CN108069673B - Calcium silicate fireproof plate and preparation method thereof - Google Patents
Calcium silicate fireproof plate and preparation method thereof Download PDFInfo
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- CN108069673B CN108069673B CN201611019163.XA CN201611019163A CN108069673B CN 108069673 B CN108069673 B CN 108069673B CN 201611019163 A CN201611019163 A CN 201611019163A CN 108069673 B CN108069673 B CN 108069673B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/10—Lime cements or magnesium oxide cements
- C04B28/12—Hydraulic lime
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
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Abstract
The invention provides a calcium silicate fireproof plate and a preparation method thereof, wherein the calcium silicate fireproof plate comprises the following raw materials in parts by weight: 0.1-80 parts of hydrated calcium silicate; 10-70 parts of quartz; 0-20 parts of cement; 0-20 parts of wood pulp fiber; 10-70 parts of lime; the calcium-silicon ratio of the raw material is 0.1-5. The preparation method of the calcium silicate fireproof plate comprises pulping, pulp flow process forming, steam curing and drying. According to the calcium silicate fireproof plate, calcium silicate hydrate is successfully applied to the fireproof plate, the high-temperature heat conductivity coefficient is less than 0.2W/(M multiplied by K), and the heat shrinkage rate is less than 0.3%; the problem that the solid waste base silicon-containing material is difficult to utilize is solved; the preparation method has simple process, mild condition and low cost, and is easy for industrial application.
Description
Technical Field
The invention belongs to the technical field of fireproof plates, relates to a calcium silicate fireproof plate and a preparation method thereof, and particularly relates to a calcium silicate fireproof plate prepared by recycling solid wastes and a preparation method thereof.
Background
With the development of national economy and the shortage of high-quality resources, the resource utilization of low-grade mineral resources and industrial solid wastes is widely concerned. The current research mainly aims at extracting the valuable elements of the solid wastes and the low-grade mineral products, and the associated large amount of silicon resources exist in the forms of waste liquid and waste residue and are difficult to be effectively utilized, so that the environmental pollution and the resource waste are caused. Therefore, the resource utilization of solid waste silicon elements needs to be solved urgently, and the synthesis of calcium silicate by taking the silicon elements as raw materials is an economical and feasible route.
In recent years, calcium silicate has been used with much attention. CN104194404A discloses a preparation method of active calcium silicate, and the active calcium silicate is compounded with a lubricant, a polymer and a compatilizer to be used for plastic filler, so that the dispersion effect and the toughening effect are good; CN104629541A is to graft activated calcium silicate and nano titanium dioxide to prepare the high heat insulation polyethylene powder coating, which shows good fluidity and adhesiveness, and the strength and toughness of the coating are improved. CN 105731475A provides a preparation method of calcium silicate powder with low pH value, high oil absorption value and specific surface area, which can be used as filler of base materials such as rubber, plastics, paper and the like, and improves the mechanical properties of the base materials. CN 105714604A and CN 105839453A adopt hydrochloric acid to treat calcium silicate, and then the calcium silicate is matched with a fine fiber composite filler to prepare filled paper, which can obviously improve the strength performance of the calcium silicate filled paper.
The calcium silicate is directly used as a raw material in the processes, and utilization of solid waste resources is not involved, CN 105439156A provides a method for preparing the rubber and plastic filler by using the micro silicon powder and the carbide slag, and the prepared calcium silicate rubber and plastic filler has stable chemical properties, uniform granularity, high whiteness and low impurity content; CN 105862501 a discloses a method for synthesizing calcium silicate filler by using desiliconized liquid, pulp fiber and lime milk, and the calcium silicate filler is used as calcium carbonate to replace the filler for papermaking. However, the annual production amount of industrial solid wastes is huge, and the consumption amount of a single calcium silicate product is difficult to meet the requirement of recycling industrial solid wastes. Thus. There is a need to develop a way to utilize waste calcium silicate hydrate.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a calcium silicate fireproof plate and a preparation method thereof.
In the present invention, the wt% means a mass percentage content unless otherwise specified.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a calcium silicate fireproof plate, which comprises the following raw materials in parts by weight:
0.1-80 parts of hydrated calcium silicate, such as 0.2 part, 0.3 part, 0.5 part, 0.8 part, 1 part, 5 parts, 10 parts, 20 parts, 40 parts, 60 parts, 70 parts or 75 parts;
10-70 parts of quartz, such as 11 parts, 12 parts, 15 parts, 18 parts, 20 parts, 25 parts, 30 parts, 40 parts, 50 parts, 60 parts or 69 parts;
0-20 parts of cement, such as 0.5 part, 1 part, 2 parts, 5 parts, 7 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 19 parts and the like;
0-20 parts of wood pulp fiber, such as 0.5 part, 1 part, 2 parts, 5 parts, 7 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 19 parts and the like;
10-70 parts of lime, such as 11 parts, 12 parts, 15 parts, 18 parts, 20 parts, 25 parts, 30 parts, 40 parts, 50 parts, 60 parts or 69 parts;
the molar ratio of calcium to silicon of the raw material is 0.1-5, such as 0.15, 0.2, 0.5, 0.6, 0.8, 1, 1.2, 1.5, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 4.8, and the like.
According to the calcium silicate fireproof plate provided by the invention, the hydrated calcium silicate is added into the raw materials, and the proper raw material ratio is determined, so that the heat conductivity coefficient and the heat shrinkage rate of the fireproof plate are greatly reduced, the high-temperature heat conductivity coefficient is less than 0.2W/(M multiplied by K), and the heat shrinkage rate is less than 0.3%. Compared with the traditional calcium silicate fireproof plate, the high-temperature heat conductivity coefficient of the fireproof plate can be reduced by 8-9%.
The calcium silicate hydrate is prepared by the following method: reacting quicklime and/or lime milk with a silicon-containing material, and carrying out solid-liquid separation on a reaction product to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product; the sodium removing agent is selected from any one or the combination of at least two of aluminum compounds, calcium compounds or magnesium compounds, or the sodium removing agent contains more than 50 wt% of any one or the combination of at least two of the aluminum compounds, the calcium compounds or the magnesium compounds.
The solid-liquid separation mode can be filtration or centrifugation.
The calcium silicate hydrate product is a mixture, the calcium-silicon ratio and the water content of the calcium silicate hydrate product can not be completely the same, and the molecular formula of the product is xCaO-ySiO2·zH2O, wherein x has a value of 1 to 10, such as 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, or 10, etc.; y has a value of 1 to 10, such as 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, or 10, etc.; z has a value of 1-20, such as 1, 1.5, 2, 2.5, 3, 5, 7, 9, 10, 12, 14, 16, 18, or 20, and the like.
