CN1462811A - Catalytic oxidation method for preparing sodium pyroantimonate from antimony ore - Google Patents
Catalytic oxidation method for preparing sodium pyroantimonate from antimony ore Download PDFInfo
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- CN1462811A CN1462811A CN03128127A CN03128127A CN1462811A CN 1462811 A CN1462811 A CN 1462811A CN 03128127 A CN03128127 A CN 03128127A CN 03128127 A CN03128127 A CN 03128127A CN 1462811 A CN1462811 A CN 1462811A
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- antimony
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- antimony ore
- pyroantimonate
- sodium pyroantimonate
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
A process for preparing sodium pyroantimonate from antimony ore by catalytic oxidizing method includes extracting the liquid extract from antimony ore, adding efficient catalyst (anthraquinone or its derivative), and introducing air or oxygen gas to it for oxidizing the soluble antimony compound to become sodium pyroantimonate. Its advantages are low requirement to grade of antimony ore, and high oxidizing efficiency.
Description
Technical Field
The present invention belongs to the field of catalytic oxidation process of preparing sodium pyroantimonate from antimony ore.
Background
There are various processes for the preparation of sodium pyroantimonate, which can be divided into two categories, depending on the starting materials used:
the first kind uses antimony trioxide (including antimony white and antimony oxide powder) as raw material to prepare sodium pyroantimonate. The related technologies include: the Chinese patent application No. 90105558 discloses a process for producing sodium pyroantimonate by using crude antimony powder as raw material and adopting chlorine (salt) oxidation methods of hydrochloric acid dissolution, chlorine or chlorate oxidation, hydrolysis, neutralization and the like. Chinese patent No. 85102490 and Chinese patent application No. 87102082 disclose a process for directly preparing sodium pyroantimonate by using antimony white as a raw material and oxidizing hydrogen peroxide; the patent application<hydrated sodium antimonate industrial production process>(application No. 96118121) discloses an industrial production process of hydrated sodium potassium antimonate, which is prepared by taking antimony oxide powder as a raw material and adopting potassium hydroxide for oxidation. The raw materials adopted by the methods are intermediate products or finished products in the antimony pyrometallurgy process, have high requirements on the quality of the raw materials, and consume a large amount of oxidant, so that the production cost is higher, the market lacks competitiveness, and the raw materials are gradually rejected.
The second kind is wet process of preparing sodium pyroantimonate with refined antimony ore or high lead antimony ore as material and through leaching with sodium sulfide and air oxidation. The patent application 'wet process for preparing sodium pyroantimonate from antimony concentrate' (application No. 86101108) discloses a method for preparing sodium pyroantimonate from antimony concentrate, wherein the catalyst adopted in the method is a compound of cupric salt and benzenediol. As the copper salt containing heavy metal is used, part of the heavy metal is inevitably precipitated into the sodium pyroantimonate product in the reaction process, so that the appearance and the internal quality of the product are difficult to reach the domestic and foreign standards. Therefore, it is difficult to industrially apply the present invention.
The patent application (application No. 94115380) discloses a method for preparing sodium pyroantimonate from antimony sulfide ore and a special device thereof, which adopts air oxidation without adding a catalyst. From the disclosure, it is clear that the process is an advance over the first class of processes for the preparation of sodium pyroantimonate. The method has the defects that special reaction equipment is needed, the height of the equipment is required to be about 25 meters, and the manufacturing cost is higher; on the other hand, the reaction time is longer, about 40 hours, the pressure is higher, the energy consumption is increased, and the production cost is increased.
Disclosure of Invention
The invention aims to solve the technical problems of reducing the requirements of soluble antimonide on process conditions and equipment during oxidation in the leaching solution, accelerating the oxidation speed and reducing the production cost of sodium pyroantimonate.
The invention solves the technical problems by adopting the following technical scheme: adding a small amount of high-efficiency catalyst into the leaching solution of the antimony ore containing soluble antimony compounds, and blowing air or oxygen to oxidize the soluble antimony compounds into insoluble sodium pyroantimonate. The catalyst can be anthraquinone or its derivatives, such as 1.5-dianthraquinone sodium xanthate, 2.6(2.7) -dianthraquinone sodium xanthate, etc. The weight of the catalyst added may be one ten thousandth to one hundredth of the weight of the antimony ore.
