CN106868319A - A kind of method that high purity tellurium is obtained in the immersion liquid from alkali containing arsenic - Google Patents
A kind of method that high purity tellurium is obtained in the immersion liquid from alkali containing arsenic Download PDFInfo
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- CN106868319A CN106868319A CN201611192834.2A CN201611192834A CN106868319A CN 106868319 A CN106868319 A CN 106868319A CN 201611192834 A CN201611192834 A CN 201611192834A CN 106868319 A CN106868319 A CN 106868319A
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- tellurium
- arsenic
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- immersion liquid
- slag
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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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
- C01B19/02—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
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- 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
Abstract
A kind of method that high purity tellurium is obtained in immersion liquid from alkali containing arsenic, the present invention relates to a kind of alkali immersion liquid of the tin of tellurium lead containing arsenic, the alkali immersion liquid is the leachate after oxygen pressure alkali leaching treatment high-arsenic antimony flue dust.Alkali immersion liquid is neutralized by sulfuric acid, neutralizer selective reduction, liquid is pure sodium arsenite solution after reduction, for the raw material of solution of zinc sulfate arsenic Cobalt Purification nickel, reducing slag and neutralization slag obtain more than 99.999% high purity tellurium through hydrogen reduction, vacuum distillation.The present invention will reclaim tellurium from arsenic solution high, and obtain pure sodium arsenite solution for zinc hydrometallurgy solution of zinc sulfate arsenic Cobalt Purification nickel raw material.Present invention process flow is short, and the rate of recovery is high, solves pollution problem in traditional handicraft extraction process.
Description
Technical field
The invention belongs to technical field of wet metallurgy, and in particular to obtain the side of high purity tellurium in a kind of immersion liquid from alkali containing arsenic
Method.
Background technology
Tellurium is widely used at aspects such as solar cell, optical disc recording, thermoelectric coolings, is also increasingly subject to state
The attention and favor of inside and outside scientific worker, tellurium are recognized as one of important support material of 21 century high-technology field.But
It is that tellurium just comes into effect large-scale industrial production in nineteen forty-two, and is quickly grown recently as high technology industry, causes tellurium
Demand is sharply increased.So in the case where tellurium reserves are limited, synthetical recovery metal tellurium just has great meaning from discarded object
Justice.In lead, the melting and roasting process of zinc, the high-arsenic antimony flue dust of output not only contains substantial amounts of arsenic, antimony, also containing a small amount of
Tellurium.After oxygen pressure alkali leaching treatment high-arsenic antimony flue dust, how the tellurium containing part in the immersion liquid of alkali containing arsenic makes dissipated metal tellurium therein
Synthetical recovery is the problem for failing fine solution at present.
Chinese invention patent publication number CN103264997A, discloses a kind of method that tellurium is extracted from low-concentration tellurium solution.
HCl solution is added in low-concentration tellurium solution, obtains pre-processing tellurium liquid water phase, wherein HCl concentration is 4.5mol/L；By compared to 1:1
Tributylphosphate/kerosene organic phase is added, 2~4min of oscillation extraction extracts series one-level, after stratification, is loaded with
Machine phase；By compared to 1:1 adds NH4Cl solution waters are mutually stripped, 0.5~2min of oscillation extraction, extract series three-level, are stood and are divided
From water phase；Water containing tellurium after above-mentioned back extraction is communicated into pervaporation method or the precipitation method, tellurium product is obtained.Invention use extraction → anti-
Extraction → depositing technology flow extracts tellurium from solution containing tellurium, and technological process is long, complex operation, while reagent consumption is big.
Chinese invention patent publication number CN101844750A, discloses a kind of method of preparing high-purity tellurium by material containing tellurium.Should
Method is to process to prepare high purity tellurium using chemical method.By materials containing tellurium through peroxidating, acidleach, be filtrated to get thick tellurium；
The lower acid solution of oxidant effect leaches thick tellurium, through being filtrated to get solution containing tellurium；Reducing agent is added in solution containing tellurium, after reaction
Heating and filtering, adds reducing agent again in filtrate, and tellurium powder is filtrated to get after reacting under heating；It is acid under oxidant effect
Reducing agent is added to obtain smart tellurium after solution dissolving tellurium powder；At 200 DEG C~800 DEG C, hydrogen treat essence tellurium obtains high purity tellurium.The hair
The bright smart tellurium technological process of tellurium-contained smelting slag extraction is long, and the tediously long complexity of flow, return period is long.
