CN105967153A - Technology for recovering tellurium from high-tellurium slag - Google Patents
Technology for recovering tellurium from high-tellurium slag Download PDFInfo
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- CN105967153A CN105967153A CN201610295603.8A CN201610295603A CN105967153A CN 105967153 A CN105967153 A CN 105967153A CN 201610295603 A CN201610295603 A CN 201610295603A CN 105967153 A CN105967153 A CN 105967153A
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- tellurium
- slag
- teo
- slag charge
- leachate
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- 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
- C01B19/004—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a technology for recovering tellurium from high-tellurium slag. The technology comprises 1, crushing high-tellurium slag until granularity is less than or equal to 10mm, 2, pouring the broken high-tellurium slag into a reactor, slowly adding aqua regia into the high-tellurium slag and carrying out oxidation leaching, 3, after the slag is completely dissolved, carrying out liquid-solid separation so that a main element tellurium enters the leachate and Pb and Ag valuable metals enter slags, returning the Pb and Ag slags to a Pb smelting system and recovering valuable metals, and 4, preparing a solution of caustic soda flakes, slowly adding the solution into the tellurium-containing leachate, adjusting pH to 5.0-6.0, carrying out solid-liquid separation to obtain TeO2 precipitates, carrying out calcining denitration on the TeO2, carrying out liquid preparation, returning the liquid to an electrodeposition process and directly recovering metal Te. The technology has the characteristics of simple processes, less equipment, low production cost and high comprehensive recovery degree and has a certain application prospect.
Description
Technical field
The present invention relates to a kind of technique reclaiming tellurium from high tellurium slag charge, belong to non-ferrous metal field of hydrometallurgy.
Background technology
Can create a kind of slag charge higher containing tellurium in tellurium smelting process, the tellurium therein overwhelming majority is with the shape of metallic tellurium
Formula exists, another containing valuable elements such as part lead, silver, antimony, if tellurium casting mold slag is exactly such a slag charge.Major part enterprise is usual
It is this slag charge directly to return silver smelt the refinement oxide pyrogenic process operation later stage and make the tellurium slag stage and carry out enriching and recovering, due to tellurium metal
The as easy as rolling off a log volatilization when high temperature, scattered characteristic, do not reach if directly returning silver smelting its metallic tellurium response rate of pyrogenic process operation
40%, not only cause the problems such as waste of raw materials, the response rate are low, the method there is also operation length, production cost height, operation simultaneously
The shortcomings such as inclement condition deficiency in economic performance.
On October 28th, 2009；Chinese invention patent application publication No.: CN101565174A, discloses a kind of from containing tellurium smelting
Refining slag in extract essence tellurium method, comprise the steps of 1), by tellurium slag by liquid-solid mass ratio 2～6: 1 ratio addition water carry out
Size mixing, add mineral acid after pulp and oxidant is stirred leaching；Mineral acid is usually the one in sulphuric acid and hydrochloric acid or two
The mixture of person, oxidant be potassium permanganate, hydrogen peroxide, manganese oxide, sodium peroxydisulfate, potassium peroxydisulfate, Ammonium persulfate., sodium chlorate,
A kind of or two of which in potassium chlorate, sodium hypochlorite, postassium hypochlorite or the mixture of two or more material；2), mineral acid
Leachate is put in displacement slot, is linked into copper coin displacement, and precipitation obtains noble metal concentrate and displaced liquid after filtering；3), toward displacement after
Liquid adds saturated Na2S solution cement copper, sulfuration copper ashes can turn copper recovery process；4), after heavy copper, liquid adds Na2CO3In,
With to pH=4.5～6.0, hydrolysis obtains TeO2Precipitation, filters to obtain thick TeO2；5), thick TeO2Alkaline leaching, Na2S remove impurity；Cross
Filter filtering residue and obtain Sodium tellurite. solution；6), concentrate Sodium tellurite. solution is proceeded to thickener, be heated to 105-115 DEG C, dense
Being reduced to tellurium content in solution is that 120-180 grams per liter obtains dense Sodium tellurite. solution；7), dense Sodium tellurite. solution proceed to electrolysis bath,
In tank voltage 1.5～2.5V, electric current density 30～60A/m2, use rustless steel anode and cathode to carry out electrodeposition, electrodeposition tellurium is scrubbed dry
Calcining 2-5 hour under 350-400 DEG C of temperature conditions after dry, the tellurium powder after calcining makes tellurium ingot.This processing step is many, flow process
Long, particularly because of the stability of tellurium element chemical property, under conditions of mineral acid, add the oxidation rate of oxidant tellurium element
Extremely slowly, the most oxidized, therefore, chemical agent consumption is many, and cost is high.
