CN113045417B - Process for producing acetoacetic ester by catalytic method - Google Patents
Process for producing acetoacetic ester by catalytic method Download PDFInfo
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- CN113045417B CN113045417B CN201911385732.6A CN201911385732A CN113045417B CN 113045417 B CN113045417 B CN 113045417B CN 201911385732 A CN201911385732 A CN 201911385732A CN 113045417 B CN113045417 B CN 113045417B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The invention discloses a process for producing acetoacetic ester, which comprises the steps of arranging a solid catalyst in an esterification reactor, introducing anhydrous alcohol into the esterification reactor, and infiltrating and dehydrating the solid catalyst; controlling the molar ratio of the diketene to the anhydrous alcohol, and introducing the diketene and the anhydrous alcohol into an esterification reactor loaded with a solid catalyst for esterification reaction to obtain a primary crude ester product; the primary crude ester product flows through a distillation unit to obtain a secondary crude ester product and alcohol, the separated alcohol returns to a storage tank for reuse, and the secondary crude ester product passes through a rectification separation unit to obtain a high-purity acetoacetate finished product. The process adopts liquid-solid phase reaction, and the solid catalyst is left in the esterification reactor without separation and can be continuously used. The green catalytic process reduces the separation energy consumption and cost, the conversion rate of the diketene is close to 100 percent, the product yield is high, the reaction condition is mild, the process operation is simple and easy to control, the process is safe and environment-friendly, and no three-waste discharge exists.
Description
Technical Field
The invention relates to the field of production of acetoacetic ester, and particularly relates to a process for producing the acetoacetic ester.
Background
Acetoacetate is an important chemical product, including methyl acetoacetate, ethyl acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate and the like, is often used as an organic intermediate or a chemical auxiliary agent, and is widely applied to the industries of medicines, pesticides and dyes. With the rapid increase of the demand of downstream products of the acetoacetate, the market demand at home and abroad is large at present.
The traditional methyl acetoacetate production method is to uniformly mix diketene, absolute methanol and a liquid acid-base catalyst, and carry out esterification reaction at a certain temperature to obtain a product, wherein the chemical reaction formula is as follows: CH (CH) 2 ＝CHOCH 2 C = O (diketene) + CH 3 OH—→CH 3 COCH 2 COOCH 3 The catalyst mainly adopts liquid acid-base catalysts, and mainly comprises concentrated sulfuric acid, sodium acetate, sodium alcoholates, pyridine, amine compounds and the like. At present, concentrated sulfuric acid is used as an acid catalyst, so that the equipment is corroded greatly, and the discharge amount of three wastes is large; sodium acetate and sodium alcoholate are used as alkaline catalysts, so that the product yield is low, the product is difficult to separate, the catalyst is seriously corroded to equipment, and the catalyst is difficult to treat in the later period; the amine compound is used as an organic base catalyst, including diethylamine, diethylenetriamine, aniline, diisopropylamine and the like, and the liquid catalyst is difficult to separate, low in product yield, high in energy consumption and cost and large in three-waste amount. The method for accelerating the diketene anhydrous methanol esterification reaction by using the liquid acid-base catalyst does not belong to the field of green catalytic reaction, and does not meet the requirements of energy conservation and emission reduction in modern chemical production. The prior art is similar to the production methods of other acetoacetic esters such as ethyl acetoacetate.
Patent document CN105384631A reports a continuous production process of methyl acetoacetate, which is to divide an esterification kettle into a cooling zone and a heat preservation zone, place crude ester at the bottom of the kettle, drop anhydrous methanol and diketene in the cooling zone to perform esterification reaction, pressurize the reaction product, overflow the reaction product into the heat preservation zone, and feed the crude ester product into a rectifying tower to obtain the product. The process engineering is complex, the reaction is difficult to control, and the semi-continuous process is not beneficial to material discharge and heat accumulation, so that the danger is brought to production.
Patent CN103864616B reports a method for preparing methyl acetoacetate, which uses extractant to extract and separate esterification crude product, the product yield is 95%, and the purity is 99.3%. In the process, the extractant is introduced into the reaction system, so that the product purification difficulty is improved, the production cost is increased, and the product purity is not high.
