Clinker-free solid waste system cement and manufacturing method thereof
阅读说明：本技术 无熟料固废体系水泥及其制造方法 (Clinker-free solid waste system cement and manufacturing method thereof ) 是由 李端乐 刘传胜 段崇国 崔勇 于 2021-09-24 设计创作，主要内容包括：本发明提供一种无熟料固废体系水泥及其制备方法,该熟料固废体系水泥由以下原料制备而得：石膏10～20％,钢渣10～20％,矿渣60～75％,钢渣-矿渣早期活性强度激发剂0.1～0.5％,所述百分比均为质量百分比。添加了钢渣-矿渣早期活性强度激发剂可以解决该水泥早期强度低,易碳化,抗风化能力差等问题,另外,无熟料固废体系水泥具有良好的颗粒级配和较低的需水量,采用较低水胶比和用水量能够保证砂浆和混凝土具有满足工程要求的强度和耐久性。而且该水泥不用熟料而用固废,既可以保护环境又可以节约生产成本。(The invention provides clinker-free solid waste system cement and a preparation method thereof, wherein the clinker-free solid waste system cement is prepared from the following raw materials: 10-20% of gypsum, 10-20% of steel slag, 60-75% of slag, and 0.1-0.5% of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percentages. The addition of the steel slag-slag early-stage active strength excitant can solve the problems of low early-stage strength, easy carbonization, poor weather resistance and the like of the cement, in addition, the cement of a clinker-free solid waste system has good particle size distribution and lower water demand, and the mortar and the concrete can be ensured to have strength and durability meeting engineering requirements by adopting lower water-cement ratio and water consumption. And the cement is solid waste without clinker, so that the environment can be protected and the production cost can be saved.)
1. A clinker-free solid waste system cement is characterized in that,
the clinker-free solid waste system cement comprises the following components: the steel slag and slag, gypsum and steel slag-slag early-stage active strength excitant used as solid waste are as follows: 10-20% of gypsum, 10-20% of steel slag, 60-75% of slag, 0.1-0.5% of steel slag-slag early-stage active strength excitant, and the percentages are mass percentages.
2. The clinker-free solid waste system cement as recited in claim 1,
the gypsum is industrial desulfurization gypsum and the density of the gypsum is 2.2g/cm3～2.3g/cm3。
3. The clinker-free solid waste system cement as recited in claim 1,
the steel slag has a density of 3.0g/cm3～3.1g/cm3The steel slag powder.
4. The clinker-free solid waste system cement as recited in claim 1,
the slag has a density of 2.9g/cm3～3.1g/cm3The tailing micro powder.
5. The clinker-free solid waste system cement as recited in claim 1,
the steel slag-slag early-stage active strength excitant is one or a mixture of more of calcium oxide, triethanolamine, triisopropanolamine, polycarboxylic acid, diethanolamine and polyhydric alcohol.
6. The clinker-free solid waste system cement as recited in claim 1,
the formula proportion of the clinker-free solid waste system cement is as follows: 10% of gypsum, 20% of steel slag, 70% of slag and 0.5% of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percentages.
7. The clinker-free solid waste system cement as recited in claim 1,
the formula proportion of the clinker-free solid waste system cement is as follows: 15% of gypsum, 10% of steel slag, 75% of slag and 0.3% of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percentages.
8. The clinker-free solid waste system cement as recited in claim 1,
the clinker-free solid waste system cement comprises the following components in percentage by weight: 17% of gypsum, 13% of steel slag, 70% of slag and 0.4% of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percentages.
9. The clinker-free solid waste system cement as claimed in claim 1, wherein the formula ratio of the clinker-free solid waste system cement is as follows: 12% of gypsum, 15% of steel slag, 73% of slag and 0.5% of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percentages.
10. A method for preparing the cement of the clinker-free solid waste system of any one of claims 1 to 9,
and adding the gypsum, the steel slag and the slag into a ball mill according to the formula proportion, adding the steel slag-slag early-stage active strength excitant according to 0.1-0.5% of the total mass of the mixed materials, grinding to a 45-micrometer sieve, and sieving with the residue not more than 10%, thereby obtaining the clinker-free solid waste system cement.
Technical Field
The invention belongs to the field of cement production, and particularly relates to clinker-free solid waste system cement and a manufacturing method thereof.
