CN102617409A - Process for purifying alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate - Google Patents
Process for purifying alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate Download PDFInfo
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- CN102617409A CN102617409A CN2012100582041A CN201210058204A CN102617409A CN 102617409 A CN102617409 A CN 102617409A CN 2012100582041 A CN2012100582041 A CN 2012100582041A CN 201210058204 A CN201210058204 A CN 201210058204A CN 102617409 A CN102617409 A CN 102617409A
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- alkyl
- ether sulphonate
- alkyl alcohol
- ether sulfonate
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Abstract
The invention provides a process for purifying alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate. According to the process, inorganic salt water solution with the mass concentration being 5 to 10 percent is prepared, alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate crude products are added into the inorganic salt water solution, the mass ratio of the alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate crude products to the inorganic salt water solution is 1:(10-50), the materials are stirred at 20 to 95 DEG C so that the alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate crude products are completely dissolved into the inorganic salt water solution to be prepared into raw material water solution, then, ethyl acetate extracting agents are added into the raw material water solution, the volume ratio of the raw material water solution to the ethyl acetate extracting agents is (1-10):1, the ethyl acetate is used for repeated extraction for three times at 20 to 70 DEG C, the upper layer extraction liquid is merged, the inorganic salt water solution is used for carrying out once reextraction on the merged extraction liquid, the obtained lower layer water phase is merged with the extracted raw material water solution, then, the concentration drying is carried out, and the high-purity alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate can be obtained. The process provided by the invention has the advantages that the operation is simple, the cost is low, the safety is high, and the process is applicable to industrialization.
Description
Technical field
The present invention relates to a kind of technology of purify alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate.
Background technology
Alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate be one type for adapting to the NEW TYPE OF COMPOSITE tensio-active agent that Development of Tertiary Oil Recovery Technology produces, have very high salt-resisting high-temperature-resisting ability and good foaming character, in oil production, show excellent performance.
At present, the technological line for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate in the world mainly contains sulphite sulfonation method and sulfoalkyl method.Wherein the sulphite sulfonation method always can relate to a kind of halogen-containing reactive group, in its preparation process, can produce some poisonous and harmfuls and have corrosive material, not only contaminate environment but also etching apparatus.The sulfoalkyl method is alkyl ethoxylated or alkyl phenol ether R-O-(R in the presence of certain temperature, pressure and catalyzer
1O)
nH and sulfoalkyl agent generation homogeneous phase or inhomogeneous reaction; On its molecule, introduce the anion sulfoacid base of a strong hydrophilicity type; Thereby make alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate, reaction principle is sulfoalkyl agent and alkyl ethoxylated or alkyl phenol ether R-O-(R
1O)
nNucleophilic substitution reaction between H.The sulfoalkyl agent of current application mainly is propane sultone, chloroethyl sodium sulfonate, sodium vinyl sulfonate, hydroxyalkylated sulfonic acid sodium etc.But propane sultone toxicity is big, and explosive is to the human and environment poor stability; Chloroethyl sodium sulfonate and sodium vinyl sulfonate are prone to respectively side reactions such as hydrolysis, polymerization take place in reaction process, and transformation efficiency is lower; Hydroxyalkylated sulfonic acid sodium is nontoxic basically, is mainly used in the emulsifying agent cocoyl sodium isethionate of producing used for cosmetic at present.Therefore, high with the technology of alkyl ethoxylated or alkyl phenol ether and hydroxyalkylated sulfonic acid salt generation sulfoalkyl prepared in reaction alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate to human body and environmental safety, meet the requirement of Green Chemistry and technology.But it is all too high by unreacted alkyl ethoxylated or alkyl phenol ether content in the alkyl alcohol ether sulphonate of this method preparation or the alkyl phenol ether sulphonate; If not carrying out purification handles; Have a strong impact on the application performance of title product alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate on the one hand, on the other hand, raw material consumption is too high; Production cost is too high, thereby influences the process of industrialization of this series products.
The pertinent literature report of relevant purification alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate is less both at home and abroad, and US4096175 and US4208280 adopt methylal and pimelinketone to extract alkyl ethoxylated or alkyl phenol ether in alcohol ether/phenolic ether sulphonate repeatedly respectively; Zhang Yongmin etc. adopt cation exchange resin column and weakly basic anion exchange resin post purification polyoxyethylene nonylphenol sodium sulfonate.
