浮选药剂性能理论分析

王纪镇; 荆茂晨; 刘睿华; 韩硕

doi:10.13779/j.cnki.issn1001-0076.2023.08.002

浮选药剂性能理论分析

西安科技大学化学与化工学院，陕西西安 710054

基金项目: 陕西省自然科学基础研究计划项目(2021JM394,2017JQ5090)

详细信息

作者简介: 王纪镇（1985— ），男，山东聊城人，博士，讲师，主要从事矿物浮选理论与工艺研究

中图分类号: TD91；TD923⁺.1

收稿日期: 2023-01-02

刊出日期: 2023-06-15

Theoretical Analysis of Flotation Reagent Performance

College of Chemistry and Chemical Engineering, Xi’an University of Science and Technology, Xi’an 710054, China

Received Date: 02 January 2023

Publish Date: 15 June 2023

摘要

摘要:
研究了浮选调整剂（石灰、硫化钠、氰化钠、金属离子活化剂）对矿物浮选的选择性以及捕收剂烃基结构与性能的关系。研究结果表明，应用溶度积判据或前线轨道能级参数研究浮选药剂性能或构效关系，应重视矿物表面性质以及矿物—药剂作用机制研究。通过分析矿物表面性质，得出硫化钠、氰化钠、铜铅金属离子对硫化矿的选择性与矿物表面位点的价电子构型存在一定对应关系，与溶度积判据分析结果一致或具有互补性。应用前线轨道能级参数研究黄药结构与活性的关系，结合溶度积判据分析矿物与黄药作用规律，得出了黄药烃基结构影响捕收性能的疏水因素、价键因素以及空间几何效应的主次关系。综上得出，应用单一的理论参数难以全面解释浮选药剂性能，建立相互耦合的药剂性能理论分析体系或是今后研究的重点之一。
- 浮选药剂性能 /
- 溶度积 /
- 前线分子轨道理论 /
- 价电子构型
Abstract:
The influence of flotation regulators (such as lime, sodium sulfide, sodium cyanide and metal ion activator) on mineral flotation and the relationship between collector structure and performance were studied. The results showed that solubility product criterion and frontier orbital energy level parameters could be used to analyze the properties or structure-activity relationship of flotation reagents, but should be paid attention to the study of mineral surface properties, non-valence bond factors of flotation reagent properties and mineral-reagent interaction mechanism. By examining mineral surface features, it has been determined that selective depression or activation of minerals by flotation regulator (such as sodium sulfide, sodium cyanide, copper and lead metal ions) had a certain relationship with the valence electron configuration of mineral lattice metal, which was consistent with or supplementary to the results of solubility product criterion analysis. The interaction mechanism between minerals and reagents was examined using the solubility product criterion and frontier orbital energy level parameters were used to study the relationship between hydrocarbon group structure and xanthate properties. As a result, the primary and secondary relationships of hydrophobic factors, valence bond factors and spatial geometric effects of xanthate’s alkyl group structure on collecting performance were obtained. In conclusion, it is difficult to fully explain the performance of flotation reagents with a single theoretical parameter. The establishment of the coupled theoretical analysis system for reagent performance should be one of the key focuses of future research.
- flotation reagent performance /
- solubility product /
- frontier molecular orbital theory /
- valence electron configuration

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图 1 硫化矿表面金属位点与黄药和氢氧根离子作用产物的溶度积

Figure 1.

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图 2 黄药的前线分子轨道能级以及金属黄原酸盐的溶度积

Figure 2.

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表 1 硫化矿晶格金属离子周期表分布与氰化钠抑制强弱顺序关系

Table 1. Relationship of the periodic table distribution of metal ions in sulfide crystal lattice and the depressing performance order of sodium cyanide

元素周期	d区元素						ds区元素		p区元素
元素周期	ⅤB	ⅥB	ⅦB		ⅧB		ⅠB	ⅡB	ⅢA	ⅣA	ⅤA
第四周期	V			[Fe]	Co	[Ni]	(Cu)	[Zn]	Ga	Ge	{As}
第五周期		Mo		Ru	Rh	[Pd]	(Ag)	(Cd)	In	{Sn}	{Sb}
第六周期		W	Re	Os	Ir	(Pt)	[Au]	(Hg)	{Tl}	{Pb}	{Bi}
注：[ ]表示NaCN抑制能力最强；（）表示NaCN抑制次之；{}表示NaCN难以抑制。

