CN113233854A - Preparation method of CaSO 4-based solid waste environment-friendly filling material - Google Patents

Preparation method of CaSO 4-based solid waste environment-friendly filling material Download PDF

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CN113233854A
CN113233854A CN202110567343.6A CN202110567343A CN113233854A CN 113233854 A CN113233854 A CN 113233854A CN 202110567343 A CN202110567343 A CN 202110567343A CN 113233854 A CN113233854 A CN 113233854A
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caso
solid waste
filling material
preparation
based environment
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瞿广飞
吴丰辉
刘珊
赵晨阳
陈帮金
刘亮亮
李军燕
杨灿
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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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
    • C04B28/14—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 calcium sulfate cements
    • C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
    • C04B28/143—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
    • 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
    • C04B28/14—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 calcium sulfate cements
    • C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
    • 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
    • C04B28/14—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 calcium sulfate cements
    • C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
    • C04B28/144—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes

Abstract

The invention discloses a CaSO4The preparation method of the solid waste-based environment-friendly filling material mainly utilizes the powder modification principle and adopts CaSO4Adding K-Q type micro-curing stabilizer powder into the solid waste powder, mixing at a stirring speed of 400-1000 rpm for 20-120 min to make the powder fully contact with each other, and then performing closed curing at 25-45 ℃ and a humidity of 50-89% for 8-24 h to obtain CaSO4Solid waste-based environment-friendly filling materials; the method has low preparation cost and CaSO4The utilization rate of the basic solid waste is more than 80 percent, various indexes of leaching toxicity of the basic solid waste compound the environmental protection requirement, and the basic solid waste can be filled in a powder form.