Patent document CN108586240A reports an esterification production process of methyl acetoacetate, which adopts a spiral wound tube microchannel reactor to perform esterification reaction, uses triethylamine as a catalyst, and obtains a product by vacuum rectification and separation of a reaction product. The industrialized realization of the reaction process is complex, and the micro-channel is easy to block and difficult to clean.
In patent documents CN110294675A, CN108299200A and CN102276464B, amine compounds are used as liquid alkali catalysts for accelerating the reaction rate of anhydrous methanol and diketene, and although the yield and quality of the product are improved to a certain extent, the liquid alkali is used as the catalyst, and the catalyst is mixed with raw materials and products, so that the separation difficulty of the product is increased, the energy consumption and the cost are increased, the amount of three wastes is large, and the standard of the three wastes in environmental protection is difficult to reach. The problem of the method for catalyzing the esterification reaction of diketene and anhydrous methanol by using the amine type ionic liquid catalyst in the patent CN103450017B also exists, and belongs to the common problem of the liquid catalyst. In addition, patent CN101337890B reports a method for preparing methyl acetoacetate by using a novel composite catalyst, which actually uses triethylene diamine and concentrated sulfuric acid as the composite catalyst, and besides the industrial production problems brought by the amine catalyst, the concentrated sulfuric acid is very corrosive to the device, and is gradually eliminated.
Therefore, there is a need to develop a method for producing acetoacetate ester in a green environment with less three wastes.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for green production of acetoacetate ester with less discharge of three wastes.
The technical scheme of the invention is that the process for producing the acetoacetate ester by the green catalytic method comprises the esterification reaction of diketene and alcohol, and comprises the following steps:
(including the esterification reaction of diketene and anhydrous alcohol, which is characterized by comprising the following steps:
(1) Loading a solid catalyst in an esterification reactor, then introducing anhydrous alcohol, and carrying out infiltration and dehydration treatment on the solid catalyst until the water content in the anhydrous alcohol at an outlet of the esterification reactor is lower than 0.5%, thus completing the dehydration treatment process of the solid catalyst;
(2) Introducing diketene and anhydrous alcohol into an esterification reactor according to a certain molar ratio, wherein the mass space velocity is 0.2-3 h at the temperature of 20-90 ℃ under normal pressure -1 Under the condition, the continuous esterification reaction of diketene and anhydrous alcohol is carried out on the surface of a solid catalyst to obtain a primary crude ester product;
(3) Distilling the primary crude ester product by a distillation unit to obtain a secondary crude ester product and corresponding alcohol, and recycling the corresponding alcohol for reuse; and rectifying the secondary crude ester product by a rectifying unit to obtain a high-purity acetoacetate ester product.
Mass space velocity = F Flow rate of diketene + alcohol /m Weight of catalyst 。
The invention controls the water content in the anhydrous alcohol within the range, ensures that no water can exist in the catalyst, and ensures the production safety.
Preferably, the anhydrous alcohol is selected from one of methanol, ethanol, n-butanol and isobutanol.
According to the green catalytic method for producing the acetoacetate ester, the solid catalyst in the step (1) is preferably one or two selected from molecular sieves, alumina, heteropoly acid and ion exchange resin. The surface of the catalyst is provided with Lewis acid sites and
acid (H) + ) And (4) the chiral site can catalyze the esterification reaction.
Further, the molecular sieve is selected from a ZSM-5 molecular sieve; the heteropoly acid is phosphotungstic heteropoly acid.
According to the green catalytic method for producing the acetoacetate ester, the reaction temperature in the step (2) is preferably 50-70 ℃.
Further, the reaction temperature in the step (2) is preferably 55 to 60 ℃.
According to the green catalytic method for producing the acetoacetate ester, the mass ratio of the anhydrous alcohol to the diketene in the step (2) is preferably 10.
According to the green catalytic method for producing the acetoacetate ester, the distillation unit in the step (3) is preferably an evaporator, and the distillation temperature is controlled to be 75-95 ℃.
