor product stirred tank, a pepper ring metering tank, a thermostatic tank, a feeding metering tank, a filtering device, a feeding pump, an air storage tank and a filtrate tank, wherein an outlet of the sulfuric acid metering tank is connected with a jacketed distributor stirred tank pipeline, a circulating liquid outlet of the thermostatic tank is respectively connected with a jacket inlet of the jacketed distributor stirred tank, a jacket inlet of the jacketed distributor emulsified tank and a jacket inlet of the jacketed distributor product stirred tank by pipelines, a circulating liquid inlet of the thermostatic tank is respectively connected with a jacket outlet of the jacketed distributor stirred tank, a jacket outlet of the jacketed distributor emulsified tank and a jacket outlet of the jacketed distributor product stirred tank by pipelines, the export of jacketed distributor stirred tank links to each other with the inlet pipeline of charge pump, the export of pepper ring metering tank links to each other with jacketed distributor emulsification cauldron pipeline, the export of reinforced metering tank with jacketed distributor product stirred tank pipeline links to each other, jacketed distributor emulsification cauldron export with jacketed distributor product stirred tank inlet pipeline links to each other, jacketed distributor product stirred tank export with filtration equipment's feed inlet pipe connection, the export of gas holder adopts the pipe connection respectively jacketed distributor stirred tank's gas distribution pipe entry the gaseous distribution pipe entry of jacketed distributor emulsification cauldron and jacketed distributor product stirred tank gas distribution pipe entry, filtration equipment liquid phase exit linkage the filter tank entry.
In the technical scheme, outlet pipes of the sulfuric acid metering tank, the pepper ring metering tank and the charging metering tank are provided with flow meters.
In the technical scheme, the jacket inlet pipe of the jacketed distributor stirring kettle, the jacket inlet pipe of the jacketed distributor emulsifying kettle and the jacket inlet pipe of the jacketed distributor product stirring kettle are all provided with liquid flow meters.
Among the above-mentioned technical scheme, all be provided with gas flowmeter on the gas distribution pipe inlet tube of jacketed distributor stirred tank, the gas distribution pipe inlet tube of jacketed distributor emulsification cauldron and the jacketed distributor product stirred tank gas distribution pipe inlet tube.
In the technical scheme, the emulsifying device and the wall scraping stirring device are arranged on the jacket type distributor emulsifying kettle.
In the technical scheme, 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 jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle are both provided with temperature detecting instruments.
The invention has the advantages and beneficial effects that:
1. the method for synthesizing the 3, 4-methylenedioxymandelic acid adopts a method for synthesizing by improving the emulsification process, and the method leads gas to be 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-methylenedioxymandelic acid, and utilizes the homogenization effect of the emulsification process in the synthesis process to uniformly disperse the piperonyl in the glyoxylic acid by tiny droplets, thereby improving the contact efficiency between reactants and improving the purity and the yield of the product.
3. The emulsifier adopted by the invention is 3, 4-methylenedioxymandelic acid, and the method takes the product as the emulsifier according to the principle that the 3, 4-methylenedioxymandelic acid has both lipophilic group and hydrophilic group, so that a stable emulsion system can be formed, and substances outside a reaction system are not introduced, so that the product separation process is simpler and easier.
4. In the reaction process, the water reducing agent is added, so that the water reducing agent can be adsorbed on the surface of oil phase liquid drops in an oriented manner, the surface of the oil phase liquid drops is charged, electrostatic repulsion is generated, the dispersion effect of the water reducing agent is exerted, the oil phase is dispersed, and the fluidity is increased. Meanwhile, the water reducing agent has a lubricating effect, increases hydrophilic groups, forms a solvation water film, reduces friction force, enables pepper ring phases in a product viscous stage to be more dispersed so as to form a water film form to play a lubricating effect, homogenizes the mass and heat transfer process of a reaction system, and improves the purity and yield of the product.
