Design and operation of integrated pilot-scale dimethyl ether synthesis system via pyrolysis/gasification of corncob

The integrated pilot-scale dimethyl ether (DME) synthesis system from corncob was demonstrated for modernizing utilization of biomass residues. The raw bio-syngas was obtained by the pyrolyzer/gasifier at the yield rate of 40-45 Nm(3)/h. The content of tar in the raw bio-syngas was decreased to less than 20 mg/Nm(3) by high temperature gasification of the pyrolysates under O-2-rich air. More than 70% CO2 in the raw bio-syngas was removed by pressure-swing adsorption unit (PSA). The bio-syngas (H-2/CO approximate to 1) was catalytically converted to DME in the fixed-bed tubular reactor directly over Cu/Zn/Al/HZSM-5 catalysts. CO conversion and space-time yield of DME were in the range of 82.0-73.6% and 124.3-203.8 kg/m(cat)(3)/h, respectively, with a similar DME selectivity when gas hourly space velocity (GHSV, volumetric flow rate of syngas at STP divided by the volume of catalyst) increased from 650 h(-1) to 1500 h(-1) at 260 degrees C and 4.3 MPa. And the selectivity to methanol and C-2(+) products was less than 0.65% under typical synthesis condition. The thermal energy conversion efficiency was ca. 32.0% and about 16.4% carbon in dried corncob was essentially converted to DME with the production cost of ca. (sic) 3737/ton DME. Cu (111) was assumed to be the active phase for DME synthesis, confirmed by X-ray diffraction (XRD) characterization.

Synthesis Gas Generation by Chemical-Looping Reforming Using Ce-Based Oxygen Carriers Modified with Fe, Cu, and Mn Oxides

Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.

Hydrogen-rich gas production from biomass air and oxygen/steam gasification in a downdraft gasifier

Biomass gasification is an important method to obtain renewable hydrogen, However, this technology still stagnates in a laboratory scale because of its high-energy consumption. In order to get maximum hydrogen yield and decrease energy consumption, this study applies a self-heated downdraft gasifier as the reactor and uses char as the catalyst to study the characteristics of hydrogen production from biomass gasification. Air and oxygen/steam are utilized as the gasifying agents. The experimental results indicate that compared to biomass air gasification, biomass oxygen/steam gasification improves hydrogen yield depending on the volume of downdraft gasifier, and also nearly doubles the heating value of fuel gas. The maximum lower heating value of fuel gas reaches 11.11 MJ/ N m(3) for biomass oxygen/steam gasification. Over the ranges of operating conditions examined, the maximum hydrogen yield reaches 45.16 g H-2/kg biomass. For biomass oxygen/steam gasification, the content of H-2 and CO reaches 63.27-72.56%, while the content Of H2 and CO gets to 52.19-63.31% for biomass air gasification. The ratio of H-2/CO for biomass oxygen/steam gasification reaches 0.70-0.90, which is lower than that of biomass air gasification, 1.06-1.27. The experimental and comparison results prove that biomass oxygen/steam gasification in a downdraft gasifier is an effective, relatively low energy consumption technology for hydrogen-rich gas production.

Experimental observation of negative lateral displacements of microwave beams transmitting through dielectric slabs

It was theoretically predicted that when a beam of light travels through a thin slab of optically denser medium in the air, the emerging beam from the slab will suffer a lateral displacement that is different from the prediction of geometrical optics, that is, the Snell's law of refraction and can be zero and negative as well as positive. These phenomena have been directly observed in microwave experiments in which large angles of incidence are chosen for the purpose of obtaining negative lateral displacements. (C) 2005 Elsevier B.V. All rights reserved.

Negative lateral shift of a light beam transmitted through a dielectric slab and interaction of boundary effects

It is found that when a light beam travels through a slab of optically denser dielectric medium in air, the lateral shift of the transmitted beam can be negative. This is a novel phenomenon that is reversed in comparison with the geometrical optic prediction according to Snell's law of refraction. A Gaussian-shaped beam is analyzed in the paraxial approximation, and a comparison with numerical simulations is made. Finally, an explanation for the negativity of the lateral shift is suggested, in terms of the interaction of boundary effects of the slab's two interfaces with air.

