CN112551975B - Wall thermal insulation material utilizing dangerous solid wastes and preparation method thereof - Google Patents
Wall thermal insulation material utilizing dangerous solid wastes and preparation method thereof Download PDFInfo
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- CN112551975B CN112551975B CN202011437594.4A CN202011437594A CN112551975B CN 112551975 B CN112551975 B CN 112551975B CN 202011437594 A CN202011437594 A CN 202011437594A CN 112551975 B CN112551975 B CN 112551975B
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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
- C04B28/04—Portland cements
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
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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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- 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
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A wall thermal insulation material utilizing dangerous solid waste and a preparation method thereof are provided, wherein the thermal insulation material comprises the following raw materials: modifying dangerous solid waste, blast furnace slag, fly ash, cement and polypropylene, wherein the modified dangerous solid waste is the dangerous solid waste which is modified by an organic multi-component phosphonic acid wet method and an amino alkyl silane coupling agent dry method. According to the invention, the hazardous solid waste is modified by using the organic poly-phosphonic acid and the aminoalkyl silane coupling agent to stabilize the heavy metal in the hazardous solid waste, and the modified hazardous solid waste is unexpectedly found to be used as a raw material of a wall thermal insulation material, so that the consumption of cement for curing can be reduced on the premise of reaching the standard of detection of leaching toxicity of the heavy metal, and the mechanical property and the thermal insulation effect are improved.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment and recycling, and particularly relates to a wall thermal insulation material utilizing dangerous solid waste and a preparation method thereof.
Background
The waste incineration fly ash is a substance collected by a flue gas dust collector after domestic waste incineration, and the main components of the waste incineration fly ash comprise CaO and SiO2，Al2O3，Fe2O3The cement is very close to the auxiliary cementing materials of blast furnace slag, fly ash and the like which are commonly used at present, and is considered as hazardous waste because the cement contains heavy metal substances (Cu, Mn, Pb, Zn, Cr and the like) which can be leached by water, and the heavy metal substances must be subjected to harmless treatment; the red mud is industrial waste residue generated in the production process of alumina, and the main component of the red mud is SiO2、Al2O3、Fe2O3CaO and MgO, and also contain a small amount of heavy metal elements such As Cr, Ni, Cu, Zn, As, Cd, Cs and Pb which can be leached by water, and also need to be subjected to a harmless treatment.
The solidification/stabilization technology is one of the main methods which are generally adopted by people at present for harmlessly treating harmful wastes, cement is the most widely applied hazardous waste stabilizer in developed countries such as Europe and America in recent years, and the technology is to mix the wastes and the cement to form a hard solidified body after hydration reaction, thereby achieving the purpose of greatly reducing the leaching of heavy metals in the wastes.
Patent CN201210129910.0 discloses a building heat-insulating wall material and a preparation method thereof, the building material is prepared by mixing, molding and maintaining the following components in percentage by weight: 20-35% of phosphogypsum, 15-25% of red mud, 15-25% of cement, 10-25% of fly ash, 5-10% of yellow sand, 4-8% of lime and 0.2-1.0% of foaming agent by mass percentage, wherein the foaming agent is Al powder which is a heat-insulating material mainly has the advantages that: the industrial waste residue phosphogypsum and the red mud are effectively utilized, so that the pollution of the phosphogypsum and the red mud to the environment is reduced, and the cyclic utilization of resources is facilitated. Patent CN201410623076.X discloses a lightweight energy-saving concrete block, the raw materials of the block mainly comprise incineration fly ash, cement, fly ash, quicklime cementing material, gypsum, aluminum powder and the like, and the block is a cement concrete product 1. firstly, the incineration fly ash of garbage is used as a main material, so that the resource recycling of engineering construction is realized, wherein the consumption of the incineration fly ash of garbage accounts for about 60 percent, and the materials of the cement, the fly ash, the quicklime cementing material, the gypsum, the aluminum powder and the like can be properly adjusted; 2. proper aluminum powder is doped as a gas forming material; 3. when the mixing proportion is determined, the components and the content of heavy metals and the like in the garbage fly ash are fully analyzed, and the cement consumption is flexibly adjusted; 4. during production, the incineration fly ash and cement are firstly added with water to prepare cement mortar, and then other materials are sequentially added; 5. the finished product of the lightweight energy-saving concrete block needs to be cured fully through high-pressure steam curing, and the curing quality is ensured. The above patents all refer to the solidification of the waste incineration fly ash or the red mud and the cement, which can realize the stabilization and harmless treatment of the waste incineration fly ash and the red mud and can also achieve the purpose of recycling the resources of the solid wastes, however, the cement solidification effect is poor when the waste incineration fly ash or the red mud is used in too much amount, the detection of the leaching toxicity of the heavy metals does not reach the standard, and the mechanical property of the prepared cement product is poor when the waste incineration fly ash or the red mud is used in too little amount.
