CN110306064A - A method of tellurium, bismuth, lead are recycled from tellurium lead slag - Google Patents
A method of tellurium, bismuth, lead are recycled from tellurium lead slag Download PDFInfo
- Publication number
- CN110306064A CN110306064A CN201910736239.8A CN201910736239A CN110306064A CN 110306064 A CN110306064 A CN 110306064A CN 201910736239 A CN201910736239 A CN 201910736239A CN 110306064 A CN110306064 A CN 110306064A
- Authority
- CN
- China
- Prior art keywords
- tellurium
- lead
- bismuth
- slag
- heavy
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
- C22B7/007—Wet processes by acid 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
- 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
-
- 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)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of methods from tellurium lead slag recycling tellurium, bismuth, lead；Include the following steps: that (1) broken, ball milling: tellurium lead slag is broken, after ball milling with the screening of 100 mesh sieve；(2) oxidation acid leaching；(3) heavy bismuth is hydrolyzed；(4) heavy tellurium is restored；Obtain tellurium dioxide product.Method of the invention solves the problems such as conventional oxidation refining treatment tellurium slag technique is tediously long, the tellurium rate of recovery is low, generation secondary residue.
Description
Technical field
The invention belongs to field of hydrometallurgy, and in particular to a method of tellurium, bismuth, lead are recycled from tellurium lead slag.
Background technique
Cerrobase alloy is the product obtained after precious metals containing lead oxidationreduction melting process is handled, and main chemical compositions remove bismuth, lead
Outside, also comprising valuable metals elements such as tellurium, silver, copper, antimony.Vacuum distillation method is a kind of cleans, at widely used cerrobase alloy
Reason method.Cerrobase alloy is evaporated in vacuo in treatment process, and the substances such as bismuth, lead in alloy enter volatilization item under vacuum conditions,
The not volatile metal such as silver, copper is retained in residue, realizes the separation of bismuth, lead and silver, copper in alloy.
When vacuum distillation method handles cerrobase alloy higher containing tellurium, tellurium and part lead form tellurium lead slag and are adhered to evaporating pan.
The fluctuation of tellurium lead slag ingredient is larger, and tellurium lead slag main component is Pb58-60%, Te24-33%, Bi15%.It is made using conventional oxidation refining
The method processing tellurium lead slag of tellurium slag the problems such as that there are techniques is tediously long, tellurium loss is big, tellurium direct yield is low.
On 09 26th, 2017, Chinese invention patent application publication No. CN107201448A was disclosed at a kind of high tellurium copper slag
Reason method, it is crushed, more than 80 mesh of ball milling granularity using high tellurium copper slag, and the high tellurium copper slag and sulfuric acid solution after screening are acidified
It is with slurry, the processing of hydrochloric acid Weak-acid leaching is added, then separating liquid and slag, NaOH solution is added into leachate and hydrolyzes heavy bismuth: mistake
Filter, filtrate are hydrolyzed heavy bismuth, obtain bismuth hydrolysis prods after filtering, drying；The phase analysis of Weak-acid leaching adds HCl treatment, so
Gold, silver, lead are separated and recovered afterwards；It separates the solution heavy antimony of iron replacement again: the leaching of NaoH solution is added in the separation slag after replacement Treatment
Na2S purification is added in tellurium processing, leaching tellurium treated separating liquid；Heavy tellurium is neutralized with sulfuric acid again, and settle out tellurium dioxide.The technical side
Material is first acidified, by the way that valuable metal to be dissolved into acid or alkaline solution, then by case in order to reach heavy tellurium purpose
Deep purifying, reduction, precipitating are carried out to it, achieve the purpose that separation；Multiple hydrochloric acid leaching process is specifically used, and uses NaOH
Soak tellurium processing；Industrial chemicals consumption is big, complex procedures, and process flow is long, operating cost is high.
Summary of the invention
The purpose of the present invention is to provide it is a kind of from tellurium lead slag recycling tellurium, bismuth, lead method, realize tellurium lead slag in tellurium, bismuth,
The high efficiente callback of lead, the technology have many advantages, such as that process flow is short, operating cost is low, the rate of recovery is high.
