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Catalytic Cracking of Heavy Oil with Iron Oxide-based Catalysts Using Hydrogen and Oxygen Species from Steam 利用蒸汽中的氢和氧,用氧化铁基催化剂催化裂化重油
Pub Date : 2015-09-01 DOI: 10.1627/jpi.58.329
E. Fumoto, Y. Sugimoto, Shinya Sato, T. Takanohashi
Upgrading of heavy oil is an important process in the petroleum industry to produce light oil for transportation fuels. The conventional processes of treating heavy oil, such as petroleum residual oil, include thermal cracking, residue fluidized catalytic cracking (RFCC), and hydrocracking1). Gas, liquid, and coke are produced by the thermal cracking of heavy oil in a coking process. Large amounts of light oil are generated at high temperature with long residence time, but the coke yield increases. The process requires hydrogenation of light oil to stabilize the product through the addition of hydrogen to the double bonds of the components. Hydrocracking is useful for producing stabilized light oil with low coke yield, but the use of hydrogen gas is expensive. The use of water as a hydrogen source has good potential for upgrading heavy oil. Several studies have reported the use of steam and supercritical water2)~7). Supercritical water can dilute the heavy oil, although the process requires high pressure and high temperature2),3). Aquaconversion is a catalytic steam conversion process to upgrade heavy oil into transportable oil, in which hydrogen is transferred from steam to hydrocarbons4). Catalytic cracking of heavy oil was achieved with iron oxide-based catalyst using steam5)~7). Oxidative decomposition of heavy oil occurred over the iron oxide-based catalysts containing zirconia and alumina to produce light oil. After the lattice oxygen of iron oxide reacted with the heavy oil, the oxygen species derived from steam were incorporated into the iron oxide lattice and reacted with the heavy oil. Zirconia promoted the generation of oxygen species from steam, and alumina suppressed the phase change of iron oxide. Generation of oxygen species from steam occurs simultaneously with generation of hydrogen species. One previous study briefly reported that hydrogen species could be incorporated into light oil7). The present study further investigated the transfer of hydrogen species from steam to product using a model compound and petroleum residual oil, and examined the effect of the flow rate ratio of steam to feedstock, as well as the effect of the zirconia content of the catalyst on hydrogen transfer. 329 Journal of the Japan Petroleum Institute, 58, (5), 329-335 (2015)
重油提质是石油工业生产运输用轻质油的重要环节。处理重油(如石油渣油)的常规工艺包括热裂化、渣油流化催化裂化(RFCC)和加氢裂化。在焦化过程中,重油的热裂解会产生气体、液体和焦炭。高温下产生大量轻质油,停留时间长,但焦炭收率提高。该工艺需要对轻质油进行加氢,通过在组分的双键上加氢来稳定产品。加氢裂化是生产低焦炭收率的稳定轻质油的有效方法,但使用氢气的成本较高。利用水作为氢源对稠油进行提质具有良好的潜力。一些研究报道了蒸汽和超临界水的使用。超临界水可以稀释重油,尽管这一过程需要高压和高温。水转化是一种将重油转化为可运输油的催化蒸汽转化过程,其中氢从蒸汽转化为碳氢化合物。以蒸汽为催化剂,采用氧化铁基催化剂实现了重油的催化裂化。在含氧化锆和氧化铝的氧化铁基催化剂上进行重油氧化分解制备轻质油。氧化铁的晶格氧与重油反应后,蒸汽衍生的氧加入到氧化铁晶格中与重油反应。氧化锆促进水蒸气生成氧气,氧化铝抑制氧化铁的相变。蒸汽产生的氧与产生的氢同时发生。先前的一项研究简要地报道了氢可以被掺入轻油中。本研究利用模型化合物和石油渣油进一步研究了氢从蒸汽到产品的转移,考察了蒸汽与原料流量比的影响,以及催化剂中氧化锆含量对氢转移的影响。[29]日本石油学院学报,58,(5),329-335 (2015)
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引用次数: 9
Desulfurization of Heavy Oil with Iron Oxide-based Catalysts Using Steam 氧化铁基催化剂蒸汽脱硫重油研究
Pub Date : 2015-09-01 DOI: 10.1627/jpi.58.336
E. Fumoto, Shinya Sato, T. Takanohashi
