CN115745460B - Cement raw material energy-saving auxiliary agent and preparation method and application thereof - Google Patents
Cement raw material energy-saving auxiliary agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of cement additives, in particular to an energy-saving auxiliary agent for cement raw materials, a preparation method and application thereof, wherein the energy-saving auxiliary agent is liquid containing composite grinding aid, polyamide, organic acid salt, polyalcohol and lipid components, and the pH value is more than or equal to 9; the energy-saving auxiliary agent for cement raw materials and the cement raw materials are mixed and ground, so that the apparent granularity of the cement raw materials is improved, and the ground particles are not easy to agglomerate for the second time, so that the ground product has good dispersibility, the decomposition rate of calcium carbonate is obviously improved, the heat consumption of silicate cement clinker is reduced, the quality of the clinker is improved, the friction resistance among cement particles is reduced, the grinding difficulty is reduced, and the grindability of the cement raw materials is improved.
Description
Technical Field
The invention relates to the technical field of cement additives, in particular to a cement raw material energy-saving auxiliary agent, a preparation method and application thereof.
Background
Along with the vigorous development of the building industry for a long time, cement is taken as one of the most important cementing materials, and is widely applied to civil construction, water conservancy, national defense and other projects. However, cement production is an industry with low energy utilization and high energy consumption due to production process limitations. Specifically, the cement production process is called two-mill one-bake process, namely raw material grinding, large kiln calcination and cement grinding, wherein the raw material grinding is a process link with higher energy consumption in the cement production process, and approximately 95% of energy in the raw material grinding process is dissipated as heat to disappear, and when the fineness of the raw material is thinned to a certain degree, the grinding condition is deteriorated due to the agglomeration phenomenon of fine particles, and the grinding efficiency is rapidly reduced. In addition, the raw material grinding step is taken as a basic link in the cement production process, has an important influence on the subsequent production link, and the quality of the grain composition after raw material grinding can influence the dispersibility of raw materials, the combustibility of raw materials, the coal consumption, the electricity consumption, the quality and the pollutant emission of clinker, thereby severely restricting the development of the cement industry.
For example, the invention patent with publication number of CN112645628A discloses a formula and a preparation process of a novel powder cement grinding aid, wherein the cement grinding aid consists of alcohol amine, potassium humate, sodium thiocyanate, anhydrous sodium sulfate, silica fume, hexavalent chromium reducer and stabilizer, the chemical stability and the reduction efficiency are greatly improved, the defect that ferrous sulfate and manganese acetate are deliquescent while the hygroscopicity of anhydrous calcium sulfate is overcome, the oxidation resistance of ferrous sulfate is greatly improved, the cement grinding time is reduced, the energy consumption is greatly saved, and the cement grinding aid has good chromium removal property, grinding aid, early strength and chemical stability, and meanwhile, no chloride salt is friendly to the environment; the cement grinding aid has good grinding aid effect, but after being mixed with cement raw materials for grinding, the particle size distribution of the raw materials is dispersed, so that the particle size distribution is poor, secondary agglomeration is easy to occur among fine particles after grinding, so that the dispersibility of the raw materials is affected, and meanwhile, in the grinding process, the grinding difficulty of the raw materials is high, so that the problem of high energy consumption still exists.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the cement raw material energy-saving auxiliary agent, the preparation method and the application thereof, and the cement raw material energy-saving auxiliary agent and the cement raw material are mixed, so that the apparent granularity of cement raw material grinding is improved, and the ground particles are not easy to agglomerate for the second time, so that the ground product has good dispersibility, the decomposition rate of calcium carbonate is obviously improved, the heat consumption of silicate cement clinker is reduced, the clinker quality is improved, meanwhile, the effect of reducing friction resistance among cement particles is achieved, the grinding difficulty is reduced, and the effect of improving grindability of the cement raw material is achieved.
In order to achieve the above purpose, the present invention provides the following technical solutions:
an energy-saving auxiliary agent for cement raw materials, wherein the energy-saving auxiliary agent is a liquid containing composite grinding aid, polyamide, organic acid salt, polyalcohol and lipid components, and the pH value is more than or equal to 9;
the preparation method of the energy-saving auxiliary agent comprises the steps of fully and uniformly stirring the composite grinding aid, polyamide, organic acid salt, polyol and lipid components;
the organic acid salt is at least one of potassium tartrate, sodium citrate and sodium salicylate;
the polyalcohol is at least one of ethylene glycol, 1, 2-propylene glycol and 1, 4-butanediol;
the lipid component is at least one of triglyceride, phospholipid and glycolipid;
the mass ratio of the composite grinding aid to the polyamide to the organic acid salt to the polyol to the lipid component is 1: (2-4): (1.0-1.5): (20-40): (3-7).
As a further preferable scheme of the invention, the composite grinding aid is prepared from a high molecular alcohol amine compound, a modified polycarboxylate water reducer and modified calcium sulfate whisker according to a mass ratio of 1: (0.5-0.8): (0.1-0.4);
the high molecular alcohol amine compound is prepared by polymerizing an intermediate obtained by reacting maleic anhydride and alcohol amine substances with methacrylic acid and methallyl alcohol polyoxyethylene ether;
the modified polycarboxylate water reducer is prepared by copolymerizing methacrylic alcohol polyoxyethylene ether serving as a large monomer with acrylic acid;
the modified calcium sulfate whisker is prepared by taking desulfurized gypsum as a raw material, adding an additive, performing a hydrothermal reaction, and constructing a hydrophilic coating on the surface of the modified calcium sulfate whisker.
