黄铜矿和方铅矿浮选分离的基础研究
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摘要
浮选的发展已有一百多年的历史,但铜铅分离至今仍是选矿难题之一。本文在查阅大量文献资料的基础上,系统总结了铜铅分离的流程结构、药剂制度、电化学性质以及铜铅分离机理的研究现状。通过试验研究、仪器检测和理论计算,探讨了捕收剂、抑制剂对硫化矿物可浮性影响的作用机理：
通过大量的浮选试验系统地研究了选择性捕收剂、Na2SO3和ZnSO4等抑制剂和新型抑制剂等浮选药剂对硫化矿物单矿物的可浮性和双矿物浮选分离以及实际矿物分离的影响；
利用矿浆电位在线检测技术系统地记录了硫化矿物浮选过程中矿浆电位的变化规律；
采用X射线衍射(XRD)、X射线光电子能谱(XPS)、红外光谱(FTIR)以及其它物理、化学等现代分析技术检测了经过不同药剂处理后的黄铜矿、方铅矿表面产物的性质变化；
利用Materials Studio等软件进行了分子力学、量子化学的计算。
重点对比研究了乙硫氨酯、丁基铵黑药和乙基钾黄药等选择性捕收剂对黄铜矿和方铅矿的浮选效果。研究结果表明：
在5.7≤pH≤7.2,10mV≤ECu≤50mV、-30mV≤EPb≤30mV、160≤EPt≤470mV
或9.0≤pH≤11.5、-50mV≤ECu≤-10mV、-100mV≤EPb≤-50mV、0mV≤EPt≤100mV区间内
乙硫氨酯可以用作黄铜矿和方铅矿浮选分离时的选择性捕收剂；且随着乙硫氨酯浓度的增大,黄铜矿和方铅矿间的浮游差基本稳定。机理研究表明,乙硫氨酯对黄铜矿的捕收作用是由于乙硫氨酯在黄铜矿表面与Cu原子或Fe原子发生作用,生成了新的表面生成物的缘故。
经过对矿浆中可能存在的难免离子进行研究后发现,实际矿石在用去离子水浸泡后,上清液中发生显著变化的金属离子有Ca2+、Mg2+、Na+、Mn2+、Fe2+、Fe3+、K+、Cu2+、Zn2+、Al3+和Li+等。利用上述离子的可溶性盐的水溶液对黄铜矿和方铅矿的可浮性进行了研究,结果表明：
上述离子对黄铜矿的浮选没有显著影响；
而对方铅矿的影响可以分成三类：有活化作用的如Cu+；有抑制作用的如Al3+、Fe3+和Fe2+等离子,尤其是Al3+、Fe3+等高价离子实际上已经对用乙硫氨酯浮选方铅矿产生了实质性的抑制；基本不起作用的如Mg2+和Ca2+等离子。
研究了ZnSO4、Na2SO3、NaHSO3、Na2S2O3、Na2SO4等化合物对黄铜矿和方铅矿单矿物浮选的影响,结果表明,在用乙硫氨酯做捕收剂的单矿物系统中,ZnSO4、Na2SO3、NaHSO3可以用作方铅矿的抑制剂,实现抑铅浮铜的目的。ZnSO4、Na2SO3对两种矿物的人工混合矿和实际矿物的分离试验结果表明：
单用ZnSO4,低浓度时不能有效抑制方铅矿,但高浓度时可以起到抑制作用；
单用Na2SO3,虽然对方铅矿具有抑制作用,但高浓度时对黄铜矿也有抑制作用。
机理研究表明,Na2SO3对方铅矿的抑制作用是SO32-在方铅矿表面与Pb2+离子反应生成亲水性的PbSO3薄膜覆盖在方铅矿表面,阻碍了捕收剂与方铅矿的作用的缘故。
根据矿浆电化学特性筛选出了三种新型方铅矿抑制剂PPD、DDT和PDA,研究表明：三种药剂对方铅矿均有抑制作用,对黄铜矿均有活化作用。用于黄铜矿和方铅矿单矿物、人工混合矿和实际矿物的铜铅分离试验结果表明,三种药剂均有可能成为铜铅分离的有效抑制剂,但三种药剂对方铅矿的抑制作用机理不同。
Under more than one hundred year, of research and development, flotation separation of Cu-Pb is not satisfying yet. On a basis of systematic literature search, this paper summarized flowsheet structure, reagent, electrochemistry property and mechanics of Cu-Pb separation. Via flotation tests, instrument detecting and calculation, extensively explored mechanics of collector and depressor's effect on sulphide floatability:
With the aid of advanced modern physical and chemical analysis technique such as XRD, XPS and FTIR, surveyed property variation of precipitates formed on chalcopyrite and galena surface processed by various reagents;
Systematically tested selective collectors, regular depressors such as Na2SO3 and ZnSO4 and newly developed depressors effect on single sulphide mineral's floatability, separation of two type of single minerals and production minerals;
Kept trace of pulp potential variation trend in the course of sulphide minerals flotation by using on-line pulp potential measurement technique;
