浆态床中二氧化碳加氢合成甲醇

研究了浆态床中自行开发的LP201甲醇合成催化剂上二氧化碳加氢合成甲醇的过程。探讨了不同操作条件，如温度、压力、气体空速、原料气配比等对反应的影响；考察了该催化剂在浆态床二氧化碳加氢合成甲醇过程中的稳定性。实验结果表明，浆态床二氧化碳加氢合成甲醇过程中主要产物为甲醇、CO和水；随温度的增加，CO2的转化率和甲醇产率呈现上升的趋势，但甲醇的选择性明显下降；压力的升高有利于CO2的转化率、甲醇产率以及甲醇的选择性提高；原料气空速的提高会增大甲醇产率，但同时降低CO2的转化率以及甲醇的选择性；CO2的转化率、甲醇收率以及甲醇的选择性在氢碳摩尔比4～5获得极大值。LP201催化剂的寿命考察结果表明，该催化剂具有较好的催化活性和稳定性。     

费托合成熔铁催化剂对液体产物的影响

实验考察了温度、压力、H2/CO和空速等不同操作条件对固定床熔铁催化剂费托合成液态产物的影响,得出了液态产物在不同操作条件下的时空产率、烃类产率、含碳量(C5～C13)、烯烷比及正构烷烃与支链烷烃(正支比)的一些变化规律。     

CO_2碳酸化石灰岩酸解产物回收乙酸及副产沉淀碳酸钙

乙酸酸解石灰石造腔是一种建造地下储库同时环保地开采石灰岩制备沉淀碳酸钙的新方法。通过耦合乙酸酸解石灰石及酸解产物乙酸钙CO2碳酸化的工艺过程,研究了乙酸酸解石灰岩的表面反应动力学和乙酸钙CO2碳酸化的工艺技术条件。采用正交实验分析法,研究了CO2碳酸化反应中乙酸钙浓度、反应温度、CO2压力、反应时间对乙酸钙碳酸化反应制沉淀碳酸钙的影响,并通过正交实验确定了最优化操作条件。实验结果表明,乙酸酸解反应速率主要受乙酸浓度控制。CO2碳酸化反应在当乙酸钙溶液浓度为0.631 mol·L-1,CO2压力为5.0 MPa,温度为80℃,反应时间为50 min时CO2碳酸化效率达到最高(23.13%),生成的沉淀碳酸钙产品各项指标均符合中国国标优级要求。     

铱催化ω-苄基苯乙酮类化合物的合成研究

以碳双三苯基膦氯化铱(Ir(Pph_3)(CO)Cl)为催化剂,3,3-二苯丙基-2-丙烯-醇类化合物(1a~1g)为原料合成ω-苄基苯乙酮类化合物(2a~g),其结构经过核磁共振氢谱、碳谱和元素分析表征确认。以3,3-二苯丙基-2-丙烯-醇(1a)为模板,研究了催化剂、物料比γ[n(3,3-二苯丙基-2-丙烯-醇):n(Ir(Pph_3)(CO)Cl)]、溶剂以及温度对2a产率的影响。确定了最终的反应条件为:温度为100℃,催化剂为3 mmol%的Ir(pph_3)(CO)Cl,溶剂为甲苯,碱性添加剂为K_2CO_3,并通过最优条件合成了7种羰基化合物2a~2g,产率介于85%~98%之间,此方法具有操作简单、原子经济性好、产率高、底物普适性良好等诸多优点。     

基于Aspen Plus甲醇合成宏观动力学研究

选取Langmuir-Hinshelwood-Hougen-Watson型动力学方程,利用Aspen Plus对C306催化剂上甲醇合成过程进行动力学模拟,模拟结果能较好地与文献值吻合。分析操作参数和氢碳比对CO、CO2转化率影响。结果显示,在恒定操作压力条件下,CO转化率在进料气入口温度为496~504K时达到最大,与之对应,CO2转化率则在490~495K时达到最大;在相同入口温度下,提高操作压力有利于增加CO、CO2转化率;氢碳比提高有利于CO转化。     

基于Ramberg-Bcklund反应的白藜芦醇合成

以3,5-二甲氧基苯甲醛、对甲氧基苄醇为原料,经合成硫醚和砜的中间产物,再利用Ramberg-Backlund反应将砜转化为反式碳碳双键,最后脱去甲基获得白藜芦醇。研究探讨了反应条件对硫醚氧化和对Ramberg-Backlund反应的影响。结果表明,在以H2O2-SeO2为氧化剂,CH3OH为溶剂的条件下,硫醚的氧化效果最佳,砜的产率可达82%;在以CCl4-KOH作为卤化试剂,V(正丁醇)∶V(水)=6∶1的正丁醇-水作为溶剂的条件下,Ramberg-Backlund反应的效果最好,反式双键产物的产率为84%。该合成路线总产率为41%。产物及各中间体的结构经1H(13C)NMR、IR和ESI-MS确证。     

