二甲醚水蒸气重整制氢双功能催化剂的研究
摘要
质子交换膜燃料电池(PEMFC)具有环境友好、工作温度低、比功率高、高可靠性等优点,因而成为便携式电源和燃料电池汽车的理想动力源。尽管目前PEMFC发展到了较高的技术水平,但是,氢源已成为其商业化应用的瓶颈之一。与其它的制氢燃料(如液化石油气、汽油、甲醇和乙醇等)相比,二甲醚(DME)具有气体的流动性、液体的存储密度、廉价易得、含氢量高(13wt.%)和无毒等优点,原则上DME现场水蒸气重整制氢能够较好地解决PEMFC汽车燃料供应的问题。更重要的是,与其它重整制氢方式相比,二甲醚水蒸气重整(SRD)制氢可以在较低的反应温度下(200-400℃)进行。因此,近几年来,SRD获得了较多的关注,但是,相关研究仍处于起步阶段。
在综合分析SRD相关文献报道及前期初步研究结果的基础上,根据SRD两步连串反应的特点,本论文以H-ZSM-5等分子筛为固体酸,与商品化Cu/ZnO/Al2O3组成双功能催化剂,从两种催化活性组分之间的协同作用角度出发,分别考察了分子筛的结构和酸性、H-ZSM-5分子筛的酸性调控,对双功能催化剂SRD性能的影响；采用不同方法,制备了具有核壳结构特征的H-ZSM-5/Cu/ZnO/Al2O3双功能催化剂,考察了其催化SRD的动力学行为。对相关催化剂进行了XRD、物理/化学吸附、扫描电子显微镜等表征分析,从催化剂的结构、酸性、孔径分布、表面形貌及不同催化功能之间的协同作用等角度,将催化剂表征结果与其SRD反应性能之间进行了合理的关联分析,明确了上述因素影响双功能催化剂的SRD反应活性和产物选择性的作用机制,并探讨了双功能催化剂的失活行为。主要研究内容及结论如下：
(1)以不同结构和酸性的H-ZSM-5(SiO2/Al2O3=25)、H-USY和H-beta (SiO2/Al2O3=20)为固体酸,分别与商品化的Cu/ZnO/Al2O3按等质量比物理混合,制备了双功能催化剂。在原料气DME/H2O/N2摩尔比为1/4/5,空速为4000mL·g-1·h-1及反应温度为290℃的条件下,系统地考察了固体酸的结构和酸性对双功能催化剂SRD反应性能的影响。结果表明,基于H-ZSM-5具有较高酸量、较强酸性和三维中孔结构等特点,相应的双功能催化剂表现出较好的SRD催化活性(DME转化率和H2收率分别为95%和80%)。尽管基于H-beta和H-USY分子筛的双功能催化剂对SRD反应也具有较高的催化活性,但由于其孔道尺寸较大,产物分布明显不同于H-ZSM-5上的结果,且首次发现生成了较多的六甲基苯(HMB)。以H-beta为固体酸,在改变反应原料组成等条件下,详细地研究了SRD反应条件下多甲基苯的生成规律。从DME和甲醇在酸催化作用下分别发生DME制烃(DTH)和甲醇制烃(MTH)副反应、分子筛的孔道尺寸等角度,对上述结果进行了较为合理的解释,认为SRD条件下的MTH等副反应极有可能是按照烃池(Hydrocarbon Pool)机理进行的,且HMB很可能就是烃池的活性物种。
(2)针对基于H-ZSM-5的双功能催化剂生成较多C2-C4烃类的问题,提出了采用负载MgO的方法,对H-ZSM-5的酸量和酸强度分布进行调变。以Mg(NO3)2为前驱体,采用浸渍法,制备了0-8.16wt.%MgO改性的H-ZSM-5。将MgO改性的H-ZSM-5与商品化的Cu/ZnO/Al2O3等质量比物理混合,制备了一系列双功能催化剂。在原料气DME/H2O/N2摩尔比为1/4/5,空速为4000mL·g·h-1及反应温度为290℃的条件下,考察了双功能催化剂的SRD反应性能。结果表明,MgO负载量显著影响DME转化率、H2收率和含碳产物选择性。MgO负载量在1.412.92wt.%之间时,双功能催化剂的SRD性能最佳(DME转化率和H2收率分别高达95%和93%)。XRD、FT-IR和低温N2吸附表征结果表明,MgO高度分散在H-ZSM-5表面,且MgO的引入对H-ZSM-5分子筛的骨架和晶型结构影响并不明显。NH3-TPD表征结果表明,MgO的引入可以显著降低H-ZSM-5的强酸量,而对弱酸量影响不大。与离子交换法相比,采用浸渍法制备的MgO改性H-ZSM-5,在SRD反应中表现出较高的催化活性和稳定性。
