CN115745460A - Energy-saving additive for cement raw material and preparation method and application thereof - Google Patents
Energy-saving additive for cement raw material 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 additive for cement raw materials, a preparation method and application thereof, wherein the energy-saving additive 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 energy-saving auxiliary agent for the cement raw material is mixed and ground with the cement raw material, so that the apparent granularity of the ground cement raw material is improved, the ground particles are not easy to agglomerate secondarily, 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, meanwhile, the effect of reducing the friction resistance among cement particles is achieved, the grinding difficulty is reduced, and the effect of improving the grindability of the cement raw material is achieved.
Description
Technical Field
The invention relates to the technical field of cement additives, in particular to an energy-saving additive for cement raw materials and a preparation method and application thereof.
Background
With the vigorous development of the construction industry, cement is one of the most important cementing materials and is widely applied to engineering of civil construction, water conservancy, national defense and the like for a long time. However, due to the limitation of production process, cement production is an industry with low energy utilization rate and high energy consumption. Specifically, the cement production process is called two-mill one-firing for short, 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, nearly 95% of energy in the raw material grinding process disappears as heat dissipation, when the fineness of the raw material is refined to a certain degree, the grinding condition is worsened due to the agglomeration phenomenon of fine particles, and the grinding efficiency is sharply reduced. Moreover, the raw material grinding step is used as a basic link in the cement production process, which has important influence on the subsequent production link, and the quality of the grain composition after the raw material grinding can influence the raw material dispersibility, the raw material burnability, the coal consumption, the power consumption, the quality and the pollutant discharge of clinker, thereby seriously restricting the development of the cement industry.
For example, the invention patent with the publication number of CN112645628A discloses a formula and a preparation process of a novel powder cement grinding aid, the cement grinding aid consists of alcohol amine, potassium humate, sodium thiocyanate, anhydrous sodium sulphate, silica fume, a hexavalent chromium reducing agent and a stabilizing agent, the chemical stability and the reduction efficiency are greatly improved, the defect that ferrous sulfate and manganese acetate are easy to deliquesce is overcome 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 performance, good grinding aid performance, early strength and chemical stability, and does not contain chloride salt and is environment-friendly; although the cement grinding aid has a good grinding-assisting effect, after the cement grinding aid is mixed and ground with cement raw materials, the particle size distribution of the raw materials is dispersed, so that the particle gradation is poor, secondary agglomeration is easy to occur between the ground fine particles, and the dispersibility of the raw materials is influenced.
Disclosure of Invention
The energy-saving auxiliary agent for the cement raw material is mixed with the cement raw material, so that the apparent granularity of ground cement raw material can be improved, the ground particles are not easy to generate secondary agglomeration, the ground product has good dispersity, 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, and meanwhile, the energy-saving auxiliary agent for the cement raw material can play a role in reducing the friction resistance among cement particles, the grinding difficulty is reduced, and the effect of improving the grindability of the cement raw material is achieved.
In order to achieve the purpose, the invention provides the following technical scheme:
an energy-saving additive for cement raw materials is a liquid containing composite grinding aid, polyamide, organic acid salt, polyalcohol and lipid components, and has a pH value of 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 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 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 polymer alcohol amine compound, a modified polycarboxylic acid water reducing agent 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 obtained by polymerizing an intermediate obtained by reacting maleic anhydride and an alcohol amine substance with methacrylic acid and methallyl alcohol polyoxyethylene ether;
the modified polycarboxylate superplasticizer is obtained by copolymerizing methyl allyl alcohol polyoxyethylene ether serving as a macromonomer and acrylic acid;
the modified calcium sulfate crystal whisker is obtained by taking desulfurized gypsum as a raw material, adding an additive, carrying out hydrothermal reaction, and constructing a hydrophilic coating on the surface of the modified calcium sulfate crystal whisker.
