脂肪酸甲酯加氢脱氧和蒸汽裂解两步法制备生物烯烃
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摘要
脂肪酸甲酯经生物烷烃制备轻质烯烃,有望缓解低原油价格导致的生物柴油产业发展困境。采用浸渍法制备了NiMo/Al_2O_3催化剂,首先考察其催化脂肪酸甲酯加氢脱氧制备生物烷烃的性能,然后进一步分析生物烷烃蒸汽裂解制烯烃的转化规律。结果表明,预硫化的NiMo/Al_2O_3能够高选择性地催化饱和脂肪酸甲酯加氢制备生物烷烃,并且催化剂的结构在反应1000 h后无明显改变。以上述烷烃为原料,在裂解炉出口温度为810℃,出口压力为0.10 MPa,物料停留时间为0.23 s和水油质量比为0.75的反应条件下进行蒸汽裂解,产物中乙烯、丙烯和丁二烯的收率分别达到36.30%、18.14%和7.46%,显著高于同等条件下石脑油原料得到的27.45%、14.74%和5.31%,表明源于脂肪酸甲酯的生物烷烃可以作为生产轻质烯烃的原料补充。
Conversion of fatty acid methyl esters(FAMEs) to bio-paraffins and further to bio-olefins offers a potential solution to the emerging problems in the biodiesel industry due to the collapse of world oil prices. NiMo/Al_2O_3 catalyst prepared via an impregnation method was evaluated in the catalytic hydrodeoxygenation of FAMEs to bio-paraffins. The obtained paraffins were used as feedstocks to produce bio-olefins via steam cracking. The presulfided NiMo/Al_2O_3 converted the saturated FAMEs selectively to paraffins, without observable changes in the catalyst structure after reaction for 1000 h. Under the cracking conditions of coil-out temperature and pressure at 810℃ and 0.10 MPa, residence time at 0.23 s, and mass ratio of water to paraffins at 0.75, the yields of ethylene, propylene and butadiene were 36.30%, 18.14% and 7.46%, respectively. These data were much higher than the values of 27.45%, 14.74% and 5.31% obtained with naphtha as feedstocks under the similar conditions, indicating that bio-paraffins derived from FAMEs are alternative feedstocks for light olefins.
Conversion of fatty acid methyl esters(FAMEs) to bio-paraffins and further to bio-olefins offers a potential solution to the emerging problems in the biodiesel industry due to the collapse of world oil prices. NiMo/Al_2O_3 catalyst prepared via an impregnation method was evaluated in the catalytic hydrodeoxygenation of FAMEs to bio-paraffins. The obtained paraffins were used as feedstocks to produce bio-olefins via steam cracking. The presulfided NiMo/Al_2O_3 converted the saturated FAMEs selectively to paraffins, without observable changes in the catalyst structure after reaction for 1000 h. Under the cracking conditions of coil-out temperature and pressure at 810℃ and 0.10 MPa, residence time at 0.23 s, and mass ratio of water to paraffins at 0.75, the yields of ethylene, propylene and butadiene were 36.30%, 18.14% and 7.46%, respectively. These data were much higher than the values of 27.45%, 14.74% and 5.31% obtained with naphtha as feedstocks under the similar conditions, indicating that bio-paraffins derived from FAMEs are alternative feedstocks for light olefins.
引文
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[29]孙培永,刘森,周玉鹏,等.镍铝合金催化油酸甲酯加氢饱和的热力学和动力学分析[J].中国油脂,2017,42(10):93-99.SUN P Y,LIU S,ZHOU Y P,et al.Thermodynamic and kinetics analysis of catalytic hydrogenation of methyl oleate over Ni-Al alloy[J].China Oils and Fats,2017,42(10):93-99.
[30]刘纪昌,沈本贤.正构烷烃含量对裂解烯烃收率的影响及乙烯裂解的原料调配[J].华东理工大学学报(自然科学版),2006,32(5):535-539.LIU J C,SHEN B X.Effect of normal paraffin content on ethylene yield and feedstock allocation of ethylene pyrolysis process[J].Journal of East China University of Science and Technology(Natural Science),2006,32(5):535-539.
