CN110066918A - A kind of system and method for solution of zinc sulfate advanced treating - Google Patents
A kind of system and method for solution of zinc sulfate advanced treating Download PDFInfo
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- CN110066918A CN110066918A CN201811230327.2A CN201811230327A CN110066918A CN 110066918 A CN110066918 A CN 110066918A CN 201811230327 A CN201811230327 A CN 201811230327A CN 110066918 A CN110066918 A CN 110066918A
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 title claims abstract description 64
- 229910000368 zinc sulfate Inorganic materials 0.000 title claims abstract description 60
- 229960001763 zinc sulfate Drugs 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000000746 purification Methods 0.000 claims abstract description 325
- 239000007788 liquid Substances 0.000 claims abstract description 117
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 41
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000003825 pressing Methods 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 19
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 17
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 238000005352 clarification Methods 0.000 claims abstract description 8
- 239000005416 organic matter Substances 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 230000002000 scavenging effect Effects 0.000 claims description 49
- 235000013495 cobalt Nutrition 0.000 claims description 39
- 229910017052 cobalt Inorganic materials 0.000 claims description 36
- 239000010941 cobalt Substances 0.000 claims description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 36
- 239000002893 slag Substances 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 30
- 229910052793 cadmium Inorganic materials 0.000 claims description 20
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 17
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 15
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010802 sludge Substances 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- -1 copper cadmium cobalt silicon Chemical compound 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000009491 slugging Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 230000003196 chaotropic effect Effects 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 131
- 239000004615 ingredient Substances 0.000 description 13
- 230000005574 cross-species transmission Effects 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 7
- 239000001263 FEMA 3042 Substances 0.000 description 7
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 7
- 229940033123 tannic acid Drugs 0.000 description 7
- 235000015523 tannic acid Nutrition 0.000 description 7
- 229920002258 tannic acid Polymers 0.000 description 7
- 229910017518 Cu Zn Inorganic materials 0.000 description 6
- 229910017752 Cu-Zn Inorganic materials 0.000 description 6
- 229910017943 Cu—Zn Inorganic materials 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 229910017816 Cu—Co Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011686 zinc sulphate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000009858 zinc metallurgy Methods 0.000 description 3
- 241000271510 Agkistrodon contortrix Species 0.000 description 2
- 229910020521 Co—Zn Inorganic materials 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910003641 H2SiO3 Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- JHXCINJSAAFBDH-UHFFFAOYSA-N [Ca].O[Si](O)(O)O Chemical group [Ca].O[Si](O)(O)O JHXCINJSAAFBDH-UHFFFAOYSA-N 0.000 description 1
- ZLHNFTFSANKMSR-UHFFFAOYSA-N [Ge].[Mg] Chemical compound [Ge].[Mg] ZLHNFTFSANKMSR-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- 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
- C22B3/02—Apparatus therefor
-
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses liquid circulating slot, concentrator, clarification overflow launder, thickened underflow filter press, zinc powder feeder, milk of lime head tank, antimonic salt head tank, copper sulphate head tank, heavy germanium agent head tanks, active carbon storehouse, flocculant head tank after a kind of system of solution of zinc sulfate advanced treating, including one section of purification tank, one section of purification filter press, two sections of purification tanks, two sections of purification filter presses, three sections of purification tanks, three sections of purification filter presses, three sections of filters pressings.The invention also discloses a kind of method of solution of zinc sulfate advanced treating, including one section of high temperature purification, two sections of high temperature purifications and three sections of purifications；This method advantageously reduces zinc powder consumption, while can remove unconventional elements Si, As, Sb, Ge deep removal and organic matter, and calcium and magnesium crystal realizes the deep purifying for being removed in depth, and then realizing solution of zinc sulfate, and zinc electrolysis direct current consumption is effectively reduced.
Description
Technical field:
The present invention relates to a kind of system and method for solution of zinc sulfate advanced treating, belong to zinc field of metallurgy.
Background technique:
Increasingly deficient with mineral resources, in zinc hydrometallurgy enterprise, zinc metallurgy raw material is increasingly insufficient, grade compared with
It is low, and the total association zinc ore for being associated with the unconventional element such as copper, cadmium, cobalt and organic matter, silicon, arsenic, antimony, germanium also has to by conduct
Zinc metallurgy feedstock processing；For zinc metallurgy raw material mostly with wet-treating, i.e. two sections of pressurized acid leaching technologies, the solution of zinc sulfate ingredient after leaching is multiple
Miscellaneous, the impurity such as cobalt especially difficult to deal with, antimony, with the increase of zinc sulfide concentrates treating capacity, zinc sulfide concentrates leachate is miscellaneous
Matter increases, and can have different degrees of impurities accumulation in wet method system solution of zinc sulfate, with the enrichment of impurity, will cause electricity
Zinc quality decline is solved, so having to pass through net liquid technique is just able to satisfy subsequent electrolysis requirement.
Net liquid technique shows process flow using three sections of purifications, i.e. first segment low temperature zinc powder copper removal, cadmium, second segment zinc
Powder, antimonic salt high temperature remove cobalt, and third section removes residual cadmium with zinc powder.Conventional purification process process, production process cobalt are easy to redissolve, zinc
Powder, antimonic salt consumption are big, and liquid is poor on limpid degree and transparency after the purification of this process output, contain a large amount of cream
The sediment of white, this sediment are crystallization, silicon, arsenic, antimony, germanium and the organic reducing object of the unconventional impurity calcium and magnesium in part in solution
Adsorption precipitation object can not well be efficiently separated sediment and precipitate, solution is clear even if being settled using concentrator
Brightness and transparency are bad containing the excessively high quality requirement for not being able to satisfy long period electrolytic solution of unconventional impurity element.
Summary of the invention:
The system that of the invention first is designed to provide a kind of solution of zinc sulfate advanced treating.