(3)为了考察MgO改性H-ZSM-5与Cu/ZnO/Al2O3组成双功能催化剂的SRD反应稳定性,以Mg(NO3)2为前驱体,采用浸渍法,进一步优化了MgO负载量,制备了1.55-2.47wt.%MgO改性的H-ZSM-5,并与商品化的Cu/ZnO/Al2O3粉末混合,制备了一系列双功能催化剂。考察了温度、空速和质量比等反应条件对双功能催化剂SRD反应性能的影响,在空速为1000ML·g-1·h-1、反应温度为290℃和MgO改性H-ZSM-5与Cu/ZnO/Al2O3质量比为3/2的条件下,H2收率最高。同时,MgO含量为2.17、wt.%的H-ZSM-5表现出最好的SRD反应活性和稳定性,反应50h后DME转化率和H2收率仍分别为93%和91%。反应前、后双功能催化剂的XPS、XRD和低温N2吸附结果表明催化剂表面积碳和Cu的烧结是导致催化剂失活的主要原因。
(4)根据SRD两步连串反应的特点,采用两种方法,分别制备了空心、实心核壳双功能催化剂。方案一：采用多孔结构的聚丙烯酰胺-甲基丙烯酸(P(AM-co-MAA))微凝胶为载体,将商品化Cu/ZnO/Al2O3填充到P(AM-co-MAA)的孔道中,得到核催化剂；以酸性硅溶胶为粘结剂,将商品化H-ZSM-5粘覆于核催化剂表面,经焙烧去除P(AM-co-MAA)后,获得空心核壳双功能催化剂。方案二：以商品化的Cu/ZnO/Al2O3(40-60目)为核催化剂,采用原位水热合成法,制备了表面包覆H-ZSM-5膜的实心核壳双功能催化剂。催化剂的SEM形貌表征结果说明,两种方法均制备了界限分明、结构规整的核壳双功能催化剂。在反应温度为300℃,空速为2000mL·g-1·h-1的反应条件下,考察了两种核壳双功能催化剂的SRD反应性能。结果表明,与空心核壳双功能催化剂相比,H-ZSM-5膜质量为12%的实心核壳双功能催化剂,表现出较高的DME转化率和H2收率。产物分布结果表明,与物理混合法制备的双功能催化剂相比,核壳结构双功能催化剂的CO和CH4选择性显著降低(<1.3%),这是由于反应物DME和水分子到达核壳双功能催化剂颗粒时,首先在分子筛膜部分进行水解反应,水解反应产物一经生成后,很快到达核催化剂进行甲醇重整反应,SRD的两步反应高度协同一致,从而很好的抑制副反应产物CO和CH4的生成。
The proton exchange membrane fuel cell (PEMFC), which is characterized by environmental benignity, low operating temperature, high efficiency, and high reliability, has been recognized as a desirable power generation system for portable devices and electric vehicles. Currently, H2source is still one of the main obstacles for the commercialization of PEMFC vehicles although big process has been made for the duel cell. Among the aviable H2carriers for PEMFC, such as liquefied petroleum gas, gasoline, methanol and ethanol, dimethyl ether (DME) is believed to be a promising candidate due to its gas-like properties and liquid storage density, low cost, high hydrogen content (13wt.%), low or no toxicity, etc. More importantly, comparing with other H2carriers, hydrogen production via steam reforming of DME (SRD) can be performed efficiently at lower temperatures of200-400℃. Thus, in recent years, SRD has received much attention as an efficient method for the on-board production of hydrogen for PEMFC. However, the related investigation on SRD is just at the very beginning stage.
