CN116003008A - New low-carbon environment-friendly nickel-iron steel slag cementitious material - Google Patents

Abstract

The invention discloses a new type of low-carbon environment-friendly nickel-iron steel slag cementitious material, including blast furnace nickel-iron slag, electric furnace refined nickel-iron slag, chemical composition control material, alkali environment control material, silicon-aluminum oxide excitation material, and calcium oxide excitation material , Magnesium oxide excitation material, coagulation adjustment material. It has technical effects: 1. The new low-carbon and environmentally friendly nickel-iron steel slag cementitious material of the present invention can fully utilize steelmaking nickel-iron waste slag as the main material, fully digest the accumulated waste slag, and has the characteristics of low carbon and environmental protection; 2. According to performance requirements , can control the comprehensive composition of blast furnace ferronickel slag and electric furnace refined ferronickel slag, and improve the activity of ferronickel slag powder; 3. It is the first time to propose the excitation of magnesia in ferronickel steel slag powder, and achieved good results; 4. For nickel The characteristics of the chemical composition of the iron-steel slag powder, the corresponding excitation materials and the corresponding excitation mechanism were proposed; 5. The optimal ratio of the cementitious material prepared by the nickel-iron steel slag powder was developed, and the strength of the prepared cementitious material cement could reach 28 days Above 42.5MPa, and can reduce carbon dioxide emissions.

Description

New low-carbon environment-friendly nickel-iron steel slag cementitious material

technical field

The invention relates to a novel low-carbon environment-friendly nickel-iron steel slag powder cementitious material, which is mainly used in the fields of concrete, rapid repair, mortar, structure reinforcement, grouting, foundation reinforcement and the like.

Background technique

In recent years, concrete has become one of the most important building materials in the field of civil engineering. Because of its easy access to raw materials, cheap price, simple production process, good compressive strength, plasticity and flexible performance, it has a wide range of engineering applications. Applicability and durability, it has been used in many fields such as roads, houses, bridges and tunnels. With the continuous growth of the economic demand of our society, the infrastructure of urban construction integration is also further promoted, and the demand for concrete is also gradually increasing. According to the latest statistics on the operation of the building materials industry by the National Development and Reform Commission of the People's Republic of China, the output of commercial concrete in my country in 2021 will be about 3.293 billion cubic meters, a year-on-year increase of 15.6%.

While the field of construction engineering is developing rapidly, concrete also brings a lot of resource consumption and environmental pollution. According to incomplete statistics, the production of 100 million cubic meters of concrete requires 36 million tons of cement and 82 million cubic meters of gravel. The production of cement requires two links of burning clinker and material grinding that consume a lot of energy, and the mining of sand and gravel will also cause certain damage to the environment. In many areas, there has been a shortage of sand and gravel resources. Based on the four aspects advocated by our country, we must persist in major research in the field of new materials and emerging industries. In the process of building an environment-friendly and resource-saving society, we need to solve a series of problems caused by the loss of building materials.

There is a certain history of mixing slag powder, metakaolin, silica fume, fly ash, zeolite powder, etc. into concrete as admixtures. Since the 21st century, with the development of green and environmentally friendly concrete, mineral admixtures have received the same attention as water, admixtures, cement, aggregates, etc., and have become an indispensable sixth component of concrete. The use of industrial waste as an admixture can improve the performance of concrete and has considerable economic benefits. It is very important for the integration of building material resources and the reduction of environmental pollution.

Nickel is an alloy material, mostly silver-white, with the characteristics of high temperature resistance, good ductility, and stable chemical properties. Therefore, it is an indispensable engineering material in national defense construction and is widely used in military, medical, metallurgy, Atomic energy, nuclear energy and other fields. At present, more than 80 nickel mines have been explored in my country, most of which are nickel sulfide mines. However, due to long-term utilization and mining, the existing storage capacity has dropped significantly, and the resource development of laterite nickel-iron slag minerals is cheap and can be better developed. is widely used. However, the huge mineral nickel-iron slag waste cannot be fully rationally utilized. In most cases, the landfill method is adopted, which not only occupies the existing land, but also causes environmental pollution, and at the same time limits the development of the nickel-iron slag industry . Therefore, the resource utilization of ferronickel slag powder is the trend of the times.

Laterite nickel ore generally adopts pyrotechnic process, wet process and pyro-wet smelting process. Due to different operating processes in the smelting process, there are two types of water quenching slag and dry slag discharge according to its formation method. The difference lies in the cooling speed. The dry slag is formed by slow cooling in the natural state. It is dark brown block. The structure contains less glass and is not active. It is usually used as aggregate for road landfill or concrete. , can improve the strength of concrete; while water-quenching slag is formed in the process of water-quenching rapid cooling, which is dark brown and spherical, and contains more vitreous body inside the structure, because of the Al ₂ O ₃ , CaO and some active oxides in the vitreous body, It has potential activity after being excited by alkaline medium. In general, for the base of stainless steel production, the chemical composition of ferronickel blast furnace slag is: 26.55% for SiO2, 28.52% for CaO, 7.32% for MgO, 27.90% for Al2O3, 2.29% for Fe2O3, 1.362% for SO3, Cr2O4 is 0.998%, MnO is 0.56%, and loss on ignition is 0.82%. The chemical composition of nickel-iron slag refined by electric furnace is: 36.73% for SiO2, 29.81% for CaO, 14.77% for MgO, 3.45% for Al2O3, 4.38% for Fe2O3, 0.6% for SO3, 2.974% for Cr2O4, 1.02% for MnO, The loss on ignition was 0.88%. Its characteristics The main chemical components of ferronickel slag powder include SiO2, CaO, Al2O3, MgO, Fe2O3, etc. It can be seen from the chemical composition of nickel-iron slag powder that for nickel-iron blast furnace slag, the contents of CaO and Al2O3 are higher, and the contents of SiO2 and MgO are lower; The content is higher and the content of Al2O3 is lower. Through the analysis of the activity index of nickel-iron slag powder, nickel-iron blast furnace slag and electric furnace refined nickel-iron slag belong to acidic slag powder, and their activity coefficient is better; electric furnace refined nickel-iron slag belongs to basic slag powder, but its activity coefficient is less than 0.2 , with low activity. Finding a reasonable and efficient technology to make good use of ferronickel slag powder is of great significance to the country's environmental protection and ecological health.

