CN112601799A - Method and system for heavy metal immobilization - Google Patents
Method and system for heavy metal immobilization Download PDFInfo
- Publication number
- CN112601799A CN112601799A CN201980045135.0A CN201980045135A CN112601799A CN 112601799 A CN112601799 A CN 112601799A CN 201980045135 A CN201980045135 A CN 201980045135A CN 112601799 A CN112601799 A CN 112601799A
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- China
- Prior art keywords
- chamber
- biochar
- calcining
- additive
- calcination
- Prior art date
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- Pending
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- 238000000034 method Methods 0.000 title claims abstract description 84
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 82
- 238000001354 calcination Methods 0.000 claims abstract description 109
- 239000000654 additive Substances 0.000 claims abstract description 56
- 230000000996 additive effect Effects 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims description 56
- 238000010304 firing Methods 0.000 claims description 36
- 239000003546 flue gas Substances 0.000 claims description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 26
- 239000011261 inert gas Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 15
- 238000004891 communication Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- -1 egg shells Substances 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000010883 coal ash Substances 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 229910002588 FeOOH Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910010084 LiAlH4 Inorganic materials 0.000 claims description 3
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 229910020091 MgCa Inorganic materials 0.000 claims description 3
- 101100003996 Mus musculus Atrn gene Proteins 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 210000003278 egg shell Anatomy 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
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- 229910052586 apatite Inorganic materials 0.000 claims description 2
- 239000002361 compost Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 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 1
- 239000007788 liquid Substances 0.000 description 23
- 239000010802 sludge Substances 0.000 description 11
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- 238000002386 leaching Methods 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
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- 239000003337 fertilizer Substances 0.000 description 5
- 239000003517 fume Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000011363 dried mixture Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 235000013980 iron oxide Nutrition 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 235000019645 odor Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
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- 235000021317 phosphate Nutrition 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
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- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
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- 244000005700 microbiome Species 0.000 description 1
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- 239000010841 municipal wastewater Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/06—Reclamation of contaminated soil thermally
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/13—Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for heavy metal immobilization, which comprises the following steps: mixing an organic-containing medium comprising a heavy metal with at least one additive to form a mixture; and calcining said mixture to form biochar, wherein said biochar immobilizes said heavy metal. The invention also provides a system for heavy metal immobilization.
Description
Technical Field
The invention relates to a method and a system for heavy metal immobilization.
Background
Due to the increase in industrial activities, many rivers, lakes, oceans, other water sources, and lands are polluted with toxic organic matter and heavy metals due to dumping. The pollution of water and land brings great risks and hazards to human health and the environment.
Common organic contaminants in soil include polycyclic aromatic hydrocarbon halides (PAHs), organophosphorus pesticides (OPPs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), Phthalates (PAEs), to name a few. These may include heavy metal contaminants.
Most industrial waste treatment processes attempt to remove or immobilize heavy metal contaminants. Removal methods may include washing and adsorption, electrochemical accumulation by electrophoresis, chelation, and precipitation. Immobilization methods may include adsorption, chelation, precipitation, bioaccumulation, and phytoremediation. However, these methods tend to lead to leaching of heavy metals over time and are costly due to solid-liquid separation, wastewater treatment and reagents used in the treatment process.
Therefore, there is a need for an improved method for heavy metal immobilization.
Disclosure of Invention
The present invention aims to solve these problems and/or to provide an improved method and system for heavy metal immobilization.
The present invention relates generally to a simple method for fixing heavy metals in a medium containing organic matter. The method is easy to expand. The end products of the process can also be used in various applications, such as fertilizers and building materials. Furthermore, the process is a fast, efficient and green process. The process also converts the media into biochar free of any biohazards, making it a useful, environmentally friendly end product.
According to a first aspect, the present invention provides a method for heavy metal immobilization, the method comprising:
-mixing an organic-containing medium comprising heavy metals with at least one additive to form a mixture; and
-calcining said mixture to form biochar, wherein said biochar immobilizes said heavy metal.
The organic-containing medium can be any suitable organic-containing medium that contains heavy metals.
According to a particular aspect, the calcination may be carried out under suitable conditions. For example, the firing may include firing in the presence of an inert gas. For the purposes of the present invention, the calcination may be carried out at a suitable temperature. For example, the calcination may be carried out at a temperature of 1 to 500 ℃.
The method may further comprise treating flue gas generated during the roasting process.
According to a particular aspect, the method may further comprise drying the mixture prior to firing. The drying may be carried out under suitable conditions. For example, the drying may include drying in the presence of an inert gas. In particular, the drying may comprise drying at a suitable temperature. For example, the temperature may be 1 to 280 ℃.