In order to realize the effective reuse of the toxic solid wastes containing heavy metals, such as the waste incineration fly ash or the red mud, and the popularization and application of the cement products in the field of heat preservation buildings, the development of a cement product of the waste incineration fly ash or the red mud with good mechanical property is urgently needed.
Disclosure of Invention
Aiming at the technical problems, the invention aims to modify the hazardous solid waste of the waste incineration fly ash or the red mud by utilizing the organic poly-phosphonic acid and the silane coupling agent, and the light cement product prepared by using the modified solid waste improves the using amount of the waste incineration fly ash or the red mud in the cement product on the premise of keeping good mechanical property, saves cement resources, and effectively stabilizes heavy metals in the solid waste.
In order to solve the technical problems, the invention adopts the following specific technical scheme:
a wall thermal insulation material utilizing dangerous solid wastes comprises the following raw materials: modifying dangerous solid waste, blast furnace slag, fly ash, cement and polypropylene, wherein the modified dangerous solid waste is the dangerous solid waste which is modified by an organic multi-component phosphonic acid wet method and an amino alkyl silane coupling agent dry method.
A wall thermal insulation material utilizing dangerous solid wastes comprises the following raw materials in parts by weight: 30-50 parts of modified dangerous solid waste, 10-20 parts of blast furnace slag, 10-20 parts of fly ash, 10-30 parts of cement and 20-40 parts of polypropylene particles.
The organic polybasic phosphonic acid comprises at least one of diethylenetriamine penta methylene phosphonic acid, dihexene triamine penta methylene phosphonic acid, aminotrimethylene phosphonic acid, ethylene diamine tetra methylene phosphonic acid and hydroxy ethylidene diphosphonic acid.
The aminoalkyl silane coupling agent includes but is not limited to at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma- (beta-aminoethyl) aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane and aniline methyl trimethoxysilane.
The dangerous solid waste comprises at least one of garbage incineration fly ash and red mud.
The preparation method of the modified dangerous solid waste comprises the following steps:
t1, preparing an aqueous solution of organic polyphosphonic acid, adding the solid waste, stirring uniformly, standing at room temperature, and finally drying;
and T2, carrying out dry modification on the product obtained after the drying in the step T1 by using an amino alkyl silane coupling agent to obtain modified dangerous solid waste.
The molar concentration of the aqueous solution of the organic polyphosphonic acid in the step T1 is 0.1-0.3 mol/L; the solid-liquid weight ratio of the dangerous solid waste to the aqueous solution of the organic polyphosphonic acid is 1.25-2: 1; the room temperature standing time is 24-72 h.
The dry modification of the step T2 specifically comprises the following steps: and D, adding the dried solid waste obtained in the step T1 into a stirrer, adding an amino alkyl silane coupling agent accounting for 0.1-0.15wt% of the mass of the solid waste, and keeping stirring until the mixture is uniform.
The particle size of the waste incineration fly ash is 10-30 mu m; the grain size of the blast furnace slag is 20-40 μm; the particle size of the fly ash is 10-30 μm.
The cement is not particularly limited, and may be ordinary portland cement commonly used in the art, including but not limited to at least one of PO32.5, PO42.5, and PO 52.5.
The melt index of the polypropylene particles is 2-5g/10min, and the particle size of the polypropylene particles is 2-5 mm.
A preparation method of a wall heat-insulating material by utilizing solid wastes comprises the following steps:
s1, adding the modified dangerous solid waste, the blast furnace slag, the fly ash and the cement into a stirrer, and uniformly mixing to obtain a mixture 1;
s2, adding water into the mixture 1, and stirring uniformly to obtain slurry 1;
s3, adding polypropylene particles into the slurry 1 and uniformly stirring to obtain slurry 2;
and S4, injecting the slurry 2 into a mold for molding, and obtaining the wall heat-insulating material utilizing the solid wastes through primary curing, demolding and secondary curing.
The ratio of the water to the mixture 1 in the step S2 is 0.1-0.2.
Compared with the prior art, the invention has the beneficial effects that:
the invention aims to modify the dangerous solid waste by utilizing organic poly phosphonic acid and amino alkyl silane coupling agent to stabilize heavy metal in the dangerous solid waste, and unexpectedly finds that the modified dangerous solid waste is used as a raw material of a wall heat-insulating material, so that the consumption of cement for curing can be reduced and the mechanical property and the heat-insulating effect can be improved on the premise that the heavy metal leaching toxicity detection reaches the standard. The possible reasons for the above effects are that the organic polyphosphonic acid forms a stable complex with heavy metal ions on one hand, and forms hydrogen bonds with the dangerous solid wastes with surfaces rich in hydroxyl groups on the other hand, so that the stability of the complex is enhanced, the heavy metals are not easily leached, the aminoalkyl silane coupling agent reacts with unreacted phosphonic acid groups and the hydroxyl groups on the surfaces of the solid wastes, the hydrophobicity of the dangerous solid wastes is improved, the suspension stability of the hazardous solid wastes in a cement solution system is enhanced, coagulation does not occur, and the mechanical properties of the thermal insulation material are further improved.
