摘要 MTO 工艺可使煤或天然气的化工利用得到新的发展空间,特别是为天然气资源或煤资源丰富的偏远地区,创造了利用天然气或煤炭大规模发展甲醇、低碳烯烃及其下游产品的机会。因而目前研究 MTO的催化剂,对我国石油依靠进口程度不断提高的状况而言,具有重要意义。主要目的是制备出性能可以跟进口MTO催化剂性能一致的催化剂,打破国外垄断。
制备的催化剂(CMTO)和进口的催化剂(UOP催化剂)在10公斤级循环流化床上模拟工业化生产条件进行对比试验,各条件试验下CMTO催化剂运行积碳控制低于参比剂,收率整体略低于参比剂,部分情况下略高于参比剂,结果表明CMTO催化剂和参比剂活性基本一致;CMTO催化剂与参比剂相比,乙烯占比高,丙烯占比少。
Abstract: MTO process can provide new development space for chemical utilization of coal or natural gas, especially for remote areas rich in natural gas resources or coal resources, and create opportunities for large-scale development of methanol, low-carbon olefin and its downstream products by using natural gas or coal. Therefore, the current research on MTO catalysts is of great significance to China's increasing dependence on oil imports. The main purpose is to prepare a catalyst whose performance can be consistent with that of imported MTO catalyst and break the foreign monopoly.The catalyst prepared by CMTO and the imported catalyst (UOP catalyst) were compared in 10 kg circulating fluidized bed simulating industrial production conditions. Under various conditions of this test, the operating carbon accumulation control of CMTO catalyst is lower than that of the reference agent, and the yield is slightly lower than that of the reference agent as a whole, and slightly higher than that of the reference agent in some cases. The results showed that the activities of CMTO catalyst and reference agent were basically the same. CMTO catalyst has higher ethylene content and lower propylene content than reference catalyst.
[ 1 ] Najafabadi A T, Fatemi S, Sohrabi M, et al. Kinetic modeling and optimization of the operating condition of MTO process on SAPO-34 catalyst[ J ]. Journal of Industrial and Engineering Chemistry, 2012, 18( 1 ): 29 - 37.
[ 2 ] KEIL F J. Methanol-to-hydrocarbons: process technology[ J ]. M-
icroporous and Mesoporous Materials, 1999, 29(1 - 2): 49 - 66.
[ 3 ] ST CKER M. Methanol-to-hydrocarbons: catalytic materials and their behavior1[ J ]. Microporous and Mesoporous Materials, 1999, 29(1 - 2): 3 - 48.
[ 4 ] CHANG C D. Methanol Conversion to Light Olefins[ J ]. Catalysis Reviews-science And Engineering, 1984, 26: 323 - 345.
[ 5 ] RABO J A, SCHOONOVER M W. Early discoveries in zeolite ch-
emistry and catalysis at Union Carbide, and follow-up in industrial catalysis[ J ]. Applied Catalysis A: General, 2001, 222(1 - 2): 261 - 275.
[ 6 ] Wakihara, Sato K, Inagaki S, et al. Fabrication of Fine Zeolite with Improved Catalytic Properties by Bead Milling and Alkali Treatment[ J ]. ACS Applied Material& Interfaces 2010, 2( 10 ): 2 715 - 2 718.
[ 7 ] Chen D, Moljord K, Holmen A. A methanol to olefins review: Diff-
usion, coke formation and deactivation on SAPO type catalysts[ J ]. Microporous and Mesoporous Materials, 2012, 164( 164 ): 239 - 250.
[ 8 ] AHMADI S M A, ASKARI S, HALLADJ R. A review on kinetic modeling of deactivation of SAPO-34 catalyst during Methanol to Olefins (MTO) process[ J ]. Afinidad, 2013, 70( 562 ): 130 - 138.
[ 9 ] TIAN P, WEI Y X, YE M, et al. Methanol to Olefins (MTO): From Fundamentals to Commercialization[ J ]. ACS Catalysis, 2015, 5( 3 ): 1 922 - 1 938.