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%.     

Steady-state conversion of methane to aromatics in high yields using an integrated recycle reaction system

Methane can be converted in high yields to aromatic products using an integrated recycle system containing both an oxidative coupling (OCM) reactor at 800°C, for conversion of CH₄ to C₂H₄, and a secondary reactor containing Ga/ZSM-5 at 520°C for subsequent conversion of ethylene to aromatics. Using this system, aromatic product yields of >70% at CH₄ conversions of ~100%, based on total CH₄ added, can be obtained. This revised version was published online in July 2006 with corrections to the Cover Date.     

Comparison of Ethylene Glycol Steam Reforming Over Pt and NiPt Catalysts on Various Supports

Steam reforming of ethylene glycol (EG) was studied on Pt and NiPt catalysts supported on γ-Al₂O₃, TiO₂, and carbon. On all supports bimetallic NiPt catalysts show higher activity for H₂ production than the corresponding Pt catalysts as predicted from model surface science studies. The kinetic trends are similar for all catalysts (Pt and NiPt) with the H₂ production rate being zero-order and fractional order with respect to water and ethylene glycol, respectively. Slight differences in selectivity to minor products are observed depending both on active metal and support. On γ-Al₂O₃, NiPt shows higher H₂ and less alkane formation than Pt. TiO₂ supported catalysts show increased water-gas shift activity but also increased selectivity to alkane precursors. NiPt/C is identified as an active and selective catalyst for EG reforming.     

Gas Separation Properties of Polyimide-Zeolite Mixed Matrix Membranes

Mixed matrix membranes (MMMs) of polyimide (PI) and zeolite 13X, ZSM-5 and 4A were prepared by a solution-casting procedure. The effect of zeolite loading, pore size, and hydrophilicity/hydrophobicity of zeolite on the gas separation properties of these mixed matrix membranes were studied. Experimental results indicate that permeability of He, H₂, CO₂, and N₂ increased with zeolite loadings. Selectivity of H₂/N₂ shows a slight improvement for low loadings of zeolites 13X and ZSM-5 but has a decreasing trend for zeolite 4A and high loadings of zeolites 13X and ZSM-5. In addition, selectivity of H₂/CO₂ remains low (1–3) while selectivity of CO₂/N₂ is significantly improved with the incorporation of the three zeolites in the polyimide membrane. Experimental permeabilities are higher than those predicted by the Maxwell model except for H₂ and N₂ permeabilities of the PI-4A system which are consistent with the predicted permeabilities. The proposed modified Maxwell model is capable of predicting the permeabilities of polyimide-zeolite 4A MMMs, but fails to simulate the permeability increase induced by interface voids in the polyimide-zeolite 13X and ZSM-5 systems.     

Gas‐Phase Hydrogenolysis of Glycerol Catalyzed by Cu/MOx Catalysts

The catalytic activities of Cu/MO_x (MO_x = Al₂O₃, TiO₂, and ZnO) catalysts in the gas‐phase hydrogenolysis of glycerol were studied at 180–300 °C under 0.1 MPa of H₂. Cu/MO_x (MO_x = Al₂O₃, TiO₂, and ZnO) catalysts were prepared by the incipient wetness impregnation method. After reduction, CuO species were converted to metallic copper (Cu⁰). Cu/Al₂O₃ catalysts with high acidity, high specific surface areas and small metallic copper size favored the formation of 1,2‐propanediol with a maximum selectivity of 87.9 % at complete conversion of glycerol and a low reaction temperature of 180 °C, and favored the formation of ethylene glycol and monohydric alcohols at high reaction temperature of 300 °C. Cu/TiO₂ and Cu/ZnO catalysts exhibited high catalytic activity toward the formation of hydroxyacetone with a selectivity of approx. 90 % in a wide range of reaction temperature.     

Oxidative reforming of methane on structured Ni-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/cordierite catalysts

