CN110683775B - Solid waste utilization type flame-retardant-high shear force integrated inorganic adhesive and preparation method thereof - Google Patents

Abstract

The invention discloses a solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive and a preparation method thereof, belonging to the field of solid waste resource utilization. The inorganic adhesive comprises a composite grinding aid, slag, stainless steel slag, high-silica bauxite, phosphorous slag, graphene oxide, a composite alkali activator, water and manganese slag. The composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine; the slag, the stainless steel slag, the high-silicon bauxite, the phosphorus slag and the manganese slag are all industrial solid wastes; the compound alkali activator is a mixture of water glass and sodium hydroxide. The invention not only reduces the production cost of the existing inorganic adhesive, but also improves the flame retardant property and the shearing force of the inorganic adhesive, realizes the integration of flame retardant and high shearing force in the inorganic adhesive, and greatly enhances the market competitiveness and the application range of the inorganic adhesive; meanwhile, a new concept of large-scale and high-added-value application of slag, stainless steel slag, high-silicon bauxite, phosphorus slag and manganese slag is expanded.

Description

Solid waste utilization type flame-retardant-high shear force integrated inorganic adhesive and preparation method thereof

Technical Field

The invention belongs to the field of solid waste resource utilization, and particularly relates to a solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive and a preparation method thereof.

Background

Slag is a byproduct in a blast furnace ironmaking process, namely solid waste, and the main components of the slag are melts of silicate and aluminosilicate; high silicon bauxite is a silicon to aluminum ratio (Al)₂O₃/SiO₂) Lower bauxite results in higher production costs and poor product quality for desiliconizing refined alumina due to its lower alumina content. Meanwhile, the stainless steel slag, the phosphorus slag and the manganese slag are common solid wastes, wherein the main components of the stainless steel slag are CaO and Fe₂O₃、SiO₂And small amount of ZnO, CuO and Cr₂O₃Heavy metal oxides such as PbO; the main components of the phosphorous slag are CaO and SiO₂、P₂O₅The manganese slag comprises CaO and SiO as main components₂And MnO. At present, a large amount of slag, high-silicon bauxite, stainless steel slag, phosphorus slag and manganese slag are piled in the open air, which not only occupies valuable land, but also causes pollution to the surrounding environment and underground water. Therefore, how to utilize slag, high-silicon bauxite, stainless steel slag, phosphorus slag and manganese slag with large scale and high added value to realize environment reduction and enterprise synergy is a problem which needs to be solved urgently.

The carbon fiber cloth and the adhesive are mainly used for adhering the carbon fiber cloth to reinforce the concrete structure. The carbon fiber cloth has excellent flame retardant performance, and the physical and mechanical properties of the carbon fiber cloth are not attenuated when the temperature is lower than 1500 ℃ under the anaerobic condition. However, the currently used matching adhesive is epoxy organic adhesive with low softening point, the thermal stability and long-term chemical stability of the adhesive are poor, and particularly the upper temperature resistance limit of the adhesive is not more than 80 ℃. The temperature of the building fire can reach thousands of degrees centigrade, if the fire resistance of the carbon fiber cloth sticking reinforced structure is not paid enough attention, the carbon fiber cloth is easy to peel off from the concrete once a fire happens, and the reinforcing and reinforcing effects are difficult to be exerted.

Disclosure of Invention

The method aims to solve the problems that the existing slag, high-silicon bauxite, stainless steel slag, phosphorus slag and manganese slag generally have poor grindability, are easy to agglomerate and cannot be large-scale and have high added value; the existing epoxy organic glue has the problems of poor thermal stability, poor long-term chemical stability and lower temperature resistance upper limit than 80 ℃; the problem of insufficient shearing force of the existing inorganic adhesive is solved; the high-silicon bauxite, the stainless steel slag and the phosphorus slag have certain flame retardance, but have the problem of incapability of realizing synergistic flame retardance. The invention provides a solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive, aiming at solving the problems.

In order to solve the above technical problems, the present invention is realized by the following technical solutions.

The invention provides a solid waste utilization type flame-retardant-high shear force integrated inorganic adhesive, which comprises the following raw materials in percentage by weight:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 4:2: 1-1: 1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the slag, the stainless steel slag, the high-silicon bauxite, the phosphorus slag and the manganese slag are all industrial solid wastes; the graphene oxide is Brodie method graphene oxide, Staudemaier method graphene oxide or Hummers method graphene oxide; the composite alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 1: 3-3: 1, the water glass is industrially pure, the modulus of the water glass is 0.8-1.6, and the sodium hydroxide is industrially pure.

