CN106477533B

CN106477533B - A kind of method of copper anode mud separation and recovery selenium and tellurium

Info

Publication number: CN106477533B
Application number: CN201610910411.3A
Authority: CN
Inventors: 王学文; 王明玉; 葛奇
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2016-10-19
Filing date: 2016-10-19
Publication date: 2018-06-29
Anticipated expiration: 2036-10-19
Also published as: CN106477533A

Abstract

A kind of method of copper anode mud separation and recovery selenium and tellurium is to carry out soda sintering through the pretreated decopper(ing) earth of positive pole of decopper(ing) to copper anode mud or copper anode mud, and sintered material adds water logging to go out, and filters to obtain selenium-rich leachate and rich tellurium leached mud；After sodium carbonate being separated and recovered to selenium-rich leachate, then with sodium sulfite or SO₂Selenium in reduction recycling selenium-rich leachate or filtrate, filters to obtain impure selenium powder, impure selenium powder further refines to obtain metallic selenium；Rich tellurium leached mud filters to obtain pickle liquor and acid leaching residue after sulfuric acid solution leaches；Pickle liquor is after chlorination point silver, with sodium sulfite or SO₂Precipitate reduction tellurium therein, filters to obtain coarse tellurium powder, and coarse tellurium powder further refines to obtain metallic tellurium.It is redesigned by the entirety of present invention process, mutual cooperation between each step, thus the process for separating and recovering route of selenium and tellurium in copper anode mud can be made greatly to be simplified, the environmental protection pressure of copper anode mud process is significantly reduced, also complies with the development trend of China's energy-conserving and emission-cutting technology transformation.The present invention has the advantages that simple for process, easy to operate, production cost is low, and the rate of recovery of selenium and tellurium is high, and operating environment is good, suitable for industrial applications.

Description

A kind of method of copper anode mud separation and recovery selenium and tellurium

Technical field

The invention discloses the methods of a kind of copper anode mud separation and recovery selenium and tellurium, belong to metallurgical and chemical technology field.

Background technology

Selenium and tellurium are all typical rare and scatter elements, are mainly enriched in the heavy non-ferrous metal electrorefining earth of positive pole, wherein copper The earth of positive pole is the primary raw material of selen-tellurjum production.Copper anode mud usually 10-30% containing Cu, Pb 5-20%, Se1-10%, Te Cu in 0.2-6%. copper anode muds mainly exists in the form of metallic copper, and Pb almost all exists in the form of lead sulfate, and Selenium and tellurium then mainly exist with the selenides and tellurides of copper and silver.Selenium is separated and recovered from copper anode mud and the method for tellurium is main Having sulfating roasting to steam selenium-water logging divides the leaching of copper-alkali to divide tellurium technique, and oxygen pressure acidleach-step-by-step reduction depositing technology and soda roasting- Extract technology.

Copper anode mud sulfating roasting steams selenium-water logging and the leaching of copper-alkali is divided to divide the technical process of tellurium to be：By copper anode mud quality 80%~110% admixes the concentrated sulfuric acid, is roasted at a temperature of 500~750 DEG C, makes selenium (metallic selenium, selenides, selenium in material Hydrochlorate) it is converted to SeO₂Volatilization.The SeO that roasting process is escaped with flue gas₂It is absorbed in absorption tower by solution, and simultaneously by SO₂ (H₂SO₃) elemental selenium Precipitation is reduced into, realize the separation and recovery of selenium.After the pulp water leaching of steaming selenium divides copper, soaked with sodium hydroxide solution Go out tellurium therein, filter alkali leaching divide tellurium liquid.It is 4.5~5.5 that alkali leaching, which divides tellurium liquid that sulfuric acid is added to be neutralized to pH value of solution, filters to neutralize Slag.It neutralizes slag and carries out secondary alkali leaching with sodium hydroxide solution again, obtained secondary alkali immersion liquid adds Na₂S+CaCl₂After purification, then add The TeO that sulfuric acid neutralizes qualified₂, TeO₂Liquid making is electrolysed to obtain metallic tellurium.Copper anode mud sulfating roasting can effectively divide selenium with tellurium From, but steam selenium process and generate a large amount of waste water and exhaust gas, pollution is big, and tellurium will be soaked by alkali twice, and reagent consumption is big, is processed into This height, metal recovery rate are low.

