CN110105083B - Red mud-based heat insulation material and preparation method and application thereof - Google Patents
Red mud-based heat insulation material and preparation method and application thereof Download PDFInfo
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract
The invention provides a red mud-based heat-insulating material, and a preparation method and application thereof, and relates to the technical field of comprehensive utilization of resources. The red mud-based thermal insulation material comprises: the red mud foaming agent comprises red mud, a first foaming agent, a second foaming agent, water and a foam stabilizer, wherein the foaming temperature of the first foaming agent is higher than that of the second foaming agent; according to the mass percentage, the addition amount of the red mud is 93-100%, the addition amount of the first foaming agent accounts for 1-3% of the mass of the red mud, the addition amount of the second foaming agent accounts for 1-3% of the mass of the red mud, the addition amount of the water accounts for 55-65% of the mass of the red mud, and the addition amount of the foam stabilizer accounts for 40-45% of the mass of the second foaming agent. The heat insulating material has the advantages of good performance stability, high utilization rate of the red mud and low heat conductivity coefficient.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of resources, relates to a heat-insulating material, and particularly relates to a red mud-based heat-insulating material as well as a preparation method and application thereof.
Background
The red mud is the most main solid waste residue in the alumina industry, and is the residual solid waste after alumina is prepared from bauxite through a series of physical and chemical reaction processes. Due to different ore grades, production methods and technical levels, about 1.0-1.8 tons of red mud is discharged for each ton of alumina produced. It is estimated that the worldwide alumina industry produces over 6 x 10 red mud annually7The annual discharge amount of red mud in 2009 of China reaches 3000 million tons, and the accumulated red mud accumulation amount reaches more than 3 hundred million tons. At present, the red mud storehouse (dam) is mostly stored by a wet method or dehydrated and dried, so that the farmland is invaded, the environment is polluted, the dam break hidden danger exists, useful components in the red mud cannot be reasonably utilized, and the secondary waste of resources is caused. Therefore, the comprehensive utilization of red mud is becoming an increasingly important research subject, and is receiving attention from scientific and technical workers in various countries.
In particular, in the field of heat insulation materials, the utilization of solid waste to prepare porous light heat insulation materials attracts great attention of researchers in recent years, but the utilization rate of the solid waste red mud in the aspect still does not reach an ideal state. At present, the energy consumption of unit area in China is about 5 times of that of developed countries, and the level of building energy conservation is far behind the average level of the developed countries. The research and the popularization of the building heat-insulating material can not only improve the resource utilization rate, protect the environment and save the energy, but also can develop the related industries, and has important practical significance. On the other hand, since the red mud contains a large amount of silicon, aluminum and other substances, the red mud can be sintered and molded to be widely applied to the building field, and high-value utilization of the red mud is realized.
At present, some relevant research reports on the preparation of heat insulation materials by using red mud exist. For example, patent publication No. CN104045374A discloses a red mud porous material, which is prepared by using red mud as a part of raw materials of synthetic materials, and adding solid water glass, slag, fly ash, a foam stabilizer, water and a foaming agent. The porous material has the advantages of uniform pore diameter, light weight, good heat preservation and the like, but the porous material of the red mud has the defect that the doping amount of the red mud is not high, and the full utilization of the red mud cannot be realized. For another example, publication No. CN106699132A discloses a method for producing a thermal insulation material from red mud, which comprises mixing red mud with sodium hydroxide, heating in a crucible, cooling to room temperature, taking out the crucible, placing in boiling water, stirring, standing for layering, drying the upper layer of suspended matter, adding borax, quartz sand, limestone and suspended matter, heating for melting, cooling, and grinding into fine powder. The method takes red mud and auxiliary liquid generated in the production of bauxite as raw materials to prepare a heat-insulating material; however, the heat insulation material obtained by the method has poor stability of heat insulation performance and high heat conductivity coefficient.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a red mud-based heat-insulating material, which is used for solving the technical problems of low utilization rate of red mud, and to-be-improved or unstable performance of the heat-insulating material in the prior art.
The second purpose of the invention is to provide a preparation method of the red mud-based heat-insulating material, which is simple in method, easy to operate, good in repeated operability, good in performance stability of the prepared heat-insulating material, low in heat conductivity coefficient, and high in red mud utilization rate of the heat-insulating material prepared by the method.
The third purpose of the invention is to provide the application of the red mud-based heat-insulating material in a heating system.
In order to achieve the purpose, the invention adopts the technical scheme that:
according to one aspect of the invention, the invention provides a red mud-based thermal insulation material, which comprises the following raw materials: the red mud foaming agent comprises red mud, a first foaming agent, a second foaming agent, water and a foam stabilizer, wherein the foaming temperature of the first foaming agent is higher than that of the second foaming agent;
according to the mass percentage, the addition amount of the red mud is 93-100%, the addition amount of the first foaming agent accounts for 1-3% of the mass of the red mud, the addition amount of the second foaming agent accounts for 1-3% of the mass of the red mud, the addition amount of the water accounts for 55-65% of the mass of the red mud, and the addition amount of the foam stabilizer accounts for 40-45% of the mass of the second foaming agent.
Further, according to the mass percentage, the addition amount of the red mud is 93-100%, the addition amount of the first foaming agent accounts for 1.5-2.5% of the mass of the red mud, the addition amount of the second foaming agent accounts for 2.2-2.8% of the mass of the red mud, the addition amount of the water accounts for 58-62% of the mass of the red mud, and the addition amount of the foam stabilizer accounts for 41-44% of the mass of the second foaming agent;
preferably, the addition amount of the red mud is 93-100% by mass, the addition amount of the first foaming agent accounts for 2% by mass of the red mud, the addition amount of the second foaming agent accounts for 2.4-2.5% by mass of the red mud, the addition amount of the water accounts for 60% by mass of the red mud, and the addition amount of the foam stabilizer accounts for 42-43% by mass of the second foaming agent.
Further, the red mud comprises bayer process red mud;
preferably, the first foaming agent comprises one or more of smoke carbon powder, coal gangue or wood dust, preferably smoke carbon powder;
preferably, the second foaming agent comprises hydrogen peroxide;
preferably, the foam stabilizer comprises one or more of methylcellulose, polyvinyl alcohol or polyethylene oxide, preferably methylcellulose.
