CN116618015A - Soil restoration agent for treating heavy metal pollution and preparation method thereof - Google Patents
Soil restoration agent for treating heavy metal pollution and preparation method thereof Download PDFInfo
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- CN116618015A CN116618015A CN202310571602.1A CN202310571602A CN116618015A CN 116618015 A CN116618015 A CN 116618015A CN 202310571602 A CN202310571602 A CN 202310571602A CN 116618015 A CN116618015 A CN 116618015A
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- metal pollution
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 73
- 239000002689 soil Substances 0.000 title claims abstract description 70
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000004113 Sepiolite Substances 0.000 claims abstract description 63
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 63
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 63
- 238000010438 heat treatment Methods 0.000 claims abstract description 57
- 238000005406 washing Methods 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 238000005067 remediation Methods 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000001291 vacuum drying Methods 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 230000007935 neutral effect Effects 0.000 claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 18
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- 150000000703 Cerium Chemical class 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 150000003746 yttrium Chemical class 0.000 claims abstract description 8
- 238000010306 acid treatment Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 60
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 30
- 244000105624 Arachis hypogaea Species 0.000 claims description 30
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 30
- 235000018262 Arachis monticola Nutrition 0.000 claims description 30
- 235000020232 peanut Nutrition 0.000 claims description 30
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 16
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 235000002867 manganese chloride Nutrition 0.000 claims description 16
- 239000011565 manganese chloride Substances 0.000 claims description 16
- 229940099607 manganese chloride Drugs 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 15
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 14
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 152
- 239000000047 product Substances 0.000 description 70
- 230000000052 comparative effect Effects 0.000 description 47
- 239000010902 straw Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 229910000616 Ferromanganese Inorganic materials 0.000 description 5
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/02—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
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The application belongs to the technical field of soil remediation, and particularly relates to a soil remediation agent for treating heavy metal pollution and a preparation method thereof. The preparation method comprises the following steps: (1) Performing heat treatment on sepiolite to obtain heat-treated sepiolite; (2) Carrying out acid treatment on biomass, washing the biomass with deionized water until the solution is neutral, drying the biomass in a vacuum oven to obtain a product A, ultrasonically dispersing the product A, ferric salt, cerium salt, yttrium salt, copper salt and manganese salt into methanol to obtain a solution B, dispersing dimethyl imidazole into a solution C in the methanol, adding the solution C into the solution B, mixing, stirring, filtering, washing and vacuum drying to obtain a product D; (3) And (3) mechanically and uniformly mixing the sepiolite obtained in the step (1), the product D obtained in the step (2) and diatomite, performing heat treatment, and cooling to room temperature to obtain the repairing agent. The soil restoration agent disclosed by the application has the characteristics of being capable of effectively restoring heavy metals in soil, good in removal effect, high in removal rate and the like.
Description
Technical Field
The application belongs to the technical field of soil modification. More particularly, relates to a soil restoration agent for treating heavy metal pollution and a preparation method thereof.
Background
Biochar is a porous material, and is a very promising soil conditioner because of its high carbon content and rich functional groups. It can improve soil structure and nutrient content, and has been proved to play a role in soil improvement and fertility improvement. Biochar is produced by burning biomass in a limited oxygen environment at relatively low temperatures (< 700 ℃). The nature of biochar depends to a large extent on the type of raw material, its carbon content generally exceeding 50% (except for biochar from faeces (44.3%), sewage sludge (39.6%) and paper sludge (8.15%), with some materials even reaching 70% -80%; and exhibits an aromatic carbon structure including a crystalline phase and an amorphous phase. The biochar is rich in porous structure and rich in surface functional groups, so that the bioavailability of heavy metals can be effectively reduced, and the degradation of organic pollutants can be promoted. The functional biochar material is reasonably applied, so that the pollution risk can be reduced, the soil quality can be improved, and the method is a repairing strategy for solving various environmental problems and has been applied to engineering.
CN115975646a discloses a preparation method of a biochar soil restoration agent, which comprises the following steps: 1) Taking rice hulls as raw materials, drying and crushing the rice hulls, and performing anaerobic carbonization to obtain biochar; 2) Adding the biochar into a magnesium salt solution for stirring, then heating to 70-90 ℃ in a water bath, adding a carbonate solution for continuous stirring, washing and drying to obtain silicon activated biochar; 3) Adding the silicon activated biochar into the hydroxyl modified solution, and stirring and reacting for 2-5 hours to obtain the biochar soil restoration agent. According to the application, by carrying out silicon activation and hydroxyl modification on the biochar, the high-efficiency fixation of the heavy metal in the soil is realized, and the bioavailability of the heavy metal in the passivated soil can be effectively reduced through complexation, precipitation and other actions.
