CN106748867A - A kind of method of dichloroacetic acid in treatment Cocoamidopropyl betaine - Google Patents
A kind of method of dichloroacetic acid in treatment Cocoamidopropyl betaine Download PDFInfo
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- CN106748867A CN106748867A CN201611077737.9A CN201611077737A CN106748867A CN 106748867 A CN106748867 A CN 106748867A CN 201611077737 A CN201611077737 A CN 201611077737A CN 106748867 A CN106748867 A CN 106748867A
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- Prior art keywords
- dichloroacetic acid
- cocoamidopropyl
- cocoamidopropyl betaine
- sodium hydroxide
- temperature
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of method for processing dichloroacetic acid in Cocoamidopropyl betaine, with the Cocoamidopropyl betaine that monoxone is produced as raw material, temperature during by adjusting PKO (intermediate cocoamidopropyl dimethylamine amine) with chloroacetic hydrolysis, pH, reaction time, in guarantee, other indexs all meet Standard, in the case of not influenceing product quality, after Cocoamidopropyl betaine synthetic reaction is finished, again to adding NaOH in system, by the temperature for controlling reaction, pH, reaction time, remove the dichloroacetic acid in reaction system, even if using the chloroethene acid starting material of run-of-the-mill, dichloroacetic acid content in amido propyl betaine can also be reduced, and do not bring other impurities into.
Description
Technical field
The invention belongs to technical field of fine, and in particular to two chloroethenes in one kind treatment Cocoamidopropyl betaine
The method of acid.
Background technology
Amido propyl betaine is by aliphatic acid or fatty acid anhydride derivative and the reaction generation of N, N- dimethylated propyl diethylenetriamine
Mesosome amido propyl dimethylamine, abbreviation PKO, reuse PKO carries out quaternary ammonium with sodium chloroacetate (monoxone and NaOH synthesize)
Change the product of reaction, such as CAB, LAB.The synthesis of amido propyl betaine needs to use monoxone, and contains one in monoxone
Quantitative by-product dichloroacetic acid.According to the difference of by-product dichloroacetic acid content, chloroacetic price differs greatly, and secondary
Product dichloroacetic acid can produce serious skin and eye infringement, with the effect of stripping off of strong cutin.Current China's light industry
Clear stipulaties chloroacetic acid residual quantity must not exceed 20mg/kg to standard, and dichloroacetic acid residual quantity is also not required, but both at home and abroad
There is strict Con trolling index in major company, reflects following development trend of surfactant industry, with the progress of society, state
All the more attention of the family to aspects such as safe and environment-friendly, sustainable developments, the control for being related to the aspect index such as safe and environment-friendly will more
Hair is strict.At present, dichloroacetic acid residual quantity is controlled essentially by high-quality chloroethene acid starting material is purchased in amido propyl betaine
, it is not effectively treated by technique subsequently, cause the purchasing of raw materials high expensive of current product, fall in profitability.
And it is less with document on reducing the patent of dichloroacetic acid content in solution at present, some correlations for using now
Technical method is as follows：1st, patent publication No. CN105646190A discloses one kind comprising chloroacetic acid, dichloroacetic acid and optional second
Acid and/or the liquid feedstock of trichloroacetic acid undergo catalytic hydrogenation and dechlorination step, by making it with hydrogen source comprising being deposited on carrier
On one or more metal of periodic table of elements group VIII solid heterogeneous hydrogenation catalyst in the presence of contact with by dichloro
Acetic acid changes into chloroacetic acid and carries out.2、《The research of 60Co- γ radiation methods degraded dichloroacetic acid》It is middle straight with 60Co- γ respectively
Radiation method, O3 oxidizing process and 60Co- γ radiation and the united method treatment di-chloroacetic acid solutions of O3 are connect, compares three kinds of drops of method
Solution effect, has inquired into the influence of absorbed dose of radiation, initial concentration solution, irradiation atmosphere to dichloroacetic acid palliating degradation degree.On degraded
The patent document of dichloroacetic acid is less in solution system, and the overwhelming majority is for the treatment of drinking water, other water solution systems
Patent document is little.
The content of the invention
For the Cocoamidopropyl betaine that above-mentioned problem, the present invention are produced with monoxone as raw material, pass through
The parameters such as temperature, pH when adjustment PKO (intermediate cocoamidopropyl dimethylamine amine) is with chloroacetic hydrolysis, in guarantee, other refer to
Mark all meets Standard, in the case of not influenceing product quality, after Cocoamidopropyl betaine synthetic reaction is finished, then
To NaOH is added in system, by controlling the temperature of reaction, pH in the reaction time, removes the dichloroacetic acid in reaction system,
Even if using the chloroethene acid starting material of run-of-the-mill, reducing dichloroacetic acid content in amido propyl betaine, and other are not brought into
Impurity.
