CN109609754A - A kind of waste recovery process that noble metal extraction process generates - Google Patents
A kind of waste recovery process that noble metal extraction process generates Download PDFInfo
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- CN109609754A CN109609754A CN201910022781.7A CN201910022781A CN109609754A CN 109609754 A CN109609754 A CN 109609754A CN 201910022781 A CN201910022781 A CN 201910022781A CN 109609754 A CN109609754 A CN 109609754A
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- copper
- selenium
- extraction
- noble metal
- mass ratio
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- 238000000605 extraction Methods 0.000 title claims abstract description 69
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 238000011084 recovery Methods 0.000 title claims abstract description 26
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 131
- 229910052802 copper Inorganic materials 0.000 claims abstract description 128
- 239000010949 copper Substances 0.000 claims abstract description 128
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 39
- 239000011669 selenium Substances 0.000 claims abstract description 39
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000004094 surface-active agent Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229920000742 Cotton Polymers 0.000 claims abstract description 13
- 239000003365 glass fiber Substances 0.000 claims abstract description 13
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 49
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 38
- 239000000284 extract Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 239000012074 organic phase Substances 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 239000003945 anionic surfactant Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002386 leaching Methods 0.000 claims description 14
- 239000002736 nonionic surfactant Substances 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 11
- 238000007127 saponification reaction Methods 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 239000003546 flue gas Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 9
- 230000011218 segmentation Effects 0.000 claims description 9
- 238000005660 chlorination reaction Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000002956 ash Substances 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 claims 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 9
- 230000001180 sulfating effect Effects 0.000 abstract description 7
- 238000010025 steaming Methods 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 229910021653 sulphate ion Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- -1 when low temperature Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009867 copper metallurgy Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/06—Chloridising
-
- 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
-
- 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
-
- 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
-
- 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
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses the waste recovery process that a kind of noble metal extraction process generates, the waste generated in noble metal extraction process is ground, it is added to sodium sulphate in sulfating roasting, the complex state of the valuable metal in material is made more fully to be changed into the state of soluble sulphate；Steaming selenium is carried out instead of traditional roaster using motoring kiln, selenium recovery improves；By copper extractant, surfactant, power-assisted surfactant reasonable utilization, extraction, back extraction copper-bath, realize efficiently concentrating and the recycling of copper；Raffinate is evaporated to and is obtained nickel sulfate by the way that nickel sulfate crystal seed is added, the spent acid of generation can be recycled；The volatilization of organic solvent is effectively reduced using polyhedron baton round and glass fiber cotton, not only reduces production cost, but also alleviates pollution and murder by poisoning of the chemical reagent to ambient enviroment and personnel.
Description
Technical field
The present invention relates to the circular regeneration fields of resource, especially from noble metal extraction process generate waste recovery copper,
The technology of the metals such as selenium, nickel, gold, silver.
Background technique
Metal smelt industry can generate a large amount of waste abatements, and it is valuable that these solid wastes all contain copper, selenium, nickel, gold, silver etc.
Element, they are widely used in every field, and can they efficiently comprehensive reutilization can be again to drive non-ferrous metal industry
The utilization in production-goods source has great importance, and China's metallurgical industry is seriously limited by the side such as resource, the energy and ecological environment
The restriction in face alleviates resource, the pressure of the energy and environment, carries out the circulation of resource for the sustainable development for guaranteeing national economy
Utilize the inevitable choice for being China's metallurgical industry development.
Traditional handicraft be by after waste sulfating roasting through ball milling, then hot water leaching, leachate, that is, copper-bath, one
As cupric in 45g/L, then through iron replacement output copper sponge, displaced liquid removes venting triple effect steaming after iron, neutralizations, heavy nickel
Hair；Full technique output object is copper sponge, returns to copper metallurgy industry, and the copper in copper sponge contains a large amount of impurities, and utilizability adds
Work performance is not high, and the meeting a large amount of waste residues of output during this, and the heavy metal element contained in waste residue, which is arbitrarily stacked, can generate perhaps
Multi-environment problem also brings huge environmental risk.
To solve the above problems, the present invention has developed a kind of waste recovery process that noble metal extraction process generates, especially
It is the technology of the metals such as waste recovery copper, selenium, the nickel generated from noble metal extraction process, by waste material in sulfating roasting
In be added to sodium sulphate, enhance reaction process, be changed into the complex state of the valuable metal in waste material more fully solvable
The state of property sulfate, high efficiente callback selenium；Copper extractant, surfactant and power-assisted surfactant etc. is recycled rationally to make
Copper-bath is enriched by extraction, back extraction with by copper-bath；Examination is reduced using polyhedron baton round, glass fiber cotton simultaneously
The volatilization of agent alleviates pollution and murder by poisoning of the chemical reagent to ambient enviroment and personnel, improves the rate of recovery of each metal, product
Added value increases.
