Catalytic partial oxidation of coke oven gas to syngas in an oxygen permeation membrane reactor combined with NiO/MgO catalyst

A high oxygen permeability and sufficient chemical and mechanical stability mixed ion and electron conductivity membrane to withstand the hash strong oxidation and reduction working conditions is significant for the membrane reactor to commercial-scale plant. In this paper, a disk-shaped Ba_1.0Co_0.7Fe_0.2Nb_0.1O_3−δ membrane was applied to a membrane reactor for the partial oxidation of methane in coke oven gas (COG) to syngas. The reaction was carried out using NiO/MgO solid solution catalyst by feeding COG. The reforming process was performed successfully; 95% CH₄ conversion, 80% H₂ selectivity, 106% CO selectivity and 16.3 ml cm⁻² min⁻¹ oxygen permeation flux were achieved at 1148 K. The reaction has been steadily carried out for more than 100 h. The NiO/MgO catalyst used in the membrane reactor exhibited good catalytic activity and resistance to coking in the COG atmosphere. Characterization of the membrane surface by SEM and XRD after long life test showed that both the surface exposed to the air side and reaction side still preserved the Perovskite structure which is implied that the practical application of this membrane as membrane reactor for partial oxidation of COG is promising.     

Steam catalytic gasification of municipal solid waste for producing tar-free fuel gas

In the paper, a two-region municipal solid waste (MSW) steam catalytic gasification process was proposed. The gasifier was composed of two individual reactors: one is the gasification reactors and the other is the catalytic reactor. The MSW was initially gasified and the produced tar was gasified in the gasification reactor, and further, the tar not gasified entered the catalytic reactor together with the fuel gas and was catalytically decomposed to fuel gas. The influences of the catalysts, steam and temperature on the content of tar, dry gas yield and composition, and carbon conversion efficiency were studied. The results indicated that under the optimum operating conditions, the dry gas yield can be up to 1.97 Nm³/kg MSW and the tar in the product can be completely eliminated. The concentration of hydrogen, carbon monoxide and methane in the fuel gas produced was 50.8%, 9.32% and 13.3%, respectively.     

A novel combined cycle with synthetic utilization of coal and natural gas

 In this paper, a novel combined cycle with synthetic utilization of coal and natural gas is proposed, in which the burning of coal provides thermal energy to the methane/steam reforming reaction. The syngas fuel, generated by the reforming reaction, is directly provided to the gas turbine as fuel. The reforming process with coal firing has been investigated based on the concept of energy level, and the equations has been derived to disclosing the mechanism of the cascade utilization of chemical energy of natural gas and coal in the reforming process with coal firing. Through the synthetic utilization of natural gas and coal, the exergy destruction of the combustion of syngas is decreased obviously compared with the direct combustion of natural gas and coal. As a result, the overall thermal efficiency of the new cycle reaches 52.9%, as energy supply by methane is about twice as much as these of coal. With the same consumption of natural gas and coal the new cycle can generate about 6% more power than the reference cycles (the combined cycle and the steam power plant). The promising results obtained here provide a new way to utilize natural gas and coal more efficiently and economically by synthetic utilization.     

Thermodynamic and kinetic model of reforming coke-oven gas with steam

The experiments of reforming the methane of coke-oven gas with steam were performed. The effects of the thermodynamic factors, such as the H₂O/CH₄ ratio, the conversion temperature (T) of methane and the reaction time (t), on the methane conversion rate have been investigated. The experimental results show that the H₂O/CH₄ ratio within the range of 1.1–1.3 and the temperature 1223–1273 K are the reasonable thermodynamic conditions for methane conversion. A methane conversion of more than 95% can be achieved when the H₂O/CH₄ ratio is 1.2, the conversion temperature is above 1223 K and the conversion time is up to 15 s respectively. In additional, kinetic data of different reaction conditions were measured, and a dynamic model of methane conversion was proposed and verified. All results demonstrated that the results of the dynamic models agree well with the experiments, of which the deviation is less than 1.5%.     

