CN103011537B - A method for treating sludge containing trivalent chromium and recovering heavy metals - Google Patents
A method for treating sludge containing trivalent chromium and recovering heavy metals Download PDFInfo
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- CN103011537B CN103011537B CN201210554118.XA CN201210554118A CN103011537B CN 103011537 B CN103011537 B CN 103011537B CN 201210554118 A CN201210554118 A CN 201210554118A CN 103011537 B CN103011537 B CN 103011537B
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- China
- Prior art keywords
- chromium
- filter residue
- acid
- sludge
- weight ratio
- Prior art date
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 107
- 239000011651 chromium Substances 0.000 title claims abstract description 107
- 239000010802 sludge Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 7
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000000706 filtrate Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229910001868 water Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004458 analytical method Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011449 brick Substances 0.000 claims 1
- 229920001429 chelating resin Polymers 0.000 claims 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 17
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009713 electroplating Methods 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 18
- 238000000926 separation method Methods 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 12
- 239000003518 caustics Substances 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000002699 waste material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000003016 phosphoric acids Chemical class 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- -1 metals ion Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- OSKILZSXDKESQH-UHFFFAOYSA-K zinc;iron(2+);phosphate Chemical group [Fe+2].[Zn+2].[O-]P([O-])([O-])=O OSKILZSXDKESQH-UHFFFAOYSA-K 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004848 nephelometry Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Treatment Of Sludge (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for treating sludge containing trivalent chromium and recovering heavy metal. The method comprises the following steps: analyzing the content of components in sludge containing chromium to dilute the sludge containing chromium; and treating the sludge containing chromium by ammonium salt, ammonia water, alkali and acid to obtain pigment grade chromium oxide, single metal or other products. The method is applied to the disposal and recovery process of the sludge containing chromium generated in the industries, such as steel, electroplating and tanning to achieve a good pollution control and resource recovery effect.
Description
Technical field
The invention belongs to environmental technology field, be specifically related to a kind of processing containing the method for trivalent chromium mud and recovery heavy metal.
Background technology
Steel rolling, plating, process hides etc. can produce a large amount of chromate waste water and mud in producing, the treatment process comparative maturity of chromate waste water, and chromium-bearing sludge there is no effective treatment process, bank up in a large number and not only can cause the waste in soil, also can cause certain pollution to environment, it is also a kind of waste that the chromium resource in while chromium-bearing sludge can not be fully used.
The patent No. is called the patent of " processing the method containing trivalent chromium mud " for [87105027.7], use sulfuric acid medium solution, make trivalent chromium mud be converted into the method that sulfate precipitation is separated out, throw out is as cement hardener, in solution, acid is 1:0.5～1.5 with the mass ratio of water, solution is 3:2～5 with the ratio of trivalent chromium mud weight, and temperature of reaction is 60 ℃～130 ℃, and drying precipitate temperature is 100 ℃～400 ℃.The method has proposed the thinking that a kind of chromium-bearing sludge is processed, but reaction time is long, and temperature is controlled higher, expends the energy larger.
The patent No. is called the patent of " utilizing chromium-bearing sludge to produce the method for chromium sesquioxide " for [200410012289.5], utilize chromium to be present in the method for producing chromium sesquioxide in chromium-bearing sludge with the form of chromium hydroxide, technical process is: (1) washes removal of impurities by chromium-bearing sludge; (2) by the chromium-bearing sludge filter-press dehydration of impurity elimination; (3) chromium-bearing sludge is dried or dried; (4) sludge-drying is entered in stoving oven and carry out roasting, chromium hydroxide is converted into chromium sesquioxide, obtain the thick product of chromium sesquioxide; (5) with hot water, remove the water solubles after rough chromium sesquioxide is come out of the stove, obtain smart product; (6) finally obtain the chromium sesquioxide product of different meshes.The method has obtained part chromium sesquioxide product, but needs high-temperature roasting, and energy consumption is higher.
The patent No. is called the patent of " method of extracting chromium in chromium-bearing sludge with sodium-salt calcination " for [200510030137.2], system utilizes sodium salt to carry out innoxious and processing resource utilization to chromium-bearing sludge, comprises the step of sludge treatment → sodium salt mixing → roasting → cooling → leaching.The method reclaims that chromium is more thorough, and the reaction times is short, but in roasting, process cooling, that leach again, power consumption is large and step is relatively loaded down with trivial details.
