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.     

Hydrogen production using integrated methanol‐steam reforming reactor with various reformer designs for PEM fuel cells

A 95 mm × 40 mm × 15 mm compact reactor for hydrogen production from methanol‐steam reforming (MSR) is constructed by integrating a vaporizer, reformer, and combustor into a single unit. CuO/ZnO/Al₂O₃ is used as the catalyst for the MSR while the required heat is provided using Platinum (Pt) ‐catalytic methanol combustion. The reactor performance is measured using three reformer designs: patterned micro‐channel; inserted catalyst layer placed in a single plain channel; and catalyst coated directly on the bottom wall of single plain channel. Because of longer reactant residence time and more effective heat transfer, slightly higher methanol conversion can be obtained from the reformer with patterned microchannels. The experimental results show that there is no significant reactor performance difference in methanol conversion, hydrogen (H₂) production rate, and carbon monoxide (CO) composition among these three reformer designs. These results indicated that the flow and heat transfer may not play important roles in compact size reactors. The reformer design with inserted catalyst layer provides convenience in replacing the aged catalyst, which may be attractive in practical applications compared with the conventional packed bed and wall‐coated reformers. Copyright © 2011 John Wiley & Sons, Ltd.     

Numerical analysis of performance enhancement and non-isothermal reactant transport of a cylindrical methanol reformer wrapped with a porous sheath under steam reforming

This paper accomplished a three-dimensional computational analysis of the methanol reformer with steam reforming by the Arrhenius form of reaction model and SIMPLE-C algorithm. The performance enhancement and non-isothermal reactant transport of the cylindrical reformer wrapped with a porous sheath were investigated. The parameters, including temperature of internal heater (T_H), porosity (ε), and thickness of porous sheath (R_P), on methanol conversion, hydrogen, carbon monoxide, carbon dioxide productions, temperature and velocity fields with the same inlet conditions have been investigated. The results present that higher methanol conversion and richer hydrogen production occur as temperature of heater, porosity, and porous sheath thickness increase. As temperature of internal heater is equal to 250 °C, employing a porous sheath with ε = 0.9 and R_P = 10 mm to wrap a reformer results in the maximum enhancements of 35.71% in methanol conversion and 21.18% in hydrogen production. Besides, a porous sheath with ε = 0.5 and R_P = 10 mm leads to the maximum reduction of 2.23% in carbon monoxide produced from the reformer at T_H = 300 °C.     

Simulation of steam reforming of biogas in an industrial reformer for hydrogen production

The paper aims to investigate the steam reforming of biogas in an industrial-scale reformer for hydrogen production. A non-isothermal one dimensional reactor model has been constituted by using mass, momentum and energy balances. The model equations have been solved using MATLAB software. The developed model has been validated with the available modeling studies on industrial steam reforming of methane as well as with the those on lab-scale steam reforming of biogas. It demonstrates excellent agreement with them. Effect of change in biogas compositions on the performance of industrial steam reformer has been investigated in terms of methane conversion, yields of hydrogen and carbon monoxide, product gas compositions, reactor temperature and total pressure. For this, compositions of biogas (CH₄/CO₂ = 40/60 to 80/20), S/C ratio, reformer feed temperature and heat flux have been varied. Preferable feed conditions to the reformer are total molar feed rate of 21 kmol/h, steam to methane ratio of 4.0, temperature of 973 K and pressure of 25 bar. Under these conditions, industrial reformer fed with biogas, provides methane conversion (93.08–85.65%) and hydrogen yield (1.02–2.28), that are close to thermodynamic equilibrium condition.     

Design of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system

The method of Computational Fluid Dynamics is used to predict the process parameters and select the optimum operating regime of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system. The analysis uses a three reactions kinetics model for methanol steam reforming, water gas shift and methanol decomposition reactions on Cu/ZnO/Al₂O₃ catalyst. Numerical simulations are performed at single channel level for a range of reformer operating temperatures and values of the molar flow rate of methanol per weight of catalyst at the reformer inlet. Two operating regimes of the fuel processor are selected which offer high methanol conversion rate and high hydrogen production while simultaneously result in a small reformer size and a reformate gas composition that can be tolerated by phosphoric acid-doped high temperature membrane electrode assemblies for proton exchange membrane fuel cells. Based on the results of the numerical simulations, the reactor is sized, and its design is optimized.     

