CN112126788A - Method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes - Google Patents
Method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes Download PDFInfo
- Publication number
- CN112126788A CN112126788A CN202010408429.XA CN202010408429A CN112126788A CN 112126788 A CN112126788 A CN 112126788A CN 202010408429 A CN202010408429 A CN 202010408429A CN 112126788 A CN112126788 A CN 112126788A
- Authority
- CN
- China
- Prior art keywords
- fly ash
- agent
- ore
- powder
- flotation
- 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.)
- Pending
Links
- 239000010881 fly ash Substances 0.000 title claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 95
- 239000002184 metal Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 80
- 150000002739 metals Chemical class 0.000 title claims abstract description 23
- 231100001261 hazardous Toxicity 0.000 title claims abstract description 6
- 239000010815 organic waste Substances 0.000 title claims abstract description 6
- 238000005188 flotation Methods 0.000 claims abstract description 67
- 239000002920 hazardous waste Substances 0.000 claims abstract description 51
- 239000000460 chlorine Substances 0.000 claims abstract description 34
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 34
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 33
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004056 waste incineration Methods 0.000 claims abstract description 23
- -1 ferrous metals Chemical class 0.000 claims abstract description 8
- 238000005453 pelletization Methods 0.000 claims abstract description 8
- 239000008188 pellet Substances 0.000 claims description 91
- 239000000843 powder Substances 0.000 claims description 57
- 239000003795 chemical substances by application Substances 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 239000003638 chemical reducing agent Substances 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- 239000004088 foaming agent Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000012216 screening Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003546 flue gas Substances 0.000 claims description 9
- 230000002000 scavenging effect Effects 0.000 claims description 9
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 8
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 8
- 239000001095 magnesium carbonate Substances 0.000 claims description 8
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 8
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 8
- 238000003801 milling Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000571 coke Substances 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000012991 xanthate Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims 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 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000009837 dry grinding Methods 0.000 claims description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010665 pine oil Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- VXLCNTLWWUDBSO-UHFFFAOYSA-N Ethiazide Chemical compound ClC1=C(S(N)(=O)=O)C=C2S(=O)(=O)NC(CC)NC2=C1 VXLCNTLWWUDBSO-UHFFFAOYSA-N 0.000 claims description 3
- QTANTQQOYSUMLC-UHFFFAOYSA-O Ethidium cation Chemical compound C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 QTANTQQOYSUMLC-UHFFFAOYSA-O 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- UOJYYXATTMQQNA-UHFFFAOYSA-N Proxan Chemical compound CC(C)OC(S)=S UOJYYXATTMQQNA-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910001570 bauxite Inorganic materials 0.000 claims description 3
- 235000012216 bentonite Nutrition 0.000 claims description 3
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 229950007164 ethiazide Drugs 0.000 claims description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- OHLQPYLQCZVHJP-UHFFFAOYSA-N o-ethyl n-butylcarbamothioate Chemical compound CCCCNC(=S)OCC OHLQPYLQCZVHJP-UHFFFAOYSA-N 0.000 claims description 3
- CMGLSTYFWSQNEC-UHFFFAOYSA-N o-ethyl n-ethylcarbamothioate Chemical compound CCNC(=S)OCC CMGLSTYFWSQNEC-UHFFFAOYSA-N 0.000 claims description 3
- GHYOYKNBJJMRDO-UHFFFAOYSA-N o-ethyl n-propylcarbamothioate Chemical compound CCCNC(=S)OCC GHYOYKNBJJMRDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 235000015424 sodium Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims 2
- QWENMOXLTHDKDL-UHFFFAOYSA-N pentoxymethanedithioic acid Chemical compound CCCCCOC(S)=S QWENMOXLTHDKDL-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 46
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 26
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 16
- 239000011707 mineral Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000005660 chlorination reaction Methods 0.000 abstract description 11
- 239000012320 chlorinating reagent Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 28
- 239000011133 lead Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000012141 concentrate Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 235000010755 mineral Nutrition 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000003814 drug Substances 0.000 description 9
- 239000013043 chemical agent Substances 0.000 description 8
- 238000005204 segregation Methods 0.000 description 8
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000001238 wet grinding Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910018965 MCl2 Inorganic materials 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical class [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910001710 laterite Inorganic materials 0.000 description 2
- 239000011504 laterite Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000009149 molecular binding Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XDRYMKDFEDOLFX-UHFFFAOYSA-N pentamidine Chemical compound C1=CC(C(=N)N)=CC=C1OCCCCCOC1=CC=C(C(N)=N)C=C1 XDRYMKDFEDOLFX-UHFFFAOYSA-N 0.000 description 2
- 229960004448 pentamidine Drugs 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 208000013738 Sleep Initiation and Maintenance disease Diseases 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Substances Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IITHIOWFUOHSOP-UHFFFAOYSA-L dichlorocobalt nickel Chemical compound [Co](Cl)Cl.[Ni] IITHIOWFUOHSOP-UHFFFAOYSA-L 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZMMJGEGLRURXTF-UHFFFAOYSA-N ethidium bromide Chemical group [Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 ZMMJGEGLRURXTF-UHFFFAOYSA-N 0.000 description 1
- 229960005542 ethidium bromide Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 206010022437 insomnia Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100001252 long-term toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100001119 organic toxicant Toxicity 0.000 description 1
- 239000012250 organic toxicant Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
- B03D1/023—Carrier flotation; Flotation of a carrier material to which the target material attaches
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/248—Binding; Briquetting ; Granulating of metal scrap or alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
-
- 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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes. The method takes non-ferrous metal ores, organic hazardous waste incineration fly ash and the like as pelletizing raw materials to carry out mixed pelletizing, and then non-ferrous metal is extracted through chloridizing roasting treatment and carrier flotation treatment. The method can deeply decompose dioxin through high-temperature roasting; meanwhile, non-ferrous metals contained in the fly ash are used as target value elements, non-ferrous metals in metal minerals and heavy metal elements in the fly ash are extracted through a high-temperature chlorination roasting process and a carrier flotation process, and the problem of heavy metal treatment in the fly ash is solved; meanwhile, the fly ash is used as a chlorinating agent for extracting nonferrous metals by utilizing the characteristic of high content of chlorine in the fly ash, and gases generated in the treatment process are collected uniformly and then treated in a centralized manner without washing the fly ash and generating chlorine-containing wastewater.
Description
Technical Field
The invention relates to recycling of organic hazardous waste incineration fly ash, in particular to a method for extracting nonferrous metals by using organic hazardous waste incineration fly ash, belonging to the technical field of recycling of waste resources of organic hazardous waste incineration fly ash.
Background
The organic hazardous waste incineration fly ash refers to residues collected in systems such as heat recovery and utilization, flue gas purification and the like after the organic hazardous waste is incinerated, and is generally fine granular substances with low water content. In 2018, the yield of organic hazardous waste in China is about 8400 ten thousand tons, the organic hazardous waste is mainly treated by an incineration method at the present stage, about 3 percent of fly ash (250 ten thousand tons) is generated in the process, and the quantity is huge. The incineration fly ash of the organic hazardous waste is solid waste with the hazard characteristics of organic toxicants (dioxin) and heavy metals, and belongs to hazardous waste in the national hazardous waste records. The organic hazardous waste incineration fly ash contains a large amount of carcinogenic and teratogenic pollutants, such as copper, lead, zinc, chlorine, dioxin and the like. If the fly ash is not reasonably disposed after being collected and is even directly discharged into the atmosphere, the fly ash enters an ecological chain through a certain way, and long-term toxicity is generated on animals, plants and human bodies. The excessive accumulation of any heavy metal in a human body can cause great harm to the health of the human body, and easily cause dizziness, insomnia, nerve disorder, calculus and even cancer.
