CN114375797A - Ecological remediation soil matrix and preparation method and application thereof - Google Patents
Ecological remediation soil matrix and preparation method and application thereof Download PDFInfo
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- CN114375797A CN114375797A CN202111514146.4A CN202111514146A CN114375797A CN 114375797 A CN114375797 A CN 114375797A CN 202111514146 A CN202111514146 A CN 202111514146A CN 114375797 A CN114375797 A CN 114375797A
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- phosphogypsum
- coal gangue
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- gangue powder
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- 239000002689 soil Substances 0.000 title claims abstract description 53
- 239000011159 matrix material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005067 remediation Methods 0.000 title claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005065 mining Methods 0.000 claims abstract description 8
- 239000003245 coal Substances 0.000 claims description 88
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 78
- 239000000843 powder Substances 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 30
- 230000000813 microbial effect Effects 0.000 claims description 28
- 239000010881 fly ash Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 26
- 239000011574 phosphorus Substances 0.000 claims description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims description 26
- 238000006477 desulfuration reaction Methods 0.000 claims description 19
- 230000023556 desulfurization Effects 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 239000002361 compost Substances 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 235000021110 pickles Nutrition 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 244000005700 microbiome Species 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000004927 clay Substances 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000011435 rock Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 241000194107 Bacillus megaterium Species 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 6
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 241000589516 Pseudomonas Species 0.000 claims description 3
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 12
- 239000003337 fertilizer Substances 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012258 culturing Methods 0.000 description 5
- 235000015097 nutrients Nutrition 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 210000003608 fece Anatomy 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000010921 garden waste Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 3
- UWHCZFSSKUSDNV-UHFFFAOYSA-N 3-(aziridin-1-yl)propanoic acid;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound OC(=O)CCN1CC1.OC(=O)CCN1CC1.OC(=O)CCN1CC1.CCC(CO)(CO)CO UWHCZFSSKUSDNV-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011243 crosslinked material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004016 soil organic matter Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
- A01G24/10—Growth substrates; Culture media; Apparatus or methods therefor based on or containing inorganic material
- A01G24/17—Growth substrates; Culture media; Apparatus or methods therefor based on or containing inorganic material containing slag
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
- A01G24/10—Growth substrates; Culture media; Apparatus or methods therefor based on or containing inorganic material
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
- A01G24/20—Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
- A01G24/20—Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material
- A01G24/22—Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material containing plant material
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/02—Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Soil Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses an ecological restoration soil matrix and a preparation method and application thereof. The ecological restoration soil matrix has stable chemical property and proper pH value, each index of the physical and chemical property meets the requirement of a culture matrix, the structure is loose, the water and fertilizer retention performance is excellent, the ecological restoration soil matrix can completely replace soil, and the ecological restoration soil matrix is particularly suitable for ecological restoration of mining areas with shortage of soil resources.
Description
Technical Field
The invention relates to the technical field of ecological environment restoration, in particular to an ecological restoration soil matrix based on coal gangue and phosphogypsum, and a preparation method and application thereof.
Background
Coal gangue is solid waste residue generated in the coal mining and processing processes, and the coal gangue is relatively close to soil in terms of element composition, chemical composition and mineral composition, so that the coal gangue is widely applied to preparation of soil conditioners, mineral fertilizers and the like at present. The coal gangue is modified by physical, chemical or biological methods to form an ecological matrix similar to soil property and structure, and plays an important role in repairing and reclaiming the damaged fields in mining areas.
The phosphogypsum is solid waste residue generated in the process of producing phosphoric acid by using phosphate ore, and elements beneficial to crop soil exist in the phosphogypsum, so that the phosphogypsum can be popularized and applied in agriculture as a resource.
