高鈦渣制備鈦硅復(fù)合催化劑中鈦的形態(tài)調(diào)控與水解控速的關(guān)鍵機(jī)制
發(fā)布時(shí)間：2018-12-29 20:17
【摘要】：針對(duì)我國(guó)高鈦渣物相復(fù)雜難處置又具有多種可利用資源的矛盾,基于高鈦渣制備鈦硅復(fù)合催化劑的資源化利用的構(gòu)想,以攀枝花西昌地區(qū)的高鈦渣為對(duì)象,通過(guò)高鈦渣熱力學(xué)轉(zhuǎn)化的物理化學(xué)過(guò)程模擬、酸堿實(shí)際體系中高鈦渣轉(zhuǎn)化行為分析等手段,研究了高鈦渣在不同介質(zhì)與條件下形成Ti O2-Si O2復(fù)合催化劑的轉(zhuǎn)化途徑與其影響機(jī)制。同時(shí),利用水熱成礦過(guò)程晶體成核-生長(zhǎng)原理,通過(guò)環(huán)境介質(zhì)與絡(luò)合劑的優(yōu)化,復(fù)合催化材料催化性能評(píng)價(jià)與過(guò)程分析等方法,深入探討了高鈦渣制備鈦硅復(fù)合材料中Ti、Si的轉(zhuǎn)化與復(fù)合過(guò)程,討論了復(fù)合材料形成過(guò)程中Ti形態(tài)調(diào)控與水解控速關(guān)鍵機(jī)制。研究結(jié)果表明:1.Na OH在低溫(150 o C以下)條件下能生成堿性玄武石。氫氟酸、硫酸和硝酸只與透輝石和玄武石發(fā)生反應(yīng)。氫氟酸能提取高鈦渣中14%~93%的硅,在該溶液中金屬離子易生成氟化物。硫酸中金屬離子主要以離子形式存在于液相,部分Ca2+與SO42+形成Ca SO4。2.鹽酸完全分解高鈦渣,得到含Ti O2的產(chǎn)品。高鈦渣鹽酸水熱浸提后的產(chǎn)物中Ti O2的晶相與Cl-離子濃度和硅含量有關(guān)。Cl-離子濃度在1 mol/L左右生成銳鈦礦型Ti O2,在2 mol/L以上則為金紅石型。無(wú)定形二氧化硅促進(jìn)Ti O2由銳鈦礦型向金紅石型轉(zhuǎn)變。添加的氫氟酸在處理高鈦渣過(guò)程中,起到調(diào)控鈦硅比和抑制金紅石型Ti O2生成的作用。EDTA對(duì)Mg、Fe、Ti、Si的沉淀有明顯的緩釋作用,會(huì)導(dǎo)致高鈦渣中的鈦向金紅石相轉(zhuǎn)化。3.高鈦渣經(jīng)鹽酸分解后,鈦與氯離子結(jié)合產(chǎn)生Ti Cl4,在含有HF的溶液中先生成Ti F4,并發(fā)生快速水解生成二氧化鈦。EDTA能直接與鈦離子絡(luò)合,減緩酸性水熱條件下鈦離子的水解。合成的材料對(duì)染料羅丹明B具有一定的吸附和光催化性能。HF0.6光催化性能最好,加入EDTA合成的材料吸附性能最佳。通過(guò)鹽酸水熱處理的調(diào)控形成和水解控速,高鈦渣可以制備具有一定光催化效果的鈦硅復(fù)合材料。論文研究結(jié)果為高鈦渣資源化利用奠定了實(shí)驗(yàn)基礎(chǔ)和理論依據(jù)。
[Abstract]:In view of the contradiction of complex and difficult phase disposal of high titanium slag in China and of many available resources, based on the conception of resource utilization of Ti-Si composite catalyst prepared from high titanium slag, the high titanium slag in Xichang area of Panzhihua was taken as the object. Through the physical and chemical simulation of thermodynamics transformation of high titanium slag and the analysis of transformation behavior of high titanium slag in acid-base actual system, The conversion pathway and its influence mechanism of high titanium slag to form Ti O2-Si O 2 composite catalyst in different media and conditions were studied. At the same time, based on the principle of crystal nucleation and growth during hydrothermal mineralization, through the optimization of environment medium and complexing agent, the evaluation of catalytic performance and process analysis of composite catalytic materials, the preparation of Ti, in titanium-silicon composites with high titanium slag was discussed. The transformation and composite process of Si were discussed. The key mechanisms of Ti morphology regulation and hydrolysis speed control in the process of composite formation were discussed. The results show that 1.Na OH can produce alkaline Black Tortoise at low temperature (below 150oC). Hydrofluoric acid, sulfuric acid and nitric acid only react with diopside and Black Tortoise. Hydrofluoric acid can extract 93% silicon from high titanium slag, and metal ions can easily form fluoride in this solution. Metal ions in sulfuric acid mainly exist in liquid phase in the form of ions, and some Ca2 and SO42 form Ca SO4.2.. The high titanium slag was completely decomposed with hydrochloric acid and the product containing Ti O 2 was obtained. The crystalline phase of Ti O 2 in the hydrochloric acid extracted from high titanium residue is related to the concentration of Cl- ion and the content of silicon. The Cl- ion concentration is about 1 mol/L to form anatase Ti O 2, and more than 2 mol/L is rutile. Amorphous silica promotes the transition of Ti O 2 from anatase to rutile. The addition of hydrofluoric acid can regulate the ratio of titanium to silicon and inhibit the formation of rutile Ti O 2 in the treatment of high titanium slag. EDTA has obvious slow release effect on the precipitation of Mg,Fe,Ti,Si. It will result in the transformation of titanium from high titanium slag to rutile phase. 3. After decomposition of high titanium slag by hydrochloric acid, titanium binds with chloride ion to form Ti Cl4, into Ti F4 in solution containing HF, and then rapidly hydrolyzes to form titanium dioxide. EDTA can directly complexate with titanium ion and slow down the hydrolysis of titanium ion under acidic hydrothermal conditions. The synthesized material has certain adsorption and photocatalytic properties to dye Rhodamine B. HF0.6 has the best photocatalytic activity, and the material synthesized with EDTA has the best adsorption performance. By controlling the formation and hydrolysis speed of hydrochloric acid hydrothermal treatment, titanium silicon composites with certain photocatalytic effect can be prepared by high titanium slag. The results of this paper lay an experimental and theoretical basis for the utilization of high titanium slag.