The first purpose of this invention is implemented by following technical solution: a kind of system of solution of zinc sulfate advanced treating, packet
Include one section of purification tank, one section of purification filter press, two sections of purification tanks, two sections of purification filter presses, three sections of purification tanks, three sections of purification filters pressings
Liquid circulating slot, concentrator, clarification overflow launder, thickened underflow filter press, zinc powder feeder, milk of lime are high-order after machine, three sections of filters pressings
Slot, antimonic salt head tank, copper sulphate head tank, heavy germanium agent head tank, active carbon storehouse, flocculant head tank；
The liquid outlet of one section of purification tank is connected to the inlet of one section of purification filter press, one section of purification pressure
The liquid outlet of filter is connected to the inlet of two sections of purification tanks, the liquid outlet of two sections of purification tanks and described two sections purifications
The inlet of filter press is connected to, and the liquid outlet of two sections of purification filter presses is connected to the inlet of three sections of purification tanks, institute
The liquid outlet for stating three sections of purification tanks is connected to the inlet of three sections of purification filter presses, and three sections of purification filter presses go out liquid
Mouthful be connected to the inlet of liquid circulating slot after three sections of filters pressings, after three sections of filters pressings the liquid outlet of liquid circulating slot with it is described dense
The inlet of close machine is connected to, and the overflow outlet of the concentrator is connected to the inlet of the clarification overflow launder, the concentrator
Underflow outlet be connected to the feed inlet of the thickened underflow filter press, the liquid outlet of the thickened underflow filter press and described three
The inlet connection of liquid circulating slot, the sludge outlet of the thickened underflow filter press are connected to filter residue processing unit after section filters pressing；
The inlet of one section of purification tank is also high with the zinc powder feeder, the milk of lime head tank, the antimonic salt
Position slot is connected to the copper sulphate head tank；The inlet of two sections of purification tanks also with the zinc powder feeder, the antimonic salt
Head tank is connected to the copper sulphate head tank；The inlet of two sections of purification tanks also with the zinc powder feeder and described heavy
The connection of germanium agent head tank；The inlet of liquid circulating slot is also connected to the inlet of flocculant head tank after three sections of filters pressings.
It further, further include one section of purification medial launder；The liquid outlet of one section of purification tank and described one section purification
The inlet of medial launder is connected to, and the liquid outlet of one section of purification medial launder and the inlet of one section of purification filter press connect
Logical, the inlet that the muddy liquid outlet of the race of one section of purification filter press purifies medial launder with described one section is connected to.
It further, further include two sections of purification medial launders, the liquid outlet of two sections of purification tanks and described two sections purifications
The inlet of medial launder is connected to, and the liquid outlet of two sections of purifications medial launder and the inlet of two sections of purification filter presses connect
Logical, the inlet that the muddy liquid outlet of the race of two sections of purification filter presses purifies medial launder with described two sections is connected to.
It further, further include three sections of purification medial launders, the liquid outlet of three sections of purification tanks and described three sections purifications
The inlet of medial launder is connected to, and the liquid outlet of three sections of purifications medial launder and the inlet of three sections of purification filter presses connect
Logical, the inlet that the muddy liquid outlet of the race of three sections of purification filter presses purifies medial launder with described three sections is connected to.
Further, further include one section of purification slag slurrying tank, the feed inlet of one section of purification slag slurrying tank with it is described
The sludge outlet connection of one section of purification filter press, the discharge port and the filter residue processing unit of one section of purification slag slurrying tank connect
It is logical.
Further, further include two sections of purification slag slurrying tanks, the feed inlet of two sections of purification slag slurrying tanks with it is described
The sludge outlet connection of two sections of purification filter presses, the discharge port and the filter residue processing unit of two sections of purification slag slurrying tanks connect
It is logical.
Further, further include three sections of purification slag slurrying tanks, the feed inlet of three sections of purification slag slurrying tanks with it is described
The sludge outlet connection of three sections of purification filter presses, the discharge port and the filter residue processing unit of three sections of purification slag slurrying tanks connect
It is logical.
A kind of method that of the invention second is designed to provide solution of zinc sulfate advanced treating.
Second object of the present invention is implemented by following technical solution: the solution of zinc sulfate that is obtained after acidleach be added zinc powder and
One section of high temperature purification removing copper of antimonic salt, cadmium, cobalt and silicon, separation of solid and liquid obtain one section of scavenging solution and copper cadmium cobalt silicon slag；Then adjust
After one section of scavenging solution pH value, two sections of zinc powder, antimonic salt and copper sulphate high temperature purifications removing cobalts is added, separation of solid and liquid obtains two sections
Scavenging solution and cobalt slag, addition zinc powder inhibits cobalt to return molten in two sections of scavenging solutions；Finally in three sections of purifications, described two sections net
Change addition zinc powder in liquid and remove residual Cd, organic matter is adsorbed in active carbon and heavy germanium agent and germanium, antimony, arsenic are separating after being separated by solid-liquid separation
Flocculant removing suspended matter and calcium and magnesium crystal are added in liquid, obtains three sections of scavenging solutions and thickened underflow after being separated by solid-liquid separation again.
In one section of high temperature purification: zinc powder being added in the solution of zinc sulfate obtained after acidleach, (antimonic salt main component is antimonic salt
K(SbO)C4H4O6) and calcium hydroxide, 1-2h is reacted in the case where 80-85 DEG C of temperature, stirring intensity are 1000-1500r/min,
Cu, Cd, Co are removed with simple substance form, are separated by solid-liquid separation and are obtained one section of scavenging solution and copper cadmium cobalt silicon slag, in one section of scavenging solution,
Cu≤0.5mg/l, Cd≤30mg/l, Co≤5mg/l, Si≤20mg/l；Cu, Cd, Co stay in one section of purification slag with simple substance form
In, Si is stayed in one section of purification slag with silicic acid calcium form, and reaction equation is as follows:
Zn+CuSO4=Cu+ZnSO4 [1]
Zn+CdSO4=Cd+ZnSO4 [2]
Zn+CoSO4=Co+ZnSO4 [3]
Ca(OH)2+H2SiO3=CaSiO3+2H2O [4]
In conjunction with the content of Cu, Cd, Co in solution of zinc sulfate, the additional amount of auxiliary material determines as follows
The zinc powder amount of being actually added into is copper and cadmium theory consumes the theoretical consumption zinc powder amount that zinc powder amount adds 98 times of cobalt；
The antimonic salt amount of being actually added into accounts for 0.6 times of determination of cobalt element quality according to antimony element quality；
The amount of the theoretical consumption calcium hydroxide for the silicon that calcium hydroxide additional amount is 2 times.