The method for preparing sodium pyroantimonate from antimony ore has the advantages of low requirement on the quality of antimony ore raw materials, short oxidation reaction time, high oxidation efficiency and low production cost, and the mother liquor from which the sodium pyroantimonate product is separated can be further processed into sodium thiosulfate pentahydrate through concentration and crystallization, so that harmful wastewater is not generated to pollute the environment.
Detailed Description
The method for preparing the sodium pyroantimonate is carried out according to the following steps:
crushing antimony ore or flotation antimony ore, adding a sodium sulfide solution or a mixed solution of sodium sulfide and sodium hydroxide, stirring and reacting for 0.1-5 hours at the temperature of 50-130 ℃, so that antimony in the antimony ore reacts with the sodium sulfide and the sodium hydroxide to generate a water-soluble antimony compound, and carrying out solid-liquid separation on the solution and waste residues. The soluble antimony compound solution obtained after separation was used for the next reaction.
In the sodium sulfide or the mixed solution thereof for leaching antimony ore, the concentration of the sodium sulfide is 50-300 g/L, and the concentration of the sodium hydroxide is 0-30 g/L. The addition amount of the sodium sulfide is 0.64-1.50 tons per ton of antimony.
The soluble antimony compound being predominantly Na3SbS3And Na3SbO3The reaction process is complicated, and one of the main reaction principles is as follows:
secondly, placing the antimony compound solution obtained in the first step into a common reactor, adding a small amount of high-efficiency catalyst, controlling the temperature at 60-120 ℃, blowing air or oxygen at normal pressure or low pressure to oxidize soluble antimony compounds into insoluble sodium pyroantimonate, and obtaining a finished product of the sodium pyroantimonate throughsolid-liquid separation, washing and drying.
The common reactor can be a glass tube or a steel tube in a laboratory, and can be a conventional reactor in industrial production; the heating mode adopts electric heating, steam heating or other modes.
The high-efficiency catalyst used in the oxidation is anthraquinone or its derivative soluble in water. Such as 1.5-dianthraquinone sodium xanthate, 2.6(2.7) -dianthraquinone sodium xanthate, or mixtures thereof.
The addition amount of the catalyst is generally one ten thousandth to one hundredth of the weight of the antimony ore.
The reaction time is generally 4 to 10 hours.
The second step reaction process is more complicated, and one of the main reaction principles is as follows:
example 1:
adding solution 1.2L containing sodium sulfide 120g/L and sodium hydroxide 12g/L into 450g of high-lead antimony ore containing 27.5% of antimony and 28.5% of lead, stirring and reacting at 100 ℃ for 1.5 hours, filtering, adding 2.6 g of dianthraquinone xanthate into filtrate, transferring the solution into a steel pipe with the length of 2 meters and the diameter of 50mm, blowing air or oxygen, controlling the temperature to be about 95 ℃, reacting for 6.5 hours, ensuring that the antimony precipitation rate reaches 99.5%, filtering, washing and drying to obtain 205 g of sodium pyroantimonate product. The product quality analysis result is as follows: 49.15% of stibium, 12.80% of sodium oxide, 0.0011% of lead, 0.005% of arsenic, 0.0056% of iron and 0.001% of copper.
Example 2:
adding solution 1.2L containing sodium sulfide 120g/L and sodium hydroxide 12g/L into antimony sulfide concentrate containing antimony 55% 220g, stirring and reacting for 50 minutes at 100 ℃, filtering, adding 2.6 g of dianthraquinone xanthate into filtrate, transferring into a steel pipe with the length of 2 meters and the diameter of 50mm, blowing air or oxygen, controlling the temperature to be about 95 ℃, reacting for 7 hours, ensuring that the antimony precipitation rate of the solution reaches 99.5%, filtering, washing and drying to obtain 210 g of sodium pyroantimonate product. The product quality analysis result is as follows: 49.10% of stibium, 12.70% of sodium oxide, 0.0014% of lead, 0.003% of arsenic, 0.0047% of iron and 0.001% of copper.
