鋁改性ZSM-5分子篩催化劑對(duì)甲醇制汽油反應(yīng)性能的影響研究
發(fā)布時(shí)間：2019-05-28 05:27
【摘要】：非石油路線,煤基甲醇制汽油技術(shù)(MTG)是應(yīng)對(duì)石油資源日漸枯竭的重要手段之一,結(jié)合我國富煤、貧油、少氣的現(xiàn)狀,MTG技術(shù)在我國具有非常重要的現(xiàn)實(shí)意義。本文以鋁離子改性的ZSM-5為催化劑,利用XRD、SEM和NH3-TPD等手段對(duì)催化劑的結(jié)構(gòu)物性進(jìn)行表征。ZSM-5分子篩在離子改性過程中的分子篩骨架沒有遭到明顯破壞。對(duì)通過水熱法合成的Na-ZSM-5進(jìn)行改性后得到具有一定B酸位或L酸位分子篩催化劑。對(duì)于商業(yè)ZSM-5分子篩,鋁離子在不同的溶液(在水或者乙醇溶液中)中對(duì)分子篩離子交換程度具有明顯影響。鋁離子乙醇溶液更容易使鋁離子進(jìn)入ZSM-5分子篩孔道。本文以固定床為反應(yīng)裝置,研究了催化劑中B酸和L酸在MTG反應(yīng)中的作用,并對(duì)商業(yè)H-ZSM-5分子篩在不同鋁離子溶液(水或乙醇溶液)中進(jìn)行改性,模擬催化劑再生后骨架脫鋁過程,研究不同鋁離子溶液對(duì)催化劑離子交換程度的影響和非骨架鋁對(duì)MTG反應(yīng)性能的影響。并探討MTG反應(yīng)的最優(yōu)工藝。通過研究實(shí)驗(yàn)室合成且改性后的ZSM-5分子篩催化劑對(duì)MTG反應(yīng)性能的影響,發(fā)現(xiàn)在一定范圍內(nèi)增加ZSM-5催化劑中的B酸濃度或強(qiáng)度可以提高其反應(yīng)活性,且ZSM-5催化劑中的B酸和L酸在MTG反應(yīng)中存在協(xié)同關(guān)系,Al-Z-0.4M-2f催化劑的壽命最長(zhǎng)(43.3 h),C5+烴類選擇性最高(57%以上)。通過分析不同硅鋁比、不同L酸含量的商業(yè)ZSM-5分子篩在MTG反應(yīng)中的反應(yīng)活性,發(fā)現(xiàn)在商業(yè)H-ZSM-5分子篩中,增加L酸含量會(huì)降低其在MTG反應(yīng)中的催化性能。在Al-Z-12.5-E系列催化劑中,L酸增加2.1倍,該催化劑的C5+烴類選擇性降低為原來的0.6倍。由于一般商業(yè)ZSM-5催化劑本身就含有大量缺陷位,只需在催化劑孔道加入少量鋁L酸,催化劑在MTG反應(yīng)中的反應(yīng)活性就會(huì)出現(xiàn)顯著下降。所以商業(yè)ZSM-5催化劑在工業(yè)應(yīng)用中的再生過程應(yīng)盡量避免骨架鋁的脫除。
[Abstract]:Non-petroleum route, coal-based methanol gasoline technology (MTG) is one of the important means to deal with the depletion of oil resources. Combined with the present situation of rich coal, poor oil and less gas in our country, MTG technology has very important practical significance in our country. In this paper, the structure and physical properties of the catalyst were characterized by XRD,SEM and NH3-TPD using aluminum ion modified ZSM-5 as catalyst. The molecular sieves skeleton of ZSM-5 molecular sieves was not obviously destroyed in the process of ion modification. Na-ZSM-5 synthesized by hydrothermal method was modified to obtain molecular sieves with certain B acid site or L acid site. For commercial ZSM-5 molecular sieves, aluminum ions have obvious effects on the ion exchange degree of molecular sieves in different solutions (in water or ethanol solution). Aluminum ion ethanol solution makes aluminum ion enter ZSM-5 molecular sieve channel more easily. In this paper, the role of B acid and L acid in MTG reaction was studied in a fixed bed reactor, and the commercial H-ZSM-5 molecular sieves were modified in different aluminum ion solutions (water or ethanol solutions). The effects of different aluminum ion solutions on the ion exchange degree of the catalyst and the effect of non-skeleton aluminum on the performance of MTG reaction were studied by simulating the process of skeleton dealumination after catalyst regeneration. The optimal process of MTG reaction was also discussed. By studying the effect of ZSM-5 molecular sieve catalyst synthesized and modified in laboratory on the performance of MTG reaction, it is found that the activity of ZSM-5 catalyst can be improved by increasing the concentration or strength of B acid in the catalyst in a certain range. There is a synergistic relationship between B acid and L acid in ZSM-5 catalyst in MTG reaction, and the lifetime of Al-Z-0.4M-2f catalyst is the longest (43.3 h), C5 hydrocarbon selectivity is the highest (more than 57%). By analyzing the reaction activity of commercial ZSM-5 molecular sieves with different Si / Al ratio and different L acid content in MTG reaction, it was found that increasing L acid content in commercial H-ZSM-5 molecular sieves would decrease the catalytic performance of commercial H-ZSM-5 molecular sieves in MTG reaction. In Al-Z-12.5-E series catalysts, L acid increased by 2.1 times, and the C 5 hydrocarbon selectivity of the catalyst decreased to 0.6 times as much as that of the original catalyst. Because the commercial ZSM-5 catalyst itself contains a large number of defect sites, the activity of the catalyst in MTG reaction will decrease significantly with the addition of a small amount of aluminum and L acid into the catalyst pore. Therefore, the regeneration process of commercial ZSM-5 catalyst in industrial application should avoid the removal of skeleton aluminum as far as possible.
