CN106978184B - Curing agent for composite heavy metal polluted soil and preparation and application methods thereof - Google Patents
Curing agent for composite heavy metal polluted soil and preparation and application methods thereof Download PDFInfo
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- CN106978184B CN106978184B CN201710243117.6A CN201710243117A CN106978184B CN 106978184 B CN106978184 B CN 106978184B CN 201710243117 A CN201710243117 A CN 201710243117A CN 106978184 B CN106978184 B CN 106978184B
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- 239000002689 soil Substances 0.000 title claims abstract description 137
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 110
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 83
- 239000002893 slag Substances 0.000 claims abstract description 73
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 62
- 239000010959 steel Substances 0.000 claims abstract description 62
- 229940036811 bone meal Drugs 0.000 claims abstract description 43
- 239000002374 bone meal Substances 0.000 claims abstract description 43
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 37
- 239000010452 phosphate Substances 0.000 claims abstract description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 27
- 210000000988 bone and bone Anatomy 0.000 claims description 80
- 238000007873 sieving Methods 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 34
- 238000000227 grinding Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000010025 steaming Methods 0.000 claims description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007885 magnetic separation Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000006641 stabilisation Effects 0.000 abstract description 7
- 238000011105 stabilization Methods 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 6
- 230000008439 repair process Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 19
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 18
- 235000019796 monopotassium phosphate Nutrition 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000005067 remediation Methods 0.000 description 10
- 231100000419 toxicity Toxicity 0.000 description 9
- 230000001988 toxicity Effects 0.000 description 9
- 230000035784 germination Effects 0.000 description 8
- 238000001994 activation Methods 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 235000010469 Glycine max Nutrition 0.000 description 5
- 244000068988 Glycine max Species 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000007226 seed germination Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 231100000783 metal toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a curing agent for composite heavy metal polluted soil and a preparation and application method thereof, wherein the curing agent comprises the following materials in percentage by mass: 40-65% of steel slag powder; light-burned magnesia 5-25%; 20-45% of phosphate activated bone meal. The invention has the advantages that: firstly, the curing agent can obviously reduce the heavy metal migration and toxic leaching amount in heavy metal polluted soil, is particularly used for an acid polluted site with high heavy metal content and more pollutant types, can be used as an environment-friendly material for resource utilization after polluted soil is repaired, and obviously reduces the environmental risk in secondary development and utilization of the polluted site; meanwhile, the curing agent has the advantages of easily available raw materials, low cost, simple preparation, convenient use and stable effect, and can be popularized and applied to curing stabilization repair of composite polluted sites on a large scale.
Description
Technical Field
The invention relates to the field of environmental geotechnical engineering, in particular to a curing agent for composite heavy metal polluted soil and preparation and application methods thereof.
Background
With the adjustment of urban functions and urban layout in China, enterprises in the central area and suburban areas of a city, such as chemical plants, metal smelting plants, electroplating plants and the like, are gradually shut down or move back to the city and enter the garden, but in the production process of the industry and the enterprises for many years, a large amount of pollutants are accumulated in the remaining land after the enterprises move, so that resistance is brought to the efficient utilization of the remaining land, and serious potential safety hazards are brought to the surrounding environment. In recent years, the action plan for preventing and treating soil pollution (ten items of soil) issued by the government also considers the remediation work of the polluted soil as one of the currently important civil engineering, and the development of the relevant remediation work of the pollution is urgent.
The heavy metal pollution of the soil in the industrial polluted site is characterized by multiple heavy metal species, high content, large acidity and the like. In the remediation of heavy metal contaminated sites, a solidification stabilization technique is widely adopted. The commonly used curing agent mainly comprises materials such as cement, lime, phosphate and the like, has good effect on curing and stabilizing heavy metals, but also has a great deal of defects, such as large energy consumption for producing cement, more greenhouse gas emission and the like; lime and phosphate are non-renewable natural minerals, and the cost is high; moreover, the application of a large amount of phosphate can seriously change the soil structure and further cause phosphorus pollution of underground water and surface water.
In summary, the conventional curing agent has many defects, and needs to reduce the use of cement and phosphate materials, and find a novel curing agent which can cure and stabilize heavy metals, and has the advantages of high curing stabilization efficiency, low cost, stable performance, wide material sources and environmental friendliness, which has become the focus of attention of environmental protection science and technology workers.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a curing agent for composite heavy metal polluted soil, which can obviously reduce the migration and toxic leaching amount of heavy metals in the heavy metal polluted soil; the second purpose of the invention is to provide a preparation method of the heavy metal polluted soil curing agent; the third purpose of the invention is to provide an application method of the heavy metal contaminated soil curing agent.
The technical scheme is as follows: the curing agent for the composite heavy metal polluted soil comprises the following materials in percentage by mass: 40-65% of steel slag powder; light-burned magnesia 5-25%; 20-45% of phosphate activated bone meal.
