四川里伍铜锌硫化矿浮选分离新工艺研究
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摘要
铜和锌都是国民经济中主要的原材料金属,国民经济的发展必然导致铜、锌需求量的增大。随着易选铜、锌矿石的逐渐减少,迫切需要对复杂难选的各类铜、锌矿石进行开发和利用。
本文以四川里伍铜矿的铜锌硫化矿矿石为研究对象,工艺矿物学研究表明:里伍矿区矿石中的铜矿物主要是黄铜矿,而锌矿物主要是铁闪锌矿,硫矿物主要是磁黄铁矿,铜-锌-硫分离较困难,属难选的多金属硫化矿。针对该矿石性质开发的“四川里伍铜锌硫化矿浮选分离新工艺”有效地实现了铜、锌、硫的分离。即:在选铜时采用新型高效铜捕收剂LP-01,可在中性介质条件下实现铜的富集,避免了由于高碱浮铜造成对铁闪锌矿的抑制而影响后续的铁闪锌矿的浮选;在锌硫分离时,粗选pH控制在9.5左右,精选时控制矿浆pH在10~11之间可有效实现锌硫分离。在原矿含铜1.42%,含锌0.98%的情况下,可获得含铜25.91%,含锌1.08%,对应铜的回收率为91.42%的铜精矿;获得含铜2.09%,含锌33.22%,对应锌的回收率为45.76%的锌精矿。
2007年5月,该新工艺在四川里伍铜矿下属选矿厂进行了工业试验,在原矿含铜1.38%,含锌1.01%的情况下,获得了含铜24.85%,含锌1.15%,对应铜回收率为90.67%的铜精矿,获得含铜2.12%,含锌35.20%,对应锌的回收率45.31%的锌精矿。初步经济分析结果表明,新工艺每年可为企业新增216.46万元的净现金流量。
采用红外光谱表面分析与电化学表面分析技术对新工艺进行了机理研究。研究结果表明:①LP-01在黄铜矿表面有明显的化学吸附现象,而在铁闪锌矿表面则基本没有吸附。②在酸性条件下,铁闪锌矿表面形成缺金属富硫的中间态ZnxFe1-x-yS2,随着电位升高,继续氧化Fe~(2+)、Zn~(2+)、SO_4~(2-);在近中性、弱碱性条件下,铁闪锌矿表面形成羟基化富硫层中间态(ZnxFe1-x(OH)_nS2),并继续氧化成Fe(OH)_3、Zn(OH)_2、SO_4~(2-);随碱性增强,这个中间态的稳定性越差,pH>10后,将直接氧化为Fe(OH)_3、Zn(OH)_2、SO_4~(2-),pH>11时,形成Zn(OH)_42-。Fe(OH)_3、Zn(OH)_2只能部分附着在矿物电极表面,电极过程由腐蚀氧化的电化学反应控制。③在高碱高钙体系中,D-在铁闪锌矿表面吸附能力较差,不存在D2电流峰;E﹥0.5V,D-和铁闪锌矿电极发生电化学反应,并生成了S2O32-和SO_4~(2-)。
There is an increasing demand for zinc and coper metals as a major raw material with the development of economy and it becomes urgently necessary to exploit refractory zinc and coper ores as the easily-separate zinc and coper ores increasingly reduce.
Zinc and coper sulfide metals of Liwu were studied in this subject, the mineralogy of sample indicates that the test material belongs to refractory metallic sulphide ore, with the primary minerals in the materials being chalcopyrite, marmatite and pyrrhotite. The efficient concentration of copper is achieved using the new copper collector LP-01 in a mild slurry medium, without the negative effect for marmatite depression due to high alkali medium during copper flotation; and the zinc-sulphide is also successfully achieved by controlling the pH values of slurry mediums at around 9.5 during roughing stage and at 10~11 during reconcentrating stage, respectively. This technology has obtained relatively qualified copper concentrate and zinc concentrate while applied in industry. The ore contain 1.42% Cu、0.98% Zn, then the copper concentrate which contain 25.91% Cu、1.08% Zn is received, and the recovery of Cu is 91.42%; the zinc concentrate which contain 2.09% Cu、33.22% Zn is received, and the recovery of Zn is 45.76%.