Investigations on the behaviour of 2 kW natural gas fuel processor

In this paper, the first experimental investigations on a pre-commercial natural gas steam reformer have been presented. The fuel processor unit contains the elements as follows: desulfurizer, steam reformer reactor, CO shift converter, CO preferential oxidation (PROX) reactor, steam generator, burner and heat exchangers.The fuel processor produces 45 Nl/min of syngas in which the hydrogen concentration is about 75 vol.% and the other chemical species are nitrogen, carbon dioxide and methane. The CO concentration is below 1 ppmv, so that this reforming system is suitable for the integration with a PEM fuel cell stack.The experimental activity has been conducted in a test station, properly designed to measure the behaviour of the fuel processor. The laboratory test facility is equipped by a National Instruments Compact DAQ real-time data acquisition and control system running Labview™ software. Several measurement instruments and controlling devices have been installed. Furthermore, a gas chromatograph is used to measure the product gas composition during the tests.The aim of this work has been to analyze the behaviour of this pre-commercial steam reforming unit during its operation cycle in different operating conditions (full and partial loads) in order to study its integration with a PEM fuel cell for developing a high efficiency microcogeneration system for residential applications.     

Simultaneous production of two types of synthesis gas by steam and tri‐reforming of methane using an integrated thermally coupled reactor: mathematical modeling

In this work, tri‐reforming and steam reforming processes have been coupled thermally together in a reactor for production of two types of synthesis gases. A multitubular reactor with 184 two‐concentric‐tubes has been proposed for coupling reactions of tri‐reforming and steam reforming of methane. Tri‐reforming reactions occur in outer tube side of the two‐concentric‐tube reactor and generate the needed energy for inner tube side, where steam reforming process is taking place. The cocurrent mode is investigated, and the simulation results of steam reforming side of the reactor are compared with corresponding predictions for thermally coupled steam reformer and also conventional fixed‐bed steam reformer reactor operated at the same feed conditions. This reactor produces two types of syngas with different H₂/CO ratios. Results revealed that H₂/CO ratio at the output of steam and tri‐reforming sides reached to 1.1 and 9.2, respectively. In this configuration, steam reforming reaction is proceeded by excess generated heat from tri‐reforming reaction instead of huge fired‐furnace in conventional steam reformer. Elimination of a low performance fired‐furnace and replacing it with a high performance reactor causes a reduction in full consumption with production of a new type of synthesis gas. The reactor performance is analyzed on the basis of methane conversion and hydrogen yield in both sides and is investigated numerically for various inlet temperature and molar flow rate of tri‐reforming side. A mathematical heterogeneous model is used to simulate both sides of the reactor. The optimum operating parameters for tri‐reforming side in thermally coupled tri‐reformer and steam reformer reactor are methane feed rate and temperature equal to 9264.4 kmol h^?1 and 1100 K, respectively. By increasing the feed flow rate of tri‐reforming side from 28,120 to 140,600 kmol h^?1, methane conversion and H₂ yield at the output of steam reforming side enhanced about 63.4% and 55.2%, respectively. Also by increasing the inlet temperature of tri‐reforming side from 900 to 1300 K, CH₄ conversion and H₂ yield at the output of steam reforming side enhanced about 82.5% and 71.5%, respectively. The results showed that methane conversion at the output of steam and tri‐reforming sides reached to 26.5% and 94%, respectively with the feed temperature of 1100 K of tri‐reforming side. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of the type of gasifying agent on gas composition in a bubbling fluidized bed reactor

It is commonly accepted that gasification of coal has a high potential for a more sustainable and clean way of coal utilization. In recent years, research and development in coal gasification areas are mainly focused on the synthetic raw gas production, raw gas cleaning and, utilization of synthesis gas for different areas such as electricity, liquid fuels and chemicals productions within the concept of poly-generation applications. The most important parameter in the design phase of the gasification process is the quality of the synthetic raw gas that depends on various parameters such as gasifier reactor itself, type of gasification agent and operational conditions. In this work, coal gasification has been investigated in a laboratory scale atmospheric pressure bubbling fluidized bed reactor, with a focus on the influence of the gasification agents on the gas composition in the synthesis raw gas. Several tests were performed at continuous coal feeding of several kg/h. Gas quality (contents in H₂, CO, CO₂, CH₄, O₂) was analyzed by using online gas analyzer through experiments. Coal was crushed to a size below 1 mm. It was found that the gas produced through experiments had a maximum energy content of 5.28 MJ/Nm³ at a bed temperature of approximately 800 °C, with the equivalence ratio at 0.23 based on air as a gasification agent for the coal feedstock. Furthermore, with the addition of steam, the yield of hydrogen increases in the synthesis gas with respect to the water–gas shift reaction. It was also found that the gas produced through experiments had a maximum energy content of 9.21 MJ/Nm³ at a bed temperature range of approximately 800–950 °C, with the equivalence ratio at 0.21 based on steam and oxygen mixtures as gasification agents for the coal feedstock. The influence of gasification agents, operational conditions of gasifier, etc. on the quality of synthetic raw gas, gas production efficiency of gasifier and coal conversion ratio are discussed in details.     

