1. Introduction
Marine diesel engines have always used heavy fuel oil, a poor-quality fuel that contains a high concentration of sulfur; therefore, among the pollutants produced, sulfur oxides (SOx) are of great importance, together with nitrogen oxides (NO
x) and particulate matter (PM) [
1]. Nitrogen oxides have a major impact on air pollution. They can damage the human respiratory system, promote secondary organic aerosols, acid rain and haze photochemical smog and contribute to ozone depletion [
2]. NO
x emissions from marine engines have been recently taken into consideration by the Tier III standards of the International Maritime Organization (IMO), introduced on January, 1st 2016 (MARPOL Annex VI). These regulations require an 80% reduction in NO
x emissions compared to Tier I, and they apply in selected sea areas called “NO
x Emission Control Areas (N-ECAs)” that comprise the coastal waters of the United States and Canada, the North Sea and the Baltic Sea. In addition to the IMO conventions, other maritime organizations such as the United States’ Environment Protection Agency (EPA), the European Union and the Chinese Ministry of Environmental Protection have also established maritime regulations for the reduction in exhaust emissions [
3].
Exhaust gas aftertreatment devices can efficiently remove pollutants from internal combustion (IC) engines’ exhausts without a penalty in engine power and fuel economy. Among them, selective catalytic reduction (SCR) systems are widely adopted in road applications for effectively reducing NO
x. SCRs can operate as a standalone technology; they show high levels of reliability and durability, and they do not require major engine modifications. This technology includes an injection of urea water into the exhaust gas; taking advantage of the exhaust gas heat, ammonia (NH
3) is produced through urea thermal decomposition. NH
3 reacts with NO
x on a catalyst to convert NO
x into molecular nitrogen (N
2) and water (H
2O). The main global reactions occurring in a SCR are presented in
Table 1.
Reaction (a) represents the overall stoichiometry of the SCR process; it occurs rapidly in the presence of catalysts when the temperature is between 250 and 450 °C and oxygen is in excess. Usually, NO2 concentration at the exhaust is very low (only 5% of the NOx), so reactions (b) and (c) play a minor role in the process.
As for the undesired oxidation reactions, those indicated with the letters d-f involve NH3 consumption and determine a reversal of NOx removal and the formation of N2O as a by-product. These reactions can take place on SCR catalysts when the feed is low in NO, but they are negligible in the presence of NOx.
Ammonia has been chosen as reducing agent in the SCR process due to its capability to selectively react with NO
x in excess of oxygen. This property is not observed in other simple reagents such as hydrocarbons and carbon monoxide. Reaction (g) is the oxidation of SO
2, responsible for the formation of salts such as ammonium sulfate [
4].
The core of the SCR technology is the catalyst system that has the role of improving the reaction efficiency by decreasing the activation energy and reaction temperature of NO
x decomposition, increasing N
2 selectivity in NO
x reduction products and preventing the incidence of side reactions. Selecting the appropriate catalysts is critical when designing an SCR; its main characteristics should be high deNO
x activity, strong anti-poisoning ability, high mechanical strength and a suitable operating temperature range [
5]. Many catalysts have been demonstrated to be effective in SCR reactions. Noble and transition metal oxides are the primary active components, with TiO
2, Al
2O
3, SiO
2, zeolite and carbon serving as carriers.
For low- and medium-speed marine engines, SCR technology is derived from power plant systems using diesel engines. While ammonia water can be used in power plants as a reducing agent, larger ships only use urea water solutions [
6] for safety and storage reasons. The size of the urea–SCR system can also be an issue; the SCR urea consumption is estimated to be 8.5% of the diesel consumption [
7]; this undoubtedly adds size and weight to the ship. Furthermore, the vibration resistance of urea tubes should be carefully considered. Pumping and dosing systems, as well as urea feed pipes, use welding connections whenever possible to avoid urea leaks [
8].
