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Surface Species Formed during Methane Oxidation over Some Rare Earth Elements Oxides 几种稀土元素氧化物甲烷氧化过程中形成的表面物质
Pub Date : 2018-01-01 DOI: 10.4236/GSC.2018.81001
M. Al-Dosari
This study has compared the ability of paramagnetic element oxides i.e. Pr, Eu, Yb in catalyst oxidation of methane. These have been prepared by precipitation, and then calcined at 600°C to get M2O3. Methane was then passed through a disk in KBr, and the reactions were conducted at room temperature; 200°C and then 300°C. The reaction products were then identified by F.T.I.R spectroscopy. It was observed that these oxides have extracted the protons from methane and the CH3·radicals were evidently formed. This focused radical react further to give CH3O, C2H6 and the formation of Propionic acid is reported as one of the catalytic reaction products. The study also indicated the presence of aromatic products and in some instances, phenol was identified. Thereafter, the mechanism of the reaction was envisaged. For all the catalysts the conversion increases relatively with increasing the reaction temperature. The study can deduce that these oxides have the same ability as those of high paramagnetic properties to extract the proton, but the products are trapped and react further on the surface of the oxide.
本研究比较了顺磁性元素氧化物Pr、Eu、Yb在甲烷催化氧化中的性能。这些都是通过沉淀法制备的,然后在600℃下煅烧得到M2O3。然后甲烷在KBr中通过一个圆盘,在室温下进行反应;200°C,然后300°C。然后用红外光谱对反应产物进行鉴定。结果表明,这些氧化物从甲烷中吸收了质子,形成了明显的CH3·自由基。该聚焦自由基进一步反应生成ch30、C2H6并生成丙酸为催化反应产物之一。该研究还表明了芳香产物的存在,在某些情况下,发现了苯酚。随后,设想了反应的机理。所有催化剂的转化率均随反应温度的升高而增加。研究可以推断,这些氧化物与那些具有高顺磁性的氧化物具有相同的提取质子的能力,但产物被捕获并在氧化物表面进一步反应。
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引用次数: 0
Solvent- and Catalyst-Free Microwave-Assisted Decarboxylation of Malonic Acid Derivatives 无溶剂和无催化剂的微波辅助丙二酸衍生物脱羧
Pub Date : 2017-11-15 DOI: 10.4236/GSC.2017.74021
Fanny A. Cabrera-Rivera, Luis G. Hernández-Vázquez, P. Flores-Sánchez, M. Durán-Galván, J. Escalante
It has been found that microwave assisted decarboxylation of malonic acid derivatives can be achieved under solvent-free and catalyst free conditions. This new method produces the corresponding carboxylic acid in a pure manner and with a high yield in a very short reaction time: 3 - 10 min. In general terms, the condition under which this reaction is carried out accelerates the decarboxylation significantly of a series of disubstituted malonic acid derivatives, and makes this new process efficient, easy and environmentally friendly.
研究发现,微波辅助丙二酸衍生物的脱羧反应可以在无溶剂和无催化剂的条件下进行。该方法在极短的反应时间内(3 - 10 min)以高收率、纯净的方式制得相应的羧酸。总的来说,该反应的进行条件显著加快了一系列二取代丙二酸衍生物的脱羧反应,使该新工艺高效、简便、环保。
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引用次数: 5
Short-Time Preparation of NaOH-Activated Carbon from Sugar Cane Bagasse Using Microwave Plasma Heating 微波等离子体加热蔗渣短时间制备氢氧化钠活性炭
Pub Date : 2017-09-21 DOI: 10.4236/GSC.2017.74020
K. Konno, Y. Oike, Yasutaka Ohba, Osamu Sasaki, Y. Takiguchi, K. Onoe, Tatsuaki Yamaguchi
The microwave induced argon plasma was applied to the preparation of NaOH-activated carbon from sugar cane bagasse. The distinguished feature of the heating technique with this cold plasma is the short operation time. The carbonization and the activation process were finalized in one step within 3 min. The prepared activated carbon with NaOH ratio 3 to bagasse characterized using N2 adsorption of type IV (IUPAC classification) to give specific surface area of 1980 m2/g and mesopore volume of 0.73 ml/g. It also showed a higher specific capacitance of 201 F/g in 1 M H2SO4 solution (with standard three electrodes) than the corresponding one by the conventional heating, previously reported. The other features were the absence of oxygen groups and the presence of carbon centered stable radicals, detected by ESR spectra, on the surface.
