Floatability of chalcopyrite and molybdenite in the presence of lignosulfonates. Part I. Adsorption studies

The adsorption of six lignosulfonates on molybdenite and chalcopyrite was studied through direct adsorption measurements and size exclusion chromatography at natural pH (5.0–5.5) and pH 11. The tests were carried out using different reagents for pH adjustments, i.e., potassium hydroxide (KOH), lime (CaO), and sodium carbonate (soda ash – Na₂CO₃). In the case of chalcopyrite, all the tests were performed in the presence of potassium ethyl xanthate – a chalcopyrite collector – added ahead of lignosulfonates. Overall, lignosulfonates give higher adsorption densities on chalcopyrite than on molybdenite. The adsorption density on both minerals was a function of not only the pH but also of the type of pH modifier used. Additions of lime enhanced lignosulfonate adsorption at higher pH but the adsorption of lignosulfonates dramatically decreased when soda ash or KOH were used for pH control. For all the lignosulfonates tested, higher molecular weight fractions tended to preferentially adsorb over lower molecular weight components. The results also indicated that electrostatic forces and chemical interactions between the anionic polyelectrolytes and metal-hydroxy sites on the mineral surfaces largely controlled the adsorption process.     

一种新型辉钼矿抑制剂及其在铜钼浮选分离中的机理研究

针对目前铜钼浮选分离所使用的传统黄铜矿抑制剂存在毒性大、对环境污染严重等问题,开发出新型辉钼矿的抑制剂以实现铜钼的有效分离具有重要的意义。本文拟开发黄腐酸(FA)作为新型高效的辉钼矿抑制剂,通过单矿物浮选试验和人工混合矿浮选试验探究抑制剂浓度、矿浆pH、捕收剂浓度等因素对黄铜矿和辉钼矿可浮性及铜钼分离效果的影响,并采用FTIR和Zeta电位表征手段探究FA在黄铜矿和辉钼矿表面的吸附行为。浮选试验结果表明,FA在pH为4~12的范围内能够有效地抑制辉钼矿的浮选,而对黄铜矿的浮选影响不大;FA能够显著地扩大辉钼矿和黄铜矿之间可浮性的差异。在pH为9,FA浓度为200mg/L,SIBX浓度为20mg/L条件下,人工混合矿试验取得了较好的结果,黄铜矿回收率高达70.20%,辉钼矿回收率仅有16.83%。FTIR和Zeta电位结果表明,FA能够克服静电斥力吸附在辉钼矿表面,并且FA与SIBX在黄铜矿表面存在竞争吸附,SIBX能够取代黄铜矿表面已吸附的FA,使其表面恢复疏水性,而SIBX几乎不影响FA在辉钼矿表面的吸附,使辉钼矿表面保持亲水性,从而能够实现铜钼的有效分离。     

黄铜矿与磁黄铁矿浮选分离行为及机理研究

通过黄铜矿与磁黄铁矿的单矿物浮选试验,研究矿浆pH、捕收剂丁黄药、抑制剂石灰对其浮选行为的影响。利用红外光谱、循环伏安测试技术,研究其浮选分离的机理。单矿物浮选试验结果表明黄铜矿和磁黄铁矿浮选分离的最佳条件为pH=10,丁黄药浓度为20 mg/L,石灰浓度为300 mg/L。红外光谱测试结果表明丁黄药在矿物表面氧化生成双黄药并通过化学吸附吸附在矿物表面,石灰在磁黄铁矿表面生成氢氧化钙和硫酸钙组成的钙膜。循环伏安测试表明在未添加丁黄药时黄铜矿表面氧化生成疏水的硫单质和硫化铜,磁黄铁矿表面会生成亲水的氢氧化物。     