The sodium removing agent is selected from any one or combination of at least two of aluminum compound, calcium compound or magnesium compound, and typical but non-limiting sodium removing agent combinations are aluminum compound and calcium compound, aluminum compound and magnesium compound, and calcium compound and magnesium compound. Or the sodium removing agent comprises more than 50 wt% of any one or combination of at least two of aluminum compounds, calcium compounds or magnesium compounds, such as 52 wt%, 53 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt%, 65 wt%, 68 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt% or 95 wt% of any one or combination of at least two of aluminum compounds, calcium compounds or magnesium compounds.
The principle of sodium removal by the sodium removal agent is as follows: the impurity sodium ions in the hydrated calcium silicate are exchanged and removed by utilizing magnesium, aluminum or calcium ions and the like in the sodium remover through an ion exchange method. The addition of the sodium removal agent greatly improves the purity of the calcium silicate hydrate, and the content of sodium oxide in the calcium silicate hydrate is lower than 1 wt% by matching with leaching.
The addition amount of the sodium removing agent is 0.001-2 times of the dry mass of the first filter cake, such as 0.002 time, 0.005 time, 0.01 time, 0.02 time, 0.05 time, 0.08 time, 0.1 time, 0.3 time, 0.5 time, 0.8 time, 1 time, 1.2 times, 1.5 times or 1.8 times.
The aluminum compound is selected from any one or a combination of at least two of aluminum oxide, aluminum oxalate, aluminum hydroxide, aluminum chloride or aluminum nitrate, typically but not limited to, a combination of aluminum oxide and aluminum oxalate, aluminum hydroxide and aluminum chloride, aluminum nitrate and aluminum oxide, aluminum oxalate and aluminum hydroxide, aluminum chloride and aluminum nitrate.
Preferably, the calcium compound is selected from any one or a combination of at least two of calcium oxide, calcium oxalate, calcium hydroxide, calcium chloride or calcium nitrate, typically but not limited to a combination of calcium oxide and calcium oxalate, calcium oxide and calcium hydroxide, calcium chloride and calcium nitrate, calcium oxalate, calcium hydroxide and calcium chloride, calcium oxide, calcium oxalate and calcium hydroxide.
Preferably, the magnesium compound is selected from any one of magnesium oxide, magnesium oxalate, magnesium hydroxide, magnesium chloride or magnesium nitrate, or a combination of at least two thereof, typically but not limited to a combination of magnesium oxide and magnesium oxalate, magnesium oxide and magnesium hydroxide, magnesium chloride and magnesium nitrate.
Preferably, the temperature of the water used in the first leaching is 10-100 ℃, such as 20 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, and the like, and the amount of the water used is 0.1-10 times, such as 0.3 times, 0.5 times, 0.8 times, 1.0 times, 1.3 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times or 9 times, and the like, of the mass of the solid phase dry-based product.
Preferably, the temperature of the water mixed with the first filter cake is 10-200 ℃, such as 20 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 130 ℃, 150 ℃, 160 ℃, 180 ℃ or 190 ℃, etc., and the amount is 0.1-10 times, such as 0.3 times, 0.5 times, 0.8 times, 1.0 times, 1.3 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times or 9 times, etc., of the mass of the solid phase dry base product.
The amount is 0.1-10 times of the dry mass of the first filter cake, such as 0.3 times, 0.5 times, 0.8 times, 1.0 times, 1.3 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times or 9 times.
Preferably, the temperature of the water used in the second leaching is 10-100 ℃, such as 20 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃ and the like, and the amount of the water used is 0.1-10 times, such as 0.3 times, 0.5 times, 0.8 times, 1.0 times, 1.3 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times or 9 times of the mass of the solid phase dry-based product.
Preferably, the water obtained by the second leaching in the first process is used for the water for the suspension in the second process, the liquid phase obtained by the solid-liquid separation in the first process is used for the first leaching washing water in the second process, the second leaching washing water in the second process is fresh water, and the first process and the second process are independently solid phase washing processes, that is, the method comprises the steps of performing the first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake; and drying the second filter cake to obtain a calcium silicate hydrate product. Thereby greatly saving the water consumption. The dosage of the washing water is only 0.1 to 10 times of the mass of the dry-based product.
The silicon-containing material is selected from silicon-containing waste liquid and/or waste residue generated in the solid waste and/or low-grade ore treatment process, preferably, the silicon-containing waste liquid and/or waste residue discharged in the chemical and metallurgical processes is selected from the mining solid waste with the main metal components (including aluminum, iron, zirconium, copper, manganese and the like) of less than 50 wt%. The problem that the produced silicon-containing waste liquid or waste solid is difficult to effectively utilize in the process of utilizing industrial solid wastes and low-grade mineral resources is solved, and the loss of silicon element in the production process is avoided.
Preferably, the silicon-containing material is selected from any one of fly ash, calcium silicon slag, zirconium silicon slag, micro silicon powder, ferrosilicon smoke dust, copper smelting water-quenched slag, silicon manganese dust, fly ash desiliconization liquid, calcium silicon slag desiliconization liquid, zirconium silicon slag desiliconization liquid, micro silicon powder desiliconization liquid, ferrosilicon smoke dust desiliconization liquid, copper smelting water-quenched slag desiliconization liquid or silicomanganese dust desiliconization liquid or a combination of at least two of the fly ash, the calcium silicon slag, the zirconium silicon slag, the silicon dust, the silicon slag. Typical but not limiting combinations are fly ash and silico-calcium slag, zirconium silico-slag and micro silicon powder, ferrosilicon smoke dust, copper smelting water-quenched slag and silico-manganese dust, fly ash desiliconization liquid, silico-calcium slag desiliconization liquid and zirconium silico-slag desiliconization liquid, micro silicon powder desiliconization liquid, ferrosilicon smoke desiliconization liquid, copper smelting water-quenched slag desiliconization liquid and silico-manganese dust desiliconization liquid.
Preferably, the mass ratio of the silicon-containing material to lime and/or lime milk is 0.1-5, such as 0.3, 0.5, 0.8, 1.0, 1.2, 1.5, 1.8, 2.1, 2.5, 3.0, 3.5, 4.0 or 4.5, etc.
Preferably, the reaction temperature is 30-250 deg.C, such as 35 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 120 deg.C, 150 deg.C, 180 deg.C, 200 deg.C, 220 deg.C or 240 deg.C, and the reaction time is 0.5-10h, such as 0.8h, 1.0h, 1.2h, 1.5h, 1.8h, 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9 h.