Technical scheme is as follows：
The method of dichloroacetic acid, comprises the following steps in a kind for the treatment of Cocoamidopropyl betaine：
(1) a certain amount of deionized water is put into there-necked flask, by intermediate cocoamidopropyl dimethylamine amine (PKO),
A certain amount of monoxone is added in there-necked flask, then adds a certain amount of sodium hydroxide solution, stirs and rise high-temperature
Reach 80 DEG C；
(2) then add a certain amount of 35% sodium hydroxide solution, addition finish after, control temperature keep 80~90
DEG C, pH value of solution is kept between 8.5~9.5,1~5h of isothermal reaction；
(3) and then add sodium hydroxide solution, improve pH value of solution to 10~14, increase the temperature to 110~150 DEG C, and
And after keeping 1~5h of reaction time, reaction to terminate, temperature is reduced to less than 70 DEG C, with citric acid and pH is between 6~8, plus
It is 35% to enter deionized water regulation solid content, detects dichloroacetic acid content.
Wherein, the cocoamidopropyl dimethylamine amine for being added in step (1) is with chloroacetic mol ratio 1：1~1：1.15 it
Between, optimum molar ratio 1：1.05；
Cocoamidopropyl dimethylamine amine is with deionized water mol ratio 1：28~1：Between 29；
Sodium hydroxide solution is with chloroacetic mol ratio 0.15：1~0.35：1, optimum molar ratio 0.2：1；
The sodium hydroxide solution added in step (2) is with chloroacetic mol ratio 0.7：1~1：1, keep pH value of solution
8.5~9.5.
NaOH is preferably added in step (3), pH value of solution to 12~13 is improved, temperature range is 120~125 DEG C, instead
It is 2~3h between seasonable.
The synthetic reaction equation of Cocoamidopropyl betaine is：
Treatment remains dichloroacetic acid reaction equation：
Beneficial effect
Compared with prior art, the present invention has following effect：The coconut oleoyl amine that the present invention is produced with monoxone as raw material
CAB, temperature during by adjusting PKO (intermediate cocoamidopropyl dimethylamine amine) with chloroacetic hydrolysis, pH, instead
Between seasonable, in guarantee, other indexs all meet Standard, in the case of not influenceing product quality, in cocamidopropyl propyl amide beet
After alkali synthetic reaction is finished, then to NaOH is added in system, by controlling the temperature of reaction, pH in the reaction time, is removed anti-
The dichloroacetic acid in system is answered, even if using the chloroethene acid starting material of run-of-the-mill, reducing dichloroacetic acid in amido propyl betaine
Content, and do not bring other impurities into.
The present invention is NaOH using strong alkaline substance, is the production intrinsic raw material of amido propyl betaine, will not be produced
Secondary harmful substance, is more beneficial for improve product quality, and whole technique is advanced, and removal dichloroacetic acid effect is obvious, in the present invention
Whole technological operation is simple, and temperature, pressure is small, not high to equipment requirement, is conducive to industrialized production.Monoxone is former in the present invention
Material can use inferior grade quality feedstocks, reduce production cost.The present invention is simple to operate, without using other raw materials,
The content of dichloroacetic acid in amido propyl betaine can be effectively reduced.
Specific embodiment：
Comparative example 1：(existing amido propyl betaine technique)
516 grams of deionized waters are put into there-necked flask, by the cocoamidopropyl dimethylamine amine and 1.05mol chloroethenes of 1mol
Sour (dichloroacetic acid content 0.6%) is added in there-necked flask, is subsequently adding 35% 24 grams of sodium hydroxide solution, is stirred and is risen
Then high-temperature adds 35% 96 grams of sodium hydroxide solution to 80 DEG C, and after addition is finished, control temperature is 80 DEG C~90
DEG C, pH between 8.5~9.5, keep 3h, then add NaOH, improve pH value of solution to 12~13, increase the temperature to
100 DEG C, reaction finishes reduction temperature to less than 70 DEG C after 3h, adds lemon acid for adjusting pH to neutral, adds deionized water regulation
Solid content is 35%.
Detection dichloroacetic acid content 420ppm (in the case of untreated residual dichloroacetic acid, is calculated, two by product formula
Chloroacetic theoretical residual volume is 506ppm).