Furthermore, the main challenges for marine SCR applications are low temperature sulfur resistance and low temperature activation. The latter issue is also a problem for cars, trucks and off-road applications and can result in the catalyst not working, for example at startup and during maneuvering [
9]. In marine engines, the turbine downstream temperatures are generally below 150 °C, making catalytic exhaust gas treatment impossible. For this reason, the SCR catalyst is usually placed on top of the turbocharger close to the engine to allow the highest possible temperature for an efficient NO
x conversion and to avoid the formation of ammonium sulfates. In this case, the system is called high-pressure SCR (HP-SCR) and it is mostly used for two-stroke low-speed diesel engines. HP-SCR is characterized by a compact layout and high exhaust gas energy utilization rate, but it has a significant impact on the working performance of diesel engines and turbochargers. Conversely, an SCR arranged after the turbocharger is referred to as low-pressure SCR (LP-SCR). This system has high adaptability and a lower impact on the engine and turbocharger but its denitration efficiency is inadequate for low-speed two-stroke diesel engines because of the low exhaust temperatures. For this reason, an exhaust gas heating device is usually installed before the SCR reactor [
10]. In the frame of the above literature, it emerges that the investigation of NO SCR catalysts for marine applications and the issues related to on-board installation deserve further efforts. Some numerical investigations have recently been performed to predict the denitration efficiency, ammonia flow rate and other parameters of SCR systems for marine applications [
11,
12]; less effort has been made for experimental studies.
Most catalysts for marine SCRs are V
2O
5–WO
3–TiO
2-based; vanadium and tungsten oxides coated on a titanium substrate [
13]. V
2O
5 is the active component (1–3%), which is usually impregnated on an anatase TiO
2 support together with WO
3 (~10%) to stabilize the vanadia and increase thermal durability. The typical maximum NO
x conversion range is between ~250 °C and ~450–500 °C. Above this temperature, selectivity is reduced because NH
3 is oxidized by O
2 instead of reacting with NO [
14]. A V
2O
5–WO
3–TiO
2 SCR is commonly used as a stationary catalyst, but it has not been commercialized for vehicles due vanadium toxicity. Conversely, this type of SCR catalyst is appropriate for ships because of its high light-off efficiency, good sulfur resistance and low cost, so its demand in the market has increased.
It is worth noting that zeolite-based catalysts can also be effective in catalytic exhaust gas aftertreatment systems because they are characterized by a high specific surface area and thermal stability. In recent years, many studies have improved the de-NO
x performance and durability of Cu-zeolite catalysts that show excellent low temperature activity [
15,
16,
17,
18]. Fe-zeolite has great durability toward high temperature and poisoning; thus, it can be successfully used in after-treatment catalysts for heavy-duty diesel engines even if it shows a high activation energy, causing low light-off performance.
Some researchers have compared V
2O
5–WO
3–TiO
2 catalysts [
19] with two kinds of Fe-zeolite (Fe-zeolite (1) and (2)). Their physicochemical characteristics were examined according to hydrothermal aging, sulfur poisoning and HCs co-existence. The results showed that V
2O
5–WO
3–TiO
2 SCR was the least susceptible to sulfur poisoning because of Brønsted acid site effects and its NO
x conversion rate was relatively higher at ~350 °C. It resulted in being the most suitable for the reduction in exhaust gas from ship engines.
Magnusson et al. [
12] investigated how sulfur, water and low temperature affect NO
x the reduction activity of a commercial SCR V
2O
5–WO
3–TiO
2 catalyst in marine applications using urea as a reducing agent. The authors proved that for temperatures higher than 300 °C, NO
x reduction could be greater than 90%. Japke et al. [
20] tested the performance of vanadia-based SCR catalysts obtained using the incipient wetness impregnation method. The study demonstrated that the preparation process had a strong effect on the catalyst’s NO
x removal efficiency with ammonia and on the oxidation activity of soot and hydrocarbons. Zhou et al. [
21] studied the catalytic activities of an extruded commercial monolithic V
2O
5–WO
3–TiO
2 catalyst at low temperatures according to the working characteristics of marine diesel engines. The authors reported that for temperature below 150 °C, the SCR reaction was mostly influenced by internal chemical reaction kinetics, and when the temperature was above 200 °C, the most relevant mechanism affecting the SCR reaction was the reactant diffusion rate. The parameters that can improve NO
x reduction were found to be space velocity, NH
3 consumption and O
2/NO
2 concentration in the gas mixture.
