1. Introduction
Hydrogen (H
2) is widely considered as the fuel of the future in terms of meeting sustainability and carbon emissions reduction goals, renewable energy storage potential, and supporting various end-uses in industrial and transport sectors. At present, the global H
2 production capacity is still dominated by fossil fuel resources [
1]. During the transition from fossil-based H
2 to renewable ‘green’ H
2 energy, there are certain requirements that pertain to H
2 purity. The reason is that H
2 from fossil fuels contains many impurities, including, but not limited to, CO, CO
2, CH
4, N
2, and H
2O.
Advancements made in the field of proton exchange membrane fuel cells (PEMFC), including their scale up, have made it possible to generate power with zero emissions at the point of generation, using H
2 as a fuel source [
2,
3]. More specifically, if a H
2 stream from fossil fuel origin is intended to be used in PEMFC, the CO (harmful to Pt catalyst) needs to be eliminated from the H
2 gas stream to ensure the long-term performance stability of PEMFC [
3]. PEMFC cells with Pt and Pt-Ru anode catalysts have the ability to tolerate CO at concentrations of <10 ppm and <100 ppm, respectively [
4,
5,
6]. Several CO abatement techniques have been proposed in the literature. Membrane separation and pressure swing adsorption (PSA) enable H
2 purities greater than 99.99% to be achieved. Unfortunately, the durability of membranes is limited because of low mechanical strength and vulnerability to H
2 embrittlement. On the other hand, the design of PSA purification units is fairly complex; it involves the use of high compression ratios and multicolumn adsorption systems. CO preferential oxidation (CO PROX) has been identified as a cost-effective CO abatement technology [
1]. Arzamendi et al. [
7] suggested that CO PROX is a simple process, supporting compact reactor technologies, and it could be used to convert CO in a H
2-rich gas stream in small-scale fuel processors and in on-board applications. CO PROX has been investigated using a variety of different H
2 gas mixtures and various heterogeneous catalysts.
The CO PROX reaction has high turnover rates in supported noble metals (e.g., Au, Pt, Pd, and Ru) and transition metal oxides (e.g., CuO). Au-based catalysts are efficient at reaction temperatures <100 °C [
8,
9,
10,
11]; however, they are prone to particle sintering [
10,
12,
13]. Transition metal catalysts are efficient and inexpensive [
13], but their catalytic activity is usually lower than that of noble metal catalysts at moderate reaction temperatures of 100–200 °C [
12]. Ru-based catalysts have the advantage of being more stable and efficient than Pt, Pd, Rh, and Co [
14,
15]. Using a 0.7 wt.% Ru/α-Al
2O
3 catalyst, Kim and Park [
16] recorded the reduction of CO to as low as 10 ppm in a feed containing 1 vol.% CO, 1 vol.% O
2, 50 vol.% H
2, and other components of CO
2, H
2O, and He, at reaction temperatures of 110–140 °C. Han et al. [
14] studied CO PROX on a 5 wt.% Ru/Al
2O
3 catalyst, and reported that an increase in temperature from 125 to 175 °C resulted in a CO conversion increase from less than 20% to 88% at an O
2/CO molar ratio of 1. Further increases in temperature at the same molar ratio resulted, first in a decrease in CO conversion, and then in an increase, due to the reverse water-gas shift (RWGS) and methanation reactions, respectively.
In reactor technologies for CO PROX, it is important to determine the fuel processor’s throughput and CO conversion efficiency. Many experimental studies of CO PROX were successfully performed using fixed-bed reactors. Heat and mass transfer limitations due to uneven temperature distributions and large pressure drops within the reactor are challenges associated with these reactors, especially when upscaled. In the case of smaller-scale fuel processors, a compact and integrated device, which can operate at near-isothermal conditions, would be ideal for H
2 processing for PEMFC applications. Microchannel reactors are well suited to satisfy these requirements due to their reduced physical dimensions (improved mass transport), compactness, and––if fabricated from high thermal conductivity materials––capability for near-isothermal operation [
7,
17]. Microchannel technology has been applied for the CO PROX process in the past. Snytnikov et al. [
18] studied the CO PROX reaction in 26 parallel microchannels, each coated with a 5 wt.% Cu/CeO
2-x catalyst, and designed to deliver H
2 to a 100 W PEMFC. To support fast turnover rates, reaction temperatures of 220–240 °C were used to reduce an initial CO concentration of 1.5 vol% to within the range 2–10 ppm, at a high space velocity (250 NL g
cat−1 h
−1) and an O
2/CO ratio of 1.5. Galletti et al. [
4] evaluated a microchannel reactor coated with a Rh/(50 wt.% γ-Al
2O
3 + 50 wt.% zeolite) catalyst for CO PROX. They recorded similar observations to those of Snytnikov et al. [
18]. For an O
2/CO ratio of 1.5, the CO concentration in the H
2 gas stream was reduced from 1 vol.% to <10 ppm at (albeit slightly lower) reaction temperatures of 140–220 °C and a space velocity of 60 NL g
cat−1 h
−1.
