CN1051761C - Process for preparing di-n-octyl succinate sodium sulfonate - Google Patents
Process for preparing di-n-octyl succinate sodium sulfonate Download PDFInfo
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- CN1051761C CN1051761C CN96117215A CN96117215A CN1051761C CN 1051761 C CN1051761 C CN 1051761C CN 96117215 A CN96117215 A CN 96117215A CN 96117215 A CN96117215 A CN 96117215A CN 1051761 C CN1051761 C CN 1051761C
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Abstract
The present invention relates to a method for preparing succinic acid bis-n-octyl sulfonate, which comprises an esterification reaction and a sulfonation reaction, and is characterized in that the input quantity of n-Octanol is reduced in the esterification reaction, the temperature of the esterification reaction is reduced, and the processing steps of an esterification product, such as wash by water, dehydration, dealcoholization, steam for pressure, distillation or catalyst removing by filtering and dealcoholization are canceled; the sulfonation reaction is not added with sulfonation catalysts or sulfonation products, externally escaping sulfur dioxide is formed into sodium bisulfite for the sulfonation reaction by easily absorbing tail gas. Compared with the prior art, the present invention has the advantages of low device requirement and no environment pollution, the raw material n-Octanol is saved about one third, and the present invention can be widely used for commercial production for various kinds of chemical enterprises.
Description
The present invention relates to a kind of preparation method of anion surfactant, the preparation method of particularly a kind of di-n-octyl succinate sodium sulfonate (having another name called Succinic Acid di-n-octyl sodium sulfonate).
Di-n-octyl succinate sodium sulfonate, belong to a kind of anion surfactant, it is low that it has micelle-forming concentration, can significantly reduce surface tension, good surface activity, seepage velocity is fast, and is wetting, emulsification, performances such as lathering property is good, be widely used in daily-use chemical industry, coating, printing and dyeing, asbestos, agricultural chemicals, the mine, papermaking, synthetic leather, sensitization industry etc., can make emulsifying agent, wetting agent, permeate agent, dispersion agent and glass antidimmer, the preparation method of relevant di-n-octyl succinate sodium sulfonate, existing both at home and abroad the report is as document 1, Ger.Offen 1,912,531 (cl.C07c), 09, Apr., 1970; Document 2, " solid superacid as catalyst ambroid acid esters sodium sulfonate ", chemistry world, 8 phases of nineteen ninety, p347.The disclosed preparation process of above-mentioned document is: carry out esterification with excessive n-Octanol (1-octanol) with MALEIC ANHYDRIDE (abbreviation cis-butenedioic anhydride) under sulfuric acid or tosic acid or solid acid catalysis, esterification time 90～120min, 140 ℃～220 ℃ of esterification temperatures.Esterification products is via diluted alkaline neutralization, washing, steam water, steam alcohol, underpressure distillation gets the maleic acid di-n-octyl again, this dibasic acid esters add under the sulfonation catalyst effect with the sulphonating agent sodium bisulfite under normal pressure with its reaction; After perhaps esterification products is removed solid acid catalyst, steaming alcohol after filtration, under normal pressure, reacting (document 2) with sulphonating agent sodium bisulfite and S-WAT under the sulfonation catalyst effect, the final finished product di-n-octyl succinate sodium sulfonate that gets.Perhaps maleic acid di-n-octyl and 5～20% di-n-octyl succinate sodium sulfonate and aqueous solvent in advance under little reflux state through homogenizing, add sodium bisulfite through 300min again, add ethanol then, under reflux state, keep 180～240min and obtain di-n-octyl succinate sodium sulfonate finished product (document 1).The defective that existing preparation method exists is: the n-Octanol input amount is big in the esterification, and the temperature of reaction height, and esterification products needs through washing, dehydration, dealcoholysis, underpressure distillation or removes steps such as solid acid catalyst, dealcoholysis, complex process after filtration.Need add sulfonation catalyst in addition in the sulfonation reaction, cause the introducing of impurity, simultaneously the sulfurous gas harmful exhaust not recycled, cause environmental pollution; Perhaps need consume a certain amount of product di-n-octyl succinate sodium sulfonate, the sulfonation operation is through a plurality of steps such as homogenizings, production cycle length, single production cycle output minimizing etc.
