本文選題：偏三甲苯　切入點(diǎn)：加氫脫烷基化反應(yīng)　出處：《吉林大學(xué)》2017年碩士論文

【摘要】：偏三甲苯(1,2,4-TMB)是重芳烴的重要組成成份,占C9+重芳烴總質(zhì)量的30.0%~40.0%。輕質(zhì)芳烴是重要的化工原料,在醫(yī)藥中間體、染料制備、農(nóng)藥合成和制作表面活性劑等領(lǐng)域有廣泛的用途。其中苯、甲苯和二甲苯(BTX)是工業(yè)生產(chǎn)中最常用的化工產(chǎn)品。由于石化資源日趨緊缺,C9+重芳烴的高效利用具有重要的現(xiàn)實(shí)意義。重芳烴催化加氫轉(zhuǎn)化是一條環(huán)保經(jīng)濟(jì)的工藝路線(xiàn)。本文針對(duì)1,2,4-TMB加氫制備BTX進(jìn)行詳細(xì)的研究。分別制備了Ni/SiO_2和Co/ZSM-5催化劑,針對(duì)催化劑酸堿性質(zhì)對(duì)反應(yīng)性能的影響進(jìn)行了詳細(xì)討論,系統(tǒng)考察了催化劑的制備條件和反應(yīng)條件的影響。論文的主要內(nèi)容如下:1.采用溶膠-凝膠法制備N(xiāo)i/SiO_2催化劑,系統(tǒng)考察催化劑對(duì)1,2,4-TMB加氫脫烷基化反應(yīng)的影響。首先,考察制備過(guò)程中無(wú)水檸檬酸(CA)的量對(duì)催化劑結(jié)構(gòu)和性能的影響。結(jié)果表明,CA對(duì)催化劑孔結(jié)構(gòu)和催化劑的整體結(jié)構(gòu)有很大影響,CA的量影響了活性物種的分散度。其次,研究了催化劑上Ni的負(fù)載量、焙燒溫度和鎳源等因素對(duì)催化性能的影響。最后,通過(guò)調(diào)變反應(yīng)溫度和反應(yīng)壓力,找到適合Ni/SiO_2催化劑體系的最佳反應(yīng)工藝。研究結(jié)果表明,催化劑負(fù)載量為10(wt)%左右、n(Ni)/n(CA)=1:2、鎳源為Ni(NO3)2·6H2O,經(jīng)過(guò)773 K空氣焙燒3 h后,催化劑在723 K、3.0 MPa條件下反應(yīng),1,2,4-TMB轉(zhuǎn)化率達(dá)到29.4%,BTX選擇性接近100%。2.運(yùn)用各種表征手段研究了催化劑酸堿性位對(duì)1,2,4-TMB加氫脫烷基化反應(yīng)的影響。提高目標(biāo)產(chǎn)物的選擇性是該反應(yīng)的研究重點(diǎn)。因此,本論文選用酸性較弱的二氧化硅為載體,制備了Ni/SiO_2催化劑,研究了其催化性能。結(jié)果表明,催化劑表面的酸性主要為L(zhǎng)ewis酸,幾乎沒(méi)有B酸中心。結(jié)合其它表征結(jié)果,可知除了金屬Ni外,1,2,4-TMB進(jìn)行脫烷基化反應(yīng)主要是與催化劑表面Lewis酸有關(guān)。3.研究了ZSM-5系列催化劑對(duì)1,2,4-TMB加氫脫烷基化反應(yīng)的影響。我們制備了Co/ZSM-5負(fù)載型催化劑,并確定了催化劑合成條件。1,2,4-TMB轉(zhuǎn)化率至73.2%,BTX的選擇性達(dá)到87.8%。
[Abstract]:Metamethyltoluene (TMB) is an important component of heavy aromatics, which accounts for 30.010% of the total mass of C9 heavy aromatics.Light aromatics are important chemical raw materials. They are widely used in pharmaceutical intermediates, dye preparation, pesticide synthesis and surfactants.Benzene, toluene and xylene are the most commonly used chemical products in industrial production.Because of the increasing shortage of petrochemical resources, the efficient utilization of C _ 9 aromatics has important practical significance.Catalytic hydrogenation of heavy aromatics is an environmental and economic process.In this paper, the preparation of BTX by hydrogenation of 1 TMB was studied in detail.Ni/SiO_2 and Co/ZSM-5 catalysts were prepared respectively. The effects of the acid-base properties of the catalysts on the reaction performance were discussed in detail. The effects of the preparation conditions and reaction conditions of the catalysts were systematically investigated.The main contents of the thesis are as follows: 1: 1.Ni/SiO_2 catalyst was prepared by sol-gel method, and the effect of catalyst on the hydrogenation and dealkylation reaction of 1zao 2o 4-TMB was investigated systematically.Firstly, the effect of the amount of anhydrous citric acid (CA) on the structure and performance of the catalyst was investigated.The results show that the amount of CA has a great influence on the pore structure of the catalyst and the overall structure of the catalyst, which affects the dispersity of the active species.Secondly, the effects of Ni loading, calcination temperature and nickel source on the catalytic performance were studied.Finally, by adjusting the reaction temperature and reaction pressure, the optimum reaction process suitable for Ni/SiO_2 catalyst system was found.The effects of acid and basic sites on the hydrogenation of 1tmb were studied by various characterization methods.Improving the selectivity of the target product is the key point of the reaction.Therefore, in this paper, Ni/SiO_2 catalyst was prepared by using silica as the carrier, and its catalytic performance was studied.The results show that the acid on the surface of the catalyst is mainly Lewis acid, and there is almost no B acid center.Combined with other characterization results, it can be seen that the dealkylation reaction of TMB except Ni is mainly related to the Lewis acid on the catalyst surface.The effect of ZSM-5 series catalysts on the hydrogenation and dealkylation of 1H 2N 4 TMB was studied.We prepared the Co/ZSM-5 supported catalyst and determined the catalyst synthesis conditions. The conversion rate of TMB was 73.22% and the selectivity of the catalyst was 87.8%.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O643.36;O621.25

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