CN113024401A - Preparation process of amino acid surfactant capable of reducing byproducts - Google Patents

Preparation process of amino acid surfactant capable of reducing byproducts Download PDF

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CN113024401A
CN113024401A CN202110182445.6A CN202110182445A CN113024401A CN 113024401 A CN113024401 A CN 113024401A CN 202110182445 A CN202110182445 A CN 202110182445A CN 113024401 A CN113024401 A CN 113024401A
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amino acid
reaction kettle
reaction
pipe
acid surfactant
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刘振华
陈胜环
张涌
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Guangzhou Flower's Song Fine Chemical Co ltd
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Abstract

A preparation process of an amino acid surfactant for reducing byproducts relates to the technical field of surfactants; the method comprises the following steps: s1, adding sodium sarcosinate and deionized water into the reaction kettle, and introducing chilled water into a coil pipe on the outer wall of the reaction kettle to cool the reaction kettle; s2, adding lauroyl chloride into the reaction kettle from the second raw material tank through a return pipe, and introducing chilled water into the heat exchanger for cooling; s3, starting a material external circulation system to fully mix and react the materials; s4, introducing steam into the coil and the heat exchanger for heating; s5, adding deionized water into the material obtained after the reaction for dilution; and S6, inputting the diluted materials from the material tank into a membrane separation device through a material pipe for separation. The invention effectively reduces the content of sodium chloride, fatty acid salt, amino acid and salt thereof, improves the reaction efficiency, improves the conversion rate of fatty acyl chloride and amino acid, and reduces the hydrolysis rate of the amino acid surfactant.

