大厂100（105）号锡石多金属矿选矿关键技术研究及应用
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摘要
广西大厂矿区所属100(105)号矿体是一个生成在生物礁灰岩内的锡石—硫化矿类型特富矿床。本文对锡石-铅锑锌多金属硫化矿的硫化矿物、锡石进行了浮选试验和理论研究。在此基础上,进行了硫化矿浮选、磁选和细粒锡石浮选流程结构的设计,实施了工业试验和现场流程改造。通过理论研究,开展大厂100(105)号矿选矿优化流程研究,总结了提高现场指标的多项关键技术。
对100(105)号矿体特有的硫化矿物的浮选行为进行研究,在酸性条件下,脆硫锑铅矿、铁闪锌矿与磁黄铁矿、黄铁矿等四种矿物均有较好的可浮性,在强碱性介质中,矿物的可浮性都变差。少量的Cu~(2+)可强烈地活化铁闪锌矿;矿浆电位对四种矿物的浮选有明显的影响,不同硫化矿浮选有不同的电位区间。对于受Cu~(2+)活化和吸附有黄药的铁闪锌矿、磁黄铁矿和黄铁矿,采用高石灰用量、高pH矿浆和适当的电位环境,可有效地抑制磁黄铁矿、黄铁矿。
应用浮选、磁选新工艺,进行大厂100(105)号特富矿铅(锑)锌硫化矿的分离研究。采用粗粒浮选工艺,将硫化矿脱除,然后采用重选回收锡石,硫化矿的浮选分离主要分为铅(锑)-锌硫浮选分离、锌硫浮选分离两大工艺。主要研究内容有:(1)矿浆pH值对锑铅浮选的影响;(2)焦亚硫酸钠、硫酸锌、CDP、对抑制锌硫的影响;(3)组合捕收剂对锑铅浮选的影响;(4)锌硫浮选分离。
通过热力学计算,建立了几种硫化矿物在不同体系中的电位E—pH图,推测了各硫化矿物在水溶液体系中表面氧化产物类型,随着pH升高、电位Eh增加,其表面氧化产物由疏水性的元素S~0向亲水性的S_2O_3~(2-)、金属氢氧化物等转换。在不同的体系中,对导电性较好的硫化矿物进行了系统的电化学测试分析,推测矿物电极表面氧化反应历程和氧化产物类型,在不同的pH值条件和扫描电位下,表面氧化产物及捕收剂作用产物各不相同,可以推断其发生的反应历程与Eh-pH图的预测基本一致。
结合现场生产工艺的不足,以药剂开发为主要手段,对100(105)号矿的微细粒锡石进行试验回收研究和理论探讨,重点研究了回收微细粒锡石的高效捕收剂-SR(一种烃基羟肟酸),借鉴凝聚浮选、分散、载体浮选等先进技术,开发合理的浮锡新工艺。根据大厂100(105)号矿石细粒锡石性质,采用新的组合药剂进行浮选,不脱出-10微米粒级的矿泥,使得细粒锡石选择性凝聚浮选。工业应用结果表明:应用新工艺和新药剂浮选锡石细泥,锡精矿品位达到11.43%,作业回收率达到88.72%,对原矿回收率达到4.05%,目前的工业应指标已经满足了市场的质量品级的要求。在理论上,用红外光谱、Zeta电位测定对SR在锡石上的作用进行了定性研究,查明SR在锡石表面作用机理。
大厂100(105)号矿中有价主金属为锡锌铅锑银。本文在系统的理论和选矿小型试验、扩大试验基础上进行了选矿流程优化,其技术特点为:(1)采用预先筛分、阶段磨矿、新型的高频细筛和第二段磨矿用铸铁段代球等项技术减少锡石过粉碎,大幅度减少锡石泥化;(2)在流程前部用磁选(入选粒度为-1.43mm)选出产率约25%的磁性物,排除磁黄铁矿对浮选和摇床选别的干扰,并且提高选厂的处理能力;(3)采用、浮选流程强化脱硫,为重选回收锡石创造条件,并且选定入选粒度为-0.25mm兼顾硫化矿浮选和摇床收锡对粒度的要求;(4)采用国内外首创的高碱无氰从脆硫锑铅矿、铁闪锌矿、磁黄铁矿和黄铁矿的混合精矿中优先选铅锑精矿新工艺,铅硫分离作业回收率达到国际先进水平。现工艺流程基本解决的锡石与硫化矿和脉石的分离及硫化矿之间的分离的关键技术。指标为:原矿锡石品位1.96%,锌8.72%,铅3.74%,锑3.87%,银140g/t;精矿品位锡(粗砂)54.92%,锌45.12%,铅锑精矿含铅29.13%,含锑25.49%;锡锌铅锑银五种金属选矿综合回收率78.88%,其中锡回收率83.72%(主流程76.70%,尾矿再选7.02%)。伴生的铟富集于锌精矿中(铟品位0.094%),选矿废水全部回用,达到了国内外同类矿石选矿的先进水平。
Dachang Tin-polymetallic ore field is located in the northwestern part of Guangxi.No.100 and No.105 ore body of Dachang Tin-polymetallic deposit should be a ore body from everywhere,and sets up and testifies the new viewpoint.No.100(105)ore body of the Dachang mine is rich in Sn,Zn,Pb,Sb,Ag,In,Cd and Au,which are of great comprehensive recovering value.