Comparative example 2：(existing amido propyl betaine technique)
516 grams of deionized waters are put into there-necked flask, by the cocoamidopropyl dimethylamine amine and 1.05mol chloroethenes of 1mol
Sour (below dichloroacetic acid content 0.1%) is added in there-necked flask, is subsequently adding 35% 24 grams of sodium hydroxide solution, is stirred
And increase the temperature to 80 DEG C, then add 35% 96 grams of sodium hydroxide solution, after addition is finished, control temperature 80 DEG C~
90 DEG C, pH 3h is kept between 8.5~9.5, then add NaOH, improve pH value of solution to 12~13, increase the temperature to
100 DEG C, reaction finishes reduction temperature to less than 70 DEG C after 3h, adds lemon acid for adjusting pH to neutral, adds deionized water regulation
Solid content is 35%.
Detection dichloroacetic acid content 73ppm (in the case of untreated residual dichloroacetic acid, is calculated, two by product formula
Chloroacetic theoretical residual volume is 82ppm).
Embodiment 1：
516 grams of deionized waters are put into there-necked flask, by the cocoamidopropyl dimethylamine amine and 1.05mol chloroethenes of 1mol
Sour (dichloroacetic acid content 0.6%) is added in there-necked flask, is subsequently adding 35% 24 grams of sodium hydroxide solution, is stirred and is risen
High-temperature is subsequently adding 35% 96 grams of sodium hydroxide solution to 80 DEG C, after addition is finished, control temperature 80 DEG C~90 DEG C,
PH keeps 3h between 8.5~9.5, then adds NaOH, improves pH value of solution to 12~13, increases the temperature to 110
DEG C, reaction finishes reduction temperature to less than 70 DEG C after 5h, adds lemon acid for adjusting pH to neutral, adds deionized water regulation to contain admittedly
Measure is 35%.
Detection dichloroacetic acid content 90ppm (in the case of untreated residual dichloroacetic acid, is calculated, two by product formula
Chloroacetic theoretical residual volume is 506ppm).
Embodiment 2：
516 grams of deionized waters are put into there-necked flask, by the cocoamidopropyl dimethylamine amine and 1.05mol chloroethenes of 1mol
Sour (dichloroacetic acid content 0.6%) is added in there-necked flask, is subsequently adding 35% 24 grams of sodium hydroxide solution, is stirred and is risen
High-temperature is subsequently adding 35% 96 grams of sodium hydroxide solution to 80 DEG C, after addition is finished, control temperature 80 DEG C~90 DEG C,
PH keeps 3h between 8.5~9.5, then adds NaOH, improves pH value of solution to 12~13, increases the temperature to 125 DEG C,
Reaction finishes reduction temperature to less than 70 DEG C after 3h, adds lemon acid for adjusting pH to neutral, adds deionized water regulation solid content
It is 35%.
Detection dichloroacetic acid content 37ppm (in the case of untreated residual dichloroacetic acid, is calculated, two by product formula
Chloroacetic theoretical residual volume is 506ppm)
Embodiment 3：
516 grams of deionized waters are put into there-necked flask, by the cocoamidopropyl dimethylamine amine and 1.05mol chloroethenes of 1mol
Sour (dichloroacetic acid content 0.6%) is added in there-necked flask, is subsequently adding 35% 24 grams of sodium hydroxide solution, is stirred and is risen
High-temperature is subsequently adding 35% 96 grams of sodium hydroxide solution to 80 DEG C, after addition is finished, control temperature 80 DEG C~90 DEG C,
PH keeps 3h between 8.5~9.5, then adds NaOH, improves pH value of solution to 12~13, increases the temperature to 150 DEG C,
Reaction finishes reduction temperature to less than 70 DEG C after 1h, adds lemon acid for adjusting pH to neutral, adds deionized water regulation solid content
It is 35%.
Detection dichloroacetic acid content 45ppm (in the case of untreated residual dichloroacetic acid, is calculated, two by product formula
Chloroacetic theoretical residual volume is 506ppm).
