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1.
利用连续流动微反研究了Rh2Co2/Al2O3上的CO加氢反应.该反应在200℃以上发生,反应活性随着温度的升高和H2/CO比的增大而增大.利用TPIR动态方法研究了Rh2Co2/Al2O3上CO和H2的共吸附及其动态行为.结果表明,在Rh2Co2/Al2O3的Rh上的孪生和桥式中心及Co上的线式中心上,CO和H2室温共吸附时即有部分孪生、桥式CO及Co上的线式CO转化为相应的羰基氢化物.随着温度的升高,剩余的孪生、桥式CO及Co上的线式CO向羰基氢化物转化,而羰基氢化物又向多氢羰基氢化物转化.在CO加氢反应温度下,Rh2Co2/Al2O3的三种吸附中心上只存在多氢羰基氢化物.与CO加氢反应和CO歧化的吸附态动态研究结果相关联,可以认为在Rh2Co2/Al2O3上CO加氢生成CH4经由了羰基氢化物多氢羰基氢化物途径. 相似文献
2.
还原温度对Ni/Al2O3催化剂上H2,CO吸附的影响 总被引:2,自引:0,他引:2
采用程序升温还原与程序升温逐步活化、H2、CO室温吸附、H2程序升温脱附相结合的方法,研究了Ni/Al2O3催化剂上还原活化温度对其吸脱附性能的影响.实验发现,Ni/Al2O3催化剂上,在不同温度还原的不同Ni氧化物物种,经相应温度活化后可形成不同性质的H2、CO吸附中心.催化剂经523K及573K活化后可形成极细的与Al2O3有一定相互作用的吸附中心,在这类中心上,H2的室温吸附量极小,但有一定的高温H2吸附量,且高温吸附的H2要在较高温度下才能脱附,CO在其上则可能是按单金属中心多CO方式吸附的.催化剂经673K和723K活化后均形成较强的H2、CO吸附中心,CO在这些中心上可能是按线式和桥式两种方式吸附的.催化剂经673K活化后,形成的中心上吸附的H2可在相对较低的温度下脱附.Ni/Al2O3经773K处理会发生烧结,因而丧失室温H2、CO吸附能力. 相似文献
3.
利用TPIR动态方法研究了Rh2Co2/Al2O3上CO吸附态的动态行为和CO歧化反应.结果表明,在CO吸附TPD(真空中)IR动态过程中,Rh上的孪生CO谱带强度逐渐同步减弱,Co上的线式CO谱带和Rh上的桥式CO谱带强度逐渐减弱的同时向低频位移.完全脱附的顺序为:桥式(150℃),孪生(350℃)和Co上的线式(400℃).该结果明显不同于Rh4/Al2O3上相同动态过程的结果,表明RhCo相互作用导致各吸附中心上CO吸附强度的改变.在CO吸附TP(CO中)IR动态过程中,三种吸附的CO谱带250℃以上才发生强度减弱直到消失.表明CO歧化在250℃以上才发生.并且Rh上桥式中心上的歧化速率与孪生中心上相等,Co上的线式中心上的CO歧化速率则大于Rh4/Al2O3的Rh线式中心. 相似文献
4.
应用加温加压气固多相催化原位红外光谱反应器,在H2/CO=2:1(mol)、0.5 ̄5.0MPa和20 ̄300℃的接近CO+H2工业反应条件下,考察了还原态和氧化态Rh/Al2O3催化剂表面CO吸附态,关联了吸附态与催化剂活性的关系。实验结果表明,还原态的Rh/Al2O3催化剂一氧化碳加氢生成烃类,其催化剂表面存在三种CO吸附态:线式Rh(CO),孪生式Rh(CO)2和桥式Rh2CO。在常温常压下 相似文献
5.
硫化态NiMoK/Al2O3变换催化剂对水的吸附性能 总被引:2,自引:0,他引:2
硫化态NiMoK/Al_2O_3变换催化剂对水的吸附性能李利民,郭益群,王贵昌,王文祥(郑州大学化学系郑州450052)关键词水煤气变换催化剂,硫化,水吸附,脉冲气相色谱CO(Ni)MoK/Al_2O_3型催化剂用于变换反应时需首先进行硫化,硫化温度... 相似文献
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7.