Recently, Lai et al. [
22] and Zhang in collaboration with some authors of the present paper [
23] have pointed out that the catalyst’s preparation method, the titania surface area and crystalline structure, the vanadium and tungsten loadings and the calcination treatments strongly affect the morphological, structural, acidic properties and NO SCR performance.
The unequivocal result emerging from all the studies is the crucial role played by the titania support with the capability to establish a proper interaction of the V2O5 and WO3 active phases. Moreover, the shape and nature of the monolith, as extruded or wash-coated by the active phases, and its manufacturing procedure are undoubtedly key factors.
On these bases, we considered an extruded monolithic catalyst worthy of investigation, provided by Hug Engineering AG (Elsau-Switzerland) containing V2O5 (3 wt%)-WO3 (7 wt%)-TiO2 (75 wt%), rest bentonite and glass fiber as the active phases. Such a catalytic device that normally is used for the abatement of NOx from stationary sources was firstly characterized in terms of its physical-chemical properties at laboratory scale. Then, it was installed and tested at the exhaust of a diesel engine in exhaust conditions representative of a marine on-board power generation engine. This kind of engine was equipped with high-pressure common rail injection systems and worked with low-sulfur diesel fuel (EN590).
The adopted methodology led to an assessment of the applicability and potentiality of the system when installed on a real engine, enlarging the scientific literature with quantitative data and information. Once the good potentiality of the system was revealed, the next step of investigation regarded the analysis of other aspects important for a future installation at the exhaust of marine engines, i.e., the poisoning resistance of the system and its thermal management. An experimental/numerical approach will be useful to enlarge the systems working conditions.
The results presented in this study are part of a wider project devoted to investigating low-impact technology solutions for power generation in marine applications.
2. Experimental Setup and Procedures
The methodology approach foresaw two different steps of investigation.
The study was initially conducted for a complete characterization of the physical-chemical properties. In this sense, the catalytic system was analyzed, as slab and/or as powder, in terms of the crystalline structure of the monolithic catalyst, specific surface areas, pore volume, pore size of the material, reduction properties and surface composition by means of proper diagnostics techniques.
The second step consisted of investigating the potentiality offered by the same SCR on an intermediate-scale engine, reducing the complexity of a test campaign on a real-scale marine engine. The experimental procedure foresaw to firstly assess the representativeness of the intermediate-scale engine, identifying test conditions typical of a real use of an SCR. Then, a monolith, representing one element of a full-scale SCR, was installed at the exhaust of the intermediate-scale engine and was characterized in terms of its NOx reduction efficiency.
The aim of such a research approach was to guarantee an in-depth analysis of the monolith potentiality, correlating the monolith features with its measured performance. The two laboratory experimental set-ups, the adopted diagnostic techniques and instrumentation are described in the following sections.
2.1. Laboratory Scale
The SCR device, provided by Hug Engineering AG, had a monolithic structure, 200 cpsi and a geometric parallelepiped shape. The chemical composition, as certified in the data sheet, is listed in
Table 2.
The crystalline structure of the catalyst (as a slab and as a powder) was determined by powder X-ray diffraction patterns (XRD), performed on a Bruker D5000 diffractometer equipped with a Cu Kα anode and graphite monochromator. The data were recorded in a 2θ range of 20–80° with a step size of 0.05° and time per step of 20 s. Moreover, a pattern with an acquisition time of 200 s/step was registered between 20 and 60° 2θ to confirm the absence of peaks ascribable to the V2O5 and/or WO3 phases. The only detected crystalline phases attributed to TiO2 were analyzed according to ICSD files (Inorganic Crystal Structure Database). The mean crystallite size was calculated by the Debye–Scherrer equation: D = 0.9λ/Bcosθ, where D represents the average crystalline size, 0.9 is the Scherrer parameter, λ is the wavelength of the X-ray radiation (0.15406 nm), B denotes the full width at half maximum of the peak (FWHM) and θ is the angular position of the peak.
