本文選題：Pr-Zr氧化物固溶體 + 甲烷選擇生氧化�。� 參考：《昆明理工大學(xué)》2015年博士論文

【摘要】：我國是個稀土大國,稀土的儲量和產(chǎn)量都居世界第一,價格也較便宜。稀土氧化物具有的特殊性質(zhì)和作用早已引起了催化界的關(guān)注。稀土氧化物晶格氧的移動性、順磁性、表面堿性以及陽離子的可變價與許多催化作用有本質(zhì)的聯(lián)系。稀土氧化物不僅本身具有催化性能,而且可作為添加劑和助催化劑,對其他催化劑進(jìn)行改性,提高催化劑的催化性能。因此,稀土材料作為催化劑在許多化學(xué)過程中得到廣泛應(yīng)用。本文以Pr-Zr氧化物固溶體氧化物新型材料為對象,系統(tǒng)研究了其物理化學(xué)性質(zhì)、應(yīng)用前景。內(nèi)容包括Pr-Zr氧化物固溶體的制備方法,制備條件對Pr-Zr氧化物固溶體形成的影響,Pr-Zr氧化物固溶體應(yīng)用于化學(xué)鏈甲烷選擇性氧化制合成氣的反應(yīng)性能,介孔Pr-Zr氧化物固溶體制備條件的篩選與優(yōu)化,介孔Pr-Zr氧化物固溶體為載體制備Au催化劑的設(shè)計及其應(yīng)用于CO氧化反應(yīng)及碳煙催化燃燒反應(yīng)性能研究等關(guān)鍵基礎(chǔ)問題。為使Pr-Zr復(fù)合氧化物具有最佳性能,首先進(jìn)行Pr-Zr氧化物固溶體的制備并探索得到最佳制備途徑,以Pr(N03)3·6H20和Zr(N03)4為前驅(qū)鹽,制備溫度2O℃,pH=12,經(jīng)過800℃焙燒可制得Pro.7Zro.302-8完全固溶體。將這種方法加以擴(kuò)展,制備成一系列Pr1-xZrxO2-δ固溶體(x=0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9)。研究了制備條件對Pr-Zr復(fù)合氧化物物化性質(zhì)的影響,發(fā)現(xiàn)制備溫度、滴定pH為影響固溶體形成的關(guān)鍵因素。老化溫度、母液濃度對完全固溶體形成的影響微弱,但延長老化時間、降低母液濃度可增強(qiáng)復(fù)合氧化物的氧活性。發(fā)現(xiàn)氧遷移性能是固溶體具有更好氧化還原性質(zhì)的原因。與純Pr6O11相比,系列Pr-Zr氧化物固溶體晶粒尺寸明顯減小,還原峰溫度降低,活性增強(qiáng)。由于其具有較高的儲氧量,將Pr1-xZrxO2-δ固溶體應(yīng)用于化學(xué)鏈選擇性氧化甲烷制合成氣的反應(yīng)�？疾斓贸�800℃為Pr-Zr復(fù)合氧化物選擇性氧化甲烷制合成氣反應(yīng)的最合適焙燒溫度,850℃為甲烷選擇性氧化制合成氣反應(yīng)的最合適反應(yīng)溫度。Pr1-xZrxO2-δ固溶體表現(xiàn)出較高的甲烷轉(zhuǎn)化率及H2、CO選擇性,最重要的是具有優(yōu)異的循環(huán)反應(yīng)穩(wěn)定性。循環(huán)前后材料均保持了固溶體結(jié)構(gòu),體相晶格氧含量和表面氧空位的增加共同保證了多次循環(huán)后反應(yīng)性能的穩(wěn)定。在Pr1-xZrxO2-δ固溶體的基礎(chǔ)上,進(jìn)一步提出介孔Pr-Zr氧化物固溶體的制備。通過溶膠凝膠法制備介孔Pr-Zr氧化物固溶體,0.4g/mL的F127為模板劑,Pr(NO3)4和ZrOCl2為前驅(qū)鹽,乙醇為溶劑,溶膠反應(yīng)溫度控制為40℃,經(jīng)過恒溫恒濕培養(yǎng),干燥、焙燒即得到產(chǎn)物�？疾炝酥苽錀l件對介孔Pr-Zr復(fù)合氧化物形成的影響,認(rèn)為制備方法,前驅(qū)鹽種類、溶膠反應(yīng)溫度、模板劑濃度及模板劑種類為制備介孔Pr-Zr復(fù)合氧化物的控制因素。對介孔鐠鋯復(fù)合氧化物形成了機(jī)理做了探討,認(rèn)為此介孔材料是按照協(xié)同作用機(jī)理進(jìn)行的。為了考察介孔Pr-Zr氧化物固溶體材料的應(yīng)用前景,研究了其在CO氧化反應(yīng)和碳煙催化燃燒反應(yīng)中的反應(yīng)性能。作為催化劑Pr-Zr氧化物固溶體依然具有杰出的催化效果,與一般催化劑不同的是,高溫老化樣品表現(xiàn)出更好的反應(yīng)結(jié)果。進(jìn)一步將其作為載體,Au為活性組分,制備出Au/Pr-Zr-O復(fù)合催化劑。同樣將其應(yīng)用于CO氧化反應(yīng)和碳煙催化燃燒反應(yīng),發(fā)現(xiàn)反應(yīng)中Au與Pr1-xZrxO 2-δ具有協(xié)同催化作用。作為載體,Pr-Zr氧化物固溶體具有良好的高溫老化性能,大幅提高了催化反應(yīng)中的反應(yīng)性能。
[Abstract]:China is a big country of rare earth. The reserves and production of rare earth are both the first and cheaper in the world. The special properties and effects of rare earth oxides have attracted the attention of the catalytic industry. The mobility, paramagnetic, surface alkalinity and cations of rare earth oxide lattice oxygen are essentially related to many catalysis. Oxides not only have catalytic properties, but also can be used as additives and Co catalysts to modify other catalysts to improve the catalytic performance of the catalysts. Therefore, rare earth materials have been widely used as catalysts in many chemical processes. In this paper, a new type of Pr-Zr oxide solid solution oxide material has been studied in this paper. Its physical and chemical properties, application prospects, including the preparation of Pr-Zr oxide solid solution, the effect of preparation conditions on the formation of Pr-Zr oxide solid solution, Pr-Zr oxide solid solution used in chemical chain methane selective oxidation to synthetic gas, screening and optimization of the preparation conditions of mesoporous Pr-Zr oxide solid solution system, mesoporous Pr- The design of the Zr oxide solid solution as the carrier for the preparation of the Au catalyst and its application to the study of the oxidation reaction of CO and the performance of the catalytic combustion of carbon smoke. In order to make the Pr-Zr compound oxide with the best performance, the preparation of the Pr-Zr oxide solid solution and the best way to prepare the Pr-Zr oxide solid solution were first explored, and Pr (N03) 3 6H20 and Zr (N03) 4 were used as the best preparation methods. Precursor salts