CN111978182A - Post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester - Google Patents

Post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester Download PDF

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CN111978182A
CN111978182A CN202010893553.XA CN202010893553A CN111978182A CN 111978182 A CN111978182 A CN 111978182A CN 202010893553 A CN202010893553 A CN 202010893553A CN 111978182 A CN111978182 A CN 111978182A
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stirring
flow guide
methyl ester
acid methyl
water
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CN111978182B (en
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王海根
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Jiangsu Hengan Chemical Co ltd
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Jiangsu Hengan Chemical Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/46Preparation of carboxylic acid esters from ketenes or polyketenes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D11/00Solvent extraction
    • B01D11/04Solvent extraction of solutions which are liquid
    • B01D11/0492Applications, solvents used
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40Mixing liquids with liquids; Emulsifying
    • B01F23/43Mixing liquids with liquids; Emulsifying using driven stirrers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05Stirrers
    • B01F27/11Stirrers characterised by the configuration of the stirrers
    • B01F27/19Stirrers with two or more mixing elements mounted in sequence on the same axis
    • B01F27/192Stirrers with two or more mixing elements mounted in sequence on the same axis with dissimilar elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/92Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with helices or screws
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/48Separation; Purification; Stabilisation; Use of additives
    • C07C67/52Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/48Separation; Purification; Stabilisation; Use of additives
    • C07C67/58Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester, which comprises the following steps: the method comprises the following steps: adopting diketene, chlorine, dichloromethane and methanol as raw materials, and preparing a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester through chlorination reaction and esterification reaction; step two: adding a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester into a water washing device, and separating an aqueous solution from an organic solution; step three: the organic solution is rectified to obtain a finished product of the 4-chloroacetoacetic acid methyl ester, the method is simple and convenient to implement, the washing device provided by the invention can be used for continuously and rapidly washing the dichloromethane solution containing the 4-chloroacetoacetic acid methyl ester, the washing effect is good, the efficiency is high, and the current use requirements are met.