Petroleum refineries utilize thermal cracking, catalytic cracking and hydrogenation processes to produce high quality oil products. Hydrodesulfurization is one of the most important methods to remove sulfur from petroleum fractions. Heavy oil contains various types of sulfur compound. The structure of the sulfur compounds affects the ease of sulfur removal1). Acyclic sulfur compounds including thiols and disulfides can be easily removed. In contrast, cyclic sulfur compounds containing a thiophene ring have lower reactivity, which decreases with a higher number of aromatic rings. The ease of sulfur removal follows the order: acyclic sulfur compounds>thiophene>benzothiophene> dibenzothiophene (DBT). The cost of sulfur removal in heavy oil upgrading may be reduced by the use of water as an alternative hydrogen source. Several studies have reported desulfurization of heavy oil using water2)~5). Benzothiophene and DBT were decomposed by hydrothermal reaction with alkali2). Upgrading of oil sand bitumen using supercritical water showed similar trends in sulfur content as upgrading in high-pressure nitrogen3), but addition of MoS2 catalysts improved the sulfur removal from Arabian Heavy crude oil in supercritical water4). Hematite nanoparticles were catalytically active to desulfurize thiophene in aquathermolysis5). We previously reported that catalytic cracking of atmospheric residual oil (AR) with iron oxide-based catalysts containing zirconia and alumina produced light oil using the oxygen and hydrogen species derived from steam6),7). The oxygen species were incorporated from steam into the iron oxide lattice, and reacted with heavy hydrocarbons. The oxygen species were transferred from steam to carbon dioxide and a small amount of oxygen-containing compounds6). This reaction produced the hydrogen species from steam. Some of the hydrogen species were added to product hydrocarbons, suppressing alkene generation6). The present study investigated desulfurization of heavy oil with iron oxide-based catalyst using hydrogen and oxygen species derived from steam, and examined desulfurization of AR and reactivity of cyclic sulfur compounds using DBT as a model compound.
炼油厂利用热裂化、催化裂化和加氢工艺生产高质量的石油产品。加氢脱硫是石油馏分中硫的重要脱除方法之一。重油含有多种含硫化合物。含硫化合物的结构影响硫的去除难易程度。包括硫醇和二硫化物在内的无环硫化合物可以很容易地去除。相反,含噻吩环的环硫化合物的反应活性较低,随着芳香环数量的增加而降低。硫的去除难易程度依次为:无环硫化合物>噻吩>苯并噻吩>二苯并噻吩(DBT)。使用水作为替代氢源可以降低重油升级过程中硫的去除成本。一些研究报道了用水对重油进行脱硫。苯并噻吩和DBT经碱水热反应分解。超临界水提质油砂沥青的硫含量变化趋势与高压氮提质相似(3),但二硫化钼催化剂的加入提高了超临界水中阿拉伯重质原油的脱硫效果(4)。纳米赤铁矿在水热裂解中对噻吩的脱硫具有催化活性。我们之前报道过,用含氧化锆和氧化铝的氧化铁基催化剂催化裂解常压渣油(AR),利用蒸汽衍生的氧和氢生成轻质油(6),7)。氧从蒸汽中加入到氧化铁晶格中,并与重碳氢化合物发生反应。氧气从蒸汽中转移到二氧化碳和少量含氧化合物中。这个反应从蒸汽中产生氢。一些氢被加入到产物烃中,抑制了烯烃的生成。本研究利用蒸汽衍生的氢和氧,研究了氧化铁基催化剂对重油的脱硫作用,并以DBT为模型化合物考察了AR的脱硫作用和环硫化合物的反应性。
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引用次数: 7
Improvement of Silica–alumina Supports for Diesel Oxidation Catalysts through Control of Both Composition and Pore Structure 通过控制组成和孔结构来改善柴油氧化催化剂的二氧化硅-氧化铝载体
Pub Date : 2015-05-01 DOI: 10.1627/jpi.58.185
J. Uchisawa, A. Obuchi, T. Tango, Tatsuro Murakami
Precious metals, primarily Pt and Pd, are indispensable as active components in industrial catalysts intended for practical applications. In particular, they are very commonly utilized in diesel exhaust gas purification catalysts, and hence an increase in the demand for these precious metals is expected as the number of vehicles in use worldwide continues to grow and as emission controls in various countries become increasingly stringent1). A typical diesel after-treatment system is shown in Fig. 1, in which the diesel oxidation catalyst (DOC) is situated on the inlet side of a series of units within the system. The DOC is necessary for the removal of the soluble organic fraction in the particulate matter (PM), as well as the removal of CO and hydrocarbons (HCs) present in the gas phase. Furthermore, to allow the regeneration of a diesel particulate filter (DPF) placed downstream of the DOC by burn-out of the filtered PM, DOCs with high catalytic activity for fuel oxidation are required so as to allow for active heating. This is performed by the catalytic combustion of fuel in the DOC, supplied by retarded combustion in the