本文關(guān)鍵詞：三維有序大孔金屬氧化物脫硫劑的合成及常溫脫硫性能研究　出處：《太原理工大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 三維有序大孔 鋅硅復(fù)合物 銅硅復(fù)合物 常溫脫硫 再生

【摘要】：隨著全球化石能源的日益枯竭和環(huán)境問題的日益嚴(yán)峻,研究與開發(fā)高效、節(jié)能、環(huán)保的能源利用新技術(shù)已迫在眉睫。正在興起的燃料電池(FC)技術(shù)是其中的典型代表。供氫原料氣的深度脫硫是FC必須解決的關(guān)鍵技術(shù)環(huán)節(jié)。且隨著FC應(yīng)用環(huán)境與目的不同,對常低溫溫和條件下深度脫硫工藝的需求也越來越多。由于金屬和硫之間很強的鍵合作用,金屬氧化物化學(xué)吸收法是非常有效而普遍使用的脫硫方法。相比其它金屬氧化物,氧化鋅和氧化銅與硫化氫反應(yīng)具有更好的熱力學(xué)優(yōu)勢,因此在常低溫條件下具有更高的脫硫精度。然而,現(xiàn)有常低溫金屬氧化物脫硫技術(shù)普遍存在硫容偏低的問題,因此硫容的提高一直是優(yōu)化其常溫脫硫性能的研究熱點。本研究采用聚苯乙烯膠晶模板法成功制備了三維有序大孔氧化鋅-氧化硅和氧化銅一氧化硅系列復(fù)合氧化物,并在固定床上對其進行了常溫動態(tài)脫硫性能評價,采用X射線衍射儀(XRD)、N2吸附、傅里葉紅外(FTIR)、掃描電子顯微鏡(SEM)、透射電子顯微鏡(TEM)、X光電子能譜(XPS)等表征手段對樣品脫硫前后的物相組成、微觀形貌以及織構(gòu)的變化進行了分析,并且與常溫脫硫機理和脫硫性能進行了關(guān)聯(lián)。表征結(jié)果顯示,所制備的3DOM鋅硅和銅硅復(fù)合氧化物三維大孔結(jié)構(gòu)整齊有序,大孔尺寸均一且長程有序度高,大孔之間有小窗口連接從而在三維空間上相互貫通。二氧化硅的摻入以及3DOM的結(jié)構(gòu)效應(yīng)使得復(fù)合物中的活性組分氧化鋅和氧化銅被高度分散。同時,二氧化硅還對三維有序大孔結(jié)構(gòu)起到一定的支撐作用。脫硫前后3DOM復(fù)合氧化物的物相組成及結(jié)構(gòu)形貌發(fā)生了明顯變化,其中的金屬氧化物轉(zhuǎn)化為相應(yīng)的金屬硫化物。硫化后樣品的孔道急劇收縮,孔容和表面積顯著下降,說明脫硫劑硫化過程是一個內(nèi)部由開孔向閉孔轉(zhuǎn)變的過程。因此,織構(gòu)對于脫硫有著重要影響。固定床評價研究顯示,3DOM金屬氧化物脫硫劑常溫脫硫性能明顯優(yōu)于常溫商品脫硫劑以及無3DOM結(jié)構(gòu)的金屬氧化物脫硫劑,脫硫性能的大幅提升主要歸功于3DOM獨特的結(jié)構(gòu)特征：發(fā)達而貫通的孔道、大的比表面積以及納米尺寸晶粒。焙燒溫度以及金屬氧化物與二氧化硅的比例直接影響著3DOM脫硫劑的脫硫性能。此外,研究中還發(fā)現(xiàn)水汽對于3DOM脫硫劑的常溫脫硫性能具有極大的促進作用,有水汽氛下與無水汽氛下的脫硫機理是不同的。通過對3DOM金屬氧化物脫硫劑進行氨化處理,其脫硫性能明顯提升,說明脫硫劑的表面性質(zhì)對于其常溫脫硫也起著關(guān)鍵作用。本實驗中對3DOM金屬氧化物脫硫劑的再生性能也進行了研究,結(jié)果顯示,再生后樣品的脫硫性能明顯下降,但是相比于商品脫硫劑來說,其再生率還是相當(dāng)可觀。而且再生性能穩(wěn)定,再生過程中孔道結(jié)構(gòu)并沒有發(fā)生明顯的破壞和坍塌。
[Abstract]:With the increasing depletion of fossil energy and global environmental problems are becoming more and more serious, the research and development of high efficiency, energy saving, environmentally friendly energy utilization of new technology has been imminent. The emerging fuel cell (FC) technology is one of the typical representatives. Deep desulfurization hydrogen supply of raw gas is the key technology to link FC to be solved with. The FC application environment and different purposes, for deep desulfurization process at low temperature under mild conditions needs more and more. Between the metal and the sulfur strong bond, metal oxide chemical absorption method is very effective and widely used method of desulfurization. Compared with other metal oxides, the thermodynamic advantage of Zinc Oxide and copper oxide and hydrogen sulfide with reaction better, so it has higher accuracy in desulfurization under the condition of low temperature. However, the existing low temperature metal oxide desulfurization technology often exists the problem of low sulfur content, therefore The sulfur content in the increase has been a hot research to optimize the desulfurization performance at room temperature. This study used polystyrene colloidal crystal template method was employed to prepare three-dimensional ordered macroporous Zinc Oxide - silicon oxide and copper oxide silicon oxide composite oxide, the dynamic evaluation and the desulfurization performance at room