加氢脱硫催化剂载体的研究进展

综述了加氢脱硫催化剂载体的研究现状及其发展趋势,分别从单组分载体、复合氧化物载体、分子筛和改性载体4个方面论述了加氢脱硫催化剂载体各自的优缺点。单组分载体重点介绍了A12O3、TiO2、炭载体;复合氧化物载体主要对铝基、钛基二元复合氧化物以及三元复合氧化物载体进行了综述;并且对以MCM-41、SBA-15和KIT为代表的介孔分子筛做了介绍;还描述了近年来以改性MCM-41、SBA-15、活性炭为主要研究对象的改性的分子筛。最后指出改性载体尤其是改性分子筛将是未来研究的焦点。     

介孔分子筛载体在油品深度加氢脱硫中的应用研究进展

介孔分子筛材料以其独特的孔道结构和孔径分布、高的比表面积及较好的热稳定性和水热稳定性等特点,近年来被广泛地用作油品深度加氢脱硫催化剂载体.本文系统综述了近年来MCM、HMS、SBA、KIT等系列介孔分子筛载体应用于油品深度加氢脱硫(HDS)的国内外研究现状.重点讨论了金属、氧化物、酸、磷、与其它载体复合等载体改性方式对...     

H2O2/固体催化剂氧化脱硫体系中载体的研究进展

从研究应用角度出发, 综述了近年来H₂O₂/固体催化剂氧化脱硫体系中载体的研究进展和发展趋势, 分别从单一氧化物载体、复合氧化物载体、活性炭载体、分子筛及复合分子筛载体4个方面论述了氧化脱硫催化剂载体各自的优缺点及应用成果。单一氧化物载体重点介绍了Al₂O₃、TiO₂、SiO₂、ZrO₂;复合氧化物载体主要对二元复合氧化物进行了综述;重点介绍了以ZSM-5、SBA-15、MCM-41、HMS为代表的分子筛及复合分子筛载体。最后将不同类型载体的结构特点、反应优缺点等进行了归纳总结, 展望了氧化脱硫催化剂载体未来的研究方向, 并提出分子筛及复合分子筛载体将是氧化脱硫催化剂载体研究的焦点。     

石油加氢脱硫催化剂载体的研究

介绍了目前加氢脱硫催化剂载体的种类和研究现状,包括氧化物载体、介孔分子筛载体、活性炭载体、酸碱载体等。分析了不同载体所具有的的优缺点,并展望了未来载体的研究方向。     

多级孔ZSM-5分子筛的加氢脱硫性能

以四头聚季铵盐为模板合成的多级孔ZSM-5分子筛为载体、Pd为金属组分制备新型介孔分子筛基Pd催化剂,考察其对4,6-二甲基二苯并噻吩的加氢脱硫活性,并与其他催化剂进行对比。结果表明,与常规ZSM-5分子筛基Pd催化剂和γ-Al2O3基Pd催化剂相比,以多级孔ZSM-5分子筛为载体制备的Pd催化剂表现出更高的加氢脱硫活性。该催化剂同时具有介孔和B酸中心,为4,6-二甲基二苯并噻吩的异构化和脱硫反应提供了更多的活性中心,使其能够发生甲基异构化反应,生成3,6-二甲基二苯并噻吩后进行氢解脱硫。     

复合氧化物在柴油加氢脱硫催化剂中的应用

加氢脱硫是石油炼制中的一个重要工艺过程,近年来,随着环境法规的日益严格和高硫原油加工量的增加,传统的加氢脱硫催化剂已经不能满足深度脱硫的要求,迫切需要开发新型深度加氢脱硫技术及催化剂,而复合氧化物载体能克服单一载体的缺陷,从而使制备的催化剂对芳烃的加氢和对二苯并噻吩及它的芳烃衍生物的转化具有较好的效果。综述了近年来复合氧化物载体在柴油加氢脱硫催化剂中的最新研究,重点介绍了含Al2O3、含TiO2和含ZrO2的复合氧化物载体的应用。     

碳基载体石油馏分加氢脱硫催化剂研究进展

总结了以活性炭、碳纳米管、介孔碳、石墨烯等碳基材料为载体的加氢脱硫催化剂的研究进展。与常规Al₂O₃基载体催化剂相比,碳基载体催化剂比表面积大,活性金属的分散性好,活性金属-碳表面间的相互作用弱,有利于形成高活性的Ⅱ类活性相。以二苯并噻吩及4,6-二甲基二苯并噻吩等含硫有机物为处理对象,碳基载体加氢脱硫催化剂总体上具有比Al₂O₃基载体催化剂更高的加氢脱硫催化活性。为满足碳基载体加氢脱硫催化剂的工业应用要求,需要降低制备成本,并针对催化体系的特点进行孔结构优化及表面改性,同时,还需要加强对碳基加氢催化剂加氢脱硫反应机理和动力学方面的研究,以促进催化剂与工艺技术的进步。     

