Method for preparing repair material for hydraulic concrete from solid waste material

Abstract

The invention provides a method for preparing a repair material for hydraulic concrete by using a solid waste material. The preparation method comprises the following steps: mixing 55-65% of a material A (water-quenched slag and copper slag), 30-40% of a material B (citric acid gypsum, red mud and spontaneous combustion coal gangue) and 4-6% of a catalytic complexing activator (cane molasses, iron ion catalytic complexing agent sodium thiocyanate leftovers, polyether amine, calcium ion catalytic complexing agent diisopropanolamine borate and water), and carrying out ball milling to obtain the concrete; the repairing material and water are uniformly stirred according to the ratio and then are brushed or sprayed on the base surface of the defective concrete, so that the effects of resisting scouring, resisting erosion and freezing and thawing can be achieved, the effect of further cracking and falling off of the concrete is inhibited, and the durability of the hydraulic concrete is improved.

Description

Technical Field

[0001] This invention belongs to the field of novel inorganic building materials technology, and relates to a method for preparing repair materials for hydraulic concrete using solid waste materials. Background Technology

[0002] Hydraulic concrete is concrete used in hydraulic structures that are in long-term contact with water. It not only bears conventional mechanical loads but also needs to meet durability requirements such as impermeability, frost resistance, and corrosion resistance. It is commonly used in water conservancy projects such as dams, sluices, and riverbanks. Based on the environment of use, it is divided into underwater, water level fluctuation zones, and above-water applications. For large-volume hydraulic concrete, the heat of hydration needs to be controlled to reduce temperature cracks. Technical requirements, in addition to strength, place greater emphasis on erosion resistance. Therefore, in addition to meeting general concrete requirements, hydraulic concrete must possess considerable durability indicators such as frost resistance, impermeability, and resistance to erosion and abrasion. Because hydraulic concrete is frequently exposed to the atmosphere and water, it is subject to long-term erosion by water, penetration and corrosion by chloride and sulfate ions in the water, exposure to sunlight, rain, snow, wind, frost, and the freeze-thaw cycle of winter. This can easily cause the surface concrete to crack and peel off, exposing aggregates and even reinforcing steel. As the depth of surface concrete damage increases, it can lead to water leakage and even the collapse of dams. Therefore, seepage prevention, crack resistance, and repair technologies for water conservancy projects are receiving increasing attention.

[0003] Currently, the main methods for crack repair in hydraulic concrete engineering are as follows: (1) Using anti-crack repair mortar. Because the mortar contains an expansion agent component, it can compensate for the volume change caused by the shrinkage of the surface mortar. When the repair mortar is applied to the concrete surface, it shows no cracking phenomenon. By reducing mortar cracking and improving density, the impermeability of the hydraulic concrete surface is improved; (2) Using two-component organic polymer coating. The coating is applied to the damaged concrete surface. Through the hydrophobicity of the coating surface, it blocks the penetration of water and reduces water penetration and freeze-thaw damage. The above scheme has the following disadvantages: (1) After the crack-resistant repair mortar is applied to the damaged hydraulic concrete surface, although there are no cracks on the concrete surface in the short term after construction, after the winter freeze-thaw cycle and water scouring, especially after the water scouring force is higher than 0.4MPa, the bonding performance between the repair mortar and the base layer will decrease, and the repair mortar will slowly crack and fall off, with poor scouring resistance; (2) The two-component organic polymer coating has poor aging resistance, especially under long-term water immersion and scouring, the aging resistance will be significantly reduced, resulting in surface peeling; (3) In addition, the above two materials are poor in terms of corrosion resistance, especially the discharge of domestic or industrial acidic sewage will erode the surface of the coating, and the surface concrete will be significantly damaged; (4) The two-component organic polymer will cause water pollution and affect water quality under long-term water scouring. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a method for preparing repair materials for hydraulic concrete using solid waste materials. Based on the characteristics of solid waste materials, this invention uses various solid waste materials, which are separately ground and then mixed with an activator before being ground together to prepare the repair material. Then, according to the degree of defects in the concrete substrate, the ratio of the repair material to water is adjusted, and the mixture is thoroughly stirred before being brushed or sprayed onto the defective concrete substrate. This provides resistance to erosion, corrosion, and freeze-thaw cycles, inhibits further cracking and spalling of the concrete, and improves the durability of hydraulic concrete.