Description

Post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester
Technical Field
The invention relates to the field of chemical preparation, in particular to a post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester.
Background
The 4-chloroacetoacetic acid methyl ester is colorless yellowish liquid, is a good medical synthetic intermediate, and is mainly used for producing oxiracetam, and the oxiracetam belongs to the medicines for treating cerebrovascular diseases.
The conventional production method of the methyl 4-chloroacetoacetate mainly used in the industrial production at present comprises the following steps: dissolving diketene in a solvent, cooling to-30 to-10 ℃, starting stirring, introducing a certain amount of chlorine into a reaction kettle at a certain flow rate, preserving heat at-30 to-10 ℃ for 1 to 2 hours, dripping a certain amount of methanol into the reaction kettle after chlorination reaction, controlling the reaction temperature to be 0 to 5 ℃, heating to 20 to 25 ℃ after dripping, preserving heat for 1 hour, carrying out alkali neutralization on the mixture after esterification reaction, evaporating the solvent, and then carrying out reduced pressure distillation to obtain a colorless liquid product, namely 4-methyl chloroacetoacetate.
At present, in the subsequent treatment after the synthesis of the 4-methyl chloroacetoacetate, the treatment effect is general, and particularly when the dichloromethane solution containing the 4-methyl chloroacetoacetate is washed by water, the washing effect is poor, the efficiency is low, and the current use requirements cannot be met.
Disclosure of Invention
In order to solve the technical problems, the invention provides a post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester, which comprises the following steps:
the method comprises the following steps: adopting diketene, chlorine, dichloromethane and methanol as raw materials, and preparing a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester through chlorination reaction and esterification reaction;
step two: adding a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester into a water washing device, and separating an aqueous solution from an organic solution;
step three: and rectifying the organic solution to obtain a finished product of the 4-chloroacetoacetic acid methyl ester.
Further: the water washing device comprises a closed tower kettle, the tower kettle is arranged along the plumb direction, an A spray head for introducing a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester and a B spray head for introducing water are arranged at the upper end of the tower kettle, the A spray head and the B spray head are correspondingly arranged, and a water washing mechanism for stirring and mixing water and the dichloromethane solution containing 4-chloroacetoacetic acid methyl ester is arranged in the tower kettle.
Through the technical scheme, the washing mechanism provided by the invention can be used for quickly and continuously carrying out mixing stirring washing treatment on a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester, has high treatment efficiency and good effect, and meets the current use requirements.
Further: the water washing mechanism comprises a guide mixing part and a stirring water washing component which are distributed up and down, the guide mixing part is used for mixing water and dichloromethane solution containing 4-chloroacetoacetic acid methyl ester and guiding the mixture to the stirring water washing component, and the stirring water washing component is used for stirring the mixed solution of the water and the dichloromethane solution.
Further: the flow guide mixing piece is a spiral plate, and the spiral center of the flow guide mixing piece is consistent with the direction of the plumb.
Further: the stirring washing subassembly includes pivot and washing subassembly, and the pivot is arranged along the plummet direction, and the washing subassembly is along pivot axial interval distribution.
Further: the water washing component comprises a flow guide part A, a flow guide part B and stirring blades, the flow guide part A and the flow guide part B are distributed at intervals up and down, the flow guide part A is a funnel-shaped component, the flow guide part B is a conical component with an upward conical tip, the central lines of the flow guide part A and the flow guide part B are consistent with the axis of a rotating shaft, the side edge of the upper end of the flow guide part A is fixedly arranged on the inner wall of a tower kettle, the lower end of the flow guide part A is provided with a water outlet for mixed liquid to fall down, the rotating shaft penetrates through the water outlet, the caliber of the water outlet is larger than the shaft diameter of the rotating shaft, the upper end of the flow guide part B is provided with a notch for the rotating shaft to penetrate, the caliber of the notch is larger than the shaft diameter of the rotating shaft and smaller than the caliber of the water outlet, a gap for mixed liquid to fall is arranged between, the stirring blade is used for stirring the mixed liquid flowing through the guide member A or the stirring member B.
