Search results for: enhanced steam reforming

Authors: Krittiya Pornmai, Sumaeth Chavadej

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The increasing in global energy demand has affected the climate change caused by the generation of greenhouse gases. Therefore, the objective of this work was to investigate a direct production of synthesis gas from a CO₂-containing natural gas by using gliding arc discharge plasma technology. In this research, the effects of steam reforming, combined steam reforming and partial oxidation, and using multistage gliding arc discharge system on the process performance have been discussed. The simulated natural gas used in this study contains 70% methane, 5% ethane, 5% propane, and 20% carbon dioxide. In comparison with different plasma reforming processes (under their optimum conditions), the steam reforming provides the highest H₂ selectivity resulting from the cracking reaction of steam. In addition, the combined steam reforming and partial oxidation process gives a very high CO production implying that the addition of both oxygen and steam can offer the acceptably highest synthesis gas production. The stage number of plasma reactor plays an important role in the improvement of CO₂ conversion. Moreover, 3 stage number of plasma reactor is considered as an optimum stage number for the reforming of CO₂-containing natural gas with steam and partial oxidation in term of providing low energy consumption as compared with other plasma reforming processes.

Keywords: natural gas, reforming process, gliding arc discharge, plasma technology

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Authors: P. Comendador, M. Suarez, L. Olazar, M. Cortazar, M. Artetxe, G. Lopez, M. Olazar

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H₂ production from fast biomass pyrolysis and line Steam Reforming (SR) has been extensively studied in the last years. However, Sorption Enhanced Steam Reforming (SESR) is gaining attention as an alternative to the conventional SR since it allows obtaining higher H₂ yields and a purity near 100 % in the product stream. In this work, both alternatives were compared through an energy analysis. The processes were modeled with PRO II v.2021 software. First, general energy balances were carried out in order to identify the total energy requirements in a wide range of operating conditions. At H₂ yield optimum conditions for both processes (steam to biomass ratio of 2 and temperature of 600 ºC), the total energy requirement for the SR alternative is 936 kJ/kgH₂, whereas for the SESR alternative is 1134 kJ/kgH₂. Then, the energy needs were grouped into operation stages, aiming at identifying the energy sinks and sources of the processes. It was determined that the SESR alternative is more energy intensive due to the need for a calcination stage for regenerating the sorbent. Finally, a configuration of the SESR alternative with energy integration was developed in order to compensate for the energy demand.

Keywords: Biomass valorization, CO₂ capture, Energy analysis, H₂ production

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Authors: A. Alkattib, M. Boumaza

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Steam reforming is industrially important as it is incorporated in several major chemical processes including the production of ammonia, methanol, hydrogen and ox alcohols. Due to the strongly endothermic nature of the process, a large amount of heat is supplied by fuel burning (commonly natural gas) in the furnace chamber. Reaction conversions, tube catalyst life, energy consumption and CO2 emission represent the principal factors affecting the performance of this unit and are directly influenced by the high operating temperatures and pressures. This study presents a simulation of the performance of the reforming of methane in a primary reformer, through a developed empirical relation which enables to investigate the effects of operating parameters such as the pressure, temperature, steam to carbon ratio on the production of hydrogen, as well as the fraction of non-converted methane. It appears from this analysis that the exit temperature Te, the operating pressure as well the steam to carbon ratio has an important effect on the reforming of methane.

Keywords: reforming, methane, performance, hydrogen, parameters

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Authors: Mahendra Singh, Narasimhareddy Ravuru

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For the past decade, the production of biodiesel has significantly increased along with its by-product, glycerol. Biodiesel-derived glycerol massive entry into the glycerol market has caused its value to plummet. Newer ways to utilize the glycerol by-product must be implemented or the biodiesel industry will face serious economic problems. The biodiesel industry should consider steam reforming glycerol to produce hydrogen gas. Steam reforming is the most efficient way of producing hydrogen and there is a lot of demand for it in the petroleum and chemical industries. This study investigates the feasibility of glycerol steam reforming in an industrial sized fixed bed reactor. In this paper, using computational fluid dynamic (CFD) simulations, the extent of the transport resistances that would occur in an industrial sized reactor can be visualized. An important parameter in reactor design is the size of the catalyst particle. The size of the catalyst cannot be too large where transport resistances are too high, but also not too small where an extraordinary amount of pressure drop occurs. The goal of this paper is to find the best catalyst size under various flow rates that will result in the highest conversion. Computational fluid dynamics simulated the transport resistances and a pseudo-homogenous reactor model was used to evaluate the pressure drop and conversion. CFD simulations showed that glycerol steam reforming has strong internal diffusion resistances resulting in extremely low effectiveness factors. In the pseudo-homogenous reactor model, the highest conversion obtained with a Reynolds number of 100 (29.5 kg/h) was 9.14% using a 1/6 inch catalyst diameter. Due to the low effectiveness factors and high carbon deposition rates, a fluidized bed is recommended as the appropriate reactor to carry out glycerol steam reforming.

Keywords: computational fluid dynamic, fixed bed reactor, glycerol, steam reforming, biodiesel

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Authors: Francisco Espinosa, Juan Chavarría

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Glycerol is a byproduct of biodiesel production that can be used for aqueous-phase reforming to obtain hydrogen. Iridium is a material that has high activity and hydrogen selectivity for steam phase reforming. Nevertheless, a drawback for the use of iridium in aqueous-phase reforming is the low activity in water-gas shift reaction. Therefore, in this work, it is proposed the use of nickel and copper as a second metal in the catalyst to reach a synergetic effect. Iridium, iridium-nickel and iridium-copper catalysts were prepared by incipient wetness impregnation and evaluated in the aqueous-phase reforming of glycerol using CeO₂ or La₂O₃ as support. The catalysts were characterized by XRD, XPS, and EDX. The reactions were carried out in a fixed bed reactor feeding a solution of glycerol 10 wt% in water at 270°C, and reaction products were analyzed by gas chromatography. It was found that IrNi/CeO₂ reached highest glycerol conversion and hydrogen production, slightly above 70% and 43 vol% respectively. In terms of conversion, iridium is a promising metal, and its activity for hydrogen production can be enhanced when adding a second metal.