Summary of the invention
The purpose of the present invention is to provide the waste recovery process that a kind of noble metal extraction process generates.The present invention include with
Lower step:
(1) grind: the waste for being generated noble metal extraction process with ball milling is levigate, 200 mesh of fineness requirement~400 mesh；
(2) more metal sulfateizations roasting: by after ball milling material and 93% concentrated sulfuric acid be in mass ratio 1:0.8~1 ratio progress
Mixing adds moderate amount of sulfuric acid sodium, and sodium sulphate additive amount is the 3~6% of dry mine weight, puts into pulp kettle and is stirred, and heats
Most of metal and metallic compound to 220~300 DEG C or so, using electric heating as heat source, in pulp kettle, in waste material
It is reacted with sulfuric acid, reaction generates sulfate, and it is more thorough that selenium is converted into selenium dioxide volatilization separation, while reducing coal-fired or day
The discharge of right tail-gas, reduces carbon emission, energy conservation and environmental protection, and sodium sulphate can play the role of delivering the concentrated sulfuric acid, when low temperature, sodium sulphate
The extra concentrated sulfuric acid is absorbed, reaction generates NaHSO4, NaHSO when high-temperature roasting4It decomposes again, provides sulphation for sulphation process
Agent, thus reaction process is enhanced significantly, keep metal sulfateization more abundant.Moreover, sodium sulphate does not consume during the reaction,
It can recycle and be used for multiple times；
(3) it is crude to steam selenium: by step (2) treated, material is fitted into motoring kiln, is put into rotary kiln and is carried out steaming selenium,
Rotary kiln baking is heated to keeping the temperature 2h at 300~400 DEG C with 60 DEG C/h heating rate, then proceedes to add with 45 DEG C/h heating rate
Heat keeps the temperature 1h to 580 DEG C~620 DEG C, and selenium is sublimated into baking flue gas in the form of selenium dioxide, and baking flue gas is passed through dress
Have in the bubbler of water, selenium dioxide is reacted with water generates selenous acid, absorbs by two-stage bubbler, selenium dioxide all turns
Selenous acid is turned to, then the selenous acid solution in bubble absorption device is discharged, puts into sodium sulfite, reaction time 2h, the Central Asia
The mass ratio of sodium sulphate and selenous acid be 1.2:1, reaction filtering selenium；
(4) Selectively leaching: by the solid material by step (3) processing in hot lower addition leaching tanks, it is pumped into rinse water
And diluted acid, solid-to-liquid ratio are 1:1~3, by mechanical stirring 2h, are pumped into filter press and carry out solid-liquor separation, 3~5 rinsings, filters pressings
Copper leached solution is obtained, resulting filter residue is focused on；
(5) it extracts, be stripped: being in mass ratio that 4~6:1 is uniformly mixed to obtain extract liquor by mixed liquor A and mixed liquid B；Wherein, it mixes
Liquid A is that the copper extractant and sulfonated kerosene after saponification are that 1:6~8 is mixed in mass ratio, the copper extractant select P204 and
M5640 is that 1:0.8~1.2 is mixed in mass ratio, and the NaOH of copper extractant equivalent is saponified；Wherein mixed liquid B right and wrong from
Sub- surfactant and power-assisted surfactant are that 1:1~3 is mixed in mass ratio, and the nonionic surfactant selects Qula
Logical X-100, power-assisted surfactant select n-butanol；
With the copper in extract liquor extraction copper leached solution, copper leached solution and extract liquor ratio are 1~3:1, and polyhedron baton round covering liquid is added
5~10min is stirred by 150r/min in body surface face, and the multitple extraction at 45~55 DEG C of temperature is then allowed to stand layering, through excessive
Grade oil-liquid separator, obtains copper load organic phases and raffinate；Copper load organic phases are collected, prepare 8%~15% it is dilute
Glass fiber cotton Covering Liguid surface, segmentation is added in the anionic surfactant mixed liquor of sulfuric acid and 0.007~0.011mol/L
It is repeatedly stripped to obtain copper-bath, copper-bath returns potroom and recycles copper using electrodeposition, can after extraction agent solution is purified
It repeatedly uses, wherein anionic surfactant selects lauryl sodium sulfate；
(6) nickel recycles: raffinate directly heats evaporation, and being concentrated by evaporation when solution terminal acidity reaches 1000g/L terminates, and nickel sulfate is brilliant
Kind is in material Temperature fall to not higher than 50 DEG C additions, and when nickel ion concentration drops to 8g/L or less in solution, crystallization terminates, sulphur
Sour nickel packs sale of weighing after centrifuge is dehydrated, and about 50% sulfuric acid is contained in centrifugate, can be used for electroplating sludge acidleach rank
Section, remaining nickel can also be handled at this stage, and acid is recycled；
(7) what step (4) obtained divides copper ashes to enter chlorination parting, point silver-colored process.
