CN115404081A - Passivator for repairing heavy metal lead, zinc and arsenic combined pollution and application - Google Patents
Passivator for repairing heavy metal lead, zinc and arsenic combined pollution and application Download PDFInfo
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- CN115404081A CN115404081A CN202210909680.3A CN202210909680A CN115404081A CN 115404081 A CN115404081 A CN 115404081A CN 202210909680 A CN202210909680 A CN 202210909680A CN 115404081 A CN115404081 A CN 115404081A
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- sepiolite
- attapulgite
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- zinc
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 46
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 28
- 239000011701 zinc Substances 0.000 title claims abstract description 28
- 239000004113 Sepiolite Substances 0.000 claims abstract description 76
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 76
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 76
- 229960000892 attapulgite Drugs 0.000 claims abstract description 70
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 70
- 241000255789 Bombyx mori Species 0.000 claims abstract description 22
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 22
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 22
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 20
- -1 melamine salt compounds Chemical class 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 229960001484 edetic acid Drugs 0.000 claims description 12
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000011282 treatment Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 230000020477 pH reduction Effects 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- HPJKLCJJNFVOEM-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrochloride Chemical compound Cl.NC1=NC(N)=NC(N)=N1 HPJKLCJJNFVOEM-UHFFFAOYSA-N 0.000 claims description 3
- IUTYMBRQELGIRS-UHFFFAOYSA-N boric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OB(O)O.NC1=NC(N)=NC(N)=N1 IUTYMBRQELGIRS-UHFFFAOYSA-N 0.000 claims description 3
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002689 soil Substances 0.000 abstract description 38
- 238000002161 passivation Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000035558 fertility Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 19
- 238000005067 remediation Methods 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000006388 chemical passivation reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004382 potting Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013401 experimental design Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 229910003471 inorganic composite material Inorganic materials 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a passivator for repairing heavy metal lead, zinc and arsenic combined pollution, which is mainly prepared from the following raw materials: silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite. The silkworm excrement, the modified sepiolite, the ferrous sulfate and the modified attapulgite are added into the raw materials of the passivator, so that exchangeable content of heavy metals in soil can be reduced, residue content of the soil can be increased, and soil property cannot be greatly changed. Meanwhile, the soil fertility can be increased, the soil restoration capability is improved, and the passivation effect of metal ions in the soil is more ideal. And no secondary pollution is caused.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a passivator for remediating heavy metal lead, zinc and arsenic combined pollution, and a preparation method and application thereof.
Background
Guangxi has abundant mineral resources, is entitled "the country of nonferrous metals", and is distributed with a large amount of manganese ores, lead-zinc ores and other nonferrous metal ores. The development of Guangxi mineral resources plays a very important role in the Guangxi economic development, but due to the reasons of poor management, improper development of mineral resources and the like, heavy metals cause serious pollution to soil, water, vegetation and the like around a mining area, and the seepage prevention design problem or the management problem of a tailing pond is the root cause of heavy metal pollution. For example, a large amount of wastes after mineral separation are stacked in a tailing pond, and are leached and dissolved by precipitation to permeate to the ground surface and the underground and migrate and convert in surrounding soil, water and vegetation to cause heavy metal pollution. Non-ferrous metal mines are heavily affected by As, cd and Pb.
The tailing pond is an artificial debris flow danger source, and dam break danger exists, so that serious accidents are easily caused. There have been many similar accidents in Guangxi. And the mining of the mine area and the surrounding land polluted mine is easy to cause pollution to the land and crop environment of the mine area and the surrounding area. The heavy metal pollution of the soil seriously affects the life and health of human beings, and the remediation of the heavy metal polluted soil is not slow enough.
