CN115537209A - Cadmium-lead-arsenic composite polluted soil remediation agent and preparation method and application thereof - Google Patents
Cadmium-lead-arsenic composite polluted soil remediation agent and preparation method and application thereof Download PDFInfo
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- CN115537209A CN115537209A CN202211232410.XA CN202211232410A CN115537209A CN 115537209 A CN115537209 A CN 115537209A CN 202211232410 A CN202211232410 A CN 202211232410A CN 115537209 A CN115537209 A CN 115537209A
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- heavy metal
- agent
- hydrothermal carbon
- cadmium
- lead
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 62
- 239000002689 soil Substances 0.000 title claims abstract description 62
- 238000005067 remediation Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VTXYFVHXMBFNNN-UHFFFAOYSA-N [As].[Cd].[Pb] Chemical compound [As].[Cd].[Pb] VTXYFVHXMBFNNN-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000002131 composite material Substances 0.000 title abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 25
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 24
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical class [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 22
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 21
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 7
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 20
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000000197 pyrolysis Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000008439 repair process Effects 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 18
- 230000006641 stabilisation Effects 0.000 abstract description 10
- 238000011105 stabilization Methods 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 7
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- 150000001495 arsenic compounds Chemical class 0.000 abstract description 2
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- 230000009286 beneficial effect Effects 0.000 description 6
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 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 6
- 229960003330 pentetic acid Drugs 0.000 description 6
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- 238000001514 detection method Methods 0.000 description 4
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- 125000000524 functional group Chemical group 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
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- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000003802 soil pollutant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229960002713 calcium chloride Drugs 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000013003 healing agent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a cadmium-lead-arsenic compound contaminated soil remediation agent and a preparation method and application thereof, and relates to the technical field of heavy metal contaminated soil treatment. The repairing agent comprises polyferric sulfate, activated iron-phosphorus modified hydrothermal carbon and a heavy metal capturing agent, and has a good repairing effect on cadmium, lead and arsenic compound contaminated soil. After the repairing agent is uniformly mixed with the cadmium-lead-arsenic composite polluted soil, the repairing agent has good stabilizing effect and long-acting property on cadmium, lead and arsenic; the cadmium stabilizing rate can reach 93.33%, the lead stabilizing rate can reach 99.68%, and the arsenic stabilizing rate can reach 99.58%; through a simulated seven-year freeze-thaw test, the change rate of the cadmium stabilization rate is kept within 20%, and the change rate of the lead and arsenic stabilization rate is kept within 6%.
Description
Technical Field
The invention relates to the technical field of heavy metal contaminated soil treatment, in particular to a cadmium-lead-arsenic compound contaminated soil remediation agent and a preparation method and application thereof.
Background
The soil is the core of resources, is the foundation of growth and reproduction of animals and plants, and is also an important medium for human survival and life. At present, the heavy metal pollution condition of soil is not optimistic, and the problem of multiple heavy metal combined pollution exists. Particularly, the over-standard position point of heavy metal in the mining area soil is As high As 33.4%, the main elements polluted by the heavy metal soil are Cd, pb and As, and the heavy metal pollution of the soil around the non-ferrous metal mining area is more serious.
At present, passivation remediation of heavy metal pollution of soil is mainly concentrated on a single element, and simultaneous remediation research on combined pollution of multiple heavy metals in soil is less. In reality, soil is usually polluted by a plurality of heavy metals, different heavy metal ions in the soil subjected to combined pollution have unique moving performance, and different elements or compounds have interaction such as antagonism, synergism and addition.
Therefore, it is desirable to provide a remediation agent that passivates multiple contaminants simultaneously.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a heavy metal contaminated soil restoration agent which has a good restoration effect on Cd, pb and As composite contaminated soil and also has good long-acting property.
The invention also provides a preparation method of the repairing agent.
The invention also provides a method for restoring the heavy metal contaminated soil.
The invention also provides application of the repairing agent.
According to the embodiment of the first aspect of the invention, the repairing agent for the heavy metal contaminated soil comprises: polymeric ferric sulfate, activated iron-phosphorus modified hydrothermal carbon and heavy metal capture agent.
