Water Gas Shift Reaction: Research Developments and Applications

Smirniotis

Chapter 1

Introduction About WGS Reaction

Abstract

This chapter mainly explains history and background of the WGS reaction. This chapter gives brief description about thermodynamic, kinetic and mechanistic aspects of the WGS reaction. This chapter also explains various ways to conduct WGS reaction, i.e., homogeneous, heterogeneous, membrane and photo-assisted WGS reactions. This chapter also gives brief introduction about various types of catalysts such as high temperature (HT), low temperature, sulphur tolerant and ultra HT catalysts used for the WGS reaction. Various metals and metal oxides investigated for the WGS reaction were also presented in this chapter.

Keywords

Water-gas shift reaction (WGSR)

Thermodynamics

Membrane reactors

Photo-catalysis

Homogeneous catalysis

Noble metals

Modified ferrites

Cu-based catalysts

1.1 History and Background

1.1.1 Water Gas

Water gas is an equimolar mixture of carbon monoxide and hydrogen. It can be synthesized by passing steam through coke. During late nineteenth century town gas developed the manufacturing process for the water gas.

(1.1)

The reaction is endothermic, so the fuel must be continually re-heated to keep the reaction going. In order to do this, an air stream, which alternates with the vapour stream, is introduced for the combustion of carbon.

(1.2)

These two reactions take place in cycle basis, as the temperature of the second reaction reaches sufficiently high the steam cycle restarts. Because of the wide temperature range in reality a small amount of carbon dioxide is always present in the water gas. Because of contamination in the air blow cycle a small amount of nitrogen is also present in the water gas.

In the early 1990s, production of water gas using steam reforming of methane received tremendous importance if the ultimate objective is generation of pure hydrogen since it provides highest molar ratio of H2/CO of Equation (1.3).

(1.3)

Partial oxidation of methane is another way to produce water gas (Equation 1.3). This process is mainly used when we need lesser H2/CO ratio and if there are difficulties in external heat supply, internal heat generation is needed as in the case of fuel processors for fuel cell applications. Partial oxidation of methane produces H2/CO in a ratio of 2. If we need H2/CO in a ratio of 1, dry reforming of methane can be done (Equation 1.4).

(1.4)

(1.5)

Water gas is used extensively in the industry for the manufacture of ammonia, methanol, hydrogen (for hydrotreating, hydrocracking of petroleum fractions and other hydrogenations in the petroleum refining and petrochemical industry), hydrocarbons (by the Fischer-Tropsch process) and metals (by the reduction of the oxide ore).

1.1.1.1 Types of Water Gas

1.1.1.1.1 Carburetted Water Gas

Water gas had a lower calorific value than coal gas, so the calorific value was often boosted by passing the gas through a heated retort into which oil was sprayed. The resulting mixed gas was called carburetted water gas.

1.1.1.1.2 Semi-Water Gas

Semi-water gas is a mixture of water gas and producer gas made by passing a mixture of air and steam through heated coke. The heat generated when producer gas is formed keeps the temperature of the coke high enough to allow water gas to be formed.

1.1.2 Water-Gas Shift Reaction

The water-gas shift reaction (WGSR) was discovered by Italian physicist Felice Fontana in 1780 [1,2]. However, the reaction was first patented by the British scientists Ludwig Mond and Langer C in 1888 for fuel cell application in coal gasification [3]. Ludwig Mond, one of the greatest chemist-industrialists of all time, focused part of his industrial chemical technology developments on the synthesis of ammonia from coal. Mond developed the process for producing the so-called Mond gas (the product of the reaction of air and steam passed through coal/coke – CO2, CO, H2, N2, etc.), which became the basis for future coal gasification processes [4]. Mond and his assistant Carl Langer were the first to use the term ‘fuel cells’ while performing experiments with the world’s first working fuel cell using coal-derived Mond gas [4]. One of the hardest tasks was to feed pure hydrogen to the ‘Mond battery’ due to the large quantities of carbon monoxide present in Mond gas, which poisoned the Pt electrode. Therefore, Mond solved this problem by passing the Mond gas mixture and steam over finely divided nickel at 400 °C, reacting the carbon monoxide and steam to give carbon dioxide and more hydrogen. This reaction is termed as ‘Water-Gas Shift Reaction’. After CO2 removal by a simple alkaline wash, the H2-rich stream obtained could be successfully fed to the hydrogen cell [5].