engine, by post injection into the engine cylinders, or by direct injection into the exhaust pipe. Additionally, the DOC works to oxidize NO to NO2 to promote the regeneration of the DPF through oxidation of the PM and the selective catalytic reduction of NOx using NH3 as a reductant2). In this catalytic system, precious metals are primarily employed in the DOC and DPF, in particular the DOC which may contain large quantities of such metals. Therefore, to reduce the amounts of such metals required in diesel exhaust systems, it is necessary to improve the efficiency with which they function in the DOC. A DOC is composed primarily of a support material such as Al2O3 and an active component such as Pt or Pd, the latter being dispersed as nano-scale particles over the interior pore surfaces of the former. In this study, we focused our attention on the support material. To date, extensive research has been carried out to improve DOC support materials with regard to their compositions and pore structures. In terms of the composition, the addition of secondary components such as Fe3), Mn4), W5), and Si6),7) to Al2O3 has been investigated as a means of improving thermal durability and controlling the acidity/basicity balance. With regard to pore structure, multidimensional-structured Al2O3 materials possessing pores of different size scales, such as micro-meso8),9), meso-macro10),11), and micro-meso9 Journal of the Japan Petroleum Institute, 58, (1), 9-19 (2015)
贵金属,主要是铂和钯,是工业催化剂中不可缺少的活性成分。特别是,它们非常普遍地用于柴油废气净化催化剂中,因此,随着世界范围内使用的车辆数量继续增长,以及各国对排放的控制越来越严格,预计对这些贵金属的需求将会增加。典型的柴油后处理系统如图1所示,其中柴油氧化催化剂(DOC)位于系统内一系列单元的入口侧。DOC对于去除颗粒物质(PM)中的可溶性有机组分以及去除气相中的CO和碳氢化合物(hc)是必需的。此外,为了使放置在DOC下游的柴油微粒过滤器(DPF)通过燃烧过滤后的PM进行再生,需要具有高催化氧化活性的DOC,以便进行主动加热。这是通过燃料在DOC中的催化燃烧来实现的,由发动机中的延迟燃烧提供,通过后喷射到发动机气缸中,或直接喷射到排气管中。此外,DOC通过氧化PM和使用NH3作为还原剂选择性催化还原NOx,将NO氧化为NO2,促进DPF的再生2)。在该催化体系中,贵金属主要用于DOC和DPF,特别是DOC中可能含有大量贵金属。因此,为了减少柴油排气系统中所需的这些金属的数量,有必要提高它们在DOC中的作用效率。DOC主要由支撑材料(如Al2O3)和活性成分(如Pt或Pd)组成,后者以纳米级颗粒的形式分散在前者的内部孔表面。在本研究中,我们将重点放在支撑材料上。迄今为止,人们对DOC支撑材料的组成和孔隙结构进行了广泛的研究。在组成方面,研究了在Al2O3中添加Fe3、Mn4、W5、Si6、si7等二次组分,以提高其耐热性和控制酸碱平衡。孔隙结构方面,具有不同孔径尺度的微孔(micro-meso8)、9)、微孔(meso-macro10)、11)、微孔(micro-meso9)等多维结构Al2O3材料。石油学报,58,(1),9-19 (2015)
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引用次数: 5
Effect of Low-concentration Furfural on Sulfur Amino Acid Biosynthesis in Saccharomyces cerevisiae 低浓度糠醛对酿酒酵母硫氨基酸生物合成的影响
Pub Date : 2015-05-01 DOI: 10.1627/jpi.58.165
M. Kanna, Y. Matsumura
Ethanol produced from lignocellulosic biomass (bioethanol) is a promising alternative fuel to gasoline. Production of bioethanol from lignocellulose requires various steps, including pretreatment, enzymatic hydrolysis and fermentation. However, many fermentation inhibitors, including furfural and 5-hydroxymethyl furfural, are generated during the hydrothermal pretreatment of lignocellulose. Recent studies have identified techniques for removing fermentation inhibitors from lignocellulosic hydrolysate. The present study focused on the effect of low-concentration furfural on ethanol production by Saccharomyces cerevisiae . Specifically, gene expression of furfural-inducible genes was analyzed using a S. cerevisiae DNA microarray. The expression of most sulfur amino acid biosynthesis genes increased in response to furfural. To determine whether furfural induces the depletion of sulfur-containing amino acids, the effect of the addition of methionine on yeast growth was investigated. However, exogenous addition of methionine did not compensate for the inhibitory effect. The findings of this study show that furfural affects amino acid synthesis, even at low concentrations, and may be important in the development of high-efficiency processes for large-scale bioethanol production from lignocellulosic biomass.