Description

CaSO4Radical solid waste ringPreparation method of filling-protecting material
Technical Field
The invention relates to a CaSO4A preparation method of a solid waste-based environment-friendly filling material belongs to the fields of solid waste resource utilization and mine restoration.
Background
CaSO4The basic solid waste belongs to the field of bulk solid waste, is an important restriction factor for the development of chemical industry, namely CaSO4The solid waste is solid waste produced in the chemical industry, and contains phosphoric acid, silicon, magnesium, iron, aluminum, organic impurities and the like besides phosphorus and fluorine. Phosphorus, fluorine and free acids are corrosive and can pollute the environment if stockpiled for a long time. For the majority of domestic manufacturing enterprises at present, CaSO4The basic solid waste is mainly simply stockpiled, and domestic CaSO4The accumulated quantity of the basic solid wastes exceeds 300 Mt, not only occupies a large amount of land, but also has high maintenance and operation cost of a slag yard. CaSO discharged by domestic enterprises every year4Basal solid waste will exceed 60 Mt. Calculated by 10m of stack height, the occupied area is 1.66 multiplied by 107 m2If the pile is stocked for 10 years, the construction cost of the storage yard is calculated according to CaSO per ton4The cost is 15 hundred million yuan for 3 yuan/t of solid waste. CaSO4The cost of transporting the basic solid waste from a production place to a slag yard is calculated according to the minimum 15 yuan/t, and the CaSO is calculated every year4The transportation cost of the solid waste is as high as 7.5 million yuan. China CaSO4The basic solid waste is mainly used for producing low-value building material products such as cement retarder, gypsum plasterboard and the like, and is subjected to CaSO4Based on the influence of high impurity content in solid wastes, high calcination energy (temperature), CaSO4The gypsum brick, the gypsum block and the gypsum board produced by the solid wastes have extremely unstable quality, poor water resistance and low strength, and the building material product is influenced and impacted by the transport distance and the desulfurization gypsum of a power plant, CaSO4The basic solid waste building material products are still further atrophied, and in recent years, CaSO is in China4The comprehensive utilization of the solid waste resources is developed quickly and achieves certain results, but still faces a great deal of pressure, especially the problems in the aspect of environmental protection. Chemical treatment of CaSO4Basal solid wastes such as: North-Lu chemical CaSO4The technology for preparing acid and co-producing cement by using the basic solid wastes is feasible, but the technology is in the process ofIs still not related economically and has not become CaSO4The main flow of the technology for resource utilization of solid wastes. To date, in the critical CaSO4The technology of utilizing the solid wastes lacks of intensive research and analysis, especially for CaSO4The formation mechanism and internal structure influence factors of the basic solid waste impurities, the influence of harmful substances on the quality of the after-delay product, impurity removal countermeasures and the like do not have a comprehensive and systematic theoretical research result, and in many technical aspects, the natural gypsum practical experience and theoretical research data can only be used; secondly, no suitable CaSO has been developed4The production process technical equipment for large-scale utilization of the solid wastes lacks guidance and example factories combining basic theories of a system and actual production. These are finally concentrated in CaSO4The input-output ratio in the comprehensive utilization process of the solid waste resources is seriously disordered.
At present, domestic CaSO4The resource utilization of the solid waste faces two problems: firstly, the purification treatment difficulty is high, and the process flow is complex; secondly, the investment is large, the cost is high, and the economic feasibility is poor. The long term study by the U.S. florida phosphate institute suggests that: CaSO4The solid waste has many economically feasible, environmentally friendly and safe uses, such as chemical raw materials, building materials and additives, but certain risks still exist in the utilization, and three thoughts are needed. CaSO (calcium oxide synthase) whether from the perspective of strategic development requirements of macroscopical scale or the needs of sustainable development and environmental protection of phosphorus compound fertilizer enterprises4The comprehensive treatment and resource utilization of the base solid wastes are the problems to be solved by the current letter of domestic chemical industry enterprises.
CaSO whose total amount has also increased year by year4For solid wastes, the best treatment mode is to carry out harmless treatment and utilization on the wastes, so that the environmental risk is reduced, the treatment capacity can be increased, and the CaSO of chemical industry enterprises can be relieved4The method solves the problem of solid waste, and a low-cost harmless treatment technology needs to be provided.
Disclosure of Invention