Keywords: aqueous-phase reforming, glycerol, hydrogen production, iridium

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Authors: Panumard Kaewmora, Thirasak Rirksomboon, Vissanu Meeyoo

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Due to the globally growing demands of petroleum fuel and fossil fuels, the scarcity or even depletion of fossil fuel sources could be inevitable. Alternatively, the utilization of renewable sources, such as biomass, has become attractive to the community. Biomass can be converted into bio-oil by fast pyrolysis. In water phase of bio-oil, acetic acid which is one of its main components can be converted to hydrogen with high selectivity over effective catalysts in steam reforming process. Steam reforming of acetic acid as model compound has been intensively investigated for hydrogen production using various metal oxide supported nickel catalysts and yet they seem to be rapidly deactivated depending on the support utilized. A catalyst support such as Ce1-xZrxO2 mixed oxide was proposed for alleviating this problem with the anticipation of enhancing hydrogen yield. However, catalyst preparation methods play a significant role in catalytic activity and performance of the catalysts. In this work, Ce0.75Zr0.25O2 mixed oxide solid solution support was prepared by urea hydrolysis using microwave as heat source. After that nickel metal was incorporated at 15 wt% by incipient wetness impregnation method. The catalysts were characterized by several techniques including BET, XRD, H2-TPR, XRF, SEM, and TEM as well as tested for the steam reforming of acetic acid at various operating conditions. Preliminary results showed that a hydrogen yield of ca. 32% with a relatively high acetic conversion was attained at 650°C.

Keywords: acetic acid, steam reforming, microwave, nickel, ceria, zirconia

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Authors: Mengying Wang, Xiaohui Wang, Chun Deng, Bei Liu, Changyu Sun, Guangjin Chen, Mahmoud El-Halwagi

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Significant amounts of natural gas hydrates (NGHs) are considered potential new sustainable energy resources in the future. However, common used methods for methane gas recovery from hydrate sediments require high investment but with low gas production efficiency, and may cause potential environment and security problems. Therefore, there is a need for effective gas production from hydrates. The natural gas hydrate production method by CO₂/H₂ replacement coupling steam methane reforming can improve the replacement effect and reduce the cost of gas separation. This paper develops a simulation model of the gas production process integrated with steam reforming and membrane separation. The process parameters (i.e., reactor temperature, pressure, H₂O/CH₄ ratio) and the composition of CO₂ and H₂ in the feed gas are analyzed. Energy analysis is also conducted. Two design scenarios with different composition of CO₂ and H₂ in the feed gas are proposed and evaluated to assess the energy efficiency of the novel system. Results show that when the composition of CO₂ in the feed gas is between 43 % and 72 %, there is a certain composition that can meet the requirement that the flow rate of recycled gas is equal to that of feed gas, so as to ensure that the subsequent production process does not need to add feed gas or discharge recycled gas. The energy efficiency of the CO₂ in feed gas at 43 % and 72 % is greater than 1, and the energy efficiency is relatively higher when the CO₂ mole fraction in feed gas is 72 %.

Keywords: Gas production, hydrate, process integration, steam reforming

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Authors: Zhenghua Dai, Jianliang Xu, Fuchen Wang

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Non-catalyst partial oxidation technology has been widely used to produce syngas by reforming of hydrocarbon, including gas (natural gas, shale gas, refinery gas, coalbed gas, coke oven gas, pyrolysis gas, etc.) and liquid (residual oil, asphalt, deoiled asphalt, biomass oil, etc.). For natural gas non-catalyst partial oxidation, the H₂/CO(v/v) of syngas is about 1.8, which is agreed well with the request of FT synthesis. But for other process, such as carbonylation and glycol, the H₂/CO(v/v) should be close to 1 and 2 respectively. So the syngas composition of non-catalyst partial oxidation should be adjusted to satisfy the request of different chemical synthesis. That means a multi-reforming method by CO₂ and H₂O addition. The natural gas non-catalytic partial oxidation hot model was established. The effects of O₂/CH4 ratio, steam, and CO₂ on the syngas composition were studied. The results of the experiment indicate that the addition of CO₂ and steam into the reformer can be applied to change the syngas H₂/CO ratio. The reactor network model (RN model) was established according to the flow partition of industrial reformer and GRI-Mech 3.0. The RN model results agree well with the industrial data. The effects of steam, CO₂ on the syngas compositions were studied with the RN model.

Keywords: non-catalyst partial oxidation, natural gas, H₂/CO, CO₂ and H₂O addition, multi-reforming method

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Authors: P. Comendador, I. Garcia, S. Orozco, L. Santamaria, M. Amutio, G. Lopez, M. Olazar

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In situ CO₂ capture in steam reforming processes has been studied in the last years as an alternative for increasing H₂ yields and H₂ purity in the product stream. For capturing the CO₂ at the reforming conditions, CaO-based sorbents are usually employed due to their properties at high temperature, low cost and high availability. However, the challenge is to develop high-capacity (gCO₂/gsorbent) materials that retain their capacity over cycles of operation. Besides, since the objective is to capture the CO₂ generated in situ, another key aspect is the sorption dynamics, which means that, in order to efficiently use the sorbent, it has to capture the CO₂ at a rate equal to or higher than the generation rate. In this work, different CaO-based materials have been prepared to aim at meeting these criteria. First, and by using the wet mixing method, different inert materials (Mg, Ce and Al) were combined with CaO. Second, and with the inert material selected (Mg), the effect of its concentration in the final material was studied. Transversally, the calcination temperature was also evaluated. It was determined that the wet mixing method is a simple procedure suitable for the preparation of CaO sorbents mixed with inert materials. The materials prepared by mixing the CaO with Mg have shown satisfactory anti-sintering properties and adequate sorption kinetics for their application in steam reforming processes. Regarding the concentration of Mg in the solid, it was concluded that high values contribute to the stability but at the expense of losing sorption capacity. Finally, it was observed that high calcination temperatures negatively affected the sorption properties of the final materials due to the decrease in the pore volume and the specific surface area.