There are two approaches to solve the heavy metal pollution of fly ash in nature: firstly, the heavy metals are deeply solidified in the fly ash particles, so that the heavy metals cannot be diffused to the external environment. Secondly, heavy metal elements are separated from the fly ash particles, and the content of heavy metals in the fly ash is reduced, so that the fly ash meets the relevant standards. The method for solving the pollution of dioxin in the fly ash mainly adopts pyrolysis (>800 ℃), and the purified tail gas obtained after treatment does not contain dioxin. Aiming at the organic hazardous waste incineration fly ash, the method of cement solidification, chemical agent stabilization, chemical extraction, melting solidification and the like is mainly adopted for treatment at the present stage.
The cement solidification technology is characterized in that organic hazardous waste incineration fly ash, cement and other additives are mixed with water, and a hard solidified body is formed after curing for a certain time, so that leaching of dangerous components such as heavy metals in the fly ash is reduced. The basic principle is that the hydration reaction of cement can reduce the specific surface area of fly ash, thus reducing the permeability of fly ash and realizing the stabilization and harmless treatment of fly ash. The cement curing technology is the most widely applied process for curing the fly ash at present due to the cheap and easily available curing materials, simple process equipment and simple curing requirement. However, the solidified body has large porosity, so that the solidified body is not ideal in fixing effect on certain heavy metals and easy to leach out again, and the final solidified body cannot meet the requirement of direct landfill.
Chemical agent stabilization is a process of converting pollutants in fly ash into low-pollution substances by adding chemical agents to carry out chemical reaction. The chemical agent treatment process has no compatibilization phenomenon, so that the overall efficiency of the fly ash harmless treatment is improved, and the economic loss of secondary treatment is reduced. The fly ash is stabilized by chemical agents, the energy consumption is low, and the risk of compatibilization is avoided. However, the heavy metals in the incineration fly ash are different in types and existing forms, so that the same chemical agent is difficult to be universally applied to the treatment of all fly ashes. The chemical agent stabilization method is limited in practical application of large-scale treatment of heavy metals in fly ash.
The melt solidification process is also known as vitrification technique. The technology is to fill the fly ash to be treated into a high-temperature electric arc furnace for high-temperature melting treatment, so that the fly ash generates a glassy silicate form and prevents the dissolution of easily soluble components. The basic principle of melting and solidifying is to reduce the volume of the fly ash through melting, increase the containment and more effectively fix the heavy metal, thereby keeping the stability of the heavy metal for a long time. The melting process of waste incineration fly ash is rapidly developed in developed countries. The melting solidification is the most stable and safe method for treating the waste incineration fly ash, but has the defects of large energy consumption and large investment on high-temperature equipment.
But the defects of the prior art are also obvious: first, the dioxin harm removal effect is poor. The mainstream treatment process of the incineration fly ash of the organic hazardous waste at the present stage is solidification/stabilization, the treatment is mainly carried out at normal temperature or low temperature, and the dioxin pollution in the fly ash cannot be effectively removed; secondly, the risk of re-leaching of heavy metals is high. Heavy metals in the fly ash solidified at normal temperature or low temperature have poor stability, and the risk of secondary leaching is higher; the heavy metal elements in the fly ash can be effectively stabilized by melting and solidifying, the re-leaching probability is small, but the melting and solidifying temperature is high (generally >1350 ℃), the defects of high energy consumption, large equipment investment and the like exist, the treatment scale is small, and the production technology needs to be mature and complete; again, the prior art produces chlorine-containing wastewater that requires secondary treatment. The content of chlorine element in the incineration fly ash of the organic hazardous waste is high, and water is needed to wash for removing chlorine before disposal (cement solidification, melt solidification and the like), so that a large amount of chlorine-containing waste water is generated. And the chloride ions have high stability in the wastewater and great treatment difficulty, thereby causing secondary pollution of the fly ash.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for extracting nonferrous metals by using incineration fly ash of organic hazardous wastes. The method utilizes the waste incineration fly ash as a chlorinating agent to extract nonferrous metals in a high-temperature (850-1500 ℃) environment, and can deeply decompose dioxin in the machine-hazardous waste incineration fly ash; meanwhile, a new method is developed, non-ferrous metals in the fly ash are taken as target value elements, and the non-ferrous metals in the metal minerals and heavy metal elements in the fly ash are extracted by a high-temperature chlorination roasting process in cooperation with a flotation process, so that the problem of heavy metal treatment in the fly ash is solved; meanwhile, the fly ash is used as a chlorinating agent for extracting nonferrous metals by utilizing the characteristic of high content of chlorine in the fly ash, and gases generated in the treatment process are collected uniformly and then treated in a centralized manner, so that the fly ash is not required to be washed, and a large amount of chlorine-containing wastewater which needs to be treated again is not generated.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes comprises the following steps:
1) mixing and pelletizing: the method comprises the steps of uniformly mixing non-ferrous metal ore, organic hazardous waste incineration fly ash, a reducing agent, a binder and a roasting auxiliary agent to obtain a mixture, and then placing the mixture into a pelletizer to prepare green pellets.
2) Drying and roasting: drying the green pellets obtained in the step 1), and then roasting to obtain roasted pellets.
3) Crushing and grinding: and (3) crushing and grinding the roasted pellets obtained in the step 2) to obtain pellet powder.
4) Carrier flotation: uniformly mixing the pellet powder obtained in the step 3) with a carrier agent, and then extracting nonferrous metals by flotation treatment in the presence of a pH regulator, an activating agent, a collecting agent and a foaming agent.
Preferably, in step 1), the non-ferrous metal ore is selected from one or more of copper ore, lead ore, zinc ore, stone coal vanadium ore, laterite nickel ore, bauxite ore and magnesite ore.
Preferably, in the step 1), the incineration fly ash of the organic hazardous waste is dust collected by a flue gas system after the organic hazardous waste is incinerated.
Preferably, in step 1), the reducing agent is selected from one or more of coke, coal dust and biomass.
Preferably, in step 1), the binder is selected from one or more of bentonite, water glass, slaked lime, sodium humate and organic composite binders.
Preferably, in step 1), the roasting aid is selected from one or more of calcium chloride, sodium chloride, calcium sulfate, calcium carbonate, magnesium carbonate and copper sulfate.
Preferably, in step 4), the carrier agent is selected from one or more of copper sulfate, copper nitrate, lead sulfate, lead nitrate, zinc sulfate and zinc nitrate.
Preferably, in step 4), the pH adjuster is one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate, sulfuric acid, hydrochloric acid, and nitric acid.
Preferably, in step 4), the activator is selected from one or more of sulfur, sodium sulfide, and sodium hydrosulfide.
Preferably, in step 4), the collector is selected from one or more of ethidium, butylated xanthate, pentamidine xanthate, isopropyl xanthate, butylamine nigride, No. 25 nigride, Y89 xanthate, ethiazide, ethylthiourethane, propylthiourethane, butylthiourethane.
Preferably, in step 4), the foaming agent is one or more of No. two oil, pine oil and cresol oil.
Preferably, in the step 1), the content of chlorine in the incineration fly ash of the organic hazardous waste is more than or equal to 15% wt, preferably more than or equal to 20% wt, and more preferably more than or equal to 25% wt.
Preferably, in the step 1), the addition amount of the organic hazardous waste incineration fly ash is 3-50% wt of the addition amount of the non-ferrous metal ore, preferably 4-40% wt, and more preferably 4-30% wt.
Preferably, in step 1), the reducing agent is added in an amount of 0.5 to 20% wt, preferably 1 to 15% wt, more preferably 2 to 10% wt, based on the amount of the non-ferrous metal ore added.
Preferably, in step 1), the binder is added in an amount of 0.3 to 9% by weight, preferably 0.4 to 7% by weight, more preferably 0.5 to 5% by weight, based on the amount of the non-ferrous metal ore added.