5. In the reaction process, a method of dropwise adding inert solvents such as dichloromethane, toluene, paraffin oil, naphthenic oil, white oil and the like is adopted, and the solvents are inert solvents and do not participate in the reaction, so that the reaction conversion rate is improved on the basis of increasing the fluidity of the product, and the problem of viscosity of the product is solved. Therefore, one of the solvents can be selected during selection, or a plurality of solvents can be selected to be combined, and methylene chloride or toluene is prevented from dissolving a large amount of piperonyl in the reaction system to influence the reaction in a dropwise adding mode.
Drawings
FIG. 1 is a schematic diagram of a process for the improved emulsion synthesis of 3, 4-methylenedioxymandelic acid.
FIG. 2 is a schematic view of example 4 of the present invention.
FIG. 3 is a schematic view of example 5 of the present invention.
Wherein:
1: jacketed distributor stirred tank, 2: sulfuric acid metering tank, 3: jacketed distributor emulsifying kettle, 4: pepper ring metering tank, 5: thermostatic bath, 6: filtration apparatus, 7: charge pump, 8: gas storage tank, 9: a filtrate tank; 12: a jacketed distributor product stirred tank; 13: a charging metering tank;
6-1: primary filtering 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: and a third liquid flow meter.
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Comparative example
1. 100g of piperonyl butoxide, 10g of water, 160g of 50% glyoxylic acid aqueous solution and 140g of 98% concentrated sulfuric acid are weighed.
2. To a jacketed reactor were added 10g of water and 160g of 50% aqueous glyoxylic acid.
3. Connecting the jacketed reactor with a thermostatic bath, setting the temperature of the thermostatic bath to 5 ℃, and operating the thermostatic bath to cool for more than half an hour to
The temperature of the liquid in the jacket reached 5 ℃.
4. Connecting an electric stirrer, and stirring the liquid in the jacket reactor by using a plastic stirring blade at the rotating speed of 400r/min
5. Dropwise adding 140g of concentrated sulfuric acid at a constant speed of 7g/min by using a constant-pressure funnel, and continuously stirring for 30min after dropwise adding.
Obtaining the mixed acid.
6. And (3) removing the mixed acid accounting for 70 percent of the total mass of the mixed acid out of the jacketed reactor, and refrigerating the mixed acid in an environment at 5 ℃.
7. 30g of piperonyl butoxide is dropwise added into the jacketed reactor at a constant speed of 3g/min by using a constant-pressure funnel. After the dropwise addition, stirring was continued for 30 min.
8. Dropwise adding 70% of the mixed acid removed in the step 6 (the adding time is 1h) and 70g of piperonyl (the adding time is 0.5h) into a jacketed reactor at a constant speed by using a constant-pressure funnel.
9. After the dropwise addition, the speed of the stirring equipment is adjusted to 500r/min, and the stirring reaction is continued for 35min
10. The reaction was terminated by adding 200mL of water to the jacketed reactor.
11. Suction filtration was performed using a 1L suction flask to obtain a solid, which was weighed, dried and checked by liquid chromatography.
12. The detection result shows that the yield is 71.42%, the purity is 68.54%, and the total yield is 44.64%.
Example one
A method for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification comprises the following steps:
s1, stirring a mixture of 10g of water and 160g of 50 wt% glyoxylic acid aqueous solution at a constant temperature of-25 ℃ and a stirring speed of 400 rpm;
s2, after stirring, dropwise adding 98 wt% concentrated sulfuric acid into the mixture, wherein the dropwise adding amount per minute is 7g/min, the total amount of the 98 wt% concentrated sulfuric acid is 140g, the stirring temperature is-25 ℃, and the stirring speed is 400 rpm;
s3, when all the 98 wt% concentrated sulfuric acid is added dropwise, continuing stirring for 30min, wherein the stirring temperature is-25 ℃;
s4, adding 3, 4-methylenedioxymandelic acid into the solution after completion of S3, wherein the amount of the added 3, 4-methylenedioxymandelic acid is 4 g;
s5, emulsifying the solution obtained after the step S4 is finished, wherein the emulsifying speed is 12Kr/min, pepper rings are added dropwise at the same time during emulsification, the adding amount per minute is 5g, and the emulsifying time is 5 min;
s6, repeating the step S5 for 4 times, wherein the interval between every two times is 3min, and adding 100g of total amount of piperonyl butoxide;
and S7, stirring the solution after the end of the S6 at a constant temperature of 5 ℃, at a stirring speed of 500rpm for 30min, dropwise adding toluene or dichloromethane 15 minutes after the start of stirring, wherein the dropwise adding amount per minute is 20g/min, and the total mass of the dropwise adding toluene or dichloromethane is 200 g. (ii) a
S8, adding 200ml of water into the solution after the end of S7, and stopping the reaction to obtain a product;
the processes from S1 to S7 also comprise a process of blowing gas into the solution, the gas blowing amount per minute is 2.5L/min, and the adopted gas blowing medium is nitrogen.
