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1.
Environ Sci Technol ; 58(15): 6704-6715, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38574268

RESUMO

The transformation of toxic arsine (AsH3) gas into valuable elemental arsenic (As0) from industrial exhaust gases is important for achieving sustainable development goals. Although advanced arsenic removal catalysts can improve the removal efficiency of AsH3, toxic arsenic oxides generated during this process have not received adequate attention. In light of this, a novel approach for obtaining stable As0 products was proposed by performing controlled moderate oxidation. We designed a tailored Ni-based catalyst through an acid etching approach to alter interactions between Ni and NaY. As a result, the 1Ni/NaY-H catalyst yielded an unprecedented proportion of As0 as the major product (65%), which is superior to those of other reported catalysts that only produced arsenic oxides. Density functional theory calculations clarified that Ni species changed the electronic structure of oxygen atoms, and the formed [NiIII-OH (µ-O)] active centers facilitated the adsorption of AsH2*, AsH*, and As* reaction intermediates for As-H bond cleavage, thereby decreasing the direct reactivity of oxygen with the arsenic intermediates. This work presents pioneering insights into inhibiting excessive oxidation during AsH3 removal, demonstrating potential environmental applications for recovery of As0 from toxic AsH3.


Assuntos
Arsênio , Zeolitas , Níquel/química , Elétrons , Oxigênio , Gases
2.
Artigo em Inglês | MEDLINE | ID: mdl-38527651

RESUMO

OBJECTIVE: KRAS G12V is one of the most common KRAS mutation variants in lung adenocarcinoma (LUAD), and yet its prognostic value is still unrevealed. In this study, we investigated the clinicopathologic characteristics and prognostic value of the KRAS G12V mutation in LUAD. METHODS: Data of 3829 patients who underwent LUAD resection between 2008 and 2020 were collected. Mutations were classified as wild-type, G12V, or non-G12V. The clinicopathologic characteristics, postoperative outcomes, and recurrence pattern were analyzed among groups. RESULTS: In total, 3554 patients were wild-type and 275 patients harbored a KRAS mutation: 60 patients with G12V (22.2%) and 215 patients with non-G12V (77.8%). The KRAS G12V mutation was more frequent in male patients, older patients (≥60 years), former/current smokers, those patients with radiologic solid nodules, and those with highly invasive histologic subtypes. Tumors carrying KRAS G12V mutation exhibited elevated programmed death-ligand 1 expression in comparison with wild-type tumors. KRAS G12V was more prevalent in older patients and had less lymphovascular invasion compared with other mutation types. FGF3, RET, and KDR co-mutations occurred more frequently in the KRAS G12V group. Multivariate analysis demonstrated that the KRAS G12V mutation was an independent prognostic factor in stage Ⅰ tumors, whereas the KRAS non-G12V mutation was not. KRAS G12V was associated with early recurrence and locoregional recurrence. CONCLUSIONS: The KRAS G12V mutation was associated with aggressive clinical-pathologic phenotype and early recurrence. To note, this mutation exhibited a significantly worse prognosis in patients with part-solid and stage Ⅰ lung adenocarcinoma. Meanwhile, the prognostic significance of KRAS G12C and G12V variants was comparable.

3.
Environ Sci Technol ; 57(29): 10882-10890, 2023 07 25.
Artigo em Inglês | MEDLINE | ID: mdl-37436147

RESUMO

Gaseous elemental mercury (Hg0) extraction from industrial flue gases is undergoing intense research due to its unique properties. Selective adsorption that renders Hg0 to HgO or HgS over metal oxide- or sulfide-based sorbents is a promising method, yet the sorbents are easily poisoned by sulfur dioxide (SO2) and H2O vapor. The Se-Cl intermediate derived from SeO2 and HCl driven by SO2 has been demonstrated to stabilize Hg0. Thus, a surface-induced method was put forward when using γ-Al2O3 supported selenite-chloride (xSeO32--yCl-, named xSe-yCl) for mercury deposition. Results confirmed that under 3000 ppm SO2 and 4% H2O, Se-2Cl exhibited the highest induced adsorption performance at 160 °C and higher humidity can accelerate the induction process. Driven by SO2 under the wet interface, the in situ generated active Se0 has high affinity toward Hg0, and the introduction of Cl- enabled the fast-trapping and stabilization of Hg0 due to its intercalation in the HgSe product. Additionally, the long-time scale-up experiment showed a gradient color change of the Se-2Cl-induced surface, which maintained almost 100% Hg0 removal efficiency over 180 h with a normalized adsorption capacity of 157.26 mg/g. This surface-induced method has the potential for practical application and offers a guideline for reversing the negative effect of SO2 on gaseous pollutant removal.


