共查询到20条相似文献,搜索用时 31 毫秒
1.
《Journal of Molecular Catalysis #》1994,86(1-3):267-285
Molybdenum (VI)-allyloxo and -allylamido complexes possessing ancillary oxo and imido ligands have been synthesised and their subsequent decomposition studied in the perspective of modelling the postulated surface intermediates of the catalytic oxidation and ammoxidation of propylene. In solution and under mild conditions, these complexes undergo two types of reactions corresponding effectively to certain elemental steps of the heterogeneous processes, i.e. oxidative dehydrogenation of the allyl groups and allyl migration to oxo and imido functions. The mechanisms and the relative rates of these reactions are compared with that proposed for the surface catalytic chemistry. The possibility of alternate reaction pathways is discussed such as for CN bond formation and the involvement of an allylideneamine intermediate in the catalytic cycle. 相似文献
2.
Coal derived oil was hydroprocessed over Ni–Mo and Ni–Co–Mo catalysts in a continuous flow laboratory unit. The effect of the reactor mode (down-flow or up-flow) and of the hydrogen circulation on the efficiency of hydrogenation were investigated in one and two reactors systems.
, , - Ni–Mo Ni–Co–Mo . ( ) - , - .相似文献
3.
水蒸气气氛煤中温催化气化动力学研究 总被引:1,自引:0,他引:1
水蒸气气氛煤中温催化气化动力学研究 《燃料化学学报》2013,41(10):1166-1172
以碳酸钾为催化剂,用热天平的等温热重法研究了四种不同变质程度煤焦常压下水蒸气催化气化反应动力学。在加和不加碳酸钾条件下,测定了温度为700~850℃煤焦的化学反应控制条件下的碳转化率与时间的关系。碳酸钾催化剂的加入对变质程度越高煤的气化催化作用越大。加碳酸钾的碳转化率与时间的关系用混合模型和修正随机孔模型可以良好的拟合关联,均相模型关联较差。利用修正随机孔模型拟合关联出了四种煤焦催化水蒸气气化反应的活化能和指前因子,活化能为90.317~167.861kJ/mol,指前因子和活化能之间具有补偿效应。 相似文献
4.
应用TG-FTIR技术研究黄土庙煤催化热解特性 总被引:1,自引:0,他引:1
用浸渍法制备过渡金属氧化物担载型催化剂MOx/USY(M=Co、Mo、Co-Mo),用热重红外联用技术考察了MOx/USY催化剂对黄土庙(HTM)煤热解失重特性和热解产物生成规律的影响。热重实验结果表明,MOx/USY催化剂可使HTM煤热解的二次脱气条件更为温和,热解峰温分别提前14、23和9℃。动力学分析结果表明,MOx/USY催化剂可降低HTM煤样热解的活化能。FT-IR研究表明,MOx/USY催化剂可有效改善HTM煤热解产物的组成和分布,CoOx/USY催化剂能显著提高HTM煤热解产物中高热值气体(CO、CH4)和轻质芳烃以及脂肪烃类化合物的含量;MoOx/USY催化剂没有明显改善HTM煤热解产物组成和分布;MoOx-CoOx/USY催化剂可促进CO、CH4、轻质芳烃和脂肪烃类化合物的生成,却使热解产物的生成向高温区移动,说明USY负载的不同过渡金属氧化物对煤样热解行为和热解产物有较大影响。 相似文献
5.
Catalytic spectrophotometric determination of iodine in coal by pyrohydrolysis decomposition 总被引:1,自引:0,他引:1
A method for the determination of iodine in coal using pyrohydrolysis for sample decomposition was proposed. A pyrohydrolysis apparatus system was constructed, and the procedure was designed to burn and hydrolyse coal steadily and completely. The parameters of pyrohydrolysis were optimized through the orthogonal experimental design. Iodine in the absorption solution was evaluated by the catalytic spectrophotometric method, and the absorbance at 420 nm was measured by a double-beam UV-visible spectrophotometer. The limit of detection and quantification of the proposed method were 0.09 μg g−1 and 0.29 μg g−1, respectively. After analysing some Chinese soil reference materials (SRMs), a reasonable agreement was found between the measured values and the certified values. The accuracy of this approach was confirmed by the analysis of eight coals spiked with SRMs with an indexed recovery from 94.97 to 109.56%, whose mean value was 102.58%. Six repeated tests were conducted for eight coal samples, including high sulfur coal and high fluorine coal. A good repeatability was obtained with a relative standard deviation value from 2.88 to 9.52%, averaging 5.87%. With such benefits as simplicity, precision, accuracy and economy, this approach can meet the requirements of the limits of detection and quantification for analysing iodine in coal, and hence it is highly suitable for routine analysis. 相似文献
6.