Aiming at the characteristics of the two solid wastes, the two solid wastes are combined to be used as raw materials for researching and developing organic compound fertilizers, microbial fertilizers, soil conditioners and the like in agriculture, and the method becomes a hotspot in industries in recent years. However, the problems of the prior art that the matching of the content of the nutrient components of the coal gangue with the crop demand needs to be improved, the risk of heavy metal pollution and high sulfur pollution still exist, the content of the nutrient of the phosphogypsum is low, impurities are contained and the like, the resource utilization is limited, and the ecological soil matrix taking the coal gangue and the phosphogypsum as raw materials is less in the market. Therefore, in order to solve the outstanding problem of resource utilization of coal gangue and phosphogypsum, a key technology for preparing an ecological soil matrix from coal gangue and phosphogypsum must be developed, and a production and utilization mode with ecological environment friendliness, low cost, strong sustainability and high safety is provided, so that the coal gangue and phosphogypsum can be widely applied to ecological restoration as an available resource.
Disclosure of Invention
The invention aims to make up for the defects of the prior art, and provides an ecological restoration soil matrix based on coal gangue and phosphogypsum and a preparation method and application thereof based on the technical problems of the coal gangue and phosphogypsum in actual treatment and resource utilization.
The technical scheme of the invention is as follows:
a preparation method of an ecological restoration soil matrix comprises the following steps:
(1) performing microbial desulfurization treatment on the coal gangue powder, and then calcining at high temperature to obtain modified coal gangue powder;
(2) carrying out acid leaching on phosphogypsum to obtain phosphogypsum acid leaching solution;
(3) mixing the modified coal gangue powder and the phosphogypsum pickle liquor, adding fly ash for reaction, and filtering to obtain filter residue enriched with effective phosphorus;
(4) adding organic compost, adhesive, water-retaining agent, microbial agent and water into the filter residue enriched with available phosphorus, and mixing uniformly;
(5) curing the mixture;
(6) drying and crushing to obtain a finished product.
The preparation method is characterized in that the raw materials are mixed,
the weight parts of the raw materials are as follows: 150-200 parts of modified coal gangue powder, 50-100 parts of phosphogypsum, 20-40 parts of organic compost, 20-50 parts of fly ash, 0.1-0.5 part of adhesive, 0.1-0.5 part of water-retaining agent and 1-3 parts of microbial agent.
The preparation method is characterized in that the raw materials are mixed,
the coal gangue powder in the step (1) is clay rock coal gangue, is crushed and then passes through a sieve of 20-100 meshes, is added with water to prepare 15-25% suspension, the pH value of the suspension is adjusted to 1.5-2.0 by using 1.0-1.5 mol/L dilute hydrochloric acid, 7-12% of desulfurization microbial liquid by mass is added, the mixture is subjected to constant temperature reaction at 25-30 ℃ for 3-7 days, and is taken out and dried to obtain the desulfurization coal gangue powder; and then calcining the desulfurized coal gangue powder at 600-800 ℃ for 2-3 h, and cooling to obtain the modified coal gangue powder.
The desulfurization microorganisms comprise one or more of thiobacillus ferrooxidans and thiobacillus thiooxidans, and are purchased from China agricultural microorganism culture Collection.
The clay rock type coal gangue comprises the following components: SiO 2230-50% of Al2O314-40% of Fe2O32 to 7 percent of CaO, 0.5 to 9.0 percent of CaO, 0.5 to 6.0 percent of MgO, and K20.5 to 3.5 percent of O and Na20.2 to 2.5 percent of O and TiO20.2-1.0 percent of the total sulfur content and 0.4-3.5 percent of the total sulfur content.
The preparation method is characterized in that the raw materials are mixed,
and (3) grinding the phosphogypsum in the step (2), sieving the ground phosphogypsum by a sieve of 50-120 meshes, taking 50-100 parts of the phosphogypsum, adding 30-60 parts of 98% sulfuric acid or 30-36% industrial hydrochloric acid, oscillating the mixture in a constant-temperature culture oscillator at 25-30 ℃ for 1-2 hours, then performing suction filtration, washing filter residues by 30-60 parts of water for 2-3 times each time, and mixing acidolysis filtrate with a cleaning solution to obtain the phosphogypsum pickle liquor.