Assuntos
Poluentes Atmosféricos , Poluentes Ambientais , Mercúrio , Dióxido de Enxofre , Mercúrio/análise , Cloretos , Óxidos , Adsorção , Poluentes Atmosféricos/análise
4.
Sci Total Environ ; 891: 164203, 2023 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-37230360

RESUMO

The steel smelting process produces extensive CO2 and Ca-containing steel slag (SS). Meanwhile, the low value utilization of steel slag results in the loss of Ca resources. CO2 sequestration utilizing SS can reduce carbon emissions while achieving Ca circulation. However, conventional SS carbon sequestration methods suffer from slow reaction rates, finite Ca usage efficiency, and difficulty separating the CaCO3 product from SS. Herein, an innovative two-step leaching (TSL) and carbonation method was presented based on the variations in leaching efficiency of activated Ca under different conditions, aiming at efficient leaching, carbon sequestration, and high-value reuse of SS. This method employed two NH4Cl solutions in sequence for two leaching operations on SS, allowing the Ca leaching rate to be effectively increased. According to the findings, TSL could increase the activated Ca leaching rate by 26.9 % and achieve 223.15 kg CO2/t SS sequestration compared to the conventional one-step leaching (CSL) method. If part of the CaCO3 is recovered as a slagging agent, about 34.1 % of the exogenous Ca introduction could be saved. In addition, the CO2 sequestration of TSL did not significantly decrease after 8 cycles. This work proposes a strategy that has the potential for recycling SS and reducing carbon emissions.

5.
Environ Sci Technol ; 57(13): 5424-5432, 2023 04 04.
Artigo em Inglês | MEDLINE | ID: mdl-36939455

RESUMO

Flue gas mercury removal is mandatory for decreasing global mercury background concentration and ecosystem protection, but it severely suffers from the instability of traditional demercury products (e.g., HgCl2, HgO, HgS, and HgSe). Herein, we demonstrate a superstable Hg3Se2Cl2 compound, which offers a promising next-generation flue gas mercury removal strategy. Theoretical calculations revealed a superstable Hg bonding structure in Hg3Se2Cl2, with the highest mercury dissociation energy (4.71 eV) among all known mercury compounds. Experiments demonstrate its unprecedentedly high thermal stability (>400 °C) and strong acid resistance (5% H2SO4). The Hg3Se2Cl2 compound could be produced via the reduction of SeO32- to nascent active Se0 by the flue gas component SO2 and the subsequent combination of Se0 with Hg0 and Cl- ions or HgCl2. During a laboratory-simulated experiment, this Hg3Se2Cl2-based strategy achieves >96% removal efficiencies of both Hg0 and HgCl2 enabling nearly zero Hg0 re-emission. As expected, real mercury removal efficiency under Se-rich industrial flue gas conditions is much more efficient than Se-poor counterparts, confirming the feasibility of this Hg3Se2Cl2-based strategy for practical applications. This study sheds light on the importance of stable demercury products in flue gas mercury treatment and also provides a highly efficient and safe flue gas demercury strategy.