According to a particular aspect, the organic-containing medium can comprise an organic content of ≧ 25 wt.%. In particular, the at least one additive may comprise a reducing agent when the organic-containing medium comprises an organic content of 25 wt.% or more. The at least one additive may be any suitable reducing agent. For example, the at least one additive may be, but is not limited to: sodium borohydride, hydrazine, aluminum powder and LiAlH4Or mixtures thereof.
According to a particular aspect, the organic-containing medium can comprise an organic content of less than 25 wt.%. In particular whenWhen the organic-containing medium comprises an organic content of less than 25 wt%, the at least one additive may comprise an inorganic additive. The at least one additive may comprise any suitable inorganic additive. For example, the at least one additive may include, but is not limited to: lime, limestone, FeCl3、Fe2(SO4)3、FeSO4Aluminum powder, iron powder, FeOOH and Fe2O3、MgCO3、MgCa(CO3)2NaOH, KOH, phosphates, monohydrogenphosphates, dihydrogenphosphates, phosphogypsum (rock phosphate), phosphoric acid, polyphosphates, hydroxyapatite, manure (millirganate), bentonite, kaolinite, zeolites, manganese oxides (mangannese oxides), iron oxides (iron oxides), or mixtures thereof.
The method may further comprise calcining the biochar after calcining to form a calcined material. The calcination may be carried out under suitable conditions. For example, the calcination may include calcination in an oxidizing atmosphere (oxidizing atmosphere). In particular, the calcination may include calcination at a suitable temperature. For example, the temperature may be 600-.
The method may further comprise treating flue gas generated during the calcination.
The method may further comprise cooling the biochar after calcination and/or cooling the calcined material.
According to one particular aspect, the method may further comprise:
-mixing biochar with at least one additional additive to form a biochar mixture; and
-shaping said biochar mixture,
wherein said mixing and said forming are prior to said calcining.
The at least one additional additive may be any suitable additive. For example, the at least one other additive may include, but is not limited to: clay, sand, stone, fly ash (flash ash), coal ash (coal ash), slag, incineration slag, construction waste, egg shells, or mixtures thereof.
According to a second aspect, the present invention provides a system for heavy metal immobilization, said system comprising:
-an inlet for receiving an organic-containing medium containing heavy metals and at least one additive;
-a mixing chamber connected to said inlet for mixing said heavy metal containing organic medium and said at least one additive; and
-a roasting chamber for roasting the mixture formed in said mixing chamber to form biochar.
The firing chamber may include an inlet for receiving an inert gas.
The system may further comprise a drying chamber for drying the mixture formed in the mixing chamber.
According to a particular aspect, the system may further comprise a calcination chamber for calcining the biochar formed in the calcination chamber. The calcination chamber can include an inlet for receiving air.
The system may further comprise a heat source for heating the firing chamber, the drying chamber, and/or the calcining chamber.
According to a particular aspect, the system may further comprise a flue gas treatment system in communication with the roasting and/or calcining chamber for treating flue gas from the roasting and/or calcining chamber.
The system may further comprise a collection chamber for collecting the formed biochar and/or calcined material.
Drawings
In order that the present invention may be fully understood and readily put into practical effect, there shall now be described by way of non-limitative example only exemplary embodiments, the description being with reference to the accompanying illustrative drawings. In the drawings:
FIG. 1 shows a schematic diagram of a system according to an embodiment of the invention;
FIG. 2 illustrates a sealing system according to an embodiment of the present invention;
FIG. 3 shows a schematic diagram of a system according to an embodiment of the invention;
figure 4 shows a thermogravimetric analysis (TGA) profile of the dried and ground sample, where the TGA was performed in air with a weight loss of 16.5 wt%; and
figure 5 shows a thermogravimetric analysis (TGA) profile of the dried and ground sample, where the TGA was performed under pure nitrogen with a weight loss of 14.7 wt%.
Detailed Description
As mentioned above, there is a need for improved methods and systems for heavy metal immobilization.
The present invention relates generally to a method and system for immobilizing heavy metals in an organic-containing medium. The process of the invention forms biochar which adsorbs and immobilizes the reduced zero-valent heavy metal or precipitated heavy metal salt. The process of the present invention is a simple process that is capable of converting contaminated organic-containing media into useful and beneficial products, such as fertilizers and building materials. With the method of the invention, the heavy metals are immobilized without leaching out the heavy metals even when the product of the method is used in further applications. This makes the process an environmentally friendly process.
The system of the present invention is a simple system that is capable of treating heavy metal-containing organic-containing media and converting it into biochar-containing material that can be further used. The system can also carry out rapid and green treatment on the medium containing the organic matters so as to fix the heavy metals in the medium containing the organic matters. By the system of the invention, the heavy metal immobilization can be carried out on site, thereby saving the time and cost for transporting the medium containing the organic matters to another place for heavy metal immobilization.