Background
Comprehensive utilization of industrial solid wastes (solid wastes for short) is an important component of new energy-saving and environment-friendly strategic industries. According to statistics, the generation amount of massive industrial solid wastes in 2019 in China is 36.98 hundred million tons, wherein the generation amount of metallurgical slag accounts for 17.85%, the generation amount of industrial by-products, namely stone plants accounts for 6.11%, the generation amount of the two is nearly 10 hundred million tons, the generation amount of steel slag in the metallurgical slag of steel is 1.5 million tons, but the comprehensive utilization rate of the steel slag is less than 40%, and the deep utilization of blast furnace water quenching slag has huge potential to be deeply excavated. A large amount of solid wastes occupy the land for piling up, which not only brings various problems of environment, safety and the like, but also causes great economic pressure to enterprises.
The problems of environmental pollution and potential safety hazards caused by improper disposal and stockpiling of industrial solid wastes are solved, and the upgrading of an industrial structure, energy conservation and emission reduction are urgently realized.
With respect to low carbonation, studies have shown that CO emissions from the manufacture of conventional cements2Occupies the global CO2The emission is 7%, and the carbon emission of the cement industry is mainly from the production process of cement clinker. The data show that 0.161-0.296 t coal is required for producing 1t clinker, and 0.383-0.704 tC0 is generated by burning the coal2Adding C0 produced by decomposition of calcium carbonate during clinker formation20.894-1.215 tC0 is discharged every 1t of cement clinker produced2. This calculation yields approximately 1tC0 for each 1t of cement clinker produced2。
The way of reducing the dosage of the cement clinker is mainly to use one or more mineral admixtures to replace the cement clinker, the common mineral admixtures comprise slag, steel slag, limestone powder and the like, and the physical properties and the hydration characteristics of the mineral admixtures are different. The slag is used as the mineral admixture, so that the hydration duration process can be prolonged, the common problems of shrinkage and cracking of the traditional concrete can be effectively prevented, the internal microstructure of the concrete is improved, and the durability and the working performance are improved; the silica fume or limestone powder is used as the mineral admixture, so that the dual functions of particle effect and activity effect can be exerted, the water-cement ratio is reduced, the pore structure of the concrete is optimized, and the strength and durability are improved. Therefore, the characteristics of various mineral admixtures are discovered, and the establishment of the synergistic effect among different mineral admixtures is an important direction for the research and development of green high-performance concrete.
However, gypsum slag cement is easily carbonized, the gypsum slag cement concrete structure is rapidly carbonized in the presence of carbon dioxide in the air, and the carbonization behavior results in the appearance of stable calcium carbonate in the form of modified aragonite and vaterite, which rapidly dissolve under the action of frozen salt to exhibit significant structural instability.
Therefore, the invention carries out intensive research on the cement of the clinker-free solid waste system by starting from the mutual synergistic action among different solid waste base materials and the excitation action mechanism of the alkaline exciting agent on the solid waste base cement, and finds that the cement produced under the condition of not using the clinker still ensures the sufficient physical property.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a novel clinker-free solid waste system cement which is environmentally friendly and cost-effective, and a method for producing the same.
The clinker-free solid waste system cement mainly comprises the following raw materials: the steel slag, gypsum and steel slag-slag early-stage active strength excitant used as solid waste are stirred and mixed according to the following composition proportion: 10-20% of gypsum, 10-20% of steel slag and 60-75% of slag, and in addition, 0.1-0.5% of an early-stage active strength excitant of the steel slag-slag is adopted.
Preferably, in the clinker-free solid waste system cement, the gypsum is industrial desulfurized gypsum and the density of the gypsum is 2.2g/cm3～2.3g/cm3。
Preferably, in the clinker-free solid waste system cement, the steel slag has a density of 3.0g/cm3～3.1g/cm3The steel slag powder.
Preferably, in the cement of clinker-free solid waste system according to the present invention, the fused slag has a density of 2.9g/cm3～3.1g/cm3The tailing micro powder.
In the clinker-free solid waste system cement, the steel slag-slag early-stage active strength excitant is one or a mixture of more of calcium oxide, triethanolamine, triisopropanolamine, polycarboxylic acid, diethanolamine and polyhydric alcohol.
Preferably, in the clinker-free solid waste system cement, the ratio of each component is as follows: 10 percent of gypsum, 20 percent of steel slag, 70 percent of slag and 0.5 percent of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percent.
Preferably, in the clinker-free solid waste system cement, the ratio of each component is as follows: 15 percent of gypsum, 10 percent of steel slag, 75 percent of slag and 0.3 percent of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percent.