The effect of antimonic salt: copper ion and zinc powder in solution act on, and first in zinc powder copper-depositing on surface, it is micro- to form Cu-Zn
Battery.Since the potential difference of the potential difference ratio Co-Zn micro cell of the micro cell is big, thus, make Co2+It is easy in Cu-Zn micro cell
It discharges and restores on cathode, form Zn-Cu-Co alloy phase.However, cobalt at this moment is still unstable, easily redissolve, when antimonic salt is added,
Sb3+Also it is restored on Cu-Zn micro cell, forms stable Sb-Cu-Co, so that the cobalt in solution be removed.
In two sections of high temperature purifications, one section of scavenging solution is adjusted by the way that waste electrolyte is added in one section of scavenging solution
PH to 4.3-4.5 is then successively continuously added to zinc powder, antimonic salt and copper sulphate, in 85-90 DEG C of temperature, stirring intensity 1000-
2-2.5h is reacted in the case where 1500r/min, is separated by solid-liquid separation and is obtained two sections of scavenging solutions and cobalt slag, in two sections of scavenging solutions, Co
≤1.0mg/l；Its reaction equation is as follows:
Zn+CoSO4=Co+ZnSO4 [5]
In conjunction with the content of Co in one section of scavenging solution, control required in pH value of solution 4.3-4.5 and two sections of scavenging solutions Co≤
The additional amount of 1.0mg/l, two sections of purification process auxiliary materials are added according to following formula:
The theoretical consumption zinc powder amount for the cobalt that the zinc powder amount of being actually added into is 800 times；
The antimonic salt amount of being actually added into accounts for 0.6 times of determination of cobalt element quality according to antimony element quality；
The cobalt content (quality of cobalt) that the copper sulphate amount of being actually added into is 0.5 times, copper sulphate are except one of cobalt process is urged
Agent is conducive to Cobalt Purification reaction after copper sulphate is added.
The effect of copper sulphate and antimonic salt: copper sulphate and zinc powder act on, and first in zinc powder copper-depositing on surface, it is micro- to form Cu-Zn
Battery.Since the potential difference of the potential difference ratio Co-Zn micro cell of the micro cell is big, thus, make Co2+It is easy in Cu-Zn micro cell
It discharges and restores on cathode, form Zn-Cu-Co alloy phase.However, cobalt at this moment is still unstable, easily redissolve, when antimonic salt is added,
Sb3+Also it is restored on Cu-Zn micro cell, forms stable Sb-Cu-Co, so that the cobalt in solution be removed.
In three sections of purifications: being successively continuously added to zinc powder, active carbon, heavy germanium agent in two sections of scavenging solutions, flocculant can
To select gelatin, the addition of heavy germanium agent can effectively remove arsenic, germanium and antimony in solution of zinc sulfate, in 70-75 DEG C of temperature, stirring
After intensity reacts 1.5-2h in the case where being 1000-1500r/min, solution squeezes into three sections of purification filter presses and carries out filters pressing, filters pressing
Liquid enters concentrator afterwards, and flocculant is added with the speed of 0.4kg/h and carries out flocculation sedimentation, flocculant can select gelatin, obtain
Three sections of scavenging solutions and thickened underflow, the addition of gelatin are conducive to the clarification of liquid after purification and are conducive to the flocculation of calcium and magnesium germanium sediment
Precipitating controls in three sections of scavenging solutions, Cd≤1.0mg/l, Sb≤0.02mg/ for the removal for returning molten and residual cadmium for preventing cobalt
L, As≤0.01mg/L, Ge≤0.05mg/l, TOC≤140mg/l；Three sections of purification auxiliary materials are added according to following amount
The zinc powder amount of being actually added into is the theoretical amount of the zinc consumption of 1.5 times of removing cadmiums；
The active carbon amount of being actually added into is the theoretical amount of the active carbon consumption of 20 times of removing TOC；
Heavy germanium agent is the theoretical amount of the 25-30 times of heavy germanium agent of consumption for removing germanium, arsenic, antimony；
Heavy germanium agent is the heavy germanium agent of tannic acid, and active chemical is tannic acid C76H52O46., it is a kind of organic compound.
Its mechanism of action are as follows: tannic acid will be added in solution of zinc sulfate and sink after germanium agent, tannic acid sink germanium in germanium agent and solution, arsenic, antimony,
The foreign ions such as iron form a complicated complexing macromolecular colloid sediment, and then realize germanium, arsenic, antimony etc. in solution of zinc sulfate
The removing of impurity.
The additional amount of flocculant according to flocculant quality (kg): liquor capacity (m3)=0.0025:1 is determined.
Advantages of the present invention: zinc powder consumption is advantageously reduced using this system advanced treating solution of zinc sulfate, while can
Unconventional elements Si, As, Sb, Ge are removed in depth and organic matter removing, calcium and magnesium crystal realize deep removal, and then realization sulphur
Zinc electrolysis direct current consumption is effectively reduced in the deep purifying of sour zinc solution.
The solution of zinc sulfate of a kind of solution of zinc sulfate deep treatment method of the present invention, zinc wet smelting process output passes through two
Section high temperature purification is removed copper, cadmium, cobalt, silicon using zinc powder, antimonic salt, wherein lime stone removing solution is added in liquid after one section of filters pressing
In silicon, fill into a small amount of waste electrolyte before two sections of purifications, inhibit Cadmium resolution, liquid adds a small amount of zinc powder after two sections, inhibits answering for cobalt
Molten, three sections of low temperature purifications realize the removing of organic matter and germanium, arsenic, antimony using zinc powder+active carbon+heavy germanium agent, wherein three sections of zinc powders
Antimony and residual cadmium are effectively removed, such method is not only able to the impurity of efficient removal solution of zinc sulfate, the redissolution of cobalt, cadmium is reduced, and
And the consumption of zinc powder, antimonic salt is few, the suspended matter and colloid in the addition of lime stone effectively absorption solution of zinc sulfate form co-precipitation
Removing, active carbon, heavy germanium agent additions ensure that taking off for the unconventional element such as organic matter in solution of zinc sulfate, silicon, arsenic, antimony, germanium
It removes, clear and transparent solution can be obtained, meet big pole plate electrolytic solution requirement, be conducive to that zinc current power consumption is greatly lowered.