Keywords: calcination temperature effect, CO₂ capture, Mg-Ce-Al stabilizers, Mg varying concentration effect, Sorbent stabilization

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Authors: Ali Zazi, Ouiza Cherifi

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The Catalysts materials Ni-SiO₂, Ni-Co-SiO₂ and Ni-Ce-SiO₂ were synthetized by classical method impregnation and supported by silica. This involves combing the silica with an adequate rate of the solution of nickel nitrates, or nickel nitrate and cobalt nitrate, or nickel nitrate and cerium nitrate, mixed, dried and calcined at 700 ° c. These catalysts have been characterized by different physicochemical analysis techniques. The atomic absorption spectrometry indicates that the real contents of nickel, cerium and cobalt are close to the theoretical contents previously assumed, which let's say that the nitrate solutions have impregnated well the silica support. The BET results show that the surface area of the specific surfaces decreases slightly after impregnation with nickel nitrates or Co and Ce metals and a further slight decrease after the reaction. This is likely due to coke deposition. X-ray diffraction shows the presence of the different SiO₂ and NiO phases for all catalysts—theCoO phase for that promoted by Co and the Ce₂O₂ phase for that promoted by Ce. The methane steam reforming reaction was carried out on a quartz reactor in a fixed bed. Reactants and products of the reaction were analyzed by a gas chromatograph. This study shows that the metal addition of Cerium or Cobalt improves the majority of the catalytic performance of Ni for the steam reforming reaction of methane. And we conclude the classification of our Catalysts in order of decreasing activity and catalytic performances as follows: Ni-Ce / SiO₂ >Ni-Co / SiO₂> Ni / SiO₂ .

Keywords: cerium, cobalt, heterogeneous catalysis, hydrogen, methane, steam reforming, synthesis gas

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Authors: Ali Zazi, Ouiza Cherifi

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Natural gas currently represents a raw material of choice for the manufacture of a wide range of chemical products via synthesis gas, among the routes of transformation of methane into synthesis gas The reaction of the oxidation of methane by gas vapor 'water. This work focuses on the study of the effect of cerieum on the nickel-based catalyst supported by silica for the methane vapor reforming reaction, with a variation of certain parameters of the reaction. The reaction temperature, the H₂O / CH₄ ratio and the flow rate of the reaction mixture (CH₄-H₂O). Two catalysts were prepared by impregnation of Degussa silica with a solution of nickel nitrates and a solution of cerium nitrates [Ni (NO₃) 2 6H₂O and Ce (NO₃) 3 6H₂O] so as to obtain the 1.5% nickel concentrations. For both catalysts and plus 1% cerium for the second catalyst. These Catalysts have been characterized by physical and chemical analysis techniques: BET technique, Atomic Absorption, IR Spectroscopy, X-ray diffraction. These characterizations indicated that the nitrates had impregnated the silica. And that the NiO and Ce₂O3 phases are present and Ni°(after reaction). The BET surface of the silica decreases without being affected. The catalytic tests carried out on the two catalysts for the steam reforming reactions show that the addition of cerium to the nickel improves the catalytic performances of the nickel. And that these performances also depend on the parameters of the reaction, namely the temperature, the rate of the reaction mixture, and the ratio (H₂O / CH₄).

Keywords: heterogeneous catalysis, steam reforming, Methane, Nickel, Cerium, synthesis gas, hydrogen

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Authors: Esther Acha, Jose Cambra, De Chen

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Hydrogen is considered an important energy vector for the 21st century. Nowadays there are some difficulties for hydrogen economy implantation, and one of them is the high purity required for hydrogen. This energy vector is still being mainly produced from fuels, from wich hydrogen is produced as a component of a mixture containing other gases, such as CO, CO2 and H2O. A forthcoming sustainable pathway for hydrogen is steam-reforming of bio-oils derived from biomass, e.g. via fast pyrolysis. Bio-oils are a mixture of acids, alcohols, aldehydes, esters, ketones, sugars phenols, guaiacols, syringols, furans, multi-functional compounds and also up to a 30 wt% of water. The sorption enhanced steam reforming (SESR) process is attracting a great deal of attention due to the fact that it combines both hydrogen production and CO2 separation. In the SESR process, carbon dioxide is captured by an in situ sorbent, which shifts the reversible reforming and water gas shift reactions to the product side, beyond their conventional thermodynamic limits, giving rise to a higher hydrogen production and lower cost. The hydrogen containing mixture has been obtained from the SESR of bio-oil type compounds. Different types of catalysts have been tested. All of them contain Ni at around a 30 wt %. Two samples have been prepared with the wet impregnation technique over conventional (gamma alumina) and non-conventional (olivine) supports. And a third catalysts has been prepared over a hydrotalcite-like material (HT). The employed sorbent is a commercial dolomite. The activity tests were performed in a bench-scale plant (PID Eng&Tech), using a stainless steel fixed bed reactor. The catalysts were reduced in situ in the reactor, before the activity tests. The effluent stream was cooled down, thus condensed liquid was collected and weighed, and the gas phase was analysed online by a microGC. The hydrogen yield, and process behavior was analysed without the sorbent (the traditional SR where a second purification step will be needed but that operates in steady state) and the SESR (where the purification step could be avoided but that operates in batch state). The influence of the support type and preparation method will be observed in the produced hydrogen yield. Additionally, the stability of the catalysts is critical, due to the fact that in SESR process sorption-desorption steps are required. The produced hydrogen yield and hydrogen purity has to be high and also stable, even after several sorption-desorption cycles. The prepared catalysts were characterized employing different techniques to determine the physicochemical properties of the fresh-reduced and used (after the activity tests) materials. The characterization results, together with the activity results show the influence of the catalysts preparation method, calcination temperature, or can even explain the observed yield and conversion.