Contents of the invention

In view of the deficiencies in the background technology, the technical problem to be solved by the present invention is to provide a new type of low-carbon environmental protection nickel-iron steel slag powder cementitious material, the preparation of the new low-carbon environmental protection nickel-iron steel slag powder cementitious material can fully utilize waste slag and more Environmental protection, but also has better strength.

For this reason, the new low-carbon environment-friendly nickel-iron steel slag cementitious material provided by the present invention includes blast furnace nickel-iron slag, electric furnace refined nickel-iron slag, chemical composition control material, alkali environment control material, silicon-aluminum oxide excitation material, calcium oxide Excitation material, magnesium oxide excitation material, setting adjustment material.

preferred,

The nickel-iron steel slag powder comprises blast furnace nickel-iron slag (50%-100%) and electric furnace refined nickel-iron slag (0%-50%), blast furnace nickel-iron slag and electric furnace refined nickel-iron slag are mixed in proportion, balanced and complementary chemical components, while improving the utilization of low-activity electric furnace refining ferronickel slag;

The chemical composition regulating material includes ordinary mineral powder, attapulgite, and metakaolin silica fume. By mixing the above materials, the chemical composition of the mixed slag is regulated to improve the alkalinity coefficient, activity coefficient and quality coefficient of the mixed material;

The alkaline environment regulating material includes potassium hydroxide and sodium hydroxide, and the chemical reaction of the mixed slag is improved and stimulated by adding the potassium hydroxide and/or sodium hydroxide to provide an alkaline environment and accelerate the chemical reaction;

The silicon-aluminum oxide excitation material includes sodium silicate and potassium silicate, and the reaction of silicon-aluminum oxide is promoted by adding sodium silicate and/or potassium silicate;

The calcium oxide excitation material includes potassium carbonate and sodium carbonate, and the potassium carbonate and/or sodium carbonate react with calcium oxide to generate nano-calcium oxide, fill gaps, increase compactness, and improve strength;

The magnesium oxide excitation material includes ammonium dihydrogen phosphate and potassium dihydrogen phosphate, and reacts with magnesium oxide to generate solid magnesium phosphate cement by adding ammonium dihydrogen phosphate and/or potassium dihydrogen phosphate;

Preferably, the activator sodium silicate is a reagent capable of dissolving aluminosilicate minerals and reacting solutes to prepare geopolymers. Its essence is a catalyst that acts in a chemical reaction process. The polymer raw material is better "depolymerized", thereby stimulating the activity of the raw material aluminosilicate to promote the disintegration of the raw material and the formation of hydration products. The reaction of the sodium silicate with the silicon aluminum oxide is as follows:

(1). At the initial stage of the reaction, the water glass is hydrolyzed, and the slag does not participate in the hydration reaction, forming a silicon-oxygen tetrahedron:

2Na ₂ O·nSiO ₂ +2(n+1)H ₂ O→n Si(OH) ₄ +2NaOH

(2). In the early stage of the reaction, the water glass continues to be hydrolyzed, and the slag glass body begins to dissolve and disperse. Under the condition of alkaline solution water glass, the Ca ²⁺ ions on the surface of the slag glass body absorb the OH ^- ions in the alkaline solution to form hydroxide thing. After the surface of the slag glass body is destroyed by OH ^- , it provides a necessary channel for Na ⁺ to enter the interior of the slag glass body, so that Ca ²⁺ undergoes a substitution reaction with OH ^- and Na ⁺ , thus destroying the network structure of the slag glass body and making the slag disperse , dissolved;

(3). In the middle and late stages of the reaction, the slag is completely hydrated, and the dehydration of silicic acid reacts with calcium hydroxide to form a calcium-oxygen gel (C-S-H), thereby making the slurry dense and improving its strength;

Si(OH) ₄ →SiO ₂ +2H ₂ O

SiO ₂ +m ₁ Ca(OH) ₂₊ m ₂ H ₂ O→m ₁ CaO·SiO ₂ ·(m ₁ +m ₂ )H ₂ O

Al ₂ O ₃ +M ₁ Ca(OH) ₂₊ M ₂ H ₂ O→M ₁ CaO Al ₂ O ₃ (M ₁ +M ₂ )H ₂ O

The reaction process is divided into 3 stages:

In the first stage, the aluminosilicate minerals undergo a dissolution reaction under the action of a strong alkali, and the covalent bonds of Si-O and Al-O are broken, because the hydrolysis product of Al ³⁺ exists in the form of [Al(OH) ₄ ]– , and Si ⁴⁺ in a strong alkaline solution, its hydrolysis products mainly exist in the form of [SiO(OH) ₃ ]-, [SiO ₂ (OH) ₂ ] ^2– , in which water is Al ³⁺ and Si ⁴⁺ Provide a place for hydrolysis and polycondensation;