Detailed description of the invention:
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is a kind of schematic diagram of the system of the solution of zinc sulfate advanced treating of embodiment 1.
In figure: one section of purification tank, 1, one section of purification 2, one sections of medial launder, 3, one sections of purification filter press purification slag slurrying tank 4, two
Section 5, two sections of purification 6, two sections of medial launder, 7, two sections of purification filter press, 8, three sections of purification slag slurrying tank, 9, three sections of purification tanks of purification tank
Liquid circulating slot 13, concentrator after purification 10, three sections of medial launder, 11, three sections of purification filter press, 12, three sections of filters pressings of purification slag slurrying tank
14, overflow launder 15, thickened underflow filter press 16, zinc powder feeder 17, milk of lime head tank 18, antimonic salt head tank 19, sulphur are clarified
Sour copper head tank 20, heavy germanium agent head tank 21, active carbon storehouse 22, flocculant head tank 23.
Specific embodiment:
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without creative efforts belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of system of solution of zinc sulfate advanced treating, including one section of 1, one section of purification tank, 2, one sections of medial launder of purification purification
3, one sections of filter press, 4, two sections of purification slag slurrying tank, 5, two sections of purification tank, 6, two sections of medial launder of purification, 7, two sections of purification filter press is net
8, three sections of slugging slurrying tank, 9, three sections of purification tank purification 10, three sections of medial launder, 11, three sections of purification filter press purification slag slurrying tank 12,
Liquid circulating slot 13, concentrator 14, clarification overflow launder 15, thickened underflow filter press 16, zinc powder feeder 17, lime after three sections of filters pressings
Newborn head tank 18, antimonic salt head tank 19, copper sulphate head tank 20, heavy germanium agent head tank 21, active carbon storehouse 22, flocculant head tank
23；
One section of purification tank, 1, two section of purification tank 5 and three sections of purification tanks 9 can be multistage purification slot；
The liquid outlet of one section of purification tank 1 is connected to the inlet of one section of purification filter press 3, and one section of purification filter press 3 goes out
Liquid mouth is connected to the inlet of two sections of purification tanks 5, and the inlet of the liquid outlet of two sections of purification tanks 5 and two sections of purification filter presses 7 connects
Logical, the liquid outlet of two sections of purification filter presses 7 is connected to the inlet of three sections of purification tanks 9, the liquid outlet of three sections of purification tanks 9 and three sections
The inlet connection of filter press 11 is purified, the feed liquor of liquid circulating slot 13 after the liquid outlet of three sections of purification filter presses 11 and three sections of filters pressings
Mouth connection, the liquid outlet of liquid circulating slot 13 is connected to the inlet of concentrator 14 after three sections of filters pressings, the overflow outlet of concentrator 14
It being connected to the inlet of clarification overflow launder 15, the underflow outlet of concentrator 14 is connected to the feed inlet of thickened underflow filter press 16,
The liquid outlet of thickened underflow filter press 16 is connected to the inlet of liquid circulating slot 13 after three sections of filters pressings, thickened underflow filter press 16
Sludge outlet is connected to filter residue processing unit；
The inlet of one section of purification tank 1 also with zinc powder feeder 17, milk of lime head tank 18, antimonic salt head tank 19 and sulfuric acid
Copper head tank 20 is connected to；The inlet of two sections of purification tanks 5 also with zinc powder feeder 17, antimonic salt head tank 19 and copper sulphate head tank
20 connections；The inlet of two sections of purification tanks 5 is also connected to zinc powder feeder 17 and heavy germanium agent head tank 21；Liquid follows after three sections of filters pressings
The inlet of annular groove 13 is also connected to the inlet of flocculant head tank 23.
The inlet that the liquid outlet of one section of purification tank 1 purifies medial launder 2 with one section is connected to, and one section purifies going out for medial launder 2
Liquid mouth is connected to the inlet of one section of purification filter press 3, and the race of one section of purification filter press 3 mixes liquid outlet and one section of purification medial launder
2 inlet connection.
The inlet that the liquid outlet of two sections of purification tanks 5 purifies medial launder 6 with two sections is connected to, and two sections purify going out for medial launder 6
Liquid mouth is connected to the inlet of two sections of purification filter presses 7, and the race of two sections of purification filter presses 7 mixes liquid outlet and two sections of purification medial launders
6 inlet connection.
The inlet that the liquid outlet of three sections of purification tanks 9 purifies medial launder 10 with three sections is connected to, and three sections purify medial launder 10
Liquid outlet is connected to the inlet of three sections of purification filter presses 11, and the race of three sections of purification filter presses 11 mixes in liquid outlet and three sections of purifications
Between slot 10 inlet connection.
The feed inlet of one section of purification slag slurrying tank 4 is connected to the sludge outlet of one section of purification filter press 3, one section of purification slurry
The discharge port for changing slot 4 is connected to filter residue processing unit.
The feed inlet of two sections of purification slag slurrying tanks 8 is connected to the sludge outlet of two sections of purification filter presses 7, two sections of purification slurries
The discharge port for changing slot 8 is connected to filter residue processing unit.
The feed inlet of three sections of purification slag slurrying tanks 12 is connected to the sludge outlet of three sections of purification filter presses 11, three sections of purification slags
The discharge port of slurrying tank 12 is connected to filter residue processing unit.
Embodiment 2:
Advanced treating is carried out to solution of zinc sulfate using system described in embodiment 1, wherein the impurity in solution of zinc sulfate
Including Cu 273.84mg/l, Cd 412.7mg/l, Co 12.79mg/l, Si 31.38mg/l, Ge 0.08mg/l, As
0.1mg/l, TOC 158.3mg/l.
