Undergraduate Journal of Mathematical

Modeling: One + Two

Volume 8 | 2018 Spring 2018 Article 5

2018

Optimization of a Water Gas Shift Reaction

Ali Albuloushi
University of South Florida

Advisors:
Arcadii Grinshpan, Mathematics and Statistics
Scott Campbell, Chemical and Biomedical Engineering

Problem Suggested By: Scott Campbell

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Recommended Citation
Albuloushi, Ali (2018) "Optimization of a Water Gas Shift Reaction," Undergraduate Journal of
Mathematical Modeling: One + Two: Vol. 8: Iss. 2, Article 5.
DOI: http://doi.org/10.5038/2326-3652.8.2.4892
Available at: https://digitalcommons.usf.edu/ujmm/vol8/iss2/5
Optimization of a Water Gas Shift Reaction

Abstract
The optimum flow rate of steam (H20) to the reactor for the purpose of producing hydrogen gas for sale
is determined.

Keywords
hydrogen gas, Fischer-Tropsch process, equilibrium constant, optimum flow rate

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 Albuloushi: Optimization of a Water Gas Shift Reaction
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PROBLEM STATEMENT
The continued use of fossil fuels all over the world leads to the increased emission of

greenhouse gases such as carbon dioxide into the atmosphere of the earth as it can be read in the

following statement from the United States Environmental Protection Agency (EPA)

“[greenhouse gases pose] significant risks to humans and the environment”. In the 2015 report

the Environmental Protection Agency estimated that an extremely high number of lives would be

saved if to increase the efforts to mitigate greenhouse gases [CIRA, 2015; EPA, 2017]. These

efforts include activities such as replacement of fossil fuels with alternatives such as sources of

biomass and hydrogen, or the use of renewable energy like geothermal, solar, and wind. The

other kinds of mitigation are to use production methods that have low emissions and reduce

carbon dioxide in the atmosphere through the expansion of forests. Hydrogen is an alternative

fuel that has recently gained worldwide support [TT, 2017]. This project focuses on the

increasing production of hydrogen in the industry.

The idea of a hydrogen economy has gained popularity over time, and the focus of the

consideration of hydrogen as a replacement source of fuel for hydrocarbons is on the increase.

Currently, hydrogen is largely produced industrially from reforming the steam; it uses fossil fuels

like coal, natural gas, or oil. This project aims to determine the maximizing conditions of the

production of hydrogen gas in industries through the use of the water gas shift reaction.

According to the United States Department of Energy (DOE), both the transportation and the

stationary energy sectors have a great potential for growth if hydrogen is used extensively.

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MOTIVATION
Knowing that fossil fuels are responsible for many forms of pollution, including the high

emission of greenhouse gases, the replacement of fossil fuels has recently been under

consideration. Given that hydrogen has been known to burn clean, i.e., it does not produce

polluting emissions and thus it does not impact negatively the environment. Maximizing its use

worldwide can be a considerable improvement for the environment. For instance, in Japan or

California, the Honda and Toyota industries have begun leasing fuel cell vehicles to the public.

However they face the challenge of high production costs of fuel cells and the lack of a refueling

network for hydrogen. These are major issues which the automakers are trying to address. Lack

of demand, safety, and cost are some of the reasons that cause oil companies to fail in setting up

hydrogen tanks at the existing gas stations.

Ditching of fossil fuels for hydrogen will come with a lot of benefits to the environment

in general. In fact, the burning of fossil fuels like natural gas, oil, and coal has been known to

take a heavy toll on the environment hence leading to a significant contribution to both global

problems like global warming and local problems like raised particulate levels. In addition, the

byproducts of running hydrogen-powered fuel cells are a trickle of water and oxygen, neither of

these byproducts can cause harm to the health of human beings or the environment. As at now, a

high fraction of the hydrogen that is available in the United States is either made by the use of

electrolytic processes which are powered by fossil fuels or extracted directly from the fossil

fuels, therefore negating real emissions savings or reducing the use of fossil fuels. A dream of a

clean hydrogen fuel can be realized if the source of the gas does not involve the use of fossil

fuels.