The steel slag powder is activated steel slag powder prepared by the following method:
(1) one or more of the high-activity steel slag such as the converter slag, the open-hearth slag, the electric furnace oxidizing slag and the like after magnetic separation are crushed and sieved;
(2) drying the material with the particle size of less than 2mm in the obtained product until the water content is less than 2%, preferably drying by adopting airflow at 100-105 ℃;
(3) grinding the obtained product, sieving the product with a sieve of 150-200 meshes (for example, ball milling can be adopted), and calcining the product at the temperature of 500-700 ℃ for 1-2h (for example, electric furnace calcination can be preferably adopted, so that the method is energy-saving and practical), thereby obtaining the activated steel slag powder.
The phosphate activated bone meal is prepared by the following method:
(1) preparing 0.01-0.05mol/L phosphate solution (the phosphate is preferably monopotassium phosphate, the water solution is acidic, and the activating effect on steel slag is better), grinding the bone powder through a 150-200-mesh sieve to obtain ground bone powder;
(2) mixing the ground bone powder and aluminum sulfate according to the mass ratio of 20-30:1 to obtain a ground bone powder mixture;
(3) mixing the obtained ground bone meal mixture and phosphate solution according to the weight ratio of 1: mixing at a ratio of 10-15, stirring at 20-30 deg.C for 10-15 hr, standing for 36-48 hr to obtain gel precipitate;
(4) drying the gel-like precipitate by airflow at the temperature of 100-250 ℃ until the water content is less than 2%, grinding the obtained product and sieving the product by a sieve of 150-200 meshes to obtain the phosphate activated bone powder, wherein, for example, the airflow drying can be adopted quickly, the medicament is not easy to agglomerate, and the subsequent medicament production is convenient.
The bone meal is steamed bone meal obtained by a bone steaming method.
The steamed bone meal is prepared by the following method: crushing the dried animal bones into blocks smaller than 5cm, steaming for 24h at the temperature of 115-130 ℃, drying at the temperature of 60-80 ℃ until the quality is constant, calcining for 0.5-1h at the temperature of 140-160 ℃, cooling, grinding and sieving with a 150-200-mesh sieve.
The dried animal bone is one or more of pig bone, ox bone or fishbone, and the steamed animal bone has a calcium content of more than 30% and a phosphorus content of more than 14%.
The preparation method of the curing agent for the composite heavy metal contaminated soil comprises the following steps: mixing the steel slag powder, the light burned magnesium oxide and the phosphate activated bone powder according to the weight percentage, stirring for 0.5-1h by a dry method until the mixture is uniform, and then sieving by a sieve with 200 meshes of 150 meshes to obtain the curing agent.
The application method of the curing agent for the composite heavy metal contaminated soil comprises the following steps: and mixing and stirring the curing agent and the heavy metal polluted soil, wherein the dosage of the curing agent is 5-15% of the dry weight of the heavy metal polluted soil, and the water content of the heavy metal polluted soil is 16-30%.
The content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 65-100%, wherein the content of heavy metal lead is more than 2000mg/kg, the content of heavy metal zinc is more than 2000mg/kg, the content of heavy metal copper is more than 2000mg/kg, and the content of heavy metal nickel is more than 2000 mg/kg.
Has the advantages that: compared with the prior art, the invention has the remarkable advantages that:
(1) the heavy metal curing effect is good. Firstly, the bone meal activation process involved in the invention can improve the surface morphological characteristics of the bone meal and the dissolution amount of available phosphorus, and effectively increase the adsorption and precipitation effects of the bone meal on heavy metal ions; secondly, the potential gelling property of the steel slag powder is shown under the excitation action of magnesium oxide, so that the phosphate precipitation and hydroxide precipitation of heavy metals are effectively wrapped, and the solidification and stabilization effects of the heavy metals by simply using phosphate are greatly enhanced; thirdly, the calcium oxide dissolved from the steel slag is hydrated to generate Ca (OH)2And acid substances in the polluted soil are neutralized through acid-base reaction.
(2) The durability is good. The traditional curing agent is easily affected by carbon dioxide erosion and acid rain erosion, and the phenomena of degradation and attenuation of environmental safety and engineering characteristics of the cured polluted soil are generated. The curing agent can effectively overcome the defects, the generated heavy metal phosphate precipitates have low solubility in various pH environments, and the contact between the heavy metal precipitates and an acidic solution can be effectively reduced under the wrapping effect of a hydration product C-S-H gel of the steel slag; meanwhile, the steel slag has strong acid buffer capacity and carbon dioxide absorption capacity, and CaCO is generated under the action of carbon dioxide erosion3The crystal further fills the pores of the solidified body, so that the infiltration amount of the acid solution is effectively reduced, and the stability of the solidified body in a severe environment is further improved.