Solution of zinc sulfate pump is squeezed into one section of purification tank 1, flow 110.6m3The volume of/h, one section of purification tank 1 is
166m3, spill-over stream on one section of purification tank 1, therefore the solution purification time is 1.5h, one section of purification temperature control is to 80 DEG C, stirring
Speed is 1500r/min, is successively continuously added to zinc powder according to 210kg/h, is continuously added to antimonic salt according to 0.85kg/h, according to
Calcium hydroxide is continuously added to by 8kg/h, and solution continuous overflow flows into one section of purification medial launder 2 through chute after purification, then by one section
One section of purified solution squeezes into one section of purification filter press 3 and carries out one section of purification filters pressing in purification medial launder 2, and one section of scavenging solution flows into one
Liquid storage tank after section purification；Waste electrolyte is added simultaneously, it is ensured that one section of scavenging solution pH=4.3-4.5.
One section of scavenging solution ingredient: Cu 0mg/l, Cd 12.88mg/l, Co 4.5mg/l, Si 18mg/l.
One section of scavenging solution pump is squeezed into two sections of purification tanks 5, flow 83m3The volume of/h, two sections of purification tanks 5 is
166m3, spill-over stream on two sections of purification tanks 5, therefore the solution purification time is 2h, two sections of purification temperatures controls are to 85 DEG C, stirring speed
Degree is 1500r/min, is continuously added to zinc powder according to 329kg/h into solution, is continuously added to antimonic salt according to 0.38kg/h, according to
1.66kg/h is continuously added to copper sulphate, and solution continuous overflow flows into two sections of purification medial launders 6 through chute after two sections of purifications, by two sections
Purification 6 two sections of purified solutions of medial launder are pumped into two sections of purification filter presses 7 and carry out two sections of purification filters pressings, and two sections of scavenging solutions flow into two sections
Liquid storage tank after purification.
Two sections of scavenging solution ingredients: Co 0.5mg/l, Cu 0mg/l, Cd 12mg/l, Si 18mg/l, Ge 0.08mg/l, As
0.1mg/l, Sb 0.06mg/l, TOC 158.3mg/l.
Two sections of purification liquid pumps squeeze into three sections of purification tanks 9, pump discharge 110.6m3/ h, the body of three sections of purification tanks 9 are 166m3,
Spill-over stream on three sections of purification tanks 9, therefore the solution purification time is 1.5h, three sections of purification temperature controls are to 70 DEG C, mixing speed
1500r/min is continuously added to zinc powder according to 25kg/h into three sections of 9 solution of purification tank, is continuously added to active carbon according to 20kg/h,
It is continuously added to the heavy germanium agent of tannic acid according to 15kg/h, continuous overflow flows into three sections of purification medial launders 10 through chute after solution reaction,
Then three sections of purification 10 solution of medial launder are squeezed into three sections of purification filter presses 11 and carries out three sections of purification filters pressings, liquid stream enters dense after filters pressing
Close machine 14, gelatin are continuously added in concentrator 14 according to 0.4kg/h, and concentrator supernatant is three sections of scavenging solutions, are supplied as new liquid
It is used to subsequent processing-electrolysis.
Three sections of scavenging solution ingredients: Cd 0.7mg/l, Cu 0mg/l, Co 0.45mg/l, Si 18mg/l, As 0.01mg/l,
Ge 0.05mg/l, Sb 0.02mg/l, TOC 110mg/l.
Embodiment 3:
Advanced treating is carried out to solution of zinc sulfate using system described in embodiment 1, wherein the impurity in solution of zinc sulfate
Including Cu 273.84mg/l, Cd 412.7mg/l, Co 12.79mg/l, Si 31.38mg/l, Ge 0.08mg/l, As
0.1mg/l, TOC 158.3mg/l.
Solution of zinc sulfate pump is squeezed into one section of purification tank 1, flow 83m3The volume of/h, one section of purification tank 1 is
166m3, spill-over stream on one section of purification tank 1, therefore the solution purification time is 2h, one section of purification temperature control is to 85 DEG C, stirring speed
Degree is 1500r/min, is successively continuously added to zinc powder according to 158kg/h, is continuously added to antimonic salt according to 0.64kg/h, according to
Calcium hydroxide is continuously added to by 6kg/h, and solution continuous overflow flows into one section of purification medial launder 2 through chute after purification, then by one section
One section of purified solution squeezes into one section of purification filter press 3 and carries out one section of purification filters pressing in purification medial launder 2, and one section of scavenging solution flows into one
Liquid storage tank after section purification；Waste electrolyte is added simultaneously, it is ensured that one section of scavenging solution pH=4.3-4.5.
One section of scavenging solution ingredient: Cu 0mg/l, Cd 30mg/l, Co 4.8mg/l, Si 20mg/l.
One section of scavenging solution pump is squeezed into two sections of purification tanks 5, flow 66.4m3The volume of/h, two sections of purification tanks 5 is
166m3, spill-over stream on two sections of purification tanks 5, therefore the solution purification time is 2.5h, two sections of purification temperatures controls are to 95 DEG C, stirring
Speed is 1500r/min, is continuously added to zinc powder according to 245.8kg/h into solution, is continuously added to antimonic salt according to 0.3kg/h, presses
It is continuously added to copper sulphate according to 1.33kg/h, solution continuous overflow flows into two sections of purification medial launders 6 through chute after two sections of purifications, by two
Section purification 6 two sections of purified solutions of medial launder are pumped into two sections of purification filter presses 7 and carry out two sections of purification filters pressings, and two sections of scavenging solutions flow into two
Liquid storage tank after section purification.
Two sections of scavenging solution ingredients: Co 0.3mg/l, Cu 0mg/l, Cd 28mg/l, Si 20mg/l, Ge 0.08mg/l, As
0.1mg/l, Sb 0.06mg/l, TOC 110mg/l.
