La改性多级孔HZSM-5在线催化提质生物油
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摘要
采用Na2CO3溶液对HZSM-5分子筛进行预处理,然后采用浸渍法对预处理后的HZSM-5进行不同负载量的La改性,通过XRD、BET、SEM-EDS和Py-IR等方法对改性前后的HZSM-5进行表征。利用改性前后的HZSM-5在两段式固定床反应器上进行生物质热解产物在线催化实验,对得到的生物油有机相进行理化特性和组成成分分析。结果表明,经过Na2CO3溶液处理后,使HZSM-5分子筛形成了含有微-介孔的多级孔孔道结构,La的改性未改变HZSM-5的MFI结构,但改变了分子筛的酸分布。随着La负载量的增加,生物油有机相产率、密度、运动黏度及氧含量先减小后增加,含氧化合物和羰基类化合物含量同样呈现先减小后增加的变化趋势。经过最佳质量分数为5%的La负载后的多级孔HZSM-5分子筛制得的生物油中,有机相高位热值高达37.7 MJ/kg,烃类物质含量达到了49.86%,含氧化合物和羰基类化合物含量分别减少了32.43%和57.03%。
To improve the characteristics of the bio-oil,La modified HZSM-5 with hierarchical structure was applied in the catalytic pyrolysis of biomass.First,the HZSM-5 zeolite was pretreated withsolution,and then the pretreated HZSM-5 was modified with different loadings of La by impregnation.The modified HZSM-5 were characterized by XRD,BET,SEM-EDS and Py-IR,respectively.The catalysts were used in the process of preparing bio-oil and the bio-oil organic phases were studied from the aspects of composition and physical properties.The results showed that the modified HZSM-5catalysts formed micro/meso-porous pore structure and retained typical MFI topology structure.But the modification of La changed the acid distribution of the zeolite.With the increase of loadings of La,the yield,density,kinematic viscosity and oxygen content of bio-oil organic phase decreased first and then increased,while the content of oxygenated compounds and carbonyl compounds showed the same tendency as well.The hierarchical porous HZSM-5(La loading were 5%)catalyst had a better effect on the removal of aldehyde and ketone contained in the bio-oil organic phase which improved the stability of the bio-oil,the oxygenated compounds and the carbonyl compounds decreased by 32.43%and 57.03%,respectively.Meanwhile,the hydrocarbon content and the higher heating value of the bio-oil organic phase reached 49.86%and 37.7MJ/Kg,respectively.
To improve the characteristics of the bio-oil,La modified HZSM-5 with hierarchical structure was applied in the catalytic pyrolysis of biomass.First,the HZSM-5 zeolite was pretreated withsolution,and then the pretreated HZSM-5 was modified with different loadings of La by impregnation.The modified HZSM-5 were characterized by XRD,BET,SEM-EDS and Py-IR,respectively.The catalysts were used in the process of preparing bio-oil and the bio-oil organic phases were studied from the aspects of composition and physical properties.The results showed that the modified HZSM-5catalysts formed micro/meso-porous pore structure and retained typical MFI topology structure.But the modification of La changed the acid distribution of the zeolite.With the increase of loadings of La,the yield,density,kinematic viscosity and oxygen content of bio-oil organic phase decreased first and then increased,while the content of oxygenated compounds and carbonyl compounds showed the same tendency as well.The hierarchical porous HZSM-5(La loading were 5%)catalyst had a better effect on the removal of aldehyde and ketone contained in the bio-oil organic phase which improved the stability of the bio-oil,the oxygenated compounds and the carbonyl compounds decreased by 32.43%and 57.03%,respectively.Meanwhile,the hydrocarbon content and the higher heating value of the bio-oil organic phase reached 49.86%and 37.7MJ/Kg,respectively.
引文
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[3] ZHANG B, ZHONG Z, CHEN P, et al. Microwave-assisted catalyticfast pyrolysis of biomass for bio-oil production using chemical vapordeposition modified HZSM-5 catalyst[J]. Bioresour Technol., 2015,197:79-84.
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[7]尚会建,张少红,赵丹,等.分子筛催化剂的研究进展[J].化工进展,2011, 30(s1):407-410.SHANG Huijian, ZHANG Shaohong, ZHAO Dan, et al. Researchprogress of molecular sieve catalyst[J]. Chemical Industry andEngineering Progress, 2011, 30(s1):407-410.
