CN108484450B - Synthetic method of oleic acid disodium salt - Google Patents
Synthetic method of oleic acid disodium salt Download PDFInfo
- Publication number
- CN108484450B CN108484450B CN201810270457.2A CN201810270457A CN108484450B CN 108484450 B CN108484450 B CN 108484450B CN 201810270457 A CN201810270457 A CN 201810270457A CN 108484450 B CN108484450 B CN 108484450B
- Authority
- CN
- China
- Prior art keywords
- methyl oleate
- ethoxylate
- reaction
- oleic acid
- sulfonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A synthetic method of oleic acid disodium salt is to react oleic acid, methanol and p-toluenesulfonic acid to obtain methyl oleate; then adding methyl oleate and ethylene oxide to obtain methyl oleate ethoxylate; the intermediate product is subjected to sulfonation addition reaction with sodium bisulfite to obtain methyl oleate ethoxylate sulfonate, and the obtained methyl oleate ethoxylate sulfonate is subjected to saponification reaction and then is subjected to extraction separation for multiple times by using ethyl acetate and a 30wt% saturated sodium chloride aqueous solution to obtain disodium oleate. The invention has the advantages that the raw materials are rich and renewable, and the sulfonation rate is higher; the solvent used in the preparation process is cheap and easy to obtain and can be recycled; mild reaction, low energy consumption, high sulfonation rate and high yield.
Description
Technical Field
The invention relates to a synthesis method of oleic acid disodium salt.
Background
Conventional disodium salts are mostly present in the production process of fatty acid Methyl Ester Sulfonate (MES), and have been recently reported because they are regarded as by-products and have been overlooked by scientists for a long time. The fact is that the disodium salt has a double hydrophilic head group, and the MES disodium salt has a high Krafft point and has good surface activity and foaming capability, so the method also has research value and significance. On the other hand, the price of petroleum is continuously rising, and the domestic alpha-olefin production still has problems. Under the premise, how to apply renewable resources to the chemical industry is also an important problem to be solved for promoting the sustainable development process. According to the structural characteristics of alpha-olefin, the subject group thinks that the structure is similar, and the renewable resource oleic acid with larger yield in China has wide practical value in the sense of sustainable development because the oleic acid has rich yield, is easy to degrade and can be regenerated. The disodium salt is prepared from oleic acid according to a conventional thought, oleic acid directly undergoes a sulfonation reaction with sodium bisulfite under the action of a catalyst, and then the oleic acid disodium salt is obtained through neutralization. The invention adopts the method that oleic acid is subjected to methyl esterification and then Ethylene Oxide (EO) is added to greatly change the hydrophilicity and hydrophobicity of the raw material, the mass transfer efficiency and the sulfonation rate are improved, and then the disodium oleate is obtained through saponification, acidification, extraction separation and neutralization, so that the search is never reported
Disclosure of Invention
The invention aims to provide a synthesis method of disodium oleate, which has short reaction time and high yield.
The molecular structural formula of the raw material oleic acid provided by the invention is as follows:
the reaction synthetic route of the invention is shown as follows:
the invention provides a synthesis method of oleic acid disodium salt, which comprises the following specific embodiments:
(1) preparation of methyl oleate
Adding oleic acid, anhydrous methanol and a catalyst p-toluenesulfonic acid into a reactor, and stirring for 2-4 h at the temperature of 60-70 ℃ in a reflux state, wherein the molar ratio of the oleic acid to the methanol is 1: 1.5-6% of p-toluenesulfonic acid, wherein the amount of the p-toluenesulfonic acid is 2% -6% of the mass of oleic acid, sodium methoxide is added to neutralize the p-toluenesulfonic acid which does not participate in the reaction after the reaction is finished, then deionized water is used for washing, redundant salt is removed, and finally, reduced pressure distillation is carried out to remove excessive methanol to obtain methyl oleate;
(2) preparation of methyl oleate ethoxylate
