CN116285998A - Rare earth contaminated soil passivation material and preparation method and application thereof - Google Patents
Rare earth contaminated soil passivation material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116285998A CN116285998A CN202211724445.5A CN202211724445A CN116285998A CN 116285998 A CN116285998 A CN 116285998A CN 202211724445 A CN202211724445 A CN 202211724445A CN 116285998 A CN116285998 A CN 116285998A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- soil
- hexametaphosphate
- passivation
- passivation material
- 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.)
- Granted
Links
- 239000002689 soil Substances 0.000 title claims abstract description 147
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 115
- 238000002161 passivation Methods 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 79
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229940005740 hexametaphosphate Drugs 0.000 claims abstract description 39
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 claims abstract description 35
- 229910004856 P—O—P Inorganic materials 0.000 claims abstract description 8
- 229910018512 Al—OH Inorganic materials 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 6
- 229910003849 O-Si Inorganic materials 0.000 claims abstract description 5
- 229910003872 O—Si Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000005067 remediation Methods 0.000 claims abstract description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052622 kaolinite Inorganic materials 0.000 claims description 30
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 21
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 21
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 19
- 239000011707 mineral Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910052900 illite Inorganic materials 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 4
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910052626 biotite Inorganic materials 0.000 claims description 3
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052627 muscovite Inorganic materials 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- -1 rare earth ions Chemical class 0.000 abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011574 phosphorus Substances 0.000 abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 13
- 235000015097 nutrients Nutrition 0.000 abstract description 13
- 229910052710 silicon Inorganic materials 0.000 abstract description 12
- 239000010703 silicon Substances 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 230000002829 reductive effect Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 5
- 239000002681 soil colloid Substances 0.000 abstract description 4
- 239000013589 supplement Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 4
- 230000005611 electricity Effects 0.000 abstract 1
- 230000003068 static effect Effects 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 235000021317 phosphate Nutrition 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- ZQKXOSJYJMDROL-UHFFFAOYSA-H aluminum;trisodium;diphosphate Chemical compound [Na+].[Na+].[Na+].[Al+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZQKXOSJYJMDROL-UHFFFAOYSA-H 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- GHHVYBBTKTVOPA-UHFFFAOYSA-K aluminum;sodium;phosphate Chemical compound [Na+].[Al+3].[O-]P([O-])([O-])=O GHHVYBBTKTVOPA-UHFFFAOYSA-K 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- 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
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- 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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention discloses a rare earth polluted soil passivation material and a preparation method and application thereof, and belongs to the technical field of soil remediation. The preparation raw materials of the passivation material comprise layered aluminosilicate minerals and hexametaphosphate, wherein Al-OH or Al-O-Si in the layered aluminosilicate minerals and P-O-P in the hexametaphosphate have a bonding effect to form Al-O-P bonds, so that the long-acting fixation of rare earth ions is facilitated. The rare earth ion-activated carbon is applied to rare earth polluted soil, and can obviously promote rare earth ions in the soil to be converted from a weak acid extraction state and a reducible state to a residue state through the actions of static electricity, interfacial precipitation and the like, so that the bioavailability and the mobility of the rare earth ion-activated carbon are reduced. The slow release of nutrient elements such as silicon, phosphorus and the like in the passivation material can effectively supplement soil nutrients, improve the physicochemical properties of the soil and improve the adsorption of soil colloid to rare earth ions. The passivation material has the effects of passivating rare earth polluted soil and slowly releasing nutrients, and has the characteristics of good passivation effect, low treatment cost, no secondary pollution and the like.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a rare earth polluted soil passivation material and a preparation method and application thereof.
Background
Rare Earth Elements (REEs) are widely used in modern industries such as optical glass, batteries, display screens, metallurgy and the like, and in the fields of the military industry and the like, because of their unique physicochemical properties, which are considered important strategic resources for a long time. Under the action of natural weathering, rare earth in the weathered crust is easy to be leached and migrated, so that precious rare earth resources are lost and enter the surrounding soil environment. In addition, the exploitation mode of the ion adsorption type rare earth ore deposit is mainly an ammonium sulfate in-situ leaching method, which is easy to cause the destabilization, activation and migration of rare earth and causes serious non-point source pollution.
The layered aluminosilicate family is an important constituent of clay minerals and is characterized in that the layered structure unit is formed by stacking a plurality of silicon oxygen tetrahedral sheets and aluminum oxygen octahedral sheets. Layered aluminosilicate minerals are ubiquitous in the surface environment, and their special nanostructures, abundant surface charges, and high surface/interface reactivity can interact with heavy metal ions, affecting their migration and bioavailability in the soil. Currently, passivating agents based on layered aluminosilicate minerals are of great interest, especially in the interaction of mineral interfaces with contaminants and in the adsorptive removal of a wide variety of contaminants. However, natural layered aluminosilicate minerals do not perform well in the field of direct environmental passivation, and chemical modification is generally required to enhance the adsorption capacity on their surfaces.
