CN115011352B - Iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, and preparation method and application method thereof - Google Patents
Iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, and preparation method and application method thereof Download PDFInfo
- Publication number
- CN115011352B CN115011352B CN202210683824.8A CN202210683824A CN115011352B CN 115011352 B CN115011352 B CN 115011352B CN 202210683824 A CN202210683824 A CN 202210683824A CN 115011352 B CN115011352 B CN 115011352B
- Authority
- CN
- China
- Prior art keywords
- iron
- repair material
- carbon
- composite
- biochar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 98
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002689 soil Substances 0.000 title claims abstract description 76
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002905 metal composite material Substances 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000002131 composite material Substances 0.000 claims abstract description 114
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 claims abstract description 48
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 9
- 230000008439 repair process Effects 0.000 claims description 61
- 238000002156 mixing Methods 0.000 claims description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000011282 treatment Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 13
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 10
- 238000003878 thermal aging Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000011418 maintenance treatment Methods 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011257 shell material Substances 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 238000002386 leaching Methods 0.000 abstract description 13
- 230000002195 synergetic effect Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 229910052785 arsenic Inorganic materials 0.000 description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000003900 soil pollution Methods 0.000 description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 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 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 241001478887 unidentified soil bacteria Species 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to an iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, a preparation method and a use method thereof, wherein the iron-carbon-based restoration material comprises the following components: iron-carbon based composite material, pH adjuster, oxidant and adsorption auxiliary; the iron-carbon-based composite material comprises a biochar-nano zero-valent iron composite material and an iron-based oxide-hydrothermal carbon composite material. The iron-carbon-based restoration material utilizes the synergistic effect among the components to simultaneously solidify and stabilize the heavy metals in the composite polluted soil, and can reduce the leaching concentration of the heavy metals, thereby further reducing the mobility of the heavy metals, and also can oxidize and decompose the organic matters in the polluted soil, and has restoration effect on various organic matters and heavy metal composite polluted soil.
Description
Technical Field
The invention belongs to the field of soil pollution treatment, and particularly relates to an iron-carbon-based restoration material for organic matter-heavy metal combined polluted soil, and a preparation method and a use method thereof.
Background
Soil is one of irreversible natural resources in nature, and provides an essential material basis for human survival. Nowadays, with the rapid development of human production and living, soil is more and more polluted. At present, organic matter-heavy metal combined pollution is a common soil pollution form, and because complex interaction exists between heavy metal and organic matter, and the repairing mechanism is different, if effective treatment is not carried out, pollution substances are accumulated, and great influence is caused on human health and soil environment. At present, the research on the polluted soil mainly stays in the research on single-kind pollutants, and the research on the restoration technology of the organic matter-heavy metal combined polluted soil is less. Therefore, the method for treating the organic matter-heavy metal composite polluted soil has important significance in the aspects of ecological environment, human health and the like.
At present, researchers have studied on restoration materials for organic matter-heavy metal composite contaminated soil. CN104327859B discloses a soil in-situ remediation agent for simultaneous remediation of heavy metal and organic pollution, the in-situ remediation agent comprising a mixture a and a mixture B, the mixture a comprising the following components: 100 parts of Hangjin No. 2 soil, 10-30 parts of activated carbon, 20-50 parts of cement and 2-5 parts of organic flocculant, wherein the mixture B comprises the following components: 16-32 parts of sodium thiosulfate and any two or more of the following components: 16-32 parts of ferric oxide, 48-96 parts of calcium sulfate, 32-80 parts of aluminum sulfate and 16-32 parts of alkali metal carbonate, wherein the mixture B accounts for 20-30% of the total mass; the mixture A also contains soil bacteria. The method can degrade and adsorb organic pollutants in soil through the synergistic effect of multiple components.
CN212494528U discloses a repairing device system for soil organic matters and heavy metal pollution, which comprises a crushing device, a screening device, a first mixing device, a rotary kiln, a gas-solid separation device, an electrode tank spray liquid storage device, a water storage device and a second mixing device; the electrode tank is provided with an anode plate and a cathode plate, and soil treated by the rotary kiln is placed between the anode plate and the cathode plate; the repairing device system can treat organic matters in the soil and can also treat heavy metals in the soil after the organic matters are removed through the arrangement of the rotary kiln and the electrode groove. The repairing device system has large occupied area and high equipment operation cost.
CN109248912a discloses a method for repairing nickel and organic contaminated soil, which comprises the following steps: (1) Crushing soil, adding the crushed soil into an acidic mixed solution containing ferric sulfate and hydrogen peroxide, stirring for reaction, filtering and drying; (2) Adding straw particles and calcium oxide powder into the soil obtained in the step (1), mixing, carrying out vacuum pyrolysis reaction at 840-850 ℃ for 30min, cooling to 400 ℃ for 1h, and cooling to room temperature; (3) Grinding the soil treated in the step (2), and sucking iron powder and nickel powder in the soil particles by adopting a magnet to obtain the treated soil. The method separates nickel and organic matters through high-temperature strengthening decomposition, carbothermal reduction and magnetic separation. However, the method needs to decompose soil at high temperature, waste gas generated by treating the soil polluted by organic matters in a thermal decomposition mode cannot be effectively purified, the problems of pollutant diffusion, migration and the like are easily caused, iron powder and nickel powder are required to be absorbed by a magnet, the process flow is complex, and the energy consumption is high.
CN107282617a discloses a method for repairing soil polluted by polycyclic aromatic hydrocarbon-heavy metal, which comprises the following steps: the weight ratio of the eluent to the soil is 10: 1-30: 1, adding a leaching agent to leach the polycyclic aromatic hydrocarbon-heavy metal polluted soil for 12 to 24 hours; the leaching agent consists of 5000-8000 mg/L of N-dodecanoyl ED3A solution and 200-300 mg/L of chitosan solution; the volume ratio of the N-dodecanoyl ED3A solution to the chitosan solution is 3-5: 1. the chelating surfactant-N-lauroyl ED3A is compounded with chitosan solution to be used as a eluting agent, but the secondary pollution of the environment such as groundwater is easy to cause, the cost is high, the radical treatment is difficult, and the chelating surfactant-N-lauroyl ED3A is not suitable for industrial application.
