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1.
研制了天然气和氧经偶联反应制环氧乙烷的Ag-Ba-Cs/Al2O3催化剂(NEO-1)。用N2+O2+C2H4和偶联产物气加氧作原料气,在250℃,空速2500h^-1时,乙烯转化率和EO选择性分别达到了30%和80%,NEO-1催化具有适宜的比表面和孔结构,用XPS分析发现,与新鲜的催化相比,经活化和反应后的催化剂表面的Ba,Cs原子浓度增高,并具有较多的吸附氧物种。 相似文献
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应用FTIR和脉冲反应技术研究了CO2和O2在Ag-Ba-Ca-K/α-Al2O3上的吸附及CO2对C2H4环氧化,完全氧化及环氧乙烷(EO)深度氧化反应的影响。研究结果表明,CO2和表面吸附氧在负载银催化剂表面存在竞争吸附,CO2对表面吸附氧有置换作用,该作用降低了银催化剂表面吸附氧的浓度,并且所形成的碳酸根物种改善了乙烯环氧化反应活性氧种的表面分布,对C2H4的环氧化反应有一定的抑制作用,但是 相似文献
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应用FTIR和脉冲反应技术研究了CO_2和O_2在Ag-Ba-Ca-K/α-Al2O3上的吸附及CO2对C2H4环氧化、完全氧化及环氧乙烷(EO)深度氧化反应的影响.研究结果表明,CO2和表面吸附氧在负载银催化剂表面存在竞争吸附,CO2对表面吸附氧有置换作用,该作用降低了银催化剂表面吸附氧的浓度,并且所形成的碳酸根物种改善了乙烯环氧化反应活住氧种的表面分布,对C_2H_4的环氧化反应有一定的抑制作用,但是对C2H4和EO的深度氧化反应的抑制作用更强,使得乙烯环氧化反应的选择性得到改善. 相似文献
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甲苯气相选择性氧化制苯甲醛 Ⅰ.V_2O_5/TiO_2-Al_2O_3催化剂研究 总被引:1,自引:0,他引:1
制备了一系列负载型V-Ti-Al-O催化剂并用于甲苯的气相选择性氧化制苯甲醛,考察了接触时间、氧浓度、V2O5负载量以及催化剂焙烧温度对反应性能的影响。用TPR、XRD和BET等测试手段,对催化剂进行了表征。研究发现,催化剂在773K时活化,接触时间1.2秒,氧浓度21%时,可获得较好的反应结果,V2O5负载量为6(wt)%的催化剂,在593K时反应,得到了转化率20.5%,苯甲醛产率8.3%的最好结果。 相似文献
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铈基氧化物催化剂上氧物种的EPR研究 总被引:2,自引:0,他引:2
选择CeO2、20%(mol)Ce/Sr及SrCO33种甲烷氧化偶联催化剂,进行了吸附氧的EPR及骤冷EPR研究,对氧物种的形式、吸附方式及在反应中的作用进行了深入讨论.实验发现,氧化铈及复合催化剂很容易吸附氧分子产生O2-超氧离子,而碳酸锶表面不利于O-2的生成.O-2可以不同方式吸附于催化剂表面,不同方式吸附的O-2具有不同的氧化能力和稳定性.不同温度下骤冷可以在复合催化剂上得到几乎相同强度的O-2EPR信号,因此O-2可能不是甲烷的选择活化中心,而是在反应条件下转化成了O2-2或O-选择性物种.复合催化剂中的SrCO3,对CeO2中氧的流动性及产生氧中间体的能力起到了调节作用,抑制了过氧化. 相似文献
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Li—Ni—La—O系复合氧化物催化剂上甲烷氧化偶联的研究 总被引:2,自引:0,他引:2
考察了Li-Ni-La-O系催化剂的组成、结构及反应条件对甲烷氧化偶联反应活性的影响。在780℃、CH4:O2:N2=2:1:7、空速15000h^-1时,C2烃收率可达25.8%。XRD、IR、XPS及SEM等的结构分析表明,在LiLa1-xNixO2催化剂中,当0.1≤x≤0.9时,该催化剂由LiNiO2和La2Ni1-yLiyO4-λ两相组成,x<0.3时出现了LiLaO2相,La2Ni1- 相似文献
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OXIDATIVE COUPLING OF METHANE IN A CIRCULAR FIXED BED REACTOR WITH 30 mL MgO/BaCO_3 CATALYST 下载免费PDF全文
在甲烷氧化偶联反应中,采用了一种薄层环形固定床反应器,这种反应器有利于反应热的转移。在环形固定床反应器中进行的MgO/BaCO3催化剂稳定性试验结果表明,催化剂在500h试验中一直保持较高的活性。在CH4:O2:H2O=5:1:2.3,CH4的GHSV为5700h-1的条件下,得到甲烷转化率为26%,C2烃收率为17.3%,C2选择性为67.5%;水蒸汽作为稀释气引入反应中,可分散和带走催化剂床层过多的反应热,减小床层温差。XRD结果表明,反应后的催化剂与新鲜催化剂的结构基本一致,催化剂具有稳定催化活性的原因,应归属于其结构的稳定性和具有一定的抗水蒸汽性能。 相似文献
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Ni/Al2O3催化剂上甲烷部分氧化制合成气 总被引:19,自引:2,他引:19
研究了Ni/Al2O3催化剂对甲烷部分氧化制合成气的反应性能.结果表明,催化剂在其活性组份Ni为10%时反应性能最好.条件实验表明,在600~900℃范围内,甲烷转化率和CO、H2的选择性随温度升高而增加;转化率和选择性在甲烷空速≤1.5×105h-1时基本不变,空速>1.5×105h-1时,转化率和选择性有所下降.随着压力的增加(0.05~0.40MPa),转化率和选择性下降.SEM和化学分析结果证明在反应过程中,Ni组份存在烧结和流失现象. 相似文献
