甲醇制烯烃多级串联流化床反应器模拟

甲醇制烯烃(MTO)是现代煤化工发展的新技术,合理的甲醇制烯烃反应器操作模式可以有效提高催化剂的效率和低碳烯烃选择性。采用在工业SAPO34催化剂上实验得到的反应与失活动力学和流化床动态两相模型,结合颗粒停留时间分布模型,对MTO单一流化床反应器、二级串联及三级串联反应器进行了模拟,考察了催化剂停留时间、气固并流和气固逆流对甲醇制烯烃反应的影响。模拟结果表明:采用多级串联反应器有利于减小颗粒的返混,使出口积炭量分布更加均匀,催化剂寿命延长;二级气固逆流操作可以提高低碳烯烃选择性及出口催化剂积炭量,催化剂单位生产能力比单级反应器提高24.4%;三级串联、气固逆流反应器可以充分利用各级反应器的不同功能,使总的低碳烯烃选择性提高到79.36%(质量分数),比单级反应器提高1%,同时单位催化剂单程生产能力比单级提高31.1%。     

用于甲醇制烯烃的非均相催化反应器评述

甲醇制低碳烯烃（MTO、MTP）是煤化工的关键环节,近年来相关技术已经在我国成功工业化,包括中国科学院大连化学物理研究所的DMTO技术、中石化的s-MTO技术、UOP的MTO+OCP技术以及Lurgi的MTP技术。从非均相催化反应角度分析甲醇制烯烃的过程特点,剖析了各类典型的非均相催化反应器用于该过程的优劣,对比了国内外各主流技术的关键指标,评述了甲醇制烯烃和催化裂化的异同。分子筛催化的甲醇制烯烃过程遵循烃池机理,呈现自催化和积炭失活特性,控制催化剂的工作状态和限制返混对提高催化活性及烯烃产物选择性尤为重要。具有多级结构的分子筛催化剂及低返混流化床反应器或反应器串联组合是未来的发展方向。     

DMTO再生催化剂经C4/C5+裂解预积炭后对MTO反应性能的影响

采用小型固定流化床,研究了MTO副产物C4/C5^+烯烃在DMTO再生催化剂上的催化裂解反应、预积炭情况,以及预积炭后再生催化剂对MTO反应性能的影响。结果表明:C4/C5^+烯烃可作为原料在DMTO再生催化剂上进行催化裂解,生成乙烯、丙烯,增加双烯产量。在此裂解过程中,DMTO再生催化剂发生预积炭,可以提高MTO反应中双烯的初始选择性,缩短反应诱导期,提高双烯收率;同时,可以减小甲醇的生焦率,降低甲醇消耗。DMTO再生催化剂预积炭会影响催化剂寿命,其经C4/C5^+裂解预积炭过程中碳质量分数以3%左右为宜。     

用于甲醇制烯烃的非均相催化反应器评述

甲醇制低碳烯烃(MTO、MTP)是煤化工的关键环节,近年来相关技术已经在我国成功工业化,包括中国科学院大连化学物理研究所的DMTO技术、中石化的s-MTO技术、UOP的MTO+OCP技术以及Lurgi的MTP技术。从非均相催化反应角度分析甲醇制烯烃的过程特点,剖析了各类典型的非均相催化反应器用于该过程的优劣,对比了国内外各主流技术的关键指标,评述了甲醇制烯烃和催化裂化的异同。分子筛催化的甲醇制烯烃过程遵循烃池机理,呈现自催化和积炭失活特性,控制催化剂的工作状态和限制返混对提高催化活性及烯烃产物选择性尤为重要。具有多级结构的分子筛催化剂及低返混流化床反应器或反应器串联组合是未来的发展方向。     

甲醇甲苯烷基化流化床反应器的数值模拟

利用甲醇甲苯烷基化工艺生产对二甲苯具有良好的应用前景。甲醇甲苯烷基化催化剂较易积炭失活,且反应存在明显热效应。流化床因传热传质性能好、易实现催化剂连续再生,适合用作甲醇甲苯烷基化反应器。本文采用离散颗粒模型,对甲醇甲苯烷基化流化床反应器进行了数值模拟研究,重点考察了进料比、反应压力、分段进料对反应特性的影响。结果表明,当甲苯进料量给定时：降低反应物中甲苯甲醇比可有效提升对二甲苯产率和选择性,但产物中对二甲苯和烯烃摩尔比值较低;提高反应压力可显著提升甲醇和甲苯转化率,但会降低对二甲苯选择性;在低苯醇比基础上采用甲醇分段进料方式不仅可有效提高甲苯利用率,还可灵活调节产物中对二甲苯和烯烃比率;流化床反应器气体返混不利于获得高对二甲苯选择性,且操作条件变化会造成流化床反应器内气固流动改变,导致气固接触效率或反应物局部分压发生改变,这亦将对反应转化特性造成显著影响。这些结果对于流化床反应器优化和放大具有一定的指导意义。     