The phosphogypsum is solid waste residue generated in the process of producing phosphoric acid from phosphate ore, is dried and ground by a sieve of 50-120 meshes, and the components of the phosphogypsum meet the following conditions: CaO content is 15.0-40.0%, SiO21.0-4.0% of Al2O30.1-0.5% of Fe2O3Content of 0.5% -1.5%, P2O5Content of 0.5% -2.0%, K20.05-0.10 percent of O and 0.05-0.20 percent of MgO.
The preparation method is characterized in that the raw materials are mixed,
mixing the modified coal gangue powder and the phosphogypsum pickle liquor, adding fly ash to adjust the pH of the mixed liquor to 7.0-8.0, carrying out oscillation reaction on the mixed liquor at 25-30 ℃ for 1-2 h, and filtering to obtain filter residue enriched with effective phosphorus;
the fly ash is powder collected from flue gas of pulverized coal furnace in power plant, C-class fly ash contains CaO not less than 10% and SO3The content is less than 3.0 percent.
The preparation method is characterized in that the raw materials are mixed,
and (4) adding organic compost, adhesive, water-retaining agent and microbial agent into the filter residue enriched with available phosphorus, mixing, and adding water in the process to ensure that the water content of the raw materials is 35-45%.
The organic compost is prepared by mixing and fermenting crushed crop straws and garden wastes with decomposed human and animal excreta.
The preparation method is characterized in that the raw materials are mixed,
and (5) curing the mixture for 7-10 days at a constant temperature of 25-30 ℃.
According to the preparation method, the microbial agent is one or more of bacillus megaterium, silicate bacteria (GY03) and pseudomonas, the bacillus megaterium and the pseudomonas are purchased from China agricultural microbial strain collection center, and the silicate bacteria (GY03) are purchased from the institute of geochemistry, China academy of sciences.
The invention dries the cured mixture, and crushes the mixture to a particle size less than 2mm to obtain a finished product.
The invention also provides the ecological restoration soil matrix prepared by the method; and the application of the substrate in culture substrates of desertification soil, saline-alkali soil, stony desertification mines, barren fields around mining areas, garden crops and crops.
The invention has the following beneficial effects:
the ecological restoration soil matrix is prepared by utilizing the coal gangue and the phosphogypsum, the raw material cost is low, the production cost of the soil matrix is reduced, and the coal gangue and the phosphogypsum can be greatly consumed, so that the coal gangue and the phosphogypsum are changed into valuables, the current situation that the existing coal gangue and phosphogypsum are excessively accumulated is solved, the produced ecological soil matrix can be used for ecological restoration of mining areas or garden crop seedling culture instead of soil, the problem of soil for vegetation reconstruction is solved, and the ecological restoration cost of the mining areas is reduced. The coal gangue is pretreated by desulfurization microorganisms, sulfur-containing compounds are oxidized, the toxicity of the ecological substrate to the environment is reduced, and the applicability of the ecological substrate is improved. The coal gangue is modified by high-temperature roasting, so that the adsorption capacity of the coal gangue is improved. Effective phosphorus is extracted from the phosphogypsum acid leaching solution, coal gangue enriched with the effective phosphorus is formed to be used as a raw material for generating an ecological restoration soil matrix, harmful elements in the phosphogypsum are prevented from entering the soil matrix, and the resource utilization of the phosphogypsum without phosphorus impurities is wider. The effective phosphorus-enriched coal gangue is cured, under the action of a microbial agent, nutrient elements fixed in the coal gangue are released, the nutrient elements are converted into effective phosphorus, quick-acting potassium, effective silicon, exchangeable calcium, effective sulfur and the like absorbed by plants, organic compost, an adhesive and a water retention agent are mixed, finally, the physical properties, chemical and biological indexes of the mixed matrix are improved, an ecological improved matrix similar to soil is formed, and a good plant growth environment is created. The fly ash is added, so that the effects of relieving matrix acidification and inhibiting heavy metal pollution are achieved. The ecological restoration soil matrix can be used for desertification soil, saline-alkali soil and fields barren around mining areas, can also be used as a culture matrix for garden crops and crops, and has the effects of improving soil fertility, optimizing soil physicochemical property, promoting plant growth and improving crop yield.
