Galvanic deposition of silver on 80‐μm‐Cu‐fiber for gas‐phase oxidation of alcohols

Microstructured Ag‐based catalysts were developed by galvanically depositing Ag onto 80‐μm‐Cu‐fibers for the gas‐phase oxidation of alcohols. By taking advantages including large voidage, open porous structure and high heat/mass transfer, as‐made catalysts provided a nice combination of high activity/selectivity and enhanced heat transfer. The best catalyst was Ag‐10/80‐Cu‐fiber‐400 (Ag‐loading: 10 wt%; Cu‐fiber pretreated at 400 °C in air), being effective for oxidizing acyclic, benzylic and polynary alcohols. For benzyl alcohol, conversion of 94% was achieved with 99% selectivity to benzaldehyde at 300 °C using a high WHSV of 20 h^?1. Computational fluid dynamics (CFD) calculation and experimental result illustrated significant enhancement of the heat transfer. The temperature difference from reactor wall to central line was about 10–20 °C for the Ag‐10/80‐Cu‐fiber‐400, much lower than that of 100–110 °C for the Ag‐10‐Cu‐2/Al₂O₃ at equivalent conversion and selectivity. Synergistic interaction between Cu₂O and Ag was discussed, being assignable to the activity improvement. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1045–1053, 2014     

Catalytic combustion kinetics of isopropanol over novel porous microfibrous‐structured ZSM‐5 coating/PSSF catalyst

Porous thin‐sheet cobalt–copper–manganese mixed oxides modified microfibrous‐structured ZSM‐5 coating/PSSF catalysts were developed by the papermaking/sintering process, secondary growth process, and incipient wetness impregnating method. Paper‐like sintered stainless steel fibers (PSSF) support with sinter‐locked three‐dimensional networks was built by the papermaking/sintering process, and ZSM‐5 coatings were fabricated on the surface of stainless steel fibers by the secondary growth process. Catalytic combustion performances of isopropanol at different concentrations over the microfibrous‐structured Co–Cu–Mn (1:1:1)/ZSM‐5 coating/PSSF catalysts were measured to obtain kinetics data. The catalytic combustion kinetics was investigated using power–rate law model and Mars–Van Krevelen model. It was found that the Mars–Van Krevelen model provided fairly good fits to the kinetic data. The catalytic combustion reaction occurred by interaction between isopropanol molecule and oxygen‐rich centers of modified microfibrous‐structured ZSM‐5 coating/PSSF catalyst. The reaction activation energies for the reduction and oxidation steps are 60.3 and 57.19 kJ/mol, respectively. © 2014 American Institute of Chemical Engineers AIChE J, 61: 620–630, 2015     

Novel Co‐Mn‐O nanosheet catalyst for CO preferential oxidation toward hydrogen purification

Co‐Mn‐O composite oxide nanosheet catalyst was successfully prepared using a facile urea‐assisted one‐step hydrothermal method in the absence of organic or organic templating reagent. Co‐Mn‐O nanosheet catalyst was optimized by varying hydrothermal process parameters such as molar ratio of Co‐Mn to urea, hydrothermal temperature, and hydrothermal time. Various characterization techniques including scanning electron microscopy, X‐ray diffraction, nitrogen adsorption, X‐ray photoelectron spectroscopy, Raman spectroscopy, and H₂ temperature‐programmed reduction were used to reveal the relationship between catalyst nature and catalytic performance in CO preferential oxidation (CO PROX) in excess H₂. The developed Co‐Mn‐O nanosheet catalyst have demonstrated much superior catalytic performance to Co‐Mn‐O nanoparticle, particularly in the low temperature range, and 100% CO conversion over the developed Co‐Mn‐O nanosheet can be achieved in temperature range of 50 to 150°C at 10,000 mL g^?1 h^?1 of gas hourly space velocity in the standard feed. Furthermore, the almost complete CO removal over Co‐Mn‐O nanosheet at 125°C of low temperature with 94.9% selectivity can be achieved even in the simulated reformed gas. The excellent catalytic performance is ascribed to nanosheet morphology, more surface Co³⁺, smaller average crystallite size, higher reducibility, and strong Co‐Mn interaction. Catalytic stability investigation indicates the developed nanostructured catalyst exhibits high catalytic stability for CO PROX reaction in simulated gas. The developed Co‐Mn‐O nanosheet catalyst can be a potential candidate for catalytic elimination of trace CO from H₂‐rich gas for Proton exchange membrane fuel cell applications. © 2014 American Institute of Chemical Engineers AIChE J, 61: 239–252, 2015     

Comparison of gas‐ and liquid‐phase polymerization of propylene with heterogeneous metallocene catalyst