The beneficial effects of the present invention are: the present invention grinds the waste generated in noble metal extraction process, sulfating roasting,
The complex state of the valuable metal in waste material is set to be changed into the state of soluble sulphate, using motoring kiln instead of tradition
Roaster carry out steaming selenium, selenium recovery improves, and passes through the reasonable fortune of copper extractant, surfactant, power-assisted surfactant
With extraction, back extraction copper-bath realize efficiently concentrating and the recycling of copper, be then evaporated raffinate and crystalline substance is added
Kind obtains nickel sulfate；Output divides copper ashes to enter the silver-colored process of chlorination parting point；
Sodium sulphate can play the role of delivering the concentrated sulfuric acid, and when low temperature, sodium sulphate absorbs the extra concentrated sulfuric acid, and reaction generates
NaHSO4, NaHSO when high-temperature roasting4It decomposes again, provides sulfating agent for sulphation process, thus enhance and reacted significantly
Journey keeps metal sulfateization more abundant.Moreover, sodium sulphate does not consume during the reaction, it can recycle and be used for multiple times；
Using the use of polyhedron baton round and glass fiber cotton in process, extraction, the reaction contact in anti-extraction process are increased
Area reduces the reaction time, and effectively reduces the volatilization of organic solvent, not only reduces production cost, but also alleviating
Learn pollution and murder by poisoning of the reagent to ambient enviroment and personnel.
The present invention can various metals in synthetical recovery waste material, improve returning for the non-ferrous metals such as copper, selenium, nickel, gold, silver
Yield, added value of product increase；Technical process is shortened, smelting cost is greatly reduced, it is easy to operate, it is easy to serialization behaviour
Make；Reduce the pollution to ambient enviroment, the cycling utilization of wastewater of entire technique has reached zero-emission.
Specific embodiment
Treatment research is carried out with the waste generated in our factory noble metal abstraction process.
Embodiment 1
(1) grind: the waste for being generated noble metal extraction process with ball milling is levigate, 200 mesh of fineness requirement；
(2) more metal sulfateizations roasting: by after ball milling material and 93% concentrated sulfuric acid be in mass ratio that the ratio of 1:0.9 is mixed
It closes, adds moderate amount of sulfuric acid sodium, sodium sulphate additive amount is the 5% of dry mine restatement, puts into pulp kettle and is stirred, and is heated to
260 DEG C or so, most of metal and metallic compound and sulfuric acid using electric heating as heat source, in pulp kettle, in waste material
It is reacted, reaction generates sulfate, and it is more thorough that selenium is converted into selenium dioxide volatilization separation；
(3) it is crude to steam selenium: will by step (2) treated material is fitted into motoring kiln, be put into rotary kiln and steamed
Selenium, rotary kiln baking are heated to keeping the temperature 2h at 300~400 DEG C with 60 DEG C/h heating rate, then proceed to the speed that heats up with 45 DEG C/h
Rate is heated to 580 DEG C~620 DEG C, keeps the temperature 1h, and selenium is sublimated into baking flue gas in the form of selenium dioxide, baking flue gas is led to
Enter in the bubbler equipped with water, selenium dioxide is reacted with water generates selenous acid, absorbs by two-stage bubbler, selenium dioxide is complete
Portion is converted into selenous acid, then the selenous acid solution in bubble absorption device is discharged, investment sodium sulfite, reaction time 2h,
The mass ratio of sulfite sodium and selenous acid be 1.2:1, reaction filtering selenium；
(4) Selectively leaching: by the solid material by step (3) processing in hot lower addition leaching tanks, it is pumped into rinse water
And diluted acid, solid-to-liquid ratio 1:2 are pumped into filter press and carry out solid-liquor separation, 4 rinsings, filters pressings are divided by mechanical stirring 2h
Copper liquid focuses on resulting filter residue；
(5) it extracts, be stripped: mixed liquor A and mixed liquid B are uniformly mixed in mass ratio for 5:1；Wherein, after mixed liquor A is saponification
Copper extractant and sulfonated kerosene be in mass ratio 1:7 mixing, the copper extractant selects the P204 and M5640 to be in mass ratio
1:1 mixing, the NaOH of copper extractant equivalent are saponified；Wherein mixed liquid B is nonionic surfactant and power-assisted surface
Activating agent is 1:2 mixing in mass ratio, and the nonionic surfactant selects triton x-100, the choosing of power-assisted surfactant
Use n-butanol；
With the copper in extract liquor extraction copper leached solution, copper leached solution and extract liquor ratio are 2:1, and polyhedron baton round covering liquid body surface is added
8min is stirred by 150r/min in face, and the multitple extraction under temperature 50 C is then allowed to stand layering, by multistage oil-liquid separator,
Obtain copper load organic phases and raffinate；Copper load organic phases are collected, 10% dilute sulfuric acid and 0.009mol/L are prepared
Anionic surfactant mixed liquor, is added glass fiber cotton Covering Liguid surface, and segmentation is repeatedly stripped to obtain copper-bath, sulfuric acid
Copper solution returns potroom and recycles copper using electrodeposition, can repeatedly use after extraction agent solution is purified, wherein anionic
Surfactant selects lauryl sodium sulfate；
(6) nickel recycles: raffinate directly heats evaporation, and being concentrated by evaporation when solution terminal acidity reaches 1000g/L terminates, and nickel sulfate is brilliant
Kind is in material Temperature fall to not higher than 50 DEG C additions, and when nickel ion concentration drops to 8g/L or less in solution, crystallization terminates, sulphur
Sour nickel packs sale of weighing after centrifuge is dehydrated, and about 50% sulfuric acid is contained in centrifugate, can be used for electroplating sludge acidleach rank
Section, remaining nickel can also be handled at this stage, and acid is recycled；
(7) what step (4) obtained divides copper ashes to enter chlorination parting, point silver-colored process.
