CN114480862A - Method for recovering valuable elements from copper dross - Google Patents
Method for recovering valuable elements from copper dross Download PDFInfo
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- CN114480862A CN114480862A CN202210085349.4A CN202210085349A CN114480862A CN 114480862 A CN114480862 A CN 114480862A CN 202210085349 A CN202210085349 A CN 202210085349A CN 114480862 A CN114480862 A CN 114480862A
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- leaching
- roasting
- copper
- slag
- acid
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- 239000010949 copper Substances 0.000 title claims abstract description 93
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 74
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002386 leaching Methods 0.000 claims abstract description 129
- 239000002893 slag Substances 0.000 claims abstract description 41
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000000779 smoke Substances 0.000 claims abstract description 21
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 20
- 239000000428 dust Substances 0.000 claims abstract description 19
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 18
- 150000007522 mineralic acids Chemical class 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000004071 soot Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 30
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000011133 lead Substances 0.000 description 37
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- 229910006069 SO3H Inorganic materials 0.000 description 13
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910000367 silver sulfate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052924 anglesite Inorganic materials 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- -1 and meanwhile Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 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
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
- C22B15/0015—Oxidizing 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
- C22B15/0063—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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- 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
- C22B30/06—Obtaining bismuth
-
- 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
-
- 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
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention relates to a method for recovering valuable elements from copper dross, which comprises the steps of crushing the copper dross to be treated to obtain copper dross powder; carrying out oxidizing roasting treatment on the copper dross powder to obtain roasting slag and smoke dust; acid leaching is carried out on the roasting slag; and (3) leaching the smoke dust by using methanesulfonic acid as a leaching agent, and performing solid-liquid separation to obtain a first leaching solution rich in bismuth and a first leaching residue rich in antimony. The method is simple and practical, has low cost, and can effectively realize the separation and recovery of various valuable metal elements in the copper dross.
Description
Technical Field
The invention relates to a method for recovering valuable elements from copper dross, belonging to the field of non-ferrous metallurgy.
Background
At present, the copper dross is usually treated in a reverberatory furnace by a soda-scrap iron method in industry, that is, the corresponding scrap iron, soda ash, coke and a small amount of lead concentrate are added according to the components of the copper dross, and then reduction smelting is carried out to produce the crude lead and the matte. However, the above treatment process has a problem that the time required for the melting operation is long, and even if the treatment time is as long as 12 hours or more, the melting lead yield is low, and a large amount of lead-containing matte is produced. Lead copper matte contains a large amount of gold and silver, and meanwhile, slag and copper matte are not well separated, the slag contains copper, the copper matte contains high lead and low copper, most of valuable metals in the slag and the copper matte are difficult to recover, so that a large amount of accumulation is caused, funds are accumulated, and the benefit of an enterprise is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for recovering valuable elements from copper dross, so as to better realize the separation and recovery of each valuable metal element in the copper dross.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for recovering valuable elements from copper dross, comprising the steps of:
s1, crushing the copper dross to be treated to obtain copper dross powder;
s2, carrying out oxidizing roasting treatment on the copper dross powder obtained in the step S1 to obtain roasting slag and smoke dust;
s3, carrying out acid leaching on the roasting slag obtained in the step S2;
and (3) leaching the smoke dust obtained in the step (S2) by using methanesulfonic acid as a leaching agent, and performing solid-liquid separation to obtain a first leaching solution rich in bismuth and a first leaching residue rich in antimony.
