CN103113037A - Low-cost low-bleeding sulfamate high-efficiency water reducing agent and preparation method thereof - Google Patents
Low-cost low-bleeding sulfamate high-efficiency water reducing agent and preparation method thereof Download PDFInfo
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- CN103113037A CN103113037A CN201310022950XA CN201310022950A CN103113037A CN 103113037 A CN103113037 A CN 103113037A CN 201310022950X A CN201310022950X A CN 201310022950XA CN 201310022950 A CN201310022950 A CN 201310022950A CN 103113037 A CN103113037 A CN 103113037A
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- reducing agent
- bleeding
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- black liquor
- sulfamate high
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Abstract
The invention discloses low-cost low-bleeding sulfamate high-efficiency water reducing agent. The low-cost low-bleeding sulfamate high-efficiency water reducing agent is prepared from the following components in percentage by weight: 7%-20% of aminobenzene sulfonic acid or aminobenzene sulfonate, 8%-15% of a phenolic compound, 12%-18% of a condensing agent, 4%-9% of an alkalinity regulator, 2%-10% of black liquor and the balance of water. The invention further discloses a preparation method of the low-cost low-bleeding sulfamate high-efficiency water reducing agent. The low-cost low-bleeding sulfamate high-efficiency water reducing agent prepared by the preparation method disclosed by the invention is capable of effectively reducing segregation and blending phenomena, improving the peaceability of the concrete; and the residual alkali in the black liquor is sufficiently utilized in the synthesis process, so that an alkali environment is provided for the whole synthesis system, the alkali additive adding amount is reduced, the 100% of black liquor is utilized and the black liquor pollution problem is completely solved.
Description
Technical field
The present invention relates to a kind of concrete high efficiency water reducing agent and preparation method thereof, refer in particular to low bleeding sulfamate high-effective water-reducing agent of a kind of low cost and preparation method thereof.
Background technology
Cement water reducing agent is an important composition composition in high performance concrete, and in prior art, high efficiency water reducing agent is take naphthalene system and poly carboxylic acid series water reducer as main.Wherein, the shortcoming of naphthalene water reducer is that slump-loss reaches more greatly and easily occurs crystalline deposit under low temperature environment; And poly carboxylic acid series water reducer uses price high.
The sulfamate high-effective water-reducing agent production technique is simple, have that water-reducing rate is high, good in the low water-cement ratio current downflow, concrete slump is large and through the time advantages such as loss is little, yet, it still has problems in producing and using: the one, and its main raw material Sodium sulfanilate and phenol are the petroleum industry product, cost of material is partially expensive, and production cost is higher; The 2nd, the concrete water-retentivity is bad in application process, the segregation excreting water phenomenon serious, even slurry harden with moisture from.
Simultaneously, paper industry extensively adopts alkali paper-making technique, produces a large amount of paper wastes, is commonly called as " black liquor ", and black liquid 30%-35% is that inorganics (is mainly NaOH, Na
2SO
4, Na
2S, Na
2SiO
4, Na
2CO
3Deng), 65%-70% is organism (being mainly xylogen, poly-pentose, organic acid, Mierocrystalline cellulose, hemicellulose etc.).In prior art, " black liquor " utilized is exactly mainly to be translated into sulfonated lignin.Chinese patent application numbers 200710030226.6 discloses a kind of preparation method of alkali lignin modified sulfamate high-effective water reducer, and the water reducer preparation cost that obtains is low, can significantly improve mobility on coagulation, improves ultimate compression strength; Chinese patent application numbers 200810070589.7 discloses a kind of sulfonated alkali lignin modified sulfamate high-effective water reducer and preparation method thereof, has overcome product to volume is responsive, bleeding rate is high, the easy shortcoming of segregation of concrete.Yet, not yet find to adopt the technology that black liquor is direct and sulfamate high-effective water-reducing agent carries out modification in prior art.
Summary of the invention
The object of the present invention is to provide a kind of use cost low and make not low bleeding sulfamate high-effective water-reducing agent of low cost and preparation method thereof of bleeding of concrete.
For reaching above-mentioned purpose, solution of the present invention is:
A kind of low cost is hanged down the bleeding sulfamate high-effective water-reducing agent, and is formulated by weight percentage by following component: aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate 7-20%, phenolic compound 8-15%, condensing agent 12-18%, alkaline conditioner 4-9%, black liquor 2-10%, all the other are water.
