阅读说明：本技术 一种用于水泥混凝土的高活性辅助胶凝材料及其制备方法 (High-activity auxiliary cementing material for cement concrete and preparation method thereof ) 是由 赵计辉 杨刚强 刘强 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种用于水泥混凝土的高活性辅助胶凝材料,包括以下质量份数的组分：风淬钢包炉精炼渣25-50份、磷尾矿15-30份、陶瓷废模石膏10-25份、磷矿渣10-30份、性能调节剂0.1-1.0份。其制备方法包括：先将风淬钢包炉精炼渣与磷尾矿、陶瓷废模石膏及磷矿渣按照质量比例或份数均匀混合；然后,在进入磨机粉磨之前,将制备的性能调节剂按质量比例或份数均匀喷洒在上述固体物料上；最后,将上述物料在球磨机中粉磨至比表面积为400m<Sup>2</Sup>/kg以上的微粉,即得到本发明的高活性辅助胶凝材料。本发明充分发挥几种工业废渣的复合叠加效应,具有水化活性高,且性能可调节,应用于水泥混凝土中的早后期强度高、综合效果好,并具有较高的适应性,推广应用前景广阔。(The invention discloses a high-activity auxiliary cementing material for cement concrete, which comprises the following components in parts by mass: 25-50 parts of air-quenched ladle furnace refining slag, 15-30 parts of phosphate tailings, 10-25 parts of ceramic waste mold gypsum, 10-30 parts of phosphate slag and 0.1-1.0 part of performance regulator. The preparation method comprises the following steps: uniformly mixing the refining slag of the air quenching ladle furnace with phosphate tailings, ceramic waste mold gypsum and phosphate slag according to the mass proportion or part; then, before the powder is ground in a grinding machine, uniformly spraying the prepared performance regulator on the solid material according to the mass proportion or parts; finally, the materials are ground in a ball mill until the specific surface area is 400m 2 And/kg of micro powder, namely obtaining the high-activity auxiliary cementing material. The invention gives full play to the composite superposition effect of several industrial residues, has high hydration activity and adjustable performance, has high early and later strength and good comprehensive effect when being applied to cement concrete, has higher adaptability and wide popularization and application prospect.)

1. The high-activity auxiliary cementing material for cement concrete is characterized by consisting of air-quenched ladle furnace refining slag, tailings, ceramic waste mold gypsum and coal-fired furnace slag, wherein the high-activity auxiliary cementing material comprises the following components in parts by mass: 25-50 parts of air-quenched ladle furnace refining slag, 15-30 parts of phosphate tailings, 10-25 parts of ceramic waste mold gypsum, 10-30 parts of phosphate slag and 0.1-1.0 part of performance regulator.

2. The high-activity auxiliary cementitious material for cement concrete as claimed in claim 1, wherein said air-quenched ladle furnace refining slag is a waste slag discharged when a ladle furnace is used for refining crude steel or waste steel, and is air-quenched and quenched in its molten state, and then crushed, magnetically separated, screened, and de-ironed to obtain a slag with a thickness of < 2mm, which is mainly amorphous C₁₂A₇And β -C₂S mineral as main component and small amount of C₃A、C₃And (5) S mineral.

3. The high-activity supplementary cementitious material for cement concrete according to claim 1, characterised in that the phosphate tailings are tailings produced during the exploitation or beneficiation of phosphate ore, mainly CaCO₃、(Ca₅(PO₄)₃(F, Cl, OH)) and SiO₂Mineral is the main, the particle size is less than 3mm, and the water content is less than 3%.

4. The high-activity supplementary cementitious material for cement concrete according to claim 1, characterised in that said ceramic waste mould gypsum is gypsum waste ceramic mould of ceramic factory, mainly CaSO₄·2H₂The mineral O is the main mineral, and the particle size is less than 3 mm.

5. The high-activity supplementary cementitious material for cement concrete as claimed in claim 1, wherein said slag of phosphorus ore is granulated electric furnace slag of phosphorus ore containing CaO, SiO as main components₂Active substance with water content less than 3%; the granulated electric furnace phosphorus slag is a vitreous mineral obtained by cold quenching a molten by-product generated in the process of preparing yellow phosphorus by an electric furnace method and granulating.

