Promotional effect of colloidal alumina on the activity of the In/HZSM-5 catalyst for the selective reduction of NO with methane

Colloidal alumina was used to improve the activity of an In/HZSM-5 catalyst for the selective reduction of NO with CH4 in the excess of oxygen. Compared with In/HZSM-5, the In/HZSM-5/Al2O3 catalyst showed higher activity in a wide range of reaction temperatures. It is visualized that a synergetic effect between In/HZSM-5 and Al2O3 enhances the conversion of NOx. The addition of Al2O3 improved the conversion of NO to NO2 and facilitated the activation of methane. An In/HZSM-5/Al2O3 pre-treated with steam for 15 h at 700 degreesC still showed a high activity for the removal of NOx with methane, while an In/HZSM-5 similarly pre-treated with steam showed a lower activity than the fresh sample. The activity of the In/HZSM-5/Al2O3 catalyst could be restored completely after water vapor was removed from the feed gas. Furthermore, it was found that the In/HZSM-5/Al2O3 remained fairly active under high GHSV and O-2 concentration conditions. It was also interesting to find that an increase in NO content could enhance the conversion of methane, and this illustrates that the existence of NO is beneficial for the activation of methane. (C) 2002 Elsevier Science B.V. All rights reserved.

Reduction of NO by CH4 with microwave heating

The reduction of NO by CH4 in the presence of excess O-2 over Co/HZSM-5, Ni/HZSM-5 and Mn/HZSM-5 catalysts with microwave heating was studied. By comparing the activities of the catalysts in the microwave heating mode with that in the conventional reaction mode, it was demonstrated that microwave heating could greatly reduce the reaction temperature, and could clearly expand the temperature window of the catalysts. Especially for the Co/HZSM-5 catalyst, the maximum conversion of NO to N-2 in the conventional reaction mode was consistent with that in the microwave heating mode. However, the temperature window for the maximum conversion in the microwave heating mode was from 260 to 360degreesC instead of a temperature of 420degreesC in the conventional reaction mode. The results suggest that microwave heating has a novel effect in the reduction of NO.

Investigation on the catalytic roles of silver species in the selective catalytic reduction of NOx with methane

Silver impregnated H-ZSM-5 zeolite catalysts with silver loading from 3 to 15 wt.% were investigated for the selective catalytic reduction (SCR) of NOx with CH4 in the excess of oxygen. X-ray diffraction (XRD) and UV-Vis measurements established the structure of silver catalysts. A relationship between the structure of silver catalysts and their catalytic functions for the SCR of NOx by CH4 was clarified. The NO conversion to N-2 showed a S-shape dependence on the increase of Ag loading. No linear dependence of catalytic activity on the amount of silver ions in the zeolite cation sites was observed. Contrastively, the activity was significantly enhanced by the nano-sized silver particles formed on the higher Ag loading samples (greater than or equal to7 wt.%). Temperature programmed desorption (TPD) and temperature programmed reduction (TPR) studies showed that nano-silver particles provided much stronger adsorption centers for active intermediates NO3-(s) on which adsorbed NO3-(s) could be effectively reduced by the activated methane. Silver ions in the zeolite cation sites might catalyze the reaction through activation of CH4 at lower temperatures. Activated CH4 reacted with NO3-(s) adsorbed on nano-silver particles to produce N-2 and CO2. (C) 2003 Elsevier B.V. All rights reserved.

Reduction property and catalytic activity of Ce1-XNiXO2 mixed oxide catalysts for CH4 oxidation

Ce1-XNiXO2 oxides with X varying from 0.05 to 0.5 were prepared by different methods and characterized by XRD and TPR techniques. Ce(0.7)Mi(0.3)O(2) sample prepared by sol-gel method shows the highest reducibility and the highest catalytic activity for methane combustion. Three kinds of Ni phases co-exist in the Ce1-XNiXO2 catalysts prepared by sol-gel method: (i) aggregated NiO on the support CeO2, (ii) highly dispersed NiO with strong interaction with CeO2 and (iii) Ni atoms incorporated into CeO2 lattice. The distribution of different Ni species strongly depends on the preparation methods. The highly dispersed NiO shows the highest activity for methane combustion. The NiO aggregated on the support CeO2 shows lower catalytic activity for methane combustion, while the least catalytic activity is found for the Ni species incorporated into CeO2. Any oxygen vacancy formed in CeO2 lattice due to the incorporating of Ni atoms adsorbs and activates the molecular oxygen to form active oxygen species. So the highest catalytic activity for methane combustion on Ce0.7Ni0.3O2 catalyst is attributed not only to the highly dispersed Ni species but also to the more active oxygen species formed. (C) 2002 Elsevier Science B.V. All rights reserved.

