铈改性丝光沸石在甲醇胺化反应中的应用

研究了氨和甲醇以铈改性丝光沸石为催化剂,在常压固定床上选择性合成二甲胺的反应。考察了温度、氨醇比、甲醇液相空速等制备条件对催化剂的活性及二甲胺选择性的影响。     

SELECTIVE SYNTHESIS OF DIMETHYLAMINE OVER RARE EARTH MODIFIED MORDENITES

研究了稀土（Ｃｅ、Ｇｄ和Ｙ）改性丝光沸石用作甲醇胺化催化剂在常压固定床反应器中选择性合成二甲胺的催化性能。结果表明，稀土阳离子交换改性能改善丝光沸石的催化性能。丝光沸石经０．１ｍｏｌ／ＬＣｅ４＋溶液处理，与膨润土成型，再于６００℃下焙烧２～３ｈ，这样制得的催化剂在常压４００℃时的活性及二甲胺选择性分别达到９９．８％和５０．３％。此外，详细探讨了不同改性及制备条件对催化剂催化性能及机械强度的影响。     

碱金属丝光沸石的表征及对甲胺合成的反应的性能

对不同碱金属含量和不同温度水汽处理的丝光沸石样品，用ＸＲＤ和ＩＲ进行了物性表征，对其中某些样品以甲醇与氨合成甲胺反应用连续反应－在线分析进行了考察。水汽处理后，沸石发生骨架脱铝并保持很结晶度，其Ｂ酸总酸量及强酸量均剧降；甲醇转化活性反而提高，二甲胺选择性也显著提高，三甲胺选择性降至很低。表明过多、过强的酸性中心于本反应无益。此外，沸石经汽处理后发生多种变化，产生了良好的择形催化效应。     

甲胺化反应催化剂稀土改性丝光沸石的研究

研究了稀土改性丝光沸石催化剂对常压固定床上甲胺化反应的活性及选择性的影响，结果表明，以钇改性丝光沸石催化剂的活性及对二甲胺的选择性最佳。催化剂表征结果表明，稀土改性丝光沸石主要是引起丝光沸石中Ｂ酸中心发生变化，而对丝光沸石的晶体结构及表面硅铝原子比基本不产生影响。稀土改性能增强催化剂的热稳定性，延长催化剂的寿命。     

改性丝光沸石上甲醇胺化的研究─—水汽处理对沸石性能的影响

采用吡啶饱和中毒、ＮＨ３－ＴＰＤ、静态吸附、ＩＲ、ＸＲＤ和分子探针反应等方法，研究了用于甲醇胺化反应的改性丝光沸石催化剂性质．结果发现，丝光沸石水汽处理脱铝后的孔道结构基本不变，晶胞的收缩和非骨架铝在孔道内的沉积，不足以严重限制甲醇胺化产物三甲胺在孔道内的进出；且在改性后，由于非骨架铝在孔道内的沉积，分子筛内表面的微环境发生了变化，致使有些活性位不利于三甲胺的吸附和生成，从而有利于进一步提高目的产物二甲胺的选择性．     

碱金属丝光沸石的表征及对甲胺合成反应的性能

对不同碱金属含量和不同温度水汽处理的丝光沸石样品，用ＸＲＤ和ＩＲ进行了物性表征，对其中某些样品以甲醇与氟合成甲胺反应用连续反应一在线分析进行了考察．水汽处理后，沸石发生骨架脱铝并保持很高的结晶度，其Ｂ酸总酸量及强酸量均剧降；甲醇转化活性反而提高，二甲胺选择性也显著提高，三甲胺选择性降至很低．表明过多、过强的酸性中心于本反应无益．此外，沸石经水汽处理后发生多种变化，产生了良好的择形催化效应．     

甲苯甲醇侧链烷基化反应中沸石催化剂酸碱中心的作用Ⅱ．改性的X型和双组分改性的X／ZSM－5双沸石催化剂

制备了改性的ｘ型和ｘ／ＺＳＭ－５型沸石催化剂，并对其进行了评价和ＴＰＤ、ＥＳＣＡ表征，将实验结果进行了关联。结果表明，采用ＫＯＨ，Ｈ＿３ＢＯ＿３和碱土金属化合物等作为改性剂，可以调变沸石催化剂的酸碱中心，其中碱酸密度比为０．５３９的ＫＸ（Ｂ＿３）·ＫＺＳＭ－５（Ｃａ）催化剂，能显著提高甲苯、甲醇侧链烷基化制取苯乙烯反应的选择性和收率。井根据对实验结果的分析，初步探讨了甲苯、甲醇侧链烷基化反应的机理。     

甲醇脱水制二甲醚的杂多酸/纳米HZSM-5复合固体酸催化剂

开发低温、高活性和良好稳定性的催化剂成为甲醇气相脱水制二甲醚乃至合成气一步法制二甲醚反应的核心.在氧化铝挤条成型的纳米HZSM-5沸石上负载Keggin结构12-磷钨酸制备了复合固体酸催化剂, 通过FT-IR、UV-Raman、³¹P MAS-NMR和XRD对所制备的样品进行表征. 以甲醇气相脱水制二甲醚为探针反应的研究结果表明, 在选定的操作条件下连续运转超过300 h, 甲醇摩尔转化率大于87%(理论转化率90.9%), 二甲醚摩尔选择性高于99.0%, 是目前该反应非常有效的催化剂之一.     

气相法苯胺N—烷基化反应研究：Ⅲ.苯胺和甲醇催化合成N,N—二甲…

本文报导了在系列复合氧化物催化剂上苯胺和甲醇反应合成Ｎ，Ｎ－二甲苯胺研究，并从中选择了活性和选择性良好的ＬＨＰ催化剂，在常压气相反应条件下说细地考察了反应温度，液时空速，苯胺和甲醇摩尔比变化等对催化剂活性和选择性的影响，提出了两段转化的新工艺流程。     

V2O5/高硅分子筛的酸性与甲苯气相选择氧化

用固体离子交换法制备了Ｖ２Ｏ５／ＺＳＭ－５和Ｖ２Ｏ５／丝光沸石两类催化剂。通过ＸＲＤ，ＬＲＳ，ＸＰＳ和Ｓｇ测定表征了Ｖ２Ｏ５在分子筛上的分散状态。用吡啶吸附红外光谱法和正丁胺非水溶液回滴法研究了催化剂的表面酸性。用ＥＳＲ研究了甲苯在催化剂上的吸附。结果表明，催化剂的酸性不同，它们吸附甲苯的能力也不同，对甲苯气相选择氧化的活性和选择性也有较大的差异。同时，甲苯选择氧化成苯甲醛的能力还与Ｖ２Ｏ５在分子     

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.     

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。     

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.

     

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.     

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.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。