CN109336458A - A kind of cement grinding aid - Google Patents

A kind of cement grinding aid Download PDF

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Publication number
CN109336458A
CN109336458A CN201811540441.5A CN201811540441A CN109336458A CN 109336458 A CN109336458 A CN 109336458A CN 201811540441 A CN201811540441 A CN 201811540441A CN 109336458 A CN109336458 A CN 109336458A
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CN
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Prior art keywords
grinding aid
acid anhydride
phosphorous acid
cement
cement grinding
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CN201811540441.5A
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CN109336458B (en
Inventor
刘伟
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Jixi Hengchang New Material Technology Co.,Ltd.
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Hangzhou Zhonghe Smart City Technology Co Ltd
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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
    • 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

Abstract

The invention belongs to technical field of cement production, disclose a kind of cement grinding aid, be made of the raw material of following weight fraction: phosphorous acid anhydride-glycol reactant 8-12%, multi-carboxy compound 1-3%, grinding aid substance 3-5%, potassium metabisulfite 1-5%, defoaming agent 0.1-1%, surplus are water.Cement grinding aid of the present invention can be improved cement grinding efficiency, also have the function of water soluble hexavalent chromium in good reduction cement.

Description

A kind of cement grinding aid
Technical field
The invention belongs to technical field of cement production, and in particular to a kind of cement grinding aid.
Background technique
Cement grinding aid is the grind -aiding effect being added in cement grinding and does not damage human health and coagulating cement The additive of soil nature energy.Grinding aid is added in cement pulverizing course, on the one hand can be improved the unit-hour output of cement mill, from And directly reduce grinding pow consumption；On the other hand, the activity that can also excite industrial residue reduces the usage amount of clinker, To save coal, electric consumption caused by due to producing clinker, and the discharge of atmosphere pollution is reduced, improves industry The utilization efficiency of waste residue improves its recycling efficiency, while realization " energy conservation " effect, has also reached the mesh of " emission reduction " 's.With the implementation of the strategy of sustainable development, resource, the energy, environmental problem greatly restrict the development of cement industry.Seldom mix The cement grinding aid of amount can improve cement granules gradation, improve mill efficiency and Cement Quality index.Therefore, grinding aid is to water Mud industrial sustainable development has irreplaceable important function.
(Cr (VI) is Cr6+) a kind of biggish element of cement heavy metal poisoning to water soluble hexavalent chromium, it can pass through skin The approach such as skin contact, respiratory tract sucking, environment contact are done harm to huamn body.Cr (VI) can bring carcinogenic, cause gene mutation etc. Cr VI is classified as carcinogen by serious adverse consequences, international cancer research institution (IARC), whether sucking or table Bark graft touching, can cause cancer.Alliance limits water-solubility Cr 6+ content in cement and is less than 2ppm (2mg/kg).China GB31893- The quarantine of 2015 " limitation and measuring method of water soluble chromium (VI) in cement " 2015 11 Nikkei national quality supervision and inspections of September is total Office's approval publication, formally implements on October 1st, 2016, changes water-solubility Cr in standard Compulsory Feature cement6+Limitation is little In 10mg/kg.Cement plant uses water-solubility Cr in more reduction cement at present6+Approach be using no chromium firebrick, greatly The production cost in cement plant is increased greatly.
Summary of the invention
The present invention in view of the above-mentioned problems, provide it is a kind of with reduction cement in Cr VI function cement grinding aid, The grinding aid is easy to use, can be improved cement grinding efficiency, raising strength of cement can also reduce content of 6-valence Cr ions in cement.For Reach above-mentioned purpose, the present invention uses following technical scheme.
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 8-12%, Multi-carboxy compound 1-3%, grinding aid substance 3-5%, potassium metabisulfite 1-5%, defoaming agent 0.1-1%, surplus are water.
Phosphorous acid anhydride-the glycol reactant is the preparation method is as follows: equipped with agitating device, thermometer, condenser pipe Ethylene glycol, phosphorous acid anhydride (P are proportionally added into four-hole boiling flask4O6), catalyst and reaction dissolvent, be warming up to 40-80 DEG C, subtract Solvent is distilled off in pressure, as described phosphorous acid anhydride-glycol reactant.
The catalyst is one of the concentrated sulfuric acid, anhydrous sodium acetate, 2- naphthalene sulfonic acids.
The solvent is one of acetone, tetrahydrofuran, hexamethylene.
Preferably, the solvent is hexamethylene.
The ethylene glycol and phosphorous acid anhydride molar ratio are 4-12:1.
Preferably, the ethylene glycol and phosphorous acid anhydride molar ratio are 6-9:1.
The catalyst amount is the 1-5% of ethylene glycol and phosphorous acid anhydride total weight.
The multi-carboxy compound is nitrilotriacetic acid trisodium salt, diethyl pentetic acid, hydroxyethylethylene diamine tri-acetic acid three One of sodium.
The grinding aid substance is one of diethyl ethylene diamine, N- aminoethyl ethanolamine, sodium lauroyl sarcosine.
Preferably, the grinding aid substance is sodium lauroyl sarcosine.