Common heavy metal contaminated soil or tailings remediation measures include chemical passivation, soil leaching, bioremediation and the like. The chemical passivation is a repairing method which reduces the bioavailability of heavy metals by enabling the heavy metals in the biologically effective state in the soil to form a new, less-soluble and more-stable state through a fixing agent. Chemical passivation utilizes chemical substances to reduce the mobility and bioavailability of heavy metals in soil, thereby reducing the absorption and accumulation of heavy metals by crops and reducing the heavy metals entering human bodies through food chains. Inorganic and organic modifiers are commonly used for chemical fixation, and the chemical fixation is easy to implement and commonly utilized due to low cost. The passivator for repairing the heavy metal polluted soil can be divided into three types of organic, inorganic and organic-inorganic composite materials, and the organic passivator mainly comprises farmyard manure, fresh plant residues, green manure such as corn straw powder and organic fertilizers such as grass peat. The inorganic passivator mainly comprises fly ash, powdered rock phosphate, calcium magnesium phosphate, hydroxyapatite, sepiolite, bentonite and the like. The organic-inorganic composite material is mainly prepared by modifying inorganic passivator with some organic solvent.
However, the heavy metal remediation work is extremely complicated due to the complexity of heavy metal substances in the soil and the difference of soil space. Aiming at complex composite heavy metal pollution, the existing passivator has unsatisfactory repairing effect.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a passivator for repairing heavy metal lead, zinc and arsenic combined pollution, thereby overcoming the defect of poor effect of the passivator for repairing mine tailing or soil.
The invention also aims to provide application of the passivator for repairing heavy metal lead, zinc and arsenic combined pollution in treatment of metal tailing pollution.
In order to achieve the aim, the invention provides a passivator for repairing heavy metal lead, zinc and arsenic composite pollution, which is mainly prepared from the following raw materials: silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite; the preparation method of the modified sepiolite comprises the following steps: crushing sepiolite, calcining, taking out, cooling to normal temperature, adding phosphoric acid to acidize sepiolite, adding ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide, stirring for reaction, filtering, drying and grinding to obtain modified sepiolite; the preparation method of the modified attapulgite comprises the following steps: crushing attapulgite, calcining, taking out, cooling to normal temperature, adding hydrochloric acid to acidify the attapulgite, adding ammonium citrate and melamine salt compounds, stirring for reaction, filtering, drying and grinding to obtain the modified attapulgite.
Preferably, in the above technical scheme, the passivating agent for repairing heavy metal lead, zinc and arsenic combined pollution comprises silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite in a mixing mass ratio of 1-5:1-5:1-5:1-5.
Preferably, in the above technical scheme, the passivating agent for repairing heavy metal lead, zinc and arsenic combined pollution comprises silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite in a mixing ratio of 1:1:1:1.
preferably, in the above technical scheme, the preparation method of the modified sepiolite comprises the following steps: crushing sepiolite, adding the crushed sepiolite at the temperature of 600-800 ℃, calcining for 5-10h, taking out, cooling to normal temperature, adding phosphoric acid with the mass concentration of 10-25%, and acidifying the sepiolite at the temperature of 50-70 ℃, wherein the solid-to-liquid ratio of the sepiolite to the phosphoric acid is 1g:5-15mL, and the reaction time for acidification is 1-5h; and adding ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide, stirring for reacting for 3-15h, filtering, drying and grinding to obtain the modified sepiolite.
Preferably, in the above technical solution, in the method for preparing modified sepiolite: the mass ratio of the sepiolite to the ethylene diamine tetraacetic acid to the cetyl trimethyl ammonium bromide is 50-150:0.1-3:0.1-3.
Preferably, in the above technical solution, the preparation method of the modified attapulgite comprises the following steps: crushing attapulgite, adding the crushed attapulgite at the temperature of 500-600 ℃, calcining for 5-10h, taking out, cooling to normal temperature, adding hydrochloric acid with the mass concentration of 15-25%, acidifying the attapulgite at the temperature of 50-70 ℃, wherein the solid-to-liquid ratio of the attapulgite to the hydrochloric acid is 1g:5-15mL, and the reaction time for acidification is 1-5h; and adding ammonium citrate and melamine salt compounds, stirring and reacting for 1-10h, filtering, drying and grinding to obtain the modified attapulgite.