Made calculation of molecular mechanics and quanta chemistry by using Materials Studio software.
In comparison, selective collectors, typically, (CH3)2CHOC(S)NHC2H5, (C4H9O)2PSSNa and C2H5OSCSK, were tested to make the difference of chalcopyrite and galena flotation result, it was indicated that,
In the case of 5.7≤pH≤7.2,10mV≤ECu≤50mV,-30mV≤EPb≤30mV, 160≤EPt≤470mV
Or,9.0≤pH≤11.5,-50mV≤ECu≤-10mV,-10mV≤ECu≤-50mV,0mV≤EPt≤100mV
(CH3)2CHOC(S)NHC2H5 can be of effective selective collector for chalcopyrite and galena separation, moreover, along with higher concentrates of (CH3)2CHOC(S)NHC2H5, the floatability difference of chalcopyrite and galena is almost fixed. The mechanism is such that (CH3)2CHOC(S)NHC2H5 makes reaction with Cu or Fe atom in surface of chalcopyrite to produce new resultant.
The study on "hard to avoid cations" which might be present in pulp indicates that after ore was soaped in ion-removing water, ions in upper water, including Ca2+, Mg2+, Na+, Mn2+, Fe2+, Fe3+, K+, Cu2+, Zn2+, Al3+ and Li+ etc, make evident change. And results from further study on chalcopyrite and galena floatability which is affected by dissoluble saline solution of the above ions are:
The above ions have no impact on chalcopyrite flotation;
But the effect on galena flotation falls into three categories:activating factor such as Cu+; depressing factor such as Al3+, Fe3+ and Fe2+, typically when using (CH3)2CHOC(S)NHC2H5 to float galena, high valence ions like Al3+, Fe3+ are strongly depressing; non-influence factor such as Mg2+ and Ca2+.
The investigation to influence of compound like ZnSO4, Na2SO3, NaHSO3, Na2S2O3 and Na2SO4 on single mineral flotation of chalcopyrite and galena reveals that ZnSO4, Na2SO3 and NaHSO3 can be used as depressor of galena to separate Cu from Pb when floating single mineral by using (CH3)2CHOC(S)NHC2H5 as collector. Test on man-made mixture of two type of minerals and production ore by using ZnSO4, Na2SO3 indicates that:
ZnSO4 solely, not at low concentrate but high concentrate, is depressing to galena;
Na2SO3 solely, is depressing to galena at low concentrate, but depressing to both galena and chalcopyrite at high concentrate.
The mechanism lies in the fact that SO32- from Na2SO3 makes reaction with Pb2+ in surface of galena to produce hydrophilic thin membrane of PbSO3 which covers surface of galena to prevent collector from making action with galena.
