CN116083721A - High-arsenic copper anode slime treatment method - Google Patents
High-arsenic copper anode slime treatment method Download PDFInfo
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- CN116083721A CN116083721A CN202211593818.XA CN202211593818A CN116083721A CN 116083721 A CN116083721 A CN 116083721A CN 202211593818 A CN202211593818 A CN 202211593818A CN 116083721 A CN116083721 A CN 116083721A
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- arsenic
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000002386 leaching Methods 0.000 claims abstract description 130
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 88
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002893 slag Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910000563 Arsenical copper Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052802 copper Inorganic materials 0.000 abstract description 26
- 239000010949 copper Substances 0.000 abstract description 26
- 229910052759 nickel Inorganic materials 0.000 abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 abstract description 8
- 239000010941 cobalt Substances 0.000 abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910017709 Ni Co Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009423 ventilation Methods 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
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
-
- 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
- C22B15/0002—Preliminary treatment
-
- 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
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a high-arsenic copper anode slime treatment method. The method adopts an alkaline leaching treatment method or an alkalization-roasting-water leaching treatment method, and arsenic is leached from copper anode slime by controlling treatment conditions. The invention can leach most arsenic from copper anode slime with high efficiency, thereby facilitating the recovery of arsenic element; the leaching slag after treatment enriches valuable elements such as nickel, cobalt, copper and the like by more than one time, and greatly reduces the leaching treatment capacity of the valuable elements such as copper, nickel and the like in the subsequent leaching slag.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a high-arsenic copper anode slime treatment method.
Background
Anode slime is a mud-like substance attached to the surface of an anode substrate or precipitated at the bottom of an electrolytic tank or suspended in an electrolyte in electrolytic refining. The anode slime produced by electrolytic refining of copper and lead, for example, is rich in most or most noble metals and some scattered elements, such as gold, silver and the like, so that the anode slime has high comprehensive recovery value. In order to further reduce the cost of treating anode slime and improve the recovery rate of rare and noble metals, research on a new anode slime treatment process is always focused at home and abroad, but an effective arsenic removal treatment method is not found for copper anode slime at present.
The copper anode slime is generally treated by adopting a traditional pressure acid leaching treatment process, wherein oxygen is introduced in the treatment process to oxidize sulfur elements in the anode slime, and finally valuable metal sulfate is obtained to recycle valuable metals. However, the inventor of the present application found that when the treatment process is used for treating anode slime containing arsenic and copper, especially anode slime containing high arsenic and copper, the treatment capacity of pressurized oxygen leaching is very large, and the subsequent process has a plurality of problems, for example, 1) highly toxic arsenate is generated; 2) Arsenic cannot be leached completely, and part of about 10% -20% of arsenic can be leached into the solution along with copper and the like in the treatment process, and the rest of arsenic can be remained in leaching slag, so that arsenic cannot be further recovered.
Disclosure of Invention
The invention aims to provide a high-arsenic copper anode slime treatment method for safely and effectively removing and recycling arsenic elements from copper anode slime.
The above object of the present invention is achieved by the following technical solutions:
according to one aspect of the invention, the first high-arsenic copper anode slime treatment method provided by the invention comprises the following steps: mixing high-arsenic copper anode slime with alkali, introducing oxygen-containing gas for alkaline leaching treatment, leaching arsenic into leaching liquid after the treatment, and leaching residues are anode slime after arsenic removal; wherein, the molar ratio of alkali to arsenic is (0.5-10): 1, leaching temperature is 25-150 ℃, leaching time is 0.5-6 h, and liquid-solid ratio is (2-10): 1.
the second high-arsenic copper anode slime treatment method provided by the invention comprises the following steps:
mixing high-arsenic copper anode slime with alkali for alkalization treatment, wherein the alkali-arsenic molar ratio is (0.5-10): 1, a step of;
filtering after alkalization treatment and roasting the filter cake, wherein the roasting temperature is 200-1000 ℃ and the roasting time is 10 min-6 h;
slurrying the roasted material with water, introducing oxygen-containing gas, carrying out water leaching treatment, leaching arsenic into leaching liquid, and leaching slag as dearsenified anode mud, wherein the liquid-solid ratio is (2-10): 1, the leaching temperature is 25-200 ℃ and the leaching time is 0.5-6 h.
