Cement coal-saving grinding aid as well as preparation method and application thereof

Abstract

The invention discloses a cement coal-saving grinding aid as well as a preparation method and application thereof. The cement coal-saving grinding aid comprises a phenol quaternary ammonium salt surfactant, a supported adsorption material, caprolactam, organic acid salt, inorganic acid salt and deionized water, the supported adsorption material is prepared by compounding copper chloride, chitosan and sodium silicate; the phenol quaternary ammonium salt surfactant has a structure as shown in a formula A. The cement coal-saving grinding aid provided by the invention has excellent grinding aiding effect and coal-saving efficiency at the same time, can effectively reduce the emission of pollutants, improves the mechanical strength of the prepared clinker, and can be widely applied to the field of cement production. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of cement production, and in particular to a cement coal-saving grinding aid and a preparation method and application thereof. Background Art

[0002] In recent years, with the rapid development of my country's cement industry, the annual cement output has exceeded 2 billion tons, of which the annual production of clinker used in cement production has reached more than 1.6 billion tons. In the clinker production process, the raw cement needs to be ground and then calcined at 1450℃, which consumes a lot of coal, and finally the clinker required for cement production is obtained.

[0003] The production process of cement is generally known as "two grindings and one burning". Among them, raw material grinding is the process of turning block materials into fine powder by overcoming the deformation stress of objects and the cohesive force between particles under the action of external forces such as impact, extrusion, and grinding. In the process of converting cement raw materials into clinker, the effective energy utilization rate of the mill has been very low for a long time, while the power consumption is very high. The power consumption of raw material grinding is generally 1 / 3 to 1 / 2 of the subsequent cement grinding power consumption. However, since the processing volume of raw materials is usually about 160% of the clinker mass, the problem of low energy utilization is very prominent.

[0004] During the development of the cement industry, its consumption of resources and energy such as limestone, clay, coal, and the resulting environmental impact has reached an alarming level. More advanced technologies are urgently needed to reduce the consumption of energy and resources in the clinker preparation process and achieve sustainable development of the cement industry. Raw material production is a basic link in the cement clinker production process. Adding energy-saving cement raw material admixtures that can affect the subsequent processes during the cement raw material grinding process will directly affect the energy consumption and quality of the raw material clinker. Energy-saving cement raw material grinding aids can reduce the power consumption and coal consumption in the clinker preparation process and increase the clinker strength, thereby saving raw material usage in the process of cement preparation and absorbing more solid waste generated by other industries. It is an effective measure to achieve energy conservation, emission reduction and sustainable development in the cement industry.

[0005] So far, the additives used in cement production mainly include coal-saving combustion aids, cement grinding aids and sulfur-fixing agents, which are respectively used in the fields of coal combustion aids, clinker grinding, cement kiln flue gas desulfurization, etc. in the process of cement clinker firing. The grinding aid effect and coal-saving efficiency of additives in the prior art still need to be improved, and it is difficult to improve the grinding aid effect and coal-saving efficiency of cement raw materials at the same time. At the same time, it cannot improve the waste gas and dust pollution such as carbon monoxide and sulfur dioxide generated in the cement production process, and the quality and strength of the obtained clinker still need to be improved again.

[0006] Therefore, there is an urgent need for a cement coal-saving grinding aid that has both excellent grinding aid effect and coal-saving efficiency, can reduce pollutant emissions, and improve the strength of the obtained clinker. Summary of the invention

[0007] Purpose of the invention: In view of the defects of the prior art, the purpose of the present invention is to provide a cement coal-saving grinding aid which has excellent grinding aid effect and coal-saving efficiency, can reduce pollutant emissions, and improve the strength of the obtained clinker, as well as its preparation method and application.

[0008] Technical solution:

[0009] A cement coal-saving grinding aid, comprising a phenol quaternary ammonium salt surfactant, a supported adsorbent material, caprolactam, an organic acid salt, an inorganic acid salt and deionized water;

[0010] The supported adsorption material is prepared by compounding copper chloride, chitosan and sodium silicate;

[0011] The phenol quaternary ammonium salt surfactant has a structure shown in the following formula A:

[0012]

[0013] The addition of phenol quaternary ammonium salt surfactant in the present invention can not only improve the grinding effect of coal powder, reduce the particle size and uniformity of dispersion of coal powder, promote the combustion of coal powder, thereby improving the utilization efficiency of coal powder, reducing coal consumption and incomplete combustion products, and reducing pollution, but also reduce the surface tension of each component, and avoid the agglomeration of small components to affect the grinding effect.

