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1.
研究了用ZSM-5沸石催化脱除焦化苯中噻吩的方法.通过对不同温度下噻吩在ZSM-5沸石上的吸附和反应的考察以及红外光谱表征,发现在较低温度下,噻吩通过氢键被可逆地吸附在酸性中心上,吸附在强B酸中心上的噻吩则部分发生反应生成类似硫醇(Olefinicthiol-likein-termediate)和硫醚的物种,随着温度的提高,一些不稳定的硫化物分解,并伴有H2S气体的生成.当反应温度低于380℃时,由于这些不稳定的硫化物不能完全分解,部分沉积在HZSM-5催化剂表面,导致催化剂活性中心中毒.当反应温度高于380℃时,这些不稳定的物种基本上完全分解,HZSM-5催化剂活性稳定. 相似文献
2.
利用程序升温脱附、程序升温还原、程序升温表面反应、程序升温反应和化学捕获反应等手段,对Rh/SiO2催化剂上甲烷部分氧化制合成气反应进行了研究.结果表明,Rh/SiO2催化剂上甲烷部分氧化制合成气机理属于热解-氧化反应机理.甲烷首先在催化剂上发生解离吸附,产生具有不同H/C比的化学吸附物种CHx(x=1~3).其中,具有较高H/C比的CHx可能是甲烷部分氧化反应的活性物种,而具有较低H/C比的CHx可能是催化剂上积碳并导致催化剂失活的来源.活性物种CHx在活性氧物种的作用下,生成含氧中间体物种CHxO或继续脱氢.含氧中间体物种进一步分解,即生成CO和H2;CO2也可由CHx或CHxO物种进一步氧
化生成. 相似文献
3.
采用连续流动微反装置考察了活性组分Ni/((Ni+W)原子比及预硫化条件对NiW/γ-Al2O3催化剂噻吩加脱硫(HDS)反应活性的影响,用X射线光电子能谱和电镜微区元素分析方法对硫化态催化剂进行了表征,结果表明,催化剂的组成、硫化方法、硫化度和反应条件等都影响NiW/γ-Al2O3催化剂的HDS反应活性,对于在较低温度(300℃)下硫化的催化剂,当反应温度较低(260-290℃)时,最佳Ni(Ni+W)原子比为0.50,而当反应温度较高(330-360℃),最佳Ni(Ni+W)原子比为0.23,当催化剂在300-500℃下硫化时,其噻吩HDS反应活性随硫化温度升高而增大,表明硫化度较高的催化剂具有较高的HDS反应活性。 相似文献
4.
对不同Mo含量的Mo/HZSM-5催化剂的结构进行了表征,并对这些催化剂的甲烷非氧气氛下的转化反应进行了考察.催化剂的BET比表面积及酸性随Mo含量的增加而降低,当Mo含量大于5%时,Mo对ZSM-5分子筛的晶型有影响,并出现MoO3物相.甲烷在700℃时可高选择性地生成苯和乙烯,最佳Mo含量大约为2%.纯的MoO3或HZSM-5上该反应几乎不进行,因此,可能是分散的钼氧离子和分子筛的酸中心是甲烷转化的活性中心,只有二者的协同作用才能促进甲烷的转化.反应后催化剂中的钼物种被还原了.催化剂上的积炭可能是催化剂失活的主要原因之一,烧炭后催化剂活性基本恢复. 相似文献
5.
对不同Mo含量的Mo/HZSM-5催化剂的结构进行了表征,并对这些催化剂的甲烷非氧气氛下的转化反应进行了考察.催化剂的BET比表面积及酸性随Mo含量的增加而降低,当Mo含量大于5%时,Mo对ZSM-5分子筛的晶型有影响,并出现MoO3物相.甲烷在700℃时可高选择性地生成苯和乙烯,最佳Mo含量大约为2%.纯的MoO3或HZSM-5上该反应几乎不进行,因此,可能是分散的钼氧离子和分子筛的酸中心是甲烷转化的活性中心,只有二者的协同作用才能促进甲烷的转化.反应后催化剂中的钼物种被还原了.催化剂上的积炭可能是催化剂失活的主要原因之一,烧炭后催化剂活性基本恢复. 相似文献
6.
