USY分子筛催化FCC汽油的烷基化脱硫反应研究

以USY分子筛催化FCC汽油中噻吩类硫化物与烯烃的烷基化反应,采用DL-2B-EE微库仑仪测定反应前后硫分布的变化,考察了USY分子筛的制备条件和烷基化反应温度对其催化性能的影响.实验结果表明,水蒸汽处理温度350℃、水蒸汽处理时间5h,反应温度120℃时,USY分子筛催化剂的比表面积为613m2/g,催化活性最佳,使得FCC汽油中<100℃馏分的硫含量减少至16.92mg/L.水蒸汽流速对USY分子筛催化烷基化反应影响不大.不同处理方法所得USY分子筛的吡啶吸附红外光谱结果表明,具有较多的酸中心的USY分子筛更有利于催化FCC汽油的烷基化脱硫反应.     

二氧化硅负载杂多酸对异丁烷与丁烯烷基化的催化作用Ⅱ.反应机理和催化剂失活的量子化学研究

 以杂多酸为催化剂,应用量子化学计算方法,从分子结构和微观角度研究了异丁烷与丁烯的多相催化反应过程及催化剂失活的原因,比较了液体酸和固体酸催化烷基化反应的差别. 结果表明,固体酸催化剂的失活问题不可避免,因而不可能长时期运转,必须配合催化剂的再生工艺才有可能实现工业化应用. 液体酸的酸中心强度较均匀,有利于催化烷基化反应,开发无毒无污染的新型液体酸烷基化催化剂也是一个良好的努力方向.     

Brnsted-Lewis有机-无机杂多酸催化模拟催化裂化汽油的烷基化脱硫反应

合成了一系列Brnsted-Lewis双酸性有机-无机杂多酸,并将其应用于催化模拟催化裂化(FCC)汽油的烷基化脱硫反应中.筛选出脱硫效果最佳的催化剂为Sm_(0.33)[MIM-PS]HPW_(12)O_(40),考察了该催化剂用量、反应温度及反应时间等因素对模拟油中噻吩类硫化物转化率的影响.获得的最佳反应条件为剂/油质量比1∶50、反应温度125℃及反应时间1 h.在最佳反应条件下,3种硫化物噻吩(T)、2-甲基噻吩(2-MT)和3-甲基噻吩(3-MT)均几乎完全转化,即脱硫率都接近100%.催化剂Sm_(0.33)[MIM-PS]HPW_(12)O_(40)具有良好的循环使用性能,循环使用12次,其催化活性基本保持不变.     

超临界流体状态下的异构烷烃与烯烃烷基化反应

成功地应用固体酸催化剂在超临界反应条件下进行了异构烷烃与丁烯的烷基化反应。在超临界反应条件下,固体酸催化剂在１４００ｈ的反应以后,仍保持１００％的烯烃转化率。探索出一个解决固体酸催化剂在烷基化反应中极易失活的有效方法。探讨了超临界流体抑制固体酸催化剂结炭失活的机制和烷基化反应中选择超临界反应条件的规律。     

碳基磺酸化固体酸材料的制备及其催化性能

以蔗糖为原料,浓硫酸为磺酸化试剂制备了碳基磺酸化固体酸材料,考察了其催化对苯二酚烷基化和乙酸乙酯水解反应的性能.结果表明,该催化剂对这两个反应都具有较高的催化活性.在150℃反应4 h后,对苯二酚转化率和2-叔丁基对苯二酚收率分别达到了91%和60%,在60℃反应12 h,乙酸乙酯达到了平衡转化率94%,但催化剂稳定性较差,尤其在对苯二酚烷基化反应中失活严重,重复使用一次后,催化剂活性下降超过30%.详细考察了反应温度和溶剂对催化剂稳定性的影响,结果表明,该固体酸在低温的水相或非极性溶剂中较为稳定.通过酸碱滴定、红外光谱和紫外可见光谱等表征手段,对催化剂的失活原因进行了探讨,初步认定催化剂的失活是由于表面磺酸基团在反应过程中脱落所致.催化剂活性可以通过再磺酸化得到恢复.     

