發(fā)布時(shí)間：2018-10-05 21:05

【摘要】：采用脈石英替代日益枯竭的水晶資源制備超高純石英,替代昂貴的進(jìn)口石英,滿足國(guó)內(nèi)市場(chǎng)需求,打破長(zhǎng)期被美國(guó)壟斷的被動(dòng)局面具有重要意義。本文從四個(gè)方面對(duì)超高純石英純化制備及機(jī)理進(jìn)行了深入的研究。采用XRD、ICP-MS、透／反射光兩用顯微鏡、偏光顯微鏡、EPMA、LRM和顯微微熱臺(tái)等分析方法,系統(tǒng)地分析了脈石英中固體、流體包裹體賦存狀態(tài)及石英晶格中雜質(zhì)元素的分布。該脈石英含有大量的包裹體,主要物相組成為鉀長(zhǎng)石、鈉長(zhǎng)石、云母、透輝石、鐵鋁榴石、鈉閃石、黃鐵礦、黃銅礦、赤鐵礦及氯化鉀晶體等。流體包裹體均為氣液兩相型,成分主要有H2O、CO2、CH4、烴類等。石英晶格中微量Al、Fe、Ti等元素類質(zhì)同象替代Si,均勻分布于石晶體中,但邊緣有所富集。采用EXCEL軟件VBA語(yǔ)言代碼,系統(tǒng)計(jì)算了硅酸鹽、鋁硅酸鹽礦物在混合酸浸出體系中的分解反應(yīng)化學(xué)平衡,構(gòu)建了化學(xué)反應(yīng)方程式、反應(yīng)的始態(tài)、終態(tài)及反應(yīng)平衡。分別計(jì)算出雜質(zhì)礦物混合酸分解過(guò)程的熱力學(xué)參數(shù)吉布斯自由能、平衡常數(shù)、ArGT(?)=A+BT等,并繪制組分分布圖、Ellingham圖�；跓崃W(xué)方法建立了雜質(zhì)礦物在混合酸浸出體系中分解排序規(guī)律與評(píng)價(jià)判據(jù)。雜質(zhì)礦物分解反應(yīng)△rGT(?)均0,且小于石英與HF、HCl分解反應(yīng)ArGl(?),雜質(zhì)礦物分解反應(yīng)均能自發(fā)進(jìn)行,且優(yōu)先于石英分解,石英純化在熱力學(xué)上是可行的。分別研究了常壓浸出、熱壓浸出、真空焙燒的最佳工藝參數(shù)與純化效果。優(yōu)化了真空焙燒-熱壓浸出聯(lián)合純化工藝,雜質(zhì)元素Al、Fe、K、Na、Ca、Mg含量分別為：7.9、0.652、1.804、15、3.276、0.344 μg·g-1,制備出Si02含量為99.996wt%的超高純石英。聯(lián)合工藝純化效果優(yōu)于單一純化工藝。通過(guò)構(gòu)建高溫Al-F-H2O系、FeS2-F-H2O系Eh-pH圖,揭示了氟鋁、氟硅和氟鐵絡(luò)合物穩(wěn)定性區(qū)域及復(fù)雜的共存關(guān)系。與離子隨著pH值增加逐漸轉(zhuǎn)化為、、及。調(diào)控好反應(yīng)體系Eh和pH,可有效控制浸出過(guò)程中雜質(zhì)礦物分解反應(yīng)條件。研究了真空焙燒對(duì)石英晶胞參數(shù)變化、晶型轉(zhuǎn)變與石英純化間的影響,揭示了Al、Fe、K, Na、Ca、Mg能譜面分布規(guī)律,元素特征X射線光子的面分布密度從大至小依次為：常壓浸出熱壓浸出真空焙燒-熱壓浸出。研究表明常壓混合酸分解純礦物的反應(yīng)均為一級(jí)反應(yīng),熱壓浸出,鈉長(zhǎng)石、黃鐵礦分解反應(yīng)屬一級(jí)反應(yīng),鉀長(zhǎng)石、白云母分解反應(yīng)為二級(jí)反應(yīng)�；陔s質(zhì)金屬的多樣性和復(fù)雜性采用差異化方法,按元素分類分別討論了動(dòng)力學(xué)理論模型并加以分析,具有重要的指導(dǎo)作用。常壓浸出,Al、Fe、Na、Ca的去除符合不同控制過(guò)程的未反應(yīng)縮核模型,而K的去除則符合Avrami模型,元素Al、Fe、K、Na、Ca、Mg純化過(guò)程的表觀活化能分別為：5.587、5.545、95.96、8.35、5.189和1.338 kJ·mol-1;熱壓浸出,Al、Fe、K、Na、Mg的去除均符合Avrami模型,而Ca的去除則符合內(nèi)擴(kuò)散控制未反應(yīng)縮核模型,元素Al、Fe、K、Na、Ca, Mg純化過(guò)程的表觀活化能分別為：58.247、80.878、20.028、3.55、127.287和3.858 kJ·mol-1。
[Abstract]:It is of great significance to use vein quartz instead of crystal resource to prepare ultra-pure quartz, to replace expensive imported quartz, to meet the domestic market demand and to break the passive situation which has been monopolized by the United States for a long time. In this paper, the preparation and mechanism of ultrapure quartz were studied in four aspects. The solid, fluid inclusions and the distribution of impurity elements in quartz crystal lattice were systematically analyzed by means of XRD,ICP-MS, / reflectance microscope, polarizing light microscope, EPMA-LRM and microthermoscope. The quartz vein contains a large number of inclusions, and the main phases are potassium feldspar, albite, mica, diopside, ferric aluminite, sodium amphibole, pyrite, chalcopyrite, hematite and potassium chloride crystals. The fluid inclusions are of gas-liquid two-phase type, mainly composed of H _ 2O _ 2 CO _ 2H _ 4, hydrocarbons and so on. In quartz lattice, trace Al,Fe,Ti and other elemental isomorphism, instead of Si, are uniformly distributed in stone crystals, but the edges are enriched. The chemical equilibrium of decomposition reaction of silicate and aluminosilicate minerals in mixed acid leaching system was calculated by VBA language code of EXCEL software. The chemical reaction equation, initial state, final state and reaction equilibrium of the reaction were established. The thermodynamic parameters, Gibbs free energy and equilibrium constant ArGT (?) of the mixed acid decomposition process of impurity minerals were calculated respectively. BT et al. Based on the thermodynamic method, the law of decomposition, ordering and evaluation criteria of impurity minerals in mixed acid leaching system were established. RGT (?) 