煤头小型低压法甲醇装置合成压力的参变的效应

本文对Ｌｕｒｇｉ低压法甲醇工艺中压力的参变效应进行了探讨．通过计算机模拟，给出了合成压力变化的效应情况．计算结果表明煤头小型低压法甲醇装置的合成压力应高于大型装置的合成压力，其值在７．３～８．０ＭＰａ之间可取得最佳的节能降耗效果．     

酒精中甲醇,水在NaA沸石上吸附性能的研究

本文测定了酒精中甲醇、水单组分及二元组分的吸附等温线,并用Langmuir方程进行了拟合。在固定床动态吸附研究申测定了酒精中甲醇、水单组分及双组分吸附穿透曲线;着重考察了流速、温度、不同甲醇和水含量对双组分吸附性能的影响。对二个组分的传质机理及置换关系进行了分析探讨。     

On-line H NMR spectroscopic investigation of hydrogen bonding in supercritical and near critical CO2–methanol up to 35 MPa and 403 K

On-line NMR spectroscopy can beneficially be applied to studies of supercritical and near-critical fluids as an alternative to optical spectroscopy. Up to now high pressure NMR experiments are predominantly accomplished using custom made NMR batch reactors. The authors present a novel high pressure cell with displacement plunger for on-line NMR experiments on compressible fluids which can be used in conjunction with commercially available SCF NMR flow probes. The on-line technique offers advantages compared to stopped flow techniques such as enhanced control of mixture composition and reaction parameters as well as the facility of engagement into the reaction. The new apparatus is used for NMR studies on hydrogen bonding of methanol in near critical and supercritical carbon dioxide up to 403 K and 35 MPa for which data on the chemical shift of the hydroxyl group and methyl group are reported and interpreted.     

Synthesis and activation of Pt nanoparticles with controlled size for fuel cell electrocatalysts

Well-dispersed Pt nanoparticles with controlled size and narrow size distribution were prepared by polyalcohol reduction of platinum acetylacetonate, using oleylamine as a capping agent. The particle size was varied from 3.5 nm to 11.5 nm by decreasing the amount of oleylamine added in the synthesis. Size selection of the as-prepared particles by solvent fractionation yielded nearly monodispersed Pt particles. The as-prepared particles were loaded on a carbon support by physical deposition, but showed no electrocatalytic activity due to the oleylamine bound to the particle surface. The particles were activated for electrocatalysis after heating the particles in air at 185 °C for 5 h, conditions that gave no particle-sintering and no oxidation. Cyclic voltammetry showed that the particles after the heat treatment in air were electrocatalytically active for methanol oxidation. The smaller 3.5 nm and 4.0 nm Pt particles had a higher intrinsic activity for methanol oxidation, but a lower tolerance to CO poisoning, compared with 6.0 nm, 9.5 nm and 11.5 nm particles. CO-stripping results suggest that CO is more easily oxidized on larger Pt particles.     

Catalyst instabilities during the liquid phase partial oxidation of methane

A promising catalytic system for the low temperature oxidation of methane to a methanol derivative has been investigated under both batch and semi-continuous operation in two different reactor types. The system comprises of a bimetallic palladium and copper(II) chloride catalyst contained in a trifluoroacetic acid (TFA) and an aqueous phase. Methane, oxygen and a co-reductant carbon monoxide constitute the gas phase. Typical operating conditions were a temperature of 85 °C and a pressure of 83 bar.

The yields of the methyl trifluoroacetate product observed in this present work were less than those obtained in other batch autoclave works, which employed only 4 ml of liquid phase, compared with 50 ml in this study. Furthermore, an encouraging initial product formation rate of ca. 40 mol/m³ h, quickly decreased after the first hour, and came to an apparent end after only 2 h. This observation had not been reported previously.

Work performed in a semi-continuous porous tube reactor (300 ml of re-circulating liquid phase) also showed the same reaction characteristics as in the batch reactor. Thus, the deteriorating product formation rate cannot be attributed to gaseous reactant depletion (batch operation). The results suggest problems associated with catalyst instabilities, e.g. with the previously elucidated Wacker chemistry.     