Theoretical study on the mechanism of the reaction of CH4+MgO

The reactions of (1) CH4 + MgO --> MgOH. + CH3. and (2) CH4 + MgO --> Mg + CH3OH have been studied on the singlet spin state potential energy surface at the MP2/6-311+G(2d,2p) level. These two reaction channels, both involving intermediates and transition states, have been rationalized by the structures of the species involved, natural bond orbital (NBO), and vibrational frequency analysis. We have considered two initial interacting models between CH4 and MgO: a collinear C-H approach to the O end of the MgO forming the MgOCH4 complex with C-3nu symmetry and three hydrogen atoms of the methane point to the Mg end of the MgO forming the OMgCH4 complex with C-1 symmetry. The calculations predict that reactions 1 and 2 are exothermic by 39.8 and 86.5 kJ mol(-1), respectively. Also, the former reaction proceeds more easily than the latter, and the complex HOMgCH3 is energetically preferred in the reaction of MgO + CH4.

Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model

The semirigid vibrating rotor target model is applied to study the isotope effect in reaction H + CH4-->H-2 + CH3 using time-dependent wave-packet method. The reaction probabilities for producing H-2 and HD product channels are calculated. The energy dependence of the reaction probabilities shows oscillating structures for both reaction channels. At low temperature or collision energies, the H atom abstraction is favored due to tunnelling effect. In partially deuterated CHxDy (x + y = 4), the breaking of the C-H bond is favored over that of the C-D bond in the entire energy range studied. In H + CHD3 reaction at high energies, the HD product dominates simply due to statistical factor. (C) 2003 American Institute of Physics.

Combination of CH4 oxidative coupling reaction with C2H6 oxidative dehydrogenation by CO2 to C2H4

A new process has been suggested for converting natural gas to ethylene by combining oxidative coupling of methane with ethane dehydrogenation to provide an efficient method for the utilization of thermicity and CO2. From their thermodynamics, it is clear that the exothermicity from CH4 oxidative coupling reaction (DeltaH(800degreesC) = -174.3 kJ mol(-1)) can support C2H6 dehydrogenation by CO2 (DeltaH(800degreesC) = + 180.2 kJ mol(-1)). Meanwhile, the two reactions can be conducted under the same reaction conditions, such as the reaction temperature and reaction pressure as well as space velocity. In addition, the CO2 yielded from CH4 oxidative coupling reaction can be directly used for C2H6 dehydrogenation. Two kinds of catalyst are developed for this combined process with an achievement, from which C2H4 content in tail gas can reach attractively 16.4%, which can be used directly to produce ethylbenzene by the alkylation of benzene. (C) 2002 Elsevier Science Ltd. All rights reserved.

Fluxes of CO2,CH4 and N2O from alpine grassland in the Tibetan Plateau

Using static chamber technique,fluxes of CO2,CH4 and N2O were measured in the alpine grassland area from July 2000 to July 2001,determinations of mean fluxes showed that CO2 and N2O were generally released from the soil,while the alpine grassland accounted for a weak CH4 sink.Fluxes of CO2,CH4 and N2O ranged widely.The highest CO2 emission occurred in August,whereas almost 90?of the whole year emission occurred in the growing season.But the variations of CH4 and N2O fluxes did not show any clear patterns over the one-year-experiment.During a daily variation,the maximum CO2 emission occurred at 16:00,and then decreased to the minimum emission in the early morning.Daily pattern analyses indicated that the variation in CO2 fluxes was positively related to air temperatures(R^2=0.73)and soil temperatures at a depth of 5 cm(R^2=0.86),whereas daily variations in CH4 and N2O fluxes were poorly explained by soil temperatures and climatic variables.CO2 emissions in this area were much lower than other grasslands in plain areas.

Short-term effect of increasing nitrogen deposition on CO2, CH4 and N2O fluxes in an alpine meadow on the Qinghai-Tibetan Plateau, China

National Key Research and Development Program [2010CB833500]; Natural Science Foundation of China [30590381]; Knowledge Innovation Project of Chinese Academy of Sciences [KZCX2-YW-432]

Effects of multiple environmental factors on CO2 emission and CH4 uptake from old-growth forest soils

National Key Research and Development Program [2010CB833502]; National Natural Science Foundation of China [30600071, 40601097, 30590381, 30721140307]; Knowledge Innovation Project of the Chinese Academy of Sciences [KZCX2-YW-432, O7V70080SZ, LENOM07LS-01

一种CO2-CH4共汽化制取合成气的方法

一种ＣＯ＃－［２］－ＣＨ＃－［４］共汽化制取合成气的方法是电源向等离子发生装置提供能量，在氩气为载气的条件下，使等离子体装置产生温度为１２００Ｋ－１５００Ｋ的高温裂解区，将体积比为１－３∶１的ＣＯ＃－［２］和ＣＨ＃－［４］混合气通入高温裂解区，得到由Ｈ＃－［２］与ＣＯ组成的合成原料气；其中电源能量、氩气流量和混合气流量的比值为１ＫＷ∶５－２０Ｌ／ｍｉｎ∶１－１００Ｌ／ｍｉｎ。本发明具有工艺简单、设备小、污染小、投资少、原料利用率和合成效率高等优点。