The WGSR is a reversible chemical reaction between carbon monoxide and steam to form carbon dioxide and hydrogen.

(1.6)

In the past, ammonia synthesis plants used water-gas process to produce hydrogen since it provides an economical way to produce hydrogen in the quantity required by the Haber ammonia synthesis process [6,7]. In the ammonia synthesis plant, first CO was removed from water gas by liquefication and scrubbing with hot caustic soda solution. Very soon they realized that the carbon monoxide liquefication process was unsuitable for large-scale plants. Then they used WGSR to convert CO into CO2 by passing steam into the water-gas mixture. In this way, in 1913, the WGSR found industrial application in the production of synthesis gas as a part of the Haber-Bosch process of ammonia manufacture. Industrially, the process integration of the WGS reaction is dependent upon the origin of the synthesis gas. By the beginning of the twentieth century, and because the major source of synthesis gas was from coal and coke, the WGS reaction was used as a standalone process. By that time, the most common and economical design was to conduct the reaction in a single stage, at temperatures around 450-600 °C, and employing Fe oxide stabilized in Cr oxide as catalyst [5]. The next evolution of the process was the introduction of a second-stage converter at temperatures around 320-360 °C using the same catalyst. The two-stage converter systems reduced the CO level to 3000-4000 ppm compared to the single-stage converters that could not reduce the CO content to much less than 10,000 ppm (1%) [8]. With the discovery, in the 1960s, of Cu-based low-temperature (LT) shift catalysts and improvements in high-temperature (HT) Fe-based shift catalysts, a CO content of < 0.5% in the reformate stream was achieved [9].

In 1914, BASF scientists Bosch and Wild [10] screened a series of metallic oxides for their ability to accelerate the attainment of the water-gas shift equilibrium and discovered iron oxide/chromium oxide type catalyst which can convert carbon monoxide to carbon dioxide by reacting with steam. In this way, Bosch and Wild reported the first industrial catalyst for the WGSR. The iron based discovered by BASF still forms the basis for today’s HT WGS catalyst.

In terms of coal gasification process to produce hydrogen for the ammonia synthesis via Haber process, coal/coke was first blasted with air in a water-gas generator, exothermically producing carbon dioxide and carbon monoxide, thereby maintaining the HT of the coal (around 1000 °C) and raising it into an incandescent form. The water gas (CO + H2) was then produced via an endothermic reaction (C + H2O → CO + H2), by passing steam through the fuel bed. After the removal of dust particles, the mixed gas was added to steam, and CO was catalytically shifted in a converter to produce more hydrogen and carbon dioxide. Then, the gas was dried and compressed and passed through caustic scrubbers for CO2 removal. By passing the gas mixture counter currently over an ammoniacal cuprous solution, the CO was posteriorly eliminated by absorption [5].

As a fundamental part of ammonia synthesis and coal gasification to produce hydrogen, the WGSR continues to maintain important position in chemical industry. From the beginning of the twentieth century until today, the use of the WGS reaction followed the increased industrial demand for hydrogen production. This has been accomplished using natural gas as feedstock instead of coal and employing better catalysts that improve the yields and permit the adjustment of the H2 to CO ratio of the product, mainly for ammonia and methanol synthesis but also for the Fisher-Tropsch process and in refining operations (desulphuration, hydrogenation processes, etc.). The WGS process facilities are economically dependent on the feedstock used for the syngas generation, both in terms of equipment and catalysts. Coal, the most abundant fossil fuel on the planet, is being looked at as the possible future major source of H2, due to the development of the integrated gasification combined cycle (IGCC) and integrated gasification fuel cell (IGFC) technologies. The gasification of coal produces syngas consisting of predominately CO and H2 with some remaining hydrocarbons, CO2 and water. The syngas then can be used directly to produce electricity or further processed and purified to give pure hydrogen product for such end uses, for ammonia production or hydrocracking of petroleum, or as a fuel for fuel cells to power vehicles and for stationary electricity production.