由木质纤维素生物质(生物乙醇)生产的乙醇是一种很有前途的汽油替代燃料。从木质纤维素生产生物乙醇需要多种步骤,包括预处理、酶解和发酵。然而,在木质纤维素的水热预处理过程中会产生许多发酵抑制剂,包括糠醛和5-羟甲基糠醛。最近的研究已经确定了从木质纤维素水解物中去除发酵抑制剂的技术。本文主要研究了低浓度糠醛对酿酒酵母生产乙醇的影响。具体来说,使用酿酒酵母DNA芯片分析了糠醛诱导基因的基因表达。多数含硫氨基酸生物合成基因的表达随糠醛的加入而增加。为了确定糠醛是否诱导含硫氨基酸的耗竭,研究了添加蛋氨酸对酵母生长的影响。然而,外源添加蛋氨酸并不能弥补抑制作用。这项研究的结果表明,即使在低浓度下,糠醛也会影响氨基酸的合成,并且可能在开发从木质纤维素生物质大规模生产生物乙醇的高效工艺中发挥重要作用。
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引用次数: 4
Development of Highly Active and Durable Platinum Core-shell Catalysts for Polymer Electrolyte Fuel Cells 聚合物电解质燃料电池用高效耐用铂核壳催化剂的研制
Pub Date : 2015-01-01 DOI: 10.1627/jpi.58.55
M. Inaba, H. Daimon
They are clean and highly efficient energy sources without emission of global warming CO2 gas. PEFCs are operated at low temperatures in the range of room temperature to 80 °C, and are thereby suitable for electric power sources in small-scale stationary co-generation systems and in electric motor-driven vehicles (so-called the fuel cell vehicles (FCVs)). In Japan, 1 kW-class stationary co-generation systems (called ENE-FARM) have been already commercialized since 2009, and quite recently Japanese motor companies announced that they are planning to commercialize FCVs in FY2014. In PEFCs, platinum is used as catalysts for both the anode and the cathode. Though hydrogen oxidation reaction (HOR) at the anode is facile, oxygen reduction reaction (ORR) at the cathode is a slow reaction. Therefore a large amount of Pt is currently used at the cathode (typically, 0.5 mg cm2). The natural resource of Pt is extremely small (probable reserve: 70,000 tons) and the price of Pt is very expensive (>5000 Yen g1 in Apr. 2014). If we continue to use Pt catalyst at the present level, the scarcity of Pt as well as its high cost will disturb the world-wide spread of FCVs in the near future. Therefore a drastic reduction of Pt usage at the cathode by improving the ORR activity of the Pt catalyst is one of the most important issues in the development of FCVs1). There have been several methods to improve the ORR activity of Pt catalysts, which include Pt_M (M: 3d transition metals such as Co, Ni, Cu, etc.) alloy catalysts2)~5) and core-shell structured catalysts in which Pt monolayer (ML) is formed on non-Pt metal core nanoparticles6)~8). We have so far developed PtML core-shell catalysts using Au and Pd core materials in a research project supported by New Energy and Industrial Technology Development Organization (NEDO), Japan with 11 academic and industrial institutions since FY20089)~13). Here we first review the concept and characteristics of PtML core-shell catalysts. We overview a novel preparation method of PtML coreshell catalysts that is suitable for mass production developed by us, and the results on the activity and durability of the resulting core-shell catalysts. On the basis of these results, the potentials and difficulties of the 55 Journal of the Japan Petroleum Institute, 58, (2), 55-63 (2015)