用原位共焦显微拉曼光谱技术考察了丙烷选择氧化反应中Ag-M\r\no-P-O催化剂的结构,讨论了催化剂动态结构的成因及其对催化剂性\r\n能的影响.实验结果表明,在773K和n(C3H8)∶n(O2)∶n(N2)=\r\n3∶1∶4的反应条件下,Ag-Mo-P-O催化剂中的Mo-O物种可转化为A\r\ngMoO2PO4中的Mo-O物种(多钼酸根),此时催化剂对丙烷选择氧化具\r\n有较高的催化活性.催化剂中Mo-O物种的转化是由MoO3中Mo-O物种和\r\nAgMoO2PO4中Mo-O物种的结构特性决定的.AgMoO2PO4中的Mo-O物种具\r\n有较强的参与MarsvanKrevelen氧化-还原循环的能力,可能是丙烷选\r\n择氧化反应的活性物种. 相似文献
7.
K+-SrO-La2O3/ZnO(KSLZ)催化体系具有很好的催化活性.在1073K反应温度下,其C2产率为18.2%,且C2选择性为68.3%.催化剂抗潮能力明显增加,在室温下经长期放置后,催化剂活性稳定.用XRD,CO2-TPD和XPS表征了KSLZ催化剂的体相组成及表面碱性、表面组成和表面活性氧物种.在此基础上讨论了La2O3,SrO和K+各组分对甲烷氧化偶联反应的作用,提出了表面碳酸盐分解生成活性氧物种的可能性. 相似文献
8.
利用现场FTIR方法对合成气制混合醇钼硫基催化剂上吸附物种进行了表征。结果表明,在反应条件下,非负载或SiO2负载的碱助钼硫基催化剂上主要的CO加氢中间物种是HC=O、CH2、HCOS、O-CH3及S=CH3,而HCOO^-和CO^2-3的红外指纹谱带却十分弱,难以辨识。推断了该催化体系的反应历程。 相似文献
9.
以正硅酸乙酯为前驱体,采用溶胶-凝胶技术将吡啶羧酸钴包埋进SiO2基体中,于80℃干燥12h后得到钴含量为2.8%(Co/Si摩尔比)的干凝胶催化剂.采用FT-IR和TG-DTA方法对包埋催化剂进行了表征,考察了成胶过程中的pH和水与正硅酸乙酯的摩尔比(R)对包埋催化剂的结构及其对甲醇氧化羰化制碳酸二甲酯反应催化性能的影响.结果表明,干凝胶催化剂有较高的比表面积(320~458m2/g).在酸性条件下,增大pH或减小R值可缩短成胶时间.最佳的包埋条件是pH=4,R=6,在此条件下制备的凝胶包埋催化剂的活性最高,反应3h,甲醇转化率为5.73%,略低于均相催化剂上的甲醇转化率.但凝胶包埋催化剂分离简便,且重复使用6次后活性保持不变. 相似文献
10.
用组合法合成了CsCuHPVAsMoO系列杂多化合物催化剂,并采用FT-IR,H2-TPR,NH3-TPD和TG-DTA等方法对催化剂进行了表征.在自制固定床反应器中对异丁烯进行选择性氧化,考察了Cs,Cu和As含量、催化剂焙烧温度及反应条件对催化剂催化性能的影响.结果表明,Cs的引入有利于提高催化剂的选择性;Cu和As的引入在提高催化剂活性的同时,也提高了催化剂的选择性;当焙烧温度为340℃时,催化剂的活性和选择性最高.组成为Cs0.1Cu0.2HxPVAs0.2Mo10Oy的催化剂对异丁烯具有很强的选择性氧化能力,在最佳反应条件下,甲基丙烯酸、甲基丙烯醛和乙酸的收率分别可达52.84%,12.05%和18.21%. 相似文献
11.
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 from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997. 相似文献
12.
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。 相似文献
13.
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. 相似文献
14.
Two vanilloids, (5 E)-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. 相似文献
15.
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. 相似文献
16.
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^-。 相似文献
17.
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. 相似文献
19.
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 from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997. 相似文献
20.
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。 相似文献
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