Methane Transformation using Light Gasoline as Co-Reactant over Zn/H-ZSM11

The catalytic conversion of methane (C1) to aromatic hydrocarbons (AH) such as benzene, toluene and xylenes (BTX) over a Zn/H-ZSM-11 catalyst using Light Gasoline (C5+C6) as co-reactant was studied. AH yields were as high as 30 %mol at 500 °C, w/f = 40 g h mol⁻¹ at C1 molar fraction = 0.20. The contact time and time-on-stream effects on the product distribution, were analyzed in detail in order to obtain information about the evolution of different species. The C1 conversion reached 36 mol% C using Zn/HZSM-11 with content of 2.13 mol of Zn²⁺ per cell unit.     

Dehydroisomerization of n-Pentane to Isopentene on Molecular Sieves Impregnated with Platinum

The direct conversion of n-pentane to isopentene by dehydrogenation and isomerization in a single step was studied on Pt supported over SAPO-11, ferrierite (FER) and HZSM5 molecular sieves. The Pt/SAPO-11 presented the best selectivity to mono-branched pentenes. The characterization of acidic sites with isomers of propylamine revealed a better capacity for SAPO-11 to diffuse mono-branched amines and that is considered a consequence of its pore geometry, which could explain the obtained selectivity.     

Catalytic conversion of natural gas with added ethane and LPG over Zn-ZSM-11

The higher hydrocarbons (C2+) from natural gas (NG), such as ethane (C2), propane (C3) and butane (C4) reached excellent levels of conversion over Zn-ZSM-11 at temperatures between 550–640°C and 1 atm total pressure, but the methane (C1) present in NG could not be converted. The C1 transformation by activation with co-reactants such as C2 and liquefied petroleum gas (LPG), over Zn-ZSM-11 was studied. The addition of amounts of C2 to a feed of commercial NG allowed to activate the C1 reaching excellent values of conversion and yield to aromatic hydrocarbons (AH). The high Lewis/Bronsted sites ratio of Zn-ZSM-11 catalyst determined by pyridine desorption at different temperatures followed by FT-IR spectroscopy, allowed us to suggest that electron-donor–acceptor complex, formed between C2+ species and unoccupied molecular orbital of the zinc species present in the catalyst, favored the interaction of C2+ through carbenium intermediate to activate methane.     

Selective Catalytic Reduction of NOx over H-ZSM-5 Under Lean Conditions Using Transient NH3 Supply

The selective catalytic reduction (SCR) of NO _x over zeolite H-ZSM-5 with ammonia was investigated using in situ FTIR spectroscopy and flow reactor measurements. The adsorption of ammonia and the reaction between NO _x , O₂ and either pre-adsorbed ammonia or transiently supplied ammonia were investigated for either NO or equimolar amounts of NO and NO₂. With transient ammonia supply the total NO reduction increased and the selectivity to N₂O formation decreased compared to continuous supply. The FTIR experiments revealed that NO _x reacts with ammonia adsorbed on Brønsted acid sites as NH₄ ⁺ ions. These experiments further indicated that adsorbed -NO₂ ^– is formed during the SCR reaction over H-ZSM-5.     

n-Pentane Hydroisomerization on Pt Containing HZSM-5, HBEA and SAPO-11

Hydroisomerization of n-pentane over platinum promoted acids zeolites was studied. The effect of structure and acidity of the support was investigated at atmospheric pressure between 250 and 400 °C. Pt/HDBEA catalyst showed the best performance at 300 °C with high activity and selectivity to isopentane, due to its structure and a proper balance between acid and metallic sites. This catalyst has a high catalytic stability and regeneration under air flow after deactivation by coking, restores its activity and selectivity.     

玄武岩催化甲烷裂解制 C2 烃

以天然玄武岩为甲烷裂解催化剂,通过XRF、XRD、SEM及XPS对催化剂组成、结构、表面活性物种进行了研究。利用固定床反应装置考察了不同反应温度、空速条件下玄武岩催化甲烷裂解制C_2烃的效果。结果表明,在气体空速为4 L·h-1条件下,当反应温度为1 225 K时,甲烷的转化率为7.66%,C_2烃的选择性为33.64%;当反应温度升至1 325 K时,甲烷的转化率可达17.13%,同时C_2烃的选择性为27.21%。相同温度下,气体空速越大,乙烷的选择性越高,乙炔的选择性越低。催化剂活性因表面积炭的产生而降低,积炭类型为芳烃积炭。     