采用微波诱导氩等离子体法制备蔗渣naoh活性炭。这种冷等离子体加热技术的显著特点是操作时间短。炭化和活化过程在3 min内一步完成。制备的NaOH比为3与甘蔗渣的活性炭采用ⅳ型N2吸附(IUPAC分级)表征,比表面积为1980 m2/g,介孔体积为0.73 ml/g。在1 M H2SO4溶液中(标准三电极),比电容为201 F/g,高于传统加热方法。其他特征是表面没有氧基团和碳中心稳定自由基的存在,通过ESR光谱检测到。
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引用次数: 5
Study on Deactivation and Regeneration of Modified Red Mud Catalyst Used in Biodiesel Production 改性赤泥催化剂在生物柴油生产中的失活与再生研究
Pub Date : 2017-09-21 DOI: 10.4236/GSC.2017.74019
A. Wahyudi, W. Kurniawan, H. Hinode
Deactivation of solid catalyst often occurs in biodiesel production. In this work, deactivated modified red mud catalysts used in biodiesel production were regenerated with hexane and calcination treatments. The deactivated and regenerated catalysts were characterized using XRD, FTIR, SEM, TG, N2 adsorption, measured for their basic strength, and tested in the transesterification of canola oil. The results revealed that the main cause of the catalyst deactivation is due to obstruction of the active sites by contaminants. The regeneration by washing with hexane followed by calcination can effectively improve the properties of the deactivated catalyst and increase its catalytic activity.
固体催化剂失活在生物柴油生产中经常发生。本研究对用于生物柴油生产的失活改性赤泥催化剂进行了正己烷和煅烧处理再生。采用XRD、FTIR、SEM、TG、N2吸附等方法对失活催化剂和再生催化剂进行了表征,测定了催化剂的碱性强度,并进行了菜籽油酯交换反应试验。结果表明,催化剂失活的主要原因是污染物对活性位点的阻碍。经正己烷洗涤后煅烧再生,可有效改善失活催化剂的性能,提高催化剂的催化活性。
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引用次数: 11
CO 2 Absorption Performance of “Dry Matter” Prepared with Amino Acid-Based Ionic Liquids 氨基酸基离子液体制备的“干物质”对co2的吸收性能
Pub Date : 2017-07-19 DOI: 10.4236/GSC.2017.73016
M. Miyake, M. Satoh
Dry Matter (DM) is a powdery substance which is composed of micro droplets and surrounding hydrophobic silica nanoparticles. Because of the much larger surface area than that of the corresponding bulk liquid, DM, which contains amino-functionalized ionic liquids (ILs), is a promising CO2 absorption material provided with quick absorption speed. In the present study, we successfully prepared powdery DMs by utilizing aqueous solutions of amino acid-based ILs (tetraethylammonium glycine [N2222][Gly], and tetraethylammonium alanine [N2222][Ala]). Although a DM with lysine-based IL (N2222) [Lys]) was also prepared, only a souffle-like material was obtained. We measured CO2 absorption performance for the DMs to find that the mass-base absorption ability (mass-base A.A.) (CO2 mol/DM kg) and the mol-base one (CO2 mol/IL mol) of [N2222][Lys] were ca. two times of [N2222][Gly] and [N2222][Ala], while the absorption speed of the former was inferior to the latter two, i.e., ca.15 min vs. 5 min for 90% absorption. In order to improve the mass-base A.A. of [N2222][Gly], we used 10% of aqueous poly(allylamine) (PAlAm) solution instead of water. The resultant mass-base A.A. proved to be significantly larger (1.9) than either of those of the respective single component systems (1.1 and 0.75 for the bulk IL and aq. PAlAm, respectively), and comparable to the A.A. (1.6 - 2.5) of 20% - 30% monoethanolamine solution which is commonly used in industrial application.
