Water-gas shift reaction

The water-gas shift reaction (WGSR) describes the reaction of carbon monoxide and water vapor to form carbon dioxide and hydrogen (the mixture of carbon monoxide and hydrogen is known as water gas):

CO + H₂O $\rightleftharpoons$ CO₂ + H₂

The water gas shift reaction was discovered by Italian physicist Felice Fontana in 1780. It was not until much later that the industrial value of this reaction was realized. Before the early 20th century, hydrogen was obtained by reacting steam under high pressure with iron to produce iron, iron oxide and hydrogen. With the development of industrial processes that required hydrogen, such as the Haber–Bosch ammonia synthesis, the demand for a less expensive and more efficient method of hydrogen production was needed.^[1] As a resolution to this problem, the WGSR was combined with the gasification of coal to produce a pure hydrogen product. As the idea of hydrogen economy gains popularity, the focus on hydrogen as a replacement fuel source for hydrocarbons is increasing.

Applications

The WGSR is an important industrial reaction that is used in the manufacture of ammonia, hydrocarbons, methanol, and hydrogen. It is also often used in conjunction with steam reforming of methane and other hydrocarbons. In the Fischer–Tropsch process, the WGSR is one of the most important reactions used to balance the H₂/CO ratio. It provides a source of hydrogen at the expense of carbon monoxide, which is important for the production of high purity hydrogen for use in ammonia synthesis.

The water-gas shift reaction may be an undesired side reaction in processes involving water and carbon monoxide, e.g. the rhodium-based Monsanto process. The iridium-based Cativa process uses less water, which suppresses this reaction.

The equilibrium of this reaction shows a significant temperature dependence and the equilibrium constant decreases with an increase in temperature, that is, higher carbon monoxide conversion is observed at lower temperatures. In order to take advantage of both the thermodynamics and kinetics of the reaction, the industrial scale water gas shift reaction is conducted in multiple adiabatic stages consisting of a high temperature shift (HTS) followed by a low temperature shift (LTS) with intersystem cooling.^[2] The initial HTS takes advantage of the high reaction rates, but is thermodynamically limited, which results in incomplete conversion of carbon monoxide and a 2-4% carbon monoxide exit composition. To shift the equilibrium toward hydrogen production, a subsequent low temperature shift reactor is employed to produce a carbon monoxide exit composition of less than 1%. The transition from the HTS to the LTS reactors necessitates intersystem cooling. Due to the different reaction conditions, different catalysts must be employed at each stage to ensure optimal activity. The commercial HTS catalyst is the iron oxide–chromium oxide catalyst and the LTS catalyst is a copper-based catalyst. The order proceeds from high to low temperature due to the susceptibility of the copper catalyst to poisoning by sulfur that may remain after the steam reformation process.^[3] This necessitates the removal of the sulfur compounds prior to the LTS reactor by a guard bed in order to protect the copper catalyst. Conversely, the iron used in the HTS reaction is generally more robust and resistant toward poisoning by sulfur compounds. While both the HTS and LTS catalysts are commercially available, their specific composition varies based on vendor. An important limitation for the HTS is the H₂O/CO ratio where low ratios may lead to side reactions such as the formation of metallic iron, methanation, carbon deposition, and Fischer–Tropsch reaction.

Low temperature shift (LTS)

The typical composition of commercial LTS catalyst has been reported as 32-33% CuO, 34-53% ZnO, 15-33% Al₂O₃.^[3] The active catalytic species is CuO. The function of ZnO is to provide structural support as well as prevent the poisoning of copper by sulfur. The Al₂O₃ prevents dispersion and pellet shrinkage. The LTS shift reactor operates at a range of 200 ^oC to 250 ^oC. Low reaction temperatures must be maintained due to the susceptibility of copper to thermal sintering. These lower temperatures also reduce the occurrence of side reactions that are observed in the case of the HTS.Noble metals such as Pt supported on ceria has been extensively used for LTS.^[4]

