CN111809046A - Process for removing lead, copper and bismuth in antimony oxide by wet method - Google Patents
Process for removing lead, copper and bismuth in antimony oxide by wet method Download PDFInfo
- Publication number
- CN111809046A CN111809046A CN202010682704.7A CN202010682704A CN111809046A CN 111809046 A CN111809046 A CN 111809046A CN 202010682704 A CN202010682704 A CN 202010682704A CN 111809046 A CN111809046 A CN 111809046A
- Authority
- CN
- China
- Prior art keywords
- lead
- antimony oxide
- copper
- bismuth
- nitric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229910000410 antimony oxide Inorganic materials 0.000 title claims abstract description 72
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000010949 copper Substances 0.000 title claims abstract description 50
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 48
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 40
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 16
- 230000005484 gravity Effects 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 abstract description 34
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 34
- 238000011084 recovery Methods 0.000 abstract description 10
- 229910052745 lead Inorganic materials 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 description 12
- 239000012452 mother liquor Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QQHJESKHUUVSIC-UHFFFAOYSA-N antimony lead Chemical compound [Sb].[Pb] QQHJESKHUUVSIC-UHFFFAOYSA-N 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- KBKGVINMNSFFOO-UHFFFAOYSA-N silver hydrochloride Chemical compound Cl.[Ag] KBKGVINMNSFFOO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0073—Leaching or slurrying with acids or salts thereof containing nitrogen
-
- 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
-
- 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)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A process for removing lead, copper and bismuth in antimony oxide by a wet method. The process comprises the steps of pretreating antimony oxide to be leached, leaching the lead, copper and bismuth from the antimony oxide in nitric acid at the temperature of 60-100 ℃, and carrying out solid-liquid separation to obtain low-lead antimony oxide and lead nitrate solution containing the copper and the bismuth; the mass concentration of the nitric acid is 10-20%. The process of the invention adopts nitric acid with specific concentration to leach antimony oxide, and lead, copper and bismuth in the antimony oxide are simultaneously dissolved out to obtain low-lead antimony oxide with Pb, Cu and Bi contents lower than 0.1%, and the antimony recovery rate reaches 99%.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal antimony smelting, and particularly relates to a process for removing lead, copper and bismuth in antimony oxide by a wet method.
Background
In the smelting process of non-ferrous antimony, lead, copper and bismuth are common impurities, which seriously affect the quality of antimony products and limit the application of antimony products in industry, so the national standard of antimony products stipulates the requirements of the content of lead, copper and bismuth in antimony products. In the pyrogenic process production process of antimony, lead is removed by adopting a lead removing agent pyrogenic process, copper is removed by adopting a copper removing agent, and bismuth does not have a proper separation technology so far.
The existing fire method lead removal technology is simple to operate, but the direct yield of antimony is greatly lost in the lead removal process, and particularly antimony oxide with high lead content has higher loss rate in the lead removal process; the produced lead slag removal amount is large, lead and antimony in the lead slag are further removed, and the process is very difficult. The existing technology for removing copper from crude antimony by a pyrogenic process has the defects of incomplete removal, or large antimony loss, and does not have a proper and effective copper removal technology. The existing fire bismuth removing technology for crude antimony is not used in industrial production. Thus, although some techniques are used in the pyrometallurgical antimony smelting of copper and bismuth, these techniques have been undesirable and require improvement or innovation.
