scholarly journals Methane Pyrolysis over Carbon Catalysts

2017 ◽  
Vol 3 (2) ◽  
pp. 67 ◽  
Author(s):  
S.D. Kushch ◽  
V.E. Muradyan ◽  
P.V. Fursikov ◽  
Eu.I. Knerelman ◽  
V.L. Kuznetsov ◽  
...  

<p>Methane pyrolysis at the temperature range of 550-1000 °C in gas flow reactor with fixed bed of mixed catalysts based on carbon materials of various structure (fullerene cocoons, fullerene black, vacuum black, cathode deposit, onion-like carbon, glassy carbon, carbon fibers, mineral shungite and graphite) has been studied. Methane pyrolysis products, including stoichiometric amount of hydrogen are C<sub>3</sub>-C<sub>4</sub> alkanes, C<sub>2</sub>-C<sub>4</sub> alkenes, aromatics and pyrolytic carbon. Methane pyrolysis is carried out both on a catalytic surface and in a volume and contribution of the surface is determined by pyrolysis temperature. Materials with curved carbon surface show an activity in methane dehydrogenation at lower temperatures, than materials with planar basic structure elements. Materials with a small specific surface area favor methane aromatization at 950–1000 °C with formation of mainly benzene, toluene and naphthalene. The primary activation of C–H bond in methane at temperatures of lower than 850 °C, as well as the multiple dehydrogenation conversions resulting in the formation of pyrolytic carbon and its precursors (aromatics), are, probably, heterogeneous reactions.</p>

Molecules ◽  
2020 ◽  
Vol 25 (8) ◽  
pp. 1961 ◽  
Author(s):  
Małgorzata Smoliło ◽  
Katarzyna Samson ◽  
Ting Zhou ◽  
Dorota Duraczyńska ◽  
Małgorzata Ruggiero-Mikołajczyk ◽  
...  

Oxidative dehydrogenation (ODH) of light alkanes to olefins—in particular, using vanadium-based catalysts—is a promising alternative to the dehydrogenation process. Here, we investigate how the activity of the vanadium phase in ODH is related to its dispersion in porous matrices. An attempt was made to synthesize catalysts in which vanadium was deposited on a microporous faujasite zeolite (FAU) with the hierarchical (desilicated) FAU as supports. These yielded different catalysts with varying amounts and types of vanadium phase and the porosity of the support. The phase composition of the catalysts was confirmed by X-ray diffraction (XRD); low temperature nitrogen sorption experiments resulted in their surface area and pore volumes, and reducibility was measured with a temperature-programmed reduction with a hydrogen (H2-TPR) method. The character of vanadium was studied by UV-VIS spectroscopy. The obtained samples were subjected to catalytic tests in the oxidative dehydrogenation of propane in a fixed-bed gas flow reactor with a gas chromatograph to detect subtract and reaction products at a temperature range from 400–500 °C, with varying contact times. The sample containing 6 wt% of vanadium deposited on the desilicated FAU appeared the most active. The activity was ascribed to the presence of the dispersed vanadium ions in the tetragonal coordination environment and support mesoporosity.


2021 ◽  
Vol 11 (2) ◽  
pp. 682
Author(s):  
Gabriele Seitz ◽  
Farid Mohammadi ◽  
Holger Class

Calcium oxide/Calcium hydroxide can be utilized as a reaction system for thermochemical heat storage. It features a high storage capacity, is cheap, and does not involve major environmental concerns. Operationally, different fixed-bed reactor concepts can be distinguished; direct reactor are characterized by gas flow through the reactive bulk material, while in indirect reactors, the heat-carrying gas flow is separated from the bulk material. This study puts a focus on the indirectly operated fixed-bed reactor setup. The fluxes of the reaction fluid and the heat-carrying flow are decoupled in order to overcome limitations due to heat conduction in the reactive bulk material. The fixed bed represents a porous medium where Darcy-type flow conditions can be assumed. Here, a numerical model for such a reactor concept is presented, which has been implemented in the software DuMux. An attempt to calibrate and validate it with experimental results from the literature is discussed in detail. This allows for the identification of a deficient insulation of the experimental setup. Accordingly, heat-loss mechanisms are included in the model. However, it can be shown that heat losses alone are not sufficient to explain the experimental results. It is evident that another effect plays a role here. Using Bayesian inference, this effect is identified as the reaction rate decreasing with progressing conversion of reactive material. The calibrated model reveals that more heat is lost over the reactor surface than transported in the heat transfer channel, which causes a considerable speed-up of the discharge reaction. An observed deceleration of the reaction rate at progressed conversion is attributed to the presence of agglomerates of the bulk material in the fixed bed. This retardation is represented phenomenologically by mofifying the reaction kinetics. After the calibration, the model is validated with a second set of experimental results. To speed up the calculations for the calibration, the numerical model is replaced by a surrogate model based on Polynomial Chaos Expansion and Principal Component Analysis.


