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.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Chemical characteristics of road dust PM2.5 fraction in oasis cities at the margin of Tarim Basin

In order to understand the compositions characteristics of particulate matter with aerodynamic diameter less than 2.5 μm (PM_2.5) fraction in road dust (RD_2.5) of oasis cities on the edge of Tarim Basin, 30 road dust (RD) samples were collected in Kashi, Cele, and Yutian in the spring, 2018, and RD_2.5 was collected using the resuspension approach. Eight water-soluble ions, 39 trace elements and 8 fractions of carbon-containing species in PM_2.5 were analyzed. Ca²⁺ and Ca were the most abundant ions and elements in RD_2.5 (7.1% and 9.5%). Cl^- in RD_2.5 was affected not only by attributed to saline-alkali soils in oasis cities of the Tarim Basin and dust from Taklimakan Desert but also by human activities. Moreover, the organic carbon/elemental carbon (OC/EC) ratio indicated that carbon components in RD_2.5 in Cele town mainly come from fossil fuel combustion, while those in Yutian and Kashi mainly come from biomass combustion. It is noteworthy that high Ca in RD_2.5 was seriously affected by anthropogenic emissions, and high Na and K contents in RD_2.5 could be derived from soil and desert dust. It was estimated that Cd, Tl, Sn and Cr were emitted from anthropogenic emissions using the enrichment factor. The coefficients of divergence (COD) result indicated that the influence of local emission on road dust emission is greater than that of long-distance transmission. This study is the first time to comprehensively analyze the chemical characteristics of road dust in oasis cities, and the results provides the sources of road dust at the margin of Tarim Basin.     

驾驶舱空气动力源致振动响应分析研究

目的分析驾驶舱外形上多处凸起对驾驶舱内若干重要部位的振动响应的影响。方法首先采用大涡模拟方法,计算多种飞行工况下分离气流产生的作用于机身前段外表面的非定常脉动压力载荷,然后将所得载荷作用于前机身详细有限元模型上,获得所关心的驾驶舱内部分站位的加速度响应。结果通过对加速度响应结果的分析处理及与试飞测试数据对比,可知驾驶舱外形上多处凸起对驾驶舱内的振动量值影响比较大,气流分离对驾驶舱舱内振动贡献,峰值位置处达到了25%左右。结论相关计算结果可用于驾驶舱工效性评估和驾驶舱外形优化。     

基于FLUS模型的湖北省生态空间多情景模拟预测

改革开放以来,中国经济在飞速发展的同时,生态环境问题日益严峻。为保障国家和地区的生态安全,对未来生态空间进行模拟预测十分必要。在长江大保护和长江经济带绿色发展背景下,以湖北省为研究区,利用FLUS模型基于湖北省2010年、2015年土地利用数据及包含自然和人文因素的15种驱动因子数据,对2035年的湖北省生态空间进行模拟预测。结果表明：利用2010年土地利用现状模拟出的2015年湖北省土地利用变化情况,总体精度达到0.976,Kappa系数达到0.961,模拟精度较高。设置的生产空间优先、生活空间优先、生态空间优先以及综合空间优化4种不同情景,基本满足未来湖北省不同发展导向的需求。从地貌单元角度来看,在不同情景下,湖北省生态空间主要分布于湖北省边陲四大山区,中部江汉平原生态空间零星分布。从数量规模上来看,不同情景下各个用地类型数量规模差异较为明显,生产空间优先情景下耕地面积增加1216 km²,生活空间优先情景下城镇用地规模增加5959 km²,生态空间优先情景下生态空间用地增长722 km²,综合空间优化情景下生态空间用地规模变化更趋于平缓。从生态空间变化分布来看,四大山区的生态空间变化不大,但中部江汉平原生态空间变化较为明显,其中从行政区划上来看,变化范围主要分布于武汉城市圈、襄阳市、宜昌市中西部地区及随州市中部地区。总而言之,FLUS模型对于湖北省生态空间模拟的适用性较好,多情景模拟结果可为湖北省未来国土空间规划及未来生态空间管控提供多角度、多方向的政策决策参考。     

珠江口夏季海陆源有机碳的模拟研究——分布特征、贡献比重及其迁移转化过程

基于经过验证的三维水动力-水质模型,对珠江口夏季有机碳进行海陆源区分,并对海陆源有机碳的分布特征、贡献比重及其通量过程进行研究.结果表明,水平方向上,珠江口夏季陆源（海源）有机碳浓度从口门到外海逐渐降低（升高）,在表、底层海水中平均浓度分别为1.45和0.87mg/L（0.97和1.05mg/L）;垂直方向上,在层化水域陆源（海源）有机碳浓度从上到下逐渐递减（升高）,在非层化水域海陆源有机碳浓度垂向分布较为均匀.珠江口夏季海源有机碳贡献率表层海水低于底层海水,平均贡献率为48.26%,沿向海方向海源有机碳贡献率逐渐增加--从内伶仃洋水域的4.43%逐渐提升到外伶仃洋东侧水域的81.20%.珠江口水动力条件复杂,在径流、潮汐、季风等因素的作用下陆源有机碳向海输送且向海输送量逐渐递减;海源有机碳在不同水域动力输送特征不同,西南水域向海输送,向海输送量逐渐递增;东北水域向岸输送,向岸输送量逐渐递减.陆源有机碳生化反应活性较弱,只有小部分被生化过程消耗,其迁移转化主要由沉降过程控制,而海源有机碳的迁移转化,则由口门的动力输送过程主控向外海的生化耗碳过程主控过渡.此外,海源有机碳沉降作用明显低于陆源有机碳,生化作用明显高于陆源有机碳.     

