Carbon dioxide conversion by reverse watergas shift. Simulation of watergasshift reaction program matlab. Approach zeolite membrane reactor for water gas shift reaction. They may in the near future act as enablers for improving carbon footprints of certain value chains. Once the kinetics is known, the reactor design can be made based on material balance. Sep 28, 2009 simulation results the highest conversion for hts inlet temperature 320. Kinetics and catalysis of the watergasshift reaction worcester. Reverse water gas shift reaction in an inconel reactor.
Water gas shift wgs7 reaction and fischer troph synthesis fts8. Schematic view of the bench scale reactor system used in the kinetic data acquisition. Five different strontiumdoped lanthanum cobaltites, la1xsrxcoo3 0. Reverse watergas shift chemical looping for syngas.
Kinetics and catalysis of the watergasshift reaction. A steadystate kinetic model for methanol synthesis and. Simulation of hightemperature watergas shift reactors. Improving feal2o3 catalysts for the reverse watergas shift. Entropy generation minimization for reverse water gas. Ceo2 catalysts with different structure were prepared by hardtemplate ceht, complex ceca, and precipitation methods cepc, and their performance in co2 reverse water gas shift rwgs reaction was investigated. The kinetics of water gas shift reaction was studied over commercial cuoznoal2o3 in an integral fixed bed reactor. Process intensification with integrated watergasshift. Water gas shift reaction over an iron oxidechromium oxide catalyst. Catalyst development for watergas shift 191 not the primary reaction, it must be considered in methanol synthesis, hydrocarbon conversion by reforming, fischer tropsch synthesis, automotive exhaust catalysis, and selective co oxidation for fuel cells. Entropy generation minimization for reverse water gas shift. In this configuration, the syngas stream, composed by co, co 2, and h 2 and fed to the methanol synthesis reactor, is produced by means of a reversewatergasshift by which a co 2 stream is partially converted in carbon monoxide.
The reverse water gas shift process rwgs for water. Methane steam reforming, methanation and water gas shift. The water gas shift reaction shift conversion is necessary because the gaseous product from a gasifier generally contains large amounts of carbon monoxide and hydrogen, plus lesser amounts of other gases. Adsorption as a viable and cost effective process for gas separation was chosen for the co 2 co separation. Zeolite membrane reactor for water gas shift reaction for hydrogen production jerry y. There is inadequate conversion of co to co 2 to achieve greater than 75% carbon capture if only one shift reactor is used. Kinetic study of the reverse water gas shift reaction in high. This thesis comprises a systematic approach for the evaluation of the reverse watergas shift chemical looping rwgscl process for co2 utilization. Evaluation of alternate water gas shift configurations for. Reactor design, modeling and optimization for the hightemperature methane pyrolysis and the reverse watergas shift reaction.
The reverse water gas shift reaction several investigations of the high temperature 1148 k, low pressure gas engineering, petroleum university of technology, ahwaz, iran. A single reactor common for the kinetic and the spectroscopic measurements was used. In particular, emissions resulting from the use of hydrogen as fuel contain only water, one of the reasons why that. Co 2 conversion amounts and rates were measured at different temperatures and partial pressures after various reduction procedures. The first reaction, the reverse water gas shift reaction, is a fast one. In this study, the reverse watergas shift reaction with chemical. Equilibrium conversion for these conditions is 55%. Compact and lightweight sabatier reactor for carbon dioxide. Project rationale designing wgs membrane reactors requires the consideration of reaction kinetics and mass transport phenomena forward and reverse water gas shift kinetics catalytic effect of reactor materials, membrane materials. Current research efforts are underway to explain this. An industrial case 57 operating pressure and hydrogen sulfide concentration with intrinsic rate expressions. Watergas shift process for hydrogen production effects. Multivariable control design for the water gas shift reactor in a fuel processor.