Most of tellurium therein and copper can be transferred to solution by the acidleach of copper anode mud oxygen pressure, and selenium is remained with silver in autoclaving slag, It realizes the separation of selen-tellurjum, filters to obtain autoclaving slag and autoclaving liquid.Autoclaving liquid adds copper powder to replace, and makes tellurium therein with Cu₂The form of Te Precipitation filters containing Cu₂The filter residue of Te.Cu₂Te filter residues are processed further obtaining metallic tellurium.Selenium master in autoclaving slag with Se and Ag₂The form of Se exists, and after granulation, through high temperature oxidation roasting, selenium therein is with SeO₂Form is volatized into flue gas.In flue gas SeO₂After water absorbs, SO is used₂Restore to obtain selenium powder.But the leaching rate of autoclaving process tellurium generally only 50~70%, the residual of tellurium is given The recycling of gold and silver increases great difficulty in copper anode mud, and also contains a certain amount of selenium in autoclaving liquid, the separating effect of tellurium and selenium It is undesirable.

The conventional process flow of copper anode mud soda roasting-leaching separation and recovery selenium and tellurium as shown in Figure 1 (Zhou Lingzhi, it is old Few pure dissipated metals Extraction metallurgy Beijing：Metallurgical industry publishing house, 2008, p309).By copper anode mud quality 10%~ 15% adds in sodium carbonate through 450~650 DEG C of roastings.Selenium in the sintering process earth of positive pole is converted to selenate and selenite, tellurium Almost all is converted to the Na of indissoluble₂TeO₄, after water logging selenium dissolving enter solution, tellurium then stayed in leached mud, so as to fulfill selenium with The separation of tellurium.But the recovery process route of selenium and tellurium is all very long in traditional handicraft, and not only reagent consumption is big, high processing costs, and The rate of recovery of tellurium is relatively low, and the rate of recovery of tellurium is typically less than 50%, now almost unmanned to use.Lead to another reason of this result It is：Lead sulfate in copper anode mud is converted to ceruse and sodium sulphate in sintering and leaching process with sodium carbonate effect major part, So that technical process is had to, increase leachate is concentrated to dryness, dry slag adds the processes such as carbon reduction to separate and recover selenium therein And sodium carbonate.

Invention content

Copper anode separation and recovery selenium easy to operate the purpose of the present invention is to provide a kind of economical and efficient, environmental-friendly With the method for tellurium.

Technical scheme of the present invention is as shown in Fig. 2, invention thinking is：In copper anode mud or copper anode mud after pretreatment Sodium carbonate is added in the obtained decopper(ing) earth of positive pole or the mixture of sodium carbonate and sodium nitrate carries out soda burning in air or oxygen Knot, sintered material directly add water logging to go out or water logging are added to go out after broken, and selenium and tellurium are enriched in leachate and leached mud respectively, Then selenium and tellurium are separated and recovered from leachate and leached mud respectively：After leachate separation and recovery sodium carbonate, then use sodium sulfite Or SO₂Selenium therein is recycled in reduction, filters to obtain impure selenium powder, impure selenium powder further refines to obtain metallic selenium；Leached mud is through sulfuric acid solution After leaching, pickle liquor and acid leaching residue are filtered to obtain；Acid leaching residue send recovery for Au and Ag process, and after chlorination point silver, stirring adds in for pickle liquor The TeO recycled in leachate₂, treat TeO₂After dissolving, then with sodium sulfite or SO₂Precipitate reduction tellurium therein, filters slightly Tellurium powder, coarse tellurium powder further refine to obtain metallic tellurium.

The method of a kind of copper anode mud separation and recovery selenium of the present invention and tellurium, includes the following steps：

Soda sintering, sintered object are carried out through the decopper(ing) pretreated decopper(ing) earth of positive pole to copper anode mud or copper anode mud Material plus water logging go out, and filter to obtain selenium-rich leachate and rich tellurium leached mud；

After sodium carbonate being separated and recovered to selenium-rich leachate, then with sodium sulfite or SO₂Reduction recycling selenium-rich leachate or filter Selenium in liquid, filters to obtain impure selenium powder, and impure selenium powder further refines to obtain metallic selenium；

Rich tellurium leached mud filters to obtain pickle liquor and acid leaching residue after sulfuric acid solution leaches；Pickle liquor after chlorination point silver, then With sodium sulfite or SO₂Precipitate reduction tellurium therein, filters to obtain coarse tellurium powder, and coarse tellurium powder further refines to obtain metallic tellurium.

