CN104445101B - A kind of method extracting copper and tellurium from telluride copper ashes - Google Patents
A kind of method extracting copper and tellurium from telluride copper ashes Download PDFInfo
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Abstract
This application provides a kind of method extracting copper and tellurium from telluride copper ashes, comprise the following steps: a) by telluride copper ashes and hydrogen peroxide and sulphuric acid mixing, carry out Oxidation Leaching, obtain leachate；B) react after oxalic acid class decopper(ing) agent being mixed with the described step a) leachate obtained, obtain liquid after cupric oxalate and oxalic acid decopper(ing)；C) react after reducing agent being mixed with liquid after described step b) the oxalic acid decopper(ing) obtained, obtain tellurium；Described reducing agent is sodium sulfite or sulfur dioxide gas。The application feature according to telluride copper ashes material, adopts Whote-wet method technique, can fully realize being kept completely separate of copper and tellurium, thus reaching copper and the purpose of tellurium synthetical recovery。Further, to have technological process simple, equipment requirements is very low and be beneficial to the advantages such as environmental protection for the application, it is easy to industrialized production。It addition, silver and selenium etc. in telluride copper ashes are enriched with by the application in Oxidation Leaching slag, it are beneficial to and reclaim silver and selenium further。
Description
Technical field
The present invention relates to non-ferrous metal metallurgy technical field, be specifically related to a kind of method extracting copper and tellurium from telluride copper ashes。
Background technology
Tellurium belongs to a kind of rare and scatter element, and it is widely used in metallurgical and chemical industry as additive。It addition, tellurium also plays an important role in the material preparations such as modern high-tech field electronics and optics。The normal association of tellurium, in the ore deposits such as copper, lead and bismuth, generally seldom has independent Te deposit to exist。
At present, tellurium is mainly obtained by synthetical recovery from the by-product that nonferrous metallurgical process produces, and copper anode mud and bismuth refining slag are the main sources that tellurium industrialization is reclaimed。Wherein, in the process processing copper anode mud, it is possible to replace tellurium by copper powder and form the mode of telluride copper, undertaken being enriched with and reclaiming by tellurium。What generally form after copper displacement is telluride copper ashes, and wherein, copper exists (copper valence state is for+1 valency) with the form of elemental copper and cuprous telluride, and tellurium exists with the form of cuprous telluride, and valence state is-divalent。By percentage to the quality, the main component of described telluride copper ashes includes: the Cu of 30%～60%, the Te of 15%～30%, 1%～5% Se, 0.1%～0.3% Bi, 0.01%～1% As, 0.01%～1% Ag。
The process technique of above-mentioned telluride copper is mainly had sulfating roasting technique, alkaline oxygenated pressure leaching technique and extraction process by prior art, but, sulfating roasting technique exists during roasting that sulfur dioxide flue gas amount is big, environmental protection is poor and the shortcoming such as equipment corrosion is serious；There is the easy peroxide of tellurium and be melted into 6 valencys and do not leached by alkali, the shortcoming that the tellurium response rate is relatively low in alkaline oxygenated pressure leaching technique；There is organic compatible easy emulsifying and aqueous phase separation weak effect and the shortcoming being easily generated mesophase spherule in extraction process。
Summary of the invention
In view of this, the application provides a kind of method extracting copper and tellurium from telluride copper ashes, and the method that the application provides can make copper and tellurium be kept completely separate, and the tellurium response rate is higher, and equipment requirements is very low, and more environmental protection。
The application provides a kind of method extracting copper and tellurium from telluride copper ashes, comprises the following steps:
A) by telluride copper ashes and hydrogen peroxide and sulphuric acid mixing, carry out Oxidation Leaching, obtain leachate；
B) react after oxalic acid class decopper(ing) agent being mixed with the described step a) leachate obtained, obtain liquid after cupric oxalate and oxalic acid decopper(ing)；