Though above-mentioned several kinds of method of purification effects still can, still have following shortcoming:
(1) methylal boiling point lower (42.3 ℃) is volatile, belongs to the one-level inflammable substance, need under heating condition, separate the product of purifying for part and be not suitable for.
(2) pimelinketone toxicity is bigger, and is inflammable, and boiling point too high (155.6 ℃), and the micro-pimelinketone that remains in after the purification in the product is difficult for removing.
(3) the ion-exchange-resin process separation cycle is long, and cost is too high, is inappropriate for carrying out the industrial mass purification processes.
Summary of the invention
The purpose of this invention is to provide a kind of simple to operate, cost is low, safe and be suitable for the technology of industrialized purification alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate.
Thereby the present invention is a kind of alkyl ethoxylated or technology of alkyl phenol ether purification alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate of separating in alkyl ethoxylated or the phenolic ether sulphonate crude product, and the concrete operations step is following:
The inorganic salt solution of preparation mass concentration 5～10%; Alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate crude product are added in the inorganic salt solution, and the mass ratio of alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate crude product and inorganic salt solution is 1:10～50, stirs down at 20～95 ℃; Alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate crude product are dissolved in fully process aqueous solution of raw material in the inorganic salt solution; Then the above-mentioned raw materials aqueous solution is added the ethyl acetate extraction agent, the volume ratio of aqueous solution of raw material and ethyl acetate extraction agent is 1～10:1, under 20～70 ℃; With ETHYLE ACETATE re-extract three times; Merge upper layer of extraction liquid, once strip, lower floor's water of gained and the aqueous solution of raw material merging through extracting with the extraction liquid that inorganic salt solution is combined; Carry out concentrate drying afterwards, obtain highly purified alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate.
The structural formula of aforesaid alkyl ethoxylated or alkyl phenol ether sulphonate is R-O-(R
1O) p-(R
2O) q-(CH
2) z-SO
3M, wherein R is C
8～C
24Alkyl or alkyl phenyl, R
1Be C
3Alkylidene group, R
2Be C
2Alkylidene group, p is 0～10, q is 0～10, z is 1～4, M is Na, K or NH
4 +
Aforesaid inorganic salt are sodium-chlor, sodium sulfate, Repone K, yellow soda ash or vitriolate of tartar etc.
Product gas purity of the present invention can adopt performance liquid chromatography external standard method and two-phase titration to measure.
The purify separating technology of alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate of the present invention has the following advantages:
(1) the used extraction agent ETHYLE ACETATE of the present invention is the common chemical raw material, and the source is wide, and toxicity is less, and equipment is not had corrosion, and is safe and reliable.And the ETHYLE ACETATE boiling point is 77 ℃, on the one hand for not segregative raw material under the normal temperature, can select warming temperature; On the other hand, the trace solvent that remains in after the purification in the product is easy to remove.
(2) separation cycle of the present invention is short, and cost is low, is fit to carry out the industrial mass purification processes.
(3) alkyl alcohol ether sulphonate or the alkyl phenol ether sulphonate purity that obtain after the present invention's purification are higher, can satisfy high temperature and high salinity oil reservoir needs, have higher utility value.
Embodiment
Embodiment 1: the sodium chloride aqueous solution of preparation mass concentration 7%, with octylphenol polyethylene oxypropylene Soxylat A 25-7 sodium sulfonate (p=10, q=5; Z=3) crude product is added in the sodium chloride aqueous solution, and the mass ratio of octylphenol polyethylene oxypropylene Soxylat A 25-7 sodium sulfonate crude product and sodium chloride aqueous solution is 1:10, stirs down at 20 ℃; Octylphenol polyethylene oxypropylene Soxylat A 25-7 sodium sulfonate crude product is dissolved in fully processes aqueous solution of raw material in the sodium chloride aqueous solution, then the above-mentioned raw materials aqueous solution is added in the liquid-liquid extraction device, add extraction agent ETHYLE ACETATE again; The volume ratio of aqueous solution of raw material and extraction agent ETHYLE ACETATE is 10:1; Under 20 ℃,, merge upper layer of extraction liquid with ETHYLE ACETATE re-extract three times; Extraction liquid with sodium chloride aqueous solution is combined is once stripped; Lower floor's water of gained through the aqueous solution of raw material merging of extraction, carries out concentrate drying with afterwards, obtains highly purified octylphenol polyethylene oxypropylene Soxylat A 25-7 sodium sulfonate.Recording product purity through the performance liquid chromatography external standard method is 98.1%.