(3) Effectively utilizes waste raw materials and is an environment-friendly curing agent. Firstly, the steel slag is used as industrial waste slag and is piled in a large area, so that serious environmental pollution is caused, the utilization value of the steel slag is effectively improved through the activation of the steel slag, and waste materials are changed into valuable materials. Secondly, the steel slag is used as a high-alkalinity material and directly used for solidification and stabilization of heavy metal polluted soil, the pH value of the solidified soil is high, a plurality of problems can be brought to later development and utilization of land, the pH value of the solidified soil is effectively reduced by adding activated bone meal, and the solidification and stabilization effect of the steel slag on heavy metals is optimal by adding potassium dihydrogen phosphate. And thirdly, the livestock bone is also industrial waste residue, and can excite the steel slag after steaming, calcining and activating treatment, so that the hydration activity of the steel slag and the solidification and stabilization effects on heavy metals are increased.
Detailed Description
Example 1
The invention relates to a curing agent for composite heavy metal polluted soil, which consists of the following materials in parts by mass: 45% of steel slag powder; light-burned magnesia accounting for 20 percent; 35% of phosphate activated bone meal.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the converter slag, and then crushing and sieving; placing the material with the particle size of less than 2mm in an oven to dry the material by adopting airflow at the temperature of 105 ℃ until the water content of the material is 1%; grinding the obtained product, sieving the ground product by a 200-mesh sieve, and calcining the product for 2 hours in an electric furnace at 700 ℃. The basicity value of the steel slag powder is 2.07.
The main components and contents of the steel slag are shown in table 1, and it should be noted that the steel slag used in the present invention is not limited to the data in table 1, and is only the steel slag used in the present embodiment:
TABLE 1 Steel slag main component and content
| Main chemical composition | CaO | SiO2 | Al2O3 | Fe2O3 | MgO | P2O5 |
| Content (%) | 36.30 | 16.26 | 3.32 | 18.66 | 8.35 | 1.26 |
The phosphate activated bone meal is prepared by the following method: preparing 0.05mol/L potassium dihydrogen phosphate solution, grinding the bone powder, and sieving with a 200-mesh sieve to obtain ground bone powder; fully mixing the ground bone powder and aluminum sulfate according to the mass ratio of 30:1 to obtain a ground bone powder mixture; and (3) mixing the obtained mixture with a potassium dihydrogen phosphate solution according to a solid-to-liquid ratio of 1: 12, oscillating and stirring for 15 hours at 25 ℃, and standing for 48 hours to obtain a gelatinous precipitate; drying the gelatinous precipitate by airflow at 200 ℃ until the water content is 1%, grinding the obtained product and sieving by a 200-mesh sieve to obtain the activated bone powder loaded with potassium dihydrogen phosphate.
The bone meal is steamed bone meal obtained by a bone steaming method.
The steamed bone meal is prepared by the following method: crushing dried animal bones into blocks smaller than 3cm, steaming at 130 deg.C for 24 hr, oven drying at 80 deg.C until the mass is constant, calcining at 160 deg.C for 1 hr, cooling, grinding, and sieving with 200 mesh sieve.
The dried animal bone is ox bone, and the steamed animal bone has calcium content of 32.2% and phosphorus content of 14.7%.
The light-burned magnesium oxide comprises the following components in percentage by weight: MgO: 88.24% of SiO2: 4.70%, CaO: 4.63% and the bulk density is 3.18g/cm3。
The curing agent for the composite heavy metal polluted soil is prepared by the following steps: mixing the steel slag powder, the light burned magnesium oxide and the phosphate activated bone powder in parts by mass, stirring for 1 hour by a dry method until the mixture is uniform, and then sieving by a 200-mesh sieve to obtain the curing agent.
The application method of the curing agent for the composite heavy metal polluted soil comprises the following steps: and (3) mixing and stirring the curing agent and the heavy metal polluted soil in situ, wherein the dosage of the curing agent is 5% of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil). There are two types of heavy metal contaminants: the polluted soil a is lead and zinc composite polluted soil taken from an industrial polluted site; and the polluted soil b is copper and nickel composite polluted soil taken from two industrial polluted sites. Other major physicochemical properties are shown in table 2.
TABLE 2 main physicochemical Properties of contaminated soil
Example 2
The same procedure as in example 1 was repeated except that the amount of the curing agent was 10% (dry weight of the heavy metal and organic compound contaminated soil).
Example 3
The same procedure as in example 1 was repeated except that 15% of the curing agent was added (based on the dry weight of the soil contaminated with heavy metals and organic compounds).
Comparative example 4
No curing agent is added, and only the soil sample polluted by the compound heavy metal in the example 1 is taken.