它们是清洁高效的能源,不会排放导致全球变暖的二氧化碳气体。pefc在室温至80℃的低温下运行,因此适用于小型固定式热电联产系统和电动汽车(所谓的燃料电池汽车(fcv))中的电源。在日本,自2009年以来,1千瓦级的固定式热电联产系统(称为ENE-FARM)已经商业化,最近日本汽车公司宣布他们计划在2014财年将燃料电池汽车商业化。在pefc中,铂被用作阳极和阴极的催化剂。阳极上的氢氧化反应(HOR)很容易,而阴极上的氧还原反应(ORR)则是一个缓慢的反应。因此,目前阴极上使用了大量的铂(通常为0.5 mg cm2)。Pt的自然资源量极小(可能储量7万吨),价格非常昂贵(2014年4月>5000日元)。如果我们继续以目前的水平使用Pt催化剂,Pt的稀缺性和高昂的成本将在不久的将来扰乱fcv在世界范围内的推广。因此,通过提高Pt催化剂的ORR活性来大幅减少阴极Pt的使用是FCVs1发展中最重要的问题之一。目前已有几种提高Pt催化剂ORR活性的方法,包括Pt_M (M:三维过渡金属如Co、Ni、Cu等)合金催化剂(s2)~5)和在非Pt金属核纳米颗粒上形成Pt单层(ML)的核壳结构催化剂(6)~8)。在日本新能源产业技术开发组织(NEDO)资助的研究项目中,我们与11个学术和工业机构合作,自2008财年以来,开发了以Au和Pd为核心材料的PtML核壳催化剂。本文首先介绍了PtML核壳催化剂的概念和特点。综述了一种适合量产的新型PtML核壳催化剂的制备方法,并对制备的核壳催化剂的活性和耐久性进行了研究。在此基础上,分析了55年油气开发的潜力和难点。日本石油学院学报,58,(2),55-63 (2015)
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引用次数: 11
Supra-Molecular Asphaltene Relaxation Technology 超分子沥青质弛豫技术
Pub Date : 2013-03-01 DOI: 10.1627/jpi.56.61
T. Takanohashi, Shinya Sato, R. Tanaka
The asphaltene components of heavy oil can become serious problems during fractionation, particularly the toluene-soluble and pentane-insoluble fractions. Asphaltenes are composed of mixtures of thousands of different molecules with complicated chemical structures that form three-dimensionally entangled macromolecular structures. In general, a “supra-molecule” refers to a molecular assembly in which each molecule cooperatively interacts with the others through different types of noncovalent bonds. The resulting supramolecule can express several complicated and specific properties. Asphaltene may form such a supramolecular structure, because asphaltene molecules interact cooperatively with each other through interactions related to poly-aromatic rings such as aromaticaromatic and charge-transfer ones. Every asphaltene supra-molecule exhibits distinct, characteristic properties and different reactivities. The chemical reactions of each individual molecule determine the reactivity of the entire assembly. Therefore, an understanding of these molecular and supra-molecular structures is essential for developing strategies to control their reactivity. Although structural analyses have been performed on asphaltenes, the true molecular weight of asphaltenes has not yet been determined. Vapor pressure osmometry (VPO) and size exclusion chromatography (SEC) 61 Journal of the Japan Petroleum Institute, 56, (2), 61-68 (2013)
重油的沥青质组分在分馏过程中会成为严重的问题,特别是甲苯溶性和戊烷不溶性馏分。沥青质是由数千种不同分子的混合物组成,这些分子具有复杂的化学结构,形成三维纠缠的大分子结构。一般来说,“超分子”指的是一个分子组合,其中每个分子通过不同类型的非共价键与其他分子合作相互作用。由此产生的超分子可以表现出几种复杂而特殊的性质。沥青质可能会形成这样的超分子结构,因为沥青质分子通过与芳香环和电荷转移环等多芳环相关的相互作用相互作用。每一种沥青质超分子都表现出独特的特性和不同的反应活性。每个分子的化学反应决定了整个组装体的反应性。因此,了解这些分子和超分子结构对于制定控制其反应性的策略至关重要。尽管对沥青质进行了结构分析,但沥青质的真正分子量尚未确定。蒸汽压渗透法(VPO)和粒径排除色谱法(SEC) [j] .日本石油学院学报,56,(2),61-68 (2013)
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引用次数: 3
Active Site Distribution of Nitrided CoMo/Al_2O_3 Catalyst during Hydrodesulfurization of Dibenzothiophene : A Non-parametric Study 氮化CoMo/Al_2O_3催化剂在二苯并噻吩加氢脱硫过程中活性位点分布的非参数研究
Pub Date : 2013-03-01 DOI: 10.1627/jpi.56.80
M. Nagai, Hiroyuki Tominaga, Shigetaka Kai
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引用次数: 1
Effect of Sulfation Using Sulfate Salt Impregnation Method on Acidity of Cobalt Oxide 硫酸盐浸渍法硫酸酸化对氧化钴酸度的影响
Pub Date : 2013-01-01 DOI: 10.1627/JPI.56.381
H. Matsuhashi, H. Taniguchi, Misako Hirai, Keita Yamamoto, Junpei Suzuki