The specific surface areas (SSA), pore volume and pore size of the material (as a slab and as a powder) were measured by N
2 adsorption–desorption isotherms using a Micromeritics ASAP2020 system. Before analysis, the samples were degassed in vacuum at 250 °C for 2 h, then the measurement was performed at liquid nitrogen temperature (−196 °C). The Brunauer–Emmett–Teller (BET) method was used to calculate the SSA. The Barrett–Joyner–Halenda (BJH) method [
24] was applied to the desorption branch to estimate the pore volume and pore size distribution.
The catalyst (0.1 g), as a powder, was studied by hydrogen temperature-programmed reduction (H2-TPR) using Micromeritics Autochem 2910 HP apparatus equipped with a thermal conductivity detector (TCD). The H2-TPR profiles were registered after pre-treatment under O2/He flow from room temperature up to 300 °C with a holding time of 30 min. Then, after cooling down up to RT under He flow, the H2-TPR analysis was carried out in the temperature range of 25–1000 °C with a 10 °C min−1 heating rate and a flowing 5 vol.% of H2 in Ar (30 mL/min).
The X-ray photoelectron spectroscopy (XPS) analyses of the samples were performed with a VG Microtech ESCA 3000 Multilab (VG Scientific, East Grinstead, UK), using unmonochromatized Al Kα source (1486.6 eV) run at 14 kV and 15 mA and a CAE (Constant Analyser Energy) mode. A pass energy of 50 eV set across the hemispheres was used for the survey spectrum, and a value of 20 eV was used for the individual peak energy regions pass energy. The constant charging of the samples was removed by referencing all the energies to the C1s peak energy set at 285.1 eV, arising from adventitious carbon. Analyses of the peaks were performed using the CASA XPS software (version 2.3.17, Casa Software Ltd., Wilmslow, UK, 2009). For the peak shape, a Gaussian (70%)–Lorentzian (30%) line shape defined in Casa XPS as GL (30) profiles were used for each component of the main peaks after a Shirley type baseline subtraction. The binding energy values were quoted with a precision of ±0.15 eV and the atomic percentage with a precision of ±10%.
2.2. Engine Intermediate Scale
The final application of the prototype after-treatment device will be a marine engine, i.e., an ISOTTA FRASCHINI (IF) 4-stroke, water-cooled 8-cylinder V engine with 2 intake and 2 exhaust valves. The rated speed and power are 1500 rpm and 685 kW, respectively. The engine is equipped with a common rail injection system with electronic control and variable injection timing. The unit displacement is 3856.7 cm3 and the nominal compression ratio is 13.2.
Nevertheless, considering the size of the naval engine and the complexity and costs of the test campaign that would result, the characterization of the prototype after treatment device was carried out on an intermediate-scale (IS) engine; a heavy-duty engine for truck or bus applications, its main specifics are presented in
Table 3.
The IS engine was compliant with the latest anti-pollution regulations for road vehicles used in truck or bus applications (EURO VI). It was equipped with an after-treatment system consisting of a diesel oxidation catalyst (DOC), particulate filter (DPF) and nitrogen oxide catalyst (SCR). All these components were engineered in a single compact unit and real-time controlled by the engine control unit to ensure its efficient operation in the various working conditions. The engine was installed on a dyno test bench and instrumented for pressure and temperature characterization both at the intake and exhaust line.
At the engine exhaust, a smoke meter was used for smoke emission measurement, while the regulated gaseous emissions (THC, CO, CO
2, NO
x/NO, O
2) were measured upstream and downstream of the aftertreatment system with an exhaust gas analyzer bench (Horiba Mexa 7100). The parallelepiped-shaped SCR prototype was housed in the box shown in
Figure 1, which was custom designed.
The engine exhaust line (originally providing a standard ATS layout) was properly modified to allow the SCR device installation. According to the scheme of
Figure 2, the exhaust gas downstream of the turbine was driven to the new device by capping the original exhaust duct output.