Industrial tests of this technology put up in concentration plant of LiWu copper ore company in Sichuan at May 2007, the result of industrial tests show that the copper concentrate which contain 24.85% Cu、1.15% Zn is received, as the green ore contain 1.38% Cu、1.01% Zn, the recovery of Cu is 90.67%, the zinc concentrate which contain 2.12% Cu、35.20% Zn is received, and the recovery of Zn is 45.31%. According to budgeting, Net cash flow will be increased 2.1646million Yuan every year.
The new technics’mechanism is studied through the FT-IR and electrochemistry surface analysis.the consqueces are as following:①the LP-01 are obviously chemical-adsobed on the surface of chalcopyrite but on the surface of the marmatite.②under the acidic condition the metaless sulphury mediacy ZnxFe1-x-yS2 is formed on the surface of the marmatite ,with the raise of the electric potential the Fe~(2+)、Zn~(2+) and SO_4~(2-) are oxidized soon after; under the alkalescence and close to the neutral conditions the hydroxylation sulphury mediacy (ZnxFe1-x(OH)_nS2) is formed on the surface of the marmatite, and then oxidized to Fe(OH)_3、Zn(OH)_2、SO_4~(2-); the stability of the mediacy is weaken as the alkalescence increased,when the pH>10 it would be oxidized immediately to Fe(OH)_3、Zn(OH)_2、SO_4~(2-) , when the pH>11, it will formed Zn(OH)_42-。Fe(OH)_3、Zn(OH)_2 can only cling to the surface of the mineral electrode.③in the high-alkaly and high-lime system, the adsorptive capacity of D- to the marmatite is poor, the peak of D2 is not exist;, the reaction between the marmatite and D- take place when E﹥0.5V, then the S2O32- and SO_4~(2-) are produced.
本文以四川里伍铜矿的铜锌硫化矿矿石为研究对象,工艺矿物学研究表明:里伍矿区矿石中的铜矿物主要是黄铜矿,而锌矿物主要是铁闪锌矿,硫矿物主要是磁黄铁矿,铜-锌-硫分离较困难,属难选的多金属硫化矿。针对该矿石性质开发的“四川里伍铜锌硫化矿浮选分离新工艺”有效地实现了铜、锌、硫的分离。即:在选铜时采用新型高效铜捕收剂LP-01,可在中性介质条件下实现铜的富集,避免了由于高碱浮铜造成对铁闪锌矿的抑制而影响后续的铁闪锌矿的浮选;在锌硫分离时,粗选pH控制在9.5左右,精选时控制矿浆pH在10~11之间可有效实现锌硫分离。在原矿含铜1.42%,含锌0.98%的情况下,可获得含铜25.91%,含锌1.08%,对应铜的回收率为91.42%的铜精矿;获得含铜2.09%,含锌33.22%,对应锌的回收率为45.76%的锌精矿。
2007年5月,该新工艺在四川里伍铜矿下属选矿厂进行了工业试验,在原矿含铜1.38%,含锌1.01%的情况下,获得了含铜24.85%,含锌1.15%,对应铜回收率为90.67%的铜精矿,获得含铜2.12%,含锌35.20%,对应锌的回收率45.31%的锌精矿。初步经济分析结果表明,新工艺每年可为企业新增216.46万元的净现金流量。
采用红外光谱表面分析与电化学表面分析技术对新工艺进行了机理研究。研究结果表明:①LP-01在黄铜矿表面有明显的化学吸附现象,而在铁闪锌矿表面则基本没有吸附。②在酸性条件下,铁闪锌矿表面形成缺金属富硫的中间态ZnxFe1-x-yS2,随着电位升高,继续氧化Fe~(2+)、Zn~(2+)、SO_4~(2-);在近中性、弱碱性条件下,铁闪锌矿表面形成羟基化富硫层中间态(ZnxFe1-x(OH)_nS2),并继续氧化成Fe(OH)_3、Zn(OH)_2、SO_4~(2-);随碱性增强,这个中间态的稳定性越差,pH>10后,将直接氧化为Fe(OH)_3、Zn(OH)_2、SO_4~(2-),pH>11时,形成Zn(OH)_42-。Fe(OH)_3、Zn(OH)_2只能部分附着在矿物电极表面,电极过程由腐蚀氧化的电化学反应控制。③在高碱高钙体系中,D-在铁闪锌矿表面吸附能力较差,不存在D2电流峰;E﹥0.5V,D-和铁闪锌矿电极发生电化学反应,并生成了S2O32-和SO_4~(2-)。
There is an increasing demand for zinc and coper metals as a major raw material with the development of economy and it becomes urgently necessary to exploit refractory zinc and coper ores as the easily-separate zinc and coper ores increasingly reduce.