Two sections of purification liquid pumps squeeze into three sections of purification tanks 9, pump discharge 83m3/ h, the body of three sections of purification tanks 9 are 166m3, three sections
Spill-over stream on purification tank 9, therefore the solution purification time is 2h, the control of three sections of purification temperatures is to 75 DEG C, mixing speed 1500r/
Min is continuously added to zinc powder according to 18kg/h into three sections of 9 solution of purification tank, is continuously added to active carbon according to 15kg/h, according to
20kg/h is continuously added to the heavy germanium agent of tannic acid, and continuous overflow flows into three sections of purification medial launders 10 through chute after solution reaction, then
Three sections of purification 10 solution of medial launder are squeezed into three sections of purification filter presses 11 and carry out three sections of purification filters pressings, liquid stream enters concentrator after filters pressing
14, gelatin is continuously added in concentrator 14 according to 0.3kg/h, and concentrator supernatant is three sections of scavenging solutions, as under the supply of new liquid
One process-electrolysis uses.
Three sections of scavenging solution ingredients: Cd 0.8mg/l, Cu 0mg/l, Co 0.3mg/l, Si 20mg/l, Ge 0.04mg/l,
Sb 0.01mg/l, As 0.01mg/l, TOC 90mg/l.
Embodiment 4:
Advanced treating is carried out to solution of zinc sulfate using system described in embodiment 1, wherein the impurity in solution of zinc sulfate
Including Cu 273.84mg/l, Cd 412.7mg/l, Co 12.79mg/l, Si 31.38mg/l, Ge 0.08mg/l, As
0.1mg/l, TOC 158.3mg/l.
Solution of zinc sulfate pump is squeezed into one section of purification tank 1, flow 92.2m3The volume of/h, one section of purification tank 1 is
166m3, spill-over stream on one section of purification tank 1, therefore the solution purification time is 1.8h, one section of purification temperature control is to 83 DEG C, stirring
Speed is 1500r/min, is successively continuously added to zinc powder according to 175kg/h, is continuously added to antimonic salt according to 0.7kg/h, according to
Calcium hydroxide is continuously added to by 6.67kg/h, and solution continuous overflow flows into one section of purification medial launder 2 through chute after purification, then by one
One section of purified solution squeezes into one section of purification filter press 3 and carries out one section of purification filters pressing in section purification medial launder 2, and one section of scavenging solution flows into
Liquid storage tank after one section of purification；Waste electrolyte is added simultaneously, it is ensured that one section of scavenging solution pH=4.3-4.5.
One section of scavenging solution ingredient: Cu 0mg/l, Cd 25mg/l, Co 4.2mg/l, Si 15mg/l.
One section of scavenging solution pump is squeezed into two sections of purification tanks 5, flow 72.1m3The volume of/h, two sections of purification tanks 5 is
166m3, spill-over stream on two sections of purification tanks 5, therefore the solution purification time is 2.3h, two sections of purification temperatures controls are to 92 DEG C, stirring
Speed is 1500r/min, is continuously added to zinc powder according to 266.9kg/h into solution, is continuously added to antimonic salt according to 0.33kg/h, presses
It is continuously added to copper sulphate according to 25kg/h, solution continuous overflow flows into two sections of purification medial launders 6 through chute after two sections of purifications, by two sections
Purification 6 two sections of purified solutions of medial launder are pumped into two sections of purification filter presses 7 and carry out two sections of purification filters pressings, and two sections of scavenging solutions flow into two sections
Liquid storage tank after purification.
Two sections of scavenging solution ingredients: Co 0.8mg/l, Cu 0mg/l, Cd 20mg/l, Si 15mg/l, Ge 0.08mg/l, As
0.1mg/l, TOC 158.3mg/l.
Two sections of purification liquid pumps squeeze into three sections of purification tanks 9, pump discharge 92.2m3/ h, the body of three sections of purification tanks 9 are 166m3, three
Spill-over stream on section purification tank 9, therefore the solution purification time is 1.8h, three sections of purification temperature controls are to 73 DEG C, mixing speed
1500r/min is continuously added to zinc powder according to 20.84kg/h into three sections of 9 solution of purification tank, is continuously added to according to 16.67kg/h
Active carbon is continuously added to the heavy germanium agent of tannic acid according to 25kg/h, and continuous overflow flows into three sections of purifications through chute after solution reaction
Between slot 10, three sections of purification 10 solution of medial launder are then squeezed into three sections of purification filter presses 11 and carry out three sections of purification filters pressings, after filters pressing
Liquid stream enters concentrator 14, and flocculant is continuously added in concentrator 14 according to 0.33kg/h, and concentrator supernatant is three sections of scavenging solutions,
It is used as the supply subsequent processing-electrolysis of new liquid.
Three sections of scavenging solution ingredients: Cu 0mg/l, Cd 0.6mg/l, Co 0.3mg/l, Si 15mg/l, Ge 0.02mg/l,
As 0.0005mg/l、Sb 0.02mg/l、TOC 90mg/l。
Embodiment 5:
Using conventional process solution of zinc sulfate: one section of low temperature (70-75 DEG C) copper removal cadmium, one section of purification control the time
2h, two sections of high temperature purifications remove cobalt nickel (85-90 DEG C), and two sections of purifications control time 3h, three sections (70-75 DEG C) of low temperature except residual cadmium, three
Section purification control time 1.5h.
One section of purification zinc powder is added according to 2.5g/l, and two sections of purification zinc powders are according to 3.5g/l, and two sections of purification antimonic salts are according to Sb:
Co=1: 1 (mass ratio) is added, and copper sulphate is added according to 20mg/l, and three sections of purification zinc powders are added according to 1.5g/l.
Impurity in solution of zinc sulfate includes Cu 273.84mg/l, Cd 412.7mg/l, Co 12.79mg/l, Si
31.38mg/l, Ge 0.08mg/l, As 0.1mg/l, TOC 158.3mg/l.
Include the following steps:
Solution of zinc sulfate pump is squeezed into one section of purification tank, flow 83m3/ h, the volume of one section of purification tank are 166m3,
Spill-over stream on one section of purification tank, therefore the solution purification time is 2h, one section of purification temperature control is to 70 DEG C, mixing speed
1500r/min, into one section of purification tank, solution is continuously added to zinc powder according to 2017.5kg/h.