The defoaming agent is one of organic silicon, polyethers, tributyl phosphate, polyacrylamide.
Preferably, the defoaming agent is polyacrylamide.
Phosphorous acid anhydride-glycol reactant in the present invention has preferable reproducibility to Cr VI, also has certain help Mill property；A large amount of carboxyl in multi-carboxy compound has stronger adsorption capacity to Cr VI, and can be with the Ca in cement2+、 Mg2+Etc. chelate is formed, while reducing the dissolution of Cr VI, strength of cement also can be improved；Potassium metabisulfite can not only accelerate Hydrated cementitious also has certain reproducibility, can restore the Cr VI in cement conducive to the raising of cement early strength；Inventor It was found that sodium lauroyl sarcosine has excellent grind -aiding effect, but also has bleed, strength of cement development is influenced, there are commonly The common defoaming agent such as machine silicon class, polyethers, tributyl phosphate can reduce foam, and it is strong to cement to reduce sodium lauroyl sarcosine The influence of degree, but cannot completely eliminate, and when sodium lauroyl sarcosine and polyacrylamide compound use, foam largely subtracts Few, the two synergistic effect does not influence strength of cement development, or even slightly improve when playing good grind -aiding effect.This hair Bright plurality of raw materials is closely connected and influences each other, by combination between interaction synergistic effect, be complementary to one another, be not only able to mention High cement grinding efficiency, raising strength of cement can also reduce content of 6-valence Cr ions in cement.
Beneficial effects of the present invention
(1) cement grinding aid of the present invention can high 10% or more mill hourly output, save cement grinding power consumption；Also have and increases Potent fruit, in the case where not changing cement mixing ratio, can make cement 3d intensity increase 3MPa or more, 28d intensity increase 5MPa with On, in the case where keeping cement performance constant, clinker dosage can be reduced, industrial residue is mostly used, economizes on resources, protects environment.
(2) cement grinding aid of the present invention has the function of water soluble hexavalent chromium in good reduction cement, varies without existing There is cement production process, it is easy to operate, it need to be only added in the form of grinding aid.
Specific embodiment
Embodiment 1
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 8%, more carboxylics Based compound 3%, grinding aid substance 3%, potassium metabisulfite 5%, defoaming agent 0.1%, surplus are water.
Phosphorous acid anhydride-the glycol reactant is the preparation method is as follows: equipped with agitating device, thermometer, condenser pipe Ethylene glycol, phosphorous acid anhydride (P are proportionally added into four-hole boiling flask4O6), catalyst and reaction dissolvent, be warming up to 80 DEG C, decompression is steamed Solvent is distillated, as described phosphorous acid anhydride-glycol reactant.
The catalyst is the concentrated sulfuric acid.
The solvent is acetone.
The ethylene glycol and phosphorous acid anhydride molar ratio are 4:1.
The catalyst amount is the 1% of ethylene glycol and phosphorous acid anhydride total weight.
The multi-carboxy compound is nitrilotriacetic acid trisodium salt.
The grinding aid substance is diethyl ethylene diamine.
The defoaming agent is organic silicon defoaming agent.
Embodiment 2
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 12%, more Carboxyl compound 1%, grinding aid substance 5%, potassium metabisulfite 1%, defoaming agent 1%, surplus are water.
Phosphorous acid anhydride-the glycol reactant is the preparation method is as follows: equipped with agitating device, thermometer, condenser pipe Ethylene glycol, phosphorous acid anhydride (P are proportionally added into four-hole boiling flask4O6), catalyst and reaction dissolvent, be warming up to 40 DEG C, decompression is steamed Solvent is distillated, as described phosphorous acid anhydride-glycol reactant.
The catalyst is anhydrous sodium acetate.
The solvent is tetrahydrofuran.
The ethylene glycol and phosphorous acid anhydride molar ratio are 12:1.
The catalyst amount is the 5% of ethylene glycol and phosphorous acid anhydride total weight.
The multi-carboxy compound is diethyl pentetic acid.
The grinding aid substance is N- aminoethyl ethanolamine.
The defoaming agent is polyethers defoaming agent.
Embodiment 3
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 10%, more Carboxyl compound 2%, grinding aid substance 4%, potassium metabisulfite 3%, defoaming agent 0.6%, surplus are water.
Phosphorous acid anhydride-the glycol reactant is the preparation method is as follows: equipped with agitating device, thermometer, condenser pipe Ethylene glycol, phosphorous acid anhydride (P are proportionally added into four-hole boiling flask4O6), catalyst and reaction dissolvent, be warming up to 60 DEG C, decompression is steamed Solvent is distillated, as described phosphorous acid anhydride-glycol reactant.
The catalyst is 2- naphthalene sulfonic acids.
The ethylene glycol and phosphorous acid anhydride molar ratio are 8:1.
The catalyst amount is the 3% of ethylene glycol and phosphorous acid anhydride total weight.
The multi-carboxy compound is trisodium hydroxyethylene diamine triacetate.
The grinding aid substance is sodium lauroyl sarcosine.
The defoaming agent is polyacrylamide.
Embodiment 4
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 9%, more carboxylics Based compound 2.5%, grinding aid substance 3.5%, potassium metabisulfite 4%, defoaming agent 0.3%, surplus are water.
