發(fā)布時間：2018-03-07 15:58

  本文選題：白鎢礦　切入點：螢石　出處：《昆明理工大學(xué)》2015年博士論文　論文類型：學(xué)位論文

【摘要】：白鎢礦與常見的含鈣脈石,如螢石、方解石的可浮性十分相近,目前我國仍有部分選廠對鈣質(zhì)脈石含量較高的白鎢礦,沿用技術(shù)相對成熟的加溫浮選,但此方法在生產(chǎn)過程中會導(dǎo)致流程操作困難、選礦廠環(huán)境差、成本高。通過對白鎢礦、方解石、螢石的晶體結(jié)構(gòu)研究發(fā)現(xiàn),白鎢礦的Ca-O布居數(shù)為0.09,鍵長為2.48A；方解石的Ca-O布居數(shù)為0.12,鍵長為2.36A；螢石的Ca-F布居數(shù)為0.07,鍵長為2.37A。相近的晶體結(jié)構(gòu)導(dǎo)致三種礦物破碎時解離面迎著金屬離子占優(yōu)勢的面產(chǎn)生,礦物表面會暴露出大量處于高能狀態(tài)的鈣離子。相似的礦物表面化學(xué)特征使得白鎢礦、方解石、螢石在礦漿中很難實現(xiàn)有效分離。硅酸鈉作為常見的脈石礦物抑制劑,在白鎢礦浮選中被用來抑制方解石和螢石。為研究硅酸鈉在抑制含鈣脈石過程中在礦物表面的吸附形式、吸附量差異,并尋找新的、合理的藥劑制度,強化對含鈣脈石的抑制作用,論文從單礦物浮選行為、溶液化學(xué)、Zeta電位、紅外光譜、光電子能譜等方面詳細、系統(tǒng)地對抑制劑的作用機理進行了研究,主要取得了以下成果：單礦物浮選試驗考查了硅酸鈉、六偏磷酸鈉、氟硅酸鈉、草酸、單寧、羧甲基纖維素、木質(zhì)素磺酸鈉在不同溶液環(huán)境(藥劑濃度與pH值)下對含鈣礦物浮選行為的影響。研究發(fā)現(xiàn),硅酸鈉對三種含鈣礦物的抑制順序是螢石方解石白鎢礦；氟硅酸鈉對三種含鈣礦物的抑制順序是方解石螢石白鎢礦；六偏磷酸鈉對三種含鈣礦物的抑制順序是螢石方解石≈白鎢礦；草酸對三種含鈣礦物的抑制順序是螢石白鎢礦方解石；單寧對三種含鈣礦物的抑制順序是螢石白鎢礦方解石；羧甲基纖維素對三種含鈣礦物的抑制順序是螢石方解石白鎢礦；木質(zhì)素磺酸鈉對三種含鈣礦物的抑制順序是螢石方解石≈白鎢礦。通過金屬離子強化硅酸鈉抑制效果的試驗中發(fā)現(xiàn),當(dāng)pH值在7.0-11.0的范圍內(nèi),A13+、Fe2+、Pb2+三種金屬離子均可對白鎢礦、方解石、螢石回收率產(chǎn)生影響。其中Fe2+離子在有效強化硅酸鈉對方解石、螢石的抑制效果同時,對白鎢礦的回收率影響不大。說明Fe2+離子不但可以起到“助抑劑”的作用,還使得硅酸鈉的選擇性增強；溶液化學(xué)研究發(fā)現(xiàn),在最佳浮選pH值下,白鎢礦、方解石、螢石的鈣離子都會優(yōu)先解離到礦漿中,而此pH值下硅酸鈉水解產(chǎn)物中占優(yōu)勢的親水基為[SiO(OH)3-]；Zeta電位研究結(jié)果顯示,硅酸鈉與白鎢礦、方解石、螢石作用后,三種礦物表面動電位均發(fā)生不同程度下降,其下降程度依次為白鎢礦方解石螢石,說明硅酸鈉在試驗pH值范圍內(nèi)水解產(chǎn)生的親水基[SiO(OH)3-]在三種礦物表面的吸附量大小同樣也為白鎢礦方解石螢石,證明了在適宜的條件下,硅酸鈉可以實現(xiàn)白鎢礦與方解石、螢石的分離；白鎢礦、螢石和方解石三種單礦物與硅酸鈉作用前后的紅外光譜對比結(jié)果顯示：硅酸鈉基團中的Si-O鍵振動峰使得白鎢礦、螢石和方解石的特征峰均發(fā)生了位移,說明硅酸鈉在三種礦物表面均發(fā)生了吸附。硅酸鈉與白鎢礦作用后,在光譜分析結(jié)果中并未出現(xiàn)新的吸收峰,峰值位移亦不明顯；硅酸鈉水解后產(chǎn)生的離子在螢石和方解石表面吸附較為明顯,在紅外光譜圖上均產(chǎn)生了新的吸收峰。硅酸鈉對白鎢礦、方解石、螢石的抑制順序為：螢石方解石白鎢礦,即在較佳的試驗條件下,通過硅酸鈉的抑制作用可以實現(xiàn)白鎢礦與螢石、方解石的分離,但和螢石相比,單獨使用硅酸鈉對方解石的抑制效果較差,需配合其他藥劑強化抑制效果才能得到高品位鎢精礦；X射線光電子能譜分析表明,白鎢礦、方解石、螢石與硅酸鈉作用后,三種礦物表面均出現(xiàn)Si-O吸收峰,且Si2p摩爾百分比大小的順序為白鎢礦方解石螢石,再次證明硅酸鈉在礦物表面吸附量會有明顯差異,進而導(dǎo)致可浮性差異而實現(xiàn)礦物間的分離；其次,在白鎢礦、方解石、螢石光電子能譜中均出現(xiàn)102.13eV的Si-O結(jié)合能,該結(jié)合能并不是硅酸鈉的Si-O集合能,經(jīng)研究發(fā)現(xiàn),該結(jié)合能為CaSiO3中Si-O標準結(jié)合能,說明前期研究中得出優(yōu)先解離的鈣離子與硅酸鈉水解產(chǎn)生的[SiO(OH)3-]會在礦漿中反應(yīng)生成CaSiO3并有濃度差異地吸附在礦物表面使之親水；第三,助抑劑FeSO4與硅酸鈉協(xié)同作用抑制脈石的過程中,只有方解石表面Si2p摩爾百分比顯著增加,說明助抑劑可以增加硅酸鈉水解產(chǎn)生的親水離子在方解石表面的吸附量,進一步降低方解石的可浮性；最后,助抑劑FeSO4與硅酸鈉協(xié)同作用后,Fe2p在三種礦物表面摩爾百分比大小順序依次為方解石螢石白鎢礦,并且助抑劑的加入使得方解石O1s峰值明顯增強,說明可能有新的化合物生成。將方解石的O1s能譜圖進行分峰擬合后發(fā)現(xiàn)出現(xiàn)一個531.9eV的新結(jié)合能,經(jīng)研究發(fā)現(xiàn),該結(jié)合能為水合氧化鐵—FeOOH中O-O結(jié)合能。作為親水的FeOOH,選擇性的吸附在方解石表面,進一步降低了方解石的可浮性；在前期機理研究的基礎(chǔ)上,針對云南文山州白鎢礦資源進行浮選試驗,抑制劑采用硅酸鈉+FeSO4的組合,礦漿pH值10.5,捕收劑為733的藥劑條件下取得了白鎢礦精礦含W0363.17%,回收率為86.32%的較佳指標,從試驗結(jié)果中驗證了機理研究的準確性。
[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.

【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TD97;TD923

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