CN110983047A - Method for recovering multiple valuable substances from waste diamond tool bit raw materials - Google Patents
Method for recovering multiple valuable substances from waste diamond tool bit raw materials Download PDFInfo
- Publication number
- CN110983047A CN110983047A CN201911227619.5A CN201911227619A CN110983047A CN 110983047 A CN110983047 A CN 110983047A CN 201911227619 A CN201911227619 A CN 201911227619A CN 110983047 A CN110983047 A CN 110983047A
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- Prior art keywords
- concentration
- solution
- cobalt
- zinc
- copper
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- Granted
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- 239000010432 diamond Substances 0.000 title claims abstract description 78
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 59
- 239000002994 raw material Substances 0.000 title claims abstract description 55
- 239000000126 substance Substances 0.000 title claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000002386 leaching Methods 0.000 claims abstract description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000002425 crystallisation Methods 0.000 claims abstract description 44
- 230000008025 crystallization Effects 0.000 claims abstract description 44
- 238000001914 filtration Methods 0.000 claims abstract description 43
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 36
- 239000010941 cobalt Substances 0.000 claims abstract description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011701 zinc Substances 0.000 claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 33
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 16
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 12
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 12
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011667 zinc carbonate Substances 0.000 claims abstract description 12
- 229910000010 zinc carbonate Inorganic materials 0.000 claims abstract description 12
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims abstract description 11
- 235000004416 zinc carbonate Nutrition 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000000706 filtrate Substances 0.000 claims description 39
- 238000000605 extraction Methods 0.000 claims description 37
- 239000000047 product Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000012452 mother liquor Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 24
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 22
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 20
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 18
- 229910001431 copper ion Inorganic materials 0.000 claims description 18
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 17
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 12
- 239000004571 lime Substances 0.000 claims description 12
- 239000008267 milk Substances 0.000 claims description 12
- 210000004080 milk Anatomy 0.000 claims description 12
- 235000013336 milk Nutrition 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 239000002912 waste gas Substances 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052602 gypsum Inorganic materials 0.000 claims description 6
- 239000010440 gypsum Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 235000014413 iron hydroxide Nutrition 0.000 claims description 5
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 3
- -1 iron ions Chemical class 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 3
- 239000010413 mother solution Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- 239000011135 tin Substances 0.000 description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 10
- 239000007832 Na2SO4 Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052925 anhydrite Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 239000004519 grease Substances 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
- 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
- 230000001788 irregular Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Images
Classifications
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- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet 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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering various valuable substances from waste diamond tool bit raw materials, which can economically, effectively and environmentally realize the high-efficiency recovery of various valuable substances in the waste diamond tool bit raw materials, is particularly suitable for low-chromium raw materials with complex components, the method comprises the steps of directly leaching out relatively easily soluble metals such as iron, nickel, cobalt, zinc, chromium and the like by using dilute sulfuric acid at normal pressure, crystallizing a leaching solution to obtain a ferrous sulfate heptahydrate product, sequentially preparing copper sulfide, zinc carbonate, cobalt carbonate and nickel sulfide products from a crystallization mother solution, filling air into a dilute sulfuric acid solution by using an innovative nano cavitation device for residues leached for the first time at normal pressure, realizing that the dissolution speed of copper is obviously improved at lower temperature and sulfuric acid concentration, filtering and screening to obtain diamond and tungsten carbide products, crystallizing the leaching solution to obtain a copper sulfate pentahydrate product, and realizing fractional recovery of valuable substances. The process has the advantages of simple flow, high recovery rate of valuable substances, low production cost, high automation degree and capability of realizing industrial production.
Description
Technical Field
The invention relates to the technical field of waste hard alloy recovery, in particular to a method for recovering various valuable substances from waste diamond tool bit raw materials.
Background
The diamond saw blade is a working main body of the diamond saw blade, and the diamond saw blade consists of diamond and a matrix binder. The diamond is a superhard material and plays a role of a cutting edge, and the matrix bonding agent plays a role of fixing the diamond and is composed of metal elementary substance powder or metal alloy powder of tungsten, copper, nickel, cobalt and the like. The application of the diamond tool bit is very wide, but about 10% -15% of the diamond tool bits can not be used and abandoned in the later period of use, and China generates considerable waste diamond tool bits every year.
At present, the methods for treating the waste diamond tool bit mainly comprise a leaching method and an electrolysis method.
The leaching method is most commonly applied, wherein nitric acid or aqua regia and the like are adopted to dissolve other metals except diamond and tungsten carbide in the waste diamond tool bit into a liquid phase, diamond and tungsten carbide solids are obtained by filtration and separation, the separation of diamond and tungsten carbide is realized by the solid through a screening method through particle size difference, and the separation of valuable metals is realized by the liquid phase through chemical precipitation, crystallization and the like. The leaching method has the advantages of relatively simple process flow, high production cost and unstable quality of byproducts, and has the disadvantages of generating a large amount of nitrogen oxides and acid mist which pollute the environment, and consuming a large amount of acid and alkali.