Drawings
FIG. 1 is a flow chart of the preparation of the ecological remediation soil matrix of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
The first embodiment is as follows:
an ecological restoration soil matrix based on coal gangue and phosphogypsum is prepared from the following raw materials in parts by weight: 150 parts of modified coal gangue powder, 50 parts of phosphogypsum, 20 parts of organic compost, 30 parts of fly ash, 0.1 part of adhesive, 0.1 part of water-retaining agent, 1 part of microbial agent and a proper amount of water.
The method comprises the following steps:
s1: testing raw materials, and performing chemical component and phase analysis on the clay rock coal gangue, the phosphogypsum and the fly ash to obtain chemical components and contents thereof; the clay rock gangue comprises the following components: SiO 2235.42% of Al2O318.84% of Fe2O3The content is 2.82 percentCaO content 0.75%, MgO content 0.55%, K2O content 1.52%, Na2O content 0.81%, TiO2The content is 0.41 percent, and the total sulfur content is 2.35 percent. The phosphogypsum comprises the following components: CaO content 20.0%, SiO22.5% of Al2O30.2% of Fe2O3Content 0.8%, P2O5Content 0.9%, K2O content 0.05%, MgO content 0.1%.
S2: pretreating raw materials, drying and grinding coal gangue and phosphogypsum, sieving the coal gangue with a 100-mesh sieve, and sieving the phosphogypsum with a 120-mesh sieve;
s3: adding water into the sieved coal gangue to prepare 20% suspension, adjusting the pH value of the coal gangue suspension to 1.7 by using 1.0mol/L dilute hydrochloric acid, adding 10% by mass of desulfurization microbial liquid, culturing for 3 days in a constant-temperature reactor at 30 ℃, taking out and drying in a drying furnace at 50 ℃ to obtain desulfurization coal gangue powder; then calcining the desulfurized coal gangue powder at 800 ℃ for 2h, and naturally cooling to room temperature to obtain modified coal gangue powder; the desulfurization microorganism is thiobacillus ferrooxidans, purchased from China agricultural microorganism culture Collection, and has a bacterial liquid content of 10 per ml8～109And (4) bacteria.
S4: and (2) preparing the phosphogypsum pickle liquor, namely taking 50 parts of phosphogypsum of S2 into a reaction vessel, adding 60 parts of 98% sulfuric acid, oscillating for 1 hour in a constant-temperature culture oscillator at 30 ℃, then carrying out suction filtration, washing filter residues for 2 times by using 60 parts of water, and mixing acidolysis filtrate with a cleaning solution to obtain the phosphogypsum pickle liquor.
S5: extracting effective phosphorus, mixing 150 parts of gangue powder obtained in the step S3 with phosphogypsum pickle liquor of S4, adding 30 parts of fly ash to adjust the pH of the mixed solution to 7, transferring the mixed solution into a reaction container, carrying out oscillation reaction in a constant-temperature culture oscillator at 30 ℃ for 2 hours, and filtering to obtain the gangue enriched with the effective phosphorus; the fly ash is powder collected from flue gas of pulverized coal furnace of electric power plant, C-class fly ash, CaO content 10.4%, SO3The content is 0.3 percent.
S6: mixing, namely adding 20 parts of organic compost, 0.1 part of adhesive, 0.1 part of water-retaining agent and 1 part of microbial agent into the phosphorus-rich coal gangue obtained in the step S5; prepared material storagePutting the mixture into a stirring device to obtain a mixture, and spraying water to the mixture in the mixing process to ensure that the water content of the raw materials is 35-45%; the organic compost is prepared by mixing and fermenting crushed crop straws and garden wastes and decomposed human and animal excreta according to the proportion of 1: 4. The microbial agent is Bacillus megaterium purchased from China agricultural culture Collection for microorganisms with inoculum size of 2.5-3.0 × 1014cfu/g. The adhesive is polyacrylamide with molecular weight of 1000W and is anionic. The water-retaining agent mainly comprises a potassium polyacrylate-polyacrylamide copolymerization cross-linked substance and comprises the following main components: acrylamide 65%, potassium acrylate 24%, water 10%, trimethylolpropane tris (3-aziridinyl propionate) 1.0%.
