1. Introduction
Between 2000 and 2013, global energy demand grew by 38%. It is estimated that the world population will reach approximately 7.5 billion in 2025, with a 50–60% increase in global energy consumption in relation to current consumption [
1]. Recently, many leading energy, transport and industrial companies have started initiatives to develop the energy transition with hydrogen [
2]. However, to satisfy the increasingly demand for it, large-scale industrial processes must be developed for producing it. One such process is partial oxidation [
3], in which a hydrocarbon feedstock is partially oxidized with oxygen to produce hydrogen after an exothermal reaction. Another method used is hydrocarbon pyrolysis, in which hydrogen is obtained after the thermal decomposition of a hydrocarbon feedstock. However, one of the best methods for large-scale hydrogen production is steam methane reforming (SMR). SMR is an endothermal process in which methane reacts with steam to produce hydrogen. In this process, high-purity hydrogen can be obtained and different by-products generated during the reforming reactions can be reused. Over 50% of the world's H
2 production comes from SMR [
4].
Therefore, large amounts of energy are required in these industrial processes, and it is essential to know the maximum amount of energy they need. To better understand this, many authors have carried out different energetic analyses in which key variables were studied to identify how to make the industrial plant, as a whole, more energy efficient. Process simulation software was used in this research as an optimal tool for modelling these chemical processes. In this respect, Imran et al. [
5] developed a simulation, validation and sensitivity analysis of typical SMR using Aspen Plus
® software. They concluded that the steam-to-carbon ratio and reformer temperature were two of the most important variables for optimizing the process. Similarly, Pashchenko [
6] studied heat integration in the reformer section. A schematic diagram was made of thermochemical recovery by steam methane reforming. Moreover, Cui et al. [
7] simulated cracking, partial oxidation, steam reforming and oxidative steam reforming of butane and propane in order to predict carbon formation and catalysts deactivation, using Gibbs free energy minimization method in Aspen Plus
®. They found that carbon formation only occurred at low steam-to-carbon ratios, while the maximum level of carbon formation was found at 550–650 °C.
With the data obtained from the software simulation, modifications in the process that may potentially improve energetic performance may be studied. Energy efficiency is evaluated as being the ratio of the amount of energy that enters and leaves a system and is obtained by energy balances. Even though this kind of analysis is quite useful for optimizing the process, it can neither identify efficiencies nor evaluate them correctly. For this reason, the second law of thermodynamics and the exergy concept are applied. The exergy of a thermodynamic system may be defined as the quantity of useful work that this system could do when it is brought into equilibrium with its surroundings.
Many authors have already developed this kind of analysis in different chemical processes. BoroumandJazi et al. [
8] used the exergetic analysis for studying different industrial sectors in a variety of countries. They evaluated the performance of the industry and linked this analysis with CO
2 emissions and life-cycle assessment studies. They found that there were significative differences between energy and exergy efficiency and stressed that the second law of thermodynamics was crucial for optimizing energy efficiency. Furthermore, Kaini and Mondal [
9] compared different hydrogen production methods such as steam methane reforming. They applied this analysis in order to identify where most exergy is lost. Most destruction of exergy is due to the high irreversibility of chemical reactions.
In particular, some authors also performed this kind of analysis in steam methane reforming. Martínez-Valiente et al. [
10] developed a kinetic, energetic and exergetic approach to tri-reform methane. They found that the chemical reactors in the process were the units in which most exergy was destroyed. This study confirms that the exergy destruction is caused by the high irreversibility of chemical reactions.
A similar exergetic analysis has been carried out for hydrogen production via dry gas reforming. Dry gas reforming was simulated, and the exergetic efficiency was calculated, showing an efficiency of 55%. [
11]. Behroozsarand et al. [
12] studied different methods for hydrogen production, with the autothermal reforming one being one of the most efficient methods from the exergetic point of view.
There are several works that recommend optimal operative conditions for different reforming processes. Zouhour Khila et al. [
13] performed environmental life-cycle assessment analyses as a tool for optimization of hydrogen production by autothermal reforming. They recommend the operation with a feed molar ratio of 4 and a reforming temperature of 800 °C.
In this paper, there was a computer-aided simulation of steam methane reforming to produce hydrogen with the Aspen HYSYS® software. This simulation was developed to evaluate where the exergetic losses are located in order to improve the energetic performance of the process. The analysis presented herein used an equilibrium model for making the chemical reactions (reformer and shift reactions) in this study. In addition, the data available from the industrial plant at the Puertollano petrochemical refinery (Spain) helped to validate the simulation and meant it was extremely reliable in terms of representing real outcomes. This plant provides hydrogen to the petrochemical refinery, also located in Puertollano, with a production capacity of up to 47.500 Nm3/h, which satisfies the demand of the refinery for sulphur-free fuels. Note that, contrary to most works on this topic, the simulation data are not based on general estimations for this process but, rather, on empirical data taken from the plant. Hence, the calculations made by the simulation accurately reproduce how the plant responds to changes in operational variables.
In addition, an energetic analysis of the simulation process could provide an insight as to what the optimal values are for some key variables [
5,
6,
7,
8,
9,
10]. In this respect, a sensitivity and optimization analysis of the most important variables—the steam-to-carbon molar ratio and the reformer temperature—were performed. Furthermore, there was an exergetic analysis of the steam methane reforming plant in order to assess precise losses in exergy, and this allowed alternatives for increasing exergy efficiency to be proposed. Finally, there was a preliminary economic analysis of any exergetic improvements.