The prior art uses the layered aluminosilicate minerals in soil improvement passivation, but the related technology only aims at the restoration of the heavy metals in the soil, the physicochemical properties of the rare earth elements and the interaction of the rare earth elements with the soil components are completely different from those of the heavy metals, and the layered aluminosilicate minerals cannot have the effects of the passivation of the rare earth polluted soil and the slow release of nutrients, and have the advantages of low treatment cost, no secondary pollution and the like.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a rare earth polluted soil passivation material for solving the technical problems.
The second purpose of the invention is to provide a preparation method of the rare earth contaminated soil passivation material.
The invention further aims to provide an application of the rare earth contaminated soil passivation material.
The application can be realized as follows:
in a first aspect, the present application provides a rare earth contaminated soil passivation material prepared from a raw material comprising a layered aluminosilicate mineral and a hexametaphosphate salt; the passivation material has Al-O-P bonds formed by the bonding of Al-OH or Al-O-Si in the layered aluminosilicate mineral with P-O-P in the hexametaphosphate salt.
In alternative embodiments, the layered aluminosilicate mineral is one or more of a silicon oxygen tetrahedron-aluminum oxygen octahedral sheet ratio of a type 1:1 mineral or a type 2:1 mineral; wherein the type 1:1 mineral is kaolinite, and the type 2:1 mineral is one or more of pyrophyllite, illite, montmorillonite, vermiculite, muscovite and biotite.
In alternative embodiments, the hexametaphosphate salt is one or more of sodium hexametaphosphate, potassium hexametaphosphate, and ammonium hexametaphosphate.
In an alternative embodiment, the mass ratio of layered aluminosilicate mineral to hexametaphosphate salt is from (25:75) to (75:25).
In a second aspect, the present application provides a method for preparing a rare earth contaminated soil passivation material according to the previous embodiment, comprising the steps of: uniformly mixing the layered aluminosilicate mineral and the hexametaphosphate solid material, putting the mixture into a ball milling tank, and performing ball milling for 1-5 h under the conditions that the ball-material ratio is (10-30): 1 and the rotating speed is 200-800 rpm; and then placing the ball-milled material into a muffle furnace, performing heat treatment for 1-5 h at the temperature of 250-750 ℃, and cooling to obtain the soil passivation material.
In a third aspect, the present application provides the use of a rare earth contaminated soil passivation material as in the previous embodiments, for example, for passivating rare earth contaminated soil.
In an alternative embodiment, the above-mentioned application includes: adding 0.1-10wt% of the rare earth polluted soil passivation material in the previous embodiment into the soil to be repaired, stirring and mixing uniformly, and performing passivation reaction for 1-30 days to obtain the repaired soil; meanwhile, the field water holding capacity is kept between 40% and 100%.
In an alternative embodiment, the rare earth elements are lanthanoid, yttrium, and scandium.
The beneficial effects of this application include:
(1) The end face of the layered aluminosilicate mineral contains a large amount of silicon hydroxyl groups and aluminum hydroxyl groups, so that the layered aluminosilicate mineral has high surface/interface reactivity, and rare earth ions can be enriched through ion exchange and surface complexation. The hexametaphosphate belongs to linear condensed phosphate and has strong complexing ability with rare earth ions. According to the method, the layered aluminosilicate mineral and the hexametaphosphate are compounded according to a specific proportion, so that on one hand, the hexametaphosphate promotes the stripping of the layered aluminosilicate mineral to form a thin layer silicate, and further more active silicon aluminum is exposed; on the other hand, the active aluminum (Al-OH or Al-O-Si) on the surface of the layered aluminosilicate mineral can form an Al-O-P bond through the bonding action with P-O-P in the hexametaphosphate, so that the loading capacity and the loading stability of the phosphate are improved, and the capability of fixing rare earth ions is enhanced.
(2) In the ball milling process, the layered aluminosilicate mineral generates a large number of broken bonds, abundant aluminum hydroxyl groups are exposed at defects and edges, the bonding with P-O-P in hexametaphosphate is enhanced, al-O-P bonds are formed, and the phosphorus loading capacity, the loading stability and the reactivity with rare earth ions are effectively improved. In addition, the structural silicon in the mineral phase is partially converted into amorphous silicon, so that the amorphous silicon has certain silicon slow release capability, and the effective silicon content of soil is improved.