The catalytic properties of Ni/Al₂O₃ composites supported on ceramic cordierite honeycomb monoliths in oxidative methane reforming are reported. The prereduced catalyst has been tested in a flow reactor using reaction mixtures of the following compositions: in methane oxidation, 2–6% CH₄, 2–9% O₂, Ar; in carbon dioxide and oxidative carbon dioxide reforming of methane, 2–6% CH₄, 6–12% CO₂, and 0–4% O₂, and Ar. Physicochemical studies include the monitoring of the formation and oxidation of carbon, the strength of the Ni-O bond, and the phase composition of the catalyst. The structured Ni-Al₂O₃ catalysts are much more productive in the carbon dioxide reforming of methane than conventional granular catalysts. The catalysts performance is made more stable by regulating the acid-base properties of their surface via the introduction of alkali metal (Na, K) oxides to retard the coking of the surface. Rare-earth metal oxides with a low redox potential (La₂O₃, CeO₂) enhance the activity and stability of Ni-Al₂O₃/cordierite catalysts in the deep and partial oxidation and carbon dioxide reforming of methane. The carbon dioxide reforming of methane on the (NiO + La₂O₃ + Al₂O₃)/cordierite catalyst can be intensified by adding oxygen to the gas feed. This reduces the temperature necessary to reach a high methane conversion and does not exert any significant effect on the selectivity with respect to H₂.     

Catalytic activation of C<Subscript>1</Subscript>—C<Subscript>3</Subscript> alkanes

The conversion of CH₄ and the C₆H₆—C₃H₈ mixture over (M, ReO _x )/Al₂O₃ (M = Ni, Co, Pt) analogues of industrial low-octane gasoline reforming catalysts containing 0.5 wt % M in a finely divided state and 0.3–1.0 wt % Re is reported. The unreduced catalysts activate the conversion of CH₄ into C₆H₆ at 650°C. Using (M, ReO _x )/Al₂O₃ + HZ catalytic mixtures (HZ = H-form of zeolite Y, M, or ZSM-5), it is possible to carry out low-temperature C₆H₆ alkylation or C₃H₈ dehydrogenation at 180–350°C. These processes are aimed at involving oil refining waste into obtaining valuable hydrocarbons. The processes can be commercial- ized at low-octane reforming and gas-phase benzene alkylation plants and can be intensified by separating the resulting H₂ in membrane reactors.     

Oxidative Reforming of Bio-Ethanol Over CuNiZnAl Mixed Oxide Catalysts for Hydrogen Production

Hydrogen (H₂) is expected to become an important fuel for the future to be used as an energy carrier in automobiles and electric power plants. A promising route for H₂ production involves catalytic reforming of a suitable primary fuel such as methanol or ethanol. Since ethanol is a renewable raw material and can be cheaply produced by the fermentation of biomass, the ethanol reforming for H₂ production is beneficial to the environment. In the present study, the steam reforming of ethanol in the presence of added O₂, which in the present study is referred to as oxidative steam reforming of ethanol (OSRE), was performed for the first time over a series of CuNiZnAl mixed oxide catalysts derived from layered double hydroxide (LDH) precursors. The effects of Cu/Ni ratio, temperature, O₂/ethanol ratio, contact time, CO co-feed and substitution of Cu/Ni by Co were investigated systematically in order to understand the influence of these parameters on the catalytic performance. An ethanol conversion close to 100% was noticed at 300 °C over all the catalysts. The Cu-rich catalysts favor the dehydrogenation of ethanol to acetaldehyde. The addition of Ni was found to favor the C–C bond rupture, producing CO, CO₂ and CH₄. Depending upon the reaction condition, a H₂ yield between 2.5 and 3.5 moles per mole of ethanol converted was obtained. A CoNi-based catalyst exhibited better catalytic performance with lower selectivity of undesirable byproducts, namely CH₃CHO, CH₄ and CO.     

Dual-membrane reactor for methane oxidative coupling and dry methane reforming: Reactor integration and process intensification

A novel dual-membrane reactor concept was introduced for integrating the oxidative coupling of methane (OCM) and CO₂ methane reforming (dry reforming) reactors. The OCM reactions occur in a conventional porous packed bed membrane reactor structure and a portion of the undesired produced CO₂ and generated heat are transferred through a molten-carbonate perm-selective membrane and consumed in the adjacent dry methane reforming catalytic bed. This integrated reactor provides a very promising thermal performance by controlling the temperature peak to be below 50 °C in reference to the average operating temperature in the OCM section. This was achieved even for the low methane-to-oxygen ratio 2 by introducing 10% CO₂ as the diluent agent and reactant in this integrated reactor structure. This contributed to the improved selective performance of 32% methane conversion and 25% C₂-yield including 21% C₂H₄-yield in the OCM section which also enhances the performance of the downstream units consequently. Around half of the unconverted methane leaving the OCM section was converted to syngas in the DRM section.The dual-membrane reactor alone can utilize a significant amount of the carbon dioxide generated in the OCM catalytic bed. In combination with adsorption unit in the downstream of the integrated process, 90% of the produced CO₂ can be recovered and further converted to valuable syngas products. The experimental data, obtained from a mini-plant scale experimental facility, were exploited to verify the performance of the OCM reactor and the CO₂ separation section.     