According to the green catalytic method for producing the acetoacetate ester, the rectifying unit in the step (3) preferably refers to a first-stage rectifying tower, a condenser and a second-stage rectifying tower.
The invention has the beneficial effects that:
the invention relates to a method for producing acetoacetate, which adopts a green catalytic process and uses a solid catalyst molecular sieve, alumina, heteropoly acid and ion exchange resin to catalyze the esterification reaction of diketene and anhydrous alcohol. After the solid catalyst is adopted, no waste liquid is generated, and the method is green and environment-friendly.
Diketene and anhydrous alcohol react in an esterification reactor loaded with a catalyst, then the reaction product enters an evaporator for separation, the corresponding alcohol is recycled, and a crude ester product is subjected to primary rectification, condensation and secondary rectification to obtain a high-purity acetoacetate ester product.
The process adopts liquid-solid phase reaction, and the solid catalyst is left in the esterification reactor without separation and can be continuously used. The green catalytic process reduces the energy consumption and cost for separation, the conversion rate of the diketene is close to 100 percent, the product yield can reach more than 99.5 percent, the reaction condition is mild, the process operation is simple and easy to control, the process is safe and environment-friendly, and no three wastes are discharged.
Detailed Description
The process for the production of methyl acetoacetate by a green catalytic process according to the invention is further illustrated by, but not limited to, the following examples.
Example 1
The esterification reaction of diketene and anhydrous methanol to generate methyl acetoacetate is carried out in an esterification reactor, before the reaction, 15g of ZSM-5 molecular sieve catalyst is loaded in the esterification reactor, and then the anhydrous methanol is introducedAnd infiltrating and dehydrating the solid catalyst until the water content in the anhydrous methanol at the outlet of the esterification reactor is lower than 0.5 percent, thus finishing the dehydration treatment process of the solid catalyst. Mixing diketene and anhydrous methanol according to a molar ratio of 1:5 is introduced into an esterification reactor, the temperature is 80 ℃, and the space velocity is 1.5h -1 And under normal pressure, carrying out esterification reaction on diketene and anhydrous methanol on the surface of a solid catalyst to obtain a primary crude ester product, wherein the conversion per pass of the diketene is 99.6%. The primary crude ester product passes through an evaporator and a distillation unit to obtain a secondary crude ester product and anhydrous methanol, and the anhydrous methanol is recycled and reused. The secondary crude ester product is rectified by a rectification unit to obtain a high-purity methyl acetoacetate product, wherein the product yield reaches 98.5%, and the purity reaches 99.8%.
Example 2
The esterification reaction of diketene and absolute methanol to generate methyl acetoacetate is carried out in an esterification reactor, before the reaction is carried out, 15g of ZSM-5 molecular sieve catalyst is loaded in the esterification reactor, then the absolute methanol is introduced, the solid catalyst is infiltrated and dehydrated until the water content in the absolute methanol at the outlet of the esterification reactor is lower than 0.5 percent, and then the dehydration treatment process of the solid catalyst is completed. Mixing diketene and anhydrous methanol according to a molar ratio of 1:5 is introduced into the esterification reactor, the temperature is 80 ℃, and the space velocity is 1.5h -1 And carrying out esterification reaction on diketene and anhydrous methanol on the surface of a solid catalyst under normal pressure to obtain a primary crude ester product, wherein the conversion per pass of the diketene is 99.6%. The primary crude ester product passes through an evaporator and a distillation unit to obtain a secondary crude ester product and anhydrous methanol, and the anhydrous methanol is recycled and reused. The secondary crude ester product is rectified by a rectification unit to obtain a high-purity methyl acetoacetate product, wherein the product yield reaches 98.5%, and the purity reaches 99.7%.