CN115960611a discloses a contaminated soil restoration agent, a preparation method and application thereof. The preparation method of the contaminated soil restoration agent provided by the application comprises the following steps: 1) Taking biomass as a raw material, grinding, drying and roasting to obtain biochar; 2) Mixing the biochar in the step 1), calcium-based material and water, stirring, centrifuging, washing and drying to obtain calcium-based modified biochar; 3) In an anaerobic environment, dripping a mixed solution formed by mixing an iron system solution and a carboxymethyl cellulose solution into a reducing agent solution, stirring for reaction, centrifuging, washing, drying and grinding to obtain a carboxymethyl cellulose-nano iron composite material; 4) And mixing and ball milling the calcium-based modified biochar and the carboxymethyl cellulose-nano iron composite material to obtain the contaminated soil restoration agent. The contaminated soil restoration agent obtained by the preparation method can efficiently restore the fluorine and chromium pollution of the soil at the same time, and has stable restoration effect.
CN115637150a discloses a preparation method of ferromanganese modified biochar for cadmium contaminated soil remediation, which comprises the following steps: (1) crushing crop straws; (2) Introducing nitrogen into the straw powder for anaerobic calcination to prepare straw biochar, then placing the straw biochar in dilute nitric acid solution, stirring and standing, washing the straw biochar with deionized water for multiple times, and then drying the straw biochar; (3) Adding straw biochar into ferric salt solution, performing intermittent ultrasonic treatment, adding manganese salt solution, performing intermittent ultrasonic treatment again, heating in water bath, evaporating to dryness, soaking in n-propanol solution, cleaning, and drying for later use; (4) Introducing nitrogen into the loaded ferromanganese biochar material for anaerobic calcination; (5) And (3) placing the prepared ferromanganese modified biochar in an ethanol solution, stirring and standing, washing for many times by using deionized water, and drying to obtain the ferromanganese modified biochar. The application also provides the ferro-manganese modified biochar prepared by the method and the application method thereof, which are suitable for repairing and treating the soil with slight and moderate severe cadmium pollution, and have the advantages of low application dosage, convenient operation and obvious effect.
In conclusion, the existing soil restoration agent has low efficiency in solidifying metal ions and the like, and the removal effect still cannot meet the actual production requirement.
Disclosure of Invention
The application aims to overcome the defects and the shortcomings in the prior art and provide a soil restoration agent for treating heavy metal pollution and a preparation method thereof. The preparation method comprises the following steps: (1) Performing heat treatment on sepiolite to obtain heat-treated sepiolite; (2) Carrying out acid treatment on biomass, washing the biomass with deionized water until the solution is neutral, drying the biomass in a vacuum oven to obtain a product A, ultrasonically dispersing the product A, ferric salt, cerium salt, yttrium salt, copper salt and manganese salt into methanol to obtain a solution B, dispersing dimethyl imidazole into a solution C in the methanol, adding the solution C into the solution B, mixing, stirring, filtering, washing and vacuum drying to obtain a product D; (3) And (3) mechanically and uniformly mixing the sepiolite obtained in the step (1), the product D obtained in the step (2) and diatomite, performing heat treatment, and cooling to room temperature to obtain the repairing agent. The soil restoration agent disclosed by the application has the characteristics of being capable of effectively restoring heavy metals in soil, good in removal effect, high in removal rate and the like.
The application aims to provide a preparation method of a soil restoration agent for treating heavy metal pollution.
The application further aims to provide a soil restoration agent for treating heavy metal pollution.
The above object of the present application is achieved by the following technical scheme:
a method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Performing heat treatment on sepiolite to obtain heat-treated sepiolite;
(2) Carrying out acid treatment on biomass, washing the biomass with deionized water until the solution is neutral, drying the biomass in a vacuum oven to obtain a product A, ultrasonically dispersing the product A, ferric salt, cerium salt, yttrium salt, copper salt and manganese salt into methanol to obtain a solution B, dispersing dimethyl imidazole into a solution C in the methanol, adding the solution C into the solution B, mixing, stirring, filtering, washing and vacuum drying to obtain a product D;
(3) Mechanically mixing the sepiolite obtained in the step (1), the product D obtained in the step (2) and diatomite uniformly, and adding the mixture into O 2 And (3) carrying out heat treatment in the presence of the catalyst, and cooling to room temperature to obtain the repairing agent.