In a further preferred embodiment of the present invention, the method for preparing the polymer alcohol amine compound comprises the following steps:
1) Sequentially adding maleic anhydride and triethanolamine into a container, then adding p-toluenesulfonic acid, uniformly mixing, and placing in a constant-temperature water bath for reaction for 3-6 hours to obtain an intermediate for later use;
2) Sequentially adding the intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid into a reactor, dropwise adding 2,4-diphenyl-4-methyl-1-pentene and ammonium persulfate at 70-75 ℃, reacting for 3-5 hours after dropwise adding is finished, and adjusting the pH value to 7 by using sodium hydroxide after the reaction is finished to obtain the high-molecular alcohol amine compound.
As a further preferable embodiment of the present invention, the molar ratio of the maleic anhydride to the triethanolamine is (1.5 to 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 ℃.
In a further preferred embodiment of the present invention, the mass ratio of the intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether, and methacrylic acid (1.5 to 2.0): (1.0-1.6): (1.2-1.8): (0.8-1.3);
the 2,4-diphenyl-4-methyl-1-pentene and the ammonium persulfate respectively account for 0.5-0.8% and 2.0-2.6% of the mass of the methallyl alcohol polyoxyethylene ether;
the reaction temperature is 60-70 ℃.
In a further preferred embodiment of the present invention, the modified polycarboxylic acid water reducing agent is prepared by the following steps:
1) Adding methyl propenyl polyoxyethylene ether into deionized water, fully stirring until the methyl propenyl polyoxyethylene ether is completely dissolved to obtain a macromonomer solution, uniformly mixing vitamin C, thioglycolic 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 45-50 ℃, then slowly dropwise adding the solution A and the solution B, respectively controlling the dropwise adding time of the solution A and the dropwise adding time of the solution B at 3-4h and 2.5-3.5h, continuously preserving the heat for 30-60min after the dropwise adding is finished, and adjusting the pH value to 7 by using sodium hydroxide to obtain the modified polycarboxylic acid water reducer.
As a further preferable scheme of the invention, in the macromonomer solution, the using amount ratio of the methyl allyl alcohol polyoxyethylene ether to the deionized water is (1-3) g: (50-70) mL;
in the solution A, the dosage ratio of the vitamin C, the thioglycolic acid and the deionized water is (0.3-0.8) g: (0.1-0.3) g: (10-20) mL;
in the solution B, the using amount ratio of acrylic acid, maleic anhydride and deionized water is (5-10) g: (1.2-2.3) g: (20-30) mL;
the volume ratio of the hydrogen peroxide to the macromonomer solution to the solution A to the solution B is (3-8): (60-80): (20-30): (10-18).
As a further preferable embodiment of the present invention, the preparation method of the modified calcium sulfate whisker is as follows:
1) Ball-milling desulfurized gypsum into powder, preparing the powder and distilled water into suspension, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, uniformly mixing, transferring the mixture into a reaction kettle, carrying out hydrothermal reaction at 125-135 ℃ for 3-5h, carrying out 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 the temperature of 95-98 ℃, 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, drying, adding silicon dioxide particles into water according to the mass ratio of 1 (125-150), dispersing, and then mixing according to the mass volume ratio of 1g: (80-100) adding the dried calcium sulfate whisker into the silicon dioxide dispersion liquid in a volume of (80-100), fully oscillating and drying to obtain the modified calcium sulfate whisker.