At present, aiming at the composivity and diversity of organic matter-heavy metal soil pollution, a pollution soil restoration material which is low in cost, easy to obtain, convenient to use, environment-friendly, efficient and has restoration effect on organic matter-heavy metal is provided, and the pollution soil restoration material is still a technical problem to be solved by a person skilled in the art.
Disclosure of Invention
In order to solve the technical problems, the invention provides the iron-carbon-based restoration material for the organic matter-heavy metal composite contaminated soil, and the preparation method and the application method thereof. The iron-carbon-based restoration material utilizes the synergistic effect of the components, and can be used for carrying out oxidative decomposition on organic pollutants and solidification and stabilization on heavy metals in the composite polluted soil.
In order to achieve the technical effects, the invention adopts the following technical scheme:
in a first aspect, the invention provides an iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, which comprises the following components: iron-carbon based composite material, pH adjuster, oxidant and adsorption auxiliary;
the iron-carbon-based composite material comprises a biochar-nano zero-valent iron composite material and an iron-based oxide-hydrothermal carbon composite material.
According to the invention, the iron-carbon-based restoration material utilizes the synergistic effect of the components to carry out oxidative decomposition on organic matters in the organic matter-heavy metal composite polluted soil and solidification and stabilization on heavy metals. The invention utilizes the synergistic effect of iron and carbon based composite materials, can oxidatively decompose easily degradable organic matters and reduce the mobility of heavy metal pollutants.
The physical and chemical synergistic effect of the iron-carbon-based composite material in the invention mainly comprises the following steps: the iron-carbon-based composite material is equivalent to a plurality of tiny iron-carbon primary batteries, has small particle size and large specific surface area, reduces mass transfer resistance, is beneficial to quick degradation of organic pollutants in soil and precipitation of heavy metal elements on the surface of the iron-carbon-based composite material in a simple substance form through electrolytic reaction, and achieves the purposes of degrading organic matters and reducing weightThe purpose of the mobility of the metal element; the metal activity sequence or the metal standard electrode potential can show that the element positioned behind the iron in the metal activity sequence can be replaced by the iron to be attached to the surface of the iron, and the iron is separated out in the form of ferrous ions; some of the more oxidizing ions or compounds are capable of being reduced by iron or ferrous ions to lower valent ions or compounds, such as hexavalent chromium to lower toxic, lower mobility trivalent chromium; when the metal element is reduced to simple substance, a large amount of Fe is accompanied 3+ And Fe (Fe) 2+ Ion precipitation, when the medium is weakly acidic to alkaline, forms Fe (OH) 2 And Fe (OH) 3 Flocs, newly formed Fe (OH) 2 And Fe (OH) 3 The flocculation precipitation capability of the floccules is far higher than that of Fe (OH) formed by the hydrolysis of common ferric trichloride, polymeric ferric sulfate and the like 2 And Fe (OH) 3 The flocculation precipitation capability of the flocs can adsorb heavy metal ions on the surface of the flocs to form coprecipitation, so that the mobility of the heavy metal ions is effectively reduced.
As a preferable technical scheme of the invention, the preparation process of the biochar-nano zero-valent iron composite material comprises the following steps: and stirring and mixing the biochar and the nano zero-valent iron to obtain the biochar-nano zero-valent iron composite material.
Preferably, the mass ratio of the biochar to the nano zero-valent iron is 1: (1-3) may be, for example, 1:1, 1:1.5, 1:2, 1:2.5, or 1:3, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the stirring speed is 200-800 r/min, for example, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min or 800r/min, etc., but the stirring speed is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the mixing time is 8 to 12 hours, for example, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours or 12 hours, etc., but not limited to the recited values, other non-recited values in the range of values are equally applicable.
Preferably, the preparation method of the biochar comprises the following steps: calcining bamboo and/or coconut shell at 600-650 ℃ for 1.5-2 h, and grinding to obtain the biochar.
In the present invention, the calcination temperature may be 600 to 650 ℃, for example, 600 ℃, 605 ℃, 610 ℃, 615 ℃, 620 ℃, 625 ℃, 630 ℃, 635 ℃, 640 ℃, 645 ℃, 650 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are equally applicable.
In the present invention, the calcination time is 1.5 to 2 hours, and may be, for example, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, or 2 hours, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
The particle size after grinding is preferably 200 to 300nm, and may be, for example, 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm or 300nm, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the preparation method of the nano zero-valent iron comprises the following steps: mixing ferrous salt, a dispersing agent and a solvent, and then adding a reducing agent to obtain the nano zero-valent iron.
Preferably, the dispersant comprises polyvinylpyrrolidone.
Preferably, the reducing agent comprises sodium borohydride and/or hydrazine hydrate.
Preferably, the mass ratio of the ferrous salt to the dispersing agent is 1: (1-20), for example, may be 1:1, 1:3, 1:5, 1:7, 1:9, 1:10, 1:15, or 1:20, etc., but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the molar ratio of the ferrous salt to the reducing agent is 1: (2-6), for example, may be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:5, or 1:6, etc., but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the preparation method of the nano zero-valent iron is a liquid-phase chemical reduction method.
As a preferred technical scheme of the invention, the iron-based oxide-hydrothermal carbon composite material comprises an iron oxide-hydrothermal carbon composite material and/or an iron zinc oxide-hydrothermal carbon composite material.
Preferably, the preparation process of the iron oxide-hydrothermal carbon composite material comprises the following steps: mixing ferric salt, glucose and water, adjusting pH, and performing thermal aging treatment.