C) react after reducing agent being mixed with liquid after described step b) the oxalic acid decopper(ing) obtained, obtain tellurium；Described reducing agent is sodium sulfite or sulfur dioxide gas。
Preferably, in described step a), the concentration of described sulphuric acid is 150g/L～300g/L, and the consumption of described hydrogen peroxide is the 10%～30% of leachate volume；Liquid-solid ratio during described Oxidation Leaching is (7～10): 1。
Preferably, in described step a), the temperature of described Oxidation Leaching is 80 DEG C～90 DEG C；The time of described Oxidation Leaching is 1h～2h。
Preferably, in described step a), also include: the sodium chloride that concentration is 2g/L～10g/L is mixed with the mixture of described telluride copper ashes and hydrogen peroxide and sulphuric acid, reoxidizes leaching, obtain leachate and leached mud。
Preferably, in described step a), the copper content of described telluride copper ashes is at more than 40%wt；
Before described telluride copper ashes and hydrogen peroxide and sulphuric acid mixing, also including: described telluride copper ashes sodium chlorate and the sulphuric acid that concentration is 60g/L～100g/L are carried out preextraction, then regulating pH value is 3～4, obtains preimpregnation and slags tap and preextraction liquid；The consumption of described sodium chlorate is the 5%～20% of described telluride copper ashes quality。
Preferably, described preextraction liquid is carried out copper recycling。
Preferably, in described step b), described oxalic acid class decopper(ing) agent is selected from one or more in oxalic acid, Disodium oxalate., ammonium oxalate and potassium oxalate。
Preferably, in described step b), the temperature of described reaction is 80 DEG C～100 DEG C；The time of described reaction is 1h～2h。
Preferably, in described step b), also include: the mixture of the leachate obtained with described oxalic acid class decopper(ing) agent and described step a) by the sodium chloride that concentration is 50g/L～100g/L mixes, then reacts, obtain cupric oxalate and the de-rear liquid of cupric oxalate。
Preferably, in described step c), the temperature of described reaction is 70 DEG C～90 DEG C；The time of described reaction is 1h～3h。
Compared with prior art, the application, with telluride copper ashes for raw material, carries out oxidizing acid leaching initially with hydrogen peroxide, makes overwhelming majority copper and tellurium in material enter liquid phase, obtains leachate, separate with silver and selenium etc.；Then, the embodiment of the present application adds oxalic acid class decopper(ing) agent, the degree of depth decopper(ing) by reaction in the leachate that described oxidation acid leaching obtains, and makes copper separate with tellurium, obtains liquid after cupric oxalate and oxalic acid decopper(ing)；Finally, after described oxalic acid decopper(ing), liquid reduces through sodium sulfite or sulfur dioxide gas, can generate coarse tellurium powder。The application feature according to telluride copper ashes material, adopts Whote-wet method technique, can fully realize being kept completely separate of copper and tellurium, thus reaching copper and the purpose of tellurium synthetical recovery。Further, to have technological process simple, equipment requirements is very low and be beneficial to the advantages such as environmental protection for the application, it is easy to industrialized production。It addition, silver and selenium etc. in telluride copper ashes are enriched with by the application in Oxidation Leaching slag, it are beneficial to and reclaim silver and selenium further。
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present application or technical scheme of the prior art, the accompanying drawing used required in embodiment or description of the prior art will be briefly described below, apparently, accompanying drawing in the following describes is only embodiments herein, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to the accompanying drawing provided。
The process chart extracting copper and tellurium from telluride copper ashes that Fig. 1 provides for the embodiment of the present invention。
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present application, the technical scheme in the embodiment of the present application is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments。Based on the embodiment in the application, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of the application protection。