In this paper, it will be critically discussed in short format why both technologies can only be operated economically and sustainably in defined. Simulation results the highest conversion for hts inlet temperature 320. Study of watergas shift reaction on molybdenum carbide coating in a microreactor. Eric grol, netl wenching yang, research and development solutions, llc saic netl contact. Average yield of co for the reverse water gas shift reaction at 1atm, p h2 p co2 1 kpa, balance he, ghsv 176000 h1, 50 mg of cu x ni 1x c catalyst 59 figure 3. Production plant comprising a synthesis gas generation step arranged to receive a hydrocarbon or carboneous feed stock and in a synthesis gas generation process provide a syngas a production step arranged to receive the syngas and produce a product stream a reverse water gas shift step arranged to receive a h 2 rich gas stream and a co 2 feed and in a rwgs step obtain a reverse shifted gas. Average yield of co for the reverse water gas shift reaction at 1atm, p h2 p co2 1 kpa, balance he, ghsv 282000 h1, 50 mg of cu x ni 1x. Pdf entropy generation minimization for reverse water gas. Analysis of design variables for watergasshift reactors by. Under certain operating conditions, co2 reduction via the bosch reaction may also occur, where co2 reacts with hydrogen to form. Methane steam reforming, methanation and watergas shift. Desireddy1, andrej pohar1, blaz likozar1 1 department of catalysis and chemical reaction engineering, national institute of chemistry, hajdrihova 19, 1001 ljubljana, slovenia.
The reverse watergas shift reaction is endothermic and is preferred in co 2rich environments. For carbon capture greater than 75%, two water gas shift reactors are required. Analysis of design variables for watergasshift reactors. Watergas shift process for hydrogen production effects of. The simulation and design of the tubular reactor requires information on thermodynamics and on. Methanol production from co2 via reversewatergasshift.
Watergas shift modeling of coal gasification in an entrained. The above reaction is actually the result of two reactions. Then the reference conditions for the reverse of the water gas shift and methanation are set. Azcan proceedings of the world congress on engineering and computer science 2012 vol ii wcecs 2012, october 2426, 2012, san francisco, usa isbn. The reverse water gas shift rwgs process is a candidate technology for water and oxygen production on mars. Design of water gas shift converter student cheresources. They consolidated a listing of the various important kinetic expressions published for both the high temperature and the low temperature water gas shift reactions along with the details of the makeup of the catalysts and the operating conditions at which the kinetics were obtained.
Pdznoal2o3 catalysts were studied for water gas shift wgs, methanol steam reforming, and reverse water gas shift rwgs reactions. Water gas shift in applications where scrubbed syngas hydrogencarbon monoxide h 2 co ratio must be increasedadjusted to meet downstream process requirements, the syngas is passed through a multistage, fixedbed reactor containing shift catalysts to convert co and water into additional h 2 and carbon dioxide co 2 according to the following reaction known as the water gas shift wgs. Increasing co 2 conversion to co requires co 2 co separation downstream of the reactor and recycling unreacted co 2 and h 2 back into the reactor. Study of the reverse watergas shift and dryreforming reactions conditions in. The results are evaluated in order to generate a reactor concept. Average yield of co for the reverse water gas shift reaction at 1atm, p h2 p co2 1 kpa, balance he, ghsv 282000 h1, 50 mg of cu x ni.
Pdf entropy generation minimization for reverse water. Modeling and simulation of water gas shift reactor. Reactors jordan university of science and technology. Most of the reaction rates for the water gas shift wgs reaction were obtained from experiments under simplified laboratory conditions with specific catalysts. Reverse watergas shift on copperbased catalyst materials. The water gas shift wgs reaction is a wellknown step for upgrading carbon monoxide to hydrogen in the production of synthesis gas. The catalysts were characterized using xrd, tem, bet, h2tpr, and insitu xps. Integration of methane steam reforming and water gas shift. A few of the reaction rates without using catalysts were obtained under supercritical water conditions, with the pressure much higher than those in a typical gasifier. This first chapter begins with the background information on the wgs reaction. The reversibility of the wgsr is important in the production of ammonia, methanol, and the fischertropsch process where the ratio of h 2 co is critical. A microkinetic and graph theoretic approach iii assemble the rr graph, namely the intermediate nodes, terminal nodes, empty reaction routes and full reaction routes, were enumerated and the graph constructed. The worlds progression towards the hydrogen economy is facilitating the production of hydrogen from various resources.