The purity of the product is 88.60% and the total yield is 83.06%.
Example two
A method for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification comprises the following steps:
s1, stirring a mixture of 10g of water and 160g of 50 wt% glyoxylic acid aqueous solution at a constant temperature of-25 ℃ and a stirring speed of 400 rpm;
s2, after stirring, dropwise adding 98 wt% concentrated sulfuric acid into the mixture, wherein the dropwise adding amount per minute is 7g/min, the total amount of the 98 wt% concentrated sulfuric acid is 140g, the stirring temperature is-25 ℃, and the stirring speed is 400 rpm;
s3, when all the 98 wt% concentrated sulfuric acid is added dropwise, continuing stirring for 30min, wherein the stirring temperature is-25 ℃;
s4, adding 3, 4-methylenedioxymandelic acid into the solution after completion of S3, wherein the amount of the added 3, 4-methylenedioxymandelic acid is 4 g;
s5, emulsifying the solution obtained after the step S4 is finished, wherein the emulsifying speed is 12Kr/min, pepper rings are added dropwise at the same time during emulsification, the adding amount per minute is 5g, and the emulsifying time is 5 min;
s6, repeating the step S5 for 4 times, wherein the interval between every two times is 3min, and adding 100g of total amount of piperonyl butoxide;
s7, stirring the solution after the step S6 is finished at a constant temperature of 5 ℃, at a stirring speed of 500rpm for 30min, dropwise adding a liquid antifreezing polycarboxylic acid high-performance water reducing agent PCE-AF-L-JG/T223-2017 when stirring is started, wherein the total mass of the dropwise adding water reducing agent is 3 g;
s8, adding 200ml of water into the solution after the end of S7, and stopping the reaction to obtain a product;
the processes from S1 to S7 also comprise a process of blowing gas into the solution, the gas blowing amount per minute is 2.5L/min, and the adopted gas blowing medium is nitrogen.
The purity of the product is 91.50% and the total yield is 85.78%.
EXAMPLE III
A method for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification comprises the following steps:
s1, stirring a mixture of 10g of water and 160g of 50 wt% glyoxylic acid aqueous solution at a constant temperature of-25 ℃ and a stirring speed of 400 rpm;
s2, after stirring, dropwise adding 98 wt% concentrated sulfuric acid into the mixture, wherein the dropwise adding amount per minute is 7g/min, the total amount of the 98 wt% concentrated sulfuric acid is 140g, the stirring temperature is-25 ℃, and the stirring speed is 400 rpm;
s3, when all the 98 wt% concentrated sulfuric acid is added dropwise, continuing stirring for 30min, wherein the stirring temperature is-25 ℃;
s4, adding 3, 4-methylenedioxymandelic acid into the solution after completion of S3, wherein the amount of the added 3, 4-methylenedioxymandelic acid is 4 g;
s5, emulsifying the solution obtained after the step S4 is finished, wherein the emulsifying speed is 12Kr/min, pepper rings are added dropwise at the same time during emulsification, the adding amount per minute is 5g, and the emulsifying time is 5 min;
s6, repeating the step S5 for 4 times, wherein the interval between every two times is 3min, and adding 100g of total amount of piperonyl butoxide;
s7, stirring the solution after S6 is finished at a constant temperature of 5 ℃, at a stirring speed of 500rpm, for 30min, dropwise adding a liquid antifreezing polycarboxylic acid high-performance water reducing agent PCE-AF-L-JG/T223-2017 at the beginning of stirring, wherein the total mass of the water reducing agent is 3g, dropwise adding toluene or dichloromethane 15 min after the beginning of stirring, the dropwise adding amount per minute is 20g/min, and the total mass of the toluene or dichloromethane is 200 g;
s8, adding 200ml of water into the solution after the end of S7, and stopping the reaction to obtain a product;
the processes from S1 to S7 also comprise a process of blowing gas into the solution, the gas blowing amount per minute is 2.5L/min, and the adopted gas blowing medium is nitrogen.