S7: curing, namely placing the mixture in a constant temperature reactor at 30 ℃ for culturing for 7 days;
s8: and (3) drying, namely drying the S7 mixture in a drying furnace at 50 ℃, and crushing to obtain a finished product with the particle size of less than 2 mm.
Example two:
an ecological restoration soil matrix based on coal gangue and phosphogypsum is prepared from the following raw materials in parts by weight: 200 parts of modified coal gangue powder, 100 parts of phosphogypsum, 30 parts of organic compost, 50 parts of fly ash, 0.3 part of adhesive, 0.3 part of water-retaining agent, 2 parts of microbial agent and a proper amount of water.
An ecological restoration soil matrix based on coal gangue and phosphogypsum and a preparation method thereof comprise the following steps:
s1: testing raw materials, and performing chemical component and phase analysis on the clay rock coal gangue, the phosphogypsum and the fly ash to obtain chemical components and contents thereof; the clay rock gangue comprises the following components: SiO 2238.82% Al2O325.24% of Fe2O33.77% of CaO, 0.55% of MgO, 0.51% of K2O content 1.85%, Na2O content 1.23%, TiO2The content is 0.39 percent, and the total sulfur content is 3.05 percent. The phosphogypsum comprises the following components: CaO content 24.5%, SiO23.15% of Al2O30.25% of Fe2O3Content 0.93%, P2O5Content 1.19%, K2O content 0.08%, MgO content 0.09%.
S2: pretreating raw materials, drying and grinding coal gangue and phosphogypsum, sieving the coal gangue with a 100-mesh sieve, and sieving the phosphogypsum with a 100-mesh sieve;
s3: adding water into the sieved coal gangue to prepare 20% suspension, adjusting the pH value of the coal gangue suspension to 1.7 by using 1.5mol/L dilute hydrochloric acid, adding 10% by mass of desulfurization microbial liquid, culturing for 3 days in a constant-temperature reactor at 30 ℃, taking out and drying in a drying furnace at 50 ℃ to obtain desulfurization coal gangue powder; then calcining the desulfurized coal gangue powder at 800 ℃ for 2h, and naturally cooling to room temperature to obtain modified coal gangue powder; the desulfurization microorganism is thiobacillus ferrooxidans, purchased from China agricultural microorganism culture Collection, and has a bacterial liquid content of 10 per ml8～109And (4) bacteria.
S4: and (2) preparing the phosphogypsum pickle liquor, namely taking 100 parts of phosphogypsum of S2 into a reaction vessel, adding 60 parts of 98% sulfuric acid, oscillating for 1 hour in a constant-temperature culture oscillator at 30 ℃, then carrying out suction filtration, washing filter residues for 2 times by using 60 parts of water, and mixing acidolysis filtrate with a cleaning solution to obtain the phosphogypsum pickle liquor.
S5: extracting effective phosphorus, mixing 200 parts of gangue powder obtained in the step S3 with phosphogypsum pickle liquor of S4, adding 40 parts of fly ash to adjust the pH of the mixed liquor to 7, transferring the mixed liquor into a reaction container, carrying out oscillation reaction in a constant-temperature culture oscillator at 30 ℃ for 2 hours, and filtering to obtain filter residue enriched with the effective phosphorus; the fly ash is powder collected from flue gas of pulverized coal furnace in power plant, C-class fly ash, CaO content 10.4%, SO3The content is 0.3 percent.