Example 3
The esterification reaction of diketene and absolute ethyl alcohol to generate ethyl acetoacetate is carried out in an esterification reactor, before the reaction is carried out, 15g of alumina catalyst is loaded in the esterification reactor, then the absolute ethyl alcohol is introduced, and the solid catalyst is infiltrated and dehydrated until the solid catalyst is discharged from an outlet of the esterification reactorThe water content in the ethanol is lower than 0.5 percent, and the dehydration treatment process of the solid catalyst is completed. Mixing diketene and ethanol according to a molar ratio of 1:10 is introduced into an esterification reactor, the temperature is 90 ℃, and the space velocity is 1.0h -1 And carrying out esterification reaction on diketene and absolute ethyl alcohol on the surface of a solid catalyst under normal pressure to obtain a primary crude ester product, wherein the conversion per pass of the diketene is 92.6%. The primary crude ester product passes through an evaporator and a distillation unit to obtain a secondary crude ester product and absolute ethyl alcohol, and the absolute ethyl alcohol is recycled and reused. The secondary crude ester product is rectified by a rectification unit to obtain a high-purity ethyl acetoacetate product, wherein the product yield reaches 97.5%, and the purity reaches 99.6%.
Example 4
The esterification reaction of diketene and absolute ethyl alcohol to generate ethyl acetoacetate is carried out in an esterification reactor, before the reaction is carried out, 5g of styrene sulfonated resin catalyst is loaded in the esterification reactor, then the absolute ethyl alcohol is introduced, and the solid catalyst is soaked and dehydrated until the water content in the absolute ethyl alcohol at the outlet of the esterification reactor is lower than 0.5 percent, thus completing the dehydration treatment process of the solid catalyst. Mixing diketene and absolute ethyl alcohol according to a molar ratio of 1:4 is introduced into the esterification reactor, the temperature is 60 ℃, and the space velocity is 1.5h -1 And carrying out esterification reaction on diketene and absolute ethyl alcohol on the surface of a solid catalyst under normal pressure to obtain a primary crude ester product, wherein the conversion per pass of the diketene is 98.6%. The primary crude ester product passes through an evaporator and a distillation unit to obtain a secondary crude ester product and absolute ethyl alcohol, and the absolute ethyl alcohol is recycled and reused. The secondary crude ester product is rectified by a rectification unit to obtain a high-purity ethyl acetoacetate product, wherein the product yield reaches 99.5%, and the purity reaches 99.8%.
Example 5
The esterification reaction of diketene and n-butyl alcohol to generate n-butyl acetoacetate is carried out in an esterification reactor, before the reaction is carried out, 15g of phosphotungstic heteropoly acid catalyst is loaded in the esterification reactor, then anhydrous n-butyl alcohol is introduced, the solid catalyst is infiltrated and dehydrated until the water content in the n-butyl alcohol which is discharged from the esterification reactor is lower than 0.5 percent, and the dehydration treatment process of the solid catalyst is finished. And (2) mixing ketene dimer and n-butyl alcohol according to a molar ratio of 1:8 is introduced into an esterification reactor, and the temperature and the space velocity are respectively controlled at 90 ℃ and 1.5h -1 And carrying out esterification reaction on diketene and n-butyl alcohol on the surface of a solid catalyst under normal pressure to obtain a primary crude ester product, wherein the conversion per pass of the diketene is 97.6%. The primary crude ester product is passed through an evaporator, a distillation unit to obtain a secondary crude ester product and n-butanol, and the n-butanol is recycled for reuse. The secondary crude ester product is rectified by a rectification unit to obtain a high-purity n-butyl acetoacetate product, wherein the product yield reaches 99.1%, and the purity reaches 99.5%.
Example 6
The esterification reaction of diketene and n-butyl alcohol to generate n-butyl acetoacetate is carried out in an esterification reactor, before the reaction is carried out, 5g of phosphotungstic heteropoly acid and 5g of ZSM-5 molecular sieve catalyst are loaded in the esterification reactor, then n-butyl alcohol is introduced, the solid catalyst is infiltrated and dehydrated until the water content in the n-butyl alcohol which is discharged from the esterification reactor is lower than 0.5 percent, and then the dehydration treatment process of the solid catalyst is completed. And (2) mixing ketene dimer and n-butyl alcohol according to a molar ratio of 1:4 is introduced into the esterification reactor, the temperature is 60 ℃, and the space velocity is 1.5h -1 And carrying out esterification reaction on diketene and n-butyl alcohol on the surface of a solid catalyst under normal pressure to obtain a primary crude ester product, wherein the conversion per pass of the diketene is 99.6%. The primary crude ester product is passed through an evaporator, a distillation unit to obtain a secondary crude ester product and n-butanol, and the n-butanol is recycled for reuse. The secondary crude ester product is rectified by a rectification unit to obtain a high-purity n-butyl acetoacetate product, wherein the product yield reaches 99.1%, and the purity reaches 99.5%.