The repairing agent provided by the embodiment of the invention has at least the following beneficial effects:
the repairing agent disclosed by the embodiment of the invention has the advantages of greenness, no pollution, safety and high efficiency. The repairing agent has good stabilizing effect and long-acting property on cadmium, lead and arsenic; the cadmium stabilizing rate is more than 65%, the lead stabilizing rate is more than 99%, and the arsenic stabilizing rate is more than 85%; through a simulated seven-year freeze-thaw test, the change rate of the cadmium stabilization rate is kept within 20%, and the change rate of the lead and arsenic stabilization rate is kept within 6%. On one hand, the modification of the hydrothermal carbon iron can increase the Cation Exchange Capacity (CEC) on the surface of the hydrothermal carbon and improve the adsorption capacity to heavy metals; on the other hand, iron ions are attached to pores of the hydrothermal carbon and can be coprecipitated with heavy metals in soil, so that the stabilizing effect on the heavy metals is improved. The modification of the hydrothermal carbon phosphorus can improve the hydrophilicity of the hydrothermal carbon, change the specific surface area and active functional groups of the hydrothermal carbon, and further improve the stabilizing effect on heavy metals (particularly Pb ions). Functional groups such As iron groups, hydroxyl groups, sulfydryl groups and the like in the heavy metal polluted soil restoration agent consisting of polymeric ferric sulfate and TMT102 can perform physical/chemical reaction with Cd, pb and As to form chelate or insoluble precipitate, thereby reducing the effective state content of Cd, pb and As.
According to some embodiments of the invention, the heavy metal contaminated soil comprises soil contaminated with at least one element selected from cadmium, lead and arsenic.
According to some embodiments of the invention, the heavy metal contaminated soil is a lead and arsenic combined contaminated soil.
According to some embodiments of the invention, the heavy metal capture agent comprises TMT102.
According to some embodiments of the invention, the method for preparing the activated iron-phosphorus modified hydrothermal carbon comprises the following steps:
s1: uniformly mixing activated hydrothermal carbon with an iron salt solution, adjusting the pH value, filtering, and carrying out first pyrolysis on filter residues to obtain the activated iron modified hydrothermal carbon;
s2: and uniformly mixing the activated iron-modified hydrothermal carbon with the phosphorus source solution, heating, filtering, and performing secondary pyrolysis on filter residues to obtain the activated iron-phosphorus-modified hydrothermal carbon.
According to some embodiments of the invention, the method of preparing the activated hydrothermal carbon comprises: adding a biomass raw material into a high-pressure reaction kettle for reaction, and drying to obtain hydrothermal carbon; and adding the hydrothermal carbon into an alkali solution, soaking at normal temperature, and pyrolyzing to obtain the activated hydrothermal carbon.
The hydrothermal carbon is added into the alkali solution, so that the basic groups such as hydroxyl, amino and the like of the hydrothermal carbon can be increased, and more adsorption sites are provided; the alkali solution has strong corrosivity on the hydrothermal carbon, so that fragments and hole walls among gaps of the hydrothermal carbon are corroded, inner pore channels of the hydrothermal carbon are dredged, micropores are formed, and the specific surface area and the pore diameter of the micropores are increased.
According to some embodiments of the invention, the biomass feedstock comprises rice straw, palm leaves, pine logs, and bamboo.
According to some embodiments of the invention, the biomass feedstock comprises palm leaves.
According to some embodiments of the invention, the reaction temperature in the autoclave is between 140 ℃ and 200 ℃.
According to some embodiments of the invention, the reaction temperature in the autoclave is 180 ℃.
According to some embodiments of the invention, the reaction time in the autoclave is between 4h and 8h.
According to some embodiments of the invention, the reaction time in the autoclave is 6h.
According to some embodiments of the invention, the time for the normal temperature impregnation is 12 to 36 hours.
According to some embodiments of the invention, the pyrolysis temperature after the normal temperature impregnation is 280 ℃ to 320 ℃.
According to some embodiments of the invention, the pyrolysis temperature after the normal temperature impregnation is 300 ℃.
According to some embodiments of the invention, the pyrolysis time after the normal temperature impregnation is 1h.
According to some embodiments of the invention, in step S1, the iron salt solution is a mixed solution of a ferrous salt and a ferric salt.
