沉淀温度对费托合成沉淀铁催化剂性能的影响
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摘要
研究了30～90℃范围内沉淀温度对连续共沉淀法制备的费托(F-T)合成Fe-Cu-K-SiO_2催化剂性能的影响,采用XRD、N_2吸附-脱附、H_2-TPR及穆斯堡尔谱对催化剂的晶型结构、晶粒尺寸、物化性质、还原性能及碳化程度进行了表征,并考察了工业条件下不同沉淀温度对催化剂性能的影响。实验结果表明,沉淀温度在30～90℃范围内,随沉淀温度的升高,催化剂晶粒增大,比表面积降低,不利于催化剂的还原和碳化,导致F-T合成反应的CO转化率明显下降,C_5~+和CO_2选择性有所增加,CH_4选择性降低,这些均与催化剂的活性物种的变化有关。
A series of Fe-Cu-K-SiO_2 catalysts were prepared by co-precipitation method at a precipitation temperature ranging from 30℃ to 90℃.The crystal structure,particle size,texture,reduction and carbonization of the catalysts were studied by XRD,N_2 adsorption-desorption,H_2-TPR and M?bssbauer effect spectroscopy.The effects of different precipitation temperatures on the performance of catalysts under industrial conditions were also investigated.The results showed thatα-Fe_2O_3 crystal particle size was increased and the specific surface area was decreased with the increasing of the precipitation temperature,which inhibited the reduction and carbonization of the iron catalysts.The Fischer-Tropsch performance of the catalysts prepared at different precipitation temperatures was tested under industrial operation conditions.It was found that the CO conversion of the iron catalysts was obviously decreased with increasing precipitation temperature ranging from 30℃ to 90℃,with C_5~+ and CO_2 selectivities increased slightly and CH_4 selectivity decreased.The performance results of Fischer-Tropsch reaction were well correlated with the active species.
A series of Fe-Cu-K-SiO_2 catalysts were prepared by co-precipitation method at a precipitation temperature ranging from 30℃ to 90℃.The crystal structure,particle size,texture,reduction and carbonization of the catalysts were studied by XRD,N_2 adsorption-desorption,H_2-TPR and M?bssbauer effect spectroscopy.The effects of different precipitation temperatures on the performance of catalysts under industrial conditions were also investigated.The results showed thatα-Fe_2O_3 crystal particle size was increased and the specific surface area was decreased with the increasing of the precipitation temperature,which inhibited the reduction and carbonization of the iron catalysts.The Fischer-Tropsch performance of the catalysts prepared at different precipitation temperatures was tested under industrial operation conditions.It was found that the CO conversion of the iron catalysts was obviously decreased with increasing precipitation temperature ranging from 30℃ to 90℃,with C_5~+ and CO_2 selectivities increased slightly and CH_4 selectivity decreased.The performance results of Fischer-Tropsch reaction were well correlated with the active species.
引文
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[2]Pravakar M,Kamal K P,Satya N N,et al.Synthesis of green fuels from biogenic waste through thermochemical route-The role of heterogeneous catalyst:A review[J].Renew Sust Energ Rev,2014,38(29):131-153.
[3]Bell A T.The impact of nanoscience on heterogeneous catalysis[J].Science,2003,299(5613):1688-1691.
[4]Murzin D Y.Sized-dependent heterogeneous catalysis[J].JMol Catal A:Chem,2010,315(2):226-230.
[5]Pour A N,Housaindokht M R.The olefin to paraffin ratio as a function of catalyst particle size in Fischer-Tropsch synthesis by iron catalyst[J].J Nat Gas Sci Eng,2013,14(9):204-210.
[6]Kang Cheng,Morella V,Ordonmsky V V,et al.Pore size effects in high-temperature Fischer-Tropsch synthesis over supported iron catalysts[J].J Catal,2015,328(1):139-150.
[7]Davis B H.Fischer-Tropsch synthesis:Reaction mechanisms for iron catalysts[J].Catal Today,2009,141(1/2):25-33.