石油污染土壤多酚氧化酶的动力学及热力学特征

土壤多酚氧化酶是一种氧化还原酶,能够将土壤中芳香族化合物氧化成醌,促进土壤中石油类物质的分解转化.以距大庆油田工作区不同距离（1、5、15 km）的石油污染地为对象,研究不同温度下石油污染裸地及羊草（Leymus chinensis）修复地的土壤多酚氧化酶活性及其动力学和热力学特征的变化.结果表明:土壤多酚氧化酶活性随温度和底物浓度的增加而逐渐增大,在温度为30℃或40℃、底物浓度为80 mmol/L或160 mmol/L时达到最大值;各样地土壤酶的动力学参数K_m（Mihaelis常数）随温度的变化规律不同,V_max（酶促反应最大速度）和V_max/K_m（催化效率）随温度升高而逐渐增大,均在30℃或40℃时达到最大值;热力学参数Q₁₀（温度系数）、ΔH（活化焓）、ΔS（活化熵）随温度变化差异不显著,ΔG（活化自由能）随温度升高呈逐渐增加趋势.在同一温度下,石油污染裸地土壤多酚氧化酶活性高于羊草修复地;K_m和V_max/K_m在各样地均表现为无规律性变化,V_max最大值出现在距油田工作区5 km处的裸地（BMP）,最小值出现在距油田工作区5 km处的羊草修复地（LMP）;Q₁₀、E_a（活化能）、ΔH、ΔS的最大值均出现在距油田工作区1 km处的裸地（BVP）,最小值均出现在距油田工作区1 km处的羊草修复地（LVP）.研究显示,升温和植物修复对土壤多酚氧化酶活性的反应特征有较大影响.      

模拟盐水入侵及Fe(III)浓度增强对河口感潮淡水沼泽湿地土壤反硝化速率及理化特征的影响

以闽江河口塔礁洲感潮淡水野慈姑(Sagittaria trifolia Linn.)湿地为研究对象,于2016年2、4、7和9月每月均在连续2个小潮日内向研究样地施加人造海水和Fe(OH)_3溶液,研究短期的盐水入侵及Fe(III)浓度增强对河口感潮淡水湿地土壤反硝化速率及理化特征的影响.结果表明,短期的盐水入侵、Fe(III)浓度增强对河口感潮淡水沼泽湿地土壤反硝化速率的影响不显著,然而,盐水和Fe(III)共同施加会显著提高湿地土壤反硝化速率,与对照(CK)相比,盐水和Fe(III)共同施加可使土壤反硝化速率提高270.9%.盐水入侵、盐水和Fe(III)共同施加均可显著提高湿地土壤、间隙水的电导率及Cl~-、SO_4~(2-)的含量;Fe(III)浓度增强可显著降低土壤和间隙水pH值,同时显著提高土壤三价铁含量.     

双区静电除尘器的数值模拟研究

采用数模拟的方法研究了双区静电除尘器内流场分布、颗粒荷电及颗粒运动等难以直接测量的物理过程,构建了双区静电除尘过程完整的数值模型.采用泊松方程、电流连续性方程和匀强电场方程描述电场,采用N-S方程和雷诺应力标准湍流模型描述流场,采用拉格朗日法描述颗粒运动轨迹.通过截面风速与颗粒去除率的模拟值与实验值的对比,验证了数值模型在模拟内部流场和颗粒运动时的准确性.数值模拟结果表明：双区静电除尘器内部流场分布对入口风速的变化非常敏感;颗粒荷电方式占比由颗粒粒径决定;荷电区内颗粒向极板的趋近过程由流体曳力和电场力共同完成,收尘区内的趋近过程则由电场力主导;入口流速通过改变颗粒前进速度和内部流场形态来影响颗粒运动轨迹.     

考虑边界条件不确定性的地下水污染风险分析

为分析边界条件不确定性对地下水污染质运移数值模拟模型输出结果的影响,运用Monte Carlo方法对一算例进行阐明,并从污染风险预报方面对模拟结果进行分析.为减少重复调用模拟模型产生的大量计算负荷,将边界条件（第一类边界条件-水头值）作为随机变量,建立地下水污染质运移数值模拟模型的Kriging替代模型,在保证较高精度的同时,实现了Monte Carlo模拟.结果表明：边界条件的不确定性,对地下水污染质运移数值模拟模型预报的结果有很大影响,考虑与未考虑边界条件不确定性得到的研究区污染羽分布差别较大.对地下水污染质运移数值模拟模型的Monte Carlo模拟结果进行统计与分析,可以评估研究区观测井1,2,3污染物浓度预报结果的可靠程度,并且可以预报出研究区观测井1,2,3遭受不同程度污染的风险.