Adding the methyl oleate obtained in the step (1) and a catalyst into a high-pressure reaction kettle, wherein the adding amount of the catalyst is 1% -2% of the mass of the methyl oleate, introducing nitrogen to replace air in the reaction kettle, heating to 120-150 ℃, introducing 3-8 g of ethylene oxide for the first time, performing an induction reaction under the reaction pressure of 0.3-0.4 MPa, and slowly introducing the ethylene oxide into the kettle when the pressure is reduced to 0.1MPa, wherein the molar ratio of the methyl oleate to the total ethylene oxide obtained in two times is 1: 15-18, introducing nitrogen when the pressure is constant and the reaction is complete and the temperature in the reaction kettle is reduced to 40-80 ℃, and leading out methyl oleate ethoxylate;
(3) preparation of methyl oleate ethoxylate sulfonate
Adding the methyl oleate ethoxylate obtained in the step (2), sodium bisulfite, water and isopropanol, a catalyst tert-butyl peroxybenzoate and a cocatalyst iron trichloride into a reactor, wherein the molar ratio of the methyl oleate ethoxylate to the sodium bisulfite is 1: 1-4, the dosage of tert-butyl peroxybenzoate accounts for 2% -8% of the weight of methyl oleate ethoxylate, the dosage of ferric trichloride accounts for 5% -10% of the mass of the catalyst, and the mass ratio of water to isopropanol is 1: 0.4-4, and the mass ratio of the methyl oleate ethoxylate to the solvent is 1: 2-6, reacting for 4-72 h at 30-50 ℃ to obtain methyl oleate ethoxylate sulfonate;
(4) preparation of oleic acid disodium salt
Mixing the methyl oleate ethoxylate sulfonate obtained in the step (3) with sodium hydroxide and deionized water, stirring vigorously, and refluxing for 1-3 h at 85-100 ℃, wherein the molar ratio of the methyl oleate ethoxylate to the sodium hydroxide is 1: 1-2, adding deionized water in an amount which is 2-4 times of the mass of the sulfonate of the methyl oleate ethoxylate, standing after complete reaction, naturally cooling to room temperature, adding a sulfuric acid aqueous solution to neutralize until the pH value is 2-3, transferring to a separating funnel, adding ethyl acetate in an amount which is 3-5 times of the mass of the sulfonate of the methyl oleate ethoxylate, fully mixing by oscillation, adding a 30wt% sodium chloride aqueous solution to repeatedly extract, collecting an ethyl acetate phase, performing reduced pressure rotary evaporation to remove the solvent, neutralizing with a sodium hydroxide aqueous solution until the pH value is 7.1-7.4, removing water and drying to obtain the disodium oleate.
The sulfuric acid aqueous solution in the step (4) is a 10-30 wt% sulfuric acid aqueous solution.
The number of extraction in the step (4) is 6-10.
The invention has the following advantages:
in order to obtain the disodium oleate, the methyl oleate is esterified and then ethoxylated, and the obtained methyl oleate ethoxylate can effectively change the hydrophilicity and hydrophobicity of oleic acid, greatly improve the mass transfer efficiency and the reaction rate, and finally improve the sulfonation rate and the yield; the raw materials used in the invention are rich and renewable, and the solvent used in the preparation process is cheap and easy to obtain and can be recycled; mild reaction and low energy consumption.
Drawings
FIG. 1 is an infrared spectrum of oleic acid disodium salt synthesized by the present invention and oleic acid as a raw material.
In the figure1, the peak of absorption of stretching vibration when carboxylic acid is changed into carboxylic acid salt C ═ O is 1711cm from the peak before-1It becomes 1159cm-1,1191cm-1And 1050cm-1The absorption peak shows that the molecule has sulfonic functional group, and the infrared spectrogram of the oleic acid disodium salt is 3000cm-1The above also does not show the characteristic absorption peak of unsaturated carbon-hydrogen bond in oleic acid, and in conclusion, the disodium oleate salt is synthesized.
Detailed Description
The following examples are intended to further illustrate the invention and are not intended to limit the invention. All changes which come within the meaning and range of equivalency of the invention are to be embraced within their scope.
The invention adopts the following test method: (1) the anionic surfactant content of the product was determined by two-phase titration and the actual yield was calculated. (2) And (3) measuring the content of the nonionic surfactant in the product through an anion and cation exchange resin column. (3) And respectively measuring iodine values of the product and the methyl oleate ethoxylate, and calculating to obtain the conversion rate in the sulfonation process. (4) And determining the sulfo-carboxyl double-active functional groups contained in the oleic acid disodium salt by infrared spectroscopy.