Optionally, before the step of mixing the high-arsenical copper anode slime with alkali, the method further comprises: ball milling is carried out on the high-arsenic anode slime until the granularity is 80 percent of minus 100 meshes to 100 percent of minus 325 meshes.
Optionally, the method further comprises: and precipitating arsenic from the leaching solution by adopting ferric salt or sulfur dioxide.
Optionally, the method further comprises: and leaching the valuable elements from the leaching slag by adopting a pressurized oxygen leaching method.
Optionally, the alkali is one or a combination of several of sodium hydroxide, potassium hydroxide, calcium oxide, magnesium oxide, sodium carbonate, sodium bicarbonate, potassium carbonate and magnesium carbonate.
Optionally, the step of mixing the high-arsenic anode slime with alkali includes: slurrying high-arsenic anode mud, and controlling the liquid-solid ratio (2-4): 1, a step of; adding alkali for mixing, and preparing alkali with mass concentration of 2-20% and mixing time of 0.5-2 h.
Optionally, before roasting the filter cake, the method further comprises: and drying the filter cake.
Optionally, when water immersion treatment is performed, the method further comprises: adding alkali into the pulpified solution to prepare alkali with the mass concentration of 0.1-20%.
The beneficial effects are that: based on the treatment method, most of arsenic can be leached from the copper anode slime with high efficiency, thereby facilitating the recovery of arsenic element and preparing arsenic salt products with higher purity after recovery; the anode slime is greatly reduced after most arsenic is leached, and valuable elements such as nickel, cobalt, copper and the like are enriched by more than one time, so that the treatment capacity of the subsequent leaching of the valuable elements such as copper, nickel and the like is greatly reduced, and the problem caused by arsenic is basically not needed to be considered in the subsequent leaching treatment of leaching residues.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In general, arsenic element in anode slime is leached with pressurized oxygen at about 1%, while for high-arsenic anode slime with arsenic element content higher than 7%, such as 9% -13%, the subsequent treatment amount is large, the efficiency is low, harmful substances are generated, and the recovery rate of each element is low. According to the treatment method for the high-arsenic copper anode slime, provided by the invention, an alkaline leaching treatment method is adopted, or an alkalization-roasting-water leaching treatment method is adopted, and most of arsenic can be efficiently leached out of the copper anode slime by controlling treatment conditions, so that the recovery of arsenic elements is facilitated; and the valuable elements such as nickel, cobalt, copper and the like in the leached slag are enriched by more than one time after arsenic leaching, so that the leaching treatment capacity of the valuable elements such as nickel, cobalt, copper and the like in the subsequent leached slag is greatly reduced.
The first processing method provided in an embodiment of the present invention: the alkaline leaching treatment method for the high-arsenic copper anode slime specifically comprises the following steps: the high arsenic copper anode mud and alkali are mixed according to the molar ratio of alkali to arsenic of (0.5-10): 1, and introducing oxygen-containing gas, and performing alkaline leaching treatment, wherein the leaching temperature is 25-200 ℃, the leaching time is 0.5-6 h, and the liquid-solid ratio is (2-10): 1, the arsenic after treatment is leached into leaching liquid, and leaching slag is anode mud after arsenic removal. The follow-up arsenic precipitation can be carried out by adopting ferric salt or sulfur dioxide, and valuable elements such as nickel, cobalt, copper and the like are leached out by adopting a pressurized oxygen leaching method. By adopting the alkaline leaching treatment method, the molar ratio of the alkaline and the arsenic, the leaching temperature and the leaching time and the liquid-solid ratio are comprehensively controlled, so that most of the arsenic is leached into the leaching liquid, and other valuable metals are enriched into leaching residues, the arsenic leaching effect is improved, and the post-treatment capacity is reduced.