Application number is called the patent of " a kind of processing is containing the method for trivalent chromium mud " for [201110240590.1], comprise that chromium-bearing sludge process → is oxidized → obtains the step of chrome liquor to component concentration analysis → acidleach processing → melt cinder separation → alkali in chromium-bearing sludge powder.The shortcoming of the method is pickling liquor complicated component, contains a large amount of acid soluble material, as iron, zinc, nickel, copper, aluminium, silicate, phosphoric acid salt etc. in chromium mud.Molten these ions that make of acid all enter pickling liquor, and further separated difficulty is larger, and alkali dissolved oxygen, has become hypertoxic sexavalent chrome by the trivalent chromium conversion of low toxicity in addition, and the difficulty of qualified discharge increases considerably.
Summary of the invention
Technical problem to be solved by this invention is to provide the method for a kind of processing containing trivalent chromium mud and recovery heavy metal for the deficiency of above-mentioned prior art existence, can be by harmful element chromium Separation and Recovery in chromium-bearing sludge.
In order to solve the problem of above-mentioned proposition, technical scheme of the present invention is:
Processing is containing a method for trivalent chromium mud and recovery heavy metal, and it comprises the steps:
1, to component concentration analysis in chromium-bearing sludge: analyze component and the content thereof of chromium-bearing sludge, contribute to judge method for subsequent processing;
2, dilution chromium-bearing sludge: take chromium-bearing sludge, add water stirring to pulp, the weight ratio of chromium-bearing sludge and water is 1:(0.5 ~ 10), make chromium-bearing sludge slurry;
3, ammonium salt and ammonia treatment: to step 2) add ammonium salt and ammoniacal liquor in described chromium-bearing sludge slurry, the weight ratio of chromium-bearing sludge and ammonium salt is 1:(0.01 ~ 10), the weight ratio of chromium-bearing sludge and ammoniacal liquor is 1:(0.01 ~ 10), limit edged stirs fully reaction 0.5 ~ 3 hour; Then filtering separation is ammonium dissolubility filtrate and filter residue, and ammonium dissolubility filtrate comprises the water of filter residue in this step of washing;
4, alkaline purification: will add alkali lye in step 3) gained filter residue, the concentration of alkali lye is 1 ~ 10mol/L, and the weight ratio of filter residue and alkali lye is 1:0.1 ~ 10, limit edged stirs, and adds rear continuation and stirs fully reaction in 0.1 ~ 10 hour; Then filtering separation is caustic solubility filtrate and filter residue, and caustic solubility filtrate comprises the water of filter residue in this step of washing;
5, acid treatment: will add acid solution in step 4) gained filter residue, the concentration of acid solution is 0.001 ~ 10mol/L, and the weight ratio of filter residue and acid solution is 1:0.1 ~ 10, limit edged stirs, and adds rear continuation and stirs fully reaction in 0.1 ~ 10 hour; Then filtering separation is solubility in acid filtrate and filter residue, and solubility in acid filtrate comprises the water of filter residue in this step of washing;
6, step 5) gained filter residue is for the filler of manufacture of cement or for brickmaking;
7, step 5) gained solubility in acid filtrate is heated to 30 ~ 80 ℃, and blowing air or negative pressure is driven the sulfurous gas of dissolving out of and absorb with alkali, regulating filtrate pH is 7 ~ 9, the form precipitation by chromium with chromium hydroxide, through washing, oven dry, calcining, obtain pigment-level chromic oxide product;
8, step 3) gained ammonium dissolubility filtrate, by resin, carry out Adsorption Concentration, metal ion after concentrated with the sour Desorption separation of different concns, acid concentration is 0.0001 ~ 1mol/L, and further carry out reducing metal ion, obtain metal simple-substance, or further concentrating metals ion, crystallization obtains metal-salt;
9,, by step 4) gained caustic solubility filtrate pH to 7.5 ~ 12, precipitation obtains ferric-polysilicate zinc as flocculation agent.