6. The high-activity auxiliary cementing material for cement concrete according to the claim 1, characterized in that the performance regulator is formed by evenly mixing 10 to 30 parts of vitamin C residue, 10 to 20 parts of alcohol amine-carboxylic acid polymer, 5 to 15 parts of calcium nitrate and 50 to 75 parts of water by mass.

7. A method for preparing the high-activity supplementary cementitious material for cement concrete according to claim 1, characterised in that it comprises the following steps:

s1, uniformly mixing the refining slag of the air quenching ladle furnace with phosphate tailings, ceramic waste mold gypsum and phosphate slag according to the mass proportion or parts;

s2, before the powder is ground in a grinding machine, the prepared performance regulator is uniformly sprayed on the solid material according to the mass proportion or parts;

s3 finally, grinding the materials in a ball mill until the specific surface area is 400m²The micro powder of more than/kg, namely the high-activity auxiliary cementing material for the cement concrete of claim 1.

Technical Field

The invention relates to the technical field of utilization of industrial solid waste building material resources, in particular to a high-activity auxiliary cementing material for cement concrete and a preparation method thereof.

Background

Cement concrete is the most recently used, most widely used artificial building material, and it is still the major building material of human society for a considerable time. However, the cement concrete industry consumes a lot of energy and resources, and has a serious environmental load, and is particularly prominent in China. In recent years, the industrial waste residues are used as auxiliary cementing materials and applied to cement concrete in large quantities, so that the use amount of cement can be reduced, energy conservation, emission reduction and consumption reduction are facilitated, solid wastes can be recycled, and green, low-carbon and sustainable development of the cement concrete is realized.

At present, the industrial waste residues used as the cement concrete auxiliary cementing material mainly comprise ground granulated blast furnace slag, fly ash, converter steel slag, furnace slag, silica fume and the like. With the rapid promotion of industrialization and urbanization construction in China, the scale of infrastructure construction is large, and the demand for auxiliary cementing materials (especially high-quality auxiliary cementing materials) is increasing; on the other hand, with the rapid development of the construction engineering technology, modern structural engineering faces the construction requirements of large span, large depth, long distance, super high rise and the like, and the requirements on the cement concrete material are continuously improved, so that the performance requirements on the auxiliary cementing material are also improved. Therefore, the auxiliary cementitious materials also have some problems in cement concrete materials at present.

For example, fly ash and ground slag are the most commonly used auxiliary cementitious materials, have wide application and good effect, and belong to high-quality auxiliary cementitious materials. However, due to the fact that China is in the peak period of infrastructure and distribution factors of coal-fired power plants and blast furnace metallurgical enterprises, the fly ash and the slag are not in demand in many areas of China (especially in big cities and southern areas of China), and the fly ash and the slag become the building material products which are in short supply. The application performance of other industrial waste residues such as ground steel slag and the like as auxiliary cementing materials in cement concrete materials is deficient, so that the development and utilization of new high-quality auxiliary cementing materials are a problem to be solved urgently in the cement concrete industry.

For another example, the auxiliary cementitious material generally has a low or slow hydration activity, and after partial cement is replaced, the early performance (especially early strength and setting time) of the cementitious material and concrete is often reduced, which affects and limits the application of the auxiliary cementitious material in large dosage in cement concrete and the application effect in high-strength cement concrete to a certain extent. Therefore, improving the activity of the auxiliary cementing material or developing the auxiliary cementing material with high activity is also a problem to be solved urgently in the cement concrete industry.

Therefore, in order to meet the requirements of increasing infrastructure construction, rapidly developing building engineering technology and the like, the development and utilization of high-activity high-quality auxiliary cementing materials are necessary trends of future cement concrete materials, and are effective ways for effectively using industrial waste residues as auxiliary cementing materials in the cement concrete materials, so that the cement concrete materials are beneficial to promoting green, low-carbon and sustainable development, and have important strategic opportunities and broad development prospects.

Disclosure of Invention

The invention aims to provide a high-activity auxiliary cementing material for cement concrete and a preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a high-activity auxiliary cementing material for cement concrete is composed of air-quenched ladle furnace refining slag, tailings, ceramic waste mold gypsum and coal-fired furnace slag, wherein the high-activity auxiliary cementing material comprises the following components in parts by mass: 25-50 parts of air-quenched ladle furnace refining slag, 15-30 parts of phosphate tailings, 10-25 parts of ceramic waste mold gypsum, 10-30 parts of phosphate slag and 0.1-1.0 part of performance regulator.