Three new depressors, PPD、DDT and PDA have been found out based on pulp electrochemistry property, which are depressing to galena and activating to chalcopyrite. Test on single mineral of chalcopyrite and galena, man-made mixture of chalcopyrite and galena and production ore conclude that possibly the three reagents will be effective depressors to separation of Cu-Pb, but response to different depressing mechanism.
通过大量的浮选试验系统地研究了选择性捕收剂、Na2SO3和ZnSO4等抑制剂和新型抑制剂等浮选药剂对硫化矿物单矿物的可浮性和双矿物浮选分离以及实际矿物分离的影响；
利用矿浆电位在线检测技术系统地记录了硫化矿物浮选过程中矿浆电位的变化规律；
采用X射线衍射(XRD)、X射线光电子能谱(XPS)、红外光谱(FTIR)以及其它物理、化学等现代分析技术检测了经过不同药剂处理后的黄铜矿、方铅矿表面产物的性质变化；
利用Materials Studio等软件进行了分子力学、量子化学的计算。
重点对比研究了乙硫氨酯、丁基铵黑药和乙基钾黄药等选择性捕收剂对黄铜矿和方铅矿的浮选效果。研究结果表明：
在5.7≤pH≤7.2,10mV≤ECu≤50mV、-30mV≤EPb≤30mV、160≤EPt≤470mV
或9.0≤pH≤11.5、-50mV≤ECu≤-10mV、-100mV≤EPb≤-50mV、0mV≤EPt≤100mV区间内
乙硫氨酯可以用作黄铜矿和方铅矿浮选分离时的选择性捕收剂；且随着乙硫氨酯浓度的增大,黄铜矿和方铅矿间的浮游差基本稳定。机理研究表明,乙硫氨酯对黄铜矿的捕收作用是由于乙硫氨酯在黄铜矿表面与Cu原子或Fe原子发生作用,生成了新的表面生成物的缘故。
经过对矿浆中可能存在的难免离子进行研究后发现,实际矿石在用去离子水浸泡后,上清液中发生显著变化的金属离子有Ca2+、Mg2+、Na+、Mn2+、Fe2+、Fe3+、K+、Cu2+、Zn2+、Al3+和Li+等。利用上述离子的可溶性盐的水溶液对黄铜矿和方铅矿的可浮性进行了研究,结果表明：
上述离子对黄铜矿的浮选没有显著影响；
而对方铅矿的影响可以分成三类：有活化作用的如Cu+；有抑制作用的如Al3+、Fe3+和Fe2+等离子,尤其是Al3+、Fe3+等高价离子实际上已经对用乙硫氨酯浮选方铅矿产生了实质性的抑制；基本不起作用的如Mg2+和Ca2+等离子。
研究了ZnSO4、Na2SO3、NaHSO3、Na2S2O3、Na2SO4等化合物对黄铜矿和方铅矿单矿物浮选的影响,结果表明,在用乙硫氨酯做捕收剂的单矿物系统中,ZnSO4、Na2SO3、NaHSO3可以用作方铅矿的抑制剂,实现抑铅浮铜的目的。ZnSO4、Na2SO3对两种矿物的人工混合矿和实际矿物的分离试验结果表明：
单用ZnSO4,低浓度时不能有效抑制方铅矿,但高浓度时可以起到抑制作用；
单用Na2SO3,虽然对方铅矿具有抑制作用,但高浓度时对黄铜矿也有抑制作用。
机理研究表明,Na2SO3对方铅矿的抑制作用是SO32-在方铅矿表面与Pb2+离子反应生成亲水性的PbSO3薄膜覆盖在方铅矿表面,阻碍了捕收剂与方铅矿的作用的缘故。
根据矿浆电化学特性筛选出了三种新型方铅矿抑制剂PPD、DDT和PDA,研究表明：三种药剂对方铅矿均有抑制作用,对黄铜矿均有活化作用。用于黄铜矿和方铅矿单矿物、人工混合矿和实际矿物的铜铅分离试验结果表明,三种药剂均有可能成为铜铅分离的有效抑制剂,但三种药剂对方铅矿的抑制作用机理不同。
Under more than one hundred year, of research and development, flotation separation of Cu-Pb is not satisfying yet. On a basis of systematic literature search, this paper summarized flowsheet structure, reagent, electrochemistry property and mechanics of Cu-Pb separation. Via flotation tests, instrument detecting and calculation, extensively explored mechanics of collector and depressor's effect on sulphide floatability:
With the aid of advanced modern physical and chemical analysis technique such as XRD, XPS and FTIR, surveyed property variation of precipitates formed on chalcopyrite and galena surface processed by various reagents;
Systematically tested selective collectors, regular depressors such as Na2SO3 and ZnSO4 and newly developed depressors effect on single sulphide mineral's floatability, separation of two type of single minerals and production minerals;
Kept trace of pulp potential variation trend in the course of sulphide minerals flotation by using on-line pulp potential measurement technique;
Made calculation of molecular mechanics and quanta chemistry by using Materials Studio software.