Cobalt is one of the important components in hydrodesulfurization catalysts. The acidity of the support for the active elements is important to increase hydrodesulfurization activity1),2), but few studies have investigated the acid properties of simple cobalt oxides3),4). In contrast, Co ions have been incorporated into many sulfated zirconia and sulfated iron oxides5)~9) to increase catalytic activity as a promoter. The acidity of metal oxides can be increased by the addition of sulfate ion to an oxide surface followed by heat treatment at elevated temperatures10). The acid strength of the metal oxides was greatly increased by such sulfation. A representative example is sulfation of iron oxide, which resulted in a large increase in acidity. Several chemical properties of iron oxide resemble those of cobalt oxide. For example, Co3O4 and Fe3O4 are the more stable s tates of each oxide. Therefore, the acidity of cobalt oxide may be increased by introducing sulfate ions on the oxide surface and heat treatment at a higher temperature. CoO has a promotion effect on sulfated iron oxide9). This study investigated the preparation of sulfated cobalt oxide and the increase in surface acidity. In general, sulfation of zirconia is performed by soaking the metal oxide in dilute sulfuric acid in the equilibrium adsorption method. However, cobalt oxide dissolves in acidic water solution. Therefore, the equilibrium adsorption method cannot be applied to introduce sulfate ions onto the cobalt oxide surface. In this study, sulfate ions were introduced onto the cobalt oxide surface by impregnation of cobalt sulfate6),11). To evaluate the effectiveness of the sulfate salt impregnation method, four types of zirconium oxides were sulfated by the impregnation method. Catalytic activities of the prepared catalysts for pentane isomerization and ethanol dehydration were compared. The order of catalytic activities for several acid-catalyzed reactions and the properties of zirconia gels are known12). The effectiveness of the sulfate salt impregnation method was confirmed by comparing the order of activities in prepared sulfated zirconia samples with reported activities. The ethanol dehydration activity of prepared sulfated cobalt oxide was compared with that of proton-type zeolites and SiO2Al2O3 to estimate its acidity.
钴是加氢脱硫催化剂的重要成分之一。活性元素载体的酸性对提高加氢脱硫活性很重要(1),2),但对简单钴氧化物的酸性研究很少(3),4)。相反,Co离子作为促进剂被掺入许多硫酸氧化锆和硫酸氧化铁中以提高催化活性。在氧化物表面加入硫酸盐离子,然后在高温下进行热处理,可以增加金属氧化物的酸度。这种磺化作用大大提高了金属氧化物的酸强度。一个典型的例子是氧化铁的硫酸化,这导致酸度大大增加。氧化铁的一些化学性质与氧化钴相似。例如,Co3O4和Fe3O4是每种氧化物中更稳定的状态。因此,通过在氧化物表面引入硫酸盐离子和在较高温度下进行热处理,可以提高氧化钴的酸度。CoO对硫酸氧化铁有促进作用。研究了硫酸氧化钴的制备及其表面酸度的提高。一般来说,氧化锆的硫化是通过平衡吸附法将金属氧化物浸泡在稀硫酸中进行的。然而,氧化钴溶于酸性水溶液。因此,平衡吸附法不能将硫酸盐离子引入钴氧化物表面。在本研究中,通过浸渍硫酸钴将硫酸盐离子引入钴氧化物表面(6),11)。为了评价硫酸盐浸渍法的有效性,对四种氧化锆进行了浸渍法硫酸处理。比较了所制备的催化剂对戊烷异构化和乙醇脱水的催化活性。几种酸催化反应的催化活性顺序和氧化锆凝胶的性质都是已知的。通过将制备的硫酸氧化锆样品的活性顺序与报道的活性顺序进行比较,证实了硫酸盐浸渍法的有效性。将制备的硫酸钴氧化物与质子型沸石和SiO2Al2O3的乙醇脱水活性进行了比较,以估计其酸度。
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引用次数: 1
Synthesis of Nano-crystalline Zeolites and Applications to Zeolite Membranes 纳米晶沸石的合成及其在沸石膜中的应用
Pub Date : 2012-05-01 DOI: 10.1627/JPI.55.149
T. Tago, Y. Nakasaka, T. Masuda
