本文選題：順酐加氫 + 丁二酸酐��； 參考：《北京化工大學(xué)》2016年碩士論文

【摘要】：順酐是一種重要的有機(jī)合成中間體,可加氫制備丁二酸酐、Y-丁內(nèi)酯以及1,4-丁二醇等一系列重要的精細(xì)化工原料。其中,丁二酸酐因其獨(dú)特的分子結(jié)構(gòu)故而可發(fā)生一系列化學(xué)反應(yīng)。具體來(lái)說(shuō),丁二酸酐由兩個(gè)酰基和一個(gè)氧原子組成,�；奈娮有�(yīng)和�；g的相互作用可增強(qiáng)酰基中碳原子的正電性,進(jìn)而易于發(fā)生水解、醇解、氨解和酯化反應(yīng)等,因此丁二酸酐在工業(yè)上具有廣泛的用途。目前丁二酸酐的主要制備方法有順酐加氫法、生物發(fā)酵法以及電化學(xué)還原法,其中順酐加氫法具有產(chǎn)品純度高、易于生產(chǎn)規(guī)模化等競(jìng)爭(zhēng)優(yōu)勢(shì),而目前對(duì)于順酐加氫的研究,多以γ-丁內(nèi)酯以及1,4-丁二醇等為主要產(chǎn)物,因此對(duì)順酐加氫制備丁二酸酐,特別是相關(guān)催化劑的研究是十分有必要的。本文研究了在順酐加氫反應(yīng)中,Pd催化劑對(duì)產(chǎn)物丁二酸酐收率的影響。結(jié)合XRD、TEM、XPS、TG-DTA等一系列表征方法,考察了催化劑制備條件和反應(yīng)條件對(duì)順酐轉(zhuǎn)化率以及丁二酸酐選擇性的影響。具體內(nèi)容如下：1.以TiO2、 Al2O3、SiO2為載體時(shí),盡管Al203和SiO2的比表面積比較大,但由于活性組分Pd在Ti02表面的分散性最好、顆粒粒徑最小,相對(duì)活性位較多,因此Pd/TiO2催化劑的順酐加氫活性最高,為53.9%；2.前驅(qū)體為Pd(NO3)2時(shí),經(jīng)過(guò)煅燒步驟處理的催化劑,其活性組分Pd顆粒明顯大,使得催化劑加氫活性較差,順酐轉(zhuǎn)化率降低10%左右；催化劑還原溫度從150℃升至450℃時(shí),活性組分Pd與Ti02之間的相互作用增強(qiáng),導(dǎo)致催化劑的加氫活性顯著降低,還原溫度為150℃時(shí),順酐轉(zhuǎn)化率為87.9%,而還原溫度為450℃時(shí),順酐轉(zhuǎn)化率僅為38.9%；載體經(jīng)浸漬干燥后于150℃直接還原制得的催化劑的加氫活性最高,為87.9%；3.隨著反應(yīng)溫度從100℃升至200℃,順酐轉(zhuǎn)化率從59.4%提高到100%,溫度升至250℃時(shí),順酐轉(zhuǎn)化率維持100%,但丁二酸酐選擇性降低,有副產(chǎn)物γ-丁內(nèi)酯生成；H2分壓和反應(yīng)時(shí)間對(duì)順酐轉(zhuǎn)化率的影響較小；最佳反應(yīng)條件為150℃-2 MPa H2-1h;另外,發(fā)現(xiàn)在溶劑中水的存在會(huì)抑制順酐加氫反應(yīng)。
[Abstract]:Maleic anhydride is an important intermediate in organic synthesis. It can be hydrogenated to produce succinic anhydride Y- butyrolactone and a series of important fine chemical raw materials. Among them, succinic anhydride can take place a series of chemical reactions because of its unique molecular structure. Specifically, succinic anhydride consists of two acyl groups and one oxygen atom. The electron-absorption effect of acyl groups and the interaction between acyl groups can enhance the positive electrical properties of carbon atoms in acyl groups, which can lead to hydrolysis, alcoholysis, ammonolysis and esterification, etc. Therefore, succinic anhydride is widely used in industry. At present, the main preparation methods of succinic anhydride are maleic anhydride hydrogenation, biological fermentation and electrochemical reduction. Among them, maleic anhydride hydrogenation has the competitive advantages of high purity and easy to produce large-scale. 緯 -butyrolactone and 1-butanediol are the main products, so it is necessary to study the hydrogenation of maleic anhydride to succinic anhydride, especially the related catalysts. The effect of PD catalyst on the yield of succinic anhydride in maleic anhydride hydrogenation was studied. The effects of preparation conditions and reaction conditions on the conversion of maleic anhydride and selectivity of succinic anhydride were investigated by means of a series of characterization methods, such as XRDX, TG-DTA and so on. The details are as follows: 1. With TIO _ 2, Al _ 2O _ 3 and Sio _ 2 as the support, although the specific surface area of Al203 and Sio _ 2 is large, the active component PD has the best dispersion on Ti02 surface, the smallest particle size and more relative active sites, so PD / TIO _ 2 catalyst has the highest maleic anhydride hydrogenation activity (53.9%). When PD (no _ 3) _ 2 is the precursor, the active component PD particles are obviously large, which makes the hydrogenation activity of the catalyst worse, the conversion of maleic anhydride decreases by about 10%, and the reduction temperature increases from 150 鈩，

本文編號(hào)：2112348