This application provides a kind of method extracting copper and tellurium from telluride copper ashes, comprise the following steps:
A) by telluride copper ashes and hydrogen peroxide and sulphuric acid mixing, carry out Oxidation Leaching, obtain leachate；
B) react after oxalic acid class decopper(ing) agent being mixed with the described step a) leachate obtained, obtain liquid after cupric oxalate and oxalic acid decopper(ing)；
C) react after reducing agent being mixed with liquid after described step b) the oxalic acid decopper(ing) obtained, obtain tellurium；Described reducing agent is sodium sulfite or sulfur dioxide gas。
This application provides a kind of technique extracting copper and tellurium from telluride copper ashes, copper and tellurium can be made to be kept completely separate, and reach the purpose of Recovering Copper and tellurium。Meanwhile, the application technological process is simple, low for equipment requirements and environmental protection, it is easy to industrialized production。
Referring to the process chart extracting copper and tellurium from telluride copper ashes that Fig. 1, Fig. 1 provide for the embodiment of the present invention。
First the embodiment of the present application carries out oxidizing acid leaching (abbreviation oxidation acid leaching), namely under the acid condition provided by sulphuric acid, is leached by telluride copper ashes hydrogen peroxide oxidation, obtains oxidizing acid leachate (abbreviation leachate)。
The embodiment of the present application is with telluride copper ashes well known to those skilled in the art for raw material, and in described raw material, copper exists (copper valence state is for+1 valency) with the form of elemental copper and cuprous telluride, and tellurium exists with the form of cuprous telluride, and valence state is-divalent。The source of described telluride copper ashes is not particularly limited by the application, by percentage to the quality, the main component of described telluride copper ashes includes: the Cu of 30%～60%, the Te of 15%～30%, 1%～5% Se, 0.1%～0.3% Bi, 0.01%～1% As, 0.01%～1% Ag。
In an embodiment of the application, the copper content of described telluride copper ashes, at more than 40%wt, belongs to high-copper telluride copper ashes；The embodiment of the present application, before described telluride copper ashes and hydrogen peroxide and sulphuric acid mixing, also includes: described telluride copper ashes sodium chlorate and sulphuric acid are carried out preextraction, and then regulating pH value is 3～4, obtains preimpregnation and slags tap and preextraction liquid。
Copper content is preferably milled to 100 orders at the telluride copper ashes of more than 40wt% by the application, then carries out preextraction by oxidation reaction under sour environment, through filtering, obtains preextraction liquid and preimpregnation is slagged tap。Described preextraction belongs to pre-decopper(ing) and processes (can be described as preimpregnation decopper(ing)), can deviate from a part of copper in material in advance, forms preextraction liquid, is beneficial to subsequent treatment and reduces cost；Ensure preextraction liquid pH=3～4 simultaneously, make oxidized tellurium hydrolysis enter preimpregnation and slag tap (can be described as preimpregnation decopper(ing) slag)。
The embodiment of the present application adopts sodium chlorate and sulphuric acid that telluride copper ashes carries out preextraction, and can pass through to add sodium carbonate adjustment pH, it is ensured that pH of leaching solution is 3～4。The consumption of described sodium chlorate is preferably the 5%～20% of described telluride copper ashes quality, more preferably 10%～15%。The liquid-solid ratio of described preextraction is preferably (4～6): 1, and herein, described liquid-solid ratio refers to the mass ratio of water well known to those skilled in the art and solid。Slagging tap to make oxidized tellurium hydrolysis enter preimpregnation, ensure that tellurium is in leached mud as far as possible, the embodiment of the present application can add saturated sodium carbonate solution and regulate pH, it is ensured that pH of leaching solution is 3～4；If added by solid sodium carbonate in liquid phase, it is possible to leachate local pH can be caused too high, and cause that copper is hydrolyzed also into slag phase。The reaction that preextraction described in the embodiment of the present application relates to can referring to formula 1～3:
3Cu+3H2SO4+NaClO3=3CuSO4+NaCl+3H2O formula 1；
3Cu2Te+6H2SO4+4NaClO3=6CuSO4+3H2TeO3+4NaCl+3H2O formula 2；