Sorption measurements are executed to study the sorption behavior of propylene in a semicrystalline polymer. Decreasing values for the Flory–Huggins interaction parameter with increasing temperature are obtained. Large deviations are found, especially at higher temperatures, compared to data from the literature. Propylene is polymerized in liquid and gaseous propylenes with Me₂Si[Ind]₂ZrCl₂/MAO/SiO₂ as the metallocene catalyst. Lower relative reaction rates are found in the gas phase compared to the experiments in the liquid phase. The activation energies from the experiments in both phases are on the same order of magnitude. However, the literature versus experimental sorption data has a large effect on the determined kinetic parameters. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1193–1206, 2001     

Multizone circulating reactor modeling for gas‐phase polymerization. I. Reactor modeling

A new gas‐phase technology for polyolefin production is being developed to be commercially available for large‐scale production between 2004 and 2005. This new technology uses a multilane circulating reactor, which consists of two interrelated zones where two distinct and different fluodynamic regimes are realized, between which the polymer particles are kept in continuous circulation. This article presents a mathematical model for the multilane circulating reactor presenting the typical behavior of the reactor operation and a parameter sensibility analysis. Simulations were conducted for polyethylene production. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1042–1052, 2004     

Polyethylene nanocomposites by gas‐phase polymerization of ethylene in the presence of a nanosilica‐supported zirconocene catalyst system

BACKGROUND: Much of the current research related to the development of in situ nanocomposites of olefins by polymerizing them with metallocenes in the presence of surface‐treated fillers is carried out in the slurry phase. In slurry‐phase methods a large amount of solvent is required and there is always a need of purification of the final product due to the possibility of traces of solvents present in the product. To overcome these drawbacks, to perform solvent‐free metallocene‐catalysed polymerizations with in situ incorporation of inorganic nanoparticles, we have used a gas‐phase polymerization technique as this does not require solvents and also utilizes monomer feed stocks efficiently. RESULTS: The catalyst used for the synthesis of in situ polyethylene nanocomposites by gas‐phase polymerization was nanosilica‐supported zirconocene. The fillers used were Cloisite‐20A, kaolin and nanosilica. Three different in situ polyethylene nanocomposites, i.e. Cloisite‐20A‐filled polyethylene (CFPE), kaolin‐filled polyethylene (KFPE) and nanosilica‐filled polyethylene (SFPE), were prepared by gas‐phase polymerization. The nanocomposites were obtained in the form of fine powder. The polyethylene content in the developed nanocomposites is in the orthorhombic crystalline phase. Using our approach, it is observed that the nanofillers are completely encapsulated by a thin layer of polyethylene. Significantly higher molecular weight polyethylene was formed in the case of KFPE in comparison to CFPE and SFPE. The thermal decomposition temperature, melting temperature and enthalpy are also observed to be higher for KFPE. CONCLUSIONS: The gas‐phase polymerization technique has been successfully carried out for the synthesis of in situ polyethylene nanocomposites. Copyright © 2007 Society of Chemical Industry     

NMR imaging of low pressure,gas‐phase transport in packed beds using hyperpolarized xenon‐129

Gas‐phase magnetic resonance imaging (MRI) has been used to investigate heterogeneity in mass transport in a packed bed of commercial, alumina, catalyst supports. Hyperpolarized ¹²⁹Xe MRI enables study of transient diffusion for microscopic porous systems using xenon chemical shift to selectively image gas within the pores, and, thence, permits study of low‐density, gas‐phase mass‐transport, such that diffusion can be studied in the Knudsen regime, and not just the molecular regime, which is the limitation with other current techniques. Knudsen‐regime diffusion is common in many industrial, catalytic processes. Significantly, larger spatial variability in mass transport rates across the packed bed was found compared to techniques using only molecular diffusion. It has thus been found that that these heterogeneities arise over length‐scales much larger than ～100 µm. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4013–4019, 2015     

Multizone circulating reactor modeling for gas‐phase polymerization. II. Reactor operating with gas barrier in the downer section

A new gas‐phase technology for polyolefin production is being developed to be commercially available for large‐scale production between 2004 and 2005. This new technology uses a multizone circulating reactor, which consists of two interrelated zones where two distinct and different fluodynamic regimes are realized, between which the polymer particles are kept in continuous circulation. In the first part, we presented a mathematical model for the reactor, and this second part of the article we present simulations when a gas barrier is introduced in the top of the downer section and its implications in the polymer characteristics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1053–1059, 2004     

