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。     

Selective chalcopyrite flotation from pyrite with glycerine-xanthate as depressant

Micro-flotation tests, adsorption, electrokinetic and FTIR measurements were carried out in order to investigate the selective depression mechanism of sodium glycerine-xanthate (SGX) on pyrite in chalcopyrite flotation. The flotation results showed a large difference in chalcopyrite (>85%) and pyrite (<30%) recovery as stirred pulp-mixing with SGX before the addition of collector sodium butyl xanthate (SBX), at the range of pH 7–10. A much stronger adsorption of SGX on pyrite than chalcopyrite was dramatically revealed by zeta potential measurements, which can explain the better floatability of chalcopyrite than pyrite. The adsorption of SBX onto pyrite was depressed intensely while that onto chalcopyrite was affected slightly when SGX was used as depressant, because of more stronger adsorption between SGX and SBX occurring onto the pyrite surfaces. The absorbed amount of SGX on chalcopyrite increases slightly, over the pH range from 3 to 12, while that on pyrite increases rapidly with the increased SGX concentration, which is consistent with the flotation results. FTIR reflection spectroscopic measurements further demonstrated the depression effect of pre-absorbed SGX on SBX adsorption, which is attributed to its hydrophilic hydroxyl groups.     

十二胺和十二烷基磺酸钠在长石石英表面的吸附

采用浮选试验、ζ-电位和FTIR光谱分析,研究了十二胺(阳离子捕收剂,DDA)和十二烷基磺酸钠(阴离子捕收剂,SDS)作捕收剂在长石石英表面的吸附。浮选结果表明,pH值在2附近时,长石和石英的浮游差最大,混合捕收剂能增大二者的浮游差,有利于长石的优先浮选。在单一捕收剂中长石和石英ζ-电位均整体向正或负方向移动,在混合捕收剂溶液中,二者ζ-电位在碱性介质中正移幅度较酸性介质明显。FTIR光谱结果表明,pH值为2时,DDA在长石和石英表面均只存在物理吸附;SDS在长石表面既存在物理吸附,还与Al-O形成化学吸附,而在石英表面仅存在物理吸附;混合捕收剂在长石表面既有物理吸附,还存在氢键作用,而在石英表面仅存在物理吸附。     

甲基纤维素作为抑制剂浮选分离黄铜矿和滑石

通过浮选试验、Zeta电位测试、TOC测试及红外光谱测试对甲基纤维素在黄铜矿与滑石浮选分离中的作用及其在两种矿物表面的吸附机理进行了研究。浮选试验结果表明,低用量的甲基纤维素可有效抑制滑石,但对黄铜矿抑制效果很弱,可实现黄铜矿与滑石的浮选分离。甲基纤维素作为滑石的抑制剂,浮选分离黄铜矿和滑石混合矿。人工混合矿Cu品位为15.19%时,可以获得铜精矿Cu品位为24.08%,回收率达74.68%的指标。检测结果表明,甲基纤维素在黄铜矿和滑石表面均发生了物理吸附,且在滑石表面的吸附强于在黄铜矿表面的吸附。     

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。     

蛇纹石对黄铜矿浮选影响的研究

在通过单矿物浮选试验、Zeta电位测试考察pH值及捕收剂用量对蛇纹石和黄铜矿浮选回收率影响的基础上,采用人工混合矿浮选试验考察蛇纹石含量与粒度对黄铜矿回收率的影响,并对其机理进行分析。结果表明,蛇纹石与黄铜矿的零电点分别为9.7和5.4,随着矿浆pH值的增大,蛇纹石和黄铜矿的ζ电位电负性增强;pH值为7时,丁基钠黄药用量对蛇纹石回收率影响不大,最高为12.3%,黄铜矿回收率随丁基钠黄药用量的增加呈现先上升后下降的趋势,最高为88.03%;颗粒之间的吸附是造成黄铜矿与蛇纹石浮选过程中交互影响的重要原因,蛇纹石的含量以及粒度很大程度上影响了黄铜矿的浮选质量。     

硫化钠对黄铜矿无捕收剂浮选的影响

给出了碱性介质中硫化钠作还原电位调整剂时黄铜矿的无捕收剂浮选(称有硫化钠无捕收剂浮选)的行为。通过矿浆电位测试、伏安曲线、HS~-在黄铜矿表面吸附量测定和中性硫的溶剂提取一化学分析,较详细地研究了HS~-降低电位的作用和在黄铜矿表面的吸附行为。研究结果表明,经硫化钠调浆的黄铜矿矿浆的铂电位(即矿浆电位)迅速下降,在硫化钠自身调控的还原电位下,HS~-难以在黄铜矿表面发生电化学吸附;但在恒电位仪控制的高电位下,HS~-可以在黄铜矿表面发生电化学吸附。因此,HS~-存在并不能明显降低黄铜矿无捕收剂浮选的矿浆电位下限,黄铜矿有硫化钠无捕收剂浮选的矿浆电位下限与无硫化钠无捕收剂浮选(称自诱导浮选)的矿浆电位下限接近。     