Preferably, in step 1), the roasting aid is added in an amount of 0.1 to 15% wt, preferably 0.2 to 12% wt, more preferably 0.3 to 10% wt, based on the amount of the non-ferrous metal ore added.
Preferably, in step 4), the carrier agent is used in an amount of 50 to 4000g, preferably 80 to 3500g, more preferably 100 to 3000 g. The above amounts are based on the pellet powder per ton.
Preferably, in the step 4), the amount of the pH regulator is 200-6000g, preferably 300-5500g, and more preferably 500-5000 g. The above amounts are based on the pellet powder per ton.
Preferably, in step 4), the activator is used in an amount of 30 to 2500g, preferably 40 to 2200g, more preferably 50 to 2000 g. The above amounts are based on the pellet powder per ton.
Preferably, in step 4), the collector is used in an amount of 60 to 4000g, preferably 80 to 3500g, more preferably 100 and 2800 g/t. The above amounts are based on the pellet powder per ton.
Preferably, in step 4), the blowing agent is used in an amount of 30 to 600g, preferably 40 to 550g, more preferably 50 to 500 g/t. The above amounts are based on the pellet powder per ton.
Preferably, in step 1), the particle size of the mix is 0.2mm or less, preferably 0.15mm or less, more preferably 0.1mm or less.
Preferably, in step 1), the green pellets have a particle size of 5 to 20mm, preferably 7 to 15mm, more preferably 9 to 12 mm.
Preferably, in the step 3), the particle size of the pellet powder is less than or equal to 0.15mm, preferably less than or equal to 0.10mm, and more preferably less than or equal to 0.07 mm.
Preferably, step 1) is specifically: according to the proportion, non-ferrous metal ore, organic hazardous waste incineration fly ash, reducing agent, binder and roasting auxiliary agent are all subjected to dry grinding treatment. Then, the undersize powder is taken out through screening (for example, screening by using a Taylor screen) and uniformly mixed to obtain a mixed material, and the oversize part returns to the dry-type ore grinding treatment and is continuously screened until the mixed material is completely changed into the mixed material. And then carrying out damp milling on the mixture (preferably adopting a damp mill for damp milling for 1-20min, preferably 3-15 min). And finally, putting the wet and ground mixture into a pelletizer to prepare the green pellets.
Preferably, step 2) is specifically: the green ball obtained in the step 1) is firstly put into an oven with the temperature of 60-120 ℃ (preferably 80-110 ℃) for drying for 0.5-5h (preferably 1-4 h). Then the dried green pellets are placed in a muffle furnace at 850-1500 ℃ (preferably at 900-1400 ℃) to be roasted for 0.5-8h (preferably 1-5h) to obtain the roasted pellets.
Preferably, step 3) is specifically: and (3) crushing and grinding (preferably wet ball milling) the roasted pellets, then taking the undersize powder as pellet powder by screening (for example, screening by using a Taylor screen), and returning the oversize part to continue grinding and screening until the undersize powder is completely changed into the pellet powder.
Preferably, the step 4) is specifically: uniformly mixing the pellet powder obtained in the step 3) with a carrier medicament, and then adding the mixture in the presence of a pH regulator, an activating agent, a collecting agent and a foaming agent in the order of regulator, activating agent, collecting agent and foaming agent. The adding time is as follows: adding another reagent after the first reagent is sufficiently stirred for 1-10min, e.g. 3min, 5min) to extract the non-ferrous metals by flotation treatment (e.g. open or closed circuit flotation, preferably comprising 1-5 roughenings, 1-8 beneficiations, 1-6 scavenges, more preferably 1-3 roughenings, 2-5 beneficiations, 2-4 scavenges).
In the invention, a mode of combining chloridizing segregation roasting-carrier flotation technology is adopted, and the characteristic of high chlorine content in the incineration fly ash of the organic hazardous waste (the chlorine content in the incineration fly ash of the organic hazardous waste is more than or equal to 15 percent by weight, preferably more than or equal to 20 percent by weight, more preferably more than or equal to 25 percent by weight) is utilized, so that the incineration fly ash of the organic hazardous waste is used as a chlorinating agent in the roasting process. Meanwhile, aiming at the characteristic that the incineration fly ash of the organic hazardous waste contains heavy metal elements, the chemical characteristics of the surface of the heavy metal in the incineration fly ash of the organic hazardous waste after roasting are similar to those of the valuable metal elements in the nonferrous metal ores, and a carrier flotation process is adopted for co-extraction. The method solves the problem that the non-ferrous metals in the organic hazardous waste incineration fly ash are difficult to treat, provides a new technical approach for extracting valuable metals (particularly inert metals) from metal ores, and obtains the technical effect of achieving multiple purposes.
In the invention, the characteristics of strong hydrophobicity and poor balling property of the incineration fly ash of the organic hazardous waste are considered, a wetting and grinding process is added or the proportion of the binder is improved in the balling process, and the particle size range of the prepared green pellets is 5-20mm (preferably 7-15mm, more preferably 9-12 mm).
In the invention, non-ferrous metal ore, organic hazardous waste incineration fly ash, a reducing agent, a binder and a roasting auxiliary agent are subjected to dry grinding treatment. Then, the undersize powder is taken out through screening (for example, screening by using a Taylor screen) and uniformly mixed to obtain a mixed material, and the oversize part returns to the dry-type ore grinding treatment and is continuously screened until the mixed material is completely changed into the mixed material. And then carrying out damp milling on the mixture (preferably adopting a damp mill for damp milling for 1-20min, preferably for 3-15 min). And finally, putting the wet and ground mixture into a pelletizer to prepare the green pellets. The green pellets obtained are then subjected to a drying treatment, generally by drying in an oven at 60-120 deg.C (preferably 80-110 deg.C) for 0.5-5h (preferably 1-4 h). Then the dried green pellets are placed in a muffle furnace at 1500 ℃ and 1500 ℃ (preferably 800 ℃ and 1300 ℃) for roasting treatment for 0.5-8h (preferably 1-5h) to obtain the roasted pellets. And then crushing and ball-milling the roasted pellets to obtain pellet powder with the particle size of less than or equal to 0.15mm (preferably less than or equal to 0.10mm, more preferably less than or equal to 0.07 mm). Finally, the pellet powder is mixed and stirred with a carrier agent, and then heavy metals in the fly ash and nonferrous metal elements in the nonferrous metal ore are extracted by a flotation treatment (such as open circuit or closed circuit flotation, preferably comprising 1-5 times of roughing, 1-8 times of concentrating, 1-6 times of scavenging, more preferably 1-3 times of roughing, 2-5 times of concentrating, and 2-4 times of scavenging) process in the presence of a pH regulator, an activator, a collector and a foaming agent. The invention adopts a process combining chloridizing, segregation, roasting and carrier flotation, fully utilizes the characteristics of the incineration fly ash of the organic hazardous waste, can effectively exert the advantage of high chlorine content of the fly ash, and jointly extracts the non-ferrous metal elements in the incineration fly ash of the organic hazardous waste and the valuable metal elements in the non-ferrous metal ores, thereby realizing the harmless and resource development and utilization of the incineration fly ash of the organic hazardous waste.
In the invention, the reducing agent is used for providing a medium for reduction reaction to reduce the high valence nonferrous metal element to a zero valence metal state. The binder has the functions of improving the balling property of materials and improving the molecular binding force between particles in green pellets so as to improve the strength and the thermal stability of the green pellets. The roasting auxiliary agent has the effects of improving the reaction rate of chlorination segregation reaction, reducing the reaction temperature and avoiding material adhesion and even ring formation in a high-chlorine high-temperature environment.
