Recent Breakthroughs and Advancements in NOx and SOx Reduction Using Nanomaterials-Based Technologies: A State-of-the-Art Review

Nitrogen and sulpher oxides (NOx, SOx) have become a global issue in recent years due to the fastest industrialization and urbanization. Numerous techniques are used to treat the harmful exhaust emissions, including dry, traditional wet and hybrid wet-scrubbing techniques. However, several difficulties, including high-energy requirement, limited scrubbing-liquid regeneration, formation of secondary pollutants and low efficiency, limit their industrial utilization. Regardless, the hybrid wet-scrubbing technology is gaining popularity due to low-costs, less-energy consumption and high-efficiency removal of air pollutants. The removal/reduction of NOx and SOx from the atmosphere has been the subject of several reviews in recent years. The goal of this review article is to help scientists grasp the fundamental ideas and requirements before using it commercially. This review paper emphasizes the use of green and electron-rich donors, new breakthroughs, reducing GHG emissions, and improved NOx and SOx removal catalytic systems, including selective/non-catalytic reduction (SCR/SNCR) and other techniques (functionalization by magnetic nanoparticles; NP, etc.,). It also explains that various wet-scrubbing techniques, synthesis of solid iron-oxide such as magnetic (Fe3O4) NP are receiving more interest from researchers due to the wide range of its application in numerous fields. In addition, EDTA coating on Fe3O4 NP is widely used due to its high stability over a wide pH range and solid catalytic systems. As a result, the Fe3O4@EDTA-Fe catalyst is projected to be an optimal catalyst in terms of stability, synergistic efficiency, and reusability. Finally, this review paper discusses the current of a heterogeneous catalytic system for environmental remedies and sustainable approaches.

Plasma technology to remove NOx from off-gases

Operation of marine diesel engines causes significant emission of sulphur and nitrogen oxides. It was noticed worldwide and the regulations concerning harmful emissions were introduced. There were several solutions elaborated; however, emission control for both SOx and NOx requires two distinctive processes realized in separated devices, which is problematic due to limited space on ship board and high overall costs. Therefore, the electron beam flue gas treatment (EBFGT) process was adopted to ensure the abatement of the problem of marine diesel off-gases. This novel solution combines two main processes: first the flue gas is irradiated with electron beam where NO and SO2 are oxidized; the second stage is wet scrubbing to remove both pollutants with high efficiency. Laboratory tests showed that this process could be effectively applied to remove SO2 and NOx from diesel engine off-gases. Different compositions of absorbing solution with three different oxidants (NaClO, NaClO2 and NaClO3) were tested. The highest NOx removal efficiency (>96%) was obtained when seawater-NaClO2-NaOH was used as scrubber solution at 10.9 kGy dose. The process was further tested in real maritime conditions at Riga shipyard, Latvia. More than 45% NOx was removed at a 5.5 kGy dose, corresponding to 4800 Nm3/h off-gases arising from ship emission. The operation of the plant was the first case of examination of the hybrid electron beam technology in real conditions. Taking into account the experiment conditions, good agreement was obtained with laboratory tests. The results obtained in Riga shipyard provided valuable information for the application of this technology for control of large cargo ship emission.

Organic pollutant removal from marine diesel engine off-gases under electron beam and hybrid electron beam and wet scrubbing process