CN1062175A discloses a method for preparing silver nitrate and recovering copper, lead and antimony from lead anode slime. The key point of the method is that the method comprises the following steps: (1) leaching with nitric acid; (2) leaching the filter residue with hydrochloric acid; (3) precipitating lead from the filtrate by using sulfuric acid; (4) hydrolyzing the hydrochloric acid leaching solution; (5) washing filter residues obtained by hydrolysis with alkali; (6) carrying out hydrochloric acid silver precipitation on the filtrate after lead precipitation by sulfuric acid, (7) combining the filter residues obtained in the steps (2) and (6), and carrying out ammonia leaching, complexing and reduction to prepare silver nitrate; (8) adding alkali into the filtrate obtained in the step (5) for neutralization, and then adding sulfide for copper precipitation; (9) and (5) mixing the filtrates obtained in the steps (5) and (8), and removing arsenic to obtain clear liquid and arsenic slag. The method mainly prepares silver nitrate and secondarily separates copper, lead and antimony. Although nitric acid leaching is used, the separation effect is not good. As in the examples, when 5N nitric acid was used at a liquid-solid ratio of 5 and the reaction was carried out at 80 to 95 ℃ for 3 hours, the leaching rate of Ag was 53.66%, the leaching rate of Cu was 99.10%, the leaching rate of Sb was 12.60%, the leaching rate of As was 53.58% and the leaching rate of Pb was 98.11%. The leaching rate of lead in this example is high, but the leaching rate of antimony also reaches 12.60%, and lead nitrate and antimony nitrate are precipitated in sulfuric acid solution to different degrees.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and providing a process for removing lead, copper and bismuth in antimony oxide by a wet method.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a process for removing lead, copper and bismuth from antimony oxide by a wet method comprises the steps of pretreating antimony oxide to be leached, leaching the lead, copper and bismuth from the antimony oxide in nitric acid at 60-100 ℃, and carrying out solid-liquid separation to obtain low-lead antimony oxide and a lead nitrate solution containing copper and bismuth; the mass concentration of the nitric acid is 10-20%.
The purpose of the antimony oxide pretreatment is to clean coarse impurities in the antimony oxide and simultaneously crush the antimony oxide with coarse particle size.
The concentration of the nitric acid is too low, and the reaction time is too long; the concentration of the nitric acid is too high, so that the leaching rate of antimony is increased, the loss of antimony is caused, and meanwhile, lead nitrate contains higher antimony; further, if the concentration of nitric acid is too high, the nitric acid is easily volatilized, and the working environment is easily deteriorated. Therefore, the concentration of the nitric acid is strictly controlled in the leaching process, and the leaching effect is very important.
Preferably, the antimony oxide is high-lead antimony oxide, and comprises, by mass, 45-65% of Sb, 5-25% of Pb, 0.5% or more of Cu, and 0.5% or more of Bi.
Preferably, in the leaching, the mass volume ratio of the antimony oxide to the nitric acid is 1g: 2-6 mL, and the leaching time is 2-6 h.
Preferably, the solid-liquid separation mode is to adopt centrifugation or filter pressing by a filter press, and then to adopt nitric acid with the mass percentage concentration of 5-8% for washing.
Preferably, the grain size of the pretreated antimony oxide is 100-300 meshes. The leaching rate of lead is reduced due to too coarse granularity of antimony oxide, and the leaching rate of lead, copper and bismuth is reduced due to the coarse granularity, so that the purpose of separating antimony from lead, copper and bismuth is difficult to achieve.
Preferably, the process further comprises: concentrating the lead nitrate solution to a specific gravity of 1.7 at 100-105 ℃ under normal pressure, carrying out hot filtration to obtain a lead nitrate crude product and a mother solution, and mixing the mother solution with a lead nitrate solution to be distilled next time and a washing solution for distillation; the distilled water obtained by distillation is used for preparing nitric acid used in leaching.