Preferably, the molar ratio of iron to carbon element in the iron oxide-hydrothermal carbon composite is 1: (1-6), for example, may be 1:1, 1:2, 1:3, 1:4, 1:5, or 1:6, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the mixing time is 0.5-1h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the pH is adjusted to 2 to 8, for example, 2, 3, 4, 5, 6, 7, or 8, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The temperature of the heat aging is preferably 160 to 180 ℃, and may be 160 to 162 ℃, 164 ℃, 166 ℃, 168 ℃, 170 ℃, 172 ℃, 174 ℃, 176 ℃, 178 ℃, 180 ℃ or the like, for example, but the heat aging is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the time of the heat aging is 8 to 12 hours, for example, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours or 12 hours, etc., but not limited to the recited values, other non-recited values in the range of values are equally applicable.
As a preferable technical scheme of the invention, the preparation process of the iron-zinc oxide-hydrothermal carbon composite material comprises the following steps: mixing trivalent ferric salt and zinc salt with glucose, adjusting pH, and performing thermal aging treatment.
Preferably, the molar ratio of iron, zinc and carbon elements in the iron-zinc oxide-hydrothermal carbon composite is 1:0.5: (1-6) may be, for example, 1:0.5:1, 1:0.5:2, 1:0.5:3, 1:0.5:4, 1:0.5:5 or 1:0.5:6, etc., but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the mixing time is 0.5-1h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the pH is adjusted to a pH of 11 to 13, for example, 11, 11.5, 12, 12.5, 13, or the like, but the pH is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The temperature of the heat aging is preferably 120 to 160 ℃, and may be 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, or the like, for example, but the heat aging is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the time of the heat aging is 8 to 12 hours, for example, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours or 12 hours, etc., but not limited to the recited values, other non-recited values in the range of values are equally applicable.
As a preferred embodiment of the present invention, the pH adjuster includes an acidic adjuster and/or a basic adjuster.
Preferably, the acidity regulator comprises any one or a combination of at least two of citric acid, malic acid or oxalic acid, typical but non-limiting examples of which are: a combination of citric acid and malic acid, a combination of malic acid and oxalic acid, or a combination of citric acid, malic acid and oxalic acid, and the like.
Preferably, the alkaline modifier comprises any one or a combination of at least two of calcium oxide, magnesium oxide, shell powder or sodium sulfide, typical but non-limiting examples of which are: a combination of calcium oxide and magnesium oxide, a combination of magnesium oxide and shell powder, or a combination of shell powder and sodium sulfide, etc.
Preferably, the oxidizing agent comprises any one or a combination of at least two of sodium thiosulfate, sodium hypochlorite or hydrogen peroxide, typical but non-limiting examples of which are: sodium thiosulfate is preferable, for example, a combination of sodium thiosulfate and sodium hypochlorite, a combination of sodium hypochlorite and hydrogen peroxide, or a combination of hydrogen peroxide and sodium thiosulfate.
Preferably, the adsorption aid comprises any one or at least two combinations of zeolite, sepiolite and montmorillonite, typical but non-limiting examples of which are: the combination of zeolite and sepiolite, the combination of sepiolite and montmorillonite, or the combination of montmorillonite and zeolite, etc., is preferably montmorillonite.
Preferably, the montmorillonite comprises an acid modified montmorillonite.
The particle size of the adsorption auxiliary is preferably 200 to 250 mesh, and may be, for example, 200 mesh, 210 mesh, 220 mesh, 230 mesh, 240 mesh, 250 mesh, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred technical scheme of the invention, the iron-carbon-based composite material further comprises an iron oxyhydroxide-hydrothermal carbon and/or biochar composite material.
Preferably, the molar ratio of iron to carbon element in the iron oxyhydroxide-hydrothermal carbon and/or biochar composite is 3: (2-5), for example, may be 3:2, 3:2.5, 3:3, 3:3.5, 3:4, 3:4.5, or 3:5, etc., but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the preparation process of the iron oxyhydroxide-hydrothermal carbon and/or biochar composite material comprises the following steps: and stirring and mixing the iron oxyhydroxide and the hydrothermal carbon and/or the biochar to obtain the iron oxyhydroxide-hydrothermal carbon and/or the biochar composite material.
Preferably, the stirring speed is 200-800 r/min, for example, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min or 800r/min, etc., but the stirring speed is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the preparation method of the hydrothermal carbon comprises the following steps: glucose and a solvent are mixed, and a hydrothermal reaction is performed after the pH is adjusted.
In the invention, the solid-to-liquid ratio of the glucose to the solvent is 1: (10-20) g/mL, for example, may be 1:10g/mL, 1:12g/mL, 1:14g/mL, 1:16g/mL, 1:18g/mL, or 1:20g/mL, etc., but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the pH is adjusted to a pH of 1.5 to 3 or 10 to 12.
In the present invention, the pH is adjusted to a pH of 1.5 to 3, and may be, for example, 1.5, 1.7, 1.9, 2, 2.2, 2.4, 2.6, 2.8, or 3, but not limited to the values recited, and other values not recited in the numerical range are equally applicable. The pH value is adjusted to 1.5-3, and the prepared acid modified hydrothermal carbon is obtained.
In the present invention, the pH is adjusted to 10 to 12, and for example, 10, 10.2, 10.4, 10.6, 10.8, 11, 11.2, 11.4, 11.6, 11.8 or 12 may be used, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable. The pH value is adjusted to 10-12, and the prepared alkali modified hydrothermal carbon is obtained.
The temperature of the hydrothermal reaction is preferably 160 to 180 ℃, and may be 160 to 162 ℃, 164 ℃, 166 ℃, 168 ℃, 170 ℃, 172 ℃, 174 ℃, 176 ℃, 178 ℃, 180 ℃ or the like, for example, but the reaction is not limited to the above-mentioned values, and other values not mentioned in the numerical range are equally applicable.