The removal of organic pollutants from ship emission was studied using two processes namely electron beam (EB) and hybrid EB with wet scrubbing process. A mobile accelerator unit was used to treat 4915 Nm3/h of flue gas emitted from a tugboat in Riga Shipyard. A volume of 3 m3 seawater containing 36.8 mM of NaClO2 oxidant was used as a wet scrubber solution. Organic pollutants, mainly volatile organic pollutants (VOCs), were collected at three different sampling points, before and after irradiation vessels, and after wet-scrubber unit, respectively. They were collected with glass sampling bottles, tedlar bags, Coconut Shell Charcoal (CSC) sorbents and XAD-2 sorbents. CH3OH and CH3OH/CH2Cl2 (1:1) were used to extract VOCs from CSC and XAD-2 sorbents, respectively. Syringe filters were used to obtain the solid-free extraction solutions. They were concentrated using a micro-extractor under continuously blowing high-purity Ar. A gas chromatography–mass spectrometry (GC-MS) was used for analysis. The identified organic compounds were: aliphatic hydrocarbons (dodecane C12H26 to eicosane C20H42), aromatic hydrocarbon (toluene), esters (C3H7COOCH3, (C4H9OCO)2C6H4), nitro compounds (C3H5NO3, C4H7NO2) and acid (C7H15COOH). After 4.2 kGy EB irradiation, around 50–100% aliphatic hydrocarbons, 83% toluene and 7.5% (C4H9OCO)2C6H4 were removed from the off-gases, and after EB hybrid wet-scrubber process, most organic compounds including nitro compounds were removed. Only trace amount of toluene, hexadecane, octadecane and dibutyl phthalate were found to be present in the gas phase.

Experimental Study on Simultaneous Desulfurization and Denitrification by DBD Combined with Wet Scrubbing

A dielectric barrier discharge (DBD) reactor combined with a wet scrubbing tower was used to carry out an experimental study on desulfurization and denitrification. The effects of the packing type, packing height, spray density, mass fraction of the NaOH solution, discharge power in the DBD reactor, and simulated flue gas flow rate on the desulfurization and denitrification efficiency were analyzed, along with the influence weight of each factor, using orthogonal testing. The experimental results showed that SO2 was easily absorbed by the scrubbing solution, while the desulfurization efficiency remained at a high level (97–100%) during the experiment. The denitration efficiency was between 12 and 96% under various operating conditions. Denitration is the key problem in this system. The influence weights of the DBD power, simulated flue gas flow rate, mass fraction of the NaOH solution, spray density, packing type, and packing height on the denitration efficiency were 56.96%, 18.02%, 11.52%, 5.02%, 4.33%, and 4.16%, respectively. This paper can provide guidance to optimize the desulfurization and denitrification efficiency of this DBD reactor combined with a wet scrubbing system.

Comparison of various chemical compounds for the removal of SO2 and NOx with wet scrubbing for marine diesel engines

Seawater, NaOH, NaClO, NaClO2, H2O2, and KMnO4 were used as scrubbing liquids to react with SOx and NOx separately in a customized wet scrubber. The absorption of SO2 in the aqueous phase was influenced by three factors: pH, ionic concentration, and oxidation potential. For NOx removal, the effectiveness of various chemical compounds can be ranked from least to most effective as follows: seawater, NaOH, H2O2 < NaClO < KMnO4 < NaClO2. This effectiveness was influenced by the chemical compound’s ability to oxidize NO to NO2, absorb the NO2 that was formed, and retaining the nitrogen in the aqueous phase. High oxidation potential promoted the oxidation of NO to NO2 but hindered the absorption of NO2. NaClO2 was superior compared to NaClO in all three categories of oxidizing, absorption and retention. NaClO could not retain a significant amount of NO2 which it absorbed in the aqueous phase. The pH around 8 provided a good balance between oxidation versus absorption/retention and reactant utilization for the chlorine-based oxidants. KMnO4 had the lowest reactant consumption rate; only half a mole was consumed for every mole of NO removed, compared to around 2–3 mol of chlorite or 3–5 mol of hypochlorite.

Valorization of SiMn Sludge for Production of Low-Phosphorus Ferroalloys

The sludge generated by wet scrubbing the off-gas from a silicomanganese plant in Norway represents a significant loss in silicon and manganese values. This work seeks to extract these values in the production of ferroalloys and slags that can be utilized by alternative industries. Carbothermic smelting the sludge together with iron or iron scraps at 1600 °C produced FeSiMn alloys consisting of 57–64 wt.% Mn, 16–22 wt.% Si and 18–25 wt.% Fe. The low level of phosphorus in the sludge allowed for beneficial phosphorus concentrations as low as 500 ppmw in the metal alloys. The addition of lime to the material mix resulted in increased evaporation of alkalis, capture of sulfur in the slags as calcium sulfides and slag compositions similar to conventional steel-making slags that can be recycled accordingly. Graphical Abstract