Comparative example 5
The steel slag in the example 1 is used for preparing the curing agent without activation, other preparation steps are not changed, and the mixing amount is 15 percent as in the example 3.
Example 4
The invention relates to a curing agent for composite heavy metal polluted soil, which consists of the following materials in parts by mass: 40% of steel slag powder; 25% of light-burned magnesium oxide; 35% of phosphate activated bone meal.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the converter slag, and then crushing and sieving; placing the material with the particle size of less than 2mm in an oven, and drying the material by adopting airflow at the temperature of 105 ℃ until the water content of the material is 0.5%; grinding the obtained product, sieving the ground product by a sieve with 150 meshes, and calcining the product for 1h by an electric furnace at 500 ℃. The basicity value of the steel slag powder is 2.6.
The phosphate activated bone meal is prepared by the following method: preparing 0.01mol/L potassium dihydrogen phosphate solution, and grinding the bone powder and sieving with a 150-mesh sieve to obtain ground bone powder; fully mixing the ground bone powder and aluminum sulfate according to the mass ratio of 20:1 to obtain a ground bone powder mixture; and (3) mixing the obtained mixture with a potassium dihydrogen phosphate solution according to a solid-to-liquid ratio of 1: 10, oscillating and stirring for 10 hours at the temperature of 20 ℃, and standing for 36 hours to obtain a gelatinous precipitate; drying the gelatinous precipitate by adopting airflow at 250 ℃ until the water content is 0.5%, grinding the obtained product and sieving the ground product by a 150-mesh sieve to obtain the activated bone powder loaded with the monopotassium phosphate.
The bone meal is steamed bone meal obtained by a bone steaming method.
The steamed bone meal is prepared by the following method: crushing dried animal bones into blocks smaller than 5cm, steaming at 115 deg.C for 24 hr, oven drying at 60 deg.C until the mass is constant, calcining at 140 deg.C for 0.5 hr, cooling, grinding, and sieving with 150 mesh sieve.
The dried animal bone is pig bone, and the steamed animal bone has a calcium content of 31.1% and a phosphorus content of 14.1%.
The light-burned magnesium oxide comprises the following components in percentage by weight: MgO: 88.24% of SiO2: 4.70%, CaO: 4.63% and the bulk density is 3.18g/cm3。
The curing agent for the composite heavy metal polluted soil is prepared by the following steps: mixing the steel slag powder, the light burned magnesium oxide and the phosphate activated bone powder in parts by mass, stirring for 0.5h by a dry method until the mixture is uniform, and then sieving by a 150-mesh sieve to obtain the curing agent.
The application method of the curing agent for the composite heavy metal polluted soil comprises the following steps: and (2) mixing and stirring a curing agent and the heavy metal polluted soil in situ, wherein the dosage of the curing agent is 5% of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), the water content of the heavy metal polluted soil is 16%, the heavy metal polluted soil is the same as the polluted soil selected in the embodiment 1, and the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 65%.
Example 5
The invention relates to a curing agent for composite heavy metal polluted soil, which consists of the following materials in parts by mass: 40% of steel slag powder; 15% of light-burned magnesium oxide; 45% of phosphate activated bone meal.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the converter slag, and then crushing and sieving; placing the material with the particle size of less than 2mm in an oven, and drying the material by adopting airflow at the temperature of 105 ℃ until the water content of the material is 1.5%; grinding the obtained product, sieving the ground product by a 180-mesh sieve, and calcining the product for 1.5 hours at 600 ℃ by an electric furnace. The basicity value of the steel slag powder is 1.8.
The phosphate activated bone meal is prepared by the following method: preparing 0.03mol/L potassium dihydrogen phosphate solution, grinding the bone powder, and sieving with 170 mesh sieve to obtain ground bone powder; fully mixing the ground bone powder and aluminum sulfate according to the mass ratio of 25:1 to obtain a ground bone powder mixture; and (3) mixing the obtained mixture with a potassium dihydrogen phosphate solution according to a solid-to-liquid ratio of 1: 15, stirring the mixture for 12 hours at the temperature of 30 ℃, and standing the mixture for 42 hours to obtain a gelatinous precipitate; drying the gelatinous precipitate by adopting airflow at 100 ℃ until the water content is 1.5%, grinding the obtained product and sieving the ground product by a 170-mesh sieve to obtain the activated bone powder loaded with the monopotassium phosphate.
The bone meal is steamed bone meal obtained by a bone steaming method.
The steamed bone meal is prepared by the following method: crushing dried animal bones into blocks smaller than 4cm, steaming at 125 deg.C for 24 hr, oven drying at 70 deg.C until the mass is constant, calcining at 150 deg.C for 0.75 hr, cooling, grinding, and sieving with 170 mesh sieve.