[8]韩伟,潘相米,谭亚南,等. Na2CO3处理制备复合孔ZSM-5分子筛及其丙烷脱氢制丙烯的催化性能[J].化工进展, 2016, 35(s2):174-178.HAN Wei, PAN Xiangmi, TAN Yanan, et al. Preparation ofhierarchical ZSM-5 zeolites treated by Na2CO3and its catalyticperformance for propane dehydrogenation topropylene[J]. ChemicalIndustry and Engineering Progress, 2016, 35(s2):174-178.
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[10]孙志岩,赵伟林,胡志君,等.多级孔Zn-La/HZSM-5制备及在甲醇芳构化中的应用[J].石油化工高等学校学报, 2013, 26(5):23-26.SUN Zhiyan, ZHAO Weilin, HU Zhijun, et al. Preparation ofhierarchical porous Zn-La/HZSM-5 zeolite and its application inmethanol aromatization[J]. Journal of Petrochemical Universities,2013, 26(5):23-26.
[11]任英杰,华伟明,乐英红,等. Ga2O3/HZSM-5催化剂上丙烷脱氢反应[J].高等学校化学学报, 2009, 30(6):1162-1167.REN Yingjie, HUA Weiming, YUE Yinghong, et al. Dehydrogenationof propane to propene over Ga2O3/HZSM-5 catalysts[J]. Chem. J.Chinese Universities, 2009, 30(6):1162-1167.
[12] HUANG W W, GONG F Y, FAN M H, et al. Production of light olefinsby catalytic conversion of lignocellulosic biomass with HZSM-5 zeoliteimpregnated with 6 wt.%lanthanum[J]. Bioresource Technol., 2012,121(7):248.
[13] SEYEDEH M T S, JAFAR T, KAMYAR K. The effect of Fe,P and Si/Al molar ratio on stability of HZSM-5 catalyst in naphtha thermal-catalytic cracking to light olefins[J]. Catalysis Communications, 2012,27:114-118.
[14]安杰,朱向学,李秀杰,等.废塑料在改性ZSM-5上裂解转化生产车用液体燃料[J].化工进展, 2012, 31(s1):448-452.AN Jie, ZHU Xiangxue, LI Xiujie, et al. Pyrolysis of waste plastics toproduce liquid fuel for vehicles by the modified ZSM-5[J]. ChemicalIndustry and Engineering Progress, 2012, 31(s1):448-452.
[15]张瑞珍,王翠,邢普,等.多级孔HZSM-5分子筛催化剂的制备及低碳烃芳构化应用[J].高等学校化学学报, 2015, 36(4):725-732.ZHANG Ruizhen, WANG Cui, XING Pu, et al. Preparation ofhierarchical porous HZSM-5 and its application in light paraffinaromatization[J]. Chem. J. Chinese Universities, 2015, 36(4):725-732.
[16] FAN Y S, CAI Y X, LI X H, et al. Catalytic upgrading of pyrolyticvapors from rape straw vacuum pyrolysis[J]. Trans. Chin. Soc. Agric.Mach., 2014, 45(12):234-240.
[17]李小华,陈磊,樊永胜,等. Zn-P复合改性HZSM-5在线催化热解获取生物油的研究[J].燃料化学学报, 2015, 43(5):567-574.LI Xiaohua, CHEN Lei, FAN Yongsheng, et al. Study on preparation ofrefined oil by upgrading of pyrolytic vapors using Zn-P/HZSM-5zeolite[J]. Journal of Fuel Chemistry&Technology, 2015, 43(5):567-574.
[18]刘莎,蔡忆昔,樊永胜,等. MCM-41和HZSM-5协同催化对油菜秸秆热解的影响[J].燃料化学学报, 2016, 44(10):1195-1202.LIU Sha, CAI Yixi, FAN Yongsheng, et al. Synergistic catalysis ofMCM-41 and HZSM-5 on rape straw pyrolysis[J]. Journal of FuelChemistry&Technology, 2016, 44(10):1195-1202.
[19] ZHANG Y W, ZHOU Y M, TANG M H, et al. Effect of La calcinationtemperature on catalytic performance of PtSnNaLa/ZSM-5 catalyst forpropane dehydrogenation[J]. Chemical Engineering Journal, 2012, 181/182(1):530-537.