Description

Preparation process of amino acid surfactant capable of reducing byproducts
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to a preparation process of an amino acid surfactant capable of reducing byproducts.
Background
The amino acid surfactant is a novel green environment-friendly surfactant derived from renewable biomass, and is an upgraded and updated product of the traditional surfactant. The amino acid surfactant has the advantages of wide biomass raw material source, small toxic and side effect, mild performance, small irritation, good biodegradability and green production process, and the good performances of emulsification, wetting, solubilization, dispersion, foaming and the like of the amino acid surfactant are paid attention to by people at present and are gradually applied to various fields of washing, personal care, food industry and the like.
The conventional amino acid surfactants on the market mainly comprise four types, namely sarcosines, alanines, glycines and glutamines, and the main by-products in the amino acid surfactants are illustrated by taking sodium lauroyl sarcosinate as an example.
The raw materials for producing sodium lauroyl sarcosinate mainly comprise lauroyl chloride, sodium sarcosinate and sodium hydroxide, and the formula is as follows:
Figure BDA0002941794450000011
as can be seen from the main reaction, there are a large amount of sodium chloride by-product, and there is not completely reacted sodium sarcosinate, and lauroyl chloride in the raw material is easily hydrolyzed, so there is also a by-product of fatty acid sodium salt, and the reaction equation of the fatty acid sodium salt is as follows:
Figure BDA0002941794450000012
in the conventional process, if the sodium chloride in the sodium lauroyl sarcosine is to be removed, excessive hydrochloric acid is added to acidify the product to generate the lauroyl sarcosine, and the lauroyl sarcosine is insoluble in water, needs to be separated by heating, needs a better desalting effect and needs to be washed once by deionized water. The equation is as follows:
Figure BDA0002941794450000021
during the acidification with excess hydrochloric acid, a small amount of lauroyl sarcosine must be hydrolyzed, resulting in more sodium fatty acid and sodium sarcosinate. The equation is as follows:
Figure BDA0002941794450000022
therefore, three major by-products, namely sodium chloride, fatty acid salts, amino acids and salts thereof, generally exist in the preparation process of the amino acid surfactant.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation process of an amino acid surfactant capable of reducing byproducts, effectively reducing the content of sodium chloride, fatty acid salt, amino acid and salt thereof, improving the reaction efficiency, improving the conversion rate of fatty acyl chloride and amino acid, and reducing the hydrolysis rate of the amino acid surfactant.
The purpose of the invention is realized by adopting the following technical scheme:
provides a preparation process of an amino acid surfactant for reducing byproducts, which comprises the following steps:
s1, adding sodium sarcosinate and water into the reaction kettle, stirring, and introducing chilled water into a coil pipe on the outer wall of the reaction kettle to cool the reaction kettle;
s2, adding lauroyl chloride into the reaction kettle from the first raw material tank through a return pipe, wherein the return pipe is provided with a heat exchanger, introducing chilled water into the heat exchanger for cooling, then adding alkali liquor into the reaction kettle from the second raw material tank through a feeding pipe, and simultaneously closing valves of the first raw material tank and the second raw material tank after adding the lauroyl chloride;
s3, starting a material external circulation system consisting of a reaction kettle, a discharge pipe connected with the bottom of the reaction kettle, a first centrifugal pump arranged on the discharge pipe and a return pipe connected with the discharge pipe, and fully mixing and reacting the materials;
s4, stopping introducing chilled water into the coil and the heat exchanger, and introducing steam into the coil and the heat exchanger for heating respectively to heat materials for reaction;
s5, after the reaction is finished, closing the return pipe, feeding the material obtained after the reaction into a material tank through a discharge pipe, and adding water into the material tank for dilution;
and S6, inputting the diluted materials from the material tank into the membrane separation equipment through the material pipe for separation, returning trapped liquid into the material tank through the circulating pipe, and inputting the permeated liquid into the wastewater tank.
Further, in step S1, the temperature of the reaction kettle is maintained at 10-20 ℃.
Further, in step S2, the molar ratio of lauroyl chloride to sodium sarcosinate is 1: 0.8-1.2.
Further, in step S2, the return pipe is connected to an annular feeding pipe installed above the inside of the reaction kettle, and a plurality of through holes are provided in the annular feeding pipe. In slowly injecting into the bed charge at the uniform velocity along reation kettle inner wall with lauroyl chloride through annular charging tube, disperse lauroyl chloride, help promoting reaction efficiency, prevent that local concentration is too high, lead to its hydrolysis aggravation, produce by-products such as fatty acid.