Based on the literature of SRD and keep the consecutive two-step mechanism for SRD in mind, we investigated the bifunctional catalyst composed of zeolites and the Cu/ZnO/Al2O3. From the synergistic effect of two different active components of SRD, we studied the effect of acidity and topological structure of zeolites, and changed the acidic sites of H-ZSM-5zeolite on the performance of the SRD reaction. Meanwhile, used different methods to preparation H-ZSM-5/Cu/ZnO/Al2O3core-shell bifunctional catalysts, and researched the reaction kinetic for SRD. The activity and the selectivity of SRD for hydrogen production were qantitatively correlated with the structure, acidity, pores size distribution, surface topography and the synergistic effect between different catalytic functions of the bifunctional catalyst, which are characterized by XRD, physical/chemical adsorption, and scanning electron microscope (SEM), etc. The mechanistic relationship between the thus mentioned factors and SRD performance of the catalyst, especially the key factor on selectively controlling the SRD products distribution, was determined, and the cause of bifunctional catalysts deactivation was determined. The experiment and main conclusions are summarized as follows:
(1) The bifunctional catalyst was prepared by physically mixing Cu/ZnO/Al2O3with H-ZSM-5(Si/Al2O3=25), H-USY, and H-beta (Si/Al2O3=20), respectively. We inversitaged the effect of the acidity and topological structure of zeolites in bifunctional catalyst for SRD under the conditions of DME/H2O/N2=1/4/5, GHSV=4000mL·g-4·h-1, T=290℃. Due to having suitable acidity and channel size, H-ZSM-5based bifunctional catalyst showed the highest SRD performance, i.e., stable DME conversion of over95%and H2yield of about80%. Unexpectedly, a large amount of hexamethyl benzene (HMB) was condensed at the outlet of the reactor when H-USY or H-beta based bifunctional catalysts were applied for SRD. To the best of our knowledge, this is the first report on the formation of HMB under SRD conditions. Based on the SRD mechanism, and the topological and acidic properties of zeolite, the formation of HMB was well explained as the side reactions of methanol to hydrocarbons (MTH) and DME to hydrocarbons (DTH) and the larger channel sizes of zeolites Y and beta than that of the HMB molecules. On the other hand, clear evidence is provided for the Hydrocarbon Pool mechanism of MTH reaction, and HMB is revealed to be the very possible species of Hydrocarbon Pool.
(2) It is well known that the strong acidic sites on H-ZSM-5zeolites promote the generation of secondary productions like hydrocarbons. Significantly, MgO-modified H-ZSM-5can effectively to tailor the acidity of H-ZSM-5. To develop an efficient acidic catalyst for SRD, H-ZSM-5was modified with a series amount of MgO (0-8.16wt.%) via the incipient impregnation method by using Mg(NO3)2as a precursor. The MgO-modified H-ZSM-5physically mixed with a commercial Cu/ZnO/Al2O3was investigated as a bifunctional catalyst for SRD. The reaction was performed under the conditions of DME/H2O/N2=1/4/5, T=290℃, and GHSV=4000mL·g-1·h-1. SRD results indicate that the DME conversion, H2yield, and selectivity of the carbon-containing products were strongly dependent on the MgO loadings over H-ZSM-5, and the highest DME conversion and H2yield of about95%and93%were achieved over the bifunctional catalyst by using1.41-2.92wt.%MgO modified H-ZSM-5as a solid acid. MgO was highly dispersed over H-ZSM-5, and very limited impact on the structure and crystallinity of the zeolite was unambiguously revealed by the techniques of XRD, FT-IR, and N2adsorption at low temperatures. On the contrary, significant effects of MgO on the acidity of H-ZSM-5, especially the stronger acidic sites, were clearly manifested from the temperature-programmed desorption of ammonia (NH3-TPD). In comparison with ion exchange method, the bifunctional catalyst showed higher SRD performance and stability via the incipient impregnation method.
