阅读说明：本技术 一种酒石酸体系浸出氧化锑物料及电积生产金属锑的方法 (Method for leaching antimony oxide material by tartaric acid system and producing metallic antimony by electrodeposition ) 是由 叶龙刚 欧阳臻 刘凌博 胡宇杰 夏志美 肖利 于 2019-11-05 设计创作，主要内容包括：本发明属于有色金属冶金领域,具体公开了一种酒石酸体系浸出氧化锑物料及电积生产金属锑的方法。该方法首先采用酒石酸-酒石酸钠对氧化锑物料进行清洁浸出,得富锑浸出液和浸出渣,对浸出液进行降温除杂净化,净化液进入隔膜电积电积锑,得锑片和酒石酸电解液,所得的电解液返回对氧化锑进行浸出。本发明的工艺为对氧化锑物料新的分离提取方法,取消了传统工艺中采用的强酸和强碱,采用更为温和、可食性的酒石酸体系,减少设备腐蚀和改善生产环境,锑的回收率达96%以上,可实现各类氧化锑资源的清洁提取。(The invention belongs to the field of nonferrous metallurgy, and particularly discloses a method for leaching an antimony oxide material by a tartaric acid system and producing metallic antimony by electrodeposition. The method comprises the steps of firstly, cleanly leaching antimony oxide materials by tartaric acid-sodium tartrate to obtain antimony-rich leachate and leaching residues, cooling the leachate, removing impurities and purifying, enabling the purified solution to enter a diaphragm to electrodeposit antimony to obtain antimony sheets and tartaric acid electrolyte, and returning the obtained electrolyte to leach the antimony oxide. The process of the invention is a new separation and extraction method for antimony oxide materials, strong acid and strong base adopted in the traditional process are eliminated, a milder and edible tartaric acid system is adopted, the corrosion of equipment is reduced, the production environment is improved, the recovery rate of antimony is more than 96%, and the clean extraction of various antimony oxide resources can be realized.)

1. A tartaric acid system antimony oxide leaching material and electrodeposition method for producing metallic antimony is characterized by comprising the following steps:

s1, leaching: leaching antimony oxide material by using a tartaric acid-tartrate mixed solution, and separating to obtain filtrate and filter residue;

s2, cooling and impurity removal: cooling and removing impurities from the filtrate produced in the step S1, and filtering out crystals to obtain a purified solution;

s3, diaphragm electrodeposition antimony and leaching agent regeneration: and (4) carrying out diaphragm electrodeposition on the purified liquid obtained in the step S2, producing antimony sheets and electrolyte at the cathode, and returning the electrolyte to the step S1 for leaching.

2. The method for leaching antimony oxide material and producing metallic antimony by electrodeposition with the tartaric acid system as claimed in claim 1, wherein the liquid-solid ratio in the leaching process of step S1 is 3 ~ 15: 1, the temperature is 30 ~ 80 ℃, the time is 1 ~ 5h, and the stirring speed is 200 ~ 800 rpm.

3. The method for leaching antimony oxide material and producing metallic antimony by electrodeposition by using the tartaric acid system as claimed in claim 1 or 2, wherein the antimony oxide material is antimony sulfide ore roasting material, antimony oxide ore or antimony-containing soot, and the content of antimony is higher than 30%.

4. The method for leaching antimony oxide material and producing metallic antimony by electrodeposition by using the tartaric acid system as claimed in claim 1 or 2, wherein in step S1, the total concentration of tartrate radical groups in the mixed solution of tartaric acid and tartrate salt is 80 ~ 300 g/L.

5. The method for leaching antimony oxide material and producing metallic antimony by electrodeposition through the tartaric acid system according to claim 4, wherein in the step S1, the mixed tartaric acid-tartrate solution is potassium hydrogen tartrate solution or sodium hydrogen tartrate solution, and preferably the molar ratio of acid to salt is 1: 0.5 ~ 2.

6. The method for leaching antimony oxide material and producing metallic antimony by electrodeposition with the tartaric acid system as claimed in claim 1, wherein in step S2, the temperature is reduced to 18 ~ 30 ℃ during the temperature reduction and impurity removal process.

7. The method for leaching antimony oxide materials by using the tartaric acid system and producing metallic antimony by electrodeposition according to claim 1 or 6, wherein in the step S2, the temperature is reduced in the process of temperature reduction and impurity removal, and then the holding time is 10 ~ 30 h.

8. The method for leaching antimony oxide materials and producing metallic antimony by electrodeposition with the tartaric acid system as claimed in claim 1, wherein in step S3, the diaphragm electrolysis employs an anion exchange membrane, the anode is graphite or titanium plate, and the cathode is titanium plate or stainless steel plate.

9. The method for leaching antimony oxide material and producing metallic antimony by electrodeposition with tartaric acid system as claimed in claim 1 or 8, wherein in step S3, the electrowinning process current intensity is 100 ~ 350A/m²The time is 10 ~ 30h, and the pole pitch is 20 ~ 60 mm.