The principle of separating lead, copper and bismuth from antimony oxide is that at the temperature of 60-100 ℃, the lead, copper and bismuth in the antimony oxide are easy to react with nitric acid to generate corresponding nitrates, and the solubilities of the nitrates are high; and the antimony oxide is rarely dissolved in the nitric acid, so that the aim of separating impurities such as lead, copper, bismuth and the like from the antimony is fulfilled. The main chemical reaction formula is as follows:
PbO+2HNO3＝Pb(NO3)2+H2O
CuO+2HNO3＝Cu(NO3)2+H2O
Bi2O3+2HNO3＝Bi(NO3)3+H2O
the invention has the beneficial effects that:
(1) in the process, at the temperature of 60-100 ℃, the antimony oxide is leached by using nitric acid with specific concentration, so that lead, copper and bismuth in the antimony oxide are dissolved out, low-lead antimony oxide with Sb more than 65%, Pb less than 0.1%, Cu less than or equal to 0.05% and Bi less than or equal to 0.02% is obtained, the lead removal rate is more than 98%, and the antimony recovery rate is 99%;
(2) in the preferred scheme of the invention, the lead sulfate solution is concentrated under normal pressure and filtered thermally to obtain crude lead nitrate, which can be used for refining lead nitrate products and improve the added value of the lead sulfate solution;
(3) compared with fire refining, the process has the advantages of simple whole treatment process, low treatment cost, no generation of waste gas, waste water and waste residue in the whole process and good environment.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
The embodiment comprises the following steps:
(1) leaching: after pretreatment, 400g of high-lead antimony oxide (Sb 45.00%, Pb 25.00%, Cu 0.50% and Bi 0.50%) with minus 100 meshes is obtained, the high-lead antimony oxide is added into 2400mL of dilute nitric acid solution (the mass percentage concentration of nitric acid is 18%, the solid-to-liquid ratio is 1: 6), the leaching temperature is controlled to be 60 ℃, the leaching time is 360 minutes, then, a filter cake is obtained through filtration, 258g of dry antimony oxide is obtained after drying, and the analysis results are Sb 69.43%, Pb 0.090%, Cu 0.030% and Bi 0.020%; 1920mL of filtrate containing lead nitrate has the chemical composition of Sb0.45g/L, Pb 51.96.96 g/L, Cu 1.00.00 g/L, Bi 1.01.01 g/L.
(2) And (3) evaporation: the lead nitrate solution was concentrated under normal pressure, and when the specific gravity was 1.7 (103 ℃ C.), the concentration was stopped, and when the specific gravity was 40 to 60 ℃ C., 171.07g of crude lead nitrate was obtained by filtration, which contained Pb58.15%, Cu1.06%, Bi 1.04%, and Sb0.37% as the main components. 192mL of mother liquor, Sb1.20g/L, Pb1.50g/L and Cu0.59g/L, Bi 0.85.85 g/L, and returning to the next concentration.
By the treatment process described in this example, the removal rate of lead in the high-lead antimony oxide was 99.77%, the removal rate of Cu was 96.13%, and the removal rate of Bi was 97.42%; the recovery of antimony was 99.52%.
Example 2
The embodiment comprises the following steps:
(1) leaching: after pretreatment, 800g of high-lead antimony oxide (Sb65.00%, Pb5.00%, Cu0.10% and Bi0.10%) with minus 150 meshes is obtained, the high-lead antimony oxide is added into 1600mL of dilute nitric acid solution (the mass percentage concentration of the nitric acid is 10%, the solid-to-liquid ratio is 1: 2), the leaching temperature is controlled to be 70 ℃, the leaching time is 300 minutes, then, a filter cake is obtained through filtration, 750g of dry antimony oxide is obtained after drying, and the analysis result is Sb69.26%, Pb0.100%, Cu0.007% and Bi 0.016%; 1200mL of lead nitrate-containing filtrate, wherein the chemical components of the lead nitrate-containing filtrate are Sb0.48g/L, Pb32.71g/L, Cu0.62g/L and Bi0.57g/L.
(2) And (3) evaporation: the lead nitrate solution was concentrated under normal pressure, and when the specific gravity was 1.7 (103 ℃ C.), the concentration was stopped, and when the specific gravity was 40 to 60 ℃ C., 67.08g of crude lead nitrate was obtained by filtration, and the crude lead nitrate contained as main components, Pb58.25%, Cu0.99%, Bi 0.93% and Sb0.62%. 120mL of mother liquor, Sb1.35g/L, Pb1.45g/L and Cu0.68g/L, Bi 0.48.48 g/L, and returned to the next concentration.
By the treatment process described in the example, the removal rate of lead in the high-lead antimony oxide was 98.13%, the removal rate of Cu was 93.44%, and the removal rate of Bi was 85.00%; the recovery of antimony was 99.89%.
Example 3
The embodiment comprises the following steps:
(1) leaching: 1000g of high-lead antimony oxide (Sb55.56%, Pb15.00%, Cu0.40% and Bi0.20%) with the particle size of minus 200 meshes is obtained after pretreatment, the high-lead antimony oxide is added into 4000mL of dilute nitric acid solution (the concentration of nitric acid is 20%, the solid-to-liquid ratio is 1: 4), the leaching temperature is controlled to be 80 ℃, the leaching time is 180 minutes, then, a filter cake is obtained through filtration, 768g of dry antimony oxide is obtained after drying, and the analysis results are Sb71.80%, Pb0.085%, Cu0.020% and Bi 0.010%; 3000mL of lead nitrate-containing filtrate contains Sb1.39g/L, Pb49.78g/L and Cu1.28g/L, Bi 0.64.64 g/L.