滴流床反应器的非定态操作

采用蒽醌加氢反应为探针,研究了脉冲流操作、周期性填充和周期性操作3种非定态操作方式对TBR反应器性能的影响.结果表明,在脉冲流区操作TBR的催化剂质量空时收率比滴流区操作提高50%以上,表观动力学研究证实脉冲流区操作TBR蒽醌加氢反应的表观活化能比滴流区操作更接近本征活化能;催化剂与惰性颗粒的交替填充周期性地强化了气液相间传质速率,提高催化剂质量空时收率40%以上;反应器的周期性操作,同时强化气液和液固相间传质速率,改善反应器内的流体力学状况,从而提高反应的空时收率和选择性10%以上.     

正丁烷氧化制顺丁烯二酸酐细粒床的流化特性

研究了正丁烷氧化制丁烯二酸酐反应使用的 Ｖ Ｐ Ｏ系催化剂及流化床的特性，确定催化剂颗粒平均最佳直径为７５２μｍ 。测定了正丁烷氧化流化床中的停留时间分布特征，求取了流化特征参数，对传质作用和返混性质进行了讨论。     

SAPO-34催化剂上C4烯烃催化裂解与甲醇转化制烯烃反应耦合

采用SAPO-34催化剂,在流化床装置上考察了甲醇制烯烃(MTO)副产C4烯烃催化裂解制乙烯和丙烯的反应行为,分析了C4烯烃转化率、产物收率等主要指标随工艺参数的变化规律,对比了C4烯烃催化裂解和MTO反应积炭催化剂的差异,提出了C4烯烃催化裂解适宜的关键工艺条件。C4烯烃催化裂解对比MTO反应需要较高的反应温度和催化剂活性。结果表明,C4烯烃裂解反应过程形成的积炭催化剂仍可用于MTO反应,并且具有较高的甲醇转化率和低碳烯烃选择性,因此可以采用SAPO-34催化剂把两个独立的反应串联耦合在一起。     

变孔径分布板减小液固流化床中液相返混

引言流化床亲合色谱蛋白质分离新方法综合了亲和吸附的快速、高选择性与液固流化床液相负荷大、传质速率高等优点,尤其是生物细胞可随液相穿透空隙率较大的吸附剂颗粒床层,因此该方法是构成连续分离-反应相耦合的蛋白质生产工艺的有效手段．但不足之处是流化床内的液相返混会严重影响分离效率,因此必须采取措施加以抑制．国外有采用磁稳定流化床来减小液相返混,但要添加体积比44％的磁性颗粒且要在75G_s的磁通密度下操作,有可能影响产品的生物活性．鉴于此,可采取不外加场源的稳定化措施来减小液相返混．本文通过对液固流化床液相返…     

甲醇制烯烃催化剂SAPO-34分子筛的改性研究进展

甲醇制烯烃（MTO）被认为是最有希望以煤或天然气为原料替代石油制取烯烃的技术路线。具有CHA结构的SAPO-34分子筛是MTO反应生产乙烯和丙烯最理想的催化剂,但在甲醇转化过程中,芳香烃类中间体受到SAPO-34分子筛八元环微孔结构的限制,使催化剂孔道堵塞并覆盖其酸性位点,造成催化剂积炭失活。为了提高SAPO-34分子筛催化剂的寿命和低碳烯烃的选择性,改善传质并延缓焦炭的沉积至关重要。从构建多级孔结构、减小晶粒尺寸及调控分子筛酸性3个方面出发,总结了SAPO-34分子筛在MTO反应中的研究进展,并对今后催化剂的粒度、孔尺寸、酸性质等方向的改进及发展进行了展望。     

