CN102746195A - Method for improving sulfonation process of naphthalene-based water reducer - Google Patents
Method for improving sulfonation process of naphthalene-based water reducer Download PDFInfo
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- CN102746195A CN102746195A CN2011101088957A CN201110108895A CN102746195A CN 102746195 A CN102746195 A CN 102746195A CN 2011101088957 A CN2011101088957 A CN 2011101088957A CN 201110108895 A CN201110108895 A CN 201110108895A CN 102746195 A CN102746195 A CN 102746195A
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- sulfonation
- water reducer
- naphthalene
- reaction
- naphthalene water
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Abstract
The invention relates to a method for improving the sulfonation process of a naphthalene-based water reducer, characterized by cascading a heat exchanger and a vacuum-pumping device to the cover of a reaction vessel, sulfonating the naphthalene-based water reducer for 0.5-1h, then generating negative pressure by extracting the gas of the reaction vessel every 0.5 h to bring out the moisture generated by the reaction; simultaneously letting in steam to the air inlet of the heat exchanger while extracting to let the industrial naphthalene volatilized and crystallized in the extracting process melt and relux to the sulfonation system and circulate continuously to be sulfonated, after finishing the sulfonation reaction, conducting hydrolysis, condensation and neutralization to obtain a powder product. According to the invention, the content of the toxic raw material industrial naphthalene in the water reducer is reduced, the production cost is reduced, the pollution of the materials to the environment is eliminated, and the method is easy to operate, and the operation is convenient.
Description
Technical field
The present invention relates to the naphthalene water reducer that concrete uses, especially a kind of method of improving the naphthalene water reducer process for sulfonation.
Background technology
Because the needs of industrial development; People have proposed increasingly high requirement to concrete performance; And a prerequisite that realizes concrete high-performanceization is to use high efficiency water reducing agent, and it not only can improve execution conditions, improves concrete resistance to compression folding intensity; But also can strengthen concrete freeze proof performance such as impervious, be considered to necessary the 5th component of concrete.At present, applied at home high efficiency water reducing agent major part is a naphthalene water reducer, accounts for more than 60% of market.
Naphthalene water reducer the working method comparative maturity, adopt compound methods such as sulfonation, hydrolysis, condensation, neutralization to form.But this method has major defect, in the naphthalene water reducer sulfonation reaction process, under temperature 160-165 ℃; Naphthalene and vitriol oil mol ratio are 1: 1.3-1.45, and through the sulfonation of 2.5-4h, it is that master, α-Nai Huangsuan are the naphthene sulfonic acid and the water of assisting that NAPTHALENE FLAKES. (INDUSTRIAL GRADE is sulfonated with the beta-naphthalenesulfonic-acid; Because the reversibility of reaction has the generation of water in the reaction, the existence of water can influence the skew of chemical equilibrium; Make molecular balance to contrary direction skew, sulfonation reaction can not be proceeded, cause sulphonation rate not high; Not having the sulfonated free naphthalene directly to get into the condensation stage after the NAPTHALENE FLAKES. (INDUSTRIAL GRADE sulfonation simultaneously is blended in the water reducer with discharging in last; Not only wasted the energy and also adsorbed a small amount of water reducer and influenced product performance, the most important thing is that free naphthalene itself has certain toxicity, is unfavorable for the protection to environment.Strive addressing this is that, take in the prior art to blow out NAPTHALENE FLAKES. (INDUSTRIAL GRADE to just in the sulfonated material, feeding steam, even but so still will pass through collection, separation and finishing sequence, process is complicated, and waste is serious.Therefore, improve the naphthalene water reducer process for sulfonation and have positive economic benefit and social benefit.
Summary of the invention
In order to overcome above defective, the technical problem that the present invention will solve is: propose a kind of method of improving the naphthalene water reducer process for sulfonation.
