白云鄂博尾矿加碳氯化反应研究
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摘要
包头白云鄂博共生矿是目前世界上已发现的最大的以铁、稀土、铌为主的大型多金属共生矿床。是我国稀土工业的主要原料基地。该矿组成复杂、矿物的物理化学性质也非常复杂。包钢选矿厂自建立以来,由于工艺技术条件的限制和选铁后的相对富集,使所产生的尾矿中的稀土氧化物(以REO计)平均品位达到8%左右,这几乎与原矿中的稀土品位相当,价值十分可观。大量的尾矿堆弃在尾矿库中造成极大浪费,又破坏周围生态环境。对尾矿中的稀土、铁等矿物进行绿色化学提取是十分必要的,既减少资源浪费又能大幅度的提高矿山企业的经济效益。
氯化法分离稀土矿是基于在高温下用氯气与矿物发生化学作用,使其中的元素生成氯化物,再利用各种元素氯化物挥发性不同及水溶性不同将其分离。碳酸钠焙烧法是以碳酸钠作为分解剂,通过高温焙烧使稀土矿中稀土氟碳酸盐和稀土磷酸盐与Na2CO3作用分解生成稀土氧化物和可溶性的磷酸稀土复盐,同时铈由三价氧化成为四价,达到分解富集稀土的目的,为后续冶金加工提供良好原料。
目前,从氟碳铈矿中提取稀土所选用的分解剂主要有：MgO、Na2CO3、SiCl4、NH4Cl。本论文以白云鄂博尾矿为研究对象,结合氯化法和碳酸钠焙烧法分解两种方法,以碳酸钠作分解剂,针对包钢选矿厂尾矿中稀土的化学提取设计了两套工艺：(1)尾矿碳热氯化除杂处理后以SiCl4为脱氟剂的加碳氯化法。经过低温氯化预处理后的尾矿,其中的铁、钙、钡、镁、钾、锰等元素大部分都以氯化物除去,从而提高了尾矿中稀土的品位。而在低温下稀土的氯化率极低,主要还是以稀土磷酸盐、稀土氟氧化物、少量稀土氟碳酸盐、少量的氟化稀土的形态存在,以SiCl4作为脱氟剂氯化法分解稀土尾矿是基于在高温下用氯气与矿物发生化学作用,使其中的元素生成氯化物。其中脱氟剂SiCl4能显著地提高了稀土尾矿的氯化率。(2)尾矿经碳酸钠焙烧分解预处理后进行碳热氯化反应。通过混入碳酸钠高温焙烧使尾矿中的稀土氟碳酸盐、稀土磷酸盐与Na2CO3发生分解反应生成稀土氧化物,经过水洗、酸洗处理后作为碳热氯化制取稀土氯化物的良好原料。
在第一种情况下考察了不同温度氯化后尾矿中各元素的氯化百分率,其中铁、钙、钡、锰等元素在540℃氯化反应2h后,氯化率都在80%以上,水不溶渣的X射线衍射结果表明：Fe2O3的特征峰已经消失,而CaF2的特征峰也大量降低。氯化后的水不溶物以SiCl4作为脱氟剂进行二次氯化,稀土回收率在600℃可达92%。
在第二种情况下考察了经过焙烧后不同氯化温度对尾矿中稀土元素氯化率的影响。稀土的回收率在500℃的低温下达到77%。
Baiyunebo Ore (located in Baotou) which contains iron, rare earth, and niobium, is the world's largest polymetallic intergrowth ore, and the main raw material base of the nation's rare earth industry. The composition, physical and chemical properties of the ore are extremely complicated. Because of the technology limitations and the relative enrichment after iron separations, the rare earth oxides (REO) of the tailings generated by the concentrator of Baotou Iron & Steel Co. Ltd. has reached an average grade of about 8% since its establishment. The value of the tailings is very impressive because the REO grade is nearly equal to the raw ore. Abandoning large quantity of tailings in the tailing dam is a great waste and destruction of the surrounding ecological environment. So it is very necessary to extract the rare earths, iron and other minerals from the tailings by green chemistry methods, not only for waste reduction but also great promotion of the economic benefits of mining enterprises.