The object of the present invention is to provide that a kind of reaction raw materials consumption is few, operation is simplified more, the reaction conditions requirement is lower and the preparation method of the di-n-octyl succinate sodium sulfonate that waste gas can be recycled.
The technical scheme that the object of the invention realizes is: a kind of preparation method of di-n-octyl succinate sodium sulfonate, comprise esterification, sulfonation reaction, it is characterized in that cis-butenedioic anhydride and n-Octanol are carried out esterification by 1: 2.20～2.25 proportioning (mol ratio) under Catalyzed by p-Toluenesulfonic Acid, be warming up to 140 ± 5 ℃, time 10～30min; Second step, insulation, dehydration, soaking time 90～150min, 140 ± 5 ℃ of temperature; In the 3rd step, cooling, neutralization are cooled to 20～80 ℃ of temperature, are neutralized to pH=7 ± 0.5; In the 4th step, sulfonation reaction, neutralized reaction product add the sulphonating agent sodium bisulfite, the contained SO of neutralized reaction product and sulphonating agent
2Ratio be 1: 1.00～1.20 (mol ratios), add solubility promoter, the solubility promoter add-on accounts for 5～20% (mass ratioes) of esterification products amount, this sulfonation reaction thing is warming up to 92 ℃, time 10～30min; In the 5th step, the sulfonation reaction thing through 150～300min maturation, gets product under 92～98 ℃ of temperature, and tail gas is absorbed by buck and returns for sulfonation reaction.
Principle of the present invention is that MALEIC ANHYDRIDE is reacted with n-Octanol under Catalyzed by p-Toluenesulfonic Acid, obtains esterification products maleic acid di-n-octyl.The esterification by product is in alkali and generate maleic acid list n-octyl sodium salt and as the sulfonation phase-transfer catalyst of esterification products, be sulphonating agent and esterification products reaction generation di-n-octyl succinate sodium sulfonate with the sodium bisulfite.
Its reaction formula is:
The present invention compared with prior art, its remarkable advantage is:
1. n-Octanol input amount (mol ratio) was reduced to 1: 2.20～2.25 by present 1: 3.00 in the esterification, and consumption of raw material significantly reduces in the reaction process;
2. after reducing the n-Octanol input amount, it is few to cross consumption, and esterification temperature reduces, and reduces to 140 ℃ from 140-220 ℃;
3. after excessive n-Octanol reduces, save the esterification products washing, steamed water, steamed alcohol, underpressure distillation or removed by filter catalyzer, steamed pure operation;
4. reduce n-Octanol and cross consumption, reduced temperature of reaction, make esterification yield between 92～98%, unreacted monoester sodium salt has completely avoided adding the influence of sulfonation catalyst impurity as the non-phase-transfer catalyst that adds, and reduces the consumption of material;
5. sulfonation reaction is carried out under normal pressure, absorbs by simple tail gas, makes to escape SO
2Become NaHSO
3The aqueous solution uses the contaminated solution problem for sulfonation reaction; And need not add sulfonated products; Sulphonating agent, aqueous solvent, solubility promoter once add before sulfonation reaction, and it is poly-to have avoided carrying out earlier in the sulfonation reaction complicated operations step such as homogenizing, has improved single production cycle output;
6. single batch of reaction times production cycle of whole technology finishes in 480min, and technology is very compact.
Accompanying drawing is the preparation method's of a di-n-octyl succinate sodium sulfonate of the present invention schematic flow sheet.
Below in conjunction with accompanying drawing the present invention is further described.
