新型含硫杂环抑制剂在钼铅分离中的应用及其量子化学分析

刘崇峻; 吴桂叶; 马艳红; 卢通; 刘慧南; 赵志强; 朱阳戈; 钟在定; 安耿; 陈丽娟

doi:10.13779/j.cnki.issn1001-0076.2022.01.011

新型含硫杂环抑制剂在钼铅分离中的应用及其量子化学分析

1.
矿冶科技集团有限公司矿物加工科学与技术国家重点实验室, 北京 100160

2.
金堆城钼业股份有限公司, 陕西西安 710077

基金项目:
矿冶科技集团有限公司院基金(02-2010);国家自然科学基金(U20A20269)

详细信息

作者简介: 刘崇峻(1985-), 男, 天津人, 博士, 工程师, 主要从事矿物综合利用研究, E-mail: liuchongjun@bgrimm.com

通讯作者: 吴桂叶(1982-), 女, 河北省人, 博士, 工程师, 主要从事矿物综合利用研究, E-mail: wuguiye@bgrimm.com

中图分类号: TD923⁺.14;TD952.2

收稿日期: 2022-02-20

刊出日期: 2022-02-25

Application and Quantum Chemical Analysis of Novel Sulfur-Containing Heterocyclic Inhibitors in Separation of Molybdenite and Galena

1.
State Key Laboratory of Mineral Processing Science and Technology, Beijing General Research Institute of Mining and Metallurgy, Beijing 100160, China

2.
Jinduicheng Molybdenum Co., Ltd., Xi' an 710077, China

More Information

Corresponding author: WU Guiye, wuguiye@bgrimm.com

Received Date: 20 February 2022

Publish Date: 25 February 2022

摘要

摘要:
传统钼铅分离过程中使用磷诺克斯作为抑制剂, 存在毒性大、污染严重等问题。为了降低金堆城钼精矿中铅的含量, 对比了毒性较弱的巯基丙醇、L-半胱氨酸、1, 3-氧硫杂戊环-羧酸、硫普罗宁的铅抑制效果, 并对抑制剂用量进行了考察, 经过比较选取1, 3-氧硫杂戊环-羧酸作为金堆城钼铅混合精矿的抑制剂。经过条件试验, 最终确定在再磨细度-38 μm占80%时, 经过一次粗选、五次精选, 可以获得钼品位52.20%、回收率85.01%、含铅0.010%的钼精矿产品, 其效果与磷诺克斯相当。采用配位化学以及密度泛函理论计算了方铅矿和辉钼矿的前线轨道特征, 并通过对方铅矿和辉钼矿中金属位点的前线轨道特征进行分析指出, 钼铅分离抑制剂的前线轨道对称性是影响抑制剂选择性的关键。
- 钼铅分离 /
- 方铅矿 /
- 抑制剂 /
- 浮选 /
- 前线轨道 /
- 密度泛函理论 /
- 配位化学
Abstract:
In the traditional separation of molybdenum and lead, phosphorus nox is used as an inhibitor, which has serious toxicity and pollution. In order to reduce the content of lead in molybdenum concentrate from Jinduicheng, the lead inhibition effects of mercaptopropanol, L-cysteine, 1, 3-oxythiopentane carboxylic acid and tiopronin with weak toxicity were compared, and the amount of inhibitor were investigated. After comparison, 1, 3-oxythiopentane carboxylic acid was selected as the inhibitor of molybdenum-lead-bearing concentrate in Jinduicheng. After condition test, molybdenum concentrate can be obtained with molybdenum grade of 52.20%, recovery rate of 85.01% and lead content of 0.010% through one roughings and five cleanings when the regrinding fineness of -38 μm was 80%. The effect of 1, 3-oxythiopentane carboxylic acid is equivalent to that of phosphorus Knox. The characteristics of frontier orbits of galena and molybdenite were calculated by means of coordination chemistry and density functional theory, and the characteristics of frontier orbits of metal sites in galena and molybdenite were analyzed. It is pointed out that the symmetry of frontier orbits of the inhibitors is the key to affect the selectivity of inhibitors.
- separation of molybdenite and galena /
- galena /
- inhibitor /
- flotation experiment /
- molecular orbital /
- density functional theory /
- coordination chemistry

HTML全文

图 1 浮选试验原则流程

Figure 1.

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图 2 铅离子配位模型和钼离子配位模型

Figure 2.

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图 3 抑制剂种类试验结果

Figure 3.

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图 4 不同抑制剂用量下的钼精矿指标

Figure 4.

