CN114918244B - Chromium-polluted muck stabilization curing agent and preparation method and application thereof - Google Patents
Chromium-polluted muck stabilization curing agent and preparation method and application thereof Download PDFInfo
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- CN114918244B CN114918244B CN202210539038.0A CN202210539038A CN114918244B CN 114918244 B CN114918244 B CN 114918244B CN 202210539038 A CN202210539038 A CN 202210539038A CN 114918244 B CN114918244 B CN 114918244B
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- 230000006641 stabilisation Effects 0.000 title claims abstract description 28
- 238000011105 stabilization Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002689 soil Substances 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- 239000002893 slag Substances 0.000 claims abstract description 46
- 239000004113 Sepiolite Substances 0.000 claims abstract description 45
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 45
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 45
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims abstract description 7
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 6
- 239000000378 calcium silicate Substances 0.000 claims abstract description 5
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 5
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 5
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims abstract description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims abstract description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims description 34
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 29
- 229910052804 chromium Inorganic materials 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000012216 screening Methods 0.000 description 14
- 239000003814 drug Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- 238000005070 sampling Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002920 hazardous waste 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
- 238000001556 precipitation Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- -1 Cr (VI) Chemical compound 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a chromium-polluted muck stabilization curing agent, a preparation method and application thereof, wherein the agent comprises the following raw materials in percentage by mass: 40-60% of reducing agent, 20-40% of adsorbent and 10-30% of regulator, wherein the adsorbent is modified sepiolite, the reducing agent is one or more of ferrous sulfate, ferrous chloride, reduced iron powder, sodium sulfide and sodium dithionite, and the regulator is one or more of calcium oxalate, calcium silicate and potassium phosphate. The stabilizing and curing agent can be mixed with chromium-polluted slag soil, water is sprayed and stirred in the mixing process, and stabilizing and curing are realized after curing. The chromium-polluted muck stabilizing and curing agent has reasonable formula and low cost, has good applicability to chromium-polluted soil with different pollution degrees, particularly has excellent treatment effect on muck with water content of 15-25%, and has long-term stability.
Description
Technical Field
The invention belongs to the technical field of heavy metal contaminated soil treatment, and particularly relates to a chromium-contaminated slag soil stabilization and solidification agent, and a preparation method and application thereof.
Background
Soil is an important resource for human beings and has an irreplaceable role in the production and life of people. However, with the rapid development of industry and economy, heavy metal soil pollution is increasingly severe, wherein chromium compounds are widely used in various industries such as metal plating, electronics, tanning, metallurgy, wood protection, etc., and chromium, particularly Cr (VI), is introduced into the soil due to improper stocking of chromium-containing waste and improper discharge of chromium-containing wastewater, causing pollution. Therefore, solving the problem of Cr (VI) contamination in the soil has become a focus of attention for environmental workers.
Hexavalent chromium in soil is mainly CrO 4 2- And HCrO 4 - In recent years, the demand for treating Cr (VI) pollution in soil in China is urgentThe stabilized curing is used as an economic, efficient, green and environment-friendly repairing technology, which is widely accepted and applied at home and abroad. The soil contaminated with chromium is mixed with a binder by which the chromium is immobilized so that the chromium no longer migrates to the surrounding environment.
The traditional stabilizing and curing technology mainly adopts one or more than two substances of lime, slaked lime, carbonate, phosphate, sulfide, curing agent and the like to mix, so that metal ions are passivated in the form of hydroxide, sulfide or phosphate and adsorbed at the same time. However, the conventional stabilization curing technology has the disadvantages of great treatment effect, poor long-acting performance of harmless stability, difficult control of the addition amount of the medicament and the like because the medicament is greatly influenced by the environment. In addition, in order to achieve the long-term stabilization effect, cement and silica are usually added as curing agents, but the curing agents cause the alkalinity of heavy metals to be treated to be increased during the curing treatment, harmful heavy metals which cause the stabilization curing treatment are dissolved out again, and the mixture is more compatibilized.
