Selective Analysis of Sulfur-Containing Species in a Heavy Crude Oil by Deuterium Labeling Reactions and Ultrahigh Resolution Mass Spectrometry

A heavy crude oil has been treated with deuterated alkylating reagents (CD₃I and C₂D₅I) and directly analyzed without any prior fractionation and chromatographic separation by high-field Orbitrap Fourier Transform Mass Spectrometry (FTMS) and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) using electrospray ionization (ESI). The reaction of a polycyclic aromatic sulfur heterocycles (PASHs) dibenzothiophene (DBT), in the presence of silver tetrafluoroborate (AgBF₄) with ethyl iodide (C₂H₅I) in anhydrous dichloroethane (DCE) was optimized as a sample reaction to study heavy crude oil mixtures, and the reaction yield was monitored and determined by proton nuclear magnetic resonance spectroscopy (¹H-NMR). The obtained conditions were then applied to a mixture of standard aromatic CH-, N-, O- and S-containing compounds and then a heavy crude oil, and only sulfur-containing compounds were selectively alkylated. The deuterium labeled alkylating reagents, iodomethane-d₃ (CD₃I) and iodoethane-d₅ (C₂D₅I), were employed to the alkylation of heavy crude oil to selectively differentiate the tagged sulfur species from the original crude oil.     

ERD facility for analysis of hydrogen and deuterium in solids

Hydrogen is the lightest element in nature, and so, its detection and quantitative analysis is difficult by the conventional methods utilized for other elements. In the recent years the technique of elastic recoil detection analysis (ERD) using 1–2 MeV He⁺ beam has been developed to quantitatively and simultaneously analyze hydrogen and its isotopes in solids. Such a facility has been set up using the 2 MeV Van-de-Graaff accelerator at IIT Kanpur. It facilitates H and D analysis in a material up to a depth of ∼ 1μm with a detection sensitivity of 0·1 at.% and depth resolution of about 300 ?. The application potential of this setup is illustrated by presenting the results of measurements performed on Al:H:D systems prepared by plasma source ion implantation and highT _c YBCO pellets exposed to humid atmosphere.     

Time-of-flight studies on catalytic model reactions

Time-of-flight spectroscopy (TOF) and REMPI-TOF (resonance enhanced multi-photon ionization-TOF) were applied to measure the angular and translational energy distribution, as well as the internal state resolved energy distribution of desorption and reaction products on some model systems. Desorption of hydrogen and deuterium from clean and modified Pd(111) surfaces was studied, where the palladium sample was part of a permeation source. Water formation by reaction of oxygen with hydrogen on palladium was investigated by using different types of hydrogen supply: molecular H₂ exposure and atomic H exposure from the gas phase, as well as H exposure by permeating hydrogen. Vanadium oxide nanostructures on Pd(111) were prepared and the influence on D₂ desorption and D₂O production was investigated with the permeation technique. Additionally, deuterium desorption from sulfur and oxygen covered V(111) and V(100) surfaces was studied by TOF and REMPI-TOF spectroscopy. From the TOF spectra information concerning the reaction and desorption dynamics (activation barriers) could be gained.     

面向等离子体材料钨中氘/氦滞留行为的研究进展

作为面向等离子体材料,钨(W)在服役的过程中不仅受到等离子体造成的高能热负荷的作用,还受到高束流粒子如氘(D)、氚(T)、氦(He)等的轰击和D-T聚变反应产生的高能中子的影响。W中D、T、He的滞留和起泡,仍是聚变堆装置中有待解决的关键问题之一。综述了D、T和He的滞留行为及其气泡形成与辐照条件之间的关系,简要评述了W的服役性能和强化机理。通过降低W中D/He滞留量、抑制气泡的形成可有效改善W的服役性能。深入研究D/He滞留行为与辐照缺陷之间的相互作用关系,进而构建D/He的宏观热脱附行为与其微观状态之间的对应关系,为寻找合适途径来改善W的服役性能提供理论支撑。     

Fuel provision for nonbreeding deuterium-tritium fusion reactors

Nontritium-breeding D-T reactors have decisive advantages in minimum size, unit cost, variety of applications, and ease of heat removal over reactors using any other fusion cycle, and significant advantages in environmental and safety characteristics over breeding D-T reactors. Considerations of relative energy production demonstrate that the most favorable source of tritium for a widely deployed system of nontritium-breeding D-T reactors is the very large (10 GW thermal) semicatalyzed-deuterium (SCD), or sub-SCD reactor, where none of the escaping³He (> 95%) or tritium (< 25%) is reinjected for burn-up. Feasibility of the ignited SCD tokamak reactor requires spatially averaged betas of 15 to 20% with a magnetic field at the TF coils of 12–13 T.On leave from Dept. of Electronic Engineering, University of Tokyo, Tokyo, Japan.     