In this thesis,the beneficiation of No.100 and No.105 ore body of Dachang tin-polymetallic deposit was studied.The beneflcation flow was designed,revised,and practical experiments were carried out.Based on the flotation theory of sulfide minerals,the mechanism of sulfide flotation and its practical application was studied.
The flotation tests of jamesonite,marmatite,pyrite and pyrrhotite were performed.The relationship of pulp potential and the pulp pH value and the concentration of collector is the crux factor of flotation.The relationship between pH value and concentration of collector(C)and floatability of forth sulfide minerals,which include jamesonite,marmatite, pyrite and pyrrhotite,were discussed.When the pulp pH value range is lower than 7.0,sulfide minerals haves well floatability.When the pulp pH value is above 12,the pyrite and pyrrhotite cannot be floated easily in the presence of CuSO_4 and xanthate used as a activator and collector respectively.
The dominant parameters of sulfide mineral floatation system were ascertained.Effective recovery of the valuable minerals can be achieved by processing the ore from No.100(105)ore body using the preferential-bulk flotation flowsheet.During the process of sulfide minerals of No.100 and No.105 ore body floatation,several important parameters including pulp pH value,depressers,collectors,flotation time and the flow structure were controlled and adjusted.
Through the thermodynamic calculation,the Eh—pH equilibrium of jamesonite,marmatite,pyrite and pyrrhotite in the absence or presence of collector were set up.In acid solution,the oxidative product is neutral sulfur but S_2O_3~(2-)ion,Fe(OH)_2 etc.The Voltammogram measurement showed that the products formated by the surface oxidation of sulfide minerals were different,and the processes of the reaction were in keeping with the calculation results of the E—pH equilibrium.
The cassiterite slime of Dachang industry contains a variety of sulfide minerals and gangues including quartz and calcite.A little of the ore particles of slime are minor than 10μm,in which the content of tin is large.Theory analysis and flotation test of slime,mineral and mixed ore were carried out in this thesis.A new kind of the collector of benzohydroxamic(SR),and the depressant of quartz and calcite and P86 were used in flotation separation of cassiterite from slime.It was shown that benzohydroxamic is a stronger collector for cassiterite,and the pH range of efficient flotation for cassiterite is much wide.P86 can improve the interaction of benzohydroxamic with cassiterite,and it reduce the consume of benzohydroxamic in flotation processing.The adsorption mechanism of benzohydroxamic on cassiterite was studied by the determination of the infraed spectra,zeta potential measurement.It was indicated that benzohydroxamic is chemically adsorbed on the surface of cassiterite.The grade of Sn concent ate is 11.43%with the recovery of 88.72%.
No.100 and No.105 ore body of Dachang is tin-polymetallic ore.In the new process,the grinding size is controlled at - 0.25mm and the principle p rocess f low is magnetic separation flotation-gravity separation.In magnetic separation,magnetite is separated out to eliminate its effect on sulfide flotation;in flotation,the selective flotation of Pb, Sb-bulk flotation-separation of Zn from S is applied;in gravity separation, concentrating table is applied to recover cassiterite in tailings from flotation.Application of this process in Bali Mineral Processing Plant indicates that the technology is reasonable and production indexes have reached design requiremen t.When the original grade of metals were: Pb3.74%,Sb3.87%,Zn8.72%and Sn1.96%,the grade of Sn concentrate is 54.92%with the recovery of 83.72%;the Pb,Sb concentrate contains 29.13%Pb,25.49%Sb,recovery 84.78%and the grade of Zn concentrate is 445.12%w ith the recovery 82.10%.Waste water was recycled in the flow.By adding flocculate reagents with high molecular weight in the major flow,the water was purified and recycled.The recycling rate was over 100%.