Because the anode slime is solid and is difficult to mix with alkali, and the mixing equipment is not good, preferably, in the step of mixing the high-arsenic anode slime with alkali, the high-arsenic anode slime can be pulped first, and the liquid-solid ratio (2-4) is controlled: 1, a step of; adding alkali for mixing to prepare alkali with the mass concentration of 2-20% and the mixing time of 0.5-2 h. Through slurrying the high-arsenic anode slurry, slurry is formed, alkali can be added under the stirring effect, so that the high-arsenic anode slurry is easier to mix uniformly, and the treatment efficiency is improved.
In order to further improve the leaching effect, the molar ratio of alkali to arsenic is controlled to be (1-6): 1, for example, may be 1:1,3:1,5:1, etc. The alkali can be selected from one or a mixture of a plurality of compounds with strong alkalinity or weak alkalinity in aqueous solution; examples of the compound include sodium hydroxide, potassium hydroxide, calcium oxide, magnesium oxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and magnesium carbonate.
In addition, in the alkaline leaching treatment process, the leaching temperature is controlled within the range of 25-150 ℃; the leaching time is 0.5 h-6 h, for example, 2h,4h,6h and the like; the liquid-solid ratio is (2-10): 1, for example, may be 2:1,4:1,6:1,8:1, 10:1, etc. The leaching rate and the treatment efficiency can reach a better state under the condition of lower energy consumption by optimizing the leaching temperature and time.
Furthermore, before the step of mixing the high-arsenic copper anode slime with alkali, the method further comprises: ball milling is carried out on the high-arsenic anode slime; further, ball milling is carried out until the granularity is 80 percent of minus 100 meshes to 100 percent of minus 325 meshes. By ball milling before mixing, the granularity is reduced after ball milling, the contact area with alkali is increased, the reaction is accelerated, and the reaction effect is improved.
A second embodiment of the present invention provides: an alkalization-roasting-water leaching treatment method for high-arsenic copper anode slime. Through filtering after the alkalization treatment and roasting filter residues, the content of other impurities in the subsequent leaching solution can be greatly reduced, arsenic can be efficiently leached out by leaching based on the roasted materials, other valuable metals are hardly leached out, the treatment efficiency of the subsequent leaching residue is improved, and the arsenic product which can be sold can be obtained by direct precipitation treatment with high arsenic content in the leaching solution. Specifically, the method may include the steps of:
1) The high arsenic copper anode mud and alkali are mixed according to the alkali-arsenic molar ratio of (0.5-10): 1, mixing and carrying out alkalization treatment.
In order to improve the subsequent leaching effect, the molar ratio of alkali to arsenic can be controlled to be (1-6): 1, for example, may be 1:1,3:1,5:1, etc. The alkali can be selected from one or a mixture of a plurality of compounds with strong alkalinity or weak alkalinity in aqueous solution; can be sodium hydroxide, potassium hydroxide, calcium oxide, magnesium oxide, sodium carbonate, sodium bicarbonate, potassium carbonate, magnesium carbonate and the like, and can leach arsenic with high efficiency.
In addition, before the step of mixing the high-arsenic copper anode slime with alkali, ball milling is carried out on the high-arsenic anode slime until the granularity is 80% -325 mesh 100%. Through ball milling of the high-arsenic anode slime and ball milling of the granularity, the contact area with alkali is increased, the reaction speed is improved, and the reaction effect is improved.
In addition, in the step of mixing the high-arsenic anode slime with alkali, the high-arsenic anode slime can be pulpified first, and the liquid-solid ratio (2-4) is controlled: 1, a step of; then adding alkali for mixing, and preparing the alkali with the mass concentration of 2-20% and the mixing time of 0.5-2 h. Because the anode slime is solid and is difficult to mix with alkali, mixing equipment is not good, pulp is formed after pulping, alkali can be added under the stirring effect, the anode slime is easier to mix evenly, and the treatment efficiency is improved.
