阅读说明：本技术 一种锰渣超硫酸盐水泥及其制备方法 (Manganese slag super-sulfate cement and preparation method thereof ) 是由 艾洪祥 李增亮 孟书灵 王军 张平 岳彩虹 于 2019-09-30 设计创作，主要内容包括：本发明属于特种水泥技术领域,具体涉及一种锰渣超硫酸盐水泥及其制备方法。所述锰渣超硫酸盐水泥由锰渣、粒化高炉矿渣粉、硫酸盐类、硫酸盐激发剂、碱性成分和碱性激发剂组成,各组分按重量百分比计为：锰渣30～40％,粒化高炉矿渣粉25～50％,硫酸盐类10～20％,硫酸盐激发剂5～10％,碱性成分1～5％,碱性激发剂0.05～2％。本发明以锰铁合金或硅锰合金在高炉冶炼过程中排放的高温炉渣废弃物—锰渣为主要原材料,结合材料学原理,以锰渣、矿渣各自的矿物特性为基础,利用硫酸盐类和碱性环境激活锰渣的潜在水化活性,从而形成初期强度,进而设计出性能优良的新型锰渣超硫酸盐水泥。(The invention belongs to the technical field of special cement, and particularly relates to manganese slag super-sulfate cement and a preparation method thereof. The manganese slag super-sulfate cement is composed of manganese slag, granulated blast furnace slag powder, sulfate, a sulfate activator, an alkaline component and an alkaline activator, and the components are calculated according to the weight percentage: 30-40% of manganese slag, 25-50% of granulated blast furnace slag powder, 10-20% of sulfate, 5-10% of sulfate activator, 1-5% of alkaline component and 0.05-2% of alkaline activator. The invention takes manganese slag, which is a high-temperature slag waste discharged in the blast furnace smelting process of ferromanganese alloy or silicon-manganese alloy, as a main raw material, combines the principle of materials science, takes the respective mineral characteristics of the manganese slag and the slag as the basis, and utilizes sulfate and alkaline environment to activate the potential hydration activity of the manganese slag, thereby forming the initial strength and further designing the novel manganese slag super-sulfate cement with excellent performance.)

1. The manganese slag super-sulfate cement is characterized by comprising manganese slag, granulated blast furnace slag powder, sulfate, a sulfate activator, an alkaline component and an alkaline activator, wherein the manganese slag super-sulfate cement comprises the following components in percentage by weight: 30-40% of manganese slag, 25-50% of granulated blast furnace slag powder, 10-20% of sulfate, 5-10% of sulfate activator, 1-5% of alkaline component and 0.05-2% of alkaline activator.

2. The manganese slag super-sulfate cement according to claim 1, wherein the manganese slag super-sulfate cement comprises the following components in percentage by weight: 30% of manganese slag, 50% of granulated blast furnace slag powder, 10% of sulfate, 5% of sulfate activator, 3% of alkaline component and 2% of alkaline activator.

3. The manganese slag super-sulfate cement according to claim 1, wherein the alkali activator is one or more of sodium silicate, potassium silicate, calcium phosphate, potassium carbonate, and calcium carbonate.

4. The manganese slag super-sulfate cement of claim 1, wherein said alkaline component is one or more of cement clinker, calcium hydroxide and magnesium hydroxide.

5. The manganese slag supersulfate cement of claim 1, wherein said sulfate is one or more of desulfurized gypsum, phosphogypsum, and dihydrate gypsum.

6. The manganese slag super-sulfate cement of claim 1, wherein the sulfate excitant is one or more of sodium sulfate, potassium sulfate and magnesium sulfate.

7. The manganese slag super-sulfate cement according to claim 1, wherein the manganese slag and the granulated blast furnace slag each have a specific surface area of 400m after grinding²/kg~450 m²Per kg; the specific surface area of the alkali component, the alkali excitant, the sulfate and the sulfate excitant is 450m after being ground²/kg~500 m²/kg。

8. The method for preparing the manganese slag super-sulfate cement as set forth in any one of claims 1 to 7, characterized by comprising the steps of: the manganese slag super-sulfate cement is prepared by a mixing grinding method, a material mixing method or a direct powder grinding method after the raw materials of the components are weighed according to the formula.

9. The preparation method according to claim 8, wherein the process of the mixed grinding method and the direct grinding method comprises the following steps: adding the raw materials into a cement mill according to the formula proportion, mixing and milling, and after the mixture is fully and uniformly mixed and milled, the specific surface area is 400m²/Kg~500 m²And when the cement is/kg, obtaining the manganese slag super-sulfate cement.

10. The preparation method according to claim 8, wherein the mixing method comprises the following steps: adding the raw materials into a forced mixer according to the formula ratio, and fully and uniformly mixing the mixture to obtain the manganese slag super-sulfate cement.

