【摘要】：論文以實(shí)現(xiàn)乙炔羰基化合成丙烯酸均相催化劑多相化為目標(biāo),制備了一系列固載活性金屬組分的雙功能催化劑,研究其用于多相反應(yīng)體系的催化性能。基于本實(shí)驗(yàn)室已有的鎳基多相催化劑的研究開發(fā)經(jīng)驗(yàn)和基礎(chǔ),本課題主要針對銅基多相催化劑進(jìn)行研究和開發(fā)。課題采用液相離子交換法將銅組份固載到Y(jié)分子篩上。同時采用XRD,XPS,ICP-AES,IC,BET,FT-IR,pyridine/CO-IR,NH3-TPD,Raman,TG-DTG 以及SEM多種儀器對催化劑的結(jié)構(gòu)、組分及酸性等多種性質(zhì)進(jìn)行表征分析,研究其與催化劑活性之間的相關(guān)性,并且對最高效的催化劑進(jìn)行失活和再生研究,提出積碳生長機(jī)理。采用不同銅活性組分前驅(qū)體(Cu(NO_3)_2、CuBr_2及CuSO_4)制備的CuY催化劑的表征結(jié)果顯示,陰離子SO_4~(2-)與催化劑中[CuOCu]~(2+)結(jié)合的方式更為有效,可以產(chǎn)生更多、更強(qiáng)的酸性中心,具有更高的催化活性。通過將催化劑前驅(qū)體在不同的氣氛下(空氣、氮?dú)饧皻錃?焙燒,獲得具有豐富銅物種(Cu0、Cu~+、Cu_2O、Cu~(2+)、CuO)分布的催化劑。XPS及pyridine-FTIR結(jié)果表明,在氮?dú)饬髦斜簾拇呋瘎?亞銅及氧化銅分布較為均衡,酸性也強(qiáng)于其他樣品。CO-FTIR及活性評價結(jié)果表明,位于FAU結(jié)構(gòu)中Ⅱ位的亞銅離子,可以與CO形成穩(wěn)定單羰基絡(luò)合物,有利于反應(yīng)的進(jìn)行。該亞銅離子在氮?dú)獗簾臉悠分泻控S富,因此該催化劑具有最高的反應(yīng)活性。失活研究表明,造成催化劑失活的因素影響程度由大到小排列依次為積碳活性組分流失酸性下降結(jié)晶度破壞。在反應(yīng)過程中,未反應(yīng)的活化的乙炔氣體在分子篩晶粒上溶解、擴(kuò)散、固化,形成碳顆粒,趨于飽和時,朝著有序的碳纖維的方向生長。熱重結(jié)果表明,碳纖維的熱穩(wěn)定性要優(yōu)于前者。
[Abstract]:In order to realize the heterogeneous catalyst for acetylene carbonylation to acrylic acid, a series of bifunctional catalysts supported on active metal components were prepared and their catalytic performance in multiphase reaction system was studied. Based on the research and development experience and basis of nickel-based multiphase catalysts in our laboratory, this paper mainly focuses on the research and development of copper-based multiphase catalysts. In this paper, copper components were supported on Y molecular sieves by liquid phase ion exchange method. At the same time, the structure, composition and acidity of the catalyst were characterized and analyzed by XRD,XPS,ICP-AES,IC,BET,FT-IR,pyridine/CO-IR,NH3-TPD,Raman,TG-DTG and SEM, and the correlation between the catalyst and the activity of the catalyst was studied. the deactivation and regeneration of the most efficient catalyst were studied, and the mechanism of carbon deposition growth was put forward. The characterization results of CuY catalysts prepared by using different copper active component precursors (Cu (NO_3 _ 2, Cubr 鈮，

本文編號：2501496