[2]张家仁,邓甜音,刘海超.油脂和木质纤维素催化转化制备生物液体燃料[J].化学进展,2013,25(2/3):192-208.ZHANG J R,DENG T Y,LIU H C.Catalytic production of liquid biofuels from triglyceride feedstocks and lignocellulose[J].Progress in Chemistry,2013,25(2/3):192-208.
[3]YAAKOB Z,MOHAMMAD M,ALHERBAWI M,et al.Overview of the production of biodiesel from waste cooking oil[J].Renewable and Sustainable Energy Reviews,2013,18:184-193.
[4]ISSARIYAKUL T,DALAI A K.Biodiesel from vegetable oils[J].Renewable&Sustainable Energy Reviews,2014,31:446-471.
[5]李顶杰,朱建军.生物柴油产业的发展现状与对策建议[J].中国石油和化工经济分析,2016,9:39-42.LI D J,ZHU J J.Developing status and corresponding countermeasures for biodiesel industry in China[J].Economic Analysis of China Petroleum and Chemical Industry,2016,9:39-42.
[6]MAHER K D,BRESSLER D C.Pyrolysis of triglyceride materials for the production of renewable fuels and chemicals[J].Bioresource Technology,2007,98(12):2351-2368.
[7]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 J,SHAO J A,YANG H P,et al.Research progresses on production of light olefins from catalytic pyrolysis of biomass[J].Chemical Industry and Engineering Progress,2017,36(5):1555-1564.
[8]李振宇,王红秋,黄格省,等.我国乙烯生产工艺现状与发展趋势分析[J].化工进展,2017,36(3):767-773.LI Z Y,WANG H Q,HUANG G S,et al.Analysis on status and development trend of ethylene production technology in China[J].Chemical Industry and Engineering Progress,2017,36(3):767-773.
[9]IDEM R O,KATITANENI S P R,BAKHSHI N N.Thermal cracking of canola oil:?reaction products in the presence and absence of steam[J].Energy&Fuels,1996,10(6):1150-1162.
[10]SADRAMELI S M,GREEN A E S.Systematics of renewable olefins from thermal cracking of canola oil[J].Journal of Analytical and Applied Pyrolysis,2007,78(2):445-451.
[11]ZáMOSTNYP,BěLOHLAV Z,?MIDRKAL J.Production of olefins via steam cracking of vegetable oils[J].Resources,Conservation and Recycling,2015,59:47-51.
[12]DE BRUYCKER R,PYL S P,MARIE-FRANCOISE R,et al.Microkinetic model for the pyrolysis of methyl esters:from model compound to industrial biodiesel[J].AICh E Journal,2015,61(12):4309-4322.
[13]臧俊娜.植物油蒸汽裂解转化规律的研究[D].山东:中国石油大学(华东),2010.ZANG J N.Studies on the conversion rule of vegetable oil by steam cracking[D].Shandong:China University of Petroleum,2010.
[14]韩蕾.废弃油脂蒸汽裂解转化规律研究[D].山东:中国石油大学(华东),2013.HAN L.Studies on the conversion rule of waste oil by steam cracking[D].Shandong:China University of Petroleum,2013.
[15]KATIKANENI S P R,ADJAYE J D,BAKHSHI N N.Catalytic conversion of canola oil to fuels and chemicals over various cracking catalysts[J].The Canadian Journal of Chemical Engineering,1995,73(4):484-497.
[16]KATIKANENI S P R,ADJAYE J D,BAKHSHI N N.Studies on the catalytic conversion of canola oil to hydrocarbons:influence of hybrid catalysts and steam[J].Energy&Fuels,1995,9(4):599-609.
[17]KATIKANENI S P R,ADJAYE J D,IDEM R O,et al.Catalytic conversion of canola oil over potassium-impregnated HZSM-5catalysts:?C2—C4 olefin production and model reaction studies[J].Industrial&Engineering Chemistry Research,1996,35(10):3332-3346.
