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氧化锑矿的湿法处理方法及其物理化学研究
康大平
Subtype硕士
Thesis Advisor柯家骏
1989-06-30
Degree Grantor中国科学院研究生院
Abstract锑是一种重要的有色金属,锑及其化合物被广泛应用于工业各部门,如以锑合金的形式应用于制造铅酸蓄电池的铅锑合金栅极,以锑氧化物的形式用于加入化纤织物和塑料中作为阻燃剂的主要成分。中国的锑资源居世界首位,也是世界上锑品产量最多的国家。湖南冷水江市锡矿务局是中国最大的锑基地,生产的锑品在国际市场上颇负盛名。自然界中具有工业价值的锑矿主要有硫化锑矿和氧化锑矿两类。氧化矿的成分一般较复杂,比较难于处理。目前工业上主要以硫化锑矿作为冶炼原料,生产方法可分为火法和湿法两大类。火法炼锑工艺较成熟,但产生的二氧化硫气体对环境污染严重。因此,湿法炼越来越受到重视。湿法炼锑又可分为碱法和酸法两种。碱法是用碱性硫化钢溶液处理锑矿,得到硫代亚锑酸钠溶液,再经电积得到产品金属锑。酸法是在盐酸介质中加入三氯化铁、氯气等做为氧化剂将硫化锑矿氧化浸取,得到三氯化锑的溶液,再通过水解得到锑白(Sb2O3)产品。对于含有高价锑(如Sb2O4、Sb6O13)的氧化锑矿,采用湿法冶炼时,无论是用碱法或用酸法都存在锑浸取率不高的问题。本工作是针对湖南冷水江市锡矿山矿务局提供的的一种含有高价锑的难处理氧化锑矿的利用问题,研究并探讨一种能够有效处理这种氧化锑矿的方法,并结合开展有关冶炼物理化学的研究。首先,通过热力学计算和分析,寻找可能的处理方法,并进行了实验研究。结果表明,氧化锑矿直接用碱法或酸法处理的浸取指标不够高。如将原矿用加碳还原预处理,使高价锑氧化物还原后再用盐酸浸取,锑的浸取率可达95%以上。为了减少碳还原时的处理量和降低碳耗,又试验了原矿先用盐酸浸取,浸取渣加碳还原后再盐酸浸取的方法,锑的浸取率可达93%左右。综合考虑后,提出了盐酸浸取-浸取渣加碳还原后盐酸浸取的建议流程。结合该氧化锑矿的浸取过程,还进行了氧化锑矿盐酸浸取动力学的实验研究,即着重考察Sb2O4在盐酸液中浸取的动力学。结果表明,Sb2O4在盐酸溶液中的溶解过程属于化学反应控制,测得的表观反应活化能值为15.2kcal/mol (63.5kJ/mol)。本工作针对我国含有高价锑的氧化锑矿的湿法处理方法及有关的冶炼物理化学进行了初步探讨,将为进一步深入研究打下基础。
Other AbstractAntimony is one of the important non-ferrous metals. Metallic antimony and antimony compounds are applied in a variety of industries, such as in plastic and textile industries where antimony oxides serve as the main content of fire-proof agents. China is abundent of antimony resource and produces the greatest amount of antimony products in the world. Sulfide ore and oxide ore are two important sorts of antimony ores. Antimony oxide ore often has complicated contents and is comparetively difficult for treating. There are mainly two antimony-producing processes. One is pyrometallurgical process which is a well-developed technology. Another is hydrometallurgical process, which do not generate substantial amounts of hazardous sulfur dioxide like the pyrometallurgical prosess. Therefore the hydrometallurgical processes receive more and more attention. Hydrometallurgcal processes may be divided into basic and acid processes. In the basic process, antimony ore is treated with sodium sulfide solution to obtain sulfa-antimonous sodium which may then be electrolyted for metal antimony product. In the acid process, antimony trichloride solution is obtained through leaching of antimony sulfide ore in hydrogen chloride solution with ferric trichloride or chlorine gas as oxident, then hydrolyzed to produce antimony trioxide. When hydrometallurgical process, no matter which one - the basic or acid process - is employed to treat the antimony oxide ore containing antimonic oxide such as Sb2O4 and Sb6O13, the results of leaching of antimony are unsatisfactory. In order to seek an efficient method to treat the antimony oxide ore, some thermodynamic computation and analysis and experiments have been carried out. The results show that it is impossible to use both of the basic and acid processes to direct leaching of the antimony oxide ore because the percentage of leaching of antimony are less than 70%. However, if pretreatment of carbon reduction is introduced to acid leaching process, the total percentage of leaching of antimony can go up to 93-95%. The aim of carbon reduction is to reduce the antimonic oxide Sb6O13 with carbon at the temperatures of 500-600 ℃ for the next leaching stage with hydrogen chloride solution. It can be applied directly to the antimony oxide ore or to the residue generated from leaching of raw ore of antimony oxide with hydrogen chloride solution. The percentage of leaching of antimony varies mainly according to the leaching results of Sb2O4. Therefore the kinetics of leaching of antimony oxide Sb2O4 has been also studied. The leaching process of Sb2O4 contained in antimony oxide ore in hydrogen chloride solution may be described by a shrinking core model. It has been found that the leaching temperature and the concentration of HCl turned out to be the significant influencing factors. The apparant activation energy for the leaching reaction was determined to be 15.2 kcal/mol (63.5 kJ/mol) within the temperature region of 50 to 90 ℃. The leaching process was controlled by the rate of the chemical reaction. The aim of the present work is to investigate from a practical standpoint the hydrometallurgical treatment of such sort of antimony oxide ore which contains antimonic oxide, and the physical chemistry of leaching process concerned. This may be useful for further research work.
Pages105
Language中文
Document Type学位论文
Identifierhttp://ir.ipe.ac.cn/handle/122111/8399
Collection研究所(批量导入)
Recommended Citation
GB/T 7714
康大平. 氧化锑矿的湿法处理方法及其物理化学研究[D]. 中国科学院研究生院,1989.
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