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BACKGROUND AIMS: Peritoneal carcinomatosis (PC) from colorectal cancer (CRC) is a highly challenging disease to treat. Systemic chimeric antigen receptor (CAR) T cells have shown impressive efficacy in hematologic malignancies but have been less effective in solid tumors. We explored whether intraperitoneal (i.p.) administration of CAR T cells could provide an effective and robust route of treatment for PC from CRC. METHODS: We generated second-generation carcinoembryonic antigen (CEA)-specific CAR T cells. Various animal models of PC with i.p. and extraperitoneal metastasis were treated by i.p. or intravenous (i.v.) administration of CEA CAR T cells. RESULTS: Intraperitoneally administered CAR T cells exhibited superior anti-tumor activity compared with systemic i.v. cell infusion in an animal model of PC. In addition, i.p. administration conferred a durable effect and protection against tumor recurrence and exerted strong anti-tumor activity in an animal model of PC with metastasis in i.p. or extraperitoneal organs. Moreover, compared with systemic delivery, i.p. transfer of CAR T cells provided increased anti-tumor activity in extraperitoneal tumors without PC. This phenomenon was further confirmed in an animal model of pancreatic carcinoma after i.p. administration of our newly constructed prostate stem cell antigen-directed CAR T cells. CONCLUSIONS: Taken together, our data suggest that i.p. administration of CAR T cells may be a robust delivery route for effective treatment of cancer.
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Neoplasias Colorretais , Neoplasias Peritoneais , Receptores de Antígenos Quiméricos , Masculino , Animais , Antígeno Carcinoembrionário , Neoplasias Peritoneais/terapia , Linfócitos T , Imunoterapia Adotiva , Recidiva Local de Neoplasia , Neoplasias Colorretais/terapia , Neoplasias Colorretais/patologiaRESUMO
Chromium released during municipal solid waste incineration (MSWI) is toxic and carcinogenic. The removal of chromium from simulated MSWI flue gas by four sorbents (CaO, bamboo charcoal (BC), powdered activated carbon (PAC), and Al2O3) and the effects of four oxides (SiO2, Al2O3, Fe2O3, and CaO) on chromium speciation transformation were investigated. The results showed that the removal rates of total Cr by the four sorbents were Al2O3 < CaO < PAC < BC, while the removal rates of Cr(VI) by the four sorbents were Al2O3 < PAC < BC < CaO. CaO had a strong oxidizing effect on Cr(III), while BC and PAC had a better-reducing effect on Cr(VI). SiO2 was better for the reduction of Na2CrO4 and K2CrO4 above 1000°C due to its strong acidity, and the addition of CaO significantly inhibited the reduction of Cr(VI). MgCrO4 decomposed above 700°C to form MgCr2O4, and the reaction between MgCrO4 and oxides also existed in the form of a more stable trivalent spinel. Furthermore, when investigating the effect of oxides on the oxidation of Cr(III) in CrCl3, it was discovered that CaO promoted the conversion of Cr(III) to Cr(VI), while the presence of chlorine caused chromium to exist in the form of Cr(V), and increasing the content of CaO and extending the heating time facilitated the oxidation of Cr(III). In addition, silicate, aluminate, and ferrite were generated after the addition of SiO2, Al2O3, and Fe2O3, which reduced the alkalinity of CaO and had an important role in inhibiting the oxidation of Cr(III). The acidic oxides can not only promote the reduction of Cr(VI) but also have an inhibitory effect on the oxidation of Cr(III) ascribed to alkali metals/alkaline earth metals, and the proportion of acidic oxides can be increased moderately to reduce the generation of harmful substances in the hazardous solid waste heat treatment.