Preferably, in the above technical solution, in the method for preparing attapulgite: the mass ratio of the attapulgite, the ammonium citrate and the melamine salt compound is 50-150:0.1-3:0.1-3.
Preferably, in the above technical solution, the melamine salt compound includes melamine phosphate, melamine hydrochloride, melamine borate or melamine sulfate.
The application of the passivator for repairing heavy metal lead, zinc and arsenic combined pollution in the treatment of metal tailing pollution.
The use method of the passivator for repairing heavy metal lead, zinc and arsenic combined pollution comprises the following steps: mixing a passivating agent with the pollutant to be repaired, wherein the mass ratio of the mixing is 0.5-5: and 100, keeping the water content of the tailing sand to be 55-75%.
Compared with the prior art, the invention has the following beneficial effects: according to the passivator for repairing heavy metal lead, zinc and arsenic combined pollution, silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite are added into raw materials, exchangeable content of heavy metals in soil can be reduced, residue content of heavy metals in soil can be increased, and soil property cannot be greatly changed. Meanwhile, the soil fertility can be increased, the soil remediation is accelerated, and the passivation effect of metal ions in the soil is more ideal. And no secondary pollution is caused.
Detailed Description
The following detailed description of the present invention will be given with reference to specific examples, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Example 1
A passivator for repairing heavy metal lead, zinc and arsenic combined pollution is mainly prepared from the following raw materials: silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite. The mass ratio of the silkworm excrement to the modified sepiolite to the ferrous sulfate to the modified attapulgite is 1:1:1:1.
a preparation method of a passivator for repairing heavy metal lead, zinc and arsenic combined pollution comprises the following steps:
(1) Preparation of modified sepiolite
Crushing sepiolite, adding the crushed sepiolite at the temperature of 750 ℃, calcining for 7 hours, taking out, cooling to normal temperature, adding phosphoric acid with the mass concentration of 18%, acidifying the sepiolite at the temperature of 60 ℃, wherein the solid-to-liquid ratio of the sepiolite to the phosphoric acid is 1g:8mL, and the reaction time for acidification is 3h; and adding ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide, stirring for reacting for 6 hours, filtering, drying and grinding to obtain the modified sepiolite. Wherein the mass ratio of the sepiolite to the ethylene diamine tetraacetic acid to the hexadecyl trimethyl ammonium bromide is 100:1:1.
(2) Preparation of modified Attapulgite
Crushing attapulgite, adding the crushed attapulgite at the temperature of 550 ℃, calcining for 7 hours, taking out, cooling to normal temperature, adding 17% hydrochloric acid, acidifying the attapulgite at the temperature of 60 ℃, wherein the solid-to-liquid ratio of the attapulgite to the hydrochloric acid is 1g:7mL, and the reaction time for acidification is 3h; and adding ammonium citrate and melamine salt compounds, stirring to react for 3 hours, filtering, drying and grinding to obtain the modified attapulgite.
Wherein the mass ratio of the attapulgite, the ammonium citrate and the melamine salt compound is 100:1.5:1. the melamine salt compound is melamine phosphate.
(3) The silkworm excrement, the modified sepiolite, the ferrous sulfate and the modified attapulgite are uniformly mixed according to the proportion for use. To obtain the passivating agent 1.
Example 2
A passivator for repairing heavy metal lead, zinc and arsenic combined pollution is mainly prepared from the following raw materials: silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite. The mass ratio of the silkworm excrement to the modified sepiolite to the ferrous sulfate to the modified attapulgite is 1:5:5:1.
a preparation method of a passivator for repairing heavy metal lead, zinc and arsenic combined pollution comprises the following steps:
(1) Preparation of modified sepiolite
Crushing sepiolite, adding the crushed sepiolite at the temperature of 600 ℃, calcining for 10 hours, taking out, cooling to normal temperature, adding phosphoric acid with the mass concentration of 25%, and acidifying the sepiolite at the temperature of 50 ℃, wherein the solid-to-liquid ratio of the sepiolite to the phosphoric acid is 1g:5mL, and the reaction time for acidification is 1h; and adding ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide, stirring for reacting for 8 hours, filtering, drying and grinding to obtain the modified sepiolite. Wherein the mass ratio of the sepiolite to the ethylene diamine tetraacetic acid to the hexadecyl trimethyl ammonium bromide is 50:0.1:0.3.