The dried animal bone is fishbone, and the steamed animal bone has a calcium content of 32.1% and a phosphorus content of 14.9%.
The light-burned magnesium oxide comprises the following components in percentage by weight: MgO: 88.24% of SiO2: 4.70%, CaO: 4.63% and the bulk density is 3.18g/cm3。。
The curing agent for the composite heavy metal polluted soil is prepared by the following steps: mixing the steel slag powder, the light-burned magnesia powder and the phosphate activated bone powder in parts by mass, stirring for 0.75h by a dry method until the mixture is uniformly mixed, and sieving by a 170-mesh sieve.
The application method of the curing agent for the composite heavy metal polluted soil comprises the following steps: and (2) mixing and stirring a curing agent and the heavy metal polluted soil in situ, wherein the dosage of the curing agent is 10% of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), the water content of the heavy metal polluted soil is 23%, the heavy metal polluted soil is the same as the polluted soil selected in the embodiment 1, and the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 82.5%.
Example 6
The invention relates to a curing agent for composite heavy metal polluted soil, which consists of the following materials in parts by mass: 65% of steel slag powder; light-burned magnesia 5 percent; 30% of phosphate activated bone meal.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the converter slag, and then crushing and sieving; placing the material with the particle size of less than 2mm in an oven, and drying the material by adopting airflow at the temperature of 105 ℃ until the water content of the material is 0.5%; grinding the obtained product, sieving the ground product by a sieve with 150 meshes, and calcining the product for 1h by an electric furnace at 500 ℃. The basicity value of the steel slag powder is 2.2.
The phosphate activated bone meal is prepared by the following method: preparing a potassium dihydrogen phosphate solution with the concentration of 0.04mol/L, and grinding the bone powder and sieving the bone powder by a 190-mesh sieve to obtain ground bone powder; fully mixing the ground bone powder and aluminum sulfate according to the mass ratio of 20:1 to obtain a ground bone powder mixture; and (3) mixing the obtained mixture with a potassium dihydrogen phosphate solution according to a solid-to-liquid ratio of 1: 10, oscillating and stirring for 10 hours at the temperature of 20 ℃, and standing for 40 hours to obtain a gelatinous precipitate; drying the gelatinous precipitate by adopting 150 ℃ airflow until the water content is 0.5%, grinding the obtained product and sieving the ground product by a 190-mesh sieve to obtain the activated bone powder loaded with the monopotassium phosphate.
The bone meal is steamed bone meal obtained by a bone steaming method.
The steamed bone meal is prepared by the following method: crushing dried animal bones into blocks smaller than 3cm, steaming at 120 deg.C for 24 hr, oven drying at 60 deg.C until the mass is constant, calcining at 140 deg.C for 0.5 hr, cooling, grinding, and sieving with 190 mesh sieve.
The dried animal bone is prepared by mixing pig bone and ox bone, steaming to obtain mixture with calcium content of 32.1% and phosphorus content of 14.2%.
The light-burned magnesium oxide comprises the following components in percentage by weight: MgO: 88.24% of SiO2: 4.70%, CaO: 4.63% and the bulk density is 3.18g/cm3。
The curing agent for the composite heavy metal polluted soil is prepared by the following steps: mixing the steel slag powder, the light burned magnesium oxide and the phosphate activated bone powder in parts by mass, stirring for 0.75h by a dry method until the mixture is uniform, and then sieving by a 190-mesh sieve to obtain the curing agent.
The application method of the curing agent for the composite heavy metal polluted soil comprises the following steps: mixing and stirring the curing agent and the heavy metal polluted soil in situ. Wherein the dosage of the curing agent is 15 percent of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), and the water content of the heavy metal polluted soil is 30 percent. The content of particles with the particle size of less than 0.075mm in the used heavy metal contaminated soil is 83%, the heavy metal contaminated soil is the same as the contaminated soil selected in the embodiment 1, and the content of the particles with the particle size of less than 0.075mm in the heavy metal contaminated soil is 100%.
Example 7
The invention relates to a curing agent for composite heavy metal polluted soil, which consists of the following materials in parts by mass: 60% of steel slag powder; light-burned magnesia accounting for 20 percent; 20% of phosphate activated bone meal.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the converter slag, and then crushing and sieving; placing the material with the particle size of less than 2mm in an oven, and drying the material by adopting airflow at the temperature of 105 ℃ until the water content of the material is 0.5%; grinding the obtained product, sieving the ground product by a sieve with 150 meshes, and calcining the product for 1h by an electric furnace at 500 ℃. The basicity value of the steel slag powder is 2.4.