The purity is 97.60 percent and the total yield is 91.50 percent.
Example four
An improved device for emulsion synthesis of 3, 4-methylenedioxymandelic acid comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor emulsified tank, a jacketed distributor product stirred tank, a pepper ring metering tank, a thermostatic tank, a feeding metering tank, a filtering device, a feeding pump, an air storage tank and a filtrate tank, wherein an outlet of the sulfuric acid metering tank is connected with a jacketed distributor stirred tank pipeline, an outlet pipe of the sulfuric acid metering tank is provided with a flowmeter, a circulating liquid outlet of the thermostatic tank is respectively connected with a jacket inlet of the jacketed distributor stirred tank, a jacket inlet of the jacketed distributor emulsified tank and a jacket inlet of the jacketed distributor product stirred tank by pipelines, a circulating liquid inlet of the thermostatic tank is respectively connected with a jacket outlet of the jacketed distributor stirred tank, a jacket outlet of the jacketed distributor emulsified tank and a jacket outlet of the jacketed distributor product stirred tank by pipelines, the outlet of the jacketed distributor stirring kettle is connected with the inlet pipeline of the feeding pump, the outlet of the pepper ring metering tank is connected with the jacketed distributor emulsifying kettle pipeline, the outlet of the feeding metering tank is connected with the pipeline of the jacketed distributor product stirring kettle, the outlet pipe of the feeding metering tank and the outlet pipe of the pepper ring metering tank are both provided with a flowmeter, the outlet of the jacketed distributor emulsifying kettle 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 a feed inlet pipeline of the filtering device, the outlet of the gas storage tank is respectively 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, and the liquid phase outlet of the filtering equipment is connected with the filtrate tank inlet. And liquid flow meters are arranged on the jacket inlet pipe of the jacket distributor stirring kettle, the jacket inlet pipe of the jacket distributor emulsifying kettle and the jacket inlet pipe of the jacket distributor product stirring kettle. Gas flow meters are arranged on the inlet pipe of the gas distribution pipe of the jacketed distributor stirring kettle, the inlet pipe of the gas distribution pipe of the jacketed distributor emulsifying kettle and the inlet pipe of the gas distribution pipe of the jacketed distributor product stirring kettle. And the jacketed distributor emulsifying kettle is provided with 2 sets of emulsifying devices and a wall scraping stirring device. Temperature detecting instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
EXAMPLE five
An improved device for emulsion synthesis of 3, 4-methylenedioxymandelic acid comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor emulsified tank, a jacketed distributor product stirred tank, a pepper ring metering tank, a thermostatic tank, a feeding metering tank, two-stage filtering equipment, a feeding pump, an air storage tank and a filtrate tank, wherein an outlet of the sulfuric acid metering tank is connected with a jacketed distributor stirred tank pipeline, an outlet pipe of the sulfuric acid metering tank is provided with a flowmeter, a circulating liquid outlet of the thermostatic tank is respectively connected with a jacket inlet of the jacketed distributor stirred tank, a jacket inlet of the jacketed distributor emulsified tank and a jacket inlet of the jacketed distributor product stirred tank by pipelines, a circulating liquid inlet of the thermostatic tank is respectively connected with a jacket outlet of the jacketed distributor stirred tank, a jacket outlet of the jacketed distributor emulsified tank and a jacket outlet of the jacketed distributor product stirred tank 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, an outlet pipe of the feeding metering tank and an 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 the jacketed distributor product stirring kettle inlet pipeline, the outlet of the jacketed distributor product stirring kettle is connected with a feed inlet pipeline of the primary filtering equipment, a discharge port of the primary