干物质(DM)是一种由微液滴和周围的疏水性二氧化硅纳米颗粒组成的粉状物质。DM含有氨基功能化离子液体(il),由于其比相应的散装液体表面积大得多,吸收速度快,是一种很有前途的CO2吸收材料。在本研究中,我们利用氨基酸基il(四乙基甘氨酸铵[N2222][Gly]和四乙基丙氨酸铵[N2222][Ala])的水溶液成功制备了粉末状DMs。虽然也制备了含有赖氨酸基IL (N2222) [Lys])的DM,但得到的只是蛋奶酥状材料。测定了DMs的CO2吸收性能,发现[N2222][Lys]的质量基吸收能力(质量基a.a) (CO2 mol/DM kg)和摩尔基吸收能力(CO2 mol/IL mol)是[N2222][Gly]和[N2222][Ala]的约2倍,而前者的吸收速度低于后两者,即吸收90%时约15 min vs. 5 min。为了提高[N2222][Gly]的质量基A.A.,我们用10%的聚烯丙胺(PAlAm)水溶液代替水。所得的质量基a.a值(1.9)明显大于各自的单组分体系(散装IL和aq. PAlAm分别为1.1和0.75),并且与工业应用中常用的20% - 30%单乙醇胺溶液的a.a值(1.6 - 2.5)相当。
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引用次数: 2
Iron (III) Chloride Catalyzed Claisen Rearrangement Reaction of Allyloxyarenes under Microwave Conditions 微波条件下氯化铁催化烯丙氧芳烃克里森重排反应
Pub Date : 2017-07-19 DOI: 10.4236/GSC.2017.73018
I. N. Pramesti, Y. Okada
The Claisen rearrangement is a [3,3]-sigmatropic rearrangement which is an important method for new C-C bond formation in organic synthesis. This reaction is a typical thermal reaction that requires a high temperature and long reaction time. In this paper, the acceleration effects of the iron (III) chloride (FeCl3) catalyst and microwave irradiation during the Claisen rearrangement reaction of allyloxyarene derivatives are reported. The FeCl3 catalyst was able to initiate the reaction at low temperature and induced the subsequent cyclization reaction. The moderation of excellent yields was obtained in a short reaction time. The formation of complex ferric-arenes under microwave irradiation conditions to efficiently absorb the microwaves was expected and confirmed.
Claisen重排是一种[3,3]-符号位重排,是有机合成中形成新碳-碳键的重要方法。该反应为典型的热反应,需要较高的温度和较长的反应时间。本文报道了氯化铁(FeCl3)催化剂和微波辐照对烯丙氧芳烃衍生物Claisen重排反应的加速作用。FeCl3催化剂能在低温下引发反应并诱导随后的环化反应。在较短的反应时间内获得了优异的产率。预期并证实了在微波辐照条件下,铁-芳烃络合物的形成能够有效地吸收微波。
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引用次数: 2
Silicon and III-V Solar Cells: From Modus Vivendi to Modus Operandi 硅和III-V型太阳能电池:从权宜之计到运作模式
Pub Date : 2017-07-19 DOI: 10.4236/GSC.2017.73017
A. Buzynin, Yu. N. Buzynin, V. Shengurov, V. Voronkov, A. Menke, A. E. Luk’yanov, V. Panov, N. Baidus
In the present paper, some novel opportunities for the development of high-efficient Si and III-V-based solar cells are considered: energy-saving environment friendly low-temperature technology of forming p-n junctions in Si (1), elaboration of structurally perfect GaAs/Ge/Si epitaxial substrates (2) and application of protective antireflecting coatings based on cubic zirconia (3). As a result: 1) New technique of forming p-n junctions in silicon has been elaborated. The technique provided easy and comparatively cheap process of production of semiconductor devices such as solar cells. The essence of the technique under the study is comprised in formation p-n junctions in silicon by a change of conductivity in the bulk of the sample occurring as a result of redistribution of the impurities, which already exists in the sample before its processing by ions. It differs from the techniques of diffusion and ion doping where change of conductivity and formation of p-n junction in the sample occur as a result of introduction of atoms of the other dopants from the outside; 2) The conditions for synthesis of GaAs/Ge/Si epitaxial substrates with a thin (200 nm) Ge buffer layer featured with (1 - 2) × 105 cm-2 density of the threading dislocation in the GaAs layer. Ge buffer was obtained by chemical vapor deposition with a hot wire and GaAs layer of 1 μm thick was grown by the metal organic chemical vapor deposition. Root mean square surface roughness of GaAs layers of the less than 1 nm and good photoluminescence properties along with their high uniformity were obtained; 3) The conditions ensuring the synthesis of uniform functional (buffer, insulating and protective) fianite layers on Si and GaAs substrates by means of magnetron and electron-beam sputtering have been determined. Fianite films have been shown to be suitable for the use as an ideal anti-reflecting material with high protective and anticorrosive properties.