As a further preferred embodiment of the invention, the concentration of the suspension is 5 to 8 wt.%;
the addition amounts of the sodium citrate and the sodium dodecyl benzene sulfonate respectively account 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 whiskers 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 energy-saving additive for the cement raw material is that the energy-saving additive is used as a processing additive to be mixed with the raw material uniformly and then ground;
the method specifically comprises the following steps:
the energy-saving additive for the cement raw materials and the cement raw materials are mixed uniformly to obtain a mixture, and the mixture is put into a mill to be milled to obtain a raw material milling product.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the energy-saving additive for the cement raw material, which is 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 ground cement raw material can be improved, the decomposition rate of calcium carbonate is obviously increased, and the energy-saving additive has obvious effects of reducing the heat consumption of silicate cement clinker and improving the quality of clinker; wherein the composite grinding aid consists of a polymer alcohol amine compound, a modified polycarboxylic acid water reducing agent and modified calcium sulfate whiskers; the polymer alcohol amine compound is prepared by a midbody obtained by reacting maleic anhydride and alcohol amine substances, and then is subjected to free radical polymerization with methacrylic acid and methallyl alcohol polyoxyethylene ether under the action of an initiator ammonium persulfate, the polymer alcohol amine compound has a functional group with very strong polarity, and can be adsorbed on the surface of cement particles to form an adsorption film, the adsorption film can shield the attraction among the particles, prevent the fine particles from reuniting, promote the formation and the expansion of particle cracks, increase the fluidity of the cement particles, enable the grinding chance of the particles to tend to be equal, thereby being beneficial to improving the grinding efficiency, improving the content of the fine particles, optimizing the particle size distribution of the particles, improving the specific surface area, improving the dispersibility of the particles and enabling the particle morphology to tend to be circular; the modified polycarboxylate superplasticizer adopts methyl allyl alcohol polyoxyethylene ether as a macromonomer and is obtained by copolymerization with acrylic acid, the acid-ether ratio and the side chain length of the methacrylate polyoxyethylene ether and the acrylic acid can be regulated and controlled by adjusting the proportion of the methacrylate polyoxyethylene ether and the acrylic acid, so that carboxylic acid groups on a main chain can be quickly hydrolyzed and carry negative charges, the methacrylate polycarboxylate superplasticizer is firmly adsorbed on the surfaces of cement particles, long side chains contained in the methacrylate polyoxyethylene ether can play a role of dispersion through steric hindrance, the agglomeration among the particles and the ball-paste grinding phenomenon can be reduced, and the grinding efficiency of cement can be further greatly improved.
In order to further improve the grinding efficiency and promote the cement raw material to achieve the effect of easy grinding, the desulfurized gypsum is used as the raw material, the additive is added and then the hydrothermal reaction is carried out, the hydrophilic coating is constructed on the surface of the desulfurized gypsum to obtain the modified calcium sulfate whisker, the hydrophilic substance polyvinyl alcohol is bonded to the surface of the calcium sulfate whisker through a covalent bond to wrap the calcium sulfate whisker, so that the calcium sulfate whisker has good lubricity, the concentration degree of aggregation of silica particles is continuously increased by regulating and controlling the dispersion ratio of the silica particles, the roughness of the surface of the calcium sulfate whisker is increased accordingly, the surface contact angle of the calcium sulfate whisker is reduced, the surface of the formed modified calcium sulfate whisker is more hydrophilic, so that the modified calcium sulfate whisker has better lubricity, and after the desulfurized gypsum is mixed with the cement raw material, the effect of reducing the friction resistance among particles can be achieved, the agglomeration of a ground product of the cement raw material can be reduced, the grinding difficulty is reduced, and the effect of improving the grindability of the cement raw material is achieved.
The energy-saving auxiliary agent for the cement raw material is mixed and ground with the cement raw material, so that the apparent granularity of the ground cement raw material is improved, the ground particles are not easy to agglomerate secondarily, 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, meanwhile, the effect of reducing the friction resistance among cement particles is achieved, the grinding difficulty is reduced, and the effect of improving the grindability of the cement raw material is achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An energy-saving additive for cement raw materials is a liquid containing a composite grinding aid, polyamide, potassium tartrate, glycol and phospholipid, 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, polyalcohol and lipid components;
the energy-saving auxiliary agent is used as a processing auxiliary agent and is uniformly mixed with the raw material to be ground;
the method specifically comprises the following steps:
mixing the energy-saving cement raw material auxiliary agent and the cement raw material uniformly 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 to the polyamide to the organic acid salt to the polyol to the lipid is 1:2:1:20:3;
the composite grinding aid is prepared from a polymer alcohol amine compound, a modified polycarboxylic acid water reducing agent and modified calcium sulfate whiskers according to a mass ratio of 1:0.5: 0.1.