2) Filtering after alkalization treatment, and roasting the filter cake at 200-1000 ℃ for 10 min-6 h. Wherein the filtrate is also available for pulping of the next batch.
In addition, in the case of firing, the firing temperature may be controlled to be lower than 800 ℃, for example, 400 ℃, 500 ℃, 600 ℃, 700 ℃, and the like, and the firing time may be 0.5 to 6 hours, for example, 12 hours, 4 hours, and the like. The preferred roasting temperature and time range can achieve better roasting effect and save energy consumption.
In addition, in order to ensure the high-temperature roasting heat treatment effect, the filter cake can be dried before being roasted to remove the moisture in the filter cake.
3) Slurrying the roasted material with water, introducing oxygen-containing gas, and carrying out water leaching treatment, wherein the liquid-solid ratio is (2-10): 1, leaching at 25-200 ℃ for 0.5-6 h, leaching the treated arsenic into the leaching solution, and leaching residues are anode slime after arsenic removal. Wherein, ferric salt or sulfur dioxide can be adopted for precipitating arsenic in the leaching solution; and leaching valuable elements such as nickel, cobalt, copper and the like from the leaching slag by adopting a pressurized oxygen leaching method.
In addition, alkali can be supplemented into the pulpified solution during water leaching treatment, so that the leaching process effect is improved, and the leaching rate is increased. Wherein, the mass concentration of the prepared alkali is 0% -20%, for example, 1%,5%,10%,15%,20% and the like.
The invention will be further described with reference to specific examples, while the effects of the invention will be further described. However, the following examples are only some, but not all, examples of the present invention.
The anode slime feed compositions of example 1 and example 2 are shown in table 1 below:
table 1 raw material composition of copper anode slime of example 1 and example 2
| As | Ni | Co | Fe | Cu | |
| wt％ | 11.84 | 3.39 | 0.0067 | 0.135 | 10.23 |
Example 1
1) Ball milling: ball milling is carried out on anode mud, and the granularity after ball milling is that-200 mesh 95%.
2) Alkalization: 100g of anode mud, 50.26g of sodium carbonate and about 3mol/mol of alkali and arsenic, and uniformly mixing;
3) Roasting: roasting at 600 ℃ for 2 hours;
4) Soaking in water: introducing air for 1L/min, and keeping the water volume at 500mL (namely, the liquid-solid ratio of 3:1), wherein the leaching temperature is 80 ℃ and the leaching time is 2h. 920mL of filtrate and 57.30g of residue were obtained.
The leachate and the leaching residue components were detected, and the detection results are shown in the following table 2:
table 2 example 1 test results
| As | Ni | Co | Fe | Cu | |
| Leachate component g/L | 10.97 | 0.052ppm | // | // | 11.63ppm |
| The leaching residue comprises the following components in percentage by weight | 2.55 | 5.08 | 0.0104 | 0.128 | 18.02 |
| Leaching rate% | 87.66 | 0 | 0 | 0 | 0.1 |
It can be seen that the final arsenic leaching rate reaches 87.66% by alkalization-roasting-water leaching in this example; other valuable metals are hardly leached, the leaching solution does not contain cobalt and iron, and anode slime, namely slag, is greatly reduced after arsenic is leached.
Example 2
1) Ball milling: ball milling is carried out on anode mud, and the granularity is-200 meshes and 95 percent after ball milling.
2) Alkaline leaching: 100g of anode mud, 40g of NaOH, about 6mol/mol of alkali and arsenic, 6:1 of liquid-solid ratio, 80 ℃ of leaching temperature, 6h of leaching time, 1L/min of air and 900rpm. 1490mL of a filtrate and 59.02g of a residue were obtained. The leachate and the leaching residue components were detected, and the detection results are shown in the following table 3:
TABLE 3 example 2 detection results
| As | Ni | Co | Fe | Cu | |
| Leachate component g/L | 6.89 | 0.656ppm | 0.072ppm | 0.124ppm | 3.61ppm |
| The leaching residue comprises the following components in percentage by weight | 2.11 | 5.29 | 0.011 | 0.214 | 16.41 |
| Leaching rate% | 89.48 | 0.03 | 1.60 | 0.14 | 0.05 |
It can be seen that the final arsenic leaching rate of the embodiment reaches 89.48% through alkaline leaching treatment; the leaching rate of other valuable metals is low, and anode slime, namely slag, is also greatly reduced after arsenic leaching.
