白钨矿与含钙脉石分离抑制剂的遴选及作用机理研究

发布时间：2018-03-07 15:58

本文选题：白钨矿　切入点：萤石　出处：《昆明理工大学》2015年博士论文　论文类型：学位论文

【摘要】：白钨矿与常见的含钙脉石,如萤石、方解石的可浮性十分相近,目前我国仍有部分选厂对钙质脉石含量较高的白钨矿,沿用技术相对成熟的加温浮选,但此方法在生产过程中会导致流程操作困难、选矿厂环境差、成本高。通过对白钨矿、方解石、萤石的晶体结构研究发现,白钨矿的Ca-O布居数为0.09,键长为2.48A；方解石的Ca-O布居数为0.12,键长为2.36A；萤石的Ca-F布居数为0.07,键长为2.37A。相近的晶体结构导致三种矿物破碎时解离面迎着金属离子占优势的面产生,矿物表面会暴露出大量处于高能状态的钙离子。相似的矿物表面化学特征使得白钨矿、方解石、萤石在矿浆中很难实现有效分离。硅酸钠作为常见的脉石矿物抑制剂,在白钨矿浮选中被用来抑制方解石和萤石。为研究硅酸钠在抑制含钙脉石过程中在矿物表面的吸附形式、吸附量差异,并寻找新的、合理的药剂制度,强化对含钙脉石的抑制作用,论文从单矿物浮选行为、溶液化学、Zeta电位、红外光谱、光电子能谱等方面详细、系统地对抑制剂的作用机理进行了研究,主要取得了以下成果：单矿物浮选试验考查了硅酸钠、六偏磷酸钠、氟硅酸钠、草酸、单宁、羧甲基纤维素、木质素磺酸钠在不同溶液环境(药剂浓度与pH值)下对含钙矿物浮选行为的影响。研究发现,硅酸钠对三种含钙矿物的抑制顺序是萤石方解石白钨矿；氟硅酸钠对三种含钙矿物的抑制顺序是方解石萤石白钨矿；六偏磷酸钠对三种含钙矿物的抑制顺序是萤石方解石≈白钨矿；草酸对三种含钙矿物的抑制顺序是萤石白钨矿方解石；单宁对三种含钙矿物的抑制顺序是萤石白钨矿方解石；羧甲基纤维素对三种含钙矿物的抑制顺序是萤石方解石白钨矿；木质素磺酸钠对三种含钙矿物的抑制顺序是萤石方解石≈白钨矿。通过金属离子强化硅酸钠抑制效果的试验中发现,当pH值在7.0-11.0的范围内,A13+、Fe2+、Pb2+三种金属离子均可对白钨矿、方解石、萤石回收率产生影响。其中Fe2+离子在有效强化硅酸钠对方解石、萤石的抑制效果同时,对白钨矿的回收率影响不大。说明Fe2+离子不但可以起到“助抑剂”的作用,还使得硅酸钠的选择性增强；溶液化学研究发现,在最佳浮选pH值下,白钨矿、方解石、萤石的钙离子都会优先解离到矿浆中,而此pH值下硅酸钠水解产物中占优势的亲水基为[SiO(OH)3-]；Zeta电位研究结果显示,硅酸钠与白钨矿、方解石、萤石作用后,三种矿物表面动电位均发生不同程度下降,其下降程度依次为白钨矿方解石萤石,说明硅酸钠在试验pH值范围内水解产生的亲水基[SiO(OH)3-]在三种矿物表面的吸附量大小同样也为白钨矿方解石萤石,证明了在适宜的条件下,硅酸钠可以实现白钨矿与方解石、萤石的分离；白钨矿、萤石和方解石三种单矿物与硅酸钠作用前后的红外光谱对比结果显示：硅酸钠基团中的Si-O键振动峰使得白钨矿、萤石和方解石的特征峰均发生了位移,说明硅酸钠在三种矿物表面均发生了吸附。硅酸钠与白钨矿作用后,在光谱分析结果中并未出现新的吸收峰,峰值位移亦不明显；硅酸钠水解后产生的离子在萤石和方解石表面吸附较为明显,在红外光谱图上均产生了新的吸收峰。硅酸钠对白钨矿、方解石、萤石的抑制顺序为：萤石方解石白钨矿,即在较佳的试验条件下,通过硅酸钠的抑制作用可以实现白钨矿与萤石、方解石的分离,但和萤石相比,单独使用硅酸钠对方解石的抑制效果较差,需配合其他药剂强化抑制效果才能得到高品位钨精矿；X射线光电子能谱分析表明,白钨矿、方解石、萤石与硅酸钠作用后,三种矿物表面均出现Si-O吸收峰,且Si2p摩尔百分比大小的顺序为白钨矿方解石萤石,再次证明硅酸钠在矿物表面吸附量会有明显差异,进而导致可浮性差异而实现矿物间的分离；其次,在白钨矿、方解石、萤石光电子能谱中均出现102.13eV的Si-O结合能,该结合能并不是硅酸钠的Si-O集合能,经研究发现,该结合能为CaSiO3中Si-O标准结合能,说明前期研究中得出优先解离的钙离子与硅酸钠水解产生的[SiO(OH)3-]会在矿浆中反应生成CaSiO3并有浓度差异地吸附在矿物表面使之亲水；第三,助抑剂FeSO4与硅酸钠协同作用抑制脉石的过程中,只有方解石表面Si2p摩尔百分比显著增加,说明助抑剂可以增加硅酸钠水解产生的亲水离子在方解石表面的吸附量,进一步降低方解石的可浮性；最后,助抑剂FeSO4与硅酸钠协同作用后,Fe2p在三种矿物表面摩尔百分比大小顺序依次为方解石萤石白钨矿,并且助抑剂的加入使得方解石O1s峰值明显增强,说明可能有新的化合物生成。将方解石的O1s能谱图进行分峰拟合后发现出现一个531.9eV的新结合能,经研究发现,该结合能为水合氧化铁—FeOOH中O-O结合能。作为亲水的FeOOH,选择性的吸附在方解石表面,进一步降低了方解石的可浮性；在前期机理研究的基础上,针对云南文山州白钨矿资源进行浮选试验,抑制剂采用硅酸钠+FeSO4的组合,矿浆pH值10.5,捕收剂为733的药剂条件下取得了白钨矿精矿含W0363.17%,回收率为86.32%的较佳指标,从试验结果中验证了机理研究的准确性。
[Abstract]:Scheelite and common calcareous gangue, such as fluorite, calcite floatability is very similar, at present our country still has high content of scheelite calcareous gangue part plant, use a relatively mature technology of heating flotation, but this method will lead to difficulties in the operation process of the production process, processing plant environment, through the high cost. Scheelite, calcite, fluorite crystal structure study found that scheelite Ca-O population was 0.09. The bond length is 2.48A; the calcite Ca-O population was 0.12. The bond length is 2.36A; fluorite Ca-F population was 0.07. The bond length is similar to the crystal structure of 2.37A. lead to three kinds of mineral crushing dissociation in the face of metal ion dominant surface, mineral surface exposed to excessive calcium in the high-energy state. Mineral surface chemistry characteristics similar to that of scheelite, calcite, fluorite is difficult to achieve effective separation in the pulp silicate. Sodium