According to a first aspect, the present invention provides a method for heavy metal immobilization, the method comprising:
-mixing an organic-containing medium comprising heavy metals with at least one additive to form a mixture; and
-calcining said mixture to form biochar, wherein said biochar immobilizes said heavy metal.
The organic-containing medium can be any suitable organic-containing medium that contains heavy metals. In particular, the organic-containing medium may comprise soil, sludge (sludge) and/or solid waste. The organic-containing medium may be industrial waste containing heavy metals or hazardous waste containing heavy metals. For example, the organic-containing medium may comprise river sludge, lake sludge, pond sludge, marine sludge, sand, soil, agricultural soil, wastewater treatment sludge, activated sludge, or any heavy metal contaminated medium.
For the purposes of the present invention, a heavy metal may be defined as any heavy metal that is toxic or harmful to a life form. For example, for animals, including humans, microorganisms or plants. Heavy metals may include, but are not limited to, metal ions, metal compounds, or metal compound anions. Examples of heavy metals include, but are not limited to, antimony, arsenic, cadmium, chromium, cobalt, copper, gallium, iron, lead, magnesium, manganese, mercury, molybdenum, nickel, silver, palladium, platinum, selenium, thallium, tin, tungsten, uranium, vanadium, and zinc.
The mixing can include mixing the heavy metal-containing organic medium with any suitable additive to form a mixture. For example, the additive may be a reducing agent and/or an inorganic additive.
According to a particular aspect, the heavy metal-containing organic medium may comprise an organic content of ≥ 25% by weight. In particular, when the organic-containing medium contains an organic content of 25 wt.% or more, the at least one additive may include a reducing agent. The at least one additive may be any suitable reducing agent. For example, the at least one additive may be, but is not limited to: sodium borohydride, hydrazine, aluminum powder and LiAlH4Or mixtures thereof. In particular, the mixing may include reducing heavy metal ions to zero valent metals.
According to a particular aspect, the organic-containing medium can comprise an organic content of less than 25 wt.%. In particular, when the organic-containing medium contains less than 25% by weight of organic matterIn amounts, the at least one additive may comprise an inorganic additive. The at least one additive may comprise any suitable inorganic additive. For example, the at least one additive may include, but is not limited to: lime, limestone, FeCl3、Fe2(SO4)3、FeSO4Aluminum powder, iron powder, FeOOH and Fe2O3、MgCO3、MgCa(CO3)2NaOH, KOH, phosphate, monohydrogenphosphate, dihydrogenphosphate, apatite, phosphoric acid, polyphosphate, hydroxyapatite, compost, bentonite, kaolinite, zeolite, oxides of manganese, iron oxide, or mixtures thereof. The at least one additive may react with the heavy metal ions to form a metal salt precipitate.
The calcination may be carried out under suitable conditions. For example, the firing may include firing in the presence of an inert gas. The inert gas can be any suitable inert gas such as, but not limited to, nitrogen, argon, helium, carbon dioxide, or combinations thereof. In this way, the biochar produced by the roasting can have a higher carbon content.
For the purposes of the present invention, the calcination may be carried out at any suitable temperature. For example, the calcination may be carried out at a temperature of 1 to 500 ℃. In particular, the calcination can be performed at 10-480 deg.C, 25-450 deg.C, 50-420 deg.C, 100 deg.C, 400 deg.C, 150 deg.C, 200 deg.C, 300 deg.C, 250 deg.C, 275 deg.C. Even more particularly, the calcination may be carried out at a temperature of 300-400 ℃.
The calcination may be continued for a suitable time. For example, the calcination may last for 3 minutes or more. In particular, the calcination may last for 3-60 minutes, 5-50 minutes, 10-45 minutes, 15-30 minutes. Even more particularly, the calcination may last for 10 to 30 minutes.
According to a particular aspect, when the calcination converts the organic component of the organic-containing medium into biochar, the biochar can adsorb and immobilize heavy metals inside the biochar fibers and/or on the surface of the biochar fibers due to the large surface area of the biochar fibers. In particular, the adsorbed and immobilized heavy metal may be a solid heavy metal salt and/or a zero valent metal that is reduced from the heavy metal during mixing. Heavy metals can be immobilized inside and/or on the biochar by physical and/or chemical adsorption. Once the heavy metals are immobilized, they are difficult for passive plants to absorb or diffuse into the environment.
The method may further comprise drying the mixture prior to the firing. The drying may be carried out under suitable conditions. For example, the drying may include drying in the presence of an inert gas. The inert gas can be any suitable inert gas such as, but not limited to, nitrogen, argon, helium, carbon dioxide, or combinations thereof.
The drying may include drying at a suitable temperature. For example, the temperature may be 1 to 280 ℃. In particular, the drying can be performed at a temperature of 1-280 ℃, 50-250 ℃, 80-220 ℃, 90-200 ℃, 100-. Even more particularly, the drying may be carried out at a temperature of 110-150 ℃.