It addition, World Nonferrous Metals the 1st phase " the direct high efficiente callback new technology of the melting waste slag containing tellurium " mention and utilize nitric acid straight
Connecing and tellurium casting mold slag carries out Oxidation Leaching, leachate adds sodium sulfide remove impurity, adds sheet alkali and neutralize to obtain tellurium dioxide, dioxy after remove impurity
Change tellurium and return electrodeposition operation through liquid making.On this technological principle feasible, but tellurium metal is more difficult oxidized, and this technique exists response speed
Slowly, cycle length and remove impurity are the most thoroughly easily caused the problems such as tellurium product is defective.Therefore exploitation is a kind of direct from tellurium casting mold slag
The technique of high efficiente callback tellurium has important practical significance.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of technique reclaiming tellurium from high tellurium slag charge.
This technology has the features such as flow process is simple, growth cycle is short, low cost, synthetical recovery degree height, process intensification.
The technique that the present invention a kind of reclaims tellurium from high tellurium slag charge is: high tellurium slag charge is poured in retort after crushing,
In retort, it is slowly added to chloroazotic acid directly carries out Oxidation Leaching, after high tellurium slag charge dissolves completely；Carry out solid-liquor separation must contain
Tellurium leachate and leached mud；Leached mud returns lead smelting system and reclaims Pb, Ag valuable metal；Nertralizer is added in leachate,
By neutralizing regulation pH to 5.0～6.0 enrichment host element tellurium, carry out settlement separate after reaching to neutralize terminal, obtain tellurium dioxide
Precipitation；Tellurium dioxide precipitation except nitre deselenization, when tellurium dioxide is white, can carry out sodium hydroxide liquid making, dioxy through calcining
Change tellurium and become again Sodium tellurite., in order to enter electrodeposition operation electrodeposition.
Concrete technology mainly comprises the steps that
The highest tellurium slag charge is crushed to granularity≤10mm；
2. in pouring broken high tellurium slag charge into retort and be slowly added to chloroazotic acid；And control chloroazotic acid and the liquid-solid body of high tellurium slag charge
Long-pending mass ratio is 2.5～4:1L/kg to carry out Oxidation Leaching, should be stirred continuously during Oxidation Leaching；Utilize the Strong oxdiative of chloroazotic acid
Metallic tellurium in high tellurium slag charge is oxidized to Te by property4+Selectivity enters in leachate, and lead, silver valuable element are with muriatic form
Enter in slag；
3., after slag charge dissolves completely, host element tellurium enters in leachate, and Pb, Ag valuable metal enters in slag；Solid-liquor separation,
Containing tellurium leachate and leached mud, leached mud returns lead smelting system and reclaims valuable metal；
4. sheet alkali being configured to solution, be slowly added to containing in tellurium leachate, regulating its terminal pH is 5.0～6.0 to be enriched with pivot
Element tellurium；TeO is obtained after the solid separation of sedimentation2Precipitation, TeO2Precipitate through calcining except nitre deselenization, then carry out liquid making, TeO2Become again tellurious
Acid sodium, in order to enter electrodeposition operation electrodeposition and directly reclaim metallic tellurium.
Above-mentioned TeO2The optimal conditions of precipitation calcining is: control temperature 350～450 DEG C, temperature retention time 5～8h, calcining
It is that tellurium dioxide is white that terminal passes judgment on mark.