as common in gangue inhibitor, Scheelite Flotation was used to inhibit calcite and fluorite. For the study of sodium silicate in the inhibition process in the form of calcic gangue mineral surface adsorption, the adsorption amount of the difference, and find a new, reasonable reagent system, strengthen the inhibition of calcic gangue, the flotation behavior of single. The mineral solution chemistry, Zeta potential, infrared spectroscopy, X-ray photoelectron spectroscopy and other aspects in detail, system of inhibitor mechanism has been studied. The main results are as follows: single mineral flotation test of sodium silicate, six sodium phosphate, sodium fluorosilicate, oxalic acid, tannin, carboxymethyl cellulose, lignin sulfonate sodium in different solution environment (drug concentration and pH value) of calcium mineral flotation behavior of. The study found that inhibition of the order of three kinds of sodium silicate calcium minerals are calcite fluorite white tungsten ore; sodium fluoride In order to inhibit three kinds of calcium minerals are scheelite fluorite calcite; inhibition of order six to three kinds of sodium hexametaphosphate calcium mineral fluorite calcite is scheelite; inhibition of three kinds of minerals containing calcium oxalate sequence is fluorite scheelite calcite; tannin on three kinds of minerals containing calcium suppression sequence is the inhibition order scheelite fluorite calcite; CMC methyl cellulose on three kinds of calcium minerals are scheelite fluorite calcite; the order of inhibition of Sodium Lignosulfonate on three kinds of calcium mineral fluorite calcite is scheelite. Through metal ion strengthening test found that the inhibitory effect of sodium silicate, when the pH value is in the range of 7.0-11.0, A13+, Fe2+, Pb2+ three kinds of metal ions can be calcite scheelite, fluorite, the recovery rate of impact. The Fe2+ ion in the enhancement of sodium silicate calcite, and the inhibitory effect of fluorite, scheelite back The yield has little effect. The results showed that Fe2+ ion can not only play a "help inhibit", also makes the selectivity of sodium silicate solution chemistry research found that enhanced; the best pH value in the flotation of scheelite, calcite, fluorite, calcium ions are preferred to dissociation of pulp, and the pH value of hydrophilic advantage the hydrolysis of sodium silicate in the product of [SiO (OH) 3-]; Zeta potential results show that sodium silicate and scheelite, calcite, fluorite after three mineral surface potential had different degrees of decline, a decline in scheelite fluorite calcite, description of sodium silicate in test pH value range of hydrolysis the hydrophilic [SiO (OH) 3-] in three kinds of mineral surface adsorption quantity also proved scheelite calcite fluorite, under suitable conditions, sodium silicate can achieve scheelite and calcite, fluorite, scheelite, fluorite separation; Infrared spectroscopy results before and after the three single minerals and calcite and sodium silicate effect showed that Si-O bond vibration peak of sodium silicate group in the scheelite, fluorite and calcite peaks were shifted, that occurred in the adsorption of