[0005] The technical solution of this invention is: a method for preparing a repair material for hydraulic concrete using solid waste materials, characterized in that 55-65% of material A, 30-40% of material B, and 4-6% of catalytic complexing activator are mixed and ball-milled to obtain the repair material with a fineness controlled to a specific surface area of ​​650-800 m². 2 / kg; The preparation method of material A is as follows: 70-80% water-quenched slag and 20-30% copper slag are mixed and then ball-milled to control the fineness to a specific surface area of ​​450-550 μm. 2 / kg; The preparation method of material B is as follows: 30-40% citric acid gypsum, 30-40% red mud and 20-30% self-igniting coal gangue are mixed and then ball-milled, and the fineness is controlled at a specific surface area of ​​350-400 μm². 2 / kg; The raw materials and weight parts of the catalytic complexing activator are: 3-10 parts of sugarcane molasses, 8-10 parts of iron ion catalytic complexing agent sodium thiocyanate by-product, 5-10 parts of polyetheramine (molecular weight 200-250), 25-35 parts of calcium ion catalytic complexing agent diisopropanolamine borate, and 40-45 parts of water. All percentages mentioned above are by weight.

[0006] Among them, water-quenched slag is slag obtained by rapid quenching with high-pressure water during the ironmaking process. Its main components and contents are: CaO 35-45%, SiO2 30-40% and Al2O3 6-10%.

[0007] Copper slag is a solid waste that floats on the surface during the copper smelting process. Its main components and contents are: SiO2 30-40%, Fe2O3 40-50%, CaO 5.0-6.0% and Al2O3 3.5-4.5%.

[0008] Citric acid gypsum is obtained by filtering and dehydrating waste materials from the citric acid production process. Its main components and contents are: CaSO4·2H2O ≥85%, citric acid ≥0.2%.

[0009] Red mud is obtained by dehydrating the slurry-like waste generated during the alumina production process. Its main components and contents are: SiO2 10-15%, Fe2O3 20-30%, CaO 30-40%, Al2O3 6-10%, and Na2O 4.0-6.0%.

[0010] Among them, spontaneously combusting coal gangue is produced during coal mining and obtained after spontaneous combustion during long-term storage. Its main components and contents are: SiO2 50-60%, Fe2O3 5.5-6.5%, CaO 4.0-6.0% and Al2O3 25-35%.

[0011] Among them, the iron ion catalytic complexing agent sodium thiocyanate waste is a crude residue by-product generated in the production of fine chemical sodium thiocyanate, and its sodium thiocyanate (NaSCN) content is 45-55%.

[0012] Further, the preparation method of calcium ion catalytic complexing agent diisopropanolamine borate ester is as follows: (1) Add liquid diisopropanolamine and xylene to a reaction stirrer, heat to 100-120℃ and reflux for 0.5-1.5h under stirring to remove water from diisopropanolamine; (2) Then add boric acid and concentrated sulfuric acid as catalyst, stir and react for 2-4h to generate diisopropanolamine borate ester mixture; (3) Finally heat to 135-145℃ and reflux for 0.5-1.5h to remove xylene and obtain calcium ion catalytic complexing agent diisopropanolamine borate ester; the mass ratio of liquid diisopropanolamine, boric acid and concentrated sulfuric acid as catalyst is 1:0.3-0.4:0.01-0.10.

[0013] Furthermore, the ball milling of material A is as follows: it first enters a vertical mill, and after initial grinding in the vertical mill, it enters an open-circuit ball mill (where the length-to-diameter ratio of the ball mill is >5) for ball milling.

[0014] Furthermore, the ball milling of material B is as follows: it is ball milled in an open-circuit ball mill (where the length-to-diameter ratio of the ball mill is >5).