H2TeO3=TeO2+H2O formula 3；
Wherein, reaction shown in formula 1 is dominant response, and reaction shown in formula 2 is secondary response, and formula 3 reaction issues raw hydrolysis for tellurous acid in sodium carbonate effect。
In order to Oxidation Leaching of being tried one's best by copper is in liquid phase, and tellurium ensures in slag as far as possible, the application is preferably in (oxidation) preextraction under Low acid and room temperature, carry out pre-decopper(ing) process, after filtration, the conventional method of the available this area of the preextraction liquid obtained reclaims copper, as generated copper sponge by iron replacement or adding sodium carbonate generation basic copper carbonate；The preimpregnation obtained is slagged tap and is entered next step process。When the embodiment of the present application Low acid room temperature preextraction, the concentration of described sulphuric acid is preferably 60g/L～100g/L, more preferably 65g/L～90g/L；The temperature of described preextraction is preferably room temperature, such as 10 DEG C～30 DEG C；The time of described preextraction is preferably 1h～2h。Under room temperature and Low acid, the embodiment of the present application preextraction can reduce sodium chlorate oxidation activity, makes sodium chlorate main oxidation elemental copper, and the degree of cuprous telluride oxidation is relatively low。If carry out preextraction when high temperature or highly acidity, sodium chlorate activity is significantly high, it is easy to by substantial amounts of tellurium Oxidation Leaching, is unfavorable for that copper and tellurium separate better。
Obtain after preimpregnation slags tap, in acid condition, it is leached by the embodiment of the present application with hydrogen peroxide oxidation, or directly by low copper telluride copper ashes, (copper content telluride copper ashes less than 40wt% belongs to low copper telluride copper ashes to the embodiment of the present application, without preextraction) leach with hydrogen peroxide oxidation, through filtering, obtain leachate and leached mud。
The acid condition that telluride copper ashes or preextraction slag oxidation are leached by the application is provided by sulphuric acid, and adopts hydrogen peroxide to carry out。The concentration of described sulphuric acid is preferably 150g/L～300g/L, more preferably 180g/L～250g/L。The consumption of described hydrogen peroxide is preferably the 10%～30% of leachate volume, more preferably 15%～25%；In an embodiment of the application, adopting industrial grade hydrogen peroxide Oxidation Leaching, hydrogen peroxide content is 28%。Liquid-solid ratio during described Oxidation Leaching is preferably (7～10): 1, more preferably (8～9): 1, and herein, described liquid-solid ratio refers to the mass ratio of water well known to those skilled in the art and solid。
In this application, hydrogen peroxide acidic oxidation telluride copper ashes or preimpregnation decopper(ing) slag so that the compositions such as the copper of the overwhelming majority and tellurium enter liquid phase, most selenium enter slag phase。The application is preferably added to sodium chloride, mix with the mixture of described telluride copper ashes and hydrogen peroxide and sulphuric acid, reoxidize leaching, the silver that is leached on a small quantity is made to form silver nitride precipitation and leached mud phase, through filtering, (oxidation) leached mud obtained is enriched the compositions such as silver and selenium, creates the compositions such as condition, recyclable selenium and silver for reclaiming silver and selenium etc.；And the leachate obtained enters next step and processes。The temperature of herein described Oxidation Leaching is preferably 80 DEG C～90 DEG C；The time of described Oxidation Leaching is preferably 1h～2h。The addition concentration of described sodium chloride (NaCl) is preferably 2g/L～10g/L, more preferably 4g/L～8g/L。
The reaction that Oxidation Leaching described in the embodiment of the present application relates to can referring to formula 4～6:
Cu2Te+2H2SO4+4H2O2=2CuSO4+H2TeO3+5H2O formula 4；
2Ag+H2SO4+H2O2+ 2NaCl=Na2SO4+2AgCl+2H2O formula 5；
Se+2H2O2=H2SeO3+H2O formula 6。
After obtaining (oxidation) leachate, the embodiment of the present application adds oxalic acid class decopper(ing) agent wherein, carries out degree of depth decopper(ing) by reacting, and obtains liquid after cupric oxalate and oxalic acid decopper(ing)。