According to some embodiments of the invention, in step S1, the molar ratio of the ferrous salt to the ferric salt is 1:0.5 to 1.5.
According to some embodiments of the invention, in step S1, the molar ratio of the ferrous salt to the ferric salt is 1:1.
according to some embodiments of the invention, the temperature of the first pyrolysis in step S1 is 280 ℃ to 320 ℃.
According to some embodiments of the invention, in step S1, the temperature of the first pyrolysis is 300 ℃.
According to some embodiments of the invention, in step S1, the time of the first pyrolysis is 0.5h to 2h.
According to some embodiments of the invention, in step S1, the time of the first pyrolysis is 1h.
According to some embodiments of the invention, in step S1, the pH is between 9 and 11.
According to some embodiments of the invention, in step S1, the pH is 10.
According to some embodiments of the invention, in step S2, the alkali solution is at least one of a KOH solution and a NaOH solution.
According to some embodiments of the invention, in step S2, the phosphorus source solution is an aqueous hydroxyapatite solution.
According to some embodiments of the invention, the temperature of the second pyrolysis in step S2 is 280 ℃ to 320 ℃.
According to some embodiments of the invention, in step S2, the time of the second pyrolysis is 0.5h to 2h.
According to some embodiments of the invention, the polymeric ferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the heavy metal capture agent are used in a ratio of 2g:2 g-6 g:2.5mL to 7mL.
According to some embodiments of the invention, the polyferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the heavy metal trapping agent are used in a ratio of 2g:2.5 g-5.5 g:3mL to 6mL.
According to some embodiments of the invention, the polyferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the heavy metal trapping agent are used in a ratio of 2g:3 g-5.5 g:4 mL-6 mL.
According to some embodiments of the invention, the polymeric ferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the heavy metal capture agent are used in a ratio of 2g:4.5 g-5.5 g:5.5mL to 6.5mL.
According to some embodiments of the invention, the polyferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the heavy metal trapping agent are used in a ratio of 2g:5g:6mL.
The preparation method of the repairing agent comprises the following steps: the components are mixed evenly.
The preparation method of the repairing agent provided by the embodiment of the invention has at least the following beneficial effects:
the preparation method is simple, only needs direct mixing, and has low professional requirements on operators.
According to the third aspect of the invention, the method for restoring the heavy metal soil comprises the following steps: the remediation agent provided by the embodiment of the first aspect of the invention is added into the heavy metal contaminated soil.
The repairing method provided by the embodiment of the invention at least has the following beneficial effects:
the repairing method provided by the embodiment of the invention is simple to operate, and only needs to directly mix the heavy metal contaminated soil and the repairing agent. The repairing method of the embodiment of the invention adopts all technical schemes of the repairing agent of the embodiment, so that the repairing method at least has all beneficial effects brought by the technical schemes of the embodiment.
According to some embodiments of the invention, the heavy metal contaminated soil comprises soil contaminated with at least one element selected from cadmium, lead and arsenic.
According to some embodiments of the invention, the heavy metal contaminated soil is lead and arsenic compound contaminated soil.
According to some embodiments of the invention, the mass ratio of the heavy metal contaminated soil to the polymeric ferric sulfate of the remediation agent is 50:1 to 2.5.
According to some embodiments of the invention, the mass ratio of the heavy metal contaminated soil to the polymeric ferric sulfate of the remediation agent is 50:1 to 12.
According to some embodiments of the invention, the mass ratio of the heavy metal contaminated soil to the polymeric ferric sulfate of the remediation agent is 25:1.
according to some embodiments of the invention, the method is in particular: the heavy metal contaminated soil is mixed with the repairing agent provided by the embodiment of the first aspect of the invention.
According to some embodiments of the invention, after the repair agent is added, a shaking treatment is also required. According to some embodiments of the invention, the oscillating process comprises: shaking for 24h on the first day, and then shaking for 2h each day.
According to some embodiments of the invention, the oscillating process is performed at a rate of 170 to 190rpm.
According to some embodiments of the invention, the frequency of the shaking treatment is 1 time per day.
According to some embodiments of the invention, the oscillating comprises: shaking for 20-28 h in the first day, and then shaking for 1-3 h every day.
