CuO修饰的赤泥载氧体废弃活性炭化学链燃烧

以拜耳法赤泥为基体,采用浸渍法制备了CuO修饰的赤泥载氧体（Cu0.5RM1、Cu1RM1）。利用SEM-EDSmapping、XRD对其进行物化表征,并在高温流化床反应器及热重分析仪中考察了赤泥载氧体的废弃活性炭化学链燃烧特性。结果表明,浸渍法可准确制备定量CuO修饰的赤泥载氧体;相比于纯赤泥载氧体,CuO修饰的赤泥载氧体具有化学链燃烧载氧体与化学链氧解耦燃烧载氧体的双重特性,能够加快碳转化速率,有效提高出口气体中CO₂浓度;Cu1RM1反应活性较高,875℃为其较优的反应温度,此时t₉₅为28min,出口气体中CO₂浓度为92.9%（体积分数）,燃烧效率达93.0%。10次循环实验表明Cu1RM1载氧体具有相对稳定的循环反应特性。     

高铝耐火砖负载CuO氧载体的化学链氧解耦特性实验

耐火砖常用作高温炉膛材料,具有较高的破碎强度和较强的抗烧结性能。以耐火砖颗粒为惰性载体,采用连续浸渍法制备CuO质量分数为10%～30%的Cu10RefBri、Cu25RefBri和Cu30RefBri氧载体样品,并在热重分析仪（TGA）和批次进料流化床反应器中900～950℃下进行了化学链氧解耦燃烧过程氧载体的释氧-吸氧循环实验测试。结果显示,在上述氧载体样品中Cu25RefBri的释氧速率最高,可达9×10^-5kgO₂/(s?kgOC),流化床中稳定的O₂体积分数可达1.1%。然而,随着循环次数增加,Cu25RefBri的释氧速率逐渐降低至2.0×10^-5kgO₂/(s?kgOC),同时流化床尾气中O₂体积分数降低至0.7%,该值远低于对应温度下的平衡O₂浓度值。氧浓度和释氧速率降低的主要原因在于：循环过程氧载体中形成的低释氧活性的CuAl₂O₄尖晶石含量逐渐增加,导致氧载体总体活性下降。此外,在950℃流化床实验过程,还检测到氧载体颗粒的烧结现象。     

CuO/Al_2O_3载氧体的制备和表征

以CuO为载氧体,通过化学链燃烧法进行煤层气脱氧的研究。采用共同沉淀法制备了一系列不同负载量的CuO/Al_2O_3载氧体,并通过TGA、XRD、BET、SEM等分析技术对载氧体进行了表征,考察了不同CuO负载量和氧气体积分数对氧化反应的影响。结果表明:CuO的负载量和氧气体积分数对氧化反应速率有很大影响。当负载量为80%时,CuO/Al_2O_3载氧体具有较高氧化活性和化学链循环稳定性。经过循环20次,还原性能和氧化性能均未见明显降低。在氧气体积分数为5.1%时,氧化反应仍然可以达到80%的转化率。     

高铁高钙煤灰载氧体反应特性及机理分析

运用TGA在CO/Air的氛围下,对灰的反应性能以及循环特性进行测试。通过XRD和SEM,研究了灰在不同温度下反应过程中物质结构和微观形貌变化。结果表明:灰的释氧量约为21%,最佳的反应温度为850℃且具有良好的反应性能及循环能力。XRD检测结果显示灰中主要载氧物质为Fe_2O_3和CaSO_4,还原过程中Fe_2O_3被还原为Fe/FeS,CaSO_4被还原为CaS。SEM结果显示,不同温度反应后灰表观形貌变化不大。灰反应机理:在样品表面,CO/O_2与反应物接触并反应;随着产物层逐渐加厚,这时反应的发生依赖于O在产物层中扩散及物质间的固固反应。     

小型流化床实验台上镍基载氧体的积炭特性

采用小型流化床反应器,研究了Ni基载氧体在不同还原气氛（CH4、CO+H2）和不同反应温度（650 ℃、750 ℃、850 ℃、950 ℃）下的反应特性。结果表明：Ni基载氧体在两种气氛下均表现出较高的反应活性,CO+H2气氛下的还原反应比CH4气氛下的还原反应更完全,两个还原过程中均有积炭的产生,CH4气氛下的积炭比CO+H2气氛下的积炭更为严重;在CH4气氛下,温度的升高有利于Ni基载氧体还原反应的进行,同时还原过程中产生的积炭量也随着温度的升高有所增加,但当温度升高到850 ℃后,温度的增加对还原反应的影响不大。另外,相比于Cu基载氧体,Ni基载氧体虽然有更好的反应活性,但在还原过程中更容易产生积炭。     