temperature in a fixed bed, by using X ray diffraction instrument (XRD), N2 adsorption, Fourier transform infrared (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X ray photoelectron spectroscopy (XPS) phase composition characterized the samples before and after desulfurization, change of microstructure and texture were analyzed, and the correlation with ambient temperature desulfurization the mechanism and the desulfurization performance. Results show that the 3DOM Zn Si and Cu Si composite oxide three-dimensional macroporous structure prepared orderly, large pore size and uniform degree of long range order is high, a small window to connect in 3D empty hole Between each other. Through the incorporation of silica and 3DOM structure effect makes the activity group complex in the Zinc Oxide and the copper oxide is highly dispersed. At the same time, silica to a supporting role in the three-dimensional ordered macroporous structure. The 3DOM composite oxides before and after desulfurization phase composition and morphology changed obviously. One of the metal oxides into the corresponding metal sulfides. Sample pore sharp contraction after curing, the pore volume and surface area decreased significantly, indicating sulfide desulfurization process is a process of transformation from an internal hole to the obturator. Because of this, the texture has a great influence on desulfurization. Evaluation of fixed bed, desulfurization performance 3DOM metal oxide desulfurizer at ambient temperature is obviously better than that of normal goods desulfurizing agent and metal oxide desulfurization agent without 3DOM structure, greatly enhance the desulfurization performance is mainly attributed to the unique 3DOM The structural characteristics: developed and through the pore, large surface area and nano grain size. The calcination temperature and the proportion of silica and metal oxides directly affect the desulfurization performance of 3DOM desulfurizing agent. In addition, the study also found that water vapor for 3DOM desulfurization desulfurization performance at room temperature has great role in promoting, with the desulfurization mechanism water vapor in atmosphere and anhydrous steam atmosphere is different. Based on the 3DOM metal oxide desulfurizer for treatments, the desulfurization performance improved significantly, indicating the surface properties of desulfurization agent for the desulfurization at normal temperature also plays a key role in the experiment. The regeneration performance of 3DOM metal oxide desulfurizer was also investigated. Results show that the regenerated desulfurization performance of samples decreased significantly, but compared to the commodity desulfurizer, the regeneration rate is still considerable. And the regeneration performance is stable, in the regeneration process of hole There is no obvious damage and collapse in the channel structure.

【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TB33;TM911.4

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