Autothermal reforming of methane for producing high-purity hydrogen in a Pd/Ag membrane reactor

Autothermal reforming of methane includes steam reforming and partial oxidizing methane. Theoretically, the required endothermic heat of steam reforming of methane could be provided by adding oxygen to partially oxidize the methane. Therefore, combining the steam reforming of methane with partial oxidation may help in achieving a heat balance that can obtain better heat efficacy. Membrane reactors offer the possibility of overcoming the equilibrium conversion through selectively removing one of the products from the reaction zone. For instance, only can hydrogen products permeate through a palladium membrane, which shifts the equilibrium toward conversions that are higher than the thermodynamic equilibrium. In this study, autothermal reforming of methane was carried out in a traditional reactor and a Pd/Ag membrane reactor, which were packed with an appropriate amount of commercial Ni/MgO/Al₂O₃ catalyst. A power analyzer was employed to measure the power consumption and to check the autothermicity. The average dense Pd/Ag membrane thickness is 24.3 μm, which was coated on a porous stainless steel tube via the electroless palladium/silver plating procedure. The experimental operating conditions had temperatures that were between 350 °C and 470 °C, pressures that were between 3 atm and 7 atm, and O₂/CH₄ = 0–0.5. The effects of the operating conditions on methane conversion, permeance of hydrogen, H₂/CO, selectivities of CO_x, amount of power supply, and the carbon deposition of the catalyst after the reaction is thoroughly discussed in this paper. The experimental results indicate that an optimum methane conversion of 95%, with a hydrogen production rate of 0.093 mol/m². S, can be obtained from the autothermal reforming of methane at H₂O/CH₄ = 1.3 and O₂/CH₄ near 0.4, at which the reaction does not consume power, and the catalysts are not subject to any carbon deposition.     

An evaluation of hydrogen production from the perspective of using blast furnace gas and coke oven gas as feedstocks

Blast furnace (BF) is a large-scale reactor for producing hot metal where coke and coal are consumed as reducing agent and fuel, respectively. As a result, a large amount of CO₂ is liberated into the atmosphere. The blast furnace gas (BFG) and coke oven gas (COG) from the ironmaking process can be used for H₂ production in association with carbon capture and storage (CCS), thereby reducing CO₂ emissions. In this study thermodynamic analyses are performed to evaluate the feasibility of H₂ production from BFG and COG. Through the water gas shift reaction (WGSR) of BFG, almost all CO contained in BFG can be converted for H₂ production if the steam/CO (S/C) ratio is no less than unity and the temperature is at 200 °C, regardless of whether CO₂ is captured or not. The maximum H₂ production from WGSR is around 0.21 Nm³ (Nm³ BFG)⁻¹. Regarding H₂ production from COG, a two-stage reaction of partial oxidation (POX) followed by WGSR is carried out. It is found the proper conditions for syngas formation from the POX of COG is at the oxygen/fuel (O/F) ratio of 0.5 and the temperature range of 1000-1750 °C where the maximum syngas yield is 2.83 mol (mol hydrocarbons)⁻¹. When WGSR is subsequently applied, the maximum H₂ production from the two-stage reaction can reach 0.83 Nm³ (Nm³ COG)⁻¹.     