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Abstract— The photolysis of aqueous solutions of cis -[Cr(C2 O4 )2 (H2 O)2 ]- at 254 nm and pH 4 produced CO2 and H2 in nearly equal yields. The quantum yield of hydrogen, φ2 , increased by 9% and the yield of carbon dioxide, φ, by 65% as the pH was lowered from 4 to I. The total gas yield, φgas , decreased in the presence of added oxalate or chromium (II) ions and when the light intensity was lowered. The gas yield in D2 O was appreciably higher than in H2 O. The variation of φgas with pH (D) and with added oxalate ion was roughly parallel in the two liquid media. The gas yield increased in the series:
A tentative mechanism is suggested to explain the results. 相似文献
A tentative mechanism is suggested to explain the results. 相似文献
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《结构化学》1991,(1)
<正> The structures of two complexes C(CuOC6H4CH2NHCH2COO)2 (H2 O)]·H2P(1) and [Co(NH3)6[Co(OC6H4CH2NHCH2COO)2]2[C1]·10H2O (2) were determined by X-ray analyses. Compound (1) crystallizes in the orthorhombic space group P212121 with a=11. 357(1),b= 24. 304(2),c=7.317(4) A,Z= 4;While compound (2) in the monoclinic space group A2/a(C2/c) with a=23. 486(9) ,b=26. 605(6) ,c= 10. 542(1) A,γ= 128. 42(4)°,Z= 4. In compound (1),two Cu(Ⅱ) ions are bonded together by the phenolic oxygen atoms of two tridentate chelating ligands and each of them is separately coordinated by the carboxyl oxygen,amino nitrogen of each chelate ligand and by the fifth oxygen atom as well (from aqua or the carbonyl group in adjacent molecule). Thus the coordination of each Cu(Ⅱ) is a square pyramid with distances of 1. 93- 1. 97A to the four corner atoms and 2. 30 and 2. 32 A to the apex atoms. The whole molecule has an approximately planar configuratioir with the two pyramid apexes pointing towards one side. Compound (2) consists of 相似文献
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《Journal of Coordination Chemistry》2012,65(3-4):267-284
Abstract Infrared spectra of the coordination compounds [MG2(py)2], M(II)=Co, Ni, Cu and Zn; G=glycolato, py=pyridine, have been fully assigned by means of py and py-d 5 and glycolato α—OH and α—OD (G-d) labelling as well as metal ion substitution in the 4000–70cm?1 region. The crystal structure of the Ni(II) compound is presented and the spectra of the compounds are discussed on the basis of their structure and their bonding to the glycolato and pyridine ligands. Vibrational frequencies obtained for the Ni(II) compound are compared to those obtained by calculations carried out using the Gaussian 94 program package. 相似文献
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四(邻N-甲基烟酰胺基)苯卟啉与Cu(Ⅱ)的反应动力学研究 总被引:3,自引:1,他引:3
在20.0±0.1℃,0.1M KCl介质及乙酸或丁二酸缓冲条件下,研究了水溶性的四(邻N—甲基烟酰胺基)苯卟啉(H_2-TM(O-Nic)PP)与Cu(Ⅱ)的反应动力学。实验结果表明,Cu(Ⅱ)嵌入H_2-TM(O-Nic)PP的反应速率对卟啉是一级反应。表观一级速率常数表达式如下:对Cu(Ⅱ)-酸盐体系,其中,对Cu(Ⅱ)-丁二酸盐体系,其中,提出了Cu(Ⅱ)嵌入H_2-TM(O-Nic)PP的反应机理,并对乙酸缓冲体系和丁二酸缓冲体系中反应动力学的差别作出了讨论。 相似文献
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《Journal of Coordination Chemistry》2012,65(3):187-191
