CN113354318A - Grinding aid and preparation method and application thereof - Google Patents
Grinding aid and preparation method and application thereof Download PDFInfo
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- CN113354318A CN113354318A CN202110654529.5A CN202110654529A CN113354318A CN 113354318 A CN113354318 A CN 113354318A CN 202110654529 A CN202110654529 A CN 202110654529A CN 113354318 A CN113354318 A CN 113354318A
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- grinding aid
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- soluble
- grinding
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
- C04B7/52—Grinding ; After-treatment of ground cement
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a grinding aid and a preparation method and application thereof, and belongs to the technical field of building materials. A grinding aid comprising, as raw materials: diethanol monoisopropanolamine, polymeric polyol, unsaturated polycarboxylic acid, water-soluble thiosulfate, water-soluble chloride and water-soluble calcium salt. According to the grinding aid provided by the invention, through the matching of the raw material components, when the grinding aid is applied to the preparation of cement, the early strength of the obtained cement can be improved on the premise of ensuring the grinding efficiency.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a grinding aid, and a preparation method and application thereof.
Background
With the continuous development of the basic building industry, the grinding aid is widely applied to the cement industry. At present, grinding aids used in cement plants mainly improve grinding conditions and reduce energy consumption. The traditional approach for reducing the energy consumption is to technically modify a cement production process and equipment, but the approach has huge early construction investment and is difficult to recover cost in a short time, so that the enthusiasm of cement enterprises is low, and the use of the cement grinding aid provides a new idea for energy conservation and consumption reduction, so that the development and research of the cement grinding aid become the first choice for energy conservation and emission reduction in the cement industry. It can raise cement yield, reduce power consumption and save cost.
With the progress of the industry, the requirement on the strength of cement is higher and higher, and the research direction on grinding aids in the industry is gradually shifted from the simple improvement of the grinding efficiency to the simultaneous improvement of the grinding efficiency and the cement performance (including the strength). As for the improvement of early strength, the improvement can be achieved by increasing the proportion of the alcohol amine substance in the grinding aid in the industry, but because the price of the alcohol amine substance is higher, the method causes the grinding aid to have higher cost and is difficult to popularize and use on a large scale. Other methods for improving the early strength of cement by using a grinding aid are difficult to consider both the early strength and the later strength.
In conclusion, the existing method for improving the early strength of the cement by using the grinding aid is high in cost or not obvious in effect.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the grinding aid provided by the invention can improve the early strength of the obtained cement and achieve the purpose of reducing the cost on the premise of ensuring the grinding efficiency of the cement by matching the raw material components.
The invention also provides a preparation method of the grinding aid.
The invention also provides an application of the grinding aid in cement preparation.
According to one aspect of the invention, a grinding aid is provided, the raw materials comprising: diethanol monoisopropanolamine, polymeric polyol, unsaturated polycarboxylic acid, water-soluble thiosulfate, water-soluble chloride and water-soluble calcium salt.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
the grinding aid provided by the invention comprises the following components in percentage by weight:
the diethanol monoisopropanolamine can be used as a chemical activator to excite the strength of cement, and the stable operation of the hydration stage of the cement is ensured by influencing the grinding process of the cement; in particular, diethanol monoisopropanolamine is used for cement particlesThe particles can promote dispersion and primary dissolution, and can complex Ca in the cement hydration process2+Thereby prolonging the induction period of hydration, prolonging the operable time after the cement is mixed with water and ensuring that the hydration is more uniform;
meanwhile, the diethanol monoisopropanolamine can accelerate the change trend of AFT (trisulfide hydrated calcium sulphoaluminate, namely ettringite) to AFM (monosulfited hydrated calcium sulphoaluminate) in the hydration process, reduce the porosity of cement and improve the later strength of the cement; however, the alcohol amine substances have limited types and too high price, and if the alcohol amine substances are used in large quantities, the alcohol amine substances are difficult to accept by manufacturers.
The polymeric polyol is used for improving the grinding-assisting effect in the cement grinding process; specifically, the surface of the polymeric polyol contains more alcoholic hydroxyl groups, the polarity of the hydroxyl groups is strong, and in the cement grinding process, the polymeric polyol can be adsorbed on the surface of cement to generate electrostatic repulsion, so that a good grinding assisting effect is generated for cement grinding, the grinding efficiency of the cement is improved, and an energy-saving effect is achieved.