The preparation method of the polymer alcohol amine compound comprises the following steps:
1) According to a molar ratio of 1.5: sequentially adding maleic anhydride and triethanolamine into a container, 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, placing into a constant-temperature water bath, and reacting for 3 hours at 110 ℃ to obtain an intermediate for later use;
2) Mixing the intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid according to the mass ratio of 1.5:1:1.2:0.8, sequentially adding the materials into a reactor, dropwise adding 2,4-diphenyl-4-methyl-1-pentene and ammonium persulfate at 70 ℃, controlling 2,4-diphenyl-4-methyl-1-pentene and ammonium persulfate to respectively account for 0.5 percent and 2 percent of the mass of the methylallyl alcohol polyoxyethylene ether, reacting for 3 hours at 60 ℃ after the dropwise addition is finished, and adjusting the pH value to 7 by using sodium hydroxide with the concentration of 35wt percent after the reaction is finished to obtain 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 macromonomer solution, uniformly mixing 0.3g of vitamin C, 0.1g of thioglycolic 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 dripped, the dripping time of the solution A and the dripping time of the solution B are respectively controlled to be 3h and 2.5h, after the dripping is finished, the temperature is continuously kept for 30min, and the pH value is adjusted to be 7 by using 30wt% of sodium hydroxide, thus obtaining the modified polycarboxylic acid water reducer.
The preparation method of the modified calcium sulfate whisker comprises the following steps:
1) Ball-milling desulfurized gypsum into powder, preparing the powder and distilled water into suspension with the concentration of 5wt%, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, controlling the addition amounts of the sodium citrate and the sodium dodecyl benzene sulfonate to respectively account for 1% and 2% of the dry basis of the desulfurized gypsum, uniformly mixing, transferring the mixture 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 ℃, continuously stirring until the polyvinyl alcohol is fully dissolved, cooling to room temperature to obtain a polyvinyl alcohol solution with the concentration of 1wt%, and mixing the polyvinyl alcohol solution with the distilled water according to the mass volume ratio of 1g: adding 50mL of calcium sulfate whiskers into a polyvinyl alcohol solution, fully oscillating, drying, adding silicon dioxide particles with the particle size of 400nm into water according to a mass ratio of 1: and adding 80mL of the dried calcium sulfate whisker into the silicon dioxide dispersion liquid, fully oscillating and drying to obtain the modified calcium sulfate whisker.
Example 2
An energy-saving additive for cement raw materials is a liquid containing a composite grinding aid, polyamide, potassium tartrate, glycol and phospholipid, 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, polyalcohol and lipid components;
the energy-saving auxiliary agent is used as a processing auxiliary agent and is uniformly mixed with the raw material to be ground;
the method specifically comprises the following steps:
mixing the energy-saving cement raw material auxiliary agent and the cement raw material uniformly 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 to the polyamide to the organic acid salt to the polyol to the lipid is 1:3:1.2:30:5;
the composite grinding aid is prepared from a polymer alcohol amine compound, a modified polycarboxylic acid water reducing agent and modified calcium sulfate whiskers according to a mass ratio of 1:0.7: 0.3.
The preparation method of the polymer alcohol amine compound comprises the following steps:
1) According to a molar ratio of 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, placing into a constant-temperature water bath, and reacting for 5 hours at 115 ℃ to obtain an intermediate for later use;
2) And (2) mixing the intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid according to a mass ratio of 1.8:1.3:1.5:1.2, sequentially adding the materials into a reactor, dropwise adding 2,4-diphenyl-4-methyl-1-pentene and ammonium persulfate at 72 ℃, controlling 2,4-diphenyl-4-methyl-1-pentene and ammonium persulfate to respectively account for 0.6 percent and 2.3 percent of the mass of the methylallyl alcohol polyoxyethylene ether, reacting for 4 hours at 65 ℃ after the dropwise adding is finished, and adjusting the pH value to be 7 by using sodium hydroxide with the concentration of 38 weight percent after the reaction is finished to obtain the high-molecular alcohol amine compound.
