Chen Feng, Wen Yuekai, Guo Yufeng, Wang Shuai, Yang Lingzhi, Zheng Yu, Li Dongyue, Ren Yuqiao
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China.
Materials (Basel). 2022 Aug 30;15(17):5983. doi: 10.3390/ma15175983.
The molten salt chlorination method is more suitable to produce TiCl using titanium-containing materials with high contents of CaO and MgO in China. However, there is a large amount of molten salt chloride slags generated from the molten salt chlorination process, which contains a variety of chlorides and is difficult to treat, often causing serious environmental problems such as direct piling or landfilling. A novel process was proposed to deal with molten salt chloride slags, and calcium chloride could be effectively removed by this process (as in our previous study). However, magnesium chloride is another impurity which can deteriorate the density and viscosity of the molten salt; it is often found in higher contents, and should be also removed from molten salt chloride slags to efficiently recycle NaCl in novel processes. NaSiO is added to the molten salt chloride slags in the molten state to produce the Mg-containing solid phase, which could be separated with the molten NaCl in novel processes. Thus, the transition of Mg-containing phases and the recovery of NaCl in molten salt chloride slags at high temperature in a novel process were systematically investigated in this work, including thermodynamic analysis, the phase transition behavior of Mg-containing phases, NaCl recovery, etc. The removal rate of Mg was 99.56% when the molar ratio of MgCl:NaSiO was 1:1.5 at 1273 K and in a N atmosphere. The recovery rate of NaCl from the molten salt chlorination slag was 97.62% and the purity of NaCl obtained was 99.35 wt%, which could be used in the molten salt chlorination process.
在中国,熔盐氯化法更适合使用氧化钙和氧化镁含量高的含钛材料来生产四氯化钛。然而,熔盐氯化过程会产生大量的熔盐氯化渣,其中含有多种氯化物,难以处理,直接堆放或填埋往往会造成严重的环境问题。提出了一种处理熔盐氯化渣的新工艺,该工艺可以有效去除氯化钙(如我们之前的研究)。然而,氯化镁是另一种会降低熔盐密度和粘度的杂质;其含量通常较高,在新工艺中也应从熔盐氯化渣中去除,以有效回收氯化钠。将硅酸钠加入到熔融状态的熔盐氯化渣中,生成含镁固相,在新工艺中可将其与熔融氯化钠分离。因此,本工作系统研究了新工艺中高温下熔盐氯化渣中含镁相的转变及氯化钠的回收,包括热力学分析、含镁相的相变行为、氯化钠回收等。在1273K、氮气气氛下,当氯化镁与硅酸钠的摩尔比为1:1.5时,镁的去除率为99.56%。熔盐氯化渣中氯化钠的回收率为97.62%,所得氯化钠的纯度为99.35 wt%,可用于熔盐氯化过程。