In the invention, the reducing agent is added in an excessive amount, so that iron elements which are difficult to reduce are easily reduced into metallic iron in the process, and the separation effect of the subsequent non-ferrous metal flotation is influenced. And meanwhile, the phenomenon of carbon residue also exists, and the carbon particles become the core of liquid phase consolidation, so that nonferrous metal grains cannot grow up, and the separation effect of the subsequent nonferrous metal flotation is influenced. And the carbon element can generate sulfide and nitrogen oxide in the roasting reaction process, so that the environmental pollution is more serious. And if the addition amount of the reducing agent is too small, the reaction is incomplete, part of the nonferrous metals are not completely converted into metal valence, and the separation effect of the subsequent nonferrous metal flotation is influenced.
In the invention, the excessive addition of the binder can influence the overall chemical grade of the material and reduce the balling rate in the balling process. And if the addition amount of the binder is too small, the molecular binding force among material particles is insufficient, and the strength and the thermal stability of the green pellets are reduced.
In the invention, the integral chemical grade of the material is influenced by too much addition amount of the roasting auxiliary agent, so that the roasting auxiliary agent is distributed too densely to easily cause local liquid phase and influence the uniformity of the material. And if the addition amount of the roasting auxiliary agent is too small, the reaction rate of chlorination segregation reaction cannot be effectively increased, the effect of reducing reaction temperature is limited, higher reaction temperature is needed, and material adhesion and even ring formation are easily caused.
In the invention, the grain diameter of the mixture is less than or equal to 0.2mm, preferably less than or equal to 0.15mm, and more preferably less than or equal to 0.1 mm. The purpose of controlling the particle size of the pelletizing raw material is to make the finer the particle size of the material, the tighter the particle arrangement in the green pellet due to the proper particle size composition, the smaller the average diameter of the capillary formed, the greater the generated capillary pressure, and the higher the green pellet strength. What is decisive for pelletizing is a content of the fraction of less than 0.045 mm. The content of this fraction is generally used to assess the fineness of the feedstock. The green strength increased with increasing size fraction of less than 0.045 mm. The fine particle size of the raw material is advantageous for improving the green pellet strength, but as the particle size of the raw material becomes finer, the pelletizing time needs to be prolonged.
In the invention, the particle size of the pellet powder is less than or equal to 0.15mm, preferably less than or equal to 0.10mm, and more preferably less than or equal to 0.07 mm. The purpose of controlling the particle size of the flotation material is: the flotation granularity is determined according to the monomer dissociation degree required by the mineral and gangue laying characteristics and the bubble load capacity determined according to the density of the mineral. The particle size is too large, and although the particle size of the undissociated mineral is suitable for bubble attachment and loading, the sorting effect is not ideal; the particle size is too small, the particle size is too fine and even argillization is caused, so that excessive dissociation is caused, and flotation is also influenced. Monomer dissociation in practice is mainly achieved by grinding. The flotation granularity upper limit of each mineral is different, the sulfide ore is generally 0.2-0.25 mm, and the non-sulfide ore is 0.25-0.30 mm. Meanwhile, the flotation behaviors of materials with different particle sizes are greatly different: generally, coarse fraction flotation is slow in speed and good in selectivity, but cannot float out when coarse fraction is too coarse, and is easily lost in tailings, which is commonly called coarse flotation. The fine fraction flotation speed is high, the selectivity is poor, and the selectivity is lost when the fine fraction flotation speed is too fine; only moderately suitable particle sizes have the best floatability. For the coarse and fine feeding materials, a special process is adopted, and the particle size change of the feeding materials and the products is measured and adjusted in time in the flotation process. When the particle size is too large, the problem of loss of materials in tailings in the flotation process is mainly solved, namely, attachment of coarse particles and bubbles is increased and the coarse particles are prevented from falling off; when the particle size is too small, the problem of poor selectivity in the flotation process is mainly solved, namely, the flotation selectivity is improved.
In the invention, in order to ensure the optimal medicament system in the ore pulp during the flotation, the medicament must be reasonably added. This includes selecting appropriate dosing sequence, dosing location, dosing mode, etc. Another reason for the rational addition is that the interaction between the chemicals added to the pulp is complex and influences and restricts due to the usually better chemical agents added to the pulp and the components present in the pulp. The good medicament system can fully utilize the effects to exert the medicament efficacy; and improper addition of the medicament can cause the whole process to be disordered. Reasonable dosing sequence, dosing place and dosing mode should be selected according to material characteristics, medicament performance, process requirements and the like. The dosing sequence should be determined according to the action and mechanism of the agent, and is generally in the following order: carrier agent → pH adjuster → activator or inhibitor → collector → frother. If the two agents affect each other and have a counteracting effect, the first agent should be added separately, and the second agent should be added after the first agent has a sufficient effect (after the first agent is fully stirred for 1-10min, for example, 3min, 5min, the other agent is added). The contact time required by the common medicament is generally 1-3 min. When the content of fine materials, especially fine mud is high, in order to improve the selectivity, batch dosing is preferably adopted, so that the medicine is in a deficiency state.
In the invention, the chloridizing segregation roasting-carrier flotation process is a process of firstly adding a certain amount of carbonaceous reducing agent (coal or coke) and chlorinating agent (sodium chloride, calcium chloride and the like) into ore, heating in neutral or reducing atmosphere to chloridize and volatilize valuable metals from the ore, reducing the valuable metals on the surfaces of carbon particles into metal particles, and then enriching by using a beneficiation method to produce metal concentrate with higher grade. And then according to the poor floatability of the metal particles, attaching the metal particles to a carrier agent for flotation, and improving the floatability of the material to obtain a concentrate product with higher grade and recovery rate.
In the present invention, the carrier agent is used for flotation in order to sufficiently react with the metal particles, thereby attaching the metal particles to the carrier agent and improving the floatability of the material. The pH adjusting agent is added to adjust the properties of the pulp to create a medium that is beneficial for some minerals flotation but not beneficial for others, such as adjusting the ionic composition of the pulp, changing the pH of the pulp, adjusting the concentration of soluble salts, etc. The activator is added to promote the action of the collector and the mineral, thereby improving the floatability of the mineral. The collecting agent is added to selectively act on the surface of the mineral to make the mineral hydrophobic, and acts on the interface of the mineral and water to enable the mineral particles to be more firmly attached to bubbles and float by improving the hydrophobicity of the mineral. The foaming agent is added to enrich the water-air interface, promote air to disperse into small bubbles in the ore pulp, prevent the bubbles from merging, improve the stability of the bubbles in the mineralization and floating processes, and ensure that the mineralized bubbles form foams after floating.
Further, by adopting the technical scheme of the invention, the heavy metals (such as copper, lead, zinc and the like) in the fly ash are effectively recovered: wherein, the chlorination segregation roasting reaction process is as follows:
(1) HCl generation
The chlorine element in the fly ash is mainlyNaCl, which is a fairly stable chloride, exists in the form of NaCl, and is almost impossible to thermally dissociate at typical firing temperatures. But because the roasted material contains SiO2、Fe2O3、Al2O3The acidic or amphoteric oxide and water vapor are added, so that the decomposition reaction of NaCl proceeds at high temperature.
At the temperature required for the chloridizing isolation (e.g. 900 ℃ C.), NaCl and SiO2Decomposition reaction occurs under the action of steam:
2NaCl+H2O+nSiO2＝Na2O·nSiO2+2HCl
thus, in the chlorination isolation process, the chlorinating agent that works is actually HCl.
(2)NiCl2And CoCl2Generation of (1):
the metals nickel and cobalt are exemplified. The reaction between oxide (MO) and HCl is the most common chlorination reaction in the chlorination roasting process, and simpler oxides are difficult to chlorinate and require higher temperatures to destroy their stability. After the HCl is produced, it undergoes the following chlorination reactions with the nickel silicates and nickel ferrites in the ore:
MO·SiO2+2HCl＝MCl2+SiO2+H2O
MO·SiO2＝MO+SiO2
MO·Fe2O3+2HCl＝MCl2+Fe2O3+H2O
MO+2HCl＝2MCl2+H2O
(3)NiCl2and CoCl2Reduction of (2):
the metals nickel and cobalt are exemplified. The separation process is carried out in a medium reducing atmosphere, the reduction of the nickel cobalt chloride is completed by coal or coke, and the coal or coke plays a role of a reducing agent and a core role of nickel cobalt deposition in the separation process. At high temperature, the chloride formed is gasified and first adsorbed on the surface of the carbon particles by H2And reduction of CO to metal, followed by adsorption, reduction and particle growth on the newly formed metal surface.