Assuntos
Poluentes Atmosféricos , Mercúrio , Mercúrio/análise , Ecossistema , Gases/química , Poluentes Atmosféricos/análise
6.
Environ Sci Technol ; 56(15): 10935-10944, 2022 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-35867955

RESUMO

Sulfur trioxide (SO3) is an unstable pollutant, and its removal from the gas phase of industrial flue gas remains a significant challenge. Herein, we propose a reverse conversion treatment (RCT) strategy to reduce S(VI) in SO3 to S(IV) by combining bench-scale experiments and theoretical studies. We first demonstrated that metastable sulfides can break the S-O bond in SO3, leading to the re-formation of sulfur dioxide (SO2). The RCT performance varied between mono- and binary-metal sulfides, and metastable CuS had a high SO3 conversion efficiency in the temperature range of 200-300 °C. Accordingly, the introduction of selenium (Se) lowered the electronegativity of the CuS host and enhanced its reducibility to SO3. Among the CuSe1-xSx composites, CuSe0.3S0.7 was the optimal RCT material and reached a SO2 yield of 6.25 mmol/g in 120 min. The low-valence state of selenium (Se2-/Se1-) exhibited a higher reduction activity for SO3 than did S2-/S1-; however, excessive Se doping degraded the SO3 conversion owing to the re-oxidation of SO2 by the generated SeO32-. The density functional theory calculations verified the stronger SO3 adsorption performance (Eads = -2.76 eV) and lower S-O bond breaking energy (Ea = 1.34 eV) over CuSe0.3S0.7 compared to those over CuS and CuSe. Thus, CuSe1-xSx can serve as a model material and the RCT strategy can make use of field temperature conditions in nonferrous smelters for SO3 emission control.

7.
Environ Sci Pollut Res Int ; 29(47): 71721-71730, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-35599289

RESUMO

Oxidation-reduction-absorption based on sulfite is a promising process for simultaneous removal of NOx and SO2. However, excessive oxidation of sulfite and competitive absorption between NOx and SO2 limit its application. A matching strategy between antioxidants and alkaline agents has been proposed to solve these problems and enhance the absorption process. The comparison results of inhibitors showed that hydroquinone exhibited long-term high-efficiency inhibition of S(IV) (SO32-/HSO3-) oxidation. The comparison of alkaline agents showed that the Na2SO3 solution with heterogeneous mixture of MgO and hydroquinone exhibited better absorption performance than that with other combinations. The absorption amounts of NOx in 0.15 mol/L Na2SO3 50 mL solution added 0.1% hydroquinone (HQ) with 0.09 mol/L MgO were 2.24 mmol, which improved 5 times than that without additives. In addition, studies on the influence of pH showed that the pH of MgO mixture could be stabilized at 9-10 for a long time, while the pH of Na2CO3 mixture decreased faster. Further studies suggested that the hydration of MgO resulted in the solution with MgO keeping high pH. This is also the main reason why the combination of MgO and hydroquinone is superior to the combination of Na2CO3 and hydroquinone in desulfurization and denitration performance.


Assuntos
Hidroquinonas , Dióxido de Enxofre , Íons , Óxido de Magnésio , Oxirredução , Sódio , Sulfitos
8.
J Hazard Mater ; 423(Pt A): 127118, 2022 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-34523480

RESUMO

Adsorption is a superior method for removing and recycling high concentration of mercury from nonferrous metal smelting flue gas, especially adsorbents with good sulfur resistance and large adsorption capacity. In this study, Co and Mn oxide-modified layered ITQ-2 zeolites were designed to capture and recycle elemental mercury (Hg0). The physicochemical characteristics of the adsorbents were characterized using BET, XRD, FESEM, TEM, and XPS, and the results showed that Mn/ITQ-2 zeolite has a large specific surface area, and MnOx was highly dispersed on ITQ-2 zeolite. The Hg0 removal efficiency and adsorption capacity of the 5%Mn/ITQ-2 zeolite at 300 °C were 97% and 2.04 mg/g in 600 min, respectively, much higher than those of the previously reported 5%Mn/MCM-22 zeolite. The 2%Co-2%Mn/ITQ-2 zeolite exhibited a higher SO2 resistance performance. The mechanism of Hg0 removal was concluded to be driven by the primary catalytic oxidation of MnOx, secondary oxidation of active chlorine, and concurrent chemisorption. However, the Hg0 adsorption capacity was determined by the specific surface area and pore structure of ITQ-2. The 2%Co-2%Mn/ITQ-2 zeolite exhibited a high SO2 resistance performance. The Mn/ITQ-2 and Co-Mn/ITQ-2 zeolites have excellent regenerability and reusability, which can realize mercury recycling from flue gas.