[0015] Furthermore, the construction method for the repair material prepared by the above method: (1) Remove the loose structure on the original surface of the concrete base. It is necessary to remove it down to the solid concrete surface and roughen it. It should be moistened and free of standing water before construction. (2) If there are large cracks on the base surface, the cracks need to be treated first. The repair material prepared in this invention is mixed with water at a mass ratio of 1:0.25-0.35 and then filled into the cracks. (3) Mix the repair material and water at a mass ratio of 1:0.2-0.3 and apply the mixture to the concrete surface by troweling or spraying. The thickness of the trowel should be 1.0-1.5 mm, and the application should be done in two coats. (4) Moisturize and maintain the surface after the plastering is completed; (5) After the curing is completed, the repair material and quartz sand (70-120 mesh) are mixed at a mass ratio of 1:0.8-1.2. After the mixture is stirred evenly with water, the surface leveling layer is constructed and cured for 3-5 days.

[0016] The technical principle of this invention is as follows: (1) By using different mills, the particle size distribution range of the repair material is wide and the sphericity of the particles is high; by the dispersion effect of -OH ions and -NH2 ions in the activator, the particle size distribution of the repair material in the air jet mill is made uniform, which promotes the formation of more compact hydration products and is conducive to the particles exerting hydration strength at different ages. (2) Two catalytic complexing agents are used to act on different ions respectively. After construction, the repair material undergoes a hydration reaction. Under the action of calcium ions and iron ions, the repair material and the concrete base surface generate a high concentration of OH in the pore solution. -Ions can directly break the Si-O and Al-O chemical bonds on the surface of the repair material and the original concrete, allowing the solid waste material and the original concrete base to dissolve faster. The more gel formed by the reaction product, the faster the material strength develops. The repair material and the original concrete base are integrated through the hydration product. (3) When the solid waste material particles in the repair material are dissolved, the ion concentration in the pore solution will affect the hydration product. When the calcium content in the initial slag is mainly calcium under the action of the calcium ion catalytic complexing agent in the repair material, an alkali calcium-alumina silicate hydrate (CaO-Na2O-Al2O3-SiO2-H2O, abbreviated as CNASH) gel will be formed. When the calcium content is consumed and the aluminum in the red mud is dominant, an alkali alumina silicate (Na2O-Al2O3-SiO2-H2O, abbreviated as NASH) gel will be formed. Both products have improved impermeability, water erosion resistance, and freeze-thaw resistance. The pore solution catalytic complexing agent is the core material that controls and promotes the formation of hydration products. In particular, the freeze-thaw resistance and abrasion resistance of alkali aluminosilicate gel are significantly better than those of hydrated calcium silicate gel in ordinary cement hydration. (4) The high durability (impermeability, freeze-thaw resistance, and corrosion resistance) of the repair material after construction largely depends on the complexing catalytic effect of the pore solution complexing catalyst on ions. On the one hand, it can maintain the stability of the internal gel, prevent it from decomposing during service, and improve the density of the gel in the pore solution; on the other hand, the alkalinity in the pore solution will form a "passivation film" on the surface of the exposed steel bars of the concrete, which prevents the corrosion of the internal steel bars under the catalytic effect of the catalytic complexing agent. (5) The retardation effect of -OH in the molasses in the activator provides an early catalytic complexing time for the complexing agent to play its role, especially in summer construction; the sodium thiocyanate waste not only controls the hydration time of the repair material at different construction stages, but also complexes iron ions to form more hydrated calcium ferrite with anti-permeability and anti-corrosion properties. This hydration product is superior to the hydrated calcium silicate formed by ordinary protective coatings; polyetheramine improves the curing and bonding effect between the repair material and the concrete base, making the repair material more resistant to impact and abrasion; (6) By controlling the water-material ratio of the repair material at different stages of use, the hydration products of the complexing agent catalyst are more conducive to the generation.

[0017] In summary, this invention, through the action of two catalytic complexing raw materials in the activator on calcium and iron ions in solid waste materials, can improve the density of the hydration product gel of concrete base layer and form new hydrated alkali aluminosilicate (NASH) gel, alkali calcium-aluminosilicate hydrate (CNASH) gel, and generate more hydrated calcium ferrite gel with anti-erosion function. On the one hand, it can block and compact the cracks of the original concrete and fuse it with the original concrete. On the other hand, it can repair the detached concrete and form erosion-resistant and scour-resistant hydration gel products, improve the concrete's impermeability, erosion resistance, scour resistance, and freeze-thaw resistance, and solve the problems of concrete surface cracking and even water seepage.

