發(fā)布時(shí)間：2018-04-30 23:39

  本文選題：鍺礦 + 熱還原��； 參考：《上海大學(xué)》2016年博士論文

【摘要】：鍺是重要的稀缺戰(zhàn)略資源,廣泛應(yīng)用于紅外光學(xué)、光纖通信、航空航天、太陽能電池、核物理探測(cè)、化學(xué)催化劑等眾多國(guó)防軍工及民用領(lǐng)域,是支撐國(guó)民經(jīng)濟(jì)發(fā)展及國(guó)防建設(shè)的關(guān)鍵材料,屬于我國(guó)戰(zhàn)略收儲(chǔ)金屬。世界鍺資源僅有美國(guó)、中國(guó)、加拿大、俄羅斯等國(guó)擁有,我國(guó)鍺資源保有儲(chǔ)量?jī)H約3500余噸,占全球鍺資源的40.7%;是世界第一大鍺生產(chǎn)供應(yīng)國(guó),高純鍺年產(chǎn)量約130噸,占全球供應(yīng)量的70%,其中云南鍺資源儲(chǔ)量占到了全國(guó)的32%,產(chǎn)量占到了全國(guó)的65%以上,是云南的特色優(yōu)勢(shì)產(chǎn)業(yè)。云南省臨滄地區(qū)擁有世界知名的褐煤鍺礦資源,褐煤鍺礦中鍺含量一般在100 g/t~600 g/t之間,經(jīng)鏈?zhǔn)芥N揮發(fā)爐火法冶煉富集后得到鍺含量為0.35%~1.50%的低品位鍺精礦。本論文主要針對(duì)云南臨滄地區(qū)褐煤鍺礦經(jīng)一步火法富集產(chǎn)出的低品位鍺精礦,進(jìn)行了二次還原揮發(fā)富集提取鍺研究,以提高鍺資源綜合利用率,降低生產(chǎn)成本,減小濕法處理的環(huán)境影響。重點(diǎn)研究開發(fā)了次亞磷酸鈉熱還原火法揮發(fā)富集提取鍺礦中鍺、次亞磷酸鈉熱還原-真空揮發(fā)富集提取低品位鍺精礦中鍺的新工藝,以及對(duì)產(chǎn)出的還原鍺精礦采用堿氧化預(yù)處理后經(jīng)鹽酸蒸餾分離提取四氯化鍺,再經(jīng)提純制備得到高純二氧化鍺的新方法。通過系統(tǒng)性實(shí)驗(yàn)對(duì)鍺礦熱還原火法富集、高溫常壓分段焙燒揮發(fā)、次亞磷酸鈉熱還原真空揮發(fā)富集及堿氧化預(yù)處理-鹽酸蒸餾分離等鍺還原揮發(fā)過程及原理進(jìn)行了研究,并分析了鍺熱還原揮發(fā)和堿氧化預(yù)處理的工藝原理,最終確定了次亞磷酸鈉熱還原揮發(fā)富集回收鍺的工藝條件及參數(shù)。首先簡(jiǎn)要介紹了世界鍺資源分布、主要用途、產(chǎn)品產(chǎn)量、生產(chǎn)工藝、主要提取方法。其次對(duì)現(xiàn)有鍺礦火法富集工藝過程進(jìn)行了研究分析,對(duì)影響鍺回收的主要因素如設(shè)備、溫度、揮發(fā)方式及還原氣氛等熱還原揮發(fā)條件進(jìn)行了剖析,提出了目前鍺礦火法富集中存在的鍺回收率低等問題及改進(jìn)方法。經(jīng)試驗(yàn)提出了在鍺礦中添加還原劑次亞磷酸鈉進(jìn)行熱還原揮發(fā)來提高鍺礦火法冶煉回收率的方法,通過添加2.5%的次亞磷酸鈉能把鍺揮發(fā)率從91%提高到接近100%,揮發(fā)殘?jiān)墟N品位降低至50 g/t.重點(diǎn)對(duì)次亞磷酸鈉熱還原-真空揮發(fā)富集鍺的工藝方法進(jìn)行了系統(tǒng)性試驗(yàn)研究,并與常壓高溫分段焙燒揮發(fā)富集方法進(jìn)行了比較分析,通過實(shí)驗(yàn)對(duì)產(chǎn)出的高品位還原鍺精礦中鍺的堿氧化預(yù)處理-鹽酸蒸餾分離提取方法進(jìn)行了深入研究。通過自行設(shè)計(jì)的鍺還原揮發(fā)爐,采用正交實(shí)驗(yàn)及單因素條件實(shí)驗(yàn),進(jìn)行了系統(tǒng)性研究分析,同時(shí)采用熱力學(xué)方法原理及擴(kuò)散理論對(duì)還原反應(yīng)及真空揮發(fā)過程進(jìn)行分析。通過對(duì)還原劑的選擇,還原反應(yīng)過程,揮發(fā)原理等方面的研究分析,優(yōu)選出最佳工藝條件為:揮發(fā)溫度1000℃,次亞磷酸鈉用量7.5%,真空度500 Pa,載氣流量2 L/min,揮發(fā)時(shí)間90 min,料層厚度30 mm,此條件下鍺揮發(fā)率達(dá)到94.76%~98.35%,揮發(fā)殘?jiān)墟N含量達(dá)到0.06%~0.13%,產(chǎn)出還原精礦品位達(dá)到12.68%~46.71%,富集倍數(shù)達(dá)27~36倍。與常壓揮發(fā)富集方法相比,還原揮發(fā)溫度低200℃,揮發(fā)時(shí)間短60分鐘,富集倍數(shù)提高了10~14倍,鍺揮發(fā)率提高了22%~32%,富集得到的精礦鍺含量提高了5%~19%,具有顯著的鍺回收效果,同時(shí)生產(chǎn)成本得到了大幅下降。自行設(shè)計(jì)了含鍺原料提鍺實(shí)驗(yàn)裝置,提出了采用氫氧化鈉+過氧化氫氧化預(yù)處理-鹽酸蒸餾分離得到四氯化鍺,再經(jīng)傳統(tǒng)工藝精餾提純水解后得到高純二氧化鍺的新工藝,解決了本方法得到的高品位還原鍺精礦在用常規(guī)濕法鹽酸蒸餾提鍺工藝回收率低的難題。通過系統(tǒng)研究,優(yōu)選的工藝參數(shù)為:水用量為鍺精礦重量的2倍,氫氧化鈉用量為鍺精礦重量的30%,過氧化氫(30%)用量為鍺精礦重量的25%,預(yù)處理時(shí)間為1.5 h,蒸餾鹽酸用量為鍺精礦重量的9倍。本方法能夠顯著提高鍺的鹽酸蒸餾回收率,采用本工藝后鍺回收率提高到了97.90%以上,而用常規(guī)鹽酸蒸餾工藝回收鍺時(shí)回收率才能達(dá)到65.16%.相對(duì)于目前的硫酸浸出-丹寧沉淀-鹽酸蒸餾分離的濕法提鍺工藝,本方法具有鍺回收效率高,流程簡(jiǎn)短,設(shè)備簡(jiǎn)單,可操作性強(qiáng),輔料消耗少,生產(chǎn)運(yùn)行成本低,避免了大量廢水、廢氣和廢渣的排放及處理,可徹底解決濕法處理工藝提鍺帶來的環(huán)境污染問題。研究結(jié)果表明,使用本工藝回收鍺礦及低品位鍺精礦中的鍺是可行的,具有回收率高,環(huán)境友好,適應(yīng)性廣等特點(diǎn),達(dá)到了提高鍺綜合回收率,降低生產(chǎn)成本,節(jié)能減排,安全環(huán)保,高效利用鍺資源的目的。本文的研究成果拓展了次亞磷酸鈉熱還原真空揮發(fā)富集回收鍺和堿氧化預(yù)處理蒸餾分離提取鍺新技術(shù)在稀有金屬領(lǐng)域的應(yīng)用范圍,具有廣闊的應(yīng)用前景。
[Abstract]:Germanium is an important scarce strategic resource. It is widely used in infrared optics, optical fiber communication, aerospace, solar cells, nuclear physics detection, chemical catalyst and many other defense industry and civil fields. It is the key material to support national economic development and national defense construction. The country owned by Da, Russia and other countries, the reserves of germanium resources in China are only about 3500 tons, accounting for 40.7% of the global germanium resources. It is the world's largest germanium production supply country. The