(3) The ball milling treatment promotes the hexa-metaphosphate to enter the interlayer of the aluminosilicate mineral and promotes the delamination of the lamellar aluminosilicate mineral. Meanwhile, the ball milling also plays a role in dispersing mineral phases and inhibiting agglomeration. The phosphorus distributed on the surface of the mineral transfers negative charges, so that the dispersion stability is further enhanced, the utilization efficiency of the modified phosphorus element on the surface of the mineral can be greatly improved, and the problems of large loss of the modified phosphorus element on the surface of the mineral in a short period and the like are avoided.
(4) Heating treatment, coupling ball milling, promoting the expansion of the layered aluminosilicate mineral and enhancing the delamination of the layered aluminosilicate mineral; meanwhile, the ball milling and the heat treatment can promote the hexametaphosphate to generate active phosphorus such as phosphate, trimetaphosphate and the like, accelerate the bonding of the phosphorus and the surface active silicon aluminum of the aluminosilicate mineral to form an Al-O-P bond or an aluminum sodium phosphate mineral, and realize the adsorption and fixation of the effective state rare earth ions.
(5) According to the rare earth contaminated soil passivation material, contaminated soil is added, the rare earth ions are fixed by means of electrostatic adsorption, interfacial precipitation and other modes depending on active sites on the surface of the material, so that the rare earth ions with higher activity are promoted to be converted into phosphate complexes with lower solubility, and the bioavailability and mobility of the rare earth ions are further reduced.
(6) The rare earth polluted soil passivation material has the slow release capability of nutrient elements such as silicon, phosphorus and the like, can effectively supplement soil nutrients, improve the physicochemical property of soil, improve the pH value and EC value of the soil and increase the content of soluble salt in a soil solution. The increase of the pH value of the soil is beneficial to promoting the electrostatic adsorption of REEs on the surface of soil colloid and minerals. The slow release of the phosphorus and the silicon in the repairing agent can increase the negative charge in the soil, enhance the adsorption of the soil mineral particles and the organic matters to the rare earth, and increase the ion product of cations and hydroxide ions in the soil solution, thereby increasing the opportunity of generating rare earth hydroxide precipitation and greatly reducing the bioavailability of the rare earth. Partially eluted phosphorus-inducible REE-PO 4 And forming an interface precipitate, and further fixing rare earth ions.The increase of the effective silicon content of the soil can form a complex with rare earth ions, so that the mobility of rare earth in the soil is reduced.
(7) The application uses a mechanochemical method to couple with a heat treatment method, and provides a modification method of the phosphorus loaded on the layered aluminosilicate mineral, wherein the method is a solid-phase reaction, does not involve liquid-phase reaction, has no secondary pollution, is simple, convenient and feasible, and has a large-scale production prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the mechanism by which the layered aluminosilicate mineral/hexametaphosphate material of the present application passivates REEs in contaminated soil;
FIG. 2 is an XRD spectrum of a composite material of kaolinite and sodium hexametaphosphate in the experimental example of the present application;
FIG. 3 is a FTIR spectrum of kaolinite and its composite with sodium hexametaphosphate in the experimental examples of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The rare earth contaminated soil passivation material provided by the application and the preparation method and application thereof are specifically described below.
The inventor creatively proposes a rare earth contaminated soil passivation material through long-term research on passivation of rare earth contaminated soil, and specifically, the rare earth contaminated soil passivation material is prepared from layered aluminosilicate minerals and hexametaphosphate.
The layered aluminosilicate family is an important constituent of clay minerals and is characterized in that the layered structure unit is formed by stacking a plurality of silicon oxygen tetrahedral sheets and aluminum oxygen octahedral sheets. Layered aluminosilicate minerals are ubiquitous in the surface environment, and their special nanostructures, abundant surface charges, and high surface/interface reactivity can interact with rare earth ions, thereby affecting the mobility and bioavailability of rare earth in the soil.
Hexametaphosphate provides a source of phosphorus for the soil passivation material. Hexametaphosphate is a mixture of polymeric metaphosphates, linear condensed phosphates (M n+2 P n O 3n+1 M is K, na or NH 4 ) Is the predominant form of hexametaphosphate in aqueous solution. In long chain phosphates, PO 4 The tetrahedra are linked together by a common oxygen atom and about 30% of the linear condensed phosphate will degrade to lower phosphate. In the pH range of 2.2 to 7.2, the hydrolysis product of the linear concentrated phosphate has a main component of [ H ] 2 PO 4 ] - The method comprises the steps of carrying out a first treatment on the surface of the In the pH range of 7.2 to 9.0, the main component is [ HPO ] 4 ] 2- Has good capability of complexing rare earth ions.
