WO3/MnO2/硅铝分子筛复合催化剂的制备及甲醛降解性能研究

以膨润土为原料通过水热合成法制备硅铝分子筛,并在其表面负载WO₃、MnO₂制备了WO₃/MnO₂/硅铝分子筛复合催化剂,研究了其孔结构、微观形貌、钨锰存在形式和分布、对甲醛的降解性能。结果表明,WO₃/MnO₂/硅铝分子筛以介孔结构存在,其孔径分布在4～5nm,比表面积大,达1665.0m²/g,而WO₃、MnO₂均匀分布在催化剂表面及内部结构中。由于WO₃/MnO₂/硅铝分子筛特殊的介孔结构、较大的比表面积和其表面钨、锰氧化物纳米颗粒均匀分散,在吸附和化学催化共同作用下,该复合催化剂在室温时对甲醛具有良好的降解性能,甲醛去除率可达92.0%。     

无机盐水解法制备介孔NiAl_2O_4纳米粉

介孔NiAl2O4材料是常用的电极材料和催化材料,目前常用溶胶-凝胶法制备。本文在不添加任何模板剂和有机溶剂的情况下,通过摩尔比为1︰2的硝酸镍和硝酸铝水溶液与碳酸铵水溶液水解的方法制备NiAl2O4介孔材料。利用热重-差热分析、X射线衍射、扫描电镜观察、透射电镜观察及N2吸附-脱附等测试手段表征。通过800℃焙烧,制备了NiAl2O4介孔材料,晶粒大小约30nm,比表面积为105.3m2/g,平均孔径为7.2nm,孔容为0.19cm3/g,孔径分布比较狭窄、规整。     

介孔SiO_2/多乙烯多胺复合固态CO_2吸附剂吸附性能的研究

针对目前CO2液态吸附剂能耗大、易挥发的问题,开发了介孔SiO_2/多乙烯多胺复合固态CO2吸附剂。通过使用磷酸作为造孔剂制备的SiO_2介孔材料,能够实现孔径在2~6nm内连续调控。用介孔SiO_2吸附液态CO2吸附剂(多乙烯多胺),可以显著提高气液接触面积,从而极大提高吸附效率。实验研究了吸附效率随多乙烯多胺质量分数的变化规律,分析了温度对吸附效果及再生效果的影响,揭示了再生效果随再生时间的变化规律。结果表明,制备的固态吸附剂能够100%吸收混合气体中的CO2,且当多乙烯多胺占介孔SiO_2的质量分数为20%、温度为60℃时,吸附剂对CO2的完全吸附效果达到最佳。     

CO2相变致裂煤的纳米孔隙尺度改造效应

为探讨不同CO₂相变致裂压力对纳米孔隙的尺度改造效应及其对瓦斯(煤层气)运移的影响，开展120,150,185 MPa作用下的CO₂相变致裂煤体实验，综合采用高压压汞、低温液氮吸附、低温CO₂吸附孔隙结构参数测试方法，分析CO₂相变致裂后煤的大孔(>50 nm)–介孔(2～50 nm)–微孔(<2 nm)结构演化特征。结果表明：CO₂相变致裂对大孔和介孔具有扩孔效应；致裂后，大孔平均孔径与孔容大幅度增大，孔表面积降低；介孔平均孔径增大，孔表面积明显降低；孔隙连通性明显增强。CO₂相变致裂过程时间极短，高压气体优先选择裂隙和大尺度孔隙进行扩展，延伸至微孔时，衰减的压力不足以改造具有化学性质的微孔。CO₂相变致裂在大孔–介孔尺度的扩孔效应，随致裂压力的增大而增强；不同变质、变形程度煤的大孔–介孔–微孔发育存在差异；因此，研发“高致裂压力–长作用时效–大能量”的CO₂相变致裂器，有助于进一步增强CO     

亚露点硫磺回收催化剂孔结构分析研究

用ASAP-2010型物理吸附仪、Autopore IV 9500型压汞仪研究了亚露点硫磺回收催化剂的比表面积、孔容积、孔径分布和孔喉比。结果表明,3种催化剂的小孔分布曲线近似为正态分布且孔径分布相似,为3.6nm左右;3种催化剂的孔型均为墨水瓶状;样品C的大孔平均孔径最大;3种催化剂的孔体积差异主要体现在大孔孔隙率上。     