[20] EMEIS C A. Determination of integrated molar extinction coefficientsfor infrared absorption bands of pyridine adsorbed on solid acidcatalysts[J]. J. Catal., 1993, 141:347-353.
[21]杨刚,王妍,周丹红,等. La/ZSM-5分子筛热稳定性及镧存在形态研究[J].物理化学学报, 2004, 20(1):60-64.YANG Gang, WANG Yan, ZHOU Danhong, et al. Investigation on thethermal stability of La/ZSM-5 zeolite and the La3+species[J]. ActaPhysico-Chimica Sinica, 2004, 20(1):60-64.
[22]武传昌,缪承明,秦关林. La浸渍改性的HZSM-5沸石上乙苯乙烯烷基化反应的研究[J].催化学报, 1991, 12(3):218-225.WU Chuanchang, MIAO Chenming, QIN Guanglin. Study ofethylbenzene alkylation with ethene on lanthanum impregnatedHZSM-5 zeolites[J]. Chinese Journal of Catalysis, 1991, 12(3):218-225.
[2] CAI J, WANG S, WANG Q, et al. The characteristics of biomassgasification in multistage heating and gradient chain gasifier[J]. Int. J.Hydrogen Energy, 2016, 41(35):15674-81.
[3] ZHANG B, ZHONG Z, CHEN P, et al. Microwave-assisted catalyticfast pyrolysis of biomass for bio-oil production using chemical vapordeposition modified HZSM-5 catalyst[J]. Bioresour Technol., 2015,197:79-84.
[4]罗俊,邵敬爱,杨海平,等.生物质催化热解制备低碳烯烃的研究进展[J].化工进展, 2017, 36(5):1555-1564.LUO Jun, SHAO Jingai, YANG Haiping, et al. Research progresses onproduction of light olefins from catalytic pyrolysis of biomass[J].Chemical Industry and Engineering Progress, 2017, 36(5):1555-1564.
[5] MOHAMMAD S, BAKHTIYOR N, KUNIO Y. A review of productionand upgrading of algal bio-oil[J]. Renew. Sust. Energ. Rev., 2016, 58:918-930.
[6]朱锡锋,陆强,郑冀鲁,等.生物质热解与生物油的特性研究[J].太阳能学报, 2006, 27(12):1285-1289.ZHU Xifeng, LU Qiang, ZHENG Jilu, et al. Research on biomasspyrolysis and bio-oil characterietics[J]. Acta Energiae Solaris Sinica,2006, 27(12):1285-1289.
[7]尚会建,张少红,赵丹,等.分子筛催化剂的研究进展[J].化工进展,2011, 30(s1):407-410.SHANG Huijian, ZHANG Shaohong, ZHAO Dan, et al. Researchprogress of molecular sieve catalyst[J]. Chemical Industry andEngineering Progress, 2011, 30(s1):407-410.
[8]韩伟,潘相米,谭亚南,等. Na2CO3处理制备复合孔ZSM-5分子筛及其丙烷脱氢制丙烯的催化性能[J].化工进展, 2016, 35(s2):174-178.HAN Wei, PAN Xiangmi, TAN Yanan, et al. Preparation ofhierarchical ZSM-5 zeolites treated by Na2CO3and its catalyticperformance for propane dehydrogenation topropylene[J]. ChemicalIndustry and Engineering Progress, 2016, 35(s2):174-178.
[9] ADJAYE J D, BAKHSHI N. Production of hydrocarbons by catalyticupgrading of a fast pyrolysis bio-oil PartⅡ:comparative catalystperformance and reaction pathways[J]. Fuel Processing Technology,1995, 45(3):185-202.
[10]孙志岩,赵伟林,胡志君,等.多级孔Zn-La/HZSM-5制备及在甲醇芳构化中的应用[J].石油化工高等学校学报, 2013, 26(5):23-26.SUN Zhiyan, ZHAO Weilin, HU Zhijun, et al. Preparation ofhierarchical porous Zn-La/HZSM-5 zeolite and its application inmethanol aromatization[J]. Journal of Petrochemical Universities,2013, 26(5):23-26.