The rare earth contaminated soil passivation material provided by the application has Al-O-P bonds formed by the bonding action of active aluminum (Al-OH or Al-O-Si) in the layered aluminosilicate mineral and P-O-P in the hexametaphosphate. The rare earth polluted soil passivation material has low cost, can have both rare earth polluted soil passivation effect and nutrient slow release effect, and can effectively reduce the mobility and biological effectiveness of rare earth in soil, as shown in figure 1.
For reference, the above-mentioned layered aluminosilicate mineral may be one or more of kaolinite, pyrophyllite, illite, montmorillonite, vermiculite, muscovite, biotite, and the like.
For reference, the hexametaphosphate salt may be one or more of sodium hexametaphosphate, potassium hexametaphosphate, and ammonium hexametaphosphate.
For reference, in the rare earth contaminated soil passivation material, the mass ratio of the hexametaphosphate salt to the layered aluminosilicate mineral may be (25:75) - (75:25), such as 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, or 75:25, etc., or any other value within the range of (25:75) - (75:25).
Correspondingly, the application also provides a preparation method of the rare earth polluted soil passivation material, specifically, the rare earth polluted soil passivation material can be obtained by ball milling kaolinite and sodium hexametaphosphate firstly, then performing heat treatment and cooling.
For reference, the ball milling process may be performed in a zirconia ball milling tank. The process conditions involved in ball milling include: the ball-material ratio is (10-30) 1 (such as 10:1, 15:1, 20:1, 25:1 or 30:1), the rotating speed is 200-800 rpm (such as 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm or 800rpm, etc.), and the time is 1-5 h (such as 1h, 2h, 3h, 4h or 5h, etc.). The ball-material ratio is too high, so that the materials are difficult to recycle after ball milling, and the lower ball-material ratio is difficult to realize uniform mixing of solid phase materials, so that the mass transfer efficiency between the solid phase materials is weakened, and the phosphorus loading efficiency of the clay mineral surface is reduced.
In some preferred embodiments, the ball milling process is performed at a ball to material ratio of 20:1 at a rotational speed of 350rpm for 2 hours.
The heat treatment may be carried out by placing the ball-milled sample in a corundum crucible and in a muffle furnace. The process conditions involved in the heat treatment include: the heat treatment temperature is 250-750 ℃ (such as 250 ℃, 350 ℃, 450 ℃, 550 ℃, 650 ℃ or 750 ℃ and the like), and the heat treatment time is 1-5 h (such as 1h, 2h, 3h, 4h or 5h and the like).
In some preferred embodiments, the heat treatment is performed at 500 ℃ for 2 hours.
Through the process, the preparation of the rare earth polluted soil passivation material can be realized.
In addition, the application of the rare earth contaminated soil passivation material is provided, for example, the rare earth contaminated soil passivation material is used for passivating rare earth contaminated soil.
Examples may include: and adding the passivation material into the soil to be repaired, and uniformly stirring.
By way of reference, the passivating material may be added to the soil in an amount of 0.1wt% to 10wt%, such as 0.1wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, 8wt% or 10wt%, etc. Fully mixing a soil sample and a material, and passivating for 1-30 days at room temperature; meanwhile, the field water holding capacity is kept between 40% and 100%.
By adding in the above manner, the following effects can be achieved:
(1) The fertilizer has better slow release capability of nutrients such as silicon, phosphorus and the like, improves the pH value and EC value of soil, and increases the content of soluble salt in soil solution;
(2) Promoting REE of soil colloid and mineral surface 3+ Electrostatic adsorption of (a);
(3) Promoting the transformation from the weak acid extraction state and the reducible state REEs of the soil to the residue state;
(4) Induction of REE-PO 4 Formation of interfacial precipitates promotes higher activity of REE 3+ To less soluble phosphate complexes, thereby reducing the bioavailability of REEs.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1: preparation of soil passivation Material (denoted as Kaolinite/sodium hexametaphosphate composite)
Sodium hexametaphosphate and kaolinite are mixed according to the mass ratio of 50:50, placed in a 500mL zirconia ball milling tank, ball milled for 2 hours under the condition of rotating speed of 350rpm according to the ball-to-material ratio of 20:1 (omega/omega). Placing the ball-milled sample into a corundum crucible, and then placing the corundum crucible into a muffle furnace for 10 ℃ for min at a heating rate -1 Heating to 500 ℃ for 2 hours, cooling and collecting a sample.
The kaolinite used for preparing the materials has the deposit type of weathered residual accumulation; the kaolinite has high crystallinity, low viscosity, good whiteness and chemical composition of 36.5wt% of Al 2 O 3 47.7wt% SiO 2 In addition, the composition contains a small amount of Mg, ca, na, K and other impurities.