Further, the paint also comprises an additive;
preferably, the mass addition amount of the additive is less than or equal to 7 percent;
preferably, the addition amount of the red mud is 93-100% and the addition amount of the additive is less than or equal to 7% in percentage by mass; the addition amount of the first foaming agent accounts for 1-3% of the total mass of the red mud and the additive, the addition amount of the second foaming agent accounts for 1-3% of the total mass of the red mud and the additive, the addition amount of the water accounts for 55-65% of the total mass of the red mud and the additive, and the addition amount of the foam stabilizer accounts for 40-45% of the mass of the second foaming agent;
preferably, the addition amount of the red mud is 93-100% and the addition amount of the additive is less than or equal to 7% in percentage by mass; the addition amount of the first foaming agent accounts for 1.5-2.5% of the total mass of the red mud and the additive, the addition amount of the second foaming agent accounts for 2.2-2.8% of the total mass of the red mud and the additive, the addition amount of the water accounts for 58-62% of the total mass of the red mud and the additive, and the addition amount of the foam stabilizer accounts for 41-44% of the mass of the second foaming agent;
preferably, the addition amount of the red mud is 93-100% and the addition amount of the additive is less than or equal to 7% in percentage by mass; the additive amount of the first foaming agent accounts for 2% of the total mass of the red mud and the additive, the additive amount of the second foaming agent accounts for 2.4-2.5% of the total mass of the red mud and the additive, the additive amount of the water accounts for 60% of the total mass of the red mud and the additive, and the additive amount of the foam stabilizer accounts for 42-43% of the mass of the second foaming agent.
Further, the additive comprises one or more of waste glass powder, boric sludge, bentonite or sludge, and preferably the waste glass powder.
According to another aspect of the present invention, the present invention provides a preparation method of the red mud-based thermal insulation material, comprising the following steps:
uniformly mixing the red mud, the first foaming agent, the foam stabilizer, the second foaming agent and water according to the formula ratio to obtain foaming slurry;
and injecting the foamed slurry into a mold for molding and calcining to obtain the red mud-based heat-insulating material.
Further, uniformly mixing the red mud, the first foaming agent and the foam stabilizer according to the formula ratio to obtain a solid mixture;
uniformly mixing the second foaming agent and water according to the formula ratio to obtain a liquid mixture;
and uniformly mixing the solid mixture and the liquid mixture to obtain foamed slurry.
Further, injecting the foaming slurry into a mould, foaming at low temperature, and curing and molding under natural conditions;
preferably, the forming time is 45-50h, preferably 46-48 h;
preferably, the temperature of the calcination is 900-1200 ℃, preferably 1100-1150 ℃;
preferably, the heating rate of the calcination is 3-10 ℃/min, preferably 4-5 ℃/min;
preferably, the calcination is followed by a heat-preservation for a period of 20-40min, preferably 25-30 min.
Further, uniformly mixing the red mud, the additive, the first foaming agent, the foam stabilizer, the second foaming agent and water according to the formula ratio to obtain foaming slurry;
preferably, the method also comprises the step of uniformly mixing the red mud, the additive, the first foaming agent and the foam stabilizer according to the formula ratio to obtain a solid mixture;
uniformly mixing the second foaming agent and water according to the formula ratio to obtain a liquid mixture;
and uniformly mixing the solid mixture and the liquid mixture to obtain foamed slurry.
According to another aspect of the invention, the invention provides an application of the red mud-based heat-insulating material or the red mud heat-insulating material obtained by the preparation method of the red mud-based heat-insulating material in a heating system;
preferably, the heating system comprises a boiler.
Compared with the prior art, the invention has the beneficial effects that:
the red mud-based thermal insulation material provided by the invention is mainly prepared from proper and proper amount of red mud, a first foaming agent, a second foaming agent, water and a foam stabilizer, wherein the foaming temperature of the first foaming agent is higher than that of the second foaming agent, and the red mud-based thermal insulation material has low thermal conductivity coefficient, the thermal conductivity coefficient can be reduced to 0.059W/m.K, and the thermal insulation material has good performance stability through the mutual cooperation and support of the functions of the raw materials and the mutual restriction and matching of the proportions.
The invention effectively utilizes solid waste, reduces environmental pollution, reduces environmental hazard and saves land, reduces and reduces the hazard of red mud to the maximum extent, makes the red mud harmless, recycled and industrialized, changes waste into valuable, makes the red mud more than or equal to 93 percent, more fully and effectively utilizes the red mud, and greatly reduces the production cost of the heat-insulating material.
According to the formula of the heat-insulating material, two foaming agents with different foaming temperatures are used at the same time, so that the material can be subjected to chemical decomposition reaction under the environment conditions of high temperature or low temperature and different temperatures, the second foaming agent and the foam stabilizer are foamed at low temperature to form uniform large holes, the first foaming agent plays a role in foaming at high temperature to form uniform small holes, the heat conductivity coefficient of the material is reduced under the combined action of the first foaming agent and the second foaming agent, the heat-insulating property of the material is improved, and the doping amount of the red mud can reach more than 93%.
The preparation method disclosed by the invention is simple and convenient to operate, low in cost, good in repeated operability and high in stability, the red mud-based heat-insulating material is prepared by adopting a secondary foaming method combining a low-temperature foaming method and a high-temperature foaming method, the utilization rate of the red mud is improved, the porous material with the low heat conductivity coefficient is obtained, a more effective solution is provided for the application of the red mud-based heat-insulating material in the fields of building heat-insulating materials, heat-insulating materials of heating systems and the like, and the red mud-based heat-insulating material has a very large potential economic.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to overcome the defects of the prior art, the invention provides a secondary foaming porous material formed by utilizing a large amount of red mud solid waste, low production cost and low product thermal conductivity coefficient and a preparation method thereof, namely a red mud-based heat-insulating material and a preparation method thereof. The invention utilizes a secondary method, namely low-temperature foaming and high-temperature foaming to prepare the porous material with low thermal conductivity, uniform large holes are formed at low temperature, uniform small holes are formed at high temperature, the thermal conductivity of the material is reduced under the combined action of the two, and the doping amount of the red mud reaches more than 93 percent.