Liquid ingredient after one section: Cu 0.2g/l, Cd 35g/l, Co 11.5mg/l, Si 31.38mg/l.
Liquid pump after one section of purification is squeezed into two sections of purification barrels, flow 55.3m3The body of/h, two sections of purification barrels is
166m3, spill-over stream on purification barrel, therefore two sections of clarification times of solution are 3h, two sections of purification temperatures controls are to 95 DEG C, mixing speed
For 1500r/min, it is continuously added to zinc powder according to 193.55kg/h into solution, is continuously added to antimonic salt according to 0.7kg/h, according to
1.1kg/h is continuously added to copper sulphate, flows into two sections of purification medial launders, medial launder solution through chute after solution continuous overflow after purification
Two sections of purification filters pressings are carried out after squeezing into two sections of purification filter presses, liquid stream enters liquid storage tank after two sections of purifications after filters pressing.
Liquid ingredient after two sections: Cu 0.2mg/l, Cd 10mg/l, Co 0.8mg/l, Si 31.38mg/l, Ge 0.08mg/
L, As 0.1mg/l, TOC 158.3mg/l.
Liquid pump after two sections of purifications is squeezed into three sections of purification barrels, flow 110.6m3/ h, the body of three purification barrels are 166m3, only
Change spill-over stream on bucket, therefore the solution purification time is 1.5h, three sections of purification temperatures control 75 DEG C, mixing speed 1500r/min,
Zinc powder is added according to 165.9kg/h into the solution of purification barrel, continuous overflow flows into medial launder through chute after solution purification, intermediate
Slot solution squeezes into three sections of purification filter presses and carries out three sections of purification filters pressings, liquid stream enters after filters pressing purify after liquid concentrator, on concentrator
Clear liquid is used as the supply subsequent processing electrolysis of new liquid.
New liquid ingredient: Zn 140g/l, Cu 0.1mg/l, Cd 0.8mg/l, Co 0.7mg/l, Si 31.38mg/l, Ge
0.08mg/l, As 0.1mg/l, TOC 158.3mg/l.
Solution of zinc sulfate deep-purifying method of the invention handles 1m3Zinc powder 6.09kg is needed, and conventional method is used to purify
Solution of zinc sulfate handles 1m3Need zinc powder 7.5kg, it is therefore apparent that the method for the present invention has using reduction zinc powder consumption, while can
Unconventional elemental silicon, arsenic, antimony, germanium and organic matter are removed, calcium and magnesium crystal, which is realized, to be removed in depth, molten compared to conventional purge procedures
Liquid clarity is relatively good, and cobalt will not return molten (two sections of purified cobalts of conventional purge procedures easily return molten), Neng Goubao after two sections of purifications
Card electrowinning process smoothly produces.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (16)
1. a kind of system of solution of zinc sulfate advanced treating, which is characterized in that it includes one section of purification tank, one section of purification filters pressing
It is liquid circulating slot after machine, two sections of purification tanks, two sections of purification filter presses, three sections of purification tanks, three sections of purification filter presses, three sections of filters pressings, dense
Close machine, clarification overflow launder, thickened underflow filter press, zinc powder feeder, milk of lime head tank, antimonic salt head tank, copper sulphate are high-order
Slot, heavy germanium agent head tank, active carbon storehouse, flocculant head tank；
The liquid outlet of one section of purification tank is connected to the inlet of one section of purification filter press, one section of purification filter press
Liquid outlet be connected to the inlet of two sections of purification tanks, the liquid outlet of two sections of purification tanks and two sections of purifications filters pressing
The inlet of machine is connected to, and the liquid outlet of two sections of purification filter presses is connected to the inlet of three sections of purification tanks, and described three
Section purification tank liquid outlet be connected to the inlet of three sections of purification filter presses, the liquid outlet of three sections of purification filter presses and
The inlet connection of liquid circulating slot, the liquid outlet of liquid circulating slot and the concentrator after three sections of filters pressings after three sections of filters pressings
Inlet connection, the concentrator overflow outlet with it is described clarify overflow launder inlet is connected to, the bottom of the concentrator
Outflux is connected to the feed inlet of the thickened underflow filter press, the liquid outlet of the thickened underflow filter press and described three sections pressures
The inlet connection of liquid circulating slot, the sludge outlet of the thickened underflow filter press are connected to filter residue processing unit after filter；
The inlet of one section of purification tank also with the zinc powder feeder, the milk of lime head tank, the antimonic salt head tank
It is connected to the copper sulphate head tank；The inlet of two sections of purification tanks is also high-order with the zinc powder feeder, the antimonic salt
Slot is connected to the copper sulphate head tank；The inlet of two sections of purification tanks also with the zinc powder feeder and the heavy germanium agent
Head tank connection；The inlet of liquid circulating slot is also connected to the inlet of flocculant head tank after three sections of filters pressings.
2. a kind of system of solution of zinc sulfate advanced treating according to claim 1, which is characterized in that it further includes a Duan Jing
Change medial launder；The inlet that the liquid outlet of one section of purification tank purifies medial launder with described one section is connected to, one section of purification
The liquid outlet of medial launder is connected to the inlet of one section of purification filter press, the muddy liquid outlet of the race of one section of purification filter press
The inlet for purifying medial launder with described one section is connected to.
3. a kind of system of solution of zinc sulfate advanced treating according to claim 1, which is characterized in that it further includes two sections net
Change medial launder, the inlet that the liquid outlet of two sections of purification tanks purifies medial launder with described two sections is connected to, two sections of purifications
The liquid outlet of medial launder is connected to the inlet of two sections of purification filter presses, the muddy liquid outlet of the race of two sections of purification filter presses
The inlet for purifying medial launder with described two sections is connected to.