The electrolytic method is often applied to the treatment of raw materials with high content of high added-value metals such as silver and the like. Since the composition of the waste diamond segments is complicated and the composition difference is large, it is difficult to obtain a stable cathode product by the electrolytic method. The waste diamond tool bits have large difference in conductivity and irregular shapes, so that the waste diamond tool bits have low electrolysis efficiency. The electrolysis method cannot be widely applied due to high energy consumption, large equipment investment and poor process adaptability.
Due to the rising price of raw materials such as artificial diamond, tungsten carbide, copper, nickel, cobalt and the like, the manufacturing cost of the diamond tool bit is continuously increased, and in addition, the national requirement on environmental protection is higher and higher, and the recovery value of valuable metals in the waste diamond tool bit is more and more obvious. The efficient and environment-friendly recovery of the diamond, the tungsten carbide, the copper, the nickel, the cobalt, the iron and other valuable elements in the waste diamond tool bit can effectively realize the recovery of secondary resources, reduce the resource waste and reduce the manufacturing cost of the diamond tool bit. For this reason, there is an urgent need to develop an efficient and environmentally friendly method of treating waste diamond segments.
Accordingly, one skilled in the art provides a method for recovering various valuable materials from waste diamond segments to solve the problems of the background art.
Disclosure of Invention
In order to achieve the purpose, the invention provides the following technical scheme: a method for recovering multiple valuable substances from waste diamond tool bit raw materials comprises the following steps:
s1, raw material pretreatment: pretreating the waste diamond tool bit raw material by using a sodium hydroxide solution with the concentration of about 50g/L at normal temperature and normal pressure;
s2, primary acid leaching: performing primary acid leaching on the raw material treated in the S1 to dissolve relatively easily-soluble metals including iron, nickel, cobalt, zinc and chromium into a liquid phase, wherein the liquid-solid mass ratio is 2.5-3: 1, the initial sulfuric acid concentration is 60-80 g/L, the reaction is performed at the temperature of 50-60 ℃ and under normal pressure, the sulfuric acid concentration and the ferrous ion concentration are uninterruptedly tested in the reaction process, when the ferrous ion concentration in the solution is lower than 130g/L, the sulfuric acid concentration is ensured to be stabilized at 50-60 g/L, and when the ferrous ion concentration is higher than 130g/L, the acid addition is stopped;
s3, preparing a ferrous sulfate heptahydrate product: when the concentration of the ferrous ions in the leachate A obtained in the step S2 is not increased any more, filtering the leachate A to obtain a filtrate A and filter residues, wherein the filter residues return to the step S2, and the filtrate A is subjected to a crystallization process of ferrous sulfate heptahydrate to prepare a ferrous sulfate heptahydrate product;
s4, preparation of copper sulfide: when the ion concentration of zinc, cobalt and nickel in the crystallization mother liquor A of S3 reaches the recoverable concentration of zinc, cobalt and nickel, the crystallization mother liquor A of S3 enters copper sulfide preparation operation, sodium hydroxide solution is added to adjust the pH value to 2, then sodium sulfide solution is added, polyacrylamide is added for precipitation, and filtration is carried out to obtain a copper sulfide product and filtrate B;
when the ion concentration of zinc, cobalt and nickel in the crystallization mother liquor A of S3 does not reach the recoverable concentration of zinc, cobalt and nickel, the crystallization mother liquor A of S3 returns to S2;
s5, preparation of zinc carbonate: adding lime milk into the filtrate B of S4, adjusting pH to 2.8, precipitating and filtering to obtain filtrate C and gypsum, performing three-stage back extraction on zinc ions in the filtrate C by using P204 resin, controlling the concentration of back extraction acid to be about 6% to obtain a high-concentration back extraction zinc solution and a zinc extraction raffinate, adding sodium carbonate into the back extraction zinc solution, precipitating and filtering to obtain a zinc carbonate product and a waste liquid B;
s6, preparing cobalt carbonate: adding lime milk into the zinc extraction residual liquid of S5, adjusting pH to 4.5, precipitating and filtering to obtain filtrate D and gypsum, carrying out three-stage back extraction on cobalt ions by using P507 resin on the filtrate D, controlling the concentration of back extraction acid to be 6 percent to obtain a back extraction cobalt solution and a cobalt extraction residual liquid with higher concentration, adding sodium carbonate into the back extraction cobalt solution, precipitating and filtering to obtain a cobalt carbonate product and a waste liquid D;
s7, preparation of nickel sulfide: adding a sodium sulfide solution into the cobalt extraction raffinate in the S6, adding polyacrylamide for precipitation, and filtering to obtain a nickel sulfide product and a waste liquid C;
s8, secondary acid leaching: performing secondary acid leaching on the residue A in the S2, wherein the liquid-solid mass ratio is 3.5-4: 1, the initial sulfuric acid concentration is 150-200 g/L, the reaction is performed at 70-75 ℃ and under normal pressure, air, hot steam and hydrogen peroxide are introduced into the solution through a nano cavitation device in the acid leaching process to enhance the oxidation leaching of copper, the sulfuric acid concentration and the copper ion concentration are tested uninterruptedly in the reaction process, when the copper ion concentration in the solution is lower than 80g/L, the sulfuric acid concentration is ensured to be stabilized at 90-120 g/L, when the copper ion concentration is higher than 80g/L, the acid addition is stopped, the temperature is increased to 85-90 ℃, and the residual acid in the solution continues to react;
