CN109504854B - Method for enriching tellurium and bismuth from low-grade tellurium and bismuth ore - Google Patents

Abstract

The invention discloses a method for enriching tellurium bismuth from low-grade tellurium bismuth ore, which is characterized by comprising the following steps: 1) leaching tellurium-bismuth ore: crushing and grinding the tellurium-bismuth ore, leaching tellurium and bismuth in the tellurium-bismuth ore in a leaching solution by adopting sulfuric acid and ferric chloride solution, and filtering to obtain a leaching solution containing tellurium and bismuth and leaching slag; the leaching solution can be chloridized and then leaching treatment is carried out on the tellurium-bismuth ore so as to improve the concentration of tellurium and bismuth in the leaching solution; 2) and (3) carrying out reduction treatment on the leaching solution: reducing tellurium and bismuth in the leaching solution by adopting reduced iron powder, precipitating, and filtering to obtain tellurium-bismuth rich aggregate and a reduced solution; 3) chlorination treatment: the reduced liquid is chloridized to remove Fe in the reduced liquid²⁺Oxidation to Fe³⁺And the waste liquid is recycled, so that the treatment capacity of the waste liquid can be reduced.

Description

Method for enriching tellurium and bismuth from low-grade tellurium and bismuth ore

Technical Field

The invention relates to the technical field of wet separation and enrichment of nonferrous metals, in particular to a method for enriching bismuth telluride from low-grade bismuth telluride ores.

Background

Tellurium and bismuth are two important strategic metal elements, and are known as 'industrial monosodium glutamate' and 'high-tech element' in modern industry and national defense. Wherein tellurium is a metalloid element and is one of seven rare and dispersive elements. The content of tellurium in the crust, the mantle and the core is 0.0006ppm, 0.01ppm and 0.52ppm, so that independent mineral deposits are difficult to form, and the tellurium is often present in minerals such as gold, silver, copper, lead, nickel and the like in a concomitant manner, so that the pure tellurium quantity obtained by human beings is very limited.

Tellurium has special physical properties and is an indispensable key material for manufacturing elements such as photoelectricity, semiconductors, refrigeration and the like. Tellurium and its products are widely used in high-tech fields such as metallurgy, rubber, petroleum, electronics, electricity, glass ceramics, aerospace, military and medicine. Bismuth is a colored heavy metal due to its excellent physical and chemical properties. The metal is widely used in the fields of alloy, metallurgy, medicine, chemical industry and the like.

Research results show that tellurium is difficult to form independent ore deposits with industrial exploitation value, tellurium produced in the world is obtained by comprehensively recovering waste residues which are byproducts of non-ferrous metal smelting processes at present, the average content of tellurium in non-ferrous metal ores such as copper, lead and zinc ores is below 0.002%, and not all copper, lead and zinc ores contain tellurium, so that comprehensive recovery of tellurium is very difficult, and refined tellurium produced in various countries is extracted from copper and lead anode slime at present.

The bismuth metal is mainly from bismuth ore, wherein bismuth aurate and bismuth sulfide ore are main raw materials for extracting bismuth. And the major part of bismuth metal comes from the by-product anode slime in the non-ferrous metal smelting process, such as lead anode slime and tin anode slime, copper converter smoke dust, floating anode slime produced in the copper electrolysis process and the like.

In 1991, the first independent tellurium mine in the world is found in a large ditch of asbestos county in Sichuan province in China, which fills a gap in the theory of mineral deposit science. The industrial development of the tellurium-bismuth resources of the large ditch in asbestos county provides sufficient raw materials for the construction of 'Chinese tellurium-valley', and is an important guarantee for the construction of 'Chinese tellurium-valley' strategic planning. This will change the world distribution pattern of tellurium resources and may make China a large tellurium resource country.

With the increase of the demand of the society on tellurium, how to separate and extract tellurium and bismuth from the tellurium-bismuth ore with high efficiency and low cost becomes the focus of attention of the majority of metallurgy workers. However, the ore contains mainly dolomite (CaCO)₃·MgCO₃) Pyrite (FeS)₂) Pyrrhotite (FeS); the tellurium-bismuth ore deposit has low tellurium and bismuth grade (W [ Te ]]<5％，w[Bi]<5%) and mainly sulfide ores; tellurium and bismuth mainly comprising bismuth tellurite (Bi)₂Te₂S), Chu Te Bi ore (BiTe), Te Bi ore (Bi)₂Te₃) Is present in the mine.

At present, domestic tellurium is mainly recovered from anode mud by methods such as an alkaline leaching method, a soda slagging method and the like. However, these techniques are limited by incomplete material processing, high energy consumption, low product yield, and the like. Therefore, the tellurium-bismuth ore needs to be subjected to mineral processing to obtain the tellurium-bismuth enriched aggregate for further utilization. Aiming at the less research of mineral separation of asbestos big ditch tellurium-bismuth ore, the prior art discloses a flotation method for flotation of asbestos big ditch tellurium-bismuth ore, but the operation efficiency is lower, the grade is lower, and the cost is higher.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a method for enriching bismuth telluride from low-grade bismuth telluride ores.

The technical scheme adopted for realizing the aim of the invention is that the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the particle size of the tellurium bismuth ore powder is 120-320 meshes;

1.2) mixing a sulfuric acid solution and an iron chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 80-200 g/L;

said Fe³⁺The concentration of (A) is 30-150 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 50-95 ℃, and the leaching time is 40-240 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 4: 1-10: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after the leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues;

the leaching solution can be subjected to chlorination and then leaching treatment on the tellurium-bismuth ore so as to improve the concentration of tellurium and bismuth in the leaching solution;

2) reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 0.8-2.0 times of the theoretical amount required for reducing tellurium and bismuth in the leachate;

in the reaction process: the temperature is 25-80 ℃, and the time is 40-240 min;

3) chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Further, the method comprises the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the particle size of the tellurium bismuth ore powder is 120-200 meshes;

1.2) mixing a sulfuric acid solution and an iron chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 100-150 g/L;

said Fe³⁺The concentration of (A) is 50-100 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80-95 ℃, and the leaching time is 60-120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 5: 1-7: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after the leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues;

the leaching solution can be subjected to chlorination and then leaching treatment on the tellurium-bismuth ore so as to improve the concentration of tellurium and bismuth in the leaching solution;

2) reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.4-1.7 times of the theoretical amount required for reducing tellurium and bismuth in the leachate;

in the reaction process: the temperature is 25-80 ℃, and the time is 60-150 min;

3) chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Further, the solid-liquid separation process in the step 1.4) adopts a mode including vacuum filtration or gravity filtration.

Further, the filtering process in the step 2) adopts a mode comprising vacuum filtration or gravity filtration.

It is worth to be noted that the process and principle of the invention are:

1) acid oxidation leaching

1) Leaching the tellurium-bismuth ore

Crushing and grinding the tellurium-bismuth ore, leaching tellurium and bismuth in the tellurium-bismuth ore in a leaching solution by adopting sulfuric acid and ferric chloride solution, and filtering to obtain a leaching solution containing tellurium and bismuth and leaching slag;

the main phase of raw ore is dolomite (CaCO)₃·MgCO₃) Pyrite (FeS)₂) Pyrrhotite (FeS); the phase containing tellurium and bismuth is mainly tellurobismuthate (Bi)₂Te₂S), Chu Te Bi ore (BiTe), Te Bi ore (Bi)₂Te₃)。

After acidic oxidative leaching, tellurium is as Te⁴⁺Or HTeO₂ ⁺In the form of Bi in the leaching solution³⁺Is present in the leachate.

The sulfur element of the raw ore exists in the filter residue in the form of elemental sulfur under the condition of acid oxidation, SO that SO brought by direct acid leaching is avoided₂And (4) pollution.

During the leaching process, there is a large amount of CO₂Gas is generated to stir the solution, so that consumption of mechanical stirring can be reduced.

The process involves the following reactions:

in the system, the tellurium bismuth material is mixed with sulfuric acid and FeCl₃The reaction of (1):

Bi₂Te₂S+14Fe³⁺＝2Bi³⁺+2Te⁴⁺+14Fe²⁺+S↓

BiTe+7Fe³⁺＝Bi³⁺+Te⁴⁺+7Fe²⁺

Bi₂Te₃+18Fe³⁺＝2Bi³⁺+3Te⁴⁺+18Fe²⁺+S↓

Bi₂Te₂S+14Fe³⁺+4H₂O＝2Bi³⁺+2HTeO₂ ⁺+14Fe²⁺+S↓+6H⁺

BiTe+7Fe³⁺+2H₂O＝Bi³⁺+HTeO₂ ⁺+7Fe²⁺+3H⁺

Bi₂Te₃+18Fe³⁺+6H₂O＝2Bi³⁺+3HTeO₂ ⁺+18Fe²⁺+S↓+9H⁺

in this system, other materials are mixed with sulfuric acid and FeCl₃The reaction of (1):

MgCO₃+2H⁺＝Mg²⁺+H₂O+CO₂↑

FeS+2Fe³⁺＝3Fe²⁺+S↓

FeS₂+2Fe³⁺＝3Fe²⁺+2S↓

2) reducing the reduced iron powder to obtain the tellurium-bismuth enriched material

Reducing tellurium and bismuth in the leaching solution by adopting reduced iron powder, precipitating, and filtering to obtain tellurium-bismuth rich aggregate and a reduced solution;

mechanical stirring is not needed in the iron powder reduction treatment process; the separation mode of the bismuth telluride enriched material and the reduced liquid adopts a vacuum filtration (suction filtration) mode, and the bismuth telluride enriched material and the reduced liquid are obtained after filtration. The relevant reactions in the process of reducing and enriching the tellurium and bismuth by the iron powder are as follows:

7Fe+2Te⁴⁺+2Bi³⁺＝7Fe²⁺+2BiTe

9Fe+2Te⁴⁺+2Bi³⁺＝9Fe²⁺+2Bi₂Te₃

Bi³⁺+Cl^-+2H₂O＝BiClO+2H⁺

3) chlorination treatment

Chlorine is introduced into the reduced solution to chloridize the reduced solution, so that ferrous ions in the reduced solution are converted into ferric ions for recycling, and the treatment capacity of waste liquid can be reduced.

The process involves the following chemical reactions:

2Fe²⁺+Cl₂＝2Fe³⁺+2Cl^-

H₂O+Cl₂＝HClO+HCl

the technical effects of the present invention are undoubted, and the present invention has the following advantages:

1) compared with the prior art, the invention adopts H₂SO₄And FeCl₃Leaching and leaching-reducing and precipitating the tellurium bismuth enriched material by iron powder for subsequent working procedures;

2) the invention has little environmental pollution and no SO in sulfur₂Is discharged in the form of simple substance and is fixed in the leaching residue;

3) the method has the advantages of simple and easy operation, no pressure equipment, high tellurium and bismuth recovery rate, short treatment time and little environmental pollution.

Drawings

FIG. 1 is a schematic process diagram of the present invention.

Detailed Description

The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.

Example 1:

a method for enriching tellurium and bismuth from low-grade tellurium and bismuth ores is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

TABLE 1 chemical composition (wt.%) of asbestos Mantle tellurium-bismuth ore

1.2) the immersion liquid is ferric chloride solution;

said Fe³⁺The concentration of (A) is 100 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium was only 1.2%, and the leaching rate of bismuth was only 14.6%.

Example 2:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

the above-mentionedH₂SO₄The concentration of (A) is 100 g/L;

said Fe³⁺The concentration of (A) is 100 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium can reach 97.83%, and the leaching rate of bismuth can reach 89.64%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.4 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 25 ℃, and the time is 240 min;

in the reduction process, the recovery rate of tellurium reaches 95.61%, and the recovery rate of bismuth reaches 96.70%.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 3:

a method for enriching tellurium and bismuth from low-grade tellurium and bismuth ores is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) the immersion liquid is H₂SO₄A solution;

said H₂SO₄The concentration of (A) is 150 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium was only 39.8%, and the leaching rate of bismuth was 64.83%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 25 ℃, and the time is 240 min;

in the reduction process, the recovery rate of tellurium reaches 98.51%, and the recovery rate of bismuth reaches 99.77%.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 4:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (2) is 30 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium was 85.43%, and the leaching rate of bismuth was 83.08%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.7 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 25 ℃, and the time is 240 min;

in the reduction process, the recovery rate of tellurium reaches 99.51%, and the recovery rate of bismuth reaches 99.87%.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 5:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium was 97.99%, and the leaching rate of bismuth was 91.53%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 40 ℃, and the time is 240 min;

in the reduction process, the recovery rate of tellurium reaches 98.04 percent, and the recovery rate of bismuth reaches 99.82 percent.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 6:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 80 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium was 77.99%, and the leaching rate of bismuth was 81.53%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 60 ℃, and the time is 240 min;

in the reduction process, the recovery rate of tellurium reaches 99.24 percent, and the recovery rate of bismuth reaches 99.67 percent.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 7:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 200 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium can reach 99.21%, and the leaching rate of bismuth can reach 92.16%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 80 ℃, and the time is 240 min;

in the reduction process, the recovery rate of tellurium reaches 99.43%, and the recovery rate of bismuth reaches 99.49%.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 8:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 4: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium can reach 94.75%, and the leaching rate of bismuth can reach 81.22%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 50 ℃ and the time is 150 min;

in the reduction process, the recovery rate of tellurium reaches 98.59 percent, and the recovery rate of bismuth reaches 99.79 percent.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 9:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 8: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium can reach 98.17%, and the leaching rate of bismuth can reach 91.56%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 40 deg.C, and the time is 120 min;

in the reduction process, the recovery rate of tellurium reaches 98.59 percent, and the recovery rate of bismuth reaches 99.79 percent.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 10:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 10: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium can reach 98.98%, and the leaching rate of bismuth can reach 91.79%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 40 ℃, and the time is 90 min;

in the reduction process, the recovery rate of tellurium reaches 99.04 percent, and the recovery rate of bismuth reaches 99.22 percent.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 11:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 40 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium was 96.77%, and the leaching rate of bismuth was 85.88%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 40 deg.C, and the time is 80 min;

in the reduction process, the recovery rate of tellurium reaches 98.23 percent, and the recovery rate of bismuth reaches 99.12 percent.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 12:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 80 ℃, and the leaching time is 120 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium can reach 98.7%, and the leaching rate of bismuth can reach 92.67%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 40 deg.C, and the time is 70 min;

in the reduction process, the recovery rate of tellurium reaches 99.23 percent, and the recovery rate of bismuth reaches 99.50 percent.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 13:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 50 ℃, and the leaching time is 60 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium can reach 92.01%, and the leaching rate of bismuth can reach 82.99%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 40 deg.C, and the time is 60 min;

in the reduction process, the recovery rate of tellurium reaches 99.43%, and the recovery rate of bismuth reaches 99.45%.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 14:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 60 ℃, and the leaching time is 60 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium can reach 94.62%, and the leaching rate of bismuth can reach 83.98%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 25 ℃ and the time is 60 min;

in the reduction process, the recovery rate of tellurium reaches 89.78%, and the recovery rate of bismuth reaches 88.84%.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Example 15:

as shown in figure 1, the method for enriching the bismuth telluride from the low-grade bismuth telluride ore is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the granularity of the tellurium bismuth ore powder is below 200 meshes;

in the embodiment, the adopted large-ditch asbestos tellurium-bismuth ore has the chemical composition shown in table 1;

1.2) mixing sulfuric acid and ferric chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 150 g/L;

said Fe³⁺The concentration of (A) is 60 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1) into the immersion liquid obtained in the step 2) for leaching treatment;

the leaching temperature is 90 ℃, and the leaching time is 60 min;

the volume-weight ratio (mL: g) of the immersion liquid to the tellurium bismuth ore powder is 6: 1;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues mainly containing calcium sulfate;

in this example, the leaching rate of tellurium can reach 99.17%, and the leaching rate of bismuth can reach 92.82%.

2) Reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.5 times of the theoretical amount required by reducing tellurium and bismuth in the leaching solution;

in the reaction process: the temperature is 25 ℃, and the time is 120 min;

in the reduction process, the recovery rate of tellurium reaches 99.69%, and the recovery rate of bismuth reaches 99.85%.

3) Chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

Claims (2)

1. A method for enriching tellurium and bismuth from low-grade tellurium and bismuth ores is characterized by comprising the following steps:

1) leaching tellurium-bismuth ore; the main phases of the raw ore are dolomite, pyrite and pyrrhotite; the phases containing tellurium and bismuth mainly comprise tellurite, Chu-tellurite and tellurite;

the tellurium-bismuth ore comprises the following chemical components in percentage by weight:

Te 1.52wt. %

Bi 2.99wt. %

S 13.67wt. %

Fe₂O₃ 36.82wt. %

SiO₂ 3.60wt. %

CaO 16.51wt. %

MgO 8.07wt. %

K₂O 0.32wt. %

Na₂O 0.16wt. %

Al₂O₃ 1.97wt. %

TiO₂ 0.11wt. %

Cu 0.09wt. %

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the particle size of the tellurium bismuth ore powder is 120-320 meshes;

1.2) mixing a sulfuric acid solution and an iron chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 80-200 g/L;

said Fe³⁺The concentration of (A) is 30-150 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1.1) into the immersion liquid obtained in the step 1.2) for leaching treatment;

the leaching temperature is 50-95 DEG C^oC, leaching for 40-240 min;

the volume-weight ratio of the immersion liquid to the tellurium bismuth mineral powder is 4: 1-10: 1; volume is in mL, weight is in g;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after the leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues;

2) reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 0.8-2.0 times of the theoretical amount required for reducing tellurium and bismuth in the leachate;

in the reaction process: the temperature is 25-80 deg.C^oC, the time is 40-240 min;

3) chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

2. The method for enriching the bismuth telluride from the low-grade bismuth telluride ore according to claim 1, which is characterized by comprising the following steps:

1) leaching the tellurium-bismuth ore

1.1) crushing and grinding the tellurium-bismuth ore to obtain tellurium-bismuth ore powder;

the particle size of the tellurium bismuth ore powder is 120-200 meshes;

1.2) mixing a sulfuric acid solution and an iron chloride solution to obtain an immersion liquid;

said H₂SO₄The concentration of (A) is 100-150 g/L;

said Fe³⁺The concentration of (A) is 50-100 g/L;

1.3) under the condition of heating in a water bath, adding the tellurium bismuth ore powder obtained in the step 1.1) into the immersion liquid obtained in the step 1.2) for leaching treatment;

the leaching temperature is 80-95%^oC, leaching for 60-120 min;

the volume-weight ratio of the immersion liquid to the tellurium bismuth ore powder is 5: 1-7: 1, wherein the volume unit is mL, and the weight unit is g;

1.4) carrying out solid-liquid separation on the mixed solution obtained in the step 1.3) after the leaching treatment to obtain a leaching solution containing tellurium and bismuth and leaching residues;

2) reducing the leaching solution

Adding reduced iron powder into the leaching solution containing tellurium and bismuth obtained in the step 1.4), and filtering after the reaction is finished to obtain tellurium and bismuth rich aggregate and a reduced solution;

the mass of the reduced iron powder is 1.4-1.7 times of the theoretical amount required for reducing tellurium and bismuth in the leachate;

in the reaction process: the temperature is 25-80 deg.C^oC, the time is 60-150 min;

3) chlorination treatment

And (3) introducing chlorine into the reduced liquid obtained in the step 2), and carrying out chlorination treatment to convert the chlorine into ferric ions for recycling.

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