CFD analysis of thermodynamic cycles in a pulse tube refrigerator

The objectives of this paper are to study the thermodynamic cycles in an inertance tube pulse tube refrigerator (ITPTR) by means of CFD method The simulation results show that gas parcels working in different parts of ITPTR undergo different thermodynamic cycles The net effects of those thermodynamic cycles are pumping heat from the low temperature part to the high temperature part of the system The simulation results also show that under different frequencies of piston movement the gas parcels working in the same part of the system will undergo the same type of thermodynamic cycles The simulated thermal cycles are compared with those thermodynamic analysis results from a reference Comparisons show that both CFD simulations and theoretical analysis predict the same type of thermal cycles at the same location However only CFD simulation can give the quantitative results while the thermodynamic analysis is still remaining in quality (C) 2010 Elsevier Ltd All rights reserved

吲哚生物碱Desbromoarborescidine A 的全合成及烯胺C-亚磺酰化反应研究

从新几内亚核桃木的树皮中分离得到的吲哚类喹诺里西定生物碱10-Desbromoarborescidine A，因发现其具有阻滞钙离子通道的活性而倍受关注。10-Desbromoarborescidine A由A、B、C、D四个环组成，只有一个手性中心，是吲哚生物碱中结构较简单的一种，常作为此类生物碱全合成方法的模型化合物。但迄今为止，能高效而简便的实现手性10-Desbromoarborescidine A不对称全合成方法线路不多，大多数以不对称诱导的方式建立其手性中心，手性催化的方式仅有一例金属催化。从逆合成分析可知，Desbromoarborescidine A的全合成可以通过亚胺不对称催化还原进行关键的手性中心构建，而本课题组在之前的研究中通过手性有机小分子催化剂的发展，已将三氯硅烷氢转移还原亚胺发展成了一类简便实用、高效、高对映选择性并具有优良底物适应范围的不对称催化反应，我们希望以这一反应作为关键手段，发展一条Desbromoarborescidine A及其类似物不对称合成新路线。 根据我们设计的新路线，首先成功合成了其关键中间体，然后我们进行了关键的不对称催化尝试。用本实验室已有的高性能有机小分子催化剂虽得到了较好的对应选择性，但是产率很低。同时，为了验证整条线路的可行性，我们也用消旋的中间体进行拉通线路的尝试。但不幸的是，在脱除保护基时遇到了很大困难。尝试换不同的保护基，或改变脱保护基的顺序，都未能成功合成目标产物。究其原因可能是由于吲哚的特殊性造成的，吲哚类亚胺与常规的芳香亚胺有较大的差异，其NH基团无论保护还是不保护，对与其2位相联接的C=N双键均有很大的影响，导致其不对称催化还原难以进行。另外，由于所设计的还原产物含有处在吲哚苄位的胺基，稳定性较差，造成保护基脱除困难。 烯胺C-亚磺酰化反应是本课题组最近发现的一个新反应，之前未见文献报道。本研究对该反应进行了反应条件优化和底物扩展，发现带Cbz，Ac，COt-Bu，CO2Et，Bz等保护基的一系列环状和非环状烯胺在亚磺酸钠、DMAc和MeSiCl3的共同作用下能高效高产率生成β-胺基烯基亚砜类新化合物，为合成多官能团化的烯基亚砜新化合物提供了一条简便实用的途径。 The main constituent of Dracontomelum mangiferum B1, indoloquinolizidine alkaloid 10-Desbromoarborescidine A, has drawn great attention due to its calcium channel blocking activity. Its molecular structure is relatively simple compared with the other alkaloids of the same type, which has only one chiral center, albeit with four cycles A, B, C, and D. This compound is often used as a model target for exploring different strategies for the total synthesis of indole alkaloids. Nevertheless, so far there still lack practical and highly efficient methods for the asymmetric total synthesis of 10-Desbromoarborescidine A. Most of the current available methods rely on stoichiometric asymmetric synthesis for the construction of the chiral center. There is only one example reporting utilization of asymmetric catalysis, but with transition metal complex as the catalyst. Our retrosynthetic analysis shows that catalytic asymmetric reduction of imine could be used as the key step for the construction of the chiral center of Desbromoarborescidine A. Since in the previous studies our group has developed the asymmetric reduction of imines by trichlorosilane into a practical and highly efficient and enantioselective method using newly designed chiral organocatalysts, we hope to apply this method to develop a novel synthetic route for the total synthesis of Desbromoarborescidine A and its analogues in this study. According to the newly designed synthetic route, we first accomplished the synthesis of the key intermediates which was then examined for the critical asymmetric catalysis. The asymmetric reduction using the highly efficient organocatalysts, developed in our lab afforded high ee but poor yield. We tried different reaction conditions to improve the yield, but failed to get any good results. Simultaneously, to vertify the feasibility of the synthetic route we designed, we also tired to go through the route toward the racemic synthesis of Desbromoarborescidine A. But unfortunately, protection and deprotection proved to be big hurdles. All the different protection groups and different sequences of protection and deprotection we tried failed to get us through the designed synthetic sequence and furnish the final product. Most likely, the indole part is the culprit behind the failures.The NH group of the indole, no matter protected or not, may impact the catalytic asymmetric reduction of C-N double bond connected with 2-C. Additionally, the reduction product we designed contains an amino group in the β-position of the indole, which may cause problems due to its instability. C-sulfenylation of enamines is a novel reaction discovered recently by our group, which has not been seen before in the literature. In this study, optimization of the reaction conditions and exploration of the substrate scope were further undertaken for this reaction, which reveal that a series of enamines with N-Cbz, Ac, COt-Bu, CO2Et protection groups could all undergo smooth C-sulfinylations with the comined use of sodium benzene sulphinate, DAMc and MeSiCl3, efficiently furnishing the β-amino vinylsulfoxide products in high yield, affording a practical and highly efficient methods for synthesis of functional vinylsulfoxides.