filtering equipment is connected with a feed inlet pipeline of the secondary filtering equipment, and the outlet of the gas 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 jacketed distributor product stirring kettle gas distribution pipe inlet by pipelines, and the liquid phase outlet of the secondary filtering equipment is connected with the inlet of the filtrate tank. And liquid flow meters are arranged on the jacket inlet pipe of the jacket distributor stirring kettle, the jacket inlet pipe of the jacket distributor emulsifying kettle and the jacket inlet pipe of the jacket distributor product stirring kettle. Gas flow meters are arranged on the inlet pipe of the gas distribution pipe of the jacketed distributor stirring kettle, the inlet pipe of the gas distribution pipe of the jacketed distributor emulsifying kettle and the inlet pipe of the gas distribution pipe of the jacketed distributor product stirring kettle. And the jacketed distributor emulsifying kettle is provided with 2 sets of emulsifying devices and a wall scraping stirring device. Temperature detecting instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
The primary filtering equipment and the secondary filtering equipment adopt filtering media with different precisions, the aperture of the filtering media adopted on the primary filtering equipment is larger, products with larger granularity in a product system can be filtered out, filtrate enters the secondary filtering equipment, the aperture of the filtering media adopted by the secondary filtering equipment is smaller, the final products, namely 3, 4-methylenedioxymandelic acid, with smaller granularity can be filtered out, and the products are more fully recovered.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A method for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification is characterized by comprising the following steps:
step 1, mixing water in a mass ratio: 50 wt% glyoxylic acid aqueous solution ═ 1: stirring the mixture of 15-20 at constant temperature, wherein the constant temperature stirring temperature is-30 ℃ to-20 ℃, and the stirring speed is 350rpm to 450 rpm;
step 2, after stirring, dripping 98 wt% of concentrated sulfuric acid into the mixture, wherein the dripping amount per minute is 0.03-0.1 time of the mass of the mixture, and the ratio of the total mass of the 98 wt% of concentrated sulfuric acid to the mass of water in the step 1 is 98 wt% of concentrated sulfuric acid: 12-15% of water: 1, stirring at-30 to-20 ℃;
step 3, after all the 98 wt% concentrated sulfuric acid is dripped, continuously stirring for 20-40 min at the stirring temperature of minus 30-minus 20 ℃;
and 4, adding 3, 4-methylenedioxymandelic acid into the solution after the step 3 is finished, wherein the ratio of the added 3, 4-methylenedioxymandelic acid to the water mass in the step 1 is 3, 4-methylenedioxymandelic acid: water is 0.1-1: 1;
step 5, emulsifying the solution obtained in the step 4 at an emulsifying speed of 10-15 Kr/min, dripping pepper rings at the same time during emulsification, wherein the dripping amount per minute is 0.1-1 time of the mass of the water obtained in the step 1, and the emulsifying time is 3-10 min;
and 6, repeating the step 5 for multiple times at intervals of 3-10 min, wherein the ratio of the total amount of added piperonyl butoxide to the mass of the water in the step 1 is piperonyl butoxide: water is 10-15: 1;
step 7, stirring the solution obtained after the step 6 at a constant temperature of 0-10 ℃, at a stirring speed of 400-600 rpm for 20-40 min, and dropwise adding an inert solvent and/or a water reducing agent 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 amount of the stop solution to the water mass in the step 1 is the stop solution: 15-30% of water: 1, terminating the reaction to obtain a product;
and the processes of the step 1 to the step 7 also comprise a process of blowing gas into the solution, wherein the gas blowing amount per minute is 7-20 times of the volume of the mixture.
2. The method for improved emulsion synthesis of 3, 4-methylenedioxymandelic acid according to claim 1, wherein in step 1, the ratio of water: 50 wt% glyoxylic acid aqueous solution ═ 1: 15-17, stirring at a constant temperature of-28 to-23 ℃ and at a stirring speed of 380 to 420 rpm.