基于铜基载氧体的化学链空分制氧系统的研究

基于铜基载氧体，运用流程模拟软件Aspen plus对化学链空分制氧系统展开了研究，构建化学链制氧系统模型，分析了反应温度，载气流量等因素对系统性能的影响，对化学链空分制氧系统进行参数优化。此外，本文也构建了传统的深冷空分制氧系统，与化学链制氧系统进行了对比分析。结果表明：较高的释氧反应器温度可提高氧气浓度和氧气的摩尔流量；水蒸气流量的增加也有利于释氧反应的进行。与深冷空分制氧技术相比，化学链空分制氧技术不仅系统能耗较低，而且制备的氧气浓度也较高。     

CuO修饰Fe基载氧体的锡盟褐煤化学链燃烧特性分析

为提高Fe基载氧体性能以及研究锡盟褐煤化学链燃烧特性,以硝酸盐试剂及CuO粉末为原料,通过共沉淀法制备了不同质量分数CuO修饰的Fe基载氧体且使用固定床制备褐煤焦样,对制得的载氧体进行表征分析,并在小型流化床反应器中进行了褐煤及其煤焦的化学链燃烧实验。结果表明:实验制得的载氧体完成了良好的结晶过程,且经CuO修饰后的载氧体中出现了CuFe₂O₄;在褐煤化学链燃烧实验中,相比于不经CuO修饰的Fe基载氧体,修饰后的载氧体具有更好的反应活性,具体表现在碳转化率方面,通过对不同质量分数CuO修饰的Fe基载氧体进行实验分析,10%CuO修饰的载氧体褐煤化学链燃烧中碳转化率为94.84%,较不修饰情况下的89.49%提升明显,同时碳转化速率峰值为23.81mol·%·min^-1,在相同时间内较不修饰情况提升4.21mol·%·min^-1,使用10%CuO修饰的载氧体进行褐煤焦化学链燃烧实验时碳转化率高达95.80%;循环实验中,15次化学链燃烧实验循环后,褐煤化学链燃烧碳转化率为88.69%,对反应后的载氧体表征分析表明,10%CuO修饰的Fe基载氧体仍保持了较为稳定的性能。     

具有自载体功能的CoFeAlO_4载氧体化学链燃烧反应特性

采用燃烧法合成了具有尖晶石结构的CoFeAlO_4载氧体材料,通过表征手段和实验研究考察了不同温度下CoFeAlO_4载氧体的化学链燃烧反应特性和循环稳定性,并对CoFeAlO_4载氧体晶相结构和表观形貌的变化规律进行了分析。结果表明,温度升高有利于提高CoFeAlO_4载氧体转化还原性气体CO的能力,使得还原反应速率更快,但高温下经"还原-氧化"会造成CoFeAlO_4载氧体相态分离,难以保持稳定的自载体尖晶石结构。对反应前后CoFeAlO_4载氧体晶相结构的分析表明,高温条件下经过"还原-氧化"后生成的CoFe2O4和CoAl2O4是导致CoFeAlO_4载氧体烧结和循环稳定性下降的主要原因。     

钙基复合载氧体的制备及反应性能

采用湿式混合成粒法得到了一种复合型钙基载氧体,并分别在综合热分析仪和流化床上考察了其反应活性和循环反应性能。结果如下:浸渍Ni离子能够明显降低载氧体与煤反应的起始温度,加快反应速率,缩短反应时间。增加Ni离子浸渍量对反应速率的影响不明显,但反应时间略有缩短。选择CaAlNi10载氧体进行了10次还原-氧化循环实验,固体产物和气体产物分析表明NiO在循环过程中对S的释放有一定控制作用;CaAlNi载氧体具有较高的再生率和良好的持续循环反应能力。结果表明,制备的CaAlNi载氧体适用于工业生产。     