Preferably, in the step (1), the heat treatment is a heat treatment at 400 to 500 ℃ for 1 to 5 hours.
Preferably, in the step (2), the acid treatment is carried out by treating with nitric acid or sulfuric acid having a concentration of 2 to 3.0mol/L for 2 to 4 hours.
Preferably, in step (2), the ratio of product a, iron salt, cerium salt, yttrium salt, copper salt, manganese salt and dimethylimidazole is: 1g:0.15 to 0.35mmol: 0.05-0.15 mmol, 0.05-0.25 mmol, 0.02-0.08 mmol:5mmol; 20-30 mmol.
Preferably, in the step (2), the stirring is performed for 6-12 hours at room temperature; the biomass is peanut shells or corn stalks.
Preferably, in the step (2), the vacuum drying is performed at 60 to 80 ℃ for 8 to 16 hours.
Preferably, in the step (2), the iron salt is at least one of ferric nitrate, ferric chloride and ferric acetate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium acetate; the yttrium salt is at least one of yttrium nitrate, yttrium chloride and yttrium acetate; the copper salt is at least one of copper nitrate, copper chloride and copper acetate; the manganese salt is at least one of manganese nitrate, manganese chloride and manganese acetate.
Preferably, in the step (3), the mass ratio of the sepiolite obtained in the heat treatment step (1) to the product D obtained in the step (2) to the diatomite is 1:3-7:1-3.
Preferably, in step (3), the heat treatment is performed in the presence of O 2 The heat treatment is carried out for 3 to 7 hours at 150 to 250 ℃ under the condition that the concentration is 3 to 7vol percent, and then the heat treatment is carried out for 4 to 8 hours at 500 to 600 ℃ under the condition that the oxygen concentration is 1 to 3vol percent.
The soil remediation agent for treating heavy metal pollution is prepared based on the preparation method of the soil remediation agent for treating heavy metal pollution.
The application has the following beneficial effects:
(1) The active groups on the surface of the biomass can be improved by acid treatment, the adhesion of metal is facilitated, the dispersibility of the metal is improved, and the adsorption capacity of the carbonized material is improved by preparing the MOF material in situ, and by heat treatment after the MOF material is compounded with sepiolite and diatomite.
(2) The application improves the heavy metal removing capacity of the soil restoration agent by utilizing the interaction between the components.
(3) The soil restoration agent disclosed by the application has excellent heavy metal removal capability and good application prospect.
Detailed Description
The present application is further illustrated below with reference to specific examples, which are not intended to limit the application in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present application are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with nitric acid with the concentration of 2.5mol/L for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.1mmol of cerium chloride, 0.15mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution B, stirring the solution C at room temperature for 10 hours, filtering, washing the solution, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Example 2
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 500 ℃ for 1h to obtain heat-treated sepiolite;
(2) Corn straw is treated by sulfuric acid with the concentration of 3.0mol/L for 3 hours, then deionized water is used for washing until the solution is neutral, and the solution is dried in a vacuum oven to obtain a product A, 1g of the product A, 0.35mmol of ferric chloride, 0.05mmol of cerium acetate, 0.25mmol of yttrium nitrate, 0.02mmol of copper chloride and 5mmol of manganese acetate are ultrasonically dispersed into methanol to obtain a solution B, 30mmol of dimethyl imidazole is dispersed into 50mL of solution C of methanol, then the solution C is added into the solution B for mixing, stirring is carried out at room temperature for 12 hours, filtering and washing are carried out, and vacuum drying is carried out at 80 ℃ for 8 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained by the heat treatment in the step (1), 70g of the product D obtained by the step (2) and 10g of diatomiteUniform at O 2 The repairing agent is obtained by heat treatment at 250 ℃ for 3 hours under the condition that the concentration is 7vol%, then heat treatment at 600 ℃ for 4 hours under the condition that the oxygen concentration is 3vol%, and cooling to room temperature.
