新型捕收剂DLZ对黄铜矿和黄铁矿浮选的作用机理研究

研究捕收剂DLZ对黄铜矿和黄铁矿的浮选行为。浮选试验结果表明,DLZ对黄铜矿的捕收能力强,最大回收率为95.7%,而对黄铁矿的捕收能力弱,回收率小于10%。动电位分析发现与DLZ作用后,黄铜矿的动电位比黄铁矿的动电位下降的更多,证明DLZ对黄铜矿和黄铁矿的捕收有选择性。红外光谱分析表明DLZ在黄铜矿表面的吸附属于化学吸附,在黄铁矿表面的吸附属于物理吸附。     

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。     

Cu-S flotation separation via the combination of sodium humate and lime in a low pH medium

The flotation separation of chalcopyrite and pyrite was studied in the presence of sodium humate. The results of flotation tests indicated that pyrite can be selectively depressed by sodium humate, and the activity of sodium humate was strongly affected by the pH of the pulp. At high pH values, pyrite was strongly depressed by sodium humate; however, the content of chalcopyrite was not affected. Ore flotation tests were successfully conducted in the laboratory and at the Dexing Copper Mine by applying sodium humate as a pyrite depressant. By adding 40-60 g/t of sodium humate to the pulp and adjusting the pH to 10-10.5 with CaO, a concentrate with a Cu content of 24% was obtained without reducing the Cu recovery rate. In addition, the dosage of CaO was reduced, and the recovery of Au, Ag and Mo in the copper concentrate was enhanced due to the reduced pH of the pulp. The zeta potential, adsorption of xanthate and contact angle of the mineral surface were measured, and the results from surface measurements indicated that there was a strong hydrophilic interaction between sodium humate and the surface of pyrite. Moreover, the results revealed that the interaction between sodium humate and chalcopyrite was weak. Infrared (IR) spectra of pyrite and sodium humate were obtained, and the results indicated that sodium humate was chemically adsorbed on the surface of pyrite.     

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。     

无捕收剂浮选的电化学及量子化学研究

本文给出了有无硫化钠存在时。黄铜矿和黄铁矿的无捕收剂浮进行为。研究表明,黄铜矿自诱导浮选良好,有较宽的电位和pH范围;弱酸性和碱性介质中,黄铁矿自诱导浮选较差,没有电位范围。硫化钠的添加,明显促进了黄铁矿的无捕收剂浮选,黄铁矿有良好的硫化钠诱导浮选。对天然矿石验证试验表明,自诱导浮选技术能够有效分离黄铜矿和黄铁矿。通过HS~-离子吸附量的测定,矿物表面中性硫量提取分析、电化学测试和量子化学计算,较详细研究了黄铜矿和黄铁矿无捕收剂浮选的机理,矿物表面中性硫是主要疏水体。     

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。      

乙硫氮作捕收剂时无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无机调整剂硫酸锌、亚硫酸钠、硫化钠和硫酸铜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。结果表明,调整剂与捕收剂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,硫酸锌对黄铜矿和方铅矿浮选的抑制作用减弱;硫酸锌、低用量硫酸铜、亚硫酸钠或硫化钠对闪锌矿浮选以及硫酸铜对黄铜矿和方铅矿浮选的抑制作用更强;硫酸锌或硫酸铜对黄铁矿浮选以及较高用量硫酸铜对闪锌矿浮选的活化作用相当;亚硫酸钠或硫化钠对黄铜矿、方铅矿和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调整剂与捕收剂的加药顺序提高矿物浮选分离效率提供借鉴。     

一种新型有机抑制剂的铜硫分离效果

为解决采用无机抑制剂进行铜硫分离时铜硫分离效果差、伴生贵金属流失严重等问题,开发了新型有机抑制剂三羧基甲基-二硫代碳酸钠。单矿物浮选试验结果表明：在pH=9~12、三羧基甲基-二硫代碳酸钠浓度为2.4×10-3 mol/L时,对黄铁矿抑制效果较好、对黄铜矿抑制作用较弱,可以实现低碱条件下的铜硫分离。采用三羧基甲基-二硫代碳酸钠进行黄铁矿、黄铜矿人工混合矿浮选试验,获得了铜品位为31.69%、回收率为91.36%的铜精矿,实现了铜硫有效分离。应用Materials Studio分子模拟软件构建药剂、矿物模型,通过分子模拟方法探讨三羧基甲基-二硫代碳酸钠的作用机理,结果表明,该药剂与黄铁矿、黄铜矿的作用能都为负值,其中与黄铁矿作用能为-98.70 kJ/mol,与黄铜矿作用能为-10.36 kJ/mol,故该药剂对黄铁矿抑制作用更强,对黄铜矿的抑制较差,并通过红外光谱和紫外光谱分析结果得到了验证。     