The content of the invention
In order to the tellurium rate of recovery is low in solving the immersion liquid of alkali containing tellurium, the complicated problem of technological process, the present invention proposes a kind of from containing
The method that high purity tellurium is obtained in arsenic alkali immersion liquid, comprises the following steps：
(1) neutralize：The immersion liquid of alkali containing arsenic is taken, the pH value of the regulation immersion liquid of alkali containing arsenic is 4-6, after solid-liquor separation, must be neutralized
Liquid and neutralization slag, wherein, neutralize slag and enter follow-up hydrogen reduction operation；
(2) selective reduction：Reduced to reducibility gas are passed through in step (1) gained neutralizer, after reduction terminates,
Reducing solution and reducing slag are obtained after solid-liquor separation；The reducing solution is pure sodium arsenite solution, net as solution of zinc sulfate arsenic
Eliminate the raw material of cobalt nickel；
(3) hydrogen reduction, vacuum distillation：Step (2) gained reducing slag neutralizes slag and carries out hydrogen reduction with step (1) gained, obtains
To thick tellurium and lead skim, used as refining leady raw materialses, thick tellurium is in two condensation segments and a vacuum distillation furnace for distilling period for lead skim
Vacuum distillation, obtains more than 99.999% high purity tellurium.
The solution of the present invention is neutralized by sulfuric acid, the tellurium of lead and a part in removing alkali immersion liquid, neutralizer selectivity
Reduction, liquid is pure sodium arsenite solution after reduction, for the raw material of solution of zinc sulfate arsenic Cobalt Purification nickel, reducing slag and neutralization
Slag obtains more than 99.999% high purity tellurium through hydrogen reduction, vacuum distillation, it is achieved thereby that each valuable metal in the immersion liquid of alkali containing arsenic
Between separation, and have effectively achieved resource and innoxious.Comprehensive resource utilization rate of the present invention is high, raw material accommodation
Extensively, the pollution problem during traditional extraction technique is solved.
The chemical equation of neutralization step is as follows：
Na2TeO3+H2SO4=TeO2↓+Na2SO4+H2O
Pb2++SO4 2—=PbSO4↓
So the sodium tellurite in solution can be transformed into tellurium dioxide so as to settle down.
The chemical equation for reducing operation is as follows：
Na3AsO4+SO2=NaAsO2+Na2SO4
TeOOH++2SO2+2H2O=Te ↓+5H++2SO4 2-
Pb2++SO2+H2O=PbSO3↓+2H+
Pure sodium arsenite solution can be so obtained, while with TeOOH in reclaiming solution+The tellurium of presence.
Then the high purity tellurium that slag and reducing slag obtain 99.999% through two operations of hydrogen reduction and vacuum distillation will be neutralized again.
This method not only solves the recovery problem of the tellurium in the flue dust of tellurium containing arsenic, and by arsenic recycling.
Alkali containing arsenic used immersion liquid in the present invention, the leaching for mainly being obtained using caustic solution treatment arsenic-containing smoke dust
Liquid.Specifically, the main component of the immersion liquid of alkali containing arsenic be As 1~60g/L, Pb 50ppm~800ppm, Sn 2ppm~
10~120g/L of 200ppm, Te 10~500ppm, NaOH.
Preferably, in step (1), the temperature of neutralization is room temperature to 80 DEG C.
Specifically, the operation of step (1) is：In room temperature to 80 DEG C, mixing speed be 100r/min~300r/min conditions
Under, solution ph is modulated 3~6 to sour (such as sulfuric acid) is added in the immersion liquid of alkali containing arsenic.
Preferably, in step (2), the reducibility gas are SO2。
Specifically, the operation of step (2) is：In room temperature under the conditions of 90 DEG C, according to the speed of 0.5~5L/min, ventilation
0.5~4h.
Preferably, the temperature control of hydrogen reduction described in step (3) is at 550 DEG C~650 DEG C.
Preferably, in step (3) temperature of two condensation segments of vacuum distillation be respectively 290 DEG C~310 DEG C and 310 DEG C~
330 DEG C, the temperature control of distilling period is at 500 DEG C~550 DEG C.
Preferably, vacuum degree control is 0.1~5Pa in step (3).
Advantages and positive effects of the present invention：
1st, the immersion liquid of alkali containing arsenic used in the present invention, what is obtained when mainly processing arsenic-containing smoke dust using caustic solution contains
The solution of arsenic and tellurium.Arsenic content is high in solution, while more than 95% tellurium is enriched in solution, and reclaims tellurium from arsenic solution high
The research of recycling arsenic has no relevant report.；
2nd, after the tellurium in flue dust is effectively dissolved and is leached, the preferential Selective Separation from leachate of present invention selection
Go out tellurium, lead, this is based on arsenic, tellurium, lead, the characteristic of tin element in leachate so that tellurium, lead, tin selective reduction are from solution
Removing, the content of Te is up to more than 55% in purification slag；
3rd, labour intensity of the invention is low, process time is short, good operational environment；
4th, preparation process non-secondary pollution thing generation, and arsenic can be enriched in after reduction in liquid, and arsenic is used as zinc sulfate
Solution purification is also significant except the raw material of cobalt nickel in terms of environmental protection；
5th, the removal efficiency of tellurium of the present invention has processed the alkali immersion liquid of tellurium containing arsenic more than 99%, not only, and has obtained pure
NaAsO2, particularly the rate of recovery of tellurium is up to more than 92%.