As an optimization, the particle sizes of the slag, the stainless steel slag, the high-silicon bauxite, the phosphorus slag and the manganese slag are all less than 5 mm.

The invention also provides a preparation method of the solid waste utilization type flame-retardant high-shear force integrated inorganic adhesive, which comprises the following steps:

(1) mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 600-800 r/min for 180-240 min to obtain the solid-waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 200-400 r/min for 96-120 h to obtain the solid-waste composite micropowder.

(2) And mixing the graphene oxide, the composite alkali activator and water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 300-600 r/min, and the stirring time is 1-3 h, so as to obtain a graphene oxide-composite alkali activator mixed solution.

(3) And mixing the solid waste composite superfine powder with the graphene oxide-composite alkali activator mixed solution at the stirring speed of 600-800 r/min for 15-25 min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

The scientific principle of the invention is as follows:

(1) the method is characterized in that surfactant molecules of glycerol, absolute ethyl alcohol and triethanolamine in the composite grinding aid are utilized to form a monomolecular adsorption film on the surfaces of slag to be ground, stainless steel slag, high-silica bauxite, phosphorus slag and manganese slag, the stainless steel slag, the high-silica bauxite, the phosphorus slag and the manganese slag are broken in the crushing process, and free electrovalence bonds generated on the broken surfaces of the broken slag and ions or molecules provided by the composite grinding aid are neutralized, so that the aggregation tendency of solid waste composite micro powder is eliminated or weakened, and the recombination of the broken surfaces is prevented.

(2) The slag contains silicate and aluminosilicate, and the stainless steel slag, the phosphorus slag and the manganese slag all contain CaO and SiO₂The slag, the stainless steel slag, the phosphorous slag and the manganese slag are chemically reacted with water to form inorganic materials with gelling property, such as tricalcium silicate, dicalcium silicate and the like; high-silicon bauxite containing Al₂O₃With SiO₂The stainless steel slag contains SiO₂With Fe₂O₃The phosphorus slag contains SiO₂And P₂O₅The nitrogen protection mechanical alloying treatment technology is adopted, namely alloying is gradually realized through atomic diffusion; in the ball milling process, powder particles are collided and extruded by high-energy balls in a ball milling tank, the particles are subjected to severe plastic deformation, fracture and cold welding, the powder is continuously refined, fresh unreacted surfaces are continuously exposed, crystals are gradually refined to form a layered structure, and the powder is combined together through the fresh surfaces to form a silicon-phosphorus-aluminum system and a silicon-phosphorus-iron system which have flame retardant property.

(3) The composite alkali activator consists of water glass and sodium hydroxide, and on one hand, the water glass can form a skeleton network and is filled or embedded in the inorganic cementing material, so that the mechanical property of the inorganic adhesive is improved; on the other hand, the water glass and the sodium hydroxide can provide an alkali environment, and are favorable for promoting inorganic materials with gelling performance, such as tricalcium silicate, dicalcium silicate and the like, to hydrate, so that the early strength of the inorganic adhesive is improved.

(4) The graphene oxide has a two-dimensional layered structure, and the surface of the graphene oxide bears various active oxygen-containing groups, so that on one hand, the graphene oxide can form a curled lamellar structure, and the impact resistance of the inorganic adhesive is improved; on the other hand, the conjugated structure of the graphene oxide sheet layer can generate van der Waals acting force, and the shearing force of the inorganic adhesive is improved.

Compared with the prior art, the invention has the following beneficial effects:

1. the invention solves the problems of poor grindability, easy agglomeration, large-scale failure and high added value of the existing slag, stainless steel slag, high-silicon bauxite, phosphorus slag and manganese slag; the existing epoxy organic glue has the problems of poor thermal stability, poor long-term chemical stability and lower temperature resistance upper limit than 80 ℃; the problem of insufficient shearing force of the existing inorganic adhesive is solved; the stainless steel slag, the high-silicon bauxite and the phosphorus slag have certain flame retardance, but have the problem of incapability of realizing synergistic flame retardance. The inorganic adhesive solves the problems that the production cost of the existing inorganic adhesive is reduced, the flame retardant property and the shearing force of the inorganic adhesive are improved, the integration of flame retardance and high shearing force in the inorganic adhesive is realized, and the market competitiveness and the application range of the inorganic adhesive are greatly enhanced.

