改性微-介孔催化剂的制备及其催化生物质热解制备芳烃

    Preparation of modified hierarchical HZSM-5 catalyst and its application on pyrolysis of biomass to enhance aromatics products

    • 摘要: 采用K2CO3对HZSM-5催化剂进行处理,制备微孔-介孔多级孔HZSM-5催化剂,研究了碱液浓度(0.2~0.6 mol/L)对制备多级孔催化剂及其多级孔催化剂对催化生物质热解制备芳烃的产率以及选择性的影响规律,同时采用比表面积和孔径分布仪、X射线衍射仪、X射线光电子能谱、扫描电镜、化学吸附仪、傅里叶红外光谱仪、热重分析对催化剂进行了表征,结果表明:碱处理后催化剂依然保持MFI结构,在脱除分子筛中非骨架硅的同时,产生介孔结构,随着预处理浓度的增加,介孔含量增加,晶内介孔的利用率以及分子筛的扩散性能增加,但使总酸量降低,同时,改性催化剂可以明显的提高木质素来源的生物质热解产物芳烃的产率(67.75%~82.81%)降低焦炭的生成(31.26%~28.06%),提高生物油中萘族产物(甲基萘以及二甲基萘)的选择性,使C10+以上芳烃含量增加,当采用0.5 mol/L的K2CO3处理时,单环芳烃质量分数最高为82.81%,而焦炭质量分数最低为28.06%。

       

      Abstract: Biomass catalytic pyrolysis vapor upgrading is an important way for converting biomass to high-value chemical products. Studies on pyrolysis behavior and products distribution of biomass are of great importance to the research on the interactions and catalytic conversion mechanism between model components of biomass and catalyst. At the same time, aromatic hydrocarbon compounds was the important chemical in nowadays, catalytic pyrolysis process produces a highly oxygenated bio-oil containing over 100 different compounds. The selectivity of fast pyrolysis can be greatly enhanced through the use of a catalyst, in particular with HZSM-5 zeolite which gives the highest selectivity toward mono-cyclic platform aromatics (such as benzene, toluene, xylene and ethyl benzene) essential to the chemical industry. Despite this high selectivity, a significant fraction of the freed-stock’s renewable carbon is lost to coke and char, two undesired byproducts. Coke formation has been attributed to the polymerization of small oxygenates on the external surface of the zeolite and to the formation of polyaromatic hydrocarbons through condensation reactions inside the micropores. So in order to improve selectivity toward desired products of aromatic and lower the formation of coke, the mesoporous HZSM-5 was synthesized by desilication method. In this paper, we used alkali treatment of commercial HZSM-5 zeolites using K2CO3 solutions to introduce mesopores into microporous system, and to investigate the effects of alkali concentration (0.2-0.6 mol/L) on aromatics yield and selectivity, The pyrolysis of experimental sample (pine, cellulose and lignin) was conducted in a fixed bed reactor with the conditions of pyrolysis temperature of 450 ℃, and catalytic temperature of 550 ℃, the ratio of biomass to catalyst of 1:2. Materials and products characteristics were investigated with various testing approaches, such as elements analysis, X-ray diffraction (XRD), surface area and pore size analyzer (BET), scanning electron microscope (SEM), Fourier infrared spectroscopy (FTIR), X-ray photoelectron spectrometer (XPS), temperature programmed desorption (NH3-TPD) and gas chromatography mass spectrograph (GC-MS) to study the effect of desilication on the structure, acidity, pore size and performance of aluminum-rich ZSM-5 as well the product distribution of pyrolysis bio-oil. The results showed that alkali treatment of HZSM-5 can remove the extra-framework Si species to enhance the diffusion property, and at the same time, creation the mesopores, and the pore diameter of mesopores increased with the increase of K2CO3 concentration however, the total acid amount decreased. Detailed characterization of the obtained zeolite catalysts indicated that mild desilication conditions significantly affect the elemental composition, crystallographic structure, microporosity, and distribution of aluminum atoms in framework and extra framework sites. The number of accessible Brønsted acid sites increased as a result of the enhanced mesoporosity. At the same time, the concentration of alkali solution, the corrosion degree, the degree of desilication and desilication, and the mesoporous degree increased, as such the hysteresis phenomenon became more and more obvious. Moreover, the hierarchical HZSM-5 catalyst produced more aromatic hydrocarbons and less coke formation in CFP of lignin and lignocelluloses’ biomass that contained the lignin component than that of the control HZSM-5, which effectively improved the selectivity for naphthalene family products (methylnaphthalene and 2-methylnaphthalene) in the bio-oil and decreased the content of aromatic hydrocarbons larger than C10. The highest aromatic yield (82.81%) and lowest coke yield (28.06%) were obtained in CFP of pine wood with mildly desilicated zeolite treated with 0.5mol/L K2CO3 solution.

       

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