Experimental validation of a pilot membrane reactor for hydrogen production by solar steam reforming of methane at maximum 550 °C using molten salts as heat transfer fluid

An innovative steam reformer for hydrogen production at temperatures lower than 550 °C has been developed in the EU project CoMETHy (Compact Multifuel-Energy To Hydrogen converter). The steam reforming process has been specifically tailored and re-designed to be combined with Concentrating Solar plants using “solar salts”: a low-temperature steam reforming reactor was developed, operating at temperatures up to 550 °C, much lower than the traditional process (usually > 850 °C). This result was obtained after extensive research, going from the development of basic components (catalysts and membranes) to their integration in an innovative membrane reformer heated with molten salts, where both hydrogen production and purification occur in a single stage. The reduction of process temperatures is achieved by applying advanced catalyst systems and hydrogen selective Pd-based membranes. Process heat is supplied by using a low-cost and environmentally friendly binary NaNO₃/KNO₃ liquid mixture (60/40 w/w) as heat transfer fluid; such mixture is commonly used for the same purpose in the concentrating solar industry, so that the process can easily be coupled with concentrating solar power (CSP) plants for the supply of renewable process heat. This paper deals with the successful operation and validation of a pilot scale reactor with a nominal capacity of 2 Nm³/h of pure hydrogen from methane. The plant was operated with molten salt circulation for about 700 h, while continuous operation of the reactor was achieved for about 150 h with several switches of operating conditions such as molten salts inlet temperature, sweep steam flow rate and steam-to-carbon feed ratio. The results obtained show that the membrane reformer allows to achieve twice as high a conversion compared to a conventional reformer operating at thermodynamic equilibrium under the same conditions considered in this paper. A highly pure hydrogen permeate stream was obtained (>99.8%), while the outlet retentate stream had low CO concentration (<2%). No macroscopic signs of reactor performance loss were observed over the experimental operation period.     

Finding a suitable catalyst for on-board ethanol reforming using exhaust heat from an internal combustion engine

Ethanol steam reforming with pure ethanol and commercial bioethanol (S/C = 3) was carried out inside the housing of the exhaust gas pipe of a gasoline internal combustion engine (ICE) by using exhaust heat (610–620 °C). Various catalytic honeycombs loaded with potassium-promoted cobalt hydrotalcite and with ceria-based rhodium–palladium catalysts were tested under different reactant loads. The hydrogen yield obtained over the cobalt-based catalytic honeycomb at low load (F/W < 25 mL_liq·g_cat^?1·h^?1, GHSV = 4·10² h^?1) was remarkably high, whereas that obtained over the noble metal-based catalytic honeycombs was much superior at high loads (F/W = 25–150 mL_liq·g_cat^?1·h^?1, GHSV = 4·10²–2.4·10³ h^?1). At higher reactant loads the overall hydrogen production was limited by heat transfer from the exhaust heat to the reformer inside the housing of the exhaust gas pipe of the ICE. Extensive carbon deposition occurred over the cobalt-based honeycomb, making its use impractical. In contrast, stability runs (>200 h) at high load (F/W = 150 mL_liq·g_cat^?1·h^?1, GHSV = 2.4·10³ h^?1) showed that promotion of the ceria-supported noble metal catalyst with alumina and zirconia is a key element for practical application using commercial bioethanol. HRTEM analysis of post mortem honeycombs loaded with RhPd/Ce_0.5Zr_0.5O₂–Al₂O₃ showed no carbon formation and no metal agglomeration.     

