NiMo/SAPO-11加氢脱氧/异构双功能催化剂的制备及性能
|
摘要
利用水热法合成了SAPO-11分子筛,并以其为载体制备了Ni Mo/SAPO-11催化剂,采用XRD,NH_3-TPD,Py-FTIR等手段对制备的SAPO-11分子筛和Ni Mo/SAPO-11催化剂进行表征,考察了硅铝比和合成介质对SAPO-11分子筛性质及Ni Mo/SAPO-11催化性能的影响。表征结果显示,适当增加硅铝比,SAPO-11分子筛的晶粒尺寸减小、介孔增多,提高了SAPO-11的酸量和中强B酸量;在醇-水两相介质中合成的SAPO-11分子筛表面形貌较规整、结晶度较高、比表面积较大,其B酸量(特别是中强B酸)明显增加,且异丙醇-水两相介质的作用效果优于乙醇-水两相介质。实验结果表明,以在异丙醇-水两相介质中合成的SAPO-11分子筛制备的Ni Mo/SAPO-11催化剂具有较优的加氢脱氧/异构性能。
A Ni Mo/SAPO-11 catalyst was obtained with SAPO-11 zeolite prepared by a hydrothermal method as the support. The prepared SAPO-11 zeolite and Ni Mo/SAPO-11 catalyst were characterized by means of XRD,NH_3-TPD,Py-FTIR with investigation on the effects of silicon to aluminum ratio and synthetic media on the properties of the SAPO-11 zeolite and the performance of the Ni Mo/SAPO-11 catalyst. The characterization results showed that an appropriately increased silicon to aluminum ratio allowed for reduction in grain size and increase in mesopores of the SAPO-11 zeolite,thereby increasing the acid amount and medium B acid amount of the SAPO-11. Additionally,the SAPO-11 synthesized in an alcohol-water two-phase media had more regular surface morphology,higher crystallinity and larger specific surface area as well as significantly increased B acid(especially medium B acid) amount,where the effect of the isopropanol-water two-phase media was more noticeable than that of the ethanol-water two-phase media. The experimental results showed that the Ni Mo/SAPO-11 catalyst prepared with the SAPO-11 zeolite synthesized in the isopropanol-water twophase media had more excellent performance in hydrodeoxygenation and isomerization.
A Ni Mo/SAPO-11 catalyst was obtained with SAPO-11 zeolite prepared by a hydrothermal method as the support. The prepared SAPO-11 zeolite and Ni Mo/SAPO-11 catalyst were characterized by means of XRD,NH_3-TPD,Py-FTIR with investigation on the effects of silicon to aluminum ratio and synthetic media on the properties of the SAPO-11 zeolite and the performance of the Ni Mo/SAPO-11 catalyst. The characterization results showed that an appropriately increased silicon to aluminum ratio allowed for reduction in grain size and increase in mesopores of the SAPO-11 zeolite,thereby increasing the acid amount and medium B acid amount of the SAPO-11. Additionally,the SAPO-11 synthesized in an alcohol-water two-phase media had more regular surface morphology,higher crystallinity and larger specific surface area as well as significantly increased B acid(especially medium B acid) amount,where the effect of the isopropanol-water two-phase media was more noticeable than that of the ethanol-water two-phase media. The experimental results showed that the Ni Mo/SAPO-11 catalyst prepared with the SAPO-11 zeolite synthesized in the isopropanol-water twophase media had more excellent performance in hydrodeoxygenation and isomerization.
引文
[1]Chen Ning,Gong Shaofeng,Qian Eika W.Effect of reduction temperature of Ni Mo O3-x/SAPO-11 on its catalytic activity in hydrodeoxygenation of methyl laurate[J].Appl Catal,B,2015,174/175(9):253-263.
[2]Gong S,Chen N,Nakayama S,et al.Isomerization of nalkanes derived from jatropha oil over bifunctional catalysts[J].J Mole Catal A:Chem,2013,370(4):14-21.
[3]Wang Congxin,Liu Qianhe,Liu Xuebin,et al.Influence of reaction conditions on one-step hydrotreatment of lipids in the production of iso-alkanes over Pt/SAPO-11[J].Chin J Catal,2013,34(6):1128-1138.