In a first aspect, there is provided in at least one embodiment a red mud-based insulation material comprising: the red mud foaming agent comprises red mud, a first foaming agent, a second foaming agent, water and a foam stabilizer, wherein the foaming temperature of the first foaming agent is higher than that of the second foaming agent;
according to the mass percentage, the addition amount of the red mud is 93-100%, the addition amount of the first foaming agent accounts for 1-3% of the mass of the red mud, the addition amount of the second foaming agent accounts for 1-3% of the mass of the red mud, the addition amount of the water accounts for 55-65% of the mass of the red mud, and the addition amount of the foam stabilizer accounts for 40-45% of the mass of the second foaming agent.
The red mud is waste of alumina industry, and has great harm to environment, the invention takes the red mud as main material to prepare porous heat-insulating material, and makes full use of solid waste-red mud in large quantity, thereby improving the utilization rate of the red mud, causing no secondary pollution, reducing and reducing the harm of the red mud to the maximum extent, making the red mud harmless, recycling and industrialization, changing waste into valuables, and having obvious economic benefit and social benefit. According to the invention, the addition amount of the red mud can reach more than 93%, so that the problems of small addition amount of the red mud and low utilization rate of the red mud in the prior art are well solved, and the production cost of the heat-insulating material is greatly reduced.
Further, in order to make the prepared porous material have lower thermal conductivity, higher red mud addition and more utilization of red mud solid waste, the invention uses two foaming agents with different foaming temperatures in the formula of the thermal insulation material simultaneously, so that the material can generate chemical decomposition reaction under the environment conditions of different temperatures at high temperature or low temperature, the thermal conductivity of the material is reduced by the combined action of the two foaming agents (the thermal conductivity can be reduced to 0.059W/m.K), namely, two cells are formed in the system by utilizing a secondary foaming mode of low-temperature foaming during low-temperature molding and high-temperature foaming during high-temperature calcination for increasing the strength, and the red mud-based thermal insulation material with high red mud content and low thermal conductivity is obtained.
It should be noted that:
in the present invention, the percentages (%) refer to the mass percentage of the composition unless otherwise specified.
In the present invention, unless otherwise specified, the percentages, ratios, proportions or parts referred to are by mass, for example 93 to 100%, and may be expressed as 93 to 100% by weight.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated. For example, the individual components mentioned or their preferred components can be combined with one another to form new solutions.
The recitation of values by ranges is to be understood in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, red mud is added in an amount of 93-100%, which is understood to include not only the explicitly recited 93% and 100%, but also individual values within the indicated range, such as 94%, 95%, 96%, 97%, 98% or 99%. The amount of the first foaming agent added is 1 to 3% by mass of the red mud, and typically, but not limited to, 1%, 1.5%, 2%, 2.5%, or 3% may be mentioned. The amount of the second foaming agent added is 1 to 3% by mass of the red mud, and typically, but not limited to, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, or 3% may be mentioned. The amount of water added is 55-65% by mass of the red mud, and typically, but not limited to, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64% or 65% by mass. The amount of the foam stabilizer added is 40 to 45% by mass of the second blowing agent, and typically, but not limited to, 40%, 41%, 42%, 43%, 44% or 45% by mass.
The term "comprising" as used herein means that it may include, in addition to the recited components, other components that impart different properties to the red mud-based insulation material. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed. For example, the red mud-based thermal insulation material may include an additive or other solid wastes that can be applied to the field of thermal insulation materials, in addition to the red mud, the first foaming agent, the second foaming agent, the water and the foam stabilizer.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art.
It is understood that the foaming temperature of the first foaming agent is higher than the foaming temperature of the second foaming agent, which means that the foaming temperatures of the first foaming agent and the second foaming agent are different, and the foaming temperature of the first foaming agent is higher than the foaming temperature of the second foaming agent; that is, the first blowing agent can achieve foaming at a higher temperature and the second blowing agent can achieve foaming at a lower temperature, relatively speaking. The first blowing agent may also be referred to as a high temperature blowing agent and the second blowing agent may also be referred to as a low temperature blowing agent.
The first blowing agent used in the present invention is not particularly limited, and optionally, the first blowing agent (high-temperature blowing agent) has a blowing temperature (or decomposition temperature) of about 500 ℃.
The second foaming agent adopted in the invention is not strictly limited, and optionally, the foaming temperature (or decomposition temperature) of the second foaming agent (low-temperature foaming agent) is similar to the foaming temperature of hydrogen peroxide, and can be, for example, less than or equal to 40 ℃.
The invention adopts the formula of matching the high-temperature foaming agent and the low-temperature foaming agent to realize secondary foaming. That is, a low temperature foaming agent is used together with a high temperature foaming agent during the preparation of the insulation material to control the size and distribution of the internal pores, reducing the thermal conductivity of the material. In addition, the total pore area ratio of the large pores to the small pores can be controlled by controlling the weight ratio or the addition amount of the low-temperature foaming agent to the high-temperature foaming agent.
The foam stabilizer is a substance capable of improving the stability of bubbles and prolonging the foam breaking half-life. The foam stabilizer is added into the thermal insulation material, so that the foam breaking time can be delayed, and the foam stability is improved. In addition, the performance of the foam stabilizer is not only related to the stability of the foam, but also has an important influence on the properties of the slurry, such as flowability, volume stability and strength. Therefore, the proper foam stabilizer can ensure better product performance of the heat-insulating material.
According to the invention, the foam stabilizer is a low-temperature foam stabilizer, the addition amount of the foam stabilizer is based on the addition amount of the second foaming agent, and a proper and appropriate amount of the foam stabilizer is matched with the second foaming agent for use, so that foam holes formed by the second foaming agent can be uniform and stable, the retention time is long, the material is uniformly molded, and deformation and cracking during high-temperature firing can be prevented.