10. The method for leaching antimony oxide material and producing metallic antimony by electrodeposition with the tartaric acid system as claimed in claim 1, wherein in step S3, the obtained electrolyte is returned to the leaching process of step S1, and tartaric acid is added, wherein the addition amount of tartaric acid is 4 ~ 30 g per liter of electrolyte.

Technical Field

The invention belongs to the field of nonferrous metallurgy, and particularly relates to a method for leaching an antimony oxide material by a tartaric acid system and producing metallic antimony by electrodeposition.

Background

Antimony is a rare heavy metal, has wide application in the fields of alloy materials, chemical flame retardance and building materials, has been exploited and smelted for more than one hundred years, and has been produced for more than one hundred years, wherein the smelting raw material of antimony is mainly sulfide ore, and antimony-containing soot is produced in the smelting process of copper, lead, tin and bismuth, and is mainly antimony oxide. At present, the main production method still continues to use the blast furnace volatile roasting (smelting) -reduction smelting process for over fifty years, and the process has strong adaptability to raw materials, is suitable for treating high-grade antimony concentrate and produces low-concentration SO₂The defects of high smoke and energy consumption, large smoke dust amount and the like are overcome, and the process is not suitable for the development requirement along with the increasing of the environmental protection requirement. The new pyrometallurgical method is studied in a large amount, but at present, no good industrial application exists, and meanwhile, the pyrometallurgical method cannot avoid the generation of smoke and dust containing antimony, arsenic and lead.

Therefore, the research on wet antimony smelting has not been stopped, and two process routes of acid leaching and alkaline leaching are mainly adopted. Wet process for leaching Na from sodium sulfide₃SbS₃The solution electrodeposition method is most representative, the process has strong adaptability to raw materials, has short industrial production and is closed due to the problems of high alkali consumption, low current efficiency and the like. The acid method is mainly used for producing antimony white by a chlorination-hydrolysis method, has the problems of solution recycling and equipment corrosion prevention, and is seriously corroded in a newly-built factory for two to three years. Therefore, the development of a new clean and nontoxic antimony wet refining process is a problem which is urgently needed to be solved by the industry.

The patent provides that the antimony oxide material is leached by tartaric acid and the salt thereof after screening the organic compound structure of antimony and considering the characteristics of organic acid to obtain tartaric acid antimony salt, and the metal antimony can be directly produced by electrolysis. Tartaric acid and its salt are clean, non-toxic and extremely low in corrosivity, and can improve production environment; the tartaric acid antimony salt is soluble and nontoxic, is often used as a medicine, and is directly subjected to electrodeposition extraction to realize the production of metal antimony and the recycling of electrolyte. The method can be applied to leaching-electrodeposition of the ash obtained by oxidizing and roasting antimony sulfide ore, can also be used for extracting antimony from antimony-containing ash generated in the smelting process of other heavy metals, and has strong applicability and obvious cleaning property.

Disclosure of Invention

Aiming at the problems in the background technology, the invention provides a tartaric acid system antimony oxide leaching material and a method for producing metal antimony by electrodeposition, which have the advantages of strong process selectivity, no corrosiveness, environmental friendliness and emission reduction.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a tartaric acid system antimony oxide leaching material and electrodeposition method for producing metal antimony comprises the following steps:

s1, leaching: leaching antimony oxide materials by using a tartaric acid-tartrate mixed solution, selectively dissolving antimony oxide to obtain antimony potassium/sodium tartrate, wherein most of the antimony potassium/sodium tartrate is insoluble accompanying substances, separating to obtain filtrate and filter residues, discarding the filter residues, and allowing the filtrate to enter the next step;

s2, cooling and impurity removal: and (4) cooling the filtrate produced in the step S1, and filtering out crystals to obtain a purified solution. Performing cooling crystallization and impurity removal by utilizing the difference that the solubility of potassium/sodium antimony tartrate is high and the solubility of tartrate of metals such as copper, lead, bismuth and the like is extremely low to obtain a pure potassium/sodium antimony tartrate solution;

s3, diaphragm electrodeposition antimony and leaching agent regeneration: and D, carrying out diaphragm electrodeposition on the purified liquid obtained in the step S2, discharging the antimony at the cathode in a complex anion form to produce antimony sheets and potassium/sodium hydrogen tartrate electrolyte, and returning the electrolyte to the step S1 for leaching.

The invention scientifically adopts a leaching system, has obvious cleaning property in the whole process, and fully utilizes material flow and energy flow.

The method firstly carries out the complexing leaching of the antimony oxide by using Sb₂O₃Forming tartaric acid antimony salt with tartaric acid and salt to realize selective leaching of antimonyIn the process, the following reactions mainly occur:

Sb₂O₃+3C₄H₆O₄＝Sb₂(C₄H₄O₄)₃+3H₂O(1)

Sb₂O₃+K₂C₄H₄O₄+C₄H₆O₄＝Sb₂K₂(C₄H₂O₄)₂+3H₂O(2)

Sb₂O₃+Na₂C₄H₄O₄+C₄H₆O₄＝Sb₂Na₂(C₄H₂O₄)₂+3H₂O(3)

tartrate radical has strong complexing ability with antimony, and the obtained Sb₂K₂(C₄H₂O₄)₂Or Sb₂Na₂(C₄H₂O₄)₂The solubility is high, so that a small amount of leached copper, lead, bismuth and the like can be removed by cooling crystallization. Meanwhile, tartaric acid is weak acid, the pH value of a solution system is more than 2, and the impurity elements such as arsenic, tin, iron and the like in the antimony oxide material are difficult to leach, so that the selective leaching of antimony is realized.