Real-time sensing of methane steam reforming by YSZ oxygen sensor

In this study, a new and convenient technique for the in-situ analyisis of methane steam reforming in the chamber was proposed. The YSZ oxygen sensor was used as the sensing device, which provided the partial pressure of oxygen in the reactor. The oxygen sensors were set in the catalytic bed of 1 wt.% Ni/Al₂O₃ along the gas flow direction and the progress of catalytic reforming was monitored at each position. The methane conversion derived from the oxygen sensor agreed well with that from the gas chromatograph set at the outlet part of the catalyst layer. Along the gas flow direction in the reactor, the change in the gas composition was clearly observed; the methane conversion changed significantly depending on the reaction temperature and space velocity of reactant gas. Furthermore, the deterioration behavior of catalytic activity was successfully monitiored when a highly humidified methane with a steam to carbon ratio of 4.0 was supplied with a high space velocity of 6250 l kg⁻¹ h⁻¹.     

A comparative study on the enhanced formation of methane hydrate using CM-95 and CM-100 MWCNTs

1 m³ of methane hydrate can be decomposed into a maximum of 216 m³ of methane gas under standard conditions. Conversely, such a large volume of methane hydrate can be utilized to store and transport a large quantity of natural gas. When methane hydrate is formed artificially by simply reversing its process of natural generation, the amount of methane gas consumed owing to hydrate formation is fairly low which would be problematic for its massive synthesis and application. In this study, experiments are carried out with the goal of increasing the amount of gas consumed by adding two kinds (CM-95 and CM-100) of multi-walled carbon nanotubes (MWCNTs) to pure water, where the physical length of CM-95 is much shorter than CM-100. When the 0.004 wt.% CM-95 MWCNT solution is compared with pure water, the gas consumption rate almost triples indicating its effect in hydrate formation. Also, the CM-95 MWCNTs decreased the hydrate formation time to a greater extent than the CM-100 MWCNTs at a low subcooling temperature.     

Sorption enhanced steam hydrogasification of coal for synthesis gas production with in-situ CO2 removal and self-sustained hydrogen supply

The in-situ removal of CO₂ and the increase of the energetic gas yield, including hydrogen and methane, by sorption enhanced steam hydrogasification (SE-SHR) process were investigated. Lignite was used in this study as the feedstock to the steam hydrogasification reaction (SHR) with the addition of calcined dolomite as a sorbent. CO₂ was reduced dramatically with the introduction of the sorbent into the reactor. The production of hydrogen and methane was increased simultaneously. The hydrogen yield was increased by 60% when the calcium oxide to carbon molar ratio was increased to 0.86 as compared to the results without the sorbent. The hydrogen in the product gas was sufficient to maintain a self-sustained supply back to the SHR when the calcium oxide to carbon molar ratio was over 0.29. The performance of the SE-SHR was determined at different temperatures ranging from 650 °C to 800 °C and at different steam to carbon molar ratios. Additionally, the char conversion was also enhanced in all cases with the sorbent introduction. The synthesis gas production using SE-SHR coupled with steam methane reforming was also modeled by Aspen Plus. The simulation results showed that the H₂/CO ratio of the synthesis gas generated based on SE-SHR process was 6 with higher overall energy efficiency of 74.5%. Summarily, the main findings of this study were that the overall performance of the SE-SHR was substantially improved compared to the conventional operation of the SHR and the quality of synthesis gas produced based on SE-SHR process was more flexible for the downstream processing.     

Development of a Solid Oxide Fuel Cell for the utilization of coal mine gas

Apart from natural gas there is another important natural source of methane. The so-called coal mine gas is a by-product of the geochemical process of the carbonization of sediments from marsh woods of the Earth's Carboniferous Period. Methane evaporates from the coal and has to be removed out of the active mines where it represents one of the main safety risks. Methane also evaporates in abandoned coal mines. In the federal state Saarland in Germany exists above ground a more than 110 km pipeline for the drained coal mine gas from 12 different sources. The content of methane varies between 25 and 90%, the oxygen content (from air) is in the range up to 10%. This wide range or variation, respectively, of fuel and oxygen content, causes a lot of problems for the use in conventional engines. Therefore the company Evonik New Energies GmbH is interested in using SOFC with coal mine gas as efficient as possible to produce electric power. For that purpose at Forschungszentrum Jülich the available SOFC technology was adapted to the use with coal mine gas and a test facility was designed to operate an SOFC stack (approximately 2 kW electrical power output) together with a pre-reformer.This paper presents the results of the coal mine gas analysis and the effect on the pre-reformer and the fuel cell. The composition of the coal mine gas was determined by means of micro-gas chromatography. The results obtained from preliminary tests using synthetic and real coal mine gas on the pre-reformer and on the fuel cell are discussed.     