The preparation method is simple, environment-friendly and pollution-free, and is suitable for large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, "parts" in the examples of the present invention are parts by weight. All reagents used are commercially available in the art.
The waste incineration fly ash used in the invention is domestic waste incineration fly ash with the particle size of 30 mu m; from beijing first steel biomass energy limited; the red mud is from Shandong Weiqiao aluminum industry.
Preparation of modified hazardous solid waste
Preparation example 1
T1, preparing a water solution of dihexyltriamine pentamethylene phosphonic acid with the molar concentration of 0.1mol/L, adding garbage incineration fly ash with the particle size of 30 mu m according to the solid-liquid weight ratio of 1.25:1, stirring uniformly, standing at room temperature for 48h, and finally carrying out vacuum drying in an oven at 60 ℃;
and T2, adding the dried solid waste obtained in the step T1 into a stirrer, adding gamma-aminopropyl triethoxysilane with the mass of 0.15wt% of the dried solid waste, and stirring uniformly to obtain the modified dangerous solid waste.
Preparation example 2
The rest was the same as in preparation example 1, except that fly ash from incineration of refuse was added in a solid-liquid weight ratio of 1.6:1 in step T1.
Preparation example 3
The rest of the process was the same as in preparation example 1, except that fly ash from waste incineration was added in step T1 at a solid-liquid weight ratio of 2: 1.
Preparation example 4
The same as in preparation example 1 except that gamma-aminopropyltriethoxysilane was added in an amount of 0.1% by weight based on the amount of the modified solid waste obtained in step T1 in step T2.
Preparation example 5
The process was carried out in the same manner as in preparation example 1 except that the waste incineration fly ash was replaced with red mud.
Comparative preparation example 1
Adding the dangerous solid waste into a stirrer, adding gamma-aminopropyl triethoxysilane with the mass of 0.15wt% of the dangerous solid waste, and stirring uniformly to obtain modified dangerous solid waste; corresponding to the absence of the modification of step T1.
Comparative preparation example 2
Preparing aqueous solution of dihexyltriamine pentamethylene phosphonic acid with the molar concentration of 0.1mol/L, adding garbage incineration fly ash with the particle size of 30 mu m according to the solid-liquid weight ratio of 1.25:1, stirring the mixture to be uniform, then placing the mixture at room temperature for 48 hours, and finally drying the mixture in a vacuum oven at 60 ℃ to obtain modified dangerous solid waste; corresponding to the absence of the modification of step T2.
Example 1
S1, adding 50 parts of the modified hazardous solid waste prepared in preparation example 1, 10 parts of blast furnace slag with the particle size of 20 microns, 20 parts of fly ash with the particle size of 30 microns and 30 parts of cement PO42.5 into a stirrer, and uniformly mixing to obtain a mixture 1;
s2, adding water into the mixture 1, wherein the weight ratio of the water to the mixture 1 is 0.12, and stirring the mixture uniformly to obtain slurry 1;
s3, adding 20 parts of polypropylene particles with the melt index of 3g/10min and the particle size of 3mm into the slurry 1, and uniformly stirring to obtain slurry 2;
s4, injecting the slurry 2 into a mold for molding, primarily curing for 7 days at 20 ℃ and 90% humidity, demolding, and curing again for 21 days at 30 ℃ and 95% humidity to obtain the wall thermal insulation material utilizing dangerous solid wastes.
Example 2
The rest of the process is the same as the process in example 1, except that the amount of the modified hazardous solid waste is 30 parts, the amount of the blast furnace slag is 20 parts, the amount of the fly ash is 10 parts, the amount of the cement is 10 parts, and the amount of the polypropylene particles is 40 parts.
Example 3
The process was the same as in example 1 except that the amount of the modified hazardous solid waste was 20 parts.
Example 4
The rest is the same as example 1 except that the amount of the modified hazardous solid waste is 70 parts.
Example 5
The rest is the same as example 1 except that modified hazardous solid waste is prepared for preparation example 2.
Example 6
The rest is the same as example 1 except that modified hazardous solid waste is prepared for preparation example 3.
Example 7
The rest is the same as example 1 except that modified hazardous solid waste is prepared for preparation example 4.
Example 8
The rest is the same as example 1 except that modified hazardous solid waste is prepared for preparation example 5.
