CN109097592A - A method of separating and recovering tellurium from earth of positive pole parting liquid - Google Patents
A method of separating and recovering tellurium from earth of positive pole parting liquid Download PDFInfo
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- CN109097592A CN109097592A CN201811058626.2A CN201811058626A CN109097592A CN 109097592 A CN109097592 A CN 109097592A CN 201811058626 A CN201811058626 A CN 201811058626A CN 109097592 A CN109097592 A CN 109097592A
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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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
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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
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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
The invention belongs to non-ferrous metal technical field of wet metallurgy, and in particular to a kind of method of tellurium into separation and recovery earth of positive pole parting liquid.This method retains the tellurium of complicated solution in the solution by selective reduction, then recycles the tellurium of solution in a manner of restoring again, obtains coarse tellurium powder.Advantages of the present invention and the good effect of generation are: the method for tellurium can efficiently separate tellurium in earth of positive pole parting liquid without complicated operation in a kind of separation and recovery earth of positive pole parting liquid provided by the invention, and realize tellurium high efficiente callback in solution;This method retains the tellurium of complicated solution in the solution by selective reduction, then recycles the tellurium of solution in a manner of reduction method again, and Selective Separation effect is good, and the rate of recovery is high.
Description
Technical field
The invention belongs to non-ferrous metal technical field of wet metallurgy, and in particular to arrive a kind of separation and recovery earth of positive pole parting liquid
The method of middle tellurium.
Background technique
Tellurium (Te) belongs to dissipated metal element, as the fields such as aerospace, atomic energy, electronics industry are to dilute including tellurium
The demand of dispersed metallic is growing day by day, so that tellurium has become electronic computer, communication and aerospace exploitation, the energy, medical and health institute
The backing material for needing new material is known as " vitamin of modern industry, national defence and sophisticated technology ", " contemporary high-tech art new material
Backing material ".
The main association of tellurium is in the mineral of copper, lead etc., and therefore, the production of tellurium is mainly in the heavy metals smelting process such as copper, lead
Synthetical recovery tellurium during middle synthetical recovery, especially Copper making.Synthetical recovery tellurium is almost all adopted in heavy metal smelting process
With wet processing, i.e., the intermediate material rich in tellurium of output in heavy metal smelting process is leached, so that tellurium is entered solution, so
Tellurium is separated and recovered from solution afterwards.
The leaching of the intermediate material containing tellurium generally uses salt Ore Leaching or sulfuric acid leaching, due to tellurium and copper mineral association,
These intermediate materials containing tellurium usually contain higher copper, and when leaching, copper enters solution together with tellurium, form the chlorination of cupric, tellurium
Object mixed solution or sulfuric acid mixed solution.It is industrial generally to use copper powder precipitate reduction tellurium for the mixed solution, it obtains main
Ingredient is the copper tellurium slag of copper telluride, and copper tellurium slag generally only has 10%~30% containing tellurium, needs to leach copper tellurium slag again, divide again
From complex process is at high cost.In addition, the leaching of the intermediate material containing tellurium can also obtain alkalinity or acid solution containing tellurium, in
The method of sum obtains tellurium dioxide, realizes the recycling of tellurium.Neutralisation is since the rate of deposition of tellurium is low, and general only 75% or so, gained
Tellurium dioxide complicated component, tellurium is also difficult to efficiently be leached in subsequent processing, and therefore, the effect of recycling tellurium is not ten sub-arguments
Think.
In recent years, increasingly tend to recycle the tellurium in solution using reduction method, by into the acid solution containing tellurium
Reducing agent is added, is precipitated out the tellurium in solution in the form of simple substance tellurium, obtains coarse tellurium powder.This method tellurium rate of recovery is higher,
It is adaptable, it is easy to operate.Nevertheless, the object of recycling tellurium is usually all to be formed from containing copper with tellurium or Au, Pt, Pd selenium with tellurium
Multi-metal complex mixed solution, pass through reduction recycling tellurium method, it is necessary to consider how from complicated solution realize tellurium and its
Its ingredient efficiently separates.For example, patent document CN102219193A discloses the side for separating and recovering tellurium in a kind of copper tellurium solution
Method is separated and recovered from the mixed solution of cupric tellurium using the technique of electrodeposition decopper(ing), sulfur dioxide or sulphite precipitate reduction
Tellurium.This method is suitble to separate and recover tellurium in the high, solution low containing tellurium from cupric.