Laboratory simulated slipstream testing of novel sulfur removal processes for gasification application

The Wabash River Integrated Methanol and Power Production from Clean Coal Technologies (IMPPCCT) project is investigating an Early Entrance Coproduction Plant (EECP) concept to evaluate integrated electrical power generation and methanol production from coal and other carbonaceous feedstocks. Research, development and testing (RD&T) that is currently being conducted under the project is evaluating cost effective process systems for removing contaminants, particularly sulfur species, from the generated gas which contains mainly synthesis gas (syngas), CO₂ and steam at concentrations acceptable for the methanol synthesis catalyst. The RD&T includes laboratory testing followed by bench-scale and field testing at the SG Solutions Gasification Plant located in West Terre Haute, Indiana. Actual synthesis gas produced by the plant was utilized at system pressure and temperature for bench-scale field testing.     

Effect of chloride ions on immersion plating of copper onto porous silicon from a methanol solution

The effect of chloride ions (Cl⁻) during the immersion plating of copper onto porous silicon (PS) from a methanol (MeOH) solution has been studied. The presence of Cl⁻ in the Cu²⁺ solution was found to slow down the rate of copper deposition, as confirmed by inductively coupled argon plasma emission spectroscopy and X-ray photoelectron spectroscopy measurements. The threshold concentration of Cl⁻ at which the deposition of copper is very severely diminished was found to be 0.1 M. The inhibition effect is discussed on the basis of the rest potential values of PS and polarization curve measurements. They revealed that the rest potential of PS upon dipping in these solutions appears to direct the metal deposition. Current density-potential curves show that at Cl⁻ concentrations higher than 0.1 M, the reduction of Cu ions proceeds in two steps; the reduction of Cu(II) to Cu(I) followed by the reduction of Cu(I) to Cu(0). This suggests that Cu(I) species in MeOH solution can be stable over a certain potential range and this stability of Cu(I) is responsible for the inhibition of metal deposition. Fourier transform infrared spectroscopy and scanning electron microscopy (SEM) were also performed to investigate the structural changes and characterizations of PS samples after the plating process.     

CONDITIONING COAL GAS WITH REFRIGERATED METHANOL IN A SYSTEM OF PACKED COLUMNS

Experience with the operation of a pilot-scale unit is used to outline potential difficulties in the operation of acid gas removal systems on gases produced from coal. The pilot plant has been used to condition gases produced from subbituminous coal, devolatilized char, peat and lignite. The solvent used in the acid gas removal system has been refrigerated methyl alcohol. Data from this study document accumulation of hydrocarbons, sulfur and nitrogen compounds, and mercury in the circulating solvent.     

A novel methanol-tolerant Ir-Se chalcogenide electrocatalyst for oyxgen reduction

A novel methanol-tolerant oxygen-reduction catalyst, Iridium-selenium (Ir-Se) chalcogenide, was synthesized by chemical precipitation in an organic solvent. Auger electron spectroscopy (AES) analysis confirmed that the synthesized Ir-Se chalcogenide had a chemical formula of Ir₄Se. This chalcogenide showed strong catalytic activity towards the oxygen reduction reaction (ORR) and a high methanol tolerance. It was found that most of the oxygen could be directly reduced to water through a four-electron pathway with less than 10% hydrogen peroxide (H₂O₂) being produced during the ORR. The improvement in catalytic activity of the Ir-Se chalcogenide in comparison with that of pure Ir might be attributed to the effect of a bimetallic interaction.     

Ti－24Al－11Nb腐蚀疲劳断口形貌的研究

Ｔｉ－２４Ａｌ－１１Ｎｂ腐蚀疲劳断口形貌的研究张跃，褚武扬，王燕斌，肖纪美（北京科技大学北京１０００８３）１引言对Ｔｉ－２４ＡＩ－１１Ｎｂ合金的断裂特征和断口形貌已进行了较多的研究［“］．在３００ｏＣ的氢气中该合金能发生氢致开裂，其断口形貌与过载断口...