The phosphate activated bone meal is prepared by the following method: preparing 0.01mol/L potassium dihydrogen phosphate solution, grinding the bone powder, and sieving with 200 mesh sieve to obtain ground bone powder; fully mixing the ground bone powder and aluminum sulfate according to the mass ratio of 20:1 to obtain a ground bone powder mixture; and (3) mixing the obtained mixture with a potassium dihydrogen phosphate solution according to a solid-to-liquid ratio of 1: 10, oscillating and stirring for 10 hours at the temperature of 20 ℃, and standing for 36 hours to obtain a gelatinous precipitate; drying the gelatinous precipitate by adopting airflow at 250 ℃ until the water content is 0.5%, grinding the obtained product and sieving the ground product by a 200-mesh sieve to obtain the activated bone powder loaded with the monopotassium phosphate.
The bone meal is steamed bone meal obtained by a bone steaming method.
The steamed bone meal is prepared by the following method: crushing dried animal bones into blocks smaller than 5cm, steaming at 115 deg.C for 24 hr, oven drying at 60 deg.C until the mass is constant, calcining at 140 deg.C for 0.5 hr, cooling, grinding, and sieving with 200 mesh sieve.
The dried animal bone is pig bone, and the steamed animal bone has a calcium content of 31.9% and a phosphorus content of 15.1%.
The light-burned magnesium oxide comprises the following components in percentage by weight: MgO: 88.24% of SiO2: 4.70%, CaO: 4.63% and the bulk density is 3.18g/cm3。
The curing agent for the composite heavy metal polluted soil is prepared by the following steps: mixing the steel slag powder, the light burned magnesium oxide and the phosphate activated bone powder in parts by mass, stirring for 0.75h by a dry method until the mixture is uniform, and sieving by a 200-mesh sieve.
The application method of the curing agent for the composite heavy metal polluted soil comprises the following steps: and (2) mixing and stirring a curing agent and the heavy metal polluted soil in situ, wherein the dosage of the curing agent is 8% of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), the water content of the heavy metal polluted soil is 25%, the heavy metal polluted soil is the same as the polluted soil selected in the embodiment 1, and the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 90%.
Example 8
The toxicity leaching test was carried out on the solidified contaminated soil after the sample soil in example 1, example 2, example 3, comparative example 1, comparative example 2, example 4, example 5, example 6 and example 7 was wrapped and sealed with a freshness protection package and cured for 28 days at 20 ℃ and a humidity of more than 95%:
test standards: the national environmental protection industry Standard sulfuric acid-nitric acid method for leaching toxicity of solid wastes (HJ/T299-2007).
The test process comprises the following steps: weighing 50g of the cured solidified polluted soil, drying at 105 ℃, and calculating to obtain the water content of the sample, wherein the error of the constant weight to the two weighing values is less than +/-1%. The dry weight of the remediation soil is calculated according to the water content, a remediation soil sample with the dry basis weight of 10g is weighed, and the test is carried out according to the method and the steps specified in the solid waste leaching toxicity leaching method, namely the sulfuric acid-nitric method (HJ/T299-2007). The test results are shown in table 3.
TABLE 3 toxicity Leaching test results (mg/L)
The sulfuric acid-nitric acid leaching method is used as a standard for evaluating whether solid waste is dangerous waste or not, and is a common method for analyzing the leaching toxicity characteristics of pollutants of the solid waste under the action of acid rainfall. From the toxicity leaching test results of Table 3, it can be seen by comparing examples 1-7: according to the remediation soil doped with the curing agent, the leaching concentrations of Zn, Pb, Ni and Cu in the leaching solution are reduced along with the increase of the doping amount of the curing agent, the comparative example 1 shows that the heavy metal migration in untreated source polluted soil is extremely strong, the leaching amounts of the heavy metals of Zn, Pb, Ni and Cu are far higher than the limit value in hazardous waste identification standard leaching toxicity identification (GB5085.3-2007), and the addition of the curing agent can be found to remarkably reduce the leaching amount of the heavy metals and increase the environmental safety by combining with the examples 1-7. As is clear from comparison between example 3 and comparative example 2, the stability of heavy metals was improved and the stabilizing effect in example 3 was more remarkable after curing for 28 days with the curing agent of the present invention added, the leaching amount is far lower than the limit value in the standard leaching toxicity identification of hazardous waste (GB5085.3-2007), whereas the steel slag powder in the curing agent of comparative example 2 was formulated only from phosphate-loaded biochar without activation, which can reduce the migration characteristics of heavy metals Zn, Pb, Ni and Cu in soil to a certain extent, reduce the harm to the environmental safety and still meet the basic requirements of the invention, therefore, the steel slag is activated and modified, so that the solidification stabilizing effect of the solidifying agent on heavy metals can be effectively enhanced, if the steel slag is not subjected to activation treatment, the technical effect of the invention can be realized to a certain extent.
