阅读说明：本技术 铜渣-矿渣基胶凝材料、制备方法及应用 (Copper slag-based cementing material, preparation method and application ) 是由 宋军伟 朱街禄 彭小英 刘方华 于 2019-10-18 设计创作，主要内容包括：本发明涉及一种铜渣-矿渣基胶凝材料、制备方法及应用,该铜渣-矿渣基胶凝材料包括：铜渣粉、矿渣粉、碱激发剂、生石灰、硅酸盐水泥、吸热材料、纤维、改性助剂、吸光剂,碱激发剂包括碱类物质、硅酸盐类物质或碱金属盐类物质中的至少一种,吸热材料包括石墨烯、石墨、丙烯酸改性环氧树脂、2,4-二羟基二苯甲酮、硝酸铬以及钛酸酯偶联剂,纤维包括氟橡胶纤维、聚丙烯纤维或石棉纤维中的至少一种,改性助剂包括碳化硅、氮化硼、三氧化二铝或氧化锌中的至少一种,吸光剂包括氧化铬、硒化镉、三氧化二铁、二氧化钛、硫化铅、氧化钴以及硫化镉。本发明提出的胶凝材料,具有较低的水化热以及抗拉抗压强度,满足了实际应用需求。(The invention relates to a copper slag-based cementing material, a preparation method and application thereof, wherein the copper slag-based cementing material comprises the following components: the heat-absorbing material comprises graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and titanate coupling agent, the fiber comprises at least one of fluororubber fiber, polypropylene fiber or asbestos fiber, the modifying auxiliary agent comprises at least one of silicon carbide, boron nitride, aluminum oxide or zinc oxide, and the light-absorbing agent comprises chromium oxide, cadmium selenide, ferric oxide, titanium dioxide, lead sulfide, cobalt oxide and cadmium sulfide. The cementing material provided by the invention has lower hydration heat and tensile and compressive strength, and meets the requirements of practical application.)

1. A copper slag-based cementing material is characterized by comprising the following components in parts by weight:

the alkali activator comprises at least one of alkali substances, silicate substances or alkali metal salt substances, the heat-absorbing material comprises graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and titanate coupling agent, the fiber comprises at least one of fluororubber fiber, polypropylene fiber or asbestos fiber, the modification auxiliary agent comprises at least one of silicon carbide, boron nitride, aluminum oxide or zinc oxide, and the light-absorbing agent comprises chromium oxide, cadmium selenide, ferric oxide, titanium dioxide, lead sulfide, cobalt oxide and cadmium sulfide.

2. The copper slag-based cementing material of claim 1, wherein the copper slag powder is obtained by drying, ball milling for 40-100 min, magnetic separation under the magnetic field strength environment of 150-200 mT to recover iron ore concentrate, and the apparent density of the ball-milled copper slag powder is 3.5-3.7 g/m³The specific surface area of the copper slag powder is more than 450m²/kg。

3. The copper slag-based cementitious material of claim 1, wherein the alkali substance comprises one or more of sodium hydroxide, potassium hydroxide or calcium hydroxide, the silicate substance comprises one or more of sodium silicate, calcium silicate, aluminum silicate or magnesium silicate, and the alkali metal salt substance comprises one or more of sodium carbonate, aluminum oxide, aluminum sulfate, potassium sulfate or calcium sulfate.

4. The copper slag-based cementing material of claim 1, wherein the slag powder is obtained by ball milling for 20-50 min and then sieving with a 200-mesh sieve, the particle size of the slag powder is 5-105 um, the particle fineness is 0.08-0.1 mm, the carbon content is less than 4%, and the ignition loss is less than 8%.

5. The copper slag-based cementitious material of claim 1, characterised in that the heat absorbing material comprises the following components in parts by weight:

10-30 parts of graphene, 10-30 parts of graphite, 5-10 parts of acrylic acid modified epoxy resin, 3-8 parts of 2, 4-dihydroxy benzophenone, 2-5 parts of chromium nitrate and 4-9 parts of titanate coupling agent.

6. The copper slag-based cementitious material of claim 1, wherein the light absorbent comprises the following components in parts by weight:

5-10 parts of chromium oxide, 8-15 parts of cadmium selenide, 10-15 parts of titanium dioxide, 3-8 parts of lead sulfide, 3-10 parts of cobalt oxide and 1-2 parts of cadmium sulfide.