(2) Preparation of modified Attapulgite
Crushing attapulgite, adding and calcining at 500 ℃ for 10 hours, taking out and cooling to normal temperature, adding hydrochloric acid with the mass concentration of 25%, acidifying the attapulgite at 70 ℃, wherein the solid-to-liquid ratio of the attapulgite to the hydrochloric acid is 1g:5mL, and the reaction time for acidification is 1h; and adding ammonium citrate and melamine salt compounds, stirring for reacting for 6 hours, filtering, drying and grinding to obtain the modified attapulgite.
Wherein the mass ratio of the attapulgite to the ammonium citrate to the melamine salt compound is 50:0.2:0.1. the melamine salt compound is melamine hydrochloride.
(3) The silkworm excrement, the modified sepiolite, the ferrous sulfate and the modified attapulgite are uniformly mixed according to the proportion for use. To obtain the passivating agent 2.
Example 3
A passivator for repairing heavy metal lead, zinc and arsenic combined pollution is mainly prepared from the following raw materials: silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite. The mass ratio of the silkworm excrement to the modified sepiolite to the ferrous sulfate to the modified attapulgite is 5:1:1:5.
a preparation method of a passivator for repairing heavy metal lead, zinc and arsenic combined pollution comprises the following steps:
(1) Preparation of modified sepiolite
Crushing sepiolite, adding the crushed sepiolite at the temperature of 800 ℃ for calcining for 5 hours, taking out the sepiolite, cooling the sepiolite to the normal temperature, adding phosphoric acid with the mass concentration of 10%, and acidifying the sepiolite at the temperature of 70 ℃, wherein the solid-to-liquid ratio of the sepiolite to the phosphoric acid is 1g:15mL, and the reaction time for acidification is 5h; and adding ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide, stirring for reacting for 3 hours, filtering, drying and grinding to obtain the modified sepiolite. Wherein the mass ratio of the sepiolite to the ethylene diamine tetraacetic acid to the cetyl trimethyl ammonium bromide is 150:2:0.7.
(2) Preparation of modified Attapulgite
Crushing attapulgite, adding and calcining the attapulgite at the temperature of 600 ℃ for 5 hours, taking out the attapulgite and cooling the attapulgite to normal temperature, adding hydrochloric acid with the mass concentration of 15%, acidifying the attapulgite at the temperature of 50 ℃, wherein the solid-to-liquid ratio of the attapulgite to the hydrochloric acid is 1g:15mL, and the reaction time for acidification is 5h; and adding ammonium citrate and melamine salt compounds, stirring for reacting for 3 hours, filtering, drying and grinding to obtain the modified attapulgite.
Wherein the mass ratio of the attapulgite to the ammonium citrate to the melamine salt compound is 150:2.1:0.9. the melamine salt compound is melamine borate.
(3) The silkworm excrement, the modified sepiolite, the ferrous sulfate and the modified attapulgite are uniformly mixed according to the proportion for use. To obtain the passivating agent 3.
Example 4
The preparation method of the passivator in the embodiment is basically the same as that of the passivator in the embodiment 1, except that the passivator is mainly prepared from the following raw materials: the mass ratio of the silkworm excrement to the modified sepiolite to the ferrous sulfate to the modified attapulgite is 1:2:3:2. denoted as passivating agent 4.
Example 5
The preparation method of the passivator in the embodiment is basically the same as that of the passivator in the embodiment 1, except that the passivator is mainly prepared from the following raw materials: the mass ratio of the silkworm excrement to the modified sepiolite to the ferrous sulfate to the modified attapulgite is 3:2:1:3. denoted as passivating agent 5.
