锗蒸馏残液的环保处理工艺研究

Treatment of Residual Solution of Germanium Chloridizing Distillation

为有效降低锗氯化蒸馏残液的产生量、回收残液中的盐酸,本文配合残液的末端处理技术,通过回收盐酸实验以及残液处理实验,研究了在锗氯化蒸馏工艺中用氯气替代硫酸的可行性。结果表明,用氯气替代硫酸是可行的,锗的蒸馏率提高了0.41%,残液中H+浓度由13.25mol.L-1降至6.5mol.L-1左右,从而更容易处理。回收的盐酸中H+浓度为6.52mol.L-1,回收率达到70.3%,残液的总量可由220m3降至66m3。按照现在的生产规模(1×10t.a-1金属锗),采用此工艺节省硫酸280t,消耗的生石灰减少390t,减少中和渣570t。针对锗蒸馏残液中主要含盐酸的工况,提出了残液资源化的处理工艺流程,即首先采用蒸馏工艺对残液中的盐酸进行回收,再用石灰中和残液,使中和上清液完全用于制备石灰乳。

The feasibility of using chlorine in stead of sulfuric acid in the process of distillation of germanium was studied. The experimental results showed that using chlorine instead of sulfuric acid was feasible in the process of distillation of germanium, the distillation rate increases by 0.41%, the concentration of H^＋ in residual solution reduces from 13.25 mol·L^-1 to 6.5 mol·L^-1. The concentration of H^＋ in recovered hydrochloric acid is 6.52 mol·L^-1, and the recovering rate can reach 70.3 %, the residual solution reduces from 220 m^3 to 66 m^3. According to the present production scale（ 10 t·a^-1 germanium） this technic can economized, 280 tons sulfuric acid and 390 tons CaO, and reduced 570 tons neutralization dreg. Meanwhile, the profitable process flow of industrial effluent with hydrochloric acid, i.e. firstly, extract hydrochloric acid with distill process, then, neutralize the residual solution with lime and the neutralized water to prepare 10% milk of lime was gotten.