【學(xué)位授予單位】：上海大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TQ426;X756
本文編號(hào)：2395338
[Abstract]:In view of the contradiction of complex and difficult phase disposal of high titanium slag in China and of many available resources, based on the conception of resource utilization of Ti-Si composite catalyst prepared from high titanium slag, the high titanium slag in Xichang area of Panzhihua was taken as the object. Through the physical and chemical simulation of thermodynamics transformation of high titanium slag and the analysis of transformation behavior of high titanium slag in acid-base actual system, The conversion pathway and its influence mechanism of high titanium slag to form Ti O2-Si O 2 composite catalyst in different media and conditions were studied. At the same time, based on the principle of crystal nucleation and growth during hydrothermal mineralization, through the optimization of environment medium and complexing agent, the evaluation of catalytic performance and process analysis of composite catalytic materials, the preparation of Ti, in titanium-silicon composites with high titanium slag was discussed. The transformation and composite process of Si were discussed. The key mechanisms of Ti morphology regulation and hydrolysis speed control in the process of composite formation were discussed. The results show that 1.Na OH can produce alkaline Black Tortoise at low temperature (below 150oC). Hydrofluoric acid, sulfuric acid and nitric acid only react with diopside and Black Tortoise. Hydrofluoric acid can extract 93% silicon from high titanium slag, and metal ions can easily form fluoride in this solution. Metal ions in sulfuric acid mainly exist in liquid phase in the form of ions, and some Ca2 and SO42 form Ca SO4.2.. The high titanium slag was completely decomposed with hydrochloric acid and the product containing Ti O 2 was obtained. The crystalline phase of Ti O 2 in the hydrochloric acid extracted from high titanium residue is related to the concentration of Cl- ion and the content of silicon. The Cl- ion concentration is about 1 mol/L to form anatase Ti O 2, and more than 2 mol/L is rutile. Amorphous silica promotes the transition of Ti O 2 from anatase to rutile. The addition of hydrofluoric acid can regulate the ratio of titanium to silicon and inhibit the formation of rutile Ti O 2 in the treatment of high titanium slag. EDTA has obvious slow release effect on the precipitation of Mg,Fe,Ti,Si. It will result in the transformation of titanium from high titanium slag to rutile phase. 3. After decomposition of high titanium slag by hydrochloric acid, titanium binds with chloride ion to form Ti Cl4, into Ti F4 in solution containing HF, and then rapidly hydrolyzes to form titanium dioxide. EDTA can directly complexate with titanium ion and slow down the hydrolysis of titanium ion under acidic hydrothermal conditions. The synthesized material has certain adsorption and photocatalytic properties to dye Rhodamine B. HF0.6 has the best photocatalytic activity, and the material synthesized with EDTA has the best adsorption performance. By controlling the formation and hydrolysis speed of hydrochloric acid hydrothermal treatment, titanium silicon composites with certain photocatalytic effect can be prepared by high titanium slag. The results of this paper lay an experimental and theoretical basis for the utilization of high titanium slag.
【學(xué)位授予單位】：上海大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TQ426;X756
【參考文獻(xiàn)】
相關(guān)期刊論文 前2條
1 石妍;楊華美;王迎春;楊華全;李家正;;高鈦礦渣對(duì)水泥基復(fù)合材料性能的影響[J];新型建筑材料;2009年09期
2 朱洪波;王培銘;張繼東;王汴文;;利用攀鋼提鈦高爐礦渣制磚[J];新型建筑材料;2010年06期
，本文編號(hào)：2395338
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