CN113880490B - Grinding aid special for vertical mill grinding cement and application thereof - Google Patents
Grinding aid special for vertical mill grinding cement and application thereof Download PDFInfo
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- CN113880490B CN113880490B CN202111248862.2A CN202111248862A CN113880490B CN 113880490 B CN113880490 B CN 113880490B CN 202111248862 A CN202111248862 A CN 202111248862A CN 113880490 B CN113880490 B CN 113880490B
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/283—Polyesters
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Disintegrating Or Milling (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a grinding aid special for vertical mill grinding cement and application thereof, wherein the grinding aid comprises the following raw materials in percentage by weight: 5-40% of water-soluble polyester; 5-20% of inorganic dispersion reinforcing agent; 5-20% of polyalcohol or alcohol amine; 40-70% of water; in the formula of the grinding aid special for vertical grinding cement, the water-soluble polyester has high viscosity and can inhibit the dispersion of the grinding aid in the grinding process to stabilize a material layer, so that materials are sufficiently ground on a grinding disc, and along with the grinding of cement, the water-soluble polyester is hydrolyzed or cracked into polyol, and/or alcohol amine, polybasic acid and low-molecular-weight water-soluble polyester polymer under high-temperature and alkaline environments and the grinding pressure of the grinding roller, and the polyol, and/or alcohol amine and an inorganic dispersion reinforcing agent in the formula of the grinding aid are matched to improve the dispersion of ground fine powder and improve the powder selection efficiency.
Description
Technical Field
The invention belongs to the field of cement grinding aids, and particularly relates to a grinding aid special for grinding cement by a vertical mill and application thereof.
Background
The vertical mill is an ideal large-scale grinding device and is widely applied to the industries of cement, electric power, metallurgy, chemical industry, non-metal ore and the like. It integrates crushing, drying, grinding and grading conveying into a whole, has high production efficiency, and can grind blocky, granular and powdery raw materials into required powdery materials. Compared with the ball milling process, has remarkable superiority. The method has the advantages of simple process, small occupied area, high grinding efficiency and low energy consumption, and is gradually accepted by domestic cement enterprises.
The cement grinding aid is a process additive added during cement grinding, and the addition of the grinding aid can greatly improve the process condition of cement grinding, improve the production efficiency without damaging the performance of cement, and aims to reduce the production cost and improve the quality of the cement. The invention of the cement grinding aid is derived from a cement ball milling process, and based on the theory of dispersing material particles, the complex chemical or physical mechanism generated by organic matters, inorganic matters or a mixture of the organic matters, the inorganic matters and a surfactant is used for solving the phenomena of electrostatic adsorption, flocculation, crack healing and the like in the process of grinding water by a ball mill so as to achieve the purposes of increasing the yield, reducing the energy consumption and improving the cement quality.
The vertical milling process is very different from the ball milling process. The grinding aid used in the ball milling process mainly has a dispersing effect on materials, improves the loose property of the materials, and has high flow speed and high grinding efficiency. The vertical grinding process is just opposite, the material flow rate is high, the retention time in the mill is short, if the material is too loose, the material is suspended in a grinding cavity under the action of wind, and the grinding roller cannot be fully ground on a grinding disc, so that the material layer is often unstable due to the use of the traditional cement grinding aid in the vertical grinding process, the vibration of the mill is large, the material layer is stabilized by spraying water in the mill, the moisture in the cement is high, the fine powder in the cement is hydrated in advance, and the problems of hydration agglomeration and strength attenuation of the stored cement are caused, so that the storage capacity and the turnover are influenced.
Part of enterprises add high-molecular cohesive components in the grinding aid to stabilize the material layer, reduce water spraying in the mill, but possibly cause agglomeration and coarsening of cement particles, influence the powder selection work of the vertical mill and be not beneficial to the improvement of the mill yield; meanwhile, the performance and the application of the cement are also influenced to a certain extent.
