铜系甲醇催化剂母体物相研究

研制了一种新型甲醇催化剂，它由分解类孔雀石（ＭＬ）相和ＦＣ型化合物组成的母体而制得。实验结果证明制备方法和组分配比对母体结构有重要的影响，由ＭＬ和ＦＣ双相结合母体制得的催化剂合成甲醇活性优良。     

液相甲醇氧化羰基法合成碳酸二甲酯

液相甲醇氧化羰基法是近年开发和工业化的合成ＤＭＣ新工艺，文中通过对该工艺所用催化剂的进展、基础气液平衡数据和工艺流程的考察，展现了其取代传统光气法合成ＤＭＣ的前景，可参考该法在“九五”期间建立我国ＤＭＣ产品的工业生产。     

液相法甲醇氧化羰基化合成DMC的工艺条件研究

液相法甲醇氧化羰基化合成ＤＭＣ工艺，已于８０年代初经ＥＮＩ公司开发成功。国内目前也正积极研究开发。本文仅就此工艺中搅拌转速、氧含量、催化剂的影响等问题进行讨论。结果表明：在选定的条件下（反应温度９０℃～１５０℃，反应压力１Ｍｐａ～５．０Ｍｐａ），生成ＤＭＣ的选择性，以甲醇计为９９％以上，以ＣＯ计为７８％以上；甲醇转化率≥２０％；催化剂生产能力在０．２５ｇ～０．３５ｇ（ＤＭＣ）／ｈｇ（ｃａｔ）范围内；催化刘可再生反复使用。     

大型甲醇装置工艺技术选择

针对天然气制乙烯装置所配套的大型甲醇装置,比较了世界上先进的甲醇合成气制备和甲醇合成工艺技术,对于日产２５００ｔ的大型甲醇装置,选用串联两步转化工艺制备甲醇合成气,用ＴＥＣ的ＭＲＦ甲醇合成塔进行甲醇合成。     

应大力开发的几种甲醇下游产品

应大力开发的几种甲醇下游产品ＳＥＶＥＲＡＬＤＥＲＩＶＡＴＥＳＯＦＭＥＴＨＡＮＯＬＤＥＳＥＲＶＩＮＧＤＥＶＥＬＯＰＥＭＰＨＡＴＩＣＡＬＬＹ王志峰１前言我国目前有甲醇生产装置１５０多套，年生产能力超过１６００ｋｔ，年总产量为１３００ｋｔ左右，至今还有部分...     

吉林油田甲醇厂现场总线控制系统

以３万吨／年甲醇装置上现场总线应用为实例，从工程应用角度介绍现场总线控制系统的结构，组态，基本性能和特点，并对ＦＣＳ与ＤＣＳ作了简要比较。     

半导体型Mo－Fe二元氧化物催化剂的研制

通过共沉淀法和进一步焙烧制得Ｍｏ－Ｆｅ二元氧化物。经ＸＲＤ定性分析表明，它们是由含量不同的Ｆｅ２（ＭｏＯ４）３和ＭｏＯ３所组成。利用固定床反应器研究了Ｍｏ－Ｆｅ氧化物／载体催化剂对甲醇氧化制甲醛的催化性能。对二元Ｍｏ－Ｆｅ氧化物进行了气体敏感性能测试，发现对甲醇具有较高的灵敏度，对氧气的灵敏度较低。其中，具有较高活性的催化剂对被测气体的灵敏度也较高     

烃与DMF物系UNIFAC参数的修订和应用

由１，３─丁二烯／ＤＭＦ和１─丁烯／ＤＭＦ二元物系汽液平衡数据，修订了ＣＨ＿２／ＤＭＦ和Ｃ＝Ｃ／ＤＭＦ两对ＵＮＩＦＡｃ基团交互作用参数值，并以此关联了Ｃ＿４─ＤＭＦ物系的全部Ｗｉｌｓｏｎ方程参数。经应用于丁二烯萃取精馏装置全流程模拟，证明所修订参数的准确度高，通用性强。     

甲醇胺化有关产品的汽—液平衡测定

本文测定了与甲醇胺化产物有关的ＮＨ３－ＣＨ３ＯＨ，ＮＨ３－二甲胺（ＤＭＡ），ＮＨ３－一甲胺（ＭＭＡ），ＮＨ３－Ｈ２Ｏ，ＤＭＡ－ＣＨ３ＯＨ，ＤＭＡ－Ｈ２Ｏ，ＭＭＡ－ＣＨ３ＯＨ，ＭＭＡ－Ｈ２Ｏ和ＭＭＡ－三甲胺（ＴＭＡ）九个二元系在２０，３０，４０，５０，６０，７０，８０，９０，１００和１２０℃下的总压Ｐ和汽液总组成数据，用间接推算法计算了等温汽－液相平衡数据，给出了以实验数据拟合所得Ｗｉｌｓｏｎ参数Ａ     