Keywords: CO2 sorbent, enhanced steam reforming, hydrogen

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Authors: Hongfang Ma, Mingchuan Zhou, Haitao Zhang, Weiyong Ying

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One dimensional pseudo-homogenous modeling has been performed for methanol steam reforming reactor. The results show that the models can well predict the industrial data. The reactor had minimum temperature along axial because of endothermic reaction. Hydrogen productions and temperature profiles along axial were investigated regarding operation conditions such as inlet mass flow rate and mass fraction of methanol, inlet temperature of external thermal oil. Low inlet mass flow rate of methanol, low inlet temperature, and high mass fraction of methanol decreased minimum temperature along axial. Low inlet mass flow rate of methanol, high mass fraction of methanol, and high inlet temperature of thermal oil made cold point forward. Low mass fraction, high mass flow rate, and high inlet temperature of thermal oil increased hydrogen production. One dimensional models can be a guide for industrial operation.

Keywords: reactor, modeling, methanol, steam reforming

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Authors: Horng-Wen Wu, Yi Chao, Rong-Fang Horng

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This study is to develop a methanol steam reformer with a heat recovery zone, which recovers heat from exhaust gas of a diesel engine, and to investigate waste heat recovery ratio at the required reaction temperature. The operation conditions of the reformer are reaction temperature (200 °C, 250 °C, and 300 °C), steam to carbonate (S/C) ratio (0.9, 1.1, and 1.3), and N2 volume flow rate (40 cm3/min, 70 cm3/min, and 100 cm3/min). Finally, the hydrogen concentration, the CO, CO2, and N2 concentrations are measured and recorded to calculate methanol conversion efficiency, hydrogen flow rate, and assisting combustion gas and impeding combustion gas ratio. The heat source of this reformer comes from electric heater and waste heat of exhaust gas from diesel engines. The objective is to recover waste heat from the engine and to make more uniform temperature distribution within the reformer. It is beneficial for the reformer to enhance the methanol conversion efficiency and hydrogen-rich gas production. Experimental results show that the highest hydrogen flow rate exists at N2 of the volume rate 40 cm3/min and reforming reaction temperature of 300 °C and the value is 19.6 l/min. With the electric heater and heat recovery from exhaust gas, the maximum heat recovery ratio is 13.18 % occurring at water-methanol (S/C) ratio of 1.3 and the reforming reaction temperature of 300 °C.

Keywords: heat recovery, hydrogen-rich production, methanol steam reformer, methanol conversion efficiency

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Authors: Athanasios A. Tountas, Geoffrey A. Ozin, Mohini M. Sain

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Renewable hydrogen (H₂) carriers such as methanol (MeOH), dimethyl ether (DME), oxymethylene dimethyl ethers (OMEs), and conceivably ammonia (NH₃) can be reformed back into H₂ and are fundamental chemical conversions for the long-term viability of the H₂ economy due to their higher densities and ease of transportability compared to H₂. MeOH is an especially important carrier as it is a simple C1 chemical that can be produced from green solar-PV-generated H₂ and direct-air-captured CO₂ with a current commercially practical solar-to-fuel efficiency of 10% from renewable solar energy. MeOH steam reforming (MSR) in stationary systems next to H₂ fuel-cell filling stations can eliminate the need for onboard mobile reformers, and the former systems can be more robust in terms of attaining strict H₂ product specifications, and MeOH is a safe, lossless, and compact medium for long-term H₂ storage. Both thermal- and photo-catalysts are viable options for achieving the stable, long-term performance of stationary MSR systems.

Keywords: fuel-cell vehicle filling stations, methanol steam reforming, hydrogen transport and storage, stationary reformer, liquid hydrogen carriers

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Authors: Rujira Jitrwung, Kuntima Krekkeitsakul, Weerawat Patthaveekongka, Chiraphat Kumpidet, Jarukit Tepkeaw, Krissana Jaikengdee, Anantachai Wannajampa

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Flue gas discharging from coal fired or gas combustion power plant contains around 12% Carbon dioxide (CO₂), 6% Oxygen (O₂), and 82% Nitrogen (N₂).CO₂ is a greenhouse gas which has been concerned to the global warming. Carbon Capture, Utilization, and Storage (CCUS) is a topic which is a tool to deal with this CO₂ realization. Flue gas is drawn down from the chimney and filtered, then it is compressed to build up the pressure until 8 bar. This compressed flue gas is sent to three stages Pressure Swing Adsorption (PSA), which is filled with activated carbon. Experiments were showed the optimum adsorption pressure at 7bar, which CO₂ can be adsorbed step by step in 1st, 2nd, and 3rd stage, obtaining CO₂ concentration 29.8, 66.4, and 96.7 %, respectively. The mixed gas concentration from the last step is composed of 96.7% CO₂,2.7% N₂, and 0.6%O₂. This mixed CO₂product gas obtained from 3 stages PSA contained high concentration CO₂, which is ready to use for methanol synthesis. The mixed CO₂ was experimented in 5 Liter/Day of methanol synthesis reactor skid by 3 step processes as followed steam reforming, reverse water gas shift, and then hydrogenation. The result showed that proportional of mixed CO₂ and CH₄ 70/30, 50/50, 30/70 % (v/v), and 10/90 yielded methanol 2.4, 4.3, 5.6, and 6.0 Liter/day and save CO₂ 40, 30, 20, and 5 % respectively. The optimum condition resulted both methanol yield and CO₂ consumption using CO₂/CH₄ ratio 43/57 % (v/v), which yielded 4.8 Liter/day methanol and save CO₂ 27% comparing with traditional methanol production from methane steam reforming (5 Liter/day)and absent CO₂ consumption.