Technical scheme of the present invention is: a kind of method of improving the naphthalene water reducer process for sulfonation; Cover heat exchanger and vacuum extractor in the series connection at reaction kettle, every next through the gas generation negative pressure of extractive reaction still behind naphthalene water reducer sulfonation 0.5h-1h to take the moisture content that reaction produces out of at a distance from 0.5h; Simultaneously in extractive process, in the interchanger inlet mouth, feed steam; Make that volatilization crystalline NAPTHALENE FLAKES. (INDUSTRIAL GRADE can melt and be back in the sulfonation system in extractive process; Circulation constantly is sulfonated, and sulfonation reaction obtains power-product through hydrolysis, condensation and neutralization after finishing again.
In preferred embodiment of the present invention, a kind of method of improving the naphthalene water reducer process for sulfonation comprises that further the gas of described extractive reaction still produces negative pressure and is as the criterion with the pressure that is controlled at 0.07-0.09MP.
In preferred embodiment of the present invention, a kind of method of improving the naphthalene water reducer process for sulfonation comprises that further the extracting time of the gas generation negative pressure of described extractive reaction still was controlled at 5-8 minute.
In preferred embodiment of the present invention, a kind of method of improving the naphthalene water reducer process for sulfonation comprises that further the gas of described extractive reaction still needs the above alkali spray processing of process spray column twice to enter into the liquid caustic soda sealing groove at last again and handles.
Beneficial effect of the present invention is: present method is simple; Easy to operate; Through on sulfonation reaction device, increasing vacuum extractor; Every separated 0.5h produces the 0.07-0.09MP negative pressure to take the moisture content that reaction produces out of in the sulfonation reaction process, effectively guaranteed carrying out smoothly of esterification, and then reaches the effect that improves sulfonation degree.Simultaneously because the crystalline NAPTHALENE FLAKES. (INDUSTRIAL GRADE that in sulfonation process, volatilizees can melt and be back in the sulfonation system; Circulation constantly is sulfonated, and the yield of product improves, and has reduced the content of poisonous material industry naphthalene in water reducer; Both reduced production cost, eliminated the pollution of material again environment.
Description of drawings
Fig. 1 is a kind of process flow sheet that improves the method for naphthalene water reducer process for sulfonation of the present invention.
Embodiment
In conjunction with a kind of process flow sheet that improves the method for naphthalene water reducer process for sulfonation of Fig. 1; Cover heat exchanger and vacuum extractor in the series connection at reaction kettle; Every next to take the moisture content that reaction produces out of through the gas generation 0.07-0.09MP negative pressure of extractive reaction still at a distance from 0.5h behind naphthalene water reducer sulfonation 0.5h-1h, the extracting time was controlled at 5-8 minute; Simultaneously in extractive process, in the interchanger inlet mouth, feed steam, make that volatilization crystalline NAPTHALENE FLAKES. (INDUSTRIAL GRADE can melt and be back in the sulfonation system in extractive process, circulation constantly is sulfonated; After sulfonation reaction finishes; Obtain power-product through hydrolysis, condensation and neutralization again, in addition, the gas of extractive reaction still is handled through the above alkali spray of spray column twice; Enter into liquid caustic soda sealing groove neutralizing treatment again, discharge at last.
Embodiment 1
1.2 tons NAPTHALENE FLAKES. (INDUSTRIAL GRADE is metered to reaction kettle, heats, begin to drip 1.3 ton of 98% vitriol oil to 120 ℃; Drip half a hour, and controlled temperature begins to be incubated 3h at 160～165 ℃; Begin every separated 0.5h from 0.5h and start negative pressure device, control still internal pressure 0.07MP, the extracting time is 8 minutes; Start the interchanger steam valve simultaneously, melt the evaporable NAPTHALENE FLAKES. (INDUSTRIAL GRADE, guarantee that whole air extractor gas flow is unimpeded; The gas of extractive reaction still is handled through the above alkali spray of spray column twice, enters into liquid caustic soda sealing groove neutralizing treatment again, discharges at last.Sulfonation finishes posthydrolysis condensation neutralization and obtains power-product, detects to such an extent that sulphonation rate is 95.50%.