对100(105)号矿体特有的硫化矿物的浮选行为进行研究,在酸性条件下,脆硫锑铅矿、铁闪锌矿与磁黄铁矿、黄铁矿等四种矿物均有较好的可浮性,在强碱性介质中,矿物的可浮性都变差。少量的Cu~(2+)可强烈地活化铁闪锌矿;矿浆电位对四种矿物的浮选有明显的影响,不同硫化矿浮选有不同的电位区间。对于受Cu~(2+)活化和吸附有黄药的铁闪锌矿、磁黄铁矿和黄铁矿,采用高石灰用量、高pH矿浆和适当的电位环境,可有效地抑制磁黄铁矿、黄铁矿。
应用浮选、磁选新工艺,进行大厂100(105)号特富矿铅(锑)锌硫化矿的分离研究。采用粗粒浮选工艺,将硫化矿脱除,然后采用重选回收锡石,硫化矿的浮选分离主要分为铅(锑)-锌硫浮选分离、锌硫浮选分离两大工艺。主要研究内容有:(1)矿浆pH值对锑铅浮选的影响;(2)焦亚硫酸钠、硫酸锌、CDP、对抑制锌硫的影响;(3)组合捕收剂对锑铅浮选的影响;(4)锌硫浮选分离。
通过热力学计算,建立了几种硫化矿物在不同体系中的电位E—pH图,推测了各硫化矿物在水溶液体系中表面氧化产物类型,随着pH升高、电位Eh增加,其表面氧化产物由疏水性的元素S~0向亲水性的S_2O_3~(2-)、金属氢氧化物等转换。在不同的体系中,对导电性较好的硫化矿物进行了系统的电化学测试分析,推测矿物电极表面氧化反应历程和氧化产物类型,在不同的pH值条件和扫描电位下,表面氧化产物及捕收剂作用产物各不相同,可以推断其发生的反应历程与Eh-pH图的预测基本一致。
结合现场生产工艺的不足,以药剂开发为主要手段,对100(105)号矿的微细粒锡石进行试验回收研究和理论探讨,重点研究了回收微细粒锡石的高效捕收剂-SR(一种烃基羟肟酸),借鉴凝聚浮选、分散、载体浮选等先进技术,开发合理的浮锡新工艺。根据大厂100(105)号矿石细粒锡石性质,采用新的组合药剂进行浮选,不脱出-10微米粒级的矿泥,使得细粒锡石选择性凝聚浮选。工业应用结果表明:应用新工艺和新药剂浮选锡石细泥,锡精矿品位达到11.43%,作业回收率达到88.72%,对原矿回收率达到4.05%,目前的工业应指标已经满足了市场的质量品级的要求。在理论上,用红外光谱、Zeta电位测定对SR在锡石上的作用进行了定性研究,查明SR在锡石表面作用机理。
大厂100(105)号矿中有价主金属为锡锌铅锑银。本文在系统的理论和选矿小型试验、扩大试验基础上进行了选矿流程优化,其技术特点为:(1)采用预先筛分、阶段磨矿、新型的高频细筛和第二段磨矿用铸铁段代球等项技术减少锡石过粉碎,大幅度减少锡石泥化;(2)在流程前部用磁选(入选粒度为-1.43mm)选出产率约25%的磁性物,排除磁黄铁矿对浮选和摇床选别的干扰,并且提高选厂的处理能力;(3)采用、浮选流程强化脱硫,为重选回收锡石创造条件,并且选定入选粒度为-0.25mm兼顾硫化矿浮选和摇床收锡对粒度的要求;(4)采用国内外首创的高碱无氰从脆硫锑铅矿、铁闪锌矿、磁黄铁矿和黄铁矿的混合精矿中优先选铅锑精矿新工艺,铅硫分离作业回收率达到国际先进水平。现工艺流程基本解决的锡石与硫化矿和脉石的分离及硫化矿之间的分离的关键技术。指标为:原矿锡石品位1.96%,锌8.72%,铅3.74%,锑3.87%,银140g/t;精矿品位锡(粗砂)54.92%,锌45.12%,铅锑精矿含铅29.13%,含锑25.49%;锡锌铅锑银五种金属选矿综合回收率78.88%,其中锡回收率83.72%(主流程76.70%,尾矿再选7.02%)。伴生的铟富集于锌精矿中(铟品位0.094%),选矿废水全部回用,达到了国内外同类矿石选矿的先进水平。
Dachang Tin-polymetallic ore field is located in the northwestern part of Guangxi.No.100 and No.105 ore body of Dachang Tin-polymetallic deposit should be a ore body from everywhere,and sets up and testifies the new viewpoint.No.100(105)ore body of the Dachang mine is rich in Sn,Zn,Pb,Sb,Ag,In,Cd and Au,which are of great comprehensive recovering value.