As one embodiment of the invention, when the content of Ag is more than 1000g/t, the content of Pb is more than 70 wt% and the content of Cu is 2-10 wt%, the temperature of oxidizing roasting in S2 is 400-750 ℃, further 500-700 ℃, further 550-650 ℃, and the roasting time is 1-4h, further 2-3 h;
in S3, after inorganic acid is used as a leaching agent to leach the roasting slag for a first time, solid-liquid separation is carried out to obtain second leaching slag and a second leaching solution rich in copper; secondly, after the second leaching residue is leached by adopting methanesulfonic acid as a leaching agent, carrying out solid-liquid separation to obtain a third leaching residue rich in silver and a third leaching solution rich in lead;
wherein the inorganic acid is sulfuric acid and/or hydrochloric acid. Thus, the main components of the obtained roasting slag are CuO, PbO and Ag, and the main components of the obtained smoke dust are Bi2O3、Sb2O3(ii) a Further leaching with inorganic acid to obtain copperThe lead and the silver are recovered after entering the second leaching solution, the lead and the silver are remained in the second leaching residue, and the silver (mainly a silver simple substance) is remained in the third leaching residue through further leaching by methanesulfonic acid, the lead is enriched in the third leaching solution, and (CH) is generated3SO3)2Pb, thereby realizing the separation, enrichment and recovery of copper, lead and silver. Therefore, the separation and recovery of Pb, Cu, Bi, Sb, Ag and other elements in scum can be realized by roasting at a lower temperature and combining with the acid leaching of specific acids, and the method is simple, practical and low in energy consumption. The Cu leaching rate can reach more than 99 percent, and the Pb leaching rate can reach more than 98 percent. The second leaching solution can be repeatedly used for leaching, and when the solution meets the requirement of copper electrodeposition concentration, the solution is sent to a copper purification and electrodeposition system. The main component of the third leaching residue is simple substance Ag, the residue rate is less than 1%, and the Ag content is more than 80%.
According to the invention, the smoke dust is leached by the methanesulfonic acid, so that bismuth is enriched in the first leaching solution, and antimony is retained in the first leaching residue (antimony mainly exists in the form of antimony oxide), thereby realizing separation, enrichment and recovery of bismuth and antimony. The first leaching slag can be further sent to an antimony smelting system to recover antimony.
Further, during the first-stage leaching, H in the reaction system is controlled+And the initial molar ratio of Cu is 2-4:1, the liquid-solid ratio is 2-6 mL:1g, leaching temperature is 50-95 ℃, and leaching time is 1-4 h; when the second stage leaching is carried out, CH in the reaction system is controlled3SO3Initial molar ratio of H to Pb 2-4:1, the liquid-solid ratio is 2-6 mL:1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
Further, in S3, when the smoke is leached, CH in the reaction system is controlled3SO3Initial molar ratio of H and Bi 3-5: 1, the liquid-solid ratio is 2-6 mL:1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
As another embodiment of the invention, when the content of Ag in the copper dross is 1000g/t, the content of Pb is 30-50 wt% and the content of Cu is 10-40 wt%, the temperature of oxidizing roasting in S2 is 900-1200 ℃, and the roasting time is 1-4 h;
in S3, when the content of Cu in the copper dross is less than or equal to 20 wt%, leaching the roasting slag by using methanesulfonic acid as a leaching agent, and performing solid-liquid separation to obtain a fourth leaching solution rich in copper and silver; thus, MSA leaching can realize leaching of Cu and Ag, so that the Cu and Ag can enter a solution. Basically no leaching residue exists, and a very small amount of unreacted leaching residue can be used as a returning material to return for leaching reaction. And after the solution is saturated, the copper and silver can be recovered, and the leaching rates of Cu and Ag can reach more than 96%.
When the content of Cu in the copper dross slag is more than 20 wt%, leaching the roasting slag by using inorganic acid as a leaching agent, and performing solid-liquid separation to obtain fifth leaching slag rich in silver and a fifth leaching solution rich in copper;
the inorganic acid is sulfuric acid and/or hydrochloric acid, so that the high-efficiency enrichment of copper can be realized, and the effective separation of Cu and Ag in the roasting slag can be realized. The inorganic acid is preferably sulfuric acid, and in this case, the main component of the fifth leaching residue is Ag2SO4The slag rate is less than 1%, the Ag content reaches 40%, and the Cu leaching rate can reach more than 99%.
Further, in S3, when the roasting slag is leached by using inorganic acid as a leaching agent, H in the reaction system is controlled+And Cu in an initial molar ratio of 2-4:1, a liquid-solid ratio of 2-6 mL:1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
Further, in S3, when the roasted slag is leached by using methanesulfonic acid as a leaching agent, the total molar weight of Cu and Ag and H in the reaction system are controlled+The initial molar weight ratio of (1: 1-5), the liquid-solid ratio of (2-6 mL): 1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
Further, in S3, when the smoke is leached, the total molar amount of Bi and Pb and the CH in the reaction system are controlled3SO3The initial molar weight ratio of H is 1:3-6, the liquid-solid ratio is 2-6 mL:1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
Further, in S1, the copper dross is crushed to-200 mesh > 85%.
Further, the oxidizing roasting is performed in a rotary kiln, so that higher roasting efficiency can be obtained.
Further, oxidizing roasting is carried out in an air atmosphere or oxygen-enriched air with the oxygen concentration of 23-26 vol%.