[0014] Furthermore, the supported adsorbent material is prepared by the following steps:

[0015] (1) In a reactor, sodium silicate, chitosan and an organic solvent are added, the pH is adjusted to 6-7 after being stirred evenly, a cupric chloride aqueous solution is added, and a hydrogel is obtained after vigorous stirring;

[0016] (2) The hydrogel of step (1) is placed at -80 to -90°C for 3 to 4 hours, freeze-dried in a vacuum freeze dryer for 36 to 48 hours, and ground into powder to obtain the supported adsorption material.

[0017] The loaded adsorbent material is added in the present invention. On the one hand, its crystal structure can increase the contact area between the components during the grinding process, thereby improving the grinding effect; on the other hand, its high specific surface area and porous gel structure have excellent adsorption effect, and can adsorb pollutants such as carbon monoxide and sulfur dioxide in the cement production process, thereby reducing the emission of pollutants; finally, the copper ions loaded thereon can not only improve the burnability of the raw material, reduce the activation energy of the clinker formation, and promote the formation of the clinker, but also be evenly dispersed in the clinker to improve its strength.

[0018] Furthermore, the organic solvent is selected from one of acetic acid, ethyl acetate or tetrahydrofuran; and the concentration of the copper chloride aqueous solution is 0.1-0.2 g / mL.

[0019] Furthermore, the mass ratio of the sodium silicate, chitosan and cupric chloride is (0.5-0.6):(0.7-0.8):(1-1.2).

[0020] Furthermore, the phenol quaternary ammonium salt surfactant is prepared by the following steps: adding n-decyl tri(dimethylamino)silane and tetrahydrofuran into a reactor, heating to 50-60° C. under nitrogen protection, stirring evenly, adding p-hydroxybenzyl bromide, keeping the temperature for reaction for 3-4 hours, cooling, filtering, washing and drying to obtain the phenol quaternary ammonium salt surfactant.

[0021] The benzene ring structure, the quaternary ammonium structure and the long-chain alkane structure in the phenol quaternary ammonium salt surfactant of the present invention can give it excellent surface activity, so that it can fully exert the effects of improving grinding and improving the degree of dispersion, and the benzene ring structure can give it excellent chemical stability, so that it can play a role in a long term in the environment of high temperature, high corrosion, grinding and the like, and is more suitable for the cement field.

[0022] Furthermore, the mass ratio of n-decyltri(dimethylamino)silane to p-hydroxybenzyl bromide is 1:1.8-2.

[0023] Furthermore, the organic acid salt is selected from at least one of aminocaproate, glutarate, adipate, and formates; and the inorganic acid salt is selected from at least one of nitrate, nitrite, and sulfate.

[0024] Furthermore, based on the total mass fraction being 100%, the mass percentage of each component in the cement coal-saving grinding aid is:

[0025]

[0026] The preparation method of the cement coal-saving grinding aid described in any one of the above items comprises the following steps: adding phenol quaternary ammonium salt surfactant, organic acid salt, inorganic acid salt, caprolactam and deionized water in proportion in a reactor, adding supported adsorption material after stirring evenly, and mixing evenly to obtain the cement coal-saving grinding aid.

[0027] Application of any one of the above-mentioned cement coal-saving grinding aids in the cement field.

[0028] Beneficial effects:

[0029] (1) The cement coal-saving grinding aid provided by the present invention is prepared by compounding a phenol quaternary ammonium salt surfactant, a supported adsorbent material, caprolactam, an organic acid salt, an inorganic acid salt and deionized water. It has excellent grinding aid effect and coal-saving efficiency, and can effectively reduce the emission of pollutants and improve the strength of the obtained clinker. It can be widely used in the field of cement production.

[0030] (2) In the cement coal-saving grinding aid provided by the present invention, caprolactam, organic acid salt and inorganic acid salt can be used as penetration components to improve the penetration degree between the coal-saving grinding aid and coal powder, so as to give full play to its coal-saving and grinding aid effects.

[0031] (3) The loaded adsorbent material is added to the cement coal-saving grinding aid provided by the present invention. On the one hand, its crystalline structure can increase the contact area between the components during the grinding process, thereby improving the grinding effect; on the other hand, its high specific surface area and porous gel structure have excellent adsorption effects, and can adsorb pollutants such as carbon monoxide and sulfur dioxide in the cement production process, thereby reducing the emission of pollutants; finally, the copper ions loaded thereon can not only improve the burnability of the raw material, reduce the activation energy of the clinker formation, and promote the formation of the clinker, but also be finally evenly dispersed in the clinker to improve its strength.

