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Ca基固体碱制备及其重油裂解气化性能
引用本文:唐瑞源 田原宇 冷桂玲 乔英云. Ca基固体碱制备及其重油裂解气化性能[J]. 石油学报(石油加工), 2016, 32(3): 486-492. DOI: 10.3969/j.issn.1001-8719.2016.03.007
作者姓名:唐瑞源 田原宇 冷桂玲 乔英云
作者单位:1 中国石油大学 重质油国家重点实验室, 山东 青岛 266580; 2山东科技大学 低碳能源研究中心, 山东 青岛 266590
基金项目:国家自然科学基金(21576293、21576294、21206185)资助
摘    要:采用固相合成法制备Ca基固体碱催化剂,并利用N2吸附技术、XRD、FT IR及Hammett指示剂法对催化剂进行表征。采用双管反应器进行常压渣油催化裂解和气化再生实验,考察了反应温度、水/油质量比、剂/油质量比等对裂解产物中烯烃分布的影响,并考察了不同积炭量对待生剂气化性能的影响。结果表明,铝酸钙催化剂具有较强的碱强度和总碱量、较小的比表面积和孔容积。在反应温度750℃、水/油质量比10、剂/油质量比70时,催化裂解性能最优,乙烯质量产率达到214%,总烯烃质量产率为296%。积炭量对待生剂气化性能影响不明显。再生剂的总碱量略有减小,合成气以H2和CO2为主且含量达到89%(体积分数)。将催化裂解和气化再生整合,实现了热量耦合,达到综合利用重油的目标。

关 键 词:固体碱催化剂  催化裂解  低碳烯烃  气化再生  
收稿时间:2015-06-16

Preparation of Ca Based Solid Basic Catalyst and its Cracking Gasification Performance for Heavy Oil
Affiliation:1State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, China;2Research Centre for Low Carbon Energy Sources, Shandong University of Science and Technology, Qingdao 266590, China
Abstract:Ca based solid base catalyst was prepared by the solid phase synthesis method. The prepared catalyst was characterized by N2 adsorption techniques, XRD, FT IR, the Hammett indicators methods. And atmospheric residue catalytic cracking and gasification reaction were carried out in the double pipe reactor to study the influences of reaction temperature, m(Water)/m(Oil) and m(Catalyst)/m(Oil) on the heavy oil cracking over solid base catalyst. Then the coke deposited gasification was also discussed. The results showed that calcium alumina catalyst had the stronger base strength and total base number, the lower specific surface area and pore volume compared with that of Al2O3. With calcium alumina as the catalyst and under the conditions of reaction temperature 750℃, m(Water)/m(Oil)=10 and m(Catalyst)/m(Oil)=70, the yields of ethylene and total olefins reached to 214% and 296%, respectively. The coke amount deposited on deactivated base catalyst had little influence to its gasification performance. Total base number of regenerated catalyst slightly reduced, and the volume fractions of H2 and CO2 in syngas could reach up to 89%. By integrating two reactions of catalytic cracking and gasification regeneration, the reaction heat coupling and comprehensive utilization for heavy oil were realized.
Keywords:solid base catalyst  catalytic cracking  light olefins  gasification regeneration  
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