In this application, described oxalic acid class decopper(ing) agent is oxalic acid or oxalates soluble in water。The application adopts described oxalic acid class decopper(ing) agent decopper(ing), and owing to oxalate does not react with tellurium, and oxalic acid precipitation copper ratio is more thoroughly, decopper(ing) better effects if。Described oxalic acid class decopper(ing) agent preferably is selected from one or more in oxalic acid, Disodium oxalate., ammonium oxalate and potassium oxalate, more preferably oxalic acid。For oxalic acid for decopper(ing) agent, when the embodiment of the present application adopts its degree of depth decopper(ing), oxalic acid and copper react generation cupric oxalate precipitation, make copper separate with tellurium, and wherein, oxalic acid addition can be 1.1～1.4 times of the required theoretical amount of reaction。Through filtering, the filtering residue obtained is cupric oxalate, and the filtrate obtained is that after oxalic acid decopper(ing), liquid enters next step process；Reaction equation is as shown in Equation 7:
CuSO4+H2C2O4=CuC2O4+H2SO4Formula 7。
Cupric oxalate granule owing to obtaining is very thin, easily produce colloid and be unfavorable for precipitation and filter, the application preferably also includes adding sodium chloride, mix with described oxalic acid class decopper(ing) agent and the mixture of leachate obtained, react again, improve settleability and the filterability of cupric oxalate, obtain cupric oxalate and the de-rear liquid of cupric oxalate；Further, add a certain amount of sodium chloride and can provide catalyst Cl-for the reduction of next step tellurium。The application controls the concentration of sodium chloride and is preferably 50g/L～100g/L, more preferably 60g/L～90g/L。The temperature of described reaction is preferably 80 DEG C～100 DEG C, more preferably 85 DEG C～95 DEG C；The time of described reaction is preferably 1h～2h。
Obtaining liquid after oxalic acid decopper(ing), the embodiment of the present application adds reducing agent wherein, carries out reducing heavy tellurium by reacting, can obtain coarse tellurium powder after reduction。
The application is with sodium sulfite or sulfur dioxide gas for reducing agent, it is preferred to use sodium sulfite restores coarse tellurium powder, and wherein, the addition of described reducing agent can be 1.5～3 times of the required theoretical amount of reaction。The temperature of described reaction is preferably 70 DEG C～90 DEG C, more preferably 75 DEG C～85 DEG C；The time of described reaction is preferably 1h～3h, more preferably 1.5h～2.5h。For sodium sulfite for reducing agent, the reaction equation of the heavy tellurium of the embodiment of the present application reduction as shown in Equation 8:
H2TeO3+2Na2SO3=2Na2SO4+Te+H2O formula 8。
After the reaction of the heavy tellurium of described reduction terminates, the product obtained is filtered by the embodiment of the present application, after obtaining the tellurium powder that restores and filter liquid namely reduce after liquid。According to method commonly used in the art, liquid after described reduction and tellurium powder are carried out component analysis by the application。It is shown that described tellurium powder can as the raw material of refine tellurium, the response rate of tellurium can be 94%, higher than the tellurium response rate (the tellurium response rate of prior art is substantially about 80%) of prior art。
In sum, the method extracting copper and tellurium from telluride copper ashes that the application provides mainly includes the steps such as Oxidation Leaching, degree of depth decopper(ing) and the heavy tellurium of reduction, fully realizes being kept completely separate of copper and tellurium by Whote-wet method technique, improves the tellurium response rate。Further, the application has the advantages such as technological process is simple, safety is high, equipment requirements is very low, equipment investment is few, and the feature of environmental protection is good and less costly, is beneficial to copper and the industrialization promotion of tellurium synthetical recovery。It addition, silver and selenium etc. in telluride copper ashes are enriched with by the application in Oxidation Leaching slag, it are beneficial to and reclaim silver and selenium further。
In order to be further appreciated by the application, a kind of method extracting copper and tellurium from telluride copper ashes the application provided below in conjunction with embodiment is specifically described。
Embodiment 1
(1) preimpregnation decopper(ing)