In this thesis,the beneficiation of No.100 and No.105 ore body of Dachang tin-polymetallic deposit was studied.The beneflcation flow was designed,revised,and practical experiments were carried out.Based on the flotation theory of sulfide minerals,the mechanism of sulfide flotation and its practical application was studied.
The flotation tests of jamesonite,marmatite,pyrite and pyrrhotite were performed.The relationship of pulp potential and the pulp pH value and the concentration of collector is the crux factor of flotation.The relationship between pH value and concentration of collector(C)and floatability of forth sulfide minerals,which include jamesonite,marmatite, pyrite and pyrrhotite,were discussed.When the pulp pH value range is lower than 7.0,sulfide minerals haves well floatability.When the pulp pH value is above 12,the pyrite and pyrrhotite cannot be floated easily in the presence of CuSO_4 and xanthate used as a activator and collector respectively.
The dominant parameters of sulfide mineral floatation system were ascertained.Effective recovery of the valuable minerals can be achieved by processing the ore from No.100(105)ore body using the preferential-bulk flotation flowsheet.During the process of sulfide minerals of No.100 and No.105 ore body floatation,several important parameters including pulp pH value,depressers,collectors,flotation time and the flow structure were controlled and adjusted.
Through the thermodynamic calculation,the Eh—pH equilibrium of jamesonite,marmatite,pyrite and pyrrhotite in the absence or presence of collector were set up.In acid solution,the oxidative product is neutral sulfur but S_2O_3~(2-)ion,Fe(OH)_2 etc.The Voltammogram measurement showed that the products formated by the surface oxidation of sulfide minerals were different,and the processes of the reaction were in keeping with the calculation results of the E—pH equilibrium.
The cassiterite slime of Dachang industry contains a variety of sulfide minerals and gangues including quartz and calcite.A little of the ore particles of slime are minor than 10μm,in which the content of tin is large.Theory analysis and flotation test of slime,mineral and mixed ore were carried out in this thesis.A new kind of the collector of benzohydroxamic(SR),and the depressant of quartz and calcite and P86 were used in flotation separation of cassiterite from slime.It was shown that benzohydroxamic is a stronger collector for cassiterite,and the pH range of efficient flotation for cassiterite is much wide.P86 can improve the interaction of benzohydroxamic with cassiterite,and it reduce the consume of benzohydroxamic in flotation processing.The adsorption mechanism of benzohydroxamic on cassiterite was studied by the determination of the infraed spectra,zeta potential measurement.It was indicated that benzohydroxamic is chemically adsorbed on the surface of cassiterite.The grade of Sn concent ate is 11.43%with the recovery of 88.72%.
No.100 and No.105 ore body of Dachang is tin-polymetallic ore.In the new process,the grinding size is controlled at - 0.25mm and the principle p rocess f low is magnetic separation flotation-gravity separation.In magnetic separation,magnetite is separated out to eliminate its effect on sulfide flotation;in flotation,the selective flotation of Pb, Sb-bulk flotation-separation of Zn from S is applied;in gravity separation, concentrating table is applied to recover cassiterite in tailings from flotation.Application of this process in Bali Mineral Processing Plant indicates that the technology is reasonable and production indexes have reached design requiremen t.When the original grade of metals were: Pb3.74%,Sb3.87%,Zn8.72%and Sn1.96%,the grade of Sn concentrate is 54.92%with the recovery of 83.72%;the Pb,Sb concentrate contains 29.13%Pb,25.49%Sb,recovery 84.78%and the grade of Zn concentrate is 445.12%w ith the recovery 82.10%.Waste water was recycled in the flow.By adding flocculate reagents with high molecular weight in the major flow,the water was purified and recycled.The recycling rate was over 100%.
引文
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