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1.
Chemistry ; : e202401803, 2024 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-39109481

RESUMO

Selective catalytic reduction of nitrogen oxides with NH3 at low temperatures remains a crucial goal for industrial applications. However, effective catalysts operating at 70-90 °C are rarely reported, limiting SCR scenarios to high-temperature conditions. Herein, we report a unique MnO2 nanofilament catalyst grown on activated semi-coke synthesized via a one-step in situ hydrothermal approach, which exhibits a stable and marked 100 % conversion rate of NO to N2 with 100 % selectivity at 90 °C, superior to the other prepared structures (nanowires, nanorods, and nanotubes). Temperature-programmed desorption shows a large number of acid sites on MnO2(NFs)/ASC, benefiting the formation of NH4 + ions. Meanwhile, diffuse reflectance infrared Fourier transform spectroscopy reveals the activation of NO with O2 to form bidentate nitrate/bridging nitrate NO2 intermediates via bidentate nitrate species, triggering the Fast SCR with NH3 at low temperatures. Such an effective, easy-to-prepare, and low-cost catalyst paves a new pathway for low-temperature SCR for a wide range of application scenarios.

2.
Chemphyschem ; 25(6): e202300632, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38199957

RESUMO

With the introduction of increasingly strict emission regulations, reducing nitrogen oxide (NOx ) emissions and nitrous oxide (N2 O) production from diesel engines have become the focus of research. At high temperature, the reaction of NO2 in the catalyst generates the intermediate product NH4 NO3 , which first crystallizes below 300 °C. These crystals tend to block the pores and inhibit the reaction. Subsequently, N2 O is produced through the decomposition of NH4 NO3 , leading to additional pollution. Therefore, the concentration of NO2 has a direct impact on both the NOx conversion efficiency and the generation of N2 O, requiring consideration of the optimal proportion of NO2 in SCR. Considering these two factors, it is concluded that the optimal amount of NO2 varies with temperature. To improve the NOx conversion rate of the Cu-SSZ-13 catalyst at low temperatures and reduce N2 O generation, the optimal NO2 ratio of the Cu-SSZ-13 catalyst under various operating conditions is studied using numerical simulations. As the temperature rises, the optimal NO2 /NOx ratio first increases and then decreases. Under the optimal NO2 /NOx ratio, the NOx conversion rate significantly increases, while N2 O generation decreases considerably. The optimal NO2 /NOx ratio also provides suggestions for the optimization of the DOC-DPF-DCR system.

3.
Environ Sci Technol ; 58(9): 4145-4154, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38381076

RESUMO

The deactivation of selective catalytic reduction (SCR) catalysts caused by alkali metal poisoning remains an insurmountable challenge. In this study, we examined the impact of Na poisoning on the performance of Fe and Mo co-doped TiO2 (FeaMobTiOx) catalysts in the SCR reaction and revealed the related alkali resistance mechanism. On the obtained Fe1Mo2.6TiOx catalyst, the synergistic catalytic effect of uniformly dispersed FeOx and MoOx species leads to remarkable catalytic activity, with over 90% NO conversion achieved in a wide temperature range of 210-410 °C. During the Na poisoning process, Na ions predominantly adsorb on the MoOx species, which exhibit stronger alkali resistance, effectively safeguarding the FeOx species. This preferential adsorption minimizes the negative effect of Na poisoning on Fe1Mo2.6TiOx. Moreover, Na poisoning has little influence on the Eley-Rideal reaction pathway involving adsorbed NHx reacting with gaseous NOx. After Na poisoning, the Lewis acid sites were deteriorated, while the abundant Brønsted acid sites ensured sufficient NHx adsorption. As a benefit from the self-defense effects of active MoOx species for alkali capture, FeaMobTiOx exhibits exceptional alkali resistance in the SCR reaction. This research provides valuable insights for the design of highly efficient and alkali-resistant SCR catalysts.