The preparation method of the modified polycarboxylic acid water reducing agent 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 macromonomer solution, uniformly mixing 0.5g of vitamin C, 0.2g of thioglycolic 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 dripped, the dripping time of the solution A and the dripping time of the solution B are respectively controlled to be 3.5h and 3h, after the dripping is finished, the temperature is continuously kept for 50min, and the pH value is adjusted to be 7 by using 32wt% of sodium hydroxide, thus obtaining the modified polycarboxylic acid water reducer.
The preparation method of the modified calcium sulfate whisker comprises the following steps:
1) Ball-milling desulfurized gypsum into powder, preparing the powder and distilled water into suspension with the concentration of 7wt%, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, controlling the addition amounts of the sodium citrate and the sodium dodecyl benzene sulfonate to be respectively 2% and 3% of the dry basis of the desulfurized gypsum, uniformly mixing, transferring the mixture into a reaction kettle, carrying out hydrothermal reaction at 130 ℃ for 4 hours, carrying out suction filtration and washing after the reaction is finished, and drying at 125 ℃ for 3 hours 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 distilled water according to the mass volume ratio of 1g:65mL of calcium sulfate whisker is added into a polyvinyl alcohol solution, the mixture is fully oscillated and dried, then silicon dioxide particles with the particle size of 500nm are added into water according to the mass ratio of 1: and adding 90mL of the dried calcium sulfate crystal whisker into the silicon dioxide dispersion liquid, fully oscillating and drying to obtain the modified calcium sulfate crystal whisker.
Example 3
An energy-saving additive for cement raw materials is a liquid containing a composite grinding aid, polyamide, potassium tartrate, glycol and phospholipid, 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, polyalcohol and lipid components;
the energy-saving auxiliary agent is used as a processing auxiliary agent and is uniformly mixed with the raw material to be ground;
the method specifically comprises the following steps:
mixing the energy-saving cement raw material auxiliary agent and the cement raw material uniformly 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 to the polyamide to the organic acid salt to the polyol to the lipid is 1:4:1.5:40:7;
the composite grinding aid is prepared from a polymer alcohol amine compound, a modified polycarboxylic acid water reducing agent and modified calcium sulfate whiskers according to a mass ratio of 1:0.8: 0.4.
The preparation method of the polymer alcohol amine compound comprises the following steps:
1) According to a molar ratio of 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, placing into a constant-temperature water bath, and reacting for 6 hours at 116 ℃ to obtain an intermediate for later use;
2) And (2) mixing the intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid according to the mass ratio of 2:1.6:1.8:1.3, sequentially adding the materials into a reactor, dropwise adding 2,4-diphenyl-4-methyl-1-pentene and ammonium persulfate at 75 ℃, controlling 2,4-diphenyl-4-methyl-1-pentene and ammonium persulfate to respectively account for 0.8 percent and 2.6 percent of the mass of the methylallyl alcohol polyoxyethylene ether, reacting for 5 hours at 70 ℃ after the dropwise adding is finished, and adjusting the pH value to be 7 by using sodium hydroxide with the concentration of 40wt percent after the reaction is finished to obtain 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 macromonomer solution, uniformly mixing 0.8g of vitamin C, 0.3g of thioglycolic 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) Adding 8mL of hydrogen peroxide into 80mL of macromonomer solution in a water bath at 50 ℃, slowly dropwise adding 30mL of solution A and 18mL of solution B, respectively controlling the dropwise adding time of the solution A and the dropwise adding time of the solution B at 4h and 3.5h, continuously preserving the temperature for 60min after the dropwise adding is finished, and adjusting the pH value to 7 by using 35wt% of sodium hydroxide to obtain the modified polycarboxylic acid water reducer.