s9, separation of diamond and tungsten carbide: according to the particle size difference of the diamond and the tungsten carbide, the residue B generated in the step S8 is screened and classified, so that the diamond and the tungsten carbide are effectively separated, and the diamond and the tungsten carbide are cleaned by clear water during screening, so that impurities are reduced;
s10, preparation of tin mud: when the concentration of copper ions in the leaching solution B obtained in the step S8 is not increased any more, filtering the leaching solution B to obtain a filtrate E and tin mud, and feeding the tin mud into a filter cake;
s11, preparation of crude copper sulfate pentahydrate: carrying out primary cooling crystallization on the filtrate E of the S10 to prepare a crude copper sulfate pentahydrate product, and returning a copper sulfate primary crystallization mother liquor B to the S8;
s12, copper sulfate secondary crystallization: dissolving the crude copper sulfate pentahydrate of S11, adding hydrogen peroxide, adjusting the pH value of the solution to 3-4 by using sodium hydroxide to enable impurity ions such as iron ions to generate precipitates, filtering, performing copper sulfate secondary crystallization on the filtrate to form copper sulfate pentahydrate, returning copper sulfate secondary crystallization mother liquor C to S12 for dissolving the crude copper sulfate pentahydrate, and returning iron hydroxide filter residue to S2;
s13, treating three wastes: the three wastes generated by the process are treated, so that the three wastes meet the environmental protection requirement. The waste gas is treated by alkali liquor, acid mist is absorbed by sodium hydroxide, supernatant after pretreatment and rinsing liquid waste water precipitation can be recycled, when the waste gas can not be recycled, the waste water is mixed with other operation waste water and then treated by an HDS (high concentration bottom slag reflux) method, lime milk is added for neutralization treatment, the pH value is adjusted to about 9, calcium sulfate and ferrous hydroxide precipitation are generated, and solid-liquid separation is realized by filtering. The solid can be sold to a cement plant as common solid waste, lime milk can be added into partial supernatant, the pH is adjusted to about 12.5, calcium sulfate and sodium hydroxide are generated, the supernatant after precipitation is recycled as alkali liquor, and the residual part can be discharged.
Compared with the prior art, the invention has the beneficial effects that:
(1) the process provided by the invention can be used for treating the waste diamond tool bit raw material with complex components and low chromium, can be used for directly leaching valuable metals by using dilute sulfuric acid under normal pressure, and recovering valuable substances step by step, and is simple in process flow, high in valuable substance recovery rate, low in production cost, high in automation degree and capable of realizing industrial production.
(2) The invention has strong adaptability to raw materials and can obtain better indexes for waste diamond tool bit raw materials with complex components and low chromium.
(3) The invention adopts an innovative nano cavitation device to fill air, hot steam and hydrogen peroxide into dilute sulfuric acid solution, and the gas-liquid mixture can form nano-scale microbubbles at high speed after being sprayed out, the oxygen content in the leaching solution can be improved by more than 25 percent compared with the common ventilation mode by the nano microbubbles, so that the oxidation potential of the leaching solution is obviously improved, the oxidation leaching speed of copper is improved by more than 40 percent compared with the common heating leaching, and the consumption of the hydrogen peroxide is reduced by more than 70 percent compared with the common dripping mode. Compared with the traditional inflation method, the oxygen content in the leaching solution is improved by more than 25%, the hydrogen peroxide consumption is reduced by more than 70%, the copper oxidation leaching speed is improved by more than 40%, the copper dissolution is realized at lower temperature and sulfuric acid concentration, the production cost is obviously reduced, and the copper dissolution efficiency is greatly improved.
(4) On the basis of fully recovering valuable substances, the waste water, waste gas and waste residues generated in the production can be effectively treated, the waste water and the waste gas meet the environment-friendly discharge requirement on the premise of effective recycling, the waste residues can be effectively recycled, and the valuable substances in the waste diamond tool bit raw materials can be efficiently recovered in an economic, effective and environment-friendly manner.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: referring to fig. 1, the present invention provides a technical solution: a method for recovering multiple valuable substances from waste diamond tool bit raw materials comprises the following steps:
s1, raw material pretreatment: at normal temperature and normal pressure, the waste diamond tool bit raw material is pretreated by sodium hydroxide solution with the concentration of about 50g/L in a rotary cleaning machine, and impurities such as silt, grease and the like on the surface of the raw material are removed. Cleaning the raw materials, passing through a sieving machine with 4mm sieve pores, feeding the sieved products into a rotary rinsing liquid tank, rinsing with clear water, and feeding the rinsed raw materials into an acid leaching reaction kettle for primary acid leaching.