The raw material compositions of examples 3-4 and comparative examples 1-2 are shown in Table 4 below:
TABLE 4 composition of copper anode slime raw materials of examples 3-4 and comparative examples 1-2
| As | Ni | Fe | Cu | |
| wt％ | 12 | 5 | 0.135 | 12 |
Example 3
1) Slurrying and then mixing the acid: 100g of anode mud, wherein the ratio of sodium to arsenic is about 3mol/mol, the slurrying ratio is 3:1, and the slurrying and acid mixing time is 0.5h;
2) Roasting: filtering, drying, roasting (i.e. heat treatment), wherein the roasting temperature is 600 ℃, and roasting for 2 hours;
3) Soaking in water: and adding water into the materials subjected to the heat treatment to slurry, stirring at the slurry ratio of 3:1 and 80 ℃ for 2 hours, filtering and drying after mixing to obtain anode slime after arsenic removal, and leaching the arsenic into the leaching solution.
The leachate was tested and the test results are shown in table 5 below:
TABLE 5 example 3 detection results
| As | Ni | Fe | Cu | |
| Leaching rate% | 88 | 0 | 0 | 0.1 |
It can be seen that the final arsenic leaching rate of the embodiment reaches 88% through alkaline leaching treatment; other valuable metals hardly leach out.
Example 4
1) Slurrying and then mixing the acid: 100g of anode mud, wherein the ratio of sodium hydroxide to arsenic is about 2mol/mol, the slurrying ratio (namely the liquid-solid ratio) is 3:1, and the slurrying and acid mixing time is 0.5h;
2) Roasting: filtering, drying, roasting at 600 ℃ for 2 hours;
3) Soaking in water: adding water after roasting, stirring at the slurry ratio of 3:1 and 80 ℃ for 2 hours, filtering and drying after mixing to obtain the anode mud after arsenic removal, and leaching the arsenic into the leaching solution. The leachate was examined, and the results of the examination are shown in table 6 below.
TABLE 6 example 4 detection results
| As | Ni | Fe | Cu | |
| Leaching rate% | 92 | 0 | 0 | 0.1 |
It can be seen that the final arsenic leaching rate of this example is as high as 92% by alkaline leaching treatment; other valuable metals hardly leach out.
Comparative example 1
Pressurized oxygen leaching: 100g of anode mud, a liquid-solid ratio of 6:1, a raw liquid volume of 600mL, an acid-arsenic ratio of about 2mol/mol, a temperature of 150 ℃, an oxygen partial pressure of 0.3MPa,800rpm, and leaching treatment for 2h.
The leaching rate of each component is detected, and the detection results are shown in the following table 7:
TABLE 7 comparative example 1 test results
| Leaching rate | As | Ni | Fe | Cu |
| ％ | 20 | 95 | 10 | 90 |
It can be seen that the arsenic leaching rate is only 92% after the pressurized oxygen leaching treatment of the comparative example, and most of nickel and copper are leached into the leaching solution, thus increasing the subsequent treatment difficulty.
Comparative example 2
Pressurized oxygen leaching: 100g of anode mud, a liquid-solid ratio of 6:1, a raw liquid volume of 600mL, an acid-arsenic ratio of about 4mol/mol, a temperature of 140 ℃, an oxygen partial pressure of 0.8MPa,800rpm and leaching treatment for 2h.