Preferably, the hydrothermal reaction time is 4 to 8 hours, and may be, for example, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, or 8 hours, etc., but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
In the invention, the iron oxyhydroxide is prepared by a solvothermal method.
In the invention, different iron-carbon-based composite materials are selected according to the types of organic matters, such as VOC, SVOC or petroleum hydrocarbon, etc., iron-based oxide-hydrothermal carbon composite materials, iron oxyhydroxide-hydrothermal carbon/biochar are selected, such as halocarbon, etc., and biochar-nano zero-valent iron composite materials are selected.
As a preferable technical scheme of the invention, the repairing material comprises the following components in parts by weight:
the iron-carbon composite material may be 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or the like, the pH adjuster may be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, the adsorption auxiliary may be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, or 12 parts, or the like, and the oxidant may be 8 parts, 9 parts, 10 parts, 11 parts, or 12 parts, or the like, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In the invention, the contents of the four components have interaction, the content of any one component is too small, and the stabilizing effect of the system is poor, so that the removing effect on organic matters and heavy metals is poor, and partial pollutants can be dissolved out secondarily; in the invention, when the content of the iron-carbon-based composite material is too small, heavy metals cannot be sufficiently stabilized and organic matters cannot be sufficiently catalyzed and removed; in the invention, when the content of the pH regulator is too small, the pH value of the repairing system cannot be effectively regulated, and the efficacy of main active ingredients is exerted; in the invention, when the content of the adsorption auxiliary agent is too small, the adsorption fixing effect of the main body adsorption material cannot be fully exerted; in the present invention, when the content of the oxidizing agent is too small, the oxidation-reduction potential of the repair environment cannot be improved.
Preferably, the repairing material comprises the following components in parts by weight:
the iron-carbon composite material may be 13 parts, 14 parts, 15 parts, etc., the pH adjuster may be 6 parts, 7 parts, 8 parts, etc., the adsorption auxiliary may be 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc., the oxidant may be 10 parts, 11 parts, 12 parts, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
In a second aspect, the present invention provides a method for preparing the iron-carbon-based repair material according to the first aspect, the method comprising: mixing the iron-carbon-based composite material with an adsorption auxiliary agent to obtain a component A, and mixing a pH regulator with an oxidant to obtain a component B to obtain the iron-carbon-based repair material containing the component A and the component B.
In the invention, the A component mainly provides basic adsorption effect and gain restoration effect, the B component mainly provides acid-base regulation and redox environment regulation functions, and the A component and the B component are used together to exert the restoration effect of the material and the condition modulation effect by using environmental factors to the greatest extent.
In the present invention, the particle size of the component A is 150 to 200 mesh, for example, 150 mesh, 160 mesh, 170 mesh, 180 mesh, 190 mesh or 200 mesh, etc., but the present invention is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In the present invention, the particle size of the component B is 100 to 150 mesh, for example, 100 mesh, 110 mesh, 120 mesh, 130 mesh, 140 mesh or 150 mesh, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
In a third aspect, the present invention also provides a method for using the iron-carbon-based repair material prepared by the preparation method of the second aspect, the method comprising: and mixing the component A and the component B in the repairing material with the composite polluted soil according to the formula amount, and then mixing with water for maintenance treatment.
In the invention, the composite polluted soil comprises organic matter and heavy metal composite polluted soil or heavy metal polluted soil.
As a preferable technical scheme of the invention, the mass ratio of the total mass of the component A and the component B in the iron-carbon-based restoration material to the mass of the composite polluted soil is (0.03-0.05): 1, for example, 0.03:1, 0.035:1, 0.04:1, 0.045:1 or 0.05:1 and the like can be adopted, but the iron-carbon-based restoration material is not limited to the listed numerical values, and other non-listed numerical values in the numerical range are applicable.
Preferably, the mass ratio of the composite polluted soil to the water is 9: (1-3), for example, may be 9:1, 9:1.5, 9:2, 9:2.5, or 9:3, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 9: (2-3).
The curing treatment is preferably carried out at a temperature of 0 to 50 ℃, and may be carried out at 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or the like, for example, but the curing treatment is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the curing treatment is carried out for a period of not less than 8 days, for example, 8 days, 10 days, 12 days, 14 days, 15 days, 16 days, 18 days or 20 days, etc., but the curing treatment is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are equally applicable, preferably 10 to 15 days.