醇原位催化转化制备芳烃及机理

以不同的醇为原料,HZSM-5分子筛为催化剂,在微型固定床与气相色谱-质谱联用装置上进行了醇催化转化制备芳烃的研究,考察了醇的碳链长度以及反应温度的影响。结果表明,醇的碳链长度对产物的分布有明显的影响,400℃下芳烃产率随着醇的碳链增长先增加,在正丙醇处获得最大的芳烃产率39.6%,而后降低并趋于稳定。随着温度的升高,甲醇、乙醇和正丙醇3种醇的产物分布变化趋势相同,芳烃产率均先增加后减小,在500℃获得最大值,分别为26.0%、36.5%和42.5%;随着温度的升高,CO、CO_2和烯烃的产率逐渐升高,但烃类产物总收率逐渐下降。高温下大分子芳烃逐渐向小分子芳烃转化,使得苯和甲苯的选择性逐渐增大。最后,结合原位红外表征和实验结果探讨了醇芳构化的反应机理:短碳链醇通过脱水得到醚和低碳烯烃,低碳烯烃再经过聚合得到长链烯烃,长碳链醇则可直接脱水得到长链烯烃,长链烯烃再通过环化反应生成环烷烃,最后环烷烃经过脱氢芳构化或分子间氢转移得到芳烃。     

Fischer-Tropsch合成中的CO活化机理

Fischer—Tropsch(F—T)合成是将煤炭、天然气和生物质等含碳资源间接转化为液体燃料的关键工艺步骤，深入了解其反应机理，对于完善F-T合成催化剂设计以及优化其工业操作条件具有重要的理论价值．对近年来有关F—T合成中关键的CO活化机理研究进行了总结和评述，着重介绍了不同过渡金属元素对CO的吸附和活化性质，并就金属晶面与CO的相互作用、催化助剂的影响以及F—T合成反应中与H2的共吸附作用等方面进行分析，为进一步的研究工作提供理     

浒苔热裂解制取生物油的试验

为了解决化石燃料短缺以及沿海浒苔过度繁殖所带来的问题,提出将浒苔做原料通过直接热裂解的方法转化为生物油。本文在实验室组装的反应器内系统地考察了温度、时间以及原料粒径对产物收率以及产物分布的影响。实验结果表明:实验原料的粒径越小,其生物油的产率越高;当反应温度为350℃,反应时间为40min,原料粒径为60目的最优条件下,生物油的产率高达30.5%,不凝气产率可达13.9%。对产物进行分析发现:生物油主要包含醛、酮、酚类以及醇、羧基酸、酯类等化合物;不凝气主要由CO2、CO、CH4以及C2～C5的小分子烃类组成。     

高折射率含硫环氧树脂的合成与表征

通过2，2‘-二巯基二乙硫醚（MES）与环氧氯丙烷反应，合成了一种新型高折射率，低色散的2，2‘－二巯基二乙硫醚缩水甘油醚型光学环氧树脂（DGEMES），采用红外光谱和核磁共振谱图表征了该树脂的结构，并详细讨论了直接法和间接法合成DGEMES的各种反应条件对产率的影响，得出直接法制取DGEMES的最佳原料配比为：n(MES):n(环氧氯丙烷）：n(NaOH)=1:5:1.9，产率为981％，折射率为1．5450，间接法制取DGEMES中的最佳原料配比为：n(MES):n(环氧氯丙烷）:n(NaOH)=1:2.4:6，产率为99．32％，折射率为1．5661。     

离子液体自模板合成多孔碳氮材料及其对二氧化碳的吸附

以多种氰基离子液体为前驱体，采用高温碳化法直接制备多孔碳氮材料，系统考察了离子液体前驱体阳离子结构、阴离子种类及合成条件等因素对碳化材料比表面积、氮元素含量及氮种类的影响，并研究其对CO2的吸附性能。结果表明，阴离子在聚合过程中起模板剂的作用。合成材料主要呈介孔结构，比表面积最高达732.6 m2/g，氮含量最高为9.9wt%，在温度25℃、压力1.8 MPa条件下，CO2的吸附量最高达20.9wt%。多孔碳氮材料经180℃真空加热后可完全脱附再生，再生稳定性良好。     

