甲醇制烯烃技术(DMTO,Dimethylether/Methanol to Olefin)是中科院大连化学物理研究所与中石化洛阳工程有限公司和新兴能源科技公司合作开发的具有自主知识产权的低碳烯烃生产新技术。2010年8月采用DMTO技术的世界上首套甲醇制烯烃工业...甲醇制烯烃技术(DMTO,Dimethylether/Methanol to Olefin)是中科院大连化学物理研究所与中石化洛阳工程有限公司和新兴能源科技公司合作开发的具有自主知识产权的低碳烯烃生产新技术。2010年8月采用DMTO技术的世界上首套甲醇制烯烃工业装置在神华包头投料开车成功;2013年2月宁波禾元的DMTO工业装置也投入运行。这两套装置的甲醇进料量均为1.80 Mt/a,烯烃产量为600 kt/a。本文对DMTO工艺机理、工程设计特点和投料运行进行了介绍。DMTO工业装置运行结果表明,DMTO专用催化剂具有非常好的活性、选择性及抗磨损性能;采用大型浅层密相流化床反应器可以发挥催化剂性能,保障反应床层恒温及提高运行可靠性。为了减少开工阶段喷燃烧油可能对催化剂带来的不利影响,两套工业装置的投料开车均采用首创的利用反应热来进行再生器和反应器升温的方法。DMTO工业装置稳定运行时甲醇转化率接近100%,双烯选择性达到80%。72 h标定结果显示,生产1 t烯烃所需要的甲醇原料约为2.97 t。展开更多
甲醇制烯烃(MTO)装置催化剂循环回路的下行流动部分是再生立管,再生立管将催化剂从再生器输送至反应器是保证MTO装置正常运行的前提条件。某0.60 Mt a MTO装置再生立管出现的催化剂输送不畅问题已成为装置高效运行的瓶颈,为此通过测量...甲醇制烯烃(MTO)装置催化剂循环回路的下行流动部分是再生立管,再生立管将催化剂从再生器输送至反应器是保证MTO装置正常运行的前提条件。某0.60 Mt a MTO装置再生立管出现的催化剂输送不畅问题已成为装置高效运行的瓶颈,为此通过测量再生立管的轴向压力分布和工艺参数分析催化剂输送不畅的原因。结果表明:由于催化剂脱气和大气泡,再生立管中催化剂从上至下形成了过渡填充流、段塞流和密相流化流,导致催化剂浓度和催化剂循环量大幅度波动。最后,根据分析结果提出了再生立管结构改造的建议。展开更多
A ZSM-5/MAPO composite catalyst was prepared by adding ZSM-5 zeolite powder to a conventional molecular sieve synthesis system, followed by modification with NH_4H_2PO_4. The samples were characterized by XRD, SEM, IR...A ZSM-5/MAPO composite catalyst was prepared by adding ZSM-5 zeolite powder to a conventional molecular sieve synthesis system, followed by modification with NH_4H_2PO_4. The samples were characterized by XRD, SEM, IR, NH_3-TPD, and BET analyses. The catalytic property of the samples toward the methanol-to-olefin(MTO) reaction was evaluated in a connected in series two-stage unit equipped with a continuous flow(once-through) fixed-bed tubular reactor similar to an industrial reactor. The first reactor mainly converted methanol into dimethyl ether and water, followed by being subject to continuous reaction in the second reactor, in which DME was converted to hydrocarbons. The composites exhibited the typical framework topology of MFI, AEI and AFI, which represented the ZSM-5 zeolite, the molecular sieves AlPO-18 or SAPO-18, AlPO-5 or SAPO-5, respectively. The composites showed several advantages for optimizing the zeolite acidity, enhancing the mass transfer, and restraining the side reactions. Catalytic reaction results showed that the composites exhibited higher selectivity to light olefins(84.0%) and lower selectivity to C_2―C_4 alkanes and C_5^+ hydrocarbons than pure ZSM-5. Moreover, the composite zeolite loaded with 3% of P demonstrated improved catalytic activity and stability for the conversion of methanol to propylene, because the coking rate was obviously suppressed.展开更多
文摘甲醇制烯烃(MTO)装置催化剂循环回路的下行流动部分是再生立管,再生立管将催化剂从再生器输送至反应器是保证MTO装置正常运行的前提条件。某0.60 Mt a MTO装置再生立管出现的催化剂输送不畅问题已成为装置高效运行的瓶颈,为此通过测量再生立管的轴向压力分布和工艺参数分析催化剂输送不畅的原因。结果表明:由于催化剂脱气和大气泡,再生立管中催化剂从上至下形成了过渡填充流、段塞流和密相流化流,导致催化剂浓度和催化剂循环量大幅度波动。最后,根据分析结果提出了再生立管结构改造的建议。
基金financially supported by the National International Cooperation S & T Project of China (No.2015DFA40660)
文摘A ZSM-5/MAPO composite catalyst was prepared by adding ZSM-5 zeolite powder to a conventional molecular sieve synthesis system, followed by modification with NH_4H_2PO_4. The samples were characterized by XRD, SEM, IR, NH_3-TPD, and BET analyses. The catalytic property of the samples toward the methanol-to-olefin(MTO) reaction was evaluated in a connected in series two-stage unit equipped with a continuous flow(once-through) fixed-bed tubular reactor similar to an industrial reactor. The first reactor mainly converted methanol into dimethyl ether and water, followed by being subject to continuous reaction in the second reactor, in which DME was converted to hydrocarbons. The composites exhibited the typical framework topology of MFI, AEI and AFI, which represented the ZSM-5 zeolite, the molecular sieves AlPO-18 or SAPO-18, AlPO-5 or SAPO-5, respectively. The composites showed several advantages for optimizing the zeolite acidity, enhancing the mass transfer, and restraining the side reactions. Catalytic reaction results showed that the composites exhibited higher selectivity to light olefins(84.0%) and lower selectivity to C_2―C_4 alkanes and C_5^+ hydrocarbons than pure ZSM-5. Moreover, the composite zeolite loaded with 3% of P demonstrated improved catalytic activity and stability for the conversion of methanol to propylene, because the coking rate was obviously suppressed.