Compared with the prior art, the invention has the following beneficial effects:
the iron-carbon-based restoration material disclosed by the invention utilizes the synergistic effect of the components, simultaneously solidifies and stabilizes the heavy metals in the composite polluted soil, and can reduce the leaching concentration of the heavy metals, so that the mobility of the heavy metals is further reduced, and the iron-carbon-based restoration material can also be used for oxidizing and decomposing organic matters in the polluted soil, has restoration effects on various organic matters and heavy metal composite polluted soil, and can effectively realize restoration of the organic matter polluted soil, wherein the restoration effects are stable for a long time and no secondary pollution; the iron-carbon-based restoration material can respectively reduce the leaching concentration of heavy metals such as arsenic below the IV restoration standard value of the groundwater quality standard (GB/T14848-2017) and reduce the organic content below the second class land screening value of the soil pollution risk management and control standard of the soil environment quality standard construction land (GB 36600-2018); the iron-carbon-based repair material has the advantages of low cost, easy obtainment, moderate dosage, strong practicability, environmental protection, high efficiency and the like.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides an iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, a preparation method and a use method thereof, wherein the iron-carbon-based restoration material comprises 14 parts of iron-carbon-based composite material, 8 parts of pH regulator, 10 parts of oxidant and 8 parts of adsorption auxiliary agent;
the iron-carbon-based composite material comprises 4.6g of biochar-nano zero-valent iron composite material, 4.7g of iron oxide-hydrothermal carbon composite material and 4.7g of iron oxyhydroxide-acid modified hydrothermal carbon composite material;
the preparation process of the biochar-nano zero-valent iron composite material comprises the following steps: stirring and mixing 5.0g of biochar and 5.0g of nano zero-valent iron for 10 hours at a rotating speed of 500 r/min; the preparation method of the biochar comprises the following steps: calcining bamboo and coconut shells at 620 ℃ for 1.7h, and then grinding to the particle size of 250nm, wherein the preparation method of the nano zero-valent iron comprises the following steps: 5.0g of ferrous chloride, 15.0g of polyvinylpyrrolidone and deionized water were mixed, and then sodium borohydride was added, the molar ratio of ferrous chloride to reducing agent being 1:2;
the preparation process of the iron oxide-hydrothermal carbon composite material comprises the following steps: mixing ferric nitrate and glucose with water for 0.7h according to the molar ratio of 1:0.5, adjusting the pH value of the solution to 5, and then carrying out thermal aging treatment at 170 ℃ for 10h;
the preparation process of the iron oxyhydroxide-acid modified hydrothermal carbon composite material comprises the following steps: the molar ratio of iron to carbon element is 3:3, stirring and mixing the iron oxyhydroxide and the hydrothermal carbon at a rotating speed of 500 r/min; the preparation method of the iron oxyhydroxide is a solvothermal method, and the preparation method of the acid-modified hydrothermal carbon comprises the following steps: according to the solid-to-liquid ratio of 1: mixing glucose and deionized water at a concentration of 10g/mL, adjusting the pH of the solution to 2, and performing hydrothermal reaction at 170 ℃ for 6 hours;
the pH regulator is citric acid;
the oxidant is sodium thiosulfate;
the adsorption auxiliary agent is montmorillonite with the particle size of 220 meshes;
the preparation method of the iron-carbon-based repair material comprises the following steps: mixing the iron-carbon-based composite material and montmorillonite, grinding until the average particle size of the mixture is 150 meshes, mixing citric acid and sodium thiosulfate as a component A, and grinding until the average particle size of the mixture is 100 meshes, and obtaining the iron-carbon-based repair material as a component B;
the iron-carbon-based restoration material is used for restoring the composite polluted soil containing arsenic and benzene, and the use method comprises the following steps:
the component A and the component B in the iron-carbon-based repair material are pre-mixed according to the formula amount, and then the mass ratio is 0.03:1, mixing the iron-carbon-based restoration material with the composite polluted soil, and then adding water for mixing, wherein the mass ratio of the composite polluted soil to the water is 9:2, curing at 25 ℃ for 12 days.
Example 2
The embodiment provides an iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, a preparation method and a use method thereof, wherein the iron-carbon-based restoration material comprises 20 parts of iron-carbon-based composite material, 5 parts of pH regulator, 12 parts of oxidant and 5 parts of adsorption auxiliary agent;
the iron-carbon-based composite material comprises 5.0g of biochar-nano zero-valent iron composite material, 5.0g of iron oxide-hydrothermal carbon composite material, 5.0g of iron zinc oxide-hydrothermal carbon composite material and 5.0g of iron oxyhydroxide-biochar composite material;
the preparation process of the biochar-nano zero-valent iron composite material comprises the following steps: stirring and mixing 5.0g of biochar and 10.0g of nano zero-valent iron for 8 hours at the rotating speed of 800 r/min; the preparation method of the biochar comprises the following steps: calcining bamboo at 600 ℃ for 2 hours, and then grinding to the grain size of 200nm, wherein the preparation method of the nano zero-valent iron comprises the following steps: 5.0g of ferrous chloride, 20g of polyvinylpyrrolidone and deionized water are mixed, and then hydrazine hydrate is added, wherein the molar ratio of the ferrous chloride to the reducing agent is 1:3, a step of;
the preparation process of the iron oxide-hydrothermal carbon composite material comprises the following steps: mixing ferric nitrate and glucose with water for 1h according to the molar ratio of 1:1, regulating the pH value of the solution to 2, and then carrying out thermal aging treatment for 12h at 160 ℃;
the preparation process of the iron-zinc oxide-hydrothermal carbon composite material comprises the following steps: mixing ferric nitrate, zinc nitrate and glucose in the molar ratio of 1:0.5:1 with water for 1h, regulating the pH value of the solution to 12, and performing thermal aging treatment at 140 ℃ for 10h;
the preparation process of the iron oxyhydroxide-biochar composite material comprises the following steps: the molar ratio of iron to carbon element is 3:2, stirring and mixing the iron oxyhydroxide and the biochar at the rotating speed of 800 r/min;
the pH regulator is calcium oxide;
the oxidant is sodium thiosulfate;
the adsorption auxiliary agent is acid modified montmorillonite with the particle size of 200 meshes;
the preparation method of the iron-carbon-based repair material comprises the following steps: mixing the iron-carbon-based composite material and acid modified montmorillonite, grinding until the average particle size of the mixture is 200 meshes, mixing calcium oxide and sodium thiosulfate as a component A, and grinding until the average particle size of the mixture is 150 meshes, and taking the mixture as a component B to obtain the iron-carbon-based repair material;
the iron-carbon-based restoration material is used for restoring the composite polluted soil containing arsenic and benzene, and the use method comprises the following steps:
the component A and the component B in the iron-carbon-based repair material are pre-mixed according to the formula amount, and then the mass ratio is 0.05:1, mixing the iron-carbon-based restoration material with the composite polluted soil, and then adding water for mixing, wherein the mass ratio of the composite polluted soil to the water is 9:1, curing treatment is carried out at 15 ℃ for 15 days.
Example 3
This example differs from example 1 only in that the conditions were the same as example 1 except that the weight part of the iron-carbon-based composite material was 10 parts, the weight part of the pH adjuster was 10 parts, and the weight part of the oxidizing agent was 12 parts.