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表 2 乙基黄原酸金属盐以及金属硫化物的溶度积

Table 2. Solubility product of metal-ethylxanthate and metal sulfide

金属离子	Pb²⁺	Zn²⁺	Cu²⁺	Fe²⁺	Sb³⁺
乙基黄原酸金属盐溶度积PL_s	16.7	8.2	24.2	7.1	24.0
PL_s/m	8.35	4.1	12.1	3.55	8.0
硫化物溶度积pK_s	27.5	22.5	36.1	18.1	92.7
注: m为金属阳离子电荷量。

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表 3 药剂化学式及非极性基结构

Table 3. Chemical formula and its nonpolar structure

药剂代号	R¹C(S)NHC(O)OR²	药剂代号	R¹C(S)SC(O)OR²
IBECTC	R¹ = CH₃CH₂，R² = CH₂CH(CH₃)₂	EXF	R¹ = CH₃CH₂，R² = CH₂CH₃
NBECTC	R¹ = CH₃CH₂，R² =(CH₂)₃ CH₃	PXF	R¹ = CH₃(CH₂)₂，R² = CH₂CH₃
AECTC	R¹ = CH₃CH₂，R² =(CH₂)₄ CH₃	BXF	R¹ =CH₃(CH₂)₃，R² = CH₂CH₃
IPECTC	R¹ = CH₃CH₂，R² = CH(CH₃)₂	IBXF	R¹ =(CH₃)₂CHCH₂，R² = (CH₂)₃CH₃
EECTC	R¹ = CH₃CH₂，R² = CH₂CH₃	BeXF	R¹ =C₆H₅CH₂，R² =CH₂CH₃
		sBSF	R¹ =CH₃CH₂CH(CH₃)，R² =CH₂CH₃
		XBF	R¹ =(CH₃)₂CH，R² =(CH₂)₃CH₃
		IPXF	R¹ =(CH₃)₂CH，R² =CH₂CH₃

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表 4 烷氧羰基硫氨酯（CTC）类药剂的前线轨道能级与选择性指数

Table 4. Frontier orbital energy level and selectivity index of CTC-type reagents

药剂代号	HOMO/eV	LUMO/eV	回收率/%		R	△ε/%
药剂代号	HOMO/eV	LUMO/eV	黄铜矿	黄铁矿	R	△ε/%
EECTC	−6.7247	−1.6149	83.2	38.2	2.178 (1)	45 (1)
NBECTC	−6.7230	−1.6124	88.2	49.6	1.778 (2)	38.6(2)
AECTC	−6.7217	−1.6121	91.1	58.3	1.563 (3)	32.8 (3)
IPECTC	−6.6839	−1.5896	90.8	67.3	1.349 (4)	23.5 (4)
IBECTC	−6.7132	−1.6072	90.6	81.3	1.114 (5)	9.3 (5)
注：黄铜矿和黄铁矿回收率数据引自文献[16]。R为黄铜矿与黄铁矿回收率比值，括号中数据为R和△ε由大到小排序的序号。

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表 5 EXF类前线轨道能级及其选择性指数R

Table 5. Frontier orbital energy level and selectivity index of EXF-type reagents

药剂代号	HOMO/eV	LUMO/eV	黄铜矿/黄铁矿回收率比值R
药剂代号	HOMO/eV	LUMO/eV	pH=5	pH=5	pH=8.5	pH=10.5
EXF	−6.8846	−1.9872	1.692 （2）^*	3.5 （3）	2.9 （4）	10.0 （3）
PXF	−6.8476	−2.0555	/	2.4 （4）	4.9 （3）	19.9 （1）
BXF	−6.8427	−2.0607	/	3.7 （2）	5.0 （1）	10.2 （2）
IBXF	−6.8367	−2.0533	2.224 （1）^*	/	/	/
BeXF	−6.8182	−2.0949	/	8.0 （1）	5.0 （1）	7.3 （4）
sBSF	−6.8057	−2.0136	/	1.8 （5）	1.5 （7）	2.4 （6）
IPXF	−6.8030	−2.0248	1.316 （4）^*	1.3 （7）	1.9 （5）	2.4 （6）
XBF	−6.8014	−2.0272	1.373 （3）^*	1.5 （6）	1.9 （5）	5.2 （5）
注：括号中数据为R由大到小排序的序号，*数据引自文献[16]，其他引自文献[17]。

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参考文献(21)

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浮选药剂性能理论分析

西安科技大学 化学与化工学院，陕西 西安 710054

作者简介: 王纪镇（1985— ），男，山东聊城人，博士，讲师，主要从事矿物浮选理论与工艺研究

Theoretical Analysis of Flotation Reagent Performance

College of Chemistry and Chemical Engineering, Xi’an University of Science and Technology, Xi’an 710054, China

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西安科技大学化学与化工学院，陕西西安 710054