Mini CHP based on the electrochemical generator and impeded fluidized bed reactor for methane steam reforming

The paper presents a configuration of mini CHP with the methane reformer and planar solid oxide fuel cell (SOFC) stacks. This mini CHP may produce electricity and superheated steam as well as preheat air and methane for the reformer along with cathode air used in the SOFC stack as an oxidant. Moreover, the mathematical model for this power plant has been created. The thermochemical reactor with impeded fluidized bed for autothermal steam reforming of methane (reformer) considered as the basis for the synthesis gas (syngas) production to fuel SOFC stacks has been studied experimentally as well. A fraction of conversion products has been oxidized by the air fed to the upper region of the impeded fluidized bed in order to carry out the endothermic methane steam reforming in a 1:3 ratio as well as to preheat products of these reactions. Studies have shown that syngas containing 55% of hydrogen could be produced by this reactor. Basic dimensions of the reactor as well as flow rates of air, water and methane for the conversion of methane have been adjusted through mathematical modelling.The paper provides heat balances for the reformer, SOFC stack and waste heat boiler (WHB) intended for generating superheated water steam along with preheating air and methane for the reformer as well as the preheated cathode air. The balances have formed the basis for calculating the following values: the useful product fraction in the reformer; fraction of hydrogen oxidized at SOFC anode; gross electric efficiency; anode temperature; exothermic effect of syngas hydrogen oxidation by air oxygen; excess entropy along with the Gibbs free energy change at standard conditions; electromotive force (EMF) of the fuel cell; specific flow rate of the equivalent fuel for producing electric and heat energy. Calculations have shown that the temperature of hydrogen oxidation products at SOFC anode is 850 °C; gross electric efficiency is 61.0%; EMF of one fuel cell is 0.985 V; fraction of hydrogen oxidized at SOFC anode is 64.6%; specific flow rate of the equivalent fuel for producing electric energy is 0.16 kg of eq.f./(kW·h) while that for heat generation amounts to 44.7 kg of eq.f./(GJ). All specific parameters are in agreement with the results of other studies.     

Modeling and Analysis of a Hydrogen Reformer for Fuel Cell Applications

Fuel cells that utilize hydrogen and oxygen to produce energy are promising power sources. However, there are operational difficulties in storing hydrogen. One way to alleviate this problem is to generate hydrogen in situ from a liquid fuel via steam reforming. In this paper, an ethanol reformer was modeled as a tubular non-isothermal, non-isobaric packed-bed reactor with an annular heat transfer jacket, operating at unsteady state. A suitable heat transfer jacket was designed that provides heat to the reformer by combustion of ethanol. The partial differential equations of the reformer model were solved numerically and model predictions of hydrogen generation were shown to be in good agreement with experimental data available in the literature for a laboratory-scale reformer. A commercial-scale reformer was designed using this high-fidelity model that can produce sufficient hydrogen to generate up to 5 kW of power when used in conjunction with a Ballard Mark V fuel-cell stack. Experimental data from the dynamic power consumption in a 3-bedroom house were used to validate the size of the reformer as well as a back-up battery that supplies power when the reformer is unable to meet the power demand.     

Kinetic investigation on butanol steam reforming over Ru/Al2O3 catalyst

Steam reforming of biomass-derived oxygenates is an attractive technique for the renewable production of hydrogen (H₂). In this work, steam reforming of n-butanol – a representative of bio-oxygenates – was studied over commercial 5% Ru/Al₂O₃ catalyst in a fixed-bed reactor. Kinetics of butanol reforming was investigated between temperatures 623 and 773 K at steam/carbon (S/C) ratio equal to 33.3 mol/mol. The W/F_A0 ratio (W: mass of catalyst, F_A0: molar flow rate of butanol in feed) was varied between 3.3 and 16.7 g h/mol. At T = 773 K, butanol conversion and H₂ yield were 93.4% and 0.61 mol/mol. Evaluation of the kinetic data showed that reaction order with respect to butanol was unity. The activation energy for the investigated reaction was 78 kJ/mol. Finally, a Langmuir-Hinshelwood model that assumed the surface reaction between the adsorbed reactants as rate-determining was used to describe the kinetic data.     