Example 4
This example differs from example 1 only in that the conditions were the same as example 1 except that the weight part of the iron-carbon-based composite material was 22 parts and the weight part of the oxidizing agent was 12 parts.
Example 5
This example differs from example 1 only in that the conditions were the same as example 1 except that the weight part of the adsorption auxiliary was 4 parts, the weight part of the pH adjuster was 10 parts, and the weight part of the oxidizing agent was 12 parts.
Example 6
This example differs from example 1 only in that the conditions were the same as example 1 except that the weight part of the oxidizing agent was 6 parts and the weight part of the iron-carbon-based composite material was 18 parts.
Example 7
This example differs from example 1 only in that the conditions were the same as example 1 except that the weight part of the pH adjuster was 4 parts and the weight part of the iron-carbon-based composite was 18 parts.
Comparative example 1
This comparative example differs from example 1 only in that the iron-carbon based composite material does not contain a biochar-nano zero-valent iron composite material, except that the iron-carbon based composite material consists of 7g of iron oxide-hydrothermal carbon composite material and 7g of iron oxyhydroxide-acid modified hydrothermal carbon composite material; other conditions were the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that the iron-carbon-based composite material is composed of 7g biochar-nano zero-valent iron composite material and 7g iron oxyhydroxide-acid modified hydrothermal carbon composite material, except that the iron-carbon-based composite material does not contain an iron oxide-hydrothermal carbon composite material; other conditions were the same as in example 1.
Comparative example 3
This comparative example differs from example 1 only in that the iron-carbon-based repair material is identical to example 1 except that it does not contain the iron-carbon-based composite material in the a-component.
Comparative example 4
This comparative example differs from example 1 only in that the iron-carbon-based repair material does not contain the acid-modified montmorillonite in the a-component, except that the conditions are the same as in example 1.
Comparative example 5
This comparative example differs from example 1 only in that the iron-carbon-based repair material does not contain calcium oxide in the B component, except that the conditions are the same as example 1.
Comparative example 6
This comparative example differs from example 1 only in that the iron-carbon-based repair material does not contain sodium thiosulfate in the B component, and the conditions are the same as example 1.
The performance test methods and results of the above examples and comparative examples are as follows:
performance test: the test was performed according to the solid waste leaching toxicity leaching method horizontal shaking method (HJ 557-2010). Wherein, the toxicity leaching concentration of arsenic in the soil sample is A1 (mg/L) respectively; the stabilized toxicity leaching concentration of arsenic is A2 (mg/L) respectively;
the organic matter testing method comprises the following steps: reference is made to the soil pollution risk management and control Standard for construction land for Standard soil environmental quality (GB 36600-2018). Wherein the content of organic matters (benzene) in the soil sample is B1 (mg/kg); the organic matter (benzene) content in the soil sample after stabilization by using the iron-carbon-based restoration material is B2 (mg/kg).
TABLE 1
From table 1, the following points can be found:
(1) The iron-carbon-based restoration material provided by the invention has good restoration effect on the composite polluted soil, can respectively reduce the leaching concentration of arsenic below the IV restoration standard value of important groundwater quality standard (GB/T14848-2017), and can reduce the benzene content below the second type land screening value of soil pollution risk management and control standard of soil environmental quality standard construction land soil (GB 36600-2018);
(2) The addition amount of the iron-carbon-based composite material in the embodiment 3 is too low, so that the stabilization active substances are insufficient, the addition amount of the iron-carbon-based composite material in the embodiment 4 is too high, so that the repair material generates deep reaction, the leaching concentration of heavy metal elements is further increased, and the residual amount of organic matters in soil is still higher;
(3) The addition of the adsorption auxiliary agent in the embodiment 5 is too low, which results in poor effect of the iron-carbon-based composite material, the addition of the oxidant in the embodiment 6 is too low, which results in lower valence state of arsenic and lower benzene oxidation degree, and the addition of the pH regulator in the embodiment 7 is too low, which results in the adsorption process being obviously weaker than the desorption process;
(4) The iron-carbon-based composite material in comparative example 1 does not contain biochar-nano zero-valent iron composite material, so that the iron-carbon-based composite material cannot be effectively reduced on oxidative metals or organic matters, the iron-carbon-based composite material in comparative example 2 does not contain iron oxide-hydrothermal carbon composite material, so that the adsorption effect is inferior, the leaching of heavy metal elements is not obviously reduced, and the residual amount of organic matters in soil is still higher;
(5) The iron-carbon-based composite material in the component A is not contained in the comparative example 3, the acid-modified montmorillonite in the component A is not contained in the comparative example 4, the calcium oxide in the component B is not contained in the comparative example 5, the sodium thiosulfate in the component B is not contained in the comparative example 6, the solidification stabilizing effect of the iron-carbon-based repair material on the heavy metal in the composite polluted soil is reduced, so that the leaching concentration of the heavy metal is not obviously reduced, and the organic pollutant cannot be sufficiently oxidized and decomposed, so that the residual amount of the organic matters in the soil is still higher; the existence of a synergistic effect among the components is proved, and the lack of any repairing component can lead to poor repairing effect on heavy metals and organic pollutants in the composite polluted soil.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (50)
1. The iron-carbon-based restoration material for the organic matter-heavy metal composite contaminated soil is characterized by comprising the following components in parts by weight: 12-20 parts of iron-carbon-based composite material, 5-10 parts of pH regulator, 5-12 parts of oxidant and 8-12 parts of adsorption auxiliary agent;
the iron-carbon-based composite material comprises a biochar-nano zero-valent iron composite material and an iron-based oxide-hydrothermal carbon composite material;
the oxidant comprises any one or at least two of sodium thiosulfate, sodium hypochlorite or hydrogen peroxide.
2. The repair material of claim 1, wherein the preparation process of the biochar-nano zero-valent iron composite material comprises: and stirring and mixing the biochar and the nano zero-valent iron to obtain the biochar-nano zero-valent iron composite material.