Disclosure of Invention
In order to solve the problems, the invention provides a grinding aid special for vertical mill grinding cement, which is prepared by polycondensing polyol, and/or alcohol amine and polybasic acid under the action of a catalyst to form water-soluble polyester, and then compounding the water-soluble polyester with the polyol, and/or alcohol amine, an inorganic dispersion reinforcing agent and water. When the grinding aid is used as a grinding aid for grinding cement in a vertical mill, no water spray in the vertical mill can be realized, the cement strength is obviously improved when the vertical mill is used for grinding cement, the problems of hydration agglomeration and strength attenuation of stock cement are solved, and the performance and the application of the cement are not influenced.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a grinding aid special for vertical mill grinding cement comprises the following raw materials in percentage by weight:
the grinding aid special for vertical mill grinding cement comprises the following raw materials in percentage by weight:
the preparation method of the water-soluble polyester comprises the following steps: mixing polyalcohol and/or alcohol amine with the same mol of polybasic acid, adding a catalyst, and reacting for 1-5h at 120-250 ℃ under the protection of inert gas; then reducing the pressure of the system to be below-0.1 MPa, and continuously reacting for 1-4h at the temperature of 150-350 ℃ to obtain the water-soluble polyester
The polyalcohol is one or more of neopentyl glycol, ethylene glycol, propylene glycol, glycerol, trimethylolpropane, trimethylolethane and diethylene glycol.
The alcohol amine is one or more of diethanolamine, triethanolamine, triisopropanolamine, diethanol monoisopropanolamine and monoethanol diisopropanolamine.
The polybasic acid is any one or more of isophthalic acid, terephthalic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, 1, 3-isophthalic acid-5-sodium sulfonate and methylsuccinic acid.
The catalyst is one or more of tetrabutyl titanate, stannous chloride, p-toluenesulfonic acid, phosphorous acid, antimony acetate, ethylene glycol antimony, bismuth trioxide and dibutyltin oxide; the dosage of the catalyst is 0.01-0.2% of the total weight of the monomers.
The inorganic dispersion reinforcing agent is any one or more of sodium chloride, sodium sulfate, sodium nitrate, sodium acetate, sodium citrate and sodium stearate.
The preparation method of the grinding aid special for grinding cement by the vertical mill comprises the following steps: the raw materials with the formula ratio are mixed and stirred uniformly.
The invention also provides application of the grinding aid special for the vertical mill grinding cement, and the grinding aid is used for vertical mill grinding of cement.
The mixing amount of the grinding aid special for grinding cement by the vertical mill is 0.03-0.3%.
In the formula of the grinding aid special for grinding cement by the vertical mill, the water-soluble polyester has higher viscosity, and can effectively stabilize a material layer in the grinding process of the vertical mill, so that no water is sprayed in the mill; meanwhile, along with the cement grinding, the water-soluble polyester is hydrolyzed or cracked into polyol, and/or alcohol amine and polybasic acid and low-molecular-weight water-soluble polyester under the high-temperature and alkaline environment and the grinding pressure of a grinding roller, and the polyol, and/or alcohol amine and polybasic acid are common dispersion enhancing components in the cement grinding process, have the dispersion enhancing effect on cement particles, and can improve the powder selection efficiency of a vertical mill; thereby improving the machine hour of the mill and the strength of the cement, solving the problems of hydration agglomeration and strength attenuation of the stored cement and accelerating the cement turnover; meanwhile, in the cement hydration process, the low molecular weight water-soluble polyester can be further hydrolyzed into polyhydric alcohol and/or alcohol amine and polybasic acid, and the performance and the application of the cement can not be influenced.
In the formula of the grinding aid special for vertical grinding cement, the water-soluble polyester has high viscosity and can inhibit the dispersion of the grinding aid in the grinding process to stabilize a material layer, so that materials are sufficiently ground on a grinding disc, the water-soluble polyester is hydrolyzed or cracked into polyol, and/or alcohol amine, polybasic acid and low-molecular water-soluble polymer under high-temperature and alkaline environments and the grinding pressure of the grinding roller along with the grinding of the cement, and the polyol, and/or alcohol amine and polybasic acid hydrolyzed by the water-soluble polyester are matched with the polyol, and/or alcohol amine and an inorganic dispersion reinforcing agent in the formula of the grinding aid to improve the dispersibility of ground fine powder and improve the powder selection efficiency.
Compared with the prior art, the grinding aid provided by the invention does not need water spraying in the mill for grinding the cement by using the vertical mill, can obviously improve the strength of the cement when the vertical mill is used, solves the problems of hydration agglomeration and strength attenuation of the stored cement, and does not influence the performance and application of the cement.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
A grinding aid special for vertical mill grinding cement comprises the following raw materials in percentage by weight: 20% of water-soluble polyester; 10% of sodium acetate; 5% of sodium sulfate; 10% of diethylene glycol; 5% of monoethanol diisopropanolamine and 50% of water.