Example 1
Adding 200g (0.708moL) of oleic acid, 46.2g (1.442moL) of anhydrous methanol and 10.02g of p-toluenesulfonic acid into a four-neck flask, stirring for 2 hours at 65 ℃ under a reflux state, adding sodium methoxide to neutralize the p-toluenesulfonic acid which does not participate in the reaction after the reaction is finished, washing with deionized water to remove excessive salts, and finally carrying out reduced pressure distillation to remove excessive methanol to obtain methyl oleate; adding 100g of methyl oleate and 1g of catalyst into a high-pressure reaction kettle, introducing nitrogen to replace air in the reaction kettle, heating to 140 ℃, introducing 5g of ethylene oxide for the first time, carrying out an induction reaction under the pressure of 0.3MPa, slowly introducing 215g of ethylene oxide into the kettle when the pressure is reduced to 0.1MPa, introducing nitrogen when the pressure is constant and the reaction is complete, and introducing 320g of methyl oleate ethoxylate when the temperature in the reaction kettle is reduced to 70 ℃; adding 51.7g (0.053moL) of methyl oleate ethoxylate, 15.95g (0.153moL) of sodium bisulfite, 100g of water and 100g of isopropanol respectively, 3.0g of tert-butyl peroxybenzoate serving as a catalyst and 0.3g of ferric trichloride serving as a cocatalyst into a flask, and reacting at 30 ℃ for 36 hours to obtain methyl oleate ethoxylate sulfonate; the flask was charged with 55.0g (0.051moL) of methyl oleate ethoxylate sulfonate, 2.4g (0.1moL) of sodium hydroxide and 150g of deionized water, stirred vigorously and refluxed at 90 ℃ for 1 h. Standing, naturally cooling to room temperature, adding a 30wt% sulfuric acid aqueous solution to neutralize until the pH value is 2.0, transferring to a separating funnel, adding 200mL of ethyl acetate, oscillating, fully mixing, adding a 30wt% sodium chloride aqueous solution, extracting for 6 times, collecting an ethyl acetate phase, performing reduced pressure rotary evaporation to remove the solvent, neutralizing with a sodium hydroxide aqueous solution until the pH value is 7.1, removing water, and drying to obtain the disodium oleate. In the above reaction process, the sulfonation rate of oleic acid was 88.5%, and the yield of oleic acid disodium salt was 95.4%.
Example 2
200g (0.708moL) of oleic acid, 34.0g (1.062moL) of anhydrous methanol and 4.00g of p-toluenesulfonic acid are added into a four-neck flask, the mixture is stirred for 3 hours under the reflux state at 60 ℃, sodium methoxide is added after the reaction is finished to neutralize the p-toluenesulfonic acid which does not participate in the reaction, then deionized water is used for washing, redundant salt is removed, and finally reduced pressure distillation is carried out to remove the excessive methanol to obtain methyl oleate; adding 100g of methyl oleate and 1.5g of catalyst into a high-pressure reaction kettle, introducing nitrogen to replace air in the reaction kettle, heating to 120 ℃, introducing 3g of ethylene oxide for the first time, carrying out an induction reaction under the pressure of 0.35MPa, slowly introducing 260g of ethylene oxide into the reaction kettle when the pressure is reduced to 0.1MPa, introducing nitrogen when the pressure is constant and the reaction is complete, and reducing the temperature in the reaction kettle to 80 ℃, and then deriving 363g of methyl oleate ethoxylate; adding 50.0g (0.051moL) of methyl oleate ethoxylate, 10.67g (0.102moL) of sodium bisulfite, 100g of isopropanol, 25g of water, 1.0g of catalyst tert-butyl peroxybenzoate and 0.05g of promoter ferric trichloride into a flask, and stirring for 4 hours at 40 ℃ to obtain methyl oleate ethoxylate sulfonate; the flask was charged with 55.0g (0.051moL) of methyl oleate ethoxylate sulfonate, 3.1g (0.08moL) of sodium hydroxide and 150g of deionized water, stirred vigorously and refluxed at 85 ℃ for 3 h. Standing, naturally cooling to room temperature, adding a 20 wt% sulfuric acid aqueous solution to neutralize until the pH value is 3.0, transferring to a separating funnel, adding 200mL of ethyl acetate, oscillating, fully mixing, adding a 30wt% sodium chloride aqueous solution, extracting for 8 times, collecting an ethyl acetate phase, performing reduced pressure rotary evaporation to remove the solvent, neutralizing with a sodium hydroxide aqueous solution until the pH value is 7.2, removing water, and drying to obtain the disodium oleate. In the above reaction process, the sulfonation rate of oleic acid was 30.3%, and the yield of oleic acid disodium salt was 39.8%.