2016 ◽  
Vol 723 ◽  
pp. 633-639
Author(s):  
Waenkaew Pantupho ◽  
Arthit Neramittagapong ◽  
Nuttawut Osakoo ◽  
Jatuporn Wittayakun ◽  
Sirinuch Loiha

Iron-supported HZSM-5 catalysts were prepared by hydrothermal (Fe-HZSM-5_HYD) and impregnation methods (Fe/HZSM-5_IMP). The active species of binuclear-iron complex and iron-substituted zeolite framework, confirmed by EXAFS analysis, were observed on Fe/HZSM-5_IMP and Fe-HZSM-5_HYD, respectively. The catalysts were used for production of dimethyl ether (DME) by methanol dehydration at 200-350 °C using fixed bed flow reactor. Fe/HZSM-5_IMP showed higher catalytic conversion than Fe-HZSM-5_HYD. However, the Fe/HZSM-5_IMP catalyst was less selective to DME product and strongly deactivated for 24h. The deactivation might due to transformation of binuclear-iron to the a-iron site which was strong acidic strengh. The iron-substituted zeolite framework of Fe-HZSM-5_HYD showed high stability toward methanol dehydration. Moreover, the catalyst showed advantages of good selective to DME and low carbon deposition on surface. These results suggested that the iron-substituted zeolite framework structure could improve catalytic performance for mrthanol dehydration.


2015 ◽  
Vol 13 (1) ◽  
pp. 103-112 ◽  
Author(s):  
Kun Lei ◽  
Hongfang Ma ◽  
Haitao Zhang ◽  
Weiyong Ying ◽  
Dingye Fang

Abstract The heat conduction performance of the methanol synthesis reactor is significant for the development of large-scale methanol production. The present work has measured the temperature distribution in the fixed bed at air volumetric flow rate 2.4–7 m3 · h−1, inlet air temperature 160–200°C and heating tube temperature 210–270°C. The effective radial thermal conductivity and effective wall heat transfer coefficient were derived based on the steady-state measurements and the two-dimensional heat transfer model. A correlation was proposed based on the experimental data, which related well the Nusselt number and the effective radial thermal conductivity to the particle Reynolds number ranging from 59.2 to 175.8. The heat transfer model combined with the correlation was used to calculate the temperature profiles. A comparison with the predicated temperature and the measurements was illustrated and the results showed that the predication agreed very well with the experimental results. All the absolute values of the relative errors were less than 10%, and the model was verified by experiments. Comparing the correlations of both this work with previously published showed that there are considerable discrepancies among them due to different experimental conditions. The influence of the particle Reynolds number on the temperature distribution inside the bed was also discussed and it was shown that improving particle Reynolds number contributed to enhance heat transfer in the fixed bed.


2019 ◽  
Vol 58 (4) ◽  
pp. 40-47
Author(s):  
Ratmir R. Dashkin ◽  
◽  
Dmitry A. Gordeev ◽  
Khusrav Kh. Gafurov ◽  
Sergey N. Mantrov ◽  
...  

Butyl isocyanate is widely distributed as a precursor for the production of a number of biologically active substances: fungicides, preservatives, insecticides, personal care products, etc. Nowadays, there are a number of methods for the preparation of isocyanates, which can be divided into liquid phase and gas phase. One of the perspective methods for the production of isocyanates is the thermolysis of carbamate and/or the actions of various reaction activating agents, accompanied by the elimination of alcohol, but this process is reversible, which greatly complicates its use in industry. The paper presents the results of studies of non-catalytic thermal decomposition of N-alkylcarbamates with the formation of alkylisocyanates on the example of butylisocyanate in the gas phase, flow reactor in a wide temperature range (200 to 450 °C). In addition, a series of experiments was carried out using a catalyst, dibutyltin dilaurate, in order to reduce the thermolysis temperature and increase the yield of the final product. To implement the isocyanate production process, an experimental laboratory setup, consisting of a gas flow meter (argon) regulator, a packed column (for heating) and a sorption solution tank, was developed and tested. The thermolysis of N-n-butylcarbamate was carried out in two variations: the preparation of an individual n-butylisocyanate and the passage of reaction products through a sorption solution linking the n-butyl isocyanate to N-n-butyl-N '-(1-phenylethyl)urea, which allows to estimate the yield of the target n-butylisocyanate without additional losses. The analysis of the obtained substances was carried out by high performance liquid chromatography with a UV detector (target product) and a mass detector (analysis of by-products). According to the results of research, a modification of the laboratory facility was proposed, as well as n-butylisocyanate was obtained with a yield of 49% on the basis of a new technique.