sodium silicate mineral surface. Three kinds of sodium silicate and scheelite after absorption did not appear a new peak in the spectrum analysis results, the peak displacement is not obvious; the hydrolysis of sodium silicate ions produced after obvious adsorption on the surface of fluorite and calcite, a new absorption peak in the infrared spectra were generated. Sodium silicate scheelite, calcite, fluorite, fluorite sequence inhibited calcite scheelite, namely in the test the better condition, the inhibitory effect of sodium silicate can realize the separation of Scheelite from fluorite, calcite and fluorite, but compared with the use of sodium silicate solution alone other than the inhibitory effect of stone Poor, need to cooperate with other agents to strengthen the inhibitory effect to get high grade tungsten concentrate; X ray photoelectron spectroscopy analysis shows that scheelite, calcite, fluorite and sodium silicate after the action of three kinds of mineral surface appeared Si-O absorption peak, and the size of the order of Si2p molar percentage of scheelite fluorite calcite, sodium silicate have proved once again significant differences in mineral surface adsorption, which leads to different floatability and realize the separation of minerals; secondly, in scheelite, calcite, fluorite and XPS were found in the 102.13eV Si-O binding energy, the binding energy is not sodium silicate Si-O collection, the study found that the binding energy of Si-O standard CaSiO3 in which, the first dissociation in the previous research of calcium ion and sodium silicate hydrolysis of [SiO (OH) 3-] generates CaSiO3 reaction in the pulp and the concentration of different adsorption on the mineral surface. The hydrophilic; third, help inhibitor FeSO4 and sodium silicate gangue inhibition process, only the surface of calcite Si2p molar percentage increased significantly, that can inhibit the hydrophilic ion can increase the hydrolysis of sodium silicate produced by adsorption on the surface of calcite, further reducing the floatability of calcite; finally, can inhibit synergistic effect of FeSO4 and sodium silicate, Fe2p in the three molar percentage of mineral surface order of calcite and scheelite fluorite, help inhibitor into the calcite O1s peak increased significantly, indicating the possible formation of new compounds. The calcite O1s can peak fitting spectrum after the discovery of a new combination of 531.9eV the energy, the study found that the binding energy of FeOOH hydrous ferric oxide in O-O binding energy. As hydrophilic FeOOH, selective adsorption on the surface of calcite, further reducing the calcite Flotability; based on the previous research on the mechanism of flotation test in Yunnan, Wenshan Scheelite Resources, using a combination of +FeSO4 inhibitor of sodium silicate, pulp pH value 10.5, the collector is obtained under the condition of 733 agents of Scheelite Concentrate Containing W0363.17%, the recovery rate is the best index of 86.32% and accuracy of mechanism research verified from the test results.

【学位授予单位】：昆明理工大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TD97;TD923

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