[0032] (4) In the cement coal-saving grinding aid provided by the present invention, by adding a phenol quaternary ammonium salt surfactant, not only can the grinding effect of coal powder be improved, the particle size and uniformity of dispersion of coal powder be reduced, and the combustion of coal powder be promoted, thereby improving the utilization efficiency of coal powder, reducing coal consumption, reducing incomplete combustion products, and reducing pollution, but also the surface tension of each component can be reduced to avoid the agglomeration of small components affecting the grinding effect.

[0033] (5) In the cement coal-saving grinding aid provided by the present invention, the benzene ring structure, quaternary ammonium structure and long-chain alkane structure in the phenol quaternary ammonium salt surfactant can give it excellent surface activity, so that it can fully exert the effect of improving grinding and improving the degree of dispersion, and its benzene ring structure can give it excellent chemical stability, so that it can play a long-term role in high temperature, high corrosion, grinding and other environments, and is more suitable for the cement field. DETAILED DESCRIPTION

[0034] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0035] The commercially available cement production additive is a raw cement grinding aid purchased from Nanjing Changjiang Jiangyu Energy Technology Co., Ltd.; the remaining reagents and equipment are conventional reagents and equipment in this technical field.

[0036] Preparation of supported adsorbent materials

[0037] The supported adsorbent material was prepared by the following steps:

[0038] (1) In a reactor, 2 g of sodium silicate, 3 g of chitosan and 100 mL of acetic acid were added, the pH was adjusted to 6 after stirring evenly, 20 mL of a 0.2 g / mL copper chloride aqueous solution was added, and the mixture was stirred vigorously to obtain a hydrogel;

[0039] (2) The hydrogel of step (1) was placed at -80°C for 3 hours, freeze-dried in a vacuum freeze dryer for 48 hours, and ground into powder to obtain the supported adsorption material.

[0040] Preparation of phenol quaternary ammonium salt surfactant

[0041] The phenol quaternary ammonium salt surfactant was prepared by the following steps:

[0042] In a reactor, 1 g of n-decyltri(dimethylamino)silane and 100 mL of tetrahydrofuran were added, the temperature was raised to 60° C. under nitrogen protection, 2 g of p-hydroxybenzyl bromide was added after stirring, the reaction was kept warm for 3 hours, and then cooled, filtered, washed and dried to obtain the phenol quaternary ammonium salt surfactant;

[0043] Mass spectrum data of phenol quaternary ammonium salt surfactant: The product was analyzed by LC-MS, and the m / z of the product was 622.44 (100.0%), 623.46 (47.5%), 624.45 (14.4%), and 625.44 (3.1%).

[0044] Example 1

[0045] The cement coal-saving grinding aid is prepared by the following steps:

[0046] In a reactor, phenol quaternary ammonium salt surfactant, organic acid salt, inorganic acid salt, caprolactam and deionized water are added in proportion, and after being stirred evenly, a supported adsorbent material is added, and after being mixed evenly, the cement coal-saving grinding aid is obtained;

[0047] Based on the total mass fraction being 100%, the mass percentage of each component in the cement coal-saving grinding aid is:

[0048]

[0049] Example 2

[0050] Basically the same as Example 1, except that, based on the total mass fraction being 100%, the components and their mass percentages in the cement coal-saving grinding aid are:

[0051]

[0052] Example 3

[0053] Basically the same as Example 1, except that, based on the total mass fraction being 100%, the components and their mass percentages in the cement coal-saving grinding aid are:

[0054]

[0055]

[0056] Comparative Example 1

[0057] Commercially available cement production additives.

[0058] Comparative Example 2

[0059] The method is basically the same as Example 1, except that the supported adsorbent material is replaced by an equal amount of deionized water.

[0060] Comparative Example 3

[0061] The method is basically the same as Example 1, except that the phenol quaternary ammonium salt surfactant is replaced by an equal amount of deionized water.

[0062] Comparative Example 4

[0063] The method is basically the same as Example 1, except that the phenol quaternary ammonium salt surfactant is replaced by an equal amount of sodium dodecyl sulfate.

[0064] Performance Testing

[0065] The products of Examples 1-3 and Comparative Examples 1-4 were mixed with coal powder in the same proportion, and the product addition amount was 0.05wt%.

[0066] Coal saving ability test: Using a thermogravimetric analyzer, take a mixture of the same mass of the products of the above embodiments 1-3 and comparative examples 1-4 and coal powder, and heat it from 30°C to 960°C under the conditions of air 40mL / min and a heating rate of 15°C / min, and record the initial ignition point according to the thermogravimetric diagram.