Cd改性拉长石催化甲烷裂解制C2烃

以Cd改性拉长石(Cd/Lab)为甲烷裂解催化剂制C2烃,通过XRD、XPS、TEM及GC对催化剂的结构、形貌和催化性能进行了表征与测试。利用固定床反应装置考察了金属掺杂量、反应温度、原料气空速等因素对拉长石催化甲烷裂解制C_2烃的影响。结果表明,当原料气空速为1 L/h、反应温度1073 K时,天然拉长石和Cd质量分数为1.0%的Cd改性拉长石催化甲烷裂解的转化率分别为3.32%和6.41%,且C_2烃的选择性99%。XRD、XPS、TEM等表征和催化性能结果表明,Cd2+进入到拉长石的碱金属位点,证明拉长石催化甲烷裂解的有效活性位点是碱金属位点。     

Ni–Pt/H-Y Zeolite Catalysts for Hydroisomerization of n-Hexane and n-Heptane

Ni–Pt/H-Y zeolite catalysts with different Ni contents were prepared and applied to the hydroisomerization of n-hexane and n-heptane in the temperature range 225-375 °C. ESCA studies show the complete reduction of Ni species up to 0.3 wt% Ni addition over 0.1 wt% Pt/H-Y and further addition leads to the occurrence of unreduced nickel species as NiAl₂O₄. A TEM study shows the formation of bimetallic (Ni–Pt) particles of nanoscale size and the average particle size is found to increase with increasing Ni loading. Acidity measurements by NH₃-TPD and pyridine-adsorbed FTIR spectroscopy show the increasing occupation of acid sites by the added nickel when increasing the nickel loading. The catalytic activity of Ni–Pt/H-Y zeolite and Pt/H-Y catalysts was compared and it was found that addition of Ni up to 0.3 wt% increases the n-hexane and n-heptane conversion, multibranched isomer selectivity and sustainability of the catalysts due to better metal-acid synergism, complete reduction of Ni species and the formation of catalytically active Ni–Pt bimetallic particles. Further Ni addition leads to a decrease in conversion and multibranched isomer selectivity and an increase in the cracked products, which may be due to the presence of unreduced Ni species and pore blockage by larger-sized bimetallic particles formed.     

NO x -Catalyzed Gas-Phase Activation of Methane: A Reaction Study

The catalytic effect of NO _x on methane oxidation in the absence of any solid catalyst has been investigated. The experimental results show that NO _x has very good catalytic activity in the partial oxidation of methane. The predominant products for reactions in a CH₄-O₂-NO _x co-feed mode are CO, CO₂, H₂O and H₂, CH₃OH, HCHO, and C₂H₄. Aromatics are also observed.     

NO x -Catalyzed Gas-Phase Activation of Methane: In Situ IR and Mechanistic Studies

The products of reactions occurring in a CH₄–O₂–NO _x mixture have been investigated by in situ FTIR spectroscopy. The results show that low temperatures favor the formation of HCHO and CH₃OH, while high temperatures favor that of C₂H₄. Possible reaction mechanisms based on the in situ observations are briefly discussed.     

Characterization of surface carbon formed during the conversion of methane to benzene over Mo/H-ZSM-5 catalysts

During the conversion of methane to benzene in the absence of oxygen over a 2 wt% Mo/H-ZSM-5 catalyst at 700°C, three different types of surface carbon have been observed by X-ray photoelectron spectroscopy: adventitious or graphitic-like C (284.6 eV), carbidic-like C (282.7 eV), and hydrogen-poor sp-type C (283.2 eV), where the C 1s binding energies for the respective forms of carbon are given in parentheses. Pretreatment of the catalyst at 700°C in CO also resulted in a strong signal at 283.2 eV; thus, the species responsible for this signal appears to be different from the usual aromatic-type coke. The coke with dominantly sp hybridization is concentrated on the external surface of the zeolite and is responsible for the gradual deactivation of the catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

Zeolite beta catalysts for n-C7 hydroisomerization

Zeolite β with Si/2Al ratios of 60, 100, and 200 were synthesized using tetraethlammonium hydroxide (TEAOH) as the structure-directing agent (SDA) in the absence of alkali metal cations. Pt, Pd and Pt-Pd catalysts supported on the zeolite β samples were studied in n-heptane (n-C7) hydroisomerization. The Pt/β catalysts showed a higher catalytic activity than the Pd/β catalysts. For the Pt/β with a Si/2Al ratio of 100, its n-C7 conversion and selectivity of C7 isomers were observed to be 87.06% and 75.48% respectively at 250^∘C. The activity of n-C7 conversion was stable for at least 82 h. However, the selectivity of C7 isomers was gradually decreased with the reaction time. Experimental data also showed that the addition of Pd to catalyst Pt/β enhanced the n-C7 conversion, but lowered the selectivity of C7 isomers. Pd catalyst was also observed to minimize the formation of aromatics in comparison with Pt catalyst.     