[4]庞新梅,朱卫东,常小平,等.SAPO-11分子筛的性质与催化应用[J].分子催化,2004,18(2):153-160.
[5]Qian Eika W,Chen Ning,Gong Shaofeng.Role of support in deoxygenation and isomerization of methyl stearate over nickelmolybdenum catalysts[J].J Mole Catal A:Chem,2014,387(2):76-85.
[6]罗洪军,吴红娇,吴红玉,等.SAPO系列分子筛催化剂应用于正构烷烃异构化的研究进展[J].工业催化,2011,19(1):16-22.
[7]武秋颖.介孔SAPO-11的合成、表征及催化应用[D].北京:北京化工大学,2016.
[8]邓鹏,聂聪,李全芝.SAPO-11中硅含量对长链烷烃加氢异构化反应的影响[J].复旦学报:自然科学版,2001,40(1):387-391.
[9]Chen N,Gong S,Shirai H,et al.Effects of Si/Al ratio and Pt/SAPO-11 catalysts in hydroconversion of Jatropha oil[J].Appl Catal,A,2013,466(36):105-115.
[10]中华人民共和国国家质量监督检验检疫局.GB/T 5534—2008动植物油脂皂化值的测定[S].北京:中国标准出版社,2008.
[11]Wen Chenglong,Han Shanlei,Xu Jundong,et al.A novel route to synthesize SAPO-11 molecular sieves with a high external surface area in the presence of ethylene glycol and supercritical carbon dioxide for 1-octene hydroisomerization to dimethylhexanes[J].J Catal,2017,356(12):100-110.
[12]李贺霞,张徽,马守涛,等.SAPO合成因素的影响研究[J].化工科技,2017,25(4):81-86.
[13]杨晓梅,徐竹生,马怀军,等.水-丁醇两相介质合成SAPO-11和Mg APO-11分子筛[J].催化学报,2007,28(3):187-189.
[14]霍玉秋,翟玉春,童华南.3种共溶剂对正硅酸乙酯水解的影响[J].东北大学学报:自然科学版,2004,25(2):133-135.
[15]Barthomeuf D.Topological model for the compared acidity of SAPOs and Si Al zeolites[J].Zeolites,1994,14(6):394-401.
[16]汪哲明,田志坚,林励吴,等.硅源与硅含量对合成的SAPO分子筛催化正十二烷异构化性能的影响[J].化学反应工程与工艺,2008,24(3):199-203.
[17]Zhang Shengzhen,Chen Shengli,Dong Peng,et al.Characterization and hydroisomerization performance of SAPO-11 molecular sieves synthesized in different media[J].Appli Catal,A,2007,332(1):46-55.
[18]徐会青,刘全杰,贾立明.催化剂酸性对正辛烷异构化反应行为研究[J].当代化工,2013,42(12):1642-1644.
[19]张胜振,陈胜利,董鹏,等.小晶粒SAPO-11分子筛的合成及其催化异构化性能[J].催化学报,2007,28(10):857-864.
[20]Alsyouri H,Lin J.Gas diffusion and microstructural properties of ordered mesoporous silica fibers[J].J Phys Chem B,2005,109(28):13623-9.
[21]徐莹,王铁军,马隆龙,等.Mo Ni/γ-Al2O3催化剂的制备及其催化乙酸临氢酯化反应性能[J].无机化学学报,2009,25(5):805-811.
[22]Kukushkin R,Bulavchenko O,Kaichev V,et al.Influence of Mo on catalytic activity of Ni-based catalysts in hydrodeoxygenation of esters[J].Appl Catal,B,2015,163:531-538.
[23]宋海涛,朱玉霞,达志坚.空速对不同Y型分子筛FCC催化剂轻柴油裂化性能的影响[J].工业催化,2009,17(7):26-29.
[2]Gong S,Chen N,Nakayama S,et al.Isomerization of nalkanes derived from jatropha oil over bifunctional catalysts[J].J Mole Catal A:Chem,2013,370(4):14-21.