The leaching rate of each component is detected, and the detection results are shown in the following table 8:
table 8 comparative example 2 test results
| Leaching rate | As | Ni | Fe | Cu |
| ％ | 15 | 97 | 3 | 87 |
It can be seen that the arsenic leaching rate is only 15% after the pressurized oxygen leaching treatment of the comparative example, and most of nickel and copper are leached into the leaching solution, thus increasing the subsequent treatment difficulty.
In summary, in the comparative example, only about 15% of arsenic is leached into the leachate, and most of other metals such as copper and nickel are leached into the leachate, which makes recycling of each metal difficult. In the embodiment of the invention, arsenic is leached and recovered by an alkaline leaching method or an alkalization-roasting-water leaching method, most of the arsenic enters a liquid phase, other metals such as copper, nickel and the like are left in slag to be leached less or not leached, meanwhile, the anode slime amount after arsenic leaching is greatly reduced, the treated solution can be precipitated to prepare an arsenic salt product, and the valuable elements such as nickel, cobalt, copper and the like are enriched by more than one time in the treated slag, so that the leaching treatment amount of the valuable elements leached by subsequent pressurization and oxygen ventilation is reduced.
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (9)
1. The high-arsenic copper anode slime treatment method is characterized by comprising the following steps of:
mixing high-arsenic copper anode slime with alkali, introducing oxygen-containing gas for alkaline leaching treatment, leaching arsenic into leaching liquid after the treatment, and leaching residues are anode slime after arsenic removal; wherein, the molar ratio of alkali to arsenic is (0.5-10): 1, leaching temperature is 25-200 ℃, leaching time is 0.5-6 h, and liquid-solid ratio is (2-10): 1.
2. the high-arsenic copper anode slime treatment method is characterized by comprising the following steps of:
mixing high-arsenic copper anode slime with alkali for alkalization treatment, wherein the alkali-arsenic molar ratio is (0.5-10): 1, a step of;
filtering after alkalization treatment and roasting a filter cake; wherein the roasting temperature is 200-1000 ℃ and the roasting time is 10 min-6 h;
slurrying the roasted material with water, introducing oxygen-containing gas, carrying out water leaching treatment, leaching arsenic into leaching liquid, and leaching residues are anode mud after arsenic removal; wherein, the liquid-solid ratio is (2-10): 1, the leaching temperature is 25-200 ℃ and the leaching time is 0.5-6 h.
3. The method for treating high-arsenic copper anode slime according to claim 1 or 2, further comprising, before the step of mixing the high-arsenic copper anode slime with alkali: ball milling is carried out on the high-arsenic anode slime until the granularity is 80 percent of minus 100 meshes to 100 percent of minus 325 meshes.
4. The method for treating high-arsenical copper anode slime according to claim 1 or 2, further comprising: and precipitating arsenic from the leaching solution by adopting ferric salt or sulfur dioxide.
5. The method for treating high-arsenical copper anode slime according to claim 1 or 2, further comprising: and leaching the valuable elements from the leaching slag by adopting a pressurized oxygen leaching method.
6. The method for treating high-arsenic copper anode slime according to claim 1 or 2, wherein the alkali is one or a combination of several of sodium hydroxide, potassium hydroxide, calcium oxide, magnesium oxide, sodium carbonate, sodium bicarbonate, potassium carbonate and magnesium carbonate.
7. The method for treating high-arsenic copper anode slime according to claim 1 or 2, wherein the step of mixing the high-arsenic anode slime with alkali includes:
slurrying high-arsenic anode mud, and controlling the liquid-solid ratio (2-4): 1, a step of;
adding alkali for mixing, and preparing alkali with mass concentration of 2-20% and mixing time of 0.5-2 h.
8. The method for treating high-arsenic copper anode slime according to claim 2, further comprising, before roasting the filter cake: and drying the filter cake.
9. The method for treating high-arsenic copper anode slime according to claim 2, further comprising, when water immersion treatment is performed: and supplementing alkali into the pulpified solution, wherein the mass concentration of the prepared alkali is 0.1-20%.
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