MCl2+H2O+C＝M+2HCl+CO
2MCl2+2H2O+C＝2M+4HCl+CO2
H2O+C＝H2+CO MCl2+H2＝M+2HCl
MO+H2＝M+H2O MO+CO＝M+CO2
The generation and presence of hydrogen has a great influence on preventing the volatilization loss of the nickel and cobalt chlorides, and the nickel and cobalt chlorides are reduced in situ due to the rapid reaction.
Generally, the chlorine-containing compound in the fly ash is reacted with O at a suitable temperature under the catalysis of ferric chloride and cupric chloride2And carrying out HCl reaction, and generating dioxin through processes of molecular rearrangement, free radical synthesis, dechlorination and the like. The dioxin is decomposed into harmless substances at high temperature, and when the temperature of the flue gas is higher than 800 ℃ and the flue gas stays in the furnace for 2s, all the dioxin is decomposed.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention fully utilizes the physicochemical property characteristics of the incineration fly ash of the organic hazardous waste as a chlorinating agent, and adopts the chlorination segregation roasting-carrier flotation process to jointly extract heavy metals in the fly ash and valuable metal elements in non-ferrous metal ores. Meanwhile, dioxin in the fly ash is decomposed into non-toxic substances in the high-temperature roasting process, so that the detoxification effect can be achieved. The invention solves the problems of dioxin, heavy metal and chlorine-containing wastewater in the conventional fly ash treatment process to the maximum extent, effectively reduces the toxic degree of the fly ash and has obvious environmental benefit.
2. The invention is suitable for treating non-ferrous metal ores of different types, non-ferrous metal concentrate with higher grade can be obtained by chlorination segregation roasting-carrier flotation process, and the non-ferrous metal concentrate can be directly prepared into qualified raw materials of subsequent smelting procedures, and the technical effect and the economic benefit are obvious.
3. The carrier flotation process adopted by the invention achieves the replacement of surface metal ions in a flotation system by adding auxiliary agents such as a carrier agent, an activating agent and the like, realizes the great improvement of the floatability of low-surface-activity minerals, and provides a new technical approach for the efficient flotation of inert metal minerals by assisting the conventional flotation process.
Drawings
FIG. 1 is a process flow chart of the method for extracting nonferrous metals by using the incineration fly ash of the organic hazardous waste of the invention.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
A method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes comprises the following steps:
1) mixing and pelletizing: the method comprises the steps of uniformly mixing non-ferrous metal ore, organic hazardous waste incineration fly ash, a reducing agent, a binder and a roasting auxiliary agent to obtain a mixture, and then placing the mixture into a pelletizer to prepare green pellets.
2) Drying and roasting: drying the green pellets obtained in the step 1), and then roasting to obtain roasted pellets.
3) Crushing and grinding: and (3) crushing and grinding the roasted pellets obtained in the step 2) to obtain pellet powder.
4) Carrier flotation: uniformly mixing the pellet powder obtained in the step 3) with a carrier agent, and then extracting nonferrous metals by flotation treatment in the presence of a pH regulator, an activating agent, a collecting agent and a foaming agent.
Preferably, in step 1), the non-ferrous metal ore is selected from one or more of copper ore, lead ore, zinc ore, stone coal vanadium ore, laterite nickel ore, bauxite ore and magnesite ore.
Preferably, in the step 1), the incineration fly ash of the organic hazardous waste is dust collected by a flue gas system after the organic hazardous waste is incinerated.
Preferably, in step 1), the reducing agent is selected from one or more of coke, coal dust and biomass.
Preferably, in step 1), the binder is selected from one or more of bentonite, water glass, slaked lime, sodium humate and organic composite binders.
Preferably, in step 1), the roasting aid is selected from one or more of calcium sulfate, calcium carbonate, magnesium carbonate and copper sulfate.
Preferably, in step 4), the carrier agent is selected from one or more of copper sulfate, copper nitrate, lead sulfate, lead nitrate, zinc sulfate and zinc nitrate.
Preferably, in step 4), the pH adjuster is one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate, sulfuric acid, hydrochloric acid, and nitric acid.
Preferably, in step 4), the activator is selected from one or more of sulfur, sodium sulfide, and sodium hydrosulfide.
Preferably, in step 4), the collector is selected from one or more of ethidium, butylated xanthate, pentamidine xanthate, isopropyl xanthate, butylamine nigride, No. 25 nigride, Y89 xanthate, ethiazide, ethylthiourethane, propylthiourethane, butylthiourethane.
Preferably, in step 4), the foaming agent is one or more of No. two oil, pine oil and cresol oil.
Preferably, in the step 1), the content of chlorine in the incineration fly ash of the organic hazardous waste is more than or equal to 15% wt, and more preferably more than or equal to 20% wt. More preferably not less than 25% wt.
Preferably, in the step 1), the addition amount of the organic hazardous waste incineration fly ash is 3-50% wt of the addition amount of the non-ferrous metal ore, preferably 4-40% wt, and more preferably 4-30% wt.
Preferably, in step 1), the reducing agent is added in an amount of 0.5 to 20% wt, preferably 1 to 15% wt, more preferably 2 to 10% wt, based on the amount of the non-ferrous metal ore added.
Preferably, in step 1), the binder is added in an amount of 0.3 to 9% by weight, preferably 0.4 to 7% by weight, more preferably 0.5 to 5% by weight, based on the amount of the non-ferrous metal ore added.
Preferably, in step 1), the roasting aid is added in an amount of 0.1 to 15% wt, preferably 0.2 to 12% wt, more preferably 0.3 to 10% wt, based on the amount of the non-ferrous metal ore added.
Preferably, in step 4), the carrier agent is used in an amount of 50 to 4000g, preferably 80 to 3500g, more preferably 100 to 3000 g. The above amounts are based on the pellet powder per ton.
Preferably, in the step 4), the amount of the pH regulator is 200-6000g, preferably 300-5500g, and more preferably 500-5000 g. The above amounts are based on the pellet powder per ton.
Preferably, in step 4), the activator is used in an amount of 30 to 2500g, preferably 40 to 2200g, more preferably 50 to 2000 g. The above amounts are based on the pellet powder per ton.
Preferably, in step 4), the collector is used in an amount of 60 to 4000g, preferably 80 to 3500g, more preferably 100 and 2800 g/t. The above amounts are based on the pellet powder per ton.
Preferably, in step 4), the blowing agent is used in an amount of 30 to 600g, preferably 40 to 550g, more preferably 50 to 500 g/t. The above amounts are based on the pellet powder per ton.
Preferably, in step 1), the particle size of the mix is 0.2mm or less, preferably 0.15mm or less, more preferably 0.1mm or less.
Preferably, in step 1), the green pellets have a particle size of 5 to 20mm, preferably 7 to 15mm, more preferably 9 to 12 mm.
And/or
Preferably, in the step 3), the particle size of the pellet powder is less than or equal to 0.15mm, preferably less than or equal to 0.10mm, and more preferably less than or equal to 0.7 mm.
Preferably, step 1) is specifically: according to the proportion, non-ferrous metal ore, organic hazardous waste incineration fly ash, reducing agent, binder and roasting auxiliary agent are all subjected to dry grinding treatment. Then, the undersize powder is taken out through screening (for example, screening by using a Taylor screen) and uniformly mixed to obtain a mixed material, and the oversize part returns to the dry-type ore grinding treatment and is continuously screened until the mixed material is completely changed into the mixed material. And then carrying out damp milling on the mixture (preferably adopting a damp mill for damp milling for 1-20min, preferably 3-15 min). And finally, putting the wet and ground mixture into a pelletizer to prepare the green pellets.