The preparation method of the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost comprises the following steps:
Step 1, front polycondensation phase: heat water to 50-60 ℃, aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate, phenolic compound and alkaline conditioner are added in reactor, warming while stirring is to 60-80 ℃; Drip condensing agent, dripped off in 60-120 minute, and maintain the temperature at 65-80 ℃; Condensing agent is added dropwise to complete rear rising temperature to 80-90 ℃, is incubated 0.5-1 hour; Be warming up to again 90-100 ℃, be incubated 3-4 hour;
Step 2 adds the black liquor stage: be cooled to 70-80 ℃, add entry and black liquor, use the pH value of alkaline conditioner regulation system at 10-12;
Step 3, the aftercondensated stage: continue to be warming up to 90-100 ℃, be incubated cooling discharge, i.e. preparing product after 1-2 hour.
Further, aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate are that Sulphanilic Acid and sodium salt thereof, 4-are amino-1, one or both in 3-phenyl disulfonic acid and sodium salt thereof or 4-kharophen Phenylsulfonic acid and sodium salt thereof.
Further, condensing agent is one or both in formaldehyde, paraformaldehyde.
Further, phenolic compound is one or more (the containing two kinds) in phenol, dihydroxyphenyl propane, bisphenol S, p-cresol, meta-cresol, cresols, Resorcinol, quinhydrones, catechol, naphthyl alcohol or 2-Naphthol.
Further, alkaline conditioner is one or more (the containing two kinds) in sodium hydroxide, potassium hydroxide, sodium phosphate, trisodium phosphate, two sodium polyphosphates, tripoly phosphate sodium STPP, sodium polyphosphate, water glass.
Further, the black liquor that makes by alkaline process for the mixture that is selected from bamboo, bagasse, straw, wheat straw, reed, Eucalyptus, birch, Pinus massoniana Lamb one or more (containing two kinds) of black liquor.
After adopting such scheme, the preparation method of the low-cost low bleeding sulfamate high-effective water-reducing agent of the present invention mainly utilizes the sulfonated lignin that contain more amount in the black liquor of alkali paper-making.Black liquor is directly applied to modification, can reduce the step of recovery, improve organic efficiency, reduce costs, and can take full advantage of the compositions such as the sulfonated lignin that contain in black liquor and residual alkali, change evil and be benefit.
simultaneously, adopt the sulfamate high-effective water-reducing agent of the present invention's preparation, because sulfonated lignin have three-dimensional structure and wherein contain a large amount of polarity hydrophilic radicals, after the water reducer after the copolycondensation modification joins in gelling system, cement granules absorption water reducer negatively charged ion, polar group in sulfonated lignin is soluble in water simultaneously, formation has the solvation aquation film of certain physical strength, not only can stop the mutual absorption of cement granules, make cement granules disperse, also can reduce simultaneously the amount of free water, make the part free water around around cement granules, wetting cement particle surface, thereby, add black liquor modified sulfamate high-effective water-reducing agent afterwards that anti-bleeding performance is preferably arranged.
Compared with prior art, beneficial effect of the present invention is:
One, the present invention adds black liquor in the condensation stage in the later stage of sulfamate high-effective water-reducing agent, has significantly reduced the modified sulfamate high-effective water-reducing agent cost.
Two, contain sulfonated lignin in black liquor, have certain diminishing and bleed effect, the condensation stage adds black liquor, make the molecular composition of the sulfonated lignin participation sulfamate high-effective water-reducing agent in black liquor, effectively reduce excreting water phenomenon, improve concrete workability.
Three, take full advantage of the residual alkali in black liquor, for whole synthetic system provides alkaline environment, reduce the alkaline conditioner addition.
Four, simplified the steps such as filtration, sulfonation and spraying drying during the prior art black liquor recovery is utilized, improved organic efficiency, realize the utilization of black liquor 100%, thoroughly solved the black liquor pollution problem.
Five, production technique is simple, and raw materials for production are easy to get, and is with short production cycle, reaction temperature and, required equipment is conventional equipment, production cost is low.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated.
Embodiment one
The preparation method of the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost comprises the following steps:
Step 1, front polycondensation phase: by mass parts, in reactor, add 42 parts of phenol, 45 parts of Sodium sulfanilates and 190 parts of water, constant temperature to 50 ℃.Add approximately 4 parts of liquid caustic soda adjust pHs to 8, be warming up to 70 ℃.Drip 60 parts of formaldehyde, dropwised in 90 minutes, temperature is controlled at 75 ℃.After formaldehyde dropwises, be warmed up to 80 ℃ of constant temperature 1 hour, then be warming up to 95 ℃ of constant temperature 3 hours.
Step 2 adds the black liquor stage: insulation is cooled to 80 ℃ after finishing, and adds 40 parts of entry, adds 35 parts of black liquor, adds 20 parts of liquid caustic soda adjust pHs to 10.
Step 3, the aftercondensated stage: be warming up to 95 ℃ of constant temperature 1 hour, be cooled to room temperature and namely get the product sulfamate high-effective water-reducing agent.