Modelling of the high temperature water gas shift reaction with stationary and transient experiments. In the carbon based hydrogen production, water gas shift reaction is the. The rwgs reactor with irreversibilities of heat transfer, chemical reaction and viscous. Thermal design and optimization for reverse water gas shift rwgs reactors is particularly important to fuel synthesis in naval or. Reactor design, modeling and optimization for the high. Tom meyer 1and robert zubrin 2, 1boulder center for science and policy, p.
Design of watergas shift reactors journal article osti. Depending on the reaction conditions, the equilibrium for the water gas shift can be pushed in either the forward or reverse direction. Pdf multivariable control design for the water gas shift. Douglas falleiros barbosa lima, fernando ademar zanella, marcelo kaminski lenzi and papa matar ndiaye march 28th 2012. Rwgs uses carbon dioxide and hydrogen as reactants to produce oxygen and carbon monoxide with a copper on alumina catalyst. Water gas shift reaction an overview sciencedirect topics. The design of active gold catalysts has several crucial requirements. Gas separation by adsorption in order to increase co. Thermal design and optimization for reverse water gas shift rwgs reactors is particularly important to fuel synthesis in naval or commercial scenarios. Pdf study of the reverse watergas shift and dryreforming.
This presentation does not contain any proprietary, confidential, or otherwise restricted information. Design of water gas shift converter posted in student. Water gas shift in applications where scrubbed syngas hydrogencarbon monoxide h 2 co ratio must be increasedadjusted to meet downstream process requirements, the syngas is passed through a multistage, fixedbed reactor containing shift catalysts to convert co and water into additional h 2 and carbon dioxide co 2 according to the following reaction known as the watergas shift wgs. The mechanism of the reverse watergas shift reaction over a cu catalyst was studied by co2 hydrogenation, temperatureprogrammed reduction of the cu catalyst and pulse reaction with qms monitoring. Conduct forward watergas shift using a membrane reactor at favorable conditions accomplishments conducted firstever high temperature and high pressure reverse wgs reaction kinetics study determined catalytic effect of reactor shell material on wgs reaction conducted cfd simulations to determine effect of reactor geometry on. Zn ratio with a maximum activity obtained at approximately 0. Lin, henk verweij, peter smirniotis and junhang dong.
Kinetics and catalysis of the water gas shift reaction. The reverse water gas shift reaction rwgs reaction was discovered in the 19th century as a method of producing water from carbon dioxide and hydrogen, with carbon monoxide as a side product. In adiabatic operation mode, for achieving a co composition of 0. The reverse water gas shift reaction, rwgsr, is the focus of this investigation. An industrial case, petrochemicals, vivek patel, intechopen, doi.
Kinetic modeling of low temperature watergas shift. Modeling and simulation of water gas sh ift reactor. Mechanism of co formation in reverse watergas shift reaction. Reverse water gas shift reaction over supported cuni nanoparticle catalysts maxime lortie. Sewgs sorption enhanced water gas shift system has been developed. Watergas shift modeling of coal gasification in an. Multisite microkinetic modelling damjan lasic jurkovic1, venkata d. Plasmaassisted catalytic reverse water gas shift reactor. An increase of the reactor temperature is thermodynamically unfavorable for the water gas shift reaction.
The funders had no role in the design of the study. Kinetic study of the reverse water gas shift reaction in. Eindhoven university of technology master study of watergas. In comparison with the reaction of co2 alone, hydrogen can significantly promote the co formation in the rwgs reaction. Dry reforming and reverse water gas shift are often discussed as potential carbon dioxide sinks. Simulation and control of water gas shift packed bed reactor with interstage cooling s z saw1. Water gas shift reactor design linkedin slideshare. Co 2 conversion studies via reverse water gas shift chemical looping were conducted using chemical looping studies in a packed bed reactor connected to an online mass spectrometer mks. Rwgs has not been industrialized yet, the thermal design and optimization of the rwgs reactor using modern thermodynamic optimization. Reduction of co 2 to co via reverse watergas shift. Conduct forward water gas shift using a membrane reactor at favorable conditions accomplishments conducted firstever high temperature and high pressure reverse wgs reaction kinetics study determined catalytic effect of reactor shell material on wgs reaction conducted cfd simulations to determine effect of reactor geometry on. Plasmaassisted catalytic reverse water gas shift reactor marshall space flight center, alabama for improving co 2 conversions for a lowtemperature co 2 methanation process, a mechanism of using reverse water gas shift rwgs reaction as an intermediate step to generate the more reactive co species for the methanation process was developed. Mar 19, 2014 carbon dioxide conversion to carbon monoxide was studied in an intensified chemical looping reverse watergas shift reaction rwgscl process using parent perovskitetype oxides as oxygen carriers.