9.
Environ Sci Technol ; 55(6): 3988-3995, 2021 03 16.
Artigo em Inglês | MEDLINE | ID: mdl-33666416

RESUMO

Direct sulfidation using a high concentration of H2S (HC-H2S) has shown potential for heavy metals removal in various acidic effluents. However, the lack of a smooth method for producing HC-H2S is a critical challenge. Herein, a novel short-process hydrolysis method was developed for the on-site production of HC-H2S. Near-perfect 100% efficiency and selectivity were obtained via CS2 hydrolysis over the ZrO2-based catalyst. Meanwhile, no apparent residual sulfur/sulfate poisoning was detected, which guaranteed long-term operation. The coexistence of CO2 in the products had a negligible effect on the complete hydrolysis of CS2. H2S production followed a sequential hydrolysis pathway, with the reactions for CS2 adsorption and dissociation being the rate-determining steps. The energy balance indicated that HC-H2S production was a mildly exothermic reaction, and the heat energy could be maintained at self-balance with approximately 80% heat recovery. The batch sulfidation efficiencies for As(III), Hg(II), Pb(II), and Cd(II) removal were over 99.9%, following the solubilities (Ksp) of the corresponding metal sulfides. CO2 in the mixed gas produced by CS2 hydrolysis did not affect heavy metals sulfidation due to the presence of abundant H+. Finally, a pilot-scale experiment successfully demonstrated the practical effects. Therefore, this novel on-site HC-H2S production method adequately achieved heavy metals removal requirements in acidic effluents.


Assuntos
Mercúrio , Metais Pesados , Adsorção , Catálise , Enxofre
10.
Environ Sci Pollut Res Int ; 28(13): 16447-16457, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33389582

RESUMO

A Co-Mn binary metal oxide-modified layered MCM-22 zeolite was designed to capture gaseous elemental mercury (Hg0) from SO2-containing flue gas. The physicochemical properties of the Co-Mn/MCM-22 zeolite were characterized by XRD, FESEM, TEM, and XPS, and the results showed that MnO2 was highly dispersed on the surface and in the channel of MCM-22 zeolite. Co3O4 was loaded onto the surface of the MCM-22 zeolite via the stepwise ion exchange method to prevent SO2 poisoning of the MnO2 active site. The Hg0 removal efficiency increased from 54 to 83% at 300 °C with 10% Co loading on the 5% Mn/MCM-22 zeolite when 200 ppm of SO2 was introduced to the flue gas. The mechanism of Hg0 removal was mainly associated with catalytic oxidation and chemisorption. Mn4+ was the main active site for catalytic oxidation of Hg0 to Hg2+, and the surface adsorbed oxygen re-oxidized Mn3+ and combined with Hg2+ to form Hg-O-Mn, in which Mn acted as a bridge. Co3+ preferentially reacted with SO2 to form CoSO4, thereby protecting the Mn active sites for Hg0 capture. Therefore, Co-Mn/MCM-22 zeolite is a promising sorbent for the removal of Hg0 and SO2 resistance from SO2-containing flue gas.


Assuntos
Mercúrio , Zeolitas , Catálise , Compostos de Manganês , Oxirredução , Óxidos
11.
Environ Sci Technol ; 54(18): 11594-11601, 2020 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-32835473

RESUMO

Transition metal elements doping is a conventional strategy for the modification of sulfide-based sorbents to obtain preferable Hg0 adsorption capability. One problem was that such a method could only obtain a temporary promotion to sulfides. To achieve continuous promotion of mercury capture performance, we use the difference of solubility product (Ksp) between sulfides to develop a postsynthesis approach for stepwise doping of PbS by Cu2+ ions. Moreover, it further demonstrated the restoration of PbS surface under a given high temperature, enabled by thermal migration of the foreign Cu2+ ions from outer to interlayer in PbS lattice and rereleased of S sites occupied previously by mercury. The Hg0 adsorption capacity of PbS was enlarged from 0.86 to 2.76 mg·g-1 after the first doping, resulting from the mild oxidization of S2- to S- in the surface layer by foreign Cu2+ ions. Furthermore, regeneration of spent PbS can be implemented by stepwise Cu2+ incorporation due to the renewability of the surface, enabling even better Hg0 adsorption capacity after six cycle tests. This stepwise incorporation method promises the precise utilization of doped elements, as well as offers a tutorial example for the activation and regeneration of sulfide sorbents to recover Hg0 from Hg0-rich flue gas.