0, and less than ArGl (?) in the decomposition of quartz with HF,HCl. The decomposition of impurity minerals can be carried out spontaneously, and the decomposition of quartz is superior to that of quartz. The purification of quartz is feasible in thermodynamics. The optimum technological parameters and purification effects of atmospheric pressure leaching, hot pressure leaching and vacuum roasting were studied respectively. The combined purification process of vacuum roasting and hot pressure leaching was optimized. The content of impurity element Al,Fe,K,Na,Ca,Mg was 1: 7.9C 0.652U 1.804U 153.276N 0.344 渭 g g-1.The ultrahigh purity quartz with Si02 content of 99.996wt% was prepared. The purification effect of combined process is better than that of single purification process. By constructing the Eh-pH diagram of high temperature Al-F-H2O system FES _ 2-F _ H _ 2O system, the stable region and complex coexistence of fluoro aluminum, fluorosilicon and fluoroiron complexes are revealed. With the increase of the pH value, the ions and ions are gradually transformed into a. Controlling the reaction system Eh and pH, can effectively control the reaction conditions of the decomposition of impurity minerals during leaching. The effects of vacuum roasting on the crystal cell parameters, crystal transformation and quartz purification were studied, and the distribution of Al,Fe,K, Na,Ca,Mg energy spectrum surface was revealed. The surface distribution density of X-ray photons is in the order of atmospheric pressure leaching hot pressure leaching vacuum roasting and hot pressing leaching. The results show that the decomposition of pure minerals by mixed acid at atmospheric pressure is a first-order reaction. The decomposition of albite and pyrite is a first-order reaction and the decomposition of potassium feldspar and Muscovite is a second-order reaction. Based on the diversity and complexity of impurity metals, the dynamic theoretical models are discussed and analyzed according to the classification of elements, which plays an important guiding role. The removal of AlFeNa-Na ~ + Ca by atmospheric pressure leaching accords with the unreacted shrinking model of different controlled processes, while the removal of K conforms to the Avrami model. The apparent activation energy of the purification process of the element Al,Fe,K,Na,Ca,Mg is: 5. 58755.545N 95.968.35c5.189 and 1.338 kJ mol-1; respectively. The removal of AlFeK / Nahmg by hot pressure leaching accords with the Avrami model. However, the removal of Ca was in accordance with the model of internal diffusion control without reaction, and the apparent activation energy of the purification process of element Al,Fe,K,Na,Ca, Mg was: 58.247 (80.878) 20.028 (3.55127.287) and 3.858 kJ mol-1. (respectively).
【學(xué)位授予單位】：武漢理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TD97