One of the purposes of the invention is also to provide a preparation method of the calcium silicate fireproof plate, wherein the preparation method comprises pulping, pulp flow process forming, steam curing and drying; the pulping raw materials comprise the following components in parts by weight: 0.1-80 parts of hydrated calcium silicate, such as 0.2 part, 0.3 part, 0.5 part, 0.8 part, 1 part, 5 parts, 10 parts, 20 parts, 40 parts, 60 parts, 70 parts or 75 parts;
10-70 parts of quartz, such as 11 parts, 12 parts, 15 parts, 18 parts, 20 parts, 25 parts, 30 parts, 40 parts, 50 parts, 60 parts or 69 parts;
0-20 parts of cement, such as 0.5 part, 1 part, 2 parts, 5 parts, 7 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 19 parts and the like;
0-20 parts of wood pulp fiber, such as 0.5 part, 1 part, 2 parts, 5 parts, 7 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 19 parts and the like;
10-70 parts of lime, such as 11 parts, 12 parts, 15 parts, 18 parts, 20 parts, 25 parts, 30 parts, 40 parts, 50 parts, 60 parts or 69 parts;
the molar ratio of calcium to silicon of the raw material is 0.1-5, such as 0.15, 0.2, 0.5, 0.6, 0.8, 1, 1.2, 1.5, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 4.8, and the like.
The calcium silicate hydrate is prepared by the following preparation method: reacting quicklime and/or lime milk with a silicon-containing material, and carrying out solid-liquid separation on a reaction product to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product; the sodium removing agent is selected from any one or the combination of at least two of aluminum compounds, calcium compounds or magnesium compounds, or the sodium removing agent contains more than 50 wt% of any one or the combination of at least two of the aluminum compounds, the calcium compounds or the magnesium compounds.
The calcium silicate hydrate product is a mixture, the calcium-silicon ratio and the water content of the calcium silicate hydrate product can not be completely the same, and the molecular formula of the product is xCaO-ySiO2·zH2O, wherein x has a value of 1 to 10, such as 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, or 10, etc.; y has a value of 1 to 10, such as 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, or 10, etc.; z has a value of 1-20, such as 1, 1.5, 2, 2.5, 3, 5, 7, 9, 10, 12, 14, 16, 18, or 20, and the like.
The sodium removing agent is selected from any one or combination of at least two of aluminum compound, calcium compound or magnesium compound, and typical but non-limiting sodium removing agent combinations are aluminum compound and calcium compound, aluminum compound and magnesium compound, and calcium compound and magnesium compound. Or the sodium removing agent comprises more than 50 wt% of any one or combination of at least two of aluminum compounds, calcium compounds or magnesium compounds, such as 52 wt%, 53 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt%, 65 wt%, 68 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt% or 95 wt% of any one or combination of at least two of aluminum compounds, calcium compounds or magnesium compounds.
The addition amount of the sodium removing agent is 0.001-2 times of the dry mass of the first filter cake, such as 0.002 time, 0.005 time, 0.01 time, 0.02 time, 0.05 time, 0.08 time, 0.1 time, 0.3 time, 0.5 time, 0.8 time, 1 time, 1.2 times, 1.5 times or 1.8 times.
Preferably, the aluminium compound is selected from any one of or a combination of at least two of aluminium oxide, aluminium oxalate, aluminium hydroxide, aluminium chloride or aluminium nitrate, typically but not limited to a combination of aluminium oxide and aluminium oxalate, aluminium hydroxide and aluminium chloride, aluminium nitrate and aluminium oxide, aluminium oxalate and aluminium hydroxide, aluminium chloride and aluminium nitrate.
Preferably, the calcium compound is selected from any one or a combination of at least two of calcium oxide, calcium oxalate, calcium hydroxide, calcium chloride or calcium nitrate, typically but not limited to a combination of calcium oxide and calcium oxalate, calcium oxide and calcium hydroxide, calcium chloride and calcium nitrate, calcium oxalate, calcium hydroxide and calcium chloride, calcium oxide, calcium oxalate and calcium hydroxide.
Preferably, the magnesium compound is selected from any one of magnesium oxide, magnesium oxalate, magnesium hydroxide, magnesium chloride or magnesium nitrate, or a combination of at least two thereof, typically but not limited to a combination of magnesium oxide and magnesium oxalate, magnesium oxide and magnesium hydroxide, magnesium chloride and magnesium nitrate.
Preferably, the temperature of the water used in the first leaching is 10-100 ℃, such as 20 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, and the like, and the amount of the water used is 0.1-10 times, such as 0.3 times, 0.5 times, 0.8 times, 1.0 times, 1.3 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times or 9 times, and the like, of the mass of the solid phase dry-based product.
Preferably, the temperature of the water mixed with the first filter cake is 10-200 ℃, such as 20 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 130 ℃, 150 ℃, 160 ℃, 180 ℃ or 190 ℃, etc., and the amount is 0.1-10 times, such as 0.3 times, 0.5 times, 0.8 times, 1.0 times, 1.3 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times or 9 times, etc., of the mass of the solid phase dry base product.
The amount is 0.1-10 times of the dry mass of the first filter cake, such as 0.3 times, 0.5 times, 0.8 times, 1.0 times, 1.3 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times or 9 times.
Preferably, the temperature of the water used in the second leaching is 10-100 ℃, such as 20 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃ and the like, and the amount of the water used is 0.1-10 times, such as 0.3 times, 0.5 times, 0.8 times, 1.0 times, 1.3 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times or 9 times of the mass of the solid phase dry-based product.
Preferably, the water obtained by the second leaching in the first process is used for the water for the suspension in the second process, the liquid phase obtained by the solid-liquid separation in the first process is used for the first leaching washing water in the second process, the second leaching washing water in the second process is fresh water, and the first process and the second process are independently solid phase washing processes, that is, the method comprises the steps of performing the first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; and carrying out second leaching on the second solid phase to obtain a second filter cake. To save water usage. The dosage of the washing water is only 0.1 to 10 times of the mass of the dry-based product.
The silicon-containing material is selected from silicon-containing waste liquid and/or waste residue generated in the solid waste and/or low-grade ore treatment process, preferably, the silicon-containing waste liquid and/or waste residue discharged in the chemical and metallurgical processes is selected from the mining solid waste with the main metal component of less than 50 wt%. The problem that the produced silicon-containing waste liquid or waste solid is difficult to effectively utilize in the process of utilizing industrial solid wastes and low-grade mineral resources is solved, and the loss of silicon element in the production process is avoided.