Assuntos
Mercúrio , Adsorção , Carvão Mineral , Gases , Sulfetos
12.
J Colloid Interface Sci ; 577: 503-511, 2020 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-32505831

RESUMO

Chalcogen-based materials have been confirmed to possess large adsorption capacities for gaseous elemental mercury (Hg0) from SO2-containing flue gas. However, the interface reaction mechanisms and the interfacial stability are still ambiguous. Here, we selected some commonly used chalcogen-based sorbents (e.g., X, ZnX, CuX. X = S, Se) to investigate the in-depth reaction mechanisms. The adsorption capacities, structure effect on thermal and surface mercury stability, and interfacial reaction mechanism in the absence/presence of SO2 were evaluated. The experimental results indicated that Cu-chalcogenide had higher Hg0 adsorption capacity and surface Hg-X bonding stability compared with zinc one, while they exhibited an opposite degree of thermal stability. Moreover, all the chalcogenides showed well SO2 tolerance but with a slight difference. Chalcogenides with the same crystal structures, like ZnX or CuX, exhibited similar properties in stability and interfacial Hg0 and SO2 reaction mechanism. X- in chalcogenides have a better affinity to mercury, while in the Hg0 capture process, the existence of multivalent metal elements (like Cu2+ and Cu+) can faster the Hg0 oxidation for the further chemical-adsorption. This work provides a basic understanding of the application for efficiently enriching and recycling gaseous Hg0 from industrial SO2-containing flue gas.

13.
Environ Sci Pollut Res Int ; 27(16): 20469-20477, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32246424

RESUMO

The installation of electrostatic demisters (ESDs) makes possible the use of sorbent injection technology for recovering Hg0 from non-ferrous smelting gas. ZnS, as a typical smelting raw material, could be a promising candidate due to the sulfur boding site for mercury. However, the low reaction rate and poor adsorption capacity limited its application. In this study, Co was incorporated into ZnS to enhance adsorption activity for recovering Hg0. Co0.2Zn0.8S exhibited the best Hg0 capture performance among the modified sorbents. The Hg0 adsorption capacity was up to 46.01 mg/g at 50 °C (with 50% breakthrough threshold), and the adsorption rate was as high as 0.017 mg/(g min). Meanwhile, SO2 and H2O had no poison effects on Hg0 adsorption. The chemical adsorption mechanism was proposed, which was Co3+, and sulfur active sites could immobilize Hg0 in the form of stable HgS, following a Mars-Maessen reaction pathway. The spent sorbent will release ultrahigh concentration mercury-containing vapor through the heating treatment, which facilitated centralized recovery of Hg0. Meanwhile, inactivated sorbent can be used as smelting raw material to recover sulfur resources. Therefore, the control of Hg0 emission from non-ferrous smelting gas by Co-adopted ZnS was cost-effective and did not form secondary pollution. Graphical abstract.


Assuntos
Mercúrio , Adsorção , Metais , Sulfetos , Compostos de Zinco
14.
J Hazard Mater ; 392: 122230, 2020 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-32066016

RESUMO

It is difficult to stabilize gaseous elemental mercury (Hg°) on a sorbent from SO2-containing industrial flue gas. Enhancing Hg° oxidation and activating surface-active sulfur (S*) can benefit the chemical mercury adsorption process. A Mn-SnS2 composite was prepared using the Mn modification of SnS2 nanosheets to expose more Mn oxidation and sulfur adsorption sites. The results indicate that Mn-Sn2 exhibits better Hg° removal performances at a wide temperature range of 100-250 °C. A sufficient amount of surface Mn with a valance state of Mn4+ is favorable for Hg° oxidation, while the electron transfer properties of Sn can accelerate this oxidation process. Oxidized mercury primary exists as HgS with surface S*. A larger surface area, stable crystal structure, and active valance state of each element are favorable for Hg° oxidation and adsorption. The Mn-SnS2 exhibits an excellent SO2 resistance when the SO2 concentration is lower than 1500 ppm. The effects of H2O and O2 were also evaluated. The results show that O2 has no influence, while H2O and SO2 coexisting in the flue gas have a toxic effect on the Hg° removal performance. The Mn-SnS2 has a great potential for the Hg° removal from SO2-containing flue gas such as non-ferrous smelting gas.

