阅读说明：本技术 一种新型粉体水泥助磨剂的配方及制备工艺 (Formula and preparation process of novel powder cement grinding aid ) 是由 宋素亚 李倩 张长帮 齐兴波 于 2020-09-10 设计创作，主要内容包括：本发明涉及水泥助磨剂技术领域,且公开了一种新型水泥助磨剂的配方及制备工艺,包括以下重量份数配比的原料：醇胺3-5份、腐植酸钾5-10份、硫氰酸钠2-5份、元明粉20-35份、硅灰25-35份、六价铬消减剂10-25份以及稳定剂7-10份。该新型粉体水泥助磨剂,化学稳定性以及还原效率大大提高,克服了无水硫酸钙的吸湿性的同时也克服了硫酸亚铁和醋酸锰易潮解的缺点,大大的增加了硫酸亚铁的抗氧化性能,降低了水泥粉磨的时间,极大程度上节约了能耗,且具有良好除铬性、助磨性、早强性及化学稳定性,同时不含氯盐对环境友好,应用范围广,值得大范围的推广使用,对我国的基建工程带来了巨大便利性,同时使得水泥在进行浇灌或者完全干燥之后的物理强度大大提高。(The invention relates to the technical field of cement grinding aids, and discloses a formula and a preparation process of a novel cement grinding aid, which comprises the following raw materials in parts by weight: 3-5 parts of alcohol amine, 5-10 parts of potassium humate, 2-5 parts of sodium thiocyanate, 20-35 parts of anhydrous sodium sulphate, 25-35 parts of silica fume, 10-25 parts of hexavalent chromium reducing agent and 7-10 parts of stabilizing agent. This novel powder cement grinding aid, chemical stability and reduction efficiency improve greatly, also overcome the shortcoming that ferrous sulfate and manganese acetate are easy to deliquesce when having overcome anhydrous calcium sulfate's hygroscopicity, great increase the antioxidant property of ferrous sulfate, the time of cement grinding has been reduced, the energy consumption has been practiced thrift to very big degree, and have good chromium removing nature, grinding aid, early strength nature and chemical stability, it is friendly to the environment not contain the chlorate simultaneously, the range of application is wide, be worth using widely on a large scale, the capital construction engineering to china has brought huge convenience, make the physical strength of cement after watering or complete drying improve greatly simultaneously.)

1. The formula and the preparation process of the novel cement grinding aid are characterized by comprising the following raw materials in parts by weight: 3-5 parts of alcohol amine, 5-10 parts of potassium humate, 2-5 parts of sodium thiocyanate, 20-35 parts of anhydrous sodium sulphate, 25-35 parts of silica fume, 10-25 parts of hexavalent chromium reducing agent and 7-10 parts of stabilizing agent.

2. The formula and the preparation process of the novel powder cement grinding aid according to claim 1 are characterized by comprising the following steps:

1) uniformly mixing alcohol amine, potassium humate, sodium thiocyanate, anhydrous sodium sulphate and silica fume;

2) uniformly mixing the hexavalent chromium reducing agent, adding the stabilizing agent, and continuously and uniformly mixing to obtain the hexavalent chromium reducing agent;

3) and mixing the powder cement grinding aid obtained in the step 1) and the step 2) to obtain the powder cement grinding aid.

3. The formula and the preparation process of the novel powder cement grinding aid according to claim 1 are characterized in that: the alcohol amine is one or two mixtures of diethanol monoisopropanolamine and triglycerol.

4. The formula and the preparation process of the novel powder cement grinding aid according to claim 1 are characterized in that: the hexavalent chromium reducing agent comprises 3-8 parts of stannous sulfate, 5-15 parts of ferrous sulfate and 2-5 parts of manganese acetate, wherein the ratio of the manganese acetate to the stannous sulfate is 2: 3.

5. The formula and the preparation process of the novel powder cement grinding aid according to claim 1 are characterized in that: the stabilizer is 5-8 parts of sodium lignosulphonate, 1-3 parts of anhydrous calcium sulfate and 0.5-1.5 parts of calcium stearate.