Furthermore, in the oxidizing roasting process, the temperature can be obtained by heating in an electric furnace or by adding coal or coke.
Further, the copper dross contained 26.8% of Cu, 42.1% of Pb, 500g/t of Ag, 7.6% of Sb, and 3.2% of Bi, and usually, Cu, Pb, Ag, Sb, and Bi were mainly present in the form of simple substances.
In the present invention, the reactions that may occur during the oxidizing roasting are as follows:
2Cu+O2＝2CuO (1)
Pb+O2＝2PbO (2)
4Bi+3O2＝2Bi2O3 (3)
4Sb+3O2＝2Sb2O3 (4)
4Ag+O2＝2Ag2O (5)
in leaching with mineral acids containing sulphuric acid, the reactions that may occur are as follows:
CuO+H2SO4＝CuSO4+H2O (6)
PbO+H2SO4＝PbSO4↓+H2O (7)
Bi2O3+3H2SO4＝Bi2(SO4)3↓+3H2O (8)
Ag2O+H2SO4＝Ag2SO4↓+H2O (9)。
when leaching is carried out with methanesulfonic acid, the reactions that may occur are as follows:
CuO+2CH3SO3H＝(CH3SO3)2Cu+H2O (10)
PbO+2CH3SO3H＝(CH3SO3)2Pb+H2O (11)
Bi2O3+6CH3SO3H＝2(CH3SO3)3Bi+3H2O (12)
Ag2O+2CH3SO3H＝2(CH3SO3)Ag+H2O (13)
PbSO4+2CH3SO3H＝(CH3SO3)2Pb+H2SO4 (14)
Bi2(SO4)3+6CH3SO3H＝2(CH3SO3)3Bi+3H2SO4 (15)
Ag2SO4+2CH3SO3H＝2(CH3SO3)Ag+H2SO4 (16)。
the invention adopts the process of copper scum oxidation roasting combined with acid leaching to recover copper, lead and silver, and the process is simple, low in cost, short in period and high in copper leaching rate.
In the invention, the smoke dust is leached and separated by adopting methanesulfonic acid. After leaching, the main component of the obtained leaching residue is Sb2O3The Sb accounts for more than 78 percent, Bi is enriched in the obtained leaching liquid, and the leaching rate of the Bi is more than 98 percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method is simple and practical, has low cost, and can effectively realize the separation and recovery of various valuable metal elements in the copper dross.
(2) The invention can flexibly control the process conditions of oxidizing roasting according to the contents of Pb, Cu, Bi, Sb, Ag and other elements in the copper dross, and realizes the high-efficiency separation and respective recovery of valuable metals in the copper dross through a subsequent specific wet recovery process.
(2) The invention can carry out inorganic acid + organic acid leaching or inorganic acid leaching or organic acid leaching on different roasted products according to respective chemical reaction characteristics of inorganic acid and methanesulfonic acid and the saturation solubility of each element, has high recovery rate of Pb, Cu, Bi, Sb and Ag, can reach more than 98 percent, thoroughly separates Bi and Sb in smoke dust, and simplifies the subsequent recovery process of Bi and Sb.
Drawings
FIG. 1 is a flowchart of example 1 of the present invention.
Fig. 2 is a flowchart of embodiment 2 of the present invention.
Fig. 3 is a flowchart of embodiment 3 of the present invention.
FIG. 4 is an XRD pattern of the roasted slag of example 1 of the present invention.
Figure 5 is an XRD spectrum of the soot of example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. The percentages referred to are percentages by mass, unless otherwise specified.
Example 1
In this embodiment, the method for recovering valuable elements from copper dross is as follows:
copper dross (Cu8.8%, Pb72.1%, Ag1200g/t, Sb5.4%, Bi2.9%) is crushed, ball milled to-200 mesh>85 vol%, then 1kg of the ground copper dross is taken to be roasted in an electric furnace by oxidation at 600 ℃ and roasted for 2.5h in air atmosphere. And roasting to obtain roasted slag and smoke dust. The main phases of the roasting slag are CuO, PbO and Ag through detection. The main component of the smoke dust is Bi2O3、Sb2O3The volatilization rates of Bi and Sb were 95% and 97%, respectively.