15.
Environ Sci Technol ; 53(8): 4511-4518, 2019 04 16.
Artigo em Inglês | MEDLINE | ID: mdl-30855949

RESUMO

The flue gases with high concentration of mercury are often encountered in the nonferrous smelting industries and the treatment of mercury-containing wastes. To recover mercury from such flue gases, sorbents with enough large adsorption capacity are required to capture and enrich mercury. ZnS is a cheap and readily prepared material, and even can be obtained from its natural ores. In this work, a simple controllable oxidation method-soaking in cupric solution-was developed to improve the interfacial activity of ZnS and its natural ores for Hg0 adsorption. The gaseous Hg0 adsorption capacity of ZnS was enhanced from 0.3 to 3.6 mg·g-1 after such treatment. Further analysis indicated that a new interface rich in S1- ions was formed and provided sufficient active sites for the chemical adsorption of Hg0. In addition, the cyclic Hg0 adsorption and recovery experiments demonstrated that the adsorption performance of spent activated-ZnS was recovered after reactivating sorbents with Cu2+, indicating the recovery of activated interface. Meanwhile, the high concentration of adsorbed mercury at the surface can be collected using a thermal treatment method. Utilization of raw materials from a zinc production process provides a promising and cost-effective method for removing and recovering mercury from nonferrous smelting flue gas.


Assuntos
Mercúrio , Adsorção , Gases , Sulfetos , Compostos de Zinco
16.
J Environ Sci (China) ; 79: 111-120, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30784437

RESUMO

Hierarchical Ag-SiO2@Fe3O4 magnetic composites were selected for elemental mercury (Hg0) removal from non-ferrous metal smelting flue gas in this study. Results showed that the hierarchical Ag-SiO2@Fe3O4 magnetic composites had favorable Hg0 removal ability at low temperature. Moreover, the adsorption capacity of hierarchical magnetic composite is much larger than that of pure Fe3O4 and SiO2@Fe3O4. The Hg0 removal efficiency reached the highest value as approximately 92% under the reaction temperature of 150°C, while the removal efficiency sharply reduced in the absence of O2. The characterization results indicated that Ag nanoparticles grew on the surface of SiO2@Fe3O4 support. The large surface area of SiO2 supplied efficient reaction room for Hg and Ag atoms. Ag-Hg amalgam is generated on the surface of the composites. In addition, this magnetic material could be easily separated from fly ashes when adopted for treating real flue gas, and the spent materials could be regenerated using a simple thermal-desorption method.


Assuntos
Poluentes Atmosféricos/química , Nanopartículas de Magnetita/química , Mercúrio/química , Nanocompostos/química , Dióxido de Silício/química , Prata/química , Poluição do Ar/prevenção & controle , Cinza de Carvão/química , Metalurgia
17.
J Hazard Mater ; 351: 301-307, 2018 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-29554527

RESUMO

Metal-organic frameworks (MOFs) adsorbent Mil-101(Cr) was introduced for the removal of elemental mercury from sintering flue gas. Physical and chemical characterization of the adsorbents showed that MIL-101(Cr) had the largest BET surface area, high thermal stability and oxidation capacity. Hg0 removal performance analysis indicated that the Hg0 removal efficiency of MIL-101(Cr) increased with the increasing temperature and oxygen content. Besides, MIL-101(Cr) had the highest Hg0 removal performance compared with Cu-BTC, UiO-66 and activated carbon, which can reach about 88% at 250 °C. The XPS and Hg-TPD methods were used to analyze the Hg0 removal mechanism; the results show that Hg0 was first adsorbed on the surface of Mil-101(Cr), and then oxidized by the open metal site Cr3+. The generated Hg2+ was then combined surface adsorbed oxygen of adsorbent to form HgO, and the open metal site Cr2+ was oxidized to Cr3+ by surface active oxygen again. Furthermore, MIL-101(Cr) had good chemical and thermal stability.