S2, primary acid leaching: performing primary acid leaching on the raw material treated in the S1, wherein the liquid-solid mass ratio is 2.5-3: 1, so that the relatively easily soluble metals including iron, nickel, cobalt, zinc and chromium are dissolved into a liquid phase, and the reaction equation generated in the process is as follows: me + H2SO4＝MeSO4+H2℃, (Me means iron, nickel, cobalt, zinc and the like), the initial sulfuric acid concentration is 60-80 g/L, the reaction is carried out at the temperature of 50-60 ℃ and under normal pressure, the sulfuric acid concentration and the ferrous ion concentration are uninterruptedly tested in the reaction process, when the ferrous ion concentration in the solution is lower than 130g/L, the sulfuric acid concentration is ensured to be stabilized at 50-60 g/L, the acid addition is stopped after the ferrous ion concentration is higher than 130g/L, and the residual acid in the solution continues to react.
S3, preparing a ferrous sulfate heptahydrate product: when the concentration of the ferrous ions in the leachate A obtained in the step S2 is not increased any more, filtering the leachate A to obtain a filtrate A and filter residues, wherein the filter residues return to the step S2, and the filtrate A is subjected to a crystallization process of ferrous sulfate heptahydrate to prepare a ferrous sulfate heptahydrate product;
s4, preparation of copper sulfide: when the ion concentration of zinc, cobalt and nickel in the crystallization mother liquor A of S3 reaches the recoverable concentration of zinc, cobalt and nickel, the crystallization mother liquor A of S3 enters the preparation operation of copper sulfide, sodium hydroxide solution is added to adjust the pH value to 2, then sodium sulfide solution is added to react to generate flocculent copper sulfide, and the main reaction equation generated in the process is as follows: na (Na)2S+CuSO4＝CuS↓+Na2SO4，Na2S+H2SO4＝H2S↑+Na2SO4. Adding polyacrylamide to flocculate copper sulfide, precipitating and filtering to obtain a copper sulfide product and a filtrate B;
when the ion concentration of zinc, cobalt and nickel in the crystallization mother liquor A of S3 does not reach the recoverable concentration of zinc, cobalt and nickel, the crystallization mother liquor A of S3 returns to S2;
s5, preparation of zinc carbonate: adding lime milk into the filtrate B of S4, pulping, adjusting the pH to 2.8, precipitating and filtering to obtain filtrate C and gypsum, wherein the reaction equation in the process is as follows: ca (OH)2+Na2SO4＝2NaOH+CaSO4↓, and the filtrate C is subjected to three-stage back extraction of zinc ions by using P204 resin, and the reaction principle is Zn2++2HR＝ZnR+2H+Three-stage stripping ZnR +2H+＝Zn2++2HR, controlling the concentration of the strip acid at about 6%, obtaining strip zinc solution and zinc extraction raffinate with higher concentration, adding sodium carbonate into the strip zinc solution to generate zinc carbonate precipitate, and the reaction equation generated in the process is as follows: na (Na)2CO3+ZnSO4＝ZnCO3↓+Na2SO4Filtering zinc carbonate to obtain a zinc carbonate product and waste liquid B;
s6, preparing cobalt carbonate: adding lime milk into the zinc extraction residual liquid of S5, adjusting the pH to about 4.5, precipitating and filtering to obtain filtrate D and gypsum, wherein the reaction equation in the process is as follows: ca (OH)2+Na2SO4＝2NaOH+CaSO4↓, the filtrate D carries out three-stage back extraction on cobalt ions by using P507 resin, and the reaction principle is Co2++2HR＝CoR+2H+Three-stage stripping CoR +2H+＝Co2++2HR, controlling the concentration of the stripping acid at about 6% to obtain a stripping cobalt solution with higher concentration and a cobalt extraction raffinate, adding sodium carbonate into the stripping cobalt solution to generate a cobalt carbonate precipitate, wherein the reaction equation generated in the process is as follows: na (Na)2CO3+CoSO4＝CoCO3↓+Na2SO4Dehydrating the cobalt carbonate by using a centrifugal filter to obtain a cobalt carbonate product and a waste liquid D;
s7, preparation of nickel sulfide: adding sodium sulfide solution into the cobalt raffinate in S6, and reacting to generate flocculent nickel sulfide, wherein the reaction equation generated in the process is as follows: na (Na)2S+NiSO4＝NiS↓+Na2SO4Adding polyacrylamide flocculating nickel sulfide, and filtering to obtain a nickel sulfide product and waste liquid C;
