【摘要】：清潔汽油的生產(chǎn)離不開深度加氫,但深度加氫必然造成汽油辛烷值損失。為解決這一矛盾,汽油異構(gòu)化過程受到日趨關(guān)注,而高效異構(gòu)化催化劑的開發(fā)是汽油異構(gòu)化工藝過程的關(guān)鍵。作為雙功能的臨氫異構(gòu)化催化劑,每一組分的功能和組分間的協(xié)同作用都將影響催化劑的性能,由此決定了優(yōu)化酸性組分功能和探究活性金屬與酸性載體間相互作用的重要性。本文首先以干凝膠法合成SAPO-11分子篩,通過硅的加入量、CTAB和HF的引入分別調(diào)控分子篩的酸量、粒度和形貌;然后以SAPO-11為載體,鎳、鉑分別為金屬組分,采用浸漬法制備了異構(gòu)化催化劑,考察了金屬擔(dān)載量和酸量對催化劑異構(gòu)化性能的影響,探究了金屬中心與酸中心的協(xié)同效應(yīng)。結(jié)果表明,硅在分子篩骨架中的取代量及化學(xué)環(huán)境決定其酸性質(zhì),硅加入量的增加使得硅原子取代方式由SM2取代向SM3發(fā)生轉(zhuǎn)換,提高了分子篩的中強(qiáng)酸量。CTAB的加入不僅能降低分子篩粒度,而且因其能促進(jìn)硅原子發(fā)生同晶取代而有利于分子篩酸量的增加,由此提高了Ni/SAPO-11催化劑的活性,但是過高的酸量會破壞Ni與SAPO-11之間的匹配關(guān)系,降低異庚烷選擇性。HF的加入改變了SAPO-11分子篩的形貌,使其由不規(guī)則的顆粒定向生長為棒狀單晶,棒狀顆粒長度的增加能提高催化劑的異庚烷選擇性。此外,分子篩粒度的降低,不僅提高了催化劑的活性,而且也增強(qiáng)了其抗積碳性能。從金屬擔(dān)載量和酸量對Ni/SAPO-11催化劑異構(gòu)化性能的影響結(jié)果可得,兩組分間存在著明顯的協(xié)同關(guān)系,酸性中心過多或過分強(qiáng)調(diào)金屬中心都會降低異構(gòu)烴的選擇性,兩活性中心適當(dāng)匹配,可使催化劑具有優(yōu)良的異構(gòu)化性能,其中正庚烷轉(zhuǎn)化率達(dá)到73.09%,異庚烷選擇性及收率分別為51.16%和37.39%,直餾汽油中異構(gòu)烷烴收率達(dá)到了39.31%。
[Abstract]:The production of clean gasoline can not be separated from deep hydrogenation, but deep hydrogenation will inevitably lead to the loss of gasoline octane number. In order to solve this contradiction, the isomerization process of gasoline has been paid more and more attention, and the development of high efficiency isomerization catalyst is the key to the isomerization process of gasoline. As a bifunctional hydroisomerization catalyst, the function of each component and the synergistic action of each component will affect the performance of the catalyst, which determines the importance of optimizing the function of the acidic component and exploring the interaction between the active metal and the acid support. In this paper, the SAPO-11 molecular sieve was synthesized by xerogel method, and the acid content, particle size and morphology of the molecular sieve were regulated by the addition of Si and HF respectively. The isomerization catalyst was prepared by impregnation method. The effects of metal loading and acid content on the isomerization performance of the catalyst were investigated, and the synergistic effect between metal center and acid center was investigated. The results show that the substitution amount and chemical environment of silicon in molecular sieve skeleton determine its acid properties, and the increase of silicon content makes the substitution of silicon atom change from SM2 substitution to SM3. The addition of CTAB can not only decrease the particle size of molecular sieve, but also increase the amount of acid in molecular sieve because it can promote the isomorphic substitution of silicon atom, thus improving the activity of Ni/SAPO-11 catalyst. However, too high acid content will destroy the matching relationship between Ni and SAPO-11, and decrease the isoheptane selectivity. HF can change the morphology of SAPO-11 molecular sieve and make it grow from irregular particles to rod-like single crystal. The increase of the length of rod-like particles can improve the selectivity of isoheptane. In addition, the decrease of molecular sieve particle size not only improved the activity of catalyst, but also enhanced its resistance to carbon deposition. From the results of the influence of metal loading and acid content on the isomerization performance of Ni/SAPO-11 catalyst, there is an obvious synergistic relationship between the two components. Too much acid center or too much emphasis on metal center will reduce the selectivity of isomerization hydrocarbon. Proper matching of the two active centers can make the catalyst have excellent isomerization performance. The conversion of n-heptane is 73.09, the selectivity and yield of isoheptane are 51.16% and 37.3939%, respectively, and the yield of iso-alkanes in straight-run gasoline reaches 39.31%.
【學(xué)位授予單位】：中國石油大學(xué)(華東)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TE624.9