Zeolites are crystalline aluminosilicate materials and possess intracrystalline pores and nanospaces of similar sizes to the molecules of the lighter hydrocarbons. Moreover, zeolites have strong acid sites on the nanopore surfaces within and on the external surfaces of the crystalline structure. These properties enable zeolites to be used as in reaction and separation processes, and these potential uses have led to the development of zeolite-based structured materials, such as zeolite films and membranes1)~3). Zeolite membranes combine the properties of zeolites with those of inorganic membranes, so are attractive materials for various applications, such as selective reaction membranes4),5) and separation membranes6)~9). ZSM-5 zeolite membranes were first prepared by Sano et al.10),11), and a great deal of subsequent research has focused on the use of zeolite membranes for reaction and separation. To prepare a zeolite membrane by hydrothermal synthesis, zeolite seed crystals are deposited on a porous support, then secondary growth of the zeolite occurs to form the zeolite membrane. The uniformity of the membrane affects the reaction/separation properties, so the seeding of the zeolite crystals and the secondary growth process must occur uniformly12)~16). Therefore, nano-sized zeolite crystals are expected to have good properties as seed crystals, because the smaller size allows for greater control of the seeding and growth processes. Mono-dispersed zeolite nanocrystals are expected to form uniform zeolite membranes. This review describes a method for preparing nanocrystalline zeolites in a solution consisting of a surfactant, an organic solvent, and water (called the emulsion method17)~21)), and a method based on the catalytic cracking of silane22) (called the CCS method) for the regioselective deactivation of acid sites using silane compounds with various organic substituents. An MFI zeolite (ZSM-5) membrane was applied to the reaction of methanol to olefins23),24), to investigate the effect of the regioselective deactivation of acid sites by the CCS method on the olefin yields. A hydrophilic silicalite-1 membrane25) was prepared using silicalite-1 nanocrystals, to examine the effect of the crystal size on the separation properties26),27).
沸石是晶体铝硅酸盐材料,具有与较轻的碳氢化合物分子相似大小的晶内孔和纳米空间。此外,沸石在晶体结构的内外表面的纳米孔表面上都有强酸位点。这些特性使沸石可以用于反应和分离过程,这些潜在的用途导致了沸石基结构材料的发展,如沸石薄膜和膜。沸石膜结合了沸石和无机膜的特性,是一种具有广泛应用前景的材料,如选择性反应膜、选择性反应膜和选择性分离膜。ZSM-5沸石膜最早是由Sano等人10),11)制备的,随后大量的研究集中在利用沸石膜进行反应和分离。水热法制备沸石膜,将沸石种子晶体沉积在多孔载体上,沸石二次生长形成沸石膜。膜的均匀性影响反应/分离性能,因此沸石晶体的播种和二次生长过程必须均匀进行[12]~[16]。因此,纳米级沸石晶体有望具有良好的种子晶体性能,因为较小的尺寸可以更好地控制种子和生长过程。单分散的沸石纳米晶有望形成均匀的沸石膜。本文介绍了在由表面活性剂、有机溶剂和水组成的溶液中制备纳米晶沸石的方法(称为乳液法)和基于硅烷催化裂化的方法(称为CCS法),该方法使用具有各种有机取代基的硅烷化合物对酸位进行区域选择性失活。将MFI沸石(ZSM-5)膜应用于甲醇制烯烃反应23),24),考察了CCS法对酸位区域选择性失活对烯烃收率的影响。用硅烷-1纳米晶体制备了亲水硅烷-1膜(25),考察了晶体尺寸对分离性能的影响(26),27)。
{"title":"Synthesis of Nano-crystalline Zeolites and Applications to Zeolite Membranes","authors":"T. Tago, Y. Nakasaka, T. Masuda","doi":"10.1627/JPI.55.149","DOIUrl":"https://doi.org/10.1627/JPI.55.149","url":null,"abstract":"Zeolites are crystalline aluminosilicate materials and possess intracrystalline pores and nanospaces of similar sizes to the molecules of the lighter hydrocarbons. Moreover, zeolites have strong acid sites on the nanopore surfaces within and on the external surfaces of the crystalline structure. These properties enable zeolites to be used as in reaction and separation processes, and these potential uses have led to the development of zeolite-based structured materials, such as zeolite films and membranes1)~3). Zeolite membranes combine the properties of zeolites