To date, computational fluid dynamic (CFD) modelling has not often been reported for CO PROX processes. Uriz et al. [
19] studied CO PROX in a microchannel reactor coated with an Au/CuO
x-CeO
2 catalyst, using representative kinetic rate expressions, and established that microchannel reactor technology could reduce CO levels to tens of ppm under specific conditions of reaction temperature and O
2/CO ratios. Arzamendi et al. [
7] carried out 3D simulations of CO PROX over CeCu and Au/CeFe catalysts in thermally coupled microchannels, and microslits. The CeCu catalyst was found to reduce CO to 10–100 ppm in the product gas, in the temperature range 170–200 °C and at space velocities of 10 000–50 000 h
−1. In follow-up CFD work, Laguna et al. [
20] established that due to the endothermic nature of the RWGS reaction, operating a CO PROX reactor at temperatures >220 °C may result in a phenomenon where the CO conversion decreases with increasing reaction temperature, despite high CO oxidation activity. Reaction kinetics of a CuO
x/CeO
2 catalyst were used to describe the multi-reaction system.
This paper presents a comprehensive experimental and modelling evaluation of a microchannel reactor, supporting a washcoated 8.5 wt.% Ru/Al
2O
3 catalyst, for the CO PROX process. First, the performance of the experimental reactor is assessed based on the reaction temperature and space velocity. There is a critical analysis of suitable operating conditions of the microchannel reactor, supporting high CO conversion and selectivity. The RWGS is a determining factor in the higher temperature range of CO PROX operation. Secondly, a CFD model is developed to assist in the evaluation of reaction and mass transport characteristics within the microchannels. It includes regressed reaction kinetics for CO oxidation and the RWGS. The model is validated on the reactor’s experimental performance for CO PROX. CFD modelling is a powerful theoretical tool that has been used in chemical reaction engineering applications to determine process characteristics that are not quantifiable experimentally, especially in compact thermo-catalytic devices, such as microchannel reactors [
21]. Due to the non-linearity of the CFD model, the popular coefficient of determination (R
2) is not applicable here to determine the model’s goodness of fit to the experimental data. Instead, the bootstrap statistical method is applied to determine if the model fits the experimental data with a confidence interval >95%.
2. Materials and Methods
This section describes the microchannel reactor, the catalyst used in the washcoating of the microchannels, other experimental apparatus, and the procedure followed to obtain experimental data for CO PROX in the microchannel reactor.
2.1. Microchannel Reactor Design
The microchannel reactor was designed and manufactured in collaboration with Fraunhofer-IMM (Mainz, Germany). The reactor was fabricated from SS314 steel (German steel classification 1.4841); it consisted of one microchannel plate and one cover plate (both 2 mm thick). The microchannel plate supported 80 microchannels and two fluid distribution manifolds (
Figure 1a). The geometric features of the microchannels and the fluid distribution manifolds were imprinted according to a wet chemical etching technique [
22]. The non-catalyst-coated microchannels had dimensions of W = 450 μm, H = 150 μm, and L = 5 cm (
Figure 1b). The catalyst coating procedure described by O’Connell et al. [
22] was followed, and the reactor was laser welded with the cover plate. Finally, the microchannel reactor was fitted with two 1/8 inch stainless steel pipes for inlet and outlet gas flows (
Figure 2).
2.2. Catalyst Preparation and Washcoating
A commercial 8.5 wt.% Ru-Cs/Al
2O
3 catalyst (10010™) was obtained from Acta S.p.A (Crespina, Italy). A Brunauer–Emmet–Teller surface area analysis revealed that the catalyst supported a surface area of 113 m
2 g
−1 and pore volume of 0.30 cm
3 g
−1. O’Connell et al. [
22] described the catalyst preparation, washcoating, drying, and calcination procedures that were used to apply the catalyst to the microchannels, with a resultant porous catalyst layer thickness of ~40 μm. Ultimately, the reactor contained 92 mg of catalyst.
