Search Results (13)

In this study, activated carbons derived from walnut shells (CA-N) and apple wood (CA-M) were used as adsorbents to remove cobalt(II) and strontium(II) ions from aqueous solutions. The novel materials were obtained using nitric acid (CA-Mox) and nitric acid/urea mixture (CA-Mox-u, CA-Nox-u) as oxidizing agents. The physical–chemical characteristics of activated carbons were determined from nitrogen sorption isotherms, SEM-EDX, FTIR, pH metric titrations, the Boehm titration method and elemental analysis. The results of batch experiments indicate that maximum adsorption can be achieved in broad pH ranges: 4–8 for Co(II) and 4–10 for Sr(II). The maximum adsorption capacities of Co(II) and Sr(II) on oxidized activated carbons at pH = 4 are: CA-Mox, 0.085 and 0.076 mmol/g; CA-Mox-u, 0.056 and 0.041 mmol/g; and CA-Nox-u, 0.041 and 0.034 mmol/g, respectively. The mathematical models (pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models, and Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin–Pyzhev isotherm models) were used to explain the adsorption kinetics, to study the adsorption mechanism and predict maximum adsorption capacity of the adsorbents. The adsorption mechanisms of toxic metal ions on activated carbons were proposed. Full article

In recent years, multifunctional inorganic−organic hybrid materials have been widely investigated in order to determine their potential synergetic, antagonist, or independent effects in terms of reactivity. The aim of this study was to design and characterize a new hybrid material by coupling well-known photocatalytic TiO₂ nanoparticles with sodium surfactin (SS), a biosurfactant showing high binding affinity for metal cations as well as the ability to interact with and disrupt microorganisms’ cell membranes. We used both chemical and colloidal synthesis methodologies and investigated how different TiO₂:SS weight ratios affected colloidal, physicochemical, and functional properties. We discovered a clear breaking point between TiO₂ and SS single-component trends and identified different ranges of applicability by considering different functional properties such as photocatalytic, heavy metal sorption capacity, and antibacterial properties. At low SS contents, the photocatalytic properties of TiO₂ are preserved (conversion of organic dye = 99% after 40 min), and the hybrid system can be used in advanced oxidation processes, taking advantage of the additional antimicrobial SS properties. At high SS contents, the TiO₂ photoactivity is inhibited, and the hybrid can be usefully exploited as a UV blocker in cosmetics, avoiding undesired oxidative effects (UV adsorption in the range between 300–400 nm). Around the breaking point (TiO₂:SS 1:1), the hybrid material preserves the high surface area of TiO₂ (specific surface area around 180 m²/g) and demonstrates NOx depletion of up to 100% in 80 min, together with improved adhesion of hybrid antibacterial coating. The last design demonstrated the best results for the concurrent removal of inorganic, organic, and biological pollutants in water/soil remediation applications. Full article

Unlike established coating formulations, functional particulate coatings often demand the omission of polymer dispersant so as to retain surface functionality. This results in heterogeneous complex rheology. We take an example from a novel development for an NO_x mitigation surface flow filter system, in which ground calcium carbonate (GCC), applied in a coating, reacts with NO₂ releasing CO₂. Inclusion of mesoporous ancillary mineral acts to capture the CO₂. The coating is applied as droplets to maximize gas-contact dynamic by forming a pixelated 2D array using a coating device consisting of protruding pins, which are loaded by submersion in the aqueous coating color such that the adhering droplets are transferred onto the substrate. The flow is driven by surface meniscus wetting causing lateral spread and bulk pore permeation. Filamentation occurs during the retraction of the pins. Stress-related viscoelastic and induced dilatancy in the suspension containing the ancillary mesoporous mineral disrupts processability. Adopting shear, oscillation and extensional rheometric methods, we show that the inclusion of an ancillary mineral that alone absorbs water, e.g., perlite (a naturally occurring porous volcanic glass), is rheologically preferable to one that in addition to absorbing water also immobilizes it on the mineral surface, e.g., sepiolite. When including micro-nanofibrillated cellulose (MNFC), critical for maintaining moisture to support NO₂ sorption, it is observed that it acts also as a flow modifier, enabling uniform coating transfer to be achieved, thus eliminating any possible detrimental effect on mineral surface activity by avoiding the use of soluble polymeric dispersant. Full article

