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1.
Anal Chem ; 96(15): 6037-6044, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38560885

RESUMO

Dopamine (DA), an essential neurotransmitter, is closely associated with various neurological disorders, whose real-time dynamic monitoring is significant for evaluating the physiological activities of neurons. Electrochemical sensing methods are commonly used to determine DA, but they mostly rely on the redox reaction of its o-phenolic hydroxyl group, which makes it difficult to distinguish it from substances with this group. Here, we design a biomimetic nanozyme inspired by the coordination structure of the copper-based active site of dopamine ß-hydroxylase, which was successfully synthesized via a urea-mediated MOF pyrolysis reconstruction strategy. Experimental studies and theoretical calculations revealed that the nanozyme with Cu-N3 coordination could hydroxylate the carbon atom of the DA ß-site at a suitable potential and that the active sites of this Cu-N3 structure have the lowest binding energy for the DA ß-site. With this property, the new oxidation peak achieves the specific detection of DA rather than the traditional electrochemical signal of o-phenol hydroxyl redox, which would effectively differentiate it from neurotransmitters, such as norepinephrine and epinephrine. The sensor exhibited good monitoring capability in DA concentrations from 0.05 to 16.7 µM, and its limit of detection was 0.03 µM. Finally, the sensor enables the monitoring of DA released from living cells and can be used to quantitatively analyze the effect of polystyrene microplastics on the amount of DA released. The research provides a method for highly specific monitoring of DA and technical support for initial screening for neurocytotoxicity of pollutants.


Assuntos
Dopamina , Oxigenases de Função Mista , Dopamina/química , Fenol , Biomimética , Cobre , Plásticos , Pirólise , Eletrodos , Neurotransmissores , Técnicas Eletroquímicas/métodos
2.
Nat Mater ; 22(1): 109-116, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36509871

RESUMO

Carbon molecular sieve (CMS) membranes with precise molecular discrimination ability and facile scalability are attractive next-generation membranes for large-scale, energy-efficient gas separations. Here, structurally engineered CMS membranes derived from a tailor-made cross-linkable copolyimide with kinked structure are reported. We demonstrate that combining two features, kinked backbones and cross-linkable backbones, to engineer polyimide precursors while controlling pyrolysis conditions allows the creation of CMS membranes with improved gas separation performance. Our results indicate that the CMS membranes provide a versatile platform for a broad spectrum of challenging gas separations. The gas transport properties of the resulting CMS membranes are interpreted in terms of a model reflecting both molecular sieving Langmuir domains and a disordered continuous phase, thereby providing insight into structure evolution from the cross-linkable polyimide precursor to a final CMS membrane. With this understanding of CMS membrane structure and separation performance, these systems are promising for environmentally friendly gas separations.


Assuntos
Carbono , Engenharia , Transporte Biológico , Pirólise
3.
Chemphyschem ; 25(4): e202300507, 2024 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-38200663

RESUMO

The nettle, sage, mint and lemon balm herbs were used for biochars preparation. The physicochemical parameters of obtained materials were related to the lignocellulose composition of the precursors. It has been proved that the content of mineral substance has a significant influence on development of surface area, whereas the amount of hemicellulose affects the content of surface functional groups. It has been also shown that the obtained biochars are characterized by great energy parameters. The higher heating values (HHV) of the carbonaceous materials are comparable to the typical energy sources. The greatest HHV value (20.36 MJ/kg) was characteristic for the biochar obtained by pyrolysis of the lemon balm. In addition, the biochars were used for ionic polymers adsorption from one- and two-components solutions. Despite the adsorbed amounts of macromolecules are not great is has been proved that polyethylenimine and polyacrylic acid have positive influence on their mutual adsorption.


Assuntos
Carvão Vegetal , Pirólise , Adsorção , Carvão Vegetal/química , Íons
4.
Environ Sci Technol ; 58(5): 2554-2563, 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38266240

RESUMO

Rapid and in situ identification of specific polymers is a challenging and crucial step in plastic recycling. However, conventional techniques continue to exhibit significant limitations in the rapid and field classification of plastic products, especially with the wide range of commercially available color polymers because of their large size, high energy consumption, and slow and complicated analysis procedures. In this work, a simple analytical system integrating a miniature and low power consumption (22.3 W) pyrolyzer (Pyr) and a low temperature, atmospheric pressure point discharge optical emission spectrometer (µPD-OES) was fabricated for rapidly identifying polymer types. Plastic debris is decomposed in the portable pyrolyzer to yield volatile products, which are then swept into the µPD-OES instrument for monitoring the optical emission patterns of the thermal pyrolysis products. With machine learning, five extensively used raw polymers and their consumer plastics were classified with an accuracy of ≥97.8%. Furthermore, the proposed method was applied to the identification of the aged polymers and plastic samples collected from a garbage recycling station, indicating its great potential for identification of environmentally weathered plastics. This portable Pyr-µPD-OES system provides a cost-effective tool for rapid and field identification of polymer types of recycled plastic for proper management and resource recycling.


Assuntos
Plásticos , Pirólise , Plásticos/análise , Polímeros , Reciclagem , Aprendizado de Máquina
5.
Environ Sci Technol ; 58(3): 1423-1440, 2024 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-38197317

RESUMO

Plastic waste has emerged as a serious issue due to its impact on environmental degradation and resource scarcity. Plastic recycling, especially of halogen-containing plastics, presents challenges due to potential secondary pollution and lower-value implementations. Chemical recycling via pyrolysis is the most versatile and robust approach for combating plastic waste. In this Review, we present recent advancements in halogen-plastic pyrolysis for resource utilization and the potential pathways from "reducing to recycling to upcycling" halogens. We emphasize the advanced management of halogen-plastics through copyrolysis with solid wastes (waste polymers, biomass, coal, etc.), which is an efficient method for dealing with mixed wastes to obtain high-value products while reducing undesirable substances. Innovations in catalyst design and reaction configurations for catalytic pyrolysis are comprehensively evaluated. In particular, a tandem catalysis system is a promising route for halogen removal and selective conversion of targeted products. Furthermore, we propose novel insights regarding the utilization and upcycling of halogens from halogen-plastics. This includes the preparation of halogen-based sorbents for elemental mercury removal, the halogenation-vaporization process for metal recovery, and the development of halogen-