CN104193213B - A kind of composite cement grinding aid of admixture CLT acid by product - Google Patents
A kind of composite cement grinding aid of admixture CLT acid by product Download PDFInfo
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- CN104193213B CN104193213B CN201410413167.0A CN201410413167A CN104193213B CN 104193213 B CN104193213 B CN 104193213B CN 201410413167 A CN201410413167 A CN 201410413167A CN 104193213 B CN104193213 B CN 104193213B
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- clt acid
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Abstract
The invention belongs to building material technical field, be specifically related to a kind of composite cement grinding aid of admixture CLT acid by product.Raw materials of the present invention comprises: CLT acid by product, trolamine, glycerol, calcium lignin sulphonate and water.Product of the present invention is placed without the bad phenomenon such as layering and precipitation for a long time, when joining grinding in cement clinker and gypsum system with suitable volume, can significantly improve mill efficiency, improve the physical propertiess such as pulverizing cement particle size distribution and strength of cement.Product of the present invention can make full use of CLT acid by product, and it is simple to have compound method, low production cost, on excellent characteristics such as the impact of water reducer and cement adaptability are little, all there is good grinding-aid effect to all kinds of grog, there is good economic benefit and social benefit.
Description
Technical field
The invention belongs to building material technical field, be specifically related to a kind of composite cement grinding aid of admixture CLT acid by product.
Background technology
Cement industry is resource consumption rich and influential family, not only consumes the mineral wealth such as Wingdale in a large number, and huge to coal equal energy source resources requirement, and Cement industry is faced with severe resource problem.Under the large policy environment of national sustainable development, in manufacture of cement, the energy-saving and emission-reduction work of links is gradually by people are paid attention to, and cement grinding aid is the important ring in cement industry chain, remarkable effect is had to carrying product consumption reduction, for cement production enterprise brings huge economic benefit, thus cement grinding aid becomes study hotspot gradually.
At present, cement grinding aid has been widely used in the grinding process of material.The grinding aid of studies in China mainly contains liquid grinding aid and solid grinding aid, its effective constituent mostly is surfactant, and other industrial by-products are applied in cement grinding aid by some researchs, disclosed in CN103304182, " a kind of high-performance composite cement grinding aid " adopts tile polished waste as the carrier of grinding aid effective constituent, prepare the good solid grinding aid of a kind of effect, which reflects the potentiality that cement grinding aid industry fully utilizes other industrial by-products.
CLT acid and the chloro-3-phenylmethylamine of 6--4-sulfonic acid, it is a kind of important organic red pigment intermediate, both at home and abroad mainly through toluene sulfonation route synthesis CLT acid, the key step of this route makes toluene sulfonation in concentrated sulfuric acid, through superchlorination, nitrated, in and, reduction after obtain product through acid out, a large amount of by product can be discharged in its production process, wherein there is the organism of a large amount of difficult degradation, comprise the various isomer of unreacting material, reaction intermediate and finished product, very serious pollution can be caused to environment.
CLT acid by product is from the appearance in reddish-brown transparent liquid, and its typical waste liquid water-quality guideline is: COD=(20000-30000) mg/L, BOD
5=(1500-2500) mg/L, pH=1-3, NH
3-N=(350-400) mg/L, Cl
-=(16000-20000) mg/L.Inorganic salt containing high density in waste liquid, wherein Cl
-, Ca
2+and Fe
2+deng total content be about 30g/L.Therefore, CLT acid by product belong to high density, high saliferous, can not be biochemical organic liquid waste.Consider that in by product, organism contains a large amount of amino and sulfonic group, it is effective group in dianionic surfactant, this is similar to some character of cement grinding aid, and the present inventor will be developed into a kind of composite cement grinding aid of dependable performance after the compounds such as itself and trolamine, glycerol and calcium lignin sulphonate.
Summary of the invention
The object of the present invention is to provide a kind of composite cement grinding aid of admixture CLT acid by product, product of the present invention makes full use of CLT acid by product, and it is simple to have compound method, low production cost, on the excellent characteristics such as the impact of water reducer and cement adaptability is little, all there is good grinding-aid effect to all kinds of cement clinker.
The composite cement grinding aid of a kind of admixture CLT acid by product that the present invention proposes, be made up of CLT acid by product, trolamine, glycerol, calcium lignin sulphonate and water, the weight ratio of each component is:
CLT acid by product 100
Trolamine 20-40
Glycerol 10-20
Calcium lignin sulphonate 10-30
Water 250-300.
Each component preferably weight ratio is:
CLT acid by product 100
Trolamine 25-35
Glycerol 12-15
Calcium lignin sulphonate 15-25
Water 260-280.