Aqueous Phase Glycerol Reforming with Pt and PtMo Bimetallic Nanoparticle Catalysts: The Role of the Mo Promoter

The turnover rate (TOR, normalized to sites measured by CO chemisorption before reaction) and selectivity for the aqueous phase reforming of glycerol have been determined for Pt/C and PtMo/C catalysts. While the TOR of PtMo/C is higher than that of Pt/C by about 4 times at comparable conversion, the selectivity to C–O bond cleavage is higher, thus reducing the H₂ yield at high conversion. Under reaction conditions on Pt/C, CO is observed as the most abundant Pt surface species with a fractional coverage of about 0.6 using operando X-ray absorption spectroscopy. Since there is little CO in the effluent (CO₂:CO ratios > 100:1, when CO is detected), it is thought that surface CO is converted to H₂ and CO₂ by the water gas shift reaction. DFT calculations suggest that the role of metallic Mo is to alter the electronic properties of Pt lowering the binding energy of CO and reducing the activation energies of dehydrogenation and C–O bond cleavage. Because the activation energy for C–O cleavage is lowered more than for dehydrogenation, the selectivity for C–O bond cleavage is increased, ultimately lowering the H₂ yield compared to Pt/C.     

Conversion of light paraffins for preparing small olefins over ZSM-5 zeolites

The conversion of C₃-C₉ paraffins to small olefins over ZSM-5 zeolite is investigated. The small olefins are primary products and are usually converted into other more stable secondary products such as aromatics on the ZSM-5 zeolites. Thermally treated HZSM-5, K/HZSM-5 and Ba/HZSM-5 catalysts were developed and favourable oxidative conditions were introduced for the conversion process to maximize selective conversion of light paraffins to small olefins at the relatively low temperature of 873 K. The role of K and Ba is to minimize bimolecular hydrogen transfer reactions and enhance the dehydrogenation activity of the catalysts. Meanwhile, the oxygen in the gas phase is effective to improve the olefin selectivity and yield. C₂-C₄ olefin selectivities of 70.4 and 66.8% have been obtained for propane andn-hexane feed-stocks, respectively, at a temperature of 873 K.     

苯酚低温催化水蒸气重整制氢

以Raney Ni为催化剂,在温和条件下(523～723 K)实现了苯酚催化水蒸气重整制氢反应。研究表明,反应温度、液体空速和原料浓度等反应条件是影响苯酚转化率和H₂选择性的重要因素,较高的反应温度和较低的液体空速有利于提高苯酚转化率,但不利于提高H₂选择性。对比苯酚水相重整制氢过程发现,尽管水蒸气重整反应温度相对较高,且需要汽化原料使反应在气相中进行,但该过程具有比水相重整更高的H₂选择性(93%～100%)。此外,Raney Ni催化剂上苯酚水蒸气重整反应与现有的文献结果比较还具有反应条件温和、催化剂稳定性好(60h)以及CO含量低(CO/CO₂摩尔比为0.01～0.2)等优点。将该技术应用于工业含酚有机废水的资源化处理制备的H₂可以直接作为氢源使用。     

Partial oxidation reforming of biomass fuel gas over nickel-based monolithic catalyst with naphthalene as model compound

With naphthalene as biomass tar model compound, partial oxidation reforming (with addition of O₂) and dry reforming of biomass fuel gas were investigated over nickel-based monoliths at the same conditions. The results showed that both processes had excellent performance in upgrading biomass raw fuel gas. Above 99% of naphthalene was converted into synthesis gases (H₂+CO). About 2.8 wt% of coke deposition was detected on the catalyst surface for dry reforming process at 750 °C during 108 h lifetime test. However, no coke deposition was detected for partial oxidation reforming process, which indicated that addition of O₂ can effectively prohibit the coke formation. O₂ can also increase the CH₄ conversion and H₂/CO ratio of the producer gas. The average conversion of CH₄ in dry and partial oxidation reforming process was 92% and 95%, respectively. The average H₂/CO ratio increased from 0.95 to 1.1 with the addition of O₂, which was suitable to be used as synthesis gas for dimethyl ether (DME) synthesis.     