Aiming at the current CaSO4The accumulation and production of solid wastes are huge, but the utilization rate is low, resulting in a lot of CaSO4The solid waste is still in a large amount of accumulation state, and restrictsThe development of chemical industry enterprises, aiming at solving the problem of CaSO4The invention provides CaSO and solves the problems of large accumulation of solid wastes, low utilization rate and the like4The invention relates to a preparation method of a solid waste environment-friendly filling material, which mainly utilizes the powder modification principle (the principle is that chemical reaction is initiated between solid and solid due to trace crystal water or attached water under nano-micro scale to form new precipitate, complex and other gelling active substances, harmful ingredients are solidified and stabilized in the form of precipitate, complex or coated to realize harmless treatment of harmful solid substances), and the solid waste environment-friendly filling material is prepared by adding CaSO4Adding K-Q type micro-curing stabilizer powder into the solid waste powder, mixing at a stirring speed of 400-1000 rpm for 20-120 min to make the powder fully contact, and then carrying out closed curing at 25-45 ℃ and a humidity of 50-89% for 8-24 h, wherein the K-Q type micro-curing stabilizer is CaSO (calcium-oxide-silicon) curing4Exciting CaSO while harmful heavy metal, phosphorus, fluorine and other toxic and harmful substances in the basic solid waste4Based on the activity of solid wastes, thereby forming CaSO4The prepared material can be used as a filling material in activities such as mining areas, mine pits, low-lying lands, reclamation of land from sea and the like formed in the mining process.
The CaSO 4-based solid waste comprises phosphogypsum, desulfurized gypsum, fluorgypsum and titanium gypsum.
The CaSO4The basic solid waste and the modified medicament are powder with the particle size of 10-800 mu m and CaSO4The water content of the basic solid waste is 10-25%, the pH = 1.5-5, and the reaction is carried out in a natural environment.
The K-Q type micro-curing stabilizer composition comprises, by mass, 1% -5% of a foaming agent, 20% -30% of a stabilizer, 1% -5% of a collecting agent, 30% -50% of a flocculating agent and 10% -48% of an acid-base regulator; mixing in a sealed environment according to the proportion in a normal temperature environment with the humidity lower than 20 percent, and preparing at any time;
the foaming agent is one or more of azo compounds, sulfonyl hydrazide compounds, nitroso compounds, calcium carbonate, magnesium carbonate, sodium bicarbonate, sodium silicate, silicon carbide, carbon black, sodium dodecyl sulfate (K12) and fatty alcohol-polyoxyethylene ether sodium sulfate (AES); the stabilizer is mainly one or more of magnesium stearate, fatty acid file, aluminum fatty acid, potassium fatty acid, cement, fly ash, asphalt, polyethylene, urea formaldehyde, polyester, ferrous sulfate, phosphate and sodium hydroxide; the collecting agent is one or more of xanthate, xanthate derivative, black drug, white drug, benzothiazole thiol, benzimidazole thiol, benzoxazole thiol, fatty acid and its sodium soap, alkyl sulfonate, alkyl sulfate, phosphate, arsenate, fatty amine and its salt, rosin amine, quaternary ammonium salt, diamine and polyamine compound, and amphoteric surfactant; the flocculating agent is a high molecular polymer and comprises one or more of polymeric ferric sulfate, polymeric aluminum chloride and polyacrylamide; the pH regulator is one or more selected from calcium oxide, carbide slag, calcium hydroxide, potassium hydroxide, sodium hydroxide, monosodium fumarate, sodium citrate, potassium citrate, monosodium citrate, phosphate, calcium sulfate, calcium lactate, and sodium acetate.
CaSO4The mass ratio of the basic solid waste to the K-Q type micro-curing stabilizer is 80: 20-95: 5.
The invention has the advantages and technical effects that:
harmful components in the CaSO 4-based solid waste mainly exist in free water and attached water in the solid waste, and the solidification is that the K-Q type micro-solidification stabilizer reacts with the harmful components in the free water and the attached water in the solid waste to generate precipitates, complexes or physical packages, so that the solidification and stabilization effects are achieved; the method has simple process, low cost and CaSO4The utilization rate of the basic solid waste is more than 90 percent, and various indexes of leaching toxicity of the basic solid waste compound the environmental protection requirement, break through the original phosphogypsum treatment technology, and greatly improve the utilization rate of the phosphogypsum.
Drawings
FIG. 1 is a schematic diagram showing the results of testing the leaching toxicity of the phosphogypsum solid waste environment-friendly filling material in example 1;
FIG. 2 is a graph showing the results of testing the pH value (A) and the water-soluble salt (B) of the phosphogypsum solid waste environment-friendly filling material in example 1;
FIG. 3 is a graph showing the results of detecting leaching toxicity of the solid waste environment-friendly filling material in example 2;
FIG. 4 is a graph showing the results of detecting pH (A) and water-soluble salt (B) of the solid waste environment-friendly filling material in example 2;
FIG. 5 shows the detection of pH (A) and F of the solid waste environment-friendly filling materials in examples 3 and 4-(B) Schematic diagram of the results of (1);
fig. 6 is a schematic diagram of the results of detecting leaching of toxic phosphate from the basic solid waste environment-friendly filling material in examples 3 and 4.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
Example 1: the preparation method of the phosphogypsum-based environment-friendly filling material comprises the following steps:
(1) crushing the phosphogypsum, and screening to obtain phosphogypsum powder with the particle size of 10-800 microns, wherein the water content of the phosphogypsum powder is 10% and the pH value is = 2;
(2) preparing a K-Q type micro-curing stabilizer in a closed environment with normal temperature and 10% of humidity, wherein the K-Q type micro-curing stabilizer comprises 5% of foaming agent azodiisobutyronitrile (azo compound), 20% of stabilizer cement, 5% of collecting agent xanthate, 40% of flocculating agent polyaluminium chloride and 30% of acid-base regulator calcium oxide in percentage by mass; the grain diameter of the K-Q type micro-curing stabilizer is 100-800 mu m;