介孔二氧化硅复合微球的制备及药物控释应用

采用溶胶-凝胶法,以三乙醇胺为碱性沉淀剂,十六烷基三甲基溴化铵(CTAB)为模板剂,正硅酸乙酯(TEOS)为硅源,制备了介孔结构介孔二氧化硅纳米粒子(MSNs)。以硅烷偶联剂3-(异丁烯酰氧)丙基三甲氧基硅烷(MPS)对介孔二氧化硅进行表面修饰,以甲基丙烯酸(MAA)为原料,采用原位聚合法制备了具有pH响应性的介孔二氧化硅纳米粒子@聚甲基丙烯酸(MSNs@PMAA)复合微球。利用小角X射线粉末衍射仪、扫描电子显微镜和透射电子显微镜等仪器对其结构和形貌进行了表征。研究结果表明:MSNs@PMAA复合微球平均直径为167 nm,具有长程有序介孔孔道,MSNs的比表面积、孔容和孔径分别从1 081 m~2/g、1.756cm~3/g和3.2 nm减小至506 m~2/g、1.340 cm~3/g和1.7 nm。以多柔比星(DOX)为模型药物,MSNs@PMAA复合微球显示了较高的载药率和包封率,在体外有明显的p H响应性。     

鄂尔多斯盆地东缘海陆过渡相页岩孔隙结构定量化表征

为定量化表征鄂尔多斯盆地东缘太原组海陆过渡相页岩孔隙结构复杂程度,对5件页岩进行了低温液氮吸附等实验测试,应用FHH模型计算了分形维数并讨论了其影响因素。依据孔径大小可以将分形维数划分为2个阶段(孔径≥4nm和孔征<4mm),结果表明:页岩样品孔隙呈现出较强的分形特征。1)孔径≥4nm时的孔隙分形维数D2高于孔径<4nm时的孔隙分形维数D1;大孔径孔隙类型与形态多样,孔隙复杂程度更高。2)分形维数D1随微孔、介孔比例及黏土矿物质量分数增加而呈现出增大趋势,随BET比表面积、平均孔径、脆性矿物质量分数、宏孔比例、TOC增加呈现减小趋势,随镜质体反射率(Ro)增大呈现出先增大后减小趋势;D2随BET比表面积、平均孔径、宏孔比例、黏土矿物及脆性矿物质量分数的增加呈现出增大趋势,随微孔、介孔比例增加呈现出减小趋势,与TOC相关性差,随Ro增大呈现出先减小后增大的趋势。     

干燥控制化学添加剂对SiO_2气凝胶结构和性能的影响

以廉价水玻璃为原料,采用酸催化一步溶胶-凝胶法,在制备过程中加入干燥控制化学添加剂,经超声处理分散均匀后制备SiO_2气凝胶。测试结果表明,添加N,N-二甲基甲酰胺所制备气凝胶结构和性能最好,密度为0.0579g/cm~3,比表面积高达704m~2/g,BJH平均孔径为18.3nm。     

硅藻土/竹炭复合材料的制备及孔结构表征

本研究以竹炭为主要原料,添加硅藻土,以硅铝复合物为粘结剂,经粘结造粒、表面包覆改性、高温煅烧等工艺,制备了一种新型硅藻土/竹炭复合材料。采用氮吸附法对其孔结构进行表征,结果表明,BET比表面积为142.563m2/g,总孔容为0.156cm3/g,相比竹炭,比表面积有所降低,但总孔容却提高了43.12%,意味着吸附容量增大了;孔隙分布也较合理,微孔率、介孔率和大孔率分别为44.23%、32.05%和23.72%,克服了硅藻土和竹炭孔径分布过窄的缺点。由此表明在竹炭中添加硅藻土制备介孔率高、孔径分布均匀、吸附容量大的吸附材料是一种可行的方法。     

介孔SO_4~(2-)/ZrO_2-SiO_2材料的合成及催化性能

硫化锆基孔材料是一类新型的具有丰富酸基的固体酸催化剂。采用一锅合成法,通过调变自组装过程中锆物种的引入量,制备了不同锆硅物质的量比的介孔SO_4~(2-)/ZrO_2-SiO_2固体酸材料。采用XRD、N_2吸附-脱附、UV-Vis等方法的表征结果表明,所得材料具有高度有序的二维六方介孔结构且孔壁为具有四方相晶相结构的氧化锆。随着锆硅物质的量比值的增加,所得固体酸材料的有序度、比表面积及孔容呈下降的趋势。与纯硅介孔分子筛SBA-15相比,该系列SO_4~(2-)/ZrO_2-SiO_2固体酸材料在环己醇的酯化反应和异丙苯的裂解反应中均表现出较高的催化活性,且当Zr、Si物质的量比值为1.7和1.3时,反应活性分别达到最高值。其原因在于,介孔SiO_2孔壁中引入经硫化后的氧化锆可在较大程度上保留SiO_2材料原有介孔有序结构的前提下,有效提高催化剂表面的酸性位。     