Example 3
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 400 ℃ for 5 hours to obtain heat-treated sepiolite;
(2) Washing biomass with nitric acid with the concentration of 2mol/L for 4 hours, washing with deionized water until the solution is neutral, drying in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.15mmol of ferric acetate, 0.15mmol of cerium chloride, 0.05mmol of yttrium acetate, 0.08mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 20mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing, stirring at room temperature for 6 hours, filtering, washing, and vacuum drying at 60 ℃ for 16 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 30g of product D obtained in step (2) and 30g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 150 ℃ for 7 hours under the condition that the concentration is 3vol%, then heat treatment at 500 ℃ for 8 hours under the condition that the oxygen concentration is 1vol%, and cooling to room temperature.
Comparative example 1
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with 2.5mol/L nitric acid for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.35mmol of ferric nitrate, 0.15mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution C, stirring the solution C at room temperature for 10 hours, filtering, washing, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 2
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with 2.5mol/L nitric acid for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.35mmol of cerium chloride, 0.15mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution C, stirring the solution C at room temperature for 10 hours, filtering, washing, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 3
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with 2.5mol/L nitric acid for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the peanut shells in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.25mmol of cerium chloride, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution C, stirring the solution C at room temperature for 10 hours, filtering, washing, and vacuum drying the solution C at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 4
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with 2.5mol/L nitric acid for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.25mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution C, stirring the solution C at room temperature for 10 hours, filtering, washing, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 5
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with 2.5mol/L nitric acid for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.1mmol of cerium chloride, 0.2mmol of yttrium acetate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution C, stirring the solution C at room temperature for 10 hours, filtering, washing, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 6
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with 2.5mol/L nitric acid for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the peanut shells in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.1mmol of cerium chloride, 0.2mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution C, stirring the solution C at room temperature for 10 hours, filtering, washing, and vacuum drying the solution C at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 7
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with nitric acid with the concentration of 2.5mol/L for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.1mmol of cerium chloride, 0.15mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution B, stirring the solution C at room temperature for 10 hours, filtering, washing the solution, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 5vol%, and cooling to room temperature.
Comparative example 8
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with nitric acid with the concentration of 2.5mol/L for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.1mmol of cerium chloride, 0.15mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution B, stirring the solution C at room temperature for 10 hours, filtering, washing the solution, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 2vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 9
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with nitric acid with the concentration of 2.5mol/L for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.1mmol of cerium chloride, 0.15mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution B, stirring the solution C at room temperature for 10 hours, filtering, washing the solution, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) And (3) mechanically and uniformly mixing 10g of sepiolite obtained in the step (1), 50g of the product D obtained in the step (2) and 20g of diatomite, performing heat treatment at 200 ℃ for 5 hours under an inert atmosphere, performing heat treatment at 550 ℃ for 6 hours, and cooling to room temperature to obtain the repairing agent.
Comparative example 10
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with hydrochloric acid with the concentration of 2.5mol/L for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.1mmol of cerium chloride, 0.15mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution B, stirring the solution C at room temperature for 10 hours, filtering, washing the solution, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1), 50g of product D obtained in step (2) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 11
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Treating peanut shells with nitric acid with the concentration of 2.5mol/L for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.1mmol of cerium chloride, 0.15mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution B, stirring the solution C at room temperature for 10 hours, filtering, washing the solution, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(2) 60g of the product D obtained in the step (1) and 20g of diatomite are mechanically mixed uniformly, and the mixture is treated with the mixture in O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 12
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Mechanically mixing 60g of sepiolite obtained in step (1) and 20g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 13
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Treating peanut shells with nitric acid with the concentration of 2.5mol/L for 3 hours, washing the peanut shells with deionized water until the solution is neutral, drying the solution in a vacuum oven to obtain a product A, ultrasonically dispersing 1g of the product A, 0.25mmol of ferric nitrate, 0.1mmol of cerium chloride, 0.15mmol of yttrium acetate, 0.05mmol of copper nitrate and 5mmol of manganese chloride into 50mL of methanol to obtain a solution B, dispersing 25mmol of dimethyl imidazole into 50mL of solution C of methanol, adding the solution C into the solution B, mixing the solution B, stirring the solution C at room temperature for 10 hours, filtering, washing the solution, and vacuum drying the solution at 70 ℃ for 12 hours to obtain a product D;
(3) Mechanically mixing 10g of sepiolite obtained in step (1) and 70g of product D obtained in step (2) uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Comparative example 14
A method for preparing a soil remediation agent for treating heavy metal pollution, the method comprising the following steps:
(1) Heat-treating sepiolite at 450 ℃ for 3 hours to obtain heat-treated sepiolite;
(2) Mechanically mixing 10g of sepiolite obtained in step (1) with 70g of diatomite uniformly, and adding the mixture into O 2 The repairing agent is obtained by heat treatment at 200 ℃ for 5 hours under the condition that the concentration is 5vol%, then heat treatment at 550 ℃ for 6 hours under the condition that the oxygen concentration is 2vol%, and cooling to room temperature.
