CO_2加氢制甲醇用高活性和高选择性催化剂的研制

研制了一种CO2加氢制甲醇用高活性和高选择性催化剂Cu-ZnO-Al2O3(简记为RK-11),测定了其催化性能.结果表明,当原料气组成(体积分数)为68.5%H2、2.0%CO、20.5%CO2、9.0%N2,温度为240℃,气体时空速度GHSV=6 000h-1,压力为8.0MPa时,CO2转化率达35.2%,CO转化率达39.8%,甲醇的时空产率达686.1g/(L·h),而甲醇在产物中的选择性达99.3%.     

N-乙基沛心达及沛心达的合成

沛心达是近年来很受重视的一个新型的防治冠心病的有效药物。我们在研究新的合成方法,由1,1-苯基-2-(2-吡啶基)乙烯进行催化氢化制备沛心达时,发现伴有N-乙基沛心达生成。经质谱、红外光谱和元素分析等试验证明了它的结构为1,1-二环己基-2-(2-N-乙基哌啶基)乙烷马来酸盐。由沛心达游离碱进行N-乙基化,也取得了相同的结果。并由药理试验表明,N-乙基沛心达有希望成为一个更好的心血管药物。     

有机硅改性双酚A型环氧树脂研究

采用二氯二甲基硅烷 (DMS) ,或DMS与α ,ω 二氯聚二甲基硅氧烷 (DPS)的混合物来改性双酚A型环氧树脂 ,通过对固化物的冲击强度、拉伸强度、断裂伸长率和玻璃化转变温度 (Tg)的测定 ,探讨了改性方法、有机硅组成与含量等对材料性能的影响 .结果表明 ,用 5 7phr的DMS改性时 ,树脂固化物的冲击强度达2 0 2kJ m2 ,拉伸强度达 6 7 0MPa ,断裂伸长率达 11 2 9% ,Tg 达 16 8 0℃ ;分别比未改性时提高了 9 4kJ m2 ,2 1 1MPa ,5 4 %以及 32 6℃ .而用 0 7phrDMS +10phrDPS共同改性时 ,除Tg 和拉伸强度略有上升外 ,冲击强度达到了 31 6kJ m2 ,断裂伸长率达到 81 6 % ,分别比纯环氧提高了 2 0 8kJ m2 和 75 7% .     

负载Ni催化剂用于乙二醇蒸汽重整制氢催化性能研究

采用等体积浸渍法和共沉淀法制备了Ni催化剂,在固定床反应器上考察了Ni负载量、焙烧温度、反应温度等因素对乙二醇低温重整制氢反应活性和选择性的影响。应用X射线衍射、氮物理吸附、H₂程序升温还原等技术对负载型Ni催化剂进行了表征。结果表明,共沉淀法制备的Ni/CeO₂催化剂具有较小的NiO颗粒与CeO₂载体颗粒粒径,催化活性较高。添加少量氧化钴到Ni/CeO₂催化剂中可使H₂收率达72.6%,EG转化率达93.1%。在CeO₂中添加Al₂O₃能提高负载Ni催化剂的活性,乙二醇转化率达94.0%,H₂收率达67.0%;但添加SiO₂则使其活性明显变差。     

MSCB吸附剂去除水体中Ni~(2+)、Cu~(2+)、Cr(Ⅵ)的机制研究

以NaOH和二硫化碳对甘蔗渣进行了改性,通过傅里叶变换红外光谱(FT-IR)、扫描电镜(SEM)对改性蔗髓纤维(MSCB)进行表征并研究了MSCB去除水中Cr(Ⅵ)、Ni~(2+)、Cu~(2+)的性能。结果表明,MSCB吸附重金属离子的平衡时间为30~60 min,处理含Cr(Ⅵ)浓度在10~40 mg/L范围内的废水去除率达97%以上,比改性前蔗髓纤维(SCB)对Cr(Ⅵ)的吸附率(23.7%)提高了74.35%。对含Ni~(2+)浓度30~60 mg/L的废水去除率达98%以上,吸附容量达59.12 mg/g、对Cu~(2+)浓度在20~55 mg/L废水的去除率在90%以上,吸附容量达49.9 mg/g。对电镀废水中Cr(Ⅵ)处理率达96.69%,吸附量8.16mg/g,出水浓度0.93 mg/L;Ni~(2+)去除率达99.13%,吸附量51.89 mg/g,出水浓度1.06 mg/L,水质澄清。     

含有多甘醇、多甘醇单醚功能基的树脂的合成及其对贵金属离子的吸附性

合成了六种含有乙二醇、多甘醇及多甘醇单醚功能基的树脂。树脂的功能基转化率达93.4—97.5％。树脂2—6对Au(Ⅲ)的吸附率达90—100％,对Pt(Ⅳ)为40—50％,但对共存的Pd(Ⅱ)、Cu~(2+)、Ni(2+)、Cd(2+)等离子甚少吸附。六种树脂的吸金容量在226.3—93.8mg Au(Ⅲ)/g树脂之间。被吸附的金可用3％。硫脲-1N盐酸容液洗脱。洗脱率达95.8％以上。     

电生成Fenton试剂及其对染料降解脱色的研究

以可溶性铁为阳极,多孔石墨电极为阴极,Na2SO4为支持电解质.通电后,铁从阳极溶解生成二价亚铁离子Fe2+,氧在阴极上还原为过氧化氢H2O2,于电解现场发生Fenton反应,产生羟基自由基即Fenton试剂.在低电流密度(10mA/cm2)下,可有效地抑制阴、阳两极副反应的发生,所产生的羟基自由基浓度足以有效地进行染料废水的降解与脱色,脱色率达100%,CODcr去除率达80%.     