电催化还原二氧化碳制一氧化碳催化剂研究进展

电催化还原CO₂作为缓解能源危机和全球变暖的有效途径已成为催化领域的研究热点。然而,不同反应途径的氧化还原电位较为接近,使产物的选择性成为电催化还原CO₂所需解决的主要问题。迄今为止,在水性电解质中可实现CO₂选择性地转化为一氧化碳（CO）和甲酸（HCOOH）。本文简述了电催化还原CO₂制CO的机理,包括CO₂吸附过程、二电子转移过程和CO脱附过程。从贵金属的晶面设计、形貌调控和表面功能化对反应活性和产物选择性的影响,铁卟啉、钴酞菁和镍三嗪在还原CO₂为CO反应中的电子转移途径,非金属碳基材料中杂原子和碳基质间的耦合效应等方面,重点介绍了近年来贵金属催化剂、过渡金属络合物催化剂和非金属碳基材料催化剂的研究进展,总结了各类催化剂的优缺点。指出在三类电催化还原CO₂制CO的催化剂中,非金属碳材料具有较高的CO法拉第效率,尤其是非金属碳材料成本较低、制备简单、结构易调控,在电催化还原中具有潜在的应用优势,是有望实现商业化应用的新型催化剂的候选材料之一。     

Reduction of CO2 to CO at Cu–ceria-gadolinia (CGO) cathode in solid oxide electrolyser

The feasibility was investigated of using a Cu/CGO cathode for CO₂ reduction to CO in a high temperature solid oxide electrolyser (CO₂–CO, Cu/CGO|YSZ|YSZ/LSM|LSM, ambient air). An adherent layer of porous Cu/CGO electrode on YSZ electrolyte was achieved by sintering Cu/CGO paste at 1,000 °C for 5 h. Comparable performance was obtained with Ni/YSZ and Cu/CGO cathodes for CO₂ reduction at 750 °C and a 50:50 CO₂–CO feed; CO oxidation rates were faster than CO₂ reduction rates. Ohmic and polarisation resistances of the Cu/CGO electrode all decreased with decreasing CO₂:CO feed ratio. In the electrolytic mode, 100 % current efficiency for CO₂ reduction to CO was achieved on the Cu/CGO cathode at potential differences up to 1.5 V, above which the electronic conductivity of the YSZ electrolyte increased, causing a loss in effective current efficiency. Further increase in potential difference to ca. >2.3 V caused irreversible damage to the YSZ electrolyte due to its partial decomposition. No significant performance degradation, Cu sintering/migration, carbon deposition or electrode delamination was evident during 2 h of operating the electrolyser at 1.85 V and 750 °C for CO₂ reduction with a Cu/CGO cathode.     

碳源对碳热法制备LiFePO4/C复合电极材料性能的影响

以廉价的Fe2O3为铁源,(NH4)H2PO4为磷源,Li2CO3为锂源,分别以乙炔黑、葡萄糖、PEG6000为还原剂和碳源,采用碳热还原法制备了LiFePO4/C复合材料。X射线衍射(XRD)分析表明用三种碳源都合成了橄榄石结构的LiFePO4。扫描电子显微镜(SEM)分析显示,以PEG6000为碳源合成的LiFePO4/C复合材料粒径较小,较均匀,且有较好的碳包覆。以充放电曲线、循环性能和交流阻抗等测试研究了材料的电化学性能,结果表明,以PEG6000为碳源合成的材料的电化学性能较好,0.1C、1C下首次放点比容量分别为144.7 mAh/g、132 mAh/g。     

The effect of current density and temperature on the degradation of nickel cermet electrodes by carbon monoxide in solid oxide fuel cells

The oxidation of dry carbon monoxide (CO) in intermediate temperature solid oxide fuel cells (IT-SOFCs) has been studied using a three electrode assembly. Ni/CGO:CGO:LSCF/CGO three electrode pellet cells at 500, 550 and 600 °C were exposed to dry carbon monoxide for fixed periods of time, at open circuit and under load at 50 and 100 mA cm⁻², in an aggressive test designed to accelerate electrode degradation. It is shown that if the anode is kept under load during exposure to dry CO, degradation in anode performance can be minimised, and that under most conditions the anode showed significant irreversible degradation in performance after subsequent load cycling on dry H₂. Only at 500 °C and at 100 mA cm⁻² was the degradation in performance after operation on dry CO and subsequent load cycling on dry H₂ within the background degradation rates measured. Where anode performance was compromised, this appeared to be caused by a reduction in the exchange current density for hydrogen oxidation, and the relatively large degradation after load cycling on dry H₂ was primarily caused by an increase in the series resistance of the anode. It is suggested that this increase in series resistance is associated with the removal of carbon deposited in the non-electrochemically active region of the electrode during operation on dry CO, and that operation under load inhibits carbon deposition in the active region.     