The thermodynamic equilibrium in the shift reaction can be enhanced to give more hydrogen yield by adding a co2 absorbent into the shift reactor. Carbon monoxide and hydrogen if they are present in the mole ratio of 1. Nov 08, 2007 an increase of the reactor temperature is thermodynamically unfavorable for the water gas shift reaction. Similarly, trace co can also catalytically react with hydrogen to produce methane and water as shown in eq. The results indicated that the structure of ceo2 catalysts was significantly affected by the. Entropy generation minimization for reverse water gas shift rwgs. Palladiumbased catalytic membrane reactors cmrs effectively remove h 2 to induce higher conversions in methane steam reforming msr and water gas shift reactions wgs.
Evaluation of alternate water gas shift configurations for igcc systems august 5, 2009 prepared by. A microkinetic and graph theoretic approach ii reverse direction of each step based solely on heats of chemisorption and bond dissociation energies of the species involved. In this configuration, the syngas stream, composed by co, co 2, and h 2 and fed to the methanol synthesis reactor, is produced by means of a reverse water gas shift by which a co 2 stream is partially converted in carbon monoxide. Scheme of the reactor thermodynamic modeling of water gas shift reaction in supercritical water e. A significant reduction in the energy of activation for the hightemperature, highpressure reverse water gas shift reaction was observed. Singh and saraf, 1977 is a go od example of this method. Reverse water gas shift reaction over supported cuni. The formate derived from association of h2 and co2 is proposed to be the. By assessing the maximum possible oxygen storage capacity and by calculating the reaction equilib. The water gas shift wgs reaction is often applied to these syn gas streams next, converting the co and added steam to carbon dioxide co.
Carbon dioxide conversion to carbon monoxide was studied in an intensified chemical looping reverse water gas shift reaction rwgscl process using parent perovskitetype oxides as oxygen carriers. Zeolite membrane reactor for watergasshift reaction for. Carbon dioxide conversion by reverse watergas shift chemical. Catalyst development for watergas shift 193 table 1. Additionally, a competing reverse water gas shift rwgs reaction, eq. Modeling and simulation of watergas shift reactors. The project has focused specifically on the conventional hightemperature shift catalysts based on oxides of iron and chromium, in particular the role of dopants such as chromium to the catalytic process. Co2 valorisation via reverse watergas shift reaction using advanced cs doped. The reverse water gas shift process rwgs for water and oxygen. Pdf mathematical modeling of reverse watergas shift reaction. Co2 valorisation via reverse watergas shift reaction using. Modeling and simulation of water gas shift reactors.
An innovative process scheme to produce methanol from carbon dioxide is here presented and assessed via simulation. Eric grol office of systems, analyses and planning 4123865463 national energy technology laboratory l. Spectrokinetic investigation of reverse watergasshift. In the near future, an increasing amount of synthesis gas production will be based on coal gasification instead of natural gas. Kinetics and catalysis of the watergasshift reaction chemical. The experimental data were collected from literature. Kinetics of the forward and reverse co shift reactions, journal of catalysis, 63, 8393. The co produced is fed to a co hydrogenation reactor for fuel. This side reaction produces h 2 o and decreases the h 2 co ratio to a value less than 1 at 400800c. The reactivity of the surface species present over a 2%ptceo2 catalyst during the reverse water gas shift rwgs reaction was investigated by a detailed operando spectrokinetic analysis. Co2 conversion by reverse water gas shift catalysis nsfpar. For an ideal cstr reactor, the residence time required for the reaction is given by.
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