【摘要】：乙二醇作為一種重要的化學(xué)工業(yè)原料,被廣泛的用于聚酯等行業(yè)的生產(chǎn)。傳統(tǒng)的生產(chǎn)方式以石油為原料來(lái)生產(chǎn),隨著石油資源的日益匱乏,“煤制乙二醇”技術(shù)逐漸受到研究者的重視。該技術(shù)是指從煤氣出發(fā),經(jīng)草酸酯選擇性加氫制備乙二醇的技術(shù)。其中的關(guān)鍵步驟是草酸酯加氫制乙二醇。目前的銅基催化劑還未能滿(mǎn)足工業(yè)化需求,且存在催化活性與穩(wěn)定性問(wèn)題。盡管?chē)?guó)內(nèi)外的研究學(xué)者對(duì)此課題進(jìn)行了大量研究,并提出了不同的關(guān)于銅基催化劑活性中心的理論(Cu0或Cu+或Cu0-Cu+協(xié)同),雖然存在分歧,但可以肯定的是,探索控制催化劑表面物種的組成、價(jià)態(tài)分布的方法是開(kāi)發(fā)高性能草酸酯加氫催化劑的根本途徑。本文采用共沉淀法制備硅酸銅催化劑,研究了沉淀過(guò)程中活性組分與載體之間的相互作用,并考察了相應(yīng)可變參數(shù)對(duì)催化劑催化性能的影響,優(yōu)化了制備工藝。此外,為解決催化劑在高溫條件下易燒結(jié)失活,因而添加了助劑鋅以提高催化劑的熱穩(wěn)定性。研究結(jié)果如下：(1)在采用沉淀法制備硅酸銅催化劑的過(guò)程中,沉淀方式對(duì)銅物種的顆粒大小及在載體上的分散度有較大的影響。硝酸銅滴入硅酸按沉淀得到的催化劑性能優(yōu)于硅酸鈉滴入硝酸銅沉淀制得催化劑,即適宜的沉淀方式制得的催化劑活性物種分散度好,活性中心多。在沉淀過(guò)程中,沉淀速率對(duì)反應(yīng)的轉(zhuǎn)化率稍有影響而對(duì)目的產(chǎn)物的選擇性影響不大。隨沉淀時(shí)間的增加即沉淀速率的減慢,草酸二甲酯的轉(zhuǎn)化率稍有提高。銅硅比對(duì)催化劑的催化性能影響較大,銅硅比過(guò)低,催化劑活性位少,催化活性弱；銅硅比過(guò)高則活性物種易相互聚集,顆粒長(zhǎng)大,分布不均從而催化劑活性也會(huì)降低。實(shí)驗(yàn)表明較優(yōu)的銅硅比為0.85：1,此時(shí)DMO轉(zhuǎn)化率為90.5%,EG選擇性為82.7%。(2)在進(jìn)行鋅改性硅酸銅催化劑研究過(guò)程中,鋅元素的引入方式對(duì)催化劑有不同的影響。實(shí)驗(yàn)表明銅組分與鋅組分同時(shí)與硅酸鈉沉淀時(shí),銅鋅之間有相互作用,鋅對(duì)銅物種的分散有促進(jìn)作用。且鋅的引入量對(duì)催化劑的性能影響較大,鋅引入量少時(shí)無(wú)法起到明顯效果,而引入量過(guò)多時(shí)則會(huì)包裹活性中心。所以適宜的催化劑組成為Cu0.8Zn0.2/SiO2,此時(shí)催化劑轉(zhuǎn)化率為99.5%,選擇性為91.5%皆為較優(yōu)結(jié)果,抗失活性能測(cè)試也顯示轉(zhuǎn)化率為99%,活性較穩(wěn)定。
[Abstract]:As an important raw material in chemical industry, ethylene glycol is widely used in the production of polyester and other industries. The traditional mode of production uses petroleum as raw material to produce. With the increasing shortage of petroleum resources, the technology of making ethylene glycol from coal has been paid more and more attention by researchers. This technology refers to the selective hydrogenation of oxalate to produce ethylene glycol from gas. The key step is the hydrogenation of oxalate to ethylene glycol. The current copper-based catalysts have not been able to meet the industrial needs, and there are problems of catalytic activity and stability. Although researchers at home and abroad have done a lot of research on this subject and put forward different theories about the active centers of copper-based catalysts (Cu0 or Cu or Cu0-Cu collaboration), although there are differences, it is certain that, The method of controlling species composition and valence distribution on the surface of catalyst is the fundamental way to develop high performance oxalate hydrogenation catalyst. In this paper, coprecipitation method was used to prepare copper silicate catalyst. The interaction between active component and carrier during precipitation was studied. The effect of variable parameters on the catalytic performance of the catalyst was investigated and the preparation process was optimized. In addition, in order to solve the problem that the catalyst is easy to be deactivated by sintering at high temperature, the additive zinc is added to improve the thermal stability of the catalyst. The results are as follows: (1) in the process of preparing copper silicate catalyst by precipitation method, the precipitation mode has a great influence on the particle size of copper species and the dispersion on the carrier. The catalytic properties of the catalyst prepared by precipitation of copper nitrate drop with silicic acid are better than that of the catalyst prepared by the precipitation of copper nitrate with sodium silicate, that is, the catalyst prepared by the appropriate precipitation method has a good dispersion of active species and more active centers. In the precipitation process, the precipitation rate had a slight effect on the conversion of the reaction, but had little effect on the selectivity of the target product. The conversion rate of dimethyl oxalate increased slightly with the increase of precipitation time. The ratio of copper to silicon has a great influence on the catalytic performance of the catalyst, the ratio of copper to silicon is too low, the activity of the catalyst is less and the catalytic activity is weak; if the ratio of copper to silicon is too high, the active species tend to aggregate mutually, the particles grow up and the distribution is uneven, thus the activity of the catalyst will also decrease. The experimental results show that the optimum copper-silicon ratio is 0.85: 1, and the DMO conversion is 90.5 and EG selectivity is 82.7%. (2) in the study of zinc modified copper silicate catalyst, The method of introducing zinc has different influence on the catalyst. The results show that when copper and zinc are precipitated with sodium silicate at the same time, there is interaction between copper and zinc, and zinc can promote the dispersion of copper species. The effect of zinc content on the performance of the catalyst is great. When the amount of zinc is low, the effect of the catalyst is not obvious, but when the amount of zinc is too much, the active center will be wrapped. Therefore, the suitable catalyst composition is Cu0.8Zn0.2/SiO2, the conversion of the catalyst is 99.5 and the selectivity of 91.5% is the best result. The deactivation resistance test also shows that the conversion is 99%, and the activity is relatively stable.
【學(xué)位授予單位】：合肥工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：TQ223.162;O643.36

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