Technical Field

The invention belongs to the technical field of special cement, and particularly relates to manganese slag super-sulfate cement and a preparation method thereof.

Background

Concrete is the most used building material, cement is one of important materials for forming concrete, and the total yield of cement is rapidly increased from 1980 along with the continuous increase of GDP and urbanization construction in China. In the last 40 years, the total GDP value and the total cement yield are steadily increased, and the increasing rate is higher and higher, and the total yield of the portland cement is increased from millions of tons to 16 hundred million tons.

The cement production is so great that the cement clinker required for the production of ordinary portland cement needs to go through a "two-mill one-firing" process, in which a large amount of raw materials such as limestone, clay and non-renewable resource coal are required, and a small amount of aluminum ore, iron ore, etc. is also required to adjust the oxide components in the raw meal to supplement the alumina and iron oxide required in the clinker. The production of portland cement is energy-intensive processing, and energy consumption per ton is about 4 GJ; at the same time, 178kg of standard coal is consumed for producing 1t of portland cement clinker, and about 1t of CO is discharged₂The gases, which are accompanied by the production of harmful gases such as CO and SOX, increase the load on the global environment in the form of greenhouse effect and acid rain.

The super-sulfate cement (also called gypsum slag cement) is a low-clinker or clinker-free cement which uses granulated blast furnace slag as main raw material, gypsum as sulfate excitant and clinker or lime as alkali excitant. It is usually composed of slag, sulfates (such as dihydrate gypsum, anhydrite, phosphogypsum, etc.) and alkaline components (such as clinker, calcium hydroxide, lime, etc.). The super-sulfate cement does not need to be calcined, but the raw materials are ground to a certain fineness and uniformly mixed, the production process is simple, the cost is low, the industrial slag can be fully utilized, and the super-sulfate cement belongs to energy-saving cement. The energy consumption for preparing the super-sulfate cement is 95 kW.h/t, and the energy consumption for preparing the ordinary portland cement is 905 kW.h/t, so that the super-sulfate cement has unique advantages in energy conservation. Meanwhile, the super-sulfate cement has good service performance, excellent durability and low heat of hydration, and is a very ideal hydraulic cementing material.

At present, 70-80M.% of slag, 10-20M.% of sulfate (such as dihydrate gypsum or desulfurized gypsum) and 1-5M.% of alkaline components (such as clinker, calcium hydroxide and alkaline hydroxide) are mainly adopted in the production formula of the super-sulfate cement. The super-sulphate cement produced in this way has two very serious drawbacks: firstly, the setting time of the super-sulfate cement is too long, and secondly, the early strength of the super-sulfate cement is too low. Aiming at the defect of overlong setting time of the traditional super-sulfate cement, laboratories in China use self-prepared chemical exciting agents to change the mixing amount of the exciting agents, and the obtained self-prepared chemical exciting agents with proper amount can effectively shorten the setting time of the super-sulfate cement; aiming at the problem of low early strength of the traditional super-sulfate cement, researches find that if high-activity slag (Al) is used₂O₃High slag content) can solve the problem of low early strength of super-sulfate cement. At present, slag is widely adopted internationally to obtain super-sulfate cement, but no relevant patent exists for producing novel manganese slag super-sulfate cement by using manganese slag.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides manganese slag super-sulfate cement and a preparation method thereof.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:

the manganese slag super-sulfate cement consists of manganese slag, granulated blast furnace slag powder, sulfate, a sulfate excitant, an alkaline component and an alkaline excitant, and the components in percentage by weight are as follows: 30-40% of manganese slag, 25-50% of granulated blast furnace slag powder, 10-20% of sulfate, 5-10% of sulfate activator, 1-5% of alkaline component and 0.05-2% of alkaline activator.

In the scheme, the manganese slag super-sulfate cement comprises the following components in percentage by weight: 30% of manganese slag, 50% of granulated blast furnace slag powder, 10% of sulfate, 5% of sulfate activator, 3% of alkaline component and 2% of alkaline activator.

In the above scheme, the alkali activator is one or more of sodium silicate, potassium silicate, calcium phosphate, potassium carbonate, and calcium carbonate.

In the above scheme, the alkaline component is one or more of cement clinker, calcium hydroxide and magnesium hydroxide.

In the scheme, the sulfate is one or more of desulfurized gypsum, phosphogypsum and dihydrate gypsum.

In the above scheme, the sulfate excitant is one or more of sodium sulfate, potassium sulfate and magnesium sulfate.