Claims (8)
1. it is a kind of process Cocoamidopropyl betaine in dichloroacetic acid method, it is characterised in that：Comprise the following steps：
(1) a certain amount of deionized water is put into there-necked flask, by intermediate cocoamidopropyl dimethylamine amine (PKO), necessarily
The monoxone of amount is added in there-necked flask, then adds a certain amount of sodium hydroxide solution, is stirred and is risen high-temperature and reach
80℃；
(2) then add a certain amount of 35% sodium hydroxide solution, addition finish after, control temperature keep 80~90 DEG C,
PH value of solution is kept between 8.5~9.5,1~5h of isothermal reaction；
(3) and then add sodium hydroxide solution, improve pH value of solution to 10~14, increase the temperature to 110~150 DEG C, and protect
Hold 1~5h of reaction time, after reaction terminates, reduce temperature to less than 70 DEG C, with citric acid and pH is between 6~8, addition is gone
Ionized water regulation solid content is 35%, detects dichloroacetic acid content.
2. a kind of method for processing dichloroacetic acid in Cocoamidopropyl betaine according to claim 1, its feature exists
In：The cocoamidopropyl dimethylamine amine added in step (1) is with chloroacetic mol ratio 1：1~1：Between 1.15.
3. a kind of method for processing dichloroacetic acid in Cocoamidopropyl betaine according to claim 2, its feature exists
In：The cocoamidopropyl dimethylamine amine added in step (1) is with chloroacetic mol ratio 1：1.05.
4. a kind of method for processing dichloroacetic acid in Cocoamidopropyl betaine according to claim 1, its feature exists
In：Cocoamidopropyl dimethylamine amine and deionized water mol ratio are 1 in step (1)：28~1：Between 29.
5. a kind of method for processing dichloroacetic acid in Cocoamidopropyl betaine according to claim 1, its feature exists
In：In step (1) sodium hydroxide solution with chloroacetic mol ratio 0.15：1~0.35：1.
6. a kind of method for processing dichloroacetic acid in Cocoamidopropyl betaine according to claim 5, its feature exists
In：In step (1) sodium hydroxide solution with chloroacetic mol ratio 0.2：1.
7. a kind of method for processing dichloroacetic acid in Cocoamidopropyl betaine according to claim 1, its feature exists
In：The sodium hydroxide solution added in step (2) is with chloroacetic mol ratio 0.7：1~1：1, make pH value of solution keep 8.5~
9.5。
8. a kind of method for processing dichloroacetic acid in Cocoamidopropyl betaine according to claim 1, its feature exists
In：NaOH is added in step (3), pH value of solution to 12~13 is improved, temperature range is 120~125 DEG C, and the reaction time is 2
~3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611077737.9A CN106748867A (en) | 2016-11-29 | 2016-11-29 | A kind of method of dichloroacetic acid in treatment Cocoamidopropyl betaine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611077737.9A CN106748867A (en) | 2016-11-29 | 2016-11-29 | A kind of method of dichloroacetic acid in treatment Cocoamidopropyl betaine |
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| WO1999031046A1 (en) * | 1997-12-13 | 1999-06-24 | Cognis Deutschland Gmbh | Betaine solutions with an improved odour |
| US6335370B1 (en) * | 1997-11-07 | 2002-01-01 | Ceca S.A. | Fluid concentrated hydroalcoholic compositions of copra or oil palm alkyl-amidopropylbetains |
| JP2003300926A (en) * | 2002-04-08 | 2003-10-21 | Nippon Shokubai Co Ltd | METHOD FOR PRODUCING alpha-HYDROXYCARBOXYLIC ACID OR alpha- OXOCARBOXYLIC ACID |
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| US5470992A (en) * | 1992-02-26 | 1995-11-28 | Th. Goldschmidt Ag | Method for the synthesis of betaines containing≦10 ppm of organically bound chlorine |
| US6335370B1 (en) * | 1997-11-07 | 2002-01-01 | Ceca S.A. | Fluid concentrated hydroalcoholic compositions of copra or oil palm alkyl-amidopropylbetains |
| WO1999031046A1 (en) * | 1997-12-13 | 1999-06-24 | Cognis Deutschland Gmbh | Betaine solutions with an improved odour |
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| US20100209723A1 (en) * | 2007-08-31 | 2010-08-19 | The Nippon Synthetic Chemical Industry Co., Ltd. | Crosslinking agent, crosslinked polymer, and uses thereof |
| CN102134202A (en) * | 2011-01-31 | 2011-07-27 | 浙江赞宇科技股份有限公司 | Technology for continuously producing alkyl amide propyl group betaine |
| CN102276442A (en) * | 2011-07-07 | 2011-12-14 | 赵永俊 | Synthetic method of dichloroacetate |
| CN102585092A (en) * | 2012-01-16 | 2012-07-18 | 西南石油大学 | Betaine type salt-resistant polymer and preparation method thereof |
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