Preferably, the silicon-containing material is selected from any one of fly ash, calcium silicon slag, zirconium silicon slag, micro silicon powder, ferrosilicon smoke dust, copper smelting water-quenched slag, silicon manganese dust, fly ash desiliconization liquid, calcium silicon slag desiliconization liquid, zirconium silicon slag desiliconization liquid, micro silicon powder desiliconization liquid, ferrosilicon smoke dust desiliconization liquid, copper smelting water-quenched slag desiliconization liquid or silicomanganese dust desiliconization liquid or a combination of at least two of the fly ash, the calcium silicon slag, the zirconium silicon slag, the silicon dust, the silicon slag. Typical but not limiting combinations are fly ash and silico-calcium slag, zirconium silico-slag and micro silicon powder, ferrosilicon smoke dust, copper smelting water-quenched slag and silico-manganese dust, fly ash desiliconization liquid, silico-calcium slag desiliconization liquid and zirconium silico-slag desiliconization liquid, micro silicon powder desiliconization liquid, ferrosilicon smoke desiliconization liquid, copper smelting water-quenched slag desiliconization liquid and silico-manganese dust desiliconization liquid.
Preferably, the mass ratio of the silicon-containing material to lime and/or lime milk is 0.1-5, such as 0.3, 0.5, 0.8, 1.0, 1.2, 1.5, 1.8, 2.1, 2.5, 3.0, 3.5, 4.0 or 4.5, etc.
Preferably, the reaction temperature is 30-250 deg.C, such as 35 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 120 deg.C, 150 deg.C, 180 deg.C, 200 deg.C, 220 deg.C or 240 deg.C, and the reaction time is 0.5-10h, such as 0.8h, 1.0h, 1.2h, 1.5h, 1.8h, 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9 h.
The pressure of the slurry process is 0.1-2MPa, such as 0.3MPa, 0.5MPa, 0.8MPa, 1.0MPa, 1.2MPa, 1.3MPa, 1.5MPa, 1.7MPa or 1.9 MPa.
The temperature of the steam curing is 150-.
Preferably, the steaming time is 2-15h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14 h.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) reacting the silicon-containing material with quicklime and/or lime milk according to the mass ratio of 0.1-5, wherein the reaction temperature is 30-250 ℃, the reaction time is 0.5-10h, and performing solid-liquid separation on a reaction product to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product; the sodium removing agent is selected from any one or the combination of at least two of aluminum compounds, calcium compounds or magnesium compounds, or the sodium removing agent contains more than 50 wt% of any one or the combination of at least two of aluminum compounds, calcium compounds or magnesium compounds; the addition amount of the sodium removing agent is 0.001-2 times of the dry basis weight of the first filter cake; wherein the temperature of the water used for the first leaching is 10-100 ℃, and the using amount of the water is 0.1-10 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 10-200 ℃, and the using amount of the water is 0.1-10 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 10-100 ℃, and the using amount of the water is 0.1-10 times of the mass of the second solid phase dry base; the silicon-containing material is selected from any one or the combination of at least two of fly ash, calcium silicon slag, zirconium silicon slag, micro silicon powder, ferrosilicon smoke dust, copper smelting water-quenched slag, silicon manganese dust, fly ash desiliconization liquid, calcium silicon slag desiliconization liquid, zirconium silicon slag desiliconization liquid, micro silicon powder desiliconization liquid, ferrosilicon smoke desiliconization liquid, copper smelting water-quenched slag desiliconization liquid or silicomanganese dust desiliconization liquid;
(2) pulping 0.1-80 parts of calcium silicate hydrate product with sodium oxide content less than 1 wt%, 10-70 parts of quartz, 0-20 parts of cement, 0-20 parts of wood pulp fiber and 10-70 parts of lime, forming by adopting a pulp flowing process, steaming, drying and obtaining the calcium silicate fireproof plate, wherein the calcium-silicon ratio of the pulping raw material is 0.1-5; the pressure of the pulp flow process forming is 0.1-2MPa, and the steam curing temperature is 150-250 ℃; the steaming time is 2-15 h.
The preparation method of the calcium silicate fireproof plate provided by the invention has the advantages of simple process, mild conditions, low cost and easiness in industrial application.
Compared with the prior art, the invention has the beneficial effects that:
due to the addition of hydrated calcium silicate, the high-temperature heat conductivity coefficient of the calcium silicate fireproof plate provided by the invention is less than 0.2W/(M multiplied by K), and the heat shrinkage rate is less than 0.3%. Compared with the traditional calcium silicate fireproof plate, the high-temperature heat conductivity coefficient of the fireproof plate is reduced by 8-9%.
Aiming at the problem that solid waste base silicon-containing materials are difficult to utilize, calcium silicate series compounds are prepared by causticization, and the calcium silicate series compounds are successfully applied to the fireproof plate, so that the problem that impurities influence calcium silicate products (the content of sodium oxide in calcium silicate hydrate is lower than 1 wt%, such as 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt% and the like) is solved, the consumption of washing water is low (the consumption of washing water is only 0.1-10 times of the quality of dry base products), and the index performance of the fireproof plate is greatly improved.
The preparation method of the calcium silicate fireproof plate provided by the invention has the advantages of simple process, mild conditions, low cost and easiness in industrial application.
Detailed Description
The technical solutions of the present invention are further described below with reference to specific embodiments, but the scope of the present invention should include the entire contents of the claims, and is not limited to the following examples.
Example 1
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 0.15.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) carrying out causticization reaction on the fly ash and 0.1 time of quicklime by mass at 50 ℃ for 7h, and carrying out solid-liquid separation on slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.95 wt%;
the sodium removing agent is a mixture of aluminum oxide and aluminum oxalate with the mass ratio of 1:1, and the adding amount of the sodium removing agent is 0.001 time of the dry mass of the first filter cake;
the temperature of water used for the first leaching is 100 ℃, and the using amount of the water is 0.1 time of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 200 ℃, and the using amount of the water is 0.1 time of the dry mass of the first filter cake; the temperature of water used for the second leaching is 100 ℃, and the using amount of the water is 0.1 time of the mass of the second solid phase dry base;
(2) mixing the raw materials according to the formula ratio to obtain slurry, forming under 0.5MPa by adopting a pulp flowing process, steaming at 200 ℃ for 5 hours, and drying to obtain the calcium silicate fireproof plate, wherein the high-temperature heat conductivity coefficient of the calcium silicate fireproof plate is 0.187W/(MxK), and the heat shrinkage rate of the calcium silicate fireproof plate is 0.235%.