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 韓磊;崔曉;劉欣梅;;SAPO-11分子篩的粒度調(diào)控[J];無機(jī)化學(xué)學(xué)報(bào);2013年03期

2 王妮;張君濤;梁生榮;;輕質(zhì)烷烴異構(gòu)化催化劑及機(jī)理研究進(jìn)展[J];當(dāng)代化工;2012年03期

3 楊德興;王鵬飛;徐華勝;呂愛玲;胡杰;呂待清;;兩步晶化法合成納米SAPO-34分子篩及其催化性能[J];高等學(xué)�；瘜W(xué)學(xué)報(bào);2011年04期

4 國海峰;楊曉東;郭峰;;采用探針分子對長鏈烷烴異構(gòu)化反應(yīng)機(jī)理研究進(jìn)展[J];化工生產(chǎn)與技術(shù);2011年01期

5 汪穎軍;吳紅玉;吳紅姣;張瑩瑩;朱光宇;;SAPO分子篩的合成及影響因素的研究進(jìn)展[J];化學(xué)研究與應(yīng)用;2011年01期

6 劉維橋;雷衛(wèi)寧;劉平;尚通明;任杰;孫予罕;;Zn對Pt/SAPO-11催化劑物化及異構(gòu)性能影響[J];化學(xué)學(xué)報(bào);2010年18期

7 劉維橋;劉平;蔣海燕;尚通明;任杰;孫予罕;;Ni對Pt/SAPO-11催化劑物化及異構(gòu)性能影響[J];無機(jī)化學(xué)學(xué)報(bào);2010年07期

8 劉維橋;尚通明;周全發(fā);任杰;孫予罕;;Physicochemical and isomerization property of Pt/SAPO-11 catalysts promoted by rare earths[J];Journal of Rare Earths;2009年06期

9 劉平;任杰;孫予罕;;改進(jìn)水熱法合成SAPO-11及其酸性和異構(gòu)化活性[J];催化學(xué)報(bào);2008年04期

10 金昌磊;馬波;張喜文;凌鳳香;張志智;;正構(gòu)烷烴加氫異構(gòu)化反應(yīng)機(jī)理的研究進(jìn)展[J];工業(yè)催化;2008年01期

相關(guān)會議論文 前2條

1 陳凌;趙天生;羅發(fā)亮;;變溫陳化法制備SAPO-34及其MTP催化性能研究[A];第五屆全國環(huán)境催化與環(huán)境材料學(xué)術(shù)會議論文集[C];2007年

2 張勝振;陳勝利;董鵬;姜?jiǎng)P;;不同合成介質(zhì)中SAPO-11分子篩的合成、表征及正十六烷臨氫異構(gòu)化反應(yīng)性能研究[A];第三屆全國化學(xué)工程與生物化工年會論文摘要集（上）[C];2006年

相關(guān)碩士學(xué)位論文 前2條

1 李小輝;SAPO-11分子篩催化劑上正庚烷異構(gòu)化性能的研究[D];大慶石油學(xué)院;2010年

2 劉進(jìn)祥;鎢基催化劑上長鏈烷烴異構(gòu)化的研究[D];大慶石油學(xué)院;2007年

，

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