Study on in-situ catalytic conversion of alcohols to aromatics and its mechanism

doi:10.16085/j.issn.1000-6613.2016-1981

Chemical Industry and Engineering Progress ›› 2017, Vol. 36 ›› Issue (07): 2517-2524.DOI: 10.16085/j.issn.1000-6613.2016-1981

Previous Articles Next Articles

Study on in-situ catalytic conversion of alcohols to aromatics and its mechanism

SHI Xu^1,3, ZHOU Feng², CHEN Hao³, FU Jie³, QIAO Kai², HUANG He^1,3

1 State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech. University, Nanjing 211816, Jiangsu, China;
2 Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, Fushun 113001, Liaoning, China;
3 Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2016-10-31 Revised:2017-03-26 Online:2017-07-05 Published:2017-07-05

醇原位催化转化制备芳烃及机理

时旭^1,3, 周峰², 陈皓³, 傅杰³, 乔凯², 黄和^1,3

1 南京工业大学生物与制药工程学院, 材料化学工程国家重点实验室, 江苏南京 211816;
2 中国石油化工股份有限公司抚顺石油化工研究院, 辽宁抚顺 113001;
3 生物质化工教育部重点实验室, 浙江大学化学工程与生物工程学院, 浙江杭州 310027

通讯作者: 黄和,教授,研究方向为生物质催化转化及微生物代谢工程。
作者简介:时旭(1992-),男,硕士研究生。
基金资助:
国家自然科学基金重点项目（21436007）及浙江省自然科学基金杰出青年项目（LR17B060002）。

Abstract

Abstract: The effects of carbon chain length of alcohol and reaction temperature on catalytic conversion of alcohols to produce aromatics over HZSM-5 were studied in a micro fixed-bed reactor coupled directly to GC/MS system.The results showed that the carbon chain length of alcohol had a significant effect on the product distribution.At 400℃,with the increase of carbon chain length of alcohol,the yield of aromatics increased firstly up to the maximum of 39.6%(1-propanol),then decreased and finally stabilized at a lower yield.As the temperature increased,the products distributions for methanol,ethanol,1-propanol showed the same tendency,and the yields of aromatics increased firstly,then decreased and the maximum values reached 26.0%,36.5% and 42.5% at 500℃ respectively.As the temperature increased,however,the yield of CO,CO₂ and olefins increased gradually while the total yield of hydrocarbons decreased.Higher temperature helped the conversion of larger aromatics to lighter aromatics,which contributed to the higher selectivity for benzene and toluene.Finally,the reaction mechanism of alcohol aromatization was discussed by the combination of in-situ FTIR and experimental results.It is supposed that the light olefins and ethers were produced by dehydration of short carbon chain alcohols,while long carbon chain olefins were produced by polymerization of the light olefins or direct dehydration of long carbon chain alcohols.The obtained long carbon chain olefins were then converted into cycloalkanes by cyclization.At last,aromatics were formed by dehydrogenation-aromatization or intermolecular hydrogen transfer of the cycloalkanes.

Key words: alcohol, catalysis, HZSM-5, aromatics, microreactor

摘要： 以不同的醇为原料，HZSM-5分子筛为催化剂，在微型固定床与气相色谱-质谱联用装置上进行了醇催化转化制备芳烃的研究，考察了醇的碳链长度以及反应温度的影响。结果表明，醇的碳链长度对产物的分布有明显的影响，400℃下芳烃产率随着醇的碳链增长先增加，在正丙醇处获得最大的芳烃产率39.6%，而后降低并趋于稳定。随着温度的升高，甲醇、乙醇和正丙醇3种醇的产物分布变化趋势相同，芳烃产率均先增加后减小，在500℃获得最大值，分别为26.0%、36.5%和42.5%；随着温度的升高，CO、CO₂ 和烯烃的产率逐渐升高，但烃类产物总收率逐渐下降。高温下大分子芳烃逐渐向小分子芳烃转化，使得苯和甲苯的选择性逐渐增大。最后，结合原位红外表征和实验结果探讨了醇芳构化的反应机理：短碳链醇通过脱水得到醚和低碳烯烃，低碳烯烃再经过聚合得到长链烯烃，长碳链醇则可直接脱水得到长链烯烃，长链烯烃再通过环化反应生成环烷烃，最后环烷烃经过脱氢芳构化或分子间氢转移得到芳烃。

关键词: 醇, 催化, HZSM-5, 芳烃, 微反应器

CLC Number:

TQ032.4

SHI Xu, ZHOU Feng, CHEN Hao, FU Jie, QIAO Kai, HUANG He. Study on in-situ catalytic conversion of alcohols to aromatics and its mechanism[J]. Chemical Industry and Engineering Progress, 2017, 36(07): 2517-2524.