Press such scheme, described a kind of processing is containing the method for trivalent chromium mud and recovery heavy metal, and it comprises following preferred steps:
1) to component concentration analysis in chromium-bearing sludge: analyze component and the content thereof of chromium-bearing sludge, contribute to judge method for subsequent processing;
2) dilution chromium-bearing sludge: take a certain amount of chromium-bearing sludge, add water stirring to pulp, the weight ratio of chromium-bearing sludge and water is 1:(0.7 ~ 1), make chromium-bearing sludge slurry;
3) ammonium salt and ammonia treatment: to step 2) add ammonium salt and ammoniacal liquor in described chromium-bearing sludge slurry, the weight ratio of chromium-bearing sludge and ammonium salt is 1:(0.2 ~ 0.6), the weight ratio of chromium-bearing sludge and ammoniacal liquor is 1:(0.02 ~ 0.05), limit edged stirs fully reaction, and the reaction times is 1 ~ 2.5 hour; Then filtering separation is ammonium dissolubility filtrate and filter residue, and ammonium dissolubility filtrate comprises the water of filter residue in this step of washing;
4) alkaline purification: will add alkali lye in step 3) gained filter residue, the concentration of alkali lye is 1 ~ 6mol/L, and the weight ratio of filter residue and alkali lye is 1:1 ~ 2, limit edged stirs, and adds rear continuation and stirs fully reaction in 1 ~ 3 hour; Then filtering separation is caustic solubility filtrate and filter residue, and caustic solubility filtrate comprises the water of filter residue in this step of washing;
5) acid treatment: will add acid solution in step 4) gained filter residue, the concentration of acid solution is 0.001 ~ 1mol/L, and the weight ratio of filter residue and acid solution is 1:1 ~ 2, limit edged stirs, and adds rear continuation and stirs fully reaction in 1 ~ 3 hour; Then filtering separation is solubility in acid filtrate and filter residue, and solubility in acid filtrate comprises the water of filter residue in this step of washing;
6) step 5) gained filter residue is for the filler of manufacture of cement or for brickmaking.
Press such scheme, described ammonium salt is one or more mixtures in any proportion in ammonium sulfate, ammonium chloride, ammonium nitrate.
Press such scheme, described ammoniacal liquor is industrial ammonia.
Press such scheme, described alkali is a kind of in sodium hydroxide, potassium hydroxide.
Press such scheme, described acid is a kind of in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
By to metallurgy, electroplate, the different industries such as tanning and sulphite, ferrous sulfate reduction, calcium oxide, the various precipitate reduction techniques such as sodium hydroxide precipitation are resulting carries out analysis containing chromic industrial solid castoff (chromium-bearing sludge), main containing chromium (III) in chromium-bearing sludge, zinc (II), iron (II) (III), copper (II), nickel (II), aluminium (III), sodium (I), calcium (II), metal ion and the silicate such as magnesium (II), phosphoric acid salt, sulphite, vitriol etc., chromium (III) wherein, zinc (II), copper (II), nickel (II) is environment to be had to the metallic element of pollution, also be the element that the present invention will reclaim.According to the composition analysis of chromium-bearing sludge, by its chemical property divide into groups decrement, separation, the present invention is divided into four groups such as molten group of ammonium, molten group of alkali, sour molten group and insolubles group, then the compound in each group is carried out to further separation, reclaims and obtain having Industrial products that the utilization of resources is worth and not containing the waste of harmful heavy metal.
Compared with prior art, the invention has the beneficial effects as follows:
1, harmful element chromium Separation and Recovery is complete, compare with existing solidify & bury technology, thoroughly removed the pollution hidden trouble of chromium to environment, chromium content is all less than 0.01 μ g/ml in discharge, (to comprise water and waste residue), be far smaller than the emission standard of GB 1 μ g/ml, the chromic oxide purity simultaneously reclaiming is high, reaches more than 90%; Through further purifying and processing the technological standard that can reach dyestuff level chromic oxide.
Separation and Recovery when 2, valuable metal in chromium-bearing sludge is equal to as zinc, copper, nickel, if these metal ion discharges, also can be to environment, they are to be again worth very high valuable source simultaneously, because content is very low, recovery difficult is large, so prior art seldom relates to the Separation and Recovery of these metal ions; The present invention in Separation and Recovery chromium also by these valuable metal ions Separation and Recovery purify one by one.Through graphite atomic absorption spectrochemical analysis, zinc content 0.02 μ g/ml in discharge water, copper, nickel can't check; The purity containing zinc product obtaining is greater than 95%, containing copper products, is greater than 99%, and nickeliferous product is greater than 98%.