Embodiment 2
(1) grind: the waste for being generated noble metal extraction process with ball milling is levigate, 200 mesh of fineness requirement；
(2) more metal sulfateizations roasting: by after ball milling material and 93% concentrated sulfuric acid be in mass ratio that the ratio of 1:0.8 is mixed
It closes, adds moderate amount of sulfuric acid sodium, sodium sulphate additive amount is the 6% of dry mine weight, puts into pulp kettle and is stirred, and is heated to 220
DEG C or so, using electric heating as heat source, in pulp kettle, most of metal and metallic compound and sulfuric acid in waste material are carried out
Reaction, reaction generate sulfate, and it is more thorough that selenium is converted into selenium dioxide volatilization separation；
(3) it is crude to steam selenium: will by step (2) treated material is fitted into motoring kiln, be put into rotary kiln and steamed
Selenium, rotary kiln baking are heated to keeping the temperature 2h at 300~400 DEG C with 60 DEG C/h heating rate, then proceed to the speed that heats up with 45 DEG C/h
Rate is heated to 580 DEG C~620 DEG C, keeps the temperature 1h, and selenium is sublimated into baking flue gas in the form of selenium dioxide, baking flue gas is led to
Enter in the bubbler equipped with water, selenium dioxide is reacted with water generates selenous acid, absorbs by two-stage bubbler, selenium dioxide is complete
Portion is converted into selenous acid, then the selenous acid solution in bubble absorption device is discharged, investment sodium sulfite, reaction time 2h,
The mass ratio of sulfite sodium and selenous acid be 1.2:1, reaction filtering selenium；
(4) Selectively leaching: by the solid material by step (3) processing in hot lower addition leaching tanks, it is pumped into rinse water
And diluted acid, solid-to-liquid ratio 1:1 are pumped into filter press and carry out solid-liquor separation, 3 rinsings, filters pressings are divided by mechanical stirring 2h
Copper liquid focuses on resulting filter residue；
(5) it extracts, be stripped: mixed liquor A and mixed liquid B are uniformly mixed in mass ratio for 6:1；Wherein, after mixed liquor A is saponification
Copper extractant and sulfonated kerosene be in mass ratio 1:6 mixing, the copper extractant selects the P204 and M5640 to be in mass ratio
1:0.8 mixing, the NaOH of copper extractant equivalent are saponified；Wherein mixed liquid B is nonionic surfactant and power-assisted table
Face activating agent is 1:3 mixing in mass ratio, and the nonionic surfactant selects triton x-100, power-assisted surfactant
Select n-butanol；
With the copper in extract liquor extraction copper leached solution, copper leached solution and extract liquor ratio are 3:1, and polyhedron baton round, which is added, makes its covering liquid
5min is stirred by 150r/min in body surface face, and the multitple extraction under temperature 45 C is then allowed to stand layering, by multistage oil liquid point
From device, copper load organic phases and raffinate are obtained；Copper load organic phases are collected, prepare 15% dilute sulfuric acid with
The anionic surfactant mixed liquor of 0.007mol/L, is added glass fiber cotton Covering Liguid surface, and segmentation is repeatedly stripped to obtain sulphur
Sour copper solution, copper-bath return potroom and recycle copper using electrodeposition, can repeatedly use after extraction agent solution is purified,
Wherein anionic surfactant selects lauryl sodium sulfate；
(6) nickel recycles: raffinate directly heats evaporation, and being concentrated by evaporation when solution terminal acidity reaches 1000g/L terminates, and nickel sulfate is brilliant
Kind is in material Temperature fall to not higher than 50 DEG C additions, and when nickel ion concentration drops to 8g/L or less in solution, crystallization terminates, sulphur
Sour nickel packs sale of weighing after centrifuge is dehydrated, and about 50% sulfuric acid is contained in centrifugate, can be used for electroplating sludge acidleach rank
Section, remaining nickel can also be handled at this stage, and acid is recycled；
(7) what step (4) obtained divides copper ashes to enter chlorination parting, point silver-colored process.