A new approach to synthesize tolunitriles is reported. Tolunitriles can be prepared by selective ammoxidation of methylbenzyl
chlorides prepared by chloromethylation of toluene. The total yields can reach 83% and the selectivity of tolunitriles is
almost 100%. This approach provides a new path for preparing alkylbenzonitriles and other aromatic nitriles. 相似文献
7.
生物质灰对煤焦加氢气化的催化作用 《燃料化学学报》2017,45(1):21-28
以小麦秸秆、马尾藻和山苦荬等三种富含碱金属和碱土金属的生物质为原料,研究了在500、600和815℃下制得的生物质灰对神府煤焦加氢气化的催化作用。结果表明,随着制灰温度由500℃升高至815℃,灰产量减少,且灰中的碱金属和氯元素的含量降低;当制灰温度达到815℃,生物质灰出现明显的熔融现象;600℃灰样对神府煤焦加氢气化具有较好的催化作用,催化效果随灰样添加比例增大而增强。山苦荬灰催化作用较好,而马尾藻灰催化作用较弱。小麦秸秆灰中较高的硅含量和马尾藻灰中较高的氯含量是其催化作用较弱的主要原因;氯元素会加剧碱金属的挥发,弱化与其结合的碱金属的催化效果,对碱金属催化所产生的抑制作用比相同摩尔数的硅更加明显。 相似文献
8.
I. A. Tarkovskaya S. S. Stavitskaya L. P. Tikhonova 《Theoretical and Experimental Chemistry》1997,33(4):223-226
An increased activity in some redox reactions was observed for some metal ions bound by ion-exchange to oxidized coals. The
similarity of the catalytic properties of oxidized coals modified by Fe(III), Cu(II), Mn(II) and other cations has been established
for various redox reactions: decomposition of H2O2, oxidation of some organic and inorganic substances by hydrogen peroxide and oxygen. The catalytic activity of the modified
coals depends on how the modifying additive is bonded to the surface and the amount of the dopant. New methods for the practical
use of catalysts with regulated activity are noted.
Translated from Teoreticheskiya i éksperimental’naya Khimiya, Vol. 33, No. 4, pp. 256–260, 1997. 相似文献
9.
A. B. Guseinov E. A. Mamedov R. G. Rizaev 《Reaction Kinetics and Catalysis Letters》1985,27(2):371-374
The increased activity of the catalyst for ammoxidation of toluene observed in the presence of ammonia is ascribed to its binding with the acidic centers. which leads to the formation of new active basic sites on the catalyst surface.
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10.
11.
D. V. Tarosova T. V. Andrushkevich V. A. Dzisko Ye. L. Sazonova T. A. Nikoro E. G. Ismailov 《Reaction Kinetics and Catalysis Letters》1976,4(2):287-292
The phase composition of a selective Fe–Bi–Mo oxide catalyst changes under the influence of the reaction medium in the ammoxidation of propylene. It represence a heterogeneous mixture of bismuth and iron(II) molybdates.
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12.
Dong Yunzhao Li Tingcheng You Xiangqian You Qingliang Sun Lang Xie Guangyong 《Research on Chemical Intermediates》2022,48(3):1151-1158
Research on Chemical Intermediates - Dichlorobenzonitriles are important organic intermediates for the production of many fine chemicals and are produced most economically and environment-friendly... 相似文献
13.