Embodiment 2: the aqueous sodium persulfate solution of preparation mass concentration 10%, with nonyl phenol poly-oxypropylene ether sodium sulfonate (p=4, q=0; Z=4) crude product is added in the aqueous sodium persulfate solution, and the mass ratio of nonyl phenol poly-oxypropylene ether sodium sulfonate crude product and aqueous sodium persulfate solution is 1:20, stirs down at 30 ℃; Nonyl phenol poly-oxypropylene ether sodium sulfonate crude product is dissolved in fully processes aqueous solution of raw material in the aqueous sodium persulfate solution, then the above-mentioned raw materials aqueous solution is added in the liquid-liquid extraction device, add extraction agent ETHYLE ACETATE again; The volume ratio of aqueous solution of raw material and extraction agent ETHYLE ACETATE is 4:1; Under 30 ℃,, merge upper layer of extraction liquid with ETHYLE ACETATE re-extract three times; Extraction liquid with aqueous sodium persulfate solution is combined is once stripped; Lower floor's water of gained through the aqueous solution of raw material merging of extraction, carries out concentrate drying with afterwards, obtains the higher nonyl phenol poly-oxypropylene ether sodium sulfonate of purity.Recording product purity through the performance liquid chromatography external standard method is 97.6%.
Embodiment 3: the potassium chloride solution of preparation mass concentration 6%, and with C
16(z=2) crude product is added in the potassium chloride solution alkyl alcohol Soxylat A 25-7 sodium sulfonate, C for p=0, q=10
16The mass ratio of alkyl alcohol Soxylat A 25-7 sodium sulfonate crude product and potassium chloride solution is 1:40, stirs down at 50 ℃, makes C
16Alkyl alcohol Soxylat A 25-7 sodium sulfonate crude product is dissolved in fully processes aqueous solution of raw material in the potassium chloride solution, then the above-mentioned raw materials aqueous solution is added in the liquid-liquid extraction device, adds extraction agent ETHYLE ACETATE again; The volume ratio of aqueous solution of raw material and extraction agent ETHYLE ACETATE is 2:1; Under 50 ℃,, merge upper layer of extraction liquid with ETHYLE ACETATE re-extract three times; Extraction liquid with potassium chloride solution is combined is once stripped; Lower floor's water of gained through the aqueous solution of raw material merging of extraction, carries out concentrate drying with afterwards, obtains the higher C of purity
16Alkyl alcohol Soxylat A 25-7 sodium sulfonate.Recording product purity through two-phase titration is 97.2%.
Embodiment 4: the aqueous sodium carbonate of preparation mass concentration 8%, and with C
24(z=1) crude product is added in the aqueous sodium carbonate alkyl alcohol polyoxyethylene polyoxypropylene ether sulfonic acid potassium, C for p=5, q=5
24The mass ratio of alkyl alcohol polyoxyethylene polyoxypropylene ether sulfonic acid potassium crude product and aqueous sodium carbonate is 1:50, stirs down at 95 ℃, makes C
24Alkyl alcohol polyoxyethylene polyoxypropylene ether sulfonic acid potassium crude product is dissolved in fully processes aqueous solution of raw material in the aqueous sodium carbonate, then the above-mentioned raw materials aqueous solution is added in the liquid-liquid extraction device, adds extraction agent ETHYLE ACETATE again; The volume ratio of aqueous solution of raw material and extraction agent ETHYLE ACETATE is 1:1; Under 70 ℃,, merge upper layer of extraction liquid with ETHYLE ACETATE re-extract three times; Extraction liquid with aqueous sodium carbonate is combined is once stripped; Lower floor's water of gained through the aqueous solution of raw material merging of extraction, carries out concentrate drying with afterwards, obtains the higher C of purity
24Alkyl alcohol polyoxyethylene polyoxypropylene ether sulfonic acid potassium.Recording product purity through two-phase titration is 96.8%.