were prepared at a temperature of 2O, pH=12, and roasted at 800 degrees centigrade to produce Pro.7Zro.302-8 solid solution. This method was extended to prepare a series of Pr1-xZrxO2- [delta] solid solution (x=0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9). The effect of preparation conditions on the physicochemical properties of Pr-Zr compound oxide was studied. The preparation temperature was found, and the titration pH was the shadow. The key factors for the formation of rounded solid solution. The aging temperature and the concentration of mother liquor have a weak effect on the formation of complete solid solution, but prolonging the aging time and reducing the concentration of the mother solution can enhance the oxygen activity of the compound oxide. It is found that the oxygen transfer performance is the reason for the better redox properties of the solid solution. Compared with the pure Pr6O11, the series of Pr-Zr oxide solid solutions The grain size is obviously reduced, the temperature of the reduction peak is reduced and the activity is enhanced. Because of its high oxygen storage capacity, Pr1-xZrxO2- delta solid solution is applied to the reaction of selective oxidation of methane to synthetic gas in chemical chain. It is found that the optimum calcination temperature for methane synthesis by selective oxidation of methane by Pr-Zr compound oxide at 800 C is the best temperature, and 850 C is one. The most suitable reaction temperature.Pr1-xZrxO2- [delta] solid solution for the reaction of alkane selective oxidation to synthetic gas shows high methane conversion and H2, CO selectivity, and the most important is the excellent stability of the cyclic reaction. The structure of solid solution is maintained in the material before and after the cycle, and the increase of the lattice oxygen content and the surface oxygen vacancy of the body phase ensures a lot. On the basis of Pr1-xZrxO2- delta solution, the preparation of mesoporous Pr-Zr oxide solid solution was further proposed on the basis of Pr1-xZrxO2- delta solution. The solution of mesoporous Pr-Zr oxide solid solution was prepared by sol-gel method, F127 of 0.4g/mL was used as template, Pr (NO3) 4 and ZrOCl2 as precursor salt, ethyl alcohol as solvent, and the sol-gel reaction temperature was controlled to 40 C. The effect of preparation conditions on the formation of mesoporous Pr-Zr compound oxide was investigated. The preparation methods, the type of precursor salt, the temperature of the sol reaction, the concentration of template and the type of template were the control factors for the preparation of mesoporous Pr-Zr compound oxide. The mechanism of the mesoporous praseodymium and zirconium oxide composite oxide was formed. In order to investigate the application prospect of the mesoporous Pr-Zr oxide solid solution materials, the reaction properties of the mesoporous materials were investigated in the CO oxidation reaction and the catalytic combustion of carbon smoke. As a catalyst, Pr-Zr oxide solid solution still has excellent catalytic effect and not with the general catalyst. The same is that the high temperature aging samples showed better reaction results. The Au/Pr-Zr-O composite catalyst was prepared by Au as the carrier and the active component was prepared. It was also applied to the oxidation reaction of CO and the catalytic combustion reaction of carbon smoke. It was found that Au and Pr1-xZrxO 2- Delta have CO catalytic action in the reaction. As a carrier, the solid solution of Pr-Zr oxide solution was used as a carrier. It has good high temperature aging property and greatly improves the reaction performance in catalytic reaction.
【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】：O643.36