[18]VU H X,SCHNEIDER M,BENTRUP U,et al.Hierarchical ZSM-5materials for an enhanced formation of gasoline-range hydrocarbons and light olefins in catalytic cracking of triglyceride-rich biomass[J].Industrial&Engineering Chemistry Research,2015,54(6):1773-1782.
[19]蔡文静,闫昊,冯翔,等.不同碳链长度脂肪酸甲酯的催化裂化产物分布规律[J].化工学报,2017,68(5):2057-2065.CAI W J,YAN H,FENG X,et al.Product distribution in catalytic cracking of fatty acid methyl esters with different carbon chain lengths[J].CIESC Journal,2017,68(5):2057-2065.
[20]BOTAS J A,SERRANO D P,GARCIA A,et al.Catalytic conversion of rapeseed oil for the production of raw chemicals,fuels and carbon nanotubes over Ni-modified nanocrystalline and hierarchical ZSM-5[J].Applied Catalysis B:Environmental,2014,145:205-215.
[21]BOTAS J A,SERRANO D P,GARCIA A,et al.Catalytic conversion of rapeseed oil into raw chemicals and fuels over Ni-and Mo-modified nanocrystalline ZSM-5 zeolite[J].Catalysis Today,2012,195(1):59-70.
[22]CHEN L G,LI H W,FU J Y,et al.Catalytic hydroprocessing of fatty acid methyl esters to renewable alkane fuels over Ni/HZSM-5 catalyst[J].Catalysis Today,2016,259:266-276.
[23]KIJKMANS T,PYL S P,REYNIERS M F,et al.Production of bio-ethene and propene:alternatives for bulk chemicals and polymers[J].Green Chemistry,2013,15(11):3064-3076.
[24]孙培永,李梦晨,刘森,等.油酸甲酯催化加氢制备生物烷烃的热力学分析[J].化工学报,2017,68(6):2258-2265.SUN P Y,LI M C,LIU S,et al.Thermodynamic analysis of catalytic hydrogenation of methyl oleate to produce bio-paraffins[J].CIESC Journal,2017,68(6):2258-2265.
[25]SMEJKAL Q,SMEJKALOVA L,KUBICKA D.Thermodynamic balance in reaction system of total vegetable oil hydrogenation[J].Chemical Engineering Journal,2009,146(1):155-160.
[26]GOSSELINK R W,HOLLAK S A W,CHANG S W,et al.Reaction pathways for the deoxygenation of vegetable oils and related model compounds[J].Chem Sus Chem,2013,6(9):1576-1594.
[27]HERMIDA L,ABDULLAH A Z,MOHAMED A R.Deoxygenation of fatty acid to produce diesel-like hydrocarbons:a review of process conditions,reaction kinetics and mechanism[J].Renewable&Sustainable Energy Reviews,2015,42:1223-1233.
[28]KUBICKA D,HORACEK J.Deactivation of HDS catalysts in deoxygenation of vegetable oils[J].Applied Catalysis A:General,2011,394(1/2):9-17.
[29]孙培永,刘森,周玉鹏,等.镍铝合金催化油酸甲酯加氢饱和的热力学和动力学分析[J].中国油脂,2017,42(10):93-99.SUN P Y,LIU S,ZHOU Y P,et al.Thermodynamic and kinetics analysis of catalytic hydrogenation of methyl oleate over Ni-Al alloy[J].China Oils and Fats,2017,42(10):93-99.
[30]刘纪昌,沈本贤.正构烷烃含量对裂解烯烃收率的影响及乙烯裂解的原料调配[J].华东理工大学学报(自然科学版),2006,32(5):535-539.LIU J C,SHEN B X.Effect of normal paraffin content on ethylene yield and feedstock allocation of ethylene pyrolysis process[J].Journal of East China University of Science and Technology(Natural Science),2006,32(5):535-539.