(3) uniformly stirring and mixing phosphogypsum powder and K-Q type micro-curing stabilizer powder according to the mass ratio of 80:20, and reacting for 20 hours at the ambient temperature of 25 ℃ and the humidity of 50% to obtain CaSO4Solid waste-based environment-friendly filling materials;
referring to the method in the Standard of solid waste Leaching toxicity Leaching method horizontal shock method (HJ 557-2010)4The leaching toxicity of the solid waste environment-friendly filling material is determined, and the results are shown in the figures 1 and 2; as can be seen from the figure, the leachate meets the requirement of the maximum concentration limit value in the Integrated wastewater discharge Standard (GB 8978-1996), and the curing stabilizer has better curing and stabilizing effects on toxic and harmful substances in the phosphogypsum.
Example 2: the preparation method of the desulfurized gypsum based environment-friendly filling material comprises the following specific operations:
(1) crushing desulfurized gypsum, and screening to obtain desulfurized gypsum powder with the particle size of 10-800 microns, wherein the water content of the desulfurized gypsum powder is 15% and the pH value is = 3;
(2) preparing a K-Q type micro-curing stabilizer in a closed environment with normal temperature and 5% of humidity, wherein the K-Q type micro-curing stabilizer comprises 3% of foaming agent calcium carbonate, 25% of stabilizer fly ash, 4% of collecting agent black powder, 30% of flocculating agent polymeric ferric sulfate and 38% of acid-base regulator potassium hydroxide in percentage by mass; the grain diameter of the K-Q type micro-curing stabilizer is 100-500 mu m;
(3) uniformly stirring and mixing phosphogypsum powder and K-Q type micro-curing stabilizer powder according to the mass ratio of 95:5, and reacting for 10 hours at the ambient temperature of 40 ℃ and the humidity of 80% to obtain CaSO4Solid waste-based environment-friendly filling materials;
referring to the method in the Standard of solid waste Leaching toxicity Leaching method horizontal shock method (HJ 557-2010)4The leaching toxicity of the basic solid waste environment-friendly filling material is measured by various harmful impurities, and the results are shown in figures 3 and 4; as can be seen from the figure, the leachate meets the requirement of the maximum concentration limit in the Integrated wastewater discharge Standard (GB 8978-1996), and the curing stabilizer has a good curing and stabilizing effect on toxic and harmful substances in the desulfurized gypsum.
Example 3: the preparation method of the fluorine gypsum-based environment-friendly filling material comprises the following steps:
(1) crushing fluorgypsum, and screening to obtain fluorgypsum powder with the particle size of 10-800 mu m, wherein the water content of the fluorgypsum powder is 20% and the pH is = 2;
(2) preparing a K-Q type micro-curing stabilizer in a closed environment with the humidity of 15% at normal temperature, wherein the K-Q type micro-curing stabilizer comprises 1% of foaming agent silicon carbide, 30% of stabilizer asphalt, 2% of collecting agent white drug, 50% of flocculating agent polyacrylamide and 17% of acid-base regulator sodium citrate by mass percent; the grain diameter of the K-Q type micro-curing stabilizer is 100-500 mu m;
(3) uniformly stirring and mixing phosphogypsum powder and K-Q type micro-curing stabilizer powder according to the mass ratio of 95:10, and reacting for 15h at the ambient temperature of 30 ℃ and the humidity of 70% to obtain CaSO4Solid waste-based environment-friendly filling materials;
refer to "Leaching toxicity Leaching method of solid waste" horizontal shaking method (HJ 557)2010) method pair CaSO in Standard4The leaching toxicity of the basic solid waste environment-friendly filling material is measured by various harmful impurities, and the results are shown in figures 5 and 6; as can be seen from the figure, the indexes of pH, phosphate and F in the leachate meet the requirement of the maximum concentration limit value in the Integrated wastewater discharge Standard (GB 8978-1996), and the curing stabilizer has better curing and stabilizing effects on toxic and harmful substances in the fluorgypsum.
Example 4: the preparation method of the titanium gypsum-based solid waste environment-friendly filling material specifically comprises the following operations:
(1) crushing titanium gypsum, and screening to obtain titanium gypsum powder with the particle size of 10-800 mu m, wherein the water content of the titanium gypsum powder is 10% and the pH is = 4;
(2) preparing a K-Q type micro-curing stabilizer in a closed environment with normal temperature and 15% of humidity, wherein the K-Q type micro-curing stabilizer comprises 2% of foaming agent sodium dodecyl sulfate, 22% of stabilizer ferrous sulfate, 1% of collector benzothiazole thiol, 30% of flocculant polyaluminium sulfate and 45% of acid-base regulator sodium acetate in percentage by mass; the grain diameter of the K-Q type micro-curing stabilizer is 100-500 mu m;
(3) uniformly stirring and mixing phosphogypsum powder and K-Q type micro-curing stabilizer powder according to the mass ratio of 85:15, and reacting for 20 hours at the ambient temperature of 45 ℃ and the humidity of 65% to obtain CaSO4Solid waste-based environment-friendly filling materials;
referring to the method in the Standard of solid waste Leaching toxicity Leaching method horizontal shock method (HJ 557-2010)4The leaching toxicity of the basic solid waste environment-friendly filling material is measured by various harmful impurities, and the results are shown in figures 5 and 6; as can be seen from the figure, the indexes of pH, phosphate and F in the leachate meet the requirement of the maximum concentration limit value in the Integrated wastewater discharge Standard (GB 8978-1996), and the curing stabilizer has a good curing and stabilizing effect on toxic and harmful substances in the titanium gypsum.