Above-mentioned purpose is achieved through the following technical solutions:
A method of tellurium, bismuth, lead being recycled from tellurium lead slag, is included the following steps:
(1) be crushed, ball milling: tellurium lead slag is broken, after ball milling with the screening of 100 mesh sieve；
(2) oxidation acid leaching: the tellurium lead slag and certain density hydrochloric acid solution after screening are with slurry, are continuously added to hydrogen peroxide leaching, slag
In tellurium, bismuth enter in solution, lead enters in slag in solid form, realize tellurium, bismuth and lead separation；
During Leach reaction, control hydrochloric acid mass concentration be 60-200g/L, 30-80 DEG C of extraction temperature, extraction time 2-8h,
Hydrogen peroxide additional amount is 2-10 times of theoretical amount, is filtered after Leach reaction, and heavy bismuth is hydrolyzed in filtrate, and leached mud puts into lead
Lead is directly refined in smelting system reduction furnace；
(3) hydrolyze heavy bismuth: it is 2-3 that NaOH solution is added in Xiang Shangshu leachate and adjusts pH, controls 70-90 DEG C of hydrolysis temperature, water
Time 1-2h is solved, bismuth hydrolysis prods are obtained after filtering, drying, filtrate is for restoring heavy tellurium；
(4) it restores heavy tellurium: saturated sodium bisulfite solution being added into the filtrate after hydrolysis, control sodium sulfite additional amount is theory
1-2 times, 60-80 DEG C of reduction temperature, recovery time 1-3h of amount obtain tellurium dioxide product after filtering, drying.
Using method of the invention, the heavy tellurium of saturated sodium bisulfite solution is added, is added than prior art CN107201448A
Na2S purification, then neutralize with sulfuric acid heavy tellurium；Realize tellurium in tellurium lead slag, bismuth, lead efficiently separate and synthetical recovery, solve biography
Uniting, refinement oxide processing tellurium slag technique is tediously long, the tellurium rate of recovery is low, generates the problems such as secondary residue.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
With reference to Fig. 1, the method for a kind of tellurium lead slag recycling tellurium, bismuth, lead, tellurium lead slag is broken, after ball milling with 100 mesh sieve sieve
Point, tellurium lead ground-slag end be added to mass concentration be 60-200g/L hydrochloric acid solution in leaching, leaching process be continuously added to for
2-10 times of theoretical amount of hydrogen peroxide controls 30-80 DEG C of extraction temperature, extraction time 2-8h, filters after leaching, and filtrate carries out
Hydrolyze heavy bismuth.Adjusting filtrate pH with NaOH solution is 2-3, controls 70-90 DEG C of hydrolysis temperature, hydrolysis time 1-2h, filtering, drying
After obtain bismuth hydrolysis prods, filtrate is for restoring heavy tellurium.Saturated sodium bisulfite solution is added into the filtrate after hydrolysis, control is sub-
Sodium sulphate additional amount is 1-2 times, 60-80 DEG C of reduction temperature, recovery time 1-3h of theoretical amount, and tellurium dioxide production is obtained after filtering
Product.
Embodiment 1
Tellurium lead slag after screening is added to leaching in the hydrochloric acid solution that mass concentration is 120g/L, and leaching process is continuously added to
For 4 times of hydrogen peroxide of theoretical amount, 30 DEG C of extraction temperature, extraction time 5h are controlled, is filtered after leaching, filtrate is hydrolyzed heavy
Bismuth.Adjusting filtrate pH with NaOH solution is 2-3, controls 70 DEG C of hydrolysis temperature, hydrolysis time 1h, obtains bismuth water after filtering, drying
Product is solved, filtrate is for restoring heavy tellurium.Saturated sodium bisulfite solution is added into the filtrate after hydrolysis, control sodium sulfite is added
Amount is 1 times, 60 DEG C of reduction temperature, recovery time 1h of theoretical amount, and tellurium dioxide product is obtained after filtering.Bismuth hydrolysis prods bismuth-containing
76.8%, tellurium dioxide purity 98.5%.
Embodiment 2
Tellurium lead slag after screening is added to leaching in the hydrochloric acid solution that mass concentration is 60g/L, and leaching process is continuously added to
For 2 times of hydrogen peroxide of theoretical amount, 50 DEG C of extraction temperature, extraction time 2h are controlled, is filtered after leaching, filtrate is hydrolyzed heavy
Bismuth.Adjusting filtrate pH with NaOH solution is 2-3, controls 80 DEG C of hydrolysis temperature, hydrolysis time 1.5h, obtains bismuth after filtering, drying
Hydrolysis prods, filtrate is for restoring heavy tellurium.Saturated sodium bisulfite solution is added into the filtrate after hydrolysis, control sodium sulfite adds
Enter 1.4 times, 70 DEG C of the reduction temperature, recovery time 2h that amount is theoretical amount, tellurium dioxide product is obtained after filtering.Bismuth hydrolysis prods
Bismuth-containing 78.2%, tellurium dioxide purity 99.6%.