Ni/Al2O3上甲烷二氧化碳氧气转化制备合成气的研究 总被引:3,自引:0,他引:3
在固定床流动反应装置上,从活性组分的负载量,载体的焙烧温度、反应温度,空速等几个方面考察了Ni/Al2O3催化剂对CH4-CO2-O2转化制备合成气的催化活性,发现采用1100℃焙烧的γ-Al2O3载体制备的镍负载量为9.17w%的Ni/Al2O3催化剂。 相似文献
8.
利用原位红外技术研究了CH3OH,CO,O2等在5%Ag/γAl2O3上的吸附情况及CH3OH和O2共吸附时表面物种的变化.结果表明,在表面纯净的Ag/γAl2O3催化剂上,甲醇的解离吸附仅发生在γAl2O3上;表面预吸附氧后,可大大增强Ag对CH3OH的解离吸附,当吸附的[CH3O]与[O]在Ag/γAl2O3上相互作用时,出现吸附态甲醛、甲二氧基、甲酸根等中间物种.O2在Ag/γAl2O3上存在非解离吸附(O-2),在真空中较易脱附,但在氧气氛下可于100℃时稳定存在. 相似文献
9.
EFFECTS OF ALKALI AND RARE EATTH METAL OXIDES ON THE THERMAL STABILITY AND THE CARBON DEPOSITION OVER A NiO/Al_2O_3 CATALYST
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LIU Sheng-Lin MIAO Qing XIONG Guo-Xing * SHENG Shi-Shan CHEN Hen-Rong State Key Laboratory of Catalysis Dalian Institute of Chemical Physics The Chinese Academy of Sciences Dalian Liaoning HKmm〗 《天然气化学杂志》1998,7(3):189-197
采用固定床流动反应装置、CO吸附、TG、TPO、XPS和XRD等手段考察了NiO/Al2O3和LiNiLaO/Al2O3催化剂上的甲烷部分氧化反应。实验结果表明,LiNiLaO/Al2O3对甲烷部分氧化反应具有较高的反应活性。锂和镧的添加不仅改善了活性组分镍的分散度,而且提高了NiO/Al2O3的抗积碳能力和热稳定性 相似文献
10.
CH4,CO2和O2制合成气反应中载体对Ni催化剂抗氧化性能的影响 总被引:7,自引:0,他引:7
在CH4、CO2 催化氧化制合成气反应中, Ni/Al2O3 催化剂在高温下生成NiAl2O4 尖晶石,是导致催化剂失活的一个重要因素. 通过向载体(Al2O3)中添加各种氧化物, 使得催化剂的抗氧化性能得到改善. 并运用TPR、XRD对催化剂进行表征, 发现催化剂的抗氧化性顺序为: Ni/CaO-Al2O3 > Ni/MgO-Al2O3 > Ni/CeO2-Al2O3 > Ni/La2O3-Al2O3 > Ni/Y2O3-Al2O3 > Ni/TiO2-Al2O3> Ni/Al2O3> Ni/Fe2O3-Al2O3. 相似文献
11.
用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%. 相似文献
12.
Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction
Laurent Gavara Thomas Boisse Jean-Pierre Hénichart Adam Daïch Philippe Gautret 《Tetrahedron》2010,66(38):7544-5571
In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments. 相似文献
13.
The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula. 相似文献
14.
Rebecca J. Burton Mandy L. CrowtherNeal J. Fazakerley Shaun M. FilleryBarry M. Hayter Jason G. KettleCaroline A. McMillan Paula PerkinsPeter Robins Peter M. SmithEmma J. Williams Gail L. Wrigley 《Tetrahedron letters》2013
The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines. 相似文献
15.
KMnO4-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields. 相似文献
16.
N. A. Nedolya 《Chemistry of Heterocyclic Compounds》2008,44(10):1165-1219
The review contains a concise historical account and information on the most significant researches undertaken by the staff
at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry
of Heterocyclic Compounds.
Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008. 相似文献
17.
Regiospecific and direct imidation of the methyl C(sp3)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products. 相似文献
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19.
《Tetrahedron》2014,70(21):3377-3384
The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative. 相似文献
20.
Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields. 相似文献