Example 3
Adding 200g (0.708moL) of oleic acid, 90.7g (2.832moL) of anhydrous methanol and 8.00g of p-toluenesulfonic acid into a four-neck flask, stirring for 4 hours at 65 ℃ under reflux, adding sodium methoxide to neutralize the p-toluenesulfonic acid which does not participate in the reaction after the reaction is finished, washing with deionized water to remove excessive salt, and finally carrying out reduced pressure distillation to remove excessive methanol to obtain methyl oleate; adding 100g of methyl oleate and 1.5g of catalyst into a high-pressure reaction kettle, introducing nitrogen to replace air in the reaction kettle, heating to 140 ℃, introducing 8g of ethylene oxide for the first time, carrying out an induction reaction under the pressure of 0.3MPa, slowly introducing 227g of ethylene oxide into the reaction kettle when the pressure is reduced to 0.1MPa, introducing nitrogen when the pressure is constant and the reaction is complete, and reducing the temperature in the reaction kettle to 40 ℃, and then introducing 335g of methyl oleate ethoxylate; adding 50.0g (0.051moL) of methyl oleate ethoxylate, 21.23g (0.204moL) of sodium bisulfite, 150g of water and 6.0g of isopropanol into a flask, adding 3.2g of tert-butyl peroxybenzoate serving as a catalyst and 0.3g of ferric trichloride serving as a cocatalyst, and stirring at 50 ℃ for 12 hours to obtain methyl oleate ethoxylate sulfonate; the flask was charged with 55.0g (0.051moL) of methyl oleate ethoxylate sulfonate, 2.0g (0.05moL) of sodium hydroxide and 110g of deionized water, stirred vigorously and refluxed at 90 ℃ for 2 h. Standing, naturally cooling to room temperature, adding a 30wt% sulfuric acid aqueous solution to neutralize until the pH value is 2.5, transferring to a separating funnel, adding 250mL of ethyl acetate, oscillating, fully mixing, adding a 30wt% sodium chloride aqueous solution, extracting for 7 times, collecting an ethyl acetate phase, performing reduced pressure rotary evaporation to remove the solvent, neutralizing with a sodium hydroxide aqueous solution until the pH value is 7.4, removing water, and drying to obtain the disodium oleate. The sulfonation rate of oleic acid in the above reaction process was 21.3%, and the final yield was 30.63%.
Example 4
Adding 200g (0.708moL) of oleic acid, 136.1g (4.248moL) of anhydrous methanol and 12.00g of p-toluenesulfonic acid into a four-neck flask, stirring for 2 hours at 70 ℃ under reflux, adding sodium methoxide to neutralize the p-toluenesulfonic acid which does not participate in the reaction after the reaction is finished, washing with deionized water to remove excessive salts, and finally carrying out reduced pressure distillation to remove excessive methanol to obtain methyl oleate; adding 100g of methyl oleate and 2.0g of catalyst into a high-pressure reaction kettle, introducing nitrogen to replace air in the reaction kettle, heating to 150 ℃, introducing 5g of ethylene oxide, carrying out an induction reaction under the pressure of 0.4MPa, slowly introducing 215g of ethylene oxide into the kettle when the pressure is reduced to 0.1MPa, introducing nitrogen when the pressure is constant and the reaction is complete, and introducing 320g of methyl oleate ethoxylate when the temperature in the reaction kettle is reduced to 60 ℃; 76.5g (0.078moL) of methyl oleate ethoxylate, 24.77g (0.238moL) of sodium bisulfite, 150g of water and 150g of isopropanol respectively, 6.1g of tert-butyl peroxybenzoate serving as a catalyst and 0.5g of ferric trichloride serving as a cocatalyst are added into a flask, and the mixture is stirred for 72 hours at 35 ℃ to obtain methyl oleate ethoxylate sulfonate; the flask was charged with 55.0g (0.051moL) of methyl oleate ethoxylate sulfonate, 2.4g (0.1moL) of sodium hydroxide and 220g of deionized water, stirred vigorously and refluxed at 100 ℃ for 2 h. Standing, naturally cooling to room temperature, adding 10 wt% sulfuric acid aqueous solution to neutralize until the pH value is 3.0, transferring to a separating funnel, adding 300mL ethyl acetate, oscillating, fully mixing, adding 30wt% sodium chloride aqueous solution, extracting for 10 times, collecting an ethyl acetate phase, performing reduced pressure rotary evaporation to remove the solvent, neutralizing with sodium hydroxide aqueous solution until the pH value is 7.1, removing water, and drying to obtain the disodium oleate. In the above reaction process, the sulfonation rate of oleic acid was 90.5%, and the yield of oleic acid disodium salt was 97.7%.