Preparing polluted soil, and measuring to obtain actual measurement values of Cd, pb and Cu in the polluted soil sample of 4.2, 256 and 523 mg.kg respectively -1 。
Weighing 500g of contaminated soil, placing the contaminated soil in 500mL beakers, repeating the adsorption treatment for 3 times each time, fully mixing 10g of the soil pollution restoration agents of examples 1-3 and comparative examples 1-14 with the contaminated soil according to the proportion, sealing each beaker by using a preservative film penetrating through holes, placing the beakers at room temperature for immobilization reaction, and supplementing deionized water into the beakers every 5d in the reaction process so as to keep the water content of the soil to be about 30%.
The immobilization effect of the soil remediation agents of examples 1-3 and comparative examples 1-14 on soil heavy metals after 15 days and 20 days was evaluated by the TCLP method, the concrete results are shown in tables 1-2, the TCLP measurement adopts the method in the environmental protection industry standard (HJ/T300-2007) of the people's republic of China, namely, the leaching process is that acetic acid and sodium hydroxide buffer solution are adopted: 30mL of TCLP extract was added to 1.5g of soilTaking liquid (solid-liquid ratio 1:20) at 30 r.min -1 Is reacted for 18h on a flip-flop oscillator and then at 2000r.min -1 Centrifuging at a speed for 20min, filtering with a 0.45 μm filter membrane, and measuring the concentration of heavy metal in the supernatant by adopting an Inductively Coupled Plasma (ICP) emission spectrometry. The preparation method of the TCLP extract comprises the following steps: adding 5.7mL of glacial acetic acid into distilled water, and adopting 1 mol.L -1 NaOH and HNO of (C) 3 The pH value of the solution is regulated to 4.9, and the volume is fixed to 1L for standby.
TABLE 1 immobilization effect of examples 1-3 and comparative examples 1-14 for 15 days
| Cd removal rate (%) | Pd removal Rate (%) | Cu removal Rate (%) | |
| Example 1 | 83.5 | 85.3 | 84.6 |
| Example 2 | 82.4 | 84.1 | 83.2 |
| Example 3 | 83.2 | 84.8 | 84.1 |
| Comparative example 1 | 81.5 | 82.6 | 81.8 |
| Comparative example 2 | 81.9 | 83.4 | 82.5 |
| Comparative example 3 | 81.3 | 82.3 | 81.5 |
| Comparative example 4 | 81.6 | 82.8 | 81.9 |
| Comparative example 5 | 81.4 | 82.5 | 81.6 |
| Comparative example 6 | 81.7 | 82.9 | 82.2 |
| Comparative example 7 | 81.8 | 83.2 | 82.3 |
| Comparative example 8 | 82.1 | 83.5 | 82.6 |
| Comparative example 9 | 80.9 | 81.9 | 81.1 |
| Comparative example 10 | 81.2 | 82.2 | 81.3 |
| Comparative example 11 | 75.9 | 81.6 | 76.1 |
| Comparative example 12 | 65.3 | 68.4 | 66.7 |
| Comparative example 13 | 76.3 | 81.8 | 77.4 |
| Comparative example 14 | 59.8 | 61.4 | 60.8 |
TABLE 2 immobilization effect of examples 1-3 and comparative examples 1-14 for 20 days
| Cd removal rate (%) | Pd removal Rate (%) | Cu removal Rate (%) | |
| Example 1 | 91.4 | 95.3 | 92.6 |
| Example 2 | 90.3 | 94.2 | 91.2 |
| Example 3 | 90.9 | 94.8 | 91.9 |
| Comparative example 1 | 89.3 | 93.1 | 90.2 |
| Comparative example 2 | 89.9 | 93.7 | 90.8 |
| Comparative example 3 | 88.9 | 92.8 | 89.7 |
| Comparative example 4 | 89.5 | 93.2 | 90.3 |
| Comparative example 5 | 89.2 | 92.9 | 89.9 |
| Comparative example 6 | 89.6 | 93.4 | 90.5 |
| Comparative example 7 | 89.8 | 93.6 | 90.7 |
| Comparative example 8 | 90.1 | 93.9 | 90.9 |
| Comparative example 9 | 88.6 | 92.4 | 89.5 |
| Comparative example 10 | 88.8 | 92.6 | 89.6 |
| Comparative example 11 | 82.9 | 85.9 | 84.1 |
| Comparative example 12 | 73.1 | 74.8 | 74.2 |
| Comparative example 13 | 83.4 | 87.2 | 84.8 |
| Comparative example 14 | 69.2 | 71.5 | 70.1 |
From the comparison of examples 1-3 and comparative examples 1-14, it can be seen that the soil restoration agent prepared by the application has excellent solidification effect and higher heavy metal removal effect by utilizing the interaction between the components, and has excellent application prospect.