7. A method for preparing a copper slag-based cementitious material according to any one of claims 1 to 6, characterised in that it comprises the following steps:

mixing and stirring copper slag powder, quicklime, a modification aid and a light absorbent, adding an alkali activator and deionized water, and stirring to obtain first slurry, wherein the modification aid comprises at least one of silicon carbide, boron nitride, aluminum oxide or zinc oxide, and the light absorbent comprises chromium oxide, cadmium selenide, ferric oxide, titanium dioxide, lead sulfide, cobalt oxide and cadmium sulfide;

continuously adding sodium hydroxide, sodium bicarbonate, portland cement and deionized water into the first slurry, uniformly stirring, standing for 15-25 min, and carrying out foaming treatment to obtain second slurry;

adding a heat absorbing material and fibers into the second slurry, then continuously stirring to obtain a third slurry, pouring the third slurry into a mold, vibrating and molding to obtain a rough blank, wherein the heat absorbing material comprises graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and a titanate coupling agent, and the fibers comprise at least one of fluororubber fibers, polypropylene fibers or asbestos fibers;

and curing the rough blank in an environment with the relative humidity of 50-60% and the temperature of 20-30 ℃ for 2-3 days, demolding to obtain a test piece, and curing the test piece in a standard room with the relative humidity of 80-95% and the temperature of 20-30 ℃ for 25-28 days to obtain the copper slag-based cementing material.

8. The method for preparing a copper slag-based cementitious material according to claim 7, characterised in that the method for preparing the copper slag powder comprises the steps of:

putting copper slag into ballsPrimarily ball-milling for 10-15 min in a mill, sieving with a 50-mesh sieve, finely grinding the sieved smaller-particle copper slag powder in a ball mill for 40-100 min, sieving with a 200-mesh sieve, and magnetically separating under the magnetic field intensity environment of 150-200 mT to recover iron ore concentrate to obtain the copper slag powder, wherein the apparent density of the copper slag powder is 3.5-3.7 g/m³The specific surface area of the copper slag powder is more than 450m²/kg；

The preparation method of the slag powder comprises the following steps:

ball-milling the slag in a ball mill for 20-50 min, and then sieving the slag with a 200-mesh sieve to obtain the slag powder, wherein the grain diameter of the slag powder is 5-105 um, the grain fineness is 0.08-0.1 mm, the carbon content is less than 4%, and the ignition loss is less than 8%.

9. The method of preparing a copper slag-based cementitious material according to claim 7, wherein the alkali substance includes one or more of sodium hydroxide, potassium hydroxide or calcium hydroxide, the silicate substance includes one or more of sodium silicate, calcium silicate, aluminum silicate or magnesium silicate, and the alkali metal salt substance includes one or more of sodium carbonate, aluminum oxide, aluminum sulfate, potassium sulfate or calcium sulfate.

10. Use of the copper slag-based cementitious material according to any one of claims 1 to 6, for the preparation of aerated bricks using the copper slag-based cementitious material.

Technical Field

The invention relates to the technical field of inorganic cementing material preparation, in particular to a copper slag-based cementing material, a preparation method and application thereof.

Background

The cement is one of the materials with the largest application amount and the widest application range in the inorganic cementing materials, is widely applied to engineering construction of buildings, roads, dams, airports and the like, and is an important basic material for national economic construction. The production of cement consumes a large amount of resources and energy, and dust and CO discharged in the production process₂The development and utilization of the novel green cementing material can reduce the resource and energy consumption and reduce the environmental pollution, and has important practical and long-term significance for the sustainable development of society and economy.

The copper slag is industrial solid waste generated in the copper smelting process and mainly exists in the form of water-quenched copper slag. The main mineral component is fayalite (Fe)₂SiO₄) Magnetite (Fe)₃O₄) Etc., and the main chemical components are iron oxide, silicon dioxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide, etc. About 2.2 tons of copper slag are produced per 1 ton of copper produced. In the prior art, the utilization rate of copper slag is low, a large amount of copper slag is not recycled and is accumulated in the area of a copper smelting factory, a large amount of land is occupied, and meanwhile, environmental pollution is caused, and the production development is influenced.

How to recycle the waste copper slag to prepare the cementing material with better performance becomes a key research topic of researchers.

Disclosure of Invention

Based on the above, the invention aims to provide a preparation method for preparing a cementing material with excellent performance by using waste raw materials such as copper slag and the like.