(2) And (3) evaporation: the lead nitrate solution was concentrated under normal pressure, and when the specific gravity was 1.7 (103 ℃ C.), the concentration was stopped, and when the specific gravity was 40 to 60 ℃ C., 258.65g of crude lead nitrate was obtained by filtration, which contained Pb57.58%, Cu1.24%, Bi 0.63%, and Sb1.46% as the main components. The mother liquor 300mL, Sb1.35g/L, Pb1.38g/L, Cu2.13g/L, Bi 0.98.98 g/L returned to the next concentration.
Through the treatment process described in the embodiment, the removal rate of lead in the high-lead antimony oxide is 99.56%, the removal rate of Cu is 96.16%, and the removal rate of Bi is 96.16%; the recovery of antimony was 99.25%.
Example 4
The embodiment comprises the following steps:
(1) leaching: after pretreatment, 1200g of high-lead antimony oxide (Sb62.18%, Pb16.78%, Cu0.61% and Bi0.31%) with minus 300 meshes is obtained, and is added into 3600mL of dilute nitric acid solution (the concentration of nitric acid is 15%, the solid-to-liquid ratio is 1: 3), the leaching temperature is controlled to be 90 ℃, the leaching time is 240 minutes, then, a filter cake is obtained through filtration, and after drying, 938g of dry antimony oxide is obtained, and the analysis results are Sb79.47%, Pb0.068%, Cu0.015% and Bi 0.012%; 2700mL of lead nitrate-containing filtrate contains Sb0.28g/L, Pb74.34g/L, Cu2.66g/L and Bi1.34g/L.
(2) And (3) evaporation: the lead nitrate solution was concentrated under normal pressure, and when the specific gravity was 1.7 (103 ℃ C.), the concentration was stopped, and when the specific gravity was 40 to 60 ℃ C., 348.23g of crude lead nitrate was obtained by filtration, which contained Pb57.51%, Cu1.85%, Bi 0.87%, and Sb0.11% as the main components. Mother liquor 270mL, Sb1.35g/L, Pb1.69g/L, Cu2.68g/L, Bi 2.15.15 g/L, returned to the next concentration.
By the treatment process described in the embodiment, the removal rate of lead in the high-lead antimony oxide is 99.68%, the removal rate of Cu is 98.08%, and the removal rate of Bi is 96.97%; the recovery of antimony was 99.90%.
Example 5
The embodiment comprises the following steps:
(1) leaching: after pretreatment, 1500g of high-lead antimony oxide (Sb51.59%, Pb22.49%, Cu0.48% and Bi0.56%) with minus 250 meshes is obtained, the high-lead antimony oxide is added into 7500mL of dilute nitric acid solution (the concentration of nitric acid is 12%, the solid-to-liquid ratio is 1: 5), the leaching temperature is controlled to be 100 ℃, the leaching time is 300 minutes, then, a filter cake is obtained through filtration, 968g of dry antimony oxide is obtained after drying, and the analysis results are Sb79.68%, Pb0.099%, Cu0.012% and Bi 0.018%; 5625mL of lead nitrate-containing filtrate has chemical compositions of Sb0.46g/L, Pb59.80g/L and Cu1.26g/L, Bi 1.46.46 g/L.
(2) And (3) evaporation: the lead nitrate solution was concentrated under normal pressure, and when the specific gravity was 1.7 (103 ℃ C.), the concentration was stopped, and when the specific gravity was 40 to 60 ℃ C., 557.16g of crude lead nitrate was obtained by filtration, which contained 60.19% of Pb19%, 1.16% of Cu1.38% of Bi1.38% and 0.33% of Sb0.33% of the main components. 562mL of mother liquor, Sb1.35g/L, Pb1.84g/L and Cu1.15g/L, Bi 0.96.96 g/L, and returning the mother liquor to the next concentration.