Silica-supported tantalum clusters: catalysts for conversion of methane with n-butane to give ethane, propane, and pentanes

Si0₂-supported tantalum clusters were prepared by adsorption of the precursor Ta(CH₂Ph)₅ (Ph is phenyl) on the support followed by treatments in H₂ at 523, 623, and 723 K. The resultant clusters, had approximate average diameters of 0.3, 0.8, and 2 nm, as determined by extended X-ray absorption fine structure (EXAFS) spectroscopy. The samples were tested as catalysts for conversion of methane with n-butane in a once-through flow reactor operated at atmospheric pressure and 523 K, and EXAFS spectroscopy was used to characterize the used catalysts. The results show that (a) the catalysts are active for the conversion of methane with n-butane to give ethane, propane, and pentanes; (b) catalytic activity decreased to nearly zero over a time on stream of 22 h; (c) the catalyst incorporating the smallest clusters exhibited the highest initial activity and that incorporating the largest clusters exhibited the lowest activity; (d) each used catalyst contained clusters of approximately the same nuclearity as the respective fresh catalyst, but with Ta–Ta bond lengths approximately 0.17 ? longer than those found in the fresh catalysts. The data are consistent with catalysis by the supported clusters, and the product distributions are consistent with disproportionation of n-butane accompanied by the reaction of methane with propane to give other alkanes.     

Direct Evidence for a Catalytically Active Role of the Hydrocarbon Pool Formed on Zeolite H-ZSM-5 During the Methanol-to-Olefin Conversion

The catalytic role of the hydrocarbon pool formed during the conversion of methanol on zeolite H-ZSM-5 was investigated by in situ MAS NMR spectroscopy under continuous-flow (CF) conditions and by changing of the methanol feed from ¹³CH₃OH to ¹²CH₃OH under steady state conditions. Utilizing this experimental approach, a decrease of the ¹³C CF MAS NMR signals of alkyl groups bound at the olefinic and aromatic skeleton atoms of the hydrocarbon pool by 40% was observed. Simultaneously performed ¹H CF MAS NMR measurements ensured that the total amount of carboneous compounds on the zeolite catalyst was constant during the experiments. The decrease of the number of ¹³C-isotopes of alkyl groups, observed after changing the ¹³C-enrichment of the methanol feed, is the first direct evidence for the side-chain methylation of olefinic and aromatic skeleton carbon atoms as an important pathway of the hydrocarbon pool mechanism for the methanol-to-olefin conversion on acidic zeolites.     

Catalytic reduction of no over perovskite-type catalysts

In the present work, we have investigated the reduction of NO by propane over perovskite-type oxides prepared by malic acid method. The catalysts were modified to enhance the activity by substitution of metal into A or B site of perovskite oxides. In addition, the reaction conditions, such as temperature, O₂ concentration, and space velocity have been varied to understand their effects on the catalytic performance. In the LaCoO₃ type catalyst, the partial substitution of Ba and Sr into A site enhanced the catalytic activity in the reduction of NO. For the La_0.6Ba (Sr)_o.4 Co_1−x Fe_xO₃ (x=0-1.0) catalyst, the partial substitution of Fe into B site enhanced the conversion of NO, but excess amount of Fe decreased the conversion of NO. The surface area and catalytic activity of perovskite catalysts prepared by malic acid method showed higher values than those of solid reaction method. The conversion of NO increased with increasing O₂ concentration and contact time. The introduction of water into reactant feed decreased the catalytic activity but the deactivation was shown to be reversible over La_0.6Ba_0.4Co_1−x ,Fe_xO₃ catalyst.     