The invention provides a copper slag-based cementing material, which comprises the following components in parts by weight:

the alkali activator comprises at least one of alkali substances, silicate substances or alkali metal salt substances, the heat-absorbing material comprises graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and titanate coupling agent, the fiber comprises at least one of fluororubber fiber, polypropylene fiber or asbestos fiber, the modification auxiliary agent comprises at least one of silicon carbide, boron nitride, aluminum oxide or zinc oxide, and the light-absorbing agent comprises chromium oxide, cadmium selenide, ferric oxide, titanium dioxide, lead sulfide, cobalt oxide and cadmium sulfide.

The copper slag-based cementing material provided by the invention comprises basic raw materials of copper slag powder, an alkali activator, Portland cement, quicklime and the like, wherein the copper slag and the cement clinker have similar chemical components and contain active SiO₂In the late stage of hydration with the hydration products Ca (OH)₂The following weak pozzolanic reaction occurs: (C-S-H gelation) has potential gelation performance, and can be used as a cementing material in concrete. The vitreous body in the copper slag is a three-dimensional and twisted network structure and has higher energy which can be excited under certain conditions. Copper slag in Ca (OH)₂And CaSO₄In the presence of the Al-containing catalyst, the surface of the glass body is damaged, the network structure of the glass body is dissociated, and the internal Al is³⁺、Fe²⁺、Fe³⁺、[AlO₄]^5-、[SiO₄]^4-Plasma precipitation with Ca²⁺Production of new hydration products and reduction of Ca (OH)₂Concentration, and the new hydration product is a C-S-H gel with a higher iron content. In addition, in the invention, because fibers (fluororubber fibers, polypropylene fibers or asbestos fibers) are added in the manufacturing process, the tensile strength of the cementing material can be enhanced, and because heat-absorbing materials (graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and titanate coupling agent) are added, the hydration heat of the cementing material can be improved, and in addition, because modification auxiliary agents (silicon carbide, boron nitride, aluminum oxide or zinc oxide) are added) The compression strength of the cementing material can be ensured.

The copper slag-based cementing material is prepared by drying copper slag powder, ball-milling for 40-100 min, performing magnetic separation under the magnetic field intensity environment of 150-200 mT to recover iron ore concentrate, and obtaining the ball-milled copper slag powder with the apparent density of 3.5-3.7 g/m³The specific surface area of the copper slag powder is more than 450m²/kg。

The copper slag-based cementing material is characterized in that the alkali substances comprise one or more of sodium hydroxide, potassium hydroxide or calcium hydroxide, the silicate substances comprise one or more of sodium silicate, calcium silicate, aluminum silicate or magnesium silicate, and the alkali metal salt substances comprise one or more of sodium carbonate, aluminum oxide, aluminum sulfate, potassium sulfate or calcium sulfate.

The copper slag-based cementing material is obtained by ball-milling slag powder for 20-50 min and then sieving the ball-milled slag powder with a 200-mesh sieve, wherein the particle size of the slag powder is 5-105 um, the particle fineness is 0.08-0.1 mm, the carbon content is less than 4%, and the ignition loss is less than 8%.

The copper slag-based cementing material comprises the following components in parts by weight:

10-30 parts of graphene, 10-30 parts of graphite, 5-10 parts of acrylic acid modified epoxy resin, 3-8 parts of 2, 4-dihydroxy benzophenone, 2-5 parts of chromium nitrate and 4-9 parts of titanate coupling agent.

The copper slag-based cementing material comprises the following components in parts by weight:

10-15 parts of chromium oxide, 8-15 parts of cadmium selenide, 10-15 parts of titanium dioxide, 3-8 parts of lead sulfide, 3-10 parts of cobalt oxide and 1-2 parts of cadmium sulfide.

The invention also provides a preparation method of the copper slag-based cementing material, wherein the method comprises the following steps:

mixing and stirring copper slag powder, quicklime, a modification aid and a light absorbent, adding an alkali activator and deionized water, and stirring to obtain first slurry, wherein the modification aid comprises at least one of silicon carbide, boron nitride, aluminum oxide or zinc oxide, and the light absorbent comprises chromium oxide, cadmium selenide, ferric oxide, titanium dioxide, lead sulfide, cobalt oxide and cadmium sulfide;

continuously adding sodium hydroxide, sodium bicarbonate, portland cement and deionized water into the first slurry, uniformly stirring, standing for 15-25 min, and carrying out foaming treatment to obtain second slurry;