2.3. Experimental Apparatus
The reactor was supported by a heating block, which makes provision for two Watlow FIREROD® 300 W heating cartridges. The reactor temperature was measured using two K-type thermocouples (2 mm OD) positioned below the reactor wall. Three Brooks SLA5850 flow controllers (Hatfield, PA, USA), controlling the flow rates of CO/H2, O2/N2 and CO2 gas supplies, were used to obtain the desired composition of the feed gas. The flow rate of the product gas was measured using a bubble flow meter at room conditions, and normalised during data processing. Prior to quantifying its composition, the product gas was dried using silica beads. The gas composition was determined by gas chromatography (GC), using an online SRI 8610 GC (Torrance, CA, USA), fitted with a HayeSep D column and two molecular sieve-13X columns. The GC instrument was fitted with a helium ionisation detector and two thermal conductivity detectors. The GC was capable of detecting CO levels up to a limit of 20 ppm.
2.4. Experimental Procedure
Prior to the experiments, the microchannel reactor was heated to 400 °C under a N2 flow of 32.6 NL gcat−1 h−1. The Ru catalyst was reduced in a flow of H2 at the same flow rate for 1 h, then cooled under a subsequent N2 flow. For each experiment, a one-factor-at-a-time approach was followed to vary the operational parameters of the reaction temperature and the space velocity. A gas mixture simulating a dry water–gas shift (WGS) reactor reformate, consisting of 1.4 vol.% (1.4 × 104 ppm) CO, 10 vol.% CO2, 68.6 vol.% H2, 2 vol.% O2, and N2 as balance, was mixed and used as the feed gas for the reactor. The reaction temperature was varied over the range 80–200 °C (in 20 °C increments). Space velocities of 32.6–130.4 NL gcat−1 h−1 (in 32.6 NL gcat−1 h−1 increments) were used in the evaluation of the reactor performance. Each experiment was conducted at a constant temperature and space velocity, over a period of 2.5 h of steady-state operation. The product gas flow rate and GC sample were quantified every 15 min, and averaged across the 10 data points for that particular experiment.
2.5. Performance Criteria
In a CO PROX reaction system, CO oxidation (Equation (1)), H
2 oxidation (Equation (2)), and WGS (Equation (3)) reactions are possible:
In the temperature range 80–200 °C, no CH
4 was detected in the product gas. The effects of any CO or CO
2 methanation reactions were therefore disregarded. Throughout this work, the CO conversion (Equation (4)) and CO selectivity (Equation (5)) were used as performance criteria:
5. Conclusions
CO poisoning is a real issue when it comes to fossil-derived hydrogen for low-temperature electrochemical processes, especially power generation using PEMFC. CO PROX is a well-known industrial process for the removal of CO from gas mixtures. For small-scale applications, microchannel reactors (with enhanced mass transfer, near isothermal operation, and high throughput characteristics) offer a compact catalytic reactor technology suitable for CO PROX. In this paper, a microchannel reactor coated with a Ru-Cs/Al2O3 catalyst demonstrated the reduction of CO at an initial concentration of 1.4 vol.% in a H2-rich gas mixture to ppm levels as low as 42 ppm at reaction temperatures of 120–140 °C and at space velocities of 65.2 and 97.8 NL gcat−1 h−1. A CO selectivity of 50.3% was achieved at 120 °C and a space velocity of 65.2 NL gcat−1 h−1—this corresponds to a H2 energy loss of only 2%. Despite this promising reactor behaviour in the range of reaction temperatures (100–200 °C) and space velocities (32.6–130.4 NL gcat−1 h−1) investigated, we did observe that non-optimal reaction conditions may lead to substandard CO conversion (<95%) and increased H2 loss (~6.5%) due to secondary catalytic reactions, i.e., H2 oxidation and RWGS. From a practical perspective, it is also recommended that future work and upscaling of the CO PROX process investigates Ru catalyst loadings less than 8.5 wt.% Ru to limit costs.
Identifying and understanding reactor operating regimes was, therefore, important to describe microchannel reactor performance for high CO conversion, selectivity, and throughput. Here, a CFD model was developed to validate experimental results and understand reaction-coupled mass transport within the microchannel reactor. Kinetic rate expressions were adapted from the literature using a method that combined manual parameter estimation and parameter regression. Indications with the bootstrap statistical method were that the model described the experimental data to a level of confidence far greater than 95%. Species transport within the microchannel reactor’s axial length provided a critical analysis of the reaction dynamics of the CO PROX system involving CO oxidation, H2 oxidation, and RWGS reactions. It is envisaged that, in future, the CFD model could guide innovation for the upscaling of microchannel reactors for CO PROX—to assist in the identification of suitable operating regimes, while limiting H2 consumption via its oxidation and the undesirable effects of the RWGS reaction.