The preparation method of the water-soluble polyester comprises the following steps: mixing diethanol monoisopropanolamine with equal mol of oxalic acid, and adding a catalyst ethylene glycol antimony, wherein the using amount of the catalyst is 0.01 percent of the total mass of the diethanol monoisopropanolamine and the oxalic acid; reacting for 2 hours at 160 ℃ under the protection of inert gas; then decompressing the system to below-0.1 MPa, and continuously reacting for 1h at 250 ℃ to obtain the water-soluble polyester.
The preparation method of the grinding aid special for grinding cement by the vertical mill comprises the following steps: the raw materials with the formula ratio are mixed and stirred uniformly.
Example 2
A grinding aid special for vertical mill grinding cement comprises the following raw materials in percentage by weight: 10% of water-soluble polyester; 10% of sodium chloride; 10% of sodium citrate; 10% of triethanolamine; 60% of water.
The preparation method of the water-soluble polyester comprises the following steps: neopentyl glycol, glycerol, trimethylolpropane, methylsuccinic acid, azelaic acid and 1, 3-isophthalic acid-5-sodium sulfonate according to a molar ratio of 1:1:1:1:1:1, mixing, adding p-toluenesulfonic acid and phosphorous acid with a molar ratio of 1; reacting for 2 hours at 120 ℃ under the protection of inert gas; then decompressing the system to below-0.1 MPa, and continuously reacting for 1h at 200 ℃ to obtain the water-soluble polyester.
The preparation method of the grinding aid special for grinding cement by the vertical mill comprises the following steps: the raw materials with the formula amount are mixed and stirred evenly.
Example 3
A grinding aid special for vertical mill grinding cement comprises the following raw materials in percentage by weight: 40% of water-soluble polyester; 5 percent of sodium stearate; 2.5 percent of glycol; 2.5 percent of propylene glycol; 10% of triisopropanolamine; 40 percent of water.
The preparation method of the water-soluble polyester comprises the following steps: mixing triethanolamine, monoethanol diisopropanolamine and succinic acid according to a molar ratio of 1; reacting for 4 hours at 200 ℃ under the protection of inert gas; then reducing the pressure of the system to be below-0.1 MPa, and continuously reacting for 1h at 350 ℃ to obtain the water-soluble polyester.
The preparation method of the grinding aid special for grinding cement by the vertical mill comprises the following steps: the raw materials with the formula ratio are mixed and stirred uniformly.
Example 4
A grinding aid special for vertical mill grinding cement comprises the following raw materials in percentage by weight: 30% of water-soluble polyester; 10% of sodium nitrate; 5% of trimethylolethane; 5% of diethylene glycol; 8% of diethanol monoisopropanolamine; 2% of triisopropanolamine; 40% of water.
The preparation method of the water-soluble polyester comprises the following steps: mixing dimethylolpropionic acid, diethanolamine, triethanolamine and glutaric acid according to the weight ratio of 1:1:1:3, adding a catalyst tetrabutyl titanate, wherein the dosage of the catalyst is 0.2 percent of the total mass of the polymerization monomers; reacting for 1h at 250 ℃ under the protection of inert gas; then reducing the pressure of the system to be below-0.1 MPa, and continuously reacting for 3h at the temperature of 300 ℃ to obtain the water-soluble polyester.
The preparation method of the grinding aid special for grinding cement by the vertical mill comprises the following steps: the raw materials with the formula ratio are mixed and stirred uniformly.
Comparative example 1
The traditional grinding aid consists of: 5% of molasses, 5% of glycerol, 7% of polymeric polyol, 13% of industrial sodium chloride, 10% of diethanol monoisopropanolamine and 60% of water.
Grinding tests are carried out on the grinding aid prepared in each embodiment and comparative example in a vertical mill of phi 5370mm, and the material ratio is as follows: clinker (78.5%) + desulfurized gypsum (4.6%) + limestone (6%) + zeolite rock (5%) + fly ash (5.9%); controlling the specific surface area of the cement to 335 +/-5 m 2 (iv) Kg. The stand-hour yield, the water content of the milled cement, the 3d compressive strength and the 28d compressive strength of the mill producing the cement were tested and the results are shown in Table 1. The performance test was carried out according to the relevant provisions of GB175-2007 Universal Portland Cement.
TABLE 1
As can be seen from table 1, in the case that no grinding aid is added or a conventional grinding aid is added in the cement grinding by the vertical mill, water needs to be sprayed during the grinding by the vertical mill, the size of the vertical mill is small, the water content of the produced cement is high, and the compressive strength of the cement at 3d and 28d is poor compared with that of the cement in the examples; if the grinding aid prepared in each embodiment of the invention is added into the cement ground by the vertical mill, water spraying is not needed during the vertical milling, the vertical milling time can reach more than 340t/h, the water content of the produced cement is low, and the compressive strengths of the cement at 3d and 28d can reach more than 31MPa and more than 50MPa respectively.