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Óxidos , Resíduos Sólidos , Dióxido de Silício , Cromo/análise , Oxirredução , IncineraçãoRESUMO
The photocatalysis conversion of CO2 into fuels has become an encouraging method to address climate and energy issues as a long-term solution. Single material suffers poor yield due to low light energy utilization and high recombination rate of photoinduced electron-hole pairs. It is an efficient approach to construct heterojunction through two or three materials to improve the photocatalytic performance. Recently, 2D-based heterojunction is getting popular for outstanding properties, such as special light collecting structure to enhance light harvest, intimate interface to facilitate charge transfer and separation, and large specific surface area to provide abundant reactive sites. Recently, some new 2D-based heterostructures materials (both structure and composition) have been developed with excellent performance. 2D materials exert structural and functional advantages in these fine composite photocatalysts. In this review, the literatures about the photocatalytic conversion of CO2 are mainly summarized based on overall structure, interface type and material type of 2D-based heterojunction, with special attention given to the preparation, characterization, structural advantages and reaction mechanism of novel 2D-based heterojunction. This work is in hope of offering a basis for designing improved composite photocatalyst for CO2 photoreduction.
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The gaseous elemental mercury (Hg0) emitted from coal-fired flue gas is extremely harmful to the atmospheric environment and human health. In this study, a 2D/2D Bi2MoO6(2 0 0)/g-C3N4 heterojunction photocatalyst was synthesized and exhibited a high visible-light driven Hg0 removal efficiency up to 99.5% in an atmosphere consisting of N2, O2 (6%), CO2 (12%), NO (100 ppm), SO2 (800 ppm), and H2O (5%). The introduction of surfactant CTAB led to further exposure of the highly active (2 0 0) crystal facet of Bi2MoO6, with a higher reactive oxygen species ratio than the original mainly exposed (1 3 1) crystal facet, and inhibited the agglomeration of Bi2MoO6, thereby greatly reducing the micro-thickness and improving the specific surface area. The smaller thickness effectively promoted the separation of photoinduced carriers and the speed of transfer to the interface. Additionally, through EPR characterization and work function calculation, we observed that the change in the exposed crystal facet regulated the Fermi level of Bi2MoO6 nanosheets, altering the direction of the built-in electric field at the interface with g-C3N4. This formation of an S-scheme 2D/2D Bi2MoO6(2 0 0)/g-C3N4 heterostructure further facilitated the recombination of unintentional carriers and strengthened the separation and catalysis of effective photogenerated carriers. To a certain extent, this work provides a guidance for the research of photocatalysis to achieve efficient and sustainable mercury removal from coal-fired flue gas.
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Mercúrio , Humanos , Catálise , Luz , Carvão MineralRESUMO
Heterogeneous agglomeration (HA) is a very potential technology for coal-fired flue gas treatment. In this paper, the distribution and migration mechanisms of trace elements (TEs) such as Se, As and Pb in CFPPs were studied on a 30,000 m3/hr pilot-scale experimental platform. The influences of HA on the removal efficiency of gaseous and particulate TEs were well analyzed. The results showed that Se, As and Pb were enriched in fly ash, and their sensitivity to particle size is quite different. The content of Se was the highest in PM1, reaching 193.04 mg/kg at the electrostatic precipitator (ESP) outlet. The average particle size of the total dust before ESP increased significantly from 21.686 to 62.612 µm after injecting the heterogeneous agglomeration adsorbent, conducive to its further removal by ESP. In addition, the concentrations of gaseous Se, As and Pb in the flue gas decreased after adsorbent spray, and accordingly, their contents in the hierarchical particles increased, indicating that the adsorbent could effectively promote the adsorption of gaseous trace elements in fly ash and reduce the possibility of their escape to the atmosphere. Total concentrations of Se, As and Pb emitted by wet flue gas desulfurization (WFGD) are 0.223, 0.668 and 0.076 µg/m3, which decreased by 59.98%, 47.69% and 90.71%, respectively. Finally, a possible HA mechanism model was proposed, where chemical adsorption, physical condensation and collision agglomeration of gaseous TEs and fine particles with adsorbent droplets occurred to form larger agglomerates.