As a further preferable embodiment of the present invention, the preparation method of the high molecular weight alcohol amine compound is as follows:
1) Sequentially adding maleic anhydride and triethanolamine into a container, then adding p-toluenesulfonic acid, uniformly mixing, and then placing the mixture in a constant-temperature water bath for reaction for 3-6 hours to obtain an intermediate for later use;
2) Sequentially adding an intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid into a reactor, then dropwise adding 2, 4-diphenyl-4-methyl-1-pentene and ammonium persulfate at 70-75 ℃, reacting for 3-5h after the dropwise adding is finished, and regulating the pH value to 7 by using sodium hydroxide after the reaction is finished, thus obtaining the high molecular alcohol amine compound.
As a further preferable mode of the invention, the molar ratio of the maleic anhydride to the triethanolamine is (1.5-2.0): 1, proportioning;
the addition amount of the p-toluenesulfonic acid is 2-6% of the mass of the maleic anhydride;
the temperature of the constant-temperature water bath is 110-116 ℃.
As a further preferable mode of the invention, the mass ratio of the intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid is (1.5-2.0): (1.0-1.6): (1.2-1.8): (0.8-1.3);
the mass of the 2, 4-diphenyl-4-methyl-1-pentene and the mass of the ammonium persulfate respectively account for 0.5-0.8% and 2.0-2.6% of that of the methallyl alcohol polyoxyethylene ether;
the reaction temperature is 60-70 ℃.
As a further preferable scheme of the invention, the preparation method of the modified polycarboxylate superplasticizer comprises the following steps:
1) Adding methyl allyl alcohol polyoxyethylene ether into deionized water, fully stirring until the methyl allyl alcohol polyoxyethylene ether is completely dissolved to obtain a large monomer solution, uniformly mixing vitamin C, thioglycollic acid and deionized water to obtain a solution A, and uniformly mixing acrylic acid, maleic anhydride and deionized water to obtain a solution B for later use;
2) Adding hydrogen peroxide into a macromonomer solution in a water bath at the temperature of 45-50 ℃, slowly dropwise adding the solution A and the solution B, controlling the dropwise adding time of the solution A and the solution B to be 3-4h and 2.5-3.5h respectively, continuously preserving heat for 30-60min after the dropwise adding is finished, and regulating the pH value to 7 by using sodium hydroxide to obtain the modified polycarboxylate water reducer.
As a further preferable scheme of the invention, the dosage ratio of the methyl allyl alcohol polyoxyethylene ether to the deionized water in the macromer solution is (1-3) g: (50-70) mL;
in the solution A, the dosage ratio of the vitamin C, the thioglycollic acid and the deionized water is (0.3-0.8) g: (0.1-0.3) g: (10-20) mL;
in the solution B, the dosage ratio of the acrylic acid, the maleic anhydride and the deionized water is (5-10) g: (1.2-2.3) g: (20-30) mL;
the volume ratio of the hydrogen peroxide to the macromer solution to the solution A to the solution B is (3-8): (60-80): (20-30): (10-18).
As a further preferable scheme of the invention, the preparation method of the modified calcium sulfate whisker comprises the following steps:
1) Ball milling desulfurized gypsum into powder, preparing suspension with distilled water, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, uniformly mixing, transferring into a reaction kettle, performing hydrothermal reaction at 125-135 ℃ for 3-5h, performing suction filtration and washing after the reaction is finished, and drying at 120-130 ℃ for 2-4h to obtain calcium sulfate whiskers;
2) Mixing polyvinyl alcohol with distilled water, heating in a water bath kettle at 95-98 ℃ and continuously stirring until the polyvinyl alcohol is fully dissolved, cooling to room temperature to obtain a polyvinyl alcohol solution, adding calcium sulfate whiskers into the polyvinyl alcohol solution, fully oscillating and drying, adding silicon dioxide particles into water according to the mass ratio of 1 (125-150), dispersing, and then obtaining the mixture according to the mass volume ratio of 1g: (80-100) mL, adding the dried calcium sulfate whisker into the silicon dioxide dispersion liquid, sufficiently oscillating and drying to obtain the modified calcium sulfate whisker.
As a further preferred embodiment of the invention, the suspension has a concentration of 5-8 wt.%;
the addition amount of the sodium citrate and the sodium dodecyl benzene sulfonate respectively accounts for 1-3% and 2-5% of the dry basis of the desulfurized gypsum;
the concentration of the polyvinyl alcohol solution is 1-2wt%;
the mass volume ratio of the calcium sulfate whisker to the polyvinyl alcohol solution is 1g: (50-80) mL;
the particle size of the silicon dioxide particles is 400-500nm.