Episodic gullying and paleomonsoon cycles on the Chinese Loess Plateau

IEECAS SKLLQG

Light alkenes preparation by the gas phase oxidative cracking or catalytic oxidative cracking of high hydrocarbons

The preparation of light alkenes by the gas phase oxidative cracking (GOC) or catalytic oxidative cracking (COC) of model high hydrocarbons ( hexane, cyclohexane, isooctane and decane in the GOC process and hexane in the COC process) was investigated in this paper. The selection for the feed in the GOC process was flexible. Excellent conversion of hydrocarbons ( over 85%) and high yield of light alkenes ( about 50%) were obtained in the GOC of various hydrocarbons including cyclohexane at 750 degreesC. In the GOC process, the utilization ratio of the carbon resources was high; CO dominated the produced COX (the selectivity to CO2 was always below 1%); and the total selectivity to light alkenes and CO was near or over 70%. In the COC of hexane over three typical catalysts (HZSM-5, 10% La2O3/HZSM-5 and 0.25% Li/MgO), the selectivity to COX was hard to decrease and the conversion of hexane and yield of light alkenes could not compete with those in the GOC process. With the addition of H-2 in the feed, the selectivity to COX was reduced below 5% over 0.1% Pt/HZSM-5 or 0.1% Pt/MgAl2O4 catalyst. The latter catalyst was superior to the former catalyst due to its perfect performance at high temperature, and with the latter, excellent selectivity to light alkenes ( 70%) and the conversion of hexane (92%) were achieved at 850 degreesC ( a yield of light alkenes of 64%, correspondingly).

NOx storage-reduction over Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios

A series of Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios were prepared. The NOx storage capacities of these catalysts were measured by isothermal storage at 350 degreesC. It was found that the NOx storage capacity increased with increasing Mg/Al atomic ratios. The catalytic behaviors of Pt/Mg-Al-O and Pt/MgO were studied with storage-reduction cycles at 400 degreesC. Under oxidizing conditions, NOx concentration in the outlet gas gradually increased with time, which indicated the catalysts could store NOx effectively. After a switch from oxidizing conditions to reducing conditions, NOx desorption peak emerged immediately due to the incomplete reduction of stored NOx, which lowered the total NOx conversion. With increasing Mg/Al atomic ratio in the catalysts, NOx conversion increases. Pt/MgO has the highest NOx conversion because of its best activity in the reduction of NOx by C3H6. It seems that with an increasing amount of MgO in the catalysts, the self-poisoning of Pt-sites by adsorbed species during the reaction of NOx with C3H6 may be inhibited effectively.