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Poluentes Atmosféricos , Oligoelementos , Oligoelementos/análise , Centrais Elétricas , Cinza de Carvão/química , Poluentes Atmosféricos/análise , Chumbo , Carvão Mineral/análise , Gases , TecnologiaRESUMO
Coal is widely utilized as an important energy source, but coal-fired power plant was considered to be an important anthropogenic lead emission source. In the present study, the distribution characteristics of lead in coal and combustion by-products are reviewed. Specifically, lead is mainly transferred to ash particles and the formation and migration mechanisms of particulate lead are summarized. Also, targeted measures are proposed to control the formation of fine particulate lead as well as to increase the removal efficiency during the low-temperature flue gas clean process. In detail, interactions between gaseous lead and some coal-bearing minerals or added adsorbents could obviously suppress the formation of fine particulate lead. On the other hand, some efforts (including promoting capture of fine particles, reducing resistivity of particles and strengthening the gas-liquid contact) could be made to improve the fine particulate lead removal capacity. Notably, the formation mechanism of fine particulate lead is still unclear due to the limitations of research methods. Some differences in the removal principles of fine particles and particulate lead make the lead emission precisely control a great challenge. Finally, the environmental potential risk of lead emission from flue gas and ash residues is addressed and further discussed.
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Poluentes Atmosféricos , Poluentes Atmosféricos/análise , China , Carvão Mineral/análise , Cinza de Carvão/química , Poeira , Monitoramento Ambiental/métodos , Gases , Chumbo , Material Particulado/análise , Centrais ElétricasRESUMO
The chemical state of Pt in cocatalysts has a major influence on the activity and selectivity of the photocatalytic reduction of CO2; however, the underlying mechanism is unclear owing to the co-existence of different Pt chemical states and mutual transformation between them. In this study, PtO/TiO2 catalysts were prepared through photodeposition and Pt/TiO2 was prepared by the photoreduction of PtO/TiO2 to avoid interference arising from co-existing Pt forms and different loading amounts. These catalysts exhibited completely reversed selectivity for CO and CH4 production during CO2 photoreduction: PtO/TiO2 tended to produce CO (100%), whereas Pt/TiO2 favored the production of CH4 (66.6%). By combining experimental analysis and theoretical calculations, the difference in selectivity was ascribed to the different charge transfer/separation and CO/H adsorption properties of PtO/TiO2 and Pt/TiO2. Photoelectric and photoluminescence (PL) analysis showed that Pt was more advantageous to the photogenerated carrier separation compared with PtO, which was conducive to the multi-electron CH4 reduction reaction. Fourier transform-infrared spectroscopy, temperature-programmed desorption/temperature-programmed reduction, and density functional theory calculations indicated that the adsorption of CO and hydrogen on Pt was stronger than that on PtO, which favored the further reduction of CO to CH4. Based on the above results, a mechanism was proposed to explain the reversed selectivity of the photocatalytic reduction of CO2 over Pt/TiO2 and PtO/TiO2.
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Nodal-ring semimetals with band crossing are the new type of quantum materials that have attracted considerable interest from scholars for research. In general, the spin-orbit coupling (SOC) effect opens a band gap at the Dirac point. Therefore, finding 2D nodal-ring semimetals with resistance to SOC has more challenges. Based on first-principles calculations, we propose here that the two-dimensional (2D) Ta2C3 monolayer is a novel nodal-ring semimetal. In particular, Ta2C3 forms six closed rings in the Brillouin zone (BZ) with SOC, which originates from the dxy,x2-y2 orbitals of Ta and the pz orbitals of C. The nodal-ring bands at the K point in Ta2C3 exhibits characteristics of valley splitting and spin polarization due to the breaking of inversion symmetry and SOC. The masximal spin-splitting at the K point is as large as 268.87 meV and 61.90 meV for the conduction band minimum (CBM) and valence band maximum (VBM), respectively. The massless Dirac fermions in the non-equivalent valley have the opposite Berry curvature and spin moment. Therefore, 2D Ta2C3 is novel spin-valley-coupled nodal-ring semimetal. In addition, we found interesting negative differential resistance effects when calculating its transport properties. Our results not only provide an ideal platform for studying the combination of new physical properties, spintronics and valleytronics, but also open the way for designing low-power and fast-transport electronic devices.