In a preferred embodiment, the addition amount of the red mud is 93-100%, the addition amount of the first foaming agent accounts for 1.5-2.5% of the mass of the red mud, the addition amount of the second foaming agent accounts for 2.2-2.8% of the mass of the red mud, the addition amount of the water accounts for 58-62% of the mass of the red mud, and the addition amount of the foam stabilizer accounts for 41-44% of the mass of the second foaming agent;
preferably, the addition amount of the red mud is 93-100% by mass, the addition amount of the first foaming agent accounts for 2% by mass of the red mud, the addition amount of the second foaming agent accounts for 2.4-2.5% by mass of the red mud, the addition amount of the water accounts for 60% by mass of the red mud, and the addition amount of the foam stabilizer accounts for 42-43% by mass of the second foaming agent.
By reasonably adjusting and optimizing the use amount of each component in the red mud-based heat-insulating material, the synergistic cooperation effect among the components is fully exerted, the heat conductivity coefficient of the material is further reduced, the heat-insulating property or the comprehensive property of the material is improved, and the production cost of the material is reduced.
The red mud used in the present invention is not strictly limited, and preferably, the red mud comprises bayer process red mud. That is, the red mud is preferably a pollutant waste discharged in the production of alumina by the bayer process.
The first foaming agent used in the present invention is not strictly limited, and preferably, the first foaming agent includes, but is not limited to, one or more of dust carbon powder, coal gangue or wood dust, and more preferably dust carbon powder. The first foaming agent can be, for example, smoke dust carbon powder, coal gangue, wood dust, a combination of smoke dust carbon powder and coal gangue, a combination of coal gangue and wood dust, and the like.
The red mud is used as a raw material, so that the production cost of the heat-insulating material is reduced, and the problems of environmental pollution and the like are solved; the waste such as smoke dust carbon powder, coal gangue and the like is further adopted as a high-temperature foaming agent, so that the resource utilization of the industrial waste such as red mud, smoke dust carbon powder and the like is realized, natural resources can be effectively and reasonably utilized, the production cost of the heat-insulating building material is effectively reduced, the environmental pollution is reduced, the natural resources are saved, the production cost of the heat-insulating material is further reduced, and the low-cost heat-insulating material has a wide application prospect in the field of the current green heat-insulating materials in China.
Particularly, the invention uses the soot carbon powder formed in the flue of the coal-fired boiler as a first foaming agent to prepare the thermal insulation material with low thermal conductivity.
According to the formula of the heat-insulating material, two foaming agents with different foaming temperatures are used at the same time, so that the material can be subjected to chemical decomposition reaction under the environment conditions of high temperature or low temperature and different temperatures, the second foaming agent and the foam stabilizer are foamed at low temperature to form uniform large holes, the first foaming agent is foamed at high temperature to form uniform small holes, the first foaming agent and the second foaming agent are combined to reduce the heat conductivity coefficient of the material and improve the heat-insulating property of the material, the first foaming agent is smoke dust carbon powder formed in a flue of a coal-fired boiler, the resource utilization of solid waste is further realized, and finally the doping amount of the red mud can reach more than 93%.
Wherein, the dust carbon powder is solid particles discharged in the coal burning and industrial production processes. Furthermore, the smoke dust carbon powder is solid waste which is formed by a coal-fired flue and has small particle size and high carbon content, has high activity and can react with oxygen in the air at high temperature to generate carbon dioxide. Therefore, the foaming agent is an excellent high-temperature foaming agent, can form a large number of micropores at high temperature to form a porous material, and can be applied to heat-insulating materials.
In the invention, the carbon element content of the smoke dust carbon powder is 75-80%. The particle size of the smoke dust carbon powder is nano-grade and can account for more than 50 percent; the particle size range of the soot carbon powder is 5nm-1 μm.
The second foaming agent used in the present invention is not strictly limited, and preferably, the second foaming agent includes hydrogen peroxide. It is understood that the second blowing agent of the present invention is hydrogen peroxide, which is commonly used in the art.
According to the invention, the second foaming agent preferably adopts hydrogen peroxide with the industrial grade mass fraction of 10-60%. Through the synergistic cooperation of the high-temperature foaming agent smoke dust carbon powder and the low-temperature foaming agent hydrogen peroxide, the prepared porous material is lower in heat conductivity coefficient and higher in red mud addition amount, more red mud solid waste is utilized, two kinds of cells are formed in a system, and the cell structure distribution is ideal.
The present invention is not restricted to the foam stabilizer used, and preferably, the foam stabilizer comprises one or more of methylcellulose, polyvinyl alcohol or polyethylene oxide, more preferably methylcellulose. The foam stabilizer may be, for example, methylcellulose, polyvinyl alcohol, polyethylene oxide, or a mixture of methylcellulose and polyvinyl alcohol.
It should be understood that the foam stabilizer involved in the red mud-based insulation material can be selected from the types commonly used in the art for preparing porous insulation materials, but in order to achieve better compounding/synergistic effect among the components, the foam stabilizer is preferably defined in the present invention, i.e. the foam stabilizer is preferably methylcellulose.
In a preferred embodiment, the red mud-based thermal insulation material further comprises an additive;
it can be understood that the red mud-based heat insulation material can be optionally added with an additive or not added with the additive; in practical application, the additive can be added according to actual conditions or process requirements. The specific type of the admixture is not particularly limited, and the type of the admixture commonly used in the art can be employed.
In a preferred embodiment, the admixture comprises one or more of waste glass powder, boric sludge, bentonite or sludge, preferably waste glass powder. Wherein, the boric sludge is waste residue generated in the production of boric acid, borax and other products; the sludge includes seabed sludge, river sludge or river bottom sludge, pond sludge and the like, and is preferably river sludge. The additive can be waste glass powder, boron mud, bentonite, river sludge, the mixture of waste glass powder and bentonite, the mixture of boron mud and river sludge and the like.
The addition of the waste glass powder can improve the silicon content in the system, is beneficial to the bonding between solid phases at high temperature and improves the mechanical property of the material.