Claims (9)

1. CaSO4The preparation method of the solid waste-based environment-friendly filling material is characterized by comprising the following steps: in CaSO4Adding K-Q type micro-curing stabilizer powder into the solid waste powder, and mixing at a stirring speed of 400-1000 rpm for 20-120min, fully contacting the materials, then sealing and maintaining for 8-24 hours at the temperature of 25-45 ℃ and the humidity of 50-89%, and curing the CaSO by using the K-Q type micro-curing stabilizer4Exciting CaSO while simultaneously exciting toxic and harmful substances in solid waste4Based on the activity of solid wastes to prepare CaSO4A solid waste based environment-friendly filling material.
2. The CaSO of claim 14The preparation method of the solid waste-based environment-friendly filling material is characterized by comprising the following steps: CaSO4The water content of the solid waste powder is 10-25%, the pH = 1.5-5, and the CaSO4The particle size of the solid waste powder and the K-Q type micro-curing stabilizer powder is 10-800 mu m.
3. The CaSO of claim 14The preparation method of the solid waste-based environment-friendly filling material is characterized by comprising the following steps: the K-Q type micro-curing stabilizer composition comprises, by mass, 1-5% of a foaming agent, 20-30% of a stabilizer, 1-5% of a collecting agent, 30-50% of a flocculating agent and 10-48% of an acid-base regulator.
4. The CaSO of claim 34The preparation method of the solid waste-based environment-friendly filling material is characterized by comprising the following steps: the foaming agent is one or more of azo compounds, sulfonyl hydrazide compounds, nitroso compounds, calcium carbonate, magnesium carbonate, sodium bicarbonate, sodium silicate, silicon carbide, carbon black, sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether sodium sulfate.
5. The CaSO of claim 34The preparation method of the solid waste-based environment-friendly filling material is characterized by comprising the following steps: the stabilizer is one or more of magnesium stearate, fatty acid file, aluminum fatty acid, potassium fatty acid, cement, lime, fly ash, asphalt, polyethylene, urea formaldehyde, polyester, ferrous sulfate, phosphate and sodium hydroxide.
6. The CaSO of claim 34The preparation method of the solid waste-based environment-friendly filling material is characterized by comprising the following steps: collecting agent is xanthate, xanthate derivative, nigella sativa, Baiyao, benzothiazole thiol, benzeneOne or more of benzimidazole mercaptan, benzooxazole mercaptan, fatty acid and sodium soap thereof, alkyl sulfonate, alkyl sulfate, phosphate, arsenate, fatty amine and salt thereof, rosin amine, quaternary ammonium salt, diamine and polyamine compounds and amphoteric surfactant.
7. The CaSO of claim 34The preparation method of the solid waste-based environment-friendly filling material is characterized by comprising the following steps: the flocculating agent is one or more of polymeric ferric sulfate, polymeric aluminum chloride and polyacrylamide.
8. The CaSO of claim 34The preparation method of the solid waste-based environment-friendly filling material is characterized by comprising the following steps: the pH regulator is one or more of calcium oxide, carbide slag, calcium hydroxide, potassium hydroxide, sodium hydroxide, monosodium fumarate, sodium citrate, potassium citrate, monosodium citrate, phosphate, calcium sulfate, calcium lactate, and sodium acetate.
9. The CaSO of claim 14The preparation method of the solid waste-based environment-friendly filling material is characterized by comprising the following steps: CaSO4The mass ratio of the basic solid waste to the K-Q type micro-curing stabilizer is 80: 20-95: 5.
CN202110567343.6A 2021-05-24 2021-05-24 Preparation method of CaSO 4-based solid waste environment-friendly filling material Pending CN113233854A (en)

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CN110723952A (en) * 2019-10-12 2020-01-24 北京科技大学 Phosphogypsum-based all-solid waste filler proportioning optimization method for improving filling roof contact rate
CN112250406A (en) * 2020-10-20 2021-01-22 陕西煤业化工技术研究院有限责任公司 Mining high-water-content high-strength filling material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1498614A (en) * 1975-10-15 1978-01-25 Hoechst Ag Process for the manufacture of foamed gypsum
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