The above detailed description of a grinding aid for cement grinding in vertical mill and its application with reference to the embodiments is illustrative and not restrictive, and several embodiments can be cited within the scope of the present invention, so that changes and modifications that do not depart from the spirit of the invention are deemed to be within the scope of the present invention.
Claims (4)
1. The grinding aid special for grinding cement by using the vertical mill is characterized by comprising the following raw materials in percentage by weight:
10-40% of water-soluble polyester;
5-20% of a dispersion reinforcing agent;
5-20% of polyalcohol and/or alcohol amine;
40-70% of water;
the preparation method of the water-soluble polyester comprises the following steps: mixing polyalcohol and/or hydramine with equimolar polybasic acid, adding a catalyst, and reacting for 1-5h at 120-250 ℃ under the protection of inert gas; then decompressing the system to be below-0.1 MPa, and continuously reacting for 1-4h at the temperature of 150-350 ℃ to obtain water-soluble polyester;
the polyalcohol is any one or more of neopentyl glycol, ethylene glycol, propylene glycol, glycerol trimethylolpropane, trimethylolethane and diethylene glycol;
the alcohol amine is any one or more of diethanol amine, triethanol amine, triisopropanol amine, diethanol monoisopropanol amine and monoethanol diisopropanol amine;
the polybasic acid is any one or more of isophthalic acid, terephthalic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, 1, 3-isophthalic acid-5-sodium sulfonate and methylsuccinic acid;
the catalyst is one or more of tetrabutyl titanate, stannous chloride, p-toluenesulfonic acid, phosphorous acid, antimony acetate, ethylene glycol antimony, bismuth trioxide and dibutyltin oxide; the dosage of the catalyst is 0.01-0.2% of the total weight of the monomer;
the dispersion reinforcing agent is any one or more of sodium chloride, sodium sulfate, sodium nitrate, sodium acetate, sodium citrate and sodium stearate.
2. The grinding aid special for vertical mill cement according to claim 1, which is characterized by comprising the following raw materials in percentage by weight:
10-40% of water-soluble polyester;
5-20% of a dispersion reinforcing agent;
5-10% of polyol;
5-10% of alcohol amine;
40-70% of water.
3. The application of the grinding aid special for vertical mill cement as claimed in claim 1 or 2, which is used for vertical mill cement grinding.
4. The application of the grinding aid special for vertical mill cement as claimed in claim 3, wherein the mixing amount of the grinding aid special for vertical mill cement is 0.03-0.3%.
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| CN113880490B true CN113880490B (en) | 2022-11-18 |
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| CN114573266B (en) * | 2022-03-07 | 2023-02-03 | 碳达(深圳)新材料技术有限责任公司 | Grinding aid for activated steel slag and method for preparing activated steel slag by using grinding aid |
| CN114634322B (en) * | 2022-04-11 | 2023-03-14 | 安徽海螺材料科技股份有限公司 | Cement strength anti-attenuation agent and preparation method and application thereof |
| CN115417616B (en) * | 2022-10-08 | 2023-09-22 | 临沂海螺新材料科技有限公司 | Grinding aid for vertical mill cement and preparation method thereof |
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| FR1489789A (en) * | 1966-06-13 | |||
| GB201010306D0 (en) * | 2010-06-21 | 2010-08-04 | Fosroc International Ltd | Grinding aid |
| CN105731855A (en) * | 2016-01-11 | 2016-07-06 | 东源县弘朝科技有限公司 | Vertical mill slag grinding aid and preparation method thereof |
| EP4073013A4 (en) * | 2019-11-13 | 2023-10-11 | Plustechno Danismanlik ve Yapi Kimyasallari Sanayi Ticaret Anonim Sirketi | A novel process for high-performance cements |
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Effective date of registration: 20221214 Address after: Room 208, No. 1 Building, No. 9 Wanjiang Avenue, Jiangbei Industrial Concentration Area, Wuhu City, Anhui Province Patentee after: Anhui Conch Material Technology Co.,Ltd. Patentee after: Ningbo conch New Material Technology Co.,Ltd. Address before: 315000 building 3, management committee of Ningbo Petrochemical Economic Development Zone, No. 226, Beihai Road, Shupu Town, Zhenhai District, Ningbo City, Zhejiang Province Patentee before: Ningbo conch New Material Technology Co.,Ltd. |