At present, the technology of disposing chromium-polluted soil by calcium polysulfide (liquid state) is relatively mature, but related data (such as principle and application of calcium polysulfide to repair Cr (VI) polluted soil, seventeenth period of environmental engineering, 7 months in 2018) show that when the leaching concentration of chromium and hexavalent chromium is 78.6mg/L and 73.8mg/L, the disposal effect of calcium polysulfide on chromium and hexavalent chromium cannot reach below 1mg/L when the adding amount of calcium polysulfide is 10%, meanwhile, the calcium polysulfide is mostly liquid state, the water content of soil is increased, the maintenance time is prolonged, and the yield of percolate is increased after entering a landfill site.
Therefore, it is necessary to develop a stabilized curing agent with low cost, good repairing effect and small capacity, so as to be beneficial to reducing engineering cost.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a medicament for stabilizing and solidifying a chromium-polluted slag soil mixture and a repairing method. The invention adds the medicament into the chromium-polluted soil according to a certain proportion according to the pollution degree, and the medicament has synergistic effects of adsorption, oxidation reduction, precipitation and the likeHexavalent chromium is caused to promote the formation of Cr (OH) under relatively alkaline environmental conditions 3 The precipitation can prevent the migration and diffusion of the environment and reduce the toxic action of hexavalent chromium in the environment.
In order to solve the technical problems, the invention adopts the following technical scheme.
The chromium-polluted muck stabilization curing agent comprises the following raw materials in percentage by mass: 40-60% of reducing agent, 20-40% of adsorbent, 10-30% of regulator, and 100% of sum of mass fractions of raw materials;
the adsorbent is modified sepiolite, and the preparation of the modified sepiolite comprises the following steps: heating sepiolite to 100-300 ℃ for roasting to remove water molecules in pore canals, then ball-milling to solid powder with the particle size of 2-5mm, and carrying out acid treatment to obtain modified sepiolite;
the reducing agent is one or more of ferrous sulfate, ferrous chloride, reduced iron powder, sodium sulfide and sodium dithionite; the regulator is one or more of calcium oxalate, calcium silicate and potassium phosphate.
In the chromium-contaminated muck stabilizing and curing agent, the acid is preferably hydrochloric acid, and the volume fraction of the hydrochloric acid is 2% -6%.
The invention also provides a preparation method of the chromium-polluted muck stabilization curing agent, which comprises the following steps of: and fully mixing the reducing agent, the adsorbent and the regulator to obtain the chromium-polluted slag soil stabilization curing agent.
As a general technical conception, the invention also provides an application of the chromium-polluted slag soil stabilization and curing agent or the chromium-polluted slag soil stabilization and curing agent prepared by the preparation method in stabilizing and curing chromium-polluted slag soil.
The above application, preferably, comprises the steps of: mixing the chromium-polluted muck stabilizing and curing agent with the pretreated chromium-polluted muck, wherein the mass of the chromium-polluted muck stabilizing and curing agent accounts for 5-10% of the mass of the chromium-polluted muck, spraying and stirring water in the mixing process, controlling the water content of the chromium-polluted muck to be 15-25%, and curing to realize stabilizing and curing.
In the above application, preferably, the stirring time is 1 h-1.5 h, and the curing time is 5 days-6 days.
For the above application, the pretreatment preferably comprises crushing and sieving chromium-contaminated muck, and controlling the particle size of the muck to be within 10 cm.
The invention transports the residue soil treated by the stirring equipment of the curing machine to a landfill site for curing, thereby ensuring that the medicament in the soil can fully react with pollutants.
The invention carries out leaching toxicity detection after fully stirring reaction with the dregs and curing for 5 days, and the concentration of the leaching liquid is far lower than the pollution control standard of hazardous waste landfill (GB 18598-2019).