s8, secondary acid leaching: carrying out secondary acid leaching on the residue A in the S2, wherein the liquid-solid mass ratio is 3.5-4: 1, the initial sulfuric acid concentration is 150-200 g/L, the reaction is carried out at the temperature of 70-75 ℃ and under normal pressure, air, hot steam and hydrogen peroxide are introduced into the solution through a nano cavitation device in the acid leaching process, so that a gas-liquid mixture is dispersed in dilute sulfuric acid in form of nano-scale microbubbles, the oxygen-containing concentration in the dilute sulfuric acid solution is greatly improved, the oxidation speed of copper can be obviously improved, the copper can react with acid after being oxidized and is dissolved into a liquid phase, and the reaction equation generated in the process is as follows: 2Cu + O2＝2CuO，CuO+H2SO4＝CuSO4+H2And O. And continuously testing the concentration of sulfuric acid and the concentration of copper ions in the reaction process, ensuring that the concentration of sulfuric acid is stabilized at 90-120 g/L when the concentration of copper ions in the solution is lower than 80g/L, stopping adding acid when the concentration of copper ions is higher than 80g/L, increasing the temperature to 85-90 ℃, and continuously reacting the residual acid in the solution. When the concentration of copper ions in the leaching solution B is not increased any more, draining acid leaching solution, separating acid leaching residue B into diamond and tungsten carbide, and filtering the leaching solution B;
s9, separation of diamond and tungsten carbide: and (2) screening and grading the residue B generated in the step S8 according to the particle size difference of diamond and tungsten carbide, wherein effective separation of the diamond and the tungsten carbide can be realized through a double-layer vibrating screen (the screen holes are 70 meshes and 150 meshes), the product on a 70-mesh screen is coarse-grained diamond, the product on a 150-mesh screen is fine-grained diamond, the product under the 150-mesh screen is tungsten carbide, and the diamond and the tungsten carbide are cleaned by clear water during screening to reduce impurities.
In order to improve the color of the diamond, the diamonds rub against each other at high speed by a high-speed scrubbing machine to remove spots on the surface of the diamonds;
s10, preparation of tin mud: and when the concentration of copper ions in the leaching solution B obtained in the step S8 is not increased any more, filtering the leaching solution B to obtain a filtrate E and tin mud, and feeding the tin mud into a filter cake.
S11, preparation of crude copper sulfate pentahydrate: and (3) carrying out primary cooling crystallization on the filtrate E of the S10 to prepare a crude copper sulfate pentahydrate product, flushing the crude copper sulfate pentahydrate product by using clear water to reduce impurities, and returning a copper sulfate primary crystallization mother liquor B to the S8.
S12, copper sulfate secondary crystallization: dissolving the crude blue vitriod in the S11, adding hydrogen peroxide, adjusting the pH value of the solution to 3-4 by using sodium hydroxide, oxidizing ferrous ions into ferric ions and forming ferric hydroxide, wherein the reaction equation generated in the process is as follows: h2O2+2FeSO4+H2SO4＝Fe2(SO4)3+2H2O，Fe2(SO4)3+6NaOH＝2Fe(OH)3↓+3Na2SO4. Filtering to effectively separate iron hydroxide and copper ions, feeding the filtrate into a copper sulfate crystallizer for secondary crystallization to form copper sulfate pentahydrate, returning the mother liquor C of the secondary crystallization of copper sulfate to S12 for dissolving crude copper sulfate pentahydrate, and returning the iron hydroxide filter residue to S2;
s13, treating three wastes: the three wastes generated by the process are treated, so that the three wastes meet the environmental protection requirement. The waste gas is treated by alkali liquor, acid mist is absorbed by sodium hydroxide, supernatant after pretreatment and rinsing liquid waste water precipitation can be recycled, when the waste gas can not be recycled, the waste water is mixed with other operation waste water and then treated by an HDS (high concentration bottom slag reflux) method, lime milk is added for neutralization treatment, the pH is adjusted to about 9, calcium sulfate and ferrous hydroxide precipitation are generated, and the reaction equation generated in the process is as follows: ca (OH)2+FeSO4＝Fe(OH)2↓+CaSO4And ↓, solid-liquid separation is realized by filtering. The solid can be sold to a cement plant as common solid waste, lime milk can be added into a part of supernatant, the pH is adjusted to be about 12.5, calcium sulfate and sodium hydroxide are generated, and the reaction equation generated in the process is as follows: ca (OH)2+Na2SO4＝2NaOH+CaSO4And ↓, the supernatant after precipitation is recycled as alkali liquor, and the redundant part can be discharged outside.
Example 2: the method is characterized in that waste diamond tool bit raw materials are collected from main granite producing areas in China, and after analysis, main valuable substances in the waste diamond tool bit raw materials comprise diamond, tungsten carbide, copper, cobalt, nickel, zinc, iron, tin and other elements. Through a large number of exploration tests, a process for recovering the valuable substances is provided, then the feasibility of the process is verified through a laboratory small-scale test, and then an industrial test is carried out.