Experimental study on partial oxidation of methane to produce hydrogen using low‐temperature plasma in AC Glidarc discharge

A reformer using low‐temperature plasma was designed and developed for hydrogen production. The reformer has three electrodes and uses AC gliding arc discharge. A reference condition, which is the highest hydrogen production, has a O₂/C ratio of 0.45, input flow rate of 4.9 l min^?1 and power supply of 1 kW. And the methane conversion rate, the high hydrogen selectivity and the reformer efficiency were 69.2, 77.8 and 35.2%, respectively. To investigate reforming characteristics, parametric studies were achieved for the gas components ratio, a gas flow rate, a reactor temperature, an input electric power and catalyst addition effect. The results are as follows: The gas components ratio was an important factor, which had maximum value. When the gas flow rate, the reactor temperature and the electric power were increased, the methane conversion rate and the hydrogen concentration also increased. Copyright © 2008 John Wiley & Sons, Ltd.     

Performance assessment and evaluation of catalytic membrane reactor for pure hydrogen production via steam reforming of methanol

The steam reforming of methanol was investigated in a catalytic Pd–Ag membrane reactor at different operating conditions on a commercial Cu/ZnO/Al₂O₃ catalyst. A comprehensive two-dimensional non-isothermal stationary mathematical model has been developed. The present model takes into account the main chemical reactions, heat and mass transfer phenomena in the membrane reactor with hydrogen permeation across the PdAg membrane in radial direction. Model validation revealed that the predicted results satisfy the experimental data reasonably well under the different operating conditions. Also the impact of different operating parameters including temperature, pressure, sweep ratio and steam ratio on the performance of reactor has been examined in terms of methanol conversion and hydrogen recovery. The modeling results have indicated the high performance of the membrane reactor which is related to continuous removal of hydrogen from retentate side through the membrane to shift the reaction equilibrium towards formation of hydrogen. The obtained results have confirmed that increasing the temperature improves the kinetic properties of the catalyst and increase in the membrane's H₂ permeance, which results in higher methanol conversion and hydrogen production. Also it is inferred that the hydrogen recovery is favored at higher temperature, pressure, sweep ratio and steam ratio. The model prediction revealed that at 573 K, 2 bar and sweep ratio of 1, the maximum hydrogen recovery improves from 64% to 100% with increasing the steam ratio from 1 to 4.     

Methanol reformer integrated phosphoric acid fuel cell (PAFC) based compact plant for field deployment

Naval Material Research Laboratory (NMRL), based on the firm confidence of her core competence on material development, started an ambitious program on development of fuel cells for various Defense and non-Defense application in early nineties. The primary emphasis of this program is to develop phosphoric acid fuel cell (PAFC) based power plants integrated with hydrogen generators along with other accessories. In the process of development, it is understood that online generation of hydrogen from a liquid fuel is the key to success. Methanol, a liquid fuel, can be reformed easily with few side products and the resultant hydrogen rich reformer gas can be directly fed to a PAFC. Such configuration keeps the basic system simple and free of complicated filters and instrumentation.NMRL has developed a series of catalytic burners with high efficiency as the primary heat transfer source from the hot catalytic surface is based on conduction rather than convection as is done normally. Vaporizer is a coiled arrangement and reformer is hollow sections filled with Cu/Al₂O₃/ZnO catalyst, and the same is integrated with catalytic burners. Such arrangement is modular in nature and each reformer has hydrogen generation capacity of 90 lpm and start-up time is around half an hour. Modular design of reformer reactor allow them to used in different capacity plants such as a 2 kW plant configured with a reformer reactor with two vaporizer and 15 kW plant configured with seven nos. of reformer reactors and seven no. of vaporizer. The waste heat of the fuel cell and the same from the reformer burner flue is used to meet most of the reformer heat load. The catalytic burner of the reformer burns both waste hydrogen and methanol with very little excess air. PAFC being tolerant to CO (up to 1%) can be directly operated with the hydrogen rich reformer gas and the lean gas from the fuel cell is burnt into the reformer system.The raw DC output power is converted into either 100 VDC or 220 V single phase, 50 Hz sinusoidal AC power through appropriate power electronics. These configurations give overall efficiency of the plant to around 35-40 % based on LHV of Hydrogen. A battery bank is also incorporated to cater for the plant start-up and other temporary auxiliary power which get charged from the fuel cell output. Such configuration lead to the development of methanol reformer integrated PAFC based power plants of capacity ranging from 2 kW to 15 kW. The system is designed for continuous power production in the field. These plants are suitable for remote area, distributed power generation and application such as battery charging, domestic load etc.     