A new design of a sorption-selective catalytic reduction (SCR) system is proposed to improve ammonia storage density and meet the ammonia demand for high NOx conversion efficiency at a relatively lower temperature (<100 °C) compared to urea-SCR systems. The major components are a main unit and a start-up unit that each contain a metal halide ammine as the sorbent. The start-up unit can operate without any external heat source, but spontaneously releases ammonia at the ambient temperature and is only used when the main unit is being warmed up for action. The selection criteria for the metal halide ammine for each unit is discussed. The working pair of SrCl₂ as the main ammine and NH₄Cl as the start-up ammine is further analyzed as an example to be used in the sorption-SCR system for a diesel engine, the NOx emissions of which were experimentally measured in different operation modes. Based on the experimental data of engine emissions and kinetic models of the chemisorption between ammines and ammonia, the dynamic performance of the sorption system with a total capacity of 180 L sorbent composite in different layouts was investigated and compared. It was found that the achievable desorption conversion degree was lower in smaller reactors and was more sensitive to operating conditions in smaller reactors compared to larger reactors. This suggests that a system using a small reactor layout requires some extra volume to completely meet the required capacity compared to a larger reactor layout. However, because systems with large reactors tend to respond slowly, as they have more thermal mass and take a longer time for preparation, there is a design trade-off required to have optimal performance and balance between the main unit and the start-up unit. In the case studied in this work, a system using three rechargeable reactors with a volume of 60 L each was found to be the preferable layout; it could have about a 90% desorption conversion degree and required around 10 min of warm-up time. Meanwhile, the coupled start-up unit should have a capacity of around 165 mL at least. Full article

In modern dual-pressure nitric acid plants, the tail gas temperature usually exceeds 300 °C. The NH₃-SCR catalyst used in this temperature range must be resistant to thermal deactivation, so commercial vanadium-based systems, such as V₂O₅-WO₃ (MoO₃)-TiO₂, are most commonly used. However, selectivity of this material significantly decreases above 350 °C due to the increase in the rate of side reactions, such as oxidation of ammonia to NO and formation of N₂O. Moreover, vanadium compounds are toxic for the environment. Thus, management of the used catalyst is complicated. One of the alternatives to commercial V₂O₅-TiO₂ catalysts are natural zeolites. These materials are abundant in the environment and are thus relatively cheap and easily accessible. Therefore, the aim of the study was to design a novel iron-modified zeolite catalyst for the reduction of NO_x emission from dual-pressure nitric acid plants via NH₃-SCR. The aim of the study was to determine the influence of iron loading in the natural zeolite-supported catalyst on its catalytic performance in NO_x conversion. The investigated support was firstly formed into pellets and then impregnated with various contents of Fe precursor. Physicochemical characteristics of the catalyst were determined by XRF, XRD, low-temperature N₂ sorption, FT-IR, and UV–Vis. The catalytic performance of the catalyst formed into pellets was tested on a laboratory scale within the range of 250–450 °C using tail gases from a pilot nitric acid plant. The results of this study indicated that the presence of various iron species, including natural isolated Fe³⁺ and the introduced FexOy oligomers, contributed to efficient NO_x reduction, especially in the high-temperature range, where the NO_x conversion rate exceeded 90%. Full article

The cement manufacturing industry has played a fundamental role in global economic development, but its production is a major facilitator to anthropogenic CO₂ release and solid waste generation. Nigeria has the largest cement industry in West Africa, with an aggregate capacity of 58.9 million metric tonnes (MMT) per year. The Ministry for Mines and Steel Development asserts that the nation possesses total limestone deposits of around 2.3 trillion MT with 568 MMT standing as established reserves and 11 MMT used. Cement industries are largely responsible for releasing air pollutants and effluents into water bodies with apparent water quality deterioration over the years. Air pollution from lime and cement-producing plants is seen as a severe instigator of occupational health hazards and work-related life threats, negatively affecting crop yields, buildings, and persons residing in the vicinity of these industries. World Bank observed in 2015 that 94% of the Nigerian populace is susceptible to air pollutants that surpass WHO guidelines. In 2017, World Bank further reported that 49,100 premature deaths emanated from atmospheric PM_2.5, with children beneath age 5 having the greatest vulnerability owing to lower respiratory infections, thereby representing approximately 60% of overall PM_2.5-induced deaths. Cement manufacturing involves the significant production of SO₂, NO_x, and CO connected to adverse health effects on humans. Sensitive populations such as infants, the aged, and persons having underlying respiratory ailments like asthmatics, emphysema, or bronchitis are seen to be most affected. Consequently, in addressing this challenge, growing interests in enacting carbon capture, usage, and storage in the cement industry is expected to alleviate the negative environmental impact of cement production. Still, no carbon capture technology is yet to achieve commercialization in the cement industry. Nonetheless, huge advancement has been made in recent years with the advent of vital research in sorption-enhanced water gas shift, underground gasification combined cycle, ammonium hydroxide solution, and the microbial-induced synthesis of calcite for CO₂ capture and storage, all considered sustainable and feasible in cement production. Full article