(3) To develop an efficient and stability acidic catalyst for SRD, H-ZSM-5was modified with a series amount of MgO (1.55-2.17wt.%) via the incipient impregnation method by using Mg(NO3)2as a precursor. The MgO-modified H-ZSM-5physically mixed with a commercial Cu/ZnO/Al2O3was investigated as a bifunctional catalyst for SRD. The activity and stability reaction for SRD was performed under the conditions of DME/H2O/N2=1/4/5, T=290℃, GHSV=1000mL·g-1·h-1, and the weight ratio of MgO modified H-ZSM-5to Cu/ZnO/Al2O3was3/2. SRD results indicate that the stable DME conversion and H2yield were obtained above93%and91%after reaction for50h over the2.17wt.%MgO modified H-ZSM-5catalysts, respectively. Coke deposition and Cu sinter leaded to catalysts deactivation was unambiguously revealed by the techniques of XRD, FT-IR, and N2adsorption at low temperatures.
(4) Based on two-step mechanism of SRD, two different methods were used to preparation of core-shell bifunctional catalysts. First one, the3D network structure poly (acrylamide-co-methacrylic acid)(P(AM-co-MAA)) microgel were prepared as a template, then filled the channel of P(AM-co-MAA) with commercial Cu/ZnO/Al2O3to be the core catalyst. Secondly, the H-ZSM-5was impregnated with silicate sols coating on core catalyst via the paste method to preparation core-shell bifunctional catalyst. Finally, the core-shell catalyst was calcined to remove the P(AM-co-MAA) templates, and then hollow core-shell bifunctional catalyst was obtained. Second one, the commercial Cu/ZnO/Al2O3was coated with H-ZSM-5, which was prepared by hydrothermal synthesis method, and the catalyst was named as solid core-shell bifunctional catalyst. The reaction was performed by using two different core-shell bifunctional catalysts under the conditions of T=300℃and GHSV=2000mL·g-1·h-1. The SRD results indicate that the solid core-shell bifunctional catalyst showed higher DME conversion and H2yield than hollow core-shell bifunctional catalyst. Moreover, the selectivity of the side reation products like CO and CH4were less than1.3%. When DME and H2O through the core-shell bifunctional catalyst, firstly, hydrolysis of DME actively takes place over zeolite, then the middle product MeOH was quickly transform to H2via SRM. The side reaction products like CO and CH4were inhibited, when the synergistic effect of two-step for SRD was increased.
在综合分析SRD相关文献报道及前期初步研究结果的基础上,根据SRD两步连串反应的特点,本论文以H-ZSM-5等分子筛为固体酸,与商品化Cu/ZnO/Al2O3组成双功能催化剂,从两种催化活性组分之间的协同作用角度出发,分别考察了分子筛的结构和酸性、H-ZSM-5分子筛的酸性调控,对双功能催化剂SRD性能的影响；采用不同方法,制备了具有核壳结构特征的H-ZSM-5/Cu/ZnO/Al2O3双功能催化剂,考察了其催化SRD的动力学行为。对相关催化剂进行了XRD、物理/化学吸附、扫描电子显微镜等表征分析,从催化剂的结构、酸性、孔径分布、表面形貌及不同催化功能之间的协同作用等角度,将催化剂表征结果与其SRD反应性能之间进行了合理的关联分析,明确了上述因素影响双功能催化剂的SRD反应活性和产物选择性的作用机制,并探讨了双功能催化剂的失活行为。主要研究内容及结论如下：