A novel integrated thermally coupled configuration for methane-steam reforming and hydrogenation of nitrobenzene to aniline

In this work, a novel thermally coupled reactor containing the steam reforming process in the endothermic side and the hydrogenation of nitrobenzene to aniline in the exothermic side has been investigated. In this novel configuration, the conventional steam reforming process has been substituted by the recuperative coupled reactors which contain the steam reforming reactions in the tube side, and the hydrogenation reaction in the shell side. The co-current mode is investigated and the simulation results are compared with corresponding predictions for an industrial fixed-bed steam reformer reactor operated at the same feed conditions. The results show that although synthesis gas productivity is the same as conventional steam reformer reactor, but aniline is also produced as an additional valuable product. Also it does not need to burn at the furnace of steam reformer. The performance of the reactor is numerically investigated for different inlet temperature and molar flow rate of exothermic side. The reactor performance is analyzed based on methane conversion, hydrogen yield and nitrobenzene conversion. The results show that exothermic feed temperature of 1270 K can produce synthesis gas with 26% methane conversion (the same as conventional) and nitrobenzene conversion in the outlet of the reactor is improved to 100%. This new configuration eliminates huge fired furnace with high energy consumption in steam reforming process.     

Coal steam-gasification model in chemical regime to produce hydrogen in a gas–solid moving bed reactor using nuclear heat

A theoretical model of the coal gasification with steam in a chemical moving bed reactor is developed. A very high temperature nuclear reactor provides the energy for accomplishing the endothermic gasification reactions. The model is developed in chemical regime giving information about the temperature profiles, the coal conversion and the specific productivity in the gasification process. For the heat transfer, the three resistances have been included (conduction, convection and radiation). The results have shown that the coal conversion in the heterogenic water “shift” reaction is smaller than the ones in mass transfer control. The gas velocity can change strongly the conversion, for velocities under 0.06 m/s, for bigger quantities the change is negligible. An increase in the gas temperature at the reactor input leads to an increase in the coal conversion; an increase in the temperature from 900 K to 1300 K increases the conversion 40%.     

Hydrogen production by absorption enhanced water gas shift (AEWGS)

AEWGS is a reaction that combines the WGS reaction and CO₂ capture by a solid absorbent to produce high purity H₂ from synthesis gas in one single step at 600–800 °C. This reactor system, if homogeneous, would not require a catalyst. However, previous research on this concept was not conclusive, since a steel reactor was used and reactor walls were suspected to act as catalyst. Therefore, there is a need to address this issue and to select and evaluate suitable CO₂ absorbents for this concept. AEWGS was studied using a quartz-made fixed-bed reactor at; SV = 3000 h⁻¹, feed; 5% CO, 15% H₂O, balance He–N₂ at 600 °C, 1 atm. CO₂ absorbents tested were CaO*MgO, and Na₂ZrO₃. Empty quartz-reactor tests leaded to conclude that a catalyst is needed for the WGS at temperatures of interest. A 97% H₂ product was obtained with calcined dolomite suggesting this last to act as a WGS catalyst.     

Ni catalyst wash-coated on metal monolith with enhanced heat-transfer capability for steam reforming

A commercial Ni-based catalyst is wash-coated on a monolith made of 50 μm-thick fecralloy plates. Compared with the same volume of coarsely powdered Ni catalysts, the monolith wash-coated Ni catalysts give higher methane conversion in the steam reforming reaction, especially at gas hourly space velocities (GHSV) higher than 28,000 h⁻¹, and with no pressure drop. A higher conversion of the monolith catalyst is obtained, even though it contains a lower amount of active catalyst (3 g versus 17 g for a powdered catalyst), which indicates that the heat-transfer capability of the wash-coated Ni catalyst is significantly enhanced by the use of a metal monolith. The efficacy of the monolith catalyst is tested using a shell-and-tube type heat-exchanger reactor with 912 cm³ of the monolith catalyst charged on to the tube side and hot combusted gas supplied to the shell side in a counter-current direction to the reactant flow. A methane conversion greater than 94% is obtained at a GHSV of 7300 h⁻¹ and an average temperature of 640 °C. Nickel catalysts should first be reduced to become active for steam reforming. Doping a small amount (0.12 wt.%) of noble metal (Ru or Pt) in the commercial Ni catalyst renders the wash-coated catalyst as active as a pre-reduced Ni catalyst. Thus, noble metal-doped Ni appears useful for steam reforming without any pre-reduction procedure.     