2. The invention utilizes the composite grinding aid, the slag, the stainless steel slag, the high-silica bauxite, the phosphorous slag, the graphene oxide, the composite alkali activator, the water and the manganese slag to prepare the solid waste utilization type flame-retardant high-shearing force integrated inorganic adhesive, and expands the new concept of large-scale high-added-value application of the slag, the stainless steel slag, the high-silica bauxite, the phosphorous slag and the manganese slag.

3. The solid waste utilization type flame-retardant high-shear force integrated inorganic adhesive and the preparation method thereof meet the policy requirements of relevant energy conservation, environmental protection and circular economy.

Detailed Description

The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples.

Example 1

The components used for preparing 100g of the product of the invention and the mass ratio thereof are as follows:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 3: 2:1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the main chemical components of the slag are as follows: MgO 8.04%, Al₂O₃14.25% of SiO₂27.21% of SO₃2.43 percent of CaO, 43.10 percent of TiO₂1.59% of Fe₂O₃0.79% of MnO, 0.38% of Na₂1.08 percent of O and 1.13 percent of the rest, and the grain diameter of the O is less than 5 mm; the stainless steel slag comprises the following main chemical components: CaO 52.35%, SiO₂23.68% of Al₂O₃8.31%, 7.56% MgO, Fe₂O₃1.96% of Cr₂O₃1.12%, PbO 0.83%, P₂0.41% of O5, 0.37% of CuO, 0.32% of MnO and 3.09% of the others, wherein the particle size of the alloy is less than 5 mm; the main chemical components of the high-silicon bauxite are as follows: al (Al)₂O₃60.67% of SiO₂13.61% of Fe₂O₃8.77 percent, 1.03 percent of CaO and TiO₂2.78% of the total weight, and 13.14% of the total weight, and the particle size is less than 5 mm; the phosphorus slag comprises the following main chemical components: CaO 45.70%, Al₂O₃2.57% of SiO₂40.80% and K₂O is 1.01%, P₂O₅3.91% of MgO, 3.32% of TiO₂0.22 percent, 0.02 percent of MnO and the balance of 2.45 percent, and the particle diameter of the material is less than 5 mm; the manganese slag comprises the following main chemical components: SiO 2₂20.05% of Al₂O₃16.42 percent of CaO, 37.62 percent of CaO, 6.52 percent of MgO and SO₃0.48% of Fe₂O₃1.23% of MnO, 10.87% of TiO₂0.42 percent of the total weight, and the balance of the total weight is 6.39 percent, and the grain diameter is less than 5 mm; the graphene oxide is graphene oxide by a Hummers method; the composite alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 3:1, the water glass is industrial pure, the modulus of the water glass is 1.0, and the sodium hydroxide is industrial pure; the water is deionized water.

(1) Mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 700r/min for 240min to obtain the solid-waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 200r/min for 102 hours to obtain the solid-waste composite micropowder.

(2) And mixing the graphene oxide, the composite alkali activator and water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 600r/min, and the stirring time is 1h, so as to obtain a graphene oxide-composite alkali activator mixed solution.

(3) And mixing the solid waste composite superfine powder with the graphene oxide-composite alkali activator mixed solution at the stirring speed of 700r/min for 20min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

Example 2

The components used for preparing 100g of the product of the invention and the mass ratio thereof are as follows:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 1:1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the main chemical components of the slag are as follows: MgO 8.04%, Al₂O₃14.25% of SiO₂27.21% of SO₃2.43 percent of CaO, 43.10 percent of TiO₂1.59% of Fe₂O₃0.79% of MnO, 0.38% of Na₂1.08 percent of O and 1.13 percent of the rest, and the grain diameter of the O is less than 5 mm; the stainless steel slag comprises the following main chemical components: CaO 52.35%, SiO₂23.68% of Al₂O₃8.31%, 7.56% MgO, Fe₂O₃1.96% of Cr₂O₃1.12%, PbO 0.83%, P₂0.41% of O5, 0.37% of CuO, and 0.37% of MnO0.32 percent of the total weight, and the balance of the total weight is 3.09 percent, and the grain diameter is less than 5 mm; the main chemical components of the high-silicon bauxite are as follows: al (Al)₂O₃60.67% of SiO₂13.61% of Fe₂O₃8.77 percent, 1.03 percent of CaO and TiO₂2.78% of the total weight, and 13.14% of the total weight, and the particle size is less than 5 mm; the phosphorus slag comprises the following main chemical components: CaO 45.70%, Al₂O₃2.57% of SiO₂40.80% and K₂O is 1.01%, P₂O₅3.91% of MgO, 3.32% of TiO₂0.22 percent, 0.02 percent of MnO and the balance of 2.45 percent, and the particle diameter of the material is less than 5 mm; the manganese slag comprises the following main chemical components: SiO 2₂20.05% of Al₂O₃16.42 percent of CaO, 37.62 percent of CaO, 6.52 percent of MgO and SO₃0.48% of Fe₂O₃1.23% of MnO, 10.87% of TiO₂0.42 percent of the total weight, and the balance of the total weight is 6.39 percent, and the grain diameter is less than 5 mm; the graphene oxide is Brodie method graphene oxide; the composite alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 1:1, the water glass is industrial pure, the modulus of the water glass is 1.6, and the sodium hydroxide is industrial pure; the water is deionized water.

