CN103113037B - 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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- CN103113037B CN103113037B CN201310022950.XA CN201310022950A CN103113037B CN 103113037 B CN103113037 B CN 103113037B CN 201310022950 A CN201310022950 A CN 201310022950A CN 103113037 B CN103113037 B CN 103113037B
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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 based on naphthalene system and poly carboxylic acid series water reducer.Wherein, the shortcoming of naphthalene water reducer is that slump-loss easily occurs crystalline deposit comparatively greatly and under low temperature environment; And poly carboxylic acid series water reducer uses price high.
Sulfamate high-effective water-reducing agent production technique is simple, the advantage such as have that water-reducing rate is high, good in low water-cement ratio current downflow, the large and gradual loss of concrete slump is little, but, it still has problems in production with application: one is that its main raw material Sodium sulfanilate and phenol are petroleum industry product, cost of material is partially expensive, and production cost is higher; Two is that concrete water-retentivity is bad in application process, and segregation excreting water phenomenon is serious, and even slurry hardens and to be separated with water.
Meanwhile, paper industry extensively adopts alkali paper-making technique, produces a large amount of paper waste, 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, utilizing " black liquor " is exactly mainly be translated into sulfonated lignin.Chinese Patent Application No. 200710030226.6 discloses a kind of preparation method of alkali lignin modified sulfamate high-effective water reducer, and the water reducer preparation cost obtained is low, can significantly improve mobility on coagulation, improves ultimate compression strength; Chinese Patent Application No. 200810070589.7 discloses a kind of sulfonated alkali lignin modified sulfamate high-effective water reducer and preparation method thereof, overcomes product to the shortcoming that volume is responsive, bleeding rate is high, concrete is easily emanated.But, not yet find in prior art to adopt black liquor directly and sulfamate high-effective water-reducing agent carry out the technology of modification.
Summary of the invention
The object of the present invention is to provide a kind of use cost low and make the low bleeding sulfamate high-effective water-reducing agent of low cost and preparation method thereof of concrete not bleeding.
For reaching above-mentioned purpose, solution of the present invention is:
The low bleeding sulfamate high-effective water-reducing agent of a kind of low cost, 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.
A preparation method for the low bleeding sulfamate high-effective water-reducing agent of low cost, comprises the following steps:
Step one, front polycondensation phase: heat water to 50-60 DEG C, add in reactor by aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate, phenolic compound and alkaline conditioner, warming while stirring is to 60-80 DEG C; Drip condensing agent, dripped off in 60-120 minute, and maintain the temperature at 65-80 DEG C; Condensing agent is added dropwise to complete rear raised temperature to 80-90 DEG C, insulation 0.5-1 hour; Be warming up to 90-100 DEG C again, insulation 3-4 hour;
Step 2, adds the black liquor stage: be cooled to 70-80 DEG C, adds water and black liquor, by the pH value of alkaline conditioner regulation system at 10-12;
Step 3, in the aftercondensated stage: continue to be warming up to 90-100 DEG C, is incubated cooling discharge, i.e. preparing product after 1-2 hour.
Further, aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate are one or both in Sulphanilic Acid and sodium salt thereof, amino-1, the 3-phenyl disulfonic acid of 4-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 (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 (containing two kinds) in sodium hydroxide, potassium hydroxide, sodium phosphate, trisodium phosphate, two sodium polyphosphates, tripoly phosphate sodium STPP, sodium polyphosphate, water glass.
Further, black liquor for be selected from bamboo, bagasse, straw, wheat straw, reed, Eucalyptus, birch, Pinus massoniana Lamb one or more (containing two kinds) mixture by the obtained black liquor of alkaline process.
After adopting such scheme, the preparation method of the low bleeding sulfamate high-effective water-reducing agent of low cost of the present invention, mainly utilizes the sulfonated lignin containing more amount in the black liquor of alkali paper-making.Black liquor is directly applied to modification, the step of recovery can be reduced, improve organic efficiency, reduce costs, and the compositions such as the sulfonated lignin that contain in black liquor and residual alkali can be made full use of, change evil for benefit.