Further: the upper side surfaces of the A flow guide part and the B flow guide part are provided with annular grooves, the grooves are distributed outwards at intervals by taking a rotating shaft axis as a central line, the stirring blades comprise stirring teeth, the stirring teeth are matched with the grooves, the stirring teeth and the grooves are arranged in a one-to-one correspondence mode, and the lower tooth ends of the stirring teeth are inserted into the grooves.
The post-treatment method for the continuous synthesis of methyl 4-chloroacetoacetate according to claim 7, characterized in that: the lower tooth end of the stirring tooth inserted into the groove comprises needle-shaped parts, the needle-shaped parts are arranged along the plumb direction, and the needle-shaped parts are distributed at intervals.
Further: the lower end of the tower kettle is provided with a liquid discharge port, a liquid distribution port and a circulation interface, the height of the liquid distribution port is larger than that of the circulation interface, the height of the circulation interface is larger than that of the liquid discharge port, the circulation interface is connected with a circulation pump through a pipeline, and the circulation pump is connected with a spray head B.
Further: the diversion mixing part is arranged on the rotating shaft.
The invention has the technical effects and advantages that: the method is simple and convenient to implement, the washing device provided by the invention can be used for continuously and rapidly washing the dichloromethane solution containing 4-chloroacetoacetic acid methyl ester, the washing effect is good, the efficiency is high, and the current use requirements are met.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment of a water washing mechanism according to the present invention.
FIG. 2 is a schematic view showing the inside structure of a column bottom in one embodiment of the water washing mechanism of the present invention.
FIG. 3 is a schematic diagram of a water washing assembly in an embodiment of the water washing mechanism of the present invention.
Description of reference numerals: 100-tower kettle, 110-liquid separation port, 120-circulation port, 130-liquid discharge port, 140-three-way valve, 150-circulation pump, 200-water washing mechanism, 210-guide mixing part, 220-stirring water washing component, 221-rotating shaft, 222-B guide part, 223-A guide part, 224-groove, 225-stirring blade, 226-stirring tooth, 227-needle part, 230-driving component, 300-A spray head and 400-B spray head.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. The embodiments of the present invention have been presented for purposes of illustration and description, and are not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Examples
The invention is described in further detail below with reference to the accompanying figures 1-3, in which:
a post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester comprises the following steps:
the method comprises the following steps: adopting diketene, chlorine, dichloromethane and methanol as raw materials, and preparing a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester through chlorination reaction and esterification reaction;
step two: adding a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester into a water washing device, and separating an aqueous solution from an organic solution;
step three: and rectifying the organic solution to obtain a finished product of the 4-chloroacetoacetic acid methyl ester.
The water washing device comprises a closed tower kettle 100, the tower kettle 100 is arranged along the plumb direction, an A spray head 300 for introducing a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester and a B spray head 400 for introducing water are arranged in the upper end of the tower kettle 100, the A spray head 300 and the B spray head 400 are correspondingly arranged, and a water washing mechanism 200 for stirring and mixing water and the dichloromethane solution containing 4-chloroacetoacetic acid methyl ester is arranged in the tower kettle 100; through the setting of A shower nozzle 300 and B shower nozzle 400, realize letting in the function that contains 4-chloroacetoacetic acid methyl ester's dichloromethane solution and water in tower cauldron 100, the two position corresponds for the dichloromethane solution that contains 4-chloroacetoacetic acid methyl ester sprays each other, realizes the function of mixing, and the setting through washing mechanism 200 in tower cauldron 100 realizes the washing processing function.
The washing mechanism 200 comprises a guide mixing part 210 and a stirring washing component 220 which are vertically distributed, wherein the guide mixing part 210 is used for mixing water and dichloromethane solution containing 4-chloroacetoacetic acid methyl ester and guiding the mixture to the stirring washing component 220, and the stirring washing component 220 is used for stirring the mixed solution of the two; by the arrangement of the pilot mixing member 210, the methylene chloride solution containing methyl 4-chloroacetoacetate and water are sprayed with each other and then fall onto the pilot mixing member 210, and then flow downward on the pilot mixing member 210, and the two are mixed while flowing.
The flow guide mixing part 210 is a spiral plate, and the spiral center of the flow guide mixing part 210 is consistent with the direction of the plumb; through the spiral arrangement, the flowing path and the flowing time of the dichloromethane solution containing the methyl 4-chloroacetoacetate and the water are prolonged, so that the two are mixed more thoroughly.