DBN的合成及其在甲醇醇碳化反应中的应用

建立了一个高收率、重复性好的１，５－二氮杂双环［４，３，０］壬烯－５（ＤＢＮ）的合成方法。所得产物ＤＢＮ及中间产物均经红外光谱验证。考察了ＤＢＮ有ＤＢＮ添加环氧丙烷（ＰＯ）体系对甲醇羰化合成甲酸甲酯（ＭＦ）反应的催化作用。数据表明ＤＢＮ添加添环氧丙烷体系的活性高、选择性好。     

Current Status of and Recent Developments in the Direct Methanol Fuel Cell

The direct methanol fuel cell (DMFC) has been discussed recently as an interesting option for a fuel‐cell‐based mobile power supply system in the power range from a few watts to several hundred kilowatts. In contrast to the favoured hydrogen‐fed fuel cell systems (e.g. the polymer electrolyte membrane fuel cell, PEMFC), the DMFC has some significant advantages. It uses a fuel which is, compared to hydrogen, easy to handle and to distribute. It also comprises a fairly simple system design compared to systems utilising liquid fuels (like methanol) to produce hydrogen from them by steam reforming or partial oxidation to finally feed a standard PEMFC. Nevertheless, many severe problems still exist for the DMFC, hindering its competitiveness as an option to hydrogen‐fed fuel cells. This work reviews the major research activities concerned with the DMFC by highlighting the problems (slow kinetics of the anodic methanol oxidation, methanol permeation through the membrane, carbon dioxide evolution at the anode) and their possible solutions. Special attention is devoted to the steady state and dynamic simulation of these fuel cell systems.     

Model-based analysis of the feasibility envelope for autonomous operation of a portable direct methanol fuel-cell system

Portable power systems based on direct methanol fuel cells (DMFC) have to provide power in various environmental conditions: it is advantageous for such a power-supply system to be autonomous, i.e. able to operate without water refills for the methanol solution. It is shown that system autonomy depends mainly on environmental humidity, condenser temperature and air excess ratio: this result is valid in general for any DMFC, as cell parameters have only a marginal role. The environmental conditions in which a portable DMFC system may be autonomous are considered, delineating a feasibility envelope. Two methods are proposed to extend this envelope: operating with a diluted methanol reservoir, which improves the autonomy of the system only marginally and at the cost of a large loss in energy density, and system pressurisation, which delivers a more significant improvement in autonomy properties, but at the cost of system efficiency and simplicity.     

A Pumpless Methanol Feeding Method for Application in Direct Methanol Fuel Cell Systems

This paper presents a simple and reliable pumpless methanol feeding (PLMF) method for application in direct methanol fuel cell (DMFC) systems. The primary feature and advantage of the PLMF is as follows: it employs an approach that allows the cathode gas pressure to be connected with a fuel container for supplying the methanol fuel into the anode fuel loop, instead of using any feeding pump or other specially designed apparatuses. The PLMF has been used in a portable 25 W DMFC system and realised feeding methanol in real time for meeting the requirements of the system. The PLMF method not only is suitable for the DMFC system, but also can be used in other liquid‐feeding fuel cell systems.     

Operation Characteristic Analysis of a Direct Methanol Fuel Cell System Using the Methanol Sensor‐less Control Method

The application of methanol sensor‐less control in a direct methanol fuel cell (DMFC) system eliminates most of the problems encountered when using a methanol sensor and is one of the major solutions currently used in commercial DMFCs. This study focuses on analyzing the effect of the operating characteristics of a DMFC system on its performance under the methanol sensor‐less control as developed by Institute of Nuclear Energy Research (INER). Notably, the influence of the dispersion of the methanol injected on the behavior of the system is investigated systematically. In addition, the mechanism of the methanol sensor‐less control is investigated by varying factors such as the timing of the injection of methanol, the cathode flow rate, and the anode inlet temperature. These results not only provide insight into the mechanism of methanol sensor‐less control but can also aid in the improvement and application of DMFC systems in portable and low‐power transportation.     