Flotation behavior and adsorption mechanism of α-hydroxyoctyl phosphinic acid to malachite

The flotation behavior and adsorption mechanism of α-hydroxyoctyl phosphinic acid (HPA) to malachite were investigated by micro-flotation tests, zeta potential measurements, and FTIR and XPS analysis. The micro-flotation results demonstrated that compared with sodium isobutyl xanthate (SIBX) and styrene phosphonic acid (SPA), HPA exhibited superior collecting performances to direct flotation recovery of malachite and floated out above 80% malachite at pH 5–10. The results of zeta potential measurement inferred that there might be covalent bonds between HPA and copper on the malachite surface. The FTIR analysis confirm that HPA might react with copper species of malachite surfaces to form Cu–HPA complex adsorption layers, with a release of H⁺ ions (from PH group). The XPS analysis provided very clear evidence that the Cu(II) species was partly reduced to Cu (I) species during HPA chemisorption on malachite surfaces, accompanying P(III) oxidation to P(V) species of HPA.     

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.     

A novel surfactant 2-amino-6-decanamidohexanoic acid: Flotation performance and adsorption mechanism to diaspore

In this paper, a novel surfactant, 2-amino-6-decanamidohexanoic acid (AHA-10) was synthesized and used as a collector for flotation separation of diaspore and aluminosilicate minerals. The adsorption mechanism of AHA-10 onto diaspore was also evaluated by FTIR spectra, zeta potential, XPS and solution chemistry. The flotation results demonstrated that AHA-10 exhibited superior collecting power to diaspore and good selectivity against kaolinite and illite, and could effectively recover diaspore from bauxite ores contained aluminosilicate minerals at pH around 10. The analyses of FTIR spectra, zeta potential and solution chemistry inferred that at pH around 10, AHA-10 might chemisorb on diaspore surfaces by formation of AlO and AlN bonds. AHA-10’s unique properties, such as characteristic bond model to Al atoms on diaspore surfaces, double hydrophobic groups and intermolecular hydrogen bonds between neighboring AHA-10 molecules coated on diaspore surfaces, rendering a weakening surface energy and enhancing hydrophobicity of diaspore particles.     

辛基异羟肟酸钠在独居石表面的吸附及浮选机理研究

通过矿物浮选试验、Zeta电位测量及红外光谱测试等手段研究了辛基异羟肟酸钠对独居石的浮选特性及其表面吸附机理。单矿物浮选试验结果表明,辛基异羟肟酸钠浮选体系中,独居石在pH值5~9可浮性较好。独居石与辛基异羟肟酸钠作用后,表面动电位降低,说明该阴离子捕收剂在独居石表面发生了吸附。当独居石表面荷负电时,吸附仍可继续,说明辛基异羟肟酸钠阴离子可克服静电斥力吸附于荷负电的独居石表面。红外光谱分析证实该吸附作用为化学吸附。     

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.     

阴离子淀粉对铝硅酸盐矿物浮选的影响及机理研究

通过浮选试验、动电位和吸附量的测定, 详细考察了阴离子淀粉(LSDZ)对高岭石、叶蜡石和伊利石浮选行为的影响及作用机理。单矿物浮选试验显示, 在整个pH范围内, 阴离子淀粉对高岭石、叶蜡石和伊利石均具有活化作用, 且在酸性条件下活化能力更强; 当pH=6, 捕收剂DTAC用量为3×10^-4 mol/L时, 低用量阴离子淀粉活化伊利石和高岭石的浮选试验结果表明, LSDZ用量较低时, 伊利石和高岭石被活化, 随着LSDZ用量增加, 伊利石和高岭石被抑制; 阴离子淀粉对叶蜡石浮选影响受阳离子捕收剂DTAC用量的制约。吸附量与动电位研究表明, 阴离子淀粉通过氢键与静电力作用吸附在铝硅矿物表面使矿物表面ζ电位负移, 低用量阴离子淀粉能促进捕收剂DTAC在矿物表面的吸附。     

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。     

3-戊基-4-氨基-1,2,4-三唑-5-硫酮浮选分离黄铜矿与闪锌矿及其机理

考察了捕收剂3-戊基-4-氨基-1,2,4-三唑-5硫酮(AATT)对黄铜矿和闪锌矿的浮选分离性能,并通过接触角、紫外光谱、吸附动力学和热力学等研究了AATT浮选分离黄铜矿和闪锌矿的作用机理。结果表明,在pH>10.0时,AATT可实现黄铜矿与闪锌矿的高效浮选分离。AATT在黄铜矿表面的吸附过程符合准二级动力学吸附方程和Langmuir等温吸附模型,为自发、吸热的化学吸附过程。pH=10.5时,AATT能显著增大黄铜矿表面疏水性,但对闪锌矿表面疏水化作用不明显,从而实现黄铜矿与闪锌矿之间的浮选分离。     