Radioisotope tracer study of co-reactions of methanol with ethanol using 11C-labelled methanol over alumina, H-ZSM-5 and Cu-ZSM-5

¹¹C-labelled methanol was introduced for study of co-reaction of methanol with ethanol over alumina, H-ZSM-5 and Cu-ZSM-5 between 200 and 320 °C. The radio-method was applied to distinguish the radio-labelled methanol derivatives and co-products from unlabelled ethanol derivatives during analysis by radio-GC. The co-reaction was compared to ¹¹C-single methanol transformations from the previous work. Besides ¹¹C-dimethyl ether, ¹¹C-methyl ethyl ether as a co-product was formed between 200–240 °C and completely transformed further between 240 and 320 °C over H-ZSM-5 and alumina and partly over Cu-ZSM-5. In view of our results the appearance of ¹¹C-methyl ethyl ether intermediate is related to higher selectivities to form ¹¹C-traced C₃ and C₄–C₅ paraffins compared to the single ¹¹C-methanol transformation over H-ZSM-5 catalyst. These results suggest a modified methanol transformation pathway in the presence of ethanol over H-ZSM-5.     

Selective Conversion of Methane to C2 Hydrocarbons Using Carbon Dioxide over Mn-SrCO3 Catalysts

The combination of Mn with SrCO₃ leads to effective catalysts for the selective conversion of CH₄ to C₂ hydrocarbons using CO₂ as an oxidant; C₂ selectivities approach 88 and 79.1% with a C₂ yield of 4.3 and 4.5% over catalysts with an Mn/Sr ratio of 0.1 and 0.2, respectively. It is assumed that the Mn³⁺/Mn²⁺ couple formed in the reaction plays an important role in the activation of CO₂ and CH₄.     

Catalytic conversion of methane to benzene over Mo/ZSM-5

Dehydroaromatization of methane to benzene occurs over a 2 wt% Mo/ZSM-5 catalyst at 700C under non-oxidizing conditions. Following an initial induction period, during which CH₄ reactant reduces the original Mo⁶⁺ ions in the zeolite to Mo₂C and deposition of coke occurs, a benzene selectivity of 70% at a CH₄ conversion of 8–10% could be sustained for more than 16 h. X-ray photoelectron spectroscopy and X-ray powder diffraction measurements indicate that the reduced Mo is highly dispersed in the channels of the zeolite. Initial activation of CH₄ reactant occurs on Mo₂C sites, leading to the formation of C₂H₄ as the primary product. The latter then undergoes subsequent oligomerization reactions on acidic sites of the zeolite to form aromatic products.     

Simultaneous Production of Syngas and Ethylene from Methane by Combining its Catalytic Oxidative Coupling over Mn/Na2WO4/SiO2 with Gas Phase Partial Oxidation

A new route of methane utilization is presented, in which methane is converted to H₂, CO and C₂H₄ simultaneously with equal mole ratio, in order that the produced mixture could be used in the synthesis of propanal via hydroformylation. Kinetically controlled free radical gas phase methane oxidation was combined with its catalytic oxidative coupling over Mn/Na₂WO₄/SiO₂ to concomitantly acquire ethylene and syngas with close concentration. Under the optimal reaction condition, a mole ratio of CO:H₂:C₂H₄=1.0:1:0.9 was obtained with a yield of 11.6% and a selectivity of 68% to the target products based on C, while the selectivity to CO₂ is as low as 18.1%.     

Performance of Pt/MgAPO-11 Catalysts in the Hydroisomerization of n-dodecane

MgAPO-11 molecular sieves with varying Mg contents synthesized by the hydrothermal method were used as supports for bifunctional Pt/MgAPO-11 catalysts. MgAPO-11 molecular sieves and the corresponding catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), temperature-programmed desorption of NH₃ (NH₃-TPD), differential thermogravimetric (DTG) analysis, temperature-programmed reduction of H₂ (H₂-TPR), H₂ chemisorption and catalytic reaction evaluation. The results indicated that the acidity generated via the substitution of Mg²⁺ for Al³⁺ in the framework increased with the Mg content. Acting as acidic components, the MgAPO-11 molecular sieves loaded with Pt were tested in the hydroisomerization of n-dodecane. Optimum isomer yield was obtained over the Pt/MgAPO-11 catalyst that had neither the highest acidity nor the highest Pt loading among the tested catalysts. In fact, the activity and the isomer yield both could attain a maximum on 0.5 wt.% Pt/MgAPO-11 catalysts with differing Mg contents. A lower Mg content resulted in an insufficient acidity, whilst a higher Mg content weakened the dehydrogenation/hydrogenation function of the Pt. These inappropriate balances between the acidic and the metallic functions of the catalysts would lead to low activities and isomer yields. On the other hand, the 0.5 wt.% Pt/MgAPO-11(3) catalyst was found to have a good balance between the acidic and the metallic functions, and thus exhibited both high activity and isomer yield in comparison with the conventional 0.5 wt.% Pt/SAPO-11 catalyst.