The preparation method of the modified calcium sulfate whisker comprises the following steps:
1) Ball-milling desulfurized gypsum into powder, preparing the powder and distilled water into suspension with the concentration of 8wt%, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, controlling the addition amounts of the sodium citrate and the sodium dodecyl benzene sulfonate to be respectively 3% and 5% of the dry basis of the desulfurized gypsum, uniformly mixing, transferring the mixture into a reaction kettle, carrying out hydrothermal reaction for 5 hours at 135 ℃, carrying out suction filtration and washing after the reaction is finished, and drying for 4 hours at 130 ℃ to obtain calcium sulfate whiskers;
2) Mixing polyvinyl alcohol with distilled water, heating in a 98 ℃ 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 2wt%, and mixing the polyvinyl alcohol solution with the distilled water according to the mass volume ratio of 1g: adding 80mL of calcium sulfate whiskers into a polyvinyl alcohol solution, fully oscillating, drying, adding silicon dioxide particles with the particle size of 500nm into water according to a mass ratio of 1: and adding 100mL of the dried calcium sulfate whisker into the silicon dioxide dispersion liquid, fully oscillating and drying to obtain the modified calcium sulfate whisker.
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 essentially the same as example 1 except that the composite grinding aid does not contain a modified polycarboxylic acid water reducer.
Comparative example 3: this comparative example is essentially the same as example 1, except that the composite grinding aid does not contain a polymeric alcohol amine compound.
Comparative example 4: this comparative example is essentially the same as example 1, except that a polycarboxylic acid water-reducing agent is used instead of the modified polycarboxylic acid water-reducing agent.
Comparative example 5: this comparative example is essentially the same as example 1, except that calcium sulfate whiskers were used instead of the modified calcium sulfate whiskers.
Test experiments:
drying 40 parts of the mixed material by weight with a dryer until the water content is 3%, and then grinding the dried 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 agent, 4 parts of excitation substance, 2 parts of carbon fiber, 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 agent 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 ℃; putting 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 microsphere, 0.1 part of defoaming agent, 0.2 part of plasticizing agent, 0.5 part of anti-settling agent and 0.5 part of water reducing agent into a stirring tank, mixing 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 and limestone;
the mixed stone powder is prepared by grinding and mixing calcite, fluorite, apatite and orthoclase in the same weight part, and the mesh number is 300 meshes;
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 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 |
| Fluidity mm at 30min | 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 fluiditymm | 280 | 300 | 320 | 330 |
| Fluidity mm at 30min | 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 above table, the energy-saving additive for the cement raw material is beneficial to realizing fine regulation and control of the granularity of the raw material, can realize easy burning property and easy grinding property of the raw material, is beneficial to improving the physicochemical quality of the clinker, and improves the compressive strength and fluidity of the clinker, thereby improving the comprehensive performance of the cement.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments 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 the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. An energy-saving additive for cement raw materials is characterized in that the energy-saving additive is a liquid containing composite grinding aids, polyamide, organic acid salts, polyhydric alcohols 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, polyalcohol 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 is 1: (2-4): (1.0-1.5): (20-40): (3-7).
2. The energy-saving additive for cement raw materials as claimed in claim 1, wherein the composite grinding aid is prepared from a polymer alcohol amine compound, a modified polycarboxylic acid water reducing agent 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 obtained by polymerizing an intermediate obtained by reacting maleic anhydride and an alcohol amine substance with methacrylic acid and methallyl alcohol polyoxyethylene ether;
the modified polycarboxylate superplasticizer is obtained by copolymerizing methyl allyl alcohol polyoxyethylene ether serving as a macromonomer and acrylic acid;
the modified calcium sulfate whisker is obtained by taking desulfurized gypsum as a raw material, adding an additive, carrying out hydrothermal reaction, and constructing a hydrophilic coating on the surface of the modified calcium sulfate whisker.