Semi-industrial test:
the chemical analysis of the waste diamond bit raw material is carried out, and the contents of main valuable substances are shown in the following table 1.
TABLE 1 content of main valuable substances in the raw material of waste diamond segments for semi-industrial test
| Components | Fe | Cu | Ni | Co | Zn | Diamond | Tungsten carbide | Mn | Cr | Sn | Others |
| Content/% | 40.3 | 36.4 | 2.02 | 0.38 | 3.45 | 2.6 | 12.27 | 0.27 | 0.03 | 1.98 | 0.3 |
(1) Pretreatment of raw materials: taking 3000kg of waste diamond tool bit raw materials, pretreating with a sodium hydroxide solution at normal temperature and normal pressure, stirring for 30min, filtering and washing with clear water.
(2) Processing a first batch of raw materials:
1) acid leaching for the first time: under normal pressure, 100kg of pretreated waste diamond tool bit raw material is added into 300L of dilute sulfuric acid with the temperature of 50-60 ℃, the concentration of the sulfuric acid is 70g/L, and the mixture is continuously stirred. The concentration of sulfuric acid and the concentration of ferrous ions are continuously tested in the reaction process, when the concentration of the ferrous ions in the solution is lower than 130g/L, the concentration of the sulfuric acid is guaranteed to be stabilized at 50-60 g/L, when the concentration of the ferrous ions is higher than 130g/L, acid addition is stopped, and the residual acid in the solution continues to react. And (3) filtering after the concentration of the ferrous ions in the leaching solution A is not increased any more, washing filter residues with a small amount of clear water for secondary acid leaching, and performing ferrous sulfate heptahydrate crystallization operation on the cleaning solution and the filtrate together.
2) Preparing a ferrous sulfate heptahydrate product: filtering after the ferrous sulfate heptahydrate crystallization is finished, drying and weighing, and using the crystallization mother liquor A for the first acid leaching operation of the second batch of raw materials.
3) Acid leaching for the second time: adding the residue A after the first acid leaching into 40L of dilute sulfuric acid at the temperature of 70-75 ℃ under normal pressure, wherein the concentration of the sulfuric acid is 150g/L, introducing air, hot steam and hydrogen peroxide into the solution through a nano cavitation device in the acid leaching process, and continuously stirring, wherein the addition amount of the hydrogen peroxide is about 40 g/min. And continuously testing the concentration of sulfuric acid and the concentration of copper ions in the reaction process, ensuring that the concentration of sulfuric acid is stabilized at 90-120 g/L when the concentration of copper ions in the solution is lower than 80g/L, stopping adding acid when the concentration of copper ions is higher than 80g/L, increasing the temperature to 85-90 ℃, and continuously reacting the residual acid in the solution. And after the concentration of copper ions in the leaching solution B is not increased any more, filtering the leaching solution B to form filtrate E and tin mud, feeding the tin mud into a filter cake, drying the filter cake and weighing.
4) Separation of diamond and tungsten carbide: and screening the residue B generated by the second acid leaching by using a screen with 70 meshes, wherein coarse diamond grains are on the screen, the residue under the screen is screened by using a screen with 150 meshes, fine diamond grains are on the screen, and tungsten carbide is under the screen. The diamond and tungsten carbide were cleaned, dried and weighed.
5) Preparation of blue vitriol: cooling and crystallizing the filtrate E by using copper sulfate, and performing secondary acid leaching operation on the crystallized mother liquor B of a second batch of raw materials. And (3) dissolving the crude copper sulfate pentahydrate of the first copper sulfate crystal, adding hydrogen peroxide, adjusting the pH value of the solution to 3-4 by using sodium hydroxide, filtering, performing second copper sulfate crystallization on the copper sulfate solution, and performing first acid leaching operation on the iron hydroxide of a second batch of raw materials. Filtering after complete crystallization, and enabling the mother liquor C to enter a second batch of copper sulfate dissolving operation, drying copper sulfate crystals and weighing.
(3) Treating a second batch of material
1) Acid leaching for the first time: under normal pressure, dilute sulfuric acid is supplemented into the crystallization mother liquor A of ferrous sulfate heptahydrate generated in the first batch of raw material treatment, the volume is adjusted to about 300L, the concentration of the sulfuric acid is adjusted to about 70g/L, the temperature is kept at 50-60 ℃, 100kg of pretreated waste diamond tool bit raw material is added, ferric hydroxide generated before the second crystallization of blue vitriol is added, and other operations and processes are the same as those of the first batch of raw material.
2) Preparing a ferrous sulfate heptahydrate product: the process is the same as that for the first batch of raw materials, and the crystallization mother liquor A with the ion concentration which does not meet the requirement is used for the first acid leaching operation of the third batch of raw materials.