(1) Mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 800r/min for 180min to obtain the solid waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 300r/min for 120h to obtain the solid-waste composite micropowder.

(2) And mixing the graphene oxide, the composite alkali activator and water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 500r/min, and the stirring time is 3 hours, so as to obtain a graphene oxide-composite alkali activator mixed solution.

(3) And mixing the solid waste composite superfine powder with the graphene oxide-composite alkali activator mixed solution at the stirring speed of 600r/min for 25min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

Example 3

The components used for preparing 100g of the product of the invention and the mass ratio thereof are as follows:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 3:1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the main chemical components of the slag are as follows: MgO 8.04%, Al₂O₃14.25% of SiO₂27.21% of SO₃2.43 percent of CaO, 43.10 percent of TiO₂1.59% of Fe₂O₃0.79% of MnO, 0.38% of Na₂1.08 percent of O and 1.13 percent of the rest, and the grain diameter of the O is less than 5 mm; the stainless steel slag comprises the following main chemical components: CaO 52.35%, SiO₂23.68% of Al₂O₃8.31%, 7.56% MgO, Fe₂O₃1.96% of Cr₂O₃1.12%, PbO 0.83%, P₂0.41% of O5, 0.37% of CuO, 0.32% of MnO and 3.09% of the others, wherein the particle size of the alloy is less than 5 mm; the main chemical components of the high-silicon bauxite are as follows: al (Al)₂O₃60.67% of SiO₂13.61% of Fe₂O₃8.77 percent, 1.03 percent of CaO and TiO₂2.78% of the total weight, and 13.14% of the total weight, and the particle size is less than 5 mm; the phosphorus slag comprises the following main chemical components: CaO 45.70%, Al₂O₃2.57% of SiO₂40.80% and K₂O is 1.01%, P₂O₅3.91% of MgO, 3.32% of TiO₂0.22 percent, 0.02 percent of MnO and the balance of 2.45 percent, and the particle diameter of the material is less than 5 mm; the manganese slag comprises the following main chemical components: SiO 2₂20.05% of Al₂O₃16.42 percent, 37.62 percent of CaO and MgO6.52％、SO₃0.48% of Fe₂O₃1.23% of MnO, 10.87% of TiO₂0.42 percent of the total weight, and the balance of the total weight is 6.39 percent, and the grain diameter is less than 5 mm; the graphene oxide is graphene oxide by a Staudemaier method; the composite alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 1:3, the water glass is industrial pure, the modulus of the water glass is 0.8, and the sodium hydroxide is industrial pure; the water is deionized water.

(1) Mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 600r/min for 220min to obtain the solid-waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 400r/min for 96h to obtain the solid-waste composite micropowder.

(2) And mixing the graphene oxide, the composite alkali activator and water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 400r/min, and the stirring time is 2 hours, so as to obtain a graphene oxide-composite alkali activator mixed solution.

(3) And mixing the solid waste composite superfine powder with the graphene oxide-composite alkali activator mixed solution at the stirring speed of 800r/min for 15min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