Assuntos
Álcalis , Amônia , Catálise , Ácidos de Lewis , Metais
4.
Environ Sci Technol ; 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39013630

RESUMO

Renewing metal-poisoned NH3-SCR catalysts holds great potential for mitigating environmental pollution and utilizing hazardous wastes simultaneously. Ionic compounds containing heavy metals often exhibit limited solubility due to their high polarizability, making traditional washing techniques ineffective in removing heavy metal poisons. This study presents a gas-based method for regenerating heavy-metal-poisoned V2O5-WO3/TiO2 catalysts employed in NH3-SCR techniques. The regeneration is achieved by employing a masking and reconstruction strategy, which involves the in situ formation of NO2 to mediate the production of SO3. This enables the effective bonding of Pb and triggers the reconstruction of active VOx sites. In situ spectroscopy confirms that the sulfation of PbO restores acidity, while the occupied effect resulting from the sulfation of TiO2 promotes the formation of more polymeric VOx species. Consequently, the regenerated catalyst exhibits enhanced activity and superior resistance to metal poisons compared with the fresh catalyst. The innovative method offers a promising solution for extending the lifespan of poisoned catalysts, reducing waste generation, and enhancing the efficiency of NH3-SCR systems.

5.
Environ Sci Technol ; 2024 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-39138907

RESUMO

Hitherto, sulfur poisoning and hydrothermal aging have still been the challenges faced in practical applications of the Cu-SSZ-13 catalyst for the selective catalytic reduction (SCR) of NOx from diesel engine exhaust. Here, we elaborately design and conduct an in-depth investigation of the synthetic effects of hydrothermal aging and SO2 poisoning on pristine Cu-SSZ-13 and Cu-SSZ-13@Ce0.75Zr0.25O2 core@shell structure catalysts (Cu@CZ). It has been discovered that Cu@CZ susceptible to 750 °C with 5 vol % H2O followed by 200 ppm SO2 with 5 vol % H2O (Cu@CZ-A-S) could still maintain nearly 100% NOx conversion across the significantly wider temperature region of 200-425 °C, which is remarkably broader than that of the Cu-SSZ-13-A-S (300-400 °C) counterpart. The experimental results show that the hydrothermal aging process results in the migration of highly active Cu species within the cage of Cu-SSZ-13 to the CZ surface, forming CuO/CZ with abundant interfaces, which significantly enhances the adsorption and subsequent activation of NO, leading to the generation of reactive N2O3 and HONO intermediates. Moreover, density functional theory (DFT) calculations reveal that the H of the HONO* species can function as Brønsted acid sites, effectively adsorbing NH3 to generate the active NH4NO2* intermediate, which readily decomposes into N2 and H2O. Furthermore, this pathway is the rate-determining step with an energy barrier of 0.93 eV, notably lower than that of the "standard SCR" pathway (1.42 eV). Therefore, the formation of the new CuO/CZ interface profoundly boosts the low-temperature NH3-SCR activity and improves the coresistance of the Cu@CZ catalyst to sulfur poisoning and hydrothermal aging.

6.
Environ Sci Technol ; 58(37): 16357-16367, 2024 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-39219475

RESUMO

Regulating vanadia-based oxides has been widely utilized for fabricating effective difunctional catalysts for the simultaneous elimination of NOx and chlorobenzene (CB). However, the notorious accumulation of polychlorinated species and excessively strong NH3 adsorption on the catalysts lead to the deterioration of multipollutant control (MPC) activity. Herein, protonated sulfate (-HSO4) supported on vanadium-titanium catalysts via a preoccupied anchoring strategy are designed to prevent polychlorinated species and alleviate NH3 adsorption for the multipollutant control. The obtained catalysts with -HSO4 modification achieve an excellent NOx and CB conversion with turnover frequency values of ∼ 3.63 and 17.7 times higher than those of the pristine, respectively. The protonated sulfate promotes the formation of polymeric vanadyl with a higher chemical state and d-band center of V. The modulated catalysts not only substantially alleviate the competitive adsorption of multipollutant via the "V 3d-O 2p-S 3p" network, but also distinctly strengthen the Brønsted acid sites. Besides, the introduced proton donor of the -HSO4 connecting polymeric structure could markedly reduce the reaction barrier of breaking the C-Cl bond. This work paves an advanced way for low-loading vanadium SCR catalysts to achieve highly efficient NOx and CB oxidation at a low temperature.