Embodiment 3
Tellurium lead slag after screening is added to leaching in the hydrochloric acid solution that mass concentration is 150g/L, and leaching process is continuously added to
For 10 times of hydrogen peroxide of theoretical amount, 80 DEG C of extraction temperature, extraction time 6h are controlled, is filtered after leaching, filtrate is hydrolyzed
Heavy bismuth.Adjusting filtrate pH with NaOH solution is 2-3, controls 90 DEG C of hydrolysis temperature, hydrolysis time 2h, obtains bismuth after filtering, drying
Hydrolysis prods, filtrate is for restoring heavy tellurium.Saturated sodium bisulfite solution is added into the filtrate after hydrolysis, control sodium sulfite adds
Enter 2 times, 80 DEG C of the reduction temperature, recovery time 3h that amount is theoretical amount, tellurium dioxide product is obtained after filtering.Bismuth hydrolysis prods contain
Bismuth 75.7%, tellurium dioxide purity 99.5%.
Embodiment 4
Tellurium lead slag after screening is added to leaching in the hydrochloric acid solution that mass concentration is 200g/L, and leaching process is continuously added to
For 5 times of hydrogen peroxide of theoretical amount, 70 DEG C of extraction temperature, extraction time 6h are controlled, is filtered after leaching, filtrate is hydrolyzed heavy
Bismuth.Adjusting filtrate pH with NaOH solution is 2-3, controls 80 DEG C of hydrolysis temperature, hydrolysis time 1h, obtains bismuth water after filtering, drying
Product is solved, filtrate is for restoring heavy tellurium.Saturated sodium bisulfite solution is added into the filtrate after hydrolysis, control sodium sulfite is added
Amount is 1.8 times, 75 DEG C of reduction temperature, recovery time 2.5h of theoretical amount, and tellurium dioxide product is obtained after filtering.Bismuth hydrolysis prods
Bismuth-containing 76.2%, tellurium dioxide purity 98.9%.
Claims (1)
1. a kind of method from tellurium lead slag recycling tellurium, bismuth, lead, spy are being to include the following steps:
(1) be crushed, ball milling: tellurium lead slag is broken, after ball milling with the screening of 100 mesh sieve；
(2) oxidation acid leaching: the tellurium lead slag and certain density hydrochloric acid solution after screening are with slurry, are continuously added to hydrogen peroxide leaching, slag
In tellurium, bismuth enter in solution, lead enters in slag in solid form, realize tellurium, bismuth and lead separation；
During Leach reaction, control hydrochloric acid mass concentration be 60-200g/L, 30-80 DEG C of extraction temperature, extraction time 2-8h,
Hydrogen peroxide additional amount is 2-10 times of theoretical amount, is filtered after Leach reaction, and heavy bismuth is hydrolyzed in filtrate, and leached mud puts into lead
Lead is directly refined in smelting system reduction furnace；
(3) hydrolyze heavy bismuth: it is 2-3 that NaOH solution is added in Xiang Shangshu leachate and adjusts pH, controls 70-90 DEG C of hydrolysis temperature, water
Time 1-2h is solved, bismuth hydrolysis prods are obtained after filtering, drying, filtrate is for restoring heavy tellurium；
(4) it restores heavy tellurium: saturated sodium bisulfite solution being added into the filtrate after hydrolysis, control sodium sulfite additional amount is theory
1-2 times, 60-80 DEG C of reduction temperature, recovery time 1-3h of amount obtain tellurium dioxide product after filtering, drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910736239.8A CN110306064A (en) | 2019-08-09 | 2019-08-09 | A method of tellurium, bismuth, lead are recycled from tellurium lead slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910736239.8A CN110306064A (en) | 2019-08-09 | 2019-08-09 | A method of tellurium, bismuth, lead are recycled from tellurium lead slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110306064A true CN110306064A (en) | 2019-10-08 |
Family
ID=68083370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910736239.8A Pending CN110306064A (en) | 2019-08-09 | 2019-08-09 | A method of tellurium, bismuth, lead are recycled from tellurium lead slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110306064A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289171A (en) * | 2008-06-02 | 2008-10-22 | 王钧 | Hydrometallurgy process for abstracting 99.99146004050f Te and 99.9926340320f Bi2O3 and comprehensively recovering accessory products |
| CN103397180A (en) * | 2013-08-07 | 2013-11-20 | 江西铜业股份有限公司 | Method for recovering tellurium, bismuth, antimony, and copper from complex material |