production of high pure germanium is about 130 tons, accounting for 70% of the global supply. The Yunnan germanium reserves accounted for 32% of the country, and the output accounted for more than 65% of the country. It is the characteristic advantage of Yunnan. Industry. The Lincang area of Yunnan province has the world famous lignite germanium mineral resources, the germanium content in the lignite germanium is generally between 100 g/t~600 g/t and the low grade germanium concentrate with the germanium content of 0.35%~1.50% after the chain germanium volatilization process is enriched. This paper mainly focuses on the one step fire enrichment and the production of the lignite germanium in Lincang area of Yunnan. The low grade germanium concentrate has been studied by two times reduction and volatilization to extract germanium, in order to improve the comprehensive utilization of germanium resources, reduce the production cost and reduce the environmental impact of the wet process. The emphasis is on the extraction of germanium in germanium from the evaporation of sodium hypophosphite by heat reduction and fire method, and the extraction of low grade germanium by the thermal reduction of sodium hypophosphite and vacuum evaporation. The new process of germanium in concentrates, and the extraction of germanium chloride from the produced germanium concentrate by alkaline oxidation pretreatment, four germanium chloride is distilled by hydrochloric acid, then a new method of high purity two germanium oxide is prepared by purification. Through systematic experiment, the germanium ore is enriched by heat reduction fire method, volatilization and evaporation of sodium hypophosphite by heat reduction, and vacuum volatilization of sodium hypophosphite. The process and principle of the reduction and volatilization of germanium by Preconcentration and alkali oxidation pretreatment, such as hydrochloric acid distillation, are studied. The process principle of germanium thermal reduction volatilization and alkali oxidation pretreatment is analyzed. The technological conditions and parameters of the recovery of germanium by thermal reduction and volatilization of sodium hypophosphite are finally determined. The distribution of germanium resources in the world is briefly introduced. The main factors affecting the recovery of germanium, such as equipment, temperature, mode of volatilization and reduction atmosphere, are analyzed, and the low recovery rate of germanium in the rich concentration of germanium fire method is put forward, and the low recovery rate of germanium is put forward. By adding 2.5% of sodium hypophosphite, the volatilization rate of germanium can be increased from 91% to 100%, and the germanium grade in the volatile residue is reduced to 50 g/t. by the addition of sodium hypophosphite in the germanium. The process method of vacuum evaporation and enrichment of germanium has been systematically studied and compared with the method of volatile enrichment in high temperature high temperature section roasting. The method of separating germanium from high grade germanium concentrate by alkali oxidation pretreatment with hydrochloric acid distillation is studied through experiments. Using orthogonal experiment and single factor condition experiment, a systematic study and analysis are carried out. At the same time, the thermodynamic method principle and diffusion theory are used to analyze the reduction reaction and vacuum