Al ₂ O ₃ +3H ₂ O+2OH ^- → 2[Al(OH) ₄ ]–

SiO ₂ +H ₂ O+OH ^- →[Si O(OH) ₃ ]-

SiO ₂ +2OH ^- →[SiO ₂ (OH) ₂ ] ^2–

In the second stage, the dissolved [Al(OH) ₄ ]-, [Si O(OH) ₃ ] ^- and [Si O ₂ (OH) ₂ ] ^2- ions undergo recombination and depolymerization reactions to form ) group of oligosilicon-aluminum tetrahedral unit gel;

In the third stage, polycondensation and dehydration reactions occur between the hydroxyl groups of the oligomeric silicon-aluminum tetrahedral unit gels, and the remaining water is gradually removed to form a layered Si-O-Al dense structure, which is consolidated and hardened into a geopolymeric block ;

Preferably, the calcium oxide excited material reaction comprises the following steps:

(1) Dissolution of calcium oxide

CaO+ _H2O →Ca(OH) ₂

(2) Generation of nano-calcium carbonate

Ca(OH) ₂ +Na ₂ CO ₃ →CaCO ₃ +NaOH

Preferably, the magnesium oxide excited material reaction step includes the following:

(1), the dissolution of phosphate. Phosphate will dissolve when it meets water, and then H ⁺ will be released, making the solution environment acidic.

The dissolution process of KH ₂ PO ₄ is as follows:

KH ₂ PO ₄ →H ₂ PO ₄ ^- +K ⁺

H ₂ PO ₄ ^- →HPO ₄ ^2- +H ⁺

HPO ₄ ^2- → PO ₄ ^3- +H ⁺ ;

(2) Dissolution of magnesium oxide in mixed ferronickel slag. MgO is slightly soluble in water, and the solubility of phosphate in water is much higher than that of MgO, so the dissolution of MgO begins to gradually occur after the solution becomes acidic after the dissolution of phosphate. The surface of Mg O particles forms a complex Mg(OH)2 under the action of H ⁺ and water, and the complex continuously releases Mg ²⁺ , and forms a hydrated gel Mg(H ₂ O) ₆ ²⁺ The form exists in aqueous solution and can be described as:

MgO+ _H2O →Mg(OH) ₂

Mg(OH) ₂ →Mg ²⁺ +OH ^-

Mg ⁺ +6H ₂ O → Mg(H ₂ O) ₆ ²⁺ ;

(3) Formation of magnesium phosphate cement stone. H ⁺ and OH ^- in the solution are neutralized, while Mg(H ₂ O) ₆ ²⁺ , PO ₄ ^3- and K ⁺ combine together to form a hydration product (Mg KPO ₄ ·6H ₂ O, MKP). The hydration reaction continues to develop, MKP and the residual MgO particles are bonded together, and finally a magnesium phosphate cement stone with MgO as the skeleton is produced. The reaction formula is:

Mg(H ₂ O) ₆ ²⁺ +PO ₄ ^3- +K ⁺ →Mg KPO ₄ ·6H ₂ O.

Preferably, the total content of the ordinary mineral powder and/or attapulgite and/or metakaolin and/or silica fume is 0-15%, and the total content of potassium hydroxide and/or sodium hydroxide is 1% -5%, the total content of the sodium silicate and/or potassium silicate is 5%-20%, the total content of the ammonium dihydrogen phosphate and/or potassium dihydrogen phosphate is 1%-6%, the The total content of sodium tripolyphosphate and/or citric acid and/or sodium polyphosphate and/or borax is 0.5%-5%.

Preferably, the nickel-iron steel slag powder is 100 parts of nickel-iron blast furnace slag; the chemical composition control material is nickel-iron steel slag powder 5%; the silicon-aluminum oxide excitation material is nickel-iron steel slag powder 10%; the alkali The environmental control material is 3% of nickel-iron steel slag powder; the calcium oxide excitation material is 3% of nickel-iron steel slag powder; the magnesium oxide excitation material is 6% of nickel-iron steel slag powder;

The setting adjusting material is 0.5% of ferronickel steel slag powder; the water-material ratio is 0.45; the 28-day compressive strength is 51.2MPa, and the 28-day flexural strength is 3.05MPa.

Preferably, the nickel-iron steel slag powder is 100 parts of nickel-iron blast furnace slag; the chemical composition control material

10% of nickel-iron steel slag powder; the silicon-aluminum oxide excitation material is nickel-iron steel slag powder 15%; the alkali environment control material is nickel-iron steel slag powder 5%; the calcium oxide excitation material is nickel-iron steel slag powder 5%; the magnesium oxide excitation material is nickel-iron steel slag powder 6%; the condensate adjusting material is nickel-iron steel slag powder 5%; the water-material ratio is 0.45; 28-day compressive strength 55.3MPa; 28-day flexural resistance Strength 3.56MPa.

Preferably, the nickel-iron steel slag powder is 100 parts of nickel-iron steel slag; the chemical composition control material is nickel-iron steel slag powder 15%; the silicon-aluminum oxide excitation material is nickel-iron steel slag powder 20%; the alkali The environmental control material is nickel-iron steel slag powder 1%; the calcium oxide excitation material is nickel-iron steel slag powder 5%; the magnesium oxide excitation material is nickel-iron steel slag powder 4%;

The setting adjusting material is 0.5% of ferronickel steel slag powder; the water-material ratio is 0.45; the 28-day compressive strength is 57.9MPa, and the 28-day flexural strength is 3.35MPa.