Example 4

The components used for preparing 100g of the product of the invention and the mass ratio thereof are as follows:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 4:2:1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the main chemical components of the slag are as follows: MgO 8.04%, Al₂O₃14.25% of SiO₂27.21% of SO₃2.43% of CaO, 43.1% of CaO0％、TiO₂1.59% of Fe₂O₃0.79% of MnO, 0.38% of Na₂1.08 percent of O and 1.13 percent of the rest, and the grain diameter of the O is less than 5 mm; the stainless steel slag comprises the following main chemical components: CaO 52.35%, SiO₂23.68% of Al₂O₃8.31%, 7.56% MgO, Fe₂O₃1.96% of Cr₂O₃1.12%, PbO 0.83%, P₂0.41% of O5, 0.37% of CuO, 0.32% of MnO and 3.09% of the others, wherein the particle size of the alloy is less than 5 mm; the main chemical components of the high-silicon bauxite are as follows: al (Al)₂O₃60.67% of SiO₂13.61% of Fe₂O₃8.77 percent, 1.03 percent of CaO and TiO₂2.78% of the total weight, and 13.14% of the total weight, and the particle size is less than 5 mm; the phosphorus slag comprises the following main chemical components: CaO 45.70%, Al₂O₃2.57% of SiO₂40.80% and K₂O is 1.01%, P₂O₅3.91% of MgO, 3.32% of TiO₂0.22 percent, 0.02 percent of MnO and the balance of 2.45 percent, and the particle diameter of the material is less than 5 mm; the manganese slag comprises the following main chemical components: SiO 2₂20.05% of Al₂O₃16.42 percent of CaO, 37.62 percent of CaO, 6.52 percent of MgO and SO₃0.48% of Fe₂O₃1.23% of MnO, 10.87% of TiO₂0.42 percent of the total weight, and the balance of the total weight is 6.39 percent, and the grain diameter is less than 5 mm; the graphene oxide is graphene oxide by a Staudemaier method; the composite alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 1: 2, the water glass is industrial pure, the modulus of the water glass is 1.2, and the sodium hydroxide is industrial pure; the water is deionized water.

(1) Mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 800r/min for 200min to obtain the solid-waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 200r/min for 108h to obtain the solid-waste composite micropowder.

(2) And mixing the graphene oxide, the composite alkali activator and water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 300r/min, and the stirring time is 2 hours, so as to obtain a graphene oxide-composite alkali activator mixed solution.

(3) And mixing the solid waste composite superfine powder with the graphene oxide-composite alkali activator mixed solution at the stirring speed of 800r/min for 20min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

Example 5

The components used for preparing 100g of the product of the invention and the mass ratio thereof are as follows:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 4: 1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the main chemical components of the slag are as follows: MgO 8.04%, Al₂O₃14.25% of SiO₂27.21% of SO₃2.43 percent of CaO, 43.10 percent of TiO₂1.59% of Fe₂O₃0.79% of MnO, 0.38% of Na₂1.08 percent of O and 1.13 percent of the rest, and the grain diameter of the O is less than 5 mm; the stainless steel slag comprises the following main chemical components: CaO 52.35%, SiO₂23.68% of Al₂O₃8.31%, 7.56% MgO, Fe₂O₃1.96% of Cr₂O₃1.12%, PbO 0.83%, P₂0.41% of O5, 0.37% of CuO, 0.32% of MnO and 3.09% of the others, wherein the particle size of the alloy is less than 5 mm; the main chemical components of the high-silicon bauxite are as follows: al (Al)₂O₃60.67% of SiO₂13.61% of Fe₂O₃8.77 percent, 1.03 percent of CaO and TiO₂2.78% of the total weight, and 13.14% of the total weight, and the particle size is less than 5 mm; the phosphorus slag comprises the following main chemical components: CaO 45.70%, Al₂O₃2.57% of SiO₂40.80% and K₂O is 1.01%, P₂O₅3.91% of MgO, 3.32% of TiO₂0.22 percent, 0.02 percent of MnO and the balance of 2.45 percent, and the particle diameter of the material is less than 5 mm; the manganese slag comprises the following main chemical components: SiO 2₂20.05% of Al₂O₃16.42 percent of CaO, 37.62 percent of CaO, 6.52 percent of MgO and SO₃0.48% of Fe₂O₃1.23% of MnO, 10.87% of TiO₂0.42 percent of the total weight, and the balance of the total weight is 6.39 percent, and the grain diameter is less than 5 mm; the graphene oxide is graphene oxide by a Hummers method; the composite alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 2:1, the water glass is industrial pure, the modulus of the water glass is 1.4, and the sodium hydroxide is industrial pure; the water is deionized water.

(1) Mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 600r/min for 240min to obtain the solid-waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 400r/min for 114h to obtain the solid-waste composite micropowder.

(2) And mixing the graphene oxide, the composite alkali activator and water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 500r/min, and the stirring time is 3 hours, so as to obtain a graphene oxide-composite alkali activator mixed solution.