[0018] Compared with existing repair materials, the repair material of this invention has the following advantages: 1. The repair material is applied to the surface of the defective concrete, and the interface area between the two is hydrated and fused together. The application can improve the erosion resistance and freeze-thaw resistance, and reduce the risk of surface peeling of hydraulic concrete in water erosion and freeze-thaw environment. 2. Reduce the penetration and erosion of sulfate and chloride ions on the surface of hydraulic concrete, and avoid surface damage caused by the penetration and destruction of the concrete surface by salt ions in the water; 3. Made of inorganic materials, it has good durability and avoids water pollution caused by organic coatings; 4. Employ industrial solid waste materials as the primary source for green manufacturing and reduce carbon emissions. Attached Figure Description

[0019] Fig. 1 Scanning electron microscope (SEM) images (28d) of hydration products formed after commercially available crack-resistant repair mortar penetrates into concrete substrates. Fig. 2 Scanning electron microscope image (28d) of hydration products formed after a commercially available two-component coating penetrates a concrete substrate. Fig. 3 This is a scanning electron microscope image (28d) of the hydration products formed after the repair material of this invention is applied to a concrete substrate. Detailed Implementation

[0020] The effects are illustrated below with reference to the embodiments and accompanying drawings. The sugarcane molasses contains 30±1% sucrose and 20±1% reducing sugar. The water-quenched slag is slag obtained by rapid quenching with high-pressure water during ironmaking, and its main components and contents are: CaO 40.5%, SiO2 34.6%, Al2O3 8.2%, MgO 3.5%, and Fe2O3 4.5%. The copper slag is solid waste floating on the surface during copper smelting, and its main components and contents are: SiO2 34.3%, Fe2O3 42.5%, CaO 5.5%, Al2O3 4.2%, MgO 2.3%, CuO 1.3%, and MnO 1.5%. The citric acid gypsum is obtained by filtering and dehydrating waste materials from citric acid production, and its main components and contents are: CaSO4·2H2O 90.9% and citric acid 0.3%. Red mud is obtained by dehydrating the slurry-like waste generated during alumina production. Its main components and contents are: SiO2 12.3%, Fe2O3 26.6%, CaO 33.1%, Al2O3 7.9%, MgO 1.3%, Na2O 4.5%. Spontaneously combusting coal gangue is obtained by spontaneously combusting during coal mining and long-term stockpiling. Its main components and contents are: SiO2 56.3%, Fe2O3 5.8%, CaO 4.5%, Al2O3 29.2%. Iron ion catalytic complexing agent sodium thiocyanate by-product is a coarse slag by-product generated during the production of the fine chemical sodium thiocyanate. It is formed by repeatedly evaporating, concentrating, cooling, and crystallizing the coarse slag during the synthesis of sodium cyanide and sulfur. Its main components and contents are: NaSCN 45%, Na2SO4 10%, NaCl 5%, water 40%.

[0021] Example 1: Preparation method of hydraulic concrete repair material: 60% material A + 35% material B + 5% catalytic complexing activator are ball-milled in an ultrafine air jet mill. The fineness of the repair material is controlled to have a specific surface area of ​​650-800 m². 2 / kg.

[0022] Preparation method of material A: 75% water-quenched slag and 25% copper slag are fed into a vertical mill. After primary grinding in the vertical mill, they are fed into an open-circuit ball mill (where the length-to-diameter ratio of the ball mill is >5) for ball milling. The fineness is controlled at a specific surface area of ​​450-550 μm². 2 / kg.

[0023] Preparation method of material B: 40% citric acid gypsum, 35% red mud and 25% self-igniting coal gangue are fed into an open-circuit ball mill (where the length-to-diameter ratio of the ball mill is >5) for ball milling, and the fineness is controlled at a specific surface area of ​​350-400 μm². 2 / kg.