Embodiment two
The preparation method of the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost comprises the following steps:
Step 1, front polycondensation phase: by mass parts, in reactor, add 45 parts of dihydroxyphenyl propanes, 40 parts of Sulphanilic Acid and 190 parts of water, constant temperature to 50 ℃.Add approximately 4.5 parts of potassium hydroxide adjust pHs to 8, be warming up to 75 ℃.Drip 62 parts of formaldehyde, dropwised in 90 minutes, temperature is controlled at 75 ℃.After formaldehyde dropwises, be warmed up to 80 ℃ of constant temperature 1 hour, then be warming up to 100 ℃ of constant temperature 3.5 hours.
Step 2 adds the black liquor stage: insulation is cooled to 80 ℃ after finishing, and adds 40 parts, water, adds 10 parts of black liquor, adds 30 parts of potassium hydroxide adjust pHs to 11.
Step 3, the aftercondensated stage: be warming up to 100 ℃ of constant temperature 1 hour, namely get the product sulfamate high-effective water-reducing agent to room temperature after cooling.
Embodiment three
The preparation method of the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost comprises the following steps:
Step 1, front polycondensation phase: by mass parts, in reactor, add 38 parts of Resorcinols, 50 parts of Sodium sulfanilates and 190 parts of water, constant temperature to 50 ℃.Add 3 parts of liquid caustic soda adjust pHs to 8, be warming up to 75 ℃.Drip 60 parts of acetaldehyde, dropwised in 120 minutes, temperature is controlled at 75 ℃.After acetaldehyde dropwises, be warmed up to 85 ℃ of constant temperature 1 hour, then be warming up to 95 ℃ of constant temperature 3 hours.
Step 2 adds the black liquor stage: insulation is cooled to 80 ℃ after finishing, and adds 40 parts, water, adds 20 parts of black liquor, adds 25 parts of liquid caustic soda adjust pHs to 11.
Step 3, the aftercondensated stage: be warming up to 95 ℃ of constant temperature 1 hour.Namely get the product sulfamate high-effective water-reducing agent to room temperature after cooling.
Embodiment four
The preparation method of the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost comprises the following steps:
Step 1, front polycondensation phase: by mass parts, in reactor, add 40 parts of bisphenol Ss, 35 parts of 4-amino-1,3-phenyl sodium disulfonate and 190 parts of water, constant temperature to 50 ℃.Add approximately 5 parts of liquid caustic soda adjust pHs to 8, be warming up to 70 ℃.Drip 60 parts of formaldehyde, dropwised in 90 minutes, temperature is controlled at 75 ℃.After formaldehyde dropwises, be warmed up to 80 ℃ of constant temperature 1 hour, then be warming up to 100 ℃ of constant temperature 3.5 hours.
Step 2 adds the black liquor stage: insulation is cooled to 80 ℃ after finishing, and adds 50 parts, water, adds 30 parts of black liquor, adds 23 parts of liquid caustic soda adjust pHs to 10.
Step 3, the aftercondensated stage: be warming up to 100 ℃ of constant temperature 1 hour.Namely get the product sulfamate high-effective water-reducing agent to room temperature after cooling.
The low bleeding sulfonate high efficiency water reducing agent of embodiment one to embodiment four prepared low cost is tested: with the synthetic sample that obtains of embodiment 1-4, ASP compares with the prior art sulfamate high-effective water-reducing agent, adopt standard cement, volume is pressed cement quality 0.45% (the solid volume of folding), according to GB 8076-2008 " concrete admixture " high efficiency water reducing agent detection method, survey its concrete water-reducing ratio and normal pressure bleeding rate ratio.Concrete mix is: cement 330kg/m
3, sand 742kg/m
3, stone 1113 kg/m
3, acquired results as shown in Table 1.
Table one embodiment performance comparison
| Sample | Embodiment one | Embodiment two | Embodiment three | Embodiment four | ASP |
| Water-reducing rate/% | 22.3 | 23.8 | 23.1 | 22.8 | 23.2 |
| Normal pressure bleeding rate ratio/% | 11.5 | 10.7 | 12.5 | 11.6 | 26.3 |
Claims (7)
1. the low bleeding sulfamate high-effective water-reducing agent of low cost, is characterized in that: formulated by weight percentage by following component: aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate 7-20%, phenolic compound 8-15%, condensing agent 12-18%, alkaline conditioner 4-9%, black liquor 2-10%, all the other are water.