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Before hydrogen can replace fossil fuels, the problems associated with its utilization and

production need to be addressed, for instance, the shortage of infrastructure for its storage and

efficient distribution [Elghawi et al., 2008]. However, in the meantime, short term solution of

this problem can be on board production of hydrogen, this kind of production may, however,

have its setbacks. For example, the performance of the utilized catalysts during the process and

process units’ compactness [Cheekatamarla et al., 2008]. One of the processes that can aid in the

production of clean hydrogen gas is through the employment of the water gas shift reaction.

In 1780, Felice Fontana, an Italian physicist, discovered the water gas shift reaction and

much later, the industrial value of the reaction was realized. Early in the 20th century, hydrogen

gas was derived through reaction of steam under extremely high pressure to yield hydrogen, iron

oxide, and iron. With time, industrial processes, such as the Haber-Bosch process of ammonia

synthesis, that required hydrogen developed and an efficient and less expensive method of

producing hydrogen was required in order to save on costs. As a solution to the problem, the

water gas shift reaction was put together with coal gasification to produce pure hydrogen.

The Fischer-Tropsch process was developed originally by Hans Tropsch and Franz

Fischer during the early 1920s, it consists of a series of chemical reactions which involve the

conversion of carbon monoxide and hydrogen into hydrocarbons of the liquid state by employing

the use of a catalyst. The process also leads to the production of synthetic fuel and lubrication oil

such as biomass, coal, and natural gas which are of a general higher quality as compared to those

obtained from means of the convention with no aromatics or Sulphur. It has therefore gained

importance as a huge source of low-sulfur fuel and also in addressing the supply and cost of

hydrocarbons that are derived from petroleum. The conditions of the FT process are normally to

favor the production of liquid fuels with a higher molecular weight, it also involves some side

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reactions, and this is where the predominance of the water-gas-shift reaction is found. The

equation is as follows:

𝐶𝑂 + 𝐻2 0 → 𝐻2 + 𝐶02 . (1)

Based on the process employed, catalyst, and the temperature, a range of hydrocarbons

from methane to paraffin and higher molecular olefins can be obtained. Although the Fischer-

Tropsch synthesis employs the usage of several catalysts, the most common catalysts used

include cobalt, nickel, iron, and ruthenium transition metals. The selection of these catalysts is

however determined by the production of the diesel fuels and linear alkanes of a high molecular

weight. The tendency of Nickel to promote the formation of methane makes it less used, cobalt is

preferred over ruthenium since ruthenium has a higher cost, and also, cobalt is generally more

active. Iron has a relatively lower cost and a higher water-gas-shift activity, thus suitable for

deriving synthetic gas that has low hydrogen/carbon monoxide ratio. Promoters like potassium,

copper, and silica or alumina which are known to be high surface area binders and also inclusive

of the active metal that makes up the catalyst. The catalysts are prone to get poisoned if sulfur

compounds exist in synthetic gas.

The produced hydrogen has an energy content which is much less in comparison to that

of the original fuel, some energy is lost in the form of excessive heat in the process of

production, the process of steam reforming also results in emissions of carbon dioxide. 4 % of

hydrogen in 2004 is produced through the process of electrolysis that involves the use of water

and electricity.

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 Albuloushi: Optimization of a Water Gas Shift Reaction
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MATHEMATICAL DESCRIPTION AND SOLUTION APPROACH

The water gas shift reaction leads to the production of carbon monoxide (CO) together

with hydrogen which requires separation so as to derive pure hydrogen suitable for polymer

electrolyte membrane fuel cell (PEMFC) in order to avoid anode corrosion and enhance the

efficiency of the fuel cell. The water gas shift reaction (WGSR) is just but one of the many

methods that are used in purification of the hydrogen produced from reforming of hydrocarbons

and has therefore proven to be the most feasible method of purification technologically [Barbieri

et al., 2008]. It involves the reaction between steam (𝐻2 𝑂) and carbon monoxide (𝐶𝑂) to form

carbon dioxide and hydrogen in accordance with the following equation:

𝐶𝑂 + 𝐻2 𝑂 = 𝐻2 + 𝐶𝑂2 . (2)

To begin, the water gas shift reaction can be assumed to operate close to equilibrium, in which

case the moles of reactants and products are related by the equilibrium expression:
𝑛𝐻2 × 𝑛𝐶𝑂2
𝐾= . (3)
𝑛𝐶𝑂 × 𝑛𝐻2 𝑂

This Equilibrium expression is the ratio of the concentration of the products over the reactants,

where 𝑛𝐻2 , 𝑛𝐶𝑂2 , 𝑛𝐶𝑂 , and 𝑛𝐻2 𝑂 are the moles/sec of hydrogen, carbon dioxide, carbon monoxide

and steam leaving the reactor, respectively. The feed into the reactor consists only of CO and

𝐻2 𝑂. At the start, there is a basis of 1 mol/s of CO and S mols/s of steam entering the reactor.