The application of the cement raw material energy-saving auxiliary agent is that the cement raw material energy-saving auxiliary agent is used as a processing auxiliary agent to be uniformly mixed with raw materials and then ground;
the method specifically comprises the following steps:
and (3) uniformly mixing the cement raw material energy-saving auxiliary agent and the cement raw material to obtain a mixture, and grinding the mixture in a mill to obtain a raw material grinding product.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, the cement raw material energy-saving auxiliary agent obtained by compounding the composite grinding aid, the polyamide, the potassium tartrate, the glycol and the phospholipid is mixed with the cement raw material, so that the apparent granularity of the cement raw material grinding is improved, the decomposition rate of calcium carbonate is obviously improved, and the energy-saving auxiliary agent has obvious effects of reducing the heat consumption of silicate cement clinker and improving the quality of clinker; the composite grinding aid consists of a high molecular alcohol amine compound, a modified polycarboxylate superplasticizer and modified calcium sulfate whiskers; the high-molecular alcohol amine compound is prepared from an intermediate obtained by reacting maleic anhydride and alcohol amine substances, and methacrylic acid and methallyl alcohol polyoxyethylene ether through free radical polymerization under the action of an initiator ammonium persulfate, and has a very strong polar functional group, so that the high-molecular alcohol amine compound can be adsorbed on the surface of cement particles to form an adsorption film, the adsorption film can shield attractive force among the particles, prevent fine particles from re-agglomerating, promote crack formation and expansion of the particles, increase the fluidity of the cement particles, enable the particles to be ground evenly, thereby being beneficial to improving grinding efficiency, improving fine particle content, optimizing particle size distribution of the particles, improving specific surface area, improving the dispersibility of the particles and enabling the particle morphology to be round; the modified polycarboxylate water reducer is obtained by copolymerizing methacrylic alcohol polyoxyethylene ether serving as a large monomer with acrylic acid, and the ratio of the methacrylic alcohol polyoxyethylene ether to the acrylic acid can be regulated and controlled by regulating the ratio of the methacrylic alcohol polyoxyethylene ether to the acrylic acid, and the length of a side chain can be regulated and controlled, so that a carboxylic acid group on a main chain of the modified polycarboxylate water reducer can be rapidly hydrolyzed and has negative charges, and is firmly adsorbed on the surface of cement particles, and the contained long side chain can play a dispersing role through steric hindrance, so that agglomeration among particles and ball pasting and grinding phenomena can be reduced, and the grinding efficiency of cement can be further greatly improved.
In order to further improve grinding efficiency and promote the cement raw material to achieve an easy grinding effect, the invention takes desulfurized gypsum as a raw material, carries out hydrothermal reaction after adding additives, builds a hydrophilic coating on the surface of the desulfurized gypsum to obtain modified calcium sulfate whisker, bonds hydrophilic substance polyvinyl alcohol to the surface of the calcium sulfate whisker through covalent bonds, forms package on the calcium sulfate whisker to ensure that the calcium sulfate whisker shows good lubricity, and promotes the concentration degree of aggregation of the silicon dioxide particles to be continuously increased by regulating the dispersion proportion of the silicon dioxide particles, so that the roughness of the surface of the calcium sulfate whisker is also increased, thereby reducing the contact angle of the surface of the calcium sulfate whisker to a certain extent, leading the formed modified calcium sulfate whisker to be more hydrophilic, leading the surface of the modified calcium sulfate whisker to have better lubricity, playing the role of reducing friction resistance among particles after being mixed with the cement raw material, not only reducing agglomeration of grinding products of the cement raw material, but also reducing grinding difficulty, thereby achieving the effect of improving the grindability of the cement raw material.
The energy-saving auxiliary agent for cement raw materials and the cement raw materials are mixed and ground, so that the apparent granularity of the cement raw materials is improved, and the ground particles are not easy to agglomerate for the second time, so that the ground product has good dispersibility, the decomposition rate of calcium carbonate is obviously improved, the heat consumption of silicate cement clinker is reduced, the quality of the clinker is improved, the friction resistance among cement particles is reduced, the grinding difficulty is reduced, and the grindability of the cement raw materials is improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An energy-saving auxiliary agent for cement raw materials is a liquid containing a composite grinding aid, polyamide, potassium tartrate, glycol and phospholipid, wherein the pH value is more than or equal to 9;
the preparation method of the energy-saving auxiliary agent comprises the steps of fully and uniformly stirring the composite grinding aid, polyamide, organic acid salt, polyalcohol and lipid components;
the energy-saving auxiliary agent is used as a processing auxiliary agent to be uniformly mixed with the raw material and then ground;
the method specifically comprises the following steps:
uniformly mixing the cement raw material energy-saving auxiliary agent and the cement raw material to obtain a mixture, and grinding the mixture in a mill to obtain a raw material grinding product;
wherein, the mass ratio of the composite grinding aid, polyamide, organic acid salt, polyol and lipid components is 1:2:1:20:3, a step of;
the composite grinding aid is prepared from a high molecular alcohol amine compound, a modified polycarboxylate water reducer and modified calcium sulfate whiskers according to a mass ratio of 1:0.5: 0.1.