The physicochemical properties of the materials were characterized by X-ray diffraction analysis (XRD) and fourier infrared spectroscopy (FTIR). The analysis method is as follows: XRD: the parameters of the testing instrument are CuK alpha target (40 Ma,40 kV), and the scanning speed is 3 degrees (2 theta). Min -1 Scan range3-70 degrees (2 theta); FTIR: weighing a proper amount of sample and KBr, fully grinding, tabletting, and measuring the wavelength range to 4000-400 cm -1 。
Figure 2 is an XRD spectrum of kaolinite and its complex with sodium hexametaphosphate. After compounding with sodium hexametaphosphate, the intensity of the (001) basal plane diffraction peak of kaolinite is obviously reduced,
diffraction peaks disappeared and +.>
The non-basal plane diffraction peak is widened, which shows that the crystal structure of the kaolinite is slightly destroyed, the peeling of the kaolinite layer structure is realized, and a small amount of sodium cyclotriphosphate and sodium aluminum phosphate phases are generated. The delamination of the kaolinite layer is achieved mainly due to the impact energy brought about during high energy ball milling and the impact energy applied to PO 4 3- And Na (Na) + Under the doping of (2), the kaolinite crystal structure is amorphized, so that the disorder of the structure is increased. In addition, under the mechanochemical action, phosphate in the weak crystal sodium hexametaphosphate is combined with silicon aluminum in the amorphized kaolinite structure, so that on one hand, lamellar stripping of kaolinite is promoted, and on the other hand, a plurality of phosphate new phases such as sodium aluminum phosphate and sodium cyclotriphosphate can be rapidly formed, and high-efficiency stable loading of phosphorus is realized.
FIG. 3 is a FTIR spectrum of kaolinite and its complex with sodium hexametaphosphate. After being compounded by sodium hexametaphosphate, the mixture is positioned at 3700 cm to 3650cm -1 The decrease of the intensity of the stretching vibration peak belonging to the surface hydroxyl shows that the crystallinity of the kaolinite is decreased and the disorder is increased after the modification by mechanochemical and heat treatment. Is positioned at 1200 cm to 650cm -1 Range (913 cm) -1 The absorption peak of (C) is attributed to Si-O-Al VI Vibration, the remainder being Si-O stretching vibration) becomes asymmetric with the absorption peak in 872cm -1 The asymmetric stretching vibration peaks of P-O-P in sodium hexametaphosphate are partially overlapped, so that Al-OH in kaolinite is bonded with P-O-P on sodium hexametaphosphate, and an Al-O-P bond is formed. Furthermore, at 1290cm -1 The p=o absorption peak appears at this point, indicating hexametaphosphateSuccessful complexation of sodium acid with kaolinite.
Example 2: passivation repairing application of soil passivation material to rare earth polluted soil
The soil polluted by the rare earth selected in the test is farmland surface soil (0-20 cm) around the rare earth mining area, the pH value of the soil selected in the test is 4.67, the total effective state contents of light rare earth (La-Sm, LREE), medium rare earth (Eu-Dy, MREE) and heavy rare earth (Ho-Lu, Y, HREE) are respectively 21.20, 1.90 and 4.12mg kg -1 . 150g of rare earth contaminated soil was weighed into a 250mL plastic bottle and 1wt% of the passivation material prepared in example 1 (kaolinite/sodium hexametaphosphate composite) was added. The soil sample and the passivation material are fully mixed and subjected to passivation reaction for 30 days at room temperature, and the water holding capacity of the soil is maintained at 60% -70%. And (3) air-drying the repaired soil sample, sieving the soil sample with a 10-mesh sieve, and analyzing the physicochemical properties of the soil and the occurrence morphology of REEs.
Analysis method
Soil pH value measurement: reference to NY/T1377-2007 at 0.01 mol.L -1 CaCl 2 The solution is an extractant and is measured by a potentiometric method.
Soil conductivity (EC) determination: the content of the soil soluble salt was analyzed with reference to the soil conductivity measurement electrode method (HJ 802-2016).
Determination of soil nutrients: soil phosphorus is measured according to soil phosphorus measurement (NY/T1121.7-2016); determining the quick-acting potassium in soil according to the determination of forest soil potassium (LY/T1234-2015); according to soil detection part 15: determination of soil available silicon (NY/T1121.15-2006), determination of available silicon.
Determination of the biological effective state content of soil REEs: through 1.0 mol.L -1 NH 4 After extraction of the Cl (ph=7.0) solution, the rare earth ion concentration in the filtrate was measured using an inductively coupled plasma mass spectrometer.
And (3) analyzing different occurrence forms of the REEs: the BCR sequential extraction method was used to determine the content distribution of the REEs in different occurrence forms (weak acid extracted, reducible, oxidizable, residual).