adding a heat absorbing material and fibers into the second slurry, then continuously stirring to obtain a third slurry, pouring the third slurry into a mold, vibrating and molding to obtain a rough blank, wherein the heat absorbing material comprises graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and a titanate coupling agent, and the fibers comprise at least one of fluororubber fibers, polypropylene fibers or asbestos fibers;

and curing the rough blank in an environment with the relative humidity of 50-60% and the temperature of 20-30 ℃ for 2-3 days, demolding to obtain a test piece, and curing the test piece in a standard room with the relative humidity of 80-95% and the temperature of 20-30 ℃ for 25-28 days to obtain the copper slag-based cementing material.

The preparation method of the copper slag-based cementing material provided by the invention has the advantages that the copper slag and the cement clinker have similar chemical components, and the contained active SiO is₂In the late stage of hydration with the hydration products Ca (OH)₂The following weak pozzolanic reaction occurs: (C-S-H gelation) has potential gelation performance, and can be used as a cementing material in concrete. The vitreous body in the copper slag is a three-dimensional and twisted network structure and has higher energy which can be excited under certain conditions. Copper slag in Ca (OH)₂And CaSO₄In the presence of the Al-containing catalyst, the surface of the glass body is damaged, the network structure of the glass body is dissociated, and the internal Al is³⁺、Fe²⁺、Fe³⁺、[AlO₄]^5-、[SiO₄]^4-Plasma precipitation with Ca²⁺Production of new hydration products and reduction of Ca (OH)₂Concentration, and the new hydration product is a C-S-H gel with a higher iron content. In addition, the method can be used for producing a composite materialIn the invention, because fibers (fluororubber fibers, polypropylene fibers or asbestos fibers) are added in the manufacturing process, the tensile strength of the cementing material can be enhanced, and the hydration heat of the cementing material can be improved because the added heat-absorbing materials (graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and titanate coupling agent) are added, and in addition, because modification auxiliary agents (silicon carbide, boron nitride, aluminum oxide or zinc oxide) are added, the compressive strength of the cementing material can be ensured.

The preparation method of the copper slag-based cementing material comprises the following steps:

primarily ball-milling copper slag in a ball mill for 10-15 min, then sieving the copper slag with a 50-mesh sieve, finely grinding the sieved smaller-particle copper slag powder in the ball mill for 40-100 min, then sieving the copper slag powder with a 200-mesh sieve, and magnetically separating the copper slag powder under the magnetic field intensity environment of 150-200 mT to recover iron ore concentrate to obtain the copper slag powder, wherein the apparent density of the copper slag powder is 3.5-3.7 g/m³The specific surface area of the copper slag powder is more than 450m²/kg；

The preparation method of the slag powder comprises the following steps:

ball-milling the slag in a ball mill for 20-50 min, and then sieving the slag with a 200-mesh sieve to obtain the slag powder, wherein the grain diameter of the slag powder is 5-105 um, the grain fineness is 0.08-0.1 mm, the carbon content is less than 4%, and the ignition loss is less than 8%.

The preparation method of the copper slag-based cementing material comprises the following steps of preparing a basic substance, wherein the basic substance comprises one or more of sodium hydroxide, potassium hydroxide or calcium hydroxide, the silicate substance comprises one or more of sodium silicate, calcium silicate, aluminum silicate or magnesium silicate, and the alkali metal salt substance comprises one or more of sodium carbonate, aluminum oxide, aluminum sulfate, potassium sulfate or calcium sulfate.

The invention also provides an application of the copper slag-based cementing material, wherein the copper slag-based cementing material is used for preparing aerated bricks.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Detailed Description

The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The embodiment of the invention provides a copper slag-based cementing material, which comprises the following components in parts by weight:

the alkali activator comprises at least one of alkali substances, silicate substances or alkali metal salt substances, the heat-absorbing material comprises graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and titanate coupling agent, the fiber comprises at least one of fluororubber fiber, polypropylene fiber or asbestos fiber, the modification auxiliary agent comprises at least one of silicon carbide, boron nitride, aluminum oxide or zinc oxide, and the light-absorbing agent comprises chromium oxide, cadmium selenide, ferric oxide, titanium dioxide, lead sulfide, cobalt oxide and cadmium sulfide.