Technical effect of the present invention:

1. The new low-carbon and environmentally friendly ferronickel steel slag cementitious material of the present invention can fully utilize nickel-iron steelmaking waste slag as the main material, fully digest the accumulated waste slag, and has the characteristics of low carbon and environmental protection;

2. Control the comprehensive composition of blast furnace ferronickel slag and electric furnace refined ferronickel slag, and improve the activity of ferronickel slag powder;

3. Proposed for the first time to excite magnesia of ferronickel steel slag powder, and achieved good results;

4. Developed the optimal ratio of nickel-iron steel slag powder to prepare cementitious materials. The strength of the prepared cementitious material cement can reach more than 42.5MPa in 28 days, and can reduce carbon dioxide emissions.

Detailed ways

In order to further explain the technical means and effects adopted by the present invention to achieve the intended purpose of the invention, the specific implementation, structure, features and effects of the present invention will be described below in conjunction with the preferred embodiments, and the detailed description is as follows.

The new low-carbon environment-friendly nickel-iron-steel slag cementitious material provided by the invention includes blast furnace nickel-iron slag, electric furnace refined nickel-iron slag, chemical composition control material, alkali environment control material, silicon-aluminum oxide excitation material, calcium oxide excitation material, Magnesium oxide excitation material, coagulation adjustment material.

The nickel-iron steel slag powder comprises blast furnace nickel-iron slag (50%-100%) and electric furnace refined nickel-iron slag (0%-50%), blast furnace nickel-iron slag and electric furnace refined nickel-iron slag are mixed in proportion, balanced and complementary chemical components, while improving the utilization of low-activity electric furnace refining ferronickel slag;

The chemical composition regulating material includes ordinary mineral powder, attapulgite, and metakaolin silica fume. By mixing the above materials, the chemical composition of the mixed slag is regulated to improve the alkalinity coefficient, activity coefficient and quality coefficient of the mixed material;

The alkaline environment regulating material includes potassium hydroxide and sodium hydroxide, and the chemical reaction of the mixed slag is improved and stimulated by adding the potassium hydroxide and/or sodium hydroxide to provide an alkaline environment and accelerate the chemical reaction;

The silicon-aluminum oxide excitation material includes sodium silicate and potassium silicate, and the reaction of silicon-aluminum oxide is promoted by adding sodium silicate and/or potassium silicate;

The calcium oxide excitation material includes potassium carbonate and sodium carbonate, and the potassium carbonate and/or sodium carbonate react with calcium oxide to generate nano-calcium oxide, fill gaps, increase compactness, and improve strength;

The magnesium oxide excitation material includes ammonium dihydrogen phosphate and potassium dihydrogen phosphate, and reacts with magnesium oxide to generate solid magnesium phosphate cement by adding ammonium dihydrogen phosphate and/or potassium dihydrogen phosphate;

The setting adjusting material includes sodium tripolyphosphate and/or citric acid and/or sodium polyphosphate and/or borax, and the sodium tripolyphosphate and/or citric acid and/or sodium polyphosphate and/or borax adsorb On the surface of reactants such as silicon and aluminum, the reaction speed is delayed and the coagulation time is adjusted.

The above-mentioned activator sodium silicate is a reagent that can dissolve aluminosilicate minerals and make the solute react to prepare geopolymers. Its essence is a catalyst that works in the chemical reaction process. "Depolymerization" occurs well, thereby stimulating the activity of the raw material aluminosilicate to promote the disintegration of the raw material and the formation of hydration products. The reaction of the sodium silicate with the silicon aluminum oxide is as follows:

(1). At the initial stage of the reaction, the water glass is hydrolyzed, and the slag does not participate in the hydration reaction, forming a silicon-oxygen tetrahedron:

2Na ₂ O·nSiO ₂ +2(n+1)H ₂ O→n Si(OH) ₄ +2NaOH

(2). In the early stage of the reaction, the water glass continues to be hydrolyzed, and the slag glass body begins to dissolve and disperse. Under the condition of alkaline solution water glass, the Ca ²⁺ ions on the surface of the slag glass body absorb the OH ^- ions in the alkaline solution to form hydroxide things. After the surface of the slag glass body is destroyed by OH ^- , it provides a necessary channel for Na ⁺ to enter the interior of the slag glass body, so that Ca ²⁺ undergoes a substitution reaction with OH ^- and Na ⁺ , thus destroying the network structure of the slag glass body and making the slag disperse , dissolved;

(3). In the middle and late stages of the reaction, the slag is completely hydrated, and the dehydration of silicic acid reacts with calcium hydroxide to form a calcium-oxygen gel (C-S-H), thereby making the slurry dense and improving its strength;

Si(OH) ₄ →SiO ₂ +2H ₂ O

SiO ₂ +m ₁ Ca(OH) ₂₊ m ₂ H ₂ O→m ₁ CaO·SiO ₂ ·(m ₁ +m ₂ )H ₂ O

Al ₂ O ₃ +M ₁ Ca(OH) ₂₊ M ₂ H ₂ O→M ₁ CaO Al ₂ O ₃ (M ₁ +M ₂ )H ₂ O

The reaction process is divided into 3 stages:

In the first stage, the aluminosilicate minerals undergo a dissolution reaction under the action of a strong alkali, and the covalent bonds of Si-O and Al-O are broken, because the hydrolysis product of Al ³⁺ exists in the form of [Al(OH) ₄ ]– , and Si ⁴⁺ in a strong alkaline solution, its hydrolysis products mainly exist in the form of [SiO(OH) ₃ ]-, [SiO ₂ (OH) ₂ ] ^2– , in which water is Al ³⁺ and Si ⁴⁺ Provide a place for hydrolysis and polycondensation;

Al ₂ O ₃ +3H ₂ O+2OH ^- → 2[Al(OH) ₄ ]–

SiO ₂ +H ₂ O+OH ^- →[Si O(OH) ₃ ]-

SiO ₂ +2OH ^- →[SiO ₂ (OH) ₂ ] ^2–

In the second stage, the dissolved [Al(OH) ₄ ]-, [Si O(OH) ₃ ] ^- and [Si O ₂ (OH) ₂ ] ^2- ions undergo recombination and depolymerization reactions to form ) group of oligosilicon-aluminum tetrahedral unit gel;

In the third stage, polycondensation and dehydration reactions occur between the hydroxyl groups of the oligomeric silicon-aluminum tetrahedral unit gels, and the remaining water is gradually removed to form a layered Si-O-Al dense structure, which is consolidated and hardened into a geopolymeric block ;

Preferably, the calcium oxide excited material reaction comprises the following steps:

(1) Dissolution of calcium oxide

CaO+ _H2O →Ca(OH) ₂

(2) Generation of nano-calcium carbonate

Ca(OH) ₂ +Na ₂ CO ₃ →CaCO ₃ +NaOH

Preferably, the magnesium oxide excitation includes the following:

(1), the dissolution of phosphate. Phosphate will dissolve when it meets water, and then H ⁺ will be released, making the solution environment acidic.

The dissolution process of KH ₂ PO ₄ is as follows:

KH ₂ PO ₄ →H ₂ PO ₄ ^- +K ⁺

H ₂ PO ₄ ^- →HPO ₄ ^2- +H ⁺

HPO ₄ ^2- → PO ₄ ^3- +H ⁺ ;

(2) Dissolution of magnesium oxide in mixed ferronickel slag. MgO is slightly soluble in water, and the solubility of phosphate in water is much higher than that of MgO, so the dissolution of MgO begins to gradually occur after the solution becomes acidic after the dissolution of phosphate. The surface of Mg O particles forms a complex Mg(OH)2 under the action of H ⁺ and water, and the complex continuously releases Mg ²⁺ , and forms a hydrated gel Mg(H ₂ O) ₆ ²⁺ The form exists in aqueous solution and can be described as:

MgO+ _H2O →Mg(OH) ₂

Mg(OH) ₂ →Mg ²⁺ +OH ^-

Mg ⁺ +6H ₂ O → Mg(H ₂ O) ₆ ²⁺ ;

(3) Formation of magnesium phosphate cement stone. H ⁺ and OH ^- in the solution are neutralized, while Mg(H ₂ O) ₆ ²⁺ , PO ₄ ^3- and K ⁺ combine together to form a hydration product (Mg KPO ₄ ·6H ₂ O, MKP). The hydration reaction continues to develop, MKP and the residual MgO particles are bonded together, and finally a magnesium phosphate cement stone with MgO as the skeleton is produced. The reaction formula is:

Mg(H ₂ O) ₆ ²⁺ +PO ₄ ^3- +K ⁺ →Mg KPO ₄ ·6H ₂ O.

The total content of the above-mentioned ordinary mineral powder and/or attapulgite and/or metakaolin and/or silica fume is 0-15%, and the total content of the potassium hydroxide and/or sodium hydroxide is 1%-5%, The total content of the sodium silicate and/or potassium silicate is 5%-20%, the total content of the ammonium dihydrogen phosphate and/or potassium dihydrogen phosphate is 1%-6%, and the sodium tripolyphosphate And/or the total content of citric acid and/or sodium polyphosphate and/or borax is 0.5%-5%.

Below enumerate embodiment to prove effect of the present invention:

Case 1

Nickel-iron steel slag powder: 50 parts of nickel-iron blast furnace slag, 50 parts of electric furnace refined nickel-iron slag; chemical composition control material: 5% of nickel-iron steel slag powder; silicon-aluminum oxide excitation material: 10% of nickel-iron steel slag powder; alkaline environment Regulatory material: 1% nickel-iron steel slag powder; calcium oxide excitation material: 1% nickel-iron steel slag powder; magnesium oxide excitation material: 2% nickel-iron steel slag powder; 0.5% nickel-iron steel slag powder; water material The ratio is 0.45; the 28-day compressive strength is 37.8MPa, and the 28-day flexural strength is 2.12MPa.

Case 2

Nickel-iron steel slag powder: 50 parts of nickel-iron blast furnace slag, 50 parts of electric furnace refined nickel-iron slag; chemical composition control material: 10% of nickel-iron steel slag powder; silicon-aluminum oxide excitation material: 15% of nickel-iron steel slag powder; alkaline environment The regulating material is nickel-iron steel slag powder 3%; the excitation material of calcium oxide is nickel-iron steel slag powder 3%; the excitation material of magnesium oxide is nickel-iron steel slag powder 4%; the setting material is nickel-iron steel slag powder 2.5%; ; 28-day compressive strength 44.3MPa, 28-day flexural strength 2.78MPa.