3. The repair material according to claim 2, wherein the mass ratio of biochar to nano zero-valent iron is 1: (1-3).
4. The repair material according to claim 2, wherein the rotational speed of the stirring is 200-800 r/min.
5. The repair material of claim 2, wherein the mixing is for a period of 8 to 12 hours.
6. The repair material according to claim 2, wherein the method of preparing biochar comprises: calcining bamboo and/or coconut shell at 600-650 ℃ for 1.5-2 h, and grinding to obtain the biochar.
7. The repairing material according to claim 6, wherein the particle size after grinding is 200 to 300nm.
8. The repair material of claim 2, wherein the method of preparing the nano zero-valent iron comprises: mixing ferrous salt, a dispersing agent and a solvent, and then adding a reducing agent to obtain the nano zero-valent iron.
9. The repair material of claim 8 wherein the dispersant comprises polyvinylpyrrolidone.
10. The repair material of claim 8, wherein the reducing agent comprises sodium borohydride and/or hydrazine hydrate.
11. The repairing material according to claim 8, wherein the mass ratio of the ferrous salt to the dispersant is 1 (2-20).
12. The repair material according to claim 8, wherein the molar ratio of the ferrous salt to the reducing agent is 1 (2-6).
13. The repair material of claim 1, wherein the iron-based oxide-hydrothermal carbon composite comprises an iron oxide-hydrothermal carbon composite and/or an iron zinc oxide-hydrothermal carbon composite.
14. The repair material of claim 13, wherein the process of preparing the iron oxide-hydrothermal carbon composite comprises: and mixing ferric salt with glucose, regulating pH value, and performing thermal ageing treatment.
15. The repair material of claim 13 wherein the molar ratio of iron to elemental carbon in the iron oxide-hydrothermal carbon composite is 1: (1-6).
16. The repair material of claim 14 wherein the mixing is for a period of 0.5 to 1 hour.
17. The repair material of claim 14 wherein the pH is adjusted to a pH of 2 to 8.
18. The repair material of claim 14, wherein the temperature of the thermal aging process is 160-180 ℃.
19. The repair material of claim 14, wherein the thermal aging treatment is for a period of 8 to 12 hours.
20. The repair material of claim 13, wherein the process of preparing the iron zinc oxide-hydrothermal carbon composite comprises: mixing trivalent ferric salt and zinc salt with glucose, adjusting pH, and performing thermal aging treatment.
21. The repair material of claim 13 wherein the iron zinc oxide-hydrothermal carbon composite has a molar ratio of iron, zinc and carbon elements of 1:0.5: (1-6).
22. The repair material of claim 20 wherein the mixing is for a period of 0.5 to 1 hour.
23. The repair material of claim 20 wherein the pH adjustment is a pH adjustment of 11 to 13.
24. The repair material of claim 20, wherein the temperature of the thermal aging process is 120-160 ℃.
25. The repair material of claim 20, wherein the thermal aging treatment is for a period of 8 to 12 hours.
26. The repair material of claim 1, wherein the pH adjuster comprises an acidic adjuster and/or a basic adjuster.
27. The repair material of claim 26 wherein the acidity regulator comprises any one or a combination of at least two of citric acid, malic acid, or oxalic acid.
28. The repair material of claim 26 wherein the alkaline modifier comprises any one or a combination of at least two of calcium oxide, magnesium oxide, shell powder, or sodium sulfide.
29. The repair material of claim 1 wherein the oxidizing agent is sodium thiosulfate.
30. The repair material of claim 1 wherein the adsorption aid comprises any one or a combination of at least two of zeolite, sepiolite and montmorillonite.
31. The repair material of claim 30 wherein the adsorption aid is montmorillonite.
32. The repair material of claim 30 wherein the montmorillonite comprises an acid modified montmorillonite.
33. The repair material of claim 1, wherein the adsorption aid has a particle size of 200 to 250 mesh.
34. The repair material of claim 1 wherein the iron carbon-based composite further comprises an iron oxyhydroxide-hydrothermal carbon and/or biochar composite.
35. The repair material of claim 34 wherein the molar ratio of iron to carbon elements in the iron oxyhydroxide-hydrothermal carbon and/or biochar composite is 3: (2-5).
36. The repair material of claim 34, wherein the process of preparing the iron oxyhydroxide-hydrothermal carbon and/or biochar composite material comprises: and stirring and mixing the iron oxyhydroxide and the hydrothermal carbon and/or the biochar to obtain the iron oxyhydroxide-hydrothermal carbon and/or the biochar composite material.
37. The repair material of claim 36 wherein the rotational speed of the agitation is 200-800 r/min.
38. The repair material of claim 36, wherein the method of preparing the hydrothermal carbon comprises: glucose and a solvent are mixed, and a hydrothermal reaction is performed after the pH is adjusted.
39. The repair material of claim 38 wherein the pH is adjusted to a pH of 1.5 to 3 or 10 to 12.
40. The repair material of claim 38, wherein the temperature of the hydrothermal reaction is 160-180 ℃.
41. The repair material of claim 38, wherein the hydrothermal reaction time is from 4 to 8 hours.
42. The repair material according to claim 1, characterized in that the repair material consists of the following components in parts by weight:
43. a method of preparing an iron carbon-based repair material according to any one of claims 1-42, comprising: mixing the iron-carbon-based composite material with an adsorption auxiliary agent to obtain a component A, and mixing a pH regulator with an oxidant to obtain a component B to obtain the iron-carbon-based repair material containing the component A and the component B.
44. A method of using the iron-carbon-based repair material prepared by the method of claim 43, the method comprising: and mixing the component A and the component B in the repairing material with the composite polluted soil according to the formula amount, and then mixing with water for maintenance treatment.