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 蔣宗軒,李燦,辛勤;稀土Pr_6O_(11)上CO和表面羥基反應(yīng)的原位FT-IR研究[J];催化學(xué)報;1993年03期

2 董照遠(yuǎn),朱明原,金紅明;NdFeB納米晶雙相復(fù)合永磁材料研究進(jìn)展[J];材料科學(xué)與工程學(xué)報;2003年03期

3 趙坤;何方;黃振;鄭安慶;李海濱;趙增立;;La_(1-x)Sr_xFeO_3鈣鈦礦型氧化物中的晶格氧用于甲烷部分氧化制合成氣[J];催化學(xué)報;2014年07期

4 孫長庚,劉宗章,張敏華;甲烷催化部分氧化制合成氣的研究進(jìn)展[J];化學(xué)工業(yè)與工程;2004年04期

5 ;Partial oxidation of methane to syngas in tubular oxygen-permeable reactor[J];Chinese Science Bulletin;2002年07期

6 ;The catalytic behavior of La-Mn-O nanoparticle perovskite-type oxide catalysts for the combustion of the soot particle from the diesel engine[J];Chinese Science Bulletin;2005年14期

7 路勇,沈師孔;甲烷催化部分氧化制合成氣研究新進(jìn)展[J];石油與天然氣化工;1997年01期

8 ;Plasma Treatment of Ni Catalyst for Partial Oxidation of Methane[J];Journal of Natural Gas Chemistry;2005年01期

9 朱玲,王學(xué)中,於俊杰,郝鄭平;K-Ce_(0.5)Zr_(0.5)O_2催化碳顆粒物燃燒性能[J];物理化學(xué)學(xué)報;2005年08期

10 郭耘;盧冠忠;;稀土催化材料的應(yīng)用及研究進(jìn)展[J];中國稀土學(xué)報;2007年01期

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