Reverse water gas shift reaction in an inconel reactor. Thermal design and optimization for reverse water gas shift rwgs reactors is particularly important to fuel synthesis in naval or commercial scenarios. Pdf multivariable control design for the water gas shift. Modeling and simulation of water gas sh ift reactor. 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. 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. Water gas shift wgs7 reaction and fischer troph synthesis fts8. Reverse rate constant of elementary reaction step k. In particular, emissions resulting from the use of hydrogen as fuel contain only water, one of the reasons why that.
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. Five different strontiumdoped lanthanum cobaltites, la1xsrxcoo3 0. 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. Zeolite membrane reactor for watergasshift reaction for. For carbon capture greater than 75%, two water gas shift reactors are required. Most of the reaction rates for the water gas shift wgs reaction were obtained from experiments under simplified laboratory conditions with specific catalysts. The reverse water gas shift reaction several investigations of the high temperature 1148 k, low pressure gas engineering, petroleum university of technology, ahwaz, iran. The experimental data were collected from literature. The reverse watergas 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.
An industrial case, petrochemicals, vivek patel, intechopen, doi. 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. The rwgs reactor with irreversibilities of heat transfer, chemical reaction and viscous. This side reaction produces h 2 o and decreases the h 2 co ratio to a value less than 1 at 400800c. 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 co produced is fed to a co hydrogenation reactor for fuel. Carbon dioxide conversion by reverse watergas shift. Pdf mathematical modeling of reverse watergas shift reaction. Similarly, trace co can also catalytically react with hydrogen to produce methane and water as shown in eq. 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. Study of watergas shift reaction on molybdenum carbide coating in a microreactor. 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. By assessing the maximum possible oxygen storage capacity and by calculating the reaction equilib. Watergas shift process for hydrogen production effects. An innovative process scheme to produce methanol from carbon dioxide is here presented and assessed via simulation. Kinetics and catalysis of the watergasshift reaction. Plasmaassisted catalytic reverse water gas shift reactor. Thermal design and optimization for reverse water gas shift rwgs reactors is particularly important to fuel synthesis in naval or.
Methane steam reforming, methanation and watergas shift. Catalyst development for watergas shift 193 table 1. In adiabatic operation mode, for achieving a co composition of 0. Evaluation of alternate water gas shift configurations for. Desireddy1, andrej pohar1, blaz likozar1 1 department of catalysis and chemical reaction engineering, national institute of chemistry, hajdrihova 19, 1001 ljubljana, slovenia. 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. In the carbon based hydrogen production, water gas shift reaction is the. The worlds progression towards the hydrogen economy is facilitating the production of hydrogen from various resources. Watergas shift process for hydrogen production effects of. Kinetics of the forward and reverse co shift reactions, journal of catalysis, 63, 8393. The simulation and design of the tubular reactor requires information on thermodynamics and on. Within such a context, this work evaluates the technical performance of a novel cmr, which utilizes two catalysts in series, rather than one. Kinetic modeling of low temperature watergas shift. The first reaction, the reverse water gas shift reaction, is a fast one.
Adsorption as a viable and cost effective process for gas separation was chosen for the co 2 co separation. The reverse water gas shift reaction, rwgsr, is the focus of this investigation. Mechanism of co formation in reverse watergas shift reaction. Rwgs has not been industrialized yet, the thermal design and optimization of the rwgs reactor using modern thermodynamic optimization. Modeling and simulation of water gas shift reactor. Palladiumbased catalytic membrane reactors cmrs effectively remove h 2 to induce higher conversions in methane steam reforming msr and water gas shift reactions wgs. The reverse water gas shift process rwgs for water.
Improving feal2o3 catalysts for the reverse watergas shift. In comparison with the reaction of co2 alone, hydrogen can significantly promote the co formation in the rwgs reaction. Eindhoven university of technology master study of watergas. Approach zeolite membrane reactor for water gas shift reaction.
Reverse watergas shift chemical looping for syngas. For an ideal cstr reactor, the residence time required for the reaction is given by. Nov 08, 2007 an increase of the reactor temperature is thermodynamically unfavorable for the water gas shift reaction. Simulation of hightemperature watergas shift reactors. Design of water gas shift converter posted in student. Water gas shift reactor design linkedin slideshare. In this paper, it will be critically discussed in short format why both technologies can only be operated economically and sustainably in defined.
They may in the near future act as enablers for improving carbon footprints of certain value chains. The formate derived from association of h2 and co2 is proposed to be the. Zeolite membrane reactor for water gas shift reaction for hydrogen production jerry y. The reverse water gas shift process rwgs for water and oxygen. Carbon monoxide and hydrogen if they are present in the mole ratio of 1.
Entropy generation minimization for reverse water gas shift. 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. 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. In the near future, an increasing amount of synthesis gas production will be based on coal gasification instead of natural gas. Water gas shift reaction over an iron oxidechromium oxide catalyst. Integration of methane steam reforming and water gas shift. 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. A significant reduction in the energy of activation for the hightemperature, highpressure reverse water gas shift reaction was observed. Evaluation of alternate water gas shift configurations for igcc systems august 5, 2009 prepared by. Gas separation by adsorption in order to increase co. Simulation results the highest conversion for hts inlet temperature 320. 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. Reactor design, modeling and optimization for the hightemperature methane pyrolysis and the reverse watergas shift reaction.