The preparation method of the high molecular alcohol amine compound comprises the following steps:
1) The molar ratio is 1.5:1, sequentially adding maleic anhydride and triethanolamine into a container, then adding p-toluenesulfonic acid, controlling the addition amount of the p-toluenesulfonic acid to be 2% of the mass of the maleic anhydride, uniformly mixing, and then placing the mixture into a constant-temperature water bath for reaction for 3 hours at 110 ℃ to obtain an intermediate for later use;
2) The intermediate, maleic anhydride, methyl allyl alcohol polyoxyethylene ether and methacrylic acid are mixed according to the mass ratio of 1.5:1:1.2:0.8, sequentially adding the mixture into a reactor, then dropwise adding 2, 4-diphenyl-4-methyl-1-pentene and ammonium persulfate at 70 ℃, controlling the mass of the 2, 4-diphenyl-4-methyl-1-pentene and the mass of the ammonium persulfate to be 0.5 percent and 2 percent of that of the methallyl alcohol polyoxyethylene ether respectively, reacting at 60 ℃ for 3 hours after the dropwise adding is finished, and regulating the pH value to 7 by using 35 weight percent sodium hydroxide after the reaction is finished, thus obtaining the high molecular alcohol amine compound.
The preparation method of the modified polycarboxylate superplasticizer comprises the following steps:
1) Adding 1g of methyl allyl alcohol polyoxyethylene ether into 50mL of deionized water, fully stirring until the methyl allyl alcohol polyoxyethylene ether is completely dissolved to obtain a large monomer solution, uniformly mixing 0.3g of vitamin C, 0.1g of thioglycollic acid and 10mL of deionized water to obtain a solution A, and uniformly mixing 5g of acrylic acid, 1.2g of maleic anhydride and 20mL of deionized water to obtain a solution B for later use;
2) In a water bath at 45 ℃, 3mL of hydrogen peroxide is added into 60mL of macromonomer solution, then 20mL of solution A and 10mL of solution B are slowly added dropwise, the dropwise adding time of the solution A and the dropwise adding time of the solution B are respectively controlled to be 3h and 2.5h, after the dropwise adding is finished, the heat preservation is continued for 30min, and the pH value is regulated to 7 by using sodium hydroxide with the concentration of 30wt%, so that the modified polycarboxylate water reducer can be obtained.
The preparation method of the modified calcium sulfate whisker comprises the following steps:
1) Grinding desulfurization gypsum into powder, preparing suspension with distilled water to obtain a concentration of 5wt%, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, controlling the addition amount of the sodium citrate and the sodium dodecyl benzene sulfonate to respectively account for 1% and 2% of the dry basis of the desulfurization gypsum, uniformly mixing, transferring into a reaction kettle, carrying out hydrothermal reaction at 125 ℃ for 3 hours, carrying out suction filtration and washing after the reaction is finished, and drying at 120 ℃ for 2 hours to obtain calcium sulfate whiskers;
2) Mixing polyvinyl alcohol with distilled water, heating in a water bath kettle at 95 ℃ and continuously stirring until the polyvinyl alcohol is fully dissolved, cooling to room temperature to obtain a polyvinyl alcohol solution with the concentration of 1wt%, wherein the mass volume ratio is 1g:50mL of calcium sulfate whisker is added into polyvinyl alcohol solution, the mixture is dried after full oscillation, then silicon dioxide particles with the particle size of 400nm are added into water according to the mass ratio of 1:125 and dispersed, and the mass volume ratio is 1g: and 80mL of dried calcium sulfate whisker is added into the silicon dioxide dispersion liquid, and the modified calcium sulfate whisker can be obtained after full oscillation and drying.
Example 2
An energy-saving auxiliary agent for cement raw materials is a liquid containing a composite grinding aid, polyamide, potassium tartrate, glycol and phospholipid, wherein the pH value is more than or equal to 9;
the preparation method of the energy-saving auxiliary agent comprises the steps of fully and uniformly stirring the composite grinding aid, polyamide, organic acid salt, polyalcohol and lipid components;
the energy-saving auxiliary agent is used as a processing auxiliary agent to be uniformly mixed with the raw material and then ground;
the method specifically comprises the following steps:
uniformly mixing the cement raw material energy-saving auxiliary agent and the cement raw material to obtain a mixture, and grinding the mixture in a mill to obtain a raw material grinding product;
wherein, the mass ratio of the composite grinding aid, polyamide, organic acid salt, polyol and lipid components is 1:3:1.2:30:5, a step of;
the composite grinding aid is prepared from a high molecular alcohol amine compound, a modified polycarboxylate water reducer and modified calcium sulfate whiskers according to a mass ratio of 1:0.7: 0.3.
The preparation method of the high molecular alcohol amine compound comprises the following steps:
1) The molar ratio is 1.8:1, sequentially adding maleic anhydride and triethanolamine into a container, then adding p-toluenesulfonic acid, controlling the addition amount of the p-toluenesulfonic acid to be 5% of the mass of the maleic anhydride, uniformly mixing, and then placing the mixture into a constant-temperature water bath for reaction for 5 hours at 115 ℃ to obtain an intermediate for later use;
2) The intermediate, maleic anhydride, methyl allyl alcohol polyoxyethylene ether and methacrylic acid are mixed according to the mass ratio of 1.8:1.3:1.5:1.2 are added into a reactor in sequence, then 2, 4-diphenyl-4-methyl-1-pentene and ammonium persulfate are added dropwise at 72 ℃, the mass of the 2, 4-diphenyl-4-methyl-1-pentene and the mass of the ammonium persulfate are controlled to be respectively 0.6 percent and 2.3 percent of that of the methallyl alcohol polyoxyethylene ether, after the dropwise addition is finished, the reaction is carried out for 4 hours at 65 ℃, and after the reaction is finished, the pH value is regulated to 7 by sodium hydroxide with the concentration of 38 weight percent, thus obtaining the high molecular alcohol amine compound.