According to some embodiments of the invention, the repair is performed for a period of 5 to 14 days.
According to some embodiments of the invention, the repair is performed for a period of 7 to 14 days.
The application of the remediation agent according to the fourth aspect of the embodiment of the invention in remediation of heavy metal contaminated soil.
The application of the repairing agent according to the embodiment of the invention has at least the following beneficial effects:
the method has the advantages that all the technical schemes of the repairing agent of the embodiment are adopted in the heavy metal contaminated soil repairing, so that at least all the beneficial effects brought by the technical schemes of the embodiment are achieved.
According to some embodiments of the invention, the heavy metal contaminated soil comprises soil contaminated with at least one element selected from cadmium, lead and arsenic.
According to some embodiments of the invention, the heavy metal contaminated soil is a lead and arsenic combined contaminated soil.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the description of the embodiments, wherein: the idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Unless otherwise specified, the ordinary temperature in the following examples means 20 ℃ to 35 ℃.
Hydroxyapatite used in the following examples was purchased from sierra biotechnology limited;
polyferric sulfate was purchased from Tianjin Dingshenxin chemical Co., ltd;
TMT102 was purchased from environmental protection, eastern source, suzhou.
In the soil for test, the pH was >5, the concentration of cadmium was 193.55mg/kg, the concentration of lead was 1801.5mg/kg, and the concentration of arsenic was 170.65mg/kg.
The activated iron-phosphorus modified hydrothermal carbon used in the following examples and comparative examples was prepared as follows:
(1) Preparing activated hydrothermal carbon: adding a biomass raw material into a high-pressure reaction kettle, reacting for 6 hours at 180 ℃, and drying to obtain hydrothermal carbon; adding the hydrothermal carbon into a 1mol/L KOH solution, soaking at normal temperature for 12-36h, and pyrolyzing at 300 ℃ for 1h to obtain the activated hydrothermal carbon.
Wherein the biomass raw material is palm leaves; water heating and charcoal: the mass-to-volume ratio of the KOH solution is 1g:2mL.
(2) Iron modification: and (2) mixing the activated hydrothermal carbon prepared in the step (1) with 0.5mol/L Fe2+/Fe3+ mixed iron solution, fully stirring for 30min, adjusting the pH of the system to 10, measuring the pH after fully stirring for 30min, adjusting the pH to 10 again when the pH changes, filtering, drying, and cracking at 300 ℃ for 1h to obtain the activated iron modified hydrothermal carbon.
Wherein, fe 2+ /Fe 3+ Mixed iron solution (FeCl) 2 ·4H 2 O/FeCl 3 ·6H 2 In O), fe 2+ With Fe 3+ In a molar ratio of 1:1; activating hydrothermal charcoal and Fe 2+ /Fe 3+ The mass-volume ratio of the mixed iron solution is 1g:5mL.
(3) Phosphorus modification: and (3) uniformly mixing the activated iron modified hydrothermal carbon prepared in the step (2) with a hydroxyapatite aqueous solution, heating, filtering, and pyrolyzing filter residues at the pyrolysis temperature of 280-320 ℃ for 0.5-2 h to obtain the activated iron-phosphorus modified hydrothermal carbon.
The preparation method of the hydroxyapatite aqueous solution comprises the following steps: 12g of hydroxyapatite (mum grade) was mixed with 2000mL of distilled water and heated for 1 hour to obtain an aqueous hydroxyapatite solution.
The calculation formula of the stabilization ratio in the following examples is: the stabilization rate of the pollutant a = (content of soil pollutant a for test-content of soil pollutant a after stabilization) × 100%/content of soil pollutant a for test. Wherein the contaminant A refers to cadmium, lead or arsenic.
Examples
This example provides 6 repair agents, the component ratios are shown in table 1.
TABLE 1
| Group of | Polymeric ferric sulfate (g) | Activated iron-phosphorus modified hydrothermal charcoal (g) | TMT102(mL) |
| Example 1 | 1 | 2.5 | 3 |
| Example 2 | 2 | 2.5 | 3 |
| Example 3 | 2 | 3 | 3 |
| Example 4 | 2 | 3 | 4 |
| Example 5 | 2 | 5 | 6 |
| Example 6 | 5 | 12.5 | 7.5 |
Comparative example
This example provides 10 healing agents, the component ratios are shown in table 2.