(3) And mixing the solid waste composite superfine powder with the graphene oxide-composite alkali activator mixed solution at the stirring speed of 600r/min for 25min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

Example 6

The components used for preparing 100g of the product of the invention and the mass ratio thereof are as follows:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 2:1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the main chemical components of the slag are as follows: MgO 8.04%, Al₂O₃14.25% of SiO₂27.21% of SO₃2.43 percent of CaO, 43.10 percent of TiO₂1.59% of Fe₂O₃0.79% of MnO, 0.38% of Na₂1.08 percent of O and 1.13 percent of the rest, and the grain diameter of the O is less than 5 mm; the stainless steel slag comprises the following main chemical components: CaO 52.35%, SiO₂23.68% of Al₂O₃8.31%, 7.56% MgO, Fe₂O₃1.96% of Cr₂O₃1.12%, PbO 0.83%, P₂0.41% of O5, 0.37% of CuO, 0.32% of MnO and 3.09% of the others, wherein the particle size of the alloy is less than 5 mm; the main chemical components of the high-silicon bauxite are as follows: al (Al)₂O₃60.67% of SiO₂13.61% of Fe₂O₃8.77 percent, 1.03 percent of CaO and TiO₂2.78% of the total weight, and 13.14% of the total weight, and the particle size is less than 5 mm; the phosphorus slag comprises the following main chemical components: CaO 45.70%, Al₂O₃2.57% of SiO₂40.80% and K₂O is 1.01%, P₂O₅3.91% of MgO, 3.32% of TiO₂0.22 percent, 0.02 percent of MnO and the balance of 2.45 percent, and the particle diameter of the material is less than 5 mm; the manganese slag comprises the following main chemical components: SiO 2₂20.05% of Al₂O₃16.42 percent of CaO, 37.62 percent of CaO, 6.52 percent of MgO and SO₃0.48% of Fe₂O₃1.23% of MnO, 10.87% of TiO₂0.42 percent of the total weight, and the balance of the total weight is 6.39 percent, and the grain diameter is less than 5 mm; the graphene oxide is Brodie method graphene oxide; the composite alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 1:1, the water glass is industrial pure, the modulus of the water glass is 1.0, and the sodium hydroxide is industrial pure; the water is deionized water.

(1) Mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 700r/min for 220min to obtain the solid-waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 300r/min for 102 hours to obtain the solid-waste composite micropowder.

(2) And mixing the graphene oxide, the composite alkali activator and water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 400r/min, and the stirring time is 1h, so as to obtain a graphene oxide-composite alkali activator mixed solution.

(3) And mixing the solid waste composite superfine powder with the graphene oxide-composite alkali activator mixed solution at the stirring speed of 700r/min for 15min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

Comparative example 1

The components used for preparing 100g of the product of the invention and the mass ratio thereof are as follows:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 2:1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the main chemical components of the slag are as follows: MgO 8.04%, Al₂O₃14.25% of SiO₂27.21% of SO₃2.43 percent of CaO, 43.10 percent of TiO₂1.59% of Fe₂O₃0.79% of MnO, 0.38% of Na₂1.08 percent of O and 1.13 percent of the rest, and the grain diameter of the O is less than 5 mm; the stainless steel slag comprises the following main chemical components: CaO 52.35%, SiO₂23.68% of Al₂O₃8.31%, 7.56% MgO, Fe₂O₃1.96% of Cr₂O₃1.12%, PbO 0.83%, P₂0.41 percent of O5 and 0.37 percent of CuOMnO accounts for 0.32 percent, the others account for 3.09 percent, and the particle size of the material is less than 5 mm; the main chemical components of the high-silicon bauxite are as follows: al (Al)₂O₃60.67% of SiO₂13.61% of Fe₂O₃8.77 percent, 1.03 percent of CaO and TiO₂2.78% of the total weight, and 13.14% of the total weight, and the particle size is less than 5 mm; the phosphorus slag comprises the following main chemical components: CaO 45.70%, Al₂O₃2.57% of SiO₂40.80% and K₂O is 1.01%, P₂O₅3.91% of MgO, 3.32% of TiO₂0.22 percent, 0.02 percent of MnO and the balance of 2.45 percent, and the particle diameter of the material is less than 5 mm; the manganese slag comprises the following main chemical components: SiO 2₂20.05% of Al₂O₃16.42 percent of CaO, 37.62 percent of CaO, 6.52 percent of MgO and SO₃0.48% of Fe₂O₃1.23% of MnO, 10.87% of TiO₂0.42 percent of the total weight, and the balance of the total weight is 6.39 percent, and the grain diameter is less than 5 mm; the composite alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 1:1, the water glass is industrial pure, the modulus of the water glass is 1.0, and the sodium hydroxide is industrial pure; the water is deionized water.

