ZSM-11分子筛用于重油催化裂解过程的研究
发布时间：2018-11-04 08:57
【摘要】：随着原料油的日益重质化以及低碳烯烃需求量的不断增加,ZSM-5分子筛作为催化裂解催化剂中提高低碳烯烃收率及选择性的活性组分已得到广泛的工业应用。ZSM-11分子筛具有与ZSM-5分子筛相似的结构及组成,但其相关研究主要集中在轻烃芳构化、甘油制丙烯腈等方面,而有关该分子筛催化裂解性能的文献报道较少。因此,本文对ZSM-11分子筛的催化裂解性能进行了系统地研究。本文采用XRD、SEM、低温氮气吸附、FT-IR以及NH3-TPD等方法对硅铝比为36的ZSM-5(LTB-2)、ZSM-11(LQM-1)进行结构性质表征及对比,表征结果显示相比于ZSM-5,ZSM-11孔道较短,孔道交叉处空间大,比表面积大且含有较多介孔,但酸量及B酸比例下降。以抚顺VGO及胜华VGO为原料,在500℃,剂油比为5条件下,使用固定床微反以及ZDT-1型中试装置对两者性能进行考察,结果表明:两种分子筛拥有相近的重油转化能力及低碳烯烃选择性,且ZSM-11分子筛在提高汽油辛烷值的同时,还能减少汽油损失,说明ZSM-11分子筛具有多产低碳烯烃兼产高辛烷值汽油的性能。在提升管中试装置上,以胜华VGO为原料,考察了模拟工业条件下LQM-1催化剂的活性衰减规律,结果表明:在反应温度540℃,剂油比为8,水油比为0.2,再生剂温度为700℃,停留时间为1.8s的条件下,连续运转60h过程中,LQM-1催化的相对结晶度、比表面积以及酸量均降低;原料转化率略有下降,维持在86%以上,干气及焦炭收率降低,汽柴油收率维持稳定;液化气收率增加4.36个百分点,液化气中丙烯收率由15.33%增至18.37%,丁烯收率则由11.22%增加到14.24%。此外,干气、液化气以及汽油中烯烃的选择性也有不同程度的提高。在提升管中试装置上,以胜华VGO为原料,考察了剂油比、反应温度以及停留时间对LQM-1催化剂裂解性能的影响,结果表明:综合考虑目的产物收率及选择性,在反应温度为540℃,剂油比7~9,停留时间2.0s条件下可获得最佳产物分布。该条件下原料转化率可达87.44%,其中干气及焦炭收率分别为7.5%和3.41%,液化气收率为40.94%,丙烯收率为20.61%,且丙烯选择性达到最大值50.34%,汽油收率为24.62%。
[Abstract]:With the increasingly heavy quality of feedstock and the increasing demand for low carbon olefins, ZSM-5 molecular sieve has been widely used as an active component in catalytic cracking catalyst to improve the yield and selectivity of low olefins. ZSM-11 molecular sieve has similar structure and composition to ZSM-5 molecular sieve. However, the related studies mainly focus on the aromatization of light hydrocarbons and the preparation of acrylonitrile from glycerol, but there are few reports on the catalytic cracking performance of this molecular sieve. Therefore, the catalytic cracking performance of ZSM-11 molecular sieve was studied systematically. In this paper, the structure and properties of ZSM-5 (LTB-2) and ZSM-11 (LQM-1) with Si-Al ratio of 36 are characterized by XRD,SEM, low temperature nitrogen adsorption, FT-IR and NH3-TPD. The results show that the structure and properties of ZSM-5 (LTB-2) and ZSM-11 (LQM-1) with Si-Al ratio 36 are compared with those of ZSM-5,. The ZSM-11 pore is short, the pore cross space is large, the specific surface area is large and contains more mesoporous, but the acid content and B acid ratio decrease. Using Fushun VGO and Victory VGO as raw materials, under the condition of 500 鈩，
本文编号：2309348
[Abstract]:With the increasingly heavy quality of feedstock and the increasing demand for low carbon olefins, ZSM-5 molecular sieve has been widely used as an active component in catalytic cracking catalyst to improve the yield and selectivity of low olefins. ZSM-11 molecular sieve has similar structure and composition to ZSM-5 molecular sieve. However, the related studies mainly focus on the aromatization of light hydrocarbons and the preparation of acrylonitrile from glycerol, but there are few reports on the catalytic cracking performance of this molecular sieve. Therefore, the catalytic cracking performance of ZSM-11 molecular sieve was studied systematically. In this paper, the structure and properties of ZSM-5 (LTB-2) and ZSM-11 (LQM-1) with Si-Al ratio of 36 are characterized by XRD,SEM, low temperature nitrogen adsorption, FT-IR and NH3-TPD. The results show that the structure and properties of ZSM-5 (LTB-2) and ZSM-11 (LQM-1) with Si-Al ratio 36 are compared with those of ZSM-5,. The ZSM-11 pore is short, the pore cross space is large, the specific surface area is large and contains more mesoporous, but the acid content and B acid ratio decrease. Using Fushun VGO and Victory VGO as raw materials, under the condition of 500 鈩，
本文编号：2309348
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