Sorption of hydrochloric acid with saponite

We have investigated sorption of hydrochloric acid with saponite of the Varvarovskii deposit, Khmelnitsky region (Ukraine) against various salt backgrounds in the solution, varied by an addition of sodium chloride. Information has been obtained on desorption of cations of Na⁺, K⁺, Ca²⁺, Mg²⁺, Feⁿ⁺, Al³⁺ from saponite at different acidity of the equilibrium solution. It has been found out that at the pH of the equilibrium solution more than 3.4 its substantial pollution by cations being desorbed from the material does not occur. We have determined the composition of the cation-exchange complex and its overall capacity. The effect of anomalously low desorption of singly charged cations have been detected.     

Interaction of trace elements in acid mine drainage solution with humic acid

The release of metal ions from a coal mining tailing area, Lamphun, Northern Thailand, is studied by leaching tests. Considerable amounts of Mn, Fe, Al, Ni and Co are dissolved in both simulated rain water (pH 4) and 10 mg L(-1) humic acid (HA) solution (Aldrich humic acid, pH 7). Due to the presence of oxidizing pyrite and sulfide minerals, the pH in both leachates decreases down to approximately 3 combined with high sulfate concentrations typical to acid mine drainage (AMD) water composition. Interaction of the acidic leachates upon mixing with ground- and surface water containing natural organic matter is simulated by subsequent dilution (1:100; 1:200; 1:300; 1:500) with a 10 mg L(-1) HA solution (ionic strength: 10(-3) mol L(-1)). Combining asymmetric flow field-flow fractionation (AsFlFFF) with UV/Vis and ICP-MS detection allows for the investigation of metal ion interaction with HA colloid and colloid size evolution. Formation of colloid aggregates is observed by filtration and AsFlFFF depending on the degree of the dilution. While the average HA size is initially found to be 2 nm, metal-HA complexes are always found to be larger. Such observation is attributed to a metal induced HA agglomeration, which is found even at low coverage of HA functional groups with metal ions. Increasing the metal ion to HA ratio, the HA bound metal ions and the HA entities are growing in size from <3 to >450 nm. At high metal ion to HA ratios, precipitation of FeOOH phases and HA agglomeration due to colloid charge neutralization by complete saturation of HA complexing sites are responsible for the fact that most of Fe and Al precipitate and are found in a size fraction >450 nm. In the more diluted solutions, HA is more relevant as a carrier for metal ion mobilization.     

The reaction of nucleotides with aqueous hypochlorous acid

It has been found that the rate of consumption of hypochlorous acid by the nucleotides cytidine monophosphate (CMP) and adenosine monophosphate (AMP) increases with decreasing pH. At pH 5.6, CMP and AMP are the primary consumers of free chlorine; at pH 7.6 guanosine monophosphate (GMP), as well as CMP and AMP, react readily with hypochlorous acid. At pH 10, the only consumer of hypochlorite is GMP. A parallel was found between the rate of inactivation of virus and the rate of consumption of free chlorine by two of the nucleotides; both the rate of virus inactivation and the rate of consumption of chlorine by AMP and CMP increase with decreasing pH. Under conditions of virus disinfection, uridine monophosphate (UMP) is quite unreactive with aqueous hypochlorous acid.     

柠檬酸废渣粉刷石膏的研制

柠檬酸废渣石膏经过处理,可制得性能优良的α型半水石膏;以α型半水石膏料为原料,加入外加剂,可配制出优质的粉刷石膏。这种粉刷石膏产品凝结硬化块,粘结力强,有较好的保温、隔热、吸声性能,体积稳定性好,质地细腻光滑,施工方便,是一种优质的内墙抹灰材料。本文就利用柠檬酸废渣石膏生产粉刷石膏的生产工艺、成本及产品性能进行了研究与分析。     