Technical Field

The invention relates to the technical field of cement grinding aids, in particular to a formula and a preparation process of a novel powder cement grinding aid.

Background

The hexavalent chromium in the cement is derived from the raw material of the cement and the metallic chromium or chromium compound mixed in during the processing. It has high solubility, strong toxicity, strong oxidation, cell membrane permeability, carcinogenic risk by inhalation, pain sensitivity by skin contact, inflammation and ulcer, and labor loss in severe cases. When the fresh concrete containing soluble hexavalent chromium contacts with underground water, the fresh concrete can pollute the underground water source and directly affect the soil cultivation and the water source drinking.

The harmfulness of hexavalent chromium is discovered in the 50 s of the 20 th century abroad, and the 2003 European Union proposes that water-soluble hexavalent chromium cement with hydration exceeding 2ppm and products thereof are prohibited from being sold and used in the market, and has formal release and effect in 2005. The comprehensive research and statistics work of the hexavalent chromium condition of domestic cement is carried out in China since 2005, and GB31893-2015 limit and determination method of water-soluble chromium in cement is formally implemented in China in 2016, the water-soluble hexavalent chromium in cement is required to be lower than 10ppm, which is different from a general recommended standard, which is a mandatory standard and has a great influence on cement enterprises.

At present, a cement plant generally selects ferrous sulfate to reduce the content of hexavalent chromium in cement, has the advantages of low price, obvious reduction effect and the like, and gradually solves the problems of poor chemical stability and large addition amount of the hexavalent chromium along with the continuous application of the hexavalent chromium. Stannous chloride, which also has excellent reducing effect, has limited wide-scale use due to its high cost. Other single-component reducing agents, such as divalent manganese salt, polysulfide compound, aldehyde compound and the like, have the restriction factors of poor reducing effect, toxicity, harm and the like, so that the popularization and the use are influenced.

In addition, the domestic powder grinding aid has single variety and function, and needs to be developed towards the research and development direction of the powder grinding aid which integrates high efficiency, compound type, environmental protection, harmlessness and low cost, so that the energy-saving and consumption-reducing force is increased from multiple angles, and the cement performance is improved.

Disclosure of Invention

Technical problem to be solved

The invention aims to solve the problems and provides a formula and a preparation process of a novel powder cement grinding aid, which have the advantages of high reduction efficiency and high chemical stability.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a formula and a preparation process of a novel powder cement grinding aid comprise the following raw materials in parts by weight: 3-5 parts of alcohol amine, 5-10 parts of potassium humate, 2-5 parts of sodium thiocyanate, 20-35 parts of anhydrous sodium sulphate, 25-35 parts of silica fume, 10-25 parts of hexavalent chromium reducing agent and 7-10 parts of stabilizing agent.

A formula and a preparation process of a novel powder cement grinding aid are characterized by comprising the following steps:

1) uniformly mixing alcohol amine, potassium humate, sodium thiocyanate, anhydrous sodium sulphate and silica fume;

2) uniformly mixing the hexavalent chromium reducing agent, adding the stabilizing agent, and continuously and uniformly mixing to obtain the hexavalent chromium reducing agent;

3) and mixing the powder cement grinding aid obtained in the step 1) and the step 2) to obtain the powder cement grinding aid.

Preferably, the alcohol amine is one or two mixtures of diethanol monoisopropanolamine and triglycerol.

Preferably, the hexavalent chromium reducing agent comprises 3-8 parts of stannous sulfate, 5-15 parts of ferrous sulfate and 2-5 parts of manganese acetate, wherein the ratio of the manganese acetate to the stannous sulfate is 2: 3.

Preferably, the stabilizer is 5-8 parts of sodium lignosulphonate, 1-3 parts of anhydrous calcium sulfate and 0.5-1.5 parts of calcium stearate.