The above examples are preferred embodiments of the present application, but the embodiments of the present application are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present application should be made in the equivalent manner, and the embodiments are included in the protection scope of the present application.
Claims (10)
1. The preparation method of the soil restoration agent for treating heavy metal pollution is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) Performing heat treatment on sepiolite to obtain heat-treated sepiolite;
(2) Carrying out acid treatment on biomass, washing the biomass with deionized water until the solution is neutral, drying the biomass in a vacuum oven to obtain a product A, ultrasonically dispersing the product A, ferric salt, cerium salt, yttrium salt, copper salt and manganese salt into methanol to obtain a solution B, dispersing dimethyl imidazole into a solution C in the methanol, adding the solution C into the solution B, mixing, stirring, filtering, washing and vacuum drying to obtain a product D;
(3) Mechanically mixing the sepiolite obtained in the step (1), the product D obtained in the step (2) and diatomite uniformly, and adding the mixture into O 2 And (3) carrying out heat treatment in the presence of the catalyst, and cooling to room temperature to obtain the repairing agent.
2. The method for preparing the soil remediation agent for treating heavy metal pollution according to claim 1, wherein the method comprises the following steps: in the step (1), the heat treatment is carried out at 400-500 ℃ for 1-5 h.
3. The method for preparing the soil remediation agent for treating heavy metal pollution according to claim 1, wherein the method comprises the following steps: in the step (2), the acid treatment is carried out by using nitric acid or sulfuric acid with the concentration of 2-3.0mol/L for 2-4 hours.
4. The method for preparing the soil remediation agent for treating heavy metal pollution according to claim 1, wherein the method comprises the following steps: in step (2), the ratio of the product A, iron salt, cerium salt, yttrium salt, copper salt, manganese salt and dimethylimidazole is: 1g:0.15 to 0.35mmol: 0.05-0.15 mmol, 0.05-0.25 mmol, 0.02-0.08 mmol:5mmol; 20-30 mmol.
5. The method for preparing the soil remediation agent for treating heavy metal pollution according to claim 1, wherein the method comprises the following steps: in the step (2), stirring is carried out for 6-12 hours at room temperature; the biomass is peanut shells or corn stalks.
6. The method for preparing the soil remediation agent for treating heavy metal pollution according to claim 1, wherein the method comprises the following steps: in the step (2), the vacuum drying is performed at 60-80 ℃ for 8-16 h.
7. The method for preparing the soil remediation agent for treating heavy metal pollution according to claim 1, wherein the method comprises the following steps: in the step (2), the ferric salt is at least one of ferric nitrate, ferric chloride and ferric acetate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium acetate; the yttrium salt is at least one of yttrium nitrate, yttrium chloride and yttrium acetate; the copper salt is at least one of copper nitrate, copper chloride and copper acetate; the manganese salt is at least one of manganese nitrate, manganese chloride and manganese acetate.
8. The method for preparing the soil remediation agent for treating heavy metal pollution according to claim 1, wherein the method comprises the following steps: in the step (3), the mass ratio of the sepiolite obtained in the heat treatment step (1) to the product D obtained in the step (2) to the diatomite is 1:3-7:1-3.
9. The method for preparing the soil remediation agent for treating heavy metal pollution according to claim 1, wherein the method comprises the following steps: in step (3), the heat treatment is performed in the presence of O 2 The heat treatment is carried out for 3 to 7 hours at 150 to 250 ℃ under the condition that the concentration is 3 to 7vol percent, and then the heat treatment is carried out for 4 to 8 hours at 500 to 600 ℃ under the condition that the oxygen concentration is 1 to 3vol percent.
10. A soil restoration agent for treating heavy metal pollution prepared by the method for preparing a soil restoration agent for treating heavy metal pollution according to any one of claims 1 to 9.
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