18.
Chemosphere ; 197: 65-72, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29331933

RESUMO

The zirconium metal-organic framework material UiO-66 was doped with Ag nanoparticles and investigated for the removal of elemental mercury (Hg0) in flue gas. Physical and chemical characterization of the adsorbents showed that adding Ag did not change the crystal structure and morphology of the UiO-66. Ag doping can improve the redox activity of UiO-66, and the adsorbent exhibited high thermal stability and surface area. Hg0 removal experiments indicated that UiO-66 exhibited the higher performance compared with P25 and activated carbon, and the addition of Ag exhibited a significant synergistic effect with the UiO-66, which had highest Hg0 adsorption capacity (3.7 mg/g) at 50 °C. Furthermore, the Hg0 removal mechanism was investigated, revealing that Hg0 is removed by the formation of an Ag amalgam and channel adsorption at low temperature, and through Ag-activated oxygen oxidation and channel capture at high temperature.


Assuntos
Poluentes Atmosféricos/química , Mercúrio/química , Modelos Químicos , Prata/química , Adsorção , Estruturas Metalorgânicas , Oxirredução , Zircônio/química
19.
Environ Sci Technol ; 51(17): 10109-10116, 2017 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-28759214

RESUMO

[MoS4]2- clusters were bridged between CoFe layered double hydroxide (LDH) layers using the ion-exchange method. [MoS4]2-/CoFe-LDH showed excellent Hg0 removal performance under low and high concentrations of SO2, highlighting the potential for such material in S-Hg mixed flue gas purification. The maximum mercury capacity was as high as 16.39 mg/g. The structure and physical-chemical properties of [MoS4]2-/CoFe-LDH composites were characterized with FT-IR, XRD, TEM&SEM, XPS, and H2-TPR. [MoS4]2- clusters intercalated into the CoFe-LDH layered sheets; then, we enlarged the layer-to-layer spacing (from 0.622 to 0.880 nm) and enlarged the surface area (from 41.4 m2/g to 112.1 m2/g) of the composite. During the adsorption process, the interlayer [MoS4]2- cluster was the primary active site for mercury uptake. The adsorbed mercury existed as HgS on the material surface. The absence of active oxygen results in a composite with high sulfur resistance. Due to its high efficiency and SO2 resistance, [MoS4]2-/CoFe-LDH is a promising adsorbent for mercury uptake from S-Hg mixed flue gas.


Assuntos
Poluição do Ar/prevenção & controle , Mercúrio/química , Adsorção , Cobalto , Hidróxidos , Ferro , Espectroscopia de Infravermelho com Transformada de Fourier , Enxofre
20.
J Hazard Mater ; 333: 186-193, 2017 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-28359035

RESUMO

MnO2/CeO2-MnO2 hierarchical binary oxide was synthesized for elemental mercury (Hg0) removal from coal-fired flue gas. CeO2 in-situ grow on the surface of carbon spheres, and that CeO2@CSs acted as precursor for porous MnO2/CeO2-MnO2. XRD, Raman, XPS, FT-IR, and H2-TPR were selected for the physical structural and chemical surface analysis. The results indicated that the composite has sufficient surface oxygen and hierarchical porous structure. The Hg0 removal experiments results indicated that MnO2/CeO2-MnO2 exhibited excellent Hg0 removal performance, with an 89% removal efficiency of total 300min at 150°C under 4% O2. MnO2 was the primary active site for Hg0 catalytic oxidation. The porous structure was beneficial for gaseous mercury physically adsorption. In addition, CeO2 enhanced the oxygen capture performance of the composite and the oxidation performance for MnO2. Moreover, the effects of O2, SO2 and H2O were also tested in this study. O2 promoted the Hg0 removal reaction. While SO2 and H2O can poison the MnO2 active site, resulted in a low Hg0 removal efficiency.

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