The objective of our study was to prepare Y-, USY- and ZSM-5-based catalysts by hydrothermal synthesis, followed by copper active-phase deposition by either conventional ion-exchange or ultrasonic irradiation. The resulting materials were characterized by XRD, BET, SEM, TEM, Raman, UV-Vis, monitoring ammonia and nitrogen oxide sorption by FT-IR and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). XRD data confirmed the purity and structure of the Y/USY or ZSM-5 zeolites. The nitrogen and ammonia sorption results indicated that the materials were highly porous and acidic. The metallic active phase was found in the form of cations in ion-exchanged zeolites and in the form of nanoparticle metal oxides in sonochemically prepared catalysts. The latter showed full activity and high stability in the SCR deNO_x reaction. The faujasite-based catalysts were fully active at 200–400 °C, whereas the ZSM-5-based catalysts reached 100% activity at 400–500 °C. Our in situ DRIFTS experiments revealed that Cu–O(NO) and Cu–NH₃ were intermediates, also indicating the role of Brønsted sites in the formation of NH₄NO₃. Furthermore, the results from our experimental in situ spectroscopic studies were compared with DFT models. Overall, our findings suggest two possible mechanisms for the deNO_x reaction, depending on the method of catalyst preparation (i.e., conventional ion-exchange vs. ultrasonic irradiation). Full article

Natural zeolite of the heulandite-type framework was modified with iron and tested as a catalyst for the selective catalytic reduction of nitrogen oxides with ammonia (NH₃-SCR) in the temperature range of 150–450 °C. The catalyst was prepared at a laboratory scale in a powder form and then the series of experiments of its shaping into tablets was conducted. Physicochemical studies of the catalyst (N₂ sorption at −196 °C, FT-IR, XRD, UV-vis) were performed to determine the textural and structural properties and identify the surface functional groups, the crystalline structure of the catalysts and the form and aggregation of the active phase. The activity tests over the shaped catalyst were performed industry-reflecting conditions, using tail gases from the pilot nitric acid plant. The influence of a temperature, catalyst load, and the amount of reducing agent (ammonia) on the NO_x reduction process were investigated. The results of catalytic tests that were performed on model gas mixture showed that non-modified clinoptilolite exhibited around 58% conversion of NO at 450 °C. The temperature window of the shaped catalyst shifted to a higher temperature range in comparison to the powder sample. The catalytic performance of the shaped Fe-clinoptilolite in the industry-reflecting conditions was satisfactory, especially at 450 °C. Additionally, it was observed that the ratio of N₂O concentration downstream and upstream of the catalytic bed was below 1, which indicated that the catalyst exhibited activity in both DeNO_x and DeN₂O process. Full article

The emission of untreated environmental harmful gases such as sulfur and nitrogen oxide (SOx and NOx) emissions is considered old fashioned, since industries are compelled by governments and legislations to meet the minimum threshold before emitting such substances into the atmosphere. Numerous research has been done and is ongoing to come up with both cost-effective equipment and regenerable catalysts that are adsorbent—or with enhanced sorption capacity—and with safer disposal methods. This work presents the general idea of a monolith/catalyst for environmental application and the technicality for improving the surface area for fast and efficient adsorption–desorption reactions. The chemical reactions, adsorption kinetics, and other properties, including deactivation, regeneration, and the disposal of a catalyst in view of environmental application, are extensively discussed. Full article

Nanosized SSZ-13 was synthesized hydrothermally by applying N,N,N-trimethyl-1-adamantammonium hydroxide (TMAdaOH) as a structure-directing agent. In the next step, the quantity of TMAdaOH in the initial synthesis mixture of SSZ-13 was reduced by half. Furthermore, we varied the sodium hydroxide concentration. After ion-exchange with copper ions (Cu²⁺ and Cu⁺), the Cu-SSZ-13 catalysts were characterized to explore their framework composition (XRD, solid-state NMR, ICP-OES), texture (N₂-sorption, SEM) and acid/redox properties (FT-IR, TPR-H₂, DR UV-Vis, EPR). Finally, the materials were tested in the selective catalytic reduction of NO_x with ammonia (NH₃-SCR). The main difference between the Cu-SSZ-13 catalysts was the number of Cu²⁺ in the double six-membered ring (6MRs). Such copper species contribute to a high NH₃-SCR activity. Nevertheless, all materials show comparable activity in NH₃-SCR up to 350 °C. Above 350 °C, NO conversion decreased for Cu-SSZ-13(2–4) due to side reaction of NH₃ oxidation. Full article