Simultaneously, adopt sulfamate high-effective water-reducing agent prepared by the present invention, due to sulfonated lignin, there is three-dimensional structure and wherein contain a large amount of polar hydrophilic groups, when the water reducer that copolycondensation is modified joins after in gelling system, cement granules absorption water reducer negatively charged ion, polar group simultaneously in sulfonated lignin is soluble in water, form the solvation hydration shell with certain physical strength, not only can stop the mutual absorption of cement granules, cement granules is disperseed, also can reduce the amount of free water simultaneously, make part free water around around cement granules, wetting cement particle surface, thus, add black liquor modified after sulfamate high-effective water-reducing agent have good anti-bleeding performance.
Compared with prior art, beneficial effect of the present invention is:
One, the present invention adds black liquor in the condensation stage in later stage of sulfamate high-effective water-reducing agent, significantly reduces modified sulfamate high-effective water-reducing agent cost.
Two, containing sulfonated lignin in black liquor, there is certain diminishing and bleed effect, the condensation stage adds black liquor, make the sulfonated lignin in black liquor participate in the molecular composition of sulfamate high-effective water-reducing agent, effectively reduce excreting water phenomenon, improve concrete workability.
Three, make full use of the residual alkali in black liquor, for whole synthetic system provides alkaline environment, reduce alkaline conditioner addition.
Four, simplify the steps such as the filtration in the utilization of prior art black liquor recovery, sulfonation and spraying dry, improve organic efficiency, realize the utilization of black liquor 100%, thoroughly solve black liquor pollution problem.
Five, production technique is simple, and raw materials for production are easy to get, with short production cycle, reaction temperature and, required equipment is conventional equipment, and production cost is low.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated.
Embodiment one
A preparation method for the low bleeding sulfamate high-effective water-reducing agent of low cost, comprises the following steps:
Step one, front polycondensation phase: by mass parts, in a kettle., adds 42 parts of phenol, 45 parts of Sodium sulfanilates and 190 parts of water, constant temperature to 50 DEG C.Add about 4 parts of liquid caustic soda adjust pHs to 8, be warming up to 70 DEG C.Drip 60 parts of formaldehyde, within 90 minutes, dropwise, temperature controls at 75 DEG C.After formaldehyde dropwises, be warmed up to 80 DEG C of constant temperature 1 hour, then be warming up to 95 DEG C of constant temperature 3 hours.
Step 2, adds the black liquor stage: after insulation terminates, be cooled to 80 DEG C, add 40 parts, water, add black liquor 35 parts, add 20 parts of liquid caustic soda adjust pHs to 10.
Step 3, in the aftercondensated stage: be warming up to 95 DEG C of constant temperature 1 hour, is cooled to room temperature and namely obtains product sulfamate high-effective water-reducing agent.
Embodiment two
A preparation method for the low bleeding sulfamate high-effective water-reducing agent of low cost, comprises the following steps:
Step one, front polycondensation phase: by mass parts, in a kettle., adds 45 parts of dihydroxyphenyl propanes, 40 parts of Sulphanilic Acid and 190 parts of water, constant temperature to 50 DEG C.Add about 4.5 parts of potassium hydroxide adjust pHs to 8, be warming up to 75 DEG C.Drip 62 parts of formaldehyde, within 90 minutes, dropwise, temperature controls at 75 DEG C.After formaldehyde dropwises, be warmed up to 80 DEG C of constant temperature 1 hour, then be warming up to 100 DEG C of constant temperature 3.5 hours.
Step 2, adds the black liquor stage: after insulation terminates, be cooled to 80 DEG C, add water 40 parts, add black liquor 10 parts, add 30 parts of potassium hydroxide adjust pHs to 11.
Step 3, in the aftercondensated stage: be warming up to 100 DEG C of constant temperature 1 hour, namely obtains product sulfamate high-effective water-reducing agent to room temperature after cooling.
Embodiment three
A preparation method for the low bleeding sulfamate high-effective water-reducing agent of low cost, comprises the following steps:
Step one, front polycondensation phase: by mass parts, in a kettle., adds 38 parts of Resorcinols, 50 parts of Sodium sulfanilates and 190 parts of water, constant temperature to 50 DEG C.Add 3 parts of liquid caustic soda adjust pHs to 8, be warming up to 75 DEG C.Drip 60 parts of acetaldehyde, within 120 minutes, dropwise, temperature controls at 75 DEG C.After acetaldehyde dropwises, be warmed up to 85 DEG C of constant temperature 1 hour, then be warming up to 95 DEG C of constant temperature 3 hours.
Step 2, adds the black liquor stage: after insulation terminates, be cooled to 80 DEG C, add water 40 parts, add black liquor 20 parts, add 25 parts of liquid caustic soda adjust pHs to 11.