Keywords: carbon capture utilization and storage, pressure swing adsorption, reforming, reverse water gas shift, methanol

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Authors: Shu-Bo Yang, Wei Wu, Yuan-Heng Liu

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This research aims to design a heat-exchanger type of methanol reformer coupled with a preheating design in gPROMS® environment. The endothermic methanol steam reforming reaction (MSR) and the exothermic preferential oxidation reaction (PROX) occur in the inner tube and the outer tube of the reformer, respectively. The effective heat transfer manner between the inner and outer tubes is investigated. It is verified that the countercurrent-flow type reformer provides the higher hydrogen yield than the cocurrent-flow type. Since the hot spot temperature appears in the outer tube, an improved scheme is proposed to suppress the hot spot temperature by splitting the excess air flowing into two sites. Finally, an optimization algorithm for maximizing the hydrogen yield is employed to determine optimal operating conditions.

Keywords: methanol reformer, methanol steam reforming, optimization, simulation

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Authors: Tie-Qing Zhang, Seunghun Jung, Young-Bae Kim

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This research is devoted to developing a membrane reactor to flexibly meet the hydrogen demand of onboard fuel cells, which is an important part of green energy development. Among many renewable chemical products, dimethyl ether (DME) has the advantages of low reaction temperature (400 °C in this study), high hydrogen atom content, low toxicity, and easy preparation. Autothermal reforming, on the other hand, has a high hydrogen recovery rate and exhibits thermal neutrality during the reaction process, so the additional heat source in the hydrogen production process can be omitted. Therefore, the DME auto thermal reforming process was adopted in this study. To control the temperature of the reaction catalyst bed and hydrogen production rate, a Model Predictive Control (MPC) scheme was designed. Taking the above two variables as the control objectives, stable operation of the reformer can be achieved by controlling the flow rates of DME, steam, and high-purity air in real-time. To prevent catalyst poisoning in the fuel cell, the hydrogen needs to be purified to reduce the carbon monoxide content to below 50 ppm. Therefore, a Pd-Ag hydrogen semi-permeable membrane with a thickness of 3-5 μm was inserted into the auto thermal reactor, and the permeation efficiency of hydrogen was improved by steam purging on the permeation side. Finally, hydrogen with a purity of 99.99 was obtained.

Keywords: hydrogen production, auto thermal reforming, membrane, fuel cell

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Authors: Sanjay Tushar Choudhary

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This paper focuses on the thermodynamic analysis of Solid Oxide Fuel Cell (SOFC). In the present work the SOFC has been modeled to work with internal reforming of fuel which takes place at high temperature and direct energy conversion from chemical energy to electrical energy takes place. The fuel-cell effluent is a high-temperature steam which can be used for co-generation purposes. Syn-gas has been used here as fuel which is essentially produced by steam reforming of methane in the internal reformer of the SOFC. A thermodynamic model of SOFC has been developed for planar cell configuration to evaluate various losses in the energy conversion process within the fuel cell. Cycle parameters like fuel utilization ratio and the air-recirculation ratio have been varied to evaluate the thermodynamic performance of the fuel cell. Output performance parameters like terminal voltage, cell-efficiency and power output have been evaluated for various values of current densities. It has been observed that a combination of a lower value of air-circulation ratio and higher values of fuel utilization efficiency gives a better overall thermodynamic performance.

Keywords: current density, SOFC, suel utilization factor, recirculation ratio

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Authors: M. Amanipour, J. Towfighi, E. Ganji Babakhani, M. Heidari

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Cylindrical alumina microfiltration membrane (GMITM Corporation, inside diameter=9 mm, outside diameter=13 mm, length= 50 mm) with an average pore size of 0.5 micrometer and porosity of about 0.35 was used as the support for membrane reactor. This support was soaked in boehmite sols, and the mean particle size was adjusted in the range of 50 to 500 nm by carefully controlling hydrolysis time, and calcined at 650 °C for two hours. This process was repeated with different boehmite solutions in order to achieve an intermediate layer with an average pore size of about 50 nm. The resulting substrate was then coated with a thin and dense layer of silica by counter current chemical vapour deposition (CVD) method. A boehmite sol with 10 wt.% of nickel which was prepared by a standard procedure was used to make the catalytic layer. BET, SEM, and XRD analysis were used to characterize this layer. The catalytic membrane reactor was placed in an experimental setup to evaluate the permeation and hydrogen separation performance for a steam reforming reaction. The setup consisted of a tubular module in which the membrane was fixed, and the reforming reaction occurred at the inner side of the membrane. Methane stream, diluted with nitrogen, and deionized water with a steam to carbon (S/C) ratio of 3.0 entered the reactor after the reactor was heated up to 500 °C with a specified rate of 2 °C/ min and the catalytic layer was reduced at presence of hydrogen for 2.5 hours. Nitrogen flow was used as sweep gas through the outer side of the reactor. Any liquid produced was trapped and separated at reactor exit by a cold trap, and the produced gases were analyzed by an on-line gas chromatograph (Agilent 7890A) to measure total CH₄ conversion and H₂ permeation. BET analysis indicated uniform size distribution for catalyst with average pore size of 280 nm and average surface area of 275 m².g^-1. Single-component permeation tests were carried out for hydrogen, methane, and carbon dioxide at temperature range of 500-800 °C, and the results showed almost the same permeance and hydrogen selectivity values for hydrogen as the composite membrane without catalytic layer. Performance of the catalytic membrane was evaluated by applying membranes as a membrane reactor for methane steam reforming reaction at gas hourly space velocity (GHSV) of 10,000 h⁻¹ and 2 bar. CH₄ conversion increased from 50% to 85% with increasing reaction temperature from 600 °C to 750 °C, which is sufficiently above equilibrium curve at reaction conditions, but slightly lower than membrane reactor with packed nickel catalytic bed because of its higher surface area compared to the catalytic layer.