具有自载体功能的CoFeAlO4载氧体化学链燃烧反应特性

采用燃烧法合成了具有尖晶石结构的CoFeAlO₄载氧体材料,通过表征手段和实验研究考察了不同温度下CoFeAlO₄载氧体的化学链燃烧反应特性和循环稳定性,并对CoFeAlO₄载氧体晶相结构和表观形貌的变化规律进行了分析。结果表明,温度升高有利于提高CoFeAlO₄载氧体转化还原性气体CO的能力,使得还原反应速率更快,但高温下经“还原-氧化”会造成CoFeAlO₄载氧体相态分离,难以保持稳定的自载体尖晶石结构。对反应前后CoFeAlO₄载氧体晶相结构的分析表明,高温条件下经过“还原-氧化”后生成的CoFe₂O₄和CoAl₂O₄是导致CoFeAlO₄载氧体烧结和循环稳定性下降的主要原因。     

Genipin,an Inhibitor of UCP2 as a Promising New Anticancer Agent: A Review of the Literature

Genipin is a protein cross-linking agent extracted from Gardenia (Gardenia jasminoides Ellis) fruits. This fruit has conventionally been used as a Chinese herbal medicine for the treatment of inflammation and jaundice and as an edible colorant in oriental countries. Uncoupling protein (UCP)-2 is a member of the family of uncoupling proteins, which are anion transporters positioned in the mitochondrial inner membrane. Genipin has been shown to have hepatoprotective activity, acting as an effective antioxidant and inhibitor of mitochondrial UCP2, and is also reported to exert significant anticancer effects. In this review, the author presents the latest progress of genipin as an anticancer agent and concisely describes its various mechanisms of action. In brief, genipin inhibits UCP2 to attenuate generation of reactive oxygen species (ROS), leading to ROS/c-Jun N-terminal kinase-dependent apoptosis of cancer cells. Genipin also increases the tissue inhibitors of matrix metalloproteases (MMP)-2, a kind of tumor promoter in a variety of cancers, as well as induces caspase-dependent apoptosis in in vitro and in vivo models. These findings suggest that genipin can serve as a promising novel antitumor agent that could be applicable for chemotherapy and/or chemoprevention for cancers.     

基于化学方法的活性污泥减量化技术

近年来,基于解耦联和化学氧化的污泥减量新方法得到了比较深入的研究。介绍了几种基于化学方法的活性污泥减量工艺,包括代谢解耦联法、高浓度溶解氧法、碱(酸)加热处理法、活性污泥-臭氧工艺、氯-活性污泥工艺和控制DO浓度工艺,阐述了这些技术的优点及其存在的不足,指出与物理法和生物法相比较,化学法在污泥减量化方面同样有非常好的应用前景。     

Chemical-looping with oxygen uncoupling using CuO/ZrO2 with petroleum coke

Oxygen carrier particles of CuO/ZrO₂ were reacted with petroleum coke using chemical-looping with oxygen uncoupling (CLOU). The fuel was burnt in gas-phase oxygen released from the oxygen carrier particles during the fuel oxidation. The particles were then regenerated in 5-21% oxygen. In this process, the carbon dioxide from the combustion is inherently separated from the rest of the flue gases without the need for an energy intensive air separation unit. Copper oxide has thermodynamic characteristics that make it suitable as an oxygen carrier in CLOU. Particles were prepared by freeze granulation and were exposed cyclically with petroleum coke and oxygen in a laboratory fluidized bed reactor of quartz. The reaction temperature and oxygen concentration during the oxidation were varied. The average conversion rate of petroleum coke was a function of temperature and varied between 0.5%/s and 5%/s in the set-point temperature interval 885-985 °C. The conversion rate is considerably higher than rates obtained with the same fuel using iron-based oxygen-carrier in chemical-looping combustion. As for the regeneration with oxygen, the reduced particles reacted at low oxygen concentrations, with a considerable part of the reaction occurring near the thermodynamic equilibrium.     

