【摘要】：在工業(yè)中被廣泛應(yīng)用的芳烴,主要依賴于傳統(tǒng)的汽油衍生技術(shù)。由于我國(guó)富煤少油,國(guó)內(nèi)生產(chǎn)能力嚴(yán)重不足,我國(guó)的芳烴主要依賴進(jìn)口�；谝陨显�,國(guó)內(nèi)芳烴供求關(guān)系嚴(yán)重失衡,價(jià)格也居高不下,尋求的一種新的芳烴非石油生產(chǎn)工藝迫在眉睫。隨著我國(guó)甲醇工業(yè)的高速發(fā)展,甲醇生產(chǎn)能力也飛速發(fā)展,但是甲醇的后續(xù)生產(chǎn)工藝開發(fā)遠(yuǎn)沒(méi)有趕上甲醇發(fā)展的速度,目前甲醇生產(chǎn)設(shè)備開工率低,價(jià)格低廉,開發(fā)甲醇的下游工藝也迫在眉睫。近些年興起的甲醇制芳烴工藝很好的緩解了甲醇和芳烴的供求矛盾,對(duì)我國(guó)也具有很重大的戰(zhàn)略意義。目前甲醇制芳烴反應(yīng)主要存在BTX(苯,甲苯,二甲苯)選擇率不高,催化劑穩(wěn)定性不強(qiáng)等問(wèn)題。針對(duì)BTX選擇率低問(wèn)題,目前主要采用負(fù)載金屬的方法解決,目前以負(fù)載Zn的效果最佳。由于反應(yīng)機(jī)理的模糊不清,對(duì)BTX選擇性相關(guān)問(wèn)題的研究遇到嚴(yán)重的瓶頸。另外一方面,對(duì)于催化劑穩(wěn)定性問(wèn)題,研究者們主要采用引入介孔的方法來(lái)解決。但是依然存在這樣或那樣的問(wèn)題,仍需要做進(jìn)一步的研究。本文從引入介孔的方向出發(fā),嘗試了使用糖原或苯基三乙氧基硅烷為模板劑來(lái)制備多級(jí)孔ZSM-5,以期望其在甲醇制芳烴中的優(yōu)良表現(xiàn)。首先,本課題嘗試將糖原作為模板劑制備多級(jí)孔ZSM-5并探究其在甲醇制芳烴中的性能表現(xiàn)。XRD表征結(jié)果發(fā)現(xiàn),分子篩的結(jié)晶度并沒(méi)有因?yàn)樘窃拇嬖诙艿教蟮挠绊?N_2吸附脫附表征結(jié)果顯示糖原確實(shí)有促進(jìn)介孔生成的作用;SEM結(jié)果表明糖原的存在阻礙了晶體生長(zhǎng)的維度從而改變了晶體的形貌,這也很可能是糖原有助于介孔生成的深層次原因;NH3-TPD結(jié)果顯示糖原也影響了分子篩酸的生成及其強(qiáng)度分布。本課題還比較了糖原對(duì)催化劑在甲醇制芳烴中的性能表現(xiàn),結(jié)果顯示糖原對(duì)催化劑穩(wěn)定性改善并不是非常的明顯,這很可能是因?yàn)橛材０逄窃乃苄圆?在結(jié)晶過(guò)程中不能很好的靠近前驅(qū)體,從而導(dǎo)致生成的介孔不能夠很好地靠近晶體表面,難以很好的起到改善質(zhì)量傳遞的作用。BTX選擇率也從19.55%提高到23.84%,這很可能是由于酸性質(zhì)以及較大的介孔比表面積所引起的。不過(guò)糖原確實(shí)很好的起到了引入介孔的作用,也在一定程度上改善了催化劑的催化性能。為了避免再出現(xiàn)上述硬模板水溶性差導(dǎo)致的易發(fā)生相分離的問(wèn)題,本課題選取了不易與前驅(qū)體發(fā)生相分離(水溶性好)的苯基三乙氧基硅烷作為模板劑。本課題以此為模板劑成功制備了多級(jí)孔ZSM-5,并在甲醇制芳烴反應(yīng)中表現(xiàn)出了很不錯(cuò)的催化性能。本文還通過(guò)調(diào)變模板劑的加入量,來(lái)探求其加入量與催化性能之間的關(guān)系。本課題發(fā)現(xiàn)催化劑穩(wěn)定性隨模板劑的量的增多呈現(xiàn)出先增后減的趨勢(shì),催化劑壽命最高可達(dá)到126 h,而BTX選擇率則逐漸增加,最高可達(dá)33.01%。為了探求催化劑不同催化性能的原因,本課題對(duì)催化劑做了一系列分析表征。N_2吸附脫附表征結(jié)果顯示介孔數(shù)量和介孔比表面積與催化劑穩(wěn)定性均呈現(xiàn)出相同的趨勢(shì);熱重結(jié)果也表明當(dāng)其適量時(shí)確實(shí)明顯改善了催化劑的抗積碳性能;SEM和NH3-TPD結(jié)果也表明它確實(shí)也影響了分子篩的形貌以及酸性質(zhì);XRD結(jié)果顯示適量的模板劑對(duì)分子篩結(jié)晶度并無(wú)太大的影響,但是當(dāng)其過(guò)量時(shí)分子篩結(jié)晶明顯受到了影響。由于苯基三乙氧基硅烷較好的水溶性,并且也參與分子篩骨架的搭建,本課題通過(guò)這種物質(zhì)將有機(jī)基團(tuán)(苯環(huán))嫁接于分子篩表面,很好的避免了相分離。本課題通過(guò)這種方式引進(jìn)的介孔可以很好地改善催化劑的質(zhì)量傳遞,從而增強(qiáng)了催化劑的穩(wěn)定性。
[Abstract]:Aromatics, which are widely used in industry, mainly depend on the traditional gasoline derivation technology. Because of our country's rich coal and less oil and serious shortage of domestic production capacity, the aromatics in our country are mainly dependent on imports. Based on the above reasons, the domestic aromatics supply and demand relationship is seriously unbalanced and the price is also high, a new aromatics non petroleum production process is sought. With the rapid development of methanol industry in China and the rapid development of methanol production capacity, the development of methanol production technology is far from the speed of methanol development. At present, the production of methanol equipment is low and the price is low. The downstream process of methanol development is also urgent. The aromatics process which has been developed by methanol is very good in recent years. It also alleviates the contradiction between the supply and demand of methanol and aromatics, which is also of great strategic significance to our country. At present, the reaction of methanol to aromatic hydrocarbons is mainly BTX (benzene, toluene, xylene), the selectivity of BTX is not high, and the stability of the catalyst is not strong. At present, the method of metal loading is mainly used to solve the problem of low selectivity of the catalyst. At present, the effect of load Zn is at present. Because of the ambiguity of the reaction mechanism, the study of BTX