Claims (3)
1. A synthetic method of oleic acid disodium salt is characterized by comprising the following steps:
(1) preparation of methyl oleate
Adding oleic acid, anhydrous methanol and a catalyst p-toluenesulfonic acid into a reactor, and stirring for 2-4 h at the temperature of 60-70 ℃ in a reflux state, wherein the molar ratio of the oleic acid to the methanol is 1: 1.5-6% of p-toluenesulfonic acid, wherein the amount of the p-toluenesulfonic acid is 2-6% of the mass of oleic acid, sodium methoxide is added to neutralize the p-toluenesulfonic acid which does not participate in the reaction after the reaction is finished, then deionized water is used for washing, redundant salt is removed, and finally, reduced pressure distillation is carried out to remove excessive methanol to obtain methyl oleate;
(2) preparation of methyl oleate ethoxylate
Adding the methyl oleate obtained in the step (1) and a catalyst into a high-pressure reaction kettle, wherein the adding amount of the catalyst is 1-2% of the mass of the methyl oleate, introducing nitrogen to replace air in the reaction kettle, heating to 120-150 ℃, introducing 3-8 g of ethylene oxide for the first time, carrying out an induction reaction under the reaction pressure of 0.3-0.4 MPa, and slowly introducing the ethylene oxide into the kettle when the pressure is reduced to 0.1MPa, wherein the molar ratio of the methyl oleate to the total ethylene oxide in two times is 1: 15-18, introducing nitrogen when the pressure is constant and the reaction is complete and the temperature in the reaction kettle is reduced to 40-80 ℃, and leading out methyl oleate ethoxylate;
(3) preparation of methyl oleate ethoxylate sulfonate
Adding the methyl oleate ethoxylate obtained in the step (2), sodium bisulfite, water and isopropanol, a catalyst tert-butyl peroxybenzoate and a cocatalyst iron trichloride into a reactor, wherein the molar ratio of the methyl oleate ethoxylate to the sodium bisulfite is 1: 1-4, the dosage of tert-butyl peroxybenzoate accounts for 2-8% of the weight of methyl oleate ethoxylate, the dosage of ferric trichloride accounts for 5-10% of the mass of the catalyst, and the mass ratio of water to isopropanol is 1: 0.4-4, and the mass ratio of the methyl oleate ethoxylate to the solvent is 1: 2-6, reacting for 4-72 h at 30-50 ℃ to obtain methyl oleate ethoxylate sulfonate;
(4) preparation of oleic acid disodium salt
Mixing the methyl oleate ethoxylate sulfonate obtained in the step (3) with sodium hydroxide and deionized water, stirring vigorously, and refluxing for 1-3 h at 85-100 ℃, wherein the molar ratio of the methyl oleate ethoxylate to the sodium hydroxide is 1: 1-2, adding deionized water in an amount which is 2-4 times of the mass of the sulfonate of the methyl oleate ethoxylate, standing after complete reaction, naturally cooling to room temperature, adding a sulfuric acid aqueous solution to neutralize until the pH value is 2-3, transferring to a separating funnel, adding ethyl acetate in an amount which is 3-5 times of the mass of the sulfonate of the methyl oleate ethoxylate, fully mixing by oscillation, adding a 30wt% sodium chloride aqueous solution to repeatedly extract, collecting an ethyl acetate phase, performing reduced pressure rotary evaporation to remove the solvent, neutralizing with a sodium hydroxide aqueous solution until the pH value is 7.1-7.4, removing water and drying to obtain the disodium oleate.
2. The method for synthesizing disodium oleate salt as claimed in claim 1, wherein the aqueous sulfuric acid solution in the step (4) is 10-30 wt% aqueous sulfuric acid solution.