[0067] Clinker strength and fineness test: A mixture of the products of Examples 1-3 and Comparative Examples 1-4 and coal powder was mixed with raw materials of the same specification, and powdered and calcined under the same conditions to prepare universal cement clinker. According to the test standard GB / T21372-2008 for silicate cement clinker, the 28d compressive strength and 0.2mm sieve residue of the clinker were tested respectively.

[0068] The test results are shown in the following table:

[0069]

[0070]

[0071] According to the comparison of the test results of Examples 1-3 with those of Comparative Example 1, the cement coal-saving grinding aid provided by the present invention has better grinding aid effect and coal-saving effect than the cement production additives in the prior art, and can further improve the mechanical strength of the obtained clinker, and can be widely used in the field of cement production.

[0072] According to the comparison of the test results of Examples 1-3 and Comparative Example 2, it can be seen that the supported adsorption material in the cement coal-saving grinding aid provided by the present invention can significantly improve the mechanical strength of the obtained clinker, and can further improve the coal-saving effect and grinding aid effect.

[0073] According to the comparison of the test results of Examples 1-3 and Comparative Examples 3-4, it can be seen that the phenol quaternary ammonium salt surfactant in the cement coal-saving grinding aid provided by the present invention can significantly improve its coal-saving effect and grinding aid effect, and can further improve the mechanical strength of the obtained clinker.

[0074] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A cement coal-saving grinding aid, characterized in that: The invention comprises a phenol quaternary ammonium salt surfactant, a supported adsorbent material, caprolactam, an organic acid salt, an inorganic acid salt and deionized water; The supported adsorption material is prepared by compounding copper chloride, chitosan and sodium silicate; The phenol quaternary ammonium salt surfactant has a structure shown in the following formula A: 。 2. The cement coal-saving grinding aid according to claim 1, characterized in that: The supported adsorbent material is prepared by the following steps: (1) In a reactor, sodium silicate, chitosan and an organic solvent are added, the pH is adjusted to 6-7 after being stirred evenly, a cupric chloride aqueous solution is added, and a hydrogel is obtained after being stirred vigorously; (2) The hydrogel of step (1) is placed at -80 to -90°C for 3 to 4 hours, freeze-dried in a vacuum freeze dryer for 36 to 48 hours, and then ground into powder to obtain the supported adsorption material.

3. The cement coal-saving grinding aid according to claim 2, characterized in that: The organic solvent is selected from one of acetic acid, ethyl acetate or tetrahydrofuran; and the concentration of the copper chloride aqueous solution is 0.1-0.2 g / mL.

4. The cement coal-saving grinding aid according to claim 2, characterized in that: The mass ratio of the sodium silicate, chitosan and copper chloride is (0.5-0.6): (0.7-0.8): (1-1.2).

5. The cement coal-saving grinding aid according to claim 1, characterized in that: The phenol quaternary ammonium salt surfactant is prepared by the following steps: adding n-decyl tri(dimethylamino)silane and tetrahydrofuran into a reactor, heating to 50-60° C. under nitrogen protection, stirring evenly, adding p-hydroxybenzyl bromide, keeping the temperature for reaction for 3-4 hours, cooling, filtering, washing and drying to obtain the phenol quaternary ammonium salt surfactant.

6. The cement coal-saving grinding aid according to claim 5, characterized in that: The mass ratio of n-decyltri(dimethylamino)silane to p-hydroxybenzyl bromide is 1:1.8-2.

7. The cement coal-saving grinding aid according to claim 1, characterized in that: The organic acid salt is selected from at least one of aminocaproate, glutarate, adipate and formates; the inorganic acid salt is selected from at least one of nitrate, nitrite and sulfate.

8. The cement coal-saving grinding aid according to claim 1, characterized in that: Based on the total mass fraction being 100%, the mass percentage of each component in the cement coal-saving grinding aid is: Phenol quaternary ammonium salt surfactant 15-20% Supported adsorption material 25-30% Caprolactam 5-10% Organic acid salt 5-10% Inorganic acid salt 3-5% The balance was deionized water.

9. The method for preparing the cement coal-saving grinding aid according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: adding phenol quaternary ammonium salt surfactant, organic acid salt, inorganic acid salt, caprolactam and deionized water in proportion in a reactor, adding supported adsorption material after stirring evenly, and mixing evenly to obtain the cement coal-saving grinding aid.

10. Use of the cement coal-saving grinding aid according to any one of claims 1 to 8 in the cement field.

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