Case 3

Nickel-iron steel slag powder: 50 parts of nickel-iron blast furnace slag, 50 parts of electric furnace refined nickel-iron slag; chemical composition control material: 15% of nickel-iron steel slag powder; silicon-aluminum oxide excitation material: 20% of nickel-iron steel slag powder; alkaline environment Regulatory material: 5% nickel-iron steel slag powder;

Calcium oxide excitation material: nickel-iron steel slag powder 5%; magnesium oxide excitation material is nickel-iron steel slag powder 6%; coagulation adjustment material is nickel-iron steel slag powder 5% water-material ratio is 0.45; 28-day compressive strength 38.4MPa, 28 Day flexural strength 2.41MPa.

Case 4

Nickel-iron steel slag powder is 70 parts of nickel-iron blast furnace slag, 30 parts of electric furnace refined nickel-iron slag; chemical composition control material is nickel-iron steel slag powder 10%; silicon-aluminum oxide excitation material is nickel-iron steel slag powder 10%; alkali environment control material 3% nickel-iron steel slag powder; calcium oxide excitation material is nickel-iron steel slag powder 1%; The daily compressive strength is 45.7MPa, and the 28-day flexural strength is 2.72MPa.

Case 5

Nickel-iron steel slag powder is 70 parts of nickel-iron blast furnace slag, 30 parts of electric furnace refined nickel-iron slag; chemical composition control material is nickel-iron steel slag powder 5%; silicon-aluminum oxide excitation material is nickel-iron steel slag powder 15%; alkali environment control material Nickel-iron steel slag powder 1%; calcium oxide excitation material is nickel-iron steel slag powder 3%; magnesium oxide excitation material is nickel-iron steel slag powder 2%; coagulation adjustment material is nickel-iron steel slag powder 2.5%; The daily compressive strength is 43.6MPa, and the 28-day flexural strength is 2.67MPa.

Case 6

The nickel-iron steel slag powder is 70 parts of nickel-iron blast furnace slag, 30 parts of electric furnace refined nickel-iron slag; the chemical composition control material is nickel-iron steel slag powder 15%; the silicon-aluminum oxide excitation material is nickel-iron steel slag powder 15% %; the alkali environment control material is nickel-iron steel slag powder 1%; the calcium oxide excitation material is nickel-iron steel slag powder 3%; the magnesium oxide excitation material is nickel-iron steel slag powder 2%; Nickel-iron steel slag powder 2.5%; the water-to-material ratio is .0.45; the 28-day compressive strength is 46.6MPa, and the 28-day flexural strength is 2.92MPa.

Case 7

The nickel-iron steel slag powder is 70 parts of nickel-iron blast furnace slag, 30 parts of electric furnace refined nickel-iron slag; the chemical composition control material is nickel-iron steel slag powder 10%; the silicon-aluminum oxide excitation material is nickel-iron steel slag powder 15% %; the alkali environment control material is nickel-iron steel slag powder 3%; the calcium oxide excitation material is nickel-iron steel slag powder 3%; the magnesium oxide excitation material is nickel-iron steel slag powder 4%; 5% nickel-iron steel slag powder; the water-to-material ratio is 0.45; the 28-day compressive strength is 45.9MPa, and the 28-day flexural strength is 2.91MPa.

Case 8

The nickel-iron steel slag powder is 100 parts of nickel-iron steel slag; the chemical composition control material is 5% of the nickel-iron steel slag powder; the silicon-aluminum oxide excitation material is 10% of the nickel-iron steel slag powder; the alkali environment The control material is 3% of nickel-iron steel slag powder; the calcium oxide excitation material is 3% of nickel-iron steel slag powder; the magnesium oxide excitation material is 6% of nickel-iron steel slag powder; 0.5% of powder; the water-material ratio is 0.45; 28-day compressive strength is 51.2MPa, and 28-day flexural strength is 3.05MPa.

Case 9

The nickel-iron steel slag powder is 100 parts of nickel-iron blast furnace slag; the chemical composition control material is nickel-iron steel slag powder 10%; the silicon-aluminum oxide excitation material is nickel-iron steel slag powder 15%; the alkali environment control The material is nickel-iron steel slag powder 5%; the calcium oxide excitation material is nickel-iron steel slag powder 5%; the magnesium oxide excitation material is nickel-iron steel slag powder 6%; the setting adjustment material is nickel-iron steel slag powder 5%; The water-material ratio is 0.45; the 28-day compressive strength is 55.3MPa; the 28-day flexural strength is 3.56MPa.

Case 10

The nickel-iron steel slag powder is 100 parts of nickel-iron blast furnace slag; the chemical composition control material is nickel-iron steel slag powder 15%; the silicon-aluminum oxide excitation material is nickel-iron steel slag powder 20%; the alkali environment control material It is nickel-iron steel slag powder 1%; the calcium oxide stimulating material is nickel-iron steel slag powder 5%; the magnesium oxide stimulating material is nickel-iron steel slag powder 4%; The water-to-material ratio is 0.45; the 28-day compressive strength is 57.9MPa, and the 28-day flexural strength is 3.35MPa.

The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Anyone skilled in the art , without departing from the scope of the technical solution of the present invention, when the technical content disclosed above can be used to make some changes or be modified into equivalent embodiments with equivalent changes, but as long as it does not depart from the technical solution of the present invention, the technical content of the present invention In essence, any brief modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solution of the present invention.

Claims (9)

1. A novel low-carbon environment-friendly ferronickel slag powder cementing material comprises blast furnace ferronickel slag, electric furnace refined ferronickel slag, chemical component regulating and controlling materials, alkali environment regulating and controlling materials, silicon aluminum oxide exciting materials, calcium oxide exciting materials, magnesium oxide exciting materials and coagulation regulating materials.