(1)以不同结构和酸性的H-ZSM-5(SiO2/Al2O3=25)、H-USY和H-beta (SiO2/Al2O3=20)为固体酸,分别与商品化的Cu/ZnO/Al2O3按等质量比物理混合,制备了双功能催化剂。在原料气DME/H2O/N2摩尔比为1/4/5,空速为4000mL·g-1·h-1及反应温度为290℃的条件下,系统地考察了固体酸的结构和酸性对双功能催化剂SRD反应性能的影响。结果表明,基于H-ZSM-5具有较高酸量、较强酸性和三维中孔结构等特点,相应的双功能催化剂表现出较好的SRD催化活性(DME转化率和H2收率分别为95%和80%)。尽管基于H-beta和H-USY分子筛的双功能催化剂对SRD反应也具有较高的催化活性,但由于其孔道尺寸较大,产物分布明显不同于H-ZSM-5上的结果,且首次发现生成了较多的六甲基苯(HMB)。以H-beta为固体酸,在改变反应原料组成等条件下,详细地研究了SRD反应条件下多甲基苯的生成规律。从DME和甲醇在酸催化作用下分别发生DME制烃(DTH)和甲醇制烃(MTH)副反应、分子筛的孔道尺寸等角度,对上述结果进行了较为合理的解释,认为SRD条件下的MTH等副反应极有可能是按照烃池(Hydrocarbon Pool)机理进行的,且HMB很可能就是烃池的活性物种。
(2)针对基于H-ZSM-5的双功能催化剂生成较多C2-C4烃类的问题,提出了采用负载MgO的方法,对H-ZSM-5的酸量和酸强度分布进行调变。以Mg(NO3)2为前驱体,采用浸渍法,制备了0-8.16wt.%MgO改性的H-ZSM-5。将MgO改性的H-ZSM-5与商品化的Cu/ZnO/Al2O3等质量比物理混合,制备了一系列双功能催化剂。在原料气DME/H2O/N2摩尔比为1/4/5,空速为4000mL·g·h-1及反应温度为290℃的条件下,考察了双功能催化剂的SRD反应性能。结果表明,MgO负载量显著影响DME转化率、H2收率和含碳产物选择性。MgO负载量在1.412.92wt.%之间时,双功能催化剂的SRD性能最佳(DME转化率和H2收率分别高达95%和93%)。XRD、FT-IR和低温N2吸附表征结果表明,MgO高度分散在H-ZSM-5表面,且MgO的引入对H-ZSM-5分子筛的骨架和晶型结构影响并不明显。NH3-TPD表征结果表明,MgO的引入可以显著降低H-ZSM-5的强酸量,而对弱酸量影响不大。与离子交换法相比,采用浸渍法制备的MgO改性H-ZSM-5,在SRD反应中表现出较高的催化活性和稳定性。
(3)为了考察MgO改性H-ZSM-5与Cu/ZnO/Al2O3组成双功能催化剂的SRD反应稳定性,以Mg(NO3)2为前驱体,采用浸渍法,进一步优化了MgO负载量,制备了1.55-2.47wt.%MgO改性的H-ZSM-5,并与商品化的Cu/ZnO/Al2O3粉末混合,制备了一系列双功能催化剂。考察了温度、空速和质量比等反应条件对双功能催化剂SRD反应性能的影响,在空速为1000ML·g-1·h-1、反应温度为290℃和MgO改性H-ZSM-5与Cu/ZnO/Al2O3质量比为3/2的条件下,H2收率最高。同时,MgO含量为2.17、wt.%的H-ZSM-5表现出最好的SRD反应活性和稳定性,反应50h后DME转化率和H2收率仍分别为93%和91%。反应前、后双功能催化剂的XPS、XRD和低温N2吸附结果表明催化剂表面积碳和Cu的烧结是导致催化剂失活的主要原因。
(4)根据SRD两步连串反应的特点,采用两种方法,分别制备了空心、实心核壳双功能催化剂。方案一：采用多孔结构的聚丙烯酰胺-甲基丙烯酸(P(AM-co-MAA))微凝胶为载体,将商品化Cu/ZnO/Al2O3填充到P(AM-co-MAA)的孔道中,得到核催化剂；以酸性硅溶胶为粘结剂,将商品化H-ZSM-5粘覆于核催化剂表面,经焙烧去除P(AM-co-MAA)后,获得空心核壳双功能催化剂。方案二：以商品化的Cu/ZnO/Al2O3(40-60目)为核催化剂,采用原位水热合成法,制备了表面包覆H-ZSM-5膜的实心核壳双功能催化剂。催化剂的SEM形貌表征结果说明,两种方法均制备了界限分明、结构规整的核壳双功能催化剂。在反应温度为300℃,空速为2000mL·g-1·h-1的反应条件下,考察了两种核壳双功能催化剂的SRD反应性能。结果表明,与空心核壳双功能催化剂相比,H-ZSM-5膜质量为12%的实心核壳双功能催化剂,表现出较高的DME转化率和H2收率。产物分布结果表明,与物理混合法制备的双功能催化剂相比,核壳结构双功能催化剂的CO和CH4选择性显著降低(<1.3%),这是由于反应物DME和水分子到达核壳双功能催化剂颗粒时,首先在分子筛膜部分进行水解反应,水解反应产物一经生成后,很快到达核催化剂进行甲醇重整反应,SRD的两步反应高度协同一致,从而很好的抑制副反应产物CO和CH4的生成。
The proton exchange membrane fuel cell (PEMFC), which is characterized by environmental benignity, low operating temperature, high efficiency, and high reliability, has been recognized as a desirable power generation system for portable devices and electric vehicles. Currently, H2source is still one of the main obstacles for the commercialization of PEMFC vehicles although big process has been made for the duel cell. Among the aviable H2carriers for PEMFC, such as liquefied petroleum gas, gasoline, methanol and ethanol, dimethyl ether (DME) is believed to be a promising candidate due to its gas-like properties and liquid storage density, low cost, high hydrogen content (13wt.%), low or no toxicity, etc. More importantly, comparing with other H2carriers, hydrogen production via steam reforming of DME (SRD) can be performed efficiently at lower temperatures of200-400℃. Thus, in recent years, SRD has received much attention as an efficient method for the on-board production of hydrogen for PEMFC. However, the related investigation on SRD is just at the very beginning stage.