Embodiment 3
(1) grind: the waste for being generated noble metal extraction process with ball milling is levigate, 400 mesh of fineness requirement；
(2) more metal sulfateizations roasting: by after ball milling material and 93% concentrated sulfuric acid mix in the ratio in mass ratio for 1:1
It closes, adds moderate amount of sulfuric acid sodium, sodium sulphate additive amount is the 3% of dry mine weight, puts into pulp kettle and is stirred, and is heated to 300
DEG C or so, using electric heating as heat source, in pulp kettle, most of metal and metallic compound and sulfuric acid in waste material are carried out
Reaction, reaction generate sulfate, and it is more thorough that selenium is converted into selenium dioxide volatilization separation；
(3) it is crude to steam selenium: will by step (2) treated material is fitted into motoring kiln, be put into rotary kiln and steamed
Selenium, rotary kiln baking are heated to keeping the temperature 2h at 300~400 DEG C with 60 DEG C/h heating rate, then proceed to the speed that heats up with 45 DEG C/h
Rate is heated to 580 DEG C~620 DEG C, keeps the temperature 1h, and selenium is sublimated into baking flue gas in the form of selenium dioxide, baking flue gas is led to
Enter in the bubbler equipped with water, selenium dioxide is reacted with water generates selenous acid, absorbs by two-stage bubbler, selenium dioxide is whole
It is converted into selenous acid, then the selenous acid solution in bubble absorption device is discharged, investment sodium sulfite, reaction time 2h, wherein
The mass ratio of sodium sulfite and selenous acid be 1.2:1, reaction filtering selenium；
(4) Selectively leaching: by the solid material by step (3) processing in hot lower addition leaching tanks, it is pumped into rinse water
And diluted acid, solid-to-liquid ratio 1:3 are pumped into filter press and carry out solid-liquor separation, 5 rinsings, filters pressings are divided by mechanical stirring 2h
Copper liquid focuses on resulting filter residue；
(5) it extracts, be stripped: mixed liquor A and mixed liquid B are uniformly mixed in mass ratio for 4:1；Wherein, after mixed liquor A is saponification
Copper extractant and sulfonated kerosene be in mass ratio 1:8 mixing, the copper extractant selects the P204 and M5640 to be in mass ratio
1:1.2 mixing, the NaOH of copper extractant equivalent are saponified；Wherein mixed liquid B is nonionic surfactant and power-assisted table
Face activating agent is 1:1 mixing in mass ratio, and the nonionic surfactant selects triton x-100, power-assisted surfactant
Select n-butanol；
With the copper in extract liquor extraction copper leached solution, copper leached solution and extract liquor ratio are 1:1, and polyhedron baton round, which is added, makes its covering liquid
15min is stirred by 150r/min in body surface face, and the multitple extraction at 55 DEG C of temperature is then allowed to stand layering, by multistage oil liquid point
From device, copper load organic phases and raffinate are obtained；Copper load organic phases are collected, prepare 8% dilute sulfuric acid with
The anionic surfactant mixed liquor of 0.011mol/L, is added glass fiber cotton Covering Liguid surface, and segmentation is repeatedly stripped to obtain sulphur
Sour copper solution, copper-bath return potroom and recycle copper using electrodeposition, can repeatedly use after extraction agent solution is purified,
Wherein anionic surfactant selects lauryl sodium sulfate；
(6) nickel recycles: raffinate directly heats evaporation, and being concentrated by evaporation when solution terminal acidity reaches 1000g/L terminates, and nickel sulfate is brilliant
Kind is in material Temperature fall to not higher than 50 DEG C additions, and when nickel ion concentration drops to 8g/L or less in solution, crystallization terminates, sulphur
Sour nickel packs sale of weighing after centrifuge is dehydrated, and about 50% sulfuric acid is contained in centrifugate, can be used for electroplating sludge acidleach rank
Section, remaining nickel can also be handled at this stage, and acid is recycled；
(7) what step (4) obtained divides copper ashes to enter chlorination parting, point silver-colored process.
Embodiment 4
(2) more metal sulfateizations roasting: by after ball milling material and 93% concentrated sulfuric acid be in mass ratio that the ratio of 1:0.9 is mixed
It closes, puts into pulp kettle and be stirred, and be heated to 260 DEG C or so, using electric heating as heat source, in pulp kettle, waste material
In most of metal and metallic compound reacted with sulfuric acid, reaction generate sulfate, allow copper, nickel to be converted to soluble sulphur
Hydrochlorate is more thorough, selenium be converted into selenium dioxide volatilization separation it is more thorough, remaining step is same as Example 1.