The preparation method of the modified polycarboxylate superplasticizer comprises the following steps:
1) Adding 2g of methyl allyl alcohol polyoxyethylene ether into 60mL of deionized water, fully stirring until the methyl allyl alcohol polyoxyethylene ether is completely dissolved to obtain a large monomer solution, uniformly mixing 0.5g of vitamin C, 0.2g of thioglycollic acid and 15mL of deionized water to obtain a solution A, and uniformly mixing 8g of acrylic acid, 1.8g of maleic anhydride and 25mL of deionized water to obtain a solution B for later use;
2) In a water bath at 48 ℃, 5mL of hydrogen peroxide is added into 70mL of macromonomer solution, then 25mL of solution A and 15mL of solution B are slowly added dropwise, the dropwise adding time of the solution A and the dropwise adding time of the solution B are respectively controlled to be 3.5h and 3h, after the dropwise adding is finished, the heat preservation is continued for 50min, and the pH value is regulated to 7 by sodium hydroxide with the concentration of 32wt%, so that the modified polycarboxylate water reducer can be obtained.
The preparation method of the modified calcium sulfate whisker comprises the following steps:
1) Grinding desulfurization gypsum into powder, preparing suspension with distilled water to obtain a concentration of 7wt%, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, controlling the addition amount of the sodium citrate and the sodium dodecyl benzene sulfonate to respectively account for 2% and 3% of the dry basis of the desulfurization gypsum, uniformly mixing, transferring into a reaction kettle, carrying out hydrothermal reaction for 4 hours at 130 ℃, carrying out suction filtration and washing after the reaction is finished, and drying for 3 hours at 125 ℃ to obtain calcium sulfate whiskers;
2) Mixing polyvinyl alcohol with distilled water, heating in a 96 ℃ water bath kettle, continuously stirring until the polyvinyl alcohol is fully dissolved, cooling to room temperature to obtain a polyvinyl alcohol solution with the concentration of 1.5wt%, and mixing the polyvinyl alcohol solution with the concentration of 1g according to the mass-volume ratio: 65mL of calcium sulfate whisker is added into polyvinyl alcohol solution, the mixture is dried after full oscillation, then silicon dioxide particles with the particle size of 500nm are added into water according to the mass ratio of 1:140 and dispersed, and the mass volume ratio is 1g:90mL of the dried calcium sulfate whisker is added into the silicon dioxide dispersion liquid, and the modified calcium sulfate whisker can be obtained after full oscillation and drying.
Example 3
An energy-saving auxiliary agent for cement raw materials is a liquid containing a composite grinding aid, polyamide, potassium tartrate, glycol and phospholipid, wherein the pH value is more than or equal to 9;
the preparation method of the energy-saving auxiliary agent comprises the steps of fully and uniformly stirring the composite grinding aid, polyamide, organic acid salt, polyalcohol and lipid components;
the energy-saving auxiliary agent is used as a processing auxiliary agent to be uniformly mixed with the raw material and then ground;
the method specifically comprises the following steps:
uniformly mixing the cement raw material energy-saving auxiliary agent and the cement raw material to obtain a mixture, and grinding the mixture in a mill to obtain a raw material grinding product;
wherein, the mass ratio of the composite grinding aid, polyamide, organic acid salt, polyol and lipid components is 1:4:1.5:40:7, preparing a base material;
the composite grinding aid is prepared from a high molecular alcohol amine compound, a modified polycarboxylate water reducer and modified calcium sulfate whiskers according to a mass ratio of 1:0.8: 0.4.
The preparation method of the high molecular alcohol amine compound comprises the following steps:
1) The molar ratio is 2.0:1, sequentially adding maleic anhydride and triethanolamine into a container, then adding p-toluenesulfonic acid, controlling the addition amount of the p-toluenesulfonic acid to be 6% of the mass of the maleic anhydride, uniformly mixing, and then placing the mixture into a constant-temperature water bath for reaction for 6 hours at 116 ℃ to obtain an intermediate for later use;
2) The intermediate, maleic anhydride, methyl allyl alcohol polyoxyethylene ether and methacrylic acid are mixed according to the mass ratio of 2:1.6:1.8:1.3 sequentially adding the mixture into a reactor, then dropwise adding 2, 4-diphenyl-4-methyl-1-pentene and ammonium persulfate at 75 ℃, controlling the mass of the 2, 4-diphenyl-4-methyl-1-pentene and the mass of the ammonium persulfate to be respectively 0.8 percent and 2.6 percent of that of the methallyl alcohol polyoxyethylene ether, reacting at 70 ℃ for 5 hours after the dropwise adding is finished, and regulating the pH value to 7 by using sodium hydroxide with the concentration of 40 weight percent after the reaction is finished, thus obtaining the high molecular alcohol amine compound.