The drying may be continued for a suitable period of time. For example, the drying may last ≧ 3 minutes. In particular, the calcination may last for 3-60 minutes, 5-50 minutes, 10-45 minutes, 15-30 minutes. Even more particularly, said drying may last for 10-30 minutes.
During the drying and/or firing, the moisture in the mixture may be evaporated and thus discharged. The moisture may be discharged through a pipe and condensed into a liquid, which is then discharged. The method may further comprise treating the condensed liquid in a liquid filtration system. Any suitable liquid filtration system may be used for treatment. In particular, the treatment may comprise treating the condensate prior to discharge in accordance with local regulations.
During the firing process, fumes may be generated. For example, the flue gas may include NOx, SO2、NH3、H2S, CO and/or CO2. Thus, the method may further comprise treating flue gas generated during roasting. The treatment may be carried out in a flue gas treatment system. Thus, from the process of the inventionCan be absorbed by the flue gas system, thereby minimizing odorous and/or environmentally harmful gas emissions. In particular, the flue gas treatment system may comprise an adsorption solution and/or solid cartridges (solid cartridges) for removing odors.
According to a particular aspect, the method may further comprise cooling the formed biochar after calcination. The method may then include collecting the formed biochar. For example, the formed biochar can be used as a fertilizer. In particular, since the heavy metals immobilized in and/or on biochar are zero-valent heavy metals, they are not absorbed or absorbed much less by plants than the non-immobilized heavy metal ions. Thus, the use of the formed biochar as a fertilizer is not harmful to the plants using the fertilizer.
According to another particular aspect, the method may further comprise calcining the biocoke formed by the roasting to form a calcined material. The calcination may be carried out under suitable conditions. For example, the calcining may comprise calcining in an oxidizing atmosphere. In particular, the calcination may be carried out in the presence of air or oxygen.
The calcining may comprise calcining at a suitable temperature. For example, the temperature may be 600-. In particular, the calcination can be performed at the temperatures of 650-1150 ℃, 700-1100 ℃, 800-1050 ℃, 850-1000 ℃ and 900-950 ℃. Even more particularly, the calcination may be carried out at a temperature of 800-1000 ℃.
The calcination may be continued for a suitable time. For example, the calcination may last for ≧ 5 minutes. In particular, the calcination may last from 5 to 120 minutes, from 10 to 90 minutes, from 15 to 60 minutes, from 30 to 45 minutes. Even more particularly, the calcination may last for 60 to 120 minutes.
In particular, the biochar formed by calcination can be used as a fuel for calcination. Thus, the calcination can be carried out at lower temperatures with lower energy input. Although calcination is generally associated with high energy consumption, the overall energy consumption of calcination is reduced in view of the biocoke used in calcination in the process of the present invention. Further, the calcining may include oxidizing the biochar to form a calcined material, thereby thermally decomposing the biochar into flue gas. Accordingly, the method may further comprise treating the flue gas generated during calcination. The treatment may be as described above in relation to the flue gas generated during firing.
The method may further comprise cooling the calcined material after calcination.
According to one particular aspect, the method may further comprise:
-mixing biochar with at least one additional additive to form a biochar mixture; and
-shaping the biochar mixture,
wherein said mixing and said shaping may be prior to said calcining.
The at least one additional additive may be any suitable additive. For example, the at least one additional additive may include, but is not limited to: clay, sand, stone, fly ash, coal ash, slag, incineration slag, construction waste, egg shells, or mixtures thereof.
The shaping can be carried out under suitable conditions. For example, the molding may be performed under a suitable pressure. The shaping may include shaping the biochar mixture into a suitably shaped prototype. For example, the forming may include forming the biochar mixture into a building material, such as, but not limited to, brick, paving material, or seafloor packing.
The shaped prototype may then be subjected to calcination as described above. Given that the biochar is present in the shaped prototypes, the heating during calcination is uniform for each shaped prototype, and thus, an improved and uniform prototype can be obtained. In view of the method of the present invention, prototypes including road pavers, bricks or sea-fill can be used without fear of leaching of heavy metals during use of the prototypes.
From the above, it can be seen that the method of the present invention can fix heavy metals, and thus, can minimize the heavy metals in the leachate. The method can also convert the heavy metal-containing organic medium into biochar which can be used as an adsorbent or fuel. In some aspects of the method, organic components of the organic-containing medium may be removed.
The invention also provides a system for heavy metal immobilization. The system may be any suitable system. For example, the system may be a system suitable for performing the above method.
According to a second aspect of the present invention, there is provided a system for heavy metal immobilization, the system comprising:
-an inlet for receiving an organic-containing medium containing heavy metals and at least one additive;
-a mixing chamber connected to said inlet for mixing said heavy metal containing organic medium and said at least one additive; and
-a roasting chamber for roasting the mixture formed in said mixing chamber to form biochar.