The water-soluble calcium salt can accelerate the early hydration process of the cement and improve the early strength of the cement; specifically, the main component of the cement comprises 3 CaO. SiO2(tricalcium silicate, C2S)、2CaO·SiO2(dicalcium silicate, C3S) and 3 CaO. Al2O3(tricalcium aluminate, C3A); 3CaO SiO2And 2 CaO. SiO2C-S-H (calcium silicate hydrate) is generated in the hydration process, and partial abundant silicon dioxide is attached to the surface of the C-S-H (the phenomenon is particularly obvious when the cement system comprises silica fume);
the water soluble calcium salt can increase Ca2+Concentration, formation of Ca (OH) in the hydration system2，Ca(OH)2The calcium silicate hydrate can generate a volcanic ash effect with silicon dioxide attached to the surface of the C-S-H to generate C-S-H (calcium silicate hydrate), and the C-S-H generated by the volcanic ash effect is mostly filled in C-S-H gel pores generated by cement hydration, so that the structural compactness is greatly improved, and the later strength of the cement is further improved;
at the same time, Ca2+Can also react with sulfate radicals to generate slightly soluble calcium sulfate, further reduce the concentration of the sulfate radicals in a cement hydration system,slow down ettringite (3 CaO. Al)2O3·3CaSO4·32H2O), namely accelerating the hydration of tricalcium aluminate (3 CaO. Al2O3), and improving the early strength of the cement.
The water-soluble chloride salt can improve the early strength of the cement, tricalcium aluminate in the cement reacts with chloride ions to generate hydrated chloroaluminate, the hydration of the tricalcium aluminate can be promoted, and the chloride ions also have an accelerating effect on the hydration of tricalcium silicate.
The water-soluble thiosulfate can improve the early strength of the cement, and concretely, both thiosulfate radical and sulfate radical can promote the hydration of tricalcium silicate in the cement and improve the early strength, but the sulfate radical applied in the common technology can react with a hydration product to cause the expansion and damage of a cement base, so that the corrosion of a steel bar in the cement-based material is accelerated, and the later strength of the cement is influenced; therefore, the invention replaces sulfate with thiosulfate, and can ensure the later strength of the cement on the premise of ensuring the early strength.
Carboxyl in unsaturated polycarboxylic acid can improve the adsorption capacity of the grinding aid and the electrostatic repulsion between cement particles and can improve the early strength of cement; in addition, under the action of sodium thiosulfate, partial unsaturated polycarboxylic acid can generate polymerization reaction to generate polycarboxylic acid polymer, so that cement particles can be dispersed, and the grinding efficiency is improved.
In conclusion, the early hydration process of tricalcium silicate, dicalcium silicate and tricalcium aluminate is promoted by combining the three water-soluble salts, the structural compactness is improved, and the grinding aid formed by matching the hydramine, the unsaturated polycarboxylic acid and the polymeric polyol is lower in cost compared with the grinding aid using the hydramine only; compared with other grinding aids, the grinding aid has the advantages of simultaneously considering grinding efficiency, early strength and later strength.
In some embodiments of the present invention, the polymeric polyol and the monomer are at least one of ethylene glycol, diethylene glycol and glycerol.
In some embodiments of the invention, the unsaturated polycarboxylic acid is itaconic acid.
In some embodiments of the present invention, the water-soluble thiosulfate salt is at least one of sodium thiosulfate and potassium thiosulfate.
The function of the thiosulfate salt is to provide thiosulfate.
In some embodiments of the invention, the water-soluble chloride salt is at least one of sodium chloride, potassium chloride, and calcium chloride.
In some embodiments of the invention, the water-soluble calcium salt is at least one of calcium nitrate and calcium silicate.
In some embodiments of the invention, the amount of species of calcium ions provided by the water-soluble calcium salt is greater than the amount of species of chloride ions provided by the water-soluble chloride salt.
In some embodiments of the invention, the grinding aid comprises, in parts by weight:
in some preferred embodiments of the invention, the grinding aid further comprises a solvent.
In some preferred embodiments of the invention, the solvent is water.
In some preferred embodiments of the present invention, the solvent is added in an amount of 33 to 47 parts by weight.
According to another aspect of the invention, the preparation method of the grinding aid is provided, and comprises the following steps:
s1, dissolving the water-soluble thiosulfate, the water-soluble chloride and the water-soluble calcium salt in water;
s2, adding the diethanol monoisopropanolamine, the polymeric polyol and the unsaturated polycarboxylic acid into the system obtained in the step S1, and dissolving and dispersing to obtain the grinding aid.
In some embodiments of the present invention, in step S1, the dissolving is performed by stirring for 10-15 min.
In some embodiments of the invention, in step S2, the dissolving is performed by stirring.
In some embodiments of the invention, in step S2, the dispersing is by sonication.
In some embodiments of the present invention, in step S2, the dispersing is performed for about 5 min.
According to a further aspect of the invention, the use of said grinding aid in the preparation of cement is proposed.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The grinding aid is prepared in the embodiment, and the specific process is as follows:
s1, weighing 10g of sodium thiosulfate, 5g of sodium chloride, 10g of calcium nitrate and 43g of water, adding into a reaction container, and stirring for 10min to dissolve;
s2, adding 18g of diethanol monoisopropanolamine, 10g of polymeric polyol and 4g of itaconic acid into the system obtained in the step S1, and performing low-frequency ultrasonic oscillation for 5min (the frequency is 50-80 Hz) to form a uniform mixed solution, namely the grinding aid.