6th, the rational operation collocation of the present invention, by strictly controlling the conditional parameter in each operation so that tellurium, arsenic are obtained
Reclaim and effectively utilization, reached environmental protection, economy, energy-conservation, the purpose of resource utilization high, realize the resource of arsenic and harmless
Change, and whole technique substantially three-waste free discharge, all resources obtain maximal efficiency utilization, and products therefrom is easy to follow-up
Treatment and processing, so the present invention has environmental protection, economy, energy-conservation, the advantage of resource utilization high.
Brief description of the drawings
Fig. 1 is from containing the flow chart that metallic tellurium is obtained in arsenic, tellurium, lead, tellurium solution.
Specific embodiment
The following is embodiments of the invention.
Embodiment 1：
By taking alkali immersion liquid in experiment as an example, wherein essential element concentration is Pb 706.67ppm, Sn 29.02ppm, Te
134.56ppm, As 28.29g/L, are processed using following steps：
(1) neutralize：Temperature be 40 DEG C, mixing speed be 200r/min under conditions of toward adding H in alkali immersion liquid2SO4By alkali
The pH of immersion liquid is adjusted to 5, and solid-liquor separation obtains neutralizer and neutralizes slag；Gained neutralizes slag and enters follow-up hydrogen reduction operation；
(2) selective reduction：Step (1) gained neutralizer enters selective reduction operation, to being passed through SO in neutralizer2,
The condition for controlling be gas flow be 2L/min, temperature be 60 DEG C, duration of ventilation be 2h.It is molten that reduction obtains sodium arsenite after terminating
Liquid and reducing slag；
After testing：The content of each element is in reducing solution：Pb 2.86ppm, Sn 0.79ppm, Te 1.08ppm, As
27.01g/L.Calculating the removal efficiency of Pb and Te is respectively：Pb 99.59%, Te 99.20%.
(3) hydrogen reduction and vacuum distillation：The reducing slag and the neutralization slag of step (1) that step (2) is obtained enter hydrogen reduction work
Sequence and vacuum distillation operation, reduce in 600 DEG C to reducing slag, obtain 99.9% Te and lead skim, and lead skim is former as refining lead
Material；Then 99.9% Te is evaporated in vacuo in two condensation segments and a vacuum distillation furnace for distilling period, one section of condensation
Temperature is 300 DEG C, two sections of condensation temperatures are 320 DEG C, distilling period temperature is 510 DEG C, vacuum is 2Pa, and distillation is obtained
99.999% high purity tellurium.
Embodiment 2：
By taking alkali immersion liquid in experiment as an example, wherein essential element concentration is Pb 647.26ppm, Sn 68.59ppm, Te
238.45ppm, As 38.46g/L, are processed using following steps：
(1) neutralize：Temperature be 80 DEG C, mixing speed be 150r/min under conditions of toward adding H in alkali immersion liquid2SO4By alkali
The pH of immersion liquid is adjusted to 4, and solid-liquor separation obtains neutralizer and neutralizes slag；Gained neutralizes slag and enters follow-up hydrogen reduction operation；
(2) selective reduction：Step (1) gained neutralizer enters reduction operation, to being passed through SO in neutralizer2, control
Condition be gas flow be 3L/min, temperature be 90 DEG C, duration of ventilation be 3h.Reduction obtains sodium arsenite solution and goes back after terminating
Former slag；
After testing：The content of each element is in reducing solution：Pb 2.43ppm, Sn 0.98ppm, Te 1.45ppm, As
37.89g/L.Calculating the removal efficiency of Pb and Te is respectively：Pb 99.62%, Te 99.39%.
(3) hydrogen reduction and vacuum distillation：The neutralization slag of step (3) gained reducing slag and step (1) enters hydrogen reduction operation
With vacuum distillation operation, reducing slag is reduced in 650 DEG C, obtain 99.8% Te and lead skim, lead skim is used as refining leady raw materialses；
Then 99.7% Te is evaporated in vacuo in two condensation segments and a vacuum distillation furnace for distilling period, one section of condensation temperature
For 295 DEG C, two sections of condensation temperatures be 330 DEG C, distilling period temperature be 530 DEG C, vacuum be 5Pa, distillation obtain 99.999% with
On high purity tellurium.