The mixing chamber may include a seal to prevent any odors of the organic containing medium from escaping the system and entering the atmosphere. In this way, odors from the organic-containing media are controlled within the system. In particular, the seal may be a rubber seal or a gasket.
The mixing chamber may comprise a mixer. The mixer may be any suitable mixer for mixing the heavy metal-containing organic medium with the at least one additive. The mixing chamber may comprise an outlet for discharging the mixture formed in the mixing chamber.
The system may further comprise a drying chamber for drying the mixture formed in the mixing chamber. According to a particular aspect, the drying chamber may be in communication with the mixing chamber. For example, the outlet of the mixing chamber may be in communication with the inlet of the drying chamber. The drying chamber may further comprise an inlet for receiving an inert gas. The inert gas can be any suitable inert gas. The inert gas may be an inert gas as described above.
The drying chamber may include an external heat source for heating the mixture received from the mixing chamber. The heat source may be any suitable heat source. For example, the heat source may be, but is not limited to, an electric heater, a microwave oven, a gas burner, or a solar panel.
The firing chamber may be any chamber suitable for firing the mixture formed in the mixing chamber. According to a particular aspect, the roasting chamber may be in communication with the drying chamber. The firing chamber may include an inlet for receiving an inert gas. The inert gas can be any suitable inert gas. The inert gas may be an inert gas as described above.
The firing chamber may include a temperature control device to regulate the temperature of the firing chamber. For example, the temperature control device may be a cooling source for cooling the drying chamber, or may be an external heat source for heating the firing chamber. The heat source may be any suitable heat source. For example, the heat source may be, but is not limited to, an electric heater, a microwave oven, a gas burner, or a solar panel.
According to a particular aspect, the system may further comprise a calcination chamber for calcining the biochar formed in the calcination chamber. In particular, the calcination chamber may be in communication with the roasting chamber to receive the biochar formed in the roasting chamber. The calcination chamber can include an inlet for receiving air.
The calcination chamber may include an external heat source for heating the calcination chamber. The heat source may be any suitable heat source. For example, the heat source may be, but is not limited to, an electric heater, a microwave oven, a gas burner, or a solar panel.
According to a particular aspect, the system may further comprise a flue gas treatment system in communication with the drying chamber, the firing chamber, and/or the calcining chamber for treating flue gas from the drying chamber, the firing chamber, and/or the calcining chamber. In use, the drying chamber, the roasting chamber and/or the calcining chamber may release fumes, which may therefore be treated before being discharged to the atmosphere. Thus, the system of the present invention does not emit any harmful and/or odorous gases into the atmosphere, making the system an environmentally friendly system. The flue gas treatment system described may be any suitable system for the purposes of the present invention.
The system may further comprise a collection chamber for collecting biochar formed in the roasting chamber and/or calcined material formed in the calcining chamber.
The system may also include a liquid collection tank. The liquid collection tank can be communicated with the drying chamber, the roasting chamber and/or the roasting chamber. For example, in use, moisture from the mixture and biochar being processed in the drying chamber, the roasting chamber and/or the calcining chamber may evaporate from the mixture and biochar, and subsequently condense and collect in a liquid collection tank. The liquid collection tank may also be in communication with or may include a liquid filtration system for treating and/or filtering the liquid collected in the liquid collection tank.
Fig. 1 shows an example of a system 100 for heavy metal immobilization according to an embodiment of the present invention. System 100 includes an inlet 102 through which an organic-containing medium containing heavy metals is fed. At least one additive may also be fed through inlet 102. The inlet 102 may be part of the feed chamber 104.
The feed chamber 104 may be in communication with a mixing chamber 106. In particular, an outlet of the feeding chamber 104 may be connected to an inlet 108 of the mixing chamber 106. The inlet 108 may include a hybrid inlet sealing system, which may be as shown in FIG. 2. A mixer 110 is also provided and included within the mixing chamber 106 to facilitate and improve mixing of the heavy metal-containing organic medium and the at least one additive.
The outlet 112 of the mixing chamber 106 may be connected to a drying chamber 114, so that the mixture of the heavy metal containing organic medium and the at least one additive is mixed in the mixing chamber 106 and subsequently transferred to the drying chamber 114. The mixture may be dried in drying chamber 114 under suitable conditions. For example, the conditions may be as described above in connection with the process of the invention. The drying chamber 114 may include an inlet 116. Additional additives may be added to the drying chamber 114 through an inlet 116. In particular, the inlet 116 may be used to introduce an inert gas into the drying chamber 114.