The VCrPO/SiO2 catalyst was obtained by doping a Cr element into VPO/SiO2. Using this catalyst for the ammoxidation of o-bromotoluene (OBT) to o-bromobenzonitrile (OBBN), we studied the influence and effect of each single factor such as reaction temperature, the molar ratio air/OBT (air ratio), the molar ratio NH3/OBT (NH3 ratio), and the molar ratio H2O/OBT (H2O ratio) in the feed and feed load on the reaction. As the results show, the most appropriate reaction conditions of the catalyst are a temperature of 360°C, an air ratio of 30, a NH3 ratio of 8, an H2O ratio of 0.6, and a feed load of 57 g/(1 Cat h). With these parameters the conversion of OBT is 99.4 mol% and the mole productivity of OBBN is 77.9%. The function of the doped Cr element is mainly to increase the lattice defects in the catalyst and improve the quantity and activity of lattice oxygen [O2?], which contributes to increasing the activity of the catalyst and to reducing the most appropriate reaction temperature. 相似文献
14.
利用自制的铜基球形甲烷催化燃烧催化剂,在小型流化床反应器中对模拟含氧煤层气进行了流化床催化燃烧脱氧的实验研究,考察了床层温度、催化剂粒径、空速对脱氧效率和CO2选择性的影响。结果表明,较高的反应床层温度使催化剂活性增强,进而提高催化脱氧效率。床层温度在450 ℃以上,脱氧效率可稳定保持在95%以上。较小的催化剂粒径降低了内扩散阻力对催化反应的影响,提高催化反应的CO2选择性。床层温度在450 ℃以下时,降低空速可提高氧气转化率,但温度高于450 ℃时,脱氧反应速率加快,空速变化对脱氧效率影响不明显。此外,通过调节CH4/Air比例模拟不同含氧量的煤层气,考察流化床反应器及催化剂对含氧煤层气中O2浓度变化的适应性。模拟含氧煤层气中氧气体积分数在5%~15%,该催化剂均表现出高的脱氧活性和选择性,反应器出口气体中氧气体积分数低于0.2%,CO2选择性高于98%。 相似文献
15.
氧化锰晶体作为催化材料调控氨氧化反应产物选择性 总被引:1,自引:0,他引:1
有机腈类化合物作为一类重要的化工原料,被广泛应用于医药/农药制造、精细化学品合成和高性能纤维/橡胶生产中.传统合成有机腈类化合物一般使用剧毒的氰化物作为腈化试剂,这类氰化物在危害人体健康的同时,也会严重污染生态环境.针对无氰化物的腈化过程,发展了很多新的反应路线,其中,采用氨气作为氮源的直接氨氧化引起了广泛关注.在该反应中,高温气固相氨氧化反应容易发生过氧化等副反应.与之相比,液相体系中的氨氧化过程反应条件则相对温和,可以有效抑制过氧化.但是,在液相反应中,腈类产物很容易被水合成酰胺类化合物,从而导致该反应的产物选择性大幅降低.本文研究发现,通过改变氧化锰晶体结构可以有效地调控醇类分子氨氧化反应中腈和酰胺产物的选择性.MnO2(包括α,β,γ和δ相)催化的氨氧化过程中,主要得到了酰胺(选择性>99.0%),而在相同反应条件下,α-Mn2O3却可以高选择性地催化醇氨氧化到腈类产物(选择性>99.0%),在该体系中,即使额外增加反应体系中水和催化剂的用量,腈类产物依然不会转化为酰胺产物.动力学研究结果表明,α-Mn2O3催化腈水合到酰胺的反应速率几乎为零,这说明该类催化剂可以有效抑制腈水合反应.原位红外光谱结果表明,α-Mn2O3表面无法有效活化水分子,并且对腈类分子的吸附较弱,这些因素都导致了腈水合反应难以进行,从而可以高选择性地形成腈类化合物.与之相反,MnO2催化材料则可以高效地活化水分子,并且对腈类分子吸附较强,从而有效促进了水合反应并获得了酰胺产物.综上,通过调控氧化锰的晶体类型就可以简单、有效地改变氨氧化反应中的产物选择性.即使在苛刻的反应条件下,例如较大量的水存在下,α-Mn2O3催化的反应体系中依然可以高选择性地获得腈类化合物.本文为高效调控氨氧化反应的产物选择性提供了一个可靠方案. 相似文献
16.