3, after separation and Extraction poisonous metal and valuable metal, can also obtain the byproducts such as poly-silicon tertiary iron phosphate zinc, waste residue can obtain the byproducts such as chemical gypsum and produce the raw material of cement and brickmaking according to the source of chromium-bearing sludge and disposing technique, can realize the zero release of industrial hazard waste.
The present invention is applied in the disposal recovery process of the chromium-bearing sludge that a plurality of industries such as iron and steel, plating, tanning produce, has all obtained the effect that good pollution treatment and resource reclaim.
Embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to the following examples.
embodiment 1:
Processing is containing a method for trivalent chromium mud and recovery heavy metal, and it comprises the steps:
1, to component, content analysis (mass percent) in chromium-bearing sludge: the chromium-bearing sludge that certain electroplating enterprise produces, water content 60%, butt amount 40%; Butt, through X-fluorescence emission spectrum analysis, contains silicate 11.7%, phosphoric acid salt 9%, vitriol 11.3%, ironic hydroxide 1.7%, aluminium hydroxide 3.7%, chromium hydroxide 47.4%, cupric oxide 0.1%, zinc oxide 11.5%, nickel oxide 0.05%, calcium hydroxide 0.7%, magnesium hydroxide 0.3% and a small amount of sylvite, sodium salt etc. by weight percentage;
2, dilution chromium-bearing sludge: claim 100kg chromium-bearing sludge, add water 70kg, stirring to pulp in agitator, makes chromium-bearing sludge slurry after chromium-bearing sludge is uniformly dispersed;
3, ammonium salt and ammonia treatment: in chromium-bearing sludge slurry described in step 2, add industrial ammonium chloride 60kg and industrial ammonia 2kg, stir leaching 60min, centrifuging, filter residue with water wash once, then be separated into ammonium dissolubility filtrate and filter residue, ammonium dissolubility filtrate comprises the leacheate of filter residue in this step of washing;
4, alkaline purification: step 3 gained filter residue is added to alkali lye, the concentration of alkali lye is 1mol/L, the weight ratio of filter residue and alkali lye is 1:1, stirring and dissolving leaching, churning time is 90min, then centrifuging, and filter residue is with water wash once, then be separated into caustic solubility filtrate and filter residue, caustic solubility filtrate comprises the leacheate of filter residue in this step of washing;
5, acid treatment: step 4 gained filter residue is added to acid solution, the concentration of acid solution is 0.1mol/L, the weight ratio of filter residue and acid solution is 1:1, be pulpous state dispersed after, adjust pH=3, stir leaching 150min, then centrifuging, filter residue with water wash once, is then separated into solubility in acid filtrate and filter residue, and acid filtrate comprises the leacheate of filter residue in this step of washing;
6, step 5 gained filter residue detects through spectrophotometric analysis by GB GB8978-1996, and chromium content 0.02 μ g/ml is less than the emission standard of 1 μ g/ml, can discharge or for brickmaking or as cement producting material;
7, step 5 obtains solubility in acid filtrate, with 1 mol/L hydrochloric acid, adjust pH=3, be heated to 40 ℃ of logical pressurized air and drive the sulfurous gas being dissolved in solution out of, gas is emptying after the scrubbing bottle sulfur dioxide absorption of saturated sodium hydroxide is housed, the chromium chloride solution obtaining is adjusted pH=8 with 1mol/L sodium hydroxide, obtain chromium hydroxide precipitation, after washing, oven dry, calcining, obtain dyestuff level chromic oxide product, by industrial chromium sesquioxide standard HG/T2775-2010, carry out analyzing and testing, compound this standard of all technical; Waste water detects through graphite Atomic Absorption Spectroscopy AAS, and chromium content is 0.01 μ g/ml;
8, step 3 gained ammonium dissolubility filtrate by the flow velocity of 120kg/h by the ion exchange column of the duolite 467 type aminophosphonic acid resins that Rhom and Hass is housed produces, then use 0.01 mol/L hydrochloric acid, flow velocity drip washing exchange resin with 60kg/h, obtain the liquor zinci chloridi of 10wt% concentration, sodium hydroxide precipitation through 10%, filter, calcining, obtain the zinc oxide product that content is greater than 95%, effluent liquid can't check after zinc, use the hydrochloric acid of 0.1mol/L instead with the flow velocity drip washing exchange resin of 20kg/h, obtain mass concentration and be 12% Cupric Chloride Solution, through condensing crystal, obtain the cupric chloride product that content is greater than 99%, exchange resin is successively with 1% sodium hydroxide and water wash regeneration,
9, the hydrochloric acid that is 1:1 by step 4 gained caustic solubility filtrate by volumetric concentration is adjusted PH=9, obtains silicon tertiary iron phosphate zinc precipitation, and washing obtains ferric-polysilicate zinc product after drying, as flocculation agent.Through humic acids nephelometry, analyze, range estimation finds to have obvious flocculating effect.