| CN103849783A (en) * | 2012-12-07 | 2014-06-11 | 广东先导稀材股份有限公司 | Method for separating and recovering tellurium and bismuth |
| CN104911366A (en) * | 2015-05-11 | 2015-09-16 | 湖南众兴环保科技有限公司 | Method for recovering valuable metals from silver-bismuth slag through using aqua regia |
| CN106381399A (en) * | 2016-09-27 | 2017-02-08 | 郴州市金贵银业股份有限公司 | Method for recovering tellurium from high-tellurium residues |
| CN107034358A (en) * | 2017-04-27 | 2017-08-11 | 中南大学 | A kind of reductive hydrolysis Enrichment and the method for reclaiming Au, Pt, Pd selen-tellurjum bismuth |
| CN107746956A (en) * | 2017-11-03 | 2018-03-02 | 郴州兴城环保股份有限公司 | Using the technique of support methods recovery tellurium from complicated solution |
-
2019
- 2019-08-09 CN CN201910736239.8A patent/CN110306064A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289171A (en) * | 2008-06-02 | 2008-10-22 | 王钧 | Hydrometallurgy process for abstracting 99.99146004050f Te and 99.9926340320f Bi2O3 and comprehensively recovering accessory products |
| CN103849783A (en) * | 2012-12-07 | 2014-06-11 | 广东先导稀材股份有限公司 | Method for separating and recovering tellurium and bismuth |
| CN103397180A (en) * | 2013-08-07 | 2013-11-20 | 江西铜业股份有限公司 | Method for recovering tellurium, bismuth, antimony, and copper from complex material |
| CN104911366A (en) * | 2015-05-11 | 2015-09-16 | 湖南众兴环保科技有限公司 | Method for recovering valuable metals from silver-bismuth slag through using aqua regia |
| CN106381399A (en) * | 2016-09-27 | 2017-02-08 | 郴州市金贵银业股份有限公司 | Method for recovering tellurium from high-tellurium residues |
| CN107034358A (en) * | 2017-04-27 | 2017-08-11 | 中南大学 | A kind of reductive hydrolysis Enrichment and the method for reclaiming Au, Pt, Pd selen-tellurjum bismuth |
| CN107746956A (en) * | 2017-11-03 | 2018-03-02 | 郴州兴城环保股份有限公司 | Using the technique of support methods recovery tellurium from complicated solution |
Non-Patent Citations (1)
| Title |
|---|
| 王俐: ""高铜高铋高碲中和渣综合利用新技术研究"", 《矿产综合利用》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101508426B (en) | Method for separating tellurium from tellurium slag | |
| CN105734299B (en) | A kind of method of oxygen pressure treatment tin anode mud comprehensively recovering valuable metal | |
| CN102086029B (en) | Method for extracting selenium from selenium-contained material | |
| CN105905874B (en) | A kind of method that tellurium is reclaimed from the earth of positive pole | |
| CN105821215B (en) | A kind of method that bismuth metal is reclaimed from the earth of positive pole | |
| CN110157913B (en) | Method for comprehensively treating copper slag | |
| NO158106B (en) | PROCEDURE FOR TREATING Aqueous SOLUTION CONTAINING Precious Metals and Undesirable Elements. | |
| CN105274359B (en) | Method for extracting and separating valuable metals from secondary lead smelting slag | |
| JP2001316736A (en) | Method for recovering silver | |
| CN112063854B (en) | Method for comprehensively recovering bismuth, silver and copper metals by taking precious lead as raw material | |
| CN101328539A (en) | Oxidation oven ash hydrometallurgical leaching process | |
| CN102876903A (en) | Direct acidity oxygen pressure leaching treatment method of crude tin copper removal residues | |
| CN104911366A (en) | Method for recovering valuable metals from silver-bismuth slag through using aqua regia | |
| CN103589873A (en) | Method for recovering valuable metals from silver-zinc slag | |
| CN108384959A (en) | A kind of preparation method of electrolytic zinc | |
| CN106222421A (en) | Gold mud treatment method | |
| CN106834705A (en) | A kind of method of copper smelting by pyrometallurgy white cigarette dust resources comprehensive utilization | |
| JP5200588B2 (en) | Method for producing high purity silver | |
| CN113481371A (en) | Method for efficiently recovering antimony, bismuth, copper and silver from silver separating slag of lead anode slime | |
| CN108070722A (en) | A kind of method that valuable metal is recycled in copper ashes of sinking from silver electrolysis mother liquor | |
| CN108411109B (en) | A kind of golden tellurium separation-extraction technology of the Gold Concentrate under Normal Pressure containing tellurium | |
| FI127003B (en) | Method and process equipment for the separation of indium and arsenic | |
| CN110306064A (en) | A method of tellurium, bismuth, lead are recycled from tellurium lead slag | |
| JP3548097B2 (en) | Separation and recovery method of bismuth and copper etc. from treatment object containing cuprous oxide and bismuth | |
| JPS6059975B2 (en) | Method for concentrating silver from copper electrolytic slime |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191008 |