2. The novel low-carbon environment-friendly ferronickel slag powder cementing material according to claim 1, which is characterized in that:

the ferronickel slag powder comprises 50% -100% of blast furnace ferronickel slag and 0% -50% of electric furnace refined ferronickel slag, wherein the blast furnace ferronickel slag and the electric furnace refined ferronickel slag are mixed in proportion, balance and complement chemical components, and simultaneously improve the utilization of the low-activity electric furnace refined ferronickel slag;

the chemical component regulating and controlling material comprises common mineral powder, attapulgite and metakaolin silica fume, and the chemical components of the mixed slag are regulated and controlled by doping the material so as to improve the alkalinity coefficient, the activity coefficient and the quality coefficient of the mixed material;

the alkali environment regulating material comprises potassium hydroxide and sodium hydroxide, and the chemical reaction of the mixed slag is improved and excited by doping the potassium hydroxide and/or the sodium hydroxide to provide an alkali environment so as to accelerate the chemical reaction;

the silicon aluminum oxide excitation material comprises sodium silicate and potassium silicate, and the reaction of the silicon aluminum oxide is promoted by adding sodium silicate and/or potassium silicate;

the calcium oxide excitation material comprises potassium carbonate and sodium carbonate, the potassium carbonate and/or the sodium carbonate reacts with calcium oxide to generate nano calcium oxide, gaps are filled, the compactness is improved, and the strength is improved;

the magnesium oxide excitation material comprises ammonium dihydrogen phosphate and potassium dihydrogen phosphate, and solid magnesium phosphate cement is generated by adding ammonium dihydrogen phosphate and/or potassium dihydrogen phosphate to react with magnesium oxide;

the coagulation regulating material comprises sodium tripolyphosphate and/or citric acid and/or sodium polyphosphate and/or borax, wherein the sodium tripolyphosphate and/or citric acid and/or sodium polyphosphate and/or borax are adsorbed on the surfaces of reactants such as silicon aluminum and the like, so that the reaction speed is delayed, and the coagulation time is regulated.

3. The novel low-carbon environment-friendly ferronickel slag powder cementing material according to claim 2, which is characterized in that: the sodium silicate serving as an exciting agent is a reagent which can dissolve aluminosilicate minerals and enable solutes to react to prepare geopolymers, and is essentially a catalyst which plays a role in the chemical reaction process, and the exciting agent enables geopolymer raw materials to be depolymerized better, so that the activity of raw aluminosilicate is excited to promote the disintegration of the raw materials and the formation of hydration products, and the sodium silicate reacts with silicon-aluminum oxides as follows:

(1) And in the initial stage of the reaction, water glass is hydrolyzed, slag does not participate in the hydration reaction, and a silicon oxygen tetrahedron is generated: 2Na ₂ O ^. nSiO ₂ +2(n+1)H ₂ O→n Si(OH) ₄ +2NaOH

(2) Early stage of reaction, continuous hydrolysis of water glass, dissolution and dispersion of slag glass body, ca on the surface of slag glass body under the condition of alkaline solution water glass ²⁺ Ion adsorption of OH in alkaline solution ^- Ions to form hydroxides. On the surface of slag glass body by OH ^- After destruction, is Na ⁺ Providing the necessary passage into the interior of the slag vitreous body to allow Ca to ²⁺ With OH ^- And Na (Na) ⁺ A displacement reaction takes place and the reaction mixture is reacted,thus, the network structure of slag vitreous body is destroyed, so that slag is dispersed and dissolved;

(3) In the middle and later stages of the reaction, slag is completely hydrated, silicic acid is dehydrated and reacts with calcium hydroxide to generate calcium oxide gel (C-S-H), so that the slurry is compact, and the strength is improved;

Si(OH) ₄ →SiO ₂ +2H ₂ O

SiO ₂ +m ₁ Ca(OH) ₂₊ m ₂ H ₂ O→m ₁ CaO ^. SiO ₂ ^. (m ₁ +m ₂ )H ₂ O

Al ₂ O ₃ +M ₁ Ca(OH) ₂₊ M ₂ H ₂ O→M ₁ CaO ^. Al ₂ O ₃ ^. (M ₁ +M ₂ )H ₂ O

the reaction process is divided into 3 stages:

in stage 1, aluminosilicate minerals undergo dissolution reaction under the action of strong alkali, and Si-O and Al-O covalent bonds are broken, because of Al ³⁺ The hydrolysis product of (C) is obtained by using [ Al (OH) ₄ ]In the form of Si ⁴⁺ In strong alkaline solution, the hydrolysis product is mainly [ Si O (OH) ₃ ]-、[SiO ₂ (OH) ₂ ] ^2– In which water is Al ³⁺ And Si (Si) ⁴⁺ Providing a location for hydrolysis and polycondensation;

Al ₂ O ₃ +3H ₂ O+2OH ^- →2[Al(OH) ₄ ]–

SiO ₂ +H ₂ O+OH ^- →[Si O(OH) ₃ ]-

SiO ₂ +2OH ^- →[SiO ₂ (OH) ₂ ] ^2–

stage 2, dissolved [ Al (OH) ₄ ]-、[Si O(OH) ₃ ] ^- 、[Si O ₂ (OH) ₂ ] ^2- Ion-generating recombination depolymerization reactionIn response, an oligomeric silicon aluminum tetrahedral unit gel with (-OH) groups is generated;

step 3, performing polycondensation and dehydration reaction among the hydroxyl groups of the formed oligomeric silicon aluminum tetrahedral unit gel, gradually removing residual water to generate a layered Si-O-Al compact structure, and solidifying and hardening to obtain a geological polymerization block;