Numerical and experimental study on hydrogen production via dimethyl ether steam reforming

This work presents the characteristics of catalytic dimethyl ether (DME)/steam reforming based on a Cu–Zn/γ-Al₂O₃ catalyst for hydrogen production. A kinetic model for a reformer that operates at low temperature (200 °C–500 °C) is simulated using COMSOL 5.2 software. Experimental verification is performed to examine the critical parameters for the reforming process. During the experiment, superior Cu–Zn/γ-Al₂O₃catalysts are manufactured using the sol-gel method, and ceramic honeycombs coated with this catalyst (1.77 g on each honeycomb, five honeycombs in the reactor) are utilized as catalyst bed in the reformer to enhance performance. The steam, DME mass ratio is stabilized at 3:1 using a mass flow controller (MFC) and a generator. The hydrogen production rate can be significantly affected depending on the reactant's mass flow rate and temperature. And the maximum hydrogen yield can reach 90% at 400 °C. Maximum 8% error for the hydrogen yield is achieved between modeling and experimental results. These experiments can be further explored for directly feeding hydrogen to proton exchange membrane fuel cell (PEMFC) under the load variations.     

Thermodynamic analysis of ethanol processors for fuel cell applications

A thermodynamic analysis of hydrogen production from ethanol has been carried out with respect to solid polymer fuel cell applications. Ethanol processors incorporating either a steam reformer or a partial oxidation reactor connected to water gas shift and CO oxidation reactors were considered and the effect of operating parameters on hydrogen yield has been examined. Employment of feeds with high H₂O/EtOH ratio results in reduced energy efficiency of the system. When hydrogen, non-converted in the fuel cell, is used to supply heat in the steam reformer, the effective hydrogen yield is essentially independent of the temperature of the reformer and the water gas shift reactor. Optimal operating conditions of partial oxidation processors have been determined assuming an upper limit for the preheat temperature of the feed. Results are discussed along with other practical considerations in view of actual applications.     

Intensification of hydrogen production from methanol steam reforming by catalyst segmentation and metallic foam insert

This paper is a numerical study about the catalyst morphology CuO/ZnO/Al₂O₃ effects on the hydrogen production from methanol steam reforming, for proton exchange membrane fuel cells (PMEFC). The study is focused on the influences of the metal foam insert, catalyst layer segmentation, and metal foam as catalyst support on the reactor performance: hydrogen yield and methanol conversion. According to the carried simulations, it is found that these configurations improve the reformer performances compared to the continuous catalyst layer configuration. The insertion of metal foam increases the efficiency of up to 75.41% at 525 K. Also, at this reaction temperature, the segmentation of the catalyst layer in similar parts increases the reformer efficiency by 2.11%, 4.23%, 6.77%, and 8.6% for 2, 4, 8, and 16 identical parts, respectively. As well as, the metal foam as catalyst support is more efficient compared to the other configurations, the efficiency is equal to 64% at T = 495 k.     

Dynamic modeling of a three-stage low-temperature ethanol reformer for fuel cell application

A low-temperature ethanol reformer based on a cobalt catalyst for the production of hydrogen has been designed aiming the feed of a fuel cell for an autonomous low-scale power production unit. The reformer comprises three stages: ethanol dehydrogenation to acetaldehyde and hydrogen over SnO₂ followed by acetaldehyde steam reforming over Co(Fe)/ZnO catalyst and water gas shift reaction. Kinetic data have been obtained under different experimental conditions and a dynamic model has been developed for a tubular reformer loaded with catalytic monoliths for the production of the hydrogen required to feed a 1 kW PEMFC.     