The reactor is operated at 300 °C degrees, and the value of the equilibrium constant is 40. The

task is to find the value of S that will maximize the profit of the production of hydrogen.

To find the number of mols/s of C𝑂2 that react, let C𝑂2 = 𝑥. Using the process of Stoichiometry,

the number of moles for each compound in the reaction can be obtained:

𝐶𝑂(𝑔) + 𝐻2 𝑂(𝑔) = 𝐻2 (𝑔) + 𝐶𝑂2 (𝑔) . (4)

We can summarize the results given by equation (4) as follows:

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1) for every x moles of 𝐶𝑂 and 𝐻2 𝑂 that react, x moles of 𝐻2 and 𝐶𝑂2 are formed;

2) for every x moles of C𝑂2 produced, 1-x moles of CO react;

3) for every x moles of C𝑂2 produced, S-x moles of 𝐻2 𝑂 react;

4) for every x moles of C𝑂2 produced, x moles of 𝐻2 are also produced.

Using the number of moles found, an equation for the profit can be obtained. In order to have a

profit, from the sales of 𝐻2 we should subtract the cost of steam:

Profit = Sales of 𝐻2 − Cost of Steam (5)

This could be also written in the following form:

$ $
× 𝑛𝐻2 − 𝑚𝑜𝑙 𝐻 × 𝑛𝐻2 𝑂, (6)
𝑚𝑜𝑙 𝐻2 2𝑂

$
where 𝑚𝑜𝑙 𝐻 has the meaning of cost of 𝐻2 per mole produced, which is 8 times the cost of 𝐻2 𝑂,
2

$
𝑛𝐻2 is equal to x as found from Equation (1), is equal to the cost of 𝐻2 𝑂 per mole, and
𝑚𝑜𝑙 𝐻2 𝑂

n𝐻2 O is equal to the amount of steam (i.e. S).

The equation for the profit could be simplified:

𝑃 = 8 × Cost of 𝐻2 𝑂 × 𝑥 − Cost of 𝐻2 𝑂 × 𝑆 . (7)

Therefore:

𝑃 = 8𝑥 − 𝑆 . (8)

Equation (3) has to be solved for the equilibrium constant which [is]was given in order to

substitute into equation (8). We have:

𝑥2
40 = (1−𝑥)(𝑆−𝑥) . (9)

We can now solve for S:

𝑥(40−39𝑥)
𝑆= . (10)
40(1−𝑥)

Equation (8) now reads as:

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𝑥(40−39𝑥)
𝑃(𝑥) = 8𝑥 − . (11)
40(1−𝑥)

With this information, the maximum value of the profit can be found by taking the derivative of

the function P(x):

281x2 −562x+280
P ′ (x) = . (12)
40(1−x)2

We can now solve the quadratic equation in order to obtain the stationary points:

𝑥 2 − 2𝑥 + 280/281 = 0 . (13)

We obtain two roots of Equation (13):

𝑥1 ≈ 1.0597, (14)

𝑥2 ≈ 0.9403. (15)

The value given by (14) is not consistent as we cannot have a reaction with more than we feed on

CO. It follows that the only reasonable value for x is given by (15). We can now use it to find the

value of S from (10):

0.9403(40−39×0.9403)
𝑆= ≈ 1.31. (16)
40(1−0.9403)

Now, this implies that for every 0.9403 moles of CO and H2O that react, 0.9403 moles of CO2

and hydrogen gas are formed. And for every 0.9403 moles of CO2 moles that are produced,

(1 – 0.9403) moles = 0.0597 moles of carbon monoxide and (S – x ⇒ 1.31 – 0.9403) moles

= 0.3697 moles steam react. Also, for every 0.9403 moles of carbon dioxide produced, 0.9403

moles of hydrogen gas are also produced.

These are the amounts of each substance that should take part in the reaction water gas

shift reaction to ensure the attainment of maximum profits.