1.2 Thermodynamic Considerations

WGSR is a reversible exothermic reaction. The equilibrium constant and equilibrium CO conversion decrease with increasing temperature. The CO conversion and H2 production favour at lower temperatures. Since the reaction is reversible, the rate of forward reaction is strongly inhibited by the reaction products. The equilibrium constant as a function of temperature is shown in Figure 1.1.

   (1.7)

Figure 1.1 Effect of temperature on equilibrium constant.

Equation (1.7) is widely seen in the literature to describe the equilibrium constant (Kp) as a function of temperature [11]: From Figure 1.1 one can say that the CO content at equilibrium can be 20 times lesser at 200 °C than at 400 °C. In the WGS reaction, the effect of reaction pressure does not affect the equilibrium of the WGS reaction because there is no variation in the number of moles during the course of the reaction.

Nevertheless, up to that point (i.e., up to the equilibrium), total pressure positively affects the CO conversion because it increases the reaction rate. However, the addition of steam effects the rate of forward reaction. Addition of more amount of steam than the stoichiometric ratio improves the CO conversion by pushing the equilibrium towards right. Figure 1.2 shows the effect of steam to CO ratio (R) and temperature on the equilibrium CO conversion for the WGSR. In the adiabatic single bed reactor, the CO conversion is thermodynamically limited – as the reaction proceeds the heat of reaction increases the operating temperature, and so restricts the conversion possible. The maximum CO conversion that can be achieved in the single bed adiabatic reactor over iron-chromia catalysts is 96-98% in the ammonia plant. Because it is necessary to operate these catalysts at relatively high inlet temperature (370-420 °C) they are known as HT shift catalysts.

Figure 1.2 Effect of steam to CO ratio ( R ) on equilibrium CO conversion as a function of temperature.

The method of producing the syngas will also affect the WGS equilibrium compositions. For example auto-thermal reforming produces a syngas with lower H2 concentration (due to the dilution with nitrogen) compared to steam reforming. The lower H2 concentration increases the equilibrium CO conversion, whereas the high H2 concentration expected with steam reforming lowers the equilibrium CO conversion. The typical outlet syngas composition of the ammonia synthesis plant and outlet syngas composition for the auto-thermal reforming process after the WGS reaction are presented in Table 1.1. The CO, H2 and CO2 contents in the outlet of auto-thermal reformate depend on several factors such as operation temperature, pressure, steam to CO ratio and oxygen to carbon ratio. The effect of temperature and water concentration on the equilibrium CO conversion for the WGS reaction is shown in Figure 1.3 for a typical dry reformate gas used in a large-scale hydrogen or syngas production plant, excluding any residual hydrocarbons. It is clear from Figure 1.3 that an increase in the molar steam to dry gas (S/G) ratio improves the equilibrium CO conversion, especially above 150 °C.

Table 1.1

Typical exit syngas compositions (%) of the ammonia synthesis plant and auto-thermal reforming for H2 production

Figure 1.3 Equilibrium CO conversions of a typical reformate stream from a methane steam reforming process at various steam to dry gas ( S / G ) ratios. Taken from D. Mendes, A. Mendes, L.M. Maderia, A. Lulianelli, J.M. Sousa, A. Basile, Asia-Pac. J. Chem. Eng. 5 (2010) 111.

Similarly, the syngas composition from the coal gasifier depends on several factors such as type of coal used, operating temperature, steam addition, etc. The syngas composition at the outlet of coal gasifier also influences the equilibrium CO conversion in the WGSR. National Energy Technology Laboratory in their report to the DOE in 2008 reported the raw syngas composition of different IGCC technologies that are operated in USA. Different syngas compositions of different IGCC plants in USA are presented in Table 1.2.

Table 1.2

Different syngas compositions in different IGCC plants

Mendes et al. [12] reported the equation to determine the equilibrium constant in the WGSR for syngas as a reactant based on the feed composition and assuming ideal gas behaviour

(1.8)

where yi refers to the molar fraction of species i at the reactor inlet.