The preparation method of the modified polycarboxylate superplasticizer comprises the following steps:
1) Adding 3g of methyl allyl alcohol polyoxyethylene ether into 70mL of deionized water, fully stirring until the methyl allyl alcohol polyoxyethylene ether is completely dissolved to obtain a large monomer solution, uniformly mixing 0.8g of vitamin C, 0.3g of thioglycollic acid and 20mL of deionized water to obtain a solution A, and uniformly mixing 10g of acrylic acid, 2.3g of maleic anhydride and 30mL of deionized water to obtain a solution B for later use;
2) In a water bath at 50 ℃, 8mL of hydrogen peroxide is added into 80mL of macromonomer solution, then 30mL of solution A and 18mL of solution B are slowly added dropwise, the dropwise adding time of the solution A and the dropwise adding time of the solution B are respectively controlled to be 4h and 3.5h, after the dropwise adding is finished, the heat preservation is continued for 60min, and the pH value is regulated to 7 by using 35wt% sodium hydroxide, so that the modified polycarboxylate water reducer can be obtained.
The preparation method of the modified calcium sulfate whisker comprises the following steps:
1) Grinding desulfurization gypsum into powder, preparing suspension with distilled water to obtain a concentration of 8wt%, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, controlling the addition amount of the sodium citrate and the sodium dodecyl benzene sulfonate to respectively account for 3% and 5% of the dry basis of the desulfurization gypsum, uniformly mixing, transferring into a reaction kettle, carrying out hydrothermal reaction at 135 ℃ for 5 hours, carrying out suction filtration and washing after the reaction is finished, and drying at 130 ℃ for 4 hours to obtain calcium sulfate whiskers;
2) Mixing polyvinyl alcohol with distilled water, heating in a water bath kettle at 98 ℃ and continuously stirring until the polyvinyl alcohol is fully dissolved, cooling to room temperature to obtain a polyvinyl alcohol solution with the concentration of 2wt%, wherein the mass volume ratio is 1g:80mL of calcium sulfate whisker is added into polyvinyl alcohol solution, the mixture is dried after full oscillation, then silicon dioxide particles with the particle size of 500nm are added into water according to the mass ratio of 1:150 and dispersed, and the mass volume ratio is 1g:100mL of the dried calcium sulfate whisker is added into the silicon dioxide dispersion liquid, and the modified calcium sulfate whisker can be obtained after full oscillation and drying.
Comparative example 1: this comparative example is essentially the same as example 1 except that the composite grinding aid does not contain modified calcium sulfate whiskers.
Comparative example 2: this comparative example is substantially the same as example 1 except that the modified polycarboxylate superplasticizer was not contained in the composite grinding aid.
Comparative example 3: this comparative example is substantially the same as example 1 except that the compound grinding aid does not contain a polymeric alcohol amine compound.
Comparative example 4: this comparative example is substantially the same as example 1 except that a polycarboxylate water reducer is used instead of the modified polycarboxylate water reducer.
Comparative example 5: this comparative example is substantially the same as example 1 except that calcium sulfate whiskers are used instead of modified calcium sulfate whiskers.
Test experiment:
drying 40 parts of the mixed material by a dryer until the water content is 3%, and grinding the mixed material by a ball mill until the granularity is 200 meshes; adding the obtained powdery mixed material, 8 parts of anhydrous gypsum, 2 parts of energy-saving auxiliary agents, 4 parts of excitation substances, 2 parts of carbon fibers, 2 parts of asbestos powder, 0.5 part of zinc oxide, 1 part of silicon nitride, 0.1 part of chromium carbide, 4 parts of calcium sulfate whisker powder and 2 parts of auxiliary agents into a stirring tank, uniformly stirring, and then putting into a ball mill for grinding until the granularity is 300 meshes, wherein the grinding temperature is 180 ℃; placing the obtained material, 50 parts of cement clinker, 5 parts of mixed stone powder, 2 parts of isobornyl acrylate, 1 part of cyclohexyl methacrylate, 1 part of dimethyl carbonate, 5 parts of rock asphalt, 1 part of aluminized glass bead, 0.1 part of defoamer, 0.2 part of plasticizer, 0.5 part of anti-settling agent and 0.5 part of water reducer into a stirring tank for mixing treatment to obtain composite cement, and measuring the performance of the obtained composite cement, wherein the results are shown in table 1;
wherein the mixed material is obtained by mixing hollow glass beads with limestone;
the mixed stone powder is prepared by grinding and mixing calcite, fluorite, apatite and orthofeldspar in the same weight parts, and the mesh number is 300;
the auxiliary agent consists of the following raw materials in percentage by weight: 50% of kaolin, 4% of tung oil, 5% of ammonium polyphosphate, 8% of calcium lignosulfonate, 5% of calcium oxide, 10% of trichloroethyl phosphate, 2% of magnesium powder, 6% of octadecyl acrylate and 10% of manganese slag;
the energy saving auxiliary agents are provided by selecting examples 1-3 and comparative examples 1-5 respectively.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Initial fluidity mm | 342 | 355 | 350 | 285 |
| 30min fluidity mm | 300 | 310 | 306 | 245 |