捕收剂烯丙基异丁基硫氨酯在硫化铜矿表面的吸附机理

烯丙基异丁基硫氨酯(ATC)是新一代酯类选矿药剂,它对黄铜矿捕收力强,黄铁矿捕收力弱,是铜硫分离的优良捕收剂。为了考察ATC对黄铜矿和黄铁矿分离的影响及吸附机理,在纯矿物浮选试验的基础上,进行了动电位、吸附量测量试验和红外光谱分析。结果表明,ATC在试验pH范围内对黄铜矿的捕收能力强于对黄铁矿的捕收能力;ATC的捕收力及选择性均强于传统捕收剂Z-200;在pH=9.0、ATC用量为11.8 mg/L时,黄铜矿与黄铁矿回收率相差55个百分点;矿浆pH对黄铜矿可浮性影响较小,对黄铁矿可浮性影响大;ATC用量对黄铜矿电位影响大,对黄铁矿电位影响小;红外光谱分析表明ATC在黄铜矿表面是化学吸附,在黄铁矿表面是物理吸附。     

Investigation on the flotation behavior and adsorption mechanism of 3-hexyl-4-amino-1,2,4-triazole-5-thione to chalcopyrite

In this paper, a novel surfactant, 3-hexyl-4-amino-1,2,4-triazole-5-thione (HATT) is first introduced as a collector for chalcopyrite flotation. Its flotation behavior and adsorption mechanism to chalcopyrite has been evaluated by micro-flotation tests, and zeta potential, FTIR spectra and adsorption quantity measurements. The results demonstrate that HATT exhibited excellent flotation performances to chalcopyrite at pH 4–8. The adsorption of HATT on to chalcopyrite agrees well with the pseudo-second-order model and Langmuir isotherm, and is a spontaneously endothermic chemisorption process. FTIR spectra and zeta potential analyses further imply that chalcopyrite might chemisorb HATT by formation of HATT–copper surface complexes.     

新型有机抑制剂RC 在铜硫矿物浮选分离中的抑制作用

研究了新型有机抑制剂RC 在黄铜矿和黄铁矿浮选分离中的作用。单矿物浮选实验表明:这种抑制剂在整个pH 范围内, 对黄铁矿具有很好的抑制作用, 在黄铜矿的浮选实验中, 仅当pH ≈4 时, 抑制剂对黄铜矿产生了一定的抑制作用, 而在pH >4.5 时, 抑制剂对黄铜矿的浮选行为影响不大, 对黄铜矿抑制作用较弱。人工混合矿实验表明:RC 能有效实现铜硫矿物浮选分离, 使得铜精矿品位达到24.73 %, 回收率为80.36%。整个研究表明:在黄铜矿和黄铁矿浮选分离中, RC 不仅显示了很强的抑制黄铁矿的效果, 而且用量低、无毒、无污染, 是一种理想的铜硫选择性浮选分离抑制剂。     

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.     

The effect of PAX/CMC addition order on chlorite/pyrite separation

Addition order of both PAX (potassium amyl xanthate) and CMC (carboxymethyl cellulose) was investigated to separate pyrite from chlorite. The investigation included both flotation and adsorption tests. The flotation results showed that CMC can depress the flotation of chlorite but was found not to be selective against pyrite. When pyrite was conditioned initially with PAX before CMC it was found that the CMC slightly depressed pyrite flotation. The depression effect of CMC on pyrite was significantly higher when pyrite was conditioned first with CMC before PAX. Flotation of chlorite was not influenced by order of addition of CMC and PAX. Adsorption tests showed that CMC and PAX compete in adsorbing on pyrite and the adsorption density of PAX decreases in the presence of the pre-adsorbed layer of CMC. PAX was found not to adsorb onto chlorite irrespective if chlorite was conditioned initially with or without CMC. Therefore there was no competitive adsorption on chlorite surface between PAX and CMC. PAX can assist to protect the pyrite surface when conditioned initially first and allow the benefits of CMC depression for chlorite.     

Floatability of chalcopyrite and molybdenite in the presence of lignosulfonates. Part II. Hallimond tube flotation

The effect of six lignosulfonates on the Hallimond tube flotation of chalcopyrite and molybdenite was studied as a function of pH, with the use of common pH modifiers (soda ash, potassium hydroxide, and lime). By comparing the flotation results with the adsorption data collected in Part I of this contribution, it becomes evident that the depression of chalcopyrite flotation takes places only when lignosulfonates adsorb on the mineral surface and, at the same time, a fraction of the xanthate collector is desorbed from the mineral surface. These two conditions are met only at high pH adjusted with lime. The depression of the natural floatability of molybdenite is relatively easy using all six lignosulfonates, but once the mineral is rendered strongly hydrophobic by the addition of an oily collector (dodecane), the depression of molybdenite by lignosulfonates is very difficult and only calcium lignosulfonates, and the highest molecular weight sodium salt, produce significant levels of depression. Overall, the results suggest that it is possible to selectively float chalcopyrite from molybdenite using lignosulfonates by depressing molybdenite. This can be achieved over a wide pH range provided that a pH modifier other than lime is used for pH control. Although the results showed that chalcopyrite flotation and molybdenite depression can be achieved under similar physicochemical conditions, further tests with real ores under industrial conditions have to be carried out with particular attention to the effect of process water quality.     