Further, in step S2, the temperature of the reaction kettle is kept at 10-20 ℃, and the pH value is 8-9; when the pH value of the reaction kettle is less than 8, adding alkali liquor through the second raw material tank to maintain the pH value stable.
Further, in step S3, the mixing time is 0.5-3 h.
Further, in step S4, the reaction temperature of the reaction kettle is 60-80 ℃, the pH value is 8-9, and the reaction time is 1-3 h. The pH value is kept between 8 and 9, which is beneficial to the forward reaction balance of the product and reduces the hydrolysis of the product.
Further, in step S5, the material and the deionized water are diluted according to the mass ratio of 1: 0.6-1.4.
Further, in step S6, the molecular weight of the membrane cut-off in the membrane separation device is 120-200 Da. At this molecular weight, the macromolecular amino acid surfactant can be trapped by sodium chloride and residual amino acid.
Compared with the prior art, the invention has the beneficial effects that:
the preparation process of the amino acid surfactant capable of reducing the byproducts effectively reduces the content of sodium chloride, fatty acid salt, amino acid and salt thereof, improves the reaction efficiency, improves the conversion rate of fatty acyl chloride and amino acid, and reduces the hydrolysis rate of the amino acid surfactant. Wherein the content of the first and second substances,
by controlling the pH and the temperature in the reaction system, the lauroyl chloride uniformly disperses along the inner wall of the reaction kettle through the annular feeding pipe and flows into the bed charge, so that the hydrolysis of the lauroyl chloride is effectively reduced, the reaction efficiency is improved, and the content of residual fatty acid in the final product is lower than 1%;
dangerous chemicals such as concentrated hydrochloric acid and the like are not needed in the reaction process, so that the safety of the reaction process is improved, the possibility of hydrolysis of reaction products under strong acidity is avoided, and the production of byproducts is reduced;
the mode that stirring formula reation kettle and extrinsic cycle combined together further lets intensive mixing between the material to because extrinsic cycle, the temperature of material in the reation kettle can be reduced well, side reactions such as further avoiding taking place to hydrolyze, oxidize, thereby effectively solved single cauldron reaction dispersibility poor, heat exchange efficiency low, the high-speed stirring easily bleeds the scheduling problem.
By using membrane separation equipment, the content of residual amino acid can be reduced while the content of main by-product sodium chloride is reduced, and the residual amount of the amino acid is lower than 0.3 percent; the conventional process uses an excessive hydrochloric acid acidification method to remove sodium chloride, which can cause hydrolysis of a small amount of amino acid surfactant and increase by-products of fatty acid salt and amino acid and salt thereof; the invention makes the material flow through the membrane separation equipment, and the sodium chloride and the micromolecule amino acid permeate the membrane through high pressure, and flow into the waste water tank along with water at the low pressure side, and the macromolecules such as active matters at the high pressure side continuously flow into the material tank, and the circulation is carried out, so that the sodium chloride of the product can be greatly reduced.
Drawings
FIG. 1 is a flow diagram of a process for the preparation of a reduced byproduct amino acid surfactant according to the present invention.
In the figure: 1. a second feed tank; 2. a reaction kettle; 21. a coil pipe; 22. an annular feed tube; 3. a first raw material tank; 4. a heat exchanger; 5. a material tank; 6. a membrane separation device; 7. a wastewater tank; 81. a discharge pipe; 82. a return pipe; 83. a material pipe; 84. a circulation pipe; 91. a first valve; 92. a second valve; 93. a third valve; 94. a fourth valve; 95. a fifth valve; 96. a sixth valve; 97. a seventh valve; 98. an eighth valve; 99. a ninth valve; 101. a first centrifugal pump; 102. a second centrifugal pump.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
Example 1
A preparation process of an amino acid surfactant with reduced by-products, referring to FIG. 1, comprises the following steps:
s1, adding sodium sarcosinate and deionized water into a reaction kettle 2, stirring, and introducing chilled water into a coil 21 on the outer wall of the reaction kettle 2 to cool, so that the temperature of the reaction kettle 2 is kept at 20 ℃;
s2, opening a third valve 93 and a fourth valve 94, starting a first centrifugal pump 101, adding lauroyl chloride into a reaction kettle 2 from a first raw material tank 3 through a return pipe 82, wherein the return pipe 82 is provided with a heat exchanger 4, introducing chilled water into the heat exchanger 4 to cool the reaction kettle 2, so that the temperature of the reaction kettle 2 is kept at 20 ℃, the return pipe 82 is connected with an annular feeding pipe 22 installed above the reaction kettle 2, a plurality of through holes are formed in the annular feeding pipe 22, and lauroyl chloride is slowly injected into a base material along the inner wall of the reaction kettle 2 at a constant speed through the through holes of the annular feeding pipe 22, and the annular feeding pipe 22 can facilitate the dispersion of the lauroyl chloride, thereby facilitating the improvement of reaction efficiency, and preventing the hydrolysis aggravation caused by over-high local concentration, and the generation of by-products such as; opening the first valve 91, adding alkali liquor into the reaction kettle 2 from the second raw material tank 1 through the feeding pipe, and controlling the pH value of the materials to be 8-9; closing the third valve 93 and the first valve 91 until the addition of the lauroyl chloride is finished; preferably, the molar ratio of lauroyl chloride to sodium sarcosinate is 1: 1;