(1) Mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 700r/min for 220min to obtain the solid-waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 300r/min for 102 hours to obtain the solid-waste composite micropowder.

(2) And (3) mixing the compound alkali activator with water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 400r/min, and the stirring time is 1h, so as to obtain a compound alkali activator solution.

(3) And mixing the solid waste composite superfine powder with the composite alkali activator solution at the stirring speed of 700r/min for 15min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

Comparative example 2

The components used for preparing 100g of the product of the invention and the mass ratio thereof are as follows:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 2:1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the main chemical components of the slag are as follows: MgO 8.04%, Al₂O₃14.25% of SiO₂27.21% of SO₃2.43 percent of CaO, 43.10 percent of TiO₂1.59% of Fe₂O₃0.79% of MnO, 0.38% of Na₂1.08 percent of O and 1.13 percent of the rest, and the grain diameter of the O is less than 5 mm; the stainless steel slag comprises the following main chemical components: CaO 52.35%, SiO₂23.68% of Al₂O₃8.31%, 7.56% MgO, Fe₂O₃1.96% of Cr₂O₃1.12%, PbO 0.83%, P₂0.41% of O5, 0.37% of CuO, 0.32% of MnO and 3.09% of the others, wherein the particle size of the alloy is less than 5 mm; the main chemical components of the high-silicon bauxite are as follows: al (Al)₂O₃60.67% of SiO₂13.61% of Fe₂O₃8.77 percent, 1.03 percent of CaO and TiO₂2.78% of the total weight, and 13.14% of the total weight, and the particle size is less than 5 mm; the manganese slag comprises the following main chemical components: SiO 2₂20.05% of Al₂O₃16.42 percent of CaO, 37.62 percent of CaO, 6.52 percent of MgO and SO₃0.48% of Fe₂O₃1.23% of MnO, 10.87% of TiO₂0.42 percent of the total weight, and the balance of the total weight is 6.39 percent, and the grain diameter is less than 5 mm; the graphene oxide is Brodie method graphene oxide; the compound alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 1:1, the water glass is industrial pure, the modulus of the water glass is 1.0, and the sodium hydroxide is industrial pure(ii) a The water is deionized water.

(1) Mixing slag, stainless steel slag, high-silicon bauxite, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 700r/min for 220min to obtain the solid-waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 300r/min for 102 hours to obtain the solid-waste composite micropowder.

(2) And mixing the graphene oxide, the composite alkali activator and water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 400r/min, and the stirring time is 1h, so as to obtain a graphene oxide-composite alkali activator mixed solution.

(3) And mixing the solid waste composite superfine powder with the graphene oxide-composite alkali activator mixed solution at the stirring speed of 700r/min for 15min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

Comparative example 3

The components used for preparing 100g of the product of the invention and the mass ratio thereof are as follows:

the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 2:1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the main chemical components of the slag are as follows: MgO 8.04%, Al₂O₃14.25% of SiO₂27.21% of SO₃2.43 percent of CaO, 43.10 percent of TiO₂1.59% of Fe₂O₃0.79% of MnO, 0.38% of Na₂1.08 percent of O and 1.13 percent of the rest, and the grain diameter of the O is less than 5 mm; the stainless steel slag comprises the following main chemical components: CaO 52.35%, SiO₂23.68% of Al₂O₃8.31%, 7.56% MgO, Fe₂O₃1.96% of Cr₂O₃1.12%, PbO 0.83%, P₂0.41% of O5, 0.37% of CuO, 0.32% of MnO and 3.09% of the others, wherein the particle size of the alloy is less than 5 mm; the main chemical components of the high-silicon bauxite are as follows: al (Al)₂O₃60.67% of SiO₂13.61% of Fe₂O₃8.77 percent, 1.03 percent of CaO and TiO₂2.78% of the total weight, and 13.14% of the total weight, and the particle size is less than 5 mm; the phosphorus slag comprises the following main chemical components: CaO 45.70%, Al₂O₃2.57% of SiO₂40.80% and K₂O is 1.01%, P₂O₅3.91% of MgO, 3.32% of TiO₂0.22 percent, 0.02 percent of MnO and the balance of 2.45 percent, and the particle diameter of the material is less than 5 mm; the manganese slag comprises the following main chemical components: SiO 2₂20.05% of Al₂O₃16.42 percent of CaO, 37.62 percent of CaO, 6.52 percent of MgO and SO₃0.48% of Fe₂O₃1.23% of MnO, 10.87% of TiO₂0.42 percent of the total weight, and the balance of the total weight is 6.39 percent, and the grain diameter is less than 5 mm; the graphene oxide is Brodie method graphene oxide; the water is deionized water.