In comparison, selective collectors, typically, (CH3)2CHOC(S)NHC2H5, (C4H9O)2PSSNa and C2H5OSCSK, were tested to make the difference of chalcopyrite and galena flotation result, it was indicated that,
In the case of 5.7≤pH≤7.2,10mV≤ECu≤50mV,-30mV≤EPb≤30mV, 160≤EPt≤470mV
Or,9.0≤pH≤11.5,-50mV≤ECu≤-10mV,-10mV≤ECu≤-50mV,0mV≤EPt≤100mV
(CH3)2CHOC(S)NHC2H5 can be of effective selective collector for chalcopyrite and galena separation, moreover, along with higher concentrates of (CH3)2CHOC(S)NHC2H5, the floatability difference of chalcopyrite and galena is almost fixed. The mechanism is such that (CH3)2CHOC(S)NHC2H5 makes reaction with Cu or Fe atom in surface of chalcopyrite to produce new resultant.
The study on "hard to avoid cations" which might be present in pulp indicates that after ore was soaped in ion-removing water, ions in upper water, including Ca2+, Mg2+, Na+, Mn2+, Fe2+, Fe3+, K+, Cu2+, Zn2+, Al3+ and Li+ etc, make evident change. And results from further study on chalcopyrite and galena floatability which is affected by dissoluble saline solution of the above ions are:
The above ions have no impact on chalcopyrite flotation;
But the effect on galena flotation falls into three categories:activating factor such as Cu+; depressing factor such as Al3+, Fe3+ and Fe2+, typically when using (CH3)2CHOC(S)NHC2H5 to float galena, high valence ions like Al3+, Fe3+ are strongly depressing; non-influence factor such as Mg2+ and Ca2+.
The investigation to influence of compound like ZnSO4, Na2SO3, NaHSO3, Na2S2O3 and Na2SO4 on single mineral flotation of chalcopyrite and galena reveals that ZnSO4, Na2SO3 and NaHSO3 can be used as depressor of galena to separate Cu from Pb when floating single mineral by using (CH3)2CHOC(S)NHC2H5 as collector. Test on man-made mixture of two type of minerals and production ore by using ZnSO4, Na2SO3 indicates that:
ZnSO4 solely, not at low concentrate but high concentrate, is depressing to galena;
Na2SO3 solely, is depressing to galena at low concentrate, but depressing to both galena and chalcopyrite at high concentrate.
The mechanism lies in the fact that SO32- from Na2SO3 makes reaction with Pb2+ in surface of galena to produce hydrophilic thin membrane of PbSO3 which covers surface of galena to prevent collector from making action with galena.
Three new depressors, PPD、DDT and PDA have been found out based on pulp electrochemistry property, which are depressing to galena and activating to chalcopyrite. Test on single mineral of chalcopyrite and galena, man-made mixture of chalcopyrite and galena and production ore conclude that possibly the three reagents will be effective depressors to separation of Cu-Pb, but response to different depressing mechanism.
引文
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