Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME) by CO_2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO_2 catalysts that were physically mixed with a commercial ferrierite(FER) zeolite.The catalysts were characterized by N_2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO_2(CO_2-TPD),temperature programmed desorption of NH_3(NH_3-TPD),and temperature programmed H2 reduction(H_2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO) species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.     

钢铁企业富余煤气制甲醇与二甲醚的研究

利用钢铁联合企业的富余煤气,制甲醇与二甲醚.提出合理可行的工艺方案,进行主要物料消耗计算和成本估算,得出在工艺上和经济上可行的结论.项目的实施,能实现钢铁联合企业资源综合利用,提高企业的经济效益,同时对实现能源的多样化、发展新型清洁能源、改善生态环境都具有重要意义,其经济效益和社会效益显著.     

两种桑科植物叶片光合及光呼吸对模拟干旱的响应

采用150 g/L的聚乙二醇(Polyethylene glycol,PEG)模拟干旱胁迫,研究两种桑科植物(构树和桑树)的叶片光合及光呼吸特征对干旱胁迫的响应。对植物培养液的相关化学参数以及叶片的光合参数进行测定,结果表明:干旱对构树根系吸水能力的影响小于桑树的;构树以中光合-低蒸腾-高水分利用率的模式适应干旱环境,桑树以低光合-低蒸腾-高水分利用率的模式来应对干旱环境;在模拟干旱环境下,构树以稳定的羧化效率-高光呼吸速率-高光呼吸利用份额来适应外界胁迫,而桑树以低羧化效率-低光呼吸速率-低光呼吸利用份额来应对外界胁迫。构树表现出对外界干旱胁迫更好的适应性,这种适应机制可能与其较强的光呼吸作用及其碳酸氢根离子利用能力有关。这种"以碳换水"的机制可能是喀斯特适生植物适应岩溶干旱的又一个重要机制。     

我国城市污泥中醚类和卤代烃类有机污染物的初步研究

应用GC／MS联机检测技术对我国大陆和香港共11个城市污泥中4种醚类和4种卤代烃类化合物进行分析。结果表明，醚类化合物的总含量在0－7．743mg/kg之间，以双（2－氯异丙基）醚为主，主要分布在兰州污泥和广州污泥中；卤代烃类化合物的总含量在0．007－3．237mg/kg之间，以六氯环戊二烯为主，主要分布在兰州污泥、佛山污泥和沙田（香港）污泥中。污泥中醚类和卤代烃类化合物的种类及其含量与污水来源、污水处理方式、污泥类型、化合物的结构和理化性质等因素有关。     

混凝沉淀-水解酸化-生物吸附-UBF-接触氧化一氧化沟-吸附工艺处理聚醚多元醇废水

对聚醚多元醇废水采用混凝沉淀-水解酸化-生物吸附-UBF-接触氧化一氧化沟-吸附等进行连续处理。结果表明，该处理工艺具有废水处理效果好、出水水质稳定（出水水质达GB8978—1996中的一级标准）、操作管理方便等优点，是处理该类化工废水的有效方法之一。     

工程菌处理高纯二甲醚生产废水的研究

工程菌LEY7是以假单胞菌D3 菌株 (Pseudomonassp.D3 )为受体 ,以缓慢牙孢杆菌 3RM2 菌株 (Bacilluslentus 3RM2 ) ,假单胞菌W1 (Pseudomonassp .W1 )和W2 (Pseudomonassp .W2 )为供体 ,用多基因转化原生质球构建而成。工程菌LEY7能同时降解 4种化合物。用工程菌LEY7处理化工废水 ,工艺采用二级氧化。处理效果 :进水COD =10 0 0mg/L ,处理后出水COD在 10 0mg/L以下。COD去除率达到 90 %以上。     

A comparative study on the autoxidation of dimethyl ether (DME) comparison with diethyl ether (DEE) and diisopropyl ether (DIPE)

The Japanese government is planning to introduce DME as a substituted energy for oil and LNG. Introduction of DME could contribute greatly to both the prevention of global warming and the formation of resource-recycling societies. In these circumstances, a safety assessment of DME is very important when DME is used on a large scale. There is a possibility that prolonged exposure in air induces autoxidation to produce explosive organic peroxides during transportation and storage of DME. Therefore, the reactivity of DME with oxygen and the mechanism of the autoxidation were investigated. Accelerating Rate Calorimetry (ARC) was used to evaluate the thermal stability of DME and DIPE, a known peroxide producers, under adiabatic and various atmospheric conditions. In ARC studies of DME under oxygen, exothermic decompositions were detected although its self-heating rate was low in comparison with DIPE. Oven storage tests were carried out and iodimetry was used to measure the concentration of peroxides produced from DME in comparison with DIPE and DEE. However, no products could be found for DME either by GC/MS or by iodimetry, while some evidence of autoxidation of both DEE and DIPE were obtained from these experiments.     

Flammability limits of binary mixtures of dimethyl ether with five diluent gases

Flammability limits of binary mixtures of dimethyl ether with five kinds of diluent gases were measured by ASHRAE method at room temperature. The five diluent gases are nitrogen, carbon dioxide, chlorodifluoromethane (HCFC-22), 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The experimental results were correlated with the extended Le Chatelier's formula. It was found that the experimental results were well reproduced by the formula. In addition, flammability limits of binary mixtures of dimethyl ether with nitrogen and carbon dioxide were compared with the estimated values based on the adiabatic flame temperature method. The experimental results were found to be in satisfactory agreement with the estimated values.     

地下水循环井技术处理土壤和地下水中甲基叔丁基醚研究

研究了MTBE在砂土中的静态吸附以及采用地下水循环井技术(GCW)去除砂土和地下水中MTBE的衰减规律。结果表明:MTBE在砂土中的吸附动力学符合准二级动力学方程,相关系数R2为0.99618,在砂土中的吸附平衡时间为24 h;吸附热力学符合Linear平衡吸附,吸附系数为0.00306 m3/kg。GCW运行30 h后,地下水饱和含水层中MTBE浓度由500 mg/L降至72.5 mg/L,去除率为85.5%;砂土中MTBE的吸附量由0.93 mg/g降至0.03 mg/g,去除率达96.4%。水平方向距GCW越近,MTBE的去除效率越快,垂直方向位于GCW上部的MTBE优先会被去除,最佳修复时间为运行15 h。GCW对砂土和地下水中高浓度MTBE具有良好的修复效果。     

典型持久性有机污染物在翅碱蓬中的分布特征

碱蓬是潮间带的常见优势种群,为了解其在持久性有机污染物从陆域向海洋迁移中所起的作用,利用GC-MS研究了东营和营口潮间带盐沼植物翅碱蓬不同器官及根系土中有机氯农药(OCPs)、多环芳烃(PAHs)、十溴联苯醚(BDE209)和多氯联苯(PCBs)的含量和分布特征.结果表明,4类持久性有机污染物在翅碱蓬中的污染水平依次为ΣPAHsΣOCPsBDE209ΣPCBs(96～1506ng/g、14～577ng/g、1.8～33ng/g和399～2161pg/g).营口潮间带沉积物中OCPs、PAHs和PCBs的污染水平高于东营,但这3类污染物在两地潮间带翅碱蓬叶子中的含量水平相当.OCPs在两地翅碱蓬各器官中的分布相同,即茎根叶,PAHs和PCBs2种污染物受根系土中有机质含量的影响,在翅碱蓬器官中呈现不同的分布.BDE209在东营潮间带的污染水平(19.7ng/g)高于营口(2.36ng/g),在碱蓬器官中呈现不同分布.