S6: mixing, namely adding 30 parts of organic compost, 0.3 part of adhesive, 0.3 part of water-retaining agent and 2 parts of microbial agent into the phosphorus-rich waste residue obtained in the step S5; putting the prepared materials into a stirring device to obtain a mixture, and spraying water to the mixture in the mixing process to ensure that the water content of the raw materials is 35-45%; the organic compost is prepared by mixing and fermenting crushed crop straws and garden wastes and decomposed human and animal excreta according to the proportion of 1: 4. The microbial agent is Bacillus megaterium purchased from China agricultural culture Collection for microorganisms with inoculation quantity of 3.5 × 1014～4.0 ×1014cfu/g. The adhesive is polyacrylamide with molecular weight of 1000W and is anionic. The water-retaining agent mainly comprises a potassium polyacrylate-polyacrylamide copolymerization cross-linked material and comprises the following main components: acrylamide 66%, potassium acrylate 23%, water 10%, trimethylolpropane tris (3-aziridinyl propionate) 1.0%.
S7: curing, namely placing the mixture in a constant temperature reactor at 30 ℃ for culturing for 7 days;
s8: and (3) drying, namely drying the S7 mixture in a drying furnace at 50 ℃, and crushing to obtain a finished product with the particle size of less than 2 mm.
Example three:
an ecological restoration soil matrix based on coal gangue and phosphogypsum is prepared from the following raw materials in parts by weight: 200 parts of modified coal gangue powder, 100 parts of phosphogypsum, 40 parts of organic compost, 50 parts of fly ash, 0.5 part of adhesive, 0.5 part of water-retaining agent, 3 parts of microbial agent and a proper amount of water.
An ecological restoration soil matrix based on coal gangue and phosphogypsum and a preparation method thereof comprise the following steps:
s1: testing raw materials, and performing chemical component and phase analysis on the clay rock coal gangue, the phosphogypsum and the fly ash to obtain chemical components and contents thereof; the clay rock gangue comprises the following components: SiO 2238.82% Al2O325.24% of Fe2O33.77% of CaO, 0.55% of MgO, 0.51% of K2O content 1.85%, Na2O content 1.23%, TiO2The content is 0.39 percent, and the total sulfur content is 3.05 percent. The phosphogypsum comprises the following components: CaO content 24.5%, SiO23.15% of Al2O30.25% of Fe2O3Content 0.93%, P2O5Content 1.19%, K2O content 0.08%, MgO content 0.09%.
S2: pretreating raw materials, drying and grinding coal gangue and phosphogypsum, sieving the coal gangue with a 100-mesh sieve, and sieving the phosphogypsum with a 100-mesh sieve;
s3: desulfurizing and modifying coal gangue, adding water into sieved coal gangue to prepare 20% suspension, and regulating with 1.5mol/L dilute hydrochloric acidThe pH value of the coal gangue suspension is 1.7, 10% of desulfurization microbial liquid by mass is added, the mixture is cultured in a constant temperature reactor at 30 ℃ for 3 days, and the mixture is taken out and dried in a drying furnace at 50 ℃ to obtain desulfurization coal gangue powder; then calcining the desulfurized coal gangue powder at 800 ℃ for 2h, and naturally cooling to room temperature to obtain modified coal gangue powder; the desulfurization microorganism is thiobacillus ferrooxidans, purchased from China agricultural microorganism culture Collection, and has a bacterial liquid content of 10 per ml8～109And (4) bacteria.
S4: and (2) preparing the phosphogypsum pickle liquor, namely taking 100 parts of phosphogypsum of S2 into a reaction vessel, adding 60 parts of 98% sulfuric acid, oscillating for 1 hour in a constant-temperature culture oscillator at 30 ℃, then carrying out suction filtration, washing filter residues for 2 times by using 60 parts of water, and mixing acidolysis filtrate with a cleaning solution to obtain the phosphogypsum pickle liquor.