| 3d compressive Strength MPa | 25.8 | 26.6 | 26.2 | 18.9 |
| 28d compressive strength MPa | 57.2 | 58.1 | 57.7 | 44.7 |
| Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Initial fluidity mm | 280 | 300 | 320 | 330 |
| 30min fluidity mm | 240 | 255 | 268 | 280 |
| 3d compressive Strength MPa | 18.3 | 20.2 | 24.5 | 25.6 |
| 28d compressive strength MPa | 43.6 | 48.6 | 53.1 | 54.7 |
Through the table, the cement raw material energy-saving auxiliary agent is beneficial to realizing fine regulation and control of raw material granularity, easy burning and easy grinding of raw materials, and is beneficial to improving the physicochemical quality of clinker and the compressive strength and fluidity of the clinker, thereby improving the comprehensive performance of cement, and the concrete prepared from the cement raw material energy-saving auxiliary agent has high strength, short setting time and small shrinkage.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (8)
1. The energy-saving auxiliary agent for the cement raw material is characterized in that the energy-saving auxiliary agent is a liquid containing a composite grinding aid, polyamide, organic acid salt, polyalcohol and lipid components, and the pH value is more than or equal to 9;
the preparation method of the energy-saving auxiliary agent comprises the steps of fully and uniformly stirring the composite grinding aid, polyamide, organic acid salt, polyol and lipid components;
the composite grinding aid is prepared from a high molecular alcohol amine compound, a modified polycarboxylate water reducer and modified calcium sulfate whiskers according to a mass ratio of 1: (0.5-0.8): (0.1-0.4);
the high molecular alcohol amine compound is prepared by polymerizing an intermediate obtained by reacting maleic anhydride and alcohol amine substances with methacrylic acid and methallyl alcohol polyoxyethylene ether;
the modified polycarboxylate water reducer is prepared by copolymerizing methacrylic alcohol polyoxyethylene ether serving as a large monomer with acrylic acid;
the modified calcium sulfate whisker is prepared by taking desulfurized gypsum as a raw material, adding an additive, performing a hydrothermal reaction, and constructing a hydrophilic coating on the surface of the modified calcium sulfate whisker;
the preparation method of the modified calcium sulfate whisker comprises the following steps:
1) Ball milling desulfurized gypsum into powder, preparing suspension with distilled water, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, uniformly mixing, transferring into a reaction kettle, performing hydrothermal reaction at 125-135 ℃ for 3-5h, performing suction filtration and washing after the reaction is finished, and drying at 120-130 ℃ for 2-4h to obtain calcium sulfate whiskers;
2) Mixing polyvinyl alcohol with distilled water, heating in a water bath kettle at 95-98 ℃ and continuously stirring until the polyvinyl alcohol is fully dissolved, cooling to room temperature to obtain a polyvinyl alcohol solution, adding calcium sulfate whiskers into the polyvinyl alcohol solution, fully oscillating and drying, adding silicon dioxide particles into water according to the mass ratio of 1 (125-150), dispersing, and then obtaining the mixture according to the mass volume ratio of 1g: (80-100) mL, adding the dried calcium sulfate whisker into the silicon dioxide dispersion liquid, sufficiently oscillating and drying to obtain the modified calcium sulfate whisker;
the organic acid salt is at least one of potassium tartrate, sodium citrate and sodium salicylate;
the polyalcohol is at least one of ethylene glycol, 1, 2-propylene glycol and 1, 4-butanediol;
the lipid component is at least one of triglyceride, phospholipid and glycolipid;
the mass ratio of the composite grinding aid to the polyamide to the organic acid salt to the polyol to the lipid component is 1: (2-4): (1.0-1.5): (20-40): (3-7).
2. The energy-saving auxiliary agent for cement raw materials according to claim 1, wherein the preparation method of the high molecular alcohol amine compound is as follows:
1) Sequentially adding maleic anhydride and triethanolamine into a container, then adding p-toluenesulfonic acid, uniformly mixing, and then placing the mixture in a constant-temperature water bath for reaction for 3-6 hours to obtain an intermediate for later use;
2) Sequentially adding an intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid into a reactor, then dropwise adding 2, 4-diphenyl-4-methyl-1-pentene and ammonium persulfate at 70-75 ℃, reacting for 3-5h after the dropwise adding is finished, and regulating the pH value to 7 by using sodium hydroxide after the reaction is finished, thus obtaining the high molecular alcohol amine compound.
3. The energy-saving auxiliary agent for cement raw materials according to claim 2, wherein the molar ratio of maleic anhydride to triethanolamine is (1.5-2.0): 1, proportioning;
the addition amount of the p-toluenesulfonic acid is 2-6% of the mass of the maleic anhydride;
the temperature of the constant-temperature water bath is 110-116 ℃.
4. The energy-saving auxiliary agent for cement raw materials according to claim 2, wherein the mass ratio of the intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid is (1.5-2.0): (1.0-1.6): (1.2-1.8): (0.8-1.3);
the mass of the 2, 4-diphenyl-4-methyl-1-pentene and the mass of the ammonium persulfate respectively account for 0.5-0.8% and 2.0-2.6% of that of the methallyl alcohol polyoxyethylene ether;
the reaction temperature is 60-70 ℃.