(III) advantageous effects

Compared with the prior art, the invention provides a formula and a preparation process of a novel powder cement grinding aid, and the formula and the preparation process have the following beneficial effects:

1. the novel powder cement grinding aid greatly improves the chemical stability and the reduction efficiency, overcomes the defects of easy deliquescence of ferrous sulfate and manganese acetate while overcoming the hygroscopicity of anhydrous calcium sulfate, greatly increases the oxidation resistance of the ferrous sulfate, reduces the cement grinding time, and greatly saves the energy consumption.

2. This novel powder cement grinding aid for the early intensity of cement has obtained very big improvement, greatly increased the mobility of cement paste, reduced the porosity, improved the intensity and the compactedness of cement, make the physical strength of cement after watering or complete drying improve greatly.

3. The novel powder cement grinding aid has good chromium removal performance, grinding aid performance, early strength and chemical stability, does not contain chloride, is environment-friendly, has wide application range, is worthy of being popularized and used in a large range, and brings great convenience to the capital construction engineering of China.

Drawings

FIG. 1 is a graph showing the results of the experiment according to the embodiment of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, 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.

According to the invention, stannous sulfate, ferrous sulfate and manganese acetate are compounded according to a certain proportion, so that stannous ions, ferrous ions and manganese ions jointly reduce water-soluble hexavalent chromium ions into insoluble trivalent chromium, in the process, the defect that ferrous sulfate and manganese acetate are easy to deliquesce is overcome by utilizing the hygroscopicity of anhydrous calcium sulfate, calcium stearate can be attached to the surface of ferrous sulfate to serve as a wrapping layer, the oxidation resistance of ferrous sulfate is greatly improved, in addition, the heat stability of calcium stearate is good, the oxidation resistance of calcium stearate can be effectively exerted in a high-temperature state in a grinding process, sodium lignosulfonate can also perform a complexing action with metal ions, so that ferrous ions and stannous ions in a solution are stably kept and are not oxidized, therefore, the compounding of the hexavalent chromium reducing agent and the reasonable collocation of the stabilizing agent enable the hexavalent chromium reducing agent to be used simply compared with the traditional method that ferrous sulfate and manganese acetate are used singly, Compared with stannous sulfate or manganese acetate, the consumption is greatly reduced, and the reduction efficiency and the chemical stability are also greatly improved.

According to the invention, liquid alcohol amine and powdery raw materials such as silica fume are premixed, alcohol amine molecules are firstly adsorbed on the surfaces of the raw materials such as silica fume, and the like, because the silica fume particles are small and the specific surface area is large, the alcohol amine molecules can be more uniformly adsorbed on the surfaces of the raw material particles such as silica fume in the premixing process, and then the alcohol amine molecules are attached to the surfaces of the cement particles through continuous friction and collision with the cement particles in the cement grinding process to form a monomolecular adsorption film to play a role in lubricating and grinding the cement particles, and meanwhile, the microscopic form of the silica fume is of an amorphous spherical structure, and the function of a micro mill is also played. The addition of the potassium humate, the sodium thiocyanate and the anhydrous sodium sulphate can participate in the hydration process of the cement, and the three synergistically excite the activity of the mineral admixture, thereby being beneficial to rapidly improving the early strength of the cement. The sodium lignosulfonate as an anionic surfactant also has a water reducing effect, so that the fluidity of cement paste can be improved, the porosity is reduced, and the strength and the compactness of cement are improved.

The prepared hexavalent chromium reducing agent is used as a part of the powder cement grinding aid, so that the powder cement grinding aid has the function of removing hexavalent chromium, and the cement grinding aid is beneficial to advancing towards a high-efficiency diversified direction. The powder grinding aid provided by the invention has good chromium removal performance, grinding aid performance, early strength and chemical stability, and meanwhile, the powder grinding aid does not contain chloride, is environment-friendly and has a wide application range.

The first embodiment is as follows:

3 parts of diethanol monoisopropanolamine, 7 parts of potassium humate, 3 parts of sodium thiocyanate, 32 parts of anhydrous sodium sulphate, 28 parts of silica fume, 20 parts of hexavalent chromium reducing agent and 7 parts of stabilizing agent.