Based on the literature of SRD and keep the consecutive two-step mechanism for SRD in mind, we investigated the bifunctional catalyst composed of zeolites and the Cu/ZnO/Al2O3. From the synergistic effect of two different active components of SRD, we studied the effect of acidity and topological structure of zeolites, and changed the acidic sites of H-ZSM-5zeolite on the performance of the SRD reaction. Meanwhile, used different methods to preparation H-ZSM-5/Cu/ZnO/Al2O3core-shell bifunctional catalysts, and researched the reaction kinetic for SRD. The activity and the selectivity of SRD for hydrogen production were qantitatively correlated with the structure, acidity, pores size distribution, surface topography and the synergistic effect between different catalytic functions of the bifunctional catalyst, which are characterized by XRD, physical/chemical adsorption, and scanning electron microscope (SEM), etc. The mechanistic relationship between the thus mentioned factors and SRD performance of the catalyst, especially the key factor on selectively controlling the SRD products distribution, was determined, and the cause of bifunctional catalysts deactivation was determined. The experiment and main conclusions are summarized as follows:
(1) The bifunctional catalyst was prepared by physically mixing Cu/ZnO/Al2O3with H-ZSM-5(Si/Al2O3=25), H-USY, and H-beta (Si/Al2O3=20), respectively. We inversitaged the effect of the acidity and topological structure of zeolites in bifunctional catalyst for SRD under the conditions of DME/H2O/N2=1/4/5, GHSV=4000mL·g-4·h-1, T=290℃. Due to having suitable acidity and channel size, H-ZSM-5based bifunctional catalyst showed the highest SRD performance, i.e., stable DME conversion of over95%and H2yield of about80%. Unexpectedly, a large amount of hexamethyl benzene (HMB) was condensed at the outlet of the reactor when H-USY or H-beta based bifunctional catalysts were applied for SRD. To the best of our knowledge, this is the first report on the formation of HMB under SRD conditions. Based on the SRD mechanism, and the topological and acidic properties of zeolite, the formation of HMB was well explained as the side reactions of methanol to hydrocarbons (MTH) and DME to hydrocarbons (DTH) and the larger channel sizes of zeolites Y and beta than that of the HMB molecules. On the other hand, clear evidence is provided for the Hydrocarbon Pool mechanism of MTH reaction, and HMB is revealed to be the very possible species of Hydrocarbon Pool.