The stirring and water washing assembly 220 comprises a rotating shaft 221 and water washing assemblies, wherein the rotating shaft 221 is arranged along the plumb direction, and the water washing assemblies are axially distributed at intervals along the rotating shaft 221; through the setting of multiunit washing subassembly, realize carrying out multistage stirring washing's function to the mixed liquid of the two, drive assembly 230 is connected to pivot 221 upper end, and drive assembly 230 comprises gearbox and motor.
The water washing component comprises an A flow guide part 223, a B flow guide part 222 and stirring blades 225, the A flow guide part 223 and the B flow guide part 222 are distributed at intervals up and down, the A flow guide part 223 is a funnel-shaped component, the B flow guide part 222 is a conical component with an upward conical tip, the central lines of the A flow guide part 223 and the B flow guide part 222 are consistent with the axis of the rotating shaft 210, the side edge of the upper end of the A flow guide part 223 is fixedly arranged on the inner wall of the tower kettle 100, the lower end of the A flow guide part 223 is provided with a water outlet for mixed liquid to fall, the rotating shaft 210 penetrates through the water outlet, the caliber of the water outlet is larger than the axial diameter of the rotating shaft 210, the upper end of the B flow guide part 222 is provided with a notch for the rotating shaft 221 to penetrate through, the caliber of the notch is larger than the axial diameter of the rotating shaft 210 and smaller than the caliber of the water outlet, a gap for the, the stirring blade 225 is arranged above the flow guide piece A223 and the flow guide piece B222, and the stirring blade 225 is used for stirring the mixed liquid flowing through the flow guide piece A223 or the stirring piece B222; through the above arrangement, the two mixed solutions continuously flow from the upper side of the A diversion part 223 or the B stirring part 222, so that the two mixed solutions are continuously gathered or scattered, the stirring blades 225 are continuously stirred and washed in the process, the two mixed solutions are repeatedly mixed, stirred and washed, and the washing effect is good.
The upper sides of the flow guide part A223 and the flow guide part B222 are provided with annular grooves 224, the grooves 224 are distributed outwards at intervals by taking the axis of the rotating shaft 210 as a central line, the stirring blades 225 comprise stirring teeth 226, the stirring teeth 226 are matched with the grooves 224, the stirring teeth 226 are arranged in one-to-one correspondence with the grooves 224, and the lower tooth ends of the stirring teeth 226 are inserted into the grooves 224; through the aforesaid setting, the two mixes in the liquid flows into the recess, carries out short stay, and the mixed liquid that the stirring tooth 226 stayed in to recess 224 stirs the washing, and the washing is effectual.
The lower tooth end of the agitating tooth 226 inserted into the groove 227 includes needle parts 227, the needle parts 227 are arranged along the plumb direction, and the needle parts 227 are distributed at intervals; through the setting of needle 227, further promoted the stirring washing effect of the two mixed liquid, promoted washing quality and efficiency.
The lower end of the tower kettle 100 is provided with a liquid outlet 130, a liquid distribution port 110 and a circulation port 120, the height of the liquid distribution port 110 is greater than that of the circulation port 120, the height of the circulation port 120 is greater than that of the liquid outlet 130, the circulation port 120 is connected with a circulation pump 150 through a pipeline, and the circulation pump 150 is connected with a spray head 400B; through the setting, the functions of circulating water, liquid drainage and liquid separation are realized, the circulating pump 150 also circulates the three-way valve 140, and the three-way valve 140 is connected with the water pipe.
The water conservancy diversion mixing part 210 is installed on pivot 221, and pivot 221 drives the rotation of water conservancy diversion mixing part 210 for the dichloromethane solution that contains 4-chloroacetoacetic acid methyl ester and water when trickling on water conservancy diversion mixing part 210, can possess pivoted kinetic energy, make the better mixture of the two, be simultaneously with the mixed liquid of the two on the mode that spills falls into the washing subassembly, the going on of the follow-up stirring washing work of being convenient for.
The method is simple and convenient to implement, the washing device provided by the invention can be used for continuously and rapidly washing the dichloromethane solution containing 4-chloroacetoacetic acid methyl ester, the washing effect is good, the efficiency is high, and the current use requirements are met.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by one of ordinary skill in the art and related arts based on the embodiments of the present invention without any creative effort, shall fall within the protection scope of the present invention. Structures, devices, and methods of operation not specifically described or illustrated herein are generally practiced in the art without specific recitation or limitation.