Preparation and luminescence properties of Eu2+ in SiO2 xerogels

Al-doped and B, Al co-doped SiO2 xerogels with Eu2+ ions were prepared only by sol-gel reaction in air without reducing heat-treatment or post-doping. The luminescence characteristics and mechanism of europium doping SiO2 xerogels were studied as a function of the concentration of Al, B, the europium concentration and the host composition. The emission spectra of the Al-doped and B, Al codoped samples all show an efficient emission broad band in the blue violet range. The blue emission of the Al-doped sample was centered at 437 nm, whereas the B, Al co-doped xerogel emission maximum shifted to 423 nm and the intensity became weaker. Concentration quenching effect occurred in both the Al-doped and B, Al co-doped samples, which probably is the result of the transfer of the excitation energy from Eu2+ ions to defects. The highest Eu2+ emission intensity was observed for samples with the Si(OC2H5)(4):C2H5OH:H2O molar ratio of 1:2:4. (c) 2006 Elsevier B.V. All rights reserved.

Lateral shift of the transmitted light beam through a left-handed slab

It is reported that when a light beam travels through a slab of left-handed medium in the air, the lateral shift of the transmitted beam can be negative as well as positive. The necessary condition for the lateral shift to be positive is given. The validity of the stationary-phase approach is demonstrated by numerical simulations for a Gaussian-shaped beam. A restriction to the slab's thickness is provided that is necessary for the beam to retain its profile in the traveling. It is shown that the lateral shift of the reflected beam is equal to that of the transmitted beam in the symmetric configuration.

Mode field diameter and nonlinear properties of air-core nanowires

Exact solutions of Maxwell's equations describing the lightwave through 3-layer-structured cylindrical waveguide are obtained and the mode field diameter and nonlinear coefficient of air-core nanowires (ACNWs) are numerically calculated. The simulation results show that ACNWs offer some unique optical properties, such as tight field confining ability and extremely high nonlinearity. At a certain wavelength and air core radius, we optimize the waveguide design to maximize the nonlinear coefficient and minimize the mode field diameter. Our results show that the ACNWs may be powerful potential tools for novel micro-photonic devices in the near future.