The soda sintering refers to add in sodium carbonate, and press by the 10~40% of copper anode mud or decopper(ing) earth of positive pole quality 0~10% addition sodium nitrate of copper anode mud or decopper(ing) earth of positive pole quality mix thoroughly or levigate mixing after, directly or granulation is after sky 450~650 DEG C of 2~4h of sintering in gas or oxygen；Sintered material presses solid-to-liquid ratio 1:After 1~3g/ml adds water, 50~100 DEG C of stirrings 1~3h is leached, filters to obtain leachate and leached mud；

Described sodium carbonate separation and recovery refers to be converted to the 1~3 of calcium sulfate theoretical amount extraordinarily by the sodium sulphate in filtrate Enter CaCO₃, 1~3h is reacted at room temperature, makes CaCO₃It is converted to CaSO₄, filter to obtain doctor solution and desulfurization slag；Desulfurization slag is through sulfuric acid solution After washing, wash water and gypsum are filtered to obtain；The directly logical CO of doctor solution₂It is dense to 0.1~1.5MPa or addition sodium chloride tune solution NaCl Spend 5~350g/L, then logical CO₂To 0.1~1.5MPa, NaHCO is crystallized in -10~30 DEG C₃, filter to obtain NaHCO₃Crystal and first Liquid after crystallization, after liquid merges with wash water after the first crystallization, with sodium sulfite or SO₂Reduction recycle selenium therein or

After sodium chloride tune NaCl concentration to 5~350g/L being added in selenium-rich leachate, in -20~20 DEG C of crystallisation by cooling, Filter sodium sulphate and sodium carbonate mixed crystal and the second crystalline mother solution；Second crystalline mother solution adds mineral acid to be first acidified to pH 6.5~4.5, it is separated by filtration the TeO of wherein Precipitation₂Afterwards, then add mineral acid to solution acidity rise to 0.1~ 2mol/L[H⁺], then with sodium sulfite or SO₂Restore selenium therein；

Gained mixed crystal first presses solid-to-liquid ratio 1:2~4g/ml adds water heating stirring and dissolving, and CO is then led into lysate₂ To 0.1~1.5MPa, NaHCO is precipitated in crystallizing at room temperature₃, filter to obtain NaHCO₃Liquid after crystal and third crystallization, liquid after third crystallization In -10~20 DEG C crystallization be precipitated saltcake after return mixed crystal dissolution process be continuing with or

1~3 times of addition CaCO of calcium sulfate theoretical amount is converted to by the sodium sulphate in lysate₃, and it is passed through CO₂Adjust solution PH to 6.5~4.5 reacts at room temperature 1~3h, makes CaCO₃It is converted to CaSO₄, liquid is in -20~10 DEG C of knots after the transition being obtained by filtration Crystalline substance filters to obtain NaHCO₃And Na₂CO₃Mixed crystal and the 4th crystallization after liquid, the 4th crystallization after liquid return mixed crystal dissolving work Sequence is continuing with；

The NaHCO of gained₃Crystal and NaHCO₃And Na₂CO₃Mixed crystal return to soda sintering circuit and recycle.

The one kind of added mineral acid in sulfuric acid, hydrochloric acid, nitric acid.

Selenium reduction refers to be reduced into 1~3 times of the theoretical amount of elemental selenium by the selenium in the mixed liquor of liquid after crystallization and wash water It adds in sodium sulfite or is passed through SO₂Reduction, 50~95 DEG C of 1~4h of reaction, filters to obtain impure selenium powder.

Sulfuric acid solution leaches rich tellurium leached mud, refers to rich tellurium leached mud by solid-to-liquid ratio 1:2~6g/ml adds in a concentration of 100 The H of~250g/L₂SO₄After solution, 50~105 DEG C of 1~3h of leaching are heated to, filter to obtain pickle liquor and acid leaching residue；Acid leaching residue Recovery for Au and Ag process is sent, being used for Reduced separating after chlorination processes point of silver of acidleach recycles tellurium.