evaporation process. Through the research and analysis of reducing agent selection, reduction reaction process, volatilization principle and so on, the optimum process conditions are as follows: volatilization is: volatilization The temperature is 1000 C, the amount of sodium hypophosphite is 7.5%, the vacuum degree is 500 Pa, the air flow rate is 2 L/min, the volatilization time is 90 min, the thickness of the material layer is 30 mm. The germanium volatilization reaches 94.76%~98.35% under this condition, the germanium content in the volatile residue reaches 0.06%~0.13%, the output of the reduced concentrate reaches 12.68%~ 46.71% and the enrichment multiplier reaches 27~36 times. Compared with the reduction volatilization temperature 200 c, the volatilization time was 60 minutes shorter, the enrichment factor increased by 10~14 times, the germanium volatilization rate increased by 22%~32%, the enriched germanium content increased by 5%~19%, the germanium recovery effect was remarkable, and the production cost was greatly reduced. The germanium containing germanium experiment device was set up by ourselves, and the use of hydrogen and oxygen was proposed. A new process of high purity two germanium oxide was obtained after distillation and hydrolysis of four germanium chloride by sodium hydroxide + hydrogen peroxide oxidation pretreatment and hydrochloric acid distillation. The problem of low recovery rate of high grade germanium concentrate obtained by this method in the process of distilling germanium by conventional hydrochloric hydrochloric distillation was solved. The parameters are: 2 times the weight of the germanium concentrate, 30% of the weight of germanium concentrate, 25% of the weight of germanium concentrate, 1.5 h and 9 times the weight of germanium concentrate. This method can improve the recovery rate of salt and acid distillation of germanium significantly, and the recovery rate of germanium after this process is improved to this process. More than 97.90%, and the recovery rate of Germanium Recovery by conventional hydrochloric acid distillation process can reach 65.16%. relative to the wet process of extracting germanium from the current sulfuric acid leaching - Denning precipitation hydrochloric acid distillation. This method has high efficiency, short process, simple equipment, strong operability, less excipient consumption, low production cost, and avoided a large amount of operation. The discharge and treatment of waste water, waste gas and waste residue can thoroughly solve the environmental pollution caused by the extraction of germanium in the wet process. The results show that the recovery of germanium in germanium and low grade germanium concentrate by this process is feasible, with high recovery, friendly environment and wide adaptability, which can improve the comprehensive recovery rate of germanium and reduce the production of germanium. Cost, energy saving, emission reduction, safety and environmental protection, and efficient use of germanium resources. The research achievements of this paper expand the application scope of new technology in the field of rare metals with the thermal reduction vacuum evaporation, vacuum evaporation and recovery of germanium and alkali oxidation, and the extraction of germanium in the rare metal field.

【學(xué)位授予單位】：上海大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TN304.11

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本文編號(hào)：1826771