熔盐电解法制备Al-Li合金的应用基础研究及其工艺初探

Al-Li合金是近年发展起来的新型航空材料，具有低密度、高强度的特点。目前世界上正就如何进一步提高其断裂韧性，使Al-Li合金尽早走出实验室，获得实际用进行广泛，深入的研究。熔盐电解法就是在这种情况下发展起来的。虽然此法现在尚处于研究的初级阶段，但已以其能够在较简单的设备上制备低Na高纯Al-Li合金的特点受到广泛的重视，是一种很有前途的发展方向。针对我国的技术、设备现状，在参考国外研究结果的基础上，采用熔盐电解法制备Al-Li母合金 → 应用合金的制备方法是可以尽快赶上世界发步伐的有效途径。因此，本文作为整个熔盐电解制备Al-Li合金系统研究的一部分，针对目前在此领域中很多应用基础问题，诸如：作为新的电解体系正在探索中的LiCl-KCl-LiF三元相图，Li在液体Al阴极中的扩散系数，利用熔盐电解法制备低Na高纯Al-Li合金的热力学基础及如何克服LiCl强烈的吸水性给电解工艺带来的种种不便等均未得到系统研究的现状，设计完成了一系列有关熔盐电化学和热力学实验，填补了本领域的一些研究空白，并为进一步系统研究工艺条件提供了重要的参考数据。1．用NH_4Cl氯化Li_2CO_3的研究 根据热力学从理论上论证了在200 ℃左右下述氯化反应：Li_2CO_3 + 2NN_4Cl = 2LiCl + 2NH_3~↑ + H_2O~↑ + CO_2~↑可以进行完全。利用DSC方法测定反应产物LiCl的纯度，并用离子色谱法分析反应产物中CO_3~=的含量，结果均证明：在Li_2CO_3:NH_4Cl = 1:4 (mol)时，Li_2CO_3可以定量转化为LiCl，剩余的NH_4Cl完全分解。根据热重分析结果推测NH_4Cl氯化Li_2CO_3的反应历程为：Li_2CO_3 + 2NH_4Cl = 2LiCl + 2NH_3~↑ + H_2O~↑ + CO_2~↑ NH_4Cl = HCl~↑ + NH_3~↑ 而并非是想像中的：NH_4Cl = HCl~↑ + NH_3~↑ 2HCl + Li_2CO_3 = 2LiCl + H2O~↑ + CO_2~↑利用X－射线衍射方法分析产物，结果亦说明氯化可以成功。将1:4（mol）= Li_2CO_3:NH_4Cl混合样品在差热分析反应炉中直接加热测定反应产物LiCl的溶点，并与纯LiCl样品熔点的测定结果相比较，二者完全一致。以上结果说明：不仅可用此氯化反应产物代替LiCl应用于熔盐电解制备Al-Li合金中，而且还可将其应用于LiCl体系的相图测定中。因Li_2CO_3，NH_4Cl均不吸水，极易处理，因此以上研究结果无论对于Al-Li合金的工艺研究还是其他有关LiCl体系的基础研究都是很有价值的。2．直接氯化法制备LiCl-KCl-LiF三元相图的研究。LiCl-KCl-LiF三元相图是研究此体系电解机制的重要基础。为将以上直接氯化法应用于差热分析中制作此三元体系相图，首先用直接氯化法测定了三个已知二元LiCl体系相图：LiCl－KCl；LiCl-LiF；LiCl-NaCl。与文献结果吻合很好。说明将此法应用于差热分析中制作LiCl体系相图结果是可靠的。在LiCl-KCl-LiF三元相图的测定中共做出七个垂直截面，在各截面上读出等温条件下的相界点投影到浓度三角形中，得到等温投影图。结果说明LiCl-KCl-LiF是固态完全不互溶的三元共晶体系，共有三个液－固两相区；三个液－固－固三相区；一个液－固－固－固四相区，（三元共晶平面）和一个固－固－固三相区。四相点温度为348 ℃，其组成在三相平衡线的交点处，在实验上测出近似等于：41.4KCl + 57.3LiCl + 1.3LiF (mol)。3．氯化物体系中Li~+, Na~+析出电位的比较及其去极化作用的研究。在正常电化序中，Li~+应先于Na~+析出。但在以Al作阴极电解LiCl体系时，则由于Li~+在Al上有较强的去极化作用而提前析出。这是熔盐电解法可以制备低Na，高纯Al-Li合金的基础。本文在理论上对此问题进行了较深入的研究。具体内容包括（1）。测定Li~+, Na~+在二元氯化物体系中的析出电位。通过在Al阴极，Mo阴极上二离子析出电位的比较，确认了Li~+在Al阴极上产生很强的去极化作用是能利用电解法制备低Na高纯Al-Li合金的根本原因。并为在工艺研究中选择合适的电流密度提供了参考依据。（2）．根据热力学理论推导出合金化反应产生的自由焓变化与去极化作用的关系：ΔG_x + ΔG_m = -nFΔE。揭示了产生去极化作用的原因。并根据ΔG_x（偏摩尔过剩自由焓）与合金结构的关系提出可以利用二元合金相图推测极化类型及极化大小。并根据动力学原理对温度对极化的影响提出了自己的看法。（3）．求出合金化反应的热效应，认为在一定条件下亦可利用此值作为判断去极化作用大小的标准。（4）．测定Li~+, Na~+在Al-Cu, -Al-RE合金上的析出电位。结果表明Cu，RE的存在均可加强Li~+在阴极上的去极化作用，进一步加大了Li~+, Na~+析出电位之间的差别，有利于制备更纯的Al-Li 使金。为直接生产Al-Cu-Li, Al-RE-Li三元母合金奠定了基础。（5）测定Li~+在不同组成配比的LiCl-KCl熔体中，在Al阴极上的析出电位，并求出LiCl的离子平均活度系数γ＝0.71 (T = 740 ℃), 熔体对理想状态产生负偏离。4．利用阳极计时电位法测定T＝720 ℃时Li在液体Al中的扩散系数D_(Li/Al) = 4.94 * 10~(-5)cm~2·s~(-1)，与利用Stocks-Einstan公式计算出的理论值D_(Li/Al) = 4.85 * 10~(-5)cm~2·s~(-1)吻合较好。5．在上述理论研究的基础之上进行了工艺初探，所得初步结论有：（1）．加入LiF可以提高电效。（2）．采用电流密度为1 A/cm~2时，不加搅拌亦可制备出成份均匀，含Li量为10％（w.f）的Al-Li合金。（3）．根据实验结果提出 Li在熔体中的熔解可能是影响电流效果的主要原因。