黄铜矿吸附O-异丙基-N,N-二乙基硫氨酯的动力学和热力学研究

O-异丙基-N,N-二乙基硫氨酯（XBE）是课题组研发的一种新型硫氨酯捕收剂,具有较好的铜硫浮选分离效果。为了进一步研究XBE的浮选性能,研究了搅拌时间、药剂浓度、pH值和温度等对XBE在黄铜矿表面吸附量的影响,并进行了吸附动力学和热力学分析。结果表明,pH值在7~11之间,XBE在黄铜矿表面的吸附量基本不变,搅拌25 min后XBE在黄铜矿表面达到吸附平衡,吸附过程符合二级反应动力学方程。随着药剂浓度的增加和温度的升高吸附量增大,XBE在黄铜矿表面上的吸附符合Freundlich多层吸附模型。      

Cu2+活化黄铁矿与黄铜矿的浮选分离

在研究丁黄药体系中黄铜矿、黄铁矿单矿物的天然可浮性,石灰（调节矿浆pH）、亚硫酸氢钠、铜离子对黄铜矿、黄铁矿可浮性的影响,柠檬酸对被Cu²⁺活化的黄铁矿、黄铜矿可浮性的影响,柠檬酸-亚硫酸氢钠-石灰组合抑制剂对被Cu²⁺活化的黄铁矿、黄铜矿可浮性的影响的基础上,采用柠檬酸-亚硫酸氢钠-石灰组合抑制剂对被Cu²⁺活化的黄铁矿-黄铜矿人工混合矿进行浮选分离,得到了铜品位和铜回收率分别为24.12%和88.48%的铜精矿,及硫品位和硫回收率分别为49.69%和72.51%的硫精矿,表明该组合抑制剂对被Cu²⁺活化的黄铁矿具有良好的选择性抑制作用。     

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。     

Adsorption of guar gum and CMC on pyrite

The depression of pyrite in sulfide flotation by two types of polysaccharides, CMC and guar, was investigated using micro-flotation tests, zeta potential measurements and adsorption tests. Environmentally and from an occupational safety standpoint – this would be a better processing option than cyanide. The range of variables tested included molecular weight of guar, degree of substitution of CMC, pH and the concentration of calcium ions in the flotation process water. The guar gums depressed pyrite considerably even at low dosages. An optimum dosage of 10 ppm was recommended. The CMC’s were not as effective as the guar gums, and required much higher dosages to achieve pyrite depression. Within the range of CMC’s tested, lower degree of substitution was more effective than high degree of substitution. This was presumably due to lower electrostatic repulsion between the negatively charged CMC and pyrite. When calcium ions were introduced with CMC’s, the adsorption of the CMC was considerably enhanced. No such effect was observed for guar gums. Both CMC and guar gums demonstrated Langmuirian behavior in their adsorption isotherms. Two different adsorption mechanisms were displayed. The guar gum adsorption was attributed to hydrogen bonding and Bronsted acid–base interaction. The CMC was considered to occur through electrostatic interaction in the presence of calcium ions, and Bronsted acid–base interaction depending on pH.     

螯合抑制剂BAPTA在菱镁矿与方解石浮选分离中的作用机理

由于菱镁矿和方解石具有相似的晶体结构和化学性质，故通过浮选较难实现二者的有效分离。BAPTA作为一种Ca-选择性螯合剂，被用以改善菱镁矿与方解石的浮选分离。浮选试验结果表明，在油酸钠体系下，BAPTA能选择性地抑制方解石上浮，且在矿浆pH值11.0、BAPTA用量30 mg/L和油酸钠用量100 mg/L的条件下，可较好实现菱镁矿(回收率91.06%)与方解石(回收率7.37%)的浮选分离。利用Zeta电位、FTIR和XPS等检测方法研究了BAPTA的选择抑制机理，结果表明，BAPTA能选择性地与方解石表面的Ca发生反应，吸附并罩盖在方解石表面，阻止油酸钠在方解石表面吸附，消除油酸钠给方解石带来的零电点负移的影响，但BAPTA对菱镁矿表面的Mg作用较小，故对菱镁矿吸附油酸钠的影响较小。      

低碱度下组合抑制剂对黄铜矿和黄铁矿可浮性的影响

研究了在pH=8的低碱度条件下,Na₂S₂O₃+焦性没食子酸、NaClO+焦性没食子酸、CaCl₂+单宁酸、KMnO₄+单宁酸、NaClO+腐殖酸钠这5种组合抑制剂对黄铜矿、黄铁矿可浮性的影响,结果表明它们都可以在铜硫浮选分离时作为黄铁矿的选择性抑制剂,只不过在选择性强弱和用量上有差异。以NaClO+腐殖酸钠为代表,比较了组合抑制剂与单一抑制剂对黄铁矿的抑制效果,结果证明组合抑制剂效果更好。最后,通过红外光谱分析,探讨了NaClO+腐殖酸钠对黄铁矿的抑制机理。