Pot culture test 1
1. Test materials: tailings 1 (yang shuo county, guilin City); tailings 2 (river pool city nandan county).
2. Addition of: control (CK); a passivating agent.
3. And (3) experimental design: accurately weighing 600g of pretreated tailings and soil, respectively placing the pretreated tailings and soil in a plastic basin with a basin mouth diameter of 13cm, a basin bottom diameter of 10cm and a height of 12cm, treating and proportioning the tailings to be tested according to the following different treatments, testing for 18 treatments in total, repeating each treatment for 3 times, and taking an average value for comparison, wherein the average value is shown in table 1.
Silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite in the passivator are respectively represented by A, B, C and D. The passivating agents modified sepiolite and modified attapulgite mentioned in the other treatments except the passivating agent 2 and the passivating agent 3 were prepared using the method of example 1. B is 1 Is unmodified sepiolite, D 1 Is the sepiolite without modification.
4. The operation method comprises the following steps: the test tailings are respectively placed into plastic kegs according to 600g in each portion. Each treated compound passivator is mixed with a test material by a small wood shovel, deionized water is supplemented into tailings by weighing at regular intervals every day, constant water content (60% of the saturation water content of the tailings) is kept, and the tailings are sealed by a preservative film and then placed in a greenhouse for culture. After the passivating agent is added, sampling analysis is carried out on 14 th days (0 d, 7d, 14d, 30d and 60 d) respectively to test the pH value, the available state Pb, the available state Cd and the available state As. The results of the measurements are shown in tables 2, 3, 4, 5 and 6
Table 1 pot experiment 1 passivator design
Table 2 influence result of the experiment of potted plant with cissus-aquatica tailings 1 on the pH value of the tailings
TABLE 3 influence of Nandan tailing 2 potting test on tailing pH
TABLE 4 1 passivation of Guilin tailings for 14 days test results
TABLE 5 Nandan tailings 2 passivation 14-day test results
Pot culture test 2
1. Test materials: contaminated soil (Yangsheng city, guilin city) around the tailings 1; tailings 2 contaminated soil (south Dan county, river basin city).
2. Addition of: control (CK); a passivating agent.
3. And (3) experimental design: accurately weighing 600g of the pretreated soil, placing the soil in plastic pots with the pot mouth diameter of 13cm, the pot bottom diameter of 10cm and the height of 12cm, respectively, treating the soil in the tailings to be tested according to the following different treatments and proportions thereof, carrying out 16 treatments in total in the test, repeating each treatment for 3 times, and taking the mean value for comparison, as shown in table 6.
Silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite in the passivator are respectively represented by A, B, C and D. The passivating agents modified sepiolite and modified attapulgite mentioned in the other treatments except the passivating agent 2 and the passivating agent 3 were prepared using the method of example 1. B is 1 Is unmodified sepiolite, D 1 Is the sepiolite without modification.
4. The operation method comprises the following steps: the test tailings are respectively placed into plastic kegs according to 600g in each portion. Each treated compound passivator and the test material are mixed uniformly by a small wooden shovel, deionized water is supplemented to the tailings every other day by weighing at regular intervals, constant water content (60 percent of the saturated water content of the tailings) is kept, and the tailings are sealed by a preservative film and then placed in a greenhouse for cultivation. After the passivating agent is added, sampling analysis is carried out on 14 th days (0 d, 7d, 14d, 30d and 60 d) respectively to test the pH value, the available state Pb, the available state Cd and the available state As. The results of the measurements are shown in tables 7, 8, 9, 10 and 11.