3) Preparation of copper sulfide: adding sodium hydroxide solution into the crystallization mother liquor A of ferrous sulfate heptahydrate to adjust the pH value to about 2, then adding sodium sulfide solution until no precipitate is generated, filtering to realize solid-liquid separation, drying copper sulfide and weighing.
4) Preparation of zinc carbonate: adding lime milk into the filtrate C after the copper sulfide preparation, adjusting the pH value to about 2.8, filtering, performing three-stage back extraction of zinc ions on the filtrate by using P204 resin, controlling the concentration of back extraction acid to be about 6%, adding sodium carbonate into the back extraction zinc solution until no precipitate is generated, filtering to realize solid-liquid separation, drying zinc carbonate, and weighing.
5) Preparing cobalt carbonate: adding lime milk into the zinc extraction residual liquid to adjust the pH value to about 4.5, filtering, performing three-stage back extraction of cobalt ions on the filtrate by using P507 resin, controlling the concentration of back extraction acid to about 6%, adding sodium carbonate into the back extraction cobalt solution until no precipitate is generated, generating cobalt carbonate precipitate, filtering to realize solid-liquid separation, drying the cobalt carbonate, and weighing.
6) Preparation of nickel sulfide: and adding a sodium sulfide solution into the cobalt extraction residual liquid until no precipitate is generated, generating a nickel sulfide precipitate, filtering to realize solid-liquid separation, drying the nickel sulfide, and weighing. .
7) Acid leaching for the second time: under normal pressure, dilute sulfuric acid is supplemented into mother liquor B of first copper sulfate crystallization generated in first raw material treatment, the volume is adjusted to be about 40L, the sulfuric acid concentration is adjusted to be about 150g/L, the temperature is kept at 70-75 ℃, and other operations and processes are the same as those of the first raw material.
8) Separation of diamond and tungsten carbide: the process was the same as for the first batch, diamond and tungsten carbide were cleaned, oven dried and weighed.
9) Preparation of blue vitriol: the process is the same as that of the first batch of raw materials, the first crystallization mother liquor B enters the second acid leaching operation of the third batch of raw materials, the second crystallization mother liquor C enters the third copper sulfate dissolving operation, and the ferric hydroxide enters the first acid leaching operation of the third batch of raw materials.
(4) The steps of processing the first batch of material and the second batch of material are repeated until the process is in equilibrium. The recovery of several valuable substances was calculated and the test results are shown in table 2.
TABLE 2 semi-Industrial test indexes
The test results show that the process has excellent recovery effect on diamond, tungsten carbide, copper and iron, and also has better recovery effect on zinc, cobalt, nickel and tin.
Example 3:
and (3) industrial test:
the industrial test was carried out using 10 tons of waste diamond segments as raw materials, the contents of main valuable substances in the raw materials are shown in table 3 below, and the test results are shown in table 4 below.
TABLE 3 content of main valuable substances in the raw material of the waste diamond segments for industrial test
| Components | Fe | Cu | Ni | Co | Zn | Diamond | Tungsten carbide | Mn | Cr | Sn | Others |
| Content/% | 35.71 | 38.52 | 2.86 | 0.01 | 4.56 | 2.93 | 13.48 | 0.33 | 0.02 | 1.27 | 0.31 |
TABLE 4 Industrial test indices
The industrial test result shows that the method is successfully industrialized, the result similar to that of a semi-industrial test is obtained, and the process can efficiently recover the main valuable substances in the waste diamond tool bit raw materials.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. A method for recovering multiple valuable substances from waste diamond tool bit raw materials is characterized by comprising the following steps:
s1, raw material pretreatment: pretreating the waste diamond tool bit raw material by using a sodium hydroxide solution with the concentration of 50 g/L;
s2, primary acid leaching: performing primary acid leaching on the raw material treated in the step S1 to dissolve relatively easily soluble metals including iron, nickel, cobalt, zinc and chromium into a liquid phase, wherein the liquid-solid mass ratio is 2.5-3: 1, the initial sulfuric acid concentration is 60-80 g/L, and the reaction is performed at the temperature of 50-60 ℃ and under normal pressure;
s3, preparing a ferrous sulfate heptahydrate product: when the concentration of the ferrous ions in the leachate A obtained in the step S2 is not increased any more, filtering the leachate A to obtain a filtrate A and filter residues, wherein the filter residues return to the step S2, and the filtrate A is subjected to a crystallization process of ferrous sulfate heptahydrate to prepare a ferrous sulfate heptahydrate product;
s4, preparation of copper sulfide: when the ion concentration of zinc, cobalt and nickel in the crystallization mother liquor A of S3 reaches the recoverable concentration of zinc, cobalt and nickel, the crystallization mother liquor A of S3 enters copper sulfide preparation operation, sodium hydroxide solution is added to adjust the pH value to 2, then sodium sulfide solution is added, polyacrylamide is added for precipitation, and filtration is carried out to obtain a copper sulfide product and filtrate B;