The hexavalent chromium reducing agent comprises 6 parts of stannous sulfate, 10 parts of ferrous sulfate and 4 parts of manganese acetate.

The stabilizer comprises 5 parts of sodium lignosulphonate, 1 part of anhydrous calcium sulfate and 1 part of calcium stearate.

The proportion of the cement is 65 percent of cement clinker; 5% of gypsum; 22% of slag; 3 percent of fly ash and 5 percent of stone powder, when the grinding time is 45 minutes and the fineness is 2.5 percent, the 3d flexural strength obtained after the cement is hardened is 6.4MPa, the 3d compressive strength is 31.5MPa, the 28d flexural strength is 9.3MPa, the 28d compressive strength is 56.2MPa, and the content of hexavalent chromium is 7.5 ppm.

Example two:

2 parts of diethanol monoisopropanolamine, 3 parts of triglycerol, 5 parts of potassium humate, 4 parts of sodium thiocyanate, 25 parts of anhydrous sodium sulphate, 35 parts of silica fume, 17 parts of hexavalent chromium reducing agent and 9 parts of stabilizing agent.

The hexavalent chromium reducing agent comprises 3 parts of stannous sulfate, 12 parts of ferrous sulfate and 2 parts of manganese acetate.

The stabilizer comprises 6 parts of sodium lignosulphonate, 2 parts of anhydrous calcium sulfate and 1 part of calcium stearate.

The proportion of the cement is 65 percent of cement clinker; 5% of gypsum; 22% of slag; 3 percent of fly ash and 5 percent of stone powder, when the grinding time is 40 minutes and the fineness is 1.8 percent, the 3d flexural strength obtained after the cement is hardened is 6.3MPa, the 3d compressive strength is 30.4MPa, the 28d flexural strength is 9.1MPa, the 28d compressive strength is 57MPa, and the content of hexavalent chromium is 8.5 ppm.

Example three:

3 parts of diethanol monoisopropanolamine, 1 part of triglycerol, 9 parts of potassium humate, 2 parts of sodium thiocyanate, 20 parts of anhydrous sodium sulphate, 30 parts of silica fume, 25 parts of hexavalent chromium reducing agent and 10 parts of stabilizing agent.

The hexavalent chromium reducing agent comprises 7.5 parts of stannous sulfate, 12.5 parts of ferrous sulfate and 5 parts of manganese acetate.

The stabilizer comprises 8 parts of sodium lignosulphonate, 1.5 parts of anhydrous calcium sulfate and 0.5 part of calcium stearate.

The proportion of the cement is 65 percent of cement clinker; 5% of gypsum; 22% of slag; 3 percent of fly ash and 5 percent of stone powder, when the grinding time is 43 minutes and the fineness is 3.3 percent, the 3d flexural strength obtained after the cement is hardened is 6.0MPa, the 3d compressive strength is 29.8Pa, the 28d flexural strength is 9.0MPa, the 28d compressive strength is 55.8MPa, and the content of hexavalent chromium is 6 ppm.

The preparation of the three groups of examples described above is described in the summary of the invention.

The three powder cement grinding aids are added according to the weight ratio of 0.5 percent of the cement, and the mixture ratio of the cement is as follows: 65% of cement clinker, 5% of gypsum, 22% of slag, 3% of fly ash and 5% of stone powder. The raw materials are subjected to a mixed grinding test in a ball mill, and the grinding time, the fineness (80um screen residue), the flexural strength, the compressive strength and the water-soluble hexavalent chromium content of the obtained 42.5 cement with the specific surface area of 450m2/kg are controlled, wherein the water-soluble hexavalent chromium content is determined by adopting the GB31893-2015 standard, and the test result is shown in the attached drawing.

In conclusion, the powder cement grinding aid greatly improves the chemical stability and the reduction efficiency, overcomes the moisture absorption of anhydrous calcium sulfate, overcomes the defect that ferrous sulfate and manganese acetate are easy to deliquesce, reduces the porosity, improves the strength and the compactness of cement, and greatly improves the physical strength of the cement after being poured or completely dried.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.