Example 2
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 3.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing fly ash desiliconized solution and lime cream with the mass of 1 time of that of the fly ash for 10 hours at 30 ℃, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.35 wt%;
the sodium removing agent is a mixture of aluminum oxalate and aluminum chloride in a mass ratio of 2:1, and the adding amount of the sodium removing agent is 2 times of the dry basis mass of the first filter cake;
the temperature of water used for the first leaching is 10 ℃, and the using amount of the water is 10 times of the mass of a solid phase dry base product; the temperature of the water mixed with the first filter cake is 10 ℃, and the using amount of the water is 10 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 10 ℃, and the using amount of the water is 10 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 0.2MPa by adopting a pulp flowing process, and is steamed and cured for 15 hours at the temperature of 150 ℃ and dried to obtain the calcium silicate fireproof plate, wherein the high-temperature heat conductivity coefficient is 0.197W/(M multiplied by K), and the heat shrinkage rate is 0.298%.
Example 3
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 0.5.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the calcium silicate slag and lime milk with 3 times of the weight of the calcium silicate slag at 100 ℃ for 6 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.51 wt%;
the mass ratio of the sodium removing agent to the aluminum hydroxide is 3:1, and the addition amount of the sodium removing agent is 0.005 time of the dry basis mass of the first filter cake;
the temperature of water used for the first leaching is 20 ℃, and the using amount of the water is 8 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 20 ℃, and the using amount of the water is 8 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 20 ℃, and the using amount of the water is 8 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 0.1MPa by adopting a pulp flowing process, the calcium silicate fireproof plate is obtained after steam curing for 2 hours at 250 ℃ and drying, and the high-temperature heat conductivity coefficient of the calcium silicate fireproof plate is 0.168W/(M multiplied by K), and the heat shrinkage rate is 0.203%.
Example 4
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 1.2.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the calcium silicate slag desiliconized solution and 5 times of quick lime by mass at 150 ℃ for 5 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.73 wt%;
the sodium removing agent is a mixture of calcium oxide and calcium oxalate with a mass ratio of 4:1, and the addition amount of the sodium removing agent is 0.01 time of the dry basis mass of the first filter cake;
the temperature of water used for the first leaching is 80 ℃, and the using amount of the water is 1 time of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 80 ℃, and the using amount of the water is 5 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 80 ℃, and the using amount of the water is 2 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 1MPa by adopting a pulp flowing process, and is steamed and cured for 5 hours at 220 ℃, and the calcium silicate fireproof plate is obtained after drying, and has the high-temperature heat conductivity coefficient of 0.159W/(M multiplied by K) and the heat shrinkage rate of 0.246 percent.
Example 5
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 1.0.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the zirconium-silicon slag and 0.7 times of quick lime by mass at 180 ℃ for 2 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.15 wt%;
the sodium removing agent is a mixture of calcium hydroxide, calcium chloride and calcium nitrate in a mass ratio of 1:1:1, and the addition amount of the sodium removing agent is 1.5 times of the dry basis mass of the first filter cake;
the temperature of water used for the first leaching is 50 ℃, and the using amount of the water is 5 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 150 ℃, and the using amount of the water is 5 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 30 ℃, and the using amount of the water is 9 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula amount are mixed to obtain slurry, the slurry is formed under 1.5MPa by adopting a pulp flowing process, and is steamed and cured for 8 hours at 210 ℃, and the calcium silicate fireproof plate is obtained after drying, and has the high-temperature heat conductivity coefficient of 0.176W/(M multiplied by K) and the heat shrinkage rate of 0.263 percent.
Example 6
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 0.8.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the desiliconized zirconium slag solution and quicklime which is 1.5 times of the desiliconized zirconium slag solution by mass at 250 ℃ for 0.5h, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.91 wt%;
the sodium removing agent is a mixture of magnesium oxide, magnesium oxalate and magnesium hydroxide with the mass ratio of 2:1:1, and the adding amount of the sodium removing agent is 1 time of the dry basis mass of the first filter cake;
the temperature of water used for the first leaching is 40 ℃, and the using amount of the water is 3 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 180 ℃, and the using amount of the water is 5 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 60 ℃, and the using amount of the water is 5 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, a pulp flowing process is adopted, the forming is carried out under 2MPa, the steaming curing is carried out for 10 hours at 190 ℃, and the drying is carried out to obtain the calcium silicate fireproof plate, wherein the high-temperature heat conductivity coefficient is 0.167W/(M multiplied by K), and the heat shrinkage rate is 0.258%.
Example 7
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 5.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the micro silicon powder and lime milk which is 1.9 times of the micro silicon powder by mass at 240 ℃ for 5 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.62 wt%;
the sodium removal agent is a mixture of magnesium chloride and magnesium nitrate in a mass ratio of 5:2, and the addition amount of the sodium removal agent is 0.05 times of the dry basis mass of the first filter cake;
the temperature of water used for the first leaching is 20 ℃, and the using amount of the water is 5 times of the mass of a solid phase dry base product; the temperature of the water mixed with the first filter cake is 30 ℃, and the using amount of the water is 2 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 70 ℃, and the using amount of the water is 7 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 1.0MPa by adopting a pulp flowing process, and is steamed and cured for 9 hours at 210 ℃, and the calcium silicate fireproof plate is obtained after drying, and has the high-temperature heat conductivity coefficient of 0.155W/(M multiplied by K) and the heat shrinkage rate of 0.203%.
Example 8
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 2.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the desiliconized micro silicon powder and lime milk 3.5 times the mass of the desiliconized micro silicon powder at 70 ℃ for 3 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.26 wt%;
the sodium removing agent is a mixture of aluminum oxide, calcium oxide and magnesium oxide in a mass ratio of 1:1:1, and the addition amount of the sodium removing agent is 0.2 times of the dry basis mass of the first filter cake;
the temperature of water used for the first leaching is 70 ℃, and the using amount of the water is 2 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 120 ℃, and the using amount of the water is 9 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 15 ℃, and the using amount of the water is 9 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 0.7MPa by adopting a pulp flowing process, and is steamed and cured for 12 hours at 190 ℃, and the calcium silicate fireproof plate is obtained after drying, and has the high-temperature heat conductivity coefficient of 0.161W/(M multiplied by K) and the heat shrinkage rate of 0.289%.