As stated above, complete CO conversion is possible only at lower temperatures, i.e., around 200 °C. However, the Fe-Cr catalyst is inactive at these temperatures. Hence, the thermodynamic equilibrium limitation can be overcome by using multi-stage water-gas shift reactor or by using two or more beds of HT shift catalyst with inter bed cooling. By late 1950s, researchers successfully reduced the CO concentration to 1% at the exit of the WGS reactor and decreased the thermodynamic limitation [13]. Even though the CO concentration was reduced to 1%, still the remaining CO has to be removed by absorption in cooper liquor. Some plants also used methanator because of the simplicity of process and accepted the attendant hydrogen loss. Hence, attempts are made to improve the CO conversion and that led to the development of cooper-based catalyst in early 1960s which can operate at much lower temperatures compared to the Fe-Cr catalyst.

Then, the significant improvement in the CO conversion was obtained by introducing multi-stage water-gas shift reactor in the ammonia synthesis plant. The first stage is characterized by working at higher temperatures, favouring fast CO consumption and minimizing catalyst bed volume. In the following stages, the reaction takes place at progressively lower temperatures for obtaining higher conversions, which are limited by the reaction equilibrium. The lower limit of the operating temperature in the LTS reactor is the dew point of water at the operating pressure (190-200 °C at 30 bars). Condensed steam affects, adversely, the catalytic activity of the Cu-based LTS catalysts. The catalyst for the first stage reactor is Fe-Cr and for the second-stage reactor is Cu-based catalyst. These copper-based catalysts are known as LT shift catalysts. During the first stage CO concentration levels reduced to 3-5% and during the second stage the CO concentration levels further reduced to 0.1-0.3% which is acceptable for subsequent methanation in an economic way. In the multi-stage water-gas shift reactor setup, the outlet gas temperature after HT water-gas shift converter will be more than 400 °C, whereas we would conduct LT shift at 200 °C. Hence, it is important to lower the temperature of the syngas at the exit of the HT shift converter. Inter-stage cooling system is used to decrease the syngas temperature before LT shift. Inter-stage cooling is usually achieved by heat exchange. In some cases the temperature may also be decreased by injecting steam or condensate into the syngas.

1.3 Ways to Conduct WGSR

There are three different ways to conduct WGS reaction with respect to the reactors.

1.3.1. WGS reaction in traditional catalytic reactor

1.3.2. WGS reaction in membrane catalytic reactor

1.3.3. Photo-catalytic WGS reaction

1.3.1 WGS Reaction in Traditional Reactor

In traditional catalytic reactor, we can conduct WGS reaction in two different ways: homogeneous catalytic WGS reaction and heterogeneous catalytic WGS reaction.

1.3.1.1 Homogeneous Catalytic WGS Reaction

If the catalyst and reactant are in the same state (in this case both are in liquid state) then the reaction is called homogeneous WGS reaction. In 1953, Reppe was the first researcher who discussed the concept of homogeneous WGS reaction [14]. Although he published a number of catalytic reactions of CO and H2O with organic substrates, Fenton was the first person who patented the homogeneous catalysis of the WGSR. He filed three patents on homogeneous WGS reaction by using group VIII metals in conjunction with phosphine, arsine or stibine ligands and amine or inorganic bases [15–17]. In 1977, Cheng et al. first ever reported homogeneous WGS reaction using Rh carbonyl iodide in open literature in aqueous solution [18]. In the same year, Laine et al. reported Rh carbonyl for the WGS reaction in the alkaline solution [19]. Kang et al. also reported the variety of group VIII metals for the homogeneous WGS catalysts as active catalysts in base medium [20]. On the other hand, Baker et al. reported the active WGS catalysts in acidic solutions over Rh carbonyl complexes in the same year [21].