Keywords: catalytic membrane, hydrogen, methane steam reforming, permeance

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Authors: Palash Kumar Mollick, Leire Olazar, Laura Santamaria, Pablo Comendador, Manomita Mollick, Gartzen Lopez, Martin Olazar

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The entire world is skeptical towards a silver line technology of converting plastic waste into valuable synthetic gas. At this junction, besides an adequately studied conventional catalytic process for steam reforming, a non-thermal plasma is being introduced. Organic volatiles are produced in the first step, pyrolysing the plastic materials. Resultant lightweight olefins and carbon monoxide are the major components that undergo a steam reforming process to achieve syngas. A non-thermal plasma consists of ionized gases and free electrons with an electronic temperature as high as 10³ K. Organic volatiles are, in general, endorganics inactive and thus demand huge bond-breaking energy. Conventional catalyst is incapable of providing the required activation energy, leading to poor thermodynamic equilibrium, whereas a non-thermal plasma can actively collide with reactants to produce a rich mix of reactive species, including vibrationally or electronically excited molecules, radicals, atoms, and ions. In addition, non-thermal plasma provides nonequilibrium conditions leading to electric discharge only in certain degrees of freedom without affecting the intrinsic chemical conditions of the participating reactants and products. In this work, we report thermodynamic and kinetic aspects of the conversion of organic volatiles into syngas using a non-thermal plasma. Detailed characteristics of plasma and its effect on the overall yield of the process will be presented.

Keywords: non thermal plasma, plasma catalysis, steam reforming, syngas, plastic waste, green energy

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Authors: Thabelo Nelushi, Michael Scurrell, Tumelo Seadira

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Global warming is one of the most important environmental issues which arise from occurrence of gases such as carbon dioxide (CO2) and methane (CH4) in the atmosphere. Exposure to these greenhouse gases results in health risk. Hydrogen is regarded as an alternative energy source which is a clean energy carrier for the future. There are different methods to produce hydrogen such as steam reforming, coal gasification etc., however the challenge with these processes is that they emit CO and CO2 gases and are costly. Photocatalytic reforming is a substitute process which is fascinating due to the combination of solar energy and renewable sources and the use of semiconductor materials such as catalysts. TiO2 is regarded as the most promising catalysts. TiO2 nanoparticles prepared by hydrothermal method and Ag/TiO2 are being investigated for photocatalytic production of hydrogen from butanol. The samples were characterized by raman spectroscopy, TEM/SEM, XRD, XPS, EDAX, DRS and BET surface area. 2 wt% Ag-doped TiO2 nanoparticle showed enhanced hydrogen production compared to a non-doped TiO2. The results of characterization and photoactivity shows that TiO2 nanoparticles play a very important role in producing high hydrogen by utilizing solar irradiation.

Keywords: butanol, hydrogen production, silver particles, TiO2 nanoparticles

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Authors: Jonni Guiller Madeira, Angel Sanchez Delgado, Ronney Mancebo Boloy

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The use bioenergy, in recent years, has become a good alternative to reduce the emission of polluting gases. Several Brazilian and foreign companies are doing studies related to waste management as an essential tool in the search for energy efficiency, taking into consideration, also, the ecological aspect. Brazil is one of the largest cassava producers in the world; the cassava sub-products are the food base of millions of Brazilians. The repertoire of results about the ecological impact of the production, by steam reforming, of biohydrogen from cassava wastewater biogas is very limited because, in general, this commodity is more common in underdeveloped countries. This hydrogen, produced from cassava wastewater, appears as an alternative fuel to fossil fuels since this is a low-cost carbon source. This paper evaluates the environmental impact of biohydrogen production, by steam reforming, from cassava wastewater biogas. The ecological efficiency methodology developed by Cardu and Baica was used as a benchmark in this study. The methodology mainly assesses the emissions of equivalent carbon dioxide (CO₂, SOₓ, CH₄ and particulate matter). As a result, some environmental parameters, such as equivalent carbon dioxide emissions, pollutant indicator, and ecological efficiency are evaluated due to the fact that they are important to energy production. The average values of the environmental parameters among different biogas compositions (different concentrations of methane) were calculated, the average pollution indicator was 10.11 kgCO₂e/kgH₂ with an average ecological efficiency of 93.37%. As a conclusion, bioenergy production using biohydrogen from cassava wastewater treatment plant is a good option from the environmental feasibility point of view. This fact can be justified by the determination of environmental parameters and comparison of the environmental parameters of hydrogen production via steam reforming from different types of fuels.