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Mercury emission is an important issue during in-situ gasification chemical-looping combustion ( iG-CLC) of coal. This work focused on experimentally "isolating" two elementary subprocesses (coal pyrolysis and char gasification) during iG-CLC of coal, identifying mercury distribution within the two subprocesses, and examining the effects of a hematite oxygen carrier (OC) on the mercury fate. The mercury measurement accuracy was carefully ensured by comparing online measurements (by a VM 3000 instrument) and benchmark measurements (by the standard Ontario Hydro Method, ASTM D6784) as well as repeated tests (10 times for each case). The mercury mass balance was 115% for the entire iG-CLC. A total of 44.7% of the mercury was released as the gas phase form within the coal pyrolysis process at a typical CLC operation temperature (950 °C), whereas 13.4% was released during the char gasification process. The release rate and amount of mercury were minimally affected by the presence of OC; however, the OC promoted the conversion of Hg0(g) to Hg2+(g). Only a small amount of mercury was absorbed by the OC and transported into the air reactor along with carbon residue, released as Hg0(g) and Hg2+(g) or remained in the OC and coal ash as particulate mercury.
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Poluentes Atmosféricos , Mercúrio , Carvão Mineral , Cinza de Carvão , Ontário , Centrais ElétricasRESUMO
Nine new and eleven known phorbol esters were isolated from an acetone extract of the seeds of Croton tiglium. Their structures were determined by extensive analysis of spectroscopic data. Eleven of these compounds were evaluated for their inhibition activity on human tumor cell lines HL-60 and lung carcinoma A549. 12-O-Tiglylphorbol-13-acetate (11), 12-O-(2-methyl)-butyrylphorbol-13-aetate (12), and 12-O-tiglylphorbol-13-isobutyrate (13) exhibited strong inhibition activity against both HL-60 and A549 cell lines with IC50 values ≤ 0.02 and ≤ 0.1 µg/mL, respectively. Compound 18 showed strong inhibition activity against the HL-60 cell line with an IC50 value of 0.02 µg/mL.
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Croton/química , Ésteres de Forbol/química , Ésteres de Forbol/isolamento & purificação , Extratos Vegetais/química , Células A549 , Antineoplásicos Fitogênicos/química , Antineoplásicos Fitogênicos/isolamento & purificação , Antineoplásicos Fitogênicos/farmacologia , Ensaios de Seleção de Medicamentos Antitumorais , Células HL-60 , Humanos , Estrutura Molecular , Ésteres de Forbol/farmacologia , Extratos Vegetais/isolamento & purificação , Extratos Vegetais/farmacologia , Sementes/químicaRESUMO
A catalyst composed of manganese oxides supported on titania (MnOx/TiO2) synthesized by a sol-gel method was selected to remove nitric oxide and mercury jointly at a relatively low temperature in simulated flue gas from coal-fired power plants. The physico-chemical characteristics of catalysts were investigated by X-ray fluorescence (XRF), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses, etc. The effects of Mn loading, reaction temperature and individual flue gas components on denitration and Hg0 removal were examined. The results indicated that the optimal Mn/Ti molar ratio was 0.8 and the best working temperature was 240°C for NO conversion. O2 and a proper ratio of [NH3]/[NO] are essential for the denitration reaction. Both NO conversion and Hg0 removal efficiency could reach more than 80% when NO and Hg0 were removed simultaneously using Mn0.8Ti at 240°C. Hg0 removal efficiency slightly declined as the Mn content increased in the catalysts. The reaction temperature had no significant effect on Hg0 removal efficiency. O2 and HCl had a promotional effect on Hg0 removal. SO2 and NH3 were observed to weaken Hg0 removal because of competitive adsorption. NO first facilitated Hg0 removal and then had an inhibiting effect as NO concentration increased without O2, and it exhibited weak inhibition of Hg0 removal efficiency in the presence of O2. The oxidation of Hg0 on MnOx/TiO2 follows the Mars-Maessen and Langmuir-Hinshelwood mechanisms.