According to the present invention, the specific type of the waste glass frits is not particularly limited, and most of the waste glass frits well known in the art may be selected; for example, the waste glass powder can be waste daily glass powder, waste medical glass powder, waste glass fiber powder and the like. The particle size of the waste glass powder is not particularly limited, but in order to make the system more uniform and the particle size of the glass powder as fine as possible, the particle size range of the waste glass powder is less than 10 μm.
The red mud-based heat-insulating material disclosed by the invention has the advantages that the preparation raw materials comprise various industrial wastes such as red mud, smoke dust carbon powder and waste glass powder, and the various industrial wastes are used as the raw materials, so that the production cost can be greatly reduced, the environmental pollution of the wastes can be reduced, the natural resources are saved, the wastes are effectively utilized, and the competitiveness of the product is favorably improved.
Preferably, the mass addition amount of the additive is less than or equal to 7 percent, namely the addition amount of the additive is more than 0 and less than or equal to 7 weight percent;
preferably, the addition amount of the red mud is 93-100% and the addition amount of the additive is less than or equal to 7% in percentage by mass; the addition amount of the first foaming agent accounts for 1-3% of the total mass of the red mud and the additive, the addition amount of the second foaming agent accounts for 1-3% of the total mass of the red mud and the additive, the addition amount of the water accounts for 55-65% of the total mass of the red mud and the additive, and the addition amount of the foam stabilizer accounts for 40-45% of the mass of the second foaming agent;
preferably, the addition amount of the red mud is 93-100% and the addition amount of the additive is less than or equal to 7% in percentage by mass; the addition amount of the first foaming agent accounts for 1.5-2.5% of the total mass of the red mud and the additive, the addition amount of the second foaming agent accounts for 2.2-2.8% of the total mass of the red mud and the additive, the addition amount of the water accounts for 58-62% of the total mass of the red mud and the additive, and the addition amount of the foam stabilizer accounts for 41-44% of the mass of the second foaming agent;
preferably, the addition amount of the red mud is 93-100% and the addition amount of the additive is less than or equal to 7% in percentage by mass; the additive amount of the first foaming agent accounts for 2% of the total mass of the red mud and the additive, the additive amount of the second foaming agent accounts for 2.4-2.5% of the total mass of the red mud and the additive, the additive amount of the water accounts for 60% of the total mass of the red mud and the additive, and the additive amount of the foam stabilizer accounts for 42-43% of the mass of the second foaming agent.
It should be understood that the red mud-based thermal insulation material may or may not be added with an additive. When the red mud-based heat insulation material does not contain an additive, the addition amounts of the first foaming agent, the second foaming agent and water are based on the mass addition amount of the red mud; when the red mud-based thermal insulation material contains the additive, the addition amounts of the first foaming agent, the second foaming agent and water are based on the total mass of the red mud and the additive.
In a second aspect, in some embodiments, there is provided a method for preparing the red mud-based thermal insulation material, comprising the following steps:
uniformly mixing the red mud, the first foaming agent, the foam stabilizer, the second foaming agent and water according to the formula ratio to obtain foaming slurry;
and injecting the foamed slurry into a mold for molding and calcining to obtain the red mud-based heat-insulating material.
The preparation method is simple to operate, easy to implement, low in cost, high in efficiency and easy to realize large-scale production.
In a preferred embodiment, the red mud, the first foaming agent, the foam stabilizer and the optional additive are uniformly mixed according to the formula ratio to obtain a solid mixture;
uniformly mixing the second foaming agent and water according to the formula ratio to obtain a liquid mixture;
and uniformly mixing the solid mixture and the liquid mixture to obtain foamed slurry.
When the heat insulation material is prepared, the solid material and the liquid material are mixed respectively, and then the uniformly mixed solid and liquid are mixed, so that the operation is easy, the mixing effect can be improved, the mixed material in flowing slurry is obtained, the production efficiency is high, the repeated operability is good, and the stability of the prepared product is good.
It is understood that the above "optional admixture" means that the admixture may be optionally added or not added, and may be selected according to actual production requirements.
In a preferred embodiment, the foaming slurry is injected into a mold, foamed at low temperature and cured and molded under natural conditions;
preferably, the forming time is 45-50h, preferably 46-48 h;
preferably, the calcination is high-temperature calcination, and the temperature of the high-temperature calcination is 900-1200 ℃, preferably 1100-1150 ℃;
preferably, the heating rate of the high-temperature calcination is 3-10 ℃/min, preferably 4-5 ℃/min;
preferably, the calcination is followed by a heat-preservation for a period of 20-40min, preferably 25-30 min.
The term "low-temperature foaming" means low-temperature foaming by the second foaming agent. Wherein the low temperature is generally less than or equal to 40 ℃.
The natural condition refers to that the place where the product is placed is in a natural environment state, no artificial factors are attached, and the product is completely in a natural state, and particularly, the temperature of the environment is not controlled artificially. Namely, the curing and molding are carried out at normal temperature and normal pressure without any equipment such as heating.
According to the invention, the flowing slurry liquid is injected into the mold, foamed, maintained and molded at a low temperature under natural conditions, and then calcined at a high temperature for foaming at a high temperature to obtain the red mud-based porous heat-insulating material, so that an effective solution is provided for the application of the red mud in the aspect of building materials.
As a preferred embodiment of the present invention, the method for preparing the red mud-based thermal insulation material comprises the following steps:
(a) crushing Bayer process red mud, and mixing the crushed Bayer process red mud with a first foaming agent, a foam stabilizer and an optional additive to obtain a uniformly mixed powdery solid mixture;
(b) adding a second foaming agent into water, and fully and uniformly mixing to obtain a liquid mixture;
(c) adding the liquid mixture obtained in the step (b) into the solid mixture obtained in the step (a), fully stirring for 1-3 minutes, injecting into a mold for low-temperature foaming, and curing and molding for about 48 hours under natural conditions;
(d) calcining the molded sample at high temperature, wherein the calcining temperature is preferably 1100 ℃, and the heating rate of the calcining is preferably 5 ℃/min; and (3) after high-temperature calcination, keeping the temperature for about half an hour, naturally cooling, and realizing secondary foaming to obtain the red mud-based porous heat-insulating material with low thermal conductivity.