Take telluride copper ashes 1kg, levigate to 100 orders；In mass fraction, the composition of described telluride copper ashes includes: Te20.1%, Cu52.6%, Se1.2%, As0.5%, Bi0.1%, Ag0.2%。Telluride copper ashes after levigate being carried out room temperature Low acid oxidation preextraction, deviates from copper and base metal, process conditions include: liquid-solid ratio is 5:1, and sulfuric acid concentration is 80g/L, and sodium chlorate consumption is 0.1kg；Reaction temperature is room temperature, after reaction 0.5h, adds saturated sodium carbonate solution, regulates pH=4, continues reaction 2h。The product obtained is filtered, obtains filtrate 5.5L (containing wash water) and filter cake after terminating by reaction, and filter cake dry weight is 0.63kg。
Described filtrate is preimpregnation decopper(ing) liquid, and its composition includes: Cu47.8g/L, Te0.04g/L, Se0.02g/L, As0.85g/L, and copper leaching rate is 50%, and tellurium leaching rate is 0.1%。The available common process of described preimpregnation decopper(ing) liquid reclaims copper, as iron replacement generates copper sponge or adds sodium carbonate generation basic copper carbonate。
Described filter cake is preimpregnation decopper(ing) slag, and its composition includes: Cu41.7%, Te31.8%, Se1.88%, As0.05%, Bi0.16%, Ag0.317%。
(2) Oxidation Leaching
It is 9:1 according to liquid-solid ratio, being sequentially added into concentration in the preimpregnation decopper(ing) slag that 0.63kg step (1) obtains be the sulphuric acid of 200g/L, concentration is the sodium chloride of 4g/L, add 1.15L hydrogen peroxide (technical grade, hydrogen peroxide content is 28%) react, reaction temperature controls at 80 DEG C, and the response time is 3h。The product obtained is filtered, obtains oxidated solution 7.1L (containing wash water) and filter cake after terminating by reaction, and filter cake dry weight is 0.025kg。
Described oxidated solution is Oxidation Leaching liquid, and its composition includes: Cu36.2g/L, Te27.6g/L, Se0.33g/L, As0.04g/L, Ag0.0005g/L, and copper leaching rate is 97.8%, and tellurium leaching rate is 98%。
Described filter cake is leached mud, and its main constituent includes: Cu22.8%, Te16%, Se38%, Ag7.96%。In described filter cake, silver, selenium are enriched with, and are beneficial to and reclaim silver, selenium further。
(3) degree of depth decopper(ing)
Adding oxalic acid to the Oxidation Leaching liquid of step (2) gained and carry out degree of depth decopper(ing) reaction, the addition of described oxalic acid is 1.1 times of the required theoretical amount of reaction, and reaction temperature is 90 DEG C, and the response time is 1h；In order to improve cupric oxalate settleability and filterability, adding concentration before decopper(ing) terminates is the sodium chloride of 60g/L。The product obtained is filtered, liquid 7.3L (containing wash water) and cupric oxalate after being filtered after terminating by reaction。
After described filter, liquid is liquid after oxalic acid decopper(ing), and its composition includes: Cu0.05g/L, Te26.3g/L, Se0.31g/L, As0.02g/L, and copper recovery is 99.8%, and the tellurium response rate is 98%。
The purity of solid copper is 99%, can as production marketing。
(4) the heavy tellurium of reduction
After the oxalic acid decopper(ing) of step (3) gained, liquid adds sodium sulfite and carries out reducing the reaction of heavy tellurium, and the addition of described sodium sulfite is 2 times of required theoretical amount, and reaction temperature is 80 DEG C, and the response time is 2h。The product obtained is filtered after terminating by reaction, liquid 7.6L (containing wash water) and the tellurium powder 194g that restores after being filtered。
After described filter, liquid is liquid after reduction, and its composition includes: Cu0.04g/L, Te0.05g/L, Se0.005g/L, As0.02g/L。
Tellurium meal component includes: Cu0.03%, Te98.7%, Se1.1%, and this tellurium powder can as the raw material of refine tellurium。
Embodiment 2
(1) preimpregnation decopper(ing)
Take telluride copper ashes 1kg, levigate to 100 orders；In mass fraction, the composition of described telluride copper ashes includes: Te21%, Cu40.2%, Se2.5%, As0.8%, Bi0.2%, Ag0.5%。Telluride copper ashes after levigate being carried out room temperature Low acid oxidation preextraction, deviates from copper and base metal, process conditions include: liquid-solid ratio is 6:1, and sulfuric acid concentration is 60g/L, and sodium chlorate consumption is 0.15kg；Reaction temperature is room temperature, after reaction 0.5h, adds saturated sodium carbonate solution, regulates pH=4, continues reaction 2h。The product obtained is filtered, obtains filtrate 6.4L (containing wash water) and filter cake after terminating by reaction, and filter cake dry weight is 0.59kg。