TABLE 6 pot experiment 2 passivator design
TABLE 7 influence of the soil pH value of the Guilin Asplastic soil 1 potting test
TABLE 8 influence of Nandan soil 2 potting test on soil pH
TABLE 9 1 passivation of Guilin soil for 14 days test results
TABLE 10 soil 2 passivation in Plumbum Preparatium 14 days test results
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The passivator for repairing heavy metal lead, zinc and arsenic combined pollution is characterized by being mainly prepared from the following raw materials: silkworm excrement, modified sepiolite, ferrous sulfate and modified attapulgite;
the preparation method of the modified sepiolite comprises the following steps: crushing sepiolite, calcining, taking out, cooling to normal temperature, adding phosphoric acid to acidize sepiolite, adding ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide, stirring for reaction, filtering, drying and grinding to obtain modified sepiolite;
the preparation method of the modified attapulgite comprises the following steps: crushing attapulgite, calcining, taking out, cooling to normal temperature, adding hydrochloric acid to acidify the attapulgite, adding ammonium citrate and melamine salt compounds, stirring for reaction, filtering, drying and grinding to obtain the modified attapulgite.
2. The passivator for repairing heavy metal lead, zinc and arsenic combined pollution according to claim 1, wherein the mass ratio of the silkworm excrement, the modified sepiolite, the ferrous sulfate and the modified attapulgite is 1-5:1-5:1-5:1-5.
3. The passivator for repairing heavy metal lead, zinc and arsenic combined pollution according to claim 1, wherein the mass ratio of the silkworm excrement, the modified sepiolite, the ferrous sulfate and the modified attapulgite is 1:1:1:1.
4. the passivator for repairing heavy metal lead, zinc and arsenic combined pollution according to claim 1, wherein the preparation method of the modified sepiolite comprises the following steps: crushing sepiolite, adding the crushed sepiolite at the temperature of 600-800 ℃, calcining for 5-10h, taking out, cooling to normal temperature, adding phosphoric acid with the mass concentration of 10-25%, and acidifying the sepiolite at the temperature of 50-70 ℃, wherein the solid-to-liquid ratio of the sepiolite to the phosphoric acid is 1g:5-15mL, and the reaction time of acidification is 1-5h; and adding ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide, stirring for reacting for 3-15h, filtering, drying and grinding to obtain the modified sepiolite.
5. The passivator for remediating heavy metal lead, zinc and arsenic combined pollution according to claim 1, wherein in the method for preparing the modified sepiolite: the mass ratio of the sepiolite to the ethylene diamine tetraacetic acid to the cetyl trimethyl ammonium bromide is 50-150:0.1-3:0.1-3.
6. The passivator for repairing heavy metal lead, zinc and arsenic composite pollution according to claim 1, wherein the preparation method of the modified attapulgite is as follows: crushing attapulgite, adding the crushed attapulgite at the temperature of 500-600 ℃, calcining for 5-10h, taking out, cooling to normal temperature, adding hydrochloric acid with the mass concentration of 15-25%, acidifying the attapulgite at the temperature of 50-70 ℃, wherein the solid-to-liquid ratio of the attapulgite to the hydrochloric acid is 1g:5-15mL, and the reaction time of acidification is 1-5h; and adding ammonium citrate and melamine salt compounds, stirring and reacting for 1-10h, filtering, drying and grinding to obtain the modified attapulgite.
7. The passivator for repairing heavy metal lead, zinc and arsenic combined pollution according to claim 1, wherein in the method for preparing attapulgite: the mass ratio of the attapulgite, the ammonium citrate and the melamine salt compound is 50-150:0.1-3:0.1-3.
8. The passivator for repairing heavy metal lead, zinc and arsenic composite pollution according to claim 1, wherein the melamine salt compound comprises melamine phosphate, melamine hydrochloride, melamine borate or melamine sulfate.
9. The application of the passivator for repairing heavy metal lead, zinc and arsenic combined pollution according to any one of claims 1 to 8 in the treatment of metal tailing pollution.
10. The use method of the passivator for repairing heavy metal lead, zinc and arsenic combined pollution according to any one of claims 1 to 8 is characterized by comprising the following steps: mixing a passivating agent with the pollutant to be repaired, wherein the mass ratio of the mixing is 0.5-5: and 100, keeping the water content of the tailing sand to be 55-75%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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