Chlorination method was based on the reactions of chlorine and minerals at high temperature to form chlorides, and made use of different volatility and water-solubility of minerals to separate the chloride products. In the sodium carbonate roasting method, sodium carbonate was used as de-fluorination agent. Mixtures were roasted at high temperature, making rare-earth fluoride carbonate and rare earth phosphate reacted with sodium carbonate to form rare earth oxides and rare earth phosphate-soluble salts. At the same time trivalent cerium oxide changed to four price cerium oxide reaching the purpose of de-fluorination and enrichment of rare earths, and then provided a good metallurgical processing of raw materials. At present, the major de-fluorination agents which had been used to extract rare earths from bastnaesite concentrate were MgO, Na2CO3, SiCl4 and NH4Cl. In this paper, the tailings produced by the concentrator of Baotou Iron & Steel Co. Ltd were researched by combining the sodium carbonate roasting method and the chloride method, and using sodium carbonate as de-fluorination agent. Two new processes were designed for Bao Steel's Concentrator tailings'green extraction of rare earths as follows:(1) The tailings were treated with carbochlorination reaction, then react with SiCl4. After the chloride pretreatment of tailings at low temperature, most Fe, Ca, Ba, Mg, K, Mn and other elements' chlorides were removed, thus the grade of rare earths in the tailings was enhanced. The chloride rate of rare earths was low at low-temperature, the main products were rare earth phosphate, rare earth fluo-oxides, a small amount of rare earth fluoride carbonates, and rare earth fluorides. Carbochlorination with SiCl4 as de-fluorination agent greatly enhanced the conversion percent. (2) The tailings were roasted with sodium carbonate for de-fluorination pretreatment and then reacted with carbon and chlorine to from rare earth chlorides. Roasting by mixing sodium carbonate with tailings to make the rare earth fluoride carbonate, rare earth phosphate and Na2CO3 de-fluorination reaction to get rare earth oxides at high-temperature. Roasted with sodium carbonate at high temperature, rare earth oxides were prepared by de-fluorination reaction among the rare earth fluoride carbonate, rare earth phosphate and Na2CO3. Then after washing and pickling, treated the products with carbochlorination reaction to form rare earth chlorides.
In the first case we studied the conversion percent of different elements after carbochlorination. The conversion percents of elements like Fe, Ca, Ba, Mn were more than 80%. XRD analysis of residue showed that the characteristic peaks of Fe2O3 and CaF2 substantially decreased, which indicates that Fe2O3 and CaF2 had been mostly removed. After the first step carbochlorination, the residue attended the second step carbochlorination with SiCl4 as de-fluorination agent. The recovery rate of rare earths was 92 percent.
In the second case we studied the conversion percent of some elements which first treated with sodium carbonate roasting before carbochlorination. Rare earth recovery was 77 percent at 500℃.
氯化法分离稀土矿是基于在高温下用氯气与矿物发生化学作用,使其中的元素生成氯化物,再利用各种元素氯化物挥发性不同及水溶性不同将其分离。碳酸钠焙烧法是以碳酸钠作为分解剂,通过高温焙烧使稀土矿中稀土氟碳酸盐和稀土磷酸盐与Na2CO3作用分解生成稀土氧化物和可溶性的磷酸稀土复盐,同时铈由三价氧化成为四价,达到分解富集稀土的目的,为后续冶金加工提供良好原料。
目前,从氟碳铈矿中提取稀土所选用的分解剂主要有：MgO、Na2CO3、SiCl4、NH4Cl。本论文以白云鄂博尾矿为研究对象,结合氯化法和碳酸钠焙烧法分解两种方法,以碳酸钠作分解剂,针对包钢选矿厂尾矿中稀土的化学提取设计了两套工艺：(1)尾矿碳热氯化除杂处理后以SiCl4为脱氟剂的加碳氯化法。经过低温氯化预处理后的尾矿,其中的铁、钙、钡、镁、钾、锰等元素大部分都以氯化物除去,从而提高了尾矿中稀土的品位。而在低温下稀土的氯化率极低,主要还是以稀土磷酸盐、稀土氟氧化物、少量稀土氟碳酸盐、少量的氟化稀土的形态存在,以SiCl4作为脱氟剂氯化法分解稀土尾矿是基于在高温下用氯气与矿物发生化学作用,使其中的元素生成氯化物。其中脱氟剂SiCl4能显著地提高了稀土尾矿的氯化率。(2)尾矿经碳酸钠焙烧分解预处理后进行碳热氯化反应。通过混入碳酸钠高温焙烧使尾矿中的稀土氟碳酸盐、稀土磷酸盐与Na2CO3发生分解反应生成稀土氧化物,经过水洗、酸洗处理后作为碳热氯化制取稀土氯化物的良好原料。
在第一种情况下考察了不同温度氯化后尾矿中各元素的氯化百分率,其中铁、钙、钡、锰等元素在540℃氯化反应2h后,氯化率都在80%以上,水不溶渣的X射线衍射结果表明：Fe2O3的特征峰已经消失,而CaF2的特征峰也大量降低。氯化后的水不溶物以SiCl4作为脱氟剂进行二次氯化,稀土回收率在600℃可达92%。
在第二种情况下考察了经过焙烧后不同氯化温度对尾矿中稀土元素氯化率的影响。稀土的回收率在500℃的低温下达到77%。