Embodiment 5
(5) it extracts, be stripped: mixed liquor A and mixed liquid B are uniformly mixed in mass ratio for 5:1；Wherein, mixed liquor A is copper extraction
Agent and sulfonated kerosene are 1:7 mixing in mass ratio, and it is 1:1 mixing that the copper extractant selects P204 and M5640 in mass ratio；
Wherein mixed liquid B is nonionic surfactant and power-assisted surfactant is 1:2 mixing, the non-ionic surface in mass ratio
Activator selects triton x-100, and power-assisted surfactant selects n-butanol；
With the copper in extract liquor extraction copper leached solution, copper leached solution and extract liquor ratio are 2:1, and polyhedron baton round, which is added, makes its covering liquid
8min is stirred by 150r/min in body surface face, and the multitple extraction under temperature 50 C is then allowed to stand layering, by multistage oil liquid point
From device, copper load organic phases and raffinate are obtained；Copper load organic phases are collected, prepare 10% dilute sulfuric acid with
The anionic surfactant mixed liquor of 0.009mol/L, is added glass fiber cotton Covering Liguid surface, and segmentation is repeatedly stripped to obtain sulphur
Sour copper solution, copper-bath return potroom and recycle copper using electrodeposition, can repeatedly use after extraction agent solution is purified,
Wherein anionic surfactant selects lauryl sodium sulfate；Remaining step is same as Example 1.
Embodiment 6
Mixed liquor A and mixed liquid B are uniformly mixed in mass ratio for 5:1；Wherein, mixed liquor A be saponification after copper extractant and
Sulfonated kerosene is 1:7 mixing in mass ratio, and the copper extractant selects P204, the NaOH of copper extractant equivalent to carry out soap
Change；Wherein mixed liquid B is nonionic surfactant and power-assisted surfactant is 1:2 mixing, the nonionic in mass ratio
Surfactant selects triton x-100, and power-assisted surfactant selects n-butanol；
With the copper in extract liquor extraction copper leached solution, copper leached solution and extract liquor ratio are 2:1, and polyhedron baton round, which is added, makes its covering liquid
8min is stirred by 150r/min in body surface face, and the multitple extraction under temperature 50 C is then allowed to stand layering, by multistage oil liquid point
From device, copper load organic phases and raffinate are obtained；Copper load organic phases are collected, prepare 10% dilute sulfuric acid with
The anionic surfactant mixed liquor of 0.009mol/L, is added glass fiber cotton Covering Liguid surface, and segmentation is repeatedly stripped to obtain sulphur
Sour copper solution, copper-bath return potroom and recycle copper using electrodeposition, can repeatedly use after extraction agent solution is purified,
Wherein anionic surfactant selects lauryl sodium sulfate；Remaining step is same as Example 1.
Embodiment 7
Mixed liquor A and mixed liquid B are uniformly mixed in mass ratio for 5:1；Wherein, mixed liquor A be saponification after copper extractant and
Sulfonated kerosene is 1:7 mixing in mass ratio, and the copper extractant selects M5640, the NaOH of copper extractant equivalent to carry out soap
Change；Wherein mixed liquid B is nonionic surfactant and power-assisted surfactant is 1:2 mixing, the nonionic in mass ratio
Surfactant selects triton x-100, and power-assisted surfactant selects n-butanol；
With the copper in extract liquor extraction copper leached solution, copper leached solution and extract liquor ratio are 2:1, and polyhedron baton round, which is added, makes its covering liquid
8min is stirred by 150r/min in body surface face, and the multitple extraction under temperature 50 C is then allowed to stand layering, by multistage oil liquid point
From device, copper load organic phases and raffinate are obtained；Copper load organic phases are collected, prepare 10% dilute sulfuric acid with
The anionic surfactant mixed liquor of 0.009mol/L, is added glass fiber cotton Covering Liguid surface, and segmentation is repeatedly stripped to obtain sulphur
Sour copper solution, copper-bath return potroom and recycle copper using electrodeposition, can repeatedly use after extraction agent solution is purified,
Wherein anionic surfactant selects lauryl sodium sulfate；Remaining step is same as Example 1.
Embodiment 8
Copper extractant and sulfonated kerosene after saponification are 1:7 mixing in mass ratio, and the copper extractant selects P204 and M5640
It is mixed in mass ratio for 1:1, the NaOH of copper extractant equivalent is saponified, and with the copper in mixed liquor extraction copper leached solution, divides copper
Liquid and extract liquor ratio are 2:1, and polyhedron baton round, which is added, makes its Covering Liguid surface, 8min are stirred by 150r/min, in temperature
Multitple extraction at 50 DEG C of degree, is then allowed to stand layering, by multistage oil-liquid separator, obtains copper load organic phases and raffinate；It will
Copper load organic phases collect, and glass fiber cotton Covering Liguid surface is added in the dilute sulfuric acid for preparing 10%, and segmentation is repeatedly stripped to obtain sulfuric acid
Copper solution, copper-bath return potroom and recycle copper using electrodeposition, can repeatedly use after extraction agent solution is purified,
Remaining step is same as Example 1.
Embodiment 9
(6) nickel recycles: raffinate directly heats evaporation, and being concentrated by evaporation when solution terminal acidity reaches 1000g/L terminates, naturally cold
But, when nickel ion concentration drops to 8g/L or less in solution, crystallization terminates, and nickel sulfate is packed after centrifuge is dehydrated and weighed out
It sells, about 50% sulfuric acid is contained in centrifugate, can be used for electroplating sludge acid leaching stage, remaining nickel can also be located at this stage
Reason, acid are recycled, remaining step is same as Example 1.