(1) Mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 700r/min for 220min to obtain the solid-waste composite micro powder. And then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micropowder by using a planetary ball mill at the rotating speed of 300r/min for 102 hours to obtain the solid-waste composite micropowder.

(2) And mixing the graphene oxide with water by using a constant-temperature magnetic stirrer at normal temperature, wherein the stirring speed is 400r/min, and the stirring time is 1h, so as to obtain a graphene oxide solution.

(3) And mixing the solid waste composite superfine powder with the graphene oxide solution at the stirring speed of 700r/min for 15min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

The performance test procedures of the preparation examples 1-6 and the comparative examples 1-3 are as follows:

firstly, the concrete test block is prepared with the size of 100mm multiplied by 100mm, the design strength grade is C40, and the mean value of the measured 28d compressive strength of 3 test pieces is 48.7 MPa. And then adhering 1 layer of carbon fiber cloth on the surface of the concrete test block by utilizing solid waste utilization type flame-retardant-high shear force integrated inorganic glue, wherein the adhering area is 70mm multiplied by 100 mm. And finally, the concrete test block adhered with the carbon fiber cloth is taken out after being respectively cured for 3d and 7d in a standard curing room, and the shearing strength of the adhered surface of the concrete test block is tested.

Firstly, preparing a solid waste utilization type flame-retardant and high-shearing force integrated inorganic adhesive test block with the size of 20mm multiplied by 20mm, curing for 28 days in a standard curing room, and drying by an electric heating constant-temperature drying oven. And then calcining the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive test block at different calcining temperatures, namely 900 ℃, 1200 ℃ and 1500 ℃ for 2 hours at constant temperature, naturally cooling to room temperature, and testing the compressive strength of the test block after high-temperature cooling.

TABLE 1 Properties of solid waste utilization type flame retardant-high shear force integrated inorganic adhesive

Claims (2)

1. The solid-waste utilization type flame-retardant high-shear force integrated inorganic adhesive is characterized by comprising the following raw materials in percentage by weight:

0.5 to 1.5 percent of composite grinding aid

25 to 30 percent of slag

5 to 10 percent of stainless steel slag

5 to 10 percent of high-silicon bauxite

10 to 15 percent of phosphorus slag

0.2 to 0.6 percent of graphene oxide

1 to 4 percent of compound alkali activator

25 to 30 percent of water

10 to 20 percent of manganese slag

The composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 4:2: 1-1: 1:1, and the glycerol, the absolute ethyl alcohol and the triethanolamine are analytically pure; the slag, the stainless steel slag, the high-silicon bauxite, the phosphorus slag and the manganese slag are all industrial solid wastes; the graphene oxide is Brodie method graphene oxide, Staudemaier method graphene oxide or Hummers method graphene oxide; the composite alkali activator is a mixture of water glass and sodium hydroxide, the mass ratio of the water glass to the sodium hydroxide is 1: 3-3: 1, the water glass is industrial pure, the modulus of the water glass is 0.8-1.6, and the sodium hydroxide is industrial pure;

the preparation method of the solid waste utilization type flame-retardant high-shear force integrated inorganic adhesive comprises the following steps:

(1) mixing slag, stainless steel slag, high-silicon bauxite, phosphorus slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 600-800 r/min for 180-240 min to obtain solid-waste composite micro powder; then, carrying out nitrogen protection mechanical alloying treatment on the solid-waste composite micro powder by using a planetary ball mill, wherein the rotating speed is 200 r/min-400 r/min, and the time is 96 h-120 h, so as to obtain solid-waste composite micro powder;

(2) mixing graphene oxide, a composite alkali activator and water at normal temperature by using a constant-temperature magnetic stirrer, wherein the stirring speed is 300-600 r/min, and the stirring time is 1-3 h, so as to obtain a graphene oxide-composite alkali activator mixed solution;

(3) and mixing the solid waste composite superfine powder with the graphene oxide-composite alkali activator mixed solution at the stirring speed of 600-800 r/min for 15-25 min to obtain the solid waste utilization type flame-retardant and high-shear force integrated inorganic adhesive.

2. The solid waste utilization type flame-retardant high-shear force integrated inorganic adhesive as claimed in claim 1, wherein the particle size of the slag, the stainless steel slag, the high-silica bauxite, the phosphorous slag and the manganese slag is less than 5 mm.