S5: extracting effective phosphorus, mixing 200 parts of gangue powder obtained in the step S3 with phosphogypsum pickle liquor of S4, adding 50 parts of fly ash to adjust the pH of the mixed liquor to 7, transferring the mixed liquor into a reaction container, carrying out oscillation reaction in a constant-temperature culture oscillator at 30 ℃ for 2 hours, and filtering to obtain filter residue enriched with the effective phosphorus; the fly ash is powder collected from flue gas of pulverized coal furnace in power plant, C-class fly ash, CaO content 10.4%, SO3The content is 0.3 percent.
S6: mixing, namely adding 40 parts of organic compost, 0.5 part of adhesive, 0.5 part of water-retaining agent and 3 parts of microbial agent into the phosphorus-rich waste residue obtained in the step S5; putting the prepared materials into a stirring device to obtain a mixture, and spraying water to the mixture in the mixing process to ensure that the water content of the raw materials is 35-45%; the organic compost is prepared by mixing and fermenting crushed crop straws and garden wastes and decomposed human and animal excreta according to the proportion of 1: 4. The microbial agent is Bacillus megaterium purchased from China agricultural culture Collection for microorganisms with inoculation amount of 4.0 × 1014～5.0 ×1014cfu/g. The adhesive is polyacrylamide with molecular weight of 1000W and is anionic. The water-retaining agent mainly comprises a potassium polyacrylate-polyacrylamide copolymerization cross-linked material and comprises the following main components: acrylamide 66%, potassium acrylate 24%, water 8.5%, trimethylolpropane tris (3-aziridinyl propionate) 0.5%.
S7: curing, namely placing the mixture in a constant temperature reactor at 30 ℃ for culturing for 7 days;
s8: and (3) drying, namely drying the S7 mixture in a drying furnace at 50 ℃, and crushing to obtain a finished product with the particle size of less than 2 mm.
To further illustrate the application value of the invention, the inventors compared the ingredients of the first, second and third examples with "planting green soil" (CJ/T340-2016), and the test results are as follows.
TABLE 1
As can be seen from the data in Table 1, the soil organic matter content, the water-soluble nitrogen, the available phosphorus, the available potassium, the available sulfur, the available magnesium and the available calcium of the ecological restoration soil matrix prepared by the invention all meet the requirements of greening planting soil (CJ/T340-2016) on the matrix, and the ecological restoration soil matrix prepared by the invention can replace soil for ecological restoration of mine areas.
In order to further illustrate the application value of the invention, the inventor manufactures a comparison group, wherein in the comparison group I, only the coal gangue in the example II is not desulfurized and modified (the amount of the coal gangue is the same as that of the modified coal gangue in the example II), and phosphogypsum is subjected to acid leaching, and the rest of the comparison group is the same as that in the example II; in the second control group, only the gangue in the second example is desulfurized and modified, and the phosphogypsum is not subjected to acid leaching (the modified gangue is directly mixed with the phosphogypsum and the fly ash, and the using amounts of the modified gangue, the phosphogypsum and the fly ash are the same as those in the second example), and the rest is the same as that in the second example; and a third control group, in the second embodiment, the coal gangue is not desulfurized and modified, the phosphogypsum is not subjected to acid leaching, the rest operations are the same as the second embodiment, the coal gangue, the phosphogypsum and the fly ash are directly mixed, then the organic compost, the adhesive, the water-retaining agent, the microbial agent and the water are added, the mixture is cured and dried to prepare a finished product, and the adding amount of each raw material is consistent with that of the second embodiment. The control composition was compared with the soil for greening planting (CJ/T340-2016) of example two, and the results were as follows.
TABLE 2
As can be seen from the data in Table 2, when the coal gangue is subjected to desulfurization modification treatment by comparing and analyzing the first control group, the second control group and the third control group, the content of nutrient elements such as water-soluble nitrogen, available phosphorus, quick-acting potassium, available sulfur, available magnesium, available calcium and the like in the matrix can be increased, and the sulfate radical concentration is reduced; after the phosphogypsum is subjected to acid leaching, the concentration of fluoride in the matrix can be reduced, and the content of available phosphorus is increased. The ecological matrix prepared by directly mixing the coal gangue and the phosphogypsum in the control group III is analyzed, the contents of soil organic matters, water-soluble nitrogen, available phosphorus, quick-acting potassium, available magnesium, available sulfur and available calcium are lower than those of the ecological restoration soil matrix prepared by the invention, and compared with the requirement of 'green planting soil' (CJ/T340-. And the fluoride and the sulfate radical in the finished product are high, which influences the use value of the finished product.