Preferably, step 2) is specifically: the green ball obtained in the step 1) is firstly put into an oven with the temperature of 60-120 ℃ (preferably 80-110 ℃) for drying for 0.5-5h (preferably 1-4 h). Then the dried green pellets are placed in a muffle furnace at 850-1500 ℃ (preferably at 900-1400 ℃) to be roasted for 0.5-8h (preferably 1-5h) to obtain the roasted pellets.
Preferably, step 3) is specifically: and (3) crushing and grinding (preferably wet ball milling) the roasted pellets, then taking the undersize powder as pellet powder by screening (for example, screening by using a Taylor screen), and returning the oversize part to continue grinding and screening until the undersize powder is completely changed into the pellet powder.
Preferably, the step 4) is specifically: mixing the pellet powder obtained in step 3) with a carrier agent uniformly, and then extracting nonferrous metals by a flotation treatment (such as open circuit or closed circuit flotation, preferably comprising 1-5 times of roughing, 1-8 times of concentrating, 1-6 times of scavenging, more preferably 1-3 times of roughing, 2-5 times of concentrating, 2-4 times of scavenging) in the presence of a pH regulator, an activator, a collector and a foaming agent.
Example 1
The raw materials comprise: the non-ferrous metal ore is laterite-nickel ore, wherein the content of nickel element is 1.1%; the fly ash from the incineration of the organic hazardous waste (wherein the chlorine content is 21.11 percent, the copper content is 0.15 percent, the lead content is 0.63 percent, and the zinc content is 0.24 percent), the addition amount of which is 17.0 percent of the mass of the nonferrous metal ores; the reducing agent is coal powder, and the addition amount of the reducing agent is 10.0 percent of the mass of the nonferrous metal ore. The adhesive is bentonite, and the addition amount of the bentonite is 3.0 wt% of the mass of the nonferrous metal ore; the roasting auxiliary agent is calcium chloride, and the addition amount of the calcium chloride is 10.0 wt% of the mass of the nonferrous metal ore. The raw materials are crushed and sieved to ensure that the particle size is less than or equal to 0.15 mm.
Manually mixing the above raw material powders for 3 times, and pouring into a wet grinding machine for 10 min; putting the wet and ground mixture into a pelletizer to prepare green pellets, wherein the average particle size of the green pellets is 9.1 mm; drying the obtained green ball in an oven at 100 ℃ for 4 h; then placing the dried green pellets in a muffle furnace at 1000 ℃ for roasting treatment for 3h to obtain roasted pellets; then carrying out wet grinding on the roasted pellets to obtain pellet powder with the particle size of less than or equal to 0.1 mm; finally, carrying out flotation on the pellet powder, wherein the carrier agent is copper sulfate, and the dosage is 1000 g/t; the pH regulator is hydrochloric acid, and the dosage is 600 g/t; the activating agent is sodium sulfide, and the using amount is 200 g/t; the collecting agent is butyl xanthate, and the dosage is 250 g/t; the foaming agent is No. two oil, and the dosage is 50 g/t; an open-circuit flotation process is adopted, and the specific flow comprises 2 times of roughing, 2 times of fine selection and 3 times of scavenging.
The flotation concentrate obtained by the process has the nickel element content of 7.9 percent, the copper content of 0.78 percent, the lead content of 2.22 percent, the zinc content of 1.02 percent and the chlorine content of 0.02 percent; the content of nickel element in the obtained flotation tailings is 0.21%, the content of copper is 0.02%, the content of lead is 0.03%, the content of zinc is 0.02%, and the content of chlorine is 0.01%. Enriching nickel elements in the laterite-nickel ore into flotation concentrate; copper, lead and zinc elements in the fly ash are enriched into flotation concentrate, and are smelted together with nickel concentrate subsequently; after the reaction is finished, chlorine elements in the fly ash are finally discharged to flue gas in the form of HCl and collected and treated in a centralized manner; the content of dioxin in the smoke is 0.01ng-TEQ/Nm3The product meets the national emission standard; the content of copper, lead, zinc and chlorine in the tailings meets the national emission standard.
Example 2
The raw materials comprise: the non-ferrous metal ore is stone coal vanadium ore, and the content of vanadium element is 0.9%; the fly ash from the incineration of the organic hazardous waste (wherein the chlorine content is 28.03 percent, the copper content is 0.38 percent, the lead content is 0.35 percent and the zinc content is 0.45 percent), and the addition amount is 25.0 percent of the mass of the nonferrous metal ores; the reducing agent is biomass, and the adding amount of the reducing agent is 12.0 percent wt of the mass of the nonferrous metal ore; the adhesive is sodium humate, and the addition amount of the adhesive is 2.8 wt% of the mass of the nonferrous metal ore; the roasting auxiliary agent is sodium chloride, and the addition amount of the sodium chloride is 12.0 wt% of the mass of the nonferrous metal ore. The raw materials are crushed and sieved to ensure that the particle size is less than or equal to 0.15 mm.
Manually mixing the above raw material powders for 3 times, and pouring into a wet grinding machine for 12 min; putting the wet and ground mixture into a pelletizer to prepare green pellets, wherein the average particle size of the green pellets is 8.9 mm; drying the obtained green ball in an oven at 100 ℃ for 4 h; then placing the dried green pellets in a boiling furnace at 900 ℃ for roasting treatment for 4 hours to obtain roasted pellets; then carrying out wet grinding on the roasted pellets to obtain pellet powder with the particle size of less than or equal to 0.1 mm; finally, performing flotation on the pellet powder, wherein the carrier agent is lead nitrate, and the using amount is 1500 g/t; the pH regulator is sulfuric acid, and the dosage is 1000 g/t; the activator is sodium hydrosulfide, and the dosage is 1000 g/t; the collecting agent is Y89 xanthate, and the dosage is 200 g/t; the foaming agent is pine oil, and the dosage is 80 g/t; an open-circuit flotation process is adopted, and the specific flow comprises 1 roughing, 2 fine concentration and 2 scavenging.
The flotation concentrate obtained by the process contains 10.1% of vanadium, 1.25% of copper, 1.67% of lead, 2.11% of zinc and 0.01% of chlorine; the content of vanadium in the obtained flotation tailings is 0.10%, the content of copper is 0.01%, the content of lead is 0.01%, the content of zinc is 0.02%, and the content of chlorine is 0.01%. Enriching vanadium elements in the stone coal vanadium ore into flotation concentrate; enriching copper, lead and zinc elements in the fly ash into flotation concentrate, and then smelting together with vanadium concentrate; after the reaction is finished, chlorine elements in the fly ash are finally discharged to flue gas in the form of HCl and collected and treated in a centralized manner; the content of dioxin in the smoke is 0.008ng-TEQ/Nm3The product meets the national emission standard; the content of copper, lead, zinc and chlorine in the tailings meets the national emission standard.
Example 3
The raw materials comprise: the non-ferrous metal ore is zinc ore, and the content of zinc element is 3.1%; the fly ash from the incineration of the organic hazardous waste (wherein, the chlorine content is 30.58 percent, the copper content is 0.29 percent, the lead content is 0.40 percent, and the zinc content is 0.47 percent), the addition amount is 30.0 percent of the mass of the nonferrous metal ores; the reducing agent is coke, and the addition amount of the reducing agent is 10.0 wt% of the mass of the nonferrous metal ore; the adhesive is bentonite, and the addition amount of the bentonite is 3.1 wt% of the mass of the nonferrous metal ore; the roasting auxiliary agent is magnesium carbonate, and the addition amount of the magnesium carbonate is 11.0 wt% of the mass of the nonferrous metal ore. The raw materials are crushed and sieved to ensure that the particle size is less than or equal to 0.15 mm.