The drying chamber 114 may further include a heater 118. The heater 118 may be any suitable heater, such as the heaters described above. The heater 118 may increase the temperature of the inert gas within the drying chamber 114 to dry the mixture received from the mixing chamber 106. In this manner, any liquid components within the mixture are vaporized and removed from the drying chamber 114 through outlet 120 a.
The outlet 122 of the drying chamber 114 may be in communication with a roasting chamber 124 so that the mixture that has been dried in the drying chamber 114 may be transferred from the drying chamber 114 to the roasting chamber 124 for roasting into biochar.
The dried mixture may be fired in firing chamber 124 under appropriate conditions. For example, the conditions may be as described above in connection with the process of the invention. Firing chamber 124 may include an inlet 126. Additional additives may be added to firing chamber 124 through inlet 126. In particular, inlet 126 may be used to introduce an inert gas into firing chamber 124.
Firing chamber 124 may further include a heater 128. The heater 128 may be any suitable heater, such as the heaters described above. The heater 128 may increase the temperature of the inert gas within the firing chamber 124 to fire the dried mixture received from the drying chamber 114 to form biochar. During firing in firing chamber 124, the flue gases may be released. The flue gas may be directed out of the firing chamber 124 through an outlet 120 b.
After the dried mixture is calcined to form biochar, the biochar may be transferred through an outlet 132 of the calcining chamber 124 into a storage chamber 130. The biochar can be cooled and stored in the storage chamber 130. The storage chamber 130 may include an outlet 120c for directing any fumes or evaporated moisture out of the storage chamber 130.
The outlets 120a, 120b, and 120c may be in fluid communication with the flue gas treatment system 134 and the liquid collection tank 140. In particular, the passages 136 in communication with the outlets 120a, 120b, and 120c allow gases from the drying chamber 114, firing chamber 124, and storage chamber 130 to be delivered to the flue gas treatment system 134 before being exhausted from the outlet 138. The flue gas treatment system 134 can be any suitable system for treating flue gas.
The channel 136 also enables any liquid that condenses in the channel 136 to be transferred to a liquid collection tank 140. The liquid collection tank 140 may include a liquid filtration system to process the collected liquid. For example, the liquid collection tank 140 may further include a funnel 142 for filtering the collected liquid and discharging only the filtered liquid through an outlet pipe 144.
Fig. 2 shows an example of a mixing inlet sealing system at the inlet 108 of the mixing chamber 106. The seal may be a horizontal cylinder divided along its horizontal axis into three equal parts by three quadrilaterals. The horizontal cylinder seal has two rounded sides with curved surfaces removed. The cylinder is configured to rotate along its horizontal axis. When a portion of the cylinder is exposed to the inlet 108, any odors are prevented from escaping from the system 100. As the cylinder rotates, the organic-containing medium containing heavy metals and the at least one additive fed by inlet 108 enter mixing chamber 106. Thus, the mixing chamber 106 is sealed at all times.
Fig. 3 shows an example of a system 200 for heavy metal immobilization according to another embodiment of the present invention. The system 200 and the system 100 have many common components, which are identified by the same reference numerals.
In system 200, after the dried mixture is calcined to form biochar, the biochar can be transferred through outlet 132 of calcining chamber 124 to calcining chamber 202. The biochar can be calcined in the calcination chamber 202 to form a calcined material. The biochar in the calcination chamber 202 can be calcined under suitable conditions. For example, the conditions may be as described above in connection with the process of the invention. The calcination chamber 202 can include an inlet 204. Additional additives may be added to the calcination chamber 202 through inlet 204. In particular, the inlet 204 may be used to introduce air into the calcination chamber 202.
The calcination chamber 202 may further include a heater 206. The heater 206 may be any suitable heater, such as the heaters described above. The heater 206 may increase the temperature of the air within the calcination chamber 202 to calcine the biochar received from the calcination chamber 124. In particular, the biochar can be oxidized to form a calcined material. During calcination, fumes may be released. Accordingly, flue gas released from the calcination of the biochar in the calcination chamber 202 can be directed out of the calcination chamber 202 through the outlet 220 d.
After calcining the biochar, the calcined material can be transferred into the storage chamber 130 through the outlet 208 of the calcining chamber 202. The calcined material can be cooled and stored in the storage chamber 130. The storage chamber 130 may include an outlet 120c for directing any fumes or evaporated moisture out of the storage chamber 130.
The outlet 220d may be in communication with the gas treatment system 134 and the liquid collection tank 140. In particular, the passage 136, which is connected to the outlet 220d and the outlets 120a, 120b and 120c, allows the gases from the calcining chamber 202 and the gases from the drying chamber 114, the calcining chamber 124 and the storage chamber 130 to be conveyed to the flue gas treatment system 134 before being discharged from the outlet 138.
While the foregoing has described exemplary embodiments, those skilled in the relevant art will recognize that many changes may be made thereto without departing from the invention. Having generally described the invention, the same will be more readily understood through reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention.