Although the present invention has been described in detail with reference to the foregoing general description and specific examples, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the ecological restoration soil matrix is characterized by comprising the following steps:
(1) performing microbial desulfurization treatment on the coal gangue powder, and then calcining at high temperature to obtain modified coal gangue powder;
(2) carrying out acid leaching on phosphogypsum to obtain phosphogypsum acid leaching solution;
(3) mixing the modified coal gangue powder and the phosphogypsum pickle liquor, adding fly ash for reaction, and filtering to obtain filter residue enriched with effective phosphorus;
(4) adding organic compost, adhesive, water-retaining agent, microbial agent and water into the filter residue enriched with available phosphorus, and mixing uniformly;
(5) curing the mixture;
(6) drying and crushing to obtain a finished product.
2. The production method according to claim 1,
the weight parts of the raw materials are as follows: 150-200 parts of modified coal gangue powder, 50-100 parts of phosphogypsum, 20-40 parts of organic compost, 20-50 parts of fly ash, 0.1-0.5 part of adhesive, 0.1-0.5 part of water-retaining agent and 1-3 parts of microbial agent.
3. The production method according to claim 1,
the coal gangue powder in the step (1) is clay rock coal gangue, is crushed and then passes through a 20-100-mesh sieve, is added with water to prepare 15-25% suspension, the pH value of the suspension is adjusted to 1.5-2.0 by using 1.0-1.5 mol/L dilute hydrochloric acid, 7-12% of desulfurization microbial liquid by mass is added, the mixture is subjected to constant temperature reaction at 25-30 ℃ for 3-7 days, and is taken out and dried to obtain desulfurization coal gangue powder; then, calcining the desulfurized coal gangue powder at 600-800 ℃ for 2-3 h, and cooling to obtain modified coal gangue powder;
the desulfurization microorganisms comprise one or more of thiobacillus ferrooxidans and thiobacillus thiooxidans.
4. The production method according to claim 1,
and (3) grinding the phosphogypsum in the step (2), sieving the ground phosphogypsum by a sieve of 50-120 meshes, taking 50-100 parts of the phosphogypsum, adding 30-60 parts of 98% sulfuric acid or 30-36% industrial hydrochloric acid, oscillating the mixture in a constant-temperature culture oscillator at 25-30 ℃ for 1-2 h, then carrying out suction filtration, washing filter residues by 30-60 parts of water for 2-3 times each time, and mixing acidolysis filtrate with a cleaning solution to obtain the phosphogypsum pickle liquor.
5. The production method according to claim 1,
and (3) mixing the modified gangue powder and the phosphogypsum pickle liquor, adding fly ash to adjust the pH of the mixed liquor to 7.0-8.0, carrying out oscillation reaction on the mixed liquor at 25-30 ℃ for 1-2 h, and filtering to obtain filter residue enriched with effective phosphorus.
6. The production method according to claim 1,
and (4) adding organic compost, an adhesive, a water-retaining agent and a microbial agent into the filter residue enriched with the available phosphorus, and mixing, wherein water is added in the process to ensure that the water content of the raw materials is 35-45%.
7. The production method according to claim 1,
and (5) curing the mixture for 7-10 days at a constant temperature of 25-30 ℃.
8. The method according to claim 1, wherein the microbial agent is one or more of Bacillus megaterium, silicate bacteria (GY03), and Pseudomonas.
9. An eco-remediating soil substrate prepared by the method of any one of claims 1-8.
10. The use of the ecological remediation soil matrix of claim 9 in a culture matrix for desertification soils, saline and alkaline lands, rocky desertification mines, marginal fields in mining areas, landscape crops and crops.
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