Mixing the roasting slag with sulfuric acid solution, reacting, and controlling H in the reaction system+Initial molar ratio of Cu 3: 1, the liquid-solid ratio is 4mL:1g, reacting for 3 hours at 50 ℃ to obtain leachate and leaching residues, wherein the content of Cu in the leachate is 21.7g/L, and the recovery rate of Cu is 98.5%.
Leaching residue and methanesulfonic acid (CH)3SO3H) Reacting, controlling CH in the reaction system3SO3H. Initial molar ratio of Pb of 31, reacting at 60 ℃ for 3 hours with a liquid-solid ratio of 4mL:1g to obtain a leaching solution containing 109.9g/L Pb and a lead recovery rate of 99.2%, wherein the leaching residue is Ag-rich residue containing 85% of silver and is sent to an Ag system for recovery, and the silver recovery rate reaches 99.6%.
Reacting smoke dust with methanesulfonic acid, and controlling CH in the reaction system3SO3H. Initial molar ratio of Bi 4:1, the liquid-solid ratio is 4mL:1g, the reaction is carried out for 3h at 60 ℃, the obtained leaching solution contains 76.2g/L of Bi, and the recovery rate of the Bi is 98.7%. The leaching residue is rich in antimony oxide (containing Sb 80%), and is sent to an antimony system for recovery, and the recovery rate of antimony reaches 99.1%.
Example 2
In this embodiment, the method for recovering valuable elements from copper dross is as follows:
copper dross (Cu26.8%, Pb42.1%, Ag500g/t, Sb7.6%, Bi3.2%) is crushed, ball milled to-200 mesh>85 vol%, and then 1kg of the finely ground copper dross was subjected to oxidizing roasting in an electric furnace at 1150 ℃ for 2 hours in an oxygen-enriched air atmosphere (oxygen concentration: 23 vol%). Roasting to obtain roasting slag and smoke dust. The main phases of the roasting slag are CuO and Ag through detection2And O. The main components of the smoke dust are PbO and Bi2O3、Sb2O3The volatilization rates of Bi and Sb were 95.6% and 97.5%, respectively.
The roasting slag reacts with sulfuric acid, and H in a reaction system is controlled+Initial molar ratio of Cu 2: 1, the solution-solid ratio is 5mL:1g, the reaction is carried out for 2 hours at 60 ℃, so as to obtain leachate and leaching slag, the leaching solution contains 52.9g/L of Cu, the copper recovery rate is 98.7%, the slag rate is 0.5%, the leaching slag is silver-rich slag and is sent to an Ag system for recovery, and the Ag recovery rate is 99.5%.
Reacting smoke dust with methanesulfonic acid, and controlling CH in the reaction system3SO3H. Initial molar ratio (Bi + Pb) of 3: 1, the liquid-solid ratio is 3mL:1g, the reaction is carried out for 3h at 60 ℃, the obtained leachate contains 18.6g/L Bi, 252g/L Pb, the recovery rate of bismuth is 98.2 percent, the recovery rate of lead is 98.9 percent, and the leachate can be used as a lead electrodeposition raw material. The leaching residue is rich in antimony oxide, contains 78% of Sb, and is sent to an antimony system for recovery, and the recovery rate of antimony reaches 99.2%.
Example 3
In this embodiment, the method for recovering valuable elements from copper dross is as follows:
copper dross (Cu16.5%, Pb49.1%, Ag500g/t, Sb7.6%, Bi3.2%) is crushed, ball milled to-200 mesh>85 vol%, then 1kg of the ground copper dross is taken to be roasted in an electric furnace by oxidation at the temperature of 1000 ℃ and roasted for 2h in the atmosphere of oxygen-enriched 23 percent air. Roasting to obtain roasting slag and smoke dust. The main phases of the roasting slag are still CuO and Ag through detection2And O. The main components of the smoke dust are PbO and Bi2O3、Sb2O3The volatilization rates of Bi and Sb were 95.2% and 97.3%, respectively.
Mixing the roasting residue with methanesulfonic acid, and controlling CH in the reaction system3SO3H. Initial molar ratio (Cu + Ag) 3: 1, the liquid-solid ratio is 5mL:1g, the reaction is carried out for 3h at 75 ℃, solid-liquid separation is carried out, a leaching solution and leaching residues are obtained, the obtained leaching solution contains Cu90.8g/L and Ag0.10 g/L, the copper recovery rate is 98.8 percent, the silver recovery rate is 99.1 percent, and Cu and Ag can be subsequently recovered from the leaching solution.