The invention utilizes a secondary foaming method, namely low-temperature foaming and high-temperature foaming to prepare the porous material with low thermal conductivity, uniform large holes are formed at low temperature, uniform small holes are formed at high temperature, the thermal conductivity of the material is reduced under the combined action of the two, and the doping amount of the red mud reaches more than 93 percent.
The red mud is waste of alumina industry, and is harmful to environment, the high-temperature foaming agent is preferably smoke dust carbon powder which is solid waste with small particle size and high carbon content formed by a coal-fired flue, and the smoke dust carbon powder has high activity, can react with oxygen in air at high temperature to generate carbon dioxide, is an excellent high-temperature foaming agent, and can form a large number of micropores at high temperature to form a porous material. In order to make the prepared porous material have lower heat conductivity coefficient, higher red mud addition amount and more utilization of red mud solid waste, the invention utilizes a secondary foaming process of low-temperature foaming during low-temperature molding and high-temperature foaming during high-temperature calcination for increasing strength to form two cells in a system, thereby preparing the heat-insulating material with high red mud content and low heat conductivity coefficient. The red mud addition amount of the heat insulation material is more than 93 percent, and the heat conductivity coefficient can be reduced to 0.059W/m.K; the method integrates the method that the low-temperature slurry is easy to form uniform pore size by foaming and the strength can be effectively improved by high-temperature foaming, and has the advantages of simple and convenient operation of the process method, low cost and very great potential economic value.
In a third aspect, in some embodiments, there is provided a use of the red mud-based thermal insulation material or the red mud thermal insulation material obtained by the method for preparing the red mud-based thermal insulation material in a heating system;
preferably, the heating system comprises a boiler.
The red mud-based heat-insulating material provided by the invention has a low heat conductivity coefficient and good heat-insulating property, so that the red mud-based heat-insulating material can be widely applied to various building material fields, such as the building heating field. Particularly, the red mud-based heat insulation material can be applied to a boiler of a heating system, is low in application cost and good in heat insulation effect, can improve the heating efficiency of the boiler, reduces heat loss, and can increase the thermal efficiency of the boiler.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
A red mud-based thermal insulation material comprises: red mud, smoke dust carbon powder, hydrogen peroxide, methyl cellulose and water;
according to the mass percentage, the addition amount of the red mud is 100%, the addition amount of the smoke dust carbon powder accounts for 2% of the mass of the red mud, the addition amount of the hydrogen peroxide accounts for 2.4% of the mass of the red mud, the addition amount of the water accounts for 60% of the mass of the red mud, and the addition amount of the methyl cellulose accounts for 42% of the mass of the hydrogen peroxide.
The preparation method of the red mud-based heat insulation material comprises the following steps:
(a) uniformly mixing the red mud, the smoke dust carbon powder and the methyl cellulose in a mixer according to the formula ratio to obtain a solid mixture;
(b) adding hydrogen peroxide into water, and fully and uniformly mixing to obtain a liquid mixture;
(c) adding the liquid mixture in the step (b) into the solid mixture in the step (a), stirring for 1-3min, injecting into a 6cm multiplied by 3cm mould for low-temperature foaming, and curing and molding for 48h under natural conditions;
(d) calcining the molded sample at high temperature, wherein the calcining temperature is 1100 ℃, and the calcining heating rate is 5 ℃/min; and (3) after high-temperature calcination, keeping the temperature for about half an hour, and naturally cooling to realize secondary foaming to obtain the red mud-based heat insulation material.
The thermal conductivity coefficient of the red mud-based thermal insulation material of the embodiment is 0.059W/m.K.
Example 2
A red mud-based thermal insulation material comprises: red mud, smoke dust carbon powder, hydrogen peroxide, methyl cellulose and water;
according to the mass percentage, the addition amount of the red mud is 100%, the addition amount of the smoke dust carbon powder accounts for 2% of the mass of the red mud, the addition amount of the hydrogen peroxide accounts for 2.5% of the mass of the red mud, the addition amount of the water accounts for 60% of the mass of the red mud, and the addition amount of the methyl cellulose accounts for 42% of the mass of the hydrogen peroxide.
The preparation method of the red mud-based heat insulation material comprises the following steps:
(a) uniformly mixing the red mud, the smoke dust carbon powder and the methyl cellulose in a mixer according to the formula ratio to obtain a solid mixture;
(b) adding hydrogen peroxide into water, and fully and uniformly mixing to obtain a liquid mixture;
(c) adding the liquid mixture in the step (b) into the solid mixture in the step (a), stirring for 1-3min, injecting into a 6cm multiplied by 3cm mould for low-temperature foaming, and curing and molding for 48h under natural conditions;
(d) and (3) calcining the molded sample at high temperature, wherein the calcining temperature is 1000 ℃, the calcining heating rate is 5 ℃/min, and the calcining time is 30min, so as to obtain the red mud-based heat-insulating material.
The red mud-based thermal insulation material of the present example had a thermal conductivity of 0.1128W/m.K.
Example 3
A red mud-based thermal insulation material comprises: red mud, smoke dust carbon powder, hydrogen peroxide, methyl cellulose and water;
according to the mass percentage, the addition amount of the red mud is 100%, the addition amount of the smoke dust carbon powder accounts for 2% of the mass of the red mud, the addition amount of the hydrogen peroxide accounts for 2.4% of the mass of the red mud, the addition amount of the water accounts for 60% of the mass of the red mud, and the addition amount of the methyl cellulose accounts for 40% of the mass of the hydrogen peroxide.
The preparation method of the red mud-based heat insulation material comprises the following steps:
(a) uniformly mixing the red mud, the waste glass powder, the smoke dust carbon powder and the methyl cellulose in a mixer according to the formula ratio to obtain a solid mixture;
(b) adding hydrogen peroxide into water, and fully and uniformly mixing to obtain a liquid mixture;
(c) adding the liquid mixture in the step (b) into the solid mixture in the step (a), stirring for 1-3min, injecting into a 6cm multiplied by 3cm mould for low-temperature foaming, and curing and molding for 48h under natural conditions;
(d) and (3) calcining the molded sample at high temperature, wherein the calcining temperature is 1100 ℃, the calcining heating rate is 5 ℃/min, and the calcining time is 30min, so as to obtain the red mud-based heat-insulating material.