Assuntos
Vanádio , Catálise , Vanádio/química , Adsorção
7.
Environ Sci Technol ; 2024 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-39083593

RESUMO

Mn-based catalysts are promising candidates for eliminating harmful nitrogen oxides (NOx) via selective catalytic reduction with ammonia (NH3-SCR) due to their inherent strong redox abilities. However, poor water tolerance and low N2 selectivity are still the main limitations for practical applications. Herein, we succeeded in preparing an active catalyst for NH3-SCR with improved water tolerance and N2 selectivity based on protecting MnOx with a secondary growth of a hydrophobic silicalite-1. This protection suppressed catalyst deactivation by water adsorption. Interestingly, impregnating MnOx on MesoTS-1 followed by silicalite-1 protection allowed for a higher dispersion of MnOx species, thus increasing the concentration of acid sites. Consequently, the level of N2O formation is decreased. These improvements resulted in a broader operating temperature of NOx conversion and a modification of the NH3-SCR mechanism. Diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that unprotected Mn/MesoTS-1 mainly followed the Eley-Rideal mechanism, while Mn/MesoTS-1@S1 followed both Langmuir-Hinshelwood and Eley-Rideal mechanisms.

8.
Environ Res ; 246: 118037, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38160964

RESUMO

Carbon monoxide (CO) has recently been considered an ideal reducing agent to replace NH3 in selective catalytic reduction of NOx (NH3-SCR). This shift is particularly relevant in diesel engines, coal-fired industry, the iron and steel industry, of which generate substantial amounts of CO due to incomplete combustion. Developing high-performance catalysts remain a critical challenge for commercializing this technology. The active sites on catalyst surface play a crucial role in the various microscopic reaction steps of this reaction. This work provides a comprehensive overview and insights into the reaction mechanism of active sites on transition metal- and noble metal-based catalysts, including the types of intermediates and active sites, as well as the conversion mechanism of active molecules or atoms. In addition, the effects of factors such as O2, SO2, and alkali metals, on NO reduction by CO were discussed, and the prospects for catalyst design are proposed. It is hoped to provide theoretical guidance for the rational design of efficient CO selective catalytic denitration materials based on the structure-activity relations.


Assuntos
Poluentes Ambientais , Gases , Catálise , Monóxido de Carbono , Indústrias
9.
Molecules ; 29(18)2024 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-39339501

RESUMO

Selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3-SCR) has been implemented in response to the regulation of NOx emissions from stationary and mobile sources above 300 °C. However, the development of NH3-SCR catalysts active at low temperatures below 200 °C is still needed to improve the energy efficiency and to cope with various fuels. In this review article, recent reports on low-temperature NH3-SCR catalysts are systematically summarized. The redox property as well as the surface acidity are two main factors that affect the catalytic activity. The strong redox property is beneficial for the low-temperature NH3-SCR activity but is responsible for N2O formation. The multiple electron transfer system is more plausible for controlling redox properties. H2O and SOx, which are often found with NOx in flue gas, have a detrimental effect on NH3-SCR activity, especially at low temperatures. The competitive adsorption of H2O can be minimized by enhancing the hydrophobic property of the catalyst. Various strategies to improve the resistance to SOx poisoning are also discussed.