Step 3, the aftercondensated stage: be warming up to 95 DEG C of constant temperature 1 hour.Namely product sulfamate high-effective water-reducing agent is obtained to room temperature after cooling.
Embodiment four
A preparation method for the low bleeding sulfamate high-effective water-reducing agent of low cost, comprises the following steps:
Step one, front polycondensation phase: by mass parts, in a kettle., adds 40 parts of bisphenol Ss, 35 parts of 4-amino-1,3-phenyl sodium disulfonates and 190 parts of water, constant temperature to 50 DEG C.Add about 5 parts of liquid caustic soda adjust pHs to 8, be warming up to 70 DEG C.Drip 60 parts of formaldehyde, within 90 minutes, dropwise, temperature controls at 75 DEG C.After formaldehyde dropwises, be warmed up to 80 DEG C of constant temperature 1 hour, then be warming up to 100 DEG C of constant temperature 3.5 hours.
Step 2, adds the black liquor stage: after insulation terminates, be cooled to 80 DEG C, add water 50 parts, add black liquor 30 parts, add 23 parts of liquid caustic soda adjust pHs to 10.
Step 3, the aftercondensated stage: be warming up to 100 DEG C of constant temperature 1 hour.Namely product sulfamate high-effective water-reducing agent is obtained to room temperature after cooling.
Low cost low bleeding sulfonate high efficiency water reducing agent obtained by embodiment one to embodiment four is tested: embodiment 1-4 is synthesized the sample obtained, contrast with prior art sulfamate high-effective water-reducing agent ASP, adopt standard cement, volume presses 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 (5)
1. a preparation method for the low bleeding sulfamate high-effective water-reducing agent of low cost, is characterized in that: comprise the following steps:
Step one, front polycondensation phase: heat water to 50-60 DEG C, add in reactor by aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate, phenolic compound and alkaline conditioner, warming while stirring is to 60-80 DEG C; Drip condensing agent, dripped off in 60-120 minute, and maintain the temperature at 65-80 DEG C; Condensing agent is added dropwise to complete rear raised temperature to 80-90 DEG C, insulation 0.5-1 hour; Be warming up to 90-100 DEG C again, insulation 3-4 hour;
Step 2, adds the black liquor stage: be cooled to 70-80 DEG C, adds water and black liquor, by the pH value of alkaline conditioner regulation system at 10-12;
Step 3, in the aftercondensated stage: continue to be warming up to 90-100 DEG C, is incubated cooling discharge, i.e. preparing product after 1-2 hour.
2. the preparation method of the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost as claimed in claim 1, it is characterized in that: aniline sulfonic acid or amino phenyl sulfonyl hydrochlorate are one or both in Sulphanilic Acid and sodium salt thereof, amino-1, the 3-phenyl disulfonic acid of 4-and sodium salt thereof or 4-kharophen Phenylsulfonic acid and sodium salt thereof.
3. the preparation method of the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost as claimed in claim 1, is characterized in that: condensing agent is one or both in formaldehyde, paraformaldehyde.
4. the preparation method of the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost as claimed in claim 1, 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.
5. the preparation method of the low bleeding sulfamate high-effective water-reducing agent of a kind of low cost as claimed in claim 1, 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.
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| 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 |
| 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 |
| CN108911559B (en) * | 2018-07-27 | 2020-11-27 | 科之杰新材料集团有限公司 | Preparation method of modified sulfamate water reducer |
| 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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| CN101941811A (en) * | 2010-07-29 | 2011-01-12 | 江苏汇迪建材有限公司 | Novel grafted sulphamate high-efficiency water reducing agent and preparation method thereof |
| CN102092979A (en) * | 2010-12-10 | 2011-06-15 | 马清浩 | Sulfamate water-reducing agent and preparation method thereof |
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| CN101941811A (en) * | 2010-07-29 | 2011-01-12 | 江苏汇迪建材有限公司 | Novel grafted sulphamate high-efficiency water reducing agent and preparation method thereof |
| CN102092979A (en) * | 2010-12-10 | 2011-06-15 | 马清浩 | Sulfamate water-reducing agent and preparation method thereof |
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| 棉浆粕黑液改性氨基磺酸系高效减水剂的研究;陈国新 等;《混凝土》;20121231(第3期);第108-110页 * |
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