When handling the intermediate material containing tellurium with wet method smelting process, gold, platinum, palladium, selenium in material can also be formed with tellurium
Mixed solution, i.e. rare precious metal solution.Sulfur dioxide or sodium sulfite reduction are generallyd use, keeps the metals such as tellurium and Au, Pt, Pd selenium total
With entering in slag, Pt Pd concentrate (rare precious metal slag) is obtained, then the metals such as Au, Pt, Pd selenium are isolated from rare precious metal slag, finally
It obtains the solution containing tellurium and recycles tellurium in a manner of sulphur dioxide reduction or neutralization.For example, patent document CN101928834A is disclosed
A kind of method recycling rare precious metal from solution, using sulfur dioxide direct-reduction process recycles rare precious metal from solution.
That is, the solution containing rare precious metal, which is added, contains Cl-Compound, be passed through sulfur dioxide reaction mistake after a certain period of time in a heated condition
Filter obtains rare precious metal slag;Separation selenium is leached with sodium sulfite solution;Divide selenium slag with sulfuric acid and hydrogen peroxide mixed solution leaching, obtains
To noble metal concentrate and solution containing tellurium;In solution containing tellurium, it is added and contains Cl-Compound, be passed through sulphur dioxide reduction and filter
To tellurium powder.For another example, patent document CN105905874A discloses a kind of method that tellurium is recycled from the earth of positive pole, by the earth of positive pole through sulphur
Hydrochlorate roasting, acidleach divide the processes such as copper, potassium cloride, obtain rare precious metal solution;Solution is through sodium sulfite Reduced separating gold;
After adding sodium chloride in the solution again, restore to obtain Pt Pd concentrate with sodium sulfite;Pt Pd concentrate isolates platinum through Oxidation Leaching
Palladium, then tellurium dioxide is obtained with the mode that leaching with sodium hydroxide, sulfuric acid neutralize, it finally restores tellurium dioxide and obtains simple substance tellurium.On
It states method to be first enriched with the tellurium in solution essentially by the mode of reduction, be leached again, the mode that separates again recycles tellurium, deposited
The problem of being suitable for the low COMPLEX MIXED solution of concentration containing tellurium and complex process.
Patent document CN105779765A discloses a kind of method by rare precious metal separation and recycling in chloridizing leach solution,
It is reducing agent with the substance without heavy metal element using the chloridizing leach solution of rare precious metal material as stoste, is aoxidized by control
Reduction potential carries out selective reduction to stoste, and the rare precious metal in solution is transformed into simple substance step by step and is precipitated out, shape
At your all kinds of dilute concentrate.There are still be suitable for the low COMPLEX MIXED solution of concentration containing tellurium, selectivity after the variation of tellurium concentration for this method
The problem of inferior separating effect.
Summary of the invention
The intermediate material rich in tellurium of output is leached in heavy metal smelting process, and tellurium is made to enter solution, then from
During separating and recovering tellurium in solution, tellurium and other rare precious metals form COMPLEX MIXED solution, for example, earth of positive pole parting liquid.
Generally use the tellurium in the method separation and recovery solution of sulfur dioxide (sodium sulfite) reduction.But this method is suitable for tellurium
The low solution of concentration needs first to be enriched with the tellurium in solution, then enriched substance leached again, separates could recycle tellurium again.It is adopting
It is then difficult to realize with the mode of control solution reduction reaction end current potential for containing the highly concentrated complicated rare precious metal solution of tellurium
The Selective Separation of tellurium recycles.It in view of the foregoing, can the purpose of the present invention is to provide a kind of operation without complexity
The method for efficiently separating tellurium in earth of positive pole parting liquid, and realize tellurium high efficiente callback in solution.