High temperature shift catalysts

The typical composition of commercial HTS catalyst has been reported as 74.2% Fe₂O₃, 10.0% Cr₂O₃, 0.2% MgO (remaining percentage attributed to volatile components).^[5] The chromium acts to stabilize the iron oxide and prevents sintering. The operation of HTS catalysts occurs within the temperature range of 310 ^oC to 450 ^oC. The temperature increases along the length of the reactor due to the exothermic nature of the reaction. As such, the inlet temperature is maintained at 350 ^oC to prevent the exit temperature from exceeding 550 ^oC. Industrial reactors operate at a range from atmospheric pressure to 8375 kPa.^[5]

Fuel cells

The WGSR can aid in the efficiency of fuel cells by increasing hydrogen production. The WGSR is considered a critical component in the reduction of carbon monoxide concentrations in cells that are susceptible to carbon monoxide poisoning such as the proton exchange membrane (PEM) fuel cell.^[1] The benefits of this application are two-fold: not only would the water gas shift reaction effectively reduce the concentration of carbon monoxide, but it would also increase the efficiency of the fuel cells by increasing hydrogen production.^[1] Unfortunately, current commercial catalysts that are used in industrial water gas shift processes are not compatible with fuel cell applications.^[3] With the high demand for clean fuel and the critical role of the water gas shift reaction in hydrogen fuel cells, the development of water gas shift catalysts for the application in fuel cell technology is an area of current research interest.

Catalysts for fuel cell application would need to operate at low temperatures. Since the WGSR is slow at lower temperatures where equilibrium favors hydrogen production, WGS reactors require large amounts of catalysts, which increases their cost and size beyond practical application.^[1] The commercial LTS catalyst used in large scale industrial plants is also pyrophoric in its inactive state and therefore presents safety concerns for consumer applications.^[3] Developing a catalyst that can overcome these limitations is relevant to implementation of a hydrogen economy.

Reaction conditions

While the WGSR has been extensively studied for over a hundred years, the mechanism remains under debate. A universal rate expression and mechanistic understanding have proven elusive, reflecting the many reaction variables, vagarities of the catalyst, and the proprietary nature of commercial processes.^[2]

Temperature dependence

A plot of the temperature dependence of K_eq, the value of which approaches 1 at 1100 K.^[3]

The water gas shift reaction is a moderately exothermic reversible reaction. Therefore with increasing temperature the reaction rate increases but the conversion of reactants to products becomes less favorable.^[6] Due to its exothermic nature, high carbon monoxide conversion is thermodynamically favored at low temperatures. Despite the thermodynamic favorability at low temperatures, the reaction is kinetically favored at high temperatures. The water-gas shift reaction is sensitive to temperature, with the tendency to shift towards reactants as temperature increases due to Le Chatelier's principle. Over the temperature range 600 – 2000 K, the logarithm of the equilibrium constant for the WGSR is given by the following equation:^[3]

$\log_{10} K_\mathrm{eq} = -2.4198 + 0.0003855T + \frac{2180.6}{T}$

Mechanism

Two main mechanisms have been proposed: an associative ‘Langmuir–Hinshelwood’ mechanism, and a regenerative ‘redox’ mechanism. While the regenerative mechanism is generally implemented to describe the WGS at higher temperatures, at low temperature both the redox and associative mechanisms are suitable explanations.^[7]

Associative and Redox Mechanism of the Water Gas Shift

Associative mechanism

In 1920 Armstrong and Hilditch first proposed the associative mechanism. In this mechanism CO and H₂O are adsorbed onto the surface of the metal catalyst followed by the formation of an intermediate and the desorption of H₂ and CO₂. In the initial step, H₂O dissociates into a metal adsorbed OH and H. The hydroxide then reacts with CO to form a carboxyl or formate intermediate which subsequently decomposes into CO₂ and the metal adsorbed H, which ultimately yields H₂. While this mechanism may be valid under LTS conditions, the redox mechanism which does not involve any long lived surface intermediates is a more suitable explanation of the WGS mechanism at higher temperatures.