Example 9
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 2.7.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the ferrosilicon smoke dust and lime milk with the mass 4.3 times of that of the ferrosilicon smoke dust for 1 hour at the temperature of 80 ℃, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.34 wt%;
the sodium removing agent contains 50 wt% of alumina, and the adding amount of the sodium removing agent is 0.05 times of the dry mass of the first filter cake;
the temperature of water used for the first leaching is 20 ℃, and the using amount of the water is 7 times of the mass of a solid phase dry base product; the temperature of the water mixed with the first filter cake is 180 ℃, and the using amount of the water is 7 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 20 ℃, and the using amount of the water is 8 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 0.4MPa by adopting a pulp flowing process, the calcium silicate fireproof plate is obtained after the steam curing is carried out for 14 hours at 160 ℃, and the calcium silicate fireproof plate is dried, wherein the high-temperature heat conductivity coefficient is 0.188W/(M multiplied by K), and the heat shrinkage rate is 0.293%.
Example 10
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 1.5.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the silicon-iron smoke desiliconized solution and lime milk which is 1.3 times of the silicon-iron smoke desiliconized solution at the temperature of 100 ℃ for 7 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.54 wt%;
the sodium removal agent contains 80 wt% of magnesium oxide, and the addition amount of the sodium removal agent is 1.5 times of the dry mass of the first filter cake;
the temperature of water used for the first leaching is 30 ℃, and the using amount of the water is 5 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 30 ℃, and the using amount of the water is 5 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 30 ℃, and the using amount of the water is 5 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula amount are mixed to obtain slurry, the slurry is formed under 0.9MPa by adopting a pulp flowing process, and is steamed and cured for 3 hours at 240 ℃ and dried to obtain the calcium silicate fireproof plate, wherein the high-temperature heat conductivity coefficient is 0.172W/(M multiplied by K), and the heat shrinkage rate is 0.225%.
Example 11
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 1.1.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the copper smelting water quenched slag and 0.8 times of quick lime by mass at 120 ℃ for 8 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.74 wt%;
the sodium removing agent is a mixture of calcium oxalate and magnesium oxalate in a mass ratio of 3:2, and the adding amount of the sodium removing agent is 0.5 time of the dry basis mass of the first filter cake;
the temperature of water used for the first leaching is 80 ℃, and the using amount of the water is 5 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 100 ℃, and the using amount of the water is 1 time of the dry mass of the first filter cake; the temperature of water used for the second leaching is 30 ℃, and the using amount of the water is 2 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 1.3MPa by adopting a pulp flowing process, and is steamed and cured for 10 hours at 200 ℃ and dried to obtain the calcium silicate fireproof plate, wherein the high-temperature heat conductivity coefficient is 0.183W/(M multiplied by K), and the heat shrinkage rate is 0.270%.
Example 12
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 2.2.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the desiliconized solution of the copper smelting water quenched slag and quicklime with the mass of 1.7 times of that of the desiliconized solution at 160 ℃ for 4 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.85 wt%;
the sodium removing agent is calcium hydroxide, and the addition amount of the sodium removing agent is 0.08 times of the dry basis weight of the first filter cake;
the temperature of water used for the first leaching is 20 ℃, and the using amount of the water is 3 times of the mass of a solid phase dry base product; the temperature of the water mixed with the first filter cake is 20 ℃, and the using amount of the water is 5 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 30 ℃, and the using amount of the water is 4 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 0.7MPa by adopting a pulp flowing process, and is steamed and cured for 11 hours at the temperature of 170 ℃, and the calcium silicate fireproof plate is obtained after drying, and has the high-temperature heat conductivity coefficient of 0.197W/(M multiplied by K) and the heat shrinkage rate of 0.281 percent.
Example 13
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 0.9.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing silicomanganese dust and quicklime 2.2 times the mass of the silicomanganese dust at 210 ℃ for 5 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.11 wt%;
the sodium removing agent is aluminum oxalate, and the adding amount of the sodium removing agent is 1.2 times of the dry basis weight of the first filter cake;
the temperature of water used for the first leaching is 30 ℃, and the using amount of the water is 10 times of the mass of a solid phase dry base product; the temperature of the water mixed with the first filter cake is 30 ℃, and the using amount of the water is 9 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 30 ℃, and the using amount of the water is 8 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula amount are mixed to obtain slurry, the slurry is formed under the pressure of 1.9MPa by adopting a pulp flowing process, and is steamed and cured for 3 hours at the temperature of 240 ℃ and dried to obtain the calcium silicate fireproof plate, the high-temperature heat conductivity coefficient of the calcium silicate fireproof plate is 0.179W/(M multiplied by K), and the heat shrinkage rate of the calcium silicate fireproof plate is 0.218%.
Example 14
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 3.7.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the silicon-manganese dust desiliconized solution and lime milk which is 1.6 times of the silicon-manganese dust desiliconized solution at 60 ℃ for 9 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.73 wt%;
the sodium removing agent is aluminum hydroxide, and the addition amount of the sodium removing agent is 0.8 time of the dry basis weight of the first filter cake;
the temperature of water used for the first leaching is 30 ℃, and the using amount of the water is 5 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 30 ℃, and the using amount of the water is 6 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 30 ℃, and the using amount of the water is 7 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 0.4MPa by adopting a pulp flowing process, the calcium silicate fireproof plate is obtained after the steam curing is carried out for 13 hours at the temperature of 170 ℃, and the calcium silicate fireproof plate is obtained after the drying, wherein the high-temperature heat conductivity coefficient is 0.180W/(M multiplied by K), and the heat shrinkage rate is 0.229%.
Example 15
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the calcium-silicon ratio of the raw material is 1.8.
A preparation method of a calcium silicate fireproof plate comprises the following steps:
(1) causticizing the fly ash desiliconized solution and lime milk which is 1.1 times of the fly ash desiliconized solution at 200 ℃ for 4 hours, and carrying out solid-liquid separation on the slurry to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product with the sodium oxide content of less than 0.87 wt%;
the sodium removing agent is aluminum nitrate, and the addition amount of the sodium removing agent is 0.1 time of the dry basis weight of the first filter cake;
the temperature of water used for the first leaching is 50 ℃, and the using amount of the water is 5 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 50 ℃, and the using amount of the water is 5 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 50 ℃, and the using amount of the water is 5 times of the mass of the second solid phase dry base;
(2) the raw materials with the formula ratio are mixed to obtain slurry, the slurry is formed under 0.8MPa by adopting a pulp flowing process, and is steamed and cured for 8 hours at 180 ℃, and the calcium silicate fireproof plate is obtained after drying, and has the high-temperature heat conductivity coefficient of 0.191W/(M multiplied by K) and the heat shrinkage rate of 0.230 percent.