Embodiment 5: the potassium sulfate solution of preparation mass concentration 5%, and with C
12～C
14(z=2) crude product is added in the potassium sulfate solution alkyl alcohol polyoxyethylene polyoxypropylene ether sulfonic acid ammonium, C for p=3, q=4
12～C
14The mass ratio of alkyl alcohol polyoxyethylene polyoxypropylene ether sulfonic acid ammonium crude product and potassium sulfate solution is 1:30, stirs down at 40 ℃, makes C
12～C
14Alkyl alcohol polyoxyethylene polyoxypropylene ether sulfonic acid ammonium crude product is dissolved in fully processes aqueous solution of raw material in the potassium sulfate solution, then the above-mentioned raw materials aqueous solution is added in the liquid-liquid extraction device, adds extraction agent ETHYLE ACETATE again; The volume ratio of aqueous solution of raw material and extraction agent ETHYLE ACETATE is 3:1; Under 40 ℃,, merge upper layer of extraction liquid with ETHYLE ACETATE re-extract three times; Extraction liquid with potassium sulfate solution is combined is once stripped; Lower floor's water of gained through the aqueous solution of raw material merging of extraction, carries out concentrate drying with afterwards, obtains the higher C of purity
12～C
14Alkyl alcohol polyoxyethylene polyoxypropylene ether sulfonic acid ammonium.Recording product purity through two-phase titration is 95.3%.
Claims (3)
1. the technology of alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate of purifying is characterized in that comprising the steps:
The inorganic salt solution of preparation mass concentration 5～10%; Alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate crude product are added in the inorganic salt solution, and the mass ratio of alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate crude product and inorganic salt solution is 1:10～50, stirs down at 20～95 ℃; Alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate crude product are dissolved in fully process aqueous solution of raw material in the inorganic salt solution; Then the above-mentioned raw materials aqueous solution is added the ethyl acetate extraction agent, the volume ratio of aqueous solution of raw material and ethyl acetate extraction agent is 1～10:1, under 20～70 ℃; With ETHYLE ACETATE re-extract three times; Merge upper layer of extraction liquid, once strip, lower floor's water of gained and the aqueous solution of raw material merging through extracting with the extraction liquid that inorganic salt solution is combined; Carry out concentrate drying afterwards, obtain highly purified alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate.
2. the technology of a kind of purify alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 is characterized in that the structural formula of described alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate is: R-O-(R
1O) p-(R
2O) q-(CH
2) z-SO
3M;
Wherein R is C
8～C
24Alkyl or alkyl phenyl, R
1Be C
3Alkylidene group, R
2Be C
2Alkylidene group, p is 0～10, q is 0～10, z is 1～4, M is Na, K or NH
4 +
3. the technology of a kind of purify alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 is characterized in that described inorganic salt are sodium-chlor, sodium sulfate, Repone K, yellow soda ash or vitriolate of tartar.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210058204.1A CN102617409B (en) | 2012-03-07 | 2012-03-07 | Process for purifying alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210058204.1A CN102617409B (en) | 2012-03-07 | 2012-03-07 | Process for purifying alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate |
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| Publication Number | Publication Date |
|---|---|
| CN102617409A true CN102617409A (en) | 2012-08-01 |
| CN102617409B CN102617409B (en) | 2014-03-26 |
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ID=46557676
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|---|---|---|---|
| CN201210058204.1A Expired - Fee Related CN102617409B (en) | 2012-03-07 | 2012-03-07 | Process for purifying alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724050A (en) * | 2020-12-30 | 2021-04-30 | 武汉奥克特种化学有限公司 | Phosphorus-free alkali-resistant solubilizer and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096175A (en) * | 1976-12-01 | 1978-06-20 | Texaco Development Corporation | Extraction method |
| US4208280A (en) * | 1978-02-13 | 1980-06-17 | Texaco Development Corp. | Extraction method |
| US4226807A (en) * | 1979-06-07 | 1980-10-07 | Texaco Development Corp. | Process for making ether sulfonates |
-
2012
- 2012-03-07 CN CN201210058204.1A patent/CN102617409B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096175A (en) * | 1976-12-01 | 1978-06-20 | Texaco Development Corporation | Extraction method |
| US4208280A (en) * | 1978-02-13 | 1980-06-17 | Texaco Development Corp. | Extraction method |
| US4226807A (en) * | 1979-06-07 | 1980-10-07 | Texaco Development Corp. | Process for making ether sulfonates |
Non-Patent Citations (2)
| Title |
|---|
| 《精细石油化工》 20090331 张永民等 "壬基酚聚氧乙烯醚磺酸钠的合成及性能" 全文 1-3 第26卷, 第2期 * |
| 张永民等: ""壬基酚聚氧乙烯醚磺酸钠的合成及性能"", 《精细石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724050A (en) * | 2020-12-30 | 2021-04-30 | 武汉奥克特种化学有限公司 | Phosphorus-free alkali-resistant solubilizer and preparation and application thereof |
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