The reaction principle related in said process is as follows:
2. step chloroazotic acid oxidation stage: 3Te+16H+ + 4NO3 - = 3Te4+ + 8H2O + 4NO↑
Process remove impurity stage: Pb2+ + 2Cl- = PbCl2↓Ag+ + Cl- = AgCl↓
4. step sheet alkali neutralization stage: Te4+ + 4OH- = TeO2 ↓+ 2H2O
Alkalescence liquid making stage: TeO2 + NaOH = Na2TeO3 + H2O。
The present invention utilizes chloroazotic acid directly to carry out Oxidation Leaching, under conditions of solving prior art use mineral acid, adds
The problem that the oxidation rate of oxidant tellurium element is the most oxidized extremely slowly.The present invention has that technological process is simple, equipment needed thereby
Less, the feature such as strong to adaptability to raw material, production cost is low, synthetical recovery degree height, process intensification, therefore there is significant economy
Benefit and certain application prospect.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Embodiment 1: by 5000 g height tellurium slag charge (Te73.18%, 3659g；Pb0.64%, 32g；Ag0.055%, 2.75g) broken
Be broken to granularity≤10mm, in the 16L wang aqueous solution prepared in advance is slowly added to retort and be stirred continuously, question response completely after
Carrying out solid-liquor separation and must contain tellurium leachate and leached mud, leached mud returns pyrometallurgical smelting of lead system and reclaims the valuable elements such as Ag, Pb.Leach
It is 6 that liquid sodium hydroxide solution is neutralized pH to terminal, obtains tellurium dioxide precipitation, through calcining except nitre deselenization after solid-liquor separation
After obtain tellurium dioxide weight 4665.85g, sample analysis tellurium content 77.3%(tellurium metal amount 3606.7g), its tellurium response rate is up to
98.57%, silver raising recovery rate ＞ 99.4%, lead recovery ＞ 97.6%.Gained tellurium dioxide enters conventional liquid making, electrodeposition operation.
Embodiment 2: by 5000 g height tellurium slag charge (Te71.08%, 3554g；Pb0.79%, 39.5g；Ag0.062%,3.1g)
Being crushed to granularity≤10mm, in the 12L wang aqueous solution prepared in advance is slowly added to retort and be stirred continuously, question response is complete
After carry out solid-liquor separation and must contain tellurium leachate and leached mud, leached mud returns pyrometallurgical smelting of lead system and reclaims the valuable elements such as Ag, Pb.Leaching
Go out liquid sodium hydroxide solution being neutralized pH to terminal is 6, obtains tellurium dioxide precipitation, take off except nitre through calcining after solid-liquor separation
Tellurium dioxide weight 4598.7g, sample analysis tellurium content 74.12%(tellurium metal amount 3408.56g is obtained after selenium), its tellurium response rate reaches
95.91%, silver raising recovery rate ＞ 99.0%, lead recovery ＞ 98.1%.Gained tellurium dioxide enters conventional liquid making, electrodeposition operation.
Claims (3)
1. the technique reclaiming tellurium from high tellurium slag charge, it is characterised in that: concrete technology mainly comprises the steps that
1. high tellurium slag charge is crushed to granularity≤10mm；
2. in pouring broken high tellurium slag charge into retort and be slowly added to chloroazotic acid；And control chloroazotic acid and the liquid-solid body of high tellurium slag charge
Long-pending mass ratio is 2.5～4:1L/kg to carry out Oxidation Leaching, should be stirred continuously during Oxidation Leaching；Utilize the Strong oxdiative of chloroazotic acid
Metallic tellurium in high tellurium slag charge is oxidized to Te by property4+Selectivity enters in leachate, and lead, silver valuable element are with muriatic form
Enter in slag；
3., after slag charge dissolves completely, host element tellurium enters in leachate, and Pb, Ag valuable metal enters in slag；Solid-liquor separation,
Containing tellurium leachate and leached mud, leached mud returns lead smelting system and reclaims valuable metal；
4. sheet alkali being configured to solution, be slowly added to containing in tellurium leachate, regulating its terminal pH is 5.0～6.0 to be enriched with pivot
Element tellurium；TeO is obtained after the solid separation of sedimentation2Precipitation, TeO2Precipitate through calcining except nitre deselenization, then carry out liquid making, TeO2Become again tellurious
Acid sodium, in order to enter electrodeposition operation electrodeposition and directly reclaim metallic tellurium.