when the ion concentration of zinc, cobalt and nickel in the crystallization mother liquor A of S3 does not reach the recoverable concentration of zinc, cobalt and nickel, the crystallization mother liquor A of S3 returns to S2;
s5, preparation of zinc carbonate: adding lime milk into the filtrate B of S4, adjusting pH to 2.8, precipitating and filtering to obtain filtrate C and gypsum, performing three-stage back extraction on zinc ions in the filtrate C by using P204 resin, controlling the concentration of back extraction acid to be 6 percent, obtaining a back extraction zinc solution and a zinc extraction raffinate with higher concentration, adding sodium carbonate into the back extraction zinc solution, precipitating and filtering to obtain a zinc carbonate product and a waste liquid B;
s6, preparing cobalt carbonate: adding lime milk into the zinc extraction residual liquid of S5, adjusting pH to 4.5, precipitating and filtering to obtain filtrate D and gypsum, carrying out three-stage back extraction on cobalt ions by using P507 resin on the filtrate D, controlling the concentration of back extraction acid to be 6 percent to obtain a back extraction cobalt solution and a cobalt extraction residual liquid with higher concentration, adding sodium carbonate into the back extraction cobalt solution, precipitating and filtering to obtain a cobalt carbonate product and a waste liquid D;
s7, preparation of nickel sulfide: adding a sodium sulfide solution into the cobalt extraction raffinate in the S6, adding polyacrylamide for precipitation, and filtering to obtain a nickel sulfide product and a waste liquid C;
s8, secondary acid leaching: performing secondary acid leaching on the residue A in the S2, wherein the liquid-solid mass ratio is 3.5-4: 1, the initial sulfuric acid concentration is 150-200 g/L, the reaction is performed at 70-75 ℃ and normal pressure, and air, hot steam and hydrogen peroxide are introduced into the solution through a nano cavitation device in the acid leaching process to enhance the oxidation leaching of copper;
s9, separation of diamond and tungsten carbide: screening and grading the residue B generated in the step S8 to effectively separate diamond and tungsten carbide;
s10, preparation of tin mud: when the concentration of copper ions in the leaching solution B obtained in the step S8 is not increased any more, filtering the leaching solution B to obtain a filtrate E and tin mud, and feeding the tin mud into a filter cake;
s11, preparation of crude copper sulfate pentahydrate: carrying out primary cooling crystallization on the filtrate E of the S10 to prepare a crude copper sulfate pentahydrate product, and returning a copper sulfate primary crystallization mother liquor B to the S8;
s12, copper sulfate secondary crystallization: dissolving the crude copper sulfate pentahydrate of S11, adding hydrogen peroxide, adjusting the pH value of the solution to 3-4 by using sodium hydroxide to enable impurity ions such as iron ions to generate precipitates, filtering, performing copper sulfate secondary crystallization on the filtrate to form copper sulfate pentahydrate, returning copper sulfate secondary crystallization mother liquor C to S12 for dissolving the crude copper sulfate pentahydrate, and returning iron hydroxide filter residue to S2;
s13, treating three wastes: the three wastes generated by the process are treated to ensure that the three wastes meet the environmental protection requirement, the waste gas is treated by alkali liquor, the supernatant fluid after the waste water is precipitated can be directly recycled, and the waste residues can be used as the raw materials of a cement plant.
2. The method for recovering multiple valuable substances from the waste diamond tool bit raw material as claimed in claim 1, wherein in S2, the sulfuric acid concentration and the ferrous ion concentration are tested continuously in the reaction process, when the ferrous ion concentration in the solution is lower than 130g/L, the sulfuric acid concentration is ensured to be stabilized at 50-60 g/L, and when the ferrous ion concentration is higher than 130g/L, the acid addition is stopped.
3. The method for recovering a plurality of valuable substances from waste diamond tool bit raw materials according to claim 1, wherein in S8, the concentration of sulfuric acid and the concentration of copper ions are continuously tested in the reaction process, when the concentration of copper ions in the solution is lower than 80g/L, the concentration of sulfuric acid is ensured to be stabilized at 90-120 g/L, when the concentration of copper ions is higher than 80g/L, the acid addition is stopped, the temperature is increased to 85-90 ℃, and the residual acid in the solution continues to react.
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| CN114686696A (en) * | 2022-04-08 | 2022-07-01 | 万载志成实业有限公司 | Circulating copper recovery method based on waste diamond tool bits |
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Denomination of invention: A method for recovering various valuable substances from waste diamond blade raw materials Granted publication date: 20210105 Pledgee: Jiangxi State-owned Venture Capital Management Co.,Ltd. Pledgor: JIANGXI YIYUAN RENEWABLE RESOURCES Co.,Ltd. Registration number: Y2024980004238 |