Example 7
The esterification reaction of diketene and isobutanol to generate isobutyl acetoacetate is carried out in an esterification reactor, before the reaction is carried out, 5g of phosphotungstic heteropoly acid and 5g of styrene sulfonated resin catalyst are loaded in the esterification reactor, then isobutanol is introduced, and the solid catalyst is infiltrated and dehydrated until the water content in the isobutanol at the outlet of the esterification reactor is lower than 0.5 percent, thus finishing the dehydration treatment process of the solid catalyst. And (2) mixing diketene and isobutanol according to a molar ratio of 1:6 introduction of esterificationIn the reactor, the space velocity is 1.5h at 70 DEG C -1 And under normal pressure, carrying out esterification reaction on diketene and isobutanol on the surface of a solid catalyst to obtain a primary crude ester product, wherein the conversion per pass of the diketene is 99.1%. The primary crude ester product is passed through an evaporator, a distillation unit to obtain a secondary crude ester product and isobutanol, and the isobutanol is recycled back for reuse. The secondary crude ester product is rectified by a rectification unit to obtain a high-purity isobutyl acetoacetate product, the product yield reaches 99.0%, and the purity reaches 99.7%.
Example 8
The esterification reaction of diketene and isobutanol to generate isobutyl acetoacetate is carried out in an esterification reactor, before the reaction is carried out, 5g of alumina and 5g of styrene sulfonated resin catalyst are loaded in the esterification reactor, then isobutanol is introduced, and the solid catalyst is infiltrated and dehydrated until the water content in the isobutanol at the outlet of the esterification reactor is lower than 0.5 percent, thus finishing the dehydration treatment process of the solid catalyst. And (2) mixing diketene and isobutanol according to a molar ratio of 1:6 is introduced into an esterification reactor, at 70 ℃ and with a space velocity of 1.5h -1 And under normal pressure, carrying out esterification reaction on diketene and isobutanol on the surface of a solid catalyst to obtain a primary crude ester product, wherein the conversion per pass of the diketene is 98.1%. The primary crude ester product is passed through an evaporator, a distillation unit to obtain a secondary crude ester product and isobutanol, and the isobutanol is recycled back for reuse. The secondary crude ester product is rectified by a rectification unit to obtain a high-purity isobutyl acetoacetate product, wherein the product yield reaches 99.0%, and the purity reaches 99.9%.
The invention adopts the green catalytic process to produce the acetoacetate ester, uses the solid catalyst to catalyze the esterification reaction of the diketene and the anhydrous alcohol, has the advantages of easy separation of products, high yield, mild reaction conditions, simple and easily controlled process operation, safety, environmental protection and no three-waste discharge.
Claims (7)
1. A green catalytic method for producing acetoacetate ester comprises the esterification reaction of diketene and anhydrous alcohol, and is characterized in that: the method comprises the following steps:
(1) Loading of solid catalyst in esterification reactorIntroducing anhydrous alcohol, and infiltrating and dehydrating the solid catalyst until the water content in the anhydrous alcohol at an outlet of the esterification reactor is lower than 0.5 percent, thereby completing the dehydration treatment process of the solid catalyst; the solid catalyst is selected from one or two of molecular sieve, alumina, heteropoly acid and ion exchange resin; the surface of the catalyst is provided with Lewis acid sites and
acid (H +) site, which can catalyze esterification reaction; the molecular sieve is selected from ZSM-5 molecular sieves; the heteropoly acid is phosphotungstic heteropoly acid; the ion exchange resin is styrene sulfonated resin;
(2) Introducing diketene and anhydrous alcohol into an esterification reactor according to a certain molar ratio, wherein the mass space velocity is 0.2-3 h at the temperature of 20-90 ℃ under normal pressure -1 Under the condition, the continuous esterification reaction of diketene and anhydrous alcohol is carried out on the surface of a solid catalyst to obtain a primary crude ester product;
(3) Distilling the primary crude ester product by a distillation unit to obtain a secondary crude ester product and corresponding alcohol, and recycling the corresponding alcohol for reuse; and rectifying the secondary crude ester product by a rectifying unit to obtain a high-purity acetoacetate ester product.