5. The energy-saving auxiliary agent for cement raw materials according to claim 1, wherein the preparation method of the modified polycarboxylate water reducer is as follows:
1) Adding methyl allyl alcohol polyoxyethylene ether into deionized water, fully stirring until the methyl allyl alcohol polyoxyethylene ether is completely dissolved to obtain a large monomer solution, uniformly mixing vitamin C, thioglycollic acid and deionized water to obtain a solution A, and uniformly mixing acrylic acid, maleic anhydride and deionized water to obtain a solution B for later use;
2) Adding hydrogen peroxide into a macromonomer solution in a water bath at the temperature of 45-50 ℃, slowly dropwise adding the solution A and the solution B, controlling the dropwise adding time of the solution A and the solution B to be 3-4h and 2.5-3.5h respectively, continuously preserving heat for 30-60min after the dropwise adding is finished, and regulating the pH value to 7 by using sodium hydroxide to obtain the modified polycarboxylate water reducer.
6. The energy-saving auxiliary agent for cement raw materials according to claim 5, wherein the dosage ratio of the methyl allyl alcohol polyoxyethylene ether to the deionized water in the macromonomer solution is (1-3) g: (50-70) mL;
in the solution A, the dosage ratio of the vitamin C, the thioglycollic acid and the deionized water is (0.3-0.8) g: (0.1-0.3) g: (10-20) mL;
in the solution B, the dosage ratio of the acrylic acid, the maleic anhydride and the deionized water is (5-10) g: (1.2-2.3) g: (20-30) mL;
the volume ratio of the hydrogen peroxide to the macromer solution to the solution A to the solution B is (3-8): (60-80): (20-30): (10-18).
7. The energy-saving auxiliary agent for cement raw materials according to claim 1, wherein in the preparation method of the modified calcium sulfate whisker, the concentration of the suspension is 5-8wt%;
the addition amount of the sodium citrate and the sodium dodecyl benzene sulfonate respectively accounts for 1-3% and 2-5% of the dry basis of the desulfurized gypsum;
the concentration of the polyvinyl alcohol solution is 1-2wt%;
the mass volume ratio of the calcium sulfate whisker to the polyvinyl alcohol solution is 1g: (50-80) mL;
the particle size of the silicon dioxide particles is 400-500nm.
8. The use of an energy-saving aid for raw cement according to any of claims 1-7, characterized in that as a processing aid, after being mixed with the raw cement, a grinding process is carried out;
the method specifically comprises the following steps:
and (3) uniformly mixing the cement raw material energy-saving auxiliary agent and the cement raw material to obtain a mixture, and grinding the mixture in a mill to obtain a raw material grinding product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053957A (en) * | 2018-08-25 | 2018-12-21 | 广州吉前化工有限公司 | A kind of cement grinding aid and preparation method thereof |
| CN115043607A (en) * | 2022-07-18 | 2022-09-13 | 洛阳奥百思特水泥技术有限公司 | Composite grinding aid for improving raw material burnability and early strength of cement and preparation method thereof |
| CN115140963A (en) * | 2022-06-30 | 2022-10-04 | 北京人众创新工贸有限公司 | Raw material activation energy-saving auxiliary agent for cement production and application thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CA2577558C (en) * | 2006-02-07 | 2014-07-29 | Nittetsu Cement Co., Ltd. | Ultrafine particle grouting composition |
| CN103641367B (en) * | 2013-12-23 | 2015-08-19 | 济南大学 | A kind of composite cement grinding aid and preparation method thereof |
| CN108147692B (en) * | 2018-02-06 | 2020-07-24 | 北京金隅水泥节能科技有限公司 | Cement grinding aid and preparation method thereof |
| CN112708051A (en) * | 2020-10-22 | 2021-04-27 | 科之杰新材料集团有限公司 | Polycarboxylate superplasticizer with high mud absorption resistance function and preparation method thereof |
| CN113999039A (en) * | 2021-10-29 | 2022-02-01 | 江苏博拓新型建筑材料股份有限公司 | In-situ whisker reinforced autoclaved aerated concrete prepared from gasified slag and preparation method thereof |
| CN114477844B (en) * | 2022-02-14 | 2022-11-04 | 株洲宏信科技发展有限公司 | Cement raw meal grinding aid and preparation method and application thereof |
| CN114656176B (en) * | 2022-03-25 | 2023-02-28 | 嘉华特种水泥股份有限公司 | Portland cement for quick setting and preparation method thereof |
| CN114890695B (en) * | 2022-05-06 | 2023-03-21 | 广东建盛高新材料有限公司 | Cement raw material grinding aid and preparation method thereof |
| CN115259839B (en) * | 2022-07-25 | 2023-03-21 | 中冶武汉冶金建筑研究院有限公司 | Integral refractory castable for preheating section side wall of belt type roasting machine and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109053957A (en) * | 2018-08-25 | 2018-12-21 | 广州吉前化工有限公司 | A kind of cement grinding aid and preparation method thereof |
| CN115140963A (en) * | 2022-06-30 | 2022-10-04 | 北京人众创新工贸有限公司 | Raw material activation energy-saving auxiliary agent for cement production and application thereof |
| CN115043607A (en) * | 2022-07-18 | 2022-09-13 | 洛阳奥百思特水泥技术有限公司 | Composite grinding aid for improving raw material burnability and early strength of cement and preparation method thereof |
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