Results
(1) Influence of passivation materials on physical and chemical properties and nutrients of soil
After the composite material of kaolinite/sodium hexametaphosphate with the weight percentage of 1 percent is applied and the passivation reaction is carried out for 30 days, the pH value of soil is increased from 4.67 to 5.34, and the conductivity is increased from 107.60 mu s cm -1 Lifting to 384.98 mu s cm -1 . At days 7, 15 and 30, the available phosphorus content was from 126.7mg kg -1 Respectively lifted to 611.2mg kg -1 、784.5mg kg -1 And 1034.3mg kg -1 The composite material is proved to have slow dissolution of nutrient elements such as silicon, phosphorus and the like, increases the content of soil soluble salt, and plays a role in improving the soil nutrient and physicochemical properties.
(2) Variation of the biological effective state content of soil REEs
After passivation reaction for 30 days, the effective total contents of LREE, MREE and HREE in the soil are respectively reduced by 20.13mg kg by applying 1wt% of kaolinite/sodium hexametaphosphate composite material -1 、1.71mg kg -1 And 3.90mg kg -1 The corresponding passivation rates (i.e., soil effective rare earth content reduction rates) were 94.94%, 92.05% and 94.68%, respectively (table 1).
TABLE 1 effective State content of rare earth ions in soil before and after passivation of kaolinite/sodium hexametaphosphate composite (unit: mg.kg) -1 )
On the one hand, the increase of the pH value of the soil is beneficial to passivation materials and soil colloid to REE 3+ On the other hand, the addition of the passivation material can increase the phosphate content of soil and induce REE-PO 4 And interface precipitation is formed, so that the content of effective rare earth ions in soil is obviously reduced. BCR analysis shows that the contents of the weak acid extracted REEs and the reducible REEs are respectively reduced by 0.68 percent and 22.45 percent compared with the original soil; the content of the oxidizable REEs and the residual REEs is respectively increased by 12.55 percent and 10.58 percent compared with the original soil. The application of the passivating agent obviously promotes the transformation of the soil REEs from the weak acid extraction state and the reducible state to the residue state, and the passivating material promotes the transformation of the soil REEs from the high-activity morphology to the low-activity morphology, thereby effectively inhibitingBiological effectiveness and migration of rare earth ions.
As mentioned above, adding the kaolinite/sodium hexametaphosphate composite material can increase the pH and EC value of soil, and increase the effective phosphorus content of soil, thereby reducing the bioavailability of REEs. Passivation mechanism of kaolinite composite soil conditioner to soil REEs mainly comprises electrostatic adsorption and REE-PO induction 4 The interface precipitation mechanism has the advantages of being good in passivation effect, low in treatment cost, free of secondary pollution and the like, and the passivating agent has the effects of passivating rare earth polluted soil and slowly releasing nutrients.
Example 3
The present embodiment provides a passivation repairing application of a soil passivation material to rare earth contaminated soil, which is different from embodiment 2 in that: 1wt% kaolinite is added for passivation experiments of rare earth contaminated soil. After 30 days of passivation reaction, the passivation rates of Σlree, Σmree and Σhree in the soil were 1.42%, 7.35% and 8.88%, respectively.
Example 4
The present embodiment provides a passivation repairing application of a soil passivation material to rare earth contaminated soil, which is different from embodiment 2 in that: only 1wt% sodium hexametaphosphate was added for use in rare earth contaminated soil passivation experiments. After 30 days of passivation reaction, the pH value of the soil is increased from 4.67 to 6.38. On days 7, 15 and 30 of the passivation reaction, the soil available phosphorus content was from 126.7mg kg -1 Respectively lifted to 2887.3mg kg -1 、3006.5mg kg -1 And 3025.8mg kg -1 . After 30 days of passivation reaction, the passivation rates of Σlree, Σmree and Σhree in the soil are 48.24%, 43.23% and 44.72%, respectively.
Example 5
The embodiment provides a preparation method of a soil passivation material and application thereof to passivation restoration of rare earth contaminated soil, which is different from embodiment 1 in that: in the preparation process, the potassium hexametaphosphate and the kaolinite are mixed according to the mass ratio of 25:75. After treatment with 1wt% passivation material, passivation rates of Σlree, Σmree and Σhree in the soil were 86.07%, 79.41% and 84.16%, respectively, after 30 days of passivation reaction.
Example 6
The embodiment provides a preparation method of a soil passivation material and application thereof to passivation restoration of rare earth contaminated soil, which is different from embodiment 1 in that: in the preparation process, the potassium hexametaphosphate and the kaolinite are mixed according to the mass ratio of 75:25. On day 30 of passivation, after treatment with 1wt% material, the passivation rates of Σlree, Σmree and Σhree in the soil were 95.01%, 91.29% and 93.75%, respectively.