本文考虑了发展高效硅基和iii - v基太阳能电池的一些新机遇:在硅中形成p-n结的节能环保低温技术(1),结构完善的GaAs/Ge/Si外延衬底的制备(2)以及基于立方氧化锆的保护性增透涂层的应用(3)。结果:1)阐述了在硅中形成p-n结的新技术。该技术为太阳能电池等半导体器件的生产提供了简单且相对便宜的工艺。本研究技术的本质是在硅中形成p-n结,这是由于样品中杂质的重新分配导致的,杂质在被离子处理之前已经存在于样品中。它不同于扩散和离子掺杂技术,在扩散和离子掺杂技术中,样品中的电导率变化和p-n结的形成是由于从外部引入其他掺杂剂原子的结果;2)制备GaAs/Ge/Si外延衬底的条件,该外延衬底具有(1 -2)× 105 cm-2密度的GaAs层中螺纹位错(ga -2)为薄(200 nm)的Ge缓冲层。采用热丝化学气相沉积法制备Ge缓冲液,采用金属有机化学气相沉积法制备了厚度为1 μm的GaAs层。获得了表面均方根粗糙度小于1 nm的GaAs层,具有良好的光致发光性能和较高的均匀性;3)确定了磁控溅射和电子束溅射在Si和GaAs衬底上合成均匀功能(缓冲、绝缘和保护)的条件。钛酸盐薄膜已被证明是一种理想的抗反射材料,具有很高的保护和防腐性能。
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引用次数: 1
A Novel Friedel-Crafts Acylation Reaction of Anisole for Production of 4-Methoxyacetophenone with High Selectivity and Sufficient Reusability of Mordenite Zeolite Catalyst 丝光沸石催化剂制备4-甲氧基苯乙酮的新型Friedel-Crafts酰化反应
Pub Date : 2017-07-19 DOI: 10.4236/GSC.2017.73014
M. Makihara, K. Komura
Zeolite catalyzed Friedel-Crafts reactions were examined using acetic anhydride as an acetylating agent and an acetic acid as a solvent. It revealed that the reaction of anisole smoothly occurred quantitatively for 3 h using mordenite zeolite with SiO2/Al2O3 = 200, and with SiO2/Al2O3 = 110, the increasing of Bronsted acidity allowed to completely react within 2 h. Furthermore the selectivity of 4-methoxyacetophenone (4-MA) among the isomers was found to be quantitative, no by-products and/or isomers were not detectable. With the excellent recyclability and reusability, the mordenite zeolite exhibited at least 30 times quantitatively both conversion of anisole and selectivity of 4-MA. The mordenite catalysts of fresh and the used after 30 times were characterized. This opportunity obviously indicates the sufficient shape selective catalyst of mordenite zeolite and gives a green synthetic tool for heterogeneous acylation reaction.
以乙酸酐为乙酰化剂,乙酸为溶剂,研究了沸石催化的Friedel-Crafts反应。结果表明,在SiO2/Al2O3 = 200的丝光沸石中,苯甲醚的定量反应顺利进行了3 h, SiO2/Al2O3 = 110时,Bronsted酸度的增加使反应在2 h内完全完成。此外,4-甲氧基苯乙酮(4-MA)在异构体中的选择性是定量的,没有检测到副产物和/或异构体。丝光沸石具有良好的可回收性和可重复使用性,其对苯甲醚的转化率和对4-MA的选择性均达到30倍以上。对新鲜的丝光沸石催化剂和使用30次后的丝光沸石催化剂进行了表征。这一机遇明显表明丝光沸石具有充分的形状选择性催化剂,为非均相酰化反应提供了绿色合成工具。
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引用次数: 4
Production of Bio-Phenols for Industrial Application: Scale-Up of the Base-Catalyzed Depolymerization of Lignin 工业用生物酚的生产:碱催化木质素解聚的放大
Pub Date : 2017-07-19 DOI: 10.4236/GSC.2017.73015
Björn Rößiger, R. Röver, Gerd Unkelbach, Daniela Pufky-Heinrich
Objective of this study was the investigation on the up-scaling of base-catalyzed depolymerization (BCD) of lignin to pilot plant dimension. The cleavage process was carried out in dilute alkaline solution at temperatures up to 340°C and a pressure of 25 MPa in a continuously operated tubular flow reactor with throughputs up to 20 kg/h. Investigations included the proof of the feasibility of the scale-up as well as a parameter study on the cleavage of hardwood Organosolv lignin and softwood Kraft lignin within the established pilot plant. Yields and molecular compositions of the isolated product fractions BCD-oil (liquid phenolic fraction) and BCD-oligomers (solid phenolic fraction) are similar to those described in technical lab scale, showing a good scalability. Here, BCD-oils rich in phenolic monomers such as guaiacol, catechol and/or syringol were obtained with a content of up to 13.3 wt% and 14.5 wt% from Organosolv lignin and Kraft lignin, respectively. Formation of BCD-oligomers strongly depends on temperature and residence times within the reactor.