IBRS2细胞电融合及融合过程研究

单层贴壁培养的IBRS2细胞在高压脉冲电场的诱导下,能发生大规模的融合。当脉冲强度达1.7kV/cm,脉冲宽度达100μs,脉冲个数达4,电击液中含lmol/LMg~(2+)时,融合率可达90％以上。电击液中钙、镁离子的浓度对细胞的电融合亦有明显的影响。实验表明,钙离子能抑制IBRS 2细胞的电融合并降低细胞对电脉冲的耐受能力。反之,镁离子则能促进IBRS 2细胞的电融合并提高细胞对电脉冲的耐受能力。仔细的实验观察表明,IBRS 2细胞的电融合是一个十分复杂、缓慢的动态过程。依据实验结果,我们对该种细胞的电融合过程和机制提出了一种可能的解释。     

聚合物假冠醚研究(Ⅴ)多胺型类氮杂冠醚聚合物的合成与性能及在化学实验室的应用

以聚乙二醇(PEG400,PEG200)为起始剂,以多乙烯多胺为交联剂,合成了4种新型多胺交联型类氮杂冠醚聚合物,研究了聚合物的溶胀性能和对金属离子的静态吸附性能.结果表明,聚合物在极性溶剂中具有良好的溶胀性能,在水中的溶胀系数达12.67,吸水容量达12.14g/g(20℃);在25℃下,对Cu2+,Ni2+,Hg2+,Pb2+的吸附量分别达1.793mmol/g,1.675mmol/g,1.849mmol/g和1.048mmol/g.测试了反应物摩尔比、溶剂温度及其pH值对溶胀性能的影响,试研究了聚合物在化学实验室的应用.     

用于CO选择氧化反应的新型Pt-Fe/Al2O3催化剂

 基于前体的概念,采用调变多元醇法制备了Pt-Fe/Al2O3催化剂,并考察了其催化CO选择氧化的性能. TEM结果表明,该方法可有效控制催化剂的金属粒子粒径为2.5～3 nm; 催化剂性能测试结果表明,在80 ℃和n(CO)/n(O2)=2的条件下,Pt-3Fe/Al2O3显示出良好的催化性能和稳定性,CO转化率达99%,CO2选择性达98%,这可能是由于Pt和Fe之间的有效相互作用所致.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Study of the thermodynamics of adsorption of hydrolyzed modified polyacrylnitrile

The thermodynamics of adsorption has been studied of hydrolyzed modified polyacrylnitrile (HMP) in water solutions with a concentration ranging from 0.25 g/l to 2.00 g/l on bleached sulphate and unbleached and bleached sulphite celluloses at temperatures of 0, 20, 40, and 60 C.It has been established that with the rise in temperature, the amount of adsorbed polymer —(HMP) decreases. The values of the enthalpy change are negative and show a linear decrease with the increase in the amount of adsorbed polymer. The adsorption equilibrium is defined by the logarithmic isotherm of Tjumkin, valid for uniform heterogeneous surfaces.With the increase in the amount of adsorbed HMP the values of the entropy change become negative and linearly decrease. A compensation effect has been noticed which results from the simultaneous action of the entropy and energy factors.The values of the change of the chemical potential for the three types of cellulose are negative and linearly decrease with the increase in the amount of adsorbed HMP and with the rise in temperature.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

NiY分子筛表面酸性影响其选择性吸附脱硫性能的机理研究

采用原位红外光谱技术,以噻吩、环己烯和苯为模型探针分子,分别考察单一烃分子在NiY分子筛上的吸附与反应行为以及噻吩与烯烃、芳烃间的竞争吸附和催化反应行为。单一探针分子吸附研究发现,NiY分子筛中与Ni物种相关的Lewis(L)酸位是噻吩的选择性吸附活性位;噻吩和环己烯在NiY分子筛中Brnsted(B)酸位上发生的质子化和低聚反应明显弱于HY分子筛。双探针分子竞争吸附研究发现,环己烯二聚体在NiY中强B酸位上的强化学吸附与噻吩存在显著的竞争吸附行为。另外,苯和噻吩在NiY上的竞争吸附现象在373K时明显减弱。由此,在选择性吸附脱硫过程中,减少吸附剂表面B酸中心可降低烯烃对噻吩的竞争吸附,另外适当提高吸附体系的温度可以有效避免芳烃对噻吩的竞争吸附。     

化学单元教学设计的探索

论述了单元教学是落实化学新课程三维目标的基本教学过程,同时对教学单元的含义、教学单元的选择与建构、化学单元教学设计及其意义进行了阐述。