Selective flotation of chalcopyrite and molybdenite with plasma pre-treatment

For pretreatment of selective flotation, plasma treatment of chalcopyrite and molybdenite was applied then the minerals were washed by solution at pH 9 with oxygen bubbling. Surface characteristics of these minerals were investigated with AFM, XPS, zeta potential and contact angle measurements. Contact angle of chalcopyrite and molybdenite decreased a lot by plasma treatment. When they were washed with pH 9 solution with oxygen bubbling, contact angle of molybdenite increased whereas chalcopyrite one kept low. Adhesion force measurements indicated similar behavior. Result of flotation experiments indicated low recovery of both chalcopyrite and molybdenite after plasma treatment and only molybdenite recovery became higher after washing. Selective flotation of chalcopyrite and molybdenite could be achieved with this process. However, flotation of mixture of chalcopyrite and molybdenite after these treatments indicated both chalcopyrite and molybdenite were depressed. Addition of emulsified kerosene changed the flotation results where molybdenite was floated and chalcopyrite was depressed. Possible mechanism of selective flotation was proposed from the results of XPS, AFM, etc.     

氧化预处理对铜钼浮选分离效果的影响

以NaClO或H₂O₂为氧化剂,研究了氧化对铜钼浮选分离试验效果的影响。探究了氧化剂用量、氧化时间和矿浆pH值等因素对黄铜矿和辉钼矿可浮性的影响以及作用机理。单矿物浮选实验结果表明,NaClO或H₂O₂氧化处理均可选择性抑制黄铜矿,且几乎不影响辉钼矿的可浮性。混合矿浮选实验结果表明,NaClO或H₂O₂氧化预处理-浮选都能实现铜钼有效分离,且分离效果均优于传统的黄铜矿抑制剂硫化钠。接触角测量结果表明,NaClO或H₂O₂氧化处理都可选择性地使黄铜矿表面亲水。Zeta电位和XPS分析结果表明,黄铜矿表面变得亲水是因为氧化处理后矿物表面生成了不溶于水的亲水性氧化物和氢氧化物。     

硫化铜矿新型捕收剂PZO的浮选性能与机理

为检验广州有色金属研究院研制的新型硫化铜矿浮选捕收剂PZO在铜硫分离中的选择性,比较了PZO、丁基黄药和丁铵黑药在不同矿浆pH值、不同用量条件下分别浮选黄铜矿和黄铁矿单矿物的效果,并借助紫外可见分光光谱仪、红外光谱仪对PZO在黄铜矿、黄铁矿表面的吸附量和作用机理进行了研究。结果显示：①在试验pH范围内,丁基黄药、丁铵黑药、PZO对黄铜矿的捕收能力均强于对黄铁矿。②矿浆的酸碱度对黄铜矿可浮性的影响均较小,且黄铜矿回收率的高点在弱酸或弱碱性环境下,黄铁矿在酸性环境下的可浮性明显强于在碱性环境。③3种捕收剂的选择性强弱顺序为PZO＞丁铵黑药＞丁基黄药,在pH=8.5时,黄铜矿与黄铁矿的回收率差值可达68.19个百分点。④PZO是一种酯类浮选药剂,与黄铁矿相比,其更容易在黄铜矿表面吸附,且以化学吸附为主。以上结果表明,PZO在pH=8.5的环境下可高效分离黄铜矿与黄铁矿。     

细粒嵌布硫化钼矿铜钼高效分离技术

在硫化钼矿选矿中,铜钼分离一直是矿物加工领域的难题,绿色高效黄铜矿抑制剂的研发是研究方向.本文针对中原某地细粒嵌布型极低品位硫化钼矿,基于其钼分选指标差、铜钼分离难度大等技术难题,依次开发出了辉钼矿组合捕收剂、黄铜矿绿色抑制剂以及浮选起泡剂,采用“阶段磨矿-铜钼富集-铜钼分离”工艺流程,获得了钼品位49.72％、钼回收率84.55％,铜含量0.16％的钼精矿,实验指标优异,研究成果为细粒嵌布型硫化钼矿铜钼高效分离提供了有益借鉴.     