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 雷紹民;裴振宇;鐘樂(lè)樂(lè);馬球林;黃冬冬;楊亞運(yùn);;脈石英砂無(wú)氟反浮選熱壓浸出技術(shù)與機(jī)理研究[J];非金屬礦;2014年02期

2 郭春平;周健;文小強(qiáng);普建;王玉香;袁德林;;鋰云母硫酸鹽法提鋰研究[J];無(wú)機(jī)鹽工業(yè);2014年03期

3 鄭雅杰;陳昆昆;;Na_2SO_3從硒碲富集物中浸出硒動(dòng)力學(xué)(英文)[J];Transactions of Nonferrous Metals Society of China;2014年02期

4 銀銳明;陳琳璋;侯清麟;袁毅;劉泰榮;;金屬鎂離子活化石英浮選的機(jī)理研究[J];功能材料;2013年15期

5 張杰;王維清;董發(fā)勤;黃陽(yáng);傅開(kāi)彬;馮啟明;;鋰輝石浮選尾礦中長(zhǎng)石和石英浮選分離[J];非金屬礦;2013年03期

6 于站良;陳家輝;謝剛;馬文會(huì);謝克強(qiáng);;加壓浸出脫除工業(yè)硅中雜質(zhì)鋁的研究[J];稀有金屬;2013年03期

7 雷紹民;王歡;王恩文;李佳;郭振華;徐騰;;工業(yè)廢水中多金屬離子的吸附凈化[J];環(huán)境工程學(xué)報(bào);2013年02期

8 曾華東;雷紹民;劉云濤;張鳳凱;;石英氧化浸出提純中的絡(luò)合離子的作用及機(jī)理[J];礦業(yè)研究與開(kāi)發(fā);2012年06期

9 劉建輝;劉敦一;張玉海;楊之青;王彥斌;李柏;倪廣深;;巖石樣品破碎新方法——SelFrag高壓脈沖破碎儀[J];巖石礦物學(xué)雜志;2012年05期

10 雷紹民;項(xiàng)婉茹;劉云濤;張鳳凱;劉祥友;;脈石英反浮選制備高純石英砂技術(shù)研究[J];非金屬礦;2012年03期

相關(guān)會(huì)議論文 前1條

1 洪璐;金小寧;;高純石英玻璃原料[A];第四屆高新技術(shù)用硅質(zhì)材料及石英制品技術(shù)與市場(chǎng)研討會(huì)論文集[C];2006年

相關(guān)博士學(xué)位論文 前3條

1 朱曉波;云母型含釩石煤活化焙燒提釩工藝及釩轉(zhuǎn)移行為研究[D];武漢理工大學(xué);2013年

2 曹占芳;輝鉬礦濕法冶金新工藝及其機(jī)理研究[D];中南大學(xué);2010年

3 于站良;超冶金級(jí)硅的制備研究[D];昆明理工大學(xué);2010年

相關(guān)碩士學(xué)位論文 前5條

1 羅超;熱酸浸出—鉛黃鐵礬法除鐵工藝研究[D];中南大學(xué);2012年

2 姜波;氨—銨鹽—水系浸出低品位氧化鎳礦的動(dòng)力學(xué)研究[D];中南大學(xué);2010年

3 胡余龍;草木灰浸取提鉀研究[D];天津大學(xué);2007年

4 孫天友;高鐵硫化鋅精礦加壓浸出的動(dòng)力學(xué)研究[D];昆明理工大學(xué);2006年

5 周廷熙;高鐵硫化鋅精礦加壓浸出工業(yè)化研究[D];昆明理工大學(xué);2005年

，

本文編號(hào)：2254865