Zinc and coper sulfide metals of Liwu were studied in this subject, the mineralogy of sample indicates that the test material belongs to refractory metallic sulphide ore, with the primary minerals in the materials being chalcopyrite, marmatite and pyrrhotite. The efficient concentration of copper is achieved using the new copper collector LP-01 in a mild slurry medium, without the negative effect for marmatite depression due to high alkali medium during copper flotation; and the zinc-sulphide is also successfully achieved by controlling the pH values of slurry mediums at around 9.5 during roughing stage and at 10~11 during reconcentrating stage, respectively. This technology has obtained relatively qualified copper concentrate and zinc concentrate while applied in industry. The ore contain 1.42% Cu、0.98% Zn, then the copper concentrate which contain 25.91% Cu、1.08% Zn is received, and the recovery of Cu is 91.42%; the zinc concentrate which contain 2.09% Cu、33.22% Zn is received, and the recovery of Zn is 45.76%.
Industrial tests of this technology put up in concentration plant of LiWu copper ore company in Sichuan at May 2007, the result of industrial tests show that the copper concentrate which contain 24.85% Cu、1.15% Zn is received, as the green ore contain 1.38% Cu、1.01% Zn, the recovery of Cu is 90.67%, the zinc concentrate which contain 2.12% Cu、35.20% Zn is received, and the recovery of Zn is 45.31%. According to budgeting, Net cash flow will be increased 2.1646million Yuan every year.
The new technics’mechanism is studied through the FT-IR and electrochemistry surface analysis.the consqueces are as following:①the LP-01 are obviously chemical-adsobed on the surface of chalcopyrite but on the surface of the marmatite.②under the acidic condition the metaless sulphury mediacy ZnxFe1-x-yS2 is formed on the surface of the marmatite ,with the raise of the electric potential the Fe~(2+)、Zn~(2+) and SO_4~(2-) are oxidized soon after; under the alkalescence and close to the neutral conditions the hydroxylation sulphury mediacy (ZnxFe1-x(OH)_nS2) is formed on the surface of the marmatite, and then oxidized to Fe(OH)_3、Zn(OH)_2、SO_4~(2-); the stability of the mediacy is weaken as the alkalescence increased,when the pH>10 it would be oxidized immediately to Fe(OH)_3、Zn(OH)_2、SO_4~(2-) , when the pH>11, it will formed Zn(OH)_42-。Fe(OH)_3、Zn(OH)_2 can only cling to the surface of the mineral electrode.③in the high-alkaly and high-lime system, the adsorptive capacity of D- to the marmatite is poor, the peak of D2 is not exist;, the reaction between the marmatite and D- take place when E﹥0.5V, then the S2O32- and SO_4~(2-) are produced.
引文
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