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Poluentes Atmosféricos/química , Poluição do Ar/prevenção & controle , Carvão Mineral , Compostos de Manganês/química , Mercúrio/química , Óxido Nítrico/química , Óxidos/química , Titânio/química , Temperatura AltaRESUMO
Novel magnetic biochars (MBC) were prepared by one-step pyrolysis of FeCl3-laden biomass and employed for Hg0 removal in simulated combustion flue gas. The sample characterization indicated that highly dispersed Fe3O4 particles could be deposited on the MBC surface. Both enhanced surface area and excellent magnetization property were obtained. With the activation of FeCl3, more oxygen-rich functional groups were formed on the MBC, especially the CâO group. The MBC exhibited far greater Hg0 removal performance compared to the nonmagnetic biochar (NMBC) under N2 + 4% O2 atmosphere in a wide reaction temperature window (120-250 °C). The optimal pyrolysis temperature for the preparation of MBC is 600 °C, and the best FeCl3/biomass impregnation mass ratio is 1.5 g/g. At the optimal temperature (120 °C), the Fe1.5MBC600 was superior in both Hg0 adsorption capacity and adsorption rate to a commercial brominated activated carbon (Br-AC) used for mercury removal in power plants. The mechanism of Hg0 removal was proposed, and there are two types of active adsorption/oxidation sites for Hg0: Fe3O4 and oxygen-rich functional groups. The role of Fe3O4 in Hg0 removal was attributed to the Fe3+(t) coordination and lattice oxygen. The CâO group could act as act as electron acceptors, facilitating the electron transfer for Hg0 oxidation.
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Carvão Vegetal , Imãs , Mercúrio , Adsorção , Oxirredução , Centrais Elétricas , TemperaturaRESUMO
It is known that the combination of TiO2 and graphene and the control of TiO2 crystal facets are both effective routes to improve the photocatalytic performance of TiO2. Here, we report the synthesis and the photocatalytic CO2 reduction performance of graphene supported TiO2 nanocrystals with coexposed {001} and {101} facets (G/TiO2-001/101). The combination of TiO2 and graphene enhanced the crystallinity of TiO2 single nanocrystals and obviously improved their dispersion on graphene. The "surface heterojunction" formed by the coexposed {001} and {101} facets can promote the spatial separation of photogenerated electrons and holes toward different facets and the supports of graphene can further enhance the separation through accelerated electron migration from TiO2 to graphene. The G/TiO2-001/101 exhibited high photocatalytic CO2-reduction activity with a maximum CO yield reaching 70.8 µmol g(-1) h(-1). The enhanced photocatalytic activity of the composites can be attributed to their high surface area, good dispersion of TiO2 nanoparticles, and effective separation of excited charges due to the synergy of graphene supports and the co-exposure of {001} and {101} facets.
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Cobalt oxide loaded magnetospheres catalyst from fly ash (Co-MF catalyst) showed good mercury removal capacity and recyclability under air combustion flue gas in our previous study. In this work, the Hg(0) removal behaviors as well as the involved reactions mechanism were investigated in oxyfuel combustion conditions. Further, the recyclability of Co-MF catalyst in oxyfuel combustion atmosphere was also evaluated. The results showed that the Hg(0) removal efficiency in oxyfuel combustion conditions was relative high compared to that in air combustion conditions. The presence of enriched CO2 (70%) in oxyfuel combustion atmosphere assisted the mercury oxidation due to the oxidation of function group of C-O formed from CO2. Under both atmospheres, the mercury removal efficiency decreased with the addition of SO2, NO, and H2O. However, the enriched CO2 in oxyfuel combustion atmosphere could somewhat weaken the inhibition of SO2, NO, and H2O. The multiple capture-regeneration cycles demonstrated that the Co-MF catalyst also present good regeneration performance in oxyfuel combustion atmosphere.
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Cinza de Carvão/química , Cobalto/química , Gases/química , Gasolina/análise , Fenômenos Magnéticos , Mercúrio/análise , Óxidos/química , Adsorção , Catálise , OxirreduçãoRESUMO
To remove Hg(0) in coal combustion flue gas and eliminate secondary mercury pollution of the spent catalyst, a new regenerable magnetic catalyst based on cobalt oxide loaded magnetospheres from fly ash (Co-MF) was developed. The catalyst, with an optimal loading of 5.8% cobalt species, attained approximately 95% Hg(0) removal efficiency at 150 °C under simulated flue gas atmosphere. O2 could enhance the Hg(0) removal activity of magnetospheres catalyst via the Mars-Maessen mechanism. SO2 displayed an inhibitive effect on Hg(0) removal capacity. NO with lower concentration could promote the Hg(0) removal efficiency. However, when increasing the NO concentration to 300 ppm, a slightly inhibitive effect of NO was observed. In the presence of 10 ppm of HCl, greater than 95.5% Hg(0) removal efficiency was attained, which was attributed to the formation of active chlorine species on the surface. H2O presented a seriously inhibitive effect on Hg(0) removal efficiency. Repeated oxidation-regeneration cycles demonstrated that the spent Co-MF catalyst could be regenerated effectively via thermally treated at 400 °C for 2 h.