KOH/甲醇溶液中Pb电极上电化学还原CO2

化学转化CO2为更有价值的物质对于缓解大气中的温室气体极为重要.以Pb片为工作电极,石墨电极为对电极,银-氯化银电极为参比电极,研究了0.1 mol(L(1 KOH/甲醇电解液中电化学还原CO2的行为.结果表明,在所考察的范围内,常压下CO和甲酸生成的法拉第效率在258 K时最大,分别为9.62%和78.74%,常温加压条件下,CO2压力为1.2 MPa时CO和甲酸生成的法拉第效率最大,分别为13.93%和24.00%.进一步进行电极反应的动力学研究,得CO2电化学还原生成CO和甲酸的反应级数分别为0.573和0.671.     

Palladium Catalysts for Fatty Acid Deoxygenation: Influence of the Support and Fatty Acid Chain Length on Decarboxylation Kinetics

Supported metal catalysts containing 5?wt% Pd on silica, alumina, and activated carbon were evaluated for liquid-phase deoxygenation of stearic (octadecanoic), lauric (dodecanoic), and capric (decanoic) acids under 5?% H₂ at 300?°C and 15?atm. On-line quadrupole mass spectrometry (QMS) was used to measure CO?+?CO₂ yield, CO₂ selectivity, H₂ consumption, and initial decarboxylation rate. Post-reaction analysis of liquid products by gas chromatography was used to determine n-alkane yields. The Pd/C catalyst was highly active and selective for stearic acid (SA) decarboxylation under these conditions. In contrast, SA deoxygenation over Pd/SiO₂ occurred primarily via decarbonylation and at a much slower rate. Pd/Al₂O₃ exhibited high initial SA decarboxylation activity but deactivated under the test conditions. Similar CO₂ selectivity patterns among the catalysts were observed for deoxygenation of lauric and capric acids; however, the initial decarboxylation rates tended to be lower for these substrates. The influence of alkyl chain length on deoxygenation kinetics was investigated for a homologous series of C₁₀?CC₁₈ fatty acids using the Pd/C catalyst. As fatty acid carbon number decreases, reaction time and H₂ consumption increase, and CO₂ selectivity and initial decarboxylation rate decrease. The increase in initial decarboxylation rates for longer chain fatty acids is attributed to their greater propensity for adsorption on the activated carbon support.     

纳米Cu电极的制备及其在电催化还原CO_2反应中的应用

Cu电极较之玻碳(GC)电极,更有利于CO2的电还原反应,而电沉积制备的纳米Cu电极可以进一步提高其电催化还原性能。本文考察了电沉积条件,包括沉积时间、H2SO4浓度、沉积电位、Cu2+浓度等对所制备的纳米Cu电极对CO2电还原反应催化性能的影响。针对该反应优化了纳米Cu电极的制备条件,并用SEM表征了其微观形貌。最后还将制备的纳米Cu电极运用于CO2与环氧丙烷的电合成反应,提高了碳酸丙烯酯的反应产率。     

Production of hydrogen and syngas via gasification of the corn and wheat dry distiller grains (DDGS) in a fixed-bed micro reactor

Production of hydrogen and syngas via gasification of the corn and wheat dry distiller grains (DDGS) with oxygen in a continuous downflow fixed bed micro reactor are studied in this paper. A series of experiments have been performed to investigate the effects of reaction time (15–45 min), reactor temperature (700–900 °C) and oxygen to nitrogen ratio (0.08–0.2 vol./vol.) on product gas composition, gas yield, low heating value (LHV) and carbon conversion efficiency. Over the ranges of the experimental conditions used, the results obtained seemed to suggest that for both biomasses the operating conditions were optimized for a gasification temperature around 900 °C, an oxygen to nitrogen ratio of 0.08 and a reaction time of 30 min, because a gas richer in hydrogen and carbon monoxide and poorer in carbon dioxide and hydrocarbons. The results showed that the product gas of corn DDGS gasification has higher H₂ and CO concentrations (11 and 56.5%) than that of wheat DDGS gasification (10.5 and 51.5%). In addition gasification of corn DDGS resulted to higher gas yield (0.42 m³/kg), LHV (10.65 MJ/m³) and carbon conversion efficiency (44.2%).