[11]任英杰,华伟明,乐英红,等. Ga2O3/HZSM-5催化剂上丙烷脱氢反应[J].高等学校化学学报, 2009, 30(6):1162-1167.REN Yingjie, HUA Weiming, YUE Yinghong, et al. Dehydrogenationof propane to propene over Ga2O3/HZSM-5 catalysts[J]. Chem. J.Chinese Universities, 2009, 30(6):1162-1167.
[12] HUANG W W, GONG F Y, FAN M H, et al. Production of light olefinsby catalytic conversion of lignocellulosic biomass with HZSM-5 zeoliteimpregnated with 6 wt.%lanthanum[J]. Bioresource Technol., 2012,121(7):248.
[13] SEYEDEH M T S, JAFAR T, KAMYAR K. The effect of Fe,P and Si/Al molar ratio on stability of HZSM-5 catalyst in naphtha thermal-catalytic cracking to light olefins[J]. Catalysis Communications, 2012,27:114-118.
[14]安杰,朱向学,李秀杰,等.废塑料在改性ZSM-5上裂解转化生产车用液体燃料[J].化工进展, 2012, 31(s1):448-452.AN Jie, ZHU Xiangxue, LI Xiujie, et al. Pyrolysis of waste plastics toproduce liquid fuel for vehicles by the modified ZSM-5[J]. ChemicalIndustry and Engineering Progress, 2012, 31(s1):448-452.
[15]张瑞珍,王翠,邢普,等.多级孔HZSM-5分子筛催化剂的制备及低碳烃芳构化应用[J].高等学校化学学报, 2015, 36(4):725-732.ZHANG Ruizhen, WANG Cui, XING Pu, et al. Preparation ofhierarchical porous HZSM-5 and its application in light paraffinaromatization[J]. Chem. J. Chinese Universities, 2015, 36(4):725-732.
[16] FAN Y S, CAI Y X, LI X H, et al. Catalytic upgrading of pyrolyticvapors from rape straw vacuum pyrolysis[J]. Trans. Chin. Soc. Agric.Mach., 2014, 45(12):234-240.
[17]李小华,陈磊,樊永胜,等. Zn-P复合改性HZSM-5在线催化热解获取生物油的研究[J].燃料化学学报, 2015, 43(5):567-574.LI Xiaohua, CHEN Lei, FAN Yongsheng, et al. Study on preparation ofrefined oil by upgrading of pyrolytic vapors using Zn-P/HZSM-5zeolite[J]. Journal of Fuel Chemistry&Technology, 2015, 43(5):567-574.
[18]刘莎,蔡忆昔,樊永胜,等. MCM-41和HZSM-5协同催化对油菜秸秆热解的影响[J].燃料化学学报, 2016, 44(10):1195-1202.LIU Sha, CAI Yixi, FAN Yongsheng, et al. Synergistic catalysis ofMCM-41 and HZSM-5 on rape straw pyrolysis[J]. Journal of FuelChemistry&Technology, 2016, 44(10):1195-1202.
[19] ZHANG Y W, ZHOU Y M, TANG M H, et al. Effect of La calcinationtemperature on catalytic performance of PtSnNaLa/ZSM-5 catalyst forpropane dehydrogenation[J]. Chemical Engineering Journal, 2012, 181/182(1):530-537.
[20] EMEIS C A. Determination of integrated molar extinction coefficientsfor infrared absorption bands of pyridine adsorbed on solid acidcatalysts[J]. J. Catal., 1993, 141:347-353.
[21]杨刚,王妍,周丹红,等. La/ZSM-5分子筛热稳定性及镧存在形态研究[J].物理化学学报, 2004, 20(1):60-64.YANG Gang, WANG Yan, ZHOU Danhong, et al. Investigation on thethermal stability of La/ZSM-5 zeolite and the La3+species[J]. ActaPhysico-Chimica Sinica, 2004, 20(1):60-64.
[22]武传昌,缪承明,秦关林. La浸渍改性的HZSM-5沸石上乙苯乙烯烷基化反应的研究[J].催化学报, 1991, 12(3):218-225.WU Chuanchang, MIAO Chenming, QIN Guanglin. Study ofethylbenzene alkylation with ethene on lanthanum impregnatedHZSM-5 zeolites[J]. Chinese Journal of Catalysis, 1991, 12(3):218-225.
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