复合氧化物在加氢脱硫催化剂中的应用

新的环境法规对车用燃料硫含量提出了严格的要求,传统加氢脱硫催化剂难以满足深度脱硫的需要。使用复合氧化物作为加氢催化剂载体,不仅能克服单一载体的缺陷,还能减弱活性金属与载体间相互作用,提高催化剂活性。综述了近年来复合氧化物(Al2O3-Ti O2和Al2O3-Zr O2)作为加氢脱硫催化剂载体的研究进展。     

高硫原油中硫化物的脱除工艺及脱硫剂

负载型过渡金属磷化物馏分油深度加氢脱硫催化剂制备方法属于新材料、石油炼制和石油化工技术领域。是采用一种新型的载体材料担载金属活性组分，并用一种新的活化方法合成表面金属磷化物，制备石油炼制工业中所用汽油、煤油、柴油、蜡油等馏分油深度加氢脱硫催化剂的方法，新型载体材料是指由中孔分子筛与多孔氧化物构成的复合载体，该方法制备出了高活性的加氢脱硫催化剂。有益效果是，可将石油馏分油中最难脱除的二苯并噻吩及其衍生物几乎全部转化。主要用于制造炼油加氢精制催化剂和石油化工生产中原料预精制加氢脱硫催化剂。     

Claus尾气加氢催化剂载体研究进展

阐述了近年来Claus尾气加氢脱硫催化剂载体的研究现状。主要介绍了Al₂O₃和TiO₂单组分载体及Al₂O₃-TiO₂复合载体。Al₂O₃载体具有比表面积大、机械性能好和容易成型的特点,应用较广,但低温加氢活性较差;TiO₂载体具有较高的低温加氢和有机硫水解活性,但比表面积较小,一般以复合载体形式使用;复合载体具有较好的低温加氢活性和抗水性能,但制备工艺复杂。介孔结构不仅可以增大载体的比表面积,同时有利于分子的扩散,具有更加优异的活性。活性组分在复合载体表面呈现不同的活性状态,从而改变反应条件。如何调控Al₂O₃载体的孔道结构,研究复合载体各组分之间的作用及对活性组分的影响是今后的发展方向。     

Disordered mesoporous KIT-1 as a support for hydrodesulfurization catalysts

MoO₃ and NiO were supported on KIT-1, a new disordered mesoporous molecular sieve. MoO₃ is homogeneously dispersed as a monolayer on the support, whereas NiO tends to form small crystallites in the mesoporous channels. KIT-1 supported MoO₃ and/or NiO catalysts exhibit higher catalytic activities for thiophene hydrodesulfurization than similar MCM-41 and NaY zeolite supported catalysts, because the three-dimensional disordered network of short channels in KIT-1 reduces the risk of blockage in the catalysts and facilitates the transport of reactant and product molecules. This revised version was published online in July 2006 with corrections to the Cover Date.     

分子筛催化剂的研究进展

综述了常用分子筛催化剂的研究现状及发展趋势,总结了烷烃异构化的反应特点,介绍了具有代表性的中孔分子筛类催化剂、硅磷铝分子筛类催化剂、杂多酸等催化剂的合成方法、条件及应用前景。着重介绍了各类催化剂的性能和最新研究状况,具体包括MCM-41、SAPO-11、沸石分子筛等,同时对目前面临研究问题进行概述。最后指出绿色、中低温合成烷烃异构化催化剂将是未来的研究热点。     

Study on the reactivity of ultrafine cerium–molybdenum oxide particles in the absence of molecular oxygen

The cracking, hydrocracking and hydrodesulfurization activities of gallium–aluminum mixed oxide catalysts, with fluoride added as promoter, were investigated. The addition of fluoride to the Ni–Mo catalyst supported on the mixed oxides leads to a significant enhancement in the cracking (no metals) and the hydrocracking (Ni–Mo) reactions of the catalysts, respectively. This enhancement of activity is attributed to the promotional effect of fluoride and the presence of gallium in the support, which leads to catalysts that are more resistant to deactivation. The results of the hydrodesulfurization experiments are not so encouraging. The activity of the catalysts was depressed by the addition of fluoride and with increasing gallium oxide content of the support. This revised version was published online in July 2006 with corrections to the Cover Date.     

