CN101844750A

CN101844750A - Method for preparing high-purity tellurium by material containing tellurium

Info

Publication number: CN101844750A
Application number: CN201010191510A
Authority: CN
Inventors: 郑雅杰; 孙召明; 刘昭成
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2010-06-04
Filing date: 2010-06-04
Publication date: 2010-09-29

Abstract

The invention relates to a method for preparing high-purity tellurium by material containing tellurium, which takes the material containing tellurium as the raw material and prepares the high-purity tellurium through a chemical method. The material containing the tellurium is oxidized, leached in acid, decoppered and filtered to obtain crude tellurium; the crude tellurium is leached in acid solution under the action of oxidant and filtered to obtain the solution containing tellurium; a reducer is added into the solution containing tellurium to react and be heated and filtered; the reducer is added into the filtrate again to be heated, react and be filtered to obtain tellurium powder; under the action of the oxidant, the tellurium powder is dissolved in the acid solution and then added with the reducer to obtain refined tellurium; and at 200 to 800DEG C, the refined tellurium is treated by hydrogen to obtain the high-purity tellurium.

Description

A kind of method of preparing high-purity tellurium by material containing tellurium

Technical field

The invention belongs to the hydrometallurgy field, particularly contain the tellurium material, the preparation high purity tellurium at the high selenium of high-copper.

Background technology

The tellurium association is in mineral such as copper, lead, zinc.At present, the tellurium major part is from copper, lead anode slurry.Roasting behind copper anode mud and the vitriol oil stirring and evenly mixing, leaching, evaporative crystallization reclaim(ed) sulfuric acid copper obtain containing the tellurium material after adding reductive agent reaction by the CN200810032022.0 patented technology in the copper sulfate mother liquor.The aforesaid method gained contains copper in the tellurium material, arsenic content height, needs through removing the high purity tellurium that impurity such as copper, arsenic wherein just can obtain having very high economic worth.

At present, generally will contain the tellurium material obtains adopting electrolysis to obtain content behind the tellurium material to be 99.99% high purity tellurium, perhaps to adopt technology such as vacuum distilling, zone melting to prepare high purity tellurium high-purity containing through removal of impurities repeatedly.Electrolytic process complex process, product yield are low; Vacuum distilling is to impurity inferior separating effect such as selenium, arsenic, lead, sodium, and requires good vacuum system; Zone melting can obtain high purity tellurium, but the operational requirement strictness, and commute and tellurium form eutectiferous impurity separation difficulty, and direct yield is low, the yielding poorly of unit equipment.

Summary of the invention

The objective of the invention is to handle, impurity such as copper, selenium, arsenic are separated with tellurium, obtain the higher high purity tellurium of economic worth containing the tellurium material.

Process of the present invention is: will contain tellurium material oxidation acid leaching decopper(ing), and filter and obtain thick tellurium; Acidic solution leaches thick tellurium under the oxygenant effect, obtain containing tellurium solution through filtering, used oxygenant is hydrogen peroxide, nitric acid, nitrate, dioxide peroxide, hypochlorous acid, hypochlorite, chloric acid or oxymuriate, and it is nitric acid, hydrochloric acid or sulfuric acid that acidic solution leaches used acid; In containing tellurium solution, add reductive agent, the reaction post-heating filters, add reductive agent in filtrate once more, the reaction after-filtration obtains the tellurium powder under 0 ℃～120 ℃ temperature, and used reductive agent is sulfurous gas, S-WAT, sodium bisulfite, vat powder, formic acid or formate; Behind acid leach solution tellurium powder under the oxygenant effect, add reductive agent and obtain smart tellurium; Under 200 ℃～800 ℃, the smart tellurium of hydrogen treat obtains content more than or equal to 99.99% high purity tellurium.

Embodiment

Embodiment 1: contain in the tellurium material at 2kg that to add 6.8L concentration be in 45% salpeter solution, start and stir, at 20 ℃ of reaction 1.5h down.Then, filtration, washing, oven dry obtain thick tellurium.It is more as shown in table 1 with thick tellurium composition to contain the tellurium material:

Table 1 contains tellurium material and thick tellurium composition comparison/%

In 7.5L concentration is to add thick tellurium in 25% the hydrochloric acid soln, starts and stirs, and adding 0.2L concentration in the reaction process is 45% salpeter solution, 75 ℃ of reactions down, when thick tellurium dissolving after-filtration.In filtrate, feed SO ₂Reaction produces red precipitate to stopped reaction after the black precipitate, heating and filtering occurring.After the filtration solution is heated to 85 ℃, feeds SO ₂Make in the solution tellurium fully reduce after-filtration, washing, oven dry and obtain 1210g tellurium powder.

In 7.5L concentration is to add gained tellurium powder in 25% the hydrochloric acid soln, starts and stirs, and adds the 2.3L hydrogen peroxide in the reaction process altogether, 80 ℃ of reactions down, when tellurium powder dissolving after-filtration, after the filtration solution is heated to 85 ℃, feeds SO ₂Make in the solution tellurium fully reduce after-filtration, washing, oven dry and obtain the smart tellurium of 1200g.Gained tellurium powder and smart tellurium composition are more as shown in table 2:

Table 2 tellurium powder and the comparison of smart tellurium composition //mgkg ^-1

Gained tellurium powder is put into quartzy stove, under the hydrogen effect, through obtain after 450 ℃ of processing 1180g purity be 99.9996% high purity tellurium, its high purity tellurium composition is as shown in table 3.

Table 3 high purity tellurium composition/mgkg ^-1

Embodiment 2: contain in the tellurium material at 2kg that to add 8L concentration be in 4% sulphuric acid soln, start and stir, add the 0.4L hydrogen peroxide in the reaction process, 20 ℃ down reaction 3.5h after-filtration, washing, oven dry to obtain purity be 76.01% thick tellurium, it is as shown in table 4 to contain the tellurium material component:

Table 4 contains tellurium material component/%

In 10L concentration is to add thick tellurium in 20% the hydrochloric acid soln, starts and stirs, and adds the 0.5L hydrogen peroxide in the reaction process, 80 ℃ of reactions down, when thick tellurium dissolving after-filtration.In filtrate, add sodium sulfite solution, produce red precipitate to stopped reaction after the black precipitate, heating and filtering occurring.After the filtration solution is heated to 85 ℃, add sodium sulfite solution make tellurium in the solution fully reduce after-filtration, washing, oven dry to obtain 1000g purity be 99.92% tellurium powder.

In 10L concentration is to add gained tellurium powder in 20% the hydrochloric acid soln, start and stir, add the 2L hydrogen peroxide in the reaction process altogether, 80 ℃ of reactions down, when tellurium powder dissolving after-filtration, after the filtration solution is heated to 85 ℃, add sodium sulfite solution make tellurium in the solution fully reduce after-filtration, washing, oven dry to obtain 995g purity be 99.99% smart tellurium.

Gained tellurium powder is put into quartzy stove, under the hydrogen effect, through obtain after 420 ℃ of processing 980g purity be 99.999% high purity tellurium, its high purity tellurium composition is as shown in table 5.

Table 5 high purity tellurium composition/mgkg ^-1

Claims

1. the method for a preparing high-purity tellurium by material containing tellurium is characterized in that comprising the steps:

A. the acidic solution leaching contains the tellurium material under the oxygenant effect, filters and obtains thick tellurium;

B. acidic solution leaches thick tellurium under the oxygenant effect, and the reaction after-filtration obtains containing tellurium solution; Add reductive agent in containing tellurium solution, the reaction post-heating filters; After the filtration, add reductive agent in filtrate, the reaction after-filtration obtains the tellurium powder;

C. acid leach solution tellurium powder under the oxygenant effect adds reductive agent, and reaction obtains smart tellurium after filtering;

D. under 200 ℃～800 ℃, the smart tellurium of hydrogen treat obtains high purity tellurium.

2. according to the method for the described a kind of preparing high-purity tellurium by material containing tellurium of claim 1, it is characterized in that: temperature of reaction is 0 ℃～120 ℃ in the solution;

3. according to the method for the described a kind of preparing high-purity tellurium by material containing tellurium of claim 1, it is characterized in that: A and the used oxygenant of B step are hydrogen peroxide, nitric acid, nitrate, dioxide peroxide, hypochlorous acid, hypochlorite, chloric acid or oxymuriate;

4. according to the method for the described a kind of preparing high-purity tellurium by material containing tellurium of claim 1, it is characterized in that: it is nitric acid, hydrochloric acid or sulfuric acid that B step acidic solution leaches used acid.

5. according to the method for the described a kind of preparing high-purity tellurium by material containing tellurium of claim 1, it is characterized in that: used reductive agent is sulfurous gas, S-WAT, sodium bisulfite, vat powder, formic acid or formate.