梯级多孔材料及其在柴油中HDS性能研究

Novel Hierarchically Porous Materials and HDSPerformance of FCC Diesel

本研究采用两步水热晶化法,以Beta 微晶乳液为原料,以聚氧乙烯-聚氧丙烯-聚氧乙烯（P123）为介孔模板剂,通过调变扩孔剂均三甲苯（TMB）与P123 的质量比（TMB/P123=0.4、0.5、1.0、2.0 和3.0）条件下合成出了Beta-MCFs（BF）系列介微孔复合材料,将其与Al2O3 机械混合（质量比1：4）制备出相应的复合载体,并浸渍活性金属Ni（3.5wt%）、Mo（15wt%）制备了相应的HDS 催化剂.然后采用XRD、IR、NH3-TPD、SEM、TEM 及N2 吸附脱附等表征方法对介微孔复合材料及相应的催化剂进行了表征;以硫含量为1013.78 μg·ml^-1 呼和浩特FCC 柴油为原料,对该系列催化剂进行了HDS 活性评价.结果表明：所合成的复合介微孔复合材料不仅具有不同大小的介孔孔径的孔道性质,同时又具有微孔材料Beta 适宜的酸性;在适宜的TMB/P123 比例范围内,比例越大,催化剂的脱硫效果越好,在TMB/P123=0.5 时,相应的催化剂达到了最高的脱硫率,高达98.1%,产品中的硫含量为19.83μg·ml^-1.

Meso-microporous composite materials of larger mesoporous aperture possess open pores of mesoporous materials andappropriate acidity, so it is helpful to the diffusion and removal of macromolecular sulfide, which could led to the result of deepdesurfurization. Beta-MCFs （TMB/P123=0.4, 0.5, 1.0, 2.0 or 3.0） meso-microporous composite materials were synthesized fromzeolite Beta nanoclusters by self-assembly method using P123 as the mesostructure directing agent under the basic condition inthis thesis. The corresponding composite supports were produced by mechanical mix with Al2O3 （14）, then the supportedNi（3.5wt%）Mo（15wt%） catalysts were prepared by two-step incipient-wetness impregnation of ammonium heptamolybdate andnickel nitrate. The typical physical-chemical properties of the supports and the catalysts were characterized by XRD, IR, NH3-TPD,SEM, TEM and Nitrogen adsorption–desorption analysis, etc. The hydro desulfurization evaluation results of FCC diesel with thesulfur content of 1013.8 μg·ml-1 showed that in the appropriate proportion of TMB/P123 range, the greater the ratio, the betterdesulfurization efficiency we received, on the TMB/P123 = 0.5, the corresponding catalyst exhibited the highest HDS activity, ashigh as 98.1%, and the product with the sulfur content of 19.8 μg·ml-1 was achieved.