The technical solution of the present invention is as follows: a kind of method for separating and recovering tellurium in earth of positive pole parting liquid, this method includes as follows
Step:
Step (1) is passed through the sulfur dioxide gas that volumetric concentration is 6~12% to earth of positive pole parting liquid,At 60 DEG C~90 DEG CInto
Row reduction reaction, obtains slag containing rare precious metal and solution A;
At a temperature of 60 DEG C~90 DEG C, it is passed through the sulfur dioxide gas that volume content is 6%~12%, regulating gas is passed through speed elder generation
It is slow after fast, total time control is passed through in 180 ~ 240min, when oxidation-reduction potential reaches 390~420mV in solution, is stopped logical
Enter sulfur dioxide and continues 60~90min of stirring;
The sodium sulfite solution that concentration is the g/L concentration of 100g/L ~ 300 is added using solution A as raw material, in solution A for step (2),
Reduction reaction is carried out at 60 DEG C~90 DEG C, after being separated by solid-liquid separation, obtains coarse tellurium powder;
At a temperature of 60 DEG C~90 DEG C, into solution A be added concentration be the g/L concentration of 100g/L ~ 300 sodium sulfite solution into
Speed is added first quick and back slow in row reduction reaction, control, and the control of reaction total time is in 180 ~ 240min, when redox electricity in solution
When position reaches 250~280mV, stops addition sodium sulfite solution and continue 60~90min of stirring, obtain thick tellurium through being separated by solid-liquid separation
Powder;
Wherein, described containing in sulfur dioxide gas, the volumetric concentration of sulfur dioxide is 6~12%, remaining is air.
Further, sulfur dioxide gas is passed through rate in the step 1 are as follows: 60min is before reacting with 200ml/s, 60min
80ml/s is gradually decrease to the rate of 2ml/min again afterwards.
Further, it is 3L/ that the addition speed of the step 2 sulfite sodium solution, which is that speed is added in 60min before reacting,
1 L/min is reduced to the speed of 2 L/h after min, 60min.
Further, this method may also include the steps of:
Step (1) is passed through the titanium dioxide that volumetric concentration is 6%~12% into earth of positive pole parting liquid using earth of positive pole parting liquid as raw material
Sulphur gas carries out reduction reaction at 20 DEG C~30 DEG C, obtains thick bronze and solution B;
At a temperature of 20 DEG C~30 DEG C, the sulfur dioxide gas that percent by volume is 6%~12% is passed through into earth of positive pole parting liquid,
Addition speed is 5ml ~ 15ml/s, and 20min is reacted before reacting with 15ml/s Ventilation Rate, again with 1 ml/min after 20min
Rate be gradually decrease to 5ml/s, be passed through total time control in 60 ~ 90min, when oxidation-reduction potential reaches 530mV in solution
When~550mV, stopping is passed through sulfur dioxide and continues to stir 60min~120min;
Step (2) using solution B as raw material, be passed through into solution B volumetric concentration be 6~12% sulfur dioxide gas, 60 DEG C~
Reduction reaction is carried out at 90 DEG C, after being separated by solid-liquid separation, obtains Pt Pd concentrate and solution C;
At a temperature of 60 DEG C~90 DEG C, the sulfur dioxide gas that volume content is 6%~12%, regulating gas are passed through into solution B
Be passed through speed first quick and back slow, be passed through total time control in 180 ~ 240min, when in solution oxidation-reduction potential reach 390~
When 420mV, stopping is passed through sulfur dioxide and continues 60~90min of stirring;
The sodium sulfite solution that concentration is the g/L concentration of 100g/L ~ 300 is added using solution C as raw material, in solution C for step (3),
Reduction reaction is carried out at 60 DEG C~90 DEG C, after being separated by solid-liquid separation, obtains coarse tellurium powder;
At a temperature of 60 DEG C~90 DEG C, into solution C be added concentration be the g/L concentration of 100g/L ~ 300 sodium sulfite solution into
Speed is added first quick and back slow in row reduction reaction, control, and the control of reaction total time is in 180 ~ 240min, when redox electricity in solution
When position reaches 250~280mV, stops addition sodium sulfite solution and continue 60~90min of stirring, obtain thick tellurium through being separated by solid-liquid separation
Powder;
Wherein, described containing in sulfur dioxide gas, the volumetric concentration of sulfur dioxide is 6~12%, remaining is air.
Further, sulfur dioxide gas is passed through rate in the step 1 are as follows: 20min is before reacting with 15ml/s Ventilation Rate
It is reacted, 5ml/s is gradually decrease to the rate of 1 ml/min again after 20min.
Further, sulfur dioxide gas is passed through rate in the step 2 are as follows: and 60min is best with 200ml/s before reacting,
Rate after 60min again with 2ml/min is gradually decrease to 80ml/s.
Further, it is 3L/ that the addition speed of the step 3 sulfite sodium solution, which is that speed is added in 60min before reacting,
1 L/min is reduced to the speed of 2 L/h after min, 60min.
Further, Cl in the earth of positive pole parting liquid-Concentration be 50000~80000 mg/L.