[3]Wang Congxin,Liu Qianhe,Liu Xuebin,et al.Influence of reaction conditions on one-step hydrotreatment of lipids in the production of iso-alkanes over Pt/SAPO-11[J].Chin J Catal,2013,34(6):1128-1138.
[4]庞新梅,朱卫东,常小平,等.SAPO-11分子筛的性质与催化应用[J].分子催化,2004,18(2):153-160.
[5]Qian Eika W,Chen Ning,Gong Shaofeng.Role of support in deoxygenation and isomerization of methyl stearate over nickelmolybdenum catalysts[J].J Mole Catal A:Chem,2014,387(2):76-85.
[6]罗洪军,吴红娇,吴红玉,等.SAPO系列分子筛催化剂应用于正构烷烃异构化的研究进展[J].工业催化,2011,19(1):16-22.
[7]武秋颖.介孔SAPO-11的合成、表征及催化应用[D].北京:北京化工大学,2016.
[8]邓鹏,聂聪,李全芝.SAPO-11中硅含量对长链烷烃加氢异构化反应的影响[J].复旦学报:自然科学版,2001,40(1):387-391.
[9]Chen N,Gong S,Shirai H,et al.Effects of Si/Al ratio and Pt/SAPO-11 catalysts in hydroconversion of Jatropha oil[J].Appl Catal,A,2013,466(36):105-115.
[10]中华人民共和国国家质量监督检验检疫局.GB/T 5534—2008动植物油脂皂化值的测定[S].北京:中国标准出版社,2008.
[11]Wen Chenglong,Han Shanlei,Xu Jundong,et al.A novel route to synthesize SAPO-11 molecular sieves with a high external surface area in the presence of ethylene glycol and supercritical carbon dioxide for 1-octene hydroisomerization to dimethylhexanes[J].J Catal,2017,356(12):100-110.
[12]李贺霞,张徽,马守涛,等.SAPO合成因素的影响研究[J].化工科技,2017,25(4):81-86.
[13]杨晓梅,徐竹生,马怀军,等.水-丁醇两相介质合成SAPO-11和Mg APO-11分子筛[J].催化学报,2007,28(3):187-189.
[14]霍玉秋,翟玉春,童华南.3种共溶剂对正硅酸乙酯水解的影响[J].东北大学学报:自然科学版,2004,25(2):133-135.
[15]Barthomeuf D.Topological model for the compared acidity of SAPOs and Si Al zeolites[J].Zeolites,1994,14(6):394-401.
[16]汪哲明,田志坚,林励吴,等.硅源与硅含量对合成的SAPO分子筛催化正十二烷异构化性能的影响[J].化学反应工程与工艺,2008,24(3):199-203.
[17]Zhang Shengzhen,Chen Shengli,Dong Peng,et al.Characterization and hydroisomerization performance of SAPO-11 molecular sieves synthesized in different media[J].Appli Catal,A,2007,332(1):46-55.
[18]徐会青,刘全杰,贾立明.催化剂酸性对正辛烷异构化反应行为研究[J].当代化工,2013,42(12):1642-1644.
[19]张胜振,陈胜利,董鹏,等.小晶粒SAPO-11分子筛的合成及其催化异构化性能[J].催化学报,2007,28(10):857-864.
[20]Alsyouri H,Lin J.Gas diffusion and microstructural properties of ordered mesoporous silica fibers[J].J Phys Chem B,2005,109(28):13623-9.
[21]徐莹,王铁军,马隆龙,等.Mo Ni/γ-Al2O3催化剂的制备及其催化乙酸临氢酯化反应性能[J].无机化学学报,2009,25(5):805-811.
[22]Kukushkin R,Bulavchenko O,Kaichev V,et al.Influence of Mo on catalytic activity of Ni-based catalysts in hydrodeoxygenation of esters[J].Appl Catal,B,2015,163:531-538.
[23]宋海涛,朱玉霞,达志坚.空速对不同Y型分子筛FCC催化剂轻柴油裂化性能的影响[J].工业催化,2009,17(7):26-29.