F改性Hβ对Mo-Ni/F-Hβ催化剂的FCC汽油硫转移反应催化性能的影响

通过添加不同含量的F对Hβ分子筛进行改性,制备Mo-Ni/F-Hβ催化剂,采用N₂吸附-脱附、NH₃-TPD、XRD、Py-FTIR和SEM等方法对该催化剂进行了表征,研究了F改性对该Mo-Ni/F-Hβ催化剂在FCC汽油中硫醇醚化和噻吩烷基化等硫转移反应中催化性能的影响。结果表明,以0.5%含量F修饰的β分子筛制备的催化剂对硫醚化反应和噻吩烷基化反应具有明显的促进作用,并能提高对二烯烃选择性加氢的选择性。F的引入可增强Hβ分子筛的中强酸量,降低强酸量,并提高了L/B酸中心比例,这些变化对催化性能改善起到重要作用。     

六方沸石分子筛催化剂用于异丁烷与丁烯的烷基化

异构烷烃与烯烃的烷基化是炼油装置制备高辛烷值汽油添加剂的重要途径.目前传统工艺仍使用矿物酸如硫酸或氢氟酸作催化剂,由于该工艺存在着产物分离困难、设备腐蚀严重及环境污染问题,从60年代起国内外开始致力于新型固体酸催化剂的研究与开发工作,已报道的有离子交换树脂[1]、分子筛催化剂[2]及SO=4/MxOy型催化剂[3]等,在分子筛催化剂中已报道的有立方沸石[4]β-分子筛[5]、ZSM系列[5]、分子筛[5]、蒙脱石[5]及MCM-22[6]等,这些催化剂的共性是催化活性较高,但失活较快.目前对分子筛催化剂的研究主要集中在改进的立方沸石体系,而六方沸石催化剂催化异丁烷与丁烯烷基化反应尚未见报道.     

Pt-SO42-/ZrO2固体超强酸上异丁烷与丁烯烷基化反应

由异丁烷和1-丁烯烷基化合成高辛烷值汽油虽已被广泛用于工业生产,但由于液体酸催化剂存在许多缺点,寻找固体酸催化剂——分子筛、磺酸树脂及固体超强酸已受到国内外学者的广泛重视。对超强酸的研究多集中在SO_4~(2-)/氧化物催化剂上,此类催化剂的酸强度高、热稳定性好、制备简单,对异丁烷、1-丁烯烷基化具有较高的反应活性,但存在着积炭、寿命     

AlCl_3/γ-Al_2O_3催化剂的制备及其催化脱除焦化苯中噻吩的性能

采用气相负载法制备了AlCl3/γ-Al2O3催化剂,考察了γ-Al2O3的粒径、温度、时间、AlCl3加入量和载气流量等制备条件对催化剂上噻吩与烯烃烷基化反应活性的影响,并采用Raman光谱、X射线衍射和N2吸附-脱附等技术对样品进行了表征,用气相色谱-质谱联用仪对反应产物进行了定性分析.结果表明,AlCl3主要通过与γ-Al2O3表面–OH结合而有效负载并均匀分布于其表面,制得的AlCl3/γ-Al2O3催化剂对噻吩和烯烃的烷基化反应具有较好的催化能力,反应产物主要是烷基噻吩.在200°C,将3g的AlCl3用100ml/min的N2向10g的γ-Al2O3(0.198～0.246mm)上负载5h,制得的AlCl3/γ-Al2O3催化剂活性最高,在液剂比为20ml/g时,噻吩脱除率可达62.11%.     

改性HZSM-5分子筛上噻吩烷基化反应和失活再生性能的研究

采用不同碱单独处理和两种碱不同方式联合处理HZSM-5分子筛,制备微孔-介孔多级孔HZSM-5分子筛催化剂并应用于噻吩烷基化反应中。结果表明,不同碱单独处理和两种碱不同方式联合处理HZSM-5分子筛后,均能够在分子筛上造出介孔孔道且能够调变分子筛的酸性,其中,采用Na₂CO₃溶液和TPAOH溶液分开处理得到的分子筛催化剂织结构最适合噻吩烷基化反应;其次考察具有最佳织结构分子筛催化剂的噻吩烷基化反应稳定性,并分析催化剂失活的原因和再生条件。结果表明,当噻吩烷基化反应进行到1050 h后,催化剂已基本失活,催化剂失活的主要原因是,在反应过程中原料中反应组分间发生烯烃齐聚、环化、脱氢和芳烃烷基化等副反应生成的大分子化合物沉积在催化剂上,堵塞催化剂的孔道和遮盖催化剂的活性中心所致;对失活催化剂进行高温再生,从高温再生的能耗较大以及多次高温再生对催化剂酸性和骨架结构不利的角度考虑,选定催化剂的再生温度为550 ℃。     

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。