[8]Jones K V,Neubauer R L,Bartholomew H C.Effects of crystallite size and support on the carbon monoxide hydrogenation activity/selectivity properties of iron/carbon[J].J Phys Chem,1986,90(20):4832-4839.
[9]Pour A N,Housaindokht M R,Irani M,et al.Size-dependent studies of Fischer-Tropsch synthesis on iron based catalyst:New kinetic model[J].Fuel,2014,116(1):787-793.
[10]Diamini H,Motjope T,Joorst G,et al.Changes in physicchemical properties of iron-based Fischer-Tropsch catalyst induced by SiO2 addition[J].Catal Lett,2002,78(1/4):201-207.
[11]武鹏,张魁,王鹏,等.硅溶胶粒径对沉淀铁催化剂费托合成性能的影响[J].石油化工,2016,45(4):398-401.
[12]武鹏,石玉林,宁文生,等.陈化时间对沉淀铁催化剂的费托合成性能影响[J].石油炼制与化工,2010,41(10):26-32.
[13]Ding Mingyue,Yang Yong,Wu Baoshan,et al.Transformation of carbonaceous species and its influence on catalytic performance for iron-based Fischer-Tropsch synthesis catalyst[J].J Mol Catal A:Chem,2011,351:165-173.
[14]Ning W S,Koizumi N,Chang H,et al.Phase transformation of unpromoted and promoted Fe catalysts and the formation of carbonaceous compounds during Fischer-Tropsch synthesis reaction[J].Appl Catal,A,2006,312(9):35-44.
[15]房德仁,刘中民,杨越,等.沉淀温度对CuO/ZnO/Al2O3催化剂前驱体物相及催化水煤气变换反应活性的影响[J].催化学报,2004,25(11):920-924.
[16]Das C K,Das N S,Choudhury D P,et al.Hydrogenation of carbon monoxide on unsupported Fe-Mn-K catalysts for the synthesis of lower alkene:Promoter effent of manganese[J].Appl Catal,A,1994,111(2):119-132.
[17]Yang Yong,Xiang Hongwei,Tian Lei,et al.Structure and Fischer-Tropsch performance of iron-manganese catalyst incorporated with SiO2[J].Appl Catal,A,2005,284(1):105-122.
[18]Tiernan M J,Barnes P A,Parkes G M B.Reduction of iron oxide catalysts:The investigation of kinetic parameters using rate perturbation and linear heating thermoanalytical techniques[J].J Phys Chem B,2001,105(1):220-228.
[19]李青山,张金朝,宋骊.共沉淀条件对纳米级Sb/SnO2粒度和电性能的影响[J].应用化学,2002,19(2):163-167.
[20]Sirimanothan N,Hamdeh H H,Zhang Y,et al.FischerTropsch synthesis changes in phase and activity during use[J].Catal Lett,2002,82(3/4):181-191.
[21]Kundig W,Bommel H,Constabaris G,et al.Some properties of supported small alpha-Fe2O3 particles determined with the M?ssbauer effect[J].Phys Rev,1966,142(2):327-333.
[22]Yang Yong,Xiang Hongwei,Zhang Rongle,et al.A highly active and stable Fe-Mn catalyst for slurry Fischer-Tropsch synthesis[J].Catal Today,2005,106(1):170-175.
[23]Li S,Meitzner G D,Iglesia E.Structure and site evolution of iron oxide catalyst precursors during the Fischer-Tropsch synthesis[J].J Phys Chem B,2001,105(24):5743-5750.
[24]Datye A K,Jin Y,Mansker L,et al.The nature of the active phase in iron Fischer-Tropsch catalysts[J].Stud Surf Sci Catal,2000,130(1):1139-1144.
[25]Newsome D S.The water-gas shift reaction[J].Catal Rev Sci Eng,1980,21(2):275-318.
[26]Yang Yong,Xiang Hongwei,Xu Yuanyuan,et al.Effect of potassium on precipitated iron-manganese catalyst for Fischer-Tropsch synthesis[J].Appl Catal,A,2004,266(2):181-194.