【學(xué)位授予單位】：中國礦業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TE665
本文編號(hào)：2486773
[Abstract]:Non-petroleum route, coal-based methanol gasoline technology (MTG) is one of the important means to deal with the depletion of oil resources. Combined with the present situation of rich coal, poor oil and less gas in our country, MTG technology has very important practical significance in our country. In this paper, the structure and physical properties of the catalyst were characterized by XRD,SEM and NH3-TPD using aluminum ion modified ZSM-5 as catalyst. The molecular sieves skeleton of ZSM-5 molecular sieves was not obviously destroyed in the process of ion modification. Na-ZSM-5 synthesized by hydrothermal method was modified to obtain molecular sieves with certain B acid site or L acid site. For commercial ZSM-5 molecular sieves, aluminum ions have obvious effects on the ion exchange degree of molecular sieves in different solutions (in water or ethanol solution). Aluminum ion ethanol solution makes aluminum ion enter ZSM-5 molecular sieve channel more easily. In this paper, the role of B acid and L acid in MTG reaction was studied in a fixed bed reactor, and the commercial H-ZSM-5 molecular sieves were modified in different aluminum ion solutions (water or ethanol solutions). The effects of different aluminum ion solutions on the ion exchange degree of the catalyst and the effect of non-skeleton aluminum on the performance of MTG reaction were studied by simulating the process of skeleton dealumination after catalyst regeneration. The optimal process of MTG reaction was also discussed. By studying the effect of ZSM-5 molecular sieve catalyst synthesized and modified in laboratory on the performance of MTG reaction, it is found that the activity of ZSM-5 catalyst can be improved by increasing the concentration or strength of B acid in the catalyst in a certain range. There is a synergistic relationship between B acid and L acid in ZSM-5 catalyst in MTG reaction, and the lifetime of Al-Z-0.4M-2f catalyst is the longest (43.3 h), C5 hydrocarbon selectivity is the highest (more than 57%). By analyzing the reaction activity of commercial ZSM-5 molecular sieves with different Si / Al ratio and different L acid content in MTG reaction, it was found that increasing L acid content in commercial H-ZSM-5 molecular sieves would decrease the catalytic performance of commercial H-ZSM-5 molecular sieves in MTG reaction. In Al-Z-12.5-E series catalysts, L acid increased by 2.1 times, and the C 5 hydrocarbon selectivity of the catalyst decreased to 0.6 times as much as that of the original catalyst. Because the commercial ZSM-5 catalyst itself contains a large number of defect sites, the activity of the catalyst in MTG reaction will decrease significantly with the addition of a small amount of aluminum and L acid into the catalyst pore. Therefore, the regeneration process of commercial ZSM-5 catalyst in industrial application should avoid the removal of skeleton aluminum as far as possible.
【學(xué)位授予單位】：中國礦業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TE665
【共引文獻(xiàn)】
相關(guān)期刊論文 前2條
1 劉艷;常琴琴;楊萌;劉恩周;樊君;;甲醇制芳烴工藝研究進(jìn)展[J];化學(xué)工程;2015年09期
2 張君濤;郝娜娜;王妮;;ZSM-5/MCM-41復(fù)合分子篩的合成與表征[J];燃料化學(xué)學(xué)報(bào);2013年10期
相關(guān)博士學(xué)位論文 前3條
1 張貴泉;Zn改性HZSM-5分子篩催化劑上甲醇轉(zhuǎn)化制輕質(zhì)芳烴反應(yīng)研究[D];西北大學(xué);2014年
2 谷云磊;甘油催化脫水制備丙烯醛的研究[D];中國石油大學(xué)（華東）;2013年
3 趙文平;甲醇在納米HZSM-5和HMCM-22沸石上芳構(gòu)化和烷基化[D];大連理工大學(xué);2014年
相關(guān)碩士學(xué)位論文 前3條
1 葛蘭英;磷化廢水的資源化處理及原位合成多孔磷酸鹽的研究[D];上海大學(xué);2013年
2 何靜宇;HZSM-5催化劑上甲醇芳構(gòu)化研究[D];北京化工大學(xué);2014年
3 周國強(qiáng);改性ZSM-5分子篩催化熱解生物質(zhì)研究[D];清華大學(xué);2014年
，本文編號(hào)：2486773
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