The red mud-based thermal insulation material of the embodiment has a thermal conductivity of 0.1378W/m.K.
Example 4
A red mud-based thermal insulation material comprises: red mud, bentonite, smoke dust carbon powder, hydrogen peroxide, methyl cellulose and water;
according to the mass percentage, the addition amount of the red mud is 93 percent, the addition amount of the bentonite is 7 percent, the addition amount of the smoke dust carbon powder accounts for 2 percent of the total mass of the red mud and the bentonite, the addition amount of the hydrogen peroxide accounts for 2.4 percent of the total mass of the red mud and the bentonite, the addition amount of the water accounts for 60 percent of the total mass of the red mud and the bentonite, and the addition amount of the methyl cellulose accounts for 42 percent of the mass of the hydrogen peroxide.
The preparation method of the red mud-based heat insulation material comprises the following steps:
(a) uniformly mixing the red mud, the bentonite, the smoke dust carbon powder and the methyl cellulose in a mixer according to the formula ratio to obtain a solid mixture;
(b) adding hydrogen peroxide into water, and fully and uniformly mixing to obtain a liquid mixture;
(c) adding the liquid mixture in the step (b) into the solid mixture in the step (a), stirring for 1-3min, injecting into a 6cm multiplied by 3cm mould for low-temperature foaming, and curing and molding for 48h under natural conditions;
(d) and (3) calcining the molded sample at high temperature, wherein the calcining temperature is 1100 ℃, the calcining heating rate is 5 ℃/min, and the calcining time is 30min, so as to obtain the red mud-based heat-insulating material.
The red mud-based thermal insulation material of the present example had a thermal conductivity of 0.2062W/m.K.
Example 5
A red mud-based thermal insulation material comprises: red mud, waste glass powder, smoke dust carbon powder, hydrogen peroxide, methyl cellulose and water;
according to the mass percentage, the addition amount of the red mud is 93 percent, the addition amount of the waste glass powder is 7 percent, the addition amount of the smoke dust carbon powder accounts for 2 percent of the total mass of the red mud and the waste glass powder, the addition amount of the hydrogen peroxide accounts for 1.2 percent of the total mass of the red mud and the waste glass powder, the addition amount of the water accounts for 60 percent of the total mass of the red mud, and the addition amount of the methyl cellulose accounts for 42 percent of the mass of the hydrogen peroxide.
The preparation method of the red mud-based heat insulation material comprises the following steps:
(a) uniformly mixing the red mud, the waste glass powder, the smoke dust carbon powder and the methyl cellulose in a mixer according to the formula ratio to obtain a solid mixture;
(b) adding hydrogen peroxide into water, and fully and uniformly mixing to obtain a liquid mixture;
(c) adding the liquid mixture in the step (b) into the solid mixture in the step (a), stirring for 1-3min, injecting into a 6cm multiplied by 3cm mould for low-temperature foaming, and curing and molding for 48h under natural conditions;
(d) and (3) calcining the molded sample at high temperature, wherein the calcining temperature is 1100 ℃, the calcining heating rate is 5 ℃/min, and the calcining time is 30min, so as to obtain the red mud-based heat-insulating material.
The red mud-based thermal insulation material of the present example had a thermal conductivity of 0.1263W/m.K.
Comparative example 1
A red mud-based thermal insulation material comprises: red mud, smoke dust carbon powder;
according to the mass percentage, the addition amount of the red mud is 100 percent, the addition amount of the smoke dust carbon powder accounts for 2.4 percent of the mass of the red mud, and the addition amount of the water accounts for 60 percent of the mass of the red mud.
The main difference between this comparative example and example 1 is that the second blowing agent, hydrogen peroxide and a foam stabilizer, is omitted.
The preparation method of the red mud-based heat-insulating material is only the high-temperature part of the embodiment 1, namely the forming calcination.
The red mud-based thermal insulation material of the comparative example has a thermal conductivity of 0.3391W/m.K.
Comparative example 2
A red mud-based thermal insulation material comprises: red mud, hydrogen peroxide, methyl cellulose and water;
according to the mass percentage, the addition amount of the red mud is 100 percent, the addition amount of the hydrogen peroxide accounts for 4.4 percent of the mass of the red mud, the addition amount of the water accounts for 60 percent of the mass of the red mud, and the addition amount of the methyl cellulose accounts for 42 percent of the mass of the hydrogen peroxide.
The main difference between this comparative example and example 1 is that the first blowing agent, the carbon dust, and its blowing action, are omitted.
The preparation method of the red mud-based heat insulation material is only the low-temperature foaming part of the embodiment 1, and the process is low-temperature foaming and drying molding at 200 ℃.
The red mud-based thermal insulation material of the comparative example has a thermal conductivity of 0.2237W/m.K.
Through the comparative analysis of the comparative examples 1-2 and the example 1, the two foaming modes are combined, so that the heat conductivity coefficient of the heat insulation material can be effectively reduced, and the volume density of the material can be reduced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (22)
1. The red mud-based heat insulation material is characterized by being prepared from the following raw materials: the red mud foaming agent comprises red mud, a first foaming agent, a second foaming agent, water and a foam stabilizer, wherein the foaming temperature of the first foaming agent is higher than that of the second foaming agent;
according to the mass percentage, the addition amount of the red mud is 93-100%, the addition amount of the first foaming agent accounts for 1-3% of the mass of the red mud, the addition amount of the second foaming agent accounts for 1-3% of the mass of the red mud, the addition amount of the water accounts for 55-65% of the mass of the red mud, and the addition amount of the foam stabilizer accounts for 40-45% of the mass of the second foaming agent;
the red mud comprises Bayer process red mud;
the first foaming agent comprises one or more of smoke dust carbon powder, coal gangue or wood dust;
the second foaming agent comprises hydrogen peroxide;
the foam stabilizer comprises one or more of methyl cellulose, polyvinyl alcohol or polyethylene oxide.
2. The red mud-based thermal insulation material according to claim 1, wherein the first foaming agent is soot carbon powder.