Preferably, in the clinker-free solid waste system cement, the ratio of each component is as follows: 20 percent of gypsum, 20 percent of steel slag, 60 percent of slag and 0.5 percent of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percent.
Preferably, in the clinker-free solid waste system cement, the ratio of each component is as follows: 17 percent of gypsum, 13 percent of steel slag, 70 percent of slag and 0.4 percent of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percent.
Preferably, in the clinker-free solid waste system cement, the ratio of each component is as follows: 12% of gypsum, 15% of steel slag, 73% of slag and 0.5% of steel slag-slag early-stage active strength excitant, wherein the percentages are mass percentages.
The invention also relates to a preparation method of the clinker-free solid waste system cement, which comprises the following steps: according to the formula proportion, solid waste gypsum, steel slag and slag are added into a ball mill, then a steel slag-slag early-stage active strength excitant is added according to 0.1-0.5% of the total mass of the mixed materials, the mixture is ground to a 45-micrometer sieve, and the sieve residue is not more than 10%, so that the clinker-free solid waste system cement is obtained.
Effects of the invention
The clinker-free solid waste system cement provided by the invention is added with the steel slag-slag early-stage active strength excitant, so that the problems of low early-stage strength, easy carbonization, poor weather resistance and the like of the cement can be solved, the clinker-free solid waste system cement has good particle size distribution and low water demand, and the mortar and the concrete can be ensured to have strength and durability meeting engineering requirements by adopting low water-cement ratio and water consumption. And the cement uses solid wastes instead of clinker, thereby greatly reducing the emission of carbon dioxide, protecting the environment and greatly saving the production cost.
Detailed Description
The present invention will be described in detail with reference to examples.
The clinker-free solid waste system cement adopts the main components of steel slag and slag, gypsum and steel slag-slag early-stage active strength excitant used as solid waste.
Different mineral admixtures show different reaction activities under the conditions of alkalinity and sulfate excitation due to different mineral compositions, so that the double synergistic optimization of the size fraction and the activity is comprehensively considered when in use. In the production process of the clinker-free solid waste system cement, the steel slag, the slag and the gypsum are promoted to interact with each other through the action of the steel slag-slag early-stage active strength excitant, the formation of ettringite and C-S-H gel is promoted, the size range and the hydration activity of each component are different in a raw material system, and the components of different size grades are reasonably matched, so that the effect of closest accumulation among unhydrated particles can be achieved, and the porosity is reduced; on the basis, if the component with the smallest size fraction has the maximum hydration activity and the component with the larger size fraction has the gradually reduced activity, the activity of each component can be better utilized, the pores of the structure are filled with hydration products to the maximum extent, a space is reserved for the continuous hydration in the later period, and the whole structure has better strength and durability.
Example 1
The clinker-free solid waste system cement in the embodiment 1 of the invention mainly comprises the following components: the steel slag, gypsum and steel slag-slag early-stage active strength excitant used as solid waste comprise the following components in percentage by weight: 10 percent of gypsum, 20 percent of steel slag, 70 percent of slag and 0.5 percent of steel slag-slag early-stage active strength excitant; the percentages are mass percentages.
Wherein, the steel slag-slag early-stage active strength excitant can be one or a mixture of more of calcium oxide, triethanolamine, triisopropanolamine, polycarboxylic acid, diethanolamine and polyalcohol.
According to the formula proportion, after gypsum, steel slag and slag are added into a ball mill, the steel slag-slag early-stage active strength excitant is added according to 0.5 percent of the total mass of the mixed materials, the mixture is ground to a 45-micrometer sieve, and the residue on the sieve is not more than 10 percent, so that a product 1 is obtained.
Example 2
The clinker-free solid waste system cement in the embodiment 2 of the invention mainly comprises the following components: the steel slag, gypsum and steel slag-slag early-stage active strength excitant used as solid waste comprise the following components in percentage by weight: 15% of gypsum, 10% of steel slag, 75% of slag and 0.3% of steel slag-slag early-stage active strength excitant; the percentages are mass percentages.
Wherein, the steel slag-slag early-stage active strength excitant can be one or a mixture of more of calcium oxide, triethanolamine, triisopropanolamine, polycarboxylic acid, diethanolamine and polyalcohol.
According to the formula proportion, after gypsum, steel slag and slag are added into a ball mill, the steel slag-slag early-stage active strength excitant is added according to 0.3 percent of the total mass of the mixed materials, the mixture is ground to a 45-micrometer sieve, and the residue on the sieve is not more than 10 percent, so that a product 2 is obtained.