Through the treatment process described in the embodiment, the removal rate of lead in the high-lead antimony oxide is 99.72%, the removal rate of Cu is 98.39%, and the removal rate of Bi is 97.93%; the recovery of antimony was 99.67%.
Comparative example 1 this comparative example comprises the following steps:
(1) leaching: after pretreatment, 500g of high-lead antimony oxide (Sb50.59%, Pb20.58%, Cu0.49% and Bi0.53%) with minus 100 meshes is obtained, the high-lead antimony oxide is added into 2000mL of dilute nitric acid solution (the concentration of nitric acid is 28%, the solid-to-liquid ratio is 1: 4), the leaching temperature is controlled to be 80 ℃, the leaching time is 180 minutes, then, a filter cake is obtained through filtration, and after drying, 318g of dry antimony oxide is obtained, and the analysis results are Sb75.29%, Pb0.058%, Cu0.010% and Bi 0.011%; 1500mL of lead nitrate-containing filtrate, the chemical composition of which is Sb7.69g/L, Pb68.48g/L and Cu1.61g/L, Bi 1.74.74 g/L.
(2) And (3) evaporation: the lead nitrate solution was concentrated under normal pressure, and when the specific gravity was 1.7 (103 ℃ C.), the concentration was stopped, and when the specific gravity was 40 to 60 ℃ C., 189.03g of crude lead nitrate was obtained by filtration, which contained Pb54.18%, Cu1.19%, Bi1.31%, and Sb5.98% as main components. 150mL of mother liquor, Sb1.52g/L, Pb2.01g/L and Cu1.18g/L, Bi 0.94.94 g/L, and returned to the next concentration.
By the treatment process described in the embodiment, the removal rate of lead in the high-lead antimony oxide is 99.82%, the removal rate of Cu is 98.70%, and the removal rate of Bi is 98.68%; the recovery of antimony was 95.44%.
In this comparative example, the mass concentration of nitric acid was 28%, with the result that more antimony entered the solution, resulting in a higher antimony content in the lead nitrate. Thus, the recovery rate of antimony is reduced, and antimony and lead are not effectively separated. Therefore, a high mass concentration of nitric acid during leaching is not suitable.
Example 7
(1) Leaching: after pretreatment, 500g of high-lead antimony oxide (Sb55.48%, Pb24.62%, Cu0.42% and Bi0.51%) with minus 80 meshes is obtained, and is added into 3000mL of dilute nitric acid solution (the concentration of nitric acid is 18%, the solid-to-liquid ratio is 1: 6), the leaching temperature is controlled to be 90 ℃, the leaching time is 300 minutes, then, a filter cake is obtained by filtration, 358g of dry antimony oxide is obtained after drying, and the analysis results are Sb76.84%, Pb6.78%, Cu0.380% and Bi 0.215%; 2250mL of lead nitrate-containing filtrate contains Sb1.02g/L, Pb43.92g/L and Cu0.33g/L, Bi 0.79.79 g/L.
(2) And (3) evaporation: the lead nitrate solution was concentrated under normal pressure, and when the specific gravity was 1.7 (103 ℃ C.), the concentration was stopped, and when the specific gravity was 40 to 60 ℃ C., 166.35g of crude lead nitrate was obtained by filtration, which contained Pb59.15%, Cu0.30%, Bi0.95%, and Sb1.23% as the main components. 225mL of mother liquor, 1.12g/L of Sb1.12g/L, 1.91g/L of Pb1.05g/L, Bi 0.86.86 g/L and Cu1.05g/L are returned to enter the next concentration.
Through the treatment process described in the embodiment, the removal rate of lead in the high-lead antimony oxide is 80.28%, the removal rate of Cu is 35.22%, and the removal rate of Bi is 69.82%; the recovery of antimony was 99.17%.
In this example, the raw material antimony oxide had coarse particles and poor leaching effect, in which the lead removal rate was 80.28%, and the lead content in the leached dry antimony oxide was 6.78%, which did not achieve the purpose of antimony-lead separation. Therefore, the size of the antimony oxide particles affects the lead removal effect.