Examples
Samples of sludge from the bottom of the lake were dried and treated for elemental composition. The sample was dried at 110 ℃ for 24 hours and then ground to homogeneity. For elemental analysis by inductively coupled plasma mass spectrometry (ICP-MS) other than Hg, 0.2g of the dried and ground sample was added to 9mL of 85 wt.% HNO3Then 2mL of 37 wt% HCl, 3mL of 50 wt% HF and 1mL of 20 wt% H were added2O2And mixing uniformly. The mixture was mixed at 180 ℃ for 20 minutes. After cooling, DI water was added thereto until the total volume reached 50 mL. The sample was then filtered through a 0.22 μm filter and analyzed by inductively coupled plasma-emission spectroscopy (ICP-OES).
When analyzing Hg by ICP-OES, 0.2g of the dried and ground sample was added to 15mL85% by weight of HNO3Then, 0.85mL of 37 wt% HCl, 6.5. mu.L of 1000ppm Au standard and 35mL of DI water were added and mixed well. The sample was filtered through a 0.22 μm filter and analyzed for Hg by ICP-OES. The results of the ICP-OES elemental analysis are summarized in Table 1. It can be seen that the heavy metals of the sample, i.e. As, Hg, Pb, Zn, Sb, Cu, all exceed or approach the upper standard limit. The main metallic elements in the sample were Si (22.14 wt%), Al (5.29 wt%), Fe (2.87 wt%), K (1.80 wt%), P (0.52 wt%). Thus, the general formula for the inorganic silicate component in this sample may be Al0.25Fe0.06K0.06MXSiO2.5+XWherein M represents other metals (M is formalized to a +2 valence).
ND-not detected
Standard GB15618-201X agricultural Land Soil Environmental Quality Standard (Chinese)
Table 1: ICP-OES elemental analysis of dried, ground and treated sludge samples
C. H, N and S are shown in Table 2.
Table 2: elemental analysis of dried and ground samples
FIGS. 4 and 5 show thermogravimetric analysis (TGA) profiles (in air) of dried and ground samplesOr N2In (1). Neutralization of the sample in air with N2The weight loss values from 25 c to 900 c were 16.5 wt% and 14.7 wt%, respectively, and thus the organic content of the dried and ground sample was 16.5 wt%, most of which (i.e., 14.7 wt%) was thermally degradable and a small amount (1.8 wt%) was thermally oxidizable to gas. The total content of organic and inorganic substances in the dried sample was 16.5 wt% and 83.5 wt%, respectively.
The method of preparing the tile samples was as follows: 1.1mL of 3% H3PO4 or DI water was added to 2g of the dried and ground sample and mixed well and aged for 1 hour by hand. 0.8g of the mixture was then pressed into disks of about 14mm diameter and 3mm thickness and dried at 60 ℃ for 24 hours.
The dried discs were then fired and calcined in a tube furnace as follows: the calcination includes heating from 25 ℃ to 400 ℃ at a rate of 5 ℃/min, N2The flow rate is 100mL/min, then calcination is carried out, including heating from 400 ℃ to 1000 ℃, the heating rate is 1.7 ℃/min, the air flow rate is 100mL/min, maintaining at 1000 ℃ for 300 minutes at the same air flow rate, and then naturally cooling at the same air flow rate. The discs containing and no phosphoric acid additive were green-grey before calcination, and after calcination, the discs without phosphoric acid additive turned orange, the discs containing the phosphoric acid additive were dark orange and the edges were somewhat reddish. This color change is mainly due to oxidation of ferrous or ferric compounds in the soil by oxygen in the air to red iron oxides at high temperatures.
The construction brick produced by the process is subjected to leaching test, and the leaching risk of heavy metals is evaluated. The leaching test procedure was carried out according to GB5086.1 "standard test method for leaching toxicity of solid waste-tumbling leaching method" (china). Specifically, the test was carried out as follows: 0.7g of the dried sample was soaked in 10mL of DI water at room temperature for 18 hours with stirring at 30 rpm. The leachate was filtered through a 0.45 μm filter and analyzed for heavy metals As, Hg, Pb, Sb, Ni, Cu, Fe, Cr, Mn and V by ICP-OES. The results of the leaching tests are summarized in table 3.
Table 3: concentration of heavy metals in the calcined brick sample leachate
The results were compared with the standard HJxxx-2010 technical Specification for sludge treatment and disposal in municipal wastewater treatment plants (China). Table 3 shows that the heavy metal concentration in the leachate of the calcined brick samples is well below the upper limit of the standard. This shows that the process of the invention has an efficient immobilization effect on heavy metals in sludge samples.