Described filtrate is preimpregnation decopper(ing) liquid, and its composition includes: Cu28.9g/L, Te0.06g/L, Se0.05g/L, As0.76g/L, and copper leaching rate is 46%, and tellurium leaching rate is 0.18%。The available common process of described preimpregnation decopper(ing) liquid reclaims copper, as iron replacement generates copper sponge or adds sodium carbonate generation basic copper carbonate。
Described filter cake is preimpregnation decopper(ing) slag, and its composition includes: Cu44.5%, Te35.5%, Se4.18%, As0.02%, Bi0.33%, Ag0.84%。
(2) Oxidation Leaching
It is 8:1 according to liquid-solid ratio, being sequentially added into concentration in the preimpregnation decopper(ing) slag that 0.59kg step (1) obtains be the sulphuric acid of 200g/L, concentration is the sodium chloride of 8g/L, add 1.18L hydrogen peroxide (technical grade, hydrogen peroxide content is 28%) react, reaction temperature controls at 80 DEG C, and the response time is 3h。The product obtained is filtered, obtains oxidated solution 6.3L (containing wash water) and filter cake, filter cake dry weight 0.050kg after terminating by reaction。
Described oxidated solution is Oxidation Leaching liquid, and its composition includes: Cu40.8g/L, Te32.2g/L, Se0.48g/L, As0.02g/L, Ag0.0005g/L, and copper leaching rate is 98%, tellurium leaching rate I 97%。
Described filter cake is leached mud, and its main constituent includes: Cu11%, Te14%, Se43.2%, Ag9.96%。In described filter cake, silver, selenium are enriched with, and are beneficial to and reclaim silver, selenium further。
(3) degree of depth decopper(ing)
Adding oxalic acid to the Oxidation Leaching liquid of step (2) gained and carry out degree of depth decopper(ing) reaction, the addition of described oxalic acid is 1.3 times of the required theoretical amount of reaction, and reaction temperature is 90 DEG C, my 1h of response time；In order to improve cupric oxalate settleability and filterability, adding concentration before decopper(ing) is the sodium chloride of 90g/L。After reaction in time, the product obtained is filtered, liquid 6.6L (containing wash water) and cupric oxalate after being filtered。
After described filter, liquid is liquid after oxalic acid decopper(ing), and its composition includes: Cu0.02g/L, Te29.8g/L, Se0.31g/L, As0.004g/L, and copper recovery is 99%, and the tellurium response rate is 97%。
The purity of solid copper is 99%, can as production marketing。
(4) the heavy tellurium of reduction
After the oxalic acid decopper(ing) of step (3) gained, liquid adds sodium sulfite and carries out reducing the reaction of heavy tellurium, and the addition of described sodium sulfite is 2.5 times of required theoretical amount, and reaction temperature is 70 DEG C, and the response time is 2h。The product obtained is filtered after terminating by reaction, liquid 7L (containing wash water) and the tellurium powder 194g that restores after being filtered。
After described filter, liquid is liquid after reduction, and its composition includes: Cu0.015g/L, Te0.05g/L, Se0.004g/L, As0.003g/L。
Tellurium meal component includes: Cu0.01%, Te98.9%, Se1%, and this tellurium powder can as the raw material of refine tellurium。
As seen from the above embodiment, the application, with telluride copper ashes for raw material, carries out oxidizing acid leaching initially with hydrogen peroxide, makes overwhelming majority copper and tellurium in material enter liquid phase, obtains leachate, separate with silver and selenium etc.；Then, the embodiment of the present application adds oxalic acid class decopper(ing) agent, the degree of depth decopper(ing) by reaction in the leachate that described oxidation acid leaching obtains, and makes copper separate with tellurium, obtains liquid after cupric oxalate and oxalic acid decopper(ing)；Finally, after described oxalic acid decopper(ing), liquid reduces through sodium sulfite or sulfur dioxide gas, can generate coarse tellurium powder。Practice have shown that, described tellurium powder can as the raw material of refine tellurium, and the response rate of tellurium can be 94%, higher than the tellurium response rate of prior art。Therefore, the application feature according to telluride copper ashes material, adopting Whote-wet method technique, fully realizing being kept completely separate of copper and tellurium, thus reaching copper and the purpose of tellurium synthetical recovery。Further, to have technological process simple, equipment requirements is very low and be beneficial to the advantages such as environmental protection for the application, it is easy to industrialized production。It addition, silver and selenium etc. in telluride copper ashes are enriched with by the application in Oxidation Leaching slag, it are beneficial to and reclaim silver and selenium further。