Claims (10)

1. A post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester is characterized in that: the method comprises the following steps:
the method comprises the following steps: adopting diketene, chlorine, dichloromethane and methanol as raw materials, and preparing a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester through chlorination reaction and esterification reaction;
step two: adding a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester into a water washing device, and separating an aqueous solution from an organic solution;
step three: and rectifying the organic solution to obtain a finished product of the 4-chloroacetoacetic acid methyl ester.
2. The post-treatment method for continuously synthesizing methyl 4-chloroacetoacetate according to claim 1, characterized in that: the water washing device comprises a closed tower kettle (100), wherein the tower kettle (100) is arranged along the plumb direction, an A spray head (300) for introducing a dichloromethane solution containing 4-chloroacetoacetic acid methyl ester and a B spray head (400) for introducing water are arranged in the upper end of the tower kettle (100), the A spray head (300) and the B spray head (400) are correspondingly arranged, and a water washing mechanism (200) for stirring and mixing water and the dichloromethane solution containing 4-chloroacetoacetic acid methyl ester is arranged in the tower kettle (100).
3. The post-treatment method for the continuous synthesis of methyl 4-chloroacetoacetate according to claim 2, characterized in that: the water washing mechanism (200) comprises a guide mixing part (210) and a stirring water washing component (220) which are distributed up and down, the guide mixing part (210) is used for mixing water and dichloromethane solution containing 4-chloroacetoacetic acid methyl ester and guiding the mixture to the stirring water washing component (220), and the stirring water washing component (220) is used for stirring the mixture of the guide mixing part and the dichloromethane solution.
4. The post-treatment method for the continuous synthesis of methyl 4-chloroacetoacetate according to claim 3, characterized in that: the flow guide mixing piece (210) is a spiral plate, and the spiral center of the flow guide mixing piece (210) is consistent with the direction of the plumb.
5. The post-treatment method for the continuous synthesis of methyl 4-chloroacetoacetate according to claim 3, characterized in that: stirring washing subassembly (220) include pivot (221) and washing subassembly, and pivot (221) are arranged along the plummet direction, and the washing subassembly is along pivot (221) axial interval distribution.
6. The post-treatment method for continuously synthesizing methyl 4-chloroacetoacetate according to claim 5, wherein: the water washing component comprises a flow guide part A (223), a flow guide part B (222) and a stirring blade (225), the flow guide part A (223) and the flow guide part B (222) are distributed at intervals up and down, the flow guide part A (223) is a funnel-shaped component, the flow guide part B (222) is a conical component with an upward conical tip, the central lines of the flow guide part A (223) and the flow guide part B (222) are consistent with the axis of the rotating shaft (210), the side edge of the upper end of the flow guide part A (223) is fixedly arranged on the inner wall of the tower kettle (100), the lower end of the flow guide part A (223) is provided with a water outlet for mixed liquid to fall down, the rotating shaft (210) penetrates through the water outlet, the caliber of the water outlet is larger than the axial diameter of the rotating shaft (210), the upper end of the flow guide part B (222) is provided with a notch for the rotating shaft (221) to penetrate through, the caliber of the notch is larger than the axial, stirring leaf (225) and A water conservancy diversion spare (223), B water conservancy diversion spare (222) one-to-one arrange, stirring leaf (225) are arranged in A water conservancy diversion spare (223) and B water conservancy diversion spare (222) top, and stirring leaf (225) are installed on pivot (221), and stirring leaf (225) are used for stirring the mixed liquid that flows through on A water conservancy diversion spare (223) or B stirring spare (222).
7. The post-treatment method for continuously synthesizing methyl 4-chloroacetoacetate according to claim 6, wherein: the upper side surface of the A flow guide piece (223) and the B flow guide piece (222) is provided with an annular groove (224), the groove (224) is distributed outwards at intervals by taking the axis of the rotating shaft (210) as a central line, the stirring blade (225) comprises stirring teeth (226), the stirring teeth (226) are matched with the groove (224), the stirring teeth (226) and the groove (224) are arranged in a one-to-one correspondence mode, and the lower tooth end of the stirring teeth (226) is inserted into the groove (224).
8. The post-treatment method for the continuous synthesis of methyl 4-chloroacetoacetate according to claim 7, characterized in that: the lower tooth end of the stirring tooth (226) inserted into the groove (227) comprises needle parts (227), the needle parts (227) are arranged along the plumb direction, and the needle parts (227) are distributed at intervals.
9. The post-treatment method for the continuous synthesis of methyl 4-chloroacetoacetate according to claim 2, characterized in that: the lower end of the tower kettle (100) is provided with a liquid outlet (130), a liquid distribution port (110) and a circulation port (120), the height of the liquid distribution port (110) is larger than that of the circulation port (120), the height of the circulation port (120) is larger than that of the liquid outlet (130), the circulation port (120) is connected with a circulation pump (150) through a pipeline, and the circulation pump (150) is connected with a spray head B (400).
10. The work-up process for the continuous synthesis of methyl 4-chloroacetoacetate of claim 3 or 5, characterized in that: the flow guide mixing piece (210) is arranged on the rotating shaft (221).
CN202010893553.XA 2020-08-31 2020-08-31 Post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester Active CN111978182B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116328575A (en) * 2023-05-23 2023-06-27 北京中鑫美达技术服务有限公司 Hyaluronic acid dressing stock solution mixer

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103360256A (en) * 2013-07-29 2013-10-23 江苏恒安化工有限公司 Preparation method of 4-chloroacetoacetic acid ethyl ester

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103360256A (en) * 2013-07-29 2013-10-23 江苏恒安化工有限公司 Preparation method of 4-chloroacetoacetic acid ethyl ester

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116328575A (en) * 2023-05-23 2023-06-27 北京中鑫美达技术服务有限公司 Hyaluronic acid dressing stock solution mixer
CN116328575B (en) * 2023-05-23 2023-08-04 北京中鑫美达技术服务有限公司 Hyaluronic acid dressing stock solution mixer

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