用PAC作捕收剂时黄铜矿和黄铁矿的浮游性研究

新型捕收剂PAC是北京矿冶研究总院于近年研制的一种硫化矿捕收剂 ,曾有研究表明对铜、金、银等矿物具有选择捕收性。用PAC、黄药作捕收剂 ,在不同条件下对黄铜矿和黄铁矿单矿物的浮选对比试验表明 ,新型捕收剂PAC对黄铜矿捕收力强 ,对黄铁矿捕收力弱 ,具有明显的选择捕收性     

Assessment of the floatability of chalcopyrite,molybdenite and pyrite using biosolids and their main components as collectors for greening the froth flotation of copper sulphide ores

Biosolids and representative compounds of their main components – humic acids, sugars, and proteins – have been tested as possible environment-friendly collectors and frothers for the flotation of copper sulphide ores. The floatability of chalcopyrite and molybdenite – both valuable sulphide minerals present in these ores – as well as non-valuable pyrite was assessed through Hallimond tube flotation tests. Humic acids exhibit similar collector ability for chalcopyrite and molybdenite as that of a commercial collector (Aero 6697 promoter). Biosolids show more affinity for pyrite. The copper recovery (85.9%) and copper grade (6.7%) of a rougher concentrate obtained using humic acids as main collector for the flotation of a copper sulphide ore from Chile, were very similar to those of a copper concentrate produced by froth flotation under the same conditions with a xanthate type commercial collector. This new and feasible end-use of biosolids and humic acids should be new environment-friendly organic froth flotation agents for greening the concentration of copper sulphide ore. Now, further research is needed in order to scale current laboratory assays to operational mining scales to determine efficiencies to industrial scale.     

L-半胱氨酸与NaHS组合抑制剂在铜钼分离浮选中的应用及其机理研究

针对目前铜钼分离中黄铜矿抑制剂用量大、环境污染严重等问题,采用L-半胱氨酸(L-CYS)与NaHS组合抑制剂,对黄铜矿和辉钼矿浮选分离进行了研究。在黄药体系下,分别考察了单一抑制剂L-CYS、NaHS和组合抑制剂对单矿物及人工混合矿的浮选影响。矿物浮选结果表明：在pH=8,药剂配比为1:30,药剂用量为310mg/L时,组合抑制剂对黄铜矿的抑制效果最佳。此时组合抑制剂相较于单一抑制剂,NaHS用量由600mg/L减少到300mg/L,药剂用量减少了一半。Zeta电位结果表明,L-CYS、NaHS均可以吸附在黄铜矿表面,同时二者在组合使用时可以在黄铜矿表面发生共吸附。红外光谱结果表明,丁基黄药在黄铜矿表面发生化学吸附,NaHS可以解吸黄铜矿表面的黄药,L-CYS单独使用无法去除黄铜矿表面的黄药。二者组合使用时,首先NaHS解吸矿物表面的黄药,然后NaHS和L-CYS共同吸附在黄铜矿表面,从而使黄铜矿表面亲水。     

氧化预处理技术在铜钼硫化矿浮选分离中的研究进展

黄铜矿和辉钼矿是两种典型的硫化矿,其浮选分离一直是业界关注的焦点.硫化矿易氧化,矿物表面氧化程度和氧化产物类型对其浮选行为有重要影响.黄铜矿、辉钼矿在浮选之前进行氧化预处理,它们会产生不同程度的氧化和不同类型的氧化产物,这些原因使矿物的表面原有的性质发生改变,从而改变矿物固有的浮选行为,实现黄铜矿和辉钼矿的浮选分离.论...     

刺槐豆胶在铜硫分离中的抑制作用及机理分析

采用浮选试验、Zeta电位和红外光谱测试, 研究了刺槐豆胶在铜硫浮选分离中的作用, 并分析了其作用机理。结果表明:当pH小于9时, 黄铜矿及黄铁矿可浮性均较好, 难以浮选分离。刺槐豆胶在黄铜矿及黄铁矿表面均发生了吸附, 使二者的电位发生变化, 并产生抑制作用, 但刺槐豆胶对黄铜矿和黄铁矿的抑制强度及吸附方式都不同:刺槐豆胶在黄铜矿表面的吸附方式是化学吸附, 而与黄铁矿是通过物理吸附方式作用。加入刺槐豆胶后, 在pH为3~11条件下, 黄铁矿的浮选回收率均较低; 而当pH小于9时刺槐豆胶对黄铜矿抑制效果差, pH为11时对黄铜矿抑制效果极强。在pH为7时使用刺槐豆胶对铜品位为15.58%的混合矿进行浮选分离后, 获得的铜精矿铜品位为21.67%、回收率为82.13%。该研究为铜硫高效分离提供了一种性能优良的有机抑制剂。      