Cap-rock integrity is an important consideration for geological storage of CO₂. While CO₂ bearing fluids are known to have reactivity to certain rock forming minerals, impurities including acid gases such as SOx, NOx, H₂S or O₂ may be present in injected industrial CO₂ streams at varying concentrations, and may induce higher reactivity to cap-rock than pure CO₂. Dissolution or precipitation of minerals may modify the porosity or permeability of cap-rocks and compromise or improve the seal. A calcite cemented cap-rock drill core sample (Evergreen Formation, Surat Basin) was experimentally reacted with formation water and CO₂ containing SO₂ and O₂ at 60 °C and 120 bar. Solution pH was quickly buffered by dissolution of calcite cement, with dissolved ions including Ca, Mn, Mg, Sr, Ba, Fe and Si released to solution. Dissolved concentrations of several elements including Ca, Ba, Si and S had a decreasing trend after 200 h. Extensive calcite cement dissolution with growth of gypsum in the formed pore space, and barite precipitation on mineral surfaces were observed after reaction via SEM-EDS. A silica and aluminium rich precipitate was also observed coating grains. Kinetic geochemical modelling of the experimental data predicted mainly calcite and chlorite dissolution, with gypsum, kaolinite, goethite, smectite and barite precipitation and a slight net increase in mineral volume (decrease in porosity). To better approximate the experimental water chemistry it required the reactive surface areas of: (1) calcite cement decreased to 1 cm²/g; and, (2) chlorite increased to 7000 cm²/g. Models were then up-scaled and run for 30 or 100 years to compare the reactivity of calcite cemented, mudstone, siderite cemented or shale cap-rock sections of the Evergreen Formation in the Surat Basin, Queensland, Australia, a proposed target for future large scale CO₂ storage. Calcite, siderite, chlorite and plagioclase were the main minerals dissolving. Smectite, siderite, ankerite, hematite and kaolinite were predicted to precipitate, with SO₂ sequestered as anhydrite, alunite, and pyrite. Predicted net changes in porosity after reaction with CO₂, CO₂-SO₂ or CO₂-SO₂-O₂ were however minimal, which is favourable for cap-rock integrity. Mineral trapping of CO₂ as siderite and ankerite however was only predicted in the CO₂ or CO₂-SO₂ simulations. This indicates a limit on the injected O₂ content may be needed to optimise mineral trapping of CO₂, the most secure form of CO₂ storage. Smectites were predicted to form in all simulations, they have relatively high CO₂ sorption capacities and provide additional storage. Full article

The catalytic behavior of zeolite catalysts for the ammonia-based selective catalytic reduction (SCR) of nitrogen oxides (NO_X) depends strongly on the type of zeolite material. An essential precondition for SCR is a previous ammonia gas adsorption that occurs on acidic sites of the zeolite. In order to understand and develop SCR active materials, it is crucial to know the amount of sorbed ammonia under reaction conditions. To support classical temperature-programmed desorption (TPD) experiments, a correlation of the dielectric properties with the catalytic properties and the ammonia sorption under reaction conditions appears promising. In this work, a laboratory test setup, which enables direct measurements of the dielectric properties of catalytic powder samples under a defined gas atmosphere and temperature by microwave cavity perturbation, has been developed. Based on previous investigations and computational simulations, a resonator cavity and a heating system were designed, installed and characterized. The resonator cavity is designed to operate in its TM₀₁₀ mode at 1.2 GHz. The first measurement of the ammonia loading of an H-ZSM-5 zeolite confirmed the operating performance of the test setup at constant temperatures of up to 300 °C. It showed how both real and imaginary parts of the relative complex permittivity are strongly correlated with the mass of stored ammonia. Full article

An impedimetric NO_x dosimeter based on the NO_x sorption material KMnO₄ is proposed. In addition to its application as a low level NO_x dosimeter, KMnO₄ shows potential as a precious metal free lean NO_x trap material (LNT) for NO_x storage catalysts (NSC) enabling electrical in-situ diagnostics. With this dosimeter, low levels of NO and NO₂ exposure can be detected electrically as instantaneous values at 380 °C by progressive NO_x accumulation in the KMnO₄ based sensitive layer. The linear NO_x sensing characteristics are recovered periodically by heating to 650 °C or switching to rich atmospheres. Further insight into the NO_x sorption-dependent conductivity of the KMnO₄-based material is obtained by the novel eTPD method that combines electrical characterization with classical temperature programmed desorption (TPD). The NO_x loading amount increases proportionally to the NO_x exposure time at sorption temperature. The cumulated NO_x exposure, as well as the corresponding NO_x loading state, can be detected linearly by electrical means in two modes: (1) time-continuously during the sorption interval including NO_x concentration information from the signal derivative or (2) during the short-term thermal NO_x release. Full article