meanwhile, the pH value of the materials in the reaction kettle 2 is periodically detected, and when the pH value of the reaction kettle 2 is less than 8, alkali liquor needs to be added through the second raw material tank 1 to maintain the pH value to be stable in the range of 8-9;
s3, opening a second valve 92, and opening a material external circulation system consisting of the reaction kettle 2, a discharge pipe 81 connected with the bottom of the reaction kettle 2, a first centrifugal pump 101 arranged on the discharge pipe 81, and a return pipe 82 connected with the discharge pipe 81 to fully mix the materials for 1 hour;
s4, stopping introducing chilled water into the coil 21 and the heat exchanger 4, and introducing steam into the coil 21 and the heat exchanger 4 respectively for heating to heat materials for reaction; the reaction temperature of the reaction kettle 2 is 70 ℃, the pH value is 8-9, and the reaction time is 2 h. The pH value is kept between 8 and 9, which is beneficial to the forward reaction balance of the product and reduces the hydrolysis of the product;
s5, after the reaction is finished, closing the fourth valve 94, opening the fifth valve 95, feeding the material obtained after the reaction into the material tank 5 through the discharge pipe 81, opening the sixth valve 96 and the seventh valve 97, starting the second centrifugal pump 102, and adding deionized water into the material tank 5 for dilution; diluting according to the mass ratio of the materials to the deionized water of 1:1, and closing the seventh valve 97 after uniform dilution;
s6, opening an eighth valve 98 and a ninth valve 99, inputting the diluted materials from the material tank 5 into the membrane separation equipment 6 through the material pipe 83 for separation, allowing the materials to flow through the membrane separation equipment 6, allowing sodium chloride and micromolecular amino acid to permeate through the membrane under high pressure, flowing into the wastewater tank 7 along with water at the low pressure side, wherein the molecular weight intercepted by the membrane in the membrane separation equipment 6 is 200Da, the high pressure side is macromolecules such as active matters, and the macromolecules continuously flow into the material tank 5 through the circulating pipe 84, and the circulation is carried out in such a way, so that the sodium chloride of the product can be reduced to 1% from about 5% of the original sodium chloride.
The solid content of the final product obtained by the reaction is 30%, wherein the by-product fatty acid salt is lower than 1%, the amino acid residue is lower than 0.3%, and the sodium chloride residue is lower than 1%, so that the quality of the amino acid product is greatly improved. The embodiment effectively reduces the content of sodium chloride, fatty acid salt, amino acid and salt thereof, improves the reaction efficiency, improves the conversion rate of fatty acyl chloride and amino acid, and reduces the hydrolysis rate of the amino acid surfactant. Wherein the content of the first and second substances,
by controlling the pH and the temperature in the reaction system, the lauroyl chloride uniformly disperses along the inner wall of the reaction kettle through the annular feeding pipe and flows into the bed charge, so that the hydrolysis of the lauroyl chloride is effectively reduced, the reaction efficiency is improved, and the content of residual fatty acid in the final product is lower than 1%;
dangerous chemicals such as concentrated hydrochloric acid and the like are not needed in the reaction process, so that the safety of the reaction process is improved, the possibility of hydrolysis of reaction products under strong acidity is avoided, and the production of byproducts is reduced;
by using the membrane separation equipment 6, the content of residual amino acid can be reduced while the content of main by-product sodium chloride is reduced; the conventional process uses an excessive hydrochloric acid acidification method to remove sodium chloride, which can cause hydrolysis of a small amount of amino acid surfactant and increase by-products of fatty acid salt and amino acid and salt thereof; the invention leads the material to flow through the membrane separation equipment 6, sodium chloride and micromolecule amino acid permeate the membrane through high pressure, the material flows into the waste water tank 7 along with water at the low pressure side, macromolecules such as active matters at the high pressure side continuously flow into the material tank 5, and the circulation is carried out, so that the sodium chloride of the product can be greatly reduced.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.

