铬铁矿无钙焙烧渣盐酸浸出

doi:10.11949/0438-1157.20190353

摘要/Abstract

摘要：

铬渣是铬铁矿生产铬盐剩下的尾矿，因含有大量铬铁铝镁元素，也是一种二次资源。采用湿法冶金工艺回收铬渣中铬、铁、铝、镁，以浓盐酸作为浸提剂，考察了液固比、浸出温度以及时间对铬、铁、铝、镁浸出效果的影响。结果表明，最佳浸出条件为：盐酸浓度12 mol·L^-1，液固比5.6 ml·g^-1，浸出温度110℃，时间6 h，该条件下铬浸出率为67.76%，同时铁铝镁浸出率分别达到89.89%、93.99%和95.21%。铬、铁、铝、镁在铬渣中存在物相不同造成了其浸出率之间的差异。此外，铬、铁、铝、镁浸出过程均符合未反应缩核模型，且主要受界面化学反应控制，其表观活化能分别为102.31、78.10、66.44和81.66 kJ·mol^-1。

关键词: 铬渣, 盐酸, 浸取, 回收, 动力学

Abstract:

Chromite ore precessing residue is the remaining tailings of chromite produced by chromite. It is also a secondary resource because it contains a lot of ferrum, chromium, aluminum and magnesium. In this work, a hydrometallurgy process was introduced to recover chromium, ferrum, aluminum and magnesium by using hydrochloride acid as a lixiviant and three variables were studied namely, liquid-solid ratio, leaching temperature and period. The results indicated that chromium, ferrum, aluminum and magnesium can successfully be recovered from COPR and the optimum leaching conditions were at the liquid-solid ratio of 5.6 with 110℃ and 6 h period. Simultaneously, the leaching efficiencies of chromium, ferrum, aluminum and magnesium reached 67.76%, 89.89%, 93.99% and 95.21%, respectively. A shrinking core model with the surface chemical reaction control can be used to describe the leaching kinetics of chromium, ferrum, aluminum and magnesium from COPR in the concentrated hydrochloride acid solution at 90—110℃, where the apparent activation energy are 102.31, 78.10, 66.44 and 81.66 kJ·mol^-1, respectively. The analysis of particle size distribution also showed a reduction in particle size, indicating the dissolution of the solid particles. The application of Toxic Leaching Characteristic Procedure (TLCP) showed nearly no Cr⁶⁺ in the effluent, indicating that the residue will not contaminate the environment through leaching, and can be used for load bearing or backfill material.

Key words: COPR, hydrochloride acid, leaching, recovery, kinetics

中图分类号:

TF 803.21

叶鹏, 全学军, 秦险峰, 封承飞, 李纲, 鹿存房, 齐学强, 蒋丽. 铬铁矿无钙焙烧渣盐酸浸出[J]. 化工学报, 2019, 70(11): 4428-4436.

Peng YE, Xuejun QUAN, Xianfeng QIN, Chengfei FENG, Gang LI, Cunfang LU, Xueqiang QI, Li JIANG. Leaching of chromite ore processing residue from non-calcium roasting with hydrochloric acid[J]. CIESC Journal, 2019, 70(11): 4428-4436.

图/表 11

图1 均相反应器 1—控制系统；2—温度表；3—转动轴；4—箱体；5—卡圈；6—羊角螺丝；7—水热合成反应釜；8—电机；9—变频器；10—开关；11—支架

Fig.1 Homogeneous reacter

图2 液固比对铬、铁、铝、镁浸出率的影响

Fig.2 Effect of liquid-solid ratio on leaching of chromium, ferrum, aluminum and magnesium

图3 浸出温度和时间对铬、铁、铝、镁浸出率的影响

Fig.3 Effect of temperature along with reaction time on leaching of ferrum, aluminum, magnesium and chromium

表1 酸浸液成分

Table 1 Composition of leaching solution/(mol·L-1)

Cr³⁺	Fe³⁺	Al³⁺	Mg²⁺	HCl
0.05	0.24	0.31	0.12	1.31

图4 铬、铁、铝、镁产物层扩散控制动力学模型

Fig.4 Diffusion through product layer controlled kinetics model of leaching of ferrum, aluminum, magnesium and chromium at various temperatures

图5 铬、铁、铝、镁化学反应控制动力学模型

Fig.5 Chemical reaction controlled kinetic model of leaching of ferrum, aluminum, magnesium and chromium at various temperatures

图6 铬、铁、铝、镁浸出Arrhenius图

Fig.6 Arrhenius plot for leaching of ferrum, aluminum, magnesium and chromium

表2 铬渣及浸出渣组成

Table 2 Composition of COPR and leaching residue/%(mass)

样品	Cr₂O₃	Fe₂O₃	Al₂O₃	MgO	Na₂O	SiO₂	TiO₂	CaO	Other
铬渣	11.34	39.49	31.55	10	3.4	2.69	1.35	0.22	0.16
浸出渣	4.11	2.41	0.28	2.35	2.31	82.81	2.35	0.25	0.24

图7 铬渣、浸出渣XRD谱图

Fig.7 XRD patterns of COPR (a) and leaching residue (b) (12 mol·L-1 HCl, 110℃, 40 r·min-1, 6 h, L/S=5.6 ml·g-1)

图8 浸出渣1100℃煅烧后XRD谱图

Fig.8 XRD pattern of leaching residue after 1100℃ calcination

图9 铬渣和浸出渣粒径分布

Fig.9 Particle size distribution of COPR (a) along with leaching residue (b)

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