Keywords: biohydrogen, ecological efficiency, cassava, pollution indicator

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Authors: Palash Kumar Mollick, Leire Olazar, Laura Santamaria, Pablo Comendador, Gartzen Lopez, Martin Olazar

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Average calorific value of a mixure of waste plastic is approximately 38 MJ/kg. Present work aims to extract maximum possible energy from a mixure of waste plastic using a DC thermal plasma in a spouted bed reactor. Plasma pyrolysis and steam reforming process has shown a potential to generate hydrogen from plastic with much below of legal limit of producing dioxins and furans as the carcinogenic gases. A spouted bed pyrolysis rector can continuously process plastic beads to produce organic volatiles, which later react with steam in presence of catalyst to results in syngas. lasma being the fourth state of matter, can carry high impact electrons to favour the activation energy of any chemical reactions. Computational Fluid Dynamic (CFD) simulation using COMSOL Multiphysics software has been performed to evaluate performance of a plasma spouted bed reactor in producing contamination free hydrogen as a green energy from waste plastic beads. The simulation results will showcase a design of a plasma spouted bed reactor for converting plastic waste into green hydrogen in a single step process. The high temperature hydrodynamics of spouted bed with plastic beads and the corresponding temperature distribution inside the reaction chamber will be critically examined for it’s near future installation of demonstration plant.

Keywords: green hydrogen, plastic waste, synthetic gas, pyrolysis, steam reforming, spouted bed, reactor design, plasma, dc palsma, cfd simulation

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Authors: Chetna Mohabeer, Luis Reyes, Lokmane Abdelouahed, Bechara Taouk

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In the transition to sustainability and the increasing use of renewable energy, hydrogen will play a key role as an energy carrier. Biomass has the potential to accelerate the realization of hydrogen as a major fuel of the future. Pyro-gasification allows the conversion of organic matter mainly into synthesis gas, or “syngas”, majorly constituted by CO, H2, CH4, and CO2. A second, condensable fraction of biomass pyro-gasification products are “tars”. Under certain conditions, tars may decompose into hydrogen and other light hydrocarbons. These conditions include two types of cracking: homogeneous cracking, where tars decompose under the effect of temperature ( > 1000 °C), and heterogeneous cracking, where catalysts such as olivine, dolomite or biochar are used. The latter process favors cracking of tars at temperatures close to pyro-gasification temperatures (~ 850 °C). Pyro-gasification of biomass coupled with water-gas shift is the most widely practiced process route for biomass to hydrogen today. In this work, an innovating solution will be proposed for this conversion route, in that all the pyro-gasification products, not only methane, will undergo processes that aim to optimize hydrogen production. First, a heterogeneous cracking step was included in the reaction scheme, using biochar (remaining solid from the pyro-gasification reaction) as catalyst and CO2 and H2O as gasifying agents. This process was followed by a catalytic steam methane reforming (SMR) step. For this, a Ni-based catalyst was tested under different reaction conditions to optimize H2 yield. Finally, a water-gas shift (WGS) reaction step with a Fe-based catalyst was added to optimize the H2 yield from CO. The reactor used for cracking was a fluidized bed reactor, and the one used for SMR and WGS was a fixed bed reactor. The gaseous products were analyzed continuously using a µ-GC (Fusion PN 074-594-P1F). With biochar as bed material, it was seen that more H2 was obtained with steam as a gasifying agent (32 mol. % vs. 15 mol. % with CO2 at 900 °C). CO and CH4 productions were also higher with steam than with CO2. Steam as gasifying agent and biochar as bed material were hence deemed efficient parameters for the first step. Among all parameters tested, CH4 conversions approaching 100 % were obtained from SMR reactions using Ni/γ-Al2O3 as a catalyst, 800 °C, and a steam/methane ratio of 5. This gave rise to about 45 mol % H2. Experiments about WGS reaction are currently being conducted. At the end of this phase, the four reactions are performed consecutively, and the results analyzed. The final aim is the development of a global kinetic model of the whole system in a multi-stage fluidized bed reactor that can be transferred on ASPEN PlusTM.

Keywords: multi-staged fluidized bed reactor, pyro-gasification, steam methane reforming, water-gas shift

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Authors: Jinrui Zhang, Tianlong Yang, Ying Pan

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Methane and carbon dioxide are major greenhouse gases contributor. CO₂ dry reforming of methane (DRM) for syngas production is a promising approach to reducing global CO₂ emission and extensive utilization of natural gas. However, the reported catalysts endured rapid deactivation due to severe carbon deposition at high temperature. Here, CO₂ reduction by CH4 on hexagonal nano-nickel flakes packed by porous SiO₂ (Ni@SiO₂) catalysts driven by thermal and solar light are tested. High resistance to carbon deposition and higher reactive activity are demonstrated under focused solar light at moderate temperature (400-500 ℃). Furthermore, the photocatalytic DRM under different wavelength is investigated, and even IR irradiation can enhance the catalytic activity. The mechanism of light-enhanced reaction reactivity and equilibrium is investigated by Infrared and Raman spectroscopy, and the unique reaction pathway with light is depicted. The photo-enhanced DRM provides a promising method of renewable solar energy conversion and CO₂ emission reduction due to the excellent activity and durability.

Keywords: CO₂ emission reduction, methane, photocatalytic DRM, resistance to carbon deposition, syngas

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Authors: C. Fúnez Guerra, B. Nieto Calderón, M. Jaén Caparrós, L. Reyes-Bozo, A. Godoy-Faúndez, E. Vyhmeister