In the present invention, described CLT acid by product be with toluene sulfonation legal system for CLT acid process in the waste liquid that produces, its solid content is 38%-42% (mass percent).
In the present invention, described trolamine is technical pure product.
In the present invention, described glycerol is technical pure product.
In the present invention, described calcium lignin sulphonate is that powder-like product is produced in industry.
In the present invention, described water is tap water.
The preparation method of the composite cement grinding aid of a kind of admixture CLT acid by product that the present invention proposes, concrete steps as: take CLT acid by product, trolamine, glycerol, calcium lignin sulphonate and water according to aforementioned mass ratio, pass through mechanical stirring, be fully mixed to homogeneous state, obtain desired product.
The using method of the composite cement grinding aid of a kind of admixture CLT acid by product that the present invention proposes, concrete steps as: the product measured evenly is sprayed (or atomized spray) in milling equipment, volume is the 0.03%-0.15% (the solid volume of folding) of cement total mass, insert the cement clinker treating grinding, starting outfit starts grinding.
Product of the present invention is a kind of composite cement grinding aid of admixture CLT acid by product, and its feature is as follows:
1., in the present invention, described CLT acid by product is the by product that CLT acid production process produces, and wherein comprises the various isomer of unreacting material, reaction intermediate and finished product.In waste liquid, organism contains a large amount of amino and sulfonic group, all belongs to dianionic surfactant, has good dissemination to cement granules, can avoid the phenomenon such as balling-up, sticky mill in cement pulverizing course.
2. in the present invention, described trolamine significantly can improve the grinding effect of cement, when reaching identical specific surface area, significantly can reduce the grinding time of cement, improve cement granules size distribution, increase fine grain volume fraction in pulverizing cement, reduce coarse grained volume fraction in pulverizing cement simultaneously.In addition, trolamine has certain short solidifying early strength function, can accelerate cement early stage hydration process, increase early strength rate of rise, and its strong polar group can metal ion in complexing cement simultaneously, is conducive to the development of intensity.
3. in the present invention, described glycerol and calcium lignin sulphonate all can improve the grinding effect of cement, when both use as grinding aid separately, when reaching identical specific surface area, all significantly can reduce the grinding time of cement, improving cement granules size distribution.Meanwhile, both add the effect can played and regulate time of coagulation, can adjust proportioning according to actual requirement of engineering, thus the time of coagulation of Reasonable adjustment cement.
Embodiment
Further illustrate the present invention below by embodiment: the present embodiment is implemented under with technical solution of the present invention prerequisite, give detailed embodiment and specific operation process.
1. grinding effect test
Specific surface area: the method specified according to GB/T8074-2008 " Method of determination for specific surface of cement (Bo Shi method) ", uses the automatic Blain specific surface determinator of full FBT-9 type to measure.Grinding effect characterizes with the specific surface area of pulverizing cement 30min, 40min and 50min.
The method that screen over-size specifies according to GB/T1345-2005 " the cement fineness method of inspection-sieve formula ", uses negative pressure sieve to test, selects 80 μm, and 60 μm and 30 μm reflect pulverizing cement size distribution situation more accurately.Screen over-size calculation formula is as follows:
η=R/W×100
Wherein: η-cement sample percentage of sieve residue, unit is mass percent (%);
R-cement screenings quality, unit is gram (g);
W-cement sample quality, unit is gram (g).
Result is calculated to 0.1%.
2. cement physical properties test
The consumptive use of water normal consistence of pulverizing cement, time of coagulation and stability etc. physical properties the method that specifies according to GB/T1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection " of detection test.
The method that strength of cement mortar specifies according to GB/T17671-1999 " Test method for strength of hydraulic cement mortar " is tested, and sand uses standard sand.
Embodiment 1, a kind of composite cement grinding aid of admixture CLT acid by product, by CLT acid by product 100, trolamine 20, glycerol 10, the weight ratio of calcium lignin sulphonate 10 and water 250 is formulated.Be 0.03% join intergrinding in cement clinker and gypsum system to roll over solid volume, test pulverizing cement 30min respectively, the specific surface area of 40min and 50min, 30 μm, the screen over-size of 60 μm and 80 μm, 3d and 28d cement mortar strength, test result as shown in Table 1 and Table 2.
Embodiment 2, a kind of composite cement grinding aid of admixture CLT acid by product, by CLT acid by product 100, trolamine 40, glycerol 20, the weight ratio of calcium lignin sulphonate 30 and water 300 is formulated.Be 0.10% join intergrinding in cement clinker and gypsum system to roll over solid volume, test pulverizing cement 30min respectively, the specific surface area of 40min and 50min, 30 μm, the screen over-size of 60 μm and 80 μm, 3d and 28d cement mortar strength, test result as shown in Table 1 and Table 2.