Abstract The kinetics of Cr2+(aq) reductions of glycinato-, D,L-alanato, D,L-phenylalanato-, and D,L-leucinatobis-(ethylenediamine)cobalt(III) ions have been investigated. The rate law is of the form d(ln[Co(III)]/dt = k[Cr2+], where the rate constant k(M?1sec?1) and associated activation parameters δHδ(kcal mol?1 and δSδ (cal deg ?1mol?1) in parentheses, are respectively 1.65 · 0.06 (9.7 · 0.1, -25 · 1), 0.367 · 0.008 (10.9 · 04,-24 ·1), 0.529 · 0.021 (11.2 · 0.4, -22 · 1); and 0.358 · 0.019 (11.5 · 0.3, -22 · 1) at 298·K and ·[CIO·] = 1.0 M. The reactions are all inner-sphere. 相似文献
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《Journal of Coordination Chemistry》2012,65(3-4):269-279
Abstract The syntheses and crystal structures of [Co(nic)2(H2O)4] (1). [Co(iso)2(H2O)4] (2). [Cu(nic)2(H2O)4] (3), and [Cu(iso)2(H2O)4] (4) (nic = nicotinate; iso = isonicotinate) are reported. Complex 1 crystallizes in monoclinic, space group C2/m with cell parameters a =14.150(4). b = 6.883(2)., c = 8.497(2) Å, β= 118.28(2)° and Z = 2. The other crystals. 2. 3. and 4. are all triclinic, Pī; a = 9.777(3), b = 6.348(4), c = 6.888(3)Å, a= 113.10(6)., β= 110.55(3). γ = 97.61(5)°, and Z=l for 2; a = 7.0281(4), b = 7.7176(6), c = 8.6978(7)Å, a = 68.103(7), β = 68.526(5), γ = 62.550(6)°, and Z=1 for 3; a = 9.1807(4), b = 6.3334(3), c = 6.8871(3)Å, a= 108.213(4), β = 99.433(4), γ= 105.190(4)°, and Z= 1 for 4. The arrangements around the metal ions are trans-octahedra with two pyridyl nitrogens and two aqua oxygens in the equatorial positions and two aqua oxygens in the axial positions, although the Cu(II) complexes show a larger Jahn-Teller distortion. 相似文献
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《Journal of Coordination Chemistry》2012,65(1-2):95-106
Abstract A cobalt(III) complex containing (R)-2-methylaziridine (R-meaz), [Co(R-meaz)(NH3)5]3+, was prepared and the two diastereomers arising from the presence of the chiral nitrogen atom (N(R) and N(S)) were separated by column chromatography. Molecular mechanics calculations estimated the N(R)-isomer to be more stable. This result was supported by the x-ray structure determination of the more abundant (ca. 94%) isomer, N(R)-[Co(R-meaz)(NH3)5]Br3H2O. Crystal data: monoclinic, P21, a = 7.357(1), b = 9.780(1), c = 10.426(1) Å, μ = 93.58(1)°, V= 748.7(3) Å3, Z= 2. Kinetic studies of isomerization (epimerization) between the two isomers revealed that inversion at the nitrogen center was very slow (5 × 10?2 M?1 S?1at 25 °C). The small rate constant seems to be related to the strained three-membered structure of the meaz ligand. The reaction of Na3[Co(N02)6] and R-meaz yielded a complex containing two dimerized R-meaz chelates, trans-[Co(NO2)2(di-R-meaz)2] (di-R-meaz =RR)-α,2-dimethyl-l-aziridineethanamine). The crystal strucrure of trans-[Co(NO2)2 (di-R-meaz)2]C1O4H2O was established by x-ray crystallography. Crystal data: orthorhombic, P212121, a = 11.784(6), b = 21.023(9), c = 8.608(7) Å, V = 2133(2) Å3, Z = 4. 相似文献