摘要
为了开发低温钛氯化工艺及解决工业副产物CCl4的再利用问题,在固定床和流化床反应器中考察了自贡法人造金红石原料与CCl4低温氯化制备TiCl4的反应过程,利用SEM、XRD、XPS等手段表征了人造金红石原料在反应前后的变化。结果显示,在450～500℃下,自贡法人造金红石能与CCl4快速反应生成TiCl4产品。少量Fe元素的掺杂是金红石相具备较高反应速率的关键原因。人造金红石原料制备过程中的弱氧化焙烧处理在颗粒表面形成的惰性金红石壳层,导致TiCl4收率极限为90%,但该壳层能在酸解过程以及低温CCl4氯化过程中维持颗粒粒度,使该原料能用于流化床操作。此过程具有显著的环保价值和工业应用前景。
The chlorination of synthetic rutile with CCl4 for the low temperature production of TICl4 was studied in both packed bed and fluidized bed reactors. Synthetic rutile samples before and after chlorination were characterized with SEM, XRD and XPS. Synthetic rutile produced by the Zigong process can be rapidly chlorinated by CCl4 at 450℃ to 500℃. The presence of Fe^3＋ ions in the lattice of the rutile phase was the key reason for the high reactivity. It was also found that an inert rutile shell was formed during the mild pre-oxidation used in the manufacturing process of the synthetic rutile material. This limited the maximum TICl4 yield in the chlorination process to 90%. However, this inert rutile shell structure maintained the particle size during the chlorination process, it was also beneficial because it allowed the chlorination of the synthetic rutile material in a fluidized bed reactor. This process of using CCl4 for the chlorination of rutile is potentially valuable as an environmental protection technology. It effectively converts the undesirable ozone destructive substance （ODS） CCl4, an industrial byproduct, into a non- ODS product.
出处
《化工学报》
EI
CAS
CSCD
北大核心
2009年第12期3026-3034,共9页
CIESC Journal
基金
国家自然科学基金项目(20736004)
国家科技支撑计划项目(2007BAB20B02)
国家重点基础研究发展计划项目(2009CB219901)~~
关键词
四氯化钛
四氯化碳
Fe掺杂人造金红石
低温氯化
titanium tetrachloride
carbon tetrachloride
Fe doped synthetic rutile
low temperature chlorination