Compared with the prior art, the invention has the advantages that:
1. the chromium-polluted slag soil stabilization curing agent is gray powder, has reasonable formula, wide sources and low cost, and has good applicability to chromium-polluted soil with different pollution degrees. The method for preparing the modified sepiolite can effectively remove water molecules in the sepiolite pore canal, so that a cavity with large inner surface area is formed, macromolecules can be adsorbed and stored, meanwhile, the cross section of a crystal internal channel is enlarged, adsorbed molecules are easier to enter, the adsorption and ion exchange capacity of the adsorbed molecules is improved, and the contact area can be increased by ball milling of solid powder with the particle size of 2-5 mm. The invention carries out acid treatment on sepiolite powder, mg in sepiolite structure 2+ Is weak base, and generates precipitate when meeting weak acid and is deposited in the microporous structure of sepiolite, so the invention preferably adopts 2 percent HCl solution, and the sepiolite is H after acid treatment + Substituted for Mg in octahedra 2+ And forms Si-OH groups with the Si-O skeleton. First, H+ is sterically hindered with Mg at the periphery of sepiolite channels 2+ And the modified sepiolite with different magnesium removal levels is formed by reaction and gradually from outside to inside. At the same time, the tetrahedral framework remains relatively stable. Compared with natural sepiolite, the acid-treated sepiolite has communicated internal channels, increased specific surface area and pores with radius smaller than 1nmThe number is reduced, the percentage of holes with the radius of 1-1.5nm is increased, so that the modified sepiolite sample has proper pore diameter and higher specific surface area for specific reaction, and the highest specific surface area of the modified sepiolite sample is 400m 2 /g: the modified sepiolite has flocculent surface, a plurality of holes are formed, the outline of the crystal is unclear, and the dispersion degree is relatively high.
2. The chromium-polluted muck stabilizing and curing agent can be well combined with the chromium-polluted muck, the method can be used for achieving a good treatment effect only by stirring and mixing the chromium-polluted muck and the stabilizing and curing agent for 1-1.5 hours, and the method is simple to operate and low in cost, and has an excellent treatment effect on soil with 15% -25% of water content. Compared with chemical leaching and chemical reduction technologies, the off-site stabilization curing treatment technology has more excellent effect, and the residue soil treated by the chromium-polluted residue soil stabilization curing agent has no rebound after being cured for 5-6 days, and the leaching concentration is slightly fallen back, so that the long-term stability is realized.
Detailed Description
The invention is further described below in connection with specific preferred embodiments, but it is not intended to limit the scope of the invention. The materials and instruments used in the examples below are all commercially available.
The method takes slag soil polluted by different degrees in a site of a chromium salt factory with long sand as an object, the pollutant is mainly hexavalent chromium, the repairing target is that the treated slag soil is stabilized and then meets the pollution control standard for hazardous waste landfill (GB 18598-2019) (wherein the total chromium control is limited to 15mg/L and the hexavalent chromium control is limited to 6 mg/L), and the analysis effect of the sulfuric acid method of the solid waste leaching toxicity leaching method is realized.
Soil pretreatment: and (3) taking a soil sample on site, removing large foreign matters, and screening by using crushing screening hopper equipment, wherein the particle size of the screened residue soil is within 10 cm.
And (3) adding a medicament: the adding proportion of the medicament is 5-10%, water is properly sprayed in the process of adding the medicament, and the water content of the dregs is controlled between 15-25% after stirring for 1-1.5 h.
After the proportion components of the stabilizing curing agent are determined, the treatment effect of the stabilizing curing agent on the low, medium and high chromium polluted slag soil is compared by controlling the adding amount of the stabilizing curing agent.
Example 1:
the chromium-polluted muck stabilizing and curing agent disclosed by the invention comprises the following raw materials in parts by mass: 40% of sodium sulfide, 10% of reduced iron powder, 20% of modified sepiolite, 15% of calcium oxalate and 15% of calcium silicate.
In this example, the preparation of the modified sepiolite comprises the following steps: heating sepiolite to 200 ℃ for 1h roasting to remove water molecules in pore canals, then ball-milling to obtain solid powder with the particle size of 2-5mm, and treating with hydrochloric acid with the volume fraction of 2% to obtain the modified sepiolite.
The preparation method of the chromium-contaminated muck stabilization curing agent in the embodiment comprises the following steps: and fully mixing the raw materials to obtain the chromium-polluted slag soil stabilization curing agent.
The application of the chromium-contaminated muck stabilizing and curing agent in stabilizing and curing chromium-contaminated muck in the embodiment is as follows:
excavating the slag soil in a polluted field to a disposal area, screening by using crushing screening hopper equipment, wherein the grain size of the screened slag soil is within 10cm, respectively adding the chromium-polluted slag soil stabilizing and solidifying agent of the embodiment 1 into the chromium-polluted slag soil with low, medium, high and higher chromium content after crushing and screening for stabilizing and solidifying treatment, wherein the using amount of the agent respectively accounts for 5%, 7% and 10% of the total mass of the chromium-polluted slag soil, spraying water in the mixing process to control the water content of the chromium-polluted slag soil to be 15% -25%, fully stirring and reacting for 1.5h, sampling and detecting, and reserving a sample for maintaining for 5 days, and then sampling and detecting. The results of the chromium content in the chromium-contaminated slag after the stabilization and solidification treatment are shown in table 1.