Manually mixing the above raw material powders for 3 times, and pouring into a wet grinding machine for 12 min; putting the wet and ground mixture into a pelletizer to prepare green pellets, wherein the average particle size of the green pellets is 9.3 mm; putting the obtained green ball into an oven at 100 ℃ for drying for 3.5 h; then placing the dried green pellets in a muffle furnace at 950 ℃ for roasting treatment for 3.5h to obtain roasted pellets; then carrying out wet grinding on the roasted pellets to obtain pellet powder with the particle size of less than or equal to 0.1 mm; finally, carrying out flotation on the pellet powder, wherein the carrier agent is zinc sulfate, and the using amount is 1800 g/t; the pH regulator is sulfuric acid, and the dosage is 1200 g/t; the activating agent is sodium sulfide, and the using amount is 950 g/t; the collecting agent is ethidium bromide, and the dosage is 300 g/t; the foaming agent is No. two oil, and the dosage is 120 g/t; an open-circuit flotation process is adopted, and the specific flow comprises 2 times of roughing, 2 times of fine selection and 3 times of scavenging.
The flotation concentrate obtained by the process has 29.9 percent of zinc element, 1.33 percent of copper, 1.73 percent of lead and 0.01 percent of chlorine; the obtained flotation tailings contain 0.12% of zinc element, 0.01% of copper, 0.01% of lead and 0.01% of chlorine. Enriching zinc elements in the zinc ore into flotation concentrate; enriching copper and lead elements in the fly ash into flotation concentrate, and then smelting together with zinc concentrate; after the reaction is finished, chlorine elements in the fly ash are finally discharged to flue gas in the form of HCl and collected and treated in a centralized manner; the content of dioxin in the smoke is 0.009ng-TEQ/Nm3The product meets the national emission standard; the content of copper, lead and chlorine in the tailings meets the national emission standard.
Claims (10)
1. A method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes is characterized by comprising the following steps: the method comprises the following steps:
1) mixing and pelletizing: uniformly mixing non-ferrous metal ore, organic hazardous waste incineration fly ash, a reducing agent, a binder and a roasting auxiliary agent to obtain a mixture, and then placing the mixture into a pelletizer to prepare green pellets;
2) drying and roasting: drying the green pellets obtained in the step 1), and then roasting to obtain roasted pellets;
3) crushing and grinding: crushing and grinding the roasted pellets obtained in the step 2) to obtain pellet powder;
4) carrier flotation: uniformly mixing the pellet powder obtained in the step 3) with a carrier agent, and then extracting nonferrous metals by flotation treatment in the presence of a pH regulator, an activating agent, a collecting agent and a foaming agent.
2. The method of claim 1, wherein: in step 1), the non-ferrous metal ore is selected from one or more of copper ore, lead ore, zinc ore, stone coal vanadium ore, laterite-nickel ore, bauxite and magnesite;
the organic hazardous waste incineration fly ash is dust collected by a flue gas system after the organic hazardous waste is incinerated;
the reducing agent is selected from one or more of coke, coal powder and biomass;
the binder is selected from one or more of bentonite, water glass, slaked lime, sodium humate and organic composite binder;
the roasting auxiliary agent is one or more selected from calcium chloride, sodium chloride, calcium sulfate, calcium carbonate, magnesium carbonate and copper sulfate.
3. The method according to claim 1 or 2, characterized in that: in step 4), the carrier agent is selected from one or more of copper sulfate, copper nitrate, lead sulfate, lead nitrate, zinc sulfate and zinc nitrate;
the pH regulator is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate, sulfuric acid, hydrochloric acid and nitric acid;
the activator is selected from one or more of sulfur, sodium sulfide and sodium hydrosulfide;
the collecting agent is selected from one or more of ethidium, butyl xanthate, amyl xanthate, isopropyl xanthate, butylamine black powder, No. 25 black powder, Y89 xanthate, ethiazide, ethyl thiourethane, propyl thiourethane and butyl thiourethane;
the foaming agent is one or more of No. two oil, pine oil and cresol oil.
4. The method according to any one of claims 1-3, wherein: the content of chlorine in the incineration fly ash of the organic hazardous waste is more than or equal to 15 percent by weight, preferably more than or equal to 20 percent by weight, and more preferably more than or equal to 25 percent by weight; the addition amount thereof is 3 to 50% by weight, preferably 4 to 40% by weight, more preferably 5 to 30% by weight of the addition amount of the nonferrous metal ore.
5. The method according to any one of claims 1-4, wherein: in step 1), the addition amount of the reducing agent is 0.5-20% wt, preferably 1-15% wt, more preferably 2-10% wt of the addition amount of the nonferrous metal ore;
the addition amount of the binder is 0.3-9% by weight of the addition amount of the non-ferrous metal ore, preferably 0.4-7% by weight, and more preferably 0.5-5% by weight;
the addition amount of the roasting aid is 0.1-15% wt of the addition amount of the non-ferrous metal ore, preferably 0.2-12% wt, and more preferably 0.3-10% wt.
6. The method according to any one of claims 1-5, wherein: in step 4), the dosage of the carrier agent is 50-4000g, preferably 80-3500g, more preferably 100-3000 g;
the dosage of the pH regulator is 200-6000g, preferably 300-5500g, and more preferably 500-5000 g;
the amount of the activating agent is 30-2500g, preferably 40-2200g, more preferably 50-2000 g;
the dosage of the collecting agent is 60-4000g, preferably 80-3500g, more preferably 100-2800 g;
the amount of the foaming agent is 30-600g, preferably 40-550g, more preferably 50-500 g;
the above amounts are based on the pellet powder per ton.
7. The method according to any one of claims 1-6, wherein: in the step 1), the grain diameter of the mixture is less than or equal to 0.2mm, preferably less than or equal to 0.15mm, and more preferably less than or equal to 0.1 mm;
the particle size of the green pellets is 5-20mm, preferably 7-15mm, and more preferably 9-12 mm; and/or
In the step 3), the particle size of the pellet powder is less than or equal to 0.15mm, preferably less than or equal to 0.10mm, and more preferably less than or equal to 0.07 mm.
8. The method according to any one of claims 1-7, wherein: the step 1) is specifically as follows: firstly, performing dry grinding treatment on non-ferrous metal ores, organic hazardous waste incineration fly ash, a reducing agent, a binder and a roasting auxiliary agent according to a proportion; then, sieving (for example, sieving by a Taylor sieve) is carried out to take the powder under the sieve, the powder is uniformly mixed to obtain a mixture, and the part above the sieve returns to the dry-type ore grinding treatment and is continuously sieved until the whole powder is changed into the mixture; then the mixture is subjected to damp milling (preferably a damp mill is adopted for damp milling for 1-20min, preferably 3-15 min); and finally, putting the wet and ground mixture into a pelletizer to prepare the green pellets.
9. The method according to any one of claims 1-8, wherein: the step 2) is specifically as follows: putting the green balls obtained in the step 1) into an oven with the temperature of 60-120 ℃ (preferably 80-110 ℃) to dry for 0.5-5h (preferably 1-4 h); then placing the dried green pellets in a muffle furnace at 850-; and/or
The step 3) is specifically as follows: and (3) crushing and grinding (preferably wet ball milling) the roasted pellets, then taking the undersize powder as pellet powder by screening (for example, screening by using a Taylor screen), and returning the oversize part to continue grinding and screening until the undersize powder is completely changed into the pellet powder.