Phosphorous acid anhydride-the glycol reactant is the preparation method is as follows: equipped with agitating device, thermometer, condenser pipe Ethylene glycol, phosphorous acid anhydride (P are proportionally added into four-hole boiling flask4O6), catalyst and reaction dissolvent, be warming up to 50 DEG C, decompression is steamed Solvent is distillated, as described phosphorous acid anhydride-glycol reactant.
The catalyst is anhydrous sodium acetate.
The solvent is hexamethylene.
The ethylene glycol and phosphorous acid anhydride molar ratio are 6:1.
The catalyst amount is the 2% of ethylene glycol and phosphorous acid anhydride total weight.
The multi-carboxy compound is diethyl pentetic acid.
The grinding aid substance is N- aminoethyl ethanolamine.
The defoaming agent is polyacrylamide.
Embodiment 5
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 11%, more Carboxyl compound 1.5%, grinding aid substance 4.5%, potassium metabisulfite 2%, defoaming agent 0.8%, surplus are water.
Embodiment 6
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 10%, more Carboxyl compound 2%, grinding aid substance 4%, potassium metabisulfite 3%, defoaming agent 0.6%, surplus are water.
Phosphorous acid anhydride-the glycol reactant is the preparation method is as follows: equipped with agitating device, thermometer, condenser pipe Ethylene glycol, phosphorous acid anhydride (P are proportionally added into four-hole boiling flask4O6), catalyst and reaction dissolvent, be warming up to 60 DEG C, decompression is steamed Solvent is distillated, as described phosphorous acid anhydride-glycol reactant.
The catalyst is 2- naphthalene sulfonic acids.
The ethylene glycol and phosphorous acid anhydride molar ratio are 8:1.
The catalyst amount is the 3% of ethylene glycol and phosphorous acid anhydride total weight.
The multi-carboxy compound is trisodium hydroxyethylene diamine triacetate.
The grinding aid substance is sodium lauroyl sarcosine.
The defoaming agent is tributyl phosphate.
Embodiment 7
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 10%, more Carboxyl compound 2%, grinding aid substance 4%, potassium metabisulfite 3%, defoaming agent 0.6%, surplus are water.
Phosphorous acid anhydride-the glycol reactant is the preparation method is as follows: equipped with agitating device, thermometer, condenser pipe Ethylene glycol, phosphorous acid anhydride (P are proportionally added into four-hole boiling flask4O6), catalyst and reaction dissolvent, be warming up to 60 DEG C, decompression is steamed Solvent is distillated, as described phosphorous acid anhydride-glycol reactant.
The catalyst is 2- naphthalene sulfonic acids.
The ethylene glycol and phosphorous acid anhydride molar ratio are 8:1.
The catalyst amount is the 3% of ethylene glycol and phosphorous acid anhydride total weight.
The multi-carboxy compound is trisodium hydroxyethylene diamine triacetate.
The grinding aid substance is diethyl ethylene diamine.
The defoaming agent is polyacrylamide.
Comparative example 1
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 10%, more Carboxyl compound 2%, grinding aid substance 4%, defoaming agent 0.6%, surplus are water.
Phosphorous acid anhydride-the glycol reactant is the preparation method is as follows: equipped with agitating device, thermometer, condenser pipe Ethylene glycol, phosphorous acid anhydride (P are proportionally added into four-hole boiling flask4O6), catalyst and reaction dissolvent, be warming up to 60 DEG C, decompression is steamed Solvent is distillated, as described phosphorous acid anhydride-glycol reactant.
The catalyst is 2- naphthalene sulfonic acids.
The ethylene glycol and phosphorous acid anhydride molar ratio are 8:1.
The catalyst amount is the 3% of ethylene glycol and phosphorous acid anhydride total weight.
The multi-carboxy compound is trisodium hydroxyethylene diamine triacetate.
The grinding aid substance is sodium lauroyl sarcosine.
The defoaming agent is polyacrylamide.
Comparative example 2
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride-glycol reactant 10% helps Grinding substance 4%, potassium metabisulfite 3%, defoaming agent 0.6%, surplus is water.
Phosphorous acid anhydride-the glycol reactant is the preparation method is as follows: equipped with agitating device, thermometer, condenser pipe Ethylene glycol, phosphorous acid anhydride (P are proportionally added into four-hole boiling flask4O6), catalyst and reaction dissolvent, be warming up to 60 DEG C, decompression is steamed Solvent is distillated, as described phosphorous acid anhydride-glycol reactant.
The catalyst is 2- naphthalene sulfonic acids.
The ethylene glycol and phosphorous acid anhydride molar ratio are 8:1.
The catalyst amount is the 3% of ethylene glycol and phosphorous acid anhydride total weight.
The grinding aid substance is sodium lauroyl sarcosine.
The defoaming agent is polyacrylamide.
Comparative example 3
A kind of cement grinding aid, by the material composition of following weight fraction: phosphorous acid anhydride 3.4%, ethylene glycol 5.6%, more Carboxyl compound 2.5%, grinding aid substance 3.5%, potassium metabisulfite 4%, defoaming agent 0.3%, surplus are water.
The multi-carboxy compound is diethyl pentetic acid.
The grinding aid substance is N- aminoethyl ethanolamine.
The defoaming agent is polyacrylamide.
Performance test
The obtained cement grinding aid of embodiment 1-7 and comparative example 1-3 is tested for the property, by clinker, gypsum, fine coal After ash and the cooperation of slag ratio, a small amount of potassium bichromate is added, uniformly sprays grinding aid on surface, volume is grinding material total weight 0.1%, enter milling mill 35min, grinding machine is Wuxi Jianyi Instrument Machinery Co., Ltd. model SM-500 produced test Mill；Strength of cement mortar measurement is carried out by GB/T17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) "；Cr VI ginseng It is tested according to method specified in GB31893-2015 " limitation and measuring method of water soluble chromium (VI) in cement ".
As a result it see the table below 1.
1 additive the performance test results of table