10.
Environ Sci Technol ; 57(38): 14472-14481, 2023 09 26.
Artigo em Inglês | MEDLINE | ID: mdl-37695840

RESUMO

Catalyst deactivation caused by alkali metal poisoning has long been a key bottleneck in the application of selective catalytic reduction of NOx with NH3 (NH3-SCR), limiting the service life of the catalyst and increasing the cost of environmental protection. Despite great efforts, continuous accumulation of alkali metal deposition makes the resistance capacity of 2 wt % K2O difficult to enhance via merely loading acid sites on the surface, resulting in rapid deactivation and frequent replacement of the NH3-SCR catalyst. To further improve the resistance of alkali metals, encapsulating alkali metals into the bulk phase could be a promising strategy. The bottleneck of 2 wt % K2O tolerance has been solved by virtue of ultrahigh potassium storage capacity in the amorphous FePO4 bulk phase. Amorphous FePO4 as a support of the NH3-SCR catalyst exhibited a self-adaptive alkali-tolerance mechanism, where potassium ions spontaneously migrated into the bulk phase of amorphous FePO4 and were anchored by PO43- with the generation of Fe2O3 at the NH3-SCR reaction temperature. This ingenious potassium storage mechanism could boost the K2O resistance capacity to 6 wt % while maintaining approximately 81% NOx conversion. Besides, amorphous FePO4 also exhibited excellent resistance to individual and coexistence of alkali (K2O and Na2O), alkali earth (CaO), and heavy metals (PbO and CdO), providing long durability for CePO4/FePO4 catalysts in flue gas with multipollutants. The cheap and accessible amorphous FePO4 paves the way for the development and implementation of poisoning-resistant NOx abatement.


Assuntos
Álcalis , Potássio , Catálise , Temperatura
11.
Environ Sci Technol ; 57(20): 7858-7866, 2023 05 23.
Artigo em Inglês | MEDLINE | ID: mdl-37161886

RESUMO

Selective catalytic reduction (SCR) of NOx with NH3 is the most efficient technology for NOx emissions control, but the activity of catalysts decreases exponentially with the decrease in reaction temperature, hindering the application of the technology in low-temperature SCR to treat industrial stack gases. Here, we present an industrially practicable technology to significantly enhance the SCR activity at low temperatures (<250 °C). By introducing an appropriate amount of O3 into the simulated stack gas, we find that O3 can stoichiometrically oxidize NO to generate NO2, which enables NO reduction to follow the fast SCR mechanism so as to accelerate SCR at low temperatures, and, in particular, an increase in SCR rate by more than four times is observed over atom-pair V1-W1 active sites supported on TiO2(001) at 200 °C. Using operando SCR tests and in situ diffuse reflectance infrared Fourier transform spectra, we reveal that the introduction of O3 allows SCR to proceed along a NH4NO3-mediated Langmuir-Hinshelwood model, in which the adsorbed nitrate species speed up the re-oxidation of the catalytic sites that is the rate-limiting step of SCR, thus leading to the enhancement of activity at low temperatures. This technology could be applicable in the real stack gas conditions because O3 exclusively oxidizes NO even in the co-presence of SO2 and H2O, which provides a general strategy to improve low-temperature SCR efficacy from another perspective beyond designing catalysts.


Assuntos
Amônia , Gases , Domínio Catalítico , Amônia/química , Oxirredução , Temperatura , Catálise
12.
Environ Sci Technol ; 57(46): 18080-18090, 2023 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-37393584

RESUMO

An iterative approach between machine learning (ML) and laboratory experiments was developed to accelerate the design and synthesis of environmental catalysts (ECs) using selective catalytic reduction (SCR) of nitrogen oxides (NOx) as an example. The main steps in the approach include training a ML model using the relevant data collected from the literature, screening candidate catalysts from the trained model, experimentally synthesizing and characterizing the candidates, updating the ML model by incorporating the new experimental results, and screening promising catalysts again with the updated model. This process is iterated with a goal to obtain an optimized catalyst. Using the iterative approach in this study, a novel SCR NOx catalyst with low cost, high activity, and a wide range of application temperatures was found and successfully synthesized after four iterations. The approach is general enough that it can be readily extended for screening and optimizing the design of other environmental catalysts and has strong implications for the discovery of other environmental materials.