Compared with prior art, advantages of the present invention and the good effect of generation are: provided by the invention a kind of to separate back
The method for receiving tellurium in earth of positive pole parting liquid can efficiently separate tellurium in earth of positive pole parting liquid without complicated operation, and realize molten
Tellurium high efficiente callback in liquid.Method of the invention by selective reduction make complicated solution tellurium retain in the solution, then again with
Reduction method mode recycles the tellurium of solution, and Selective Separation effect is good, and the rate of recovery is high.
Detailed description of the invention
Fig. 1 is the process flow chart of the embodiment of the present invention.
Fig. 2 is the process flow chart of another embodiment of the invention.
Specific embodiment
Technical scheme is described further in the following with reference to the drawings and specific embodiments.
It is formed in COMPLEX MIXED solution, is recycled by reduction method or controlling potential reduction method molten in tellurium and other rare precious metals
During tellurium in liquid, tellurium is easy to restore jointly with rare precious metal, and reduction process is caused to be difficult to realize the Selective Separation of tellurium.
Applicant is by a large amount of the study found that if the sulfur dioxide gas of low concentration is used to carry out controlling potential also for reducing agent
It is former, so that it may which that so that the Au, Pt, Pd in solution is first restored and separated, and tellurium remains in solution, so as to realize tellurium
It is separated with the efficient selective of Au, Pt, Pd.
The method that Fig. 1 example goes out tellurium in a kind of separation and recovery earth of positive pole parting liquid provided by the invention, includes the following steps:
S1 is passed through sulfur dioxide gas to earth of positive pole parting liquid, obtains after being separated by solid-liquid separation in 60~90 DEG C of progress reduction reactions
Rare precious metal slag containing Au, Pt, Pd and the mixed solution A containing tellurium;S2, mixed solution A containing tellurium be added reducing agent sodium sulfite into
Row reduction reaction obtains coarse tellurium powder after being separated by solid-liquid separation.
The method that Fig. 2 example goes out tellurium in a kind of separation and recovery earth of positive pole parting liquid provided by the invention, includes the following steps:
S11 is passed through sulfur dioxide gas into earth of positive pole parting liquid, reduction reaction is carried out at 20~30 DEG C, after being separated by solid-liquid separation,
Obtain the mixed solution B of thick bronze and platiniferous palladium tellurium;S12 is passed through sulfur dioxide gas into the mixed solution B of platiniferous palladium tellurium,
Reduction reaction is carried out at 60~90 DEG C, after being separated by solid-liquid separation, obtains Pt Pd concentrate and the mixed solution C containing tellurium;S20 contains
The mixed solution C of tellurium is added reducing agent and carries out reduction reaction, after being separated by solid-liquid separation, obtains coarse tellurium powder.
In above-mentioned sulfur dioxide gas, the volume ratio of sulfur dioxide is 6~12%, remaining is air.
Materials containing tellurium of the earth of positive pole parting liquid during ANODE SLIME TREATMENT in the present invention, as process object
(such as copper anode mud divides copper ashes), potassium cloride obtained solution.The earth of positive pole obtains after sulfating roasting, sulfuric acid divide copper step process
Divide copper ashes, then through potassium cloride to get arriving earth of positive pole parting liquid.Wherein, contain H in parting liquid+For 1600~2500 mg/
L, the also Cl containing 50000~80000 mg/L-.In addition, metal component is to contain 15000~30000 in earth of positive pole parting liquid
The Pd of the Au of the Te of mg/L and 1000~3000 mg/L, the Pt of 10~50 mg/L, 50~300 mg/L, and a small amount of
Copper, bismuth etc..
In the present invention, under 60~90 DEG C of higher temperature, it is passed through sulfur dioxide gas into earth of positive pole parting liquid, is carried out
Reduction reaction restores the Au, Pt, Pd in solution sufficiently, and tellurium remains in solution, to realize tellurium and Au, Pt, Pd
Metal efficiently separates.Wherein, reaction temperature is 60~90 DEG C, and preferably 70~80 DEG C, gas is passed through 60min before speed responsing
It is preferred that gas is passed through the preferred 80ml/s of speed after 200ml/s, 120min, Au, Pt, Pd reduction can be carried out sufficiently, rate of recovery effect
Fruit is good, and tellurium is retained in solution A;In addition, the dosage of sulfur dioxide gas can be determined with oxidation-reduction potential in solution, i.e.,
When in solution oxidation-reduction potential stablize in 390~430 mV range, stopping be passed through sulfur dioxide and continue stirring 60~
After 120min, it is separated by solid-liquid separation.In this way, the reduction of one side Au, Pt, Pd is sufficiently, Au, Pt, Pd content is less than in obtained solution A
1mg/L;On the other hand tellurium can be reduced because restoring the loss entered in slag, improve Selective Separation effect.