Preferably, the air-quenched ladle furnace refining slag is waste slag discharged when a ladle furnace is used for refining crude steel or waste steel, is subjected to air quenching and quenching treatment in a molten state, is crushed, magnetically separated, screened and deironized to obtain the slag with the particle size of less than 2mm, and is mainly amorphous C₁₂A₇And β -C₂S mineral as main component and small amount of C₃A、C₃S and the like.

Preferably, the phosphorus tailings are tailings generated in the process of mining or concentrating the phosphorus ore, and mainly comprise CaCO₃、(Ca₅(PO₄)₃(F, Cl, OH)) and SiO₂Mineral is the main, the particle size is less than 3mm, and the water content is less than 3%.

Preferably, the ceramic waste mould gypsum is a gypsum waste ceramic mould of a ceramic factory, mainly comprising CaSO₄·2H₂The mineral O is the main mineral, and the particle size is less than 3 mm.

Preferably, the phosphate slag is granulated electric furnace phosphate slag, and the main components of the phosphate slag are CaO and SiO₂Active substances with water content less than 3 percent; the granulated electric furnace phosphorus slag is a molten by-product produced when yellow phosphorus is prepared by an electric furnace method, and is subjected to cold quenching to obtain vitreous minerals.

Preferably, the performance regulator is prepared by uniformly mixing 10-30 parts of vitamin C residues, 10-20 parts of alcohol amine-carboxylic acid polymer, 5-15 parts of calcium nitrate and 50-75 parts of water in parts by mass.

The present invention also provides a method for preparing a high-activity supplementary cementitious material for cement concrete, comprising the steps of:

s1, uniformly mixing the refining slag of the air quenching ladle furnace with phosphate tailings, ceramic waste mold gypsum and phosphate slag according to the mass proportion or parts;

s2, before the powder is ground in a grinding machine, the prepared performance regulator is uniformly sprayed on the solid material according to the mass proportion or parts;

s3 finally, grinding the materials in a ball mill until the specific surface area is 400m²The micro powder of more than/kg, namely the high-activity auxiliary cementing material for the cement concrete of claim 1.

The invention has the beneficial effects that:

1. the auxiliary cementing material developed by the invention has high hydration activity, has the advantages of high early and later strength, large application mixing amount and good comprehensive effect when being applied to cement concrete, and overcomes the defects of slow development of the cementing material strength and low early strength caused by low early activity of the traditional industrial waste residue as the auxiliary cementing material.

2. The invention relates to a wind quenching ladle furnace refining slag which is one of the main components and is rich in amorphous C₁₂A₇And β -C₂S mineral in which C is amorphous₁₂A₇The mineral has high hydration activity and fast setting and hardening rate, and the auxiliary cementing material of the present invention has high early activity, β -C₂C in S mineral and portland cement₂The mineral phase and the crystal form of S are consistent, and the S is used for improving the hydration hardening performance at higher hydration hardening performanceAssisting the later activity of the gelled material.

3. The ceramic waste mold gypsum of the invention has CaSO as the main mineral phase₄·2H₂O for optimizing amorphous C₁₂A₇Hydration products of minerals (CaSO)₄·2H₂O and C₁₂A₇The mineral phase can form ettringite in early and medium stages, improve the composition of hydration products and increase the structural compactness), thereby preventing C₁₂A₇The mineral phase self hydration product generates crystal form transformation to influence the later performance of the material, and C can be regulated and controlled₁₂A₇Hydration hardening rate of mineral phase, improvement of factor C₁₂A₇The hydration products formed by the early and rapid hydration of the mineral phase can be greatly wrapped in the unhydrated β -C₂S mineral surface, hindering its later stage hydration.

4. The main mineral phase of the phosphorus tailings serving as the component of the invention is dolomite (CaCO)₃) Apatite (Ca)₅(PO₄)₃(F, Cl, OH)), and the like, the carbonate component of which can combine with part of the ettringite in the system to form a carbonate ettringite phase (CO)₃AFt) to prevent the ettringite from going to mono-sulphur hydrated calcium sulphoaluminate (which is difficult to act as ettringite) when the gypsum is exhausted, acting as ettringite stability, thus improving the stability of the cementitious material in the later hardening stage.

5. The phosphorous slag of the invention comprises the main components of CaO and SiO₂The active substances have volcanic ash activity, can perform volcanic ash reaction in an alkaline environment in cement concrete, fill the pore structure of the material, and improve the compactness, strength and durability of the material.