10. The method according to any one of claims 1-9, wherein: the step 4) is specifically as follows: uniformly mixing the pellet powder obtained in the step 3) with a carrier agent, and then performing flotation treatment (such as open-circuit or closed-circuit flotation, preferably comprising 1-5 times of rough flotation, 1-8 times of fine flotation and 1-6 times of scavenging in the presence of a pH regulator, an activating agent, a collecting agent and a foaming agent; more preferably 1-3 roughing, 2-5 concentrating, 2-4 scavenging) to extract the non-ferrous metals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010408429.XA CN112126788A (en) | 2020-05-14 | 2020-05-14 | Method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010408429.XA CN112126788A (en) | 2020-05-14 | 2020-05-14 | Method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112126788A true CN112126788A (en) | 2020-12-25 |
Family
ID=73851131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010408429.XA Pending CN112126788A (en) | 2020-05-14 | 2020-05-14 | Method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112126788A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113280345A (en) * | 2021-06-25 | 2021-08-20 | 中国科学院山西煤炭化学研究所 | Method for generating electricity by coupling high-temperature melting and harmless treatment of waste fly ash with incineration |
| CN113718108A (en) * | 2021-07-16 | 2021-11-30 | 清远金谷智联环保产业研究院有限公司 | Harmless treatment process for heavy nonferrous metal dangerous waste |
| CN114192273A (en) * | 2021-11-29 | 2022-03-18 | 浙江遂昌汇金有色金属有限公司 | Harmless and recycling treatment process for solid waste containing precious metals |
| CN114749283A (en) * | 2022-04-07 | 2022-07-15 | 深圳市小荷环保技术有限公司 | Domestic garbage incineration fly ash flotation separation method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002136943A (en) * | 2000-11-02 | 2002-05-14 | Sintokogio Ltd | Method and system for decomposition of dioxins contained in fly ash, and for recovering heavy metal. |
| US6461400B1 (en) * | 2000-04-12 | 2002-10-08 | Art J. Parker | Process for extracting quantities of precious metals |
| CN101550483A (en) * | 2009-04-28 | 2009-10-07 | 云南锡业集团（控股）有限责任公司 | Combined flow path processing method of laterite nickel |
| CN109423558A (en) * | 2017-08-25 | 2019-03-05 | 中冶长天国际工程有限责任公司 | A kind of technique of municipal administration and metallurgical difficult solid waste collaboration resource utilization |
| CN109420662A (en) * | 2017-08-25 | 2019-03-05 | 中冶长天国际工程有限责任公司 | A kind of system of municipal administration and metallurgical difficult solid waste collaboration resource utilization |
| CN109680156A (en) * | 2019-01-31 | 2019-04-26 | 龙岩山青冶金科技有限公司 | A kind of waste incineration and generating electricity cinder resourceization utilizes system and method |
| CN110106368A (en) * | 2019-04-19 | 2019-08-09 | 长沙矿冶研究院有限责任公司 | A kind of method of lateritic nickel ore indirect heating compound roasting-floating and enriching nickel cobalt |
-
2020
- 2020-05-14 CN CN202010408429.XA patent/CN112126788A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6461400B1 (en) * | 2000-04-12 | 2002-10-08 | Art J. Parker | Process for extracting quantities of precious metals |
| JP2002136943A (en) * | 2000-11-02 | 2002-05-14 | Sintokogio Ltd | Method and system for decomposition of dioxins contained in fly ash, and for recovering heavy metal. |
| CN101550483A (en) * | 2009-04-28 | 2009-10-07 | 云南锡业集团（控股）有限责任公司 | Combined flow path processing method of laterite nickel |
| CN109423558A (en) * | 2017-08-25 | 2019-03-05 | 中冶长天国际工程有限责任公司 | A kind of technique of municipal administration and metallurgical difficult solid waste collaboration resource utilization |
| CN109420662A (en) * | 2017-08-25 | 2019-03-05 | 中冶长天国际工程有限责任公司 | A kind of system of municipal administration and metallurgical difficult solid waste collaboration resource utilization |
| CN109680156A (en) * | 2019-01-31 | 2019-04-26 | 龙岩山青冶金科技有限公司 | A kind of waste incineration and generating electricity cinder resourceization utilizes system and method |
| CN110106368A (en) * | 2019-04-19 | 2019-08-09 | 长沙矿冶研究院有限责任公司 | A kind of method of lateritic nickel ore indirect heating compound roasting-floating and enriching nickel cobalt |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113280345A (en) * | 2021-06-25 | 2021-08-20 | 中国科学院山西煤炭化学研究所 | Method for generating electricity by coupling high-temperature melting and harmless treatment of waste fly ash with incineration |
| CN113718108A (en) * | 2021-07-16 | 2021-11-30 | 清远金谷智联环保产业研究院有限公司 | Harmless treatment process for heavy nonferrous metal dangerous waste |
| CN114192273A (en) * | 2021-11-29 | 2022-03-18 | 浙江遂昌汇金有色金属有限公司 | Harmless and recycling treatment process for solid waste containing precious metals |
| CN114749283A (en) * | 2022-04-07 | 2022-07-15 | 深圳市小荷环保技术有限公司 | Domestic garbage incineration fly ash flotation separation method |
| CN114749283B (en) * | 2022-04-07 | 2024-02-02 | 深圳市小荷环保技术有限公司 | Household garbage incineration fly ash flotation separation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112126788A (en) | Method for extracting nonferrous metals by using incineration fly ash of hazardous organic wastes | |
| CN104911356B (en) | A kind of solid waste gas ash, the comprehensive recycling process of vanadium slag containing zinc-iron | |
| Geng et al. | Recovery of metals from municipal solid waste incineration fly ash and red mud via a co-reduction process | |
| CN106498177B (en) | The recycling of gold and silver iron and innoxious method is synchronized in a kind of baking cyaniding tailings | |
| CN107254585B (en) | A method of recycling zinc, indium, iron, gallium from iron vitriol slag | |
| CN101348859A (en) | Method for comprehensively recovering gold, iron and sulphur resource from gold-containing sulfurous iron ore | |
| CN107352819A (en) | A kind of aluminium cell carbonaceous waste material is used for the method for producing calcium aluminum fluoride clinker | |
| CN107267745B (en) | The extracting method of valuable element in a kind of iron vitriol slag | |
| CN110284004B (en) | Method for synergistically recycling copper slag and sodium sulfate waste slag | |
| CN107299218B (en) | A kind of iron vitriol slag desulfurization pelletizing, preparation and its application | |
| CN111020175A (en) | Method for comprehensively recycling zinc-rich gypsum slag resources | |
| CN104028366B (en) | A kind of recoverying and utilizing method of dedusting ash or gas ash | |
| CN107363074A (en) | A kind of aluminium cell carbonaceous materials recycling is alternative coal-fired method | |
| Liu et al. | The pretreatment of non-ferrous metallurgical waste slag and its research progress in the preparation of glass-ceramics | |
| CN110951966B (en) | Method for harmlessly treating electroplating sludge | |
| CN109517980A (en) | A kind of method of synthetical recovery Copper in Electroplating Sludge nickel | |
| CN113755704B (en) | Method for step separation and comprehensive recovery of carbon-containing arsenic gold concentrate | |
| CN107352542A (en) | A kind of regeneration method and its application of aluminium cell carbonaceous waste material | |
| CN114480859A (en) | Method for cooperatively utilizing all components of red mud and iron ore sintering dedusting ash | |
| CN111057854B (en) | Treatment method of metal tailings | |
| CN102242282B (en) | Alkaline reduction smelting method for vanadium polymetallic ore | |
| CN107082428B (en) | A method of cementite is prepared using more metal sulfate slags | |
| CN107200488A (en) | The method that dry-process rotary kiln station-service aluminium cell carbonaceous waste material produces fluoroaluminate cement | |
| CN107159688A (en) | A kind of aluminium cell carbonaceous materials recycling make a living electricity production stone raw material method | |
| CN115679096A (en) | Process method for recycling carbon slag and red mud by cooperative treatment |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201225 |