The production of maximum amounts of oxygen is required in order for maximum profits

to be obtained by the company, we have seen that for this to be achieved, the application of

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calculus is essential in the calculation of the values of the number of substances that are taking

part in the reaction to obtain maximum hydrogen gas, thus maximum profit. Through the use of

the maximum profit formula in Equation (3), the value of the maximum profit that can be

attainable by the company can then be calculated.

Discussion
The water gas shift reaction discussed is used in the Fischer-Tropsch reactor to adjust the

ratio of Carbon monoxide to Hydrogen gas while producing liquid fuels. Utilization of the water

gas shift reaction in the production of hydrogen, therefore, plays a vital role in the Fischer-

Tropsch reactor since hydrogen is one of the input gases. This process involves the combination

of hydrogen and carbon monoxide which are produced from natural gas, biomass, or coal in the

gasification process; it then turns the gases into a synthetic fuel and synthetic lubrication oil. This

process produces a wide variety of hydrocarbons (with the general formula CnH2n+2) through the

occurrence of a series of chemical reactions that lead to the production of alkanes as shown in

the following formula:

(2𝑛 + 1)𝐻2 + 𝑛𝐶𝑂 → 𝐶𝑛 𝐻2𝑛+2 + 𝑛𝐻2 𝑂,

where the value of n ranges between 10 and 20. Most alkanes that are produced through this

process are usually straight-chain and mostly used as diesel fuels. In addition, competing

reactions result in the formation of alcohols, alkenes, and even oxygenated hydrocarbons. The

conversion of the combination of CO and H2 into the different products is a multi-step reaction

that also produces several intermediates. The C-O bond in carbon monoxide is split and thus a

new bond of the form C-C is formed. For the production of one -CH2- group through the reaction

CO + 2H2 → (CH2) + H2O, the following reactions should take place:

• Adsorption of CO associatively;

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• The splitting of the C-O bond in carbon monoxide;

• Adsorption of 2H2 associatively;

• Formation of H2O through the transfer of 2H to the oxygen;

• H2O desorption;

• Formation of CH2 through the transfer of 2H to the carbon.

The product becomes incorporated with alcohol if isotopically labelled alcohol is added to the

feed stream.

CONCLUSION AND RECOMMENDATIONS

For profit maximization to occur in a company, maximum production of hydrogen gas is

required. For instance, if the reactor operates at a temperature of 300 °C and an equilibrium

constant K of 40, the number of moles of steam required for the water gas shift reaction as

calculated above is 1.31 moles. Given that when one mole of hydrogen is sold it yields 8 times

the cost of one mole of steam required for the feed, then the producing company can obtain more

steam which can in turn facilitate production of more hydrogen, required in large amounts for

more profits.

The water gas shift reaction, as it has been seen, yields carbon dioxide as one of its

products. Since the latter is a gas that may contribute to global warming, it would be relevant to

study other means of reducing the emission of carbon dioxide. An efficient method is through

dissolution in water at a pressure of approximately ten atmospheres. Carbon dioxide can also be

solidified to form dry ice and then used in this form as a refrigerant, this can then play a big role

during the shipping of perishable products. The formation of dry ice takes place when liquefied

and compressed carbon dioxide at a temperature of -57 °C or even lower is subjected to

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expansion till atmospheric pressure is attained. Spontaneous cooling will therefore occur and the

liquid will freeze to a solid, usually referred to as dry ice.

According to the results obtained above, the better results would be obtained if the use of

catalysts that are impregnated under vacuum conditions are used as opposed to those

impregnated under atmospheric conditions. Also, the optimum reaction temperature for the water

gas shift reaction process is found to be 500 °C, either operating at 550 °C or at 450 °C. This

process should therefore be carried out at its optimum conditions in order to obtain maximum

output, i.e. more hydrogen gas, which will in turn increase the profits.

For future research, it is recommendable to study the ratio of steam to carbon monoxide

and also that of hydrogen gas to carbon dioxide be varied in the experiments in order to correctly

find out the rate of dependence on the concentration of steam, carbon dioxide and hydrogen gas.

NOMENCLATURE
SYMBOL DESCRIPTION

C𝑂2 Carbon dioxide

CO Carbon monoxide

𝐻2 Hydrogen

𝐻2 O Steam

K Equilibrium constant

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°C Degrees Celsius

WGSR Water gas shift reaction

P Profit

S Steam

n Number of moles

x C𝑂2

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