阅读说明：本技术 一种立磨粉磨水泥专用助磨剂及其应用 (Grinding aid special for vertical mill grinding cement and application thereof ) 是由 孟凡军 陈烽 曾君 赵伟 潘玉杰 武春江 张胜男 于 2021-10-26 设计创作，主要内容包括：本发明公开了一种立磨粉磨水泥专用助磨剂及其应用,所述助磨剂包括以下重量百分比的原料：水溶性聚酯5-40％；无机分散增强剂5-20％；多元醇或醇胺5-20％；水40-70％；本发明提供的立磨粉磨水泥专用助磨剂的配方中,水溶性聚酯具有的高粘度可抑制助磨剂在粉磨过程中的分散作用以稳定料层,使物料在在磨盘上得到磨辊的充分的碾磨,随着水泥粉磨的进行,水溶性聚酯在高温和碱性环境以及磨辊的碾压力下水解或裂解成多元醇、和/或醇胺和多元酸以及低分子量水溶性聚酯聚合物,其与助磨剂配方中的多元醇、和/或醇胺以及无机分散增强剂配合来提高粉磨后的细粉的分散性,提高选粉效率。(The invention discloses a grinding aid special for grinding cement by a vertical mill 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 grinding cement by the vertical mill, 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 roller, and along with the grinding of the 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 the high-temperature and alkaline environment and the grinding pressure of the grinding roller, and the water-soluble polyester polymer is matched with the polyol, and/or alcohol amine and an inorganic dispersion reinforcing agent in the formula of the grinding aid to improve the dispersion of ground fine powder and improve the powder selection efficiency.)

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:

2. the grinding aid special for vertical mill cement of claim 1, which is characterized by comprising the following raw materials in percentage by weight:

3. the grinding aid special for vertical mill cement of claim 1, wherein the preparation method of the water-soluble polyester comprises the following steps: mixing polyalcohol and/or alcohol amine with equimolar polybasic acid, adding a catalyst, and reacting for 1-5h at 120-250 ℃ under the protection of inert gas; and 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.

4. The grinding aid special for vertical mill cement as claimed in any one of claims 1 to 3, wherein the polyhydric alcohol is any one or more of neopentyl glycol, ethylene glycol, propylene glycol, glycerol trimethylolpropane, trimethylolethane and diethylene glycol.

5. The grinding aid special for vertical mill cement as claimed in any one of claims 1 to 3, wherein the alcohol amine is any one or more of diethanolamine, triethanolamine, triisopropanolamine, diethanol monoisopropanolamine and monoethanol diisopropanolamine.

6. The grinding aid special for vertical mill grinding cement of claim 3, wherein 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.

7. The grinding aid special for vertical mill grinding cement according to claim 3, wherein the catalyst is any 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.

8. The grinding aid special for vertical mill cement as claimed in any one of claims 1 to 3, wherein the inorganic dispersion enhancer is any one or more of sodium chloride, sodium sulfate, sodium nitrate, sodium acetate, sodium citrate and sodium stearate.

9. The use of the grinding aid special for vertical mill grinding cement as claimed in any one of claims 1 to 8, which is used for vertical mill grinding of cement.

10. The application of the grinding aid special for vertical mill cement as claimed in claim 9, wherein the mixing amount of the grinding aid special for vertical mill cement is 0.03-0.3%.

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, the method has remarkable advantages. 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, the addition of the grinding aid can greatly improve the process condition of cement grinding, improve the production efficiency without damaging the cement performance, and aims to reduce the production cost and improve the cement quality. 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 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 is sprayed in the vertical mill, the cement strength is obviously improved when a vertical mill is used, the problems of hydration agglomeration and strength attenuation of stored cement are solved, and the performance and 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 grinding cement by using the vertical mill 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 equimolar 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 the vertical mill grinding of the 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 grinding cement by the vertical mill, 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 roller, the water-soluble polyester is hydrolyzed or cracked into polyol, and/or alcohol amine, polybasic acid and low-molecular water-soluble polymer under the high-temperature and alkaline environment and the grinding pressure of the grinding roller along with the grinding of the cement, and the polyol, and/or alcohol amine, polybasic acid hydrolyzed by the water-soluble polyester, the polyol, and/or alcohol amine and inorganic dispersion reinforcing agent in the formula of the grinding aid are matched to improve the dispersibility of the 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 mole of oxalic acid, and adding ethylene glycol antimony serving as a catalyst, 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 reducing the pressure of the system to be 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 1:1 as a catalyst, wherein the dosage of the catalyst is 0.1 percent of the total mass of the polymerized monomers; reacting for 2 hours at 120 ℃ 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 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 ratio are mixed and stirred uniformly.

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% of sodium stearate; 2.5 percent of ethylene glycol; 2.5 percent of propylene glycol; 10% of triisopropanolamine; 40% 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 1:1:2, and adding stannous chloride as a catalyst, wherein the dosage of the catalyst is 0.15 percent of the total mass of the polymerization monomers; 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 m²Perkg. 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 grinding by the vertical mill, the grinding time of the vertical mill 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 special for cement grinding in vertical mill and its application with reference to the embodiments is illustrative and not restrictive, and several embodiments can be enumerated within the limits of the invention, so that changes and modifications without departing from the general concept of the invention shall fall within the protection scope of the invention.