新型捕收剂BK-330优先浮选黄铜矿的研究

BK-330是北京矿冶研究总院新近研制的一种铜硫分离选择性捕收剂。用BK-330、Z-200和黄药作捕收剂,在不同条件下进行了黄铜矿和黄铁矿浮选对比试验。结果表明,新型捕收剂BK-330对黄铜矿捕收能力强,对黄铁矿捕收能力弱,具有较好的选择性。实际矿样试验验证了这一结论。     

The use of canola oil as an environmentally friendly flotation collector in sulphide mineral processing

The efficiency of mineral flotation relies on the ability to selectively recover different value minerals into their respective concentrates at optimum grades and recoveries based on the differing hydrophobicities. Many of the common hydrophobizing reagents (collectors) currently used in flotation have significant occupational and environmental implications, and hence there is a quest for environmentally benign chemical additives that give similar or better performance than the more toxic conventional reagents. In this paper, we provide substantial experimental evidence that the use of edible, fatty acid-based oils (canola and palm) can foster the flotation recovery of chalcopyrite and molybdenite minerals more selectively against pyrite than the conventional collectors, sodium isopropyl, potassium amyl xanthates and diesel oil.Single and mixed chalcopyrite/pyrite minerals and plant sulphide ores’ flotation studies using canola and palm oils, in contrast with conventional collectors, are reported herein. The results indicate greater efficacy of the canola and palm oils in comparison with the conventional collectors for chalcopyrite and molybdenite recoveries and product upgrades. This is believed to be due to the edible oils’ specific interactions with iron oxides sites preferentially formed in situ on the surfaces of the chalcopyrite or molybdenite in the pulp rather than on the pyrite surfaces, causing limited recovery of the pyrite. Complementary contact angle results confirmed that more canola oil is adsorbed onto chalcopyrite surfaces than onto pyrite surfaces. For the mineral mixtures tested, the edible oil’s degree of unsaturation had a noticeable effect on its performance as a collector. A higher pyrite recovery and slightly lower chalcopyrite grade was obtained with palm oil than with canola oil. These findings suggest that the use of canola oil has a potential to add to the existing array of flotation collectors and would represent a combined opportunity for both the mining and agricultural sectors, with concomitant health, environmental and economic benefits.     

乙硫氮作捕收剂时有机调整剂加药顺序对典型硫化矿物浮选的影响

研究了乙硫氮作捕收剂时有机大分子调整剂糊精、腐殖酸钠、阳离子瓜尔胶和DP115(改性聚丙烯酰胺有机大分子)不同加药顺序对典型硫化矿物黄铜矿、方铅矿、闪锌矿和黄铁矿浮选行为的影响。单矿物浮选试验结果表明,有机大分子调整剂与捕收剂乙硫氮的加药顺序对硫化矿物浮选的影响不同。与调整剂先加时相比,乙硫氮先加时,糊精对黄铜矿、方铅矿和闪锌矿浮选的抑制作用更强;腐殖酸钠对黄铜矿和方铅矿浮选的抑制作用不同程度增强,较低用量腐殖酸钠对闪锌矿浮选的抑制作用减弱,而较高用量时则强烈抑制闪锌矿;阳离子瓜尔胶对黄铜矿和方铅矿浮选的抑制作用减弱,对闪锌矿浮选的抑制作用略强;DP115对黄铜矿浮选的抑制作用减弱,低用量DP115对方铅矿浮选的抑制作用相当而对闪锌矿浮选的抑制作用减弱,较高用量时对方铅矿浮选的抑制作用更强而对闪锌矿浮选的抑制作用相当;糊精、腐殖酸钠、阳离子瓜尔胶和DP115对黄铁矿浮选的影响很小。研究结果可为部分硫化矿通过改变有机大分子调整剂与捕收剂的加药顺序提高矿物浮选分离的选择性和效率提供借鉴。     