selectivity related problems encountered serious bottlenecks. On the other hand, the researchers mainly adopted mesoporous methods to solve the problem of catalyst stability. However, further research still needs to be done. In the direction, we tried to use glycogen or phenyl triethoxy silane as a template to prepare multilevel pore ZSM-5, so as to expect its excellent performance in methanol aromatics. First, we tried to prepare multilevel hole ZSM-5 by using glycogen as a template and explore its performance in methanol to aromatics,.XRD characterization results and molecular sieves. The crystallinity was not greatly influenced by the presence of glycogen; the results of N_2 adsorption desorption showed that glycogen did promote mesoporous formation; SEM results showed that the presence of glycogen hindered the dimension of crystal growth and changed the morphology of the crystal, which was also probably the deep cause of glycogen to facilitate mesoporous formation; NH3- TPD results show that glycogen also affects the formation and intensity distribution of molecular sieve acid. The performance of glycogen in methanol to aromatics is also compared. The results show that the stability of the catalyst is not very obvious. This is probably due to the poor water solubility of the hard template glycogen, which can not be very good during the crystallization process. It is close to the precursor so that the mesoporous pores can not be well close to the crystal surface, and it is difficult to improve the mass transfer by improving the selection rate of.BTX from 19.55% to 23.84%, which is probably due to the acid properties and the larger mesoporous surface area. In order to avoid the problem of the easy phase separation caused by the poor water solubility of the above hard templates, this topic selected the phenyl triethoxy silane which is not easy to separate from the precursor (water solubility) as a template. This topic is a successful preparation of the template. The multilevel hole ZSM-5 has shown good catalytic performance in the reaction of methanol to aromatics. The relationship between the addition amount of the modulating agent and the catalytic performance is also explored in this paper. It is found that the stability of the catalyst increases first and then decreases with the increase of the amount of the template, and the life span of the catalyst is up to the highest. To 126 h, the selection rate of BTX increased gradually, up to 33.01%. in order to find the reasons for the catalytic performance of the catalyst. A series of analysis and characterization of.N_2 adsorption desorption showed that the number of mesoporous and the surface area of the mesoporous ratio showed the same trend as the stability of the catalyst. SEM and NH3-TPD results also showed that it did also affect the morphology and acid properties of molecular sieves. XRD results showed that a proper amount of templates had no significant influence on the crystallinity of molecular sieves, but the crystallization of molecular sieves was obviously affected when they were excessive. Silane is well water-soluble and also participates in the construction of molecular sieve framework. This subject grafted the organic group (benzene ring) on the surface of molecular sieve through this material. It is good to avoid phase separation. The mesoporous mesopore introduced in this way can improve the mass transfer of the catalyst so as to enhance the stability of the catalyst.
【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ241;O643.36

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