Embodiment 10
(5) it extracts, be stripped: mixed liquor A and mixed liquid B are uniformly mixed in mass ratio for 5:1；Wherein, after mixed liquor A is saponification
Copper extractant and sulfonated kerosene be in mass ratio 1:7 mixing, the copper extractant selects the P204 and M5640 to be in mass ratio
1:1 mixing, the NaOH of copper extractant equivalent are saponified；Wherein mixed liquid B is nonionic surfactant and power-assisted surface
Activating agent is 1:2 mixing in mass ratio, and the nonionic surfactant selects triton x-100, the choosing of power-assisted surfactant
Use n-butanol；
With the copper in extract liquor extraction copper leached solution, copper leached solution and extract liquor ratio are 2:1,8min are stirred by 150r/min, in temperature
Multitple extraction at 50 DEG C of degree, is then allowed to stand layering, by multistage oil-liquid separator, obtains copper load organic phases and raffinate；It will
Copper load organic phases collect, and prepare 10% dilute sulfuric acid and the anionic surfactant mixed liquor of 0.009mol/L, point
Duan Duoci is stripped to obtain copper-bath, and copper-bath returns potroom and recycles copper using electrodeposition, after extraction agent solution is purified
It can repeatedly use, wherein anionic surfactant selects lauryl sodium sulfate, remaining step and 1 phase of embodiment
Together.
Measure selenium, the copper, nickel recovery of embodiment 1-10 preparation；Extract liquor disengaging time；Extractant consumption (processing 1t
Copper extractant consumed by waste material)
| Embodiment | Selenium recovery (%) | Copper recovery (%) | Nickel recovery (%) | Extract liquor disengaging time (min) | Extractant consumption (kg) |
| 1 | 98.9 | 98.3 | 95.7 | 10 | 18.6 |
| 2 | 98.8 | 97.9 | 95.3 | 12 | 18.6 |
| 3 | 98.7 | 98.0 | 95.4 | 11 | 18.6 |
| 4 | 97.5 | 96.8 | 94.7 | 12 | 18.6 |
| 5 | 98.7 | 97.1 | 95.0 | 15 | 18.6 |
| 6 | 98.6 | 96.5 | 94.5 | 14 | 18.6 |
| 7 | 98.7 | 96.8 | 94.4 | 13 | 18.6 |
| 8 | 98.7 | 95.5 | 94.1 | 20 | 18.6 |
| 9 | 98.7 | 97.9 | 94.8 | 12 | 18.6 |
| 10 | 98.6 | 97.6 | 95.0 | 15 | 20.4 |
Data can be seen that embodiment 1-3 using the invention patent technology in analytical table, and wherein embodiment 1 is optimal；Embodiment 4
Sulfating roasting does not add sodium sulphate, it is seen that the rate of recovery of metal substantially reduces；5 extractant of embodiment without saponification, copper
The rate of recovery is lower；P204 is applied alone in 6 copper extractant of embodiment, and M5640 is applied alone in 7 copper extractant of embodiment, and copper, nickel recovery are low
Effect is used in combination in copper extractant；Embodiment 8 does not use surfactant, power-assisted surfactant, and effect of extracting is less
Ideal and extraction, time-consuming for back extraction；Crystal seed is not added for the crystallization process of nickel sulfate in embodiment 9, and nickel sulfate crystalline rate is slow
And crystallization is few；Polyhedron baton round, glass fiber cotton is not added in embodiment 10, extractant consumption increased significantly；Therefore, it can obtain
Conclusion out, the present invention grind the waste generated in noble metal extraction process, and sulfating roasting makes the valuable metal in waste material
Complex state is changed into the state of soluble sulphate, carries out steaming selenium, selenium instead of traditional roaster using motoring kiln
The rate of recovery improve, by copper extractant, surfactant, power-assisted surfactant reasonable utilization, extraction, back extraction copper sulphate it is molten
Liquid realizes efficiently concentrating and the recycling of copper, is then evaporated raffinate and crystal seed is added and obtain nickel sulfate.