黄铜矿、黄铁矿电化学调控浮选分离与机理研究

研究了电化学调控下黄铜矿、黄铁矿在以黄药为捕收剂和无捕收剂的条件下的浮选行为以及浮选调整剂,如CaO,CaOCl_2,对黄铁矿浮选的抑制作用。发现黄铜矿,黄铁矿的分离浮选不仅依靠矿浆高pH值和高氧化作用,而且,当使用化学药剂调节矿浆电位时,还与所使用的调整剂的化学组成有关。CaOCl_2能很好地用于铜硫分离,是由于它既能提高矿浆pH值,又能产生强的氧化作用。最后讨论了浮选机理。     

Effect of calcium ions and citric acid on the flotation separation of chalcopyrite from galena using dextrin

Using NaOH to adjust pH, dextrin selectively depressed galena while chalcopyrite was floated with a xanthate collector. However, when the pH was adjusted with lime, or when calcium ions were present in the pulp, the flotation of galena was “restored” while chalcopyrite was depressed in an alkaline pH, causing deteriorated flotation separations. It was found that calcium ions adsorbed preferably on chalcopyrite surfaces but not on galena, thus increasing the adsorption of dextrin on chalcopyrite. The addition of citric acid was found to eliminate the detrimental effects of calcium ions and to restore the selectivity of chalcopyrite-galena separation using dextrin.     

采用捕收剂KYY-1提高钼的浮选回收率

云南迪庆某斑岩铜钼矿石的选矿试验中,遇到黄铜矿可浮性良好,而辉钼矿在细磨后精选过程中极易脱落进入中矿,导致用常规药剂浮选时,钼的回收率偏低的问题,通过对多种捕收剂的研究,采用捕收剂KYY-1,提高了钼的回收率,达到了88%。     

江西某铜硫矿石浮选工艺研究

江西某大型铅锌矿山在深部接替资源勘查中探获了资源量达到中型规模以上的铜硫矿石资源。为了合理开发利用该矿石资源,在矿石性质研究和探索试验基础上,采用铜硫混合浮选-铜硫分离浮选工艺对其进行了选矿试验。试验结果表明：原矿磨至-0.074 mm占75%后以石灰为pH调整剂、丁黄药为捕收剂、2号油为起泡剂进行1粗2扫混合浮选,所获混合精矿再磨至-0.038 mm占80%后以石灰为pH调整剂、LP-01为捕收剂进行1粗2精2扫抑硫浮铜分离浮选,可获得铜品位为14.22%、铜回收率为87.58%的铜精矿和硫品位为34.01%、硫回收率为80.84%的硫精矿,从而使矿石中的铜、硫得到较好的综合回收。     

铜钼混合精矿浮选分离工艺及分离抑制剂研究进展

铜钼硫化矿常常紧密共生而且可浮性相近,二者的浮选分离一直是科研工作者研究的重点。从工艺和药剂2个方面对铜钼混合精矿的浮选分离进行了介绍。铜钼浮选常采用混合浮选工艺,黄铜矿和辉钼矿在与捕收剂作用后,二者的可浮性差异减小,在对二者进行浮选分离前,通常先进行脱药预处理,以降低抑制剂的使用量。常见的预处理工艺有加热处理、浓缩脱药处理、氧化脱药处理、等离子体处理等。针对铜钼分离工艺存在的问题,选矿工作者提出了充氮浮选、浮选柱分离、脉动高梯度磁选分离、加温分离等铜钼分离工艺。介绍了铜钼浮选分离过程关键药剂抑制剂的种类及应用情况。无机抑制剂有硫化钠类、氰化物、诺克斯类药剂等,有机抑制剂有巯基类、硫代类、黄原酸类等。指出在进行铜钼浮选分离之前铜钼混合精矿的预处理方法需要进一步优化,以增加黄铜矿与辉钼矿的可浮性差异。现在工业上使用的铜钼分离抑制剂仍然存在易氧化、药耗大、毒性高、价格贵等缺陷,需要加大投入进行高效、低毒、价廉、易降解的新型浮选抑制剂的开发。