本研究的目的是探讨碱催化木质素解聚(BCD)的规模扩大到中试规模。裂解过程在稀碱性溶液中进行,温度高达340℃,压力为25 MPa,在连续运行的管流式反应器中进行,裂解速率可达20 kg/h。调查包括证明扩大规模的可行性,以及在建立的中试工厂内对硬木有机溶剂木质素和软木硫酸盐木质素的裂解进行参数研究。分离产物馏分bcd油(液体酚类馏分)和bcd低聚物(固体酚类馏分)的产率和分子组成与技术实验室规模描述的相似,具有良好的可扩展性。在这里,从Organosolv木质素和Kraft木质素中分别获得了富含愈创木酚、儿茶酚和/或丁香醇等酚类单体的bcd油,含量分别高达13.3 wt%和14.5%。bcd低聚物的形成在很大程度上取决于反应器内的温度和停留时间。
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引用次数: 31
Nutrients Extracted from Chicken Manure Accelerate Growth of Microalga Scenedesmus obliquus HTB1 鸡粪中提取的营养物质促进斜花斑微藻HTB1的生长
Pub Date : 2017-03-15 DOI: 10.4236/GSC.2017.72009
Xiaotian Han, Nicole Rusconi, P. Ali, Kevin Pagkatipunan, Feng Chen
Sustainable development using wastes as resources is a new paradigm. Chicken manure contains rich amounts of nitrogen and phosphorus and has been used as crop fertilizer. However, little is known about whether nutrients of chicken manure are suitable and efficient to support the rapid growth of microalgae. In this study, we explore the possibility of using nutrient extracted from chicken manure to grow microalgae. We used an algal strain Scenedesmus sp. HTB1, which is an oleaginous species with high CO2 tolerance capability. The growth performance of HTB1 on various media amended with nutrient extracted from three different chicken manure sources was monitored and compared to the growth rate of HTB1 grown in the standard medium BG11. Meanwhile, the changes of total nitrogen (N) and phosphorus (P), both organic and inorganic, were measured during the growth period. Culture media enriched with the nutrient extracted from two chicken manure sources outperformed the standard culture medium BG11 in terms of algal biomass production. When cultivated with manure nutrient, HTB1 utilized inorganic N efficiently, but consumed very little organic N during the experimental growth period. However, HTB1 was able to utilize both organic and inorganic phosphorus. We demonstrate that nutrient extracted from chicken manure support rapid growth and high biomass yield in microalgae Scenedesmus obliquus HTB1. Therefore chicken manure holds great promise to be used as a cost-effective and efficient fertilizer for large-scale production of microalgae.
以废物为资源的可持续发展是一种新的发展模式。鸡粪含有丰富的氮和磷,已被用作作物肥料。然而,关于鸡粪中的营养成分是否适合和有效地支持微藻的快速生长,人们知之甚少。在本研究中,我们探索了利用鸡粪提取的营养物质来培养微藻的可能性。我们选用了一种耐CO2能力强的产油藻类——Scenedesmus sp. HTB1。研究了HTB1在添加了三种不同鸡粪源提取的营养物质的培养基上的生长性能,并与HTB1在标准培养基BG11中的生长速率进行了比较。同时,测定了各生育期总氮(N)和总磷(P)的变化,包括有机氮和无机氮。从两种鸡粪中提取营养物质的培养基在藻类生物量生产方面优于标准培养基BG11。施用粪肥时,HTB1对无机氮的利用效率较高,但在试验生育期消耗的有机氮很少。然而,HTB1能够利用有机和无机磷。研究表明,从鸡粪中提取的营养物质支持微藻Scenedesmus obliquus HTB1的快速生长和高生物量产量。因此,鸡粪作为一种经济高效的肥料用于微藻的大规模生产具有很大的前景。
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引用次数: 10
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Green and Sustainable Chemistry
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