The preparation method of the copper slag-based cementing material comprises the following steps:

the method comprises the following steps: mixing and stirring copper slag powder, quicklime, a modification aid and a light absorbent, adding an alkali activator and deionized water, and stirring to obtain first slurry, wherein the modification aid comprises at least one of silicon carbide, boron nitride, aluminum oxide or zinc oxide, and the light absorbent comprises chromium oxide, cadmium selenide, ferric oxide, titanium dioxide, lead sulfide, cobalt oxide and cadmium sulfide;

step two: continuously adding sodium hydroxide, sodium bicarbonate, portland cement and deionized water into the first slurry, uniformly stirring, standing for 15-25 min, and carrying out foaming treatment to obtain second slurry;

step three: adding a heat absorbing material and fibers into the second slurry, then continuously stirring to obtain a third slurry, pouring the third slurry into a mold, vibrating and molding to obtain a rough blank, wherein the heat absorbing material comprises graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and a titanate coupling agent, and the fibers comprise at least one of fluororubber fibers, polypropylene fibers or asbestos fibers;

step four: and curing the rough blank in an environment with the relative humidity of 50-60% and the temperature of 20-30 ℃ for 2-3 days, demolding to obtain a test piece, and curing the test piece in a standard room with the relative humidity of 80-95% and the temperature of 20-30 ℃ for 25-28 days to obtain the copper slag-based cementing material.

The preparation principle is as follows: the copper slag-based cementing material provided by the invention comprises basic raw materials of copper slag powder, an alkali activator, Portland cement, quicklime and the like, wherein the copper slag and the cement clinker have similar chemical components and contain active SiO₂In the late stage of hydration with the hydration products Ca (OH)₂The following weak pozzolanic reaction occurs: (C-S-H gelation) has potential gelation performance, and can be used as a cementing material in concrete. The vitreous body in the copper slag is a three-dimensional and twisted network structure and has higher energy which can be excited under certain conditions. Copper slag in Ca (OH)₂And CaSO₄In the presence of the Al-containing catalyst, the surface of the glass body is damaged, the network structure of the glass body is dissociated, and the internal Al is³⁺、Fe²⁺、Fe³⁺、[AlO₄]^5-、[SiO₄]^4-Plasma precipitation with Ca²⁺Produce new hydration product and reduce Ca (OH))₂Concentration, and the new hydration product is a C-S-H gel with a higher iron content. In addition, in the invention, because fibers (fluororubber fibers, polypropylene fibers or asbestos fibers) are added in the manufacturing process, the tensile strength of the cementing material can be enhanced, and the hydration heat of the cementing material can be improved because the added heat-absorbing materials (graphene, graphite, acrylic acid modified epoxy resin, 2, 4-dihydroxy benzophenone, chromium nitrate and titanate coupling agent) are added, and in addition, because modification auxiliary agents (silicon carbide, boron nitride, aluminum oxide or zinc oxide) are added, the compressive strength of the cementing material can be ensured. It should be noted that, in the manufacturing process of the gel material of the present invention, since the light absorption machine (including chromium oxide, cadmium selenide, ferric oxide, titanium dioxide, lead sulfide, cobalt oxide and cadmium sulfide) is added, the light absorption machine is a light stabilizer and can absorb sunlight and ultraviolet part in a fluorescent light source, and the prepared gel material can meet the special application requirements in the fields of photocatalysis and the like.

The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific examples. The present invention can be modified and implemented as appropriate within the scope of the main claim.

The performance test methods in the following examples are as follows:

(1) measurement of mechanical properties:

the bending strength and the compressive strength are carried out according to GB/T17671-1999 method for detecting the strength of the cement mortar, and the specification of the forming die is 40mm multiplied by 160 mm; and (3) the maintenance requirement of the test piece is as follows: and (5) standard maintenance.

(2) Measurement of hydration Heat:

the hydration heat determination is carried out according to GB/T12959-2008 'cement hydration heat determination method', and a dissolution heat method is adopted for testing.

(3) And (3) measuring the granularity of the copper slag:

the measurement reference of the copper slag granularity is as follows: GB/T19077-2016 laser diffraction particle size analysis.

(4) Determination of specific surface area of copper slag:

the specific surface area of the copper slag is measured by reference to GB/T8074 and 2008 'cement specific surface area measuring method Bosch method'.

(5) Determination of setting time and autoclaving stability:

the setting time and the pressure distillation stability of the material are measured according to GB/T1346-2011 inspection method for water consumption, setting time and stability of standard consistency of cement.