精四氯化钛中主要杂质的分析及其工艺控制研究

发布时间：2018-04-19 21:47

本文选题：四氯化钛 + 杂质分析　；参考：《北京理工大学》2015年博士论文

【摘要】：钛具有密度小、比强度高、耐高温以及耐腐蚀性能好等一系列优异特性,从而被广泛的应用于化工、冶金、航空、航天、医药等领域。为了去除精TiCl_4中的杂质,需要对主要杂质(氧、碳)进行分析,对精TiCl_4质量进行严格控制。至今,我国钛厂执行的标准中,TiCl_4的杂质检测仅包括FeCl_3、SiCl_4、VOCl_3和色度这几个分析指标,由于缺少有效的TiCl_4中主要杂质(碳、氧)的分析,从而造成TiCl_4执行标准较低,导致海绵钛产品质量受到较大影响,严重的影响我国钛产业的发展。本研究课题来源于科技部创新方法专项项目(No.2011IM030700)资助,以国内钛企业对精TiCl_4中主要杂质分析方法的迫切需求为导向,本研究的目的是建立主要杂质的分析方法,研究成果应用于企业控制精TiCl_4的质量。以遵义钛业股份有限公司提供的精Ti Cl_4为样品,对含量较高的主要杂质(碳、氧)进行测定及控制分析,具体研究成果归纳如下:(1)针对精TiCl_4腐蚀性强的特性,以及红外光谱分析的特点,设计了一种密封性能良好、便于清洗和操作、可重复使用、不同光程的红外吸收池测定装置,通过红外光谱法定量分析精TiCl_4中的杂质。(2)选用TiOCl_2为红外光谱研究目标物,通过单标法测得精TiCl_4中TiOCl_2含量为833.8±80.0mg/kg,相对标准偏差(RSD)在0.95%~1.94%之间;方法检出限为26.7mg/kg,加标回收率在88.5%~93.1%。折算成氧含量为98.8mg/kg,TiOCl_2是精TiCl_4中氧杂质的主要提供者。(3)选用CO_2为红外光谱研究目标物,通过单标法测得精TiCl_4中CO_2含量为1.53±0.11mg/kg,相对标准偏差(RSD)在0.53%~1.27%之间;方法检出限为0.92mg/kg,加标回收率在91.9%~94.7%。(4)选用有机杂质为红外光谱研究目标物,通过标准加入法测得Ti Cl_4中CS_2、CH_2ClCOCl、CHCl_2COCl含量为6.6±0.1mg/kg、17.9±0.3mg/kg、2.2±0.4mg/kg;检出限分别为0.1mg/kg、2.0mg/kg、1.0mg/kg;酰氯类峰有重叠,导致红外分别定量分析难度较大,定量相对偏差较大。(5)选用CCl_3COCl为研究目标物,通过离子色谱法测得TiCl_4中CCl_3COCl含量为41.3mg/kg,相对标准偏差(RSD)为7.7%;方法检出限为0.6mg/kg,加标回收率在84.1%~87.3%。折算成碳含量为5.4mg/kg,酰氯类杂质是精TiCl_4中碳杂质的主要提供者之一。(6)选取CCl_4为研究目标物,通过气相色谱法(ECD)测得精TiCl_4中CCl_4含量为0.17mg/kg,相对标准偏差(RSD)为2.4%;方法检出限为0.001mg/kg,加标回收率在95%~104%之间。
[Abstract]:Titanium has a series of excellent properties such as low density, high specific strength, high temperature resistance and good corrosion resistance, so it is widely used in chemical, metallurgical, aerospace, medical and other fields. In order to remove impurities in refined TiCl_4, it is necessary to analyze the main impurities (oxygen, carbon) and strictly control the quality of refined TiCl_4. Up to now, the impurity detection of TiClCO4 in the standard implemented by Chinese titanium plants only includes the analysis indexes of FeClS3SiCl4SiCl4VO Cl3 and chromaticity. Due to the lack of effective analysis of the main impurities (carbon, oxygen) in TiCl_4, the implementation standard of TiCl_4 is low. As a result, the quality of sponge titanium products is greatly affected, which seriously affects the development of China's titanium industry. This research project comes from the special project No. 2011IM030700 of the Ministry of Science and Technology. It is guided by the urgent need of domestic titanium enterprises to analyze the main impurity in TiCl_4. The purpose of this research is to establish the analytical method of the main impurity. The research results are applied to enterprises to control the quality of fine TiCl_4. Taking the refined Ti Cl_4 provided by Zunyi Titanium Industry Co., Ltd. as the sample, the main impurity (carbon, oxygen) with high content is determined and controlled. The concrete research results are summarized as follows: 1) the characteristic of high corrosivity of refined TiCl_4. As well as the characteristics of infrared spectrum analysis, a kind of infrared absorption cell measuring device with good sealing performance, easy cleaning and operation, reusability and different optical path is designed. The content of TiOCl_2 in refined TiCl_4 was 833.8 卤80.0 mg / kg, the relative standard deviation was between 0.95mg / kg and 1.94%, the detection limit was 26.7 mg / kg and the recovery rate was 88.5mg / kg. The converted oxygen content of 98.8 mg / kg TiOCl2 is the main provider of oxygen impurity in refined TiCl_4. CO_2 is chosen as the target of infrared spectroscopy. The content of CO_2 in refined TiCl_4 is 1.53 卤0.11 mg / kg, and the relative standard deviation is between 1.27% and 1.27% by single standard method. As a result, IR quantitative analysis is difficult, the relative deviation of quantitative analysis is large. CCl_3COCl is chosen as the research object. The content of CCl_3COCl in TiCl_4 is 41.3 mg / kg by ion chromatography, and the relative standard deviation is 7.7.The detection limit of the method is 0.6 mg / kg, and the recovery rate is 87.30.The detection limit of the method is 0.6 mg / kg. The carbon content is 5.4 mg / kg. Acyl chloride impurity is one of the main carbon impurities in refined TiCl_4. The content of CCl_4 in TiCl_4 was 0.17 mg / kg, the relative standard deviation (RSD) was 2.4%, the detection limit was 0.001 mg / kg and the recovery rate was between 95% and 104%.
【学位授予单位】：北京理工大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TQ134.11

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