Claims (9)

1. A preparation process of an amino acid surfactant capable of reducing byproducts is characterized by comprising the following steps:
s1, adding sodium sarcosinate and water into the reaction kettle, stirring, and introducing chilled water into a coil pipe on the outer wall of the reaction kettle to cool the reaction kettle;
s2, adding lauroyl chloride into the reaction kettle from the first raw material tank through a return pipe, wherein the return pipe is provided with a heat exchanger, introducing chilled water into the heat exchanger for cooling, then adding alkali liquor into the reaction kettle from the second raw material tank through a feeding pipe, and simultaneously closing valves of the first raw material tank and the second raw material tank after adding the lauroyl chloride;
s3, starting a material external circulation system consisting of a reaction kettle, a discharge pipe connected with the bottom of the reaction kettle, a first centrifugal pump arranged on the discharge pipe and a return pipe connected with the discharge pipe, and fully mixing and reacting the materials;
s4, stopping introducing chilled water into the coil and the heat exchanger, and introducing steam into the coil and the heat exchanger for heating respectively to heat materials for reaction;
s5, after the reaction is finished, closing the return pipe, feeding the material obtained after the reaction into a material tank through a discharge pipe, and adding water into the material tank for dilution;
and S6, inputting the diluted materials from the material tank into the membrane separation equipment through the material pipe for separation, returning trapped liquid into the material tank through the circulating pipe, and inputting the permeated liquid into the wastewater tank.
2. The process for preparing a by-product-reducing amino acid surfactant according to claim 1, wherein: in step S1, the temperature of the reaction kettle is maintained at 10-20 ℃.
3. The process for preparing a by-product-reducing amino acid surfactant according to claim 1, wherein: in step S2, the molar ratio of lauroyl chloride to sodium sarcosinate is 1: 0.8-1.2.
4. The process for preparing a by-product-reducing amino acid surfactant according to claim 1, wherein: in step S2, the return pipe is connected to an annular feed pipe installed above the inside of the reaction kettle, and a plurality of through holes are provided in the annular feed pipe.
5. The process for preparing a by-product-reducing amino acid surfactant according to claim 1, wherein: in step S2, the temperature of the reaction kettle is kept at 10-20 ℃, and the pH value is 8-9; when the pH value of the reaction kettle is less than 8, adding alkali liquor through the second raw material tank to maintain the pH value stable.
6. The process for preparing a by-product-reducing amino acid surfactant according to claim 1, wherein: in step S3, the mixing time is 0.5-3 h.
7. The process for preparing a by-product-reducing amino acid surfactant according to claim 1, wherein: in step S4, the reaction temperature of the reaction kettle is 60-80 ℃, the pH value is 8-9, and the reaction time is 1-3 h.
8. The process for preparing a by-product-reducing amino acid surfactant according to claim 1, wherein: in step S5, diluting according to the mass ratio of the material to the deionized water of 1: 0.6-1.4.
9. The process for preparing a by-product-reducing amino acid surfactant according to claim 1, wherein: in step S6, the molecular weight of the membrane cut-off in the membrane separation device is 120-200 Da.
CN202110182445.6A 2021-02-07 2021-02-07 Preparation process of amino acid surfactant capable of reducing byproducts Pending CN113024401A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023184806A1 (en) * 2022-04-01 2023-10-05 岳阳科罗德联合化学工业有限公司 Production system and preparation method for continuous-flow production of salt-free amino acid surfactant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH072747A (en) * 1990-12-14 1995-01-06 Hoechst Japan Ltd Purification of n-long chain-acyl acidic amino acid salt
US20040063980A1 (en) * 2001-01-18 2004-04-01 Hans-Christian Raths Method for producing acyl amino acids
CN102126984A (en) * 2010-12-30 2011-07-20 上海奥利实业有限公司 Condensation production process and special device of N-long-chain acyl amino acid salt
CN103242206A (en) * 2013-05-30 2013-08-14 湖南众业科技实业有限公司 Production process for preparing fatty acyl-N-sodium methyl taurate surfactant
CN111333531A (en) * 2020-03-10 2020-06-26 上海利盛生化有限公司 Preparation process of sodium lauroyl sarcosinate and application of sodium lauroyl sarcosinate in field of daily chemicals

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH072747A (en) * 1990-12-14 1995-01-06 Hoechst Japan Ltd Purification of n-long chain-acyl acidic amino acid salt
US20040063980A1 (en) * 2001-01-18 2004-04-01 Hans-Christian Raths Method for producing acyl amino acids
CN102126984A (en) * 2010-12-30 2011-07-20 上海奥利实业有限公司 Condensation production process and special device of N-long-chain acyl amino acid salt
CN103242206A (en) * 2013-05-30 2013-08-14 湖南众业科技实业有限公司 Production process for preparing fatty acyl-N-sodium methyl taurate surfactant
CN111333531A (en) * 2020-03-10 2020-06-26 上海利盛生化有限公司 Preparation process of sodium lauroyl sarcosinate and application of sodium lauroyl sarcosinate in field of daily chemicals

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023184806A1 (en) * 2022-04-01 2023-10-05 岳阳科罗德联合化学工业有限公司 Production system and preparation method for continuous-flow production of salt-free amino acid surfactant

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