embodiment 2:
Processing is containing a method for trivalent chromium mud and recovery heavy metal, and it comprises the steps:
1, to component concentration analysis in chromium-bearing sludge: the chromium-bearing sludge that certain iron and steel enterprise produces, water content 50wt%, butt 50wt%; Butt, through Xray fluorescence spectrometer analysis, contains silicate 19.5%, phosphoric acid salt 4.5%, vitriol 36.7%, ferric oxide 0.7%, aluminum oxide 2.9%, chromic oxide 3.4%, zinc oxide 1.6%, calcium oxide 29.3%, magnesium hydroxide 0.4% and a small amount of sylvite, sodium salt etc. by weight percentage; 2, dilution chromium-bearing sludge: claim 100kg chromium-bearing sludge, add water 100kg, stirring to pulp in agitator, makes chromium-bearing sludge slurry after chromium-bearing sludge is uniformly dispersed;
3, ammonium salt and ammonia treatment: in chromium-bearing sludge slurry described in step 2, add industrial sulphuric acid ammonium 20kg and industrial ammonia 5kg, stir leaching 150min, centrifuging, filter residue with water wash once, then be separated into ammonium dissolubility filtrate and filter residue, ammonium dissolubility filtrate comprises the leacheate of filter residue in this step of washing;
4, alkaline purification: step 3 gained filter residue is added to alkali lye, the concentration of alkali lye is 4mol/L, the weight ratio of filter residue and alkali lye is 1:1, dispersed with stirring, be pulpous state dispersed after, churning time is 120min, then centrifuging, filter residue with water wash once, is then separated into caustic solubility filtrate and filter residue, and caustic solubility filtrate comprises the leacheate of filter residue in this step of washing;
5, acid treatment: step 4 gained filter residue is added to acid solution, the concentration of acid solution is 0.5mol/L, the weight ratio of filter residue and acid solution is 1:0.5, adjusts pH=2.5, dispersed with stirring, be pulpous state dispersed after, stir leaching 180min, then centrifuging, filter residue is with water wash once, then be separated into solubility in acid filtrate and filter residue, acid filtrate comprises the leacheate of filter residue in this step of washing;
6, step 5 gained filter residue after testing main component be calcium sulfate precipitation, chromium content reaches GB GB8978-1996, can sell as chemical gypsum, product detects through spectrophotometric analysis, chromium content 0.05 μ g/ml;
7, step 5 obtains solubility in acid filtrate, with 1mol/L sulfuric acid, adjust pH=3.5, be heated to the logical pressurized air of 50 degree and drive the sulfurous gas being dissolved in solution out of, gas is emptying after the scrubbing bottle sulfur dioxide absorption of saturated sodium hydroxide is housed, the chromium chloride solution obtaining is adjusted pH=8.5 with 1mol/L sodium hydroxide, obtain chromium hydroxide precipitation, after washing, oven dry, calcining, obtain dyestuff level chromic oxide product, meet industrial chromium sesquioxide standard HG/T2775-2010; Waste water detects through graphite Atomic Absorption Spectroscopy AAS, and chromium content is 0.02 μ g/ml.
