混合丙烷、C4烃同步转化制丙烯复合多功能催化剂的研究

Activation transformation and utilization of short chain alkanes is crucial to raise the added-value of energy resources. For the conversion of mixed propane and C4 hydrocarbons (butane and butylene) to propene, the design and preparation of multifunctional composite catalysts of oxide(II)/oxide(I)-SAPO-11 molecular zeolite, the evaluation of catalytic activity and the reaction dynamic analysis will be carrried out in order to intensify the catalytic activity for dehydrogenation, cracking and metathesis reactions and enhance the synchronous transformation of mixed hydrocarbons to light olefins. Meanwhile the activity for the secondery side reactions as hydrolysis and hydrogen transfer will be suppressed to increase the selectivity of light olefin products, to reduce the formation of C1-C3 alkanes and C5+ hydrocarbons, and to raise the ratio of propylene to ethylene. The effective preparation methods of multifunctional composite catalysts will be established to meet the catalytic performance for the synchronous transformation. The improved mesopore-micropore distribution , redox states, and acidity of the catalysts and their effects on the product distribution of the simultaneous transformation will be achieved. Through studies on the reaction pathway and mechanism, the relationships between the structure and properties of the catalysts, and the effects of the mixed feed constitution on the product distribution will be disclosed. These results will provide a scientific foundation for the design and preparation of catalysts with high-performance and developing the cost-effective utilization of short chain hydrocarbons.

低碳烷烃的活化转化利用是提升能源资源附加值的重要途径。结合混合丙烷、C4烃（丁烷、丁烯）转化制丙烯，通过多功能复合氧化物(II)/氧化物(I)-SAPO-11分子筛催化剂的设计、制备优化、催化反应活性评价及动力学分析，加强其对脱氢、裂解、易位反应的催化活性，实现混合烃向低碳烯烃的同步转化，同时抑制其对氢解、氢转移等二次副反应的催化活性，增加产物丙烯、乙烯的选择性，减少C1-C3烷烃和C5+烃产物的生成，提高丙烯/乙烯比。获得多功能复合催化剂的制备规律及其介孔-微孔分布、氧化还原态和酸性质等对混合烃同步转化反应产物分布的影响规律。通过混合烃向丙烯选择转化的催化反应途径及机理研究，揭示催化剂组成-结构-性能关系，以及混合烃组成对转化反应产物分布的影响，为轻烃相互转化高活性催化剂的设计、制备，轻烃合理利用工艺的发展提供科学依据。

围绕煤基甲醇制丙烯（MTP）和煤制油（CTL）工艺过程液化石油气（LPG）副产的增值转化利用，基于原料同步转化为乙烯和丙烯涉及的脱氢、裂解、聚合-裂解反应，完成了复合MO(II)/MO(I)-SAPO-11类型复合催化剂（MO/γ-Al2O3/SAPO-11、Cr2O3/AT-HZSM-5、SAPO-5/HZSM-5、SAPO-11/HZSM-5、HZSM-5/SAPO-18）的设计、制备研究；通过工艺条件优化、结构性能表征，具备合适粒度、比例分布的微孔-介孔结构、酸强度和酸密度、氧化还原性等。完成了反应条件优化、反应途径研究，优化了催化剂的复合配比、孔结构、酸性质、氧化还原态，强化催化剂表面，促进了转化反应所需的脱氢、裂解、易位反应活性，同时减少了氢解、氢转移等二次副反应活性。实现了混合丙烷、C4 烃向低碳烯烃的同步转化，最高转化率81.6%；提高了丙烯、乙烯产物选择性，最高选择性达到71.77%，提高了产物中丙烯/乙烯比（1.9），减少了CH4（＜8%）和C5+烃产物（＜9%）。获得了多功能复合催化剂制备、组成-结构-性能规律。