Example 7
The embodiment provides a preparation method of a soil passivation material and application thereof to passivation restoration of rare earth contaminated soil, which is different from embodiment 1 in that: during the preparation, potassium hexametaphosphate and serpentine (Mg 6 [Si 4 O 10 ](OH) 8 Layered magnesium silicate minerals) in a mass ratio of 50:50. On day 30 of passivation, after treatment with 1wt% material, the passivation rates of Σlree, Σmree and Σhree in the soil were 16.13%, 10.46% and 13.57%, respectively.
Example 8
The embodiment provides a preparation method of a soil passivation material and application thereof to passivation restoration of rare earth contaminated soil, which is different from embodiment 1 in that: in the preparation process, the potassium hexametaphosphate and the montmorillonite are mixed according to the mass ratio of 50:50. On day 30 of passivation, after treatment with 1wt% material, the passivation rates of Σlree, Σmree and Σhree in the soil were 25.46%, 21.52% and 20.26%, respectively.
Example 9
The embodiment provides a preparation method of a soil passivation material and application thereof to passivation restoration of rare earth contaminated soil, which is different from embodiment 1 in that: in the preparation process, the potassium hexametaphosphate and the illite are mixed according to the mass ratio of 50:50. On day 30 of passivation, after treatment with 1wt% material, the passivation rates of Σlree, Σmree and Σhree in the soil were 64.53%, 58.44% and 60.98%, respectively.
Example 10
The embodiment provides a preparation method of a soil passivation material and application thereof to passivation restoration of rare earth contaminated soil, which is different from embodiment 1 in that: in the preparation process, the potassium hexametaphosphate and the pyrophyllite are mixed according to the mass ratio of 50:50. On day 30 of passivation, after treatment with 1wt% material, the passivation rates of Σlree, Σmree and Σhree in the soil were 56.65%, 50.84% and 51.49%, respectively.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The rare earth polluted soil passivation material is characterized in that the preparation raw materials of the rare earth polluted soil passivation material comprise layered aluminosilicate minerals and hexametaphosphate; the rare earth contaminated soil passivation material has Al-O-P bonds formed by the bonding action of Al-OH or Al-O-Si in the layered aluminosilicate mineral and P-O-P in the hexametaphosphate;
preferably, the mass ratio of the layered aluminosilicate mineral to the hexametaphosphate salt is (25:75) - (75:25).
2. The method for preparing a rare earth contaminated soil passivation material according to claim 1, comprising the steps of:
(1) Uniformly mixing the layered aluminosilicate mineral and the hexametaphosphate solid material, putting the mixture into a ball milling tank, and performing ball milling for 1-5 h under the conditions that the ball-material ratio is (10-30): 1 and the rotating speed is 200-800 rpm;
(2) And (3) carrying out heat treatment on the material obtained in the step (1) for 1-5 hours at the temperature of 250-750 ℃ to obtain the rare earth contaminated soil passivation material.
3. The method of claim 2, wherein the layered aluminosilicate mineral is one or more of a type 1:1 mineral or a type 2:1 mineral having a silicon oxygen tetrahedron-aluminum oxygen octahedral sheet ratio; wherein the type 1:1 mineral is kaolinite, and the type 2:1 mineral is one or more of pyrophyllite, illite, montmorillonite, vermiculite, muscovite and biotite.
4. The method of claim 2, wherein the hexametaphosphate salt is one or more of sodium hexametaphosphate, potassium hexametaphosphate, and ammonium hexametaphosphate.
5. Use of a rare earth contaminated soil passivation material according to claim 1, wherein the passivation material is used for passivation remediation of rare earth contaminated soil.
6. The use according to claim 5, wherein 0.1-10 wt% of the rare earth contaminated soil passivation material is added into the soil to be repaired, stirred and mixed uniformly, and the passivation reaction is carried out for 1-30 days, during which the soil water holding capacity is kept at 40-100%.