NiO-MgO固溶体蜂窝催化剂部分氧化重整净化生物质气特性

采用分步浸渍法制备了NiO-MgO固溶体蜂窝催化剂,以60 h连续重整实验,考察了不同临氧条件下MCM催化剂催化生物质气重整净化的性能。利用TG-DSC对催化剂的表面积炭进行了分析,采用GC、GC-MS等手段对生物质气组成及焦油转化产物进行了分析。结果表明：加入O₂后进行临氧重整,可改善出口合成气的品质,H₂/CO摩尔比较干重整时提高了10%左右。但当O₂/fuel摩尔比超过0.127时,H₂/CO摩尔比有所下降。O₂的加入可明显提高催化剂的催化活性和稳定性,随着O₂ 含量的增加出口合成气中的CH₄含量降低,临氧重整条件下焦油的转化率较无氧条件时提高了5%,转化率达到99%以上。热重分析表明,O₂ 含量的增加会减少催化剂表面积炭量。实验中添加从气化现场提取的生物质焦油,经检测焦油大部分转化为H₂、CO及痕量轻质组分,且对干重整中难于转化的含氧有机化合物等转化更为彻底。     

Liquid‐phase axial dispersion of turbulent gas–liquid co‐current flow through screen‐type static mixers

This article discusses the characteristics of turbulent gas–liquid flow through tubular reactors/contactors equipped with screen‐type static mixers from a macromixing perspective. The effect of changing the reactor configuration, and the operating conditions, were investigated by using four different screen geometries of varying mesh numbers. Residence time distribution experiments were conducted in the turbulent regime (4500 < Re < 29,000). Using a deconvolution technique, the RTD function was extracted to quantify the axial/longitudinal liquid‐phase dispersion coefficient. The findings highlight that axial dispersion increases with an increasing flow rate and/or gas‐phase volume fraction. However, regardless of the number and geometry of the mixing elements, reactor configuration, and/or operating conditions, the recorded liquid‐phase axial dispersion coefficients in the presence of screens was lower than that for an empty pipe. Furthermore, the geometry of the screen was found to directly affect the axial dispersion coefficient in the reactor. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1390–1403, 2017     

Chain structure of polyethylene/polypropylene in‐reactor alloy synthesized in gas phase with spherical Ziegler–Natta catalyst

Two polyethylene/polypropylene (PE/PP) in‐reactor alloy samples were synthesized by multi‐stage gas‐phase polymerization using a spherical Ziegler–Natta catalyst. The alloys show excellent toughness and stiffness. FTIR, ¹³C‐NMR and thermal analysis proved that the alloys are mainly composed of polyethylene, PE‐block‐PP copolymer and polypropylene. There are also a few percent of ethylene‐propylene segmented copolymer with very low crystallinity. The block copolymer fraction accounts for more than 25 % of the alloy. The role of the block copolymer as compatibilizer between PE and PP is believed to be the key factor that results in the excellent toughness–stiffness balance of the material. Copyright © 2004 Society of Chemical Industry     

Development of gas‐phase SMB technology for light olefin/paraffin separations

The separation of ethylene from ethane is particularly complex due to their similar physical properties. Cryogenic distillation is the most common technology employed for this separation and is one of the most expensive operations in industry, being the driving force for the ongoing research to find a more cost‐effective alternative. In the present work, a gas‐phase simulated moving bed (SMB) bench unit was employed to produce polymer‐grade ethylene from ethane/ethylene mixtures, using binderless 13X zeolite beads as adsorbent, and propane as desorbent. The achieved performance parameters demonstrated the high efficiency of the current technology, since ethylene was obtained with a purity of 99.8%, a recovery of 99.8%, and a productivity of 59.7 kg_C2H4·h^?1· . Considering the encouraging results obtained it is fair to say that the gas‐phase SMB is a competitive and strong candidate as alternative to the conventional process, especially when combined with enhanced performance adsorbents, such as binderless zeolites. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2490–2500, 2016     

Measurement of intrinsic rates for homogeneous gas‐phase reactions at high temperatures

A coiled quartz tubular reactor has been designed to measure the intrinsic reaction kinetics for homogeneous reactions at high temperatures up to 1100°C. Actual gas residence times were less than 100 ms. A simple and well‐studied test reaction (i.e., the decomposition of nitrous oxide, N₂O), with published intrinsic kinetics, was used to verify the operation of the experimental reactor. For this system, Peclet numbers (Pe = uL/DL) computed from experimental conversion data were greater than 1000, indicating that the plug flow assumption could be used with this reactor system to determine intrinsic rate expressions with errors of less than 5% for the conditions studied.     