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Poluentes Atmosféricos/química , Cobalto/química , Mercúrio/química , Óxidos/química , Poluição do Ar/prevenção & controle , Catálise , Carvão Mineral , Cinza de Carvão/química , Ácido Clorídrico/química , Fenômenos Magnéticos , Óxido Nítrico/química , Oxirredução , Oxigênio/química , Centrais Elétricas , Reciclagem , Dióxido de Enxofre/químicaRESUMO
Expanding the utility of chimeric antigen receptor (CAR)-T cells in solid tumors requires improving their efficacy and safety. Hypoxia is a feature of most solid tumors that could be used to help CAR-T cells discriminate tumors from normal tissues. In this study, we developed hypoxia-responsive CAR-T cells by engineering the CAR to be under regulation of hypoxia-responsive elements and selected the optimal structure (5H1P-CEA CAR), which can be activated in the tumor hypoxic microenvironment to induce CAR-T cells with high polyfunctionality. Hypoxia-responsive CAR T cells were in a "resting" state with low CAR expression under normoxic conditions. Compared with conventional CAR-T cells, hypoxia-responsive CAR-T cells maintained lower differentiation and displayed enhanced oxidative metabolism and proliferation during cultivation, and they sowed a capacity to alleviate the negative effects of hypoxia on T-cell proliferation and metabolism. Furthermore, 5H1P-CEA CAR-T cells exhibited decreased T-cell exhaustion and improved T-cell phenotype in vivo. In patient-derived xenograft models, hypoxia-responsive CAR-T cells induced more durable antitumor activity than their conventional counterparts. Overall, this study provides an approach to limit CAR expression to the hypoxic tumor microenvironment that could help to enhance CAR T-cell efficacy and safety in solid tumors. SIGNIFICANCE: Engineering CAR-T cells to upregulate CAR expression under hypoxic conditions induces metabolic reprogramming, reduces differentiation, and increases proliferation to enhance their antitumor activity, providing a strategy to improve efficacy and safety.
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Imunoterapia Adotiva , Neoplasias , Humanos , Neoplasias/metabolismo , Linfócitos T , Hipóxia/metabolismo , Microambiente Tumoral , Ensaios Antitumorais Modelo de XenoenxertoRESUMO
Isoquinoline (IQL), as a typical nitrogen-containing heterocyclic contaminant in coking wastewater, poses a serious threat to the aquatic environment and human health. Due to its chemical stability, traditional sewage treatment technology is not highly efficient in IQL removal. Advanced oxidation processes (AOPs) driven by ultraviolet radiation could be an effective treatment method, but it could generate toxic byproducts. In this work, the removal of IQL initiated by HOâ¢, ClOâ¢, Clâ¢, and SO4â¢- in UV/chlorine and UV/persulfate (PDS) process was comprehensively investigated, clarifying the degradation mechanism, reaction kinetics, and ecological toxicity. The findings indicate that the dominant oxidation mechanism of IQL by HOâ¢, ClOâ¢, and Cl⢠is radical adduct formation (RAF), while single electron transfer (SET) is the main reaction pathway of SO4â¢- with IQL. At 298 K and 1 atm, the order of rate constants for the reactions of IQL with active radicals is Cl⢠(6.23 × 1010 M-1 s-1) > SO4â¢- (8.81 × 109 M-1 s-1) > HO⢠(1.66 × 109 M-1 s-1) > ClO⢠(1.62 × 108 M-1 s-1). The acute and chronic toxicity of IQL and its degradation byproducts at three different trophic levels were evaluated using ECOSAR program. The byproducts produced by the oxidative degradation of IQL by HO⢠and SO4â¢- are mostly "not harmful", and their toxicity shows a decreasing trend compared to that of IQL. The byproducts derived from the reaction of IQL with Cl⢠are all "toxic" or "harmful", and the ranking of harm to three types of aquatic organisms is green algae > fish > daphnia. Hence, UV/PDS process could be more secure in pollutant disposal in wastewater. In actual water treatment process, merit attention should be paid to the potential hazards of the byproducts generated by various contaminants.