The remarkable effect of In2O3 on the catalytic activity of In/HZSM-5 for the reduction of NO with CH4

In/HZSM-5/ln(2)O(3) catalyst that contained two different kinds of In induced by the impregnating and the physical mixing method respectively has shown remarkable activity for the CH4-SCR of NOx comparing with In/HZSM-5. The addition of In2O3 into In/HZSM-5 improved the NO conversion through enhancing the adsorption of NOx over In/HZSM-5.

Pd/sulfated alumina - a new effective catalyst for the selective catalytic reduction of NO with CH4

Sulfated alumina (SA) is firstly found to be an effective support for Pd catalyst used in the SCR of NO with methane. The sulfation is important to increase support's acidity which is essential for the reduction of NO over Pd catalysts. On consideration of the lower cost and easier availability of SA, we believe that SA is more promising to act as the commercial support for Pd catalyst used in the SCR of NO with methane.

Probing into the catalytic nature of Co/sulfated zirconia for selective reduction of NO with methane

In this work, the structural and surface properties of Co-loaded sulfated zirconia (SZ) catalysts were studied by X-ray diffraction (XRD), N-2 adsorption, NH3-TPD, FT-IR spectroscopy, H-2-TPR, UV-vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and NO-TPD. NH3-TPD and FT-IR spectra results of the catalysts showed that the sulfation process of the support resulted in the generation of strong Bronsted and Lewis acid sites, which is essential for the SCR of NO with methane. On the other hand, the N-2 adsorption, H-2-TPR, UV/vis DRS, and XPS of the catalysts demonstrated that the presence of the SO42- species promoted the dispersion of the Co species and prevented the formation Of Co3O4. Such an increased dispersion of Co species suppressed the combustion reaction of CH4 by O-2 and increased the selectivity toward NO reduction. The NO-TPD proved that the loading of Co increased the adsorption of NO over SZ catalysts, which is another reason for the promoting effect of Co. (C) 2004 Elsevier Inc. All rights reserved.

The reaction route and active site of catalytic decomposition of hydrazine over molybdenum nitride catalyst

The catalytic properties of the passivated, reduced passivated, and fresh bulk molybdenum nitride for hydrazine decomposition were evaluated in a microreactor. The reaction route of hydrazine decomposition over molybdenum nitride catalysts seems to be the same as that of Ir/gamma-Al2O3 catalysts. Below 673 K, the hydrazine decomposes into N-2 and NH3. Above 673 K, the hydrazine decomposes into N-2 and NH3 first, and then the produced NH3 further dissociates into N-2 and H-2. From the in situ FT-IR spectroscopy, hydrazine is adsorbed and decomposes mainly on the Mo site of the Mo2N/gamma-Al2O3 catalyst. (C) 2004 Elsevier Inc. All rights reserved.

Trichloroisocyanuric acid: A convenient oxidation reagent for phase-transfer catalytic epoxidation of enones under non-aqueous conditions

Trichloroisocyanuric acid (TCCA) is a cheap, safe and readily available alternative to the commonly used hydrogen peroxide and hypochlorite for the phase-transfer catalytic epoxidation of alpha,beta-enones under non-aqueous conditions. A variety of chalcone derivatives give the corresponding epoxides with quantitative conversion and satisfactory yields in just a few hours under mild conditions. An asymmetric variant of the epoxidation can be carried out in the presence of chiral N-anthracenylmethylcinchonidine bromide catalyst giving 73-93% ees and 76-94% yields.

Catalytic performance of MCM-22 zeolite for alkylation of toluene with methanol

MCM-22 zeolite with mid-strong acidity and openings of 10-membered ring channels may obtain a high catalytic activity and selectivity for alkylation of toluene with methanol. The acidic sites, for catalyzing alkylation of toluene with methanol, are weaker than that for catalyzing toluene disproportionation. Compared with silicon as a modifier, modification of MCM-22 with La(NO3)(3) is a promising way to improve the catalytic selectivity of para-xylene. In addition, the experimental results also clearly indicate the characteristics of MCM-22 structure consisting of large intracrystalline cages, some of which may locate on surface of MCM-22. (C) 2004 Elsevier B.V. All rights reserved.