3. The process for improved emulsion synthesis of 3, 4-methylenedioxymandelic acid according to claim 1, wherein the ratio of the amount of 3, 4-methylenedioxymandelic acid added in step 4 to the amount of water in step 1 is 3, 4-methylenedioxymandelic acid: water is 0.4-1: 1.
4. the method for improved emulsification synthesis of 3, 4-methylenedioxymandelic acid according to claim 1, wherein in the step 5, the emulsification rate is 12-15 Kr/min, pepper rings are added dropwise during emulsification, the amount of the added pepper rings is 0.5-1 time of the mass of the water in the step 1 per minute, and the emulsification time is 5-10 min.
5. The method for improved emulsion synthesis of 3, 4-methylenedioxymandelic acid according to claim 1, wherein the step 6, the step 5 are repeated 3-8 times with 3-10 min intervals, and the ratio of the total amount of piperonyl chloride added to the water in the step 1 is piperonyl chloride: water is 10-12: 1.
6. the method for improved emulsion synthesis of 3, 4-methylenedioxymandelic acid according to claim 1, wherein in step 7, the inert solvent is dichloromethane, toluene, paraffin oil, naphthenic oil or white oil, the amount of the inert solvent added per minute is 1.5-3 times of the mass of the water in step 1, and the total mass of the inert solvent added is 15-30 times of the mass of the water in step 1.
7. The method for improving the emulsion synthesis of 3, 4-methylenedioxymandelic acid according to claim 1, wherein in step 7, the water reducing agent is a polycarboxylic acid-based high-performance water reducing agent, and the ratio of the total amount of the polycarboxylic acid-based high-performance water reducing agent added to the water in step 1 is: water is 0.15 to 0.3: 1.
8. the method for improved emulsion synthesis of 3, 4-methylenedioxymandelic acid according to claim 1, wherein in step 7, the inert solvent is added dropwise during stirring in such a manner that the inert solvent is added dropwise 10 to 20 minutes after the start of step 7, the amount of the added dropwise added inert solvent is 1.5 to 3 times of the mass of the water in step 1 per minute, and the total mass of the added dropwise added inert solvent is 15 to 30 times of the mass of the water in step 1.
9. The method for improved emulsion synthesis of 3, 4-methylenedioxymandelic acid according to claim 1, wherein in step 8, the stop solution is added as water, and the ratio of the total amount of the stop solution added to the mass of the water in step 1 is stop solution: 15-25% of water: 1.
10. an improved device for synthesizing 3, 4-methylenedioxymandelic acid by emulsification comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor emulsified tank, a jacketed distributor product stirred tank, a pepper ring metering tank, a thermostatic tank, a feeding metering tank, a filtering device, a feeding pump, an air storage tank and a filtrate tank, wherein an outlet of the sulfuric acid metering tank is connected with a jacketed distributor stirred tank pipeline, a circulating liquid outlet of the thermostatic tank is respectively connected with a jacket inlet of the jacketed distributor stirred tank, a jacket inlet of the jacketed distributor emulsified tank and a jacket inlet of the jacketed distributor product stirred tank by pipelines, a circulating liquid inlet of the thermostatic tank is respectively connected with a jacket outlet of the jacketed distributor stirred tank, a jacket outlet of the jacketed distributor emulsified tank and a jacket outlet of the jacketed distributor product stirred tank by pipelines, the export of jacketed distributor stirred tank links to each other with the inlet pipeline of charge pump, the export of pepper ring metering tank links to each other with jacketed distributor emulsification cauldron pipeline, the export of reinforced metering tank with jacketed distributor product stirred tank pipeline links to each other, jacketed distributor emulsification cauldron export with jacketed distributor product stirred tank inlet pipeline links to each other, jacketed distributor product stirred tank export with filtration equipment's feed inlet pipe connection, the export of gas holder adopts the pipe connection respectively jacketed distributor stirred tank's gas distribution pipe entry the gaseous distribution pipe entry of jacketed distributor emulsification cauldron and jacketed distributor product stirred tank gas distribution pipe entry, filtration equipment liquid phase exit linkage the filter tank entry.
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