The chlorination divides silver to refer to add in sodium chloride in pickle liquor, adjusts Cl in solution^-Up to 0.05~50g/L, make it In silver in the form of AgCl Precipitation, filter to obtain AgCl filter residues, gained AgCl filter residues send recovery for Au and Ag process.

The Reduced separating recycling tellurium refers to first stir to add in selenium-rich leachate in liquid after chlorination point silver to recycle The TeO arrived₂, treat TeO₂After dissolving, then be reduced by the tellurium in solution 1~3 times of theoretical amount of simple substance tellurium add in sodium sulfite or It is passed through SO₂Reduction reacts at room temperature 1~4h, filters to obtain coarse tellurium powder.

The present invention with traditional handicraft difference lies in：The technique of copper anode mud soda sintering-leaching separation and recovery selenium and tellurium Difference, the recovery process route of selenium, tellurium and sodium carbonate are different.

Traditional handicraft separates and recovers sodium carbonate and the process route of selenium from leachate：First leachate is evaporated, dry slag Add carbon reduction that the sodium salt of selenium is converted to Na₂Se, and sulphur therein is converted to SO₂It is removed, Na₂Through air after Se is water-soluble Oxidation, filters to obtain selenium powder and oxidated solution, oxidated solution is again through CO₂Sodium carbonate is precipitated in acidizing crystal.

Na₂SeO₄+ C=Na₂Se+2CO₂↑ (1)

2Na₂SO₄+C+CO₂=2Na₂CO₃+2SO₂↑ (2)

2Na₂Se+2H₂O+O₂=2Se ↓+4NaOH (3)

2NaOH+CO₂=Na₂CO₃+H₂O (4)

The present invention separates and recovers sodium carbonate and the process route of selenium from leachate：Under conditions of pH is 6.5~4.5 Calcium carbonate is converted to calcium bicarbonate with the carbonic acid effect in solution, and calcium bicarbonate acts on generation calcium sulfate precipitation analysis with sodium sulphate again Go out to remove the sulphur in solution, filter to obtain desulfurization slag and doctor solution；Gained doctor solution uses CO again after adding in sodium chloride₂Acidizing crystal is analysed Go out NaHCO₃, the NaHCO that is obtained by filtration₃Crystalline mother solution is through SO₂Restore to obtain impure selenium powder.The purpose for adding in sodium chloride is to utilize Na⁺Production Raw common-ion effect, makes NaHCO₃Solubility reduce；The NaHCO of gained₃It is converted in copper anode mud soda sintering process Na₂CO₃。

CaCO₃+H₂CO₃=Ca (HCO₃)₂ (5)

Ca(HCO₃)₂+Na₂SO₄+2H₂O=2NaHCO₃+CaSO₄·2HO↓ (6)

2NaHCO₃=Na₂CO₃+H₂O+CO₂↑ (7)

Na₂SeO₃+2SO₂+H₂O=Na₂SO₄+Se↓+H₂SO₄ (8)

The process route that traditional handicraft separates and recovers tellurium from leached mud is：Leached mud adds sodium carbonate and flux slag making, tellurium It is first enriched in soda slag, soda slag water logging again, infusion adds sulfuric acid to neutralize to obtain TeO₂, TeO₂It is electrolysed golden through alkali soluble liquid making again Belong to tellurium.

The process route that the present invention separates and recovers tellurium from leached mud is：Leached mud is first leached therein with sulfuric acid solution Then tellurium adds in Cl in pickle liquor^-Precipitation silver therein, filtering, filtrate add reducing agent Precipitation metallic tellurium, And by Cl^-Complexing, promote tellurium reduction the later stage combined to form Cu with the copper in solution₂Te is precipitated, and realizes the depth of tellurium Precipitate reduction.

Na₂TeO₄+2H₂SO₄=Na₂SO₄+H₂TeO₄ (9)

CuO+2H₂SO₄=CuSO₄+H₂O (10)

Cl^-+Ag⁺=AgCl ↓ (11)

H₂TeO₄+SO₂+H₂O=H₂TeO₃+H₂SO₄ (12)

H₂TeO₃+2SO₂+H₂O=Te ↓+2H₂SO₄ (13)

H₂TeO₃+6Cl^-+4H⁺=TeCl₆ ^2-+3H₂O (14)

TeCl₆ ^2-+4SO₂+2Cu²⁺+8H₂O=Cu₂Te↓+4SO₄ ^2-+6Cl^-+16H⁺ (15)

It is of the invention to be had the following advantages compared with existing technology and effect：

The present invention dexterously using calcium bicarbonate and the deliquescent difference of calcium sulfate, is revived copper anode mud by being acidified transition The sulphur removing in the leachate that clinker adds water logging to go out is played, NaCl is then added in liquid after desulfurization, utilizes Na⁺It generates Common-ion effect significantly improves infusion CO₂Acidization NaHCO₃Percent crystallization in massecuite, and then realize solution middle soda and selenium Recycling is efficiently separated, then in NaHCO₃Crystallization after reducing agent Precipitation metallic selenium is added in liquid, successfully simplify selenium Recovery process route；And NaCl is added in the pickle liquor of leached mud, it not only efficiently separates and has recycled silver therein, Er Qie The reduction later stage of tellurium is due to Cl^-Complexing, promote remaining tellurium and Cu in solution²⁺With reference to precipitation Cu₂Te is greatly reduced After reduction in liquid Te concentration.It is redesigned by the entirety of present invention process, the mutual cooperation between each step, thus can be with The process for separating and recovering route of selenium and tellurium in copper anode mud is made greatly to be simplified, significantly reduces copper anode mud process Environmental protection pressure, also comply with the development trend of China energy-conserving and emission-cutting technology transformation.

Description of the drawings

Attached drawing 1 separates and recovers the conventional process flow of selenium and tellurium for copper anode mud soda sintering-leaching.

Attached drawing 2 separates and recovers the modified technique flow of selenium and tellurium for copper anode mud soda sintering of the present invention-leaching.

Specific embodiment

With reference to embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than it is right The further restriction of the present invention.

Embodiment 1

Copper anode mud 100g is taken, after adding in the levigate mixing of 35g natrium carbonicum calcinatums, 600 DEG C of sintering 3.5h, burn in Muffle furnace Solid-to-liquid ratio 1 is pressed after slagging is levigate:3g/ml adds water, and 95 DEG C of leaching 1.5h filter to obtain leachate and leached mud.Leachate adds It is 5.1 that sulfuric acid, which is acidified to pH, is separated by filtration the TeO being wherein precipitated₂Afterwards, continue plus sulfuric acid is acidified to H⁺A concentration of 1mol/L, according to reason 2 times of stoichiometric are slowly added to sodium sulfite and restore Se therein, stir 2.5h Precipitations selenium therein in 85 DEG C, filter slightly Liquid after selenium powder and heavy selenium；For impure selenium powder containing Se up to 98.7%, the liquid that sinks after selenium containing Se is 0.02g/L.Leached mud presses solid-to-liquid ratio 1:5g/ml Add in the H of 100g/L₂SO₄Solution in 95 DEG C of leaching 1.5h, filters to obtain pickle liquor and acid leaching residue；Acid leaching residue is used to recycle gold Silver, pickle liquor first add in the Cl of sodium chloride tune solution^-To 1.5g/L, make silver Precipitation in the form of AgCl therein, filter Liquid after AgCl filter residues and point silver, liquid is reduced into 2 times of theoretical amount of simple substance tellurium by tellurium therein and adds in slow sulfurous again after point silver Sour sodium reduction, 45 DEG C of reaction 2h filter to obtain coarse tellurium powder and liquid after reduction；Coarse tellurium powder containing Te up to 97.6%, Te in liquid after reduction A concentration of 0.05g/L.The experimental result of copper anode mud soda roasting-leaching separation and recovery selenium and tellurium is as follows：

	Se	Te	Ag	Cu	Pb
						Copper anode mud, %	0.33	0.67	10.93	14.89	7.21
Acid leaching residue, %	0.03	0.11	18.02	0.58	12.26

Embodiment 2

Decopper(ing) earth of positive pole 10kg, addition 2kg natrium carbonicum calcinatums and 0.2kg sodium nitrate is taken to pelletize after mixing thoroughly, in more stoves Solid-to-liquid ratio 1 is pressed in 550~630 DEG C of sintering 3.5h, clinker:1.5g/ml adds water, and 85 DEG C of leaching 2.5h filter to obtain leachate And leached mud.Infusion first leads to CO₂It is 5.5 to be acidified to pH, is separated by filtration the TeO being wherein precipitated₂Afterwards, by the sulfate radical in solution CaCO is added in 2 times of gypsum form Precipitation theoretical amount₃, reaction 2.5h is stirred at room temperature, filters to get filtrate and filter residue；Filter residue By solid-to-liquid ratio 1:2g/ml adds in the sulfuric acid solution of 1mol/L, and washing 1h is stirred at room temperature, filters to obtain gypsum and wash water；Filtrate adds in Lead to CO after 4kg sodium chloride again₂To 0.3MPa, in 15 DEG C of crystallisation by cooling, NaHCO is filtered to obtain₃Crystal and crystalline mother solution, NaHCO₃'s Percent crystallization in massecuite is 93.8%；Gained NaHCO₃Crystal return for copper anode mud soda be sintered, crystalline mother solution mixed with wash water after 75 DEG C of logical SO₂It is restored to Se concentration in solution and is down to 0.03g/L, filter to obtain impure selenium powder, impure selenium powder is through sodium sulfite crystallization of the dissolution and precipitation After method refining, then through being distilled in vacuum to give purity up to 99.99% metallic selenium；Leached mud presses solid-to-liquid ratio 1:4g/ml is added in containing H₂SO₄ The solution of 150g/L in 85 DEG C of leaching 2h, filters to obtain pickle liquor and acid leaching residue；Acid leaching residue send recovery for Au and Ag process, acidleach Liquid first adds in sodium chloride tune Cl^-To 5g/L, make silver Precipitation in the form of AgCl therein, filter after AgCl filter residues and point silver Liquid；AgCl filter residues send recovery for Au and Ag process, and liquid adds in the TeO of Precipitation in leachate after point silver₂After dissolving, then by therein Te, which is reduced into 1.2 times of the theoretical amount of simple substance tellurium and adds in sodium sulfites (solution), to restore, and reacts at room temperature 3h, filter coarse tellurium powder and Liquid after reduction；After reduction in liquid Te a concentration of 0.06g/L, for synthetical recovery after liquid merges with copper leached solution after reduction, thick tellurium Powder is through being distilled in vacuum to give purity up to 99.99% metallic tellurium.The reality of decopper(ing) earth of positive pole soda roasting-leaching separation and recovery selenium and tellurium It is as follows to test result：

	Cu	Ag	Se	Te	Pb
						The de- earth of positive pole, %	7.83	8.38	4.98	3.16	13.15
Acid leaching residue, %	0.53	13.28	0.05	0.08	21.81

Embodiment 3

Take decopper(ing) earth of positive pole 100kg, after adding in that 25kg natrium carbonicum calcinatums are levigate and mixing thoroughly, 450~650 DEG C of burnings in rotary kiln 2.5h is tied, solid-to-liquid ratio 1 is pressed in clinker:2g/ml adds water, and 100 DEG C of leaching 2h filter to obtain leachate and leached mud.Leachate Sodium chloride tune solution NaCl concentration is first added in up to 150g/L, 0 DEG C of crystallization is subsequently cooled to, filters to obtain sodium carbonate and sodium sulphate mixing Crystal and its crystalline mother solution；It is 5.1 that crystalline mother solution, which first adds sulfuric acid to be acidified to pH, is separated by filtration the TeO being wherein precipitated₂Afterwards, then add Sulfuric acid is acidified to solution acidity [H⁺] it is 0.1mol/L, then lead to SO₂It is restored to Se concentration in solution and drops to 0.02g/L, filter Impure selenium powder, impure selenium powder is after the refining of sodium sulfite crystallization of the dissolution and precipitation method, then through being distilled in vacuum to give purity up to 99.99% metal Selenium；Gained sodium carbonate and sodium sulphate mixed crystal first press solid-to-liquid ratio 1:2 add water heating stirring and dissolving, then lead into lysate CO₂To 0.1MPa, NaHCO is precipitated in room temperature crystallisation by cooling₃, filter to obtain NaHCO₃Liquid after crystal and its crystallization, liquid is in 0 DEG C after crystallization Return mixed crystal dissolution process is continuing with after saltcake is precipitated in crystallization, NaHCO₃Crystal returns to be burnt for copper anode mud soda Knot；Leached mud presses solid-to-liquid ratio 1:3g/ml adds in the H of 180g/L₂SO₄Solution, 90 DEG C of leaching 2.5h, filter pickle liquor and Acid leaching residue；Acid leaching residue send recovery for Au and Ag process, and pickle liquor first adds in sodium chloride tune Cl^-To 25g/L, make silver therein with AgCl shapes Formula Precipitation filters to obtain AgCl filter residues and liquid after point silver；AgCl filter residues send recovery for Au and Ag process, and liquid adds in leachate after point silver The TeO of middle Precipitation₂After dissolving, then logical SO₂It is restored to Te concentration in solution and drops to 0.5g/L, stirring adds in 0.35kg iron Powder continues reductase 12 h, filters to obtain coarse tellurium powder and liquid after reduction；After reduction in liquid Te a concentration of 0.01g/L, after reduction liquid with point Copper liquid is used to recycle the valuable metals such as copper therein after merging, and coarse tellurium powder is through being distilled in vacuum to give purity up to 99.99% metallic tellurium. The experimental result of decopper(ing) earth of positive pole soda roasting-leaching separation and recovery selenium and tellurium is as follows：

	Cu	Ag	Se	Te	Pb
						The de- earth of positive pole, %	7.83	8.38	4.98	3.16	13.15
Acid leaching residue, %	0.48	13.28	0.02	0.06	21.81

Claims

1. a kind of method of copper anode mud separation and recovery selenium and tellurium, includes the following steps：

Soda sintering is carried out through the decopper(ing) pretreated decopper(ing) earth of positive pole to copper anode mud or copper anode mud, sintered material adds Water logging goes out, and filters to obtain selenium-rich leachate and rich tellurium leached mud；

After sodium carbonate being separated and recovered to selenium-rich leachate, then with sodium sulfite or SO₂In reduction recycling selenium-rich leachate or filtrate Selenium, filters to obtain impure selenium powder, and impure selenium powder further refines to obtain metallic selenium；

Sodium carbonate is separated and recovered to selenium-rich leachate, is first to be passed through CO into selenium-rich leachate₂Adjust pH to 6.5~4.5, filtering point TeO from wherein Precipitation₂Afterwards, then by the sodium sulphate in filtrate it is converted to 1~3 times of addition CaCO of calcium sulfate theoretical amount₃, 1~3h is reacted at room temperature, makes CaCO₃It is converted to CaSO₄, filter to obtain doctor solution and desulfurization slag；Desulfurization slag after sulfuric acid solution washs, Filter to obtain wash water and gypsum；The directly logical CO of doctor solution₂To 0.1~1.5MPa or add in sodium chloride tune solution NaCl concentration 5~ 350g/L, then logical CO₂To 0.1~1.5MPa, NaHCO is crystallized in -10~30 DEG C₃, filter to obtain NaHCO₃After crystal and the first crystallization Liquid, after liquid merges with wash water after the first crystallization, with sodium sulfite or SO₂Selenium therein is recycled in reduction；Or

After adding in sodium chloride tune NaCl concentration to 5~350g/L in selenium-rich leachate, in -20~20 DEG C of crystallisation by cooling, filtering Obtain the mixed crystal and the second crystalline mother solution of sodium sulphate and sodium carbonate；Second crystalline mother solution add mineral acid be first acidified to pH 6.5~ 4.5, it is separated by filtration the TeO of wherein Precipitation₂Afterwards, then add mineral acid to solution acidity with H⁺0.1~2mol/L is calculated as, Then sodium sulfite or SO are used₂Restore selenium therein；

Rich tellurium leached mud filters to obtain pickle liquor and acid leaching residue after sulfuric acid solution leaches；Pickle liquor uses sulfurous after chlorination point silver Sour sodium or SO₂Precipitate reduction tellurium therein, filters to obtain coarse tellurium powder, and coarse tellurium powder further refines to obtain metallic tellurium.

2. the method for a kind of copper anode mud separation and recovery selenium according to claim 1 and tellurium, which is characterized in that gained mixes Crystal first presses solid-to-liquid ratio 1:2~4 add water heating to stir to obtain lysate, and CO is then led into lysate₂To 0.1~1.5MPa, room NaHCO is precipitated in temperature crystallization₃, filter to obtain NaHCO₃Liquid after crystal and third crystallization, liquid is in -10~20 DEG C of crystallization analysis after third crystallization Return mixed crystal dissolution process is continuing with after going out saltcake；Or

1~3 times of addition CaCO of calcium sulfate theoretical amount is converted to by the sodium sulphate in lysate₃, and it is passed through CO₂Adjust pH value of solution To 6.5~4.5,1~3h is reacted at room temperature, makes CaCO₃It is converted to CaSO₄, liquid is crystallized in -20~10 DEG C after the transition being obtained by filtration, Filter to obtain NaHCO₃And Na₂CO₃Mixed crystal and the 4th crystallization after liquid, the 4th crystallization after liquid return mixed crystal dissolution process It is continuing with.

3. the method for a kind of copper anode mud separation and recovery selenium according to claim 2 and tellurium, which is characterized in that gained NaHCO₃Crystal and NaHCO₃And Na₂CO₃Mixed crystal return to soda sintering circuit and recycle.

4. the method for a kind of copper anode mud separation and recovery selenium according to claim 2 and tellurium, which is characterized in that added ore deposit The one kind of object acid in sulfuric acid, hydrochloric acid, nitric acid.

5. the method for a kind of copper anode mud separation and recovery selenium according to claim 2 and tellurium, which is characterized in that reduction recycling Selenium refers to that 1~3 times of the theoretical amount for being reduced into elemental selenium by the selenium in solution adds in sodium sulfite or is passed through SO₂, 50~95 DEG C 1~4h is reacted, filters to obtain impure selenium powder.

6. the method for a kind of copper anode mud separation and recovery selenium and tellurium according to claim 1-5 any one, feature exist In sulfuric acid solution leaches rich tellurium leached mud and refers to by solid-to-liquid ratio 1:2~6g/mL adds in the H containing a concentration of 100~250g/L₂SO₄ After solution, 50~105 DEG C of 1~3h of leaching are heated to, filter to obtain pickle liquor and acid leaching residue；Acid leaching residue send recovery for Au and Ag work Sequence, pickle liquor recycle tellurium after chlorination point silver for Reduced separating.

7. the method for a kind of copper anode mud separation and recovery selenium according to claim 6 and tellurium, which is characterized in that the chlorine Change divides silver to refer to add in sodium chloride in pickle liquor, adjusts Cl in solution^-Up to 0.05~50g/L, make silver therein in the form of AgCl Precipitation, filter after AgCl filter residues and chlorination point silver liquid, gained AgCl filter residues send recovery for Au and Ag process.

8. the method for a kind of copper anode mud separation and recovery selenium according to claim 7 and tellurium, which is characterized in that Reduced separating Recycling tellurium refers to that first stirring adds in the TeO recycled in selenium-rich leachate in liquid after chlorination point silver₂, treat TeO₂After dissolving, then 1~3 times that the theoretical amount of simple substance tellurium is reduced by the tellurium in solution adds in sodium sulfite or is passed through SO₂, 1~4h is reacted at room temperature, Filter to obtain coarse tellurium powder.

9. the method for a kind of copper anode mud separation and recovery selenium according to claim 8 and tellurium, which is characterized in that the Soviet Union Sintering is played to refer to add in sodium carbonate, and by copper anode mud or decopper(ing) sun by the 10~40% of copper anode mud or decopper(ing) earth of positive pole quality Pole shale amount 0~10% addition sodium nitrate mix thoroughly or levigate mixing after, directly or granulation after in air or oxygen 450~650 DEG C sintering 2~4h.

10. the method for a kind of copper anode mud separation and recovery selenium according to claim 9 and tellurium, which is characterized in that after sintering Material press solid-to-liquid ratio 1:After 1~3g/mL adds water, 50~100 DEG C of 1~3h of leaching filter to obtain leachate and leached mud.