Compared with the preparation method of the grinding aid in the embodiment 1, the grinding aid is prepared in the comparative examples 1-9 respectively, and the specific process is as follows:
(1) the specific components of the raw materials are different, and the specific components are shown in table 1.
TABLE 1 raw Material composition of grinding aids in example 1 and comparative examples 1-9
Wherein unfilled cells indicate no additions; comparative example 9 differs from example 1 in that diethanol monoisopropanolamine is replaced by triethanolamine.
Test examples
This test example tested the performance of the grinding aids prepared in the examples and comparative examples.
Specifically, after mixing cement clinker with other components, a grinding aid is dripped into the mixture for grinding, and the performance of the ground cement material is characterized. The mixing amount of the grinding aid is 0.08 percent (accounting for the mass percentage of the cement clinker), and the grinding equipment and the grinding time of the cement clinker and various performance characterization methods of the ground cement are determined by referring to standard documents, wherein the reference standard documents comprise the national standard (number GB26748-2011) of the cement grinding aid and the industrial standard 'technical specification for application of the cement grinding aid'. The composition of the cement material is shown in table 2.
TABLE 2 composition of cement materials used in the test examples in terms of mass percent
| Material | Clinker | Gypsum plaster | Limestone | Coal cinder |
| Ratio of occupation of | 83％ | 5％ | 6％ | 6％ |
The properties of the cement material after grinding are shown in table 3.
TABLE 3 Performance results of cementitious materials ground without grinding aid and with grinding aids of the examples and comparative examples
Wherein, blank indicates that no grinding aid is added, fineness (45 μm)/% indicates the ground cement material, after sieving with a sieve with an aperture of 45 μm, the mass of the sieved residue accounts for the percentage of the total mass, and the smaller the numerical value, the more sufficient the grinding is, the higher the grinding efficiency is.
The results in Table 3 show that the grinding aid provided by the invention can improve the grinding efficiency of cement (the larger the specific surface area is, the smaller the particle size is), and simultaneously improve the early strength (1d, namely 1 day) and the later strength (28d) of a cement material;
meanwhile, the results in Table 3 also show that the synergistic effect of the components is generated, any one (or more) raw material (comparative examples 1-8) is lacked, or the diethanol monoisopropanolamine is replaced by triethanolamine (comparative example 9), so that the effect of the grinding aid provided by the invention cannot be achieved.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A grinding aid, characterized in that the raw materials comprise: diethanol monoisopropanolamine, polymeric polyol, unsaturated polycarboxylic acid, water-soluble thiosulfate, water-soluble chloride and water-soluble calcium salt.
2. The grinding aid of claim 1 wherein the polymeric polyol and the monomer are at least one of ethylene glycol, diethylene glycol and glycerol.
3. The grinding aid of claim 1 wherein the unsaturated polycarboxylic acid is itaconic acid.
4. The grinding aid of claim 1 wherein said water soluble thiosulfate salt is at least one of sodium thiosulfate and potassium thiosulfate.
5. The grinding aid of claim 1 wherein said water soluble chloride salt is at least one of sodium chloride, potassium chloride and calcium chloride.
6. The grinding aid of claim 1, wherein the water-soluble calcium salt is at least one of calcium nitrate and calcium silicate.
7. The grinding aid of claim 1, wherein the grinding aid comprises, in parts by weight:
8. a method for preparing a grinding aid according to any one of claims 1 to 7, comprising the steps of:
s1, dissolving the water-soluble thiosulfate, the water-soluble chloride and the water-soluble calcium salt in water;
s2, adding the diethanol monoisopropanolamine, the polymeric polyol and the unsaturated polycarboxylic acid into the system obtained in the step S1, and dissolving and dispersing to obtain the grinding aid.
9. The method of claim 8, wherein the dispersing step S2 is carried out by sonication.
10. Use of a grinding aid as claimed in any one of claims 1 to 7 in the preparation of cement.
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| Application Number | Priority Date | Filing Date | Title |
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| CN113354318B CN113354318B (en) | 2022-05-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114804710A (en) * | 2022-05-25 | 2022-07-29 | 刘江平 | Concrete performance improving agent and preparation method thereof |
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| CN106348631A (en) * | 2016-08-25 | 2017-01-25 | 辽宁天宝华瑞建材有限公司 | High-efficiency cement compound grinding aid added with industrial effluent and preparation method thereof |
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2021
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| AU2002246049A1 (en) * | 2001-01-24 | 2002-08-06 | Basf Aktiengesellschaft | Water-absorbing agent, method for the production thereof and use of the same |
| CN102992687A (en) * | 2012-08-21 | 2013-03-27 | 江苏百瑞吉新材料有限公司 | Cement grinding aid and preparation method thereof |
| CN105130254A (en) * | 2015-09-18 | 2015-12-09 | 广西路佳道桥勘察设计有限公司 | Efficient cement grinding aid and cement containing same |
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