Then under 60~90 DEG C of higher temperature, excessive sulfurous is added with sodium sulfite at 60~90 DEG C in solution A
Sour sodium, sufficiently, the tellurium content after reduction in solution is low for tellurium reduction, and the tellurium rate of recovery is high.Wherein, 60 DEG C~90 DEG C of reaction temperature, it is excellent
70~80 DEG C are selected as, sodium sulfite solution concentration is 180-200g/L, and speed is added first quick and back slow in sodium sulfite solution, preceding
The preferred 3L/min of speed is added in 60min, and speed preferably 1 L/min is added in 120min, and tellurium can be restored sufficiently, after reduction in solution
Tellurium content < 0.1g/L;In addition, sodium sulfite solution dosage can be determined with oxidation-reduction potential in solution, that is, work as solution
In oxidation-reduction potential stablize in 250~280 mV range, stop be added sodium sulfite solution continue stirring 60~
90min is separated by solid-liquid separation.
In the present invention, it first can also be passed through sulfur dioxide gas into earth of positive pole parting liquid, be gone back at 20~30 DEG C
Original reaction, restores the gold in solution preferentially.Wherein, gas is passed through 20min preferred 15ml/s, 30min before speed responsing
Gas is passed through the preferred 5ml/s of speed afterwards, and gold reduction can be carried out sufficiently, and rate of recovery effect is good, and platinum palladium tellurium is retained in solution A
In;In addition, the dosage of sulfur dioxide gas can be determined with oxidation-reduction potential in solution, i.e., when the redox in solution
Current potential is stablized in 530~550mV range, after stopping is passed through sulfur dioxide and continues 60~120min of stirring, carries out solid-liquid point
From obtaining thick bronze.In this way, on the one hand sufficiently, gold content is less than 1mg/L in obtained solution B for gold reduction;It on the other hand can be with
Platinum palladium tellurium is reduced because restoring the loss entered in slag, improves Selective Separation effect.
Solution B is passed through sulfur dioxide gas at 60~90 DEG C and restores again, obtains Pt Pd concentrate, and tellurium remains in
In solution C, to realize that tellurium and gold, tellurium and platinum palladium metal efficiently separate.Wherein, reaction temperature is 60~90 DEG C, preferably
70~80 DEG C, gas is passed through before speed responsing that gas is passed through the preferred 80ml/ of speed after 60min preferred 200ml/min, 120min
Min, the reduction of platinum palladium can be carried out sufficiently, and rate of recovery effect is good, and tellurium is retained in solution C;In addition, the use of sulfur dioxide gas
Amount can be determined with oxidation-reduction potential in solution, i.e., when the oxidation-reduction potential in solution is stablized in 390~420mV range
When, after stopping is passed through sulfur dioxide and continues 60~120min of stirring, it is separated by solid-liquid separation to obtain Pt Pd concentrate and contains tellurium
Mixed solution C.In this way, the reduction of one side platinum palladium is sufficiently, platinum palladium content is less than 1mg/L in obtained solution C;On the other hand,
Tellurium remains in solution C, to realize that tellurium and gold, tellurium and platinum palladium metal efficiently separate, reduces tellurium because reduction enters slag
In loss, improve Selective Separation effect.
Solution C sodium sulfite is at 60~90 DEG C, and under 60~90 DEG C of higher temperature, excessive sodium sulfite is added,
Sufficiently, the tellurium content after reduction in solution is low for tellurium reduction, and the tellurium rate of recovery is high.Wherein, 60 DEG C of reaction temperature~90 DEG C, preferably 70
~80 DEG C, the preferred 180-200g/L of sodium sulfite solution concentration, speed is added first quick and back slow in sodium sulfite solution, and preceding 60min adds
Enter the preferred 3L/min of speed, speed preferably 1 L/min is added in 120min, and tellurium can be restored sufficiently, and the tellurium after reduction in solution contains
Measure < 0.1g/L;In addition, sodium sulfite solution dosage can be determined with oxidation-reduction potential in solution, i.e., when the oxygen in solution
Change reduction potential to stablize in 250~280 mV range, stops addition sodium sulfite solution and continue 60~90min of stirring, carry out
It is separated by solid-liquid separation.