1.3.1.1.1 Heterogeneous Catalytic WGS Reaction

If the catalyst and reactant are in different states (in this case catalyst was in solid state and reactant was in gaseous state) then the reaction is called heterogeneous WGS reaction. All the industries use heterogeneous WGS reaction to conduct WGS reaction. Two different catalyst beds are utilized, one at higher temperature and the other at lower temperature to achieve 100% CO conversion. The different catalysts used for heterogeneous WGS reaction are presented in the following section.

1.3.2 WGSR in Membrane Reactors

1.3.2.1 Membrane Reactor

Membrane reactor is a catalytic reactor that additionally contains cylinder of some porous material within it, the tube within the shell of a shell-and-tube heat exchanger. This porous inner cylinder is the membrane that gives the membrane reactor its name.

A simple example of catalytic ceramic membrane reactor is shown in Figure 1.4. The membrane is a barrier that allows only certain components to pass through it. The selectivity of the membrane is controlled by its pore diameter, which can be on the order of Angstroms, for micro-porous layers, or on the order of microns for macro-porous layers. Membrane reactors combine reaction with separation to increase conversion. One of the products of a given reaction is removed from the reactor through the membrane, thus forcing the equilibrium of the reaction ‘to the right’ (according to Le Chatelier’s principle), so that more of that product is generated. A catalytic membrane reactor has a membrane that has either been coated with or is made of a material that contains catalyst, which means that the membrane itself participates in the reaction. Some of the reaction products (those that are small enough) pass through the membrane and exit the reactor on the permeate side.

Figure 1.4 Schematic diagram of the membrane reactor.

We know that due to thermodynamic limitations it is difficult to achieve 100% CO conversion. The CO conversion depends on the nature of the catalyst and temperature range, and therefore the reaction is clearly more effective in membrane reactors. In the WGS membrane reactor it is possible to achieve 100% CO conversion in single stage and H2/CO2 separation. Based on the membrane properties WGS membrane reactors are classified into two categories, namely, CO2 selective membrane reactors and H2 selective membrane reactors. In the CO2 selective membrane reactors, CO2 was removed from the catalytic membrane reactor and the reaction mixture becomes H2 rich steam. This may cause over reduction of Fe- or Cu-based catalysts. However, in the H2 selective membrane, CO2 will be present at a higher concentration in the reaction medium, affecting the reaction rate. The membrane reactor offers many potential advantages: reduced capital and downstream separation costs, as well as enhanced yields and selectivity. From the viewpoint of the WGS process in an membrane reactor, a reaction product moves to the permeate side, enabling the WGS reaction to proceed towards completion and so making it possible to achieve the following: (1) higher conversion than a TR working under the same operating conditions or (2) the same conversion as a TR, but working under milder operative conditions. Among the various membrane reactors, both Pd and zeolites membrane reactors received much attention because of their thermal stability, sulphur tolerance and better permeation properties. Among the various catalysts, Cu-, Pt-, Au-based catalysts are suitable for membrane reactor applications. More description about the type of the membranes, catalysts used, mechanism and kinetics of WGS membrane reactors will be presented in future chapters.

1.3.3 Photo-Catalytic WGS Reaction

In the photo-catalytic reaction we use visible or UV-light to irradiate the catalyst instead of light. The reaction is conducted at room temperature. Sato and White first reported the first photo-catalytic WGS reaction on Pt/TiO2 catalyst [22]. Then, they prepared NaOH-coated Pt/TiO2 catalysts for the photo-WGS reaction. When Pt/TiO2 was coated with NaOH, the photo-catalytic activity for WGS reaction increased significantly [23]. Yixuan et al. [24] proved that HT hydrogen treatment increases the photo-catalytic activity of Pt-TiO2 for the WGS reaction. They explained the new concept of strong metal-semiconductor interaction (SMScI) in connection with a proposed novel charge transfer mechanism for the WGS reaction. Tsai et al. [25] prepared Pt/TiO2 (100) catalyst and investigated for the photo-catalytic WGS reaction. Cole-Hamilton et al. has evaluated the [RuCl(CO)(bipy)2]C complex for the photochemical homogeneous WGS reaction [26]. However, not much research effort has been focused on photo-assisted WGS reaction because of its disadvantages for the