时旭, 周峰, 陈皓, 傅杰, 乔凯, 黄和. 醇原位催化转化制备芳烃及机理[J]. 化工进展, 2017, 36(07): 2517-2524.

References

[1] 董丽. 生物质制芳烃技术进展与发展前景[J]. 化工进展,2013,32(7):1526-1533. DONG L. Development of aromatics production from biomass[J]. Chemical Industry and Engineering Progress,2013,32(7):1526-1533.
[2] CHANG C D,SILVESTRI A J. The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts[J]. Journal of Catalysis,1977,47(2):249-259.
[3] 张一成,王洪学,章序文,等. 甲醇制芳烃反应的催化研究进展[J]. 化工进展,2016,35(3):801-806. ZHANG Y C,WANG H X,ZHANG X W,et al. Advances in the catalysis of methanol to aromatics reaction[J]. Chemical Industry and Engineering Progress,2016,35(3):801-806.
[4] 孙富伟,劳国瑞,卢秀荣,等. 煤基甲醇芳构化技术的研究及应用进展[J]. 现代化工,2014,34(2):27-32. SUN F W,LAO G R,LU X R,et al. Research and application on coal based methanol aromatization process[J]. Modern Chemical Industry,2014,34(2):27-32.
[5] 任浩楠,李剑,杨丽娜. 改性ZSM-5甲醇芳构化催化剂研究进展[J]. 天然气化工,2015,40(3):83-87. REN H N,LI J,YANG L N. Research progress in modified ZSM-5 catalysts for methanol to aromatics[J]. Natural Gas Chemical Industry,2015,40(3):83-87.
[6] 钱伯章. 甲醇制芳烃技术新进展[J]. 化学工业,2013,31(12):19-22. QIAN B Z. Methanol to aromatics technology progress[J]. Chemical Industry,2013,31(12):19-22.
[7] 刘艳,常琴琴,杨萌,等. 甲醇制芳烃工艺研究进展[J]. 化学工程,2015,43(9):74-78. LIU Y,CHANG Q Q,YANG M,et al. Research progress of methanol to aromatics[J]. Chemical Engineering(China),2015,43(9):74-78.
[8] 邵长丽. 甲醇制芳烃技术研究与工业化示范进展[J]. 广州化工,2016,44(1):41-43. SHAO C L. Research and industrial demonstration on methanol aromatics technology[J]. Guangzhou Chemical Industry,2016,44(1):41-43.
[9] 胡徐腾. 纤维素乙醇研究开发进展[J]. 化工进展,2011,30(1):137-143. HU X T. Progress of cellulose ethanol research & development[J]. Chemical Industry and Engineering Progress,2011,30(1):137-143.
[10] 贾宝莹,杜平,杜风光,等. 生物乙醇制乙烯初探[J]. 化工进展,2012,31(5):1028-1031. JIA B Y,DU P,DU F G,et al. Research on the preparation of ethylene from bio-ethanol[J]. Chemical Industry and Engineering Progress,2012,31(5):1028-1031.
[11] ZHU X,LOBBAN L L,MALLINSON R G,et al. Tailoring the mesopore structure of HZSM-5 to control product distribution in the conversion of propanal[J]. Journal of Catalysis,2010,71(1):88-98.
[12] ERICHSEN M W,SVELLE S,OLSBYE U. The influence of catalyst acid strength on the methanol to hydrocarbons(MTH)reaction[J]. Catalysis Today,2013,215:216-223.
[13] OLSBYE U,BJØRGEN M,SVELLE S,et al. Mechanistic insight into the methanol-to-hydrocarbons reaction[J]. Catalysis Today,2005,106(1):108-111.
[14] ILIAS S,BHAN A. Tuning the selectivity of methanol-to-hydrocarbons conversion on H-ZSM-5 by co-processing olefin or aromatic compounds[J]. Journal of Catalysis,2012,290:186-192.
[15] TEKETEL S,ERICHSEN M W,BLEKEN F L,et al. Shape selectivity in zeolite catalysis-The methanol to hydrocarbons(MTH) reaction[J]. Catalysis,2014,26:179-217.
[16] ZHANG H Y,CARLSON T R,XIAO R,et al. Catalytic fast pyrolysis of wood and alcohol mixtures in a fluidized bed reactor[J]. Green Chemistry,2012,14(1):98-110.
[17] PALUMBO L,BONINO F,BEATO P,et al. Conversion of methanol to hydrocarbons:spectroscopic characterization of carbonaceous species formed over H-ZSM-5[J]. The Journal of Physical Chemistry C,2008,112(26):9710-9716.
[18] HEMELSOET K,GHYSELS A,MORES D,et al. Experimental and theoretical IR study of methanol and ethanol conversion over H-SAPO-34[J]. Catalysis Today,2011,177(1):12-24.
[19] PETKOVIC L M,GINOSAR D M,BURCH K C. Supercritical fluid removal of hydrocarbons adsorbed on wide-pore zeolite catalysts[J]. Journal of Catalysis,2005,234(2):328-339.
[20] BJØRGEN M,BONINO F,ARSTAD B,et al. Persistent methylbenzenium ions in protonated zeolites:the required proton affinity of the guest hydrocarbon[J]. ChemPhysChem,2005,6(2):232-235.
[21] PARK J W,SEO G. IR study on methanol-to-olefin reaction over zeolites with different pore structures and acidities[J]. Applied Catalysis A:General,2009,356(2):180-188.
[22] DAI W,WANG X,WU G,et al. Methanol-to-olefin conversion catalyzed by low-silica AlPO-34 with traces of Brønsted acid sites:combined catalytic and spectroscopic investigations[J]. ChemCatChem,2012,4(9):1428-1435.
[23] INABA M,MURATA K,SAITO M,et al. Ethanol conversion to aromatic hydrocarbons over several zeolite catalysts[J]. Reaction Kinetics and Catalysis Letters,2006,88(1):135-141.
[24] YU L,HUANG S,ZHANG S,et al. Transformation of isobutyl alcohol to aromatics over zeolite-based catalysts[J]. ACS Catalysis,2012,2(6):1203-1210.