Comparative example 1
A method for producing a calcium silicate fire-proof plate, which is the same as that of example 1 except that the amount of calcium silicate hydrate added is 0.05 part. The obtained calcium silicate fireproof plate has the high-temperature thermal conductivity coefficient of 0.247W/(M multiplied by K) and the thermal shrinkage rate of 0.451%.
In addition, the calcium silicate hydrate fire-proof plate obtained by replacing the amount of the calcium silicate hydrate added in examples 2 to 15 with 0.05 part had a high-temperature thermal conductivity of 0.249 to 0.256W/(M.times.K) and a heat shrinkage of 0.501 to 0.654%.
Comparative example 2
A method for producing a calcium silicate fire-proof plate, which is the same as that of example 1 except that 82 parts by weight of calcium silicate hydrate was added. The high-temperature thermal conductivity coefficient of the obtained calcium silicate fireproof plate is 0.301W/(M multiplied by K), and the thermal shrinkage rate is 0.472%.
In addition, the amount of the calcium silicate hydrate added in examples 2 to 15 was replaced with 82 parts, and the resulting calcium silicate fire-proof plate had a high-temperature thermal conductivity of 0.278 to 0.300W/(M.times.K) and a heat shrinkage of 0.472 to 0.521%.
Comparative example 3
A method for producing a calcium silicate fire-proof plate, which is the same as that of example 1 except that calcium silicate hydrate used in the step (2) is replaced with analytically pure calcium silicate hydrate. The obtained calcium silicate fireproof plate has the high-temperature heat conductivity coefficient of 0.227W/(M multiplied by K) and the heat shrinkage rate of 0.265%.
In addition, the calcium silicate hydrate in the step (2) of the examples 2 to 15 is replaced by analytically pure calcium silicate hydrate, and the high-temperature thermal conductivity coefficient of the obtained calcium silicate fireproof plate is 0.218 to 0.225W/(M multiplied by K), and the thermal shrinkage rate is 0.251 to 0.263 percent.
Comparative example 4
A method for preparing a calcium silicate fireproof plate, which is the same as the method in the embodiment 1 except that the solid phase in the step (1) is not washed. The obtained calcium silicate fireproof plate has the high-temperature heat conductivity coefficient of 0.327W/(M multiplied by K) and the heat shrinkage rate of 0.315%.
In addition, the calcium silicate hydrate in the step (2) of the examples 2 to 15 is replaced by analytically pure calcium silicate hydrate, and the high-temperature thermal conductivity coefficient of the obtained calcium silicate fireproof plate is 0.228 to 0.255W/(M multiplied by K), and the thermal shrinkage rate is 0.261 to 0.273%.
Comparative example 5
A method for producing a calcium silicate fire-proof plate, which is the same as that of example 1 except that no sodium remover is added in the step (1). The high-temperature thermal conductivity coefficient of the obtained calcium silicate fireproof plate is 0.337W/(M multiplied by K), and the thermal shrinkage rate is 0.325%.
In addition, the calcium silicate hydrate in the step (2) of the examples 2 to 15 is replaced by analytically pure calcium silicate hydrate, and the high-temperature thermal conductivity coefficient of the obtained calcium silicate fireproof plate is 0.238 to 0.245W/(M multiplied by K), and the thermal shrinkage rate is 0.311 to 0.321%.
Comparative example 6
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
0.05 part of calcium silicate hydrate
9 parts of quartz
9 parts of lime;
the preparation method is the same as that described in example 1.
The high-temperature heat conductivity coefficient of the calcium silicate fireproof plate is 0.251W/(M multiplied by K), and the heat shrinkage rate is 0.330%.
Comparative example 7
The calcium silicate fireproof plate comprises the following raw materials in parts by weight:
the preparation method is the same as that described in example 1.
The high-temperature heat conductivity coefficient of the calcium silicate fireproof plate is 0.262W/(M multiplied by K), and the heat shrinkage rate is 0.321%.
The invention has not been described in detail and is part of the common general knowledge of a person skilled in the art.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (15)
1. The calcium silicate fireproof plate is characterized by comprising the following raw materials in parts by weight:
the calcium-silicon molar ratio of the raw materials is 0.1-5;
the molecular formula of the calcium silicate hydrate is xCaO ySiO2·zH2O, wherein the value of x is 1 to 10; the value of y is 1 to 10; the value of z is 1-20;
the calcium silicate hydrate is prepared by the following method: reacting quicklime and/or lime milk with a silicon-containing material, wherein the mass ratio of the silicon-containing material to the lime and/or lime milk is 0.1-5, the reaction temperature is 30-250 ℃, the reaction time is 0.5-10h, and performing solid-liquid separation on a reaction product to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake; drying the second filter cake to obtain a calcium silicate hydrate product;
the sodium removing agent is selected from any one or the combination of at least two of aluminum compounds, calcium compounds or magnesium compounds, or the sodium removing agent contains more than 50 wt% of any one or the combination of at least two of aluminum compounds, calcium compounds or magnesium compounds; the addition amount of the sodium removing agent is 0.001-2 times of the dry basis weight of the first filter cake;
the silicon-containing material is selected from silicon-containing waste liquid and/or waste residue generated in the process of treating solid waste and/or low-grade ore;
the sodium oxide content of the calcium silicate hydrate product is less than 1 wt%.
2. The calcium silicate fire protection plate according to claim 1, wherein the aluminum compound is selected from any one of or a combination of at least two of aluminum oxide, aluminum oxalate, aluminum hydroxide, aluminum chloride, or aluminum nitrate.
3. The calcium silicate fire protection plate according to claim 1, wherein the calcium compound is selected from any one of calcium oxide, calcium oxalate, calcium hydroxide, calcium chloride or calcium nitrate or a combination of at least two thereof.
4. The calcium silicate fire protection plate according to claim 1, wherein the magnesium compound is selected from any one of magnesium oxide, magnesium oxalate, magnesium hydroxide, magnesium chloride or magnesium nitrate or a combination of at least two thereof.
5. The calcium silicate fire protection plate according to claim 1, wherein the first rinsing uses water at a temperature of 10-100 ℃ in an amount of 0.1-10 times the mass of the solid dry base product.
6. The calcium silicate fire protection plate according to claim 1, wherein the temperature of the water mixed with the first filter cake is 10 to 200 ℃, and the amount is 0.1 to 10 times of the dry mass of the first filter cake.