Claims (6)
1. A process for removing lead, copper and bismuth from antimony oxide by a wet method is characterized in that antimony oxide to be leached is pretreated, then the lead, copper and bismuth are leached from the antimony oxide in nitric acid at 60-100 ℃, and solid-liquid separation is carried out to obtain low-lead antimony oxide and lead nitrate solution containing copper and bismuth; the mass concentration of the nitric acid is 10-20%.
2. The process for removing lead, copper and bismuth from antimony oxide by a wet method according to claim 1, wherein the antimony oxide is high-lead antimony oxide and comprises, by mass, 45-65% of Sb, 5-25% of Pb, 0.5% or more of Cu and 0.5% or more of Bi.
3. The process for removing lead, copper and bismuth from antimony oxide by a wet method according to claim 1 or 2, wherein the mass volume ratio of antimony oxide to nitric acid in the leaching process is 1g: 2-6 mL, and the leaching time is 2-6 h.
4. The wet process for removing lead, copper and bismuth from antimony oxide according to any one of claims 1 to 3, wherein the solid-liquid separation is performed by adopting centrifugation or filter pressing of a filter press, and then washing with nitric acid with a mass percentage concentration of 5-8%.
5. The process for removing lead, copper and bismuth from antimony oxide by a wet method according to any one of claims 1 to 4, wherein the grain size of the pretreated antimony oxide is 100-300 meshes.
6. The wet process for removing lead, copper and bismuth in antimony oxide according to any one of claims 1 to 5, further comprising: concentrating the lead nitrate solution to a specific gravity of 1.7 at 100-105 ℃ under normal pressure, carrying out hot filtration to obtain a lead nitrate crude product and a mother solution, and mixing the mother solution with a lead nitrate solution to be distilled next time and a washing solution for distillation; and distilling the obtained distilled water to prepare nitric acid for leaching.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010682704.7A CN111809046A (en) | 2020-07-15 | 2020-07-15 | Process for removing lead, copper and bismuth in antimony oxide by wet method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010682704.7A CN111809046A (en) | 2020-07-15 | 2020-07-15 | Process for removing lead, copper and bismuth in antimony oxide by wet method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111809046A true CN111809046A (en) | 2020-10-23 |
Family
ID=72865180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010682704.7A Withdrawn CN111809046A (en) | 2020-07-15 | 2020-07-15 | Process for removing lead, copper and bismuth in antimony oxide by wet method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111809046A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117466334A (en) * | 2023-10-31 | 2024-01-30 | 益阳生力材料科技股份有限公司 | A method for preparing high-quality sodium pyroantimonate through pre-oxidation metathesis |
| CN117466333A (en) * | 2023-10-31 | 2024-01-30 | 益阳生力材料科技股份有限公司 | Method for preparing high-quality sodium pyroantimonate through preoxidation conversion |
| CN117486257A (en) * | 2023-10-31 | 2024-02-02 | 益阳生力材料科技股份有限公司 | Preparation method for high-quality sodium pyroantimonate precursor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA72576B (en) * | 1971-12-30 | 1972-10-25 | Occidental Petroleum Corp | Hydro metallurgical preparation of the oxides of antimony and antimonic acid |
| US3883635A (en) * | 1971-12-30 | 1975-05-13 | Occidental Petroleum Corp | Hydro-metallurgical preparation of the oxides of antimony and antimonic acid |
| CN1062175A (en) * | 1990-12-06 | 1992-06-24 | 昆明化工厂 | Produce the method for Silver Nitrate, recovery copper, lead, antimony by lead anode slurry |
| CN1150605A (en) * | 1995-11-17 | 1997-05-28 | 闵学书 | Process for removing lead, selenium and arsenic in smelting lead-containing antimony ore |
| CN103757424A (en) * | 2014-02-26 | 2014-04-30 | 锡矿山闪星锑业有限责任公司 | Comprehensive recovery method of smoke with high arsenic and antimony oxide contents |
| CN106065437A (en) * | 2016-07-22 | 2016-11-02 | 锡矿山闪星锑业有限责任公司 | The phosphate-containing lead slag-removed separation antimony lead phosphorus technique that a kind of antimony regulus produces |
-
2020