2015 ◽  
Vol 15 (6) ◽  
pp. 9573-9629 ◽  
Author(s):  
J. C. Corbin ◽  
U. Lohmann ◽  
B. Sierau ◽  
A. Keller ◽  
H. Burtscher ◽  
...  

Abstract. Soot particles are the most strongly light-absorbing particles commonly found in the atmosphere. They are major contributors to the radiative budget of the Earth and to the toxicity of atmospheric pollution. Atmospheric aging of soot may change its health- and climate-relevant properties by oxidizing the primary black carbon (BC) or organic particulate matter (OM) which, together with ash, comprise soot. This atmospheric aging, which entails the condensation of secondary particulate matter as well as the oxidation of the primary OM and BC emissions, is currently poorly understood. In this study, atmospheric aging of wood-stove soot aerosols was simulated in a continuous-flow reactor. The composition of fresh and aged soot particles was measured in real time by a dual-vaporizer aerosol-particle mass spectrometer (SP-AMS). The SP-AMS provided information on the OM, BC, and surface composition of the soot. The OM appeared to be generated largely by cellulose and/or hemicellulose pyrolysis, and was only present in large amounts when new wood was added to the stove. BC signals otherwise dominated the mass spectrum. These signals consisted of ions related to refractory BC (rBC, C+1−5), oxygenated surface groups (CO+1−2), potassium (K+) and water (H+2O and related fragments). The C+4 : C+3 ratio, but not the C+1 : C+3 ratio, was consistent with the BC-structure trends of Corbin et al. (2015c). The CO+1−2 signals likely originated from BC surface groups: upon aging, both CO+ and CO+2 increased relative to C+1−3 while CO+2 simultaneously increased relative to CO+. Factor analysis (PMF) of SP-AMS and AMS data, using a new error model to account for peak-integration uncertainties, indicated that the surface composition of the BC was approximately constant across all stages of combustion for both fresh and aged samples. These results represent the first time-resolved measurements of in-situ BC-surface aging and suggest that the surface of beech-wood BC may be modelled as a single chemical species.


Author(s):  
Nasir Memon ◽  
Yogesh Jaluria

An experimental study is undertaken to investigate the flow structure and heat transfer in a stagnation flow Chemical Vapor Deposition (CVD) reactor at atmospheric pressure. It is critical to develop models that predict flow patterns in such a reactor to achieve uniform deposition across the substrate. Free convection can negatively affect the gas flow as cold inlet gas impinges on the heated substrate, leading to vortices and disturbances in the normal flow path. This experimental research will be used to understand the buoyancy-induced and momentum-driven flow structure encountered in an impinging jet CVD reactor. Investigations are conducted for various operating and design parameters. A modified stagnation flow reactor is built where the height between the inlet and substrate is reduced when compared to a prototypical stagnation flow reactor. By operating such a reactor at certain Reynolds and Grashof numbers it is feasible to sustain smooth and vortex free flow at atmospheric pressure. The modified stagnation flow reactor is compared to other stagnation flow geometries with either a varied inlet length or varied heights between the inlet and substrate. Comparisons are made to understand the impact of such geometric changes on the flow structure and the thermal boundary layer. In addition, heat transfer correlations are obtained for the substrate temperature. Overall, the results obtained provide guidelines for curbing the effects of buoyancy and for improving the flow field to obtain greater film uniformity when operating a stagnation flow CVD reactor at atmospheric pressure.


2018 ◽  
Vol 924 ◽  
pp. 96-99
Author(s):  
Kohei Shioda ◽  
Keisuke Kurashima ◽  
Hitoshi Habuka ◽  
Hideki Ito ◽  
Shinichi Mitani ◽  
...  

In order to develop a quick and practical cleaning process for the silicon carbide chemical vapor deposition reactor, the pyrolytic carbon-coated susceptor was used. The 30-μm-thick silicon carbide film was formed on the susceptor; the film was cleaning by chlorine trifluoride gas at 460 °C for 15 min. The remained fluorine was removed by the annealing at 900 °C in ambient hydrogen. The pyrolytic carbon surface did not suffer from any damage, because the pyrolytic carbon film surface morphology after the cleaning process was the same as that before the silicon carbide film deposition.


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