Claims (3)
1. A process for preparing sodium pyroantimonate from antimony ore by catalytic oxidation includes such steps as adding sodium sulfide solution or the mixture of sodium sulfide and sodium hydroxide to antimony ore powder, immersing to obtain water-soluble antimony compound, solid-liquid separation, blowing air or oxygen to the liquid, oxidizing the soluble antimony compound to obtain insoluble sodium pyroantimonate, solid-liquid separation, washing and drying.
2. The process for preparing sodium pyroantimonate from antimony ore by catalytic oxidation according to claim 1, wherein the catalyst is anthraquinone or its derivative, such as 1.5-dianthraquinone xanthate, 2.6(2.7) -dianthraquinone xanthate, etc.
3. The process for preparing sodium pyroantimonate from antimony ore by catalytic oxidation according to claim 1 or 2, wherein the amount of the catalyst added is one ten thousandth to one hundredth of the weight of antimony ore.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031281273A CN1228462C (en) | 2003-06-04 | 2003-06-04 | Catalytic oxidation method for preparing sodium pyroantimonate from antimony ore |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB031281273A CN1228462C (en) | 2003-06-04 | 2003-06-04 | Catalytic oxidation method for preparing sodium pyroantimonate from antimony ore |
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| CN1462811A true CN1462811A (en) | 2003-12-24 |
| CN1228462C CN1228462C (en) | 2005-11-23 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912125A (en) * | 2012-10-29 | 2013-02-06 | 云南锡业集团有限责任公司研究设计院 | Method for separating lead and antimony in antimony-containing lead concentrates |
| CN107326188A (en) * | 2017-06-29 | 2017-11-07 | 郴州市金贵银业股份有限公司 | A kind of method for preparing sodium pyroantimonate with leaded silver-colored arsenic antimony cigarette ash |
| CN108517404A (en) * | 2018-04-25 | 2018-09-11 | 广西大学 | The method for preparing sodium pyroantimonate as catalyst air oxidation using plant polyphenol |
| CN114574716A (en) * | 2022-02-28 | 2022-06-03 | 中南大学 | Method for removing arsenic from antimony-containing high-arsenic soot and recovering valuable antimony |
| CN115159570A (en) * | 2022-07-21 | 2022-10-11 | 株洲安特新材料科技有限公司 | Preparation method of efficient environment-friendly sodium pyroantimonate |
-
2003
- 2003-06-04 CN CNB031281273A patent/CN1228462C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912125A (en) * | 2012-10-29 | 2013-02-06 | 云南锡业集团有限责任公司研究设计院 | Method for separating lead and antimony in antimony-containing lead concentrates |
| CN102912125B (en) * | 2012-10-29 | 2014-10-15 | 云南锡业集团有限责任公司研究设计院 | Method for separating lead and antimony in antimony-containing lead concentrates |
| CN107326188A (en) * | 2017-06-29 | 2017-11-07 | 郴州市金贵银业股份有限公司 | A kind of method for preparing sodium pyroantimonate with leaded silver-colored arsenic antimony cigarette ash |
| CN107326188B (en) * | 2017-06-29 | 2019-03-08 | 郴州市金贵银业股份有限公司 | A method of sodium pyroantimonate is prepared with leaded silver-colored arsenic antimony cigarette ash |
| CN108517404A (en) * | 2018-04-25 | 2018-09-11 | 广西大学 | The method for preparing sodium pyroantimonate as catalyst air oxidation using plant polyphenol |
| CN108517404B (en) * | 2018-04-25 | 2020-01-07 | 广西大学 | Method for preparing sodium pyroantimonate by catalyzing air oxidation with plant polyphenol as catalyst |
| CN114574716A (en) * | 2022-02-28 | 2022-06-03 | 中南大学 | Method for removing arsenic from antimony-containing high-arsenic soot and recovering valuable antimony |
| CN115159570A (en) * | 2022-07-21 | 2022-10-11 | 株洲安特新材料科技有限公司 | Preparation method of efficient environment-friendly sodium pyroantimonate |
| CN115159570B (en) * | 2022-07-21 | 2023-08-22 | 株洲安特新材料科技有限公司 | Preparation method of efficient and environment-friendly sodium pyroantimonate |
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| CN1228462C (en) | 2005-11-23 |
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