7. The use according to claim 5, wherein the rare earth elements are lanthanoid elements, yttrium and scandium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211724445.5A CN116285998B (en) | 2022-12-30 | 2022-12-30 | Rare earth contaminated soil passivation material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211724445.5A CN116285998B (en) | 2022-12-30 | 2022-12-30 | Rare earth contaminated soil passivation material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116285998A true CN116285998A (en) | 2023-06-23 |
| CN116285998B CN116285998B (en) | 2024-07-02 |
Family
ID=86780406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211724445.5A Active CN116285998B (en) | 2022-12-30 | 2022-12-30 | Rare earth contaminated soil passivation material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116285998B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008230917A (en) * | 2007-03-20 | 2008-10-02 | Dowa Holdings Co Ltd | Soil improvement fertilizer |
| CN104383890A (en) * | 2014-11-26 | 2015-03-04 | 云南省农业科学院质量标准与检测技术研究所 | Soil heavy metal ion absorbent and preparation method thereof |
| US20150176105A1 (en) * | 2012-05-10 | 2015-06-25 | Imerys Pigments, Inc. | Rare Earth Element Compositions Obtained from Particulate Material Comprising Kaolinite and Methods for Obtaining Rare Earth Element Compositions from Particulate Material Comprising Kaolinite |
| CN114223343A (en) * | 2021-11-04 | 2022-03-25 | 中国科学院广州地球化学研究所 | Ecological management method for rare earth tailings restoration |
| CN114807601A (en) * | 2022-05-24 | 2022-07-29 | 中国科学院赣江创新研究院 | Method for adsorbing rare earth element lanthanum by using phosphoric acid modified kaolin |
-
2022
- 2022-12-30 CN CN202211724445.5A patent/CN116285998B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008230917A (en) * | 2007-03-20 | 2008-10-02 | Dowa Holdings Co Ltd | Soil improvement fertilizer |
| US20150176105A1 (en) * | 2012-05-10 | 2015-06-25 | Imerys Pigments, Inc. | Rare Earth Element Compositions Obtained from Particulate Material Comprising Kaolinite and Methods for Obtaining Rare Earth Element Compositions from Particulate Material Comprising Kaolinite |
| CN104383890A (en) * | 2014-11-26 | 2015-03-04 | 云南省农业科学院质量标准与检测技术研究所 | Soil heavy metal ion absorbent and preparation method thereof |
| CN114223343A (en) * | 2021-11-04 | 2022-03-25 | 中国科学院广州地球化学研究所 | Ecological management method for rare earth tailings restoration |
| CN114807601A (en) * | 2022-05-24 | 2022-07-29 | 中国科学院赣江创新研究院 | Method for adsorbing rare earth element lanthanum by using phosphoric acid modified kaolin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116285998B (en) | 2024-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106903132B (en) | A kind of method of cationic heavy metal contaminants in stable environment medium | |
| CN101293754A (en) | Method for preparing titanium dioxide composite material with fine silica flour | |
| WO2022160711A1 (en) | Gelling agent for curing heavy metal ions in tailings and use method thereof | |
| CN101457306B (en) | Waste residue modification method for preparing magnesium metal by pidgeon process | |
| CN108584969A (en) | Preparation method of hydrated calcium silicate nanosheet | |
| CN107188506A (en) | A kind of electrolytic manganese slag brick and its preparation technology | |
| CN109988047A (en) | A kind of formula and preparation method thereof preparing mineral composite bacterial fertilizer using gangue | |
| CN114985413B (en) | Improvement method for realizing harmless treatment of waste incineration fly ash based on magnesium phosphate cement | |
| Wang et al. | Gradient removal of Si and P impurities from phosphogypsum and preparation of anhydrous calcium sulfate | |
| Guan et al. | Promotion of conversion activity of flue gas desulfurization gypsum into α-hemihydrate gypsum by calcination-hydration treatment | |
| Li et al. | Clean dealkalization technology from aluminum industry hazardous tailings—red mud by displacement with Mg-based agent | |
| CN116285998B (en) | Rare earth contaminated soil passivation material and preparation method and application thereof | |
| CN113636565A (en) | Method for preparing industrial vermiculite from phlogopite under normal pressure and industrial vermiculite | |
| Chen et al. | Preparation of high-purity crystalline aluminum chloride based on aluminum separation from circulating fluidized bed fly ash | |
| CN101891219B (en) | Method for preparing special magnesium borate for oriented silicon steel | |
| CN110016349A (en) | A method of heavy metal soil remediation material is prepared using gangue | |
| CN109319896A (en) | The method for preparing flocculant with flyash and vanadium titano-magnetite | |
| CN111018417B (en) | Method for preparing geopolymer finished product by using typical rare earth tailings in Sichuan | |
| CN102642858A (en) | Method for leaching aluminum oxide in fly ash by using microwave acid dissolution | |
| CN102351206A (en) | Carbide slag calcium characteristic-based preparation method of phosphorus recovery material | |
| CN103979512B (en) | A kind of phosphorus reclaims the preparation method of crystal | |
| CN109913232A (en) | A method of bastard coal ground mass biological nano heavy metal soil-repairing agent is prepared using gangue | |
| CN109608072A (en) | A kind of metallurgical slag processing geo-polymer and preparation method thereof | |
| CN115572842B (en) | Method for directly leaching vanadium from vanadium shale | |
| Diao et al. | Characterization of mechanical behavior and cementing mechanism of high-strength composites using biomimetic chemically induced calcium carbonate precipitation method |
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 |