It must be it is noted that oxidation-reduction potential be that measurement reference electrode uses silver-silver chloride electrode, insertion in the present invention
Reference electrode into aqueous solution and value (mV) obtained from the potential difference of metal electrode.
Embodiment (1~3):
(1) it is passed through the sulfur dioxide gas that volumetric concentration is 6~12% to earth of positive pole parting liquid, is restored at 60~90 DEG C
Reaction is stablized when solution oxide reduction potential in 400~450 mV range, and stopping is passed through sulfur dioxide and continues stirring 60
~120min obtains the rare precious metal slag containing Au, Pt, Pd and solution A containing tellurium after being separated by solid-liquid separation;(2) solution A containing tellurium is added
Reducing agent sodium sulfite carries out reduction reaction, after being separated by solid-liquid separation, obtains coarse tellurium powder.Examples 1 to 3 the results are shown in Table 1.
Table 1
Comparative example (1~2)::
Reducing agent sodium sulfite is added to earth of positive pole parting liquid, reduction reaction is carried out at 60 DEG C, to solution oxide reduction potential
Stablize in 600mV, continue to stir 60min, after being separated by solid-liquid separation, obtains rare precious metal slag containing Au, Pt, Pd and molten containing tellurium
Liquid.It the results are shown in Table 1.
Embodiment (4~6):
(1) it is passed through the sulfur dioxide gas that volumetric concentration is 6~12% into earth of positive pole parting liquid, is gone back at 20~30 DEG C
Original reaction, stablizes when solution oxide reduction potential in 550~600 mV range, and stopping is passed through sulfur dioxide and continues stirring 30
~60min obtains thick bronze and solution B containing tellurium after being separated by solid-liquid separation;(2) it is 6 that volumetric concentration is passed through into solution B containing tellurium
~12% sulfur dioxide gas carries out reduction reaction at 60~90 DEG C, when the oxidation-reduction potential of solution B stablizes 400~
When 450 mV range, stopping is passed through sulfur dioxide and continues 60~120min of stirring, after being separated by solid-liquid separation, obtains Pt Pd concentrate
With solution C containing tellurium;(3) solution C containing tellurium copper is added reducing agent sodium sulfite and carries out reduction reaction, after being separated by solid-liquid separation, obtains
Coarse tellurium powder.Embodiment 4~6 the results are shown in Table 2.
Table 2
From the embodiment of the present invention 1~6 and comparative example 1~2 as can be seen that the tellurium property of can choose in parting liquid of the present invention restores,
And tellurium is not reduced reservation in the solution, and after separation of solid and liquid, the high-grade that amount containing tellurium is greater than 90% can be obtained using reduction
Coarse tellurium powder.According to embodiments of the present invention, tellurium is reduced the amount of metal into other materials lower than 5%.Far superior to comparative example is said
The selectivity of bright method of the invention is more preferable.
Claims (8)
1. a kind of method of tellurium in separation and recovery earth of positive pole parting liquid, which comprises the steps of:
Step (1) is passed through the sulfur dioxide gas that volumetric concentration is 6~12% to earth of positive pole parting liquid,At 60 DEG C~90 DEG CInto
Row reduction reaction, obtains slag containing rare precious metal and solution A;
At a temperature of 60 DEG C~90 DEG C, it is passed through the sulfur dioxide gas that volume content is 6%~12%, regulating gas is passed through speed elder generation
It is slow after fast, total time control is passed through in 180 ~ 240min, when oxidation-reduction potential reaches 390~420mV in solution, is stopped logical
Enter sulfur dioxide and continues 60~90min of stirring;
The sodium sulfite solution that concentration is the g/L concentration of 100g/L ~ 300 is added using solution A as raw material, in solution A for step (2),
Reduction reaction is carried out at 60 DEG C~90 DEG C, after being separated by solid-liquid separation, obtains coarse tellurium powder;
At a temperature of 60 DEG C~90 DEG C, into solution A be added concentration be the g/L concentration of 100g/L ~ 300 sodium sulfite solution into
Speed is added first quick and back slow in row reduction reaction, control, and the control of reaction total time is in 180 ~ 240min, when redox electricity in solution
When position reaches 250~280mV, stops addition sodium sulfite solution and continue 60~90min of stirring, obtain thick tellurium through being separated by solid-liquid separation
Powder;
Wherein, described containing in sulfur dioxide gas, the volumetric concentration of sulfur dioxide is 6~12%, remaining is air.