Comparative example 1
The rest is the same as example 1 except that modified hazardous solid waste is prepared for comparative preparation example 1.
Comparative example 2
The rest is the same as example 1 except that modified hazardous solid waste is prepared for comparative preparation example 2.
Comparative example 3
The rest is the same as example 1, except that the hazardous solid waste is not modified.
The cement products prepared in the above examples and comparative examples were subjected to the following performance tests, and the results are shown in tables 1 to 2: breaking strength: the test was carried out with reference to the standard GB/T17671-1999.
Compressive strength: the test was carried out with reference to the standard GB/T17671-1999.
And (3) detecting the leaching toxicity of the heavy metal: the tests were carried out with reference to the standards GB8978-1996 and the standard HJ 557-2009. Coefficient of thermal conductivity: the test was performed with reference to standard JC/T1062-2007.
TABLE 1
TABLE 2
Example 1 is a cement product prepared by using hazardous solid waste modified twice by organic polyphosphonic acid and amino alkyl silane coupling agent, and example 1 has lower heavy metal leaching amount and lower heat conductivity coefficient compared with comparative examples 1-3, and experiments of different factor levels in examples 2-8 further verify that heavy metal in hazardous solid waste modified twice is effectively stabilized, so that the dosage of cement for curing can be reduced on the premise of reaching the standard of heavy metal leaching toxicity detection, and the mechanical property and the heat preservation effect are improved. The probable reason for the above effect is presumed to be that the organic polyphosphonic acid forms a stable complex with heavy metal ions on one hand, and forms hydrogen bonds with the dangerous solid wastes with rich hydroxyl groups on the surface on the other hand, so that the stability of the complex is enhanced, the heavy metals are not easily leached, the aminoalkyl silane coupling agent reacts with unreacted phosphonic acid groups and the hydroxyl groups on the surface of the solid wastes, the hydrophobicity of the dangerous solid wastes is improved, the suspension stability of the hazardous solid wastes in a cement solution system is enhanced, no coagulation occurs, and the mechanical property of the thermal insulation material is further improved.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (7)
1. The wall thermal insulation material utilizing the dangerous solid wastes is characterized by comprising the following raw materials in parts by weight: 30-50 parts of modified dangerous solid waste, 10-20 parts of blast furnace slag, 10-20 parts of fly ash, 10-30 parts of cement and 20-40 parts of polypropylene particles, wherein the dangerous solid waste comprises at least one of garbage incineration fly ash and red mud, and the modified dangerous solid waste is obtained by wet modification of organic multi-component phosphonic acid and dry modification of amino alkyl silane coupling agent;
the preparation method of the modified dangerous solid waste comprises the following steps:
t1, preparing an aqueous solution of organic polyphosphonic acid, adding the solid waste, stirring uniformly, standing at room temperature, and finally drying;
and T2, carrying out dry modification on the product obtained after the drying in the step T1 by using an amino alkyl silane coupling agent to obtain modified dangerous solid waste.
2. The insulating material according to claim 1, wherein the organic polyphosphonic acid comprises at least one of diethylenetriamine pentamethylenephosphonic acid, dihexyltriamine pentamethylenephosphonic acid, aminotrimethylenephosphonic acid, ethylenediamine tetramethylene phosphonic acid, and hydroxyethylidene diphosphonic acid.
3. The insulating material according to claim 1, wherein the aminoalkyl silane coupling agent includes, but is not limited to, at least one of γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, γ - (β -aminoethyl) aminopropyltrimethoxysilane, γ -ureidopropyltriethoxysilane, and anilinomethyltrimethoxysilane.
4. The insulating material according to claim 1, wherein the molar concentration of the aqueous solution of organic polyphosphonic acid in step T1 is 0.1 to 0.3 mol/L; the solid-liquid weight ratio of the dangerous solid waste to the aqueous solution of the organic polyphosphonic acid is 1.25-2: 1; the dosage of the amino alkyl silane coupling agent in the step T2 is 0.1-0.15wt% of the hazardous solid waste obtained in the step T1.
5. The thermal insulation material according to claim 1, wherein the fly ash from waste incineration has a particle size of 10 to 30 μm; the grain size of the blast furnace slag is 20-40 μm; the particle size of the fly ash is 10-30 μm.
6. The insulating material according to claim 1, wherein the polypropylene particles have a melt index of 2 to 5g/10min and a particle size of 2 to 5 mm.
7. A method for preparing the thermal insulation material of any one of claims 1 to 6, comprising the steps of:
s1, adding the modified dangerous solid waste, the blast furnace slag, the fly ash and the cement into a stirrer, and uniformly mixing to obtain a mixture 1;
s2, adding water into the mixture 1, and stirring uniformly to obtain slurry 1;
and S3, adding the polypropylene particles into the slurry 1, and uniformly stirring to obtain slurry 2.
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