Embodiment 2
1.2 tons NAPTHALENE FLAKES. (INDUSTRIAL GRADE is metered to reaction kettle, heats, begin to drip 1.3 ton of 98% vitriol oil to 120 ℃; Drip half a hour, and controlled temperature begins to be incubated 3h at 160～165 ℃; Begin every separated 0.5h from 0.5h and start negative pressure device, control still internal pressure 0.08MP, the extracting time is 6 minutes; Start the interchanger steam valve simultaneously, melt the evaporable NAPTHALENE FLAKES. (INDUSTRIAL GRADE, guarantee that whole air extractor gas flow is unimpeded.Sulfonation finishes posthydrolysis condensation neutralization and obtains power-product, detects to such an extent that sulphonation rate is 96.20%.
Embodiment 3
1.2 tons NAPTHALENE FLAKES. (INDUSTRIAL GRADE is metered to reaction kettle, heats, begin to drip 1.3 ton of 98% vitriol oil to 120 ℃; Drip half a hour, and controlled temperature begins to be incubated 3h at 160～165 ℃; Begin every separated 0.5h from 0.5h and start negative pressure device, control still internal pressure 0.09MP, the extracting time is 5 minutes; Start the interchanger steam valve simultaneously, melt the evaporable NAPTHALENE FLAKES. (INDUSTRIAL GRADE, guarantee that whole air extractor gas flow is unimpeded.Sulfonation finishes posthydrolysis condensation neutralization and obtains power-product, detects to such an extent that sulphonation rate is 96.50%.
Comparative example 1
1.2 tons NAPTHALENE FLAKES. (INDUSTRIAL GRADE is metered to reaction kettle, heats, begin to drip 1.3 ton of 98% vitriol oil to 120 ℃; Drip half a hour, and controlled temperature begins to be incubated 3h at 160～165 ℃; Sulfonation finishes posthydrolysis condensation neutralization and obtains power-product, detects to such an extent that sulphonation rate is 88.40%.
Embodiment 1-3 and comparative example are compared, and it is following that it detects test-results:
| Test name | Sulphonation rate (%) | Naphthalene discharging (%) | Concrete water-reducing ratio (%) | Clean slurry degree of mobilization (87,1.2%) (mm) |
| Embodiment 1 | 95.50 | 0.05 | 19.2 | 241 |
| Embodiment 2 | 96.20 | 0.04 | 19.5 | 245 |
| Embodiment 3 | 96.50 | 0.03 | 19.3 | 240 |
| Comparative example 1 | 88.40 | 0.12 | 16.5 | 225 |
The above; Be merely embodiment of the present invention; But protection scope of the present invention is not limited thereto; Any those of ordinary skill in the art are in the technical scope that the present invention disclosed, and variation or the replacement that can expect without creative work all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (4)
1. method of improving the naphthalene water reducer process for sulfonation; It is characterized in that: cover heat exchanger and vacuum extractor in the series connection at reaction kettle, every next through the gas generation negative pressure of extractive reaction still behind naphthalene water reducer sulfonation 0.5h-1h to take the moisture content that reaction produces out of at a distance from 0.5h; Simultaneously in extractive process, in the interchanger inlet mouth, feed steam; Make that volatilization crystalline NAPTHALENE FLAKES. (INDUSTRIAL GRADE can melt and be back in the sulfonation system in extractive process; Circulation constantly is sulfonated, and sulfonation reaction obtains power-product through hydrolysis, condensation and neutralization after finishing again.
2. the method for improvement naphthalene water reducer process for sulfonation according to claim 1 is characterized in that: the gas of described extractive reaction still produces negative pressure and is as the criterion with the pressure that is controlled at 0.07-0.09MP.
3. the method for improvement naphthalene water reducer process for sulfonation according to claim 1 is characterized in that: the extracting time that the gas of described extractive reaction still produces negative pressure was controlled at 5-8 minute.