TABLE 2
| Group of | Polymeric ferric sulfate (g) | Activated iron-phosphorus modified hydrothermal charcoal (g) | TMT102(mL) |
| Comparative example 1 | / | 3 | 3 |
| Comparative example 2 | 2 | 3 | / |
| Comparative example 3 | / | 3 | / |
| Comparative example 4 | 2 | / | / |
| Comparative example 5 | / | / | 3 |
| Comparative example 6 | 0.5 | 2.5 | 1 |
| Comparative example 7 | 1 | 2.5 | 1 |
| Comparative example 8 | 1.5 | 2.5 | 1 |
| Comparative example 9 | 1 | 2.5 | 1.5 |
| Comparative example 10 | 1 | 2.5 | 2 |
Test example 1
The detection example detects the stabilizing effect of the repairing agent provided in the above examples 1-5 and comparative examples 1-10 on heavy metals in the cadmium-lead-arsenic combined contaminated soil. The test procedure was as follows:
after 50g of the soil for test was weighed in a 100mL polyethylene bottle, the repairing agents provided in examples 1 to 5 and comparative examples 1 to 10 were added, respectively, mixed well, 50mL of distilled water was added, shaken (24 hours on the first day and 2 hours each day thereafter), and after standing and curing for seven days, a sample was taken, air-dried, and ground. And detecting the contents of cadmium (Cd), lead (Pb) and arsenic (As) in the soil DTPA leaching liquor so As to evaluate the stabilization rates of the Cd, the Pb and the As.
Wherein, in the DTPA leaching liquor for treating soil, the concentration of Triethanolamine (TEA) is 0.1mol/L, and calcium chloride (CaCl) 2 ) The concentration of (2) is 0.01mol/L, the concentration of Diethylene Triamine Pentaacetic Acid (DTPA) is 0.005mol/L, and the pH value is 7.3. The preparation method comprises the following steps: adding 14.92g (accurate to 0.0001 g) of triethanolamine, 1.967g (accurate to 0.0001 g) of diethylenetriamine pentaacetic acid and 1.470g (accurate to 0.0001 g) of calcium chloride dihydrate into a beaker in sequence, adding water, stirring to completely dissolve, continuously adding water to dilute to about 800mL, adjusting the pH to 7.3 +/-0.2 by using a hydrochloric acid solution (measured by using a pH meter), transferring into a 1000mL volumetric flask to fix the volume to a scale, and shaking up.
The results are shown in Table 3.
TABLE 3 detection results of cadmium, lead and arsenic
As can be seen from Table 3, the repairing agents provided in examples 1-5 can simultaneously achieve a good stabilizing effect on cadmium, lead and arsenic. The repairing agents provided in the comparative examples 1 to 10 can only simultaneously stabilize two heavy metals, and the stabilizing effect is poor when the proportion or the dosage of the components is not within the range of the examples 1 to 3 or one or two of the polyferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the TMT102 are absent. The repairing agent of the comparative examples 1 to 5 only comprises one or two of polymeric ferric sulfate, activated iron-phosphorus modified hydrothermal carbon and TMT102, and at the moment, the stabilization of cadmium, lead and arsenic has a competitive effect, so that the three heavy metals cannot be stabilized at the same time. The repairing agent of the comparative examples 6 to 8 simultaneously contains polymeric ferric sulfate, activated iron-phosphorus modified hydrothermal carbon and TMT102, but the mixture ratio of the polymeric ferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the TMT102 is not 2g:2 g-6 g: 2.5-7 mL (polymeric ferric sulfate: activated iron-phosphorus modified hydrothermal carbon: TMT 102), so that the stabilizing characteristics of heavy metals are remarkably different, and the stabilizing effect is reduced due to the antagonistic action of partial functional groups. Although the ratio of the repairing agent of the comparative examples 9-10 is 2g:2 g-6 g: although the amount of the stabilizer was in the range of 2.5 to 7mL (iron polysulfate: activated iron-phosphorus-modified hydrothermal charcoal: TMT 102), the stabilizing effect was deteriorated when the test soil was treated with the stabilizer in the examples 1 to 5, since the amount of the stabilizer was smaller than the amount of the stabilizer added.