负载型中孔分子筛催化剂的研究进展

本文对M41S中孔分子筛作载体的负载试剂的研究进展进行了综述，主要介绍了负载酸型、负载碱型和负载氧化型催化剂的研究现状，以及对其应用和发展前景作了总结和评述。     

La-Ni2P/SBA-15/堇青石整体式催化剂及加氢脱硫性能

以介孔分子筛SBA-15为载体,制备一系列不同La含量的La-Ni₂P/SBA-15催化剂前驱体,将La-Ni₂P/SBA-15前驱体涂覆在预处理的整体式载体堇青石上,在H2气氛程序升温还原,制备不同La含量的La-Ni2P/SBA-15/堇青石整体式催化剂。对合成的催化剂进行X射线衍射和N2吸附-脱附结构表征,并评价对二苯并噻吩的加氢脱硫活性。结果表明,Ni₂P存在于所有的La-Ni2P/SBA-15/堇青石整体式催化剂中,且随着La含量的增加,La-Ni2P/SBA-15/堇青石整体式催化剂的比表面积和孔体积均有一定程度的提高,催化活性也提高。对于Ni2P/SBA-15/堇青石整体式催化剂,在300 ℃和380 ℃时,二苯并噻吩加氢脱硫转化率仅为27.2%和91.3%;而1.5%La-Ni₂P/SBA-15/堇青石催化剂在300 ℃和380 ℃时,二苯并噻吩转化率分别为36.8%和96.3%,显示出较好的二苯并噻吩加氢脱硫活性。La-Ni₂P/SBA-15/堇青石整体式催化剂在对二苯并噻吩的加氢脱硫过程中,以直接脱硫和加氢脱硫两种脱硫方式同时进行,并且以直接脱硫为主。     

固体酸催化酯化反应的研究进展

对目前研究较多的 3类新型催化酯化固体酸催化剂 :固体超强酸、分子筛和杂多酸进行了概述。以SO2 -4/MxOy 型金属氧化物固体超强酸为例 ,介绍了其负载物的结构特点、催化机理及其在酯化反应中的应用 ;按分子筛的发展历程分别简介了沸石类分子筛、中孔分子筛和复合型分子筛 ;并对杂多酸及其化合物的结构组成和催化特点进行了简要评述。最后通过固体酸催化剂目前存在的问题 ,展望了其今后的研究方向和重点。     

Al-MCM-41 supported palladium catalyst for methane combustion: Effect of the preparation methodologies

This work aimed at elucidating the beneficial effect of plasma treatment on the catalytic performance of palladium (Pd) catalysts in methane combustion with the ordered mesoporous molecular sieve Al-MCM-41 as the model support. The plasma treated Pd/Al-MCM-41 catalyst exhibited a higher initial activity and a better stability in comparison with the untreated counterpart catalyst. To clarify the plasma effect, the catalysts were characterized by N₂ sorption analysis, X-ray diffraction (XRD), temperature-programmed desorption of ammonia (NH₃-TPD), pyridine adsorption-infrared spectroscopy (Py-IR), high resolution-transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (CH₄-TPR) experiments. The results obtained confirmed that palladium oxide (PdO) was the active phase. Plasma treatment enhanced the acidity of catalyst and improved the dispersion of PdO particles, which lead to a higher initial activity. The better stability for plasma treated Pd-based catalyst was proved to be closely related to the stronger interaction between palladium oxide and the molecular sieve support. In addition, the sintering of PdO particles over the plasma treated catalyst was not significant during the stability test. These findings may provide useful guidelines for further catalyst design for methane combustion.     

Effect of the preparation method on the structural stability and hydrodesulfurization activity of NiMo/SBA-15 catalysts

Defined hexagonal cylindrical pore structure SBA-15 material was synthesized as support for hydrotreating catalysts. The stability of the mesoporous material under acid and basic environments commonly used to prepare hydrotreating catalysts was investigated. The effects of the acid and basic treatments on the stability of SBA-15 and NiMo/SBA-15 catalysts were evidenced by different characterization techniques such as N₂ adsorption–desorption, X-ray diffraction (XRD), Raman Spectroscopy and high resolution transmission electron microscopy (HRTEM). Supported NiMo/SBA-15 catalysts prepared by pore volume co-impregnation in acidic, neutral and basic solutions of the Ni and Mo precursor salts were characterized to evaluate the textural and structural changes caused by the method of preparation. Characterization of the support after accelerated stability tests indicates large deterioration of the SBA-15 structural order at basic pH. The characterization results of oxide and sulfided catalysts indicate, for the catalysts prepared at high pH, an increasing presence of β–NiMoO₄ phase in the oxide catalysts, and a relatively lower population of MoS₂ in the sulfided catalysts. The activity of the different catalysts evaluated in the thiophene hydrodesulfurization reaction was higher for the catalysts prepared at low pH.