甲醇制烯烃催化剂SAPO-34分子筛的制备和喷雾成型

SAPO-34分子筛用于催化甲醇转化制烯烃,乙烯和丙烯选择性高,是很好的甲醇制烯烃催化剂。由于SAPO-34分子筛失活速率快,甲醇制烯烃反应器通常是连续循环再生的流化床反应器,SAPO-34分子筛必须喷雾成型并达到一定抗磨强度后才能使用。在50 L反应釜合成了SAPO-34分子筛,并在中试喷雾装置上,以SAPO-34为活性组分喷雾成型甲醇制烯烃催化剂。结果表明,喷雾成型甲醇制烯烃催化剂的抗磨损指数为1.58%·h-1,抗磨性能达到工业应用要求,与两种工业甲醇制烯烃催化剂对比,喷雾成型甲醇制烯烃催化剂寿命最长,达260 min,乙烯、丙烯选择性以及乙烯+丙烯总选择性在对应的各个反应时间点均最高,260 min分别达到49.09%、35.05%和84.98%。     

甲醇制烯烃反应工艺、反应机理及其动力学研究进展

甲醇制烯烃工艺近年来已成为煤化工领域的研究热点。不同的甲醇制烯烃催化剂将导致不同的反应过程,以SAPO-34为催化剂时,甲醇主要遵循烃池机理,通过快速的平行反应直接生产乙烯和丙烯(MTO)等低碳烯烃;以ZSM-5为催化剂时,甲醇主要遵循双循环机理中的烯烃循环机理,通过甲基化-裂解等多步反应间接生产丙烯(MTP)。这种反应特征的不同也决定着反应器类型和工艺条件的不同:SAPO-34催化剂易失活的特性决定了工业MTO过程通常采用易再生的流化床反应器从甲醇一步生成乙烯和丙烯,而具有良好抗结焦能力的ZSM-5催化剂使得工业MTP过程通常选择易放大的固定床反应器,通过大量烯烃循环与分离逐步获得丙烯。针对SAPO-34催化剂上MTO过程以及ZSM-5催化剂上MTP过程的不同反应情况,综述了近年来甲醇制烯烃代表性的反应工艺、反应机理以及反应动力学等方面的研究进展,并根据其存在的问题提出了相应的发展方向。     

高岭土微球原位合成SAPO-34分子筛及其在流化床甲醇/二甲醚制烯烃过程中的应用(英文)

SAPO-34 zeolite is considered to be an effective catalyst for methanol or dimethyl ether conversion to olefins. In this study, we developed the in situ synthesis technology to prepare SAPO-34 zeolite in kaolin microspheres as a catalyst for fluidized methanol or dimethyl ether to olefins process. The silicoaluminophosphate zeolite was first time reported to be synthesized in kaolin microspheres. The SAPO-34 content of synthesized catalyst was about 22% as measured by three different quantitative methods (micropore area, X-ray fluorescence and energy dispersive spectroscopy element analysis). Most of the SAPO-34 zeolites were in nanoscale size and distributed uniformly inside the spheres. The catalytic performance was evaluated in fixed bed and fluidized bed reactors. Compared with the conventional spray-dry catalyst, SAPO/kaolin catalyst showed superior catalytic activities, better olefin selectivities (up to 94%, exclusive coke), and very good hydrothermal stability. The in situ synthesis of SAPO-34 in kaolin microspheres is a facile and economically feasible way to prepare more effective catalyst for fluidized MTO/DTO (methanol to olefins/dimethyl ether to olefins) process.     

碱金属改性对SAPO-34分子筛催化性能的影响

通过等体积浸渍法,制备得到碱金属(Li、Na、K、Rb、Cs)改性的SAPO-34催化剂。并在常压连续固定床反应器上评价了各催化剂的甲醇制低碳烯烃(MTO)的性能,同时对催化剂进行了XRD、FT-IR、NH₃-TPD等表征分析。结果表明,碱金属负载量为2%时,除Cs离子改性的催化剂低碳烯烃的选择性和寿命有所降低外,其他碱金属离子改性的SAPO-34催化剂低碳烯烃的选择性和寿命都有了明显的提高,尤其是Li离子改性的催化剂乙烯+丙烯的选择性达77%左右,寿命相对延长了2.5倍;将该催化剂再生3次后乙烯、丙烯的选择性几乎保持不变。     

Busting the efficiency of SAPO-34 catalysts for the methanol-to-olefin conversion by post-synthesis methods