Steam reforming of ethanol on Ni–CeO2–ZrO2 catalysts: Effect of doping with copper, cobalt and calcium

Steam reforming (SR) and oxidative steam reforming (OSR) of ethanol were investigated over undoped and Cu, Co and Ca doped Ni/CeO₂–ZrO₂ catalyst in the temperature range of 400–650 °C. The nickel loading was kept fixed at 30 wt.% and the loading of Cu and Co was varied from 2 to 10 wt% whereas the Ca loading was varied from 5 to 15 wt.%. The catalysts were characterized by various techniques, such as surface area, temperature programmed reduction, X-Ray diffraction and H₂ chemisorption. For Cu and Co doped catalyst, CuO and Co₃O₄ phases were detected at high loading whereas for Ca doped catalyst, no separate phase of CaO was found. The reducibility and the metal support interactions were different for doped catalysts and varied with the amount and nature of dopants. The hydrogen uptake, nickel dispersion and nickel surface area was reduced with the metal loading and for the Co loaded catalysts the dispersion of Ni and nickel surface area was very low. For Cu and Ca doped catalysts, the activity was increased significantly and the main products were H₂, CO, CH₄ and CO₂. However, the Co doped catalysts showed poor activity and a relatively large amount of C₂H₄, C₂H₆, CH₃CHO and CH₃COCH₃ were obtained. For SR, the maximum enhancement in catalytic activity was obtained with in the order of NCu5. For Cu–Ni catalysts, CH₃CHO decomposition and reforming reaction was faster than ethanol dehydrogenation reaction. Addition of Cu and Ca enhanced the water gas shift (WGS) and acetaldehyde reforming reactions, as a result the selectivity to CO₂ and H₂ were increased and the selectivity to CH₃CHO was reduced significantly. The maximum hydrogen selectivity was obtained for Catalyst N (93.4%) at 650 °C whereas nearly the same selectivity to hydrogen (89%) was obtained for NCa10 catalyst at 550 °C. In OSR, the catalytic activity was in the order N > NCu5 > NCa15 > NCo5. In the presence of oxygen, oxidation of ethanol was appreciable together with ethanol dehydrogenation. For SR reaction, the highest hydrogen yield was obtained on the undoped catalyst at 600 °C. However, with calcium doping the hydrogen yields are higher than the undoped catalyst in the temperature range of 400–550 °C.     

Steam Reforming of Ethanol Over Supported Co and Ni Catalysts

The ethanol steam reforming has been investigated over supported cobalt catalysts at atmospheric pressure. About 12% cobalt was supported on Al₂O₃, SiO₂ and TiO₂, and a commercial Ni/Al₂O₃ catalyst (G90B) was included for comparative purposes. The selectivity was found to depend strongly on the support, especially at low and medium temperatures. The initial activity of the cobalt catalysts correlated well with the metal dispersion. Acetaldehyde was an important C-containing product at low temperatures, whereas at high temperatures CO, CO₂ and CH₄ dominated the product spectrum. A significant production of ethene was observed, especially on the alumina-supported catalysts. The results are in agreement with a mechanism involving acetaldehyde as an intermediate in the steam reforming. At high temperatures (>550 °C) the conversion was complete and the product distribution approaches the equilibrium. The H₂ yield approached 5 moles H₂/mole ethanol converted, which is close to the maximum according to thermodynamic calculations. The alumina-supported catalysts (both Co and Ni) showed acceptable deactivation rates, but high carbon formation.     

Catalytic monoliths for ethanol steam reforming

Cordierite monoliths coated with Co/ZnO catalysts were prepared by washcoating, urea, and sol–gel techniques and characterized by confocal microscopy, scanning electron microscopy (SEM), transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), and adherence tests. The performance of the catalytic monoliths for practical application in the production of hydrogen through ethanol steam reforming (ESR) and water gas shift (WGS) reactions was evaluated. Monoliths prepared by the urea method exhibited excellent dispersion and adherence of catalyst coatings and performed better for the reforming of ethanol. 5.6 mol H₂/mol C₂H₅OH were obtained from a C₂H₅OH:H₂O = 1:6 gaseous mixture at 723 K and 0.33 mL min⁻¹ of C₂H₅OH. Under these conditions and total ethanol conversion the composition of the effluent stream was 73.9% H₂, 23.7% CO₂, 1.2% CO, and 1.0% CH₄. The amount of CO was kept low due to the activity of monoliths for the WGS reaction under ethanol steam reforming conditions.     