with those of inorganic membranes, so are attractive materials for various applications, such as selective reaction membranes4),5) and separation membranes6)~9). ZSM-5 zeolite membranes were first prepared by Sano et al.10),11), and a great deal of subsequent research has focused on the use of zeolite membranes for reaction and separation. To prepare a zeolite membrane by hydrothermal synthesis, zeolite seed crystals are deposited on a porous support, then secondary growth of the zeolite occurs to form the zeolite membrane. The uniformity of the membrane affects the reaction/separation properties, so the seeding of the zeolite crystals and the secondary growth process must occur uniformly12)~16). Therefore, nano-sized zeolite crystals are expected to have good properties as seed crystals, because the smaller size allows for greater control of the seeding and growth processes. Mono-dispersed zeolite nanocrystals are expected to form uniform zeolite membranes. This review describes a method for preparing nanocrystalline zeolites in a solution consisting of a surfactant, an organic solvent, and water (called the emulsion method17)~21)), and a method based on the catalytic cracking of silane22) (called the CCS method) for the regioselective deactivation of acid sites using silane compounds with various organic substituents. An MFI zeolite (ZSM-5) membrane was applied to the reaction of methanol to olefins23),24), to investigate the effect of the regioselective deactivation of acid sites by the CCS method on the olefin yields. A hydrophilic silicalite-1 membrane25) was prepared using silicalite-1 nanocrystals, to examine the effect of the crystal size on the separation properties26),27).","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2012-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76492520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 5
Dealumination of USY Zeolites by Thermal Treatment (Part 3) Effect of Exchangeable Sodium Ion.:Effect of Exchangeable Sodium Ion USY沸石的热处理脱铝(三)交换性钠离子的作用。:交换性钠离子的作用
Pub Date : 2002-01-01 DOI: 10.1627/JPI.45.45
K. Hagiwara, Takeshi Ebihara, Hidenori Yamada, Tadashi Shibuya, Junko Naito, S. Ozawa, S. Nakata
USYゼオライトを熱処理したときの脱アルミニウム挙動において, イオン交換性Naと雰囲気中のH2Oとの相乗効果をXRD, 固体NMRを用いて考察した。物理吸着水が除去されたUSYゼオライトを乾燥空気中で熱処理したところ, 交換性Naイオンの含有量の増加に伴い脱アルミニウムが進行しにくくなった。さらに, Na含有量の少ない試料では, 熱処理によりSi-OH基が増加した。一方, 100%スチーム雰囲気中でUSYゼオライトを熱処理したところ, Na含有量の増加に伴い結晶性だけでなくNMRでみられる短距離秩序も著しく低下した。このことから, 交換性Naイオンと雰囲気中のH2Oとの相乗効果により, 脱アルミニウムが促進されることが示された。ただし, 熱処理後に残存した結晶領域では, Na含有量が増加すると脱アルミニウムが進行しにくくなった。これは, 一次粒子内でのH2Oの拡散性に起因しているものと推測される。さらに, 熱処理後にいくつかの試料において, 通常-95ppm付近に観測されるSi(2Al)に帰属されるピークが約-92ppmに現れたのは, 脱アルミニウムに伴う骨格構造のゆがみによるものと考えられる。
利用XRD和固体NMR考察了热处理USY沸石时的脱铝行为中离子交换性Na和气氛中的H2O的协同效果。将去除物理吸附水的USY沸石在干燥空气中进行热处理后发现,随着交换性Na离子含量的增加,脱铝现象难以进行。此外,Na含量低的样品通过热处理增加了Si-OH基团。另一方面,在100%蒸汽氛围中对USY沸石进行热处理后发现,随着Na含量的增加,不仅结晶性下降,NMR所见的短距离秩序也显著下降。由此可见,通过交换性Na离子与气氛中的H2O的协同效应,可以促进脱铝。不过,热处理后残留的结晶区域中,随着Na含量的增加,脱铝现象就难以进行。据推测,这是因为H2O在初级粒子中的扩散性。另外,在热处理后的一些样品中,通常在-95ppm附近观测到的归属于Si(2al)的峰值约为-92ppm。被认为是由于脱铝引起的骨骼结构的变形。
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引用次数: 3
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Bulletin of The Japan Petroleum Institute
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