4. the method for improvement naphthalene water reducer process for sulfonation according to claim 1 is characterized in that: the gas of described extractive reaction still need pass through the above alkali spray of spray column twice and handle, and enters into liquid caustic soda sealing groove neutralizing treatment again, discharges at last.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2011101088957A CN102746195A (en) | 2011-04-27 | 2011-04-27 | Method for improving sulfonation process of naphthalene-based water reducer |
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| CN2011101088957A CN102746195A (en) | 2011-04-27 | 2011-04-27 | Method for improving sulfonation process of naphthalene-based water reducer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632938A (en) * | 2016-09-20 | 2017-05-10 | 江苏苏博特新材料股份有限公司 | Energy-saving preparation method of naphthalene water reducer and equipment special for energy-saving preparation method |
Citations (7)
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|---|---|---|---|---|
| US3941810A (en) * | 1972-10-30 | 1976-03-02 | Adolf Koebner | Sulfonation of aromatic compounds in the presence of solvents |
| CN1052476A (en) * | 1989-11-14 | 1991-06-26 | 赫彻斯特股份公司 | The method of hydrolysis α-Nai Huangsuan in the naphthalene sulfonation mixture |
| US5434301A (en) * | 1993-09-01 | 1995-07-18 | Henkel Corporation | Methods for recovery of acids |
| CN101314556A (en) * | 2007-05-28 | 2008-12-03 | 重庆达华砼外加剂科技发展有限公司 | Process for recovering residual naphthalin in naphthalin series water reducing agent synthesis |
| CN101423482A (en) * | 2008-11-27 | 2009-05-06 | 中国日用化学工业研究院 | Integrated method of sulphonation and neutralization reaction |
| CN101585675A (en) * | 2009-06-22 | 2009-11-25 | 江苏特密斯混凝土外加剂有限公司 | Sulphonation method for naphthalene series water reducing agent without naphthalene discharging |
| CN101880247A (en) * | 2010-05-31 | 2010-11-10 | 杭州吉华江东化工有限公司 | Method for producing naphthalene sulfonic formaldehyde condensation compound |
-
2011
- 2011-04-27 CN CN2011101088957A patent/CN102746195A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3941810A (en) * | 1972-10-30 | 1976-03-02 | Adolf Koebner | Sulfonation of aromatic compounds in the presence of solvents |
| CN1052476A (en) * | 1989-11-14 | 1991-06-26 | 赫彻斯特股份公司 | The method of hydrolysis α-Nai Huangsuan in the naphthalene sulfonation mixture |
| US5434301A (en) * | 1993-09-01 | 1995-07-18 | Henkel Corporation | Methods for recovery of acids |
| CN101314556A (en) * | 2007-05-28 | 2008-12-03 | 重庆达华砼外加剂科技发展有限公司 | Process for recovering residual naphthalin in naphthalin series water reducing agent synthesis |
| CN101423482A (en) * | 2008-11-27 | 2009-05-06 | 中国日用化学工业研究院 | Integrated method of sulphonation and neutralization reaction |
| CN101585675A (en) * | 2009-06-22 | 2009-11-25 | 江苏特密斯混凝土外加剂有限公司 | Sulphonation method for naphthalene series water reducing agent without naphthalene discharging |
| CN101880247A (en) * | 2010-05-31 | 2010-11-10 | 杭州吉华江东化工有限公司 | Method for producing naphthalene sulfonic formaldehyde condensation compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632938A (en) * | 2016-09-20 | 2017-05-10 | 江苏苏博特新材料股份有限公司 | Energy-saving preparation method of naphthalene water reducer and equipment special for energy-saving preparation method |
| CN106632938B (en) * | 2016-09-20 | 2019-01-01 | 江苏苏博特新材料股份有限公司 | A kind of energy saving preparation method and its special equipment of naphthalene water reducer |
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