Example 3
The clinker-free solid waste system cement in the embodiment 3 of the invention mainly comprises the following components: the steel slag, gypsum and steel slag-slag early-stage active strength excitant used as solid waste comprise the following components in percentage by weight: 20 percent of gypsum, 20 percent of steel slag, 60 percent of slag and 0.5 percent of steel slag-slag early-stage active strength excitant; the percentages are mass percentages.
Wherein, the steel slag-slag early-stage active strength excitant can be one or a mixture of more of calcium oxide, triethanolamine, triisopropanolamine, polycarboxylic acid, diethanolamine and polyalcohol.
According to the formula proportion, after gypsum, steel slag and slag are added into a ball mill, the steel slag-slag early-stage active strength excitant is added according to 0.5 percent of the total mass of the mixed materials, the mixture is ground to a 45-micrometer sieve, and the residue on the sieve is not more than 10 percent, so that a product 3 is obtained.
Example 4
The clinker-free solid waste system cement in the embodiment 4 of the invention mainly comprises the following components: the steel slag, gypsum and steel slag-slag early-stage active strength excitant used as solid waste comprise the following components in percentage by weight: 17% of gypsum, 13% of steel slag, 70% of slag and 0.4% of steel slag-slag early-stage active strength excitant; the percentages are mass percentages.
Wherein, the steel slag-slag early-stage active strength excitant can be one or a mixture of more of calcium oxide, triethanolamine, triisopropanolamine, polycarboxylic acid, diethanolamine and polyalcohol.
According to the formula proportion, after gypsum, steel slag and slag are added into a ball mill, the steel slag-slag early-stage active strength excitant is added according to 0.4 percent of the total mass of the mixed materials, the mixed materials are ground to be a 45-micrometer sieve, and the residue on the sieve is not more than 10 percent, so that a product 4 is obtained.
The clinker-free solid waste system cement is added with the steel slag-slag early active strength excitant, so that the problems of low early strength, easy carbonization, poor weather resistance and the like of the cement can be solved, the clinker-free solid waste system cement has good particle size distribution and low water demand, and the mortar and the concrete can have strength and durability meeting engineering requirements by adopting low water-cement ratio and water consumption.
Hereinafter, the cement products obtained in the above examples 1 to 4 were subjected to a performance test and compared with ordinary standard cement.
As a comparative example, the composition of ordinary standard cement was clinker and gypsum, wherein clinker accounted for 95% and gypsum accounted for 5%.
The cement was sampled according to the cement sampling method GB/T12573, and the physical properties of the cement products of comparative examples and examples 1 to 4 were determined according to the test method for cement property detection. The fineness of each cement product is measured according to GB/T1345 'Cement fineness test method screening method', and the strength of the cement mortar is measured according to GB/T17671-1999 'Cement mortar Strength test method (ISO method)'.
Specifically, the flexural strength and compressive strength of each cement product were tested for 3 days and 28 days, respectively, and compared. The measurement results are shown below.
From the above values, it can be seen that although the clinker-free solid waste system cement in examples 1 to 4 of the present invention uses solid waste instead of clinker, the cement still maintains good flexural strength and compressive strength. Therefore, the purposes of environmental protection and cost saving can be achieved. In particular, the cement of the clinker-free solid waste system in example 4 has a flexural strength of 5.0 in three days, which is better than that of 4.9 in the standard cement, and 8.3 in 28 days, which is the same as that of the standard cement. In addition, the compressive strength was 22.6 in the case of 3 days and was comparable to 22.8 in the case of 28 days, and 44.7 in the case of 28 days and was comparable to 45.4 in the case of standard cement.
In conclusion, as the clinker is not adopted in the clinker-free solid waste system cement, the emission of carbon dioxide is greatly reduced on the premise of meeting the physical properties required by normal cement, and the clinker-free solid waste system cement is very beneficial to environmental protection, and the raw materials are solid waste, so that the problems of land occupation and storage occupied by a large amount of solid waste and environmental protection caused by the land occupation and the storage can be solved, the cost can be saved, and the clinker-free solid waste system cement has very important significance for realizing industrial structure upgrading, energy conservation and emission reduction.
The invention has been described in terms of the preferred embodiment, but is not intended to be limited to the embodiment, and all technical solutions that can be obtained by means of equivalents or equivalent changes fall within the scope of the invention.