4. the novel low-carbon environment-friendly ferronickel slag powder cementing material according to claim 2, which is characterized in that: the calcium oxide activated material reaction comprises the following steps:

(1) Dissolution of calcium oxide

CaO+H ₂ O→Ca(OH) ₂

(2) Production of nano calcium carbonate

Ca(OH) ₂ +Na ₂ CO ₃ →CaCO ₃ +NaOH

5. The novel low-carbon environment-friendly ferronickel slag powder cementing material according to claim 2, which is characterized in that: the magnesium oxide excitation material reaction comprises the following steps:

(1) And dissolving phosphate. The phosphate can be dissolved in water and then has H ⁺ Releasing the acid to make the solution environment acidic.

KH ₂ PO ₄ The dissolution process of (2) is as follows:

KH ₂ PO ₄ →H ₂ PO ₄ ^- +K ⁺

H ₂ PO ₄ ^- →HPO ₄ ^2- +H ⁺

HPO ₄ ^2- →PO ₄ ^3- +H ⁺

(2) And dissolving magnesium oxide in the mixed nickel-iron slag. Mg O is slightly water-soluble and the solubility of phosphate in water is much higher than Mg O, so that MgO dissolution begins to occur after phosphate dissolution causes the solution to become an acidic environment. The surface of Mg O particles is H ⁺ And water to form complex Mg (OH) 2, the complex continuously releases Mg ²⁺ And in hydrated gel Mg (H) ₂ O) ₆ ²⁺ The form of (c) is present in an aqueous solution and can be described as:

Mg O+H ₂ O→Mg(OH) ₂

Mg(OH) ₂ →Mg ²⁺ +OH ^-

Mg ⁺ +6H ₂ O→Mg(H ₂ O) ₆ ²⁺

(3) And forming the magnesium phosphate cement. H in solution ⁺ With OH ^- Neutralization is carried out, and Mg (H) ₂ O) ₆ ²⁺ 、PO ₄ ^3- And K ⁺ Then combine together to form a hydration product (Mg KPO ₄ ·6H ₂ O, MKP). The hydration reaction is continuously developed, MKP and Mg O particles remained after the reaction are bonded together, and finally the magnesium phosphate cement stone taking Mg O as a framework is produced, and the reaction formula is as follows:

Mg(H ₂ O) ₆ ²⁺ +PO ₄ ^3- +K ⁺ →Mg KPO ₄ °6H ₂ O。

6. the novel low-carbon environment-friendly ferronickel slag powder cementing material according to claim 2, 3 or 4, which is characterized in that: the total content of the common mineral powder and/or attapulgite and/or metakaolin and/or silica fume is 0-15%, the total content of potassium hydroxide and/or sodium hydroxide is 1-5%, the total content of sodium silicate and/or potassium silicate is 5-20%, the total content of ammonium dihydrogen phosphate and/or potassium dihydrogen phosphate is 1-6%, and the total content of sodium tripolyphosphate and/or citric acid and/or sodium polyphosphate and/or borax is 0.5-5%.

7. The novel low-carbon environment-friendly ferronickel slag powder cementing material according to claim 5, which is characterized in that:

the ferronickel slag powder is 100 parts of ferronickel blast furnace slag; the chemical component regulating and controlling material is ferronickel slag powder 5%; the silicon aluminum oxide excitation material is ferronickel slag powder 10%; the alkali environment regulating material is ferronickel slag powder 3%; the calcium oxide excitation material is ferronickel slag powder 3%; the magnesium oxide excitation material is 6% of ferronickel slag powder; the setting material is ferronickel slag powder 0.5%; the water-material ratio is 0.45; the compressive strength of the steel plate is 51.2MPa in 28 days, and the flexural strength of the steel plate is 3.05MPa in 28 days.

8. The novel low-carbon environment-friendly ferronickel slag powder cementing material according to claim 5, which is characterized in that:

the ferronickel slag powder is 100 parts of ferronickel blast furnace slag; the chemical component regulating and controlling material is 10% of ferronickel slag powder; the silicon aluminum oxide excitation material is ferronickel slag powder 15%; the alkali environment regulating material is ferronickel slag powder 5%; the calcium oxide excitation material is ferronickel slag powder 5%; the magnesium oxide excitation material is 6% of ferronickel slag powder; the coagulation regulating material is ferronickel slag powder 5%; the water-material ratio is 0.45; the 28-day compression strength is 55.3MPa; the flexural strength of the steel plate is 3.56MPa after 28 days.

9. The novel low-carbon environment-friendly ferronickel slag powder cementing material according to claim 5, which is characterized in that:

the ferronickel slag powder is 100 parts of ferronickel blast furnace slag; the chemical component regulating and controlling material is ferronickel slag powder 15%; the silicon aluminum oxide excitation material is ferronickel slag powder 20%; the alkali environment regulating material is 1% of ferronickel slag powder; the calcium oxide excitation material is ferronickel slag powder 5%; the magnesium oxide excitation material is ferronickel slag powder 4%; the setting material is ferronickel slag powder 0.5%; the water-material ratio is 0.45; the compressive strength of the steel plate is 57.9MPa in 28 days, and the flexural strength of the steel plate is 3.35MPa in 28 days.