In the scheme, the specific surface areas of the manganese slag and the granulated blast furnace slag after being ground are both 400m²/kg～450m²Per kg; the specific surface area of the alkali component, the alkali excitant, the sulfate and the sulfate excitant is 450m after being ground²/kg～500m²/kg。

The preparation method of the manganese slag super-sulfate cement comprises the following steps: the manganese slag super-sulfate cement is prepared by a mixing grinding method, a material mixing method or a direct powder grinding method after the raw materials of the components are weighed according to the formula.

In the scheme, the processes of the mixed grinding method and the direct grinding method are as follows: adding the raw materials into a cement mill according to the formula proportion, mixing and milling, and after the mixture is fully and uniformly mixed and milled, the specific surface area is 400m²/Kg～500m²And when the cement is/kg, obtaining the manganese slag super-sulfate cement.

In the above scheme, the mixing method comprises the following steps: adding the raw materials into a forced mixer according to the formula ratio, and fully and uniformly mixing the mixture to obtain the manganese slag super-sulfate cement.

The invention has the beneficial effects that:

(1) the industrial waste generated in China every year is more, the resource advantage is certain, the slag with higher price is replaced by the manganese slag with low price, and the phosphogypsum or the desulfurized gypsum and the dihydrate gypsum are used, so that the industrial waste can be fully utilized, and the purposes of saving resources, protecting the environment and utilizing the waste are achieved; in addition, because the main raw materials are industrial solid wastes which are used as the building cementing materials, the industrial wastes which are difficult to be utilized can be recycled, the stockpiling land can be saved, and the method has important significance for protecting natural resources such as limestone, fuel and the like.

(2) The invention takes manganese slag, which is a high-temperature slag waste discharged in the blast furnace smelting process of ferromanganese alloy or silicon-manganese alloy, as a main raw material, combines the principle of materials science, takes the respective mineral characteristics of the manganese slag and the slag as the basis, and utilizes sulfate and alkaline environment to activate the potential hydration activity of the manganese slag, thereby forming the initial strength and further designing the novel manganese slag super-sulfate cement with excellent performance.

(3) The use of the phosphogypsum, the desulfurized gypsum or the dihydrate gypsum in the formula design is beneficial to the development of the strength of the super-sulfate cement, so that the induction period in the hydration process of the super-sulfate cement is longer (more than 2 d), the acceleration period and the deceleration period are also prolonged to a certain extent, and the super-sulfate cement releases a large amount of S0 at the initial stage of hydration₄ ^2-Sufficient ettringite and hydrated calcium silicate are formed to ensure early strength of the cement.

(4) In the formula design, under the condition that the alkalinity is less than that required by formation of ettringite, proper alkaline components and alkaline exciting agents are added to meet the alkalinity required by formation of ettringite and accelerate the exertion of slag potential activity and manganese slag potential hydration activity.

(5) The novel manganese slag super-sulfate cement with less clinker or no clinker has the strength of 32.5MPa or 42.5MPa, the content of disulfide trioxide is controlled to be not less than 4.5 percent in the invention, and other indexes all meet the requirements of national standards on ordinary portland cement with corresponding strength grade.

(6) Energy conservation and environmental protection: compared with the production of the traditional ordinary Portland cement, 1 ton of manganese slag super-sulfate cement can save energy by 80-90%, and has extremely low environmental load, and CO discharged in the production process₂The amount is only 10% of the conventional ordinary portland cement.

(7) The cost is low: the manufacturing cost of the manganese slag super-sulfate cement is about 50-60% of that of the conventional ordinary Portland cement.

(8) The preparation process of the manganese slag super-sulfate cement is simple, practical, reliable and suitable for industrial production.

(9) The manganese slag super-sulfate cement has the advantages of lower hydration heat, smaller volume change rate, excellent sulfate corrosion resistance and higher later strength, and the basic components are materials for inhibiting alkali-aggregate reaction, so that the damage of the alkali-aggregate reaction does not exist in practical application.

(10) Compared with the traditional super-sulfate cement, the manganese slag super-sulfate cement has shorter initial setting time and improves the early strength of the super-sulfate cement, the initial setting time can be advanced from 6 hours of the common super-sulfate cement to about 2.5 hours, and the final setting time can be advanced from 10 hours of the common super-sulfate cement to about 6 hours.

In summary, the following steps: the manganese slag super-sulfate cement provided by the invention is clinker-free or clinker-less cement with excellent durability, the used raw materials are mainly industrial solid wastes, and the industrial solid wastes are used as building cementing materials, so that the industrial wastes which are difficult to utilize can be recycled, the stockpiling land can be saved, the cost is reduced, the environment is protected, the resources are saved, the preparation process is simple and reliable, and the manganese slag super-sulfate cement is suitable for industrial production and practical engineering application.

Detailed Description

In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.