论波德莱尔在1949—1976年间中国的译介

在中国当代翻译文学史上,波德莱尔和他的《恶之花》是一个异数。随着1949年中国社会和意识形态的剧变,现代主义文学成为禁忌,但波德莱尔在中国的翻译、阅读与接受却并未完全中断。通过梳理波德莱尔在1949—1976年间在中国的译介历程,可以清楚地看到以《译文》杂志和陈敬容等的公开译介与改写,以施蛰存、钱春绮等为代表的地下翻译与当时流行的地下读书活动等相辅相成,将波德莱尔"比冰和铁还刺人心肠的快乐"撒播到中国地下诗坛,出人意料地与其他现代派诗歌一起,催生了新时期以朦胧诗为代表的新诗群的崛起。     

冰乙酸改性狐尾藻对铜离子的吸附

以廉价而且易种植培育的沉水植物为原料,吸附重金属离子,降低废水中重金属离子浓度.采用冰乙酸对沉水植物狐尾藻进行改性,然后,取酸改性狐尾藻置于600 mg/L,pH=4的硝酸铜溶液搅拌处理2h,测试吸附重金属Cu~(2+)的能力.结果表明,狐尾藻经冰乙酸改性之后,吸附性能更好,对废水中重金属Cu~(2+)的吸附效率达到92.2%,高于未改性狐尾藻的吸附效率(85.6%).三次循环吸附后,吸附效率仍达到86.3%,拟合Elovich方程,第一次循环吸附R~2=0.9998,第四次循环吸附R~2=0.9999,线性关系均较好,表明拟合的二级动力学方程得到的最大吸附量与实验值基本吻合,为生物吸附材料的开发提供了理论依据.     

Gel permeation chromatography of humic acid Problems associated with sephadex gel

Gel permeation chromatography with Sephadex gels has become a widely used method for analysing naturally occurring organic materials in raw and treated waters. Several problems in the interpretation of molecular weight profiles from these gels have become apparent and the usefulness of the method is questioned.     

Anaerobic digestion of glucose with separated acid production and methane formation

In a two-phase anaerobic digestion system, with separate reactors for the acidification phase and the methane fermentation phase, the glucose of a 1% glucose solution was almost completely converted into biomass and gases. The acid reactor was operated at 30°C and pH 6.0, with a retention time of 10 h. Main products of the acid-forming phase were hydrogen, carbon dioxide, butyrate and acetate. On a molar base, these products represented over 96% of all products formed. On average, 12% of the COD content of the influent was evolved as hydrogen. The effluent of the first reactor was pumped to the methane reactor after passing through a storage vessel. The methane reactor was operated at 30°C, pH 7.8, and a retention time of 100 h was given. Approximately 98% of the organic substances fed to this reactor were converted to methane, carbon dioxide and biomass. About 11% of the glucose fed to the digesting system was converted to bacterial mass.     

3-nitrobenzenesulfonic acid and 3-aminobenzesulfonic acid in a laboratory trickling filter: Biodegradability with different activated sludges

The biodegradation of 3-nitrobenzenesulfonate (3-NBS) or 3-aminobenzenesulfonate (3-ABS) was examined in a laboratory trickling filter device containing one of six activated sludges as the biocatalyst. No activated sludge from four communal treatment plants could degrade 3-NBS or 3-ABS. In contrast, each of the sludges from two plants treating wastes from the textile industry was able to completely degrade 3-NBS or 3-ABS. Under certain conditions, communal activated sludge could acclimate to degrade 3-NBS, even though inoculation with a degradative sludge was a more efficient process. In the absence of a carbon source, the degradative ability of trickling filters was retained for at least 1 week; thereafter, an adaptation phase was required before rapid and extensive degradation of recovered 3-NBS. Degradation was monitored by global parameters (DOC and release of CO₂) and specific determinations of substrate (HPLC). The global parameters indicated incomplete metabolism of 3-NBS, but this effect was found to be due to the presence of a non-degraded impurity (5%), 4-NBS, found in most commercial preparations of 3-NBS.     

用聚水解马来酸酐合成聚羧酸减水剂研究

使用聚水解马来酸酐与聚乙二醇单甲醚进行酯化反应合成聚羧酸减水剂,测试了酸醇摩尔比、催化剂种类及用量、反应温度、反应时间及带水剂用量对所合成减水剂性能的影响。结果表明,最佳的反应条件是酸醇摩尔比为15:1,浓硫酸为催化剂,用量为反应物总质量的3wt%,反应温度90℃,反应时间6h,带水剂用量为反应物总质量的12wt%。