Study on in-situ catalytic conversion of alcohols to aromatics and its mechanism

醇原位催化转化制备芳烃及机理

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHENG Qian, GUAN Xiushuai, JIN Shanbiao, ZHANG Changming, ZHANG Xiaochao. Photothermal catalysis synthesis of DMC from CO₂ and methanol over Ce_0.25Zr_0.75O₂ solid solution [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 319-327.
[2]	WANG Zhengkun, LI Sifang. Green synthesis of gemini surfactant decyne diol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 400-410.
[3]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[4]	LI Mengyuan, GUO Fan, LI Qunsheng. Simulation and optimization of the third and fourth distillation columns in the recovery section of polyvinyl alcohol production [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 113-123.
[5]	SHENG Weiwu, CHENG Yongpan, CHEN Qiang, LI Xiaoting, WEI Jia, LI Linge, CHEN Xianfeng. Operating condition analysis of the microbubble and microdroplet dual-enhanced desulfurization reactor [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 142-147.
[6]	GENG Yuanze, ZHOU Junhu, ZHANG Tianyou, ZHU Xiaoyu, YANG Weijuan. Homogeneous/heterogeneous coupled combustion of heptane in a partially packed bed burner [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4514-4521.
[7]	GAO Yanjing. Analysis of international research trend of single-atom catalysis technology [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4667-4676.
[8]	LI Dongze, ZHANG Xiang, TIAN Jian, HU Pan, YAO Jie, ZHU Lin, BU Changsheng, WANG Xinye. Research progress of NO _x reduction by carbonaceous substances for denitration in cement kiln [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4882-4893.
[9]	WANG Chen, BAI Haoliang, KANG Xue. Performance study of high power UV-LED heat dissipation and nano-TiO₂ photocatalytic acid red 26 coupling system [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4905-4916.
[10]	WU Haibo, WANG Xilun, FANG Yanxiong, JI Hongbing. Progress of the development and application of 3D printing catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3956-3964.
[11]	HUANG Yufei, LI Ziyi, HUANG Yangqiang, JIN Bo, LUO Xiao, LIANG Zhiwu. Research progress on catalysts for photocatalytic CO₂ and CH₄ reforming [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4247-4263.
[12]	GUO Lixing, PANG Weiying, MA Keyao, YANG Jiahan, SUN Zehui, ZHANG Pan, FU Dong, ZHAO Kun. Hierarchically multilayered TiO₂ with spatial pore-structure for efficient photocatalytic CO₂ reduction [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3643-3651.
[13]	LI Yanling, ZHUO Zhen, CHI Liang, CHEN Xi, SUN Tanglei, LIU Peng, LEI Tingzhou. Research progress on preparation and application of nitrogen-doped biochar [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3720-3735.
[14]	LIU Weixiao, LIU Yang, GAO Fulei, WANG Wei, WANG Yinglei. Application of microreactor in synthesis and quality improvement of energetic materials [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3349-3364.
[15]	HAN Hengwen, HAN Wei, LI Mingfeng. Research progress in olefin hydration process and the catalysts [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3489-3500.