T. E. Suleimanov V. P. Vislovskii E. A. Mamedov R. G. Rizaev 《Reaction Kinetics and Catalysis Letters》1986,31(2):409-412
Introduction of small quantities of alkaline and alkalineearth metal oxides into supported Sb–Bi–V oxide catalysts increasses the concentration of surface basic centers and increases significantly its activity in m-xylene ammoxidation. Promoting effect is suggested to be due to the heterolytic type of the primary activation of hydrocarbon.
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17.
Mo和Ni改性的HZSM催化剂对煤热解焦油的改质 《燃料化学学报》2016,44(1):30-36
考察了Mo和Ni改性的HZSM-5催化剂对煤热解焦油的改质性能,分析了催化改质前后焦油中轻质芳烃分布的变化规律。结果表明,经HZSM-5催化剂褐煤(XM)热解轻质芳烃总量的增加率为220%,这与煤热解产物在HZSM-5催化剂中发生烯烃和烷烃的芳构化以及酚羟基脱除等作用有关。负载活性金属Mo和Ni后,可以有效促进轻质芳烃的生成;Ni对焦油中带脂肪侧链化合物具有更强的裂解作用,而Mo则有利于带侧链化合物如甲苯和二甲苯的形成。焦煤(FX)热解过程中轻质芳烃的释放量分别是XM煤和年轻烟煤(PS)的2.2和2.4倍。经催化改质后,XM煤产物中轻质芳烃产率明显大于PS煤,并接近FX煤;这主要是因为XM煤结构中含有较多的含氧官能团和脂肪结构,在HZSM-5作用下可催化形成轻质芳烃。 相似文献
18.
Weicheng Pan Mingjun Jia Honglei Lian Yongchen Shang Tonghao Wu Wenxiang Zhang 《Reaction Kinetics and Catalysis Letters》2005,86(1):67-73
Summary Ion-exchanged Co-Na-MCM-49 and Co-H-MCM-49 zeolites are active catalysts for the selective oxidation and ammoxidation of ethane. The presence of ammonia in the feeds can considerably improve the selectivity and yield of the sum of ethylene and acetonitrile. 相似文献
19.
基于碱金属和过渡金属修饰铁矿石载氧体的煤催化燃烧 总被引:4,自引:1,他引:3
基于碱金属和过渡金属修饰铁矿石载氧体的煤催化燃烧 《燃料化学学报》2012,40(10):1179-1187
煤气化反应是煤化学链燃烧过程的控制步骤,其反应速率慢。采用碱金属Na和过渡金属Ni对铁矿石载氧体进行修饰,在流化床反应器上研究了Na、Ni负载量和反应温度对煤化学链催化燃烧的影响。结果表明,在920℃时,Na-铁矿石的催化活性高于Ni-铁矿石,随着Na、Ni负载量的增加,煤化学链燃烧的反应速率加快,气体反应产物浓度达到峰值的时间缩短,反应后期气体产物的衰减速率变大,整个反应期间CO体积浓度明显减少,而CO2、H2体积浓度增大。当Na、Ni负载量均为6%时,两者进行比较分析,Ni在960℃时对煤化学链的催化燃烧效果最为显著,碳转化率高达92.7%,高于纯铁矿石约15.5%,而在800~920℃下,催化效果不明显;Na在800~960℃对煤气化反应的催化效果均较显著。SEM-EDX分析显示,反应结束后,Na-铁矿石载氧体表面Na盐流失严重,而Ni-铁矿石表面Ni盐负载较好。 相似文献
20.
Tang Wanjun Liu Yunyi Ding Shuang Zhao Dongmei Li Tingcheng Xie Guangyong 《Research on Chemical Intermediates》2022,48(10):4105-4118
Research on Chemical Intermediates - MoV2O8 micro-cuboids were environment-friendly prepared via a facile one-step solvothermal route followed by thermal treatment with vanadium pentoxide and... 相似文献