2. the preparation method of the low bleeding sulfamate high-effective water-reducing agent of a low cost is characterized in that: comprise the following steps:
Step 1, front polycondensation phase: heat water to 50-60 ℃, aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate, phenolic compound and alkaline conditioner are added in reactor, warming while stirring is to 60-80 ℃; Drip condensing agent, dripped off in 60-120 minute, and maintain the temperature at 65-80 ℃; Condensing agent is added dropwise to complete rear rising temperature to 80-90 ℃, is incubated 0.5-1 hour; Be warming up to again 90-100 ℃, be incubated 3-4 hour;
Step 2 adds the black liquor stage: be cooled to 70-80 ℃, add entry and black liquor, use the pH value of alkaline conditioner regulation system at 10-12;
Step 3, the aftercondensated stage: continue to be warming up to 90-100 ℃, be incubated cooling discharge, i.e. preparing product after 1-2 hour.
3. a kind of low cost as claimed in claim 1 is hanged down the bleeding sulfamate high-effective water-reducing agent, it is characterized in that: aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate are that Sulphanilic Acid and sodium salt thereof, 4-are amino-1, one or both in 3-phenyl disulfonic acid and sodium salt thereof or 4-kharophen Phenylsulfonic acid and sodium salt thereof.
4. a kind of low cost as claimed in claim 1 is hanged down the bleeding sulfamate high-effective water-reducing agent, and it is characterized in that: condensing agent is one or both in formaldehyde, paraformaldehyde.
5. a kind of low cost as claimed in claim 1 is hanged down the bleeding sulfamate high-effective water-reducing agent, and it is characterized in that: phenolic compound is one or more in phenol, dihydroxyphenyl propane, bisphenol S, p-cresol, meta-cresol, cresols, Resorcinol, quinhydrones, catechol, naphthyl alcohol or 2-Naphthol.
6. a kind of low cost as claimed in claim 1 is hanged down the bleeding sulfamate high-effective water-reducing agent, and it is characterized in that: alkaline conditioner is one or more in sodium hydroxide, potassium hydroxide, sodium phosphate, trisodium phosphate, two sodium polyphosphates, tripoly phosphate sodium STPP, sodium polyphosphate, water glass.
7. the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost as claimed in claim 1 is characterized in that: black liquor is to be selected from the black liquor that one or more mixture of bamboo, bagasse, straw, wheat straw, reed, Eucalyptus, birch, Pinus massoniana Lamb makes by alkaline process.
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| CN103496871A (en) * | 2013-09-24 | 2014-01-08 | 金陵科技学院 | Method for preparing environment-friendly low-cost sulfamate superplasticizer |
| CN107602788A (en) * | 2017-08-31 | 2018-01-19 | 浙江吉盛化学建材有限公司 | A kind of production technology of sulfamate water reducer |
| CN107759756A (en) * | 2017-10-17 | 2018-03-06 | 江苏苏博特新材料股份有限公司 | A kind of sulfamate water reducer and preparation method thereof |
| CN108503253A (en) * | 2018-05-18 | 2018-09-07 | 萧县沃德化工科技有限公司 | The method that the spent lye of mercerization prepares modified amido sulfoacid series high-efficiency water reducer |
| CN108911559A (en) * | 2018-07-27 | 2018-11-30 | 科之杰新材料集团有限公司 | A kind of preparation method of modified sulfamate water reducer |
| CN114230731A (en) * | 2022-02-24 | 2022-03-25 | 天津冶建特种材料有限公司 | Modified polycarboxylate superplasticizer and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103496871A (en) * | 2013-09-24 | 2014-01-08 | 金陵科技学院 | Method for preparing environment-friendly low-cost sulfamate superplasticizer |
| CN103496871B (en) * | 2013-09-24 | 2015-11-18 | 金陵科技学院 | A kind of eco-friendly low cost sulfamate high-effective water-reducing agent preparation method |
| CN107602788A (en) * | 2017-08-31 | 2018-01-19 | 浙江吉盛化学建材有限公司 | A kind of production technology of sulfamate water reducer |
| CN107759756A (en) * | 2017-10-17 | 2018-03-06 | 江苏苏博特新材料股份有限公司 | A kind of sulfamate water reducer and preparation method thereof |
| CN107759756B (en) * | 2017-10-17 | 2020-08-11 | 江苏苏博特新材料股份有限公司 | Sulfamate water reducer and preparation method thereof |
| CN108503253A (en) * | 2018-05-18 | 2018-09-07 | 萧县沃德化工科技有限公司 | The method that the spent lye of mercerization prepares modified amido sulfoacid series high-efficiency water reducer |
| CN108911559A (en) * | 2018-07-27 | 2018-11-30 | 科之杰新材料集团有限公司 | A kind of preparation method of modified sulfamate water reducer |
| CN114230731A (en) * | 2022-02-24 | 2022-03-25 | 天津冶建特种材料有限公司 | Modified polycarboxylate superplasticizer and preparation method thereof |
| CN114230731B (en) * | 2022-02-24 | 2022-05-03 | 天津冶建特种材料有限公司 | Modified polycarboxylate superplasticizer and preparation method thereof |
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