Assuntos
Amônia , Óxidos , Óxidos de Nitrogênio , Oxirredução , Temperatura , Catálise
13.
Environ Sci Technol ; 57(28): 10211-10220, 2023 07 18.
Artigo em Inglês | MEDLINE | ID: mdl-37427417

RESUMO

Modulating vanadia-based metal oxides is one of the effective methods for designing difunctional catalysts for simultaneous control of NOx and chlorobenzene (CB) from the emissions of industrial sources. Excessive NH3 adsorption and polychlorinated species accumulation on the surface are the primary issues poisoning catalysts and reducing their lifetime. Herein, Sb is selected as an NH3 adsorption alleviator and polychlorinated species preventor dopant on V2O5-WO3/TiO2. The catalyst exhibits an excellent performance for total NOx and 90% CB conversions at 300-400 °C under a gas hourly space velocity (GHSV) of 60,000 mL g-1 h-1. The HCl and N2 selectivities are maintained at 90 and 98%, respectively. The anti-poisoning ability could be attributed to the generated V-O-Sb chains on the surface: the band gap of vanadium is narrowed and the electron capability is strengthened. The above variation weakens the Lewis acid sites and blocks the electrophilic chlorination reactions of the catalyst surface (formation of polychlorinated species). In addition, oxygen vacancies on Sb-O-Ti also increase: the ring opening of benzoates is accelerated and NH3 adsorption energy is weakened. The above variation lowers the energy barriers of C-Cl cleavage even under NH3 pre-adsorption models and enhances NOx reduction thermodynamically and kinetically.


Assuntos
Poluentes Ambientais , Titânio , Amônia , Óxidos , Catálise
14.
Environ Sci Technol ; 57(43): 16685-16694, 2023 10 31.
Artigo em Inglês | MEDLINE | ID: mdl-37864569

RESUMO

Selective catalytic reduction of NOx by NH3 (NH3-SCR) for diesel emission control at low temperatures is still a great challenge due to the limit of the urea injection threshold and inferior SCR activity of state-of-the-art catalyst systems below 200 °C. Fabricating bifunctional catalysts with both low temperature NOx adsorption-storage capacity and medium-high temperature NOx reduction activity is an effective strategy to solve the issues mentioned above but is rarely investigated. Herein, the WO3/Ce0.68Zr0.32Ox (W/CZ) catalyst containing the κ-Ce2Zr2O8 pyrochlore structure was successfully developed by a simple H2 reduction method, not only showing superior NOx adsorption-storage ability below 180 °C but also exhibiting excellent NH3-SCR activity above 180 °C. The presence of the pyrochlore structure effectively increased the oxygen vacancies on the κ-Ce2Zr2O8-containing W/CZ catalyst with enhanced redox property, which significantly promoted the NOx adsorption-storage as active nitrate species below 180 °C. Upon NH3 introduction above 180 °C, the κ-Ce2Zr2O8-containing W/CZ catalyst showed greatly improved NOx reduction performance, suggesting that the pyrochlore structure played a vital role in improving the NOx adsorption-selective catalytic reduction (AdSCR) performance. This work provides a new perspective for designing bifunctional CeZrOx-based catalysts to efficiently control the NOx emissions from diesel engines during the cold-start process.