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图 5 开路浮选原则流程

Figure 5.

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图 6 抑制剂前线轨道

Figure 6.

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图 7 方铅矿和辉钼矿前线轨道

Figure 7.

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表 1 原料多元素分析结果

Table 1. Multi-composition analysis result of raw ores /%

元素	Mo	Fe	Pb	Zn	Cu	K₂O	Na₂O
含量	16.61	8	0.21	0.23	1.04	2.39	0.38

元素	P	S	CaO	Ti	MgO	SiO₂	Al₂O₃
含量	0.052	18.21	2.32	0.24	1.24	40.25	7.97

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表 2 矿石的矿物组成及相对含量

Table 2. Mineral composition and relative content of ore /%

矿物名称	含量	矿物名称	含量
辉钼矿	27.69	石英	33.19
黄铁矿	17.18	钾长石	13.58
闪锌矿	0.34	钠长石	3.22
黄铜矿	2.98	磷灰石	0.28
方铅矿	0.24	其他	0.89
金红石	0.41

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表 3 分子结构示意图

Table 3. Molecular structures of depressant reagents

抑制剂	分子结构
巯基丙醇
L-半胱氨酸
1, 3-氧硫杂戊环-羧酸
硫普罗宁

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表 4 钼精矿降铅工艺开路试验结果

Table 4. Results of open circuit for lead reduction in molybdenum concentrate /%

抑制剂种类	产品名称	作业产率	品位				作业回收率
抑制剂种类	产品名称	作业产率	Cu	Mo	Pb	SiO₂	Cu	Mo	Pb	SiO₂
1, 3-氧硫杂戊环-羧酸	钼精矿	24.07	0.057	52.20	0.010	5.74	1.03	85.01	1.10	3.65
	中矿1	1.60	0.27	29.26	0.33	30.12	0.33	3.16	2.43	1.27
	中矿2	5.40	0.69	5.68	0.38	58.52	2.80	2.08	9.42	8.34
	中矿3	3.08	2.54	15.90	0.75	38.31	5.91	3.31	10.46	3.11
	中矿4	5.87	4.89	5.96	0.82	41.03	21.72	2.37	21.77	6.35
	中矿5	20.92	2.10	1.21	0.30	54.09	33.25	1.71	28.31	29.84
	精尾	39.07	1.18	0.89	0.15	46.03	34.95	2.36	26.52	47.44
	给矿	100.00	1.32	14.78	0.22	37.91	100.00	100.00	100.00	100.00
磷诺克斯	钼精矿	24.41	0.044	51.92	0.010	5.34	0.84	85.20	1.08	3.41
	中矿1	1.13	0.21	23.96	0.069	31.81	0.19	1.82	0.35	0.94
	中矿2	5.62	0.41	7.58	0.11	52.30	1.78	2.86	2.73	7.69
	中矿3	3.39	1.49	19.23	0.25	36.75	3.89	4.38	3.81	3.26
	中矿4	4.56	3.83	4.14	0.61	44.93	13.51	1.27	12.40	5.36
	中矿5	20.57	2.07	1.46	0.37	54.38	32.87	2.01	33.32	29.28
	精尾	40.33	1.51	0.91	0.26	47.43	46.92	2.45	46.32	50.06
	给矿	100.00	1.29	14.87	0.23	38.21	100.00	100.00	100.00	100.00

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表 5 前线轨道分析

Table 5. The analysis of frontier molecular orbitals /eV

前线轨道能	巯基丙醇	L-半胱氨酸	1, 3-氧硫杂戊环-羧酸	硫普罗宁	方铅矿	辉钼矿
E(HOMO)	-5.215	-5.540	-5.479	-6.044	-11.464	-22.612
E(LUMO)	-1.077	-2.331	-2.113	-2.745	-9.253	-22.146
ΔE₁	4.038	3.68	3.774	3.656
ΔE₂	10.387	9.933	9.351	9.724
ΔE₃	16.931	16.573	16.667	16.549
ΔE₄	21.535	21.081	20.499	20.872
注：ΔE₁=\|E_{(HOMO-药剂)}-E_{(LUMO-方铅矿)}\|; ΔE₂=\|E_{(HOMO-方铅矿)}-E_{(LUMO-药剂)}\|；ΔE₃=\|E_{(HOMO-药剂)}-E_{(LUMO-辉钼矿)}\|；ΔE₄=\|E_{(HOMO-辉钼矿)}-E_{(LUMO-药剂)}\|。

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