Production and examination of oxygen‐carrier materials based on manganese ores and Ca(OH)2 in chemical looping with oxygen uncoupling

This study concerns production of oxygen‐carrier particles using six different manganese ores. The ores were made to react with Ca(OH)₂ at elevated temperature, forming calcium manganite. The method utilized to manufacture particles was extrusion. Methane and syngas conversion and oxygen release of the samples in inert atmosphere were investigated. The oxygen carrier based on South African (B) manganese ore, showed good methane conversion and was able to transfer oxygen corresponding to 1.5% of its mass during reduction with gaseous fuel. All examined oxygen carriers were capable of converting syngas completely. The ability to release gaseous oxygen was examined by adding wood char in a stream of nitrogen for four selected samples sintered at 1300°C/6 h. These samples released an amount of oxygen corresponding to 0.37–0.68% of their mass. The reactivity of all the ores was improved after the proposed treatments. Reactivity results of the oxygen carrier made from South African (B) ore and Ca(OH)₂, sintered at 1300°C for 6 h were the most promising. Attrition measurements with a jet cup of the oxygen carriers sintered at 1300°C/6 h showed that all the samples made from ores were at least three times more resistant to mechanical attrition compared to particles made from synthetic Mn₂O₃. Producing feasible oxygen carriers directly from ores could potentially cut the cost of chemical looping with oxygen uncoupling and have a significant impact on its competitiveness among other carbon capture technologies. © 2013 American Institute of Chemical Engineers AIChE J 60: 645–656, 2014     

我国石化产业碳排放脱钩效应研究

以我国石化产业为研究对象,结合弹性脱钩理论,建立我国石化产业集群碳排放弹性分析的脱钩模型,对石化产业的减排脱钩弹性、能耗脱钩弹性、产业发展弹性效应分别进行计算与评价,并结合评价结果为我国石化产业的低碳化路径提出建议。结果表明:石化产业CO2排放量增长速率呈现先增后减的趋势,碳减排工作水平在2006年以后稳固提升;石化产业的能耗增长量整体处于较低水平,产业节能工作效果良好;石化产业发展迅速,特别是近几年来保持较高的速度,整体拉动了国家经济的发展。     

(MnzFe1—z)yOx combined oxides as oxygen carrier for chemical‐looping with oxygen uncoupling

Oxygen carrier particles with the composition (Mn_0.8,Fe_0.2)₂O₃ were found to readily release gas phase oxygen at 850°C, and were capable to oxidize CH₄ completely and convert wood char rapidly to CO₂ during experiments in a batch fluidized bed reactor. The particles were able to release oxygen corresponding to more than 3% of their mass in less than 40 s. Because of the low price and favourable environmental properties of manganese and iron oxides, this finding could be of great importance for the development of chemical‐looping combustion with oxygen uncoupling. © 2012 American Institute of Chemical Engineers AIChE J, 59: 582–588, 2013     

Reactivity study and kinetic evaluation of CuO-based oxygen carriers modified by three different ores in chemical looping with oxygen uncoupling (CLOU) process

In the chemical looping with oxygen uncoupling (CLOU) process,CuO is a promising material due to the high oxygen carrier capacity and exothermic reaction in fuel reactor but limited by the low melting point.The combustion rate of carbon is faster than the decoupling rate of oxygen carrier (OC).Hence,high tem-perature tolerance and rapid oxygen release rate of CuO modified by three different ores were investi-gated in this study.The kinetics analysis of oxygen decoupling with Cu-based oxygen carriers was also evaluated.Results showed that CuO modified by chrysolite had faster oxygen release rate than that of CuO.Limestone showed obvious positive effect on the oxidization process.The selected OCs could keep stable in at least 20 cycles,for about 1200 min.Shrinking core model (SCM) fitted well for the decoupling process in the temperature range of 1123-1223 K.Reduction rate kinetic information may aid in the development of chemical looping with oxygen uncoupling (CLOU) technologies during reactor design and process modeling.Ternary doped copper oxide with chrysolite and limestone could improve the reactivity of CuO in decoupling and coupling process and also improve the high temperature tolerance.     

新型抗肝片吸虫病药物的合成及构效研究

本论文总结了我们课题组以前研究工作中的规律和经验 ,合成了 1 3个新型抗肝片吸虫病药物化合物。对化合物的高效液相色谱、红外、紫光及核磁共振氢谱物理性质、结构特征进行了表征 ,同时还做了生物活性的测试。综合几项测试指标 ,分析了药物化合物的物理性质、结构特征对其药效的影响。结果表明 :适宜的弱酸性 ( pka=3.6～ 6.0 )和较大的脂溶性是药物具有良好药效的重要条件