Assuntos
Amônia , Nióbio , Adsorção , Amônia/química , Oxirredução , Catálise
15.
Environ Res ; 227: 115707, 2023 06 15.
Artigo em Inglês | MEDLINE | ID: mdl-36931382

RESUMO

Superior de-NOx activity and N2 selectivity of the Pd/ZSM-5 catalyst was observed at low temperature (<200 °C) for the selective catalytic reduction of NOx by H2 (H2-SCR). Various Pd/ZSM-5 catalysts were prepared by calcinating at different temperatures (e.g., 500 °C, 650 °C, 750 °C, and 850 °C) and treated at reductive conditions before the H2-SCR reaction was performed. Among the prepared catalysts, the one prepared at the calcination temperature at 750 °C resulted in 96.7% NOx conversion and 96.8% N2 selectivity at 150 °C. Based on the H2-O2 reaction, the higher activity of the Pd/ZSM-5 catalyst calcined at 750 °C was attributed to its superior H2 activation ability for the H2-SCR reaction. The combined X-ray diffraction (XRD), temperature-programmed hydride decomposition (TPHD), and transmission electron microscopy (TEM) results revealed that highly dispersed Pd particles were generated on the catalyst calcined at 750 °C, while large Pd agglomerates were formed on the one calcined at 500 °C. It can be concluded that the catalytic activity of Pd/ZSM-5 improves by optimizing the calcination temperature, resulting in high Pd dispersion. Moreover, the Pd catalyst calcined at 750 °C showed high resistance to CO, maintaining >94% NOx conversion at 175 °C under 1000 ppm CO in the feed gas. Therefore, the catalyst calcined at 750 °C can be potentially used for industrial applications because of its simple preparation method and high resistance to CO.


Assuntos
Amônia , Temperatura Baixa , Temperatura , Catálise , Oxirredução
16.
Environ Res ; 227: 115744, 2023 06 15.
Artigo em Inglês | MEDLINE | ID: mdl-36963711

RESUMO

This study investigated the effect of Nb doping into V2O5-WO3/TiO2 (VWT) catalyst for removing NOxvia the SCR (selective catalytic reduction) by NH3. The experimental results exhibited that Nb can improve the reactivity of the VWT catalyst at low temperatures. The addition of Nb also enhanced the tolerance to SO2 and H2O. The de-NOx efficiency of the V2O5-WO3-Nb2O5/TiO2 (VWNbT) catalyst was increased up to 12% over that of the VWT catalyst at 240 °C when the catalyst was poisoned for 24 h. The prepared catalysts were characterized by FT-IR, XRD, XPS, and N2 physisorption, elemental analysis. The results showed that the ammonium bisulfate (ABS) was less formed in the VWNbT than in the VWT. Moreover, evolved gas analysis was performed to examine the thermal decomposition behavior of the poisoned catalyst, and confirmed that the ABS deposited on the catalyst was sufficiently decomposed between about 300 and 400 °C. In particular, to most effectively recover the characteristics and activity of the catalysts, thermal treatment at a temperature of 400 °C is suitable.


Assuntos
Amônia , Nióbio , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura , Titânio , Catálise
17.
J Environ Manage ; 347: 119107, 2023 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-37801947

RESUMO

Spent selective catalytic reduction (SCR) catalysts are environmentally hazardous and resource-enriching. In this work, V, W, and As in a spent SCR catalyst was extracted by alkali pressure leaching. Results showed that the V, W, and As were loaded on the anatase TiO2 crystal grains as amorphous oxides. The optimum pressure leaching conditions were NaOH concentration of 20 wt%, reaction temperature of 180 °C, reaction time of 120 min, L/S of 10 mL/g, and stirring speed of 300 rpm. The leaching efficiency of W, V, and As reached 98.83%, 100%, and 100%, respectively. The experiment revealed the preferential leaching of V and As rather than W, and the leaching mechanisms of V, W, and As were studied through experiment and density functional theory (DFT). The leaching kinetics of W conformed to a variant of the shrinking core model and the leaching process of W is controlled by both chemical reactions and diffusion processes. During the leaching process, Na2Ti2O4(OH)2 product powder layer was generated, which affects the mass transfer of W. The destruction of the TiO2 skeleton in the spent SCR catalyst is essential for adequate W extraction, especially for the extraction of W embedded in the TiO2 lattice. The DFT simulation result indicated that the V and As loaded onto the TiO2 support are easier to absorb hydroxide ions rather than W, and the leaching reaction energy of V and As was lower than W, As, and V has leaching priority over the leaching of W. Furthermore, an anatase TiO2 photocatalyst with the {001} crystal surface exposed was successfully prepared from the alkali pressure leaching residue. This work provides theoretical support for the metal leaching and utilization of spent SCR catalysts via alkali pressure leaching.