Hydrogen production from methane under the interaction of catalytic partial oxidation,water gas shift reaction and heat recovery

Hydrogen production from the combination of catalytic partial oxidation of methane (CPOM) and water gas shift reaction (WGSR), viz. the two-stage reaction, in a Swiss-roll reactor is investigated numerically. Particular emphasis is placed on the interaction among the reaction of CPOM, the cooling effect due to steam injection and the excess enthalpy recovery with heat recirculation. A rhodium (Rh) catalyst bed sitting at the center of the reactor is used to trigger CPOM, and two different WGSRs, with the aids of a high-temperature (Fe–Cr-based) shift catalyst and a low-temperature (Cu–Zn-based) shift catalyst, are excited. Two important parameters, including the oxygen/methane (O/C) ratio and the steam/methane (S/C) ratio, affecting the efficiencies of methane conversion and hydrogen production are taken into account. The predictions indicate that the O/C ratio of 1.2 provides the best production of H₂ from the two-stage reaction. For a fixed O/C ratio, the H₂ yield is relatively low at a lower S/C ratio, stemming from the lower performance of WGSR, even though the cooling effect of steam is lower. On the contrary, the cooling effect becomes pronounced as the S/C ratio is high to a certain extent and the lessened CPOM leads to a lower H₂ yield. As a result, with the condition of gas hourly space velocity (GHSV) of 10,000 h⁻¹, the optimal operation for hydrogen production in the Swiss-roll reactor is suggested at O/C = 1.2 and S/C = 4–6.     

Hydrogen production from solar thermal dissociation of natural gas: development of a 10 kW solar chemical reactor prototype

This study addresses the solar thermal decomposition of natural gas for the co-production of hydrogen, as well as Carbon Black as a high-value nano-material, with the bonus of zero CO₂ emissions. The work focused on the development of a medium-scale solar reactor (10 kW) based on the concept of indirect heating. The solar reactor is composed of a cubic cavity receiver (20 cm side), which absorbs concentrated solar irradiation through a quartz window via a 9 cm-diameter aperture. The reacting gas flows inside four graphite tubular reaction zones that are settled vertically inside the cavity. Experimental results were as follows: methane conversion and hydrogen yield of up to 98% and 90%, respectively, were achieved at 1770 K, and acetylene was the most important by-product, with a mole fraction up to about 5%. The effect of the methane mole fraction in the feed gas, the residence time and the temperature on the reaction extent was analyzed. In addition to the experimental section, thermal simulations were carried out. They showed a homogeneous temperature distribution inside the cavity receiver of the reactor and permit to draw up a thermal balance.     

Hydrogen production with CO2 capture by coupling steam reforming of methane and chemical-looping combustion: Use of an iron-based waste product as oxygen carrier burning a PSA tail gas

In this work it is analyzed the performance of an iron waste material as oxygen carrier for a chemical-looping combustion (CLC) system. CLC is a novel combustion technology with the benefit of inherent CO₂ separation that can be used as a source of energy for the methane steam reforming process (SR). The tail gas from the PSA unit is used as fuel in the CLC system.The oxygen carrier behaviour with respect to gas combustion was evaluated in a continuous 500 W_th CLC prototype using a simulated PSA off-gas stream as fuel. Methane or syngas as fuel were also studied for comparison purposes. The oxygen carrier showed enough high oxygen transport capacity and reactivity to fully convert syngas at 880 °C. However, lower conversion of the fuel was observed with methane containing fuels. An estimated solids inventory of 1600 kg MW_th⁻¹ would be necessary to fully convert the PSA off-gas to CO₂ and H₂O. An important positive effect of the oxygen carrier-to-fuel ratio up to 1.5 and the reactor temperature on the combustion efficiency was found.A characterization of the calcined and after-used particles was carried out showing that this iron-based material can be used as oxygen carrier in a CLC plant since particles maintain their properties (reactivity, no agglomeration, high durability, etc.) after more than 111 h of continuous operation.