(2) It is well known that the strong acidic sites on H-ZSM-5zeolites promote the generation of secondary productions like hydrocarbons. Significantly, MgO-modified H-ZSM-5can effectively to tailor the acidity of H-ZSM-5. To develop an efficient acidic catalyst for SRD, H-ZSM-5was modified with a series amount of MgO (0-8.16wt.%) via the incipient impregnation method by using Mg(NO3)2as a precursor. The MgO-modified H-ZSM-5physically mixed with a commercial Cu/ZnO/Al2O3was investigated as a bifunctional catalyst for SRD. The reaction was performed under the conditions of DME/H2O/N2=1/4/5, T=290℃, and GHSV=4000mL·g-1·h-1. SRD results indicate that the DME conversion, H2yield, and selectivity of the carbon-containing products were strongly dependent on the MgO loadings over H-ZSM-5, and the highest DME conversion and H2yield of about95%and93%were achieved over the bifunctional catalyst by using1.41-2.92wt.%MgO modified H-ZSM-5as a solid acid. MgO was highly dispersed over H-ZSM-5, and very limited impact on the structure and crystallinity of the zeolite was unambiguously revealed by the techniques of XRD, FT-IR, and N2adsorption at low temperatures. On the contrary, significant effects of MgO on the acidity of H-ZSM-5, especially the stronger acidic sites, were clearly manifested from the temperature-programmed desorption of ammonia (NH3-TPD). In comparison with ion exchange method, the bifunctional catalyst showed higher SRD performance and stability via the incipient impregnation method.
(3) To develop an efficient and stability acidic catalyst for SRD, H-ZSM-5was modified with a series amount of MgO (1.55-2.17wt.%) via the incipient impregnation method by using Mg(NO3)2as a precursor. The MgO-modified H-ZSM-5physically mixed with a commercial Cu/ZnO/Al2O3was investigated as a bifunctional catalyst for SRD. The activity and stability reaction for SRD was performed under the conditions of DME/H2O/N2=1/4/5, T=290℃, GHSV=1000mL·g-1·h-1, and the weight ratio of MgO modified H-ZSM-5to Cu/ZnO/Al2O3was3/2. SRD results indicate that the stable DME conversion and H2yield were obtained above93%and91%after reaction for50h over the2.17wt.%MgO modified H-ZSM-5catalysts, respectively. Coke deposition and Cu sinter leaded to catalysts deactivation was unambiguously revealed by the techniques of XRD, FT-IR, and N2adsorption at low temperatures.
(4) Based on two-step mechanism of SRD, two different methods were used to preparation of core-shell bifunctional catalysts. First one, the3D network structure poly (acrylamide-co-methacrylic acid)(P(AM-co-MAA)) microgel were prepared as a template, then filled the channel of P(AM-co-MAA) with commercial Cu/ZnO/Al2O3to be the core catalyst. Secondly, the H-ZSM-5was impregnated with silicate sols coating on core catalyst via the paste method to preparation core-shell bifunctional catalyst. Finally, the core-shell catalyst was calcined to remove the P(AM-co-MAA) templates, and then hollow core-shell bifunctional catalyst was obtained. Second one, the commercial Cu/ZnO/Al2O3was coated with H-ZSM-5, which was prepared by hydrothermal synthesis method, and the catalyst was named as solid core-shell bifunctional catalyst. The reaction was performed by using two different core-shell bifunctional catalysts under the conditions of T=300℃and GHSV=2000mL·g-1·h-1. The SRD results indicate that the solid core-shell bifunctional catalyst showed higher DME conversion and H2yield than hollow core-shell bifunctional catalyst. Moreover, the selectivity of the side reation products like CO and CH4were less than1.3%. When DME and H2O through the core-shell bifunctional catalyst, firstly, hydrolysis of DME actively takes place over zeolite, then the middle product MeOH was quickly transform to H2via SRM. The side reaction products like CO and CH4were inhibited, when the synergistic effect of two-step for SRD was increased.
引文
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