Table 1 example 1 comparison of chromium contaminated slag before and after treatment
Comparative example 1:
the chromium-polluted muck stabilization curing agent comprises the following raw materials in percentage by mass: 40% of sodium sulfide, 10% of reduced iron powder, 20% of ordinary sepiolite, 15% of calcium oxalate and 15% of calcium silicate.
Excavating the slag soil in a polluted field to a disposal area, screening by using crushing screening hopper equipment, wherein the grain diameter of the screened slag soil is within 10cm, respectively adding the stabilized curing agent in comparative example 1 into the chromium-polluted slag soil with low, medium, high and higher chromium content after crushing and screening for stabilizing and curing treatment, wherein the usage amount of the agent in each chromium-polluted slag soil respectively accounts for 5%, 7% and 10% of the total mass of the chromium-polluted slag soil, spraying water in the mixing process to control the water content of the chromium-polluted slag soil to be 15% -25%, fully stirring and reacting for 1.5 hours, sampling and detecting, and preserving samples for 5 days and then sampling and detecting. The results of the chromium content in the chromium contaminated slag after the stabilization treatment are shown in table 2.
Table 2 comparative example 1 comparative table before and after treatment of chromium contaminated slag
As is clear from Table 2, the curing rebound phenomenon occurs when the stabilized curing agent is prepared from the ordinary sepiolite, and the addition of the modified sepiolite of the present invention can effectively enhance the stability and the long-acting property.
Example 2:
the chromium-polluted muck stabilizing and curing agent disclosed by the invention comprises the following raw materials in parts by mass: 40% of ferrous sulfate, 20% of reduced iron powder, 30% of modified sepiolite and 10% of calcium oxalate.
In this example, the preparation of the modified sepiolite comprises the following steps: heating sepiolite to 200 ℃ for 1h roasting to remove water molecules in pore canals, then ball-milling to obtain solid powder with the particle size of 2-5mm, and treating with hydrochloric acid with the volume fraction of 2% to obtain the modified sepiolite.
The preparation method of the chromium-contaminated muck stabilization curing agent in the embodiment comprises the following steps: and fully mixing the raw materials to obtain the chromium-polluted slag soil stabilization curing agent.
The application of the chromium-contaminated muck stabilizing and curing agent in stabilizing and curing chromium-contaminated muck in the embodiment is as follows:
excavating the slag soil in a polluted field to a disposal area, screening by using crushing screening hopper equipment, wherein the particle size of the screened slag soil is within 10cm, respectively adding the stabilizing and solidifying agent in the embodiment 2 into the chromium-polluted slag soil with low, medium, high and higher chromium content after crushing and screening for stabilizing treatment, wherein the using amount of the agent respectively accounts for 5%, 7% and 10% of the total mass of the chromium-polluted slag soil, spraying water in the mixing process to control the water content of the chromium-polluted slag soil to be 15% -25%, fully stirring and reacting for 1.5h, sampling and detecting, and simultaneously maintaining the sample for 5 days and then sampling and detecting. The results of the chromium content in the chromium contaminated slag after the stabilization treatment are shown in table 3.
TABLE 3 EXAMPLE 2 comparison of chromium contaminated slag before and after treatment
Comparative example 2:
the chromium-polluted muck stabilization curing agent comprises the following raw materials in percentage by mass: 40% of ferrous sulfate, 20% of reduced iron powder, 30% of ordinary sepiolite and 10% of calcium oxalate.
Excavating the slag soil in a polluted field to a disposal area, screening by using crushing screening hopper equipment, wherein the grain size of the screened slag soil is within 10cm, respectively adding the stabilizing and solidifying agent in comparative example 2 into the chromium-polluted slag soil with low, medium, high and higher chromium content after crushing and screening for stabilizing and solidifying treatment, wherein the using amount of the agent respectively accounts for 5%, 7% and 10% of the total mass of the chromium-polluted slag soil, spraying water in the mixing process to control the water content of the chromium-polluted slag soil to be 15% -25%, fully stirring and reacting for 1.5h, sampling and detecting, and simultaneously, reserving a sample for maintaining for 5 days, and then sampling and detecting. The results of the chromium content in the chromium contaminated slag after the stabilization treatment are shown in table 4.