Redox mechanism

The regenerative ‘redox’ mechanism is the most commonly accepted mechanism for the WGSR. It involves a regenerative change in the oxidation state of the catalytic metal. In this mechanism, H₂O is activated first by the abstraction of H from water followed by dissociation or disproportionation of the resulting OH to afford atomic O. The CO is then oxidized by the atomic O forming CO₂ which returns the catalytic surface back to its pre-reaction state. Alternatively, CO may be directly oxidized by the OH to form a carboxyl intermediate, followed by the dissociation or disproportionation of the carboxyl. Finally H is recombined to H₂ and CO₂ and H₂ are desorbed from the metal. The principal difference in these mechanisms is the formation of CO₂. The redox mechanism generates CO₂ by reaction with adsorbed oxygen, while the associative mechanism forms CO₂ via the dissociation of an intermediate. The mechanism of decarboxylation is debated; it may involve β-hydride elimination, or it may require the action of an external base.

Homogeneous models

Useful mechanistic insights resulted from the discovery that metal carbonyls catalyze the WGSR.^[8] The basic reaction entails nucleophilic attack of water or hydroxide on a M-CO center, generating a metallacarboxylic acid.^[1][9]

Reverse water-gas shift

Reverse water-gas shift flow cycle

Depending on the reaction conditions, the equilibrium for the water gas shift can be pushed in either the forward or reverse direction. The reversibility of the WGSR is important in the production of ammonia, methanol, and Fischer–Tropsch synthesis where the ratio of H₂/CO is critical. The RWGS reaction is also gaining interest in the context of the human missions to Mars primarily for its potential to produce water and oxygen.^[10][11] The Mars atmosphere is about 95% CO₂ which can be utilized by the RWGS reaction given a source of hydrogen. Coupling the RWGS with the water electrolysis process will yield methane and oxygen. Post electrolysis, the hydrogen produced can be recycled back into the RWGS reactor for the continued conversion of CO₂. Because this reaction is only mildly endothermic, the thermal power needed to drive this reaction can potentially be produced by a Sabatier reactor.

See also

• In-situ resource utilization
• Lane hydrogen producer
• PROX
• Industrial catalysts

References

1. Lamm, editors, Wolf Vielstich, Hubert Gasteiger, Arnold (2003). Handbook of fuel cells : fundamentals, technology, applications (Reprinted ed.). New York: Wiley. ISBN 0-471-49926-9.
2. Smith R J, Byron; Muruganandam Loganthan; Murthy Shekhar Shantha (2010). "A Review of the Water Gas Shift Reaction". International Journal of Chemical Reactor Engineering 8: 1–32. doi:10.2202/1542-6580.2238.
3. Callaghan, Caitlin (2006). "Kinetics and Catalysis of the Water-Gas-Shift Reaction".
4. Jain, Rishabh. "Synthesis of nano-Pt onto ceria support as catalyst for water–gas shift reaction by Reactive Spray Deposition Technology". Applied Catalysis A: General 475: 461–468. doi:10.1016/j.apcata.2014.01.053. Retrieved 14 September 2014.
5. Newsome, David S. (1980). "The Water-Gas Shift Reaction". Catalysis Reviews: Science and Engineering 21 (2): 275–318. doi:10.1080/03602458008067535.
6. Ratnasamy, Chandra; Wagner, Jon P. (September 2009). "Water Gas Shift Catalysis". Catalysis Reviews 51 (3): 325–440. doi:10.1080/01614940903048661.
7. Giuseppe, Brenna (2010). "NEW CATALYST FOR THE H2 PRODUCTION BY WATER-GAS SHIFT REACTION PROCESSES". Dissertation.
8. Jacobs, G.; B. H. Davis (2007). "Low temperature water-gas shift catalysts". Catalysis 20: 122–285. doi:10.1039/B601305H.
9. Barakat, Tarek; Rooke, Joanna C.; Genty, Eric; Cousin, Renaud; Siffert, Stéphane; Su, Bao-Lian (1 January 2013). "Gold catalysts in environmental remediation and water-gas shift technologies". Energy & Environmental Science 6 (2): 371. doi:10.1039/c2ee22859a.
10. Whitlow, Jonathan E.; Parish (2003). "Operation, Modeling and Analysis of the Reverse Water Gas Shift Process". doi:10.1063/1.1541409.
11. Zubrin, R. The Case for Mars. p. 153. ISBN 0-684-83550-9.