3. The method for synthesizing disodium oleate salt as claimed in claim 1, wherein the number of times of extraction in the step (4) is 6-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810270457.2A CN108484450B (en) | 2018-03-29 | 2018-03-29 | Synthetic method of oleic acid disodium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810270457.2A CN108484450B (en) | 2018-03-29 | 2018-03-29 | Synthetic method of oleic acid disodium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108484450A CN108484450A (en) | 2018-09-04 |
| CN108484450B true CN108484450B (en) | 2020-12-01 |
Family
ID=63316792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810270457.2A Active CN108484450B (en) | 2018-03-29 | 2018-03-29 | Synthetic method of oleic acid disodium salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484450B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110639426A (en) * | 2019-10-10 | 2020-01-03 | 太原理工大学 | Branched alkyl sulfonate surfactant and preparation process thereof |
| CN111111547A (en) * | 2019-12-26 | 2020-05-08 | 中国日用化学研究院有限公司 | Low-temperature stable liquid fatty acid methyl ester sulfonate and preparation method thereof |
| CN112300032B (en) * | 2020-11-20 | 2022-11-11 | 太原理工大学 | Branched alkyl sulfonate anionic surfactant and preparation process thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES303823A1 (en) * | 1963-09-18 | 1965-11-01 | Montecatini Soc Generale Per L'industria Mine Raria E Ch | A procedure to purify the kainite of sodium chloride by washing with water. (Machine-translation by Google Translate, not legally binding) |
| CA2815670C (en) * | 2010-10-25 | 2017-02-28 | Stepan Company | Light-duty liquid detergents based on compositions derived from natural oil metathesis |
| CN102653518B (en) * | 2012-03-30 | 2014-04-09 | 谢仁华 | Alpha-sulfo-fatty acid disodium, and preparation method and application thereof |
| CN106588707B (en) * | 2016-11-11 | 2018-04-27 | 中国日用化学工业研究院 | A kind of method of synthetic castor oil acid formicester ethoxylate sulfonates |
| CN106588706B (en) * | 2016-11-11 | 2018-04-27 | 中国日用化学工业研究院 | The synthetic method of castor oil acid formicester ethoxylate sulfonates |
| CN107138285A (en) * | 2017-05-23 | 2017-09-08 | 西北矿冶研究院 | Lead sulfide and zinc ore flotation combined collecting agent and using method thereof |
-
2018
- 2018-03-29 CN CN201810270457.2A patent/CN108484450B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108484450A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108484450B (en) | Synthetic method of oleic acid disodium salt | |
| CN101759612B (en) | Method for producing sodium fatty acid methyl ester sulfonate | |
| CN102659514A (en) | Method for producing sec-butyl alcohol | |
| CN102633929B (en) | Preparation method of acid ionic liquid mesoporous polymeric material | |
| CN101648894A (en) | N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid and preparation method thereof | |
| CN102060738A (en) | Ionic liquid combining B acid site and L acid site as well as preparation method and application thereof | |
| CN101781172A (en) | Novel process for efficiently and continuously synthesizing 2-naphthol | |
| CN116328790A (en) | Preparation method of solid acid catalyst and application of solid acid catalyst in diethylene glycol dibenzoate synthesis | |
| CN103073426A (en) | Preparation process for catalyzing and synthesizing tert-butyl acrylate by using strong acid cation exchange resin as catalyst | |
| CN112939798A (en) | Preparation method of amantadine | |
| CN109824466B (en) | Method for preparing 2-methyl-1, 3-pentadiene | |
| CN102504233A (en) | Preparation method of triphenylethylene phenol polyoxyethylene ether oleate | |
| CN106883403A (en) | The preparation method of maleic acid mono alkyl ester polyether | |
| CN110156573A (en) | A kind of synthesis technology of trimethylolpropane allyl ether | |
| CN103641747A (en) | Method for ultrasound-microwave synthesis of stearyl alcohol polyoxyethylene (5) ether succinic acid diester sodium sulfonate | |
| CN111036294A (en) | Polyacid site ionic liquid catalyst based on polyethyleneimine and preparation method and application thereof | |
| CN106518620B (en) | A kind of method and device preparing sec-butyl alcohol | |
| CN112830912A (en) | Method for continuously preparing 2, 5-furan dicarboxaldehyde oxime by solid acid catalysis | |
| CN108003096B (en) | Method for preparing ethoxyquinoline through WO3/AC/SO3H concerted catalysis | |
| CN106916063A (en) | A kind of method that functionalized acidic ionic liquid catalysis prepares geranyl acetate | |
| CN113548957B (en) | Production method of tertiary carbonic acid | |
| CN106588707A (en) | Method for synthesizing methyl ricinoleate ethoxylate sulfonate | |
| CN104164304A (en) | Novel method for preparing biodiesel under catalysis of modified resin | |
| CN107952479B (en) | Functionalized polyacid ionic liquid catalyst, preparation method and method for catalyzing direct esterification of cyclohexene by functionalized polyacid ionic liquid catalyst | |
| CN105712882B (en) | A kind of tung oil polyalcohol and synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |