CN1194237A

CN1194237A - Wet process for preparing industrial pure antimony sulfide by removing load, arsenic, selenium, tin and mercury impurities in antimonic ore

Info

Publication number: CN1194237A
Application number: CN97112604A
Authority: CN
Inventors: 张至德
Original assignee: Individual
Current assignee: Individual
Priority date: 1997-03-24
Filing date: 1997-05-16
Publication date: 1998-09-30
Anticipated expiration: 2017-05-16
Also published as: CN1057069C

Abstract

By utilizing the solubility of antimonic ore and insolubility of lead in the solution of alkali sulfide, strong alkali or their mixture, the present invention realizes the separation of antimonide from lead. By further adding acid compound into the solution, is precipitated out antimony oxide or sulfide, and through filtration, washing and stoving the product is obtained. The solution after antimonide precipitation is processed with lime or SO2 before returning to lixiviation for reuse. The said technological process can process antimonic ore with any lead content.

Description

Process for preparing industrial pure antimony sulfide by removing impurities of lead, arsenic, selenium, tin and mercury in antimony minerals by wet method

The invention relates toa process for removing impurities such as lead, arsenic, selenium, tin, mercury and the like in antimony minerals by a wet method for preparing industrial pure antimony sulfide and antimony oxide.

As is known, lead is an impurity element which is difficult to remove in an antimony smelting process, and many antimony minerals are reduced in use value or even not utilized due to high lead content. At present, various lead-antimony separation technologies exist in the world, but the separation efficiency is low, and the application range is narrow; or is not easy to be used in industrial production due to its difficult process.

The invention aims to: provides an applicable process for removing lead, arsenic, selenium, tin, mercury and other impurities in antimony minerals, in particular to a process for preparing industrial pure antimony sulfide and antimony oxide by removing the lead impurities in the antimony minerals.

The principle of the invention is as follows:

1. antimony minerals such as antimony sulfide and antimony oxide and alkali sulfides are used: na (Na)₂S、K₂S、CaS、BaS、(NH₄)₂S or strongly basic hydroxides such as: NaOH, KOH or mixed alkali thereof form a complex, so that the water solubility of the complex and the difficult solubility of impurities such as lead, iron, zinc, copper, manganese, calcium, magnesium, aluminum, silicon and the like in the solution are realized, the separation of antimony and the impurities is realized, and the reaction formula is as follows:

when the antimony ore is leached by using an aqueous solution of alkali hydroxide, an appropriate amount of alkali sulfide should be added to the leachate as a precipitation separating agent for lead.

2. Adding acidic compound into antimony leaching solution prepared according to principle 1, reducing alkalinity of the solution to precipitate 3b₂S₃And Sb₂O₃Precipitation, reaction formula is as follows

The acidic compound added was:

a. acid oxide: CO 2₂、SO₂、SO₃、NO₂，

b. Inorganic acid: h₂SO₄、HNO₃、H₃PO₃，

c. Organic acid: formic acid and acetic acid are added into the mixture,

d. acid salts: NaHSO₄、KHSO₄、NaHSO₃、KHSO₃、NaH₂PO₄。

3. As Ca and Ba have precipitation effect on arsenic and can inhibit the dissolution of selenium and tin, CaS or BaS, CaOH or BaOH and other calcium and barium salts are selected to separate arsenic, selenium and tin.

4. When the acid compound is added to precipitate the antimony, the adding amount of the acid compound is controlled, the arsenic, the selenium, the tin, the mercury and the antimony are separated from the antimony by a fractional precipitation method by utilizing the difference of the pH conditions when the arsenic, the selenium, the tin, the mercury and the antimony are precipitated, and the pH value of a precipitation endpoint is 8.

5. Regeneration and recycling of alkali liquor after precipitation, in the process of using CO₂When the antimony-containing alkaline solution is used as an antimony precipitator, lime with the amount being 1-5 times of the theoretical amount is added into the alkaline solution after antimony is filtered out, and the mixture is stirred at room temperature for 0.5-5 hours to remove CO₂，CO₂Reacting with lime to generate calcium carbonate precipitate, and returning the activated solution to leach antimony ore, wherein the reaction formula is as follows:

the product obtained after the treatment by the process can be used as a high-quality raw material for pyrometallurgy of antimony or other antimony chemical industries. The method can treat antimony minerals with any lead content, lead sulfide in leaching residue can be used as lead concentrate for sale after enrichment. The process is also suitable for the deleading of the artificial antimony oxide powder.

The process operation comprises the following steps:

mineral powder with the granularity of-1 mm to-300 meshes is put into a dissolving tank with a heating sleeve, alkaline leaching liquid (1-10% of sodium sulfide is added when alkali hydroxide is adopted for preparation) is poured, and 1-5% of calcium alkali (CaOH or CaS) or barium alkali (BaOH or BaS) or other calcium barium salt is dissolved into the alkaline leaching liquid if arsenic is removed simultaneously. The concentration of the alkali liquor is 1% -50%, the dosage is 1-10 times of the theoretical dosage, and the solid-liquid ratio is 1: 2-10.

And(3) introducing steam into the jacket to heat the leaching solution, starting the stirrer to stir and dissolve the leaching solution, wherein the temperature range of the leaching solution is from room temperature to the boiling point, and the stirring and dissolving time is 0.5-5 hours.

Filtering the leaching solution after dissolving antimony, piling and recovering lead from filter residues, putting the filtrate into an antimony precipitation tank, adding an acidic compound to precipitate antimony, filtering, washing and drying to obtain an industrial pure product.

And (4) transferring the alkali liquor after antimony precipitation to regeneration treatment according to the type of the precipitant.

Compared with the prior art, the method has the advantages of high separation efficiency, wide application range, simple process and the like, and is particularly suitable for removing lead impurities in antimony minerals and simultaneously removing arsenic, selenium, tin, mercury and other impurities.

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

The embodiment of the invention comprises the following steps:

200 g of mineral powder containing 45.3 percent of antimony, 10.2 percent of lead and 2.3 percent of arsenic is crushed to-120 meshes, the mineral powder is put into a glass jar, 1000 ml of sodium sulfide solution with the concentration of 10 percent is added, 20 g of lime is added, the mixture is heated and stirred on a water bath to be dissolved, the temperature of the solution is 85 ℃, the stirring time is 40 minutes, and then the mixture is filtered to be dry, and filter residue is discarded.

Putting the filtrate in awide-mouth bottle, introducing carbon dioxide from the bottom of the bottle by using a glass guide tube to reduce the pH value of the antimony leaching solution, stopping introducing when the pH value is controlled to be 8, and filtering to dry after the antimony sulfide is completely precipitated.

Washing the antimony sulfide precipitate with water for 2 times, washing with 2% dilute sulphuric acid for one time, washing with water for one time, filtering, drying and drying to obtain the earthy red pure antimony trisulfide block. The product contains 69.5% of antimony, 0.002% of lead and 0.25% of arsenic, and the recovery rate of antimony is up to 90.8%.

And (3) placing the solution after the antimony precipitation into a glass cylinder, adding 150 g of lime, stirring for 2 hours, filtering, discarding filter residues, and using the regenerated active sodium sulfide filtrate for redissolving the lead-antimony-containing ore.

Claims

1. Wet removalThe process for preparing the industrial pure antimony sulfide from the lead, arsenic, selenium, tin and mercury impurities in the antimony minerals is characterized by comprising the following steps of: dissolving antimony mineral in water solution prepared from sodium sulfide, strong alkali hydroxide or their mixture under heating and stirring, treating with acidic compound, precipitating, filtering to obtain solution, and adding lime or SO₂And recycling the mixture after stirring reaction.

2. The process for preparing industrial pure antimony sulfide by removing impurities of lead, arsenic, selenium, tin and mercury in antimony minerals by a wet method according to claim 1, which is characterized by comprising the following steps: the sodium sulfide is Na₂S、K₂S、CaS、BaS、(NH₄)₂S, strong alkali hydroxide is NaOH or KOH, and an acidic compound is NaOH or KOH;

a. acid oxide: CO 2₂、SO₂、SO₃、NO₂，

b. Inorganic acid: h₂SO₄、HNO₃、H₃PO₃，

c. Organic acid: formic acid and acetic acid are added into the mixture,

d. acid salts: NaHSO₄、KHSO₄、NaHSO₃、KHSO₃、NaH₂PO₄。

3. The process for preparing industrial pure antimony sulfide by removing impurities of lead, arsenic, selenium, tin and mercury in antimony minerals by a wet method according to claim 1, which is characterized by comprising the following steps: in the mixed alkali, the content of the sodium sulfide is 1-100%.

4. The process for preparing industrial pure antimony sulfide by removing impurities of lead, arsenic, selenium, tin and mercury in antimony minerals by a wet method according to claim 1, which is characterized by comprising the following steps: adding 1-5% calcium barium salt, calcium alkali (CaOH or CaS) or barium alkali (BaOH or BaS) into the alkaline leaching solution to remove arsenic.

5. The process for preparing industrial pure antimony sulfide by removing impurities of lead, arsenic, selenium, tin and mercury in antimony minerals by a wet method according to claims 1 and 4, which is characterized by comprising the following steps: the concentration of the alkali leaching solution is 1% -50%, the dosage is 1-10 times of the theoretical dosage, the granularity of the dissolved ore is-1 MM to-300M mesh,the solid-liquid ratio is 1: 2-10, the stirring and dissolving temperature is from room temperature to boiling point, and the time is 0.5-5 hours.

6. The process for preparing industrial pure antimony sulfide by removing impurities of lead, arsenic, selenium, tin and mercury in antimony minerals by a wet method according to claims 1 and 4, which is characterized by comprising the following steps: 1-10% of sodium sulfide is added in the preparation of the caustic soda leach solution.

7. The process for preparing industrial pure antimony sulfide by removing impurities of lead, arsenic, selenium, tin and mercury in antimony minerals by a wet method according to claim 1, which is characterized by comprising the following steps: the addition amount of the acidic compound is controlled to be 8 at the pH value of the antimony precipitation endpoint.

8. The process for preparing industrial pure antimony sulfide by removing impurities of lead, arsenic, selenium, tin and mercury in antimony minerals by a wet method according to claims 1 and 7, which is characterized by comprising the following steps: using CO₂When the antimony is used as a precipitator of antimony, lime with the theoretical dosage of 1-5 times is added into the filtrate after antimony is filtered out, and the mixture is stirred for 0.5-5 hours at room temperature.