Detection example 2
This test example tests the long-lasting effect of the repairing agent of the above example 6. The test procedure was as follows:
120g of test soil was weighed, added with the repairing agent of example 6, mixed well and cultured for three days. Then placing the mixture into a plastic self-sealing bag, adding deionized water, and fully and uniformly mixing to keep the water content of the soil at 50%. Placing the plastic self-sealing bag containing the soil sample into a freezing cabinet, setting the freezing temperature to be-20 ℃ and the freezing time to be 12 hours, then placing the plastic self-sealing bag into an incubator, setting the temperature to be 30 ℃ and the freezing time to be 12 hours, wherein the time is one freezing and thawing cycle, and the freezing and thawing cycles are respectively 1, 3, 5 and 7 times to simulate a freezing and thawing test. After the test is finished, the soil sample is air-dried through a 2mm sieve, and the content of cadmium (Cd), lead (Pb) and arsenic (As) in the DTPA leaching liquor is detected so As to evaluate the long-acting property.
The results are shown in Table 4.
TABLE 4 detection results of cadmium, lead and arsenic
As can be seen from Table 4, the repairing agent of example 6 has very good long-term effect, and through a simulated seven-year freeze-thaw test, the change rate of the stabilizing rate of cadmium is kept within 20%, and the change rate of the stabilizing rate of lead and arsenic is kept within 6%. Wherein the lead stabilization rate is stabilized to more than 98%.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The heavy metal contaminated soil remediation agent is characterized by comprising the following components: polymeric ferric sulfate, activated iron-phosphorus modified hydrothermal carbon and heavy metal capture agent.
2. The remediation agent of claim 1, wherein said heavy metal capture agent comprises TMT102.
3. The repair agent according to claim 1, wherein the preparation method of the activated iron-phosphorus modified hydrothermal carbon comprises the following steps:
s1: uniformly mixing activated hydrothermal carbon with an iron salt solution, adjusting the pH value, filtering, and carrying out first pyrolysis on filter residues to obtain the activated iron modified hydrothermal carbon;
s2: uniformly mixing the activated iron-modified hydrothermal carbon with a phosphorus source solution, heating, filtering, and performing secondary pyrolysis on filter residues to obtain the activated iron-phosphorus-modified hydrothermal carbon;
preferably, the preparation method of the activated hydrothermal carbon comprises the following steps: adding a biomass raw material into a high-pressure reaction kettle for reaction, and drying to obtain hydrothermal carbon; and adding the hydrothermal carbon into an alkali solution, soaking at normal temperature, and pyrolyzing to obtain the activated hydrothermal carbon.
4. The repairing agent of claim 1, wherein the polyferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the heavy metal capturing agent are used in a ratio of 2g:2 g-6 g:2.5 mL-7 mL; preferably, the dosage ratio of the polymeric ferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the heavy metal trapping agent is 2g:2.5 g-5.5 g:3mL to 6mL.
5. The method for preparing a repairing agent according to any one of claims 1 to 4, characterized by comprising the steps of: and uniformly mixing the polymeric ferric sulfate, the activated iron-phosphorus modified hydrothermal carbon and the heavy metal capture agent.
6. A method for restoring heavy metal contaminated soil is characterized by comprising the following steps: repairing heavy metal soil to be repaired with the repairing agent described in any one of claims 1 to 4.
7. The remediation method of claim 6, wherein the mass ratio of the heavy metal contaminated soil to the polymeric ferric sulfate of the remediation agent is 50:1 to 2.5; preferably, the mass ratio of the heavy metal contaminated soil to the polymeric ferric sulfate of the repairing agent is 50:1 to 2.
8. The repair method according to claim 6, wherein the repair time is 5 to 14 days; preferably, the repair time is 7 to 14 days.
9. The remediation method of claim 6, wherein the heavy metal contaminated soil comprises soil contaminated with at least one element selected from cadmium, lead and arsenic.
10. Use of the remediation agent of any one of claims 1 to 4 for remediation of heavy metal contaminated soil.
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