Example 9
The soil conditioner ph test was performed on the solidified contaminated soil after the curing in examples 1, 2, 3, 1, 2, 4, 5, 6 and 7 by the method of example 8:
test standards: method 4972-01 for pH of soil.
The test process comprises the following steps: weighing 50g of the cured solidified polluted soil, drying at 105 ℃, and calculating to obtain the water content of the sample, wherein the error of the constant weight to the two weighing values is less than +/-1%. And calculating the dry weight of the remediation soil according to the water content, sieving the remediation soil by using a 1mm sieve, weighing a remediation soil sample with the dry basis weight of 10g, stirring and mixing the remediation soil sample with 10g of distilled water, standing the mixture for 1h, and then testing the pH value of the solution. The test results are shown in table 4.
TABLE 4 PH value test results
The pH value of the solidified soil body is an important index for evaluating the effect of the solidifying agent for solidifying the heavy metal, and has great influence on the development mode and the degree of secondary utilization of the repair field. From the test results of the pH value in the table 4, as can be seen from the comparison between the examples 1 to 3 and the comparative example 1, after the curing agent is added, the pH value of the cured soil is significantly increased, after 28 days of curing, the pH value of the contaminated soil is between 6 and 9 and is close to neutral, which is beneficial to the utilization of a repair site, meanwhile, the pH value of the cured soil in the examples 4 to 7 is also significantly increased, and after 28 days of curing, the pH value of the contaminated soil is also between 6 and 9 and is close to neutral; compared with the example 3, the comparative example 2 has slightly higher pH value because the steel slag is not subjected to the activation treatment, but can basically realize the technical scheme of the invention, and if the pH value is continuously increased, a plurality of problems are brought to the later development and utilization of the land.
By comparing comparative example 1 and comparative example 2, it can be found that the potassium dihydrogen phosphate activated bone meal can neutralize part of OH dissolved from the steel slag-The pH value of the solidified body is favorably reduced, so that the solidified body tends to be neutral; further, in comparison with Table 3, it was found that a moderate decrease in the pH of the cured body is also advantageous for the fixation of heavy metals.
Example 10
Unconfined compressive strength test
Test standards: highway soil engineering test regulation JTG E40-2007.
The test process comprises the following steps: the strain control type YS H-2 unconfined compressive strength meter is adopted for carrying out the strain control type unconfined compressive strength meter, and the axial strain rate is 1%/min. And (3) testing the unconfined compressive strength of the solidified soil at the corresponding curing age, and averaging 3 parallel samples. The test results are shown in table 5.
TABLE 5 unconfined compressive strength test results (kPa)
| Soil sample | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Example 4 | Example 5 | Example 6 | Example 7 |
| a | 132.4 | 209.6 | 293.4 | 75.3 | 169.7 | 132.1 | 207.8 | 288.9 | 198.9 |
| b | 123.6 | 200.1 | 289.3 | 91.2 | 201.8 | 122.8 | 199.1 | 298.2 | 188.1 |
As can be seen from Table 5: the strength of examples 1 to 7 and comparative example 2 was significantly increased compared to that of the plain soil, and increased as the amount of the curing agent added was increased. As can be seen from comparison between example 3 and comparative example 2, the steel slag after activation has a significant strength advantage, and the strength advantage is also an important factor affecting the leaching amount of heavy metal toxicity.
Example 11
Phytotoxicity tests (seed germination rate tests) were performed on contaminated soils maintained in examples 1, 2, 3, 1, 2, 4, 5, 6 and 7 in the same manner as in example 8:
the test process comprises the following steps: the germination rate test of the seeds adopts soybeans which are sensitive to the content of heavy metal pollutants in soil, and the germination rate of the soybeans is used as an ecological index for carrying out toxicity analysis on the soil with heavy metal and organic compound pollution, so that the method is a commonly used important method for measuring the soil environment quality and the soil pollution from the ecological toxicology perspective. Firstly, the plain soil and the repair soil after 28 days of maintenance are naturally air-dried and sieved by a 2mm sieve for later use. Taking 4kg of soil (plain soil or each repair soil) for each sample, potting (the diameter of the upper opening is 25cm, the diameter of the bottom is 20cm, the height is 20cm), and the ridging height is 18 cm; the soil in the pot is thoroughly watered with distilled water until the water retention rate is 60 percent, and then the water retention rate is kept unchanged and the soil is soaked and placed indoors for 2 days; finally, soybean is sown, the soybean is sown at the depth of about 0.3cm, and 100 grains are sown in each pot; after sowing, the proper soil humidity is maintained by regularly spraying, so that the seeds germinate in the indoor sunny place at the room temperature of 18-22 ℃ under the condition of natural lighting. The germination rate (number of germinated seeds/number of test seeds) × 100%. The test results are shown in table 6.