Baiyunebo Ore (located in Baotou) which contains iron, rare earth, and niobium, is the world's largest polymetallic intergrowth ore, and the main raw material base of the nation's rare earth industry. The composition, physical and chemical properties of the ore are extremely complicated. Because of the technology limitations and the relative enrichment after iron separations, the rare earth oxides (REO) of the tailings generated by the concentrator of Baotou Iron & Steel Co. Ltd. has reached an average grade of about 8% since its establishment. The value of the tailings is very impressive because the REO grade is nearly equal to the raw ore. Abandoning large quantity of tailings in the tailing dam is a great waste and destruction of the surrounding ecological environment. So it is very necessary to extract the rare earths, iron and other minerals from the tailings by green chemistry methods, not only for waste reduction but also great promotion of the economic benefits of mining enterprises.
Chlorination method was based on the reactions of chlorine and minerals at high temperature to form chlorides, and made use of different volatility and water-solubility of minerals to separate the chloride products. In the sodium carbonate roasting method, sodium carbonate was used as de-fluorination agent. Mixtures were roasted at high temperature, making rare-earth fluoride carbonate and rare earth phosphate reacted with sodium carbonate to form rare earth oxides and rare earth phosphate-soluble salts. At the same time trivalent cerium oxide changed to four price cerium oxide reaching the purpose of de-fluorination and enrichment of rare earths, and then provided a good metallurgical processing of raw materials. At present, the major de-fluorination agents which had been used to extract rare earths from bastnaesite concentrate were MgO, Na2CO3, SiCl4 and NH4Cl. In this paper, the tailings produced by the concentrator of Baotou Iron & Steel Co. Ltd were researched by combining the sodium carbonate roasting method and the chloride method, and using sodium carbonate as de-fluorination agent. Two new processes were designed for Bao Steel's Concentrator tailings'green extraction of rare earths as follows:(1) The tailings were treated with carbochlorination reaction, then react with SiCl4. After the chloride pretreatment of tailings at low temperature, most Fe, Ca, Ba, Mg, K, Mn and other elements' chlorides were removed, thus the grade of rare earths in the tailings was enhanced. The chloride rate of rare earths was low at low-temperature, the main products were rare earth phosphate, rare earth fluo-oxides, a small amount of rare earth fluoride carbonates, and rare earth fluorides. Carbochlorination with SiCl4 as de-fluorination agent greatly enhanced the conversion percent. (2) The tailings were roasted with sodium carbonate for de-fluorination pretreatment and then reacted with carbon and chlorine to from rare earth chlorides. Roasting by mixing sodium carbonate with tailings to make the rare earth fluoride carbonate, rare earth phosphate and Na2CO3 de-fluorination reaction to get rare earth oxides at high-temperature. Roasted with sodium carbonate at high temperature, rare earth oxides were prepared by de-fluorination reaction among the rare earth fluoride carbonate, rare earth phosphate and Na2CO3. Then after washing and pickling, treated the products with carbochlorination reaction to form rare earth chlorides.
In the first case we studied the conversion percent of different elements after carbochlorination. The conversion percents of elements like Fe, Ca, Ba, Mn were more than 80%. XRD analysis of residue showed that the characteristic peaks of Fe2O3 and CaF2 substantially decreased, which indicates that Fe2O3 and CaF2 had been mostly removed. After the first step carbochlorination, the residue attended the second step carbochlorination with SiCl4 as de-fluorination agent. The recovery rate of rare earths was 92 percent.
In the second case we studied the conversion percent of some elements which first treated with sodium carbonate roasting before carbochlorination. Rare earth recovery was 77 percent at 500℃.
引文
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