45. The method of claim 44, wherein the total mass of the A component and the B component in the iron-carbon-based repair material to the mass of the composite contaminated soil is (0.03-0.05): 1.
46. the method of claim 44, wherein the mass ratio of the combined contaminated soil to water is 9: (1-3).
47. The method of claim 46, wherein the mass ratio of the combined contaminated soil to water is 9: (2-3).
48. The method of claim 44, wherein the curing process is at a temperature of 0 to 50 ℃.
49. The method of claim 44, wherein the curing is carried out for a period of 8 days or longer.
50. A method of using according to claim 49, wherein the maintenance treatment is performed for a period of 10 to 15 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210683824.8A CN115011352B (en) | 2022-06-16 | 2022-06-16 | Iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, and preparation method and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210683824.8A CN115011352B (en) | 2022-06-16 | 2022-06-16 | Iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, and preparation method and application method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115011352A CN115011352A (en) | 2022-09-06 |
| CN115011352B true CN115011352B (en) | 2023-12-19 |
Family
ID=83074866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210683824.8A Active CN115011352B (en) | 2022-06-16 | 2022-06-16 | Iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, and preparation method and application method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115011352B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115991995A (en) * | 2023-02-10 | 2023-04-21 | 中国科学院生态环境研究中心 | Nanometer zero-valent iron-biochar composite material, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388094A (en) * | 2014-10-13 | 2015-03-04 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron-based bio-char material, preparation process thereof, and application thereof in soil pollution treatment |
| CN110423622A (en) * | 2019-08-08 | 2019-11-08 | 北京润鸣环境科技有限公司 | A kind of low sulfur type chromium-polluted soil renovation agent and preparation method thereof and application method |
| WO2021129137A1 (en) * | 2019-12-25 | 2021-07-01 | 华南理工大学 | Carbon-loaded nano zero-valent iron material, preparation method therefor and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524623B (en) * | 2016-02-01 | 2017-02-22 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Preparation and use methods of slow-release type iron-based biochar soil heavy metal passivator |
-
2022
- 2022-06-16 CN CN202210683824.8A patent/CN115011352B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388094A (en) * | 2014-10-13 | 2015-03-04 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron-based bio-char material, preparation process thereof, and application thereof in soil pollution treatment |
| CN110423622A (en) * | 2019-08-08 | 2019-11-08 | 北京润鸣环境科技有限公司 | A kind of low sulfur type chromium-polluted soil renovation agent and preparation method thereof and application method |
| WO2021129137A1 (en) * | 2019-12-25 | 2021-07-01 | 华南理工大学 | Carbon-loaded nano zero-valent iron material, preparation method therefor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115011352A (en) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110423622B (en) | Low-sulfur chromium-polluted soil remediation agent and preparation method and use method thereof | |
| CN108722349B (en) | Preparation method and application of magnetic hydrothermal carbon | |
| CN102179253B (en) | Method for preparing catalyst by using electrolysis waste water and electrolysis sludge | |
| CN104148007A (en) | Preparation method and application of multifunctional material for water treatment | |
| CN110314651B (en) | Magnetic sulfur-iron-carbon composite porous environment-friendly material and green preparation method and application thereof | |
| Sun et al. | MOF-derived N-Co/Fe-PC composite as heterogeneous electro-Fenton catalysis combined with electrocoagulation process for enhanced degradation of Cu-CIP complexes from wastewater | |
| CN109762569B (en) | Heavy metal cadmium and arsenic composite contaminated soil remediation agent and preparation method thereof | |
| CN112439417B (en) | Iron-aluminum-carbon composite catalytic material, preparation method and organic wastewater degradation method | |
| Ji et al. | A review of metallurgical slag for efficient wastewater treatment: Pretreatment, performance and mechanism | |
| CN115011352B (en) | Iron-carbon-based restoration material for organic matter-heavy metal composite contaminated soil, and preparation method and application method thereof | |
| CN109608021A (en) | Deep dehydration method for sludge | |
| Mao et al. | Simultaneous removal of arsenite and cadmium by a manganese-crosslinking sodium alginate modified biochar and zerovalent iron composite from aqueous solutions | |
| Shih et al. | Granulation for extended-release of nanoscale zero-valent iron exemplified by hexavalent chromium reduction in aqueous solution | |
| Fu et al. | Three-dimensional electro-Fenton oxidation of landfill leachate concentrates using MnO2-doped TiO2-coated granular activated carbon as catalytic particle electrodes | |
| KR101419425B1 (en) | Manufacturing method of ceramic powder for removing heavy metals and water treatment method thereof | |
| Anwar et al. | Prospect of utilizing coal mine drainage sludge as an iron source for value-creating applications | |
| CN115353189B (en) | Method for treating ciprofloxacin-containing wastewater by regulating and controlling dissolved oxygen | |
| KR20110132709A (en) | Magnetite nano particle-carrer complex, method for fabricating the same and sewage-pollution water purifying system including the same | |
| CN106242013A (en) | Natural magnetic iron ore and the method for Zero-valent Iron mixed processing heavy metal ion-containing waste water | |
| CN110713250A (en) | Preparation method of Fe-Cu bimetallic tourmaline synergistic microorganism Cr (VI) removing filler | |
| CN106219692B (en) | Tourmaline used as water body dephosphorization filter material and preparation method thereof | |
| CN111362507B (en) | Efficient chemical-biological degradation combined industrial wastewater treatment method | |
| CN114988826A (en) | Heavy metal combined contaminated soil solidification stabilization repair material and preparation method and use method thereof | |
| Zhuang et al. | Recycling rice straw derived, activated carbon supported, nanoscaled Fe 3 O 4 as a highly efficient catalyst for Fenton oxidation of real coal gasification wastewater | |
| Liu et al. | Insights into the practicability of electrochemical enhanced heterogeneous activation of peroxymonosulfate for the treatment of liquid waste during penicillin g production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |