CN109336458B - Cement grinding aid - Google Patents
Cement grinding aid Download PDFInfo
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- CN109336458B CN109336458B CN201811540441.5A CN201811540441A CN109336458B CN 109336458 B CN109336458 B CN 109336458B CN 201811540441 A CN201811540441 A CN 201811540441A CN 109336458 B CN109336458 B CN 109336458B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical field of cement production, and discloses a cement grinding aid which is prepared from the following raw materials in parts by weight: 8-12% of phosphite anhydride-ethylene glycol reactant, 1-3% of polycarboxylic compound, 3-5% of grinding aid substance, 1-5% of potassium metabisulfite, 0.1-1% of defoaming agent and the balance of water. The cement grinding aid disclosed by the invention can improve the grinding efficiency of cement and also has a good function of reducing water-soluble hexavalent chromium in cement.
Description
Technical Field
The invention belongs to the technical field of cement production, and particularly relates to a cement grinding aid.
Background
The cement grinding aid is an additive which is added during the grinding of cement powder and has the function of grinding aid without damaging the human health and the performance of cement concrete. The grinding aid is added in the cement grinding process, so that on one hand, the machine-hour output of a cement grinding machine can be improved, and the power consumption of grinding is directly reduced; on the other hand, the activity of the industrial waste residue can be excited, the usage amount of the cement clinker is reduced, so that the coal and electricity consumption caused by the production of the cement clinker is saved, the emission of atmospheric pollutants is reduced, the utilization efficiency of the industrial waste residue is improved, the resource utilization efficiency is improved, and the purpose of emission reduction is achieved while the energy-saving effect is realized. With the implementation of the strategy of sustainable development, the development of the cement industry is greatly restricted by the problems of resources, energy and environment. The cement grinding aid with a very small mixing amount can improve the grading of cement particles, and improve the grinding efficiency and the cement quality index. Therefore, the grinding aid has irreplaceable important effect on the sustainable development of the cement industry.
The water-soluble hexavalent chromium (Cr (VI) or Cr6+) is an element with high heavy metal poisoning property of cement, and can cause harm to human bodies through skin contact, respiratory tract inhalation, environmental contact and other ways. Cr (VI) has serious adverse effects of carcinogenesis and gene mutation, and hexavalent chromium is classified as a carcinogen by the International agency for research on cancer (IARC), and can cause cancer by inhalation or epidermal contact. The water soluble Cr6+ content in cement is less than 2ppm (2mg/kg) by the restriction of the Allium. GB31893-2015 limit and determination method of water-soluble chromium (VI) in cement 2015 11 th day 9 approved by the State administration of quality supervision, inspection and quarantine, formally implemented 10 th 1 th day 2016, and mandatorily requires changing standard to require water-soluble Cr in cement6+The limit amount is not more than 10 mg/kg. At present, more water-soluble Cr in cement is reduced by using in cement plants6+The method adopts the chromium-free refractory bricks, thereby greatly increasing the production cost of cement plants.
Disclosure of Invention
Aiming at the problems, the invention provides the cement grinding aid with the function of reducing hexavalent chromium in cement, which is convenient to use, can improve the grinding efficiency of cement, improve the strength of cement and reduce the content of hexavalent chromium in cement. In order to achieve the purpose, the invention adopts the following technical scheme.
A cement grinding aid is composed of the following substances in parts by weight: 8-12% of phosphite anhydride-ethylene glycol reactant, 1-3% of polycarboxylic compound, 3-5% of grinding aid substance, 1-5% of potassium metabisulfite, 0.1-1% of defoaming agent and the balance of water.
The preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: proportionally adding ethylene glycol and phosphorous anhydride (P) into a four-neck flask with a stirring device, a thermometer and a condenser4O6) Heating the reaction solution to 40-80 ℃, and distilling under reduced pressure to remove the solvent, namely the reaction product of the phosphorous anhydride and the ethylene glycol.
The catalyst is one of concentrated sulfuric acid, anhydrous sodium acetate and 2-naphthalene sulfonic acid.
The solvent is one of acetone, tetrahydrofuran and cyclohexane.
Preferably, the solvent is cyclohexane.
The molar ratio of the ethylene glycol to the phosphorous anhydride is 4-12: 1.
Preferably, the molar ratio of the ethylene glycol to the phosphorous anhydride is 6-9: 1.
The dosage of the catalyst is 1-5% of the total weight of the glycol and the phosphorous anhydride.
The polycarboxyl compound is one of trisodium nitrilotriacetate, diethyltriaminepentaacetic acid and trisodium hydroxyethylethylenediamine triacetate.
The grinding aid is one of diethylethanolamine, N-aminoethyl ethanolamine and sodium lauroyl sarcosinate.
Preferably, the grinding aid substance is sodium lauroyl sarcosinate.
The defoaming agent is one of organic silicon, polyether, tributyl phosphate and polyacrylamide.
Preferably, the defoamer is polyacrylamide.
The phosphorous anhydride-ethylene glycol reactant in the invention has better reducibility to hexavalent chromium and also has certain grinding aiding property; a large amount of carboxyl in the polycarboxyl compound has stronger adsorption capacity to hexavalent chromium and can be mixed with Ca in cement2+、Mg2+Forming chelate, reducing the dissolution of hexavalent chromium, and improving the strength of cement; the potassium metabisulfite not only can accelerate the hydration of cement and is beneficial to improving the early strength of the cement, but also has certain reducibility and can reduce hexavalent chromium in the cement; the inventor finds that sodium lauroyl sarcosinate has an excellent grinding aid effect, but also has an air-guiding property and influences the development of cement strength, common defoaming agents such as common organic silicon, polyether and tributyl phosphate can reduce foam and reduce the influence of the sodium lauroyl sarcosinate on the cement strength, but cannot completely eliminate the influence, and when the sodium lauroyl sarcosinate and polyacrylamide are used in a compounding way, the foam is greatly reduced, the two synergistic effects do not influence the development of the cement strength and even slightly improve the cement strength when the good grinding aid effect is achieved. The multiple raw materials are closely associated and mutually influenced, and the mutual supplement is realized through the interactive superposition effect between the combinations, so that the cement grinding efficiency can be improved, the cement strength can be improved, and the content of hexavalent chromium in the cement can be reduced.
The invention has the advantages of
(1) The cement grinding aid can increase the output per machine hour of a grinder by more than 10 percent, and save the power consumption of cement grinding; the cement reinforcing agent also has the reinforcing effect, under the condition of not changing the cement mixing proportion, the 3d strength of the cement can be increased by more than 3MPa, the 28d strength of the cement can be increased by more than 5MPa, under the condition of keeping the cement performance unchanged, the clinker consumption can be reduced, the industrial waste residue is used for multiple purposes, the resource is saved, and the environment is protected.
(2) The cement grinding aid has a good function of reducing water-soluble hexavalent chromium in cement, does not need to change the existing cement production process, is simple to operate, and only needs to be added in the form of the grinding aid.
Detailed Description
Example 1
A cement grinding aid is composed of the following substances in parts by weight: 8% of phosphite anhydride-ethylene glycol reactant, 3% of polycarboxylic compound, 3% of grinding aid substance, 5% of potassium metabisulfite, 0.1% of defoaming agent and the balance of water.
The preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: proportionally adding ethylene glycol and phosphorous anhydride (P) into a four-neck flask with a stirring device, a thermometer and a condenser4O6) Heating the catalyst and the reaction solvent to 80 ℃, and distilling under reduced pressure to remove the solvent, namely the reaction product of the phosphorous anhydride and the ethylene glycol.
The catalyst is concentrated sulfuric acid.
The solvent is acetone.
The molar ratio of the ethylene glycol to the phosphorous anhydride is 4: 1.
The dosage of the catalyst is 1 percent of the total weight of the glycol and the phosphorous anhydride.
The polycarboxyl compound is trisodium nitrilotriacetate.
The grinding aid is diethylethanolamine.
The defoaming agent is an organic silicon defoaming agent.
Example 2
A cement grinding aid is composed of the following substances in parts by weight: 12% of phosphite anhydride-ethylene glycol reactant, 1% of polycarboxylic compound, 5% of grinding aid substance, 1% of potassium metabisulfite, 1% of defoaming agent and the balance of water.
The preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: proportionally adding ethylene glycol and phosphorous anhydride (P) into a four-neck flask with a stirring device, a thermometer and a condenser4O6) Heating the catalyst and the reaction solvent to 40 ℃, and distilling under reduced pressure to remove the solvent, namely the phosphite anhydride-ethylene glycol reactant.
The catalyst is anhydrous sodium acetate.
The solvent is tetrahydrofuran.
The molar ratio of the ethylene glycol to the phosphorous anhydride is 12: 1.
The dosage of the catalyst is 5 percent of the total weight of the glycol and the phosphorous anhydride.
The polycarboxyl compound is diethyl triaminepentaacetic acid.
The grinding aid substance is N-aminoethyl ethanolamine.
The defoaming agent is a polyether defoaming agent.
Example 3
A cement grinding aid is composed of the following substances in parts by weight: 10% of phosphite anhydride-ethylene glycol reactant, 2% of polycarboxylic compound, 4% of grinding aid substance, 3% of potassium metabisulfite, 0.6% of defoaming agent and the balance of water.
The preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: proportionally adding ethylene glycol and phosphorous anhydride (P) into a four-neck flask with a stirring device, a thermometer and a condenser4O6) Heating the reaction solution to 60 ℃, and distilling under reduced pressure to remove the solvent, namely the reaction product of the phosphorous anhydride and the ethylene glycol.
The catalyst is 2-naphthalene sulfonic acid.
The molar ratio of the ethylene glycol to the phosphorous anhydride is 8: 1.
The dosage of the catalyst is 3 percent of the total weight of the glycol and the phosphorous anhydride.
The polycarboxyl compound is trisodium hydroxyethylethylenediamine triacetate.
The grinding aid substance is sodium lauroyl sarcosinate.
The defoaming agent is polyacrylamide.
Example 4
A cement grinding aid is composed of the following substances in parts by weight: 9% of phosphite anhydride-ethylene glycol reactant, 2.5% of polycarboxylic compound, 3.5% of grinding aid substance, 4% of potassium metabisulfite, 0.3% of defoaming agent and the balance of water.
The preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: proportionally adding ethylene glycol and phosphorous anhydride (P) into a four-neck flask with a stirring device, a thermometer and a condenser4O6) Heating the reaction solution to 50 ℃, and distilling the reaction solution under reduced pressure to remove the solvent, thereby obtaining the phosphite anhydride-ethylene glycol reaction product.
The catalyst is anhydrous sodium acetate.
The solvent is cyclohexane.
The molar ratio of the ethylene glycol to the phosphorous anhydride is 6: 1.
The dosage of the catalyst is 2 percent of the total weight of the glycol and the phosphorous anhydride.
The polycarboxyl compound is diethyl triaminepentaacetic acid.
The grinding aid substance is N-aminoethyl ethanolamine.
The defoaming agent is polyacrylamide.
Example 5
A cement grinding aid is composed of the following substances in parts by weight: 11% of phosphite anhydride-ethylene glycol reactant, 1.5% of polycarboxylic compound, 4.5% of grinding aid substance, 2% of potassium metabisulfite, 0.8% of defoaming agent and the balance of water.
Example 6
A cement grinding aid is composed of the following substances in parts by weight: 10% of phosphite anhydride-ethylene glycol reactant, 2% of polycarboxylic compound, 4% of grinding aid substance, 3% of potassium metabisulfite, 0.6% of defoaming agent and the balance of water.
The preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: proportionally adding ethylene glycol and phosphorous anhydride (P) into a four-neck flask with a stirring device, a thermometer and a condenser4O6) Heating the reaction solution to 60 ℃, and distilling under reduced pressure to remove the solvent, namely the reaction product of the phosphorous anhydride and the ethylene glycol.
The catalyst is 2-naphthalene sulfonic acid.
The molar ratio of the ethylene glycol to the phosphorous anhydride is 8: 1.
The dosage of the catalyst is 3 percent of the total weight of the glycol and the phosphorous anhydride.
The polycarboxyl compound is trisodium hydroxyethylethylenediamine triacetate.
The grinding aid substance is sodium lauroyl sarcosinate.
The defoaming agent is tributyl phosphate.
Example 7
A cement grinding aid is composed of the following substances in parts by weight: 10% of phosphite anhydride-ethylene glycol reactant, 2% of polycarboxylic compound, 4% of grinding aid substance, 3% of potassium metabisulfite, 0.6% of defoaming agent and the balance of water.
The preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: proportionally adding ethylene glycol and phosphorous anhydride (P) into a four-neck flask with a stirring device, a thermometer and a condenser4O6) Heating the reaction solution to 60 ℃, and distilling under reduced pressure to remove the solvent, namely the reaction product of the phosphorous anhydride and the ethylene glycol.
The catalyst is 2-naphthalene sulfonic acid.
The molar ratio of the ethylene glycol to the phosphorous anhydride is 8: 1.
The dosage of the catalyst is 3 percent of the total weight of the glycol and the phosphorous anhydride.
The polycarboxyl compound is trisodium hydroxyethylethylenediamine triacetate.
The grinding aid is diethylethanolamine.
The defoaming agent is polyacrylamide.
Comparative example 1
A cement grinding aid is composed of the following substances in parts by weight: 10% of phosphite anhydride-ethylene glycol reactant, 2% of polycarboxylic compound, 4% of grinding aid substance, 0.6% of defoaming agent and the balance of water.
The preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: proportionally adding ethylene glycol and phosphorous anhydride (P) into a four-neck flask with a stirring device, a thermometer and a condenser4O6) Heating the reaction solution to 60 ℃, and distilling under reduced pressure to remove the solvent, namely the reaction product of the phosphorous anhydride and the ethylene glycol.
The catalyst is 2-naphthalene sulfonic acid.
The molar ratio of the ethylene glycol to the phosphorous anhydride is 8: 1.
The dosage of the catalyst is 3 percent of the total weight of the glycol and the phosphorous anhydride.
The polycarboxyl compound is trisodium hydroxyethylethylenediamine triacetate.
The grinding aid substance is sodium lauroyl sarcosinate.
The defoaming agent is polyacrylamide.
Comparative example 2
A cement grinding aid is composed of the following substances in parts by weight: 10% of phosphite anhydride-ethylene glycol reactant, 4% of grinding aid substance, 3% of potassium metabisulfite, 0.6% of defoaming agent and the balance of water.
The preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: proportionally adding ethylene glycol and phosphorous anhydride (P) into a four-neck flask with a stirring device, a thermometer and a condenser4O6) Heating the reaction solution to 60 ℃, and distilling under reduced pressure to remove the solvent, namely the reaction product of the phosphorous anhydride and the ethylene glycol.
The catalyst is 2-naphthalene sulfonic acid.
The molar ratio of the ethylene glycol to the phosphorous anhydride is 8: 1.
The dosage of the catalyst is 3 percent of the total weight of the glycol and the phosphorous anhydride.
The grinding aid substance is sodium lauroyl sarcosinate.
The defoaming agent is polyacrylamide.
Comparative example 3
A cement grinding aid is composed of the following substances in parts by weight: 3.4% of phosphorous anhydride, 5.6% of ethylene glycol, 2.5% of polycarboxylic compound, 3.5% of grinding aid substance, 4% of potassium metabisulfite, 0.3% of defoaming agent and the balance of water.
The polycarboxyl compound is diethyl triaminepentaacetic acid.
The grinding aid substance is N-aminoethyl ethanolamine.
The defoaming agent is polyacrylamide.
Performance testing
The cement grinding aid obtained in the examples 1-7 and the comparative examples 1-3 is subjected to performance test, clinker, gypsum, fly ash and slag are mixed in proportion, a small amount of potassium dichromate is added, the grinding aid is uniformly sprayed on the surface, the mixing amount is 0.1 percent of the total weight of the ground materials, the ground materials are ground for 35min, and a grinding machine is a model SM-500 test mill produced by a tin-free instrument and machinery limited company; the strength of the cement mortar is measured according to GB/T17671-1999 method for testing the strength of the cement mortar (ISO method); hexavalent chromium is tested according to the method specified in GB31893-2015 limit and determination of water soluble chromium (vi) in cement.
The results are shown in Table 1 below.
TABLE 1 additive Performance test results
Claims (4)
1. The cement grinding aid is characterized by consisting of the following substances in parts by weight: 8-12% of phosphite anhydride-ethylene glycol reactant, 1-3% of polycarboxylic compound, 3-5% of grinding aid substance, 1-5% of potassium metabisulfite, 0.1-1% of defoaming agent and the balance of water; the preparation method of the phosphite anhydride-ethylene glycol reactant comprises the following steps: adding ethylene glycol, phosphorous anhydride, a catalyst and a reaction solvent into a four-neck flask with a stirring device, a thermometer and a condenser in proportion, heating to 40-80 ℃, and distilling under reduced pressure to remove the solvent, namely the phosphorous anhydride-ethylene glycol reactant; the polycarboxyl compound is one of trisodium nitrilotriacetate, diethyltriaminepentaacetic acid and trisodium hydroxyethylethylenediamine triacetate; the defoaming agent is polyacrylamide; the grinding aid substance is sodium lauroyl sarcosinate.
2. The cement grinding aid of claim 1, wherein the catalyst is one of concentrated sulfuric acid, anhydrous sodium acetate, and 2-naphthalenesulfonic acid.
3. The cement grinding aid according to claim 1, wherein the solvent is one of acetone, tetrahydrofuran and cyclohexane.
4. The cement grinding aid according to claim 1, wherein the molar ratio of ethylene glycol to phosphorous anhydride is (4-12): 1.
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| CN110054434A (en) * | 2019-06-05 | 2019-07-26 | 杭州中齐新材料科技有限公司 | A kind of non-dispersible underwater concrete flocculant |
| CN110981238B (en) * | 2019-12-21 | 2022-02-01 | 安徽海螺新材料科技有限公司 | Additive for cement raw material |
| CN111186940A (en) * | 2020-01-19 | 2020-05-22 | 西安瑞联新材料股份有限公司 | Industrial treatment method of high-valence chromium wastewater |
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| CN101626994A (en) * | 2007-05-10 | 2010-01-13 | 拉法基公司 | Process to reduce the amount of cr (vi) in a cement-containing composition and a composition comprising cement and coated metallic sulphate particles |
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| CN108585597A (en) * | 2018-07-24 | 2018-09-28 | 青神鑫统领建材有限公司 | A kind of reduction of hexavalent chromium type grinding aid and preparation method thereof |
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| CN101184702A (en) * | 2005-06-02 | 2008-05-21 | 格雷斯公司 | Biomass-derived grinding aids |
| CN104045254A (en) * | 2005-06-02 | 2014-09-17 | 格雷斯公司 | Biomass-derived grinding aids |
| CN101626994A (en) * | 2007-05-10 | 2010-01-13 | 拉法基公司 | Process to reduce the amount of cr (vi) in a cement-containing composition and a composition comprising cement and coated metallic sulphate particles |
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