[0024] The catalytic complexing activator is composed of: 4 parts sugarcane molasses, 9 parts iron ion catalytic complexing agent sodium thiocyanate waste, 8 parts polyetheramine (molecular weight 200-250), 30 parts calcium ion catalytic complexing agent diisopropanolamine borate, and 42 parts water. Preparation method of calcium ion catalytic complexing agent diisopropanolamine borate: (1) Add 150g liquid diisopropanolamine (concentration 95%) and 50g xylene to a reaction stirrer, heat to 100-120℃ and reflux for 1h under stirring to remove water from diisopropanolamine; (2) Then add 50g boric acid and 8g concentrated sulfuric acid catalyst, stir and react for 3h to generate diisopropanolamine borate mixture; (3) Finally heat to 140℃ and reflux for 1h to remove xylene and obtain calcium ion catalytic complexing agent diisopropanolamine borate.

[0025] Construction method of the repair material prepared by the above method: (1) Remove the loose structure on the original surface of the concrete base. It is necessary to remove it down to the solid concrete surface and roughen it. It should be moistened and free of standing water before construction. (2) If there are large cracks on the base surface, the cracks need to be treated first. Remove debris and dust from the cracks, and use the repair material prepared in this invention to mix with water at a mass ratio of 1:0.3 to fill the cracks evenly. (3) Use the repair material and water at a mass ratio of 1:0.25, mix them evenly, and apply them to the concrete surface by troweling or spraying. The thickness of the trowel is 1.2 mm. Apply it in two layers. The first layer is 0.5 mm. After the first layer of repair material has initially set, apply the second layer of 0.7 mm. (4) After the surface is finished, keep it moist and maintain it. You can use water spray or cover it with a damp cloth to keep it moist and maintain it for at least 72 hours. (5) After the curing is completed, the repair material and quartz sand (70-120 mesh) are mixed in a 1:1 ratio, and the mixture is mixed with water in a 1:0.2 mass ratio. After stirring evenly, the surface leveling layer is constructed and cured for 3-5 days.

[0026] The following is a comparative test of hydraulic concrete repair materials and commercially available repair materials.

[0027] 1. The durability test of hydraulic concrete was conducted in accordance with GB / T50082 "Test Methods for Long-Term Performance and Durability of Concrete"; the abrasion resistance test of hydraulic concrete was conducted in accordance with DL / T 5150-2017 "Hydraulic Concrete" to test the 28-day impact abrasion strength ratio, and the concrete mix design was based on the C30 concrete test (see Table 1). The test results are as follows: Table 1. Mix proportions of C30 hydraulic concrete (kg / m³) 3 )

[0028] Note: Cement is PO42.5 grade, mineral powder is S95 grade, fly ash is grade II, manufactured sand fineness modulus is 2.8, crushed stone particle size is 5-25mm, and polycarboxylate superplasticizer has a water reduction rate of 25%. 2. After the concrete is formed, the surface is coated with commercially available crack-resistant mortar, commercially available two-component material, and the repair material prepared in this invention (the three are applied in the same way, and the construction method of this invention is the same). After curing for 28 days, the durability index is tested. The test results are shown in Table 2 below.

[0029] Table 2 Indicator Test Results

[0030] Note: The main components of crack-resistant repair mortar are 20% ordinary silicate cement, 20% sulfoaluminate cement, 40% quartz sand, and 20% magnesium oxide expansion agent; commercially available two-component coatings are composed of component A (acrylic emulsion) and component B (cement 60% and quartz sand 40%).

[0031] Analysis: The repair material prepared in this invention showed significantly reduced strength and mass loss in sulfate attack resistance and freeze-thaw cycle resistance tests, indicating that the hydration products of the repair material improved its freeze-thaw resistance and sulfate attack resistance. Furthermore, the water erosion resistance reached 160%, indicating that after application to concrete surfaces, the concrete became denser, more wear-resistant, and significantly improved its erosion resistance. The water permeability resistance grade increased from P6 to P10, and the chloride ion permeability coefficient was 2.0*10. -12 The m / s flow rate significantly improves impermeability, indicating that the concrete surface soil produces more products and has a denser internal structure.

[0032] 3. Electron microscopy scanning comparison of the hydration products formed after the above coatings penetrated onto the concrete substrate. Figs. 1-3 As shown in the scanning electron microscope images above, the repair material prepared in this invention, when applied to a concrete substrate, forms needle-like, dense structures of alkali-calcium-aluminosilicate hydrate (CNASH) gel and alkali-aluminosilicate (NASH) gel. In contrast, the hydration products of commercially available crack-resistant repair mortars and two-component coatings on the concrete substrate are primarily hydrated calcium silicate (CSH) gel. This indicates that the repair material prepared in this invention forms erosion-resistant products on the concrete substrate through penetration. In contrast, the hydration products formed by commercially available crack-resistant repair mortars and two-component coatings on concrete substrates are insufficient to prevent water erosion and sewage corrosion.