Table 4 comparative example 2 comparative table before and after treatment of chromium contaminated slag
The following conclusions can be drawn from the above embodiments:
(1) By comparing example 1 with comparative example 1 and example 2 with comparative example 2, the effect of chromium removal by the stabilized curing agent added with the modified sepiolite is obviously better than that by the composite agent added with the ordinary sepiolite under the condition of the same agent proportion, because the modified sepiolite has the following advantages: on the one hand, the mesh pore diameter in the sepiolite is enlarged, and on the other hand, part of metal compounds in the sepiolite are dissolved, so that more surface acid hydrocarbon groups of the sepiolite are exposed, the exposed surface acid hydrocarbon groups and water molecules can form stable aldehyde molecules with free heavy metal ions, the composition takes hydrocarbon groups or water molecules as carriers to adsorb the heavy metal ions, the surface complexing adsorption effect is generated, and in the adsorption process, the heavy metal ions and exchangeable cations in the modified sepiolite are subjected to ion exchange reaction, and the adsorption belongs to ion exchange adsorption. In addition, the modified sepiolite has large specific surface area, and has certain physical adsorption on heavy metal ions, thereby enhancing the adsorption effect on pollutants.
(2) The invention has good treatment effect on chromium-polluted slag soil with slight, moderate and high pollution degree by reasonably controlling the adding amount of the composite medicament consisting of the reducing agent, the adsorbent (modified sepiolite) and the regulator, thereby indicating that the chromium-polluted slag soil stabilizing and curing medicament has less influence on environment and wide application range.
(3) The chromium-contaminated muck stabilizing and curing agent is in powder form, and has advantages in treatment effect and later management compared with liquid agents.
(4) The invention can be seen from the comparison of the above examples: compared with the common modified sepiolite, the modified sepiolite has stronger treatment capacity and high stability and long-acting property. The stabilization curing agent can effectively treat hexavalent chromium in soil and effectively improve heavy metal pollution of the soil. The agent can carry out ectopic repair on soil after the original chromium pollution concentration of the dregs is measured preliminarily, and has high timeliness, low cost and simple and convenient operation.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (6)
1. The chromium-polluted muck stabilization curing agent is characterized by comprising the following raw materials in percentage by mass: 40-60% of reducing agent, 20-40% of adsorbent, 10-30% of regulator, and 100% of sum of mass fractions of raw materials;
the adsorbent is modified sepiolite, and the preparation of the modified sepiolite comprises the following steps: heating sepiolite to 100-300 ℃ for roasting to remove water molecules in pore canals, then ball-milling to solid powder with the particle size of 2-5mm, and carrying out acid treatment to obtain modified sepiolite;
the reducing agent is one or more of ferrous sulfate, ferrous chloride, reduced iron powder, sodium sulfide and sodium dithionite; the regulator is one or more of calcium oxalate, calcium silicate and potassium phosphate;
the acid is hydrochloric acid, and the volume fraction of the hydrochloric acid is 2% -6%.
2. A method for preparing the chromium-contaminated muck stabilizing and solidifying agent according to claim 1, comprising the steps of: and fully mixing the reducing agent, the adsorbent and the regulator to obtain the chromium-polluted slag soil stabilization curing agent.
3. Use of the chromium-contaminated muck stabilizing and solidifying agent according to claim 1 or the chromium-contaminated muck stabilizing and solidifying agent prepared by the preparation method according to claim 2 for stabilizing and solidifying chromium-contaminated muck.
4. The use according to claim 3, characterized by the following steps: mixing the chromium-polluted muck stabilizing and curing agent with the pretreated chromium-polluted muck, wherein the mass of the chromium-polluted muck stabilizing and curing agent accounts for 5-10% of the mass of the chromium-polluted muck, spraying and stirring water in the mixing process, controlling the water content of the chromium-polluted muck to be 15-25%, and curing to realize stabilizing and curing.
5. The use according to claim 4, wherein the stirring time is 1h to 1.5h and the curing time is 5 days to 6 days.
6. The use according to claim 4 or 5, wherein the pretreatment comprises crushing and sieving chromium contaminated muck, controlling the particle size of the muck to be within 10 cm.
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