环境同位素示踪技术在地热地球化学研究中的应用

介绍了环境同位素示踪技术在地热地球化学研究中的最新应用和进展。包括温泉气体的同位素(He、C)示踪;H、O同位素示踪地下热水的来源及成因;环境同位素方法(T和14C法)确定地下热水的年龄,以及氘过量参数(d)在地热研究中的优势。最后指出,同位素示踪技术与其他分析方法结合才能在地热地球化学研究中发挥更大的作用。     

Investigating the performance of a Rh metal catalyst in hydrogen–deuterium exchange reactions in methane for application in low-temperature membrane separators

The development of safe, efficient, and cost effective methods to recover waste components of deuterium–tritium (D–T) plasma reactors, including hydrogen and methane, has attracted much interest in the scientific community. Typically, membrane separators are used for this process, although several problems occur when performing separations at higher temperatures. The application of noble metal catalysts may improve the reaction dynamics and allow the separation process to occur at lower temperatures. In this paper, a series of noble metal catalysts were prepared by a traditional dipping method. Based on an analysis of catalytic performance, the Rh/Al₂O₃ catalyst was determined to be the most suitable for the exchange of hydrogen and deuterium in methane. The catalyst was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and temperature programmed reduction analyses. The effects of the metal loading and experimental conditions were also investigated.     

金属氧化物陶瓷涂层高温阻氘渗透性能研究

采用射频磁控溅射方法在316L不锈钢表面沉积了 Al2O3,Cr2O3,Y2O3和ZrO2(8％Y2O3)4种单层氧化物陶瓷涂层.选用X射线衍射(XRD)和扫描电镜(SEM)对4种氧化物陶瓷涂层相组成、微观组织结构进行表征,结果表明,Al2O3涂层为非晶态,其他3种氧化物陶瓷涂层均为晶体结构,且涂层沉积致密,无明显微观...     

氘重氧水液相催化交换法氢正常化工艺研究

液相催化交换法是有效的氢同位素分离方法之一,传统电解法进行氘重氧水氢正常化安全风险大,生产成本高,为此利用液相催化交换法对含氘重氧水进行除氘实验。结果表明,反应温度在30~70 ℃内,随着温度升高,含氘重氧水除氘过程的总体积传质系数（Kya）值先变大后变小,当温度大于60 ℃后,总体积传质系数Kya值逐渐变小,最优反应温度为60 ℃;气液比（摩尔比）在0.5~3.0之间,随着气液比增加,含氘重氧水除氘过程的Kya值愈大,含氘重氧水除氘效果越好,但过大的气液比会引起气液夹带甚至导致液泛,降低反应效率。实验结果可为开展高氘浓度氘重氧水液相催化交换法氢正常化工艺研究提供依据。     

生活垃圾热解半焦-热解油重整过程中水分的消耗与转移

热解炭原位重整城市固体废物的挥发分是改善热解产物的良好方法。在这个过程中,水蒸气在产品转化中起着重要作用。为了了解水分在重整过程中的作用,本研究中将热解液中的油相和水相分离,然后用D₂O代替重整过程中的水相,以跟踪液体、气体和固体之间的氢转移。热解油/焦炭重整过程在600、700和800℃下进行。用GC-MS（气相色谱质谱法）分析重整后液体中的油相;IR-MS（同位素比质谱法）分析重整后液体和固体中的氘浓度。研究发现,在实验温度范围内,水蒸气对焦炭的气化作用非常弱,当D₂O/焦炭的比例为2/1时,D₂O中2％（质量）的氘在反应后残留在炭中;但水蒸气与热解油的气化反应很强烈,在800℃时,78.68％（质量）的热解液（水油混合物）被气化,且热解油中脂肪烃被大量分解,重整液的油相组分中芳香烃占到96.17%;同时,当D₂O/油的比例为2/3时,D₂O中59％的氘转移到合成气中。研究结果将为生活垃圾热解处理控制最终产物提供理论指导。