4. a kind of system of solution of zinc sulfate advanced treating according to claim 1, which is characterized in that it further includes three Duan Jing
Change medial launder, the inlet that the liquid outlet of three sections of purification tanks purifies medial launder with described three sections is connected to, three sections of purifications
The liquid outlet of medial launder is connected to the inlet of three sections of purification filter presses, the muddy liquid outlet of the race of three sections of purification filter presses
The inlet for purifying medial launder with described three sections is connected to.
5. a kind of system of solution of zinc sulfate advanced treating according to claim 1, which is characterized in that it further includes a Duan Jing
The feed inlet of slugging slurrying tank, one section of purification slag slurrying tank is connected to the sludge outlet of one section of purification filter press, institute
The discharge port for stating one section of purification slag slurrying tank is connected to the filter residue processing unit.
6. a kind of system of solution of zinc sulfate advanced treating according to claim 1, which is characterized in that it further includes two sections net
The feed inlet of slugging slurrying tank, two sections of purification slag slurrying tanks is connected to the sludge outlet of two sections of purification filter presses, institute
The discharge port for stating two sections of purification slag slurrying tanks is connected to the filter residue processing unit.
7. a kind of system of solution of zinc sulfate advanced treating according to claim 1, which is characterized in that it further includes three Duan Jing
The feed inlet of slugging slurrying tank, three sections of purification slag slurrying tanks is connected to the sludge outlet of three sections of purification filter presses, institute
The discharge port for stating three sections of purification slag slurrying tanks is connected to the filter residue processing unit.
8. a kind of method of solution of zinc sulfate advanced treating, which is characterized in that zinc powder is added in the solution of zinc sulfate obtained after acidleach
One section of scavenging solution and copper cadmium cobalt silicon slag are obtained with one section of high temperature purification removing copper of antimonic salt, cadmium, cobalt and silicon, separation of solid and liquid；Then adjust
After saving one section of scavenging solution pH value, two sections of zinc powder, antimonic salt and copper sulphate high temperature purifications removing cobalts is added, separation of solid and liquid obtains two
Section scavenging solution and cobalt slag, addition zinc powder inhibits cobalt to return molten in two sections of scavenging solutions；Finally in three sections of purifications, described two sections
Zinc powder is added in scavenging solution and removes residual Cd, active carbon and heavy germanium agent absorption organic matter and germanium, antimony, arsenic, after being separated by solid-liquid separation, is being divided
Flocculant removing suspended matter and calcium and magnesium crystal are added in chaotropic, obtains three sections of scavenging solutions and dense bottom after being separated by solid-liquid separation again
Stream.
9. a kind of method of solution of zinc sulfate advanced treating according to claim 8, which is characterized in that one section of scavenging solution
In, Cu≤0.2mg/l, Cd≤30mg/l, Co≤5mg/l, Si≤20mg/l；And in one section of high temperature purification, the zinc powder and institute
The additional amount for stating calcium hydroxide is determined according to copper, cadmium, cobalt, silicon removing amount in solution of zinc sulfate.
10. a kind of method of solution of zinc sulfate advanced treating according to claim 9, which is characterized in that one section of high temperature purification
In, the additional amount of the zinc powder, the antimonic salt and the calcium hydroxide determines as follows:
The zinc powder amount of being actually added into is copper and cadmium theory consumes the theoretical consumption zinc powder amount that zinc powder amount adds 98 times of cobalt；
The antimonic salt amount of being actually added into accounts for 0.6 times of determination of cobalt element quality according to antimony element quality；
The amount of the theoretical consumption calcium hydroxide for the silicon that calcium hydroxide additional amount is 2 times；
Theoretical consumption is calculated all in accordance with reaction equation.
11. a kind of method of solution of zinc sulfate advanced treating according to claim 8, which is characterized in that two sections of purifications
Co≤1.0mg/l in liquid；And in two sections of high temperature purifications, except the zinc powder amount of cobalt process addition is according in one section of scavenging solution
The removing amount of cobalt determines.
12. a kind of method of solution of zinc sulfate advanced treating according to claim 11, which is characterized in that two sections of high temperature purifications
In, the additional amount of the zinc powder, the antimonic salt and the copper sulphate determines as follows:
The theoretical consumption zinc powder amount for the cobalt that the zinc powder amount of being actually added into is 800 times, theoretical consumption are calculated according to reaction equation；
The antimonic salt amount of being actually added into accounts for 0.6 times of determination of cobalt element quality according to antimony element quality；
The cobalt content that the copper sulphate amount of being actually added into is 0.5 times.
13. a kind of method of solution of zinc sulfate advanced treating according to claim 8, which is characterized in that in three sections of scavenging solutions,
Cd≤1.0mg/l, Sb≤0.02mg/l, As≤0.01mg/l, Ge≤0.05mg/l, TOC≤110mg/l；And in three sections of purifications
Zinc powder amount determines that the additional amount of the heavy germanium agent is purified according to described two sections according to the removing amount of cadmium in liquid after described two sections purifications
Germanium, arsenic, the removing amount of antimony are determining in liquid.
14. 3 a kind of method of solution of zinc sulfate advanced treating according to claim 1, which is characterized in that in three sections of purifications,
The additional amount of the zinc powder, the antimonic salt and the copper sulphate determines as follows: the zinc powder amount of being actually added into is 1.5 times de-
Except the theoretical amount of the zinc consumption of cadmium；
The active carbon amount of being actually added into is the theoretical amount of the active carbon consumption of 20 times of removing TOC；
Heavy germanium agent is the theoretical amount of the 25-30 times of heavy germanium agent of consumption for removing germanium, arsenic, antimony；
The additional amount of flocculant according to flocculant quality (kg): liquor capacity (m3)=0.0025:1 is determined.
15. according to a kind of any method of solution of zinc sulfate advanced treating of claim 8-14, which is characterized in that one section of height
In temperature purification, reaction temperature is 80-85 DEG C.
16. a kind of method of solution of zinc sulfate advanced treating according to claim 8, which is characterized in that the antimonic salt is K
(SbO)C4H4O6。
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| CN114540879A (en) * | 2022-01-24 | 2022-05-27 | 吉首市金湘资源科技开发有限公司 | Method for deeply purifying electrolytic zinc by ammonia-chlorine method |
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