6. The other important component of the invention is a performance regulator, which is prepared from vitamin C residue, alcohol amine-carboxylic acid polymer, calcium nitrate and water, and has low mixing amount and obvious effect. It makes full use of the waste residue of pharmaceutical factory, i.e. vitamin C residue, which contains a large amount of hydroxyl and carboxyl, and can adjust C in the invention₁₂A₇The hydration rate and progress of the mineral; the alcohol amine-carboxylic acid polymer is patent application No. 201310116104.4 entitled "an alcohol amine-carboxylic acid polymer and its preparation method and applicationThe alcohol amine-carboxylic acid polymer not only has the functions of grinding aid, dispersion and prevention of powder agglomeration, but also has the effect of improving the workability of cement-based materials and is beneficial to chelating β -C₂Ca in silicate mineral phases such as S²⁺Promoting the hydration of the plant; while nitrate helps to optimize the hydration process and product type of the aluminate mineral phase in the material (formation of nitrate ettringite phase NO)₃-AFt)。

7. The different industrial waste residues selected by the invention respectively contain aluminate (amorphous C)₁₂A₇) Silicate (β -C)₂S), sulfate (CaSO)₄·2H₂O), carbonate (CaCO)₃) And active SiO₂The composite superposition effect of the cement concrete is fully exerted by the characteristics of the same mineral phase, and the performance of the auxiliary cementing material is adjustable and controllable by adjusting the component proportion and the performance regulator, so that the requirements of different cement concrete materials are met or matched, and the adaptability and the application range of the auxiliary cementing material are greatly improved.

Detailed Description

The present invention will be further described with reference to the following examples, which are provided for the purpose of illustrating the present invention, and the scope of the present invention is not limited to the following examples.

The invention relates to a high-activity auxiliary cementing material for cement concrete, which consists of air-quenched ladle furnace refining slag, tailings, ceramic waste mold gypsum and coal-fired furnace slag, wherein the mass parts of the components are as follows: 25-50 parts of air-quenched ladle furnace refining slag, 15-30 parts of phosphate tailings, 10-25 parts of ceramic waste mold gypsum, 10-30 parts of phosphate slag and 0.1-1.0 part of performance regulator.

Preferably, the air-quenched ladle furnace refining slag is waste slag discharged when a ladle furnace is used for refining crude steel or waste steel, is subjected to air quenching and quenching treatment in a molten state, is crushed, magnetically separated, screened and deironized to obtain the slag with the particle size of less than 2mm, and is mainly amorphous C₁₂A₇And β -C₂S mineral as main component and small amount of C₃A、C₃S and the like.

Preferably, the phosphorus tailings are tailings generated in the process of mining or concentrating the phosphorus ore, and mainly comprise CaCO₃、(Ca₅(PO₄)₃(F, Cl, OH)) and SiO₂Mineral is the main, the particle size is less than 3mm, and the water content is less than 3%.

Preferably, the ceramic waste mould gypsum is a gypsum waste ceramic mould of a ceramic factory, mainly comprising CaSO₄·2H₂The mineral O is the main mineral, and the particle size is less than 3 mm.

Preferably, the phosphate slag is granulated electric furnace phosphate slag, and the main components of the phosphate slag are CaO and SiO₂Active substances with water content less than 3 percent; the granulated electric furnace phosphorus slag is a molten by-product produced when yellow phosphorus is prepared by an electric furnace method, and is subjected to cold quenching to obtain vitreous minerals.

Preferably, the performance regulator is prepared by uniformly mixing 10-30 parts of vitamin C residues, 10-20 parts of alcohol amine-carboxylic acid polymer, 5-15 parts of calcium nitrate and 50-75 parts of water in parts by mass.

The present invention also provides a method for preparing a high-activity supplementary cementitious material for cement concrete, comprising the steps of:

s1, uniformly mixing the refining slag of the air quenching ladle furnace with phosphate tailings, ceramic waste mold gypsum and phosphate slag according to the mass proportion or parts;

s2, before the powder is ground in a grinding machine, the prepared performance regulator is uniformly sprayed on the solid material according to the mass proportion or parts;

s3 finally, grinding the materials in a ball mill until the specific surface area is 400m²The micro powder of more than/kg, namely the high-activity auxiliary cementing material for the cement concrete of claim 1.