The monolith had the following sizes: 150 × 150 × 300 mm and a volume of 6.75 dm3. The single monolith represented one of the twenty “bricks”, of which the catalyst for the reference marine engine should be constituted. This solution, although different from the typical layouts for road applications (cylindrical), could be the most suitable for a large and perhaps modular naval application.
To stabilize the flow of exhaust gases and direct them to each part of the monolith, a connecting section with an exhaust manifold was designed. Due to the high temperature of the exhaust gases and to ensure the least interference from a chemical point of view with the gas stream, the whole exhaust line was made of stainless steel. The monolith box could be completely disassembled; this ensured easy and safe installation and replacement of the prototype to be characterized. For the SCR operation, a solution of water and urea was continuously nebulized in the exhaust gas stream; a standard urea injection system was used, consisting of an AdBlue tank, dosing unit, pressurization unit and an injector positioned along the exhaust duct. The injector actuation was controlled by the engine control unit and the AdBlue quantity could be properly dosed. In this way, it was possible to characterize the prototypes not only with respect to the quality of the exhaust gas (NOx concentration and temperature, which varied according to the engine point) but also to the concentration of reducing agent.
The test bench was equipped with the following sensors:
A thermocouple mounted at the entrance of the box to monitor the temperature of the inlet exhaust gases;
A thermocouple mounted at the outlet of the box to evaluate the temperature variation in the exhaust gases that cool down flowing through the SCR;
Exhaust gas sampling outlets “upstream” and “downstream” of the SCR to characterize the gas composition.
In a preliminary phase of this activity, the exhaust of the IF marine engine was characterized in the operating conditions representative of its standard working map in terms of flow rates, temperatures, gaseous pollutants and particulate matter concentrations, with the aim of subsequently reproducing such conditions at the exhaust of the intermediate-scale engine. E2/D2 test cycles were performed in controlled ambient conditions for five operating modes at a fixed speed of 1500 rpm and with torque values between 10 and 100%. The concentration of NOx, CO, CO2, THC, smoke and the thermodynamic properties of the exhaust gases were measured. Starting from this analysis, the first part of the experimental activity was aimed at the identification of five IS engine test points characterized by the same exhaust line conditions found during the above-described operation of the marine engine. Then, the experiments were focused on the characterization of the SCR prototype at the engine exhaust in the selected conditions.
4. Conclusions
The comparative study of the monolithic SCR device conducted at the laboratory scale, as a slab and/or as a powder, in terms of its physical-chemical properties and the second step investigating the potentiality offered by the same SCR on an intermediate-scale engine proved to be an original approach of investigation.
The structural, morphological and reduction properties of the monolithic device were revealed as the key parameters governing the NOx removal efficiency. The high reducibility of the mixed V-O-W species, synergistically interacting with the titania support, stabilized as an anatase phase, as well as the presence of a vanadium-enriched catalytic surface, were likely the main factors responsible for the NH3 SCR activity.
The use of the intermediate scale engine revealed a powerful and reliable tool for reproducing the exhaust line conditions that will be encountered by the SCR device in its final installation, reducing the complexity of a test campaign on the real-scale marine engine.
The results of the experimental investigation highlighted the good potentiality of the tested monolith, offering useful insights from a quantitative point of view of a commercial V2O5-WO3-TiO2 SCR when applied in real working conditions.
The methodological approach corroborated the findings; the engine test results, in fact, were perfectly in agreement with the laboratory-scale ones, already identifying a good reactivity of the formulation of the tested SCR at relatively low temperatures (at 200 °C the NOx reduction capacity was still around 50%).
Starting from the obtained results, further studies can be performed with the same method to evaluate the potentiality of proper thermal management or of control strategies in the system optimization in critical conditions, such as a cold-engine start or low load for example.
Moreover, aspects related to the poisoning resistance of the catalytic systems and to ammonia slipping at the exhaust are critical issues to further investigate in the case of marine applications. Considering the well-known issue of the NOx reduction efficiency of SCR systems in the case of using fuel with high sulfur content, the authors have also planned an experimental activity, which is currently ongoing, properly devoted to the evaluation of the applicability of such technology in the case of high-Sulfur fuel content in any case lower than 0.5%.