7. The calcium silicate fire protection plate according to claim 1, wherein the water used for the second rinsing has a temperature of 10 to 100 ℃ and is used in an amount of 0.1 to 10 times the mass of the second solid phase on a dry basis.
8. The calcium silicate fireproof plate according to claim 1, wherein water obtained by the second leaching in the first process is used for water for suspension in the second process, a liquid phase obtained by solid-liquid separation in the first process is used for first leaching washing water in the second process, and fresh water is used for the second leaching washing water in the second process, wherein the first process and the second process are independently solid-phase washing processes, namely the first leaching of the solid phase is carried out to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; and carrying out second leaching on the second solid phase to obtain a second filter cake.
9. The calcium silicate fire barrier according to claim 1, wherein the silicon-containing material is selected from the group consisting of mining solid waste having a main metal component of less than 50%, silicon-containing waste liquid and/or slag discharged from chemical and metallurgical processes.
10. The calcium silicate fireproof plate according to claim 9, wherein the silicon-containing material is selected from any one or a combination of at least two of fly ash, silico-calcium slag, zirconium silico-slag, micro silicon powder, ferrosilicon smoke, copper smelting water quenched slag, silico-manganese dust, fly ash desiliconization liquid, silico-calcium slag desiliconization liquid, zirconium silico-slag desiliconization liquid, micro silicon powder desiliconization liquid, ferrosilicon smoke desiliconization liquid, copper smelting water quenched slag desiliconization liquid, or silico-manganese dust desiliconization liquid.
11. The method for manufacturing a calcium silicate fire proof plate according to any one of claims 1 to 10, wherein the manufacturing method comprises pulping, forming by a pulp flow process, steam curing and drying; wherein, the pulping raw materials comprise the following components in parts by weight: 10-80 parts of calcium silicate hydrate; 10-70 parts of quartz; 0.5-20 parts of cement; 0.5-20 parts of wood pulp fiber; 10-70 parts of lime; the molar ratio of calcium to silicon of the raw materials is 0.1-5.
12. The method of claim 11, wherein the pressure at which the slurry process forms is between 0.1 and 2 MPa.
13. The method as claimed in claim 11, wherein the temperature of the steam curing is 150 ℃ to 250 ℃.
14. The method of claim 11, wherein the steam-curing time is 2 to 15 hours.
15. The method of claim 11, comprising the steps of:
(1) reacting the silicon-containing material with quicklime and/or lime milk according to the mass ratio of 0.1-5, wherein the reaction temperature is 30-250 ℃, the reaction time is 0.5-10h, and performing solid-liquid separation on a reaction product to obtain a solid phase; carrying out first leaching on the solid phase to obtain a first filter cake; mixing the first filter cake with water to form a suspension, mixing the suspension with a sodium removal agent, and carrying out solid-liquid separation to obtain a second solid phase; carrying out second leaching on the second solid phase to obtain a second filter cake, and drying the second filter cake to obtain a calcium silicate hydrate product; the sodium removing agent is selected from any one or the combination of at least two of aluminum compounds, calcium compounds or magnesium compounds, or the sodium removing agent contains more than 50 wt% of any one or the combination of at least two of aluminum compounds, calcium compounds or magnesium compounds; the addition amount of the sodium removing agent is 0.001-2 times of the dry basis weight of the first filter cake; wherein the temperature of the water used for the first leaching is 10-100 ℃, and the using amount of the water is 0.1-10 times of the mass of the solid phase dry base product; the temperature of the water mixed with the first filter cake is 10-200 ℃, and the using amount of the water is 0.1-10 times of the dry mass of the first filter cake; the temperature of water used for the second leaching is 10-100 ℃, and the using amount of the water is 0.1-10 times of the mass of the second solid phase dry base; the silicon-containing material is selected from any one or the combination of at least two of fly ash, calcium silicon slag, zirconium silicon slag, micro silicon powder, ferrosilicon smoke dust, copper smelting water-quenched slag, silicon manganese dust, fly ash desiliconization liquid, calcium silicon slag desiliconization liquid, zirconium silicon slag desiliconization liquid, micro silicon powder desiliconization liquid, ferrosilicon smoke desiliconization liquid, copper smelting water-quenched slag desiliconization liquid or silicomanganese dust desiliconization liquid;
(2) pulping 10-80 parts of calcium silicate hydrate product with sodium oxide content less than 1 wt%, 10-70 parts of quartz, 0.5-20 parts of cement, 0.5-20 parts of wood pulp fiber and 10-70 parts of lime, forming by adopting a pulp flowing process, steaming and drying to obtain the calcium silicate fireproof plate, wherein the calcium-silicon ratio of the pulping raw material is 0.1-5; the pressure of the pulp flow process forming is 0.1-2MPa, and the steam curing temperature is 150-250 ℃; the steaming time is 2-15 h.
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| CN110885223B (en) * | 2018-09-07 | 2021-09-07 | 中国科学院过程工程研究所 | Calcium silicate powder, preparation method thereof, fireproof plate using calcium silicate powder and preparation method of fireproof plate |
| CN109160798A (en) * | 2018-11-02 | 2019-01-08 | 肇庆三乐集成房屋制造有限公司 | A kind of environmental protection calcium silicate board and preparation method thereof |
| CN111592289A (en) * | 2020-05-27 | 2020-08-28 | 常州优纳新材料科技有限公司 | Mesoporous material composite calcium silicate fireproof plate and preparation method thereof |
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| CN101066852A (en) * | 2007-05-24 | 2007-11-07 | 广东工业大学 | Process of modifying calcium silicate plate with water-base epoxy resin |
| CN102190309A (en) * | 2011-01-06 | 2011-09-21 | 内蒙古大唐国际再生资源开发有限公司 | Method for lowering pH value of active calcium silicate |
| CN103011732A (en) * | 2012-11-26 | 2013-04-03 | 莱州明光隔热材料有限公司 | Xonotlite reinforced and foamed cement and production method thereof |
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| CN101066852A (en) * | 2007-05-24 | 2007-11-07 | 广东工业大学 | Process of modifying calcium silicate plate with water-base epoxy resin |
| CN102190309A (en) * | 2011-01-06 | 2011-09-21 | 内蒙古大唐国际再生资源开发有限公司 | Method for lowering pH value of active calcium silicate |
| CN103011732A (en) * | 2012-11-26 | 2013-04-03 | 莱州明光隔热材料有限公司 | Xonotlite reinforced and foamed cement and production method thereof |
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