Claims (7)
1. the waste recovery process that a kind of noble metal extraction process generates, it is characterised in that: grind (2) more metal sulphur including (1)
Acidizing fired (3) steam crude (4) Selectively leaching (5) extraction of selenium, back extraction (6) nickel recycling (7) chlorination parting, point silver；
Wherein, step (1) grinds concrete technology: the waste for being generated noble metal extraction process with ball milling is levigate, fineness requirement 200
Mesh~400 mesh；
Wherein, the more metal sulfateizations of step (2) roast concrete technologies: by the material and 93% concentrated sulfuric acid in mass ratio 1 after ball milling:
0.8~1 ratio is mixed, and sodium sulphate is added, and is put into pulp kettle and is stirred, using electric heating as heat source, and
It is heated to 220~300 DEG C or so；
Wherein, step (3) steams the crude concrete technology of selenium: will by step (2) treated, material is fitted into motoring kiln, into
Row steams selenium, and rotary kiln baking is heated to keeping the temperature 2h at 300~400 DEG C with 60 DEG C/h heating rate, be then proceeded to 45 DEG C/h liter
Warm rate is heated to 580 DEG C~620 DEG C, keeps the temperature 1h, and selenium is sublimated into baking flue gas in the form of selenium dioxide, baking flue gas
Through two-stage bubble absorption, selenium dioxide, which react with water, generates the selenous acid for being dissolved in water, periodically by the Asia in bubble absorption kettle
The discharge of selenic acid solution puts into sodium sulfite, and reaction time 2h, wherein the mass ratio of sodium sulfite and selenous acid is 1.2:1, instead
Should filter selenium；
Wherein, step (4) Selectively leaching: by the solid material by step (3) processing in hot lower addition leaching tanks, pump
Entering rinse water and diluted acid, solid-to-liquid ratio is 1:1~3, by mechanical stirring 2h, it is pumped into filter press and carries out solid-liquor separation, 3~5 times
Rinsing, filters pressing obtain copper leached solution, and resulting filter residue is focused on；
Wherein, step (5) extraction, back extraction: being that 4~6:1 is uniformly mixed by mixed liquor A and mixed liquid B in mass ratio；Wherein, it mixes
Closing liquid A is copper extractant and the sulfonated kerosene mixing after saponification；Mixed liquid B is nonionic surfactant and power-assisted surface-active
Agent mixing；
With the copper in extract liquor extraction copper leached solution, copper leached solution and extract liquor ratio are 1~3:1, and polyhedron baton round, which is added, covers it
Lid liquid surface stirs 5~10min by 150r/min, and the multitple extraction at 45~55 DEG C of temperature is then allowed to stand layering, passes through
Multistage oil-liquid separator is crossed, copper load organic phases and raffinate are obtained；Copper load organic phases are collected, prepare 8%~15%
Dilute sulfuric acid and 0.007~0.011mol/L anionic surfactant mixed liquor, be added glass fiber cotton Covering Liguid surface,
Segmentation is repeatedly stripped to obtain copper-bath, and copper-bath returns potroom and recycles copper using electrodeposition, and extraction agent solution is purified
After can repeatedly use；
Wherein, step (6) nickel recycles concrete technology: raffinate directly heats concentration, and solution terminal acidity is evaporated when reaching 1000g/L
Concentration terminates, and nickel sulfate crystal seed is added in material Temperature fall to not higher than 50 DEG C, when nickel ion concentration drops to 8g/L in solution
When following, crystallization terminates, and nickel sulfate packs sale of weighing after centrifuge is dehydrated, and about 50% sulfuric acid is contained in centrifugate, can be used
In electroplating sludge acid leaching stage, remaining nickel can also be handled at this stage, and acid is recycled；
Wherein, step (7) chlorination parting, point silver-colored concrete technology: what step (4) obtained divides copper ashes to enter chlorination parting, point silver-colored work
Sequence.
2. the waste recovery process that a kind of noble metal extraction process according to claim 1 generates, which is characterized in that described
The more metal sulfateization roastings of step (2): sodium sulphate additive amount is the 3~6% of dry mine restatement.
3. the waste recovery process according to claim 1 generated from a kind of noble metal extraction process, which is characterized in that institute
The copper extractant stated selects the composite extractant of P204 and M5640, and mass ratio is 1:0.8~1.2.
4. the waste recovery process according to claim 1 generated from a kind of noble metal extraction process, which is characterized in that institute
Copper extractant after stating saponification is to be saponified copper extractant with the NaOH of equivalent.
5. the waste recovery process according to claim 1 generated from a kind of noble metal extraction process, which is characterized in that copper
Extractant and sulfonated kerosene diluent mass ratio are 1:6~8.
6. the waste recovery process according to claim 1 generated from a kind of noble metal extraction process, which is characterized in that non-
Ionic surfactant selects triton x-100, and power-assisted surfactant selects n-butanol, and mass ratio is 1:1~3.
7. the waste recovery process according to claim 1 generated from a kind of noble metal extraction process, which is characterized in that institute
It states anionic surfactant and selects lauryl sodium sulfate.
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| WO2020211757A1 (en) * | 2019-04-16 | 2020-10-22 | 中国恩菲工程技术有限公司 | Method for recovering copper from phosphoric acid extractant-containing solution |
| CN113186402A (en) * | 2021-04-29 | 2021-07-30 | 大冶有色金属有限责任公司 | Method for recovering metallic copper in selenium steaming slag |
| CN113604673A (en) * | 2021-08-11 | 2021-11-05 | 山东国大黄金股份有限公司 | Method for extracting gold from cyanidation tailings by sulfuric acid curing roasting |
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