[0033] Example 2: (Preparation of hydraulic concrete repair materials, construction in water conservancy projects, and core sampling testing of technical indicators): 1. Preparation of hydraulic concrete repair materials 60% material A, 35% material B, and 5% catalytic complexing activator were mixed and then ground in an air jet mill to control the fineness and specific surface area of ​​the repair material to 680 m². 2 / kg.

[0034] Material A consists of 80% water-quenched slag and 20% copper slag, which are fed into a vertical mill in a specific ratio. After grinding, the mixture enters an open-circuit ball mill with a length-to-diameter ratio of 6, and the fineness is controlled at a specific surface area of ​​530 μm³. 2 / kg.

[0035] Material B, consisting of 35% citric acid gypsum, 40% red mud, and 25% self-igniting coal gangue, enters an open-circuit ball mill with a length-to-diameter ratio of 6, and its fineness is controlled at a specific surface area of ​​380 m² / g. 2 / kg.

[0036] The catalytic complexing activator is composed of: 8 parts sugarcane molasses, 10 parts sodium thiocyanate by-product (iron ion catalytic complexing agent), 10 parts polyetheramine (molecular weight 220), 27 parts diisopropanolamine borate (calcium ion catalytic complexing agent), and 45 parts water. The preparation method of diisopropanolamine borate (calcium ion catalytic complexing agent) is the same as in Example 1.

[0037] 2. Application of repair materials in the construction of a water conservancy project in Dezhou (1) Remove the original loose concrete base surface. It is necessary to remove it to a solid base surface and roughen it. Wet it but there should be no standing water. (2) Treat the surface cracks by mixing the repair material with water at a mass ratio of 1:0.3 and filling the cracks evenly; (3) Mix the repair material and water at a mass ratio of 1:0.25, apply the mixture to the concrete surface, and apply the mixture in two coats with a thickness of 1.2 mm. (4) Moisturize and maintain the surface after applying the product. You can use water spray or cover it with a damp cloth to maintain moisture. The maintenance period should not be less than 72 hours.

[0038] (5) After the curing is completed, the repair material and quartz sand (70-120 mesh) are mixed in a 1:1 ratio, and the mixture is mixed with water in a mass ratio of 1:0.23. After stirring evenly, the surface leveling layer is constructed and water is sprayed for curing for 5 days.

[0039] 3. Core sampling test indicators of hydraulic concrete 28 days after the application of hydraulic concrete repair materials. The tests were conducted in accordance with GB / T50082 "Test Methods for Long-Term Performance and Durability of Concrete"; the abrasion resistance was tested according to DL / T 5150-2017 "Hydraulic Concrete" for 28-day impact and abrasion resistance ratio. The test data are shown in Table 3 below.

[0040] Table 3 Indicator Test Results

[0041] Analysis: Through application of the repair material to concrete in hydraulic engineering projects, the strength and mass loss were significantly reduced in sulfate attack resistance and freeze-thaw cycle resistance tests, indicating a significant improvement in the repair material's freeze-thaw resistance and corrosion resistance. The water-wash abrasion resistance reached 175%, and the chloride ion permeability coefficient was 2.1*10⁻⁶. -12 With a permeability of m / s and a permeability of P10, the risk of concrete cracking is reduced after the concrete base is repaired, and the erosion resistance is significantly improved.

Claims

1. A method for preparing repair materials for hydraulic concrete using solid waste materials, characterized in that, The material is obtained by mixing 55-65% of material A, 30-40% of material B, and 4-6% of catalytic complexing activator, followed by ball milling, to achieve a fineness control of the repair material with a specific surface area of ​​650-800 m². 2 / kg; The preparation method of material A is as follows: 70-80% water-quenched slag and 20-30% copper slag are mixed and then ball-milled to control the fineness to a specific surface area of ​​450-550 μm. 2 / kg; The preparation method of material B is as follows: 30-40% citric acid gypsum, 30-40% red mud and 20-30% self-igniting coal gangue are mixed and then ball-milled, and the fineness is controlled at a specific surface area of ​​350-400 μm². 2 / kg; The raw materials and weight parts of the catalytic complexing activator are: 3-10 parts of sugarcane molasses, 8-10 parts of iron ion catalytic complexing agent sodium thiocyanate waste, 5-10 parts of polyetheramine, 25-35 parts of calcium ion catalytic complexing agent diisopropanolamine borate ester, and 40-45 parts of water. All percentages mentioned above are by weight.