8, step 3 gained ammonium dissolubility filtrate by the flow velocity of 90kg/h by the ion exchange column of D-401 macroporous chelate resin is housed, the effluent liquid of the ammonium salt-containing now obtaining can be used for the making beating of step 1, then use 0.5 mol/L sulfuric acid, flow velocity drip washing exchange resin with 60kg/h, until effluent liquid can't check after zinc, obtain the solution of zinc sulfate of 20% concentration, through condensing crystal, obtain the zinc sulfate product that content is greater than 95%; Exchange resin is successively with 1% sodium hydroxide and water wash regeneration;
9, by step 4 gained caustic solubility filtrate, by volumetric concentration, be that 1:1 sulfuric acid adjusts PH to 11 to obtain ferric-polysilicate zinc precipitation, washing obtains ferric-polysilicate zinc product after drying, as flocculation agent.
embodiment 3
Be with the difference of embodiment 1:
Step 2, add water 1000 kg; Step 3 adds industrial ammonium chloride 900kg, industrial ammonia, 1000kg; In step 4, the concentration of aqueous sodium hydroxide solution is 1mol/L, and the weight ratio of filter residue and aqueous sodium hydroxide solution is 1:10, churning time 10h; In step 5, the concentration of hydrochloric acid is 10 mol/L, and the weight ratio of filter residue and acid solution is 1:10.Waste residue and the waste water of discharge are respectively 0.02 μ g/ml and 0.02 μ g/ml. through 721 spectrophotometer analytical review chromium content.
Slurry concentration that embodiment 3 obtains is little, viscosity is low, is convenient to dispersed with stirring, the torsion of equipment is required little, is convenient to lectotype selection.Each product of gained all can reach the effect described in embodiment 1.But because the input ratio of every raw material in this situation of embodiment 3 is larger, cost is high, relatively time-consuming, so pay the utmost attention to embodiment 1 and embodiment 2, pays the utmost attention to the preferred steps in specification sheets in actual application.
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention, at this, do not enumerate embodiment.
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| CN104609683B (en) * | 2014-12-12 | 2016-10-05 | 浙江工商大学 | A kind of regeneration method of heavy metal chromium in chrome tanning sludge |
| CN104961277B (en) * | 2015-07-09 | 2017-01-25 | 常州大学 | A method for recycling chromium in tannery wastewater |
| CN106872445B (en) * | 2015-12-11 | 2020-08-07 | 上海梅山钢铁股份有限公司 | Method for detecting chromium content on surface of cold-rolled tin-plated steel plate |
| CN107287428B (en) * | 2017-07-05 | 2018-08-17 | 盛隆资源再生（无锡）有限公司 | A method of Copper in Electroplating Sludge, nickel, zinc is separately recovered |
| CN107519901A (en) * | 2017-08-25 | 2017-12-29 | 乳源东阳光氟有限公司 | A kind of method that chromate waste water recovery prepares fluorination catalyst |
| CN108672714A (en) * | 2018-04-24 | 2018-10-19 | 上海大学 | The method that alloy powder is directly prepared by cold rolling sludge |
| CN111057857A (en) * | 2019-12-31 | 2020-04-24 | 安徽工业大学 | A high-efficiency precipitant for trace selenium in copper smelting multi-component mixed waste acid and a method for precipitating trace selenium and synergistically recovering sulfur dioxide |
| CN111215441B (en) * | 2020-01-22 | 2022-02-22 | 湖南金旅环保股份有限公司 | Heavy metal chromium contaminated soil remediation step-by-step leaching method |
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| US5389262A (en) * | 1991-04-08 | 1995-02-14 | Romar Technologies, Inc. | Process for removing heavy metals from solutions with ferrous dithionite and hydroxide |
| JP4292454B2 (en) * | 2002-02-15 | 2009-07-08 | 住友金属工業株式会社 | Method for treating aqueous solution containing metal fluoride |
| CN1696064A (en) * | 2004-05-14 | 2005-11-16 | 高志远 | Method for producing chromic oxide by using sludge of containing chrome |
| CN100402676C (en) * | 2006-03-24 | 2008-07-16 | 浙江工业大学 | Method for recovering valuable metals from electroplating sludge |
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| CN102303940B (en) * | 2011-08-22 | 2013-06-05 | 陕西科技大学 | Method for treating sludge containing trivalent chromium |
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