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The global energy system is experiencing a change of scenery. Unstable energy markets, an increasing focus on climate change and its sustainable development is forcing businesses to pursue new solutions in order to ensure future economic growth. This has led to the interest in using hydrogen as an energy carrier in transportation and industrial applications. As an energy carrier, hydrogen is accessible and holds a high gravimetric energy density. Abundant in hydrocarbons, hydrogen can play an important role in the shift towards low-emission fossil value chains. By combining hydrogen production by natural gas reforming with carbon capture and storage, the overall CO2 emissions are significantly reduced. In addition, the flexibility of hydrogen as an energy storage makes it applicable as a stabilizer in the renewable energy mix. The recent development in hydrogen fuel cells is also raising the expectations for a hydrogen powered transportation sector. Hydrogen value chains exist to a large extent in the industry today. The global hydrogen consumption was approximately 50 million tonnes (7.2 EJ) in 2013, where refineries, ammonia, methanol production and metal processing were main consumers. Natural gas reforming produced 48% of this hydrogen, but without carbon capture and storage (CCS). The total emissions from the production reached 500 million tonnes of CO2, hence alternative production methods with lower emissions will be necessary in future value chains. Hydrogen from electrolysis is used for a wide range of industrial chemical reactions for many years. Possibly, the earliest use was for the production of ammonia-based fertilisers by Norsk Hydro, with a test reactor set up in Notodden, Norway, in 1927. This application also claims one of the world’s largest electrolyser installations, at Sable Chemicals in Zimbabwe. Its array of 28 electrolysers consumes 80 MW per hour, producing around 21,000 Nm3/h of hydrogen. These electrolysers can compete if cheap sources of electricity are available and natural gas for steam reforming is relatively expensive. Because electrolysis of water produces oxygen as a by-product, a system of Autothermal Reforming (ATR) utilizing this oxygen has been analyzed. Replacing the air separation unit with electrolysers produces the required amount of oxygen to the ATR as well as additional hydrogen. The aim of this paper is to evaluate the technical and economic potential of large-scale production of hydrogen for oil refining industry. Sensitivity analysis of parameters such as investment costs, plant operating hours, electricity price and sale price of hydrogen and oxygen are performed.

Keywords: autothermal reforming, electrolyser, hydrogen, natural gas, steam methane reforming

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Authors: A. Odoom, A. Salama, H. Ibrahim

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Hydrogen is a clean source of energy for power production and transportation. The main source of hydrogen in this research is biodiesel. Glycerol also called glycerine is a by-product of biodiesel production by transesterification of vegetable oils and methanol. This is a reliable and environmentally-friendly source of hydrogen production than fossil fuels. A typical composition of crude glycerol comprises of glycerol, water, organic and inorganic salts, soap, methanol and small amounts of glycerides. Crude glycerol has limited industrial application due to its low purity thus, the usage of crude glycerol can significantly enhance the sustainability and production of biodiesel. Reforming techniques is an approach for hydrogen production mainly Steam Reforming (SR), Autothermal Reforming (ATR) and Partial Oxidation Reforming (POR). SR produces high hydrogen conversions and yield but is highly endothermic whereas POR is exothermic. On the downside, PO yields lower hydrogen as well as large amount of side reactions. ATR which is a fusion of partial oxidation reforming and steam reforming is thermally neutral because net reactor heat duty is zero. It has relatively high hydrogen yield, selectivity as well as limits coke formation. The complex chemical processes that take place during the production phases makes it relatively difficult to construct a reliable and robust numerical model. Numerical model is a tool to mimic reality and provide insight into the influence of the parameters. In this work, we introduce a finite volume numerical study for an 'in-house' lab-scale experiment of ATR. Previous numerical studies on this process have considered either using Comsol or nodal finite difference analysis. Since Comsol is a commercial package which is not readily available everywhere and lab-scale experiment can be considered well mixed in the radial direction. One spatial dimension suffices to capture the essential feature of ATR, in this work, we consider developing our own numerical approach using MATLAB. A continuum fixed bed reactor is modelled using MATLAB with both pseudo homogeneous and heterogeneous models. The drawback of nodal finite difference formulation is that it is not locally conservative which means that materials and momenta can be generated inside the domain as an artifact of the discretization. Control volume, on the other hand, is locally conservative and suites very well problems where materials are generated and consumed inside the domain. In this work, species mass balance, Darcy’s equation and energy equations are solved using operator splitting technique. Therefore, diffusion-like terms are discretized implicitly while advection-like terms are discretized explicitly. An upwind scheme is adapted for the advection term to ensure accuracy and positivity. Comparisons with the experimental data show very good agreements which build confidence in our modeling approach. The models obtained were validated and optimized for better results.

Keywords: autothermal reforming, crude glycerol, hydrogen, numerical model

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Authors: Saeed Moarrefi, Shou-Han Zhou, Liyuan Fan

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Coupling with solid oxide fuel cells, methane dry reforming is a promising pathway for energy production while mitigating carbon emissions. However, the influence of carbon dioxide and electrochemical reactions on the internal dry reforming reaction within the fuel cells remains debatable, requiring accurate kinetic models to describe the internal reforming behaviors. We employed the Power-Law and Langmuir Hinshelwood–Hougen Watson models in an electrolyte-supported solid oxide fuel cell with a NiO-GDC-YSZ anode. The current density used in this study ranges from 0 to 1000 A/m2 at 973 K to 1173 K to estimate various kinetic parameters. The influence of the electrochemical reactions on the adsorption terms, the equilibrium of the reactions, the activation energy, the pre-exponential factor of the rate constant, and the adsorption equilibrium constant were studied. This study provides essential parameters for future simulations and highlights the need for a more detailed examination of reforming kinetic models.

Keywords: dry reforming kinetics, Langmuir Hinshelwood–Hougen Watson, power-law, SOFC

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Authors: Sui Yan Wong, Keat Ping Yeoh, Chi Wai Hui

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In this study, supercritical steam is introduced to Combined Cycle Power Plant (CCPP) in an attempt to further optimize energy recovery. Subcritical steam is commonly used in the CCPP, operating at maximum pressures around 150-160 bar. Supercritical steam is an alternative to increase heat recovery during vaporization period of water. The idea of improvement using supercritical steam is further examined with the use of exergy, pinch analysis and Aspen Plus simulation.

Keywords: exergy, pinch, combined cycle power plant, supercritical steam

Procedia PDF Downloads 141