2. The method as described in claim 1, characterized in that, The preparation method of the calcium ion catalytic complexing agent diisopropanolamine borate ester is as follows: (1) Add liquid diisopropanolamine and xylene to a reaction stirrer, heat to 100-120℃ and reflux for 0.5-1.5h under stirring to remove water from diisopropanolamine; (2) Then add boric acid and concentrated sulfuric acid as catalyst, stir and react for 2-4h to generate a diisopropanolamine borate ester mixture; (3) Finally heat to 135-145℃ and reflux for 0.5-1.5h to remove xylene and obtain calcium ion catalytic complexing agent diisopropanolamine borate ester; the mass ratio of liquid diisopropanolamine, boric acid and concentrated sulfuric acid as catalyst is 1:0.3-0.4:0.01-0.

10.

3. The method as described in claim 1, characterized in that, The water-quenched slag is slag obtained by rapid quenching with high-pressure water during the ironmaking process, and its main components and contents are: CaO 35-45%, SiO2 30-40% and Al2O3 6-10%; The copper slag is a solid waste that floats on the surface during the copper smelting process. Its main components and contents are: SiO2 30-40%, Fe2O3 40-50%, CaO 5.0-6.0% and Al2O3 3.5-4.5%.

4. The method as described in claim 1, characterized in that, The citric acid gypsum is obtained by filtering and dehydrating waste materials from the citric acid production process. Its main components and contents are: CaSO4·2H2O ≥85%, citric acid ≥0.2%; The red mud is obtained by dehydrating the slurry-like waste generated during the alumina production process. Its main components and contents are: SiO2 10-15%, Fe2O3 20-30%, CaO 30-40%, Al2O3 6-10%, and Na2O 4.0-6.0%.

5. The method as described in claim 1, characterized in that, The self-igniting coal gangue is produced during coal mining and obtained after spontaneous combustion during long-term storage. Its main components and contents are: SiO2 50-60%, Fe2O3 5.5-6.5%, CaO 4.0-6.0% and Al2O3 25-35%.

6. The method as described in claim 1, characterized in that, The iron ion catalytic complexing agent sodium thiocyanate waste is a coarse slag by-product generated during the production of sodium thiocyanate, and its sodium thiocyanate content is 45-55%; the polyetheramine has a molecular weight of 200-250.

7. The method as described in claim 1, characterized in that, The ball milling of material A is as follows: it first enters a vertical mill, and after primary grinding in the vertical mill, it enters an open-circuit ball mill for ball milling. The ball milling of material B is as follows: it is fed into an open-circuit ball mill for ball milling.

8. The method of claim 7, characterized in that, The length-to-diameter ratio of the open-circuit ball mill is >5.

9. The concrete repair material prepared by the method of any one of claims 1-8.

10. The construction method of the concrete repair material according to claim 9, characterized in that, (1) Remove the loose structure on the original surface of the concrete base. It is necessary to remove it down to the solid concrete surface and roughen it. It should be moistened and free of standing water before construction. (2) If there are large cracks on the base surface, the cracks need to be treated first. The repair material prepared in this invention is mixed with water at a mass ratio of 1:0.25-0.35 and then filled into the cracks. (3) Mix the repair material and water at a mass ratio of 1:0.2-0.3 and apply the mixture to the concrete surface by troweling or spraying. The thickness of the trowel should be 1.0-1.5 mm, and the application should be done in two coats. (4) Moisturize and maintain the surface after the plastering is completed; (5) After the curing is completed, the repair material and quartz sand are mixed at a mass ratio of 1:0.8-1.

2. After the mixture is stirred evenly with water, the surface leveling layer is constructed and cured for 3-5 days.

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