A kind of embodiment by flow process shown in the accompanying drawing is:
The first step: in the reactor of water trap is housed, add cis-butenedioic anhydride 90Kg, n-Octanol 263Kg (is industrial goods, content 〉=99%), makes catalyzer (industrial goods, content 〉=95%) with tosic acid 0.9Kg, stir down and be warming up to 140 ± 5 ℃ in the 30min, carry out esterification;
Second step: the reactant of esterification to the first step obtains, at 140 ± 5 ℃ of following insulations, stirring, dehydration, dealcoholysis 90～120min, obtain esterification products, tell the next esterification of a small amount of alcohol and use;
The 3rd step: the esterification products that second step was obtained is cooled to below 80 ℃, stirs down, is neutralized to pH=7 ± 0.5 with the 30%NaOH aqueous solution;
The 4th step: the neutralized reaction product that above-mentioned the 3rd step obtains adds water 335L and (can contain and reclaim NaHSO
3-H
2O, the insufficient section water is supplied), add sodium bisulfite 102Kg (industrial goods, content 〉=95%), add ethanol 34Kg again after, change water trap into reflux exchanger, reactor is inserted in its underpart, top connects conduit and feeds 30%NaOH-H
2The SO of O
2Below the liquid level of resorber, sulfonation reaction liquid then stirs, heats up;
The 5th step: will be above-mentioned the 4th go on foot the reaction solution that obtains in 92～98 ℃ of maturation 180～240min, promptly get product di-n-octyl succinate sodium sulfonate 800Kg, solid content 50 ± 2%, outward appearance are water white transparency or light yellow transparent thickness gelatinoid, and rate of permeation is 1.55 seconds (1.5 * 1.5cm
2Chafer duck sheet, 1 ‰ strength of solution, 50 ℃ of down tests), than low 0.3 second of mentioned product Aerosol OT rate of permeation under the same conditions in the 961 16865.X Chinese patent application number.
Claims (5)
- A kind of preparation method of di-n-octyl succinate sodium sulfonate comprises esterification, sulfonation reaction, it is characterized in that technical process and reaction conditions carry out in the following manner:1. cis-butenedioic anhydride and n-Octanol carry out esterification by 1: 2.20～2.25 mol ratio under Catalyzed by p-Toluenesulfonic Acid, are warmed up to 140 ℃, and the time is 10～30min;
- 2. insulation, dehydration: soaking time is 90～150min, 140 ± 5 ℃ of temperature;
- 3. cooling, neutralization: be cooled to 20～80 ℃, be neutralized to pH=7 ± 0.5;
- 4. sulfonation reaction: add sulphonating agent, the contained SO of neutralized reaction product and sulphonating agent 2Mol ratio be 1: 1.00～1.20, add solubility promoter, neutralized reaction product and solubility promoter mass ratio are 1: 0.05～0.20, are warming up to 92 ℃, time 10～30min;
- 5. ripe: time 150～300min, 92～98 ℃ of temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117215A CN1051761C (en) | 1996-12-17 | 1996-12-17 | Process for preparing di-n-octyl succinate sodium sulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117215A CN1051761C (en) | 1996-12-17 | 1996-12-17 | Process for preparing di-n-octyl succinate sodium sulfonate |
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| Publication Number | Publication Date |
|---|---|
| CN1185429A CN1185429A (en) | 1998-06-24 |
| CN1051761C true CN1051761C (en) | 2000-04-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN96117215A Expired - Fee Related CN1051761C (en) | 1996-12-17 | 1996-12-17 | Process for preparing di-n-octyl succinate sodium sulfonate |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260199B (en) * | 2011-05-18 | 2013-12-18 | 清新县汉科化工科技有限公司 | Composite sulfonating agent and application thereof |
| CN103450049A (en) * | 2013-08-26 | 2013-12-18 | 南通大学 | Preparation method of 1,3-propylene glycol gemini di-n-octyl succinate sodium sulfonate |
| CN106187828A (en) * | 2016-07-19 | 2016-12-07 | 南通市晗泰化工有限公司 | Alkylbenzene methanol polyoxyethylene ether disodium succinate salt and preparation method thereof |
| CN106187834A (en) * | 2016-07-19 | 2016-12-07 | 南京林业大学 | α phenylalkyl polyoxyethylenated alcohol disodium succinate salt and preparation method |
| CN111747871A (en) * | 2020-07-31 | 2020-10-09 | 潍坊市埃里特化学有限公司 | Production process of surfactant dioctyl sodium sulfosuccinate |
| CN114249673B (en) * | 2021-11-29 | 2023-03-14 | 四川科宏达集团有限责任公司 | Method for catalytically synthesizing succinate sulfonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1912531A1 (en) * | 1968-03-25 | 1970-04-09 | Melle Bezons Saint Leger Les M | Process for the preparation of dialkyl sulfosuccinic acid salts |
-
1996
- 1996-12-17 CN CN96117215A patent/CN1051761C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1912531A1 (en) * | 1968-03-25 | 1970-04-09 | Melle Bezons Saint Leger Les M | Process for the preparation of dialkyl sulfosuccinic acid salts |
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