Performance evaluation of the incorporation of different wire meshes in between perforated current collectors and membrane electrodeassembly on the Passive Direct methanol fuel cell

Passive Direct methanol fuel cells (DMFC) are more suitable for charging small capacity electronic devices. In passive DMFC, the fuel and oxidant are supplied by diffusion and natural convection process on the anode and cathode sides respectively. Current collectors (CC) play a vital importance in fuel cell performance. This paper presents the combined impact of perforated and wire mesh current collectors (WMCC) on passive DMFC performance. Three types of open ratios of perforated current collectors (PCC), such as 45.40％, 55.40％and 63.40％and two types of wire mesh current collectors with open ratios of 38.70％and 45.40％were chosen for the experimental work. A combination of Taguchi-L9 rule is con-sidered. A combination of three PCC and two WMCC on both anode and cathode was used. Methanol con-centration was varied from 1 mol·L-1–5 mol·L-1 for nine combinations of PCC and WMCC. From the experimental results, it is noticed that the combination of PCC and WMCC with an open ratio of 55.40％ and 38.70％ incorporated passive DMFC produced peak power density at 5 mol·L-1 of methanol concentration. The passive DMFC performance was evaluated in terms of maximum power density and maximum current density. The combined current collectors of PCC and WMCC open ratios of 55.40％+38.70％ have more stable voltage than single PCC of open ratio 63.40％ at 4 mol·L-1 of methanol concentration.     

直接甲醇燃料电池质子交换膜研究进展

直接甲醇燃料电池(DMFC)以其燃料来源丰富、储存方便、结构简单、安全等优点而日益受到广泛的关注。预计将在很多领域中能得到广泛的应用。过去,人们对DMFC做了很多研究,针对直接甲醇燃料电池中的质子交换膜(PEM)的阻甲醇性能方面的研究进展作如下评述。     

电解重整式甲醇燃料电池系统

为解决直接甲醇燃料电池中甲醇氧化活性低及甲醇穿透问题,提出一种新型的电解重整式甲醇燃料电池系统。在系统中,高温电解重整器重整甲醇为常温燃料电池供氢,燃料电池的部分电能供给电解重整器使用。通过对系统的物料流、焓流、有效能流的分析,确定了系统中的不可逆因素。结果表明:电解重整器电压是影响系统效率的重要参数;升高重整器温度可以显著降低其电压,但必须采用合理的压力、甲醇溶液浓度以抑制甲醇溶液的蒸发,降低热量损失。与传统的直接甲醇燃料电池系统以及高温甲醇热重整联合质子交换膜燃料电池系统相比,该系统性能较高、结构紧凑。     

直接甲醇燃料电池阳极催化剂的制备

直接甲醇燃料电池（DMFC）阳极催化剂是DMFC的关键材料之一,其电化学活性的大小对燃料电池的输出性能及成本起着关键作用。不同催化剂的制备技术决定了催化剂电化学活性的高低。介绍了DMFC阳极催化剂的几种制备方法,并对这些方法进行了评述,对制备DMFC阳极催化剂具有很好的参考价值。     

Portable Size DMFC‐Stack

A small, low temperature, direct methanol fuel cell stack for portable applications has been developed. Several flow field designs were investigated with respect to stable operation and high performance. Due to carbon dioxide and water production on the anode and cathode, respectively, methanol and oxygen access to the electrodes is hindered. During single cell operation the effect of both carbon dioxide evolution and water production on the current output was observed. The difference between parallel and serial feeding of both fuel and oxidant to the DMFC stack was also investigated. It was found that it is very important to remove reaction products from the active cell surface in order to ensure stable stack operation at low temperatures. The maximal power realised with the 12‐cell direct methanol fuel cell stack was 30 W.     

Effect of operating conditions on energy efficiency for a small passive direct methanol fuel cell

Energy conversion efficiency was studied in a direct methanol fuel cell (DMFC) with an air-breathing cathode using Nafion 117 as electrolyte membrane. The effect of operating conditions, such as methanol concentration, discharge voltage and temperature, on Faradic and energy conversion efficiencies was analyzed under constant voltage discharge with quantitative amount of fuel. Both of Faradic and energy conversion efficiencies decrease significantly with increasing methanol concentration and environmental temperature. The Faradic conversion efficiency can be as high as 94.8%, and the energy conversion efficiency can be as high as 23.9% if the environmental temperature is low enough (10 °C) under constant voltage discharge at 0.6 V with 3 M methanol for a DMFC bi-cell. Although higher temperature and higher methanol concentration can achieve higher discharge power, it will result in considerable losses of Faradic and energy conversion efficiencies for using Nafion electrolyte membrane. Development of alternative highly conductive membranes with significantly lower methanol crossover is necessary to avoid loss of Faradic conversion efficiency with temperature and with fuel concentration.