- 2020-07-15 CN CN202010682704.7A patent/CN111809046A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA72576B (en) * | 1971-12-30 | 1972-10-25 | Occidental Petroleum Corp | Hydro metallurgical preparation of the oxides of antimony and antimonic acid |
| US3883635A (en) * | 1971-12-30 | 1975-05-13 | Occidental Petroleum Corp | Hydro-metallurgical preparation of the oxides of antimony and antimonic acid |
| CN1062175A (en) * | 1990-12-06 | 1992-06-24 | 昆明化工厂 | Produce the method for Silver Nitrate, recovery copper, lead, antimony by lead anode slurry |
| CN1150605A (en) * | 1995-11-17 | 1997-05-28 | 闵学书 | Process for removing lead, selenium and arsenic in smelting lead-containing antimony ore |
| CN103757424A (en) * | 2014-02-26 | 2014-04-30 | 锡矿山闪星锑业有限责任公司 | Comprehensive recovery method of smoke with high arsenic and antimony oxide contents |
| CN106065437A (en) * | 2016-07-22 | 2016-11-02 | 锡矿山闪星锑业有限责任公司 | The phosphate-containing lead slag-removed separation antimony lead phosphorus technique that a kind of antimony regulus produces |
Non-Patent Citations (1)
| Title |
|---|
| 雷霆等: "《锑冶金》", 28 February 2009, 北京：冶金工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117466334A (en) * | 2023-10-31 | 2024-01-30 | 益阳生力材料科技股份有限公司 | A method for preparing high-quality sodium pyroantimonate through pre-oxidation metathesis |
| CN117466333A (en) * | 2023-10-31 | 2024-01-30 | 益阳生力材料科技股份有限公司 | Method for preparing high-quality sodium pyroantimonate through preoxidation conversion |
| CN117486257A (en) * | 2023-10-31 | 2024-02-02 | 益阳生力材料科技股份有限公司 | Preparation method for high-quality sodium pyroantimonate precursor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102508038B1 (en) | Lithium recovery method | |
| CN111809046A (en) | Process for removing lead, copper and bismuth in antimony oxide by wet method | |
| CN102390819B (en) | Method for preparing tellurium dioxide from tellurium slag | |
| CN111092273A (en) | Novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste | |
| CN110205482B (en) | A comprehensive recovery method for removing cobalt slag from organic matter in zinc smelting | |
| CN104046784A (en) | Method of recycling silver-containing soldering tin slag | |
| CN103112833A (en) | Method for recycling tellurium from copper anode slime | |
| CN111197119A (en) | Method for recovering valuable metals from bismuth-containing waste residues | |
| CN112553468A (en) | Method for producing high-purity manganese sulfate by adopting metal manganese anode mud | |
| CN105948104A (en) | Method for preparing sodium stannate by using tin anode slime oxygen pressure alkaline leaching | |
| CN114959311B (en) | Method for comprehensively recovering rare noble metals from high-copper molybdenum concentrate | |
| CN102173448A (en) | Method for preparing alkali metal stannate | |
| CN111471870A (en) | A process for comprehensive recovery of copper, tellurium and bismuth from complex copper tellurium bismuth slag | |
| CN119234048A (en) | Method for processing black pellets into battery chemicals | |
| CN108411128B (en) | Method for efficiently enriching indium from low-grade indium-containing smelting slag | |
| CN106755994A (en) | A kind of production method for comprehensively utilizing zinc cobalt raw material high | |
| CN120060652A (en) | Comprehensive utilization process of sintering machine head ash | |
| CN110983062A (en) | Comprehensive recovery method for preferentially extracting copper in wet smelting of copper-containing bismuth material | |
| CN112551591B (en) | Method for preparing high-purity manganese sulfate qualified liquid by electrolyzing metal manganese anode slime | |
| JP2001207225A (en) | Separation method of Ga, Ge, In | |
| CN110078100A (en) | A method of extracting high-purity cesium carbonate from pollucite | |
| CN116254415A (en) | Method for preparing battery-grade manganese sulfate by utilizing zinc electrodeposited manganese-containing anode slime | |
| CN115261644A (en) | Method for purifying germanium-containing material | |
| CN118547157B (en) | A process for directly recovering tellurium and copper from tellurium-containing waste slag | |
| CN104131171A (en) | Method for producing copper sulfate pentahydrate by combination of zinc and copper systems based on chlorine removal as link |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201023 |