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The direct aqueous mineral carbonation of wood combustion ash (WCA), which is a representative high-calcium waste from combustion process, was systematically investigated by varying complex operating conditions, including reaction time, liquid-to-solid ratio (L/S), CO2 concentration, and particle size. The WCA exhibited high CO2 sequestration characteristics with an optimal carbonation efficiency of 76.4%, corresponding to a CO2 sequestration capacity of 0.314 g CO2/g WCA. In addition to solid carbonates, dry residues from liquid products with high potassium contents are potential feedstocks for quality potash fertilizer. Modified shrinking core models based on diffusion-controlled mechanism were proposed to evaluate the carbonation process. The theoretical framework assumes a contracting interface mechanism where active CaO reacts with CO2 to form a product layer. The effective diffusion coefficient of CO2 through the product layer decreases over time, giving deficient carbonation efficiency. The newly proposed models corresponding to different geometrical dimensions provided more perfect fit to the experimental data when compared with the most commonly used kinetic equations. The low apparent activation energy of the carbonation reaction demonstrated the diffusion-controlled mechanism. This work is useful for improving the economics and feasibility of bioenergy carbon capture and storage (CCS) technology chain.
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Dióxido de Carbono , Madeira , Dióxido de Carbono/química , Cinética , Carbonatos/química , Minerais/química , Cinza de Carvão/químicaRESUMO
The elemental mercury was catalytically removed by V2O5/TiO2 and Ce doped V2O5/TiO2 catalysts under the UV irradiation at 30-160 °C to determine whether the catalysts could simultaneously have both thermo- and photo-catalytic activities. The physicochemical properties of catalysts were characterized by XRD, SEM, EDX, BET, XPS, UV-visible, PER and EIS. The experimental results demonstrated that V2O5/TiO2 and Ce-doped catalysts possessed both thermo- and photo-catalytic reactivities. A suitable reaction temperature (120 °C) and UV light had promoting effects on mercury removal efficiency. In addition, owing to the high oxidation capability as well good oxygen storage performance of Ce4+, Ce doping could greatly improve the mercury removal properties of the catalyst, reduce the inhibition of SO2 and make NO the component with enhanced effect. Ce doping also had the capability of enhancing the light absorption intensity in the UV region as well as the separation rate of photoinduced carriers. Finally, DFT calculations of V-Ti and Ce-V-Ti for Hg0 removal were investigated to further verify the experimental conclusion.
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Mercúrio , Catálise , Oxirredução , TitânioRESUMO
Mercury is a highly toxic heavy metal pollutant. It is of great significance to develop cost-effective mercury pollution control technologies of coal-fired flue gas. Among various mercury from flue gas removal methods, the application of existing air pollution control devices (APCDs) to remove mercury from flue gas is one of the most valuable methods because it doesn't need to install additional mercury removal equipment, reducing the cost of mercury removal. This review summarizes the recent progress of mercury from flue gas removal by APCDs (e.g., SCR denitration device, WFGD system and dust removal device). SCR denitration device can achieve partial removal of mercury in flue gas through combined with WFGD system, but easy inactivation and poor sulfur/water/heavy metals resistance of SCR catalyzers are still the main problems. WFGD systems can remove most of Hg2+ (80%-95%), but have low treatment ability for Hg0. Various oxidants can effectively oxidize Hg0 into Hg2+. However, traditional oxidants have high prices and secondary pollution due to the formation of by-products. Fabric filters (FFs), electrostatic precipitators (ESPs) and hybrid fabric filters (HFs) can all control the emission of mercury in the flue gas to a certain extent, especially can effectively remove most of HgP and part of Hg2+, but has low removal capacity for Hg0. Compared with ESP, FF has better capture efficiency for Hg2+ and Hg0, and a combination of ESP and FF, that is HF, can effectively improve the mercury removal capacity.