Kinetics of homogeneous 5‐hydroxymethylfurfural oxidation to 2,5‐furandicarboxylic acid with Co/Mn/Br catalyst

2,5‐furandicarboxylic acid (FDCA) is a potential non‐phthalate based bio‐renewable substitute for terephthalic acid‐based plastics. Herein, we present an investigation of the oxidation rate of 5‐hydroxymethylfurfural (HMF) to FDCA in acetic acid medium using Co/Mn/Br catalyst. Transient concentration profiles of the reactant (HMF), intermediates [2,5‐diformylfuran (DFF), 5‐formyl‐2‐furancarboxylic acid (FFCA)], and the desired product (FDCA) were obtained for this relatively fast reaction in a stirred semi‐batch reactor using rapid in‐line sampling. Comparison of the effective rate constants for the series oxidation steps with predicted gas–liquid mass transfer coefficients reveals that except for the FFCA → FDCA step, the first two oxidation steps are subject to gas–liquid mass transfer limitations even at high stirrer speeds. Novel reactor configurations, such as a reactor in which the reaction mixture is dispersed as fine droplets into a gas phase containing oxygen, are required to overcome oxygen starvation in the liquid phase and further intensify FDCA production. © 2016 American Institute of Chemical Engineers AIChE J, 63: 162–171, 2017     

空气气氛下RuO2/ZSM-5催化醇的部分氧化反应

通过原位反应法制备了RuO₂/ZSM-5催化剂，并用XRD、XPS和TEM对合成的催化剂进行了表征，结果表明，RuO₂主要以20 nm左右的微晶分散在载体中，原位反应引入钌物种，没有改变载体ZSM-5的结构，大部分钌为四价。催化试验表明，在以空气为氧化剂的温和条件下，RuO₂/ZSM-5不仅可有效地催化芳香醇和带烯丙基的醇类（激活醇）氧化生成醛酮，而且对一些非激活醇也有较好的催化效果。     

离子液体相转移催化氧化苯甲醛制备苯甲酸

以N-甲基咪唑、四氟硼酸铵、正丁醇、溴化钠为主要原料合成了1-正丁基-3-甲基咪唑四氟硼酸咪唑盐型离子液体。以该离子液体作相转移催化剂研究了双氧水氧化苯甲醛制备苯甲酸的反应。结果表明,该氧化反应中加入离子液体可起到溶剂及相转移催化剂的作用,当反应5 h时,苯甲醛可达最大转化率88%。反应后离子液体可回收再利用。     

Accurate determination of hexanal in beef bouillons by headspace solid‐phase microextraction gas‐chromatography mass‐spectrometry

Lipid oxidation has great impact on the quality of food products through flavor and taste deterioration, reduction in nutritive value, and potential toxicity of the oxidized food components. Flavor and taste deterioration can be easily perceived and it represents one of the major causes of consumer complaints in the food industry. The deterioration of sensory properties is due to the decomposition products of hydroperoxides that easily isomerize and degrade into volatile compounds. Volatile products are responsible for flavor and taste deterioration. In this study, we present the development of the solid‐phase microextraction gas chromatography‐mass spectrometry (SPME‐GC‐MS) technique to quantify low amounts (μg/g range) of secondary oxidation products, i.e. hexanal. The optimization of SPME parameters is a difficult task because of the possibility of further formation of volatile products during analysis. Different parameters such as type of fiber, exposure time of the fiber to the sample headspace and the optimal temperature of absorption have also been investigated. The complete validation of the method was achieved by the determination of linearity, limits of detection and quantification and repeatability. We demonstrated that the SPME method is a valuable tool for the quantification of low amounts of secondary oxidation products such as hexanal. Therefore, this technique can be used to detect early formation of volatiles.     

Metal sols as a useful tool for heterogeneous gold catalyst preparation: reinvestigation of a liquid phase oxidation

Differently stabilised metal sols have been used as precursors in the preparation of heterogeneous gold catalysts for liquid phase oxidation in water solution. The methodology of sols generation appears to be fundamental to obtaining nanoparticles; the support, instead, plays an important role in maintaining particle dimension and morphology.

Three different materials (γ-Al₂O₃, SiO₂ and activated carbon) have been used as the supporting agents for different gold sols that were obtained by reducing HAuCl₄ with NaBH₄ in the presence of polyvinylalcohol (PVA) or polyvinylpirrolidone (PVP) and with the tetrakis(hydroxymethyl)phosphonium chloride (THPC)/NaOH system. During the immobilisation step, the maintenance of the particle dimension observed in solution depends on both the support and the type of sol. The gold particle mean size of the colloidal suspension is more easily maintained on oxidic supports than on carbon, the latter apparently needing both steric and polar stabilisation of the gold particle.

Comparison of Au/γ-Al₂O₃ and Au/C catalyst activity in the liquid phase oxidation of ethylene glycol to glycolate highlighted the peculiarity of gold on carbon catalysts; in fact, the normally observed trend of reactivity is partially reversed, medium sized gold particle being the most active.