And (4) after impurity removal and purification, carrying out diaphragm electrodeposition on the solution to obtain an antimony sheet at the cathode, wherein the antimony sheet is a final product, carrying out oxygen evolution reaction at the anode to obtain potassium/sodium hydrogen tartrate, and returning to the leaching step in the first step. The following reactions mainly occur in the process:

cathode: [ Sb ]₂(C₄H₂O₄)₂]^2-+6e-＝2Sb+2(C₄H₂O₄)₂ ^4- (4)

Anode: 2H₂O-4e^-＝4H⁺+O₂(g) (5)

And (3) total reaction:

→4(C₄H₄O₄)₂ ^2-+3O₂(g)

according to the method, the whole process realizes the cyclic clean extraction of antimony oxide materials, the antimony oxide is selectively leached through a tartaric acid complex reaction, the leaching solution is subjected to deep impurity removal through cooling and purification, and finally, the production of metal antimony and the regeneration of a leaching agent are realized through diaphragm electrolysis.

As one of preferable schemes, the liquid-solid ratio in the leaching process of step S1 is 3-15: 1, the temperature is 30-80 ℃, the time is 1-5 h, and the stirring speed is 200-800 rpm; further preferably, the liquid-solid ratio is 5-8: 1, the temperature is 40-60 ℃.

As one of the preferable schemes, in step S1, the antimony oxide material is an antimony sulfide ore calcine, an antimony oxide ore or an antimony-containing soot, the antimony content is higher than 30%, and more preferably the antimony sulfide ore calcine.

In a preferable embodiment, in step S1, the total concentration of tartrate groups in the mixed solution of tartaric acid and tartrate salts is 80 to 300g/L, and more preferably 100 to 200 g/L.

As one preferable embodiment, in step S1, the tartaric acid-tartrate mixed solution is a potassium tartrate-hydrogen tartrate solution or a sodium tartrate-hydrogen tartrate solution; more preferably, a tartaric acid-sodium hydrogen tartrate mixed solution. Further preferably, the molar ratio of acid to salt is 1: 0.5 to 2.

As one preferable scheme, in the step S2, the temperature is reduced to 18-30 ℃ in the process of temperature reduction and impurity removal.

As one preferable scheme, in the step S2, the temperature is reduced in the process of temperature reduction and impurity removal, and then the heat preservation time is 10-30 h.

In a preferable embodiment, in step S3, the diaphragm electrolysis uses an anion exchange membrane, the anode is graphite or a titanium plate, and the cathode is a titanium plate or a stainless steel plate.

Preferably, in step S3, the current intensity in the electrodeposition process is 100-350A/m²The time is 10-30 h, and the polar distance is 20-60 mm; more preferably, the current intensity is 100～200A/m²。

In a preferable scheme, in the step S3, the obtained electrolyte returns to the leaching process in the step S1, tartaric acid needs to be added, and the adding amount of the tartaric acid is 4-30 g per liter of the electrolyte.

Compared with the prior art, the invention has the following beneficial effects:

(1) the process of the invention is a new separation and extraction method for antimony oxide materials, strong acid and strong base adopted in the traditional process are cancelled, the whole flow of leaching, purification and electrodeposition of the antimony oxide materials is creatively adopted in a milder and edible tartaric acid-tartrate mixed acid system, the low toxicity is proved by the wide application of the tartaric acid in the food, beverage and medicine industries, and compared with the prior method of separating and extracting the antimony oxide materials by FeCl₃、FeCl₃-HCl、Na₂The new system of the S-NaOH leaching system is milder and cleaner, has stronger selectivity and small corrosivity on production equipment, so that the existing leaching and high-selectivity antimony separation and extraction can be realized, the recovery rate of antimony can reach 97.74 percent, and the clean extraction of various antimony oxide resources can be realized.

(2) The method of the invention utilizes the high water solubility of the tartaric acid antimony salt, adopts simple temperature reduction and impurity removal measures to crystallize and remove other metal impurities, and obtains the high-purity pre-electrodeposition solution. The electrowinning of antimony is directly carried out in a tartaric acid system, the produced metal antimony and the regenerated electrolyte are returned to the leaching process, and the solution circulation in the whole process is realized. The whole process is clean and efficient, the reagent consumption is low, the industrial production is easy, and the clean extraction of various antimony oxide materials can be realized.

Drawings

FIG. 1 is a process flow chart of the method for leaching antimony oxide materials by a tartaric acid system and producing metallic antimony by electrodeposition.

FIG. 2 is a diagram of an antimony plate produced in example 1 of the present invention.

FIG. 3 is an XRD pattern of an antimony plate produced in example 1 of the present invention.

Detailed Description

In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.

Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.