3. The red mud-based thermal insulation material according to claim 1, wherein the addition amount of the red mud is 93-100%, the addition amount of the first foaming agent accounts for 1.5-2.5% of the mass of the red mud, the addition amount of the second foaming agent accounts for 2.2-2.8% of the mass of the red mud, the addition amount of the water accounts for 58-62% of the mass of the red mud, and the addition amount of the foam stabilizer accounts for 41-44% of the mass of the second foaming agent.
4. The red mud-based thermal insulation material according to claim 3, wherein the addition amount of the red mud is 93-100%, the addition amount of the first foaming agent accounts for 2% of the mass of the red mud, the addition amount of the second foaming agent accounts for 2.4-2.5% of the mass of the red mud, the addition amount of the water accounts for 60% of the mass of the red mud, and the addition amount of the foam stabilizer accounts for 42-43% of the mass of the second foaming agent.
5. The red mud-based thermal insulation material according to claim 1, wherein the foam stabilizer is methylcellulose.
6. The red mud-based thermal insulation material according to any one of claims 1 to 5, further comprising an additive.
7. The red mud-based thermal insulation material as claimed in claim 6, wherein the mass addition amount of the additive is less than or equal to 7%.
8. The red mud-based thermal insulation material as claimed in claim 6, wherein the addition amount of the red mud is 93-100% and the addition amount of the additive is less than or equal to 7% by mass percent; the additive amount of the first foaming agent accounts for 1-3% of the total mass of the red mud and the additive, the additive amount of the second foaming agent accounts for 1-3% of the total mass of the red mud and the additive, the additive amount of the water accounts for 55-65% of the total mass of the red mud and the additive, and the additive amount of the foam stabilizer accounts for 40-45% of the mass of the second foaming agent.
9. The red mud-based thermal insulation material as claimed in claim 6, wherein the addition amount of the red mud is 93-100% and the addition amount of the additive is less than or equal to 7% by mass percent; the addition amount of the first foaming agent accounts for 1.5-2.5% of the total mass of the red mud and the additive, the addition amount of the second foaming agent accounts for 2.2-2.8% of the total mass of the red mud and the additive, the addition amount of the water accounts for 58-62% of the total mass of the red mud and the additive, and the addition amount of the foam stabilizer accounts for 41-44% of the mass of the second foaming agent.
10. The red mud-based thermal insulation material as claimed in claim 6, wherein the addition amount of the red mud is 93-100% and the addition amount of the additive is less than or equal to 7% by mass percent; the additive amount of the first foaming agent accounts for 2% of the total mass of the red mud and the additive, the additive amount of the second foaming agent accounts for 2.4-2.5% of the total mass of the red mud and the additive, the additive amount of the water accounts for 60% of the total mass of the red mud and the additive, and the additive amount of the foam stabilizer accounts for 42-43% of the mass of the second foaming agent.
11. The red mud-based thermal insulation material according to claim 6, wherein the admixture comprises one or more of waste glass powder, boric sludge, bentonite or sludge.
12. The method for preparing the red mud-based thermal insulation material according to any one of claims 1 to 11, comprising the steps of:
uniformly mixing the red mud, the first foaming agent, the foam stabilizer, the second foaming agent and water according to the formula ratio to obtain foaming slurry;
and injecting the foamed slurry into a mold for molding and calcining to obtain the red mud-based heat-insulating material.
13. The preparation method of the red mud-based heat-insulating material according to claim 12, wherein the red mud, the first foaming agent and the foam stabilizer in the formula amount are uniformly mixed to obtain a solid mixture;
uniformly mixing the second foaming agent and water according to the formula ratio to obtain a liquid mixture;
and uniformly mixing the solid mixture and the liquid mixture to obtain foamed slurry.
14. The preparation method of the red mud-based thermal insulation material according to claim 12, wherein the foaming slurry is injected into a mold, foamed at a low temperature, and cured and molded under natural conditions.
15. The preparation method of the red mud-based thermal insulation material according to claim 12, wherein the forming time is 45-50 h.
16. The preparation method of the red mud-based thermal insulation material as claimed in claim 12, wherein the calcining temperature is 900-1200 ℃.
17. The preparation method of the red mud-based thermal insulation material according to claim 12, wherein the temperature rise rate of calcination is 3-10 ℃/min.
18. The preparation method of the red mud-based heat-insulating material according to claim 12, wherein the heat preservation is carried out after the calcination, and the heat preservation time is 20-40 min.
19. The method for preparing the red mud-based thermal insulation material according to claim 12, wherein the method for preparing the foaming slurry can be replaced by: uniformly mixing the red mud, the additive, the first foaming agent, the foam stabilizing agent, the second foaming agent and water according to the formula ratio to obtain foaming slurry.
20. The preparation method of the red mud-based thermal insulation material according to claim 19, wherein the preparation method of the foaming slurry specifically comprises the following steps: uniformly mixing the red mud, the additive, the first foaming agent and the foam stabilizer according to the formula ratio to obtain a solid mixture;
uniformly mixing the second foaming agent and water according to the formula ratio to obtain a liquid mixture;
and uniformly mixing the solid mixture and the liquid mixture to obtain foamed slurry.
21. Use of the red mud insulation material according to any one of claims 1 to 11 or obtained by the method for preparing the red mud insulation material according to any one of claims 12 to 20 in a heating system.
22. The use of red mud insulation according to claim 21 in a heating system, wherein the heating system comprises a boiler.
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| CN112960965A (en) * | 2021-02-24 | 2021-06-15 | 中骥新材料有限公司 | Method for utilizing industrial red mud waste powder |
| CN113603406B (en) * | 2021-08-23 | 2022-06-28 | 中国地质大学（北京） | Baking-free and steaming-free foam heat-insulation composite material and preparation method thereof |
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| CN102173858B (en) * | 2011-01-10 | 2012-10-31 | 济南大学 | Red mud foaming lightweight heat-preserving plate |
| CN103804012B (en) * | 2012-11-14 | 2015-07-29 | 神华集团有限责任公司 | A kind of fire-retardant heat-insulation material and its preparation method and application |
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