On-board reforming of biodiesel and bioethanol for high temperature PEM fuel cells: Comparison of autothermal reforming and steam reforming

In the 21st century biofuels will play an important role as alternative fuels in the transportation sector. In this paper different reforming options (steam reforming (SR) and autothermal reforming (ATR)) for the on-board conversion of bioethanol and biodiesel into a hydrogen-rich gas suitable for high temperature PEM (HTPEM) fuel cells are investigated using the simulation tool Aspen Plus. Special emphasis is placed on thermal heat integration. Methyl-oleate (C₁₉H₃₆O₂) is chosen as reference substance for biodiesel. Bioethanol is represented by ethanol (C₂H₅OH). For the steam reforming concept with heat integration a maximum fuel processing efficiency of 75.6% (76.3%) is obtained for biodiesel (bioethanol) at S/C = 3. For the autothermal reforming concept with heat integration a maximum fuel processing efficiency of 74.1% (75.1%) is obtained for biodiesel (bioethanol) at S/C = 2 and λ = 0.36 (0.35). Taking into account the better dynamic behaviour and lower system complexity of the reforming concept based on ATR, autothermal reforming in combination with a water gas shift reactor is considered as the preferred option for on-board reforming of biodiesel and bioethanol. Based on the simulation results optimum operating conditions for a novel 5 kW biofuel processor are derived.     

Modeling and simulation of methane steam reforming in a thermally coupled membrane reactor

A distributed mathematical model for thermally coupled membrane reactor that is composed of three channels is developed for methane steam reforming. Methane combustion takes place in the first channel on a Pt/δ–Al₂O₃$\text{Pt}/\delta \text{–}{\text{Al}}_2{\text{O}}_3$ catalyst layer that supplies the necessary heat for the endothermic steam reforming reaction. In the second channel, catalytic steam reforming reactions take place in the presence of Ni/MgO–Al₂O₃ catalyst. The combustion catalyst forms a thin layer next to the reactor wall to minimize the heat transfer resistance. Selective permeation of hydrogen through the palladium membrane is achieved either by co-current or counter-current flow of sweep gas through the third channel. The burner is modeled as a monolith reactor and the reformer is assumed to behave as a pseudo-homogenous reactor. The mass and energy balance equations for the thermally coupled membrane reactor form a set of 22 coupled ordinary differential equations. With the application of appropriate boundary conditions, the distributed reactor model for steady-state operation is solved as a boundary value problem. The model equations are discretized using spline collocation on finite elements. The discretized nonlinear modeling equations, along with the boundary conditions, form a system of algebraic equations that are solved using the trust region dogleg method. The performance of the reactor is numerically investigated for various key operating variables such as inlet fuel concentration, inlet steam/methane ratio, inlet reformer gas temperature and inlet reformer gas velocity. Simulations for both the co-current and the countercurrent flow modes are also performed using different sweep gas flow rates. For each case, the reactor performance is analyzed based on methane conversion and hydrogen recovery yield.     

Steam reforming of propionic acid: Thermodynamic analysis of a model compound for hydrogen production from bio-oil

The thermodynamic equilibrium of steam reforming of propionic acid (HPAc) as a bio-oil model compound was studied over a wide range of reaction conditions (T = 500–900 °C, P = 1–10 bar and H₂O/HPAc = 0–4 mol/mol) using non-stoichiometric equilibrium models. The effect of operating conditions on equilibrium conversion, product composition and coke formation was studied. The equilibrium calculations indicate nearly complete conversion of propionic acid under these conditions. Additionally, carbon and methane formation are unfavorable at high temperatures and high steam to carbon (S/C) ratios. The hydrogen yield versus S/C ratio passes a maximum, the value and position of which depends on temperature. The thermodynamic equilibrium results for HPAc fit favorably with experimental data for real bio-oil steam reforming under same reaction conditions.