Mixing the smoke dust with methanesulfonic acid to control CH in the reaction system3SO3H. Initial molar ratio (Bi + Pb) of 3: 1, controlling the liquid-solid ratio to be 4mL:1g, reacting for 2h at 75 ℃, and carrying out solid-liquid separation to obtain a leaching solution and leaching residues. The leaching solution contains 12.7g/L of Bi and 141.8g/L of Pb, the Bi and the Pb are recovered from the leaching solution, the recovery rate of the bismuth is 98.9 percent, and the recovery rate of the lead is 99.2 percent. The leaching slag is rich in antimony oxide, contains 79% of Sb, and is sent to an antimony system for recovery, and the antimony recovery rate is 99.2%.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (9)
1. A method for recovering valuable elements from copper dross, which is characterized by comprising the following steps:
s1, crushing the copper dross to be processed to obtain copper dross powder;
s2, carrying out oxidizing roasting treatment on the copper dross powder obtained in the step S1 to obtain roasting slag and smoke dust;
s3, carrying out acid leaching on the roasting slag obtained in the step S2;
and (3) leaching the smoke dust obtained in the step (S2) by using methanesulfonic acid as a leaching agent, and performing solid-liquid separation to obtain a first leaching solution rich in bismuth and a first leaching residue rich in antimony.
2. The method as claimed in claim 1, wherein when the content of Ag in the copper dross is >1000g/t, the content of Pb is >70 wt%, and the content of Cu is 2-10 wt%, the temperature of the oxidizing roasting in S2 is 400-750 ℃, and the roasting time is 1-4 h;
in S3, after inorganic acid is used as a leaching agent to leach the roasting slag for a first time, solid-liquid separation is carried out to obtain second leaching slag and a second leaching solution rich in copper; secondly, after the second leaching residue is leached by adopting methanesulfonic acid as a leaching agent, carrying out solid-liquid separation to obtain a third leaching residue rich in silver and a third leaching solution rich in lead;
wherein the inorganic acid is sulfuric acid and/or hydrochloric acid.
3. The method as claimed in claim 2, wherein the H in the reaction system is controlled in the case of one-stage leaching+And Cu in an initial molar ratio of 2-4:1, the liquid-solid ratio is 2-6 mL:1g, leaching temperature is 50-95 ℃, and leaching time is 1-4 h; when the second stage leaching is carried out, CH in the reaction system is controlled3SO3Initial molar ratio of H to Pb 2-4:1, the liquid-solid ratio is 2-6 mL:1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
4. The method according to claim 2 or 3, wherein in the step S3, CH in the reaction system is controlled when the soot is leached3SO3Initial molar ratio of H and Bi 3-5: 1, the liquid-solid ratio is 2-6 mL:1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
5. The method as claimed in claim 1, wherein the Ag content is 500-1000g/t and the Pb content is 500-1000g/t in the copper dross
30-50 wt% and 10-40 wt% Cu, wherein in S2, the oxidizing roasting temperature is 900-1200 ℃, and the roasting time is 1-4 h; in S3, after the roasting residue is leached by adopting methanesulfonic acid as a leaching agent, carrying out solid-liquid separation to obtain a fourth leaching solution rich in copper and silver; or after leaching the roasting slag by using inorganic acid as a leaching agent, performing solid-liquid separation to obtain a fifth leaching slag rich in silver and a fifth leaching solution rich in copper;
wherein the inorganic acid is sulfuric acid and/or hydrochloric acid.
6. The method as claimed in claim 5, wherein in S3, when leaching the roasted slag by using inorganic acid as leaching agent, H in the reaction system is controlled+And Cu in an initial molar ratio of 2-4:1, a liquid-solid ratio of 2-6 mL:1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
7. The method as claimed in claim 5, wherein in S3, when the roasted slag is leached by using methanesulfonic acid as a leaching agent, the total molar amount of Cu and Ag and H in the reaction system are controlled+The initial molar weight ratio of (1: 1-5), the liquid-solid ratio of (2-6 mL): 1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
8. The method as claimed in any one of claims 5 to 7, wherein in S3, when leaching the soot, the total molar amount of Bi and Pb and CH in the reaction system are controlled3SO3The initial molar weight ratio of H is 1:3-6, the liquid-solid ratio is 2-6 mL:1g, the leaching temperature is 50-95 ℃, and the leaching time is 1-4 h.
9. The method of claim 1, wherein in S1, the copper dross is crushed to-200 mesh > 85%.
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