Claims (10)
1. the method extracting copper and tellurium from telluride copper ashes, comprises the following steps:
A) by telluride copper ashes and hydrogen peroxide and sulphuric acid mixing, carry out Oxidation Leaching, obtain leachate；
B) react after oxalic acid class decopper(ing) agent being mixed with the described step a) leachate obtained, obtain liquid after cupric oxalate and oxalic acid decopper(ing)；
C) react after reducing agent being mixed with liquid after described step b) the oxalic acid decopper(ing) obtained, obtain tellurium；Described reducing agent is sodium sulfite or sulfur dioxide gas。
2. method according to claim 1, it is characterised in that in described step a), the concentration of described sulphuric acid is 150g/L～300g/L, and the consumption of described hydrogen peroxide is the 10%～30% of leachate volume；Liquid-solid ratio during described Oxidation Leaching is (7～10): 1。
3. method according to claim 1, it is characterised in that in described step a), the temperature of described Oxidation Leaching is 80 DEG C～90 DEG C；The time of described Oxidation Leaching is 1h～2h。
4. method according to claim 1, it is characterized in that, in described step a), also include: the sodium chloride that concentration is 2g/L～10g/L is mixed with the mixture of described telluride copper ashes and hydrogen peroxide and sulphuric acid, reoxidize leaching, obtain leachate and leached mud。
5. the method according to Claims 1-4 any one, it is characterised in that in described step a), the copper content of described telluride copper ashes is at more than 40%wt；
Before described telluride copper ashes and hydrogen peroxide and sulphuric acid mixing, also including: described telluride copper ashes sodium chlorate and the sulphuric acid that concentration is 60g/L～100g/L are carried out preextraction, then regulating pH value is 3～4, obtains preimpregnation and slags tap and preextraction liquid；The consumption of described sodium chlorate is the 5%～20% of described telluride copper ashes quality。
6. method according to claim 5, it is characterised in that described preextraction liquid is carried out copper recycling。
7. method according to claim 5, it is characterised in that in described step b), described oxalic acid class decopper(ing) agent is selected from one or more in oxalic acid, Disodium oxalate., ammonium oxalate and potassium oxalate。
8. the method according to claim 1 or 7, it is characterised in that in described step b), the temperature of described reaction is 80 DEG C～100 DEG C；The time of described reaction is 1h～2h。
9. method according to claim 8, it is characterized in that, in described step b), also include: the mixture of the leachate obtained with described oxalic acid class decopper(ing) agent and described step a) by the sodium chloride that concentration is 50g/L～100g/L mixes, react again, obtain cupric oxalate and the de-rear liquid of cupric oxalate。
10. the method according to claim 1 or 9, it is characterised in that in described step c), the temperature of described reaction is 70 DEG C～90 DEG C；The time of described reaction is 1h～3h。
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| CN106381399B (en) * | 2016-09-27 | 2018-10-02 | 郴州市金贵银业股份有限公司 | A method of recycling tellurium from high tellurium slag charge |
| CN108545706B (en) * | 2018-05-31 | 2021-05-07 | 阳谷祥光铜业有限公司 | Treatment method of tellurium-containing waste liquid |
| CN109112560A (en) * | 2018-09-19 | 2019-01-01 | 云南铜业股份有限公司西南铜业分公司 | A method of high purity tellurium is prepared using copper telluride |
| CN112960654A (en) * | 2020-04-20 | 2021-06-15 | 金川集团股份有限公司 | Method for efficiently separating selenium and tellurium from acidic liquid |
| CN111471870A (en) * | 2020-04-28 | 2020-07-31 | 西部矿业股份有限公司 | Process for comprehensively recovering copper, tellurium and bismuth from complex copper, tellurium and bismuth slag |
| CN113308606B (en) * | 2021-06-04 | 2022-10-18 | 昆明理工大学 | Method for leaching and separating valuable metals from silver-gold-rich selenium steaming slag |
| CN113697778B (en) * | 2021-08-20 | 2023-12-26 | 金隆铜业有限公司 | Copper tellurium slag treatment method |
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