Claims (30)
1. A method for heavy metal immobilization, the method comprising:
-mixing an organic-containing medium comprising heavy metals with at least one additive to form a mixture; and
-calcining said mixture to form biochar, wherein said biochar immobilizes said heavy metal.
2. The method of claim 1, wherein the firing comprises firing in the presence of an inert gas.
3. The method of claim 1 or 2, wherein the firing is carried out at a temperature of 1-500 ℃.
4. The method of any of the above claims, further comprising treating flue gas generated during firing.
5. The method of any of the preceding claims, further comprising drying the mixture prior to the firing.
6. The method of claim 5, wherein said drying comprises drying in the presence of an inert gas.
7. The method of claim 5 or 6, wherein the drying is carried out at a temperature of 1-280 ℃.
8. The method of any one of the preceding claims, further comprising cooling the biochar after the firing.
9. The method according to any of the preceding claims, wherein the organic-containing medium comprises an organic content of 25 wt. > or more.
10. The method of claim 9, wherein the at least one additive comprises a reducing agent.
11. The method of claim 9 or 10, wherein the at least one additive comprises sodium borohydride, hydrazine, aluminum powder, LiAlH4Or mixtures thereof.
12. The method of any of claims 1 to 8, wherein the organic-containing medium comprises an organic content of less than 25 wt.%.
13. The method of claim 12, wherein the at least one additive comprises an inorganic additive.
14. The method of claim 13, wherein the at least one additive comprises: lime, limestone, FeCl3、Fe2(SO4)3、FeSO4Aluminum powder, iron powder, FeOOH and Fe2O3、MgCO3、MgCa(CO3)2NaOH, KOH, phosphate, monohydrogenphosphate, dihydrogenphosphate, apatite, phosphoric acid, polyphosphate, hydroxyapatite, compost, bentonite, kaolinite, zeolite, oxides of manganese, iron oxide, or mixtures thereof.
15. The method of any one of claims 12 to 14, further comprising calcining the biochar after calcining to form a calcined material.
16. The method of claim 15, wherein said calcining comprises calcining in an oxidizing atmosphere.
17. The method as claimed in claim 15 or 16, wherein the calcination is carried out at a temperature of 600-1200 ℃.
18. The method of any one of claims 15 to 17, further comprising treating flue gas generated during calcination.
19. The method of any one of claims 15 to 18, further comprising cooling the calcined material.
20. The method of any of claims 15-19, further comprising:
-mixing biochar with at least one additional additive to form a biochar mixture; and
-shaping the biochar mixture,
wherein said mixing and said forming are prior to said calcining.
21. The method of claim 20, wherein the at least one additional additive comprises: clay, sand, stone, fly ash, coal ash, slag, incineration slag, construction waste, egg shells, or mixtures thereof.
22. A system for heavy metal immobilization, the system comprising:
-an inlet for receiving an organic-containing medium containing heavy metals and at least one additive;
-a mixing chamber connected to said inlet for mixing said heavy metal containing organic medium and said at least one additive; and
-a roasting chamber for roasting the mixture formed in said mixing chamber to form biochar.
23. The system of claim 22, wherein the firing chamber includes an inlet for receiving an inert gas.
24. The system of claim 22 or 23, further comprising a drying chamber for drying the mixture formed in the mixing chamber.
25. The system of any one of claims 22 to 24, further comprising a calcination chamber for calcining biochar formed in the calcination chamber.
26. The system of claim 25, wherein the calcining chamber comprises an inlet for receiving air.
27. The system of any one of claims 24 to 26, further comprising a heat source for heating the roasting chamber, the drying chamber and/or the calcining chamber.
28. The system of any one of claims 25 to 27, further comprising a flue gas treatment system in communication with the roasting chamber and/or the calcining chamber for treating flue gas from the roasting chamber.
29. The system of any one of claims 25 to 28, further comprising a collection chamber for collecting calcined material.
30. The system of any one of claims 22 to 24, further comprising a collection chamber for collecting the formed biochar.
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| CN115970649A (en) * | 2023-03-20 | 2023-04-18 | 四川省冶勘设计集团生态环境工程有限公司 | Citrus biochar and preparation method and application thereof |
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| CN111392710A (en) * | 2020-04-03 | 2020-07-10 | 成都农业科技中心 | Biochar based on waste egg shells and preparation method and application thereof |
| CN114275986A (en) * | 2022-01-10 | 2022-04-05 | 武汉市秀谷科技有限公司 | In-situ remediation method for heavy metal polluted bottom mud in mining area watershed |
| CN116693272B (en) * | 2023-08-10 | 2023-11-03 | 北京建工环境修复股份有限公司 | Tungsten slag recycling method and tungsten slag curing material |
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| CN104388094B (en) * | 2014-10-13 | 2017-04-05 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | A kind of iron-based biological carbon materials, its preparation technology and its application in remediation contaminated soil |
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