The effect of surface oxidation of copper sulfide minerals on clay slime coating in flotation

The industry is well aware of the difficulty in treating copper ores in the presence of clay minerals. In this study, the effect of bentonite on the flotation of chalcopyrite (a primary copper sulfide mineral) and chalcocite (a secondary copper sulfide mineral) was investigated in terms of surface coating. Based on the flotation of copper ores containing both chalcopyrite and chalcocite, the flotation of chalcopyrite and chalcocite single minerals in the presence and absence of bentonite, and the zeta potential measurement of chalcopyrite, chalcocite and bentonite, it was found that the oxidation of chalcopyrite and chalcocite had a different effect on their interaction with bentonite. Under the normal grinding and flotation condition, significant oxidation occurred on the surface of chalcocite which was electrostatically attractive to bentonite resulting in bentonite slime coating and the depressed flotation of chalcocite. The reduction of oxidation on chalcocite could mitigate bentonite slime coating due to electrostatic repulsion between unoxidized chalcocite and bentonite. Unlike chalcocite, chalcopyrite with and without surface oxidation exhibited an electrostatic repulsion to bentonite. Its flotation was less affected by bentonite slimes.     

组合捕收剂浮选菱锌矿的分子头基尺寸响应

通过单矿物浮选、动电位测试以及荧光探针检测对比研究了不同头基尺寸捕收剂组合油酸钠/十二胺和油酸钠/溴代十六烷基吡啶在菱锌矿表面的吸附特性及其对矿物浮选行为的影响。单一捕收剂体系浮选试验结果表明,3种捕收剂体系下,随着捕收剂浓度增加,矿物浮选回收率均呈现先增加后下降的趋势,油酸钠、溴代十六烷基吡啶、十二胺分别在pH值为5.8、8.4和10.1处达到最大回收率,3种捕收剂对菱锌矿的捕收能力顺序为油酸钠>溴代十六烷基吡啶>十二胺。混合捕收剂体系中,固定油酸钠浓度为2×10^-4 mol/L,加入适量的十二胺可以大幅促进矿物浮选,而加入溴代十六烷基吡啶几乎没有影响。动电位测试结果表明,在pH=6时经2×10^-4 mol/L 油酸钠溶液处理的菱锌矿表面电位为-30.5 mV,随着十二胺用量增加,已吸附油酸钠的菱锌矿表面电位逐渐上升,在十二胺浓度2×10^-4 mol/L时其表面动电位升高到接近菱锌矿在纯水中的动电位值22.3 mV,这是由于十二胺阳离子在已吸附了油酸钠阴离子的菱锌矿表面发生吸附; 而溴代十六烷基吡啶的加入对菱锌矿表面电位几乎没有影响,说明溴代十六烷基吡啶阳离子基本没有在矿物表面吸附,这与浮选试验结果一致。矿物表面微极性测试结果验证了上述推论,在此基础上给出了两种组合捕收剂在菱锌矿表面的吸附模型。     

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。      

磁黄铁矿与乙硫氮相互作用电化学浮选红外光谱的研究

考察了乙硫氮为捕收剂时磁黄铁矿的浮选行为,发现在pH2-12的范围内,磁黄铁矿均可表现良好的可浮性。只有pH>12时,可浮性下降。通过用氧化剂过硫酸铵、还原剂硫代硫酸钠调节矿浆电位, 考察了磁黄铁矿在不同pH值下,可浮性与矿浆电位之关系,得出了矿物可浮电位-pH区间。通过红外光谱测试技术的研究,探讨了乙硫氮在磁黄铁矿表面作用机理及生成产物,不同pH值下与乙硫氮作用后,磁黄铁矿浮选回收率与乙硫氮红外吸收强度有对应关系,乙硫氮的二硫化物秋兰姆是主要吸附产物。     

Electrokinetic behavior and flotation of kaolinite in CTAB solution

The electrokinetics and flotation behavior of kaolinite in cetyltrimethylammonium bromide (CTAB) solution were studied. The point of zero charge (PZC) of kaolinite is 4.3. The possible mode of CTAB adsorption on kaolinite is due to Coulombic and Van der Waals forces revealed by zeta-potential and FTIR measurements. The negative zeta potential of kaolinite and the adsorption of cationic collectors on kaolinite were higher in alkaline media than in acidic media. However, the flotation tests show that the kaolinite exhibited much better floatability in the acid range than in the basic pH range in the 2 × 10⁻⁴ M CTAB solution. The surface charge of the basal plane is negative and that of the edge is positive in the acid pH range. The aggregation occurs possibly by electrostatic interaction between particles because of different charged based plane and edges, and makes floatability of kaolinite better in an acid pH range.