Embodiment 3, a kind of composite cement grinding aid of admixture CLT acid by product, by CLT acid by product 100, trolamine 25, glycerol 12, the weight ratio of calcium lignin sulphonate 15 and water 260 is formulated.Be 0.15% join intergrinding in cement clinker and gypsum system to roll over solid volume, test pulverizing cement 30min respectively, the specific surface area of 40min and 50min, 30 μm, the screen over-size of 60 μm and 80 μm, 3d and 28d cement mortar strength, test result as shown in Table 1 and Table 2.
Embodiment 4, a kind of composite cement grinding aid of admixture CLT acid by product, by CLT acid by product 100, trolamine 35, glycerol 15, the weight ratio of calcium lignin sulphonate 25 and water 280 is formulated.Be 0.10% join intergrinding in cement clinker and gypsum system to roll over solid volume, test pulverizing cement 30min respectively, the specific surface area of 40min and 50min, 30 μm, the screen over-size of 60 μm and 80 μm, 3d and 28d cement mortar strength, test result as shown in Table 1 and Table 2.
The grinding-aid effect of table 1 grinding aid
Table 2 pulverizing cement physical properties
Claims (7)
1. a composite cement grinding aid for admixture CLT acid by product, it is characterized in that being made up of CLT acid by product, trolamine, glycerol, calcium lignin sulphonate and water, the weight ratio of each component is:
CLT acid by product 100
Trolamine 20-40
Glycerol 10-20
Calcium lignin sulphonate 10-30
Water 250-300;
Described CLT acid by product for toluene sulfonation legal system for CLT acid process in the by product that produces, its solid content is 38wt%-42wt%.
2. the composite cement grinding aid of a kind of admixture CLT acid by product according to claim 1, is characterized in that the weight ratio of each component is:
CLT acid by product 100
Trolamine 25-35
Glycerol 12-15
Calcium lignin sulphonate 15-25
Water 260-280.
3. the composite cement grinding aid of a kind of admixture CLT acid by product according to claim 1, is characterized in that described trolamine is technical pure product.
4. the composite cement grinding aid of a kind of admixture CLT acid by product according to claim 1, is characterized in that described glycerol is technical pure product.
5. the composite cement grinding aid of a kind of admixture CLT acid by product according to claim 1, is characterized in that described calcium lignin sulphonate is powder-like product.
6. the composite cement grinding aid of a kind of admixture CLT acid by product according to claim 1, is characterized in that described water is tap water.
7. the using method of the composite cement grinding aid of an a kind of admixture CLT acid by product as claimed in claim 1, concrete steps are: the product measured evenly is sprayed or atomized spray in milling equipment, after folding is solid, volume is the 0.03%-0.15% of cement total mass, insert the cement clinker treating grinding, starting outfit starts grinding.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008542182A (en) * | 2005-06-02 | 2008-11-27 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Biomass-derived grinding aid |
| CN101898879A (en) * | 2010-08-06 | 2010-12-01 | 天津振兴水泥有限公司 | Output-increased composite portland cement grinding additive |
| CN102643043A (en) * | 2012-04-06 | 2012-08-22 | 安徽省振华工贸股份有限公司 | Cement grinding aid |
| CN103570269A (en) * | 2013-10-23 | 2014-02-12 | 沈阳建筑大学 | Mineral waste residue liquid composite grinding aid and preparation method thereof |
| CN103922630A (en) * | 2014-03-27 | 2014-07-16 | 沭阳县沂淮水泥有限公司 | Enhanced type cement composite grinding aid |
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2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008542182A (en) * | 2005-06-02 | 2008-11-27 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Biomass-derived grinding aid |
| CN101898879A (en) * | 2010-08-06 | 2010-12-01 | 天津振兴水泥有限公司 | Output-increased composite portland cement grinding additive |
| CN102643043A (en) * | 2012-04-06 | 2012-08-22 | 安徽省振华工贸股份有限公司 | Cement grinding aid |
| CN103570269A (en) * | 2013-10-23 | 2014-02-12 | 沈阳建筑大学 | Mineral waste residue liquid composite grinding aid and preparation method thereof |
| CN103922630A (en) * | 2014-03-27 | 2014-07-16 | 沭阳县沂淮水泥有限公司 | Enhanced type cement composite grinding aid |
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Effective date of registration: 20170616 Address after: 221000, 17, rhubarb village, rhubarb Town, Jiawang District, Xuzhou economic and Technological Development Zone, Jiangsu, China Patentee after: Xuzhou casting Building Material Technology Co., Ltd. Address before: 200092 Shanghai City, Yangpu District Siping Road No. 1239 Patentee before: Tongji University |
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