Claims (8)

1. a kind of cement grinding aid, which is characterized in that by the material composition of following weight fraction: phosphorous acid anhydride-glycol reaction Object 8-12%, multi-carboxy compound 1-3%, grinding aid substance 3-5%, potassium metabisulfite 1-5%, defoaming agent 0.1-1%, surplus are Water.
2. cement grinding aid according to claim 1, which is characterized in that the phosphorous acid anhydride-glycol reactant preparation Method is as follows: being proportionally added into ethylene glycol, phosphorous acid anhydride in the four-hole boiling flask for being furnished with agitating device, thermometer, condenser pipe (P4O6), catalyst and reaction dissolvent, are warming up to 40-80 DEG C, are evaporated under reduced pressure away solvent, as described phosphorous acid anhydride-second Diol reactant.
3. cement grinding aid according to claim 2, which is characterized in that the catalyst be the concentrated sulfuric acid, anhydrous sodium acetate, One of 2- naphthalene sulfonic acids.
4. cement grinding aid according to claim 2, which is characterized in that the solvent is acetone, tetrahydrofuran, hexamethylene One of.
5. cement grinding aid according to claim 2, which is characterized in that the ethylene glycol is 4- with phosphorous acid anhydride molar ratio 12:1。
6. cement grinding aid according to claim 1, which is characterized in that the multi-carboxy compound is nitrilotriacetic acid three One of sodium, diethyl pentetic acid, trisodium hydroxyethylene diamine triacetate.
7. cement grinding aid according to claim 1, which is characterized in that the grinding aid substance is diethyl ethylene diamine, N- One of aminoethyl ethanolamine, sodium lauroyl sarcosine.
8. cement grinding aid according to claim 1, which is characterized in that the defoaming agent is organic silicon, polyethers, phosphorus One of sour tributyl, polyacrylamide.
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Cited By (3)

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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
CN110981238A (en) * 2019-12-21 2020-04-10 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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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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