As an effective non-petroleum based process for producing light olefins, the methanol-to-olefin(MTO) route has become an indispensable alternative to the industrial production of light olefins. The silicoaluminophosphate SAPO-34 zeolite(CHA-type structure) has proven to be an efficient industrial catalyst for the production of ethylene and propylene by the MTO reaction. However, the inherent structure and related diffusion limitations of SAPO-34 limit the mass transport and thus cause rapid deactivation of the catalyst. Fabrication of hierarchical SAPO-34 zeolite is one of the most effective strategies to address the intrinsic diffusion limitation. As simple, inexpensive, and efficient approach, the post-synthetic route has attracted considerable attention and widely used to introduce secondary meso-/macropores into the microporous SAPO-34 material. Significant effort has been dedicated to the development of post-synthesis strategies to prepare hierarchical SAPO-34 zeolite, thereby enhancing its catalytic performance in the MTO process. This mini-review addresses the post-synthesis preparation of hierarchical SAPO-34 catalysts and their MTO performance. Furthermore, some current problems and prospects of the post-synthesis route to hierarchical SAPO-34 catalysts are also revised. We expect this minireview to inspire the more efficient preparation of hierarchical SAPO-34 catalysts for the MTO process.     

Study of Catalyst Coke Distribution Based on Population Balance Theory: Application to Methanol to Olefins Process

A coke distribution model of catalyst particles in three-dimensional space was developed based on population balance theory, and an analytic expression of coke distribution for zero-dimensional time-independent problem was deduced. The expression shows that the coke distribution is determined by the average catalyst residence time, coke deposition (or burning) rate, and coke distribution of catalyst inflow. The coke distribution model was further applied to the methanol to olefins (MTO) process. The critical factors influencing coke distribution in MTO process, as well as the effect of coke distribution on product selectivity, were investigated. Three scales of MTO fluidized bed reactor–regenerator systems, i.e., pilot-scale, demonstration-scale and commercial-scale with the reactor diameter of 0.261, 1.25, and 10.5 m, respectively, were simulated. The simulated results were in good agreement with the operation data. The model could be helpful in the operation optimization and reactor design. © 2018 American Institute of Chemical Engineers AIChE J, 65: 1149–1161, 2019     

Busting the efficiency of SAPO-34 catalysts for the methanol-to-olefin conversion by post-synthesis methods

As an effective non-petroleum based process for producing light olefins, the methanol-to-olefin (MTO) route has become an indispensable alternative to the industrial production of light olefins. The silicoaluminophosphate SAPO-34 zeolite (CHA-type structure) has proven to be an efficient industrial catalyst for the production of ethylene and propylene by the MTO reaction. However, the inherent structure and related diffusion limitations of SAPO-34 limit the mass transport and thus cause rapid deactivation of the catalyst. Fabrication of hierarchical SAPO-34 zeolite is one of the most effective strategies to address the intrinsic diffusion limitation. As simple, inexpensive, and efficient approach, the post-synthetic route has attracted considerable attention and widely used to introduce secondary meso-/macropores into the microporous SAPO-34 material. Significant effort has been dedicated to the development of post-synthesis strategies to prepare hierarchical SAPO-34 zeolite, thereby enhancing its catalytic performance in the MTO process. This mini-review addresses the post-synthesis preparation of hierarchical SAPO-34 catalysts and their MTO performance. Furthermore, some current problems and prospects of the post-synthesis route to hierarchical SAPO-34 catalysts are also revised. We expect this minireview to inspire the more efficient preparation of hierarchical SAPO-34 catalysts for the MTO process.     

反应条件对D803C-Ⅱ01催化剂上甲醇制低碳烯烃的影响

采用小孔SAPO-34分子筛为活性基质,经过改性、喷雾干燥成型及适当温度焙烧后,得到适用于流化床的二甲醚或甲醇高选择性转化为低碳烯烃的催化剂D803C-Ⅱ01。研究反应温度、反应压力和催化剂停留时间对甲醇制低碳烯烃反应的影响以及D803C-Ⅱ01催化剂再生过程及其变化规律。结果表明,乙烯+丙烯选择性约在425℃达到最大值,在反应总压力不大于0.2 MPa、催化剂停留时间为55 min、催化剂与物料接触时间大于0.2 s条件下,均能保证反应转化率接近100%,但反应接触时间从0.6 s增大至3 s,会造成乙烯+丙烯选择性降低3～5个百分点。