Oxidative coupling of methane. The effect of alkali chlorides on molybdate based catalyst leading to high selectivity in C3-product formation

LiCl-Na₂MoO₄ was found to be an active catalyst for oxidative coupling of methane at temperatures around 620 °C. In these systems, the selectivity for the formation of C₃-products exceeds the selectivity for the formation of C₂-products. While the homogeneous reaction of CH₄ and O₂ leads to C₃H₆ as C₃-product, the 50% LiCl-50% Na₂MoO₄ catalyst leads to C₃H₈ as the predominant C₃-product, indicating that in the latter case the reaction cannot be purely homogeneous. The dependency of the product distribution on temperature, gas composition, reactor dimensions, flow rate, CH₄/O₂ ratio and type of catalyst has been studied. The reaction was studied by co-feeding CH₄, O₂ and a diluent gas at atmospheric pressure continuously in a conventional flow reactor containing the catalyst. The reaction products observed were: C₂H₄, C₂H₆, C₃H₆, C₃H₈, H₂O and CO + CO₂. The two latter gases were the main oxidation products observed. Characterization of the catalysts used was carried out by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD).     

Effective parameters for DME steam reforming catalysts for the formation of H2 and CO

Recently, DME has received attention as a clean fuel and is now considered an alternative fuel for diesel engines. DME diesels need de-NOx catalysts such as LNT (Lean NOx Trap) and SCR (Selective Catalytic Reduction) systems. DME is an attractive source of hydrogen because it can be stored easily and is a good transportation fuel. Hydrogen and CO enriched gas as a reductant was used with the LNT catalyst in order to reduce NOx emissions. The steam reforming catalyst of DME was used to formation of hydrogen. It has been reported that Cu-based catalysts have high selectivity and activity in the steam reforming of DME. This research used 600 cPsi cordierite as a catalyst, which was coated with copper. The catalysts were made via a sol–gel and impregnation methods. The formation of H₂ and CO under the prepared catalysts was tested by a model gas. Experimental parameters were considered; the space velocity (SV) and concentrations of H₂O, O₂, and CO₂ were evaluated. The Cu 30%/γ-Al₂O₃ catalyst from the sol–gel method exhibited high and stable activity in the production of hydrogen from the steam reforming of DME. Both DME conversion and the selectivity of hydrogen were affected by SV and the concentrations of H₂O, O₂, and CO₂.     

Enhancing the Production of Light Olefins by Catalytic Cracking of FCC Naphtha over Mesoporous ZSM-5 Catalyst

The enhanced production of light olefins from the catalytic cracking of FCC naphtha was investigated over a mesoporous ZSM-5 (Meso-Z) catalyst. The effects of acidity and pore structure on conversion, yields and selectivity to light olefins were studied in microactivity test (MAT) unit at 600 °C and different catalyst-to-naphtha (C/N) ratios. The catalytic performance of Meso-Z catalyst was compared with three conventional ZSM-5 catalysts having different SiO₂/Al₂O₃ (Si/Al) ratios of 22 (Z-22), 27 (Z-27) and 150 (Z-150). The yields of propylene (16 wt%) and ethylene (10 wt%) were significantly higher for Meso-Z compared with the conventional ZSM-5 catalysts. Almost 90% of the olefins in the FCC naphtha feed were converted to lighter olefins, mostly propylene. The aromatics fraction in cracked naphtha almost doubled in all catalysts indicating some level of aromatization activity. The enhanced production of light olefins for Meso-Z is attributed to its small crystals that suppressed secondary and hydrogen transfer reactions and to its mesopores that offered easier transport and access to active sites.     

Numerical simulation of particle/monolithic two-stage catalyst bed reactor with beds-interspace distributed dioxygen feeding for oxidative coupling of methane

A three-dimensional geometry model of the particle/monolithic two-stage reactor with beds-interspace distributed dioxygen feeding for oxidative coupling of methane (OCM) was set up. The improved Stansch kinetic model adapting different operating temperatures was established to calculate the OCM reactor performance using computational fluid dynamics (CFD) and FLUENT software. The results showed that the calculated values matched well with the experimental values of the conversion of CH₄ and the selectivity of products (C₂H₆, C₂H₄, CO₂, CO) in the OCM reactor. The distributed dioxygen feeding with the percentage of 5–20% based oxygen flow rate of top inlet promoted the OCM reaction in monolithic catalyst bed and led to the conversion of CH₄ and the selectivity and yield of C₂ (C₂H₆ and C₂H₄) increase obviously. The distributed dioxygen feeding was 15%, the conversion of CH₄, the selectivity and the yield of C₂ reached 34.1%, 68.2% and 23.3%, respectively.