Assuntos
Álcalis , Titânio , Álcalis/química , Titânio/química , Metais , Óxidos/química , Catálise
18.
Molecules ; 28(5)2023 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-36903585

RESUMO

The thermal analysis kinetic method was employed to solve the activation energies of the thermal decomposition reactions of urea and cyanuric acid, with the purpose of understanding the formation of deposits in the diesel engine SCR system. The deposit reaction kinetic model was established by optimizing the reaction paths and reaction kinetic parameters based on the thermal analysis test data of the key components in the deposit. The result shows that the established deposit reaction kinetic model can accurately describe the decomposition process of the key components in the deposit. Compared to the Ebrahimian model, the simulation precision of the established deposit reaction kinetic model is significantly improved above 600 K. The activation energies of the urea and cyanuric acid decomposition reactions are 84 kJ/mol and 152 kJ/mol, respectively, after model parameters identification. The identified activation energies were closest to those of the Friedman one-interval method indicating that the Friedman one-interval method is reasonable to solve the activation energies of deposit reactions.

19.
Molecules ; 28(5)2023 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-36903617

RESUMO

γ-Fe2O3 is considered to be a promising catalyst for the selective catalytic reduction (SCR) of nitrogen oxide (NOx). In this study, first-principle calculations based on the density function theory (DFT) were utilized to explore the adsorption mechanism of NH3, NO, and other molecules on γ-Fe2O3, which is identified as a crucial step in the SCR process to eliminate NOx from coal-fired flue gas. The adsorption characteristics of reactants (NH3 and NOx) and products (N2 and H2O) at different active sites of the γ-Fe2O3 (111) surface were investigated. The results show that the NH3 was preferably adsorbed on the octahedral Fe site, with the N atom bonding to the octahedral Fe site. Both octahedral and tetrahedral Fe atoms were likely involved in bonding with the N and O atoms during the NO adsorption. The NO tended to be adsorbed on the tetrahedral Fe site though the combination of the N atom and the Fe site. Meanwhile, the simultaneous bonding of N and O atoms with surface sites made the adsorption more stable than that of single atom bonding. The γ-Fe2O3 (111) surface exhibited a low adsorption energy for N2 and H2O, suggesting that they could be adsorbed onto the surface but were readily desorbed, thus facilitating the SCR reaction. This work is conducive to reveal the reaction mechanism of SCR on γ-Fe2O3 and contributes to the development of low-temperature iron-based SCR catalysts.

20.
J Environ Sci (China) ; 123: 212-221, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36521985

RESUMO

Vessel emissions have contributed a great deal to air quality deterioration in China. Hence, the Chinese government has promulgated a series of stringent emission regulations. It is in this context that vessel emission control technology research is in full swing. In particular, during the 13th Five-Year Plan, the air pollution control technology of vessels has greatly improved. Vessel emission control has followed two main governance routes: source emission reduction and aftertreatment technology. Source control focuses on alternative fuels, with two main directions, the development of new fuels and the modification of existing fuels. Moreover, after-treatment technologies have also been developed, including wet desulfurization technology using seawater or alkaline liquids as wet washing liquids and selective catalytic reduction (SCR) for the control of NOx emission. Due to China's increasingly stringent emissions standards and regulations, work on the development of clean alternative fuels and further upgrading the collaborative application of after-treatment technologies to meet the near-zero-emissions requirements of vessels is still necessary.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Emissões de Veículos/análise , Poluentes Atmosféricos/análise , Poluição do Ar/prevenção & controle , Poluição do Ar/análise , China , Catálise
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