2. The process for the green catalytic production of acetoacetate ester according to claim 1, wherein: the anhydrous alcohol in the step (1) is one of anhydrous methanol, ethanol, n-butanol and isobutanol.
3. The process for the green catalytic production of acetoacetate ester according to claim 1, wherein: the reaction temperature in the step (2) is 50-70 ℃.
4. The process for preparing acetoacetate ester according to claim 3, wherein the process comprises the following steps: the reaction temperature in the step (2) is 55-60 ℃.
5. The process for the green catalytic production of acetoacetate ester according to claim 1, wherein: in the step (2), the mass ratio of the added anhydrous alcohol to the added diketene is 10.
6. The process for the green catalytic production of acetoacetate ester according to claim 1, wherein: and (3) the distillation unit is an evaporator, and the distillation temperature is controlled to be 75-95 ℃.
7. The process for the green catalytic production of acetoacetate ester according to claim 1, wherein: and (3) the rectifying unit refers to a first-stage rectifying tower, a condenser and a second-stage rectifying tower.
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| CN102557932A (en) * | 2011-12-16 | 2012-07-11 | 浙江建业化工股份有限公司 | Method for producing isobutyl acetate |
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| CN103787883A (en) * | 2014-02-18 | 2014-05-14 | 山东汇海医药化工有限公司 | Preparation method of 4-chloracetyl ethyl acetate |
| CN103864616A (en) * | 2014-03-11 | 2014-06-18 | 南京师范大学 | Method for preparing methyl acetoacetate |
| CN106748788A (en) * | 2016-12-07 | 2017-05-31 | 南通醋酸化工股份有限公司 | The production method that a kind of ethyl acetoacetate low boiling is reclaimed |
| CN106749112A (en) * | 2016-12-08 | 2017-05-31 | 南通醋酸化工股份有限公司 | A kind of ketene dimer continuous rectificating technique |
| CN107827749A (en) * | 2017-10-31 | 2018-03-23 | 南通醋酸化工股份有限公司 | A kind of synthetic method of tert-butyl acetoacetate |
| CN107840802A (en) * | 2017-10-31 | 2018-03-27 | 南通醋酸化工股份有限公司 | A kind of preparation technology of isopropyl acetoacetate |
| CN109748790A (en) * | 2017-11-01 | 2019-05-14 | 中国石油化工股份有限公司 | The method for producing dimethyl adipate |
| CN107986966A (en) * | 2017-12-14 | 2018-05-04 | 山东汇海医药化工有限公司 | A kind of preparation method of isopropyl acetoacetate |
| CN107986962A (en) * | 2017-12-14 | 2018-05-04 | 山东汇海医药化工有限公司 | A kind of method that acetoacetic ester is recycled in the bottoms from acetoacetic ester |
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| CN110294674A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of tubular type continuous flow reaction unit and the method for preparing isopropyl acetoacetate |
| CN110294675A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of method and system preparing methyl acetoacetate using tubular type continuous flow reactor |
| CN109503381A (en) * | 2018-12-12 | 2019-03-22 | 安徽金禾实业股份有限公司 | 4- chloroacetyl acetacetic ester microchannel plate induction method and device |
| CN109704971A (en) * | 2018-12-20 | 2019-05-03 | 江苏恒安化工有限公司 | A kind of preparation method of 4- chloroacetyl acetacetic ester |
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