有机添加剂法制备原位晶化型大孔催化裂化催化剂
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摘要
采用淀粉及聚合物-PDDA(聚二甲基二烯丙基氯化铵)分别作为有机添加剂,通过原位晶化方法制备NaY/高岭土复合物及催化裂化催化剂,并采用XRD、N_2吸附及ACE装置进行表征和评价。结果表明:引入淀粉或者聚合物-PDDA后,NaY/高岭土复合物结晶度从18%增加到24%,引入淀粉后,复合物介孔孔体积从0.180cm~3/g提升到0.355cm~3/g,而引入PDDA后,复合物介孔孔体积进一步增加到0.431cm~3/g;与空白试验相比,使用引入淀粉和PDDA所制备的催化剂时,油浆产率分别降低1.98百分点和2.43百分点,总液体收率增加2.55百分点和3.07百分点。
NaY/kaolin composite microspheres and the corresponding FCC catalysts were prepared via in-situ synthesis by adding organic additives(starch and polymer PDDA).XRD,N_2-adsorption and ACE were used to study the crystallinity,pore structures,and the cracking performances of the NaY/kaolin composites and catalysts.The results showed that the crystallinity of the composites is increased from 18% to 24% by adding starch or PDDA.The mesopore volume of the composites adding starch are increased from 0.180 cm~3/g to 0.355 cm~3/g,and further increased to 0.431 cm~3/g by using PDDA additive.ACE tests showed the as-made catalyst using starch or PDDA improves the catalytic performances,the slurry yields are 1.98 and 2.43 percentage points lower than the reference,respectively,while the liquid yields increase 2.55 and 3.07 percentage points,respectively,compared to the catalysts prepared without additive.
NaY/kaolin composite microspheres and the corresponding FCC catalysts were prepared via in-situ synthesis by adding organic additives(starch and polymer PDDA).XRD,N_2-adsorption and ACE were used to study the crystallinity,pore structures,and the cracking performances of the NaY/kaolin composites and catalysts.The results showed that the crystallinity of the composites is increased from 18% to 24% by adding starch or PDDA.The mesopore volume of the composites adding starch are increased from 0.180 cm~3/g to 0.355 cm~3/g,and further increased to 0.431 cm~3/g by using PDDA additive.ACE tests showed the as-made catalyst using starch or PDDA improves the catalytic performances,the slurry yields are 1.98 and 2.43 percentage points lower than the reference,respectively,while the liquid yields increase 2.55 and 3.07 percentage points,respectively,compared to the catalysts prepared without additive.
引文
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[2]Lu Yong,He Mingyuan,Song Jiaqing,et al.Active site accessibility of resid cracking catalysts[J].Studies in Surface Science&Catalysis,2001,134(4):209-217
[3]Lam Y L,Silva S A,Roncolatto R E,et al.Cracking catalyst composition:The United States,US 6776899[P].2004-08-17
[4]Chen Shenli,Dong Peng,Xu Keqi,et al.Large pore heavy oil processing catalysts prepared using colloidal particles as templates[J].Catal Today,2007,125(3):143-148
[5]Hettinger J W,Lewis J E.Large pore catalysts for heavy hydrocarbon conversion:The United States,US 4624773[P].1986-11-25
[6]Stockwell D M,Nagel P.Distributed matrix structures-novel technology for high performance in short contact time FCC[J].Studies in Surface Science&Catalysis,2004,149:257-285
[7]Adkins B,Gavalda S.Commercialization of GO-ULTRA:Optimization of kinetic model and review of FCCU trials[C]∥NPRA Annual Meeting,AM-10-175,2010
[8]Brown S M,Durante V A,Reagan W J,et al.Fluid catalytic cracking catalyst comprising microspheres containing more than about 40percent by weight Y-faujasite and methods for making:The United States,US 4493902[P].1985-01-15
[9]Dight L B,Bogert D C,Leskowicz M A.Ultra high zeolite content FCC catalysts and method for making same from microspheres composed of a mixture of calcined kaolin clays:The United States,US 5023220[P].1991-06-11
[10]Basaldella Elena I,Bonetto Rita,Tara Juan C.Synthesis of NaY zeolite on preformed kaolinite spheres.Evolution of zeolite content and textural properties with the reaction time[J].Ind Eng Chem Res,1993,32(4):751-752
[11]Xu Mingcan,Cheng Mojie,Bao Xinhe.Growth of ultrafine zeolite Y crystals on metakaolin microspheres[J].Chem Commun,2000,19(19):1873-1874
[12]Shen Baojian,Wang Ping,Yi Zhou,et al.Synthesis of zeoliteβfrom kaolin and its catalytic performance for FCC naphtha aromatization[J].Energy&Fuels,2009,23(1):60-64
[13]Liu Honghai,Zhao Hongjuan,Gao Xionghou,et al.A novel FCC catalyst synthesized via in situ overgrowth of NaY zeolite on kaolin microspheres for maximizing propylene yield[J].Catal Today,2007,125(3):163-168
[14]Gao Xionghou,Liu Honghai,Wang Baojie,et al.Method for the preparation of high-content NaY molecular sieves synthesized from kaolin sprayed microspheres:The United States,US 7390762[P].2008-06-24