Table 6 seed germination (%)
The seed germination rate test can reflect the toxic action of the soil to plants. As can be seen from table 6: the heavy metal content in the plain soil (comparative example 1, namely the polluted soil without the curing agent) is very high, the germination rate of the seeds is seriously influenced, and the germination rates of the soybean seeds in the polluted soil are only 9% and 12%. The curing agent in the comparative example 2 improves the germination rate to a certain extent, but the improvement range is limited, and the germination rate can only reach 60 percent and 68 percent, which shows that the curing agent prepared by using the unactivated steel slag powder has a certain stabilizing effect on heavy metals in the polluted soil and has limited effect at that time; in contrast, the germination rates of the seeds of the firming agent restoring soil in the examples 1 to 7 of the invention are more than 87% and even up to 99% under the condition of various mixing amounts. The differences of the examples 1, 2 and 3 and the comparative example 1 show that the curing agent disclosed by the invention is ecological and friendly in repairing the composite heavy metal contaminated soil, and is beneficial to the development and growth of plants and microorganisms around the repaired site, and the comparison of the example 3 and the comparative example 2 shows that the activating treatment on the steel slag can also effectively reduce the toxic action of the soil on the plants, so that the curing stability of the curing agent on the heavy metals is reflected from the side surface.
Claims (8)
1. The curing agent for the composite heavy metal polluted soil is characterized by comprising the following components in parts by weight: the material composition comprises the following materials in percentage by mass: 40-65% of steel slag powder; light-burned magnesia 5-25%; 20-45% of phosphate activated bone meal;
the phosphate activated bone meal is prepared by the following method:
(1) preparing phosphate solution with the concentration of 0.01-0.05mol/L, grinding the bone powder through a sieve of 150-200 meshes to obtain ground bone powder;
(2) mixing the ground bone powder and aluminum sulfate according to the mass ratio of 20-30:1 to obtain a ground bone powder mixture;
(3) and mixing the obtained ground bone meal mixture and a phosphate solution according to a solid-to-liquid ratio of 1: mixing at a ratio of 10-15, stirring at 20-30 deg.C for 10-15 hr, standing for 36-48 hr to obtain gel precipitate;
(4) drying the gelatinous precipitate by adopting 100-250 ℃ airflow until the water content is less than 2%, grinding the obtained product and sieving the ground product by a 150-200 mesh sieve to obtain the phosphate activated bone powder.
2. The curing agent for soil polluted with heavy metals according to claim 1, wherein: the steel slag powder is activated steel slag powder and is prepared by the following method:
(1) one or more of the converter slag, the open hearth furnace slag and the electric furnace oxidation slag after magnetic separation are crushed and sieved;
(2) drying the material with the particle size of less than 2mm in the obtained product until the water content is less than 2%;
(3) grinding the obtained product, sieving the product by a sieve with 150-200 meshes, and calcining the product for 1-2h at the temperature of 500-700 ℃ to obtain the activated steel slag powder.
3. The curing agent for soil polluted with heavy metals according to claim 1, wherein: the bone meal is steamed bone meal obtained by a bone steaming method.
4. The curing agent for soil polluted with heavy metals according to claim 3, wherein: the steamed bone meal is prepared by the following method: crushing the dried animal bones into blocks smaller than 5cm, steaming for 24h at the temperature of 115-130 ℃, drying at the temperature of 60-80 ℃ until the quality is constant, calcining for 0.5-1h at the temperature of 140-160 ℃, cooling, grinding and sieving with a 150-200-mesh sieve.
5. The curing agent for soil polluted with heavy metals according to claim 4, wherein: the dried animal bone is one or more of pig bone, ox bone or fishbone, and the steamed animal bone has a calcium content of more than 30% and a phosphorus content of more than 14%.
6. The method for preparing the curing agent for soil polluted by complex heavy metals according to claim 1, characterized by comprising the steps of: mixing the steel slag powder, the light burned magnesium oxide and the phosphate activated bone powder according to the weight percentage, stirring for 0.5-1h by a dry method until the mixture is uniform, and then sieving by a sieve with 200 meshes of 150 meshes to obtain the curing agent.
7. The method for applying the curing agent for soil polluted by composite heavy metals according to claim 1, wherein the curing agent comprises the following components: and mixing and stirring the curing agent and the heavy metal polluted soil, wherein the dosage of the curing agent is 5-15% of the dry weight of the heavy metal polluted soil, and the water content of the heavy metal polluted soil is 16-30%.
8. The application method of the curing agent for soil polluted by heavy metals according to claim 7, wherein: the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 65-100%, wherein the content of heavy metal lead is more than 2000mg/kg, the content of heavy metal zinc is more than 2000mg/kg, the content of heavy metal copper is more than 2000mg/kg, and the content of heavy metal nickel is more than 2000 mg/kg.
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