2. a kind of method of tellurium in separation and recovery earth of positive pole parting liquid, which comprises the steps of:
Step (1) is passed through the titanium dioxide that volumetric concentration is 6%~12% into earth of positive pole parting liquid using earth of positive pole parting liquid as raw material
Sulphur gas carries out reduction reaction at 20 DEG C~30 DEG C, obtains thick bronze and solution B;
At a temperature of 20 DEG C~30 DEG C, the sulfur dioxide gas that percent by volume is 6%~12% is passed through into earth of positive pole parting liquid,
Addition speed is 5ml ~ 15ml/s, and 20min is reacted before reacting with 15ml/s Ventilation Rate, again with 1 ml/min after 20min
Rate be gradually decrease to 5ml/s, be passed through total time control in 60 ~ 90min, when oxidation-reduction potential reaches 530mV in solution
When~550mV, stopping is passed through sulfur dioxide and continues to stir 60min~120min;
Step (2) using solution B as raw material, be passed through into solution B volumetric concentration be 6~12% sulfur dioxide gas, 60 DEG C~
Reduction reaction is carried out at 90 DEG C, after being separated by solid-liquid separation, obtains Pt Pd concentrate and solution C;
At a temperature of 60 DEG C~90 DEG C, the sulfur dioxide gas that volume content is 6%~12%, regulating gas are passed through into solution B
Be passed through speed first quick and back slow, be passed through total time control in 180 ~ 240min, when in solution oxidation-reduction potential reach 390~
When 420mV, stopping is passed through sulfur dioxide and continues 60~90min of stirring;
The sodium sulfite solution that concentration is the g/L concentration of 100g/L ~ 300 is added using solution C as raw material, in solution C for step (3),
Reduction reaction is carried out at 60 DEG C~90 DEG C, after being separated by solid-liquid separation, obtains coarse tellurium powder;
At a temperature of 60 DEG C~90 DEG C, into solution C be added concentration be the g/L concentration of 100g/L ~ 300 sodium sulfite solution into
Row reduction reaction controls and speed is added first quick and back slow, and speed is added for 3L/min, with 2 L/h's after 60min in 60min before reacting
Speed is reduced to 1 L/min, the control of reaction total time in 180 ~ 240min, when in solution oxidation-reduction potential reach 250~
When 280mV, stops addition sodium sulfite solution and continue 60~90min of stirring, obtain coarse tellurium powder through being separated by solid-liquid separation;
Wherein, described containing in sulfur dioxide gas, the volumetric concentration of sulfur dioxide is 6~12%, remaining is air.
3. method according to claim 1 or 2, which is characterized in that Cl in the earth of positive pole parting liquid-Concentration be
50000~80000 mg/L.
4. the method according to claim 1, wherein sulfur dioxide gas is passed through rate in the step (1)
Are as follows: 60min is gradually decrease to 80ml/s again after 60min with the rate of 2ml/min with 200ml/s before reacting.
5. the method according to claim 1, wherein the addition speed of the step (2) sulfite sodium solution
It is 3L/min that speed, which is added, for 60min before reacting, and is reduced to 1 L/min after 60min with the speed of 2 L/h.
6. according to the method described in claim 2, it is characterized in that, sulfur dioxide gas is passed through rate in the step (1)
Are as follows: 20min is reacted before reacting with 15ml/s Ventilation Rate, is gradually decrease to again with the rate of 1 ml/min after 20min
5ml/s。
7. according to the method described in claim 2, it is characterized in that, sulfur dioxide gas is passed through rate in the step (2)
Are as follows: 60min is best with 200ml/s before reacting, and the rate after 60min again with 2ml/min is gradually decrease to 80ml/s.
8. according to the method described in claim 2, it is characterized in that, the addition speed of the step (3) sulfite sodium solution
It is 3L/min that speed, which is added, for 60min before reacting, and is reduced to 1 L/min after 60min with the speed of 2 L/h.
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