3. The energy-saving additive for cement raw meal as claimed in claim 2, wherein the method for preparing the polymer alcohol amine compound comprises the following steps:
1) Sequentially adding maleic anhydride and triethanolamine into a container, then adding p-toluenesulfonic acid, uniformly mixing, and placing in a constant-temperature water bath for reaction for 3-6 hours to obtain an intermediate for later use;
2) Sequentially adding the intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid into a reactor, dropwise adding 2,4-diphenyl-4-methyl-1-pentene and ammonium persulfate at 70-75 ℃, reacting for 3-5 hours after dropwise adding is finished, and adjusting the pH value to 7 by using sodium hydroxide after the reaction is finished to obtain the high-molecular alcohol amine compound.
4. The energy-saving additive for cement raw material as claimed in claim 3, 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 ℃.
5. The energy-saving auxiliary agent for cement raw material as claimed in claim 3, wherein the mass ratio of the intermediate, maleic anhydride, methallyl alcohol polyoxyethylene ether and methacrylic acid (1.5-2.0): (1.0-1.6): (1.2-1.8): (0.8-1.3);
the 2,4-diphenyl-4-methyl-1-pentene and the ammonium persulfate respectively account for 0.5-0.8% and 2.0-2.6% of the mass of the methallyl alcohol polyoxyethylene ether;
the reaction temperature is 60-70 ℃.
6. The energy-saving additive for cement raw meal as claimed in claim 2, wherein the preparation method of the modified polycarboxylic acid water reducing agent is as follows:
1) Adding methyl propenyl polyoxyethylene ether into deionized water, fully stirring until the methyl propenyl polyoxyethylene ether is completely dissolved to obtain a macromonomer solution, uniformly mixing vitamin C, thioglycolic 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) In a water bath at 45-50 ℃, adding hydrogen peroxide into a macromonomer solution, 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, after dropwise adding is finished, continuously preserving the heat for 30-60min, and adjusting the pH value to 7 by using sodium hydroxide to obtain the modified polycarboxylic acid water reducer.
7. The energy-saving additive for cement raw materials as claimed in claim 6, wherein the ratio of the amount of the methacryl alcohol polyoxyethylene ether to the amount of 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 thioglycolic acid and the deionized water is (0.3-0.8) g: (0.1-0.3) g: (10-20) mL;
in the solution B, the using amount ratio of acrylic acid, maleic anhydride and deionized water is (5-10) g: (1.2-2.3) g: (20-30) mL;
the volume ratio of the hydrogen peroxide to the macromonomer solution to the solution A to the solution B is (3-8): (60-80): (20-30): (10-18).
8. The energy-saving additive for cement raw material as claimed in claim 2, wherein the preparation method of the modified calcium sulfate whisker comprises the following steps:
1) Ball-milling desulfurized gypsum into powder, preparing the powder and distilled water into suspension, adding sodium citrate and sodium dodecyl benzene sulfonate into the suspension, uniformly mixing, transferring the mixture into a reaction kettle, carrying out hydrothermal reaction at 125-135 ℃ for 3-5h, carrying out 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 the temperature of 95-98 ℃, 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, drying, adding silicon dioxide particles into water according to the mass ratio of 1 (125-150), dispersing, and then mixing according to the mass volume ratio of 1g: (80-100) adding the dried calcium sulfate whisker into the silicon dioxide dispersion liquid, fully oscillating and drying to obtain the modified calcium sulfate whisker.
9. The energy-saving additive for cement raw meal as claimed in claim 8, wherein the concentration of the suspension is 5-8wt%;
the addition amounts of the sodium citrate and the sodium dodecyl benzene sulfonate respectively account 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 whiskers to the polyvinyl alcohol solution is 1g: (50-80) mL;
the particle size of the silicon dioxide particles is 400-500nm.
10. The use of the energy-saving additive for cement raw meal as claimed in any one of claims 1 to 9, wherein the energy-saving additive is used as a processing aid to be mixed with raw meal and then subjected to grinding treatment;
the method specifically comprises the following steps:
the energy-saving additive for the cement raw materials and the cement raw materials are mixed uniformly to obtain a mixture, and the mixture is put into a mill to be milled to obtain a raw material milling product.
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