Embodiment 3：
By taking alkali immersion liquid in experiment as an example, wherein essential element concentration is Pb 547.85ppm, Sn 67.43ppm, Te
164.27ppm, As 19.44g/L, are processed using following steps：
(1) neutralize：Temperature be 40 DEG C, mixing speed be 100r/min under conditions of toward adding H in alkali immersion liquid2SO4By alkali
The pH of immersion liquid is adjusted to 5, and solid-liquor separation obtains neutralizer and neutralizes slag；Gained neutralizes slag and enters follow-up hydrogen reduction operation；
(2) selective reduction：Step (1) gained neutralizer enters reduction operation, neutralizes slag and enters hydrogen reduction operation.In
With SO is passed through in liquid2, the condition for controlling be gas flow be 5L/min, temperature be 70 DEG C, duration of ventilation be 0.5h.Reduction terminates
After obtain sodium arsenite solution and reducing slag；
After testing：The content of each element is in reducing solution：Pb 3.04ppm, Sn 1.34ppm, Te 1.12ppm, As
18.51g/L.Calculating the removal efficiency of Pb and Te is respectively：Pb 99.45%, Te 99.32%.
(3) hydrogen reduction and vacuum distillation：The neutralization slag of step (3) gained reducing slag and step (1) enters hydrogen reduction operation
With vacuum distillation operation, reducing slag is reduced in 620 DEG C, obtain 99.5% Te and lead skim, lead skim is used as refining leady raw materialses；
Then 99% Te is evaporated in vacuo in two condensation segments and a vacuum distillation furnace for distilling period, and one section of condensation temperature is
310 DEG C, two sections of condensation temperatures be 315 DEG C, distilling period temperature be 500 DEG C, vacuum be 3Pa, distillation obtains more than 99.99%
High purity tellurium.
Although above having used general explanation, specific embodiment and experiment, the present invention is made to retouch in detail
State, but on the basis of the present invention, it can be made some modifications or improvements, this is to those skilled in the art apparent
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (8)
1. a kind of method that high purity tellurium is obtained in immersion liquid from alkali containing arsenic, it is characterised in that comprise the following steps：
(1) neutralize：Take the immersion liquid of alkali containing arsenic, the pH value of the regulation immersion liquid of alkali containing arsenic is 4-6, after solid-liquor separation, obtain neutralizer with
Slag is neutralized, wherein, neutralize slag and enter follow-up hydrogen reduction operation；
(2) selective reduction：Reduced to reducibility gas are passed through in step (1) gained neutralizer, after reduction terminates, liquid is solid
Reducing solution and reducing slag are obtained after separation；The reducing solution is pure sodium arsenite solution, is removed as the purification of solution of zinc sulfate arsenic
The raw material of cobalt nickel；
(3) hydrogen reduction, vacuum distillation：Step (2) gained reducing slag neutralizes slag and carries out hydrogen reduction with step (1) gained, obtains thick
Tellurium and lead skim, lead skim is used as refining leady raw materialses, thick tellurium vacuum in two condensation segments and a vacuum distillation furnace for distilling period
Distillation, obtains more than 99.999% high purity tellurium.
2. method according to claim 1, it is characterised in that：In step (1), the main component of the arsenic containing solution is：
10~120g/L of As 1~60g/L, Pb 50ppm~800ppm, Sn 2ppm~200ppm, Te 10~500ppm, NaOH.
3. method according to claim 1, it is characterised in that：Described in step (1) neutralize when control temperature be room temperature extremely
80℃。
4. the method according to claim any one of 1-3, it is characterised in that：Reducibility gas described in step (2) are SO2。
5. method according to claim 4, it is characterised in that：In step (2), in room temperature under the conditions of 90 DEG C, according to 0.5
The speed of~5L/min, leads to SO2Gas time is 0.5~4h.
6. method according to claim 1, it is characterised in that：In step (3), the temperature of the hydrogen reduction for 550 DEG C~
650℃。
7. the method according to claim 1 or 6, it is characterised in that：In step (3), two condensation segments of vacuum distillation
Temperature is respectively 290 DEG C~310 DEG C and 310 DEG C~330 DEG C, and the temperature of distilling period is 500 DEG C~550 DEG C.
8. method according to claim 7, it is characterised in that：The vacuum of vacuum distillation is 0.1~5Pa.
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| CN201611192834.2A CN106868319B (en) | 2016-12-21 | 2016-12-21 | A method of obtaining high purity tellurium from the immersion liquid of alkali containing arsenic |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110894065A (en) * | 2019-12-18 | 2020-03-20 | 中南大学 | Equipment and method for preparing high-purity tellurium |
| CN111575491A (en) * | 2020-06-29 | 2020-08-25 | 株洲冶炼集团科技开发有限责任公司 | Resource comprehensive utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt |
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