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. Reverse water gas shift reaction over supported cuni. Entropy generation minimization for reverse water gas. Study of the reverse watergas shift and dryreforming reactions conditions in. 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. Lin, henk verweij, peter smirniotis and junhang dong. The above reaction is actually the result of two reactions. Current research efforts are underway to explain this. The funders had no role in the design of the study. 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. 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.
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 thermodynamic equilibrium in the shift reaction can be enhanced to give more hydrogen yield by adding a co2 absorbent into the shift reactor. Once the kinetics is known, the reactor design can be made based on material balance. Modeling and simulation of water gas shift reactors. An increase of the reactor temperature is thermodynamically unfavorable for the water gas shift reaction. Design of watergas shift reactors journal article osti. Kinetic study of the reverse water gas shift reaction in. 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. Modeling and simulation of watergas shift reactors. Pdf study of the reverse watergas shift and dryreforming. Tom meyer 1and robert zubrin 2, 1boulder center for science and policy, p. Azcan proceedings of the world congress on engineering and computer science 2012 vol ii wcecs 2012, october 2426, 2012, san francisco, usa isbn.
Schematic view of the bench scale reactor system used in the kinetic data acquisition. Multisite microkinetic modelling damjan lasic jurkovic1, venkata d. 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. 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. Scheme of the reactor thermodynamic modeling of water gas shift reaction in supercritical water e. Modelling of the high temperature water gas shift reaction with stationary and transient experiments. Depending on the reaction conditions, the equilibrium for the water gas shift can be pushed in either the forward or reverse direction. Pdf entropy generation minimization for reverse water.
A steadystate kinetic model for methanol synthesis and. The design of active gold catalysts has several crucial requirements. Reactors jordan university of science and technology. 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. Reverse water gas shift reaction over supported cuni nanoparticle catalysts maxime lortie. The catalysts were characterized using xrd, tem, bet, h2tpr, and insitu xps. Analysis of design variables for watergasshift reactors by. Watergas shift modeling of coal gasification in an entrained.
Design of water gas shift converter student cheresources. This presentation does not contain any proprietary, confidential, or otherwise restricted information. Carbon dioxide conversion by reverse watergas shift chemical. Multivariable control design for the water gas shift reactor in a fuel processor. 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. Watergas shift modeling of coal gasification in an. 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. Eric grol, netl wenching yang, research and development solutions, llc saic netl contact. Process intensification with integrated watergasshift. The results indicated that the structure of ceo2 catalysts was significantly affected by the. Singh and saraf, 1977 is a go od example of this method. Reduction of co 2 to co via reverse watergas shift.
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. This first chapter begins with the background information on the wgs reaction. 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. Under certain operating conditions, co2 reduction via the bosch reaction may also occur, where co2 reacts with hydrogen to form. 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. Reactor design, modeling and optimization for the high. Co2 valorisation via reverse watergas shift reaction using advanced cs doped. The results are evaluated in order to generate a reactor concept. Zn ratio with a maximum activity obtained at approximately 0.
Simulation and control of water gas shift packed bed reactor with interstage cooling s z saw1. The reverse watergas shift reaction is endothermic and is preferred in co 2rich environments. Spectrokinetic investigation of reverse watergasshift. Compact and lightweight sabatier reactor for carbon dioxide. Pdf entropy generation minimization for reverse water gas. In this study, the reverse watergas shift reaction with chemical. Kinetics and catalysis of the water gas shift reaction. Sep 28, 2009 simulation results the highest conversion for hts inlet temperature 320. Reverse watergas shift on copperbased catalyst materials.
Additionally, a competing reverse water gas shift rwgs reaction, eq. An industrial case 57 operating pressure and hydrogen sulfide concentration with intrinsic rate expressions. Then the reference conditions for the reverse of the water gas shift and methanation are set. Pdznoal2o3 catalysts were studied for water gas shift wgs, methanol steam reforming, and reverse water gas shift rwgs reactions. This thesis comprises a systematic approach for the evaluation of the reverse watergas shift chemical looping rwgscl process for co2 utilization. Methane steam reforming, methanation and water gas shift. Eric grol office of systems, analyses and planning 4123865463 national energy technology laboratory l. Methanol production from co2 via reversewatergasshift. Simulation of watergasshift reaction program matlab. A single reactor common for the kinetic and the spectroscopic measurements was used. 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. The water gas shift wgs reaction is a wellknown step for upgrading carbon monoxide to hydrogen in the production of synthesis gas. Entropy generation minimization for reverse water gas shift rwgs. Analysis of design variables for watergasshift reactors.
Kinetics and catalysis of the watergasshift reaction worcester. The reverse water gas shift rwgs process is a candidate technology for water and oxygen production on mars. 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. There is inadequate conversion of co to co 2 to achieve greater than 75% carbon capture if only one shift reactor is used. Co 2 conversion amounts and rates were measured at different temperatures and partial pressures after various reduction procedures. Dry reforming and reverse water gas shift are often discussed as potential carbon dioxide sinks. Water gas shift reaction an overview sciencedirect topics. Equilibrium conversion for these conditions is 55%. Kinetics and catalysis of the watergasshift reaction chemical. The kinetics of water gas shift reaction was studied over commercial cuoznoal2o3 in an integral fixed bed reactor.
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