A kind of technique reclaiming tellurium from high tellurium slag charge the most according to claim 1, it is characterised in that: described TeO2Precipitation
The optimal conditions of calcining is: control temperature 350～450 DEG C, temperature retention time 5～8h, and it is titanium dioxide that the terminal of calcining passes judgment on mark
Tellurium is white.
A kind of technique reclaiming tellurium from high tellurium slag charge the most according to claim 1, it is characterised in that: described 2. step king
The reaction principle of water oxidation stage is: 3Te+16H+ + 4NO3 - = 3Te4+ + 8H2O + 4NO↑；The described process remove impurity stage
Reaction principle be: Pb2+ + 2Cl- = PbCl2↓Ag+ + Cl-= AgCl↓；The reaction of described 4. step sheet alkali neutralization stage
Principle is: Te4+ + 4OH- = TeO2 ↓+ 2H2O ；The reaction principle in described alkalescence liquid making stage is: TeO2 + NaOH =
Na2TeO3 + H2O。
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| CN201610295603.8A CN105967153A (en) | 2016-05-06 | 2016-05-06 | Technology for recovering tellurium from high-tellurium slag |
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| CN201610295603.8A CN105967153A (en) | 2016-05-06 | 2016-05-06 | Technology for recovering tellurium from high-tellurium slag |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142377A (en) * | 2017-04-27 | 2017-09-08 | 永兴鑫裕环保镍业有限公司 | The technique of extracting and developing copper and tellurium from copper tellurium slag |
| 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 |
| CN108545706A (en) * | 2018-05-31 | 2018-09-18 | 阳谷祥光铜业有限公司 | A kind of processing method of the waste liquid containing tellurium |
| CN114852970A (en) * | 2022-05-30 | 2022-08-05 | 铜陵有色金属集团股份有限公司 | Short-process preparation method of refined selenium |
| CN116253296A (en) * | 2023-01-06 | 2023-06-13 | 永兴县鸿福金属有限公司 | Method for extracting tellurium from matte |
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| CN101508426A (en) * | 2009-03-24 | 2009-08-19 | 中南大学 | Method for separating tellurium from tellurium slag |
| CN101565174A (en) * | 2009-06-05 | 2009-10-28 | 永兴县鑫泰银业有限责任公司 | Method for extracting refined tellurium from tellurium-contained smelting slag |
| 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 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142377A (en) * | 2017-04-27 | 2017-09-08 | 永兴鑫裕环保镍业有限公司 | The technique of extracting and developing copper and tellurium from copper tellurium slag |
| CN107142377B (en) * | 2017-04-27 | 2018-12-21 | 永兴鑫裕环保镍业有限公司 | The technique of extracting and developing copper and tellurium from copper tellurium slag |
| 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 |
| CN107746956B (en) * | 2017-11-03 | 2019-05-28 | 郴州兴城环保股份有限公司 | Using the technique of support methods recycling tellurium from complicated solution |
| CN108545706A (en) * | 2018-05-31 | 2018-09-18 | 阳谷祥光铜业有限公司 | A kind of processing method of the waste liquid containing tellurium |
| CN114852970A (en) * | 2022-05-30 | 2022-08-05 | 铜陵有色金属集团股份有限公司 | Short-process preparation method of refined selenium |
| CN114852970B (en) * | 2022-05-30 | 2024-03-29 | 铜陵有色金属集团股份有限公司 | Short-process preparation method of refined selenium |
| CN116253296A (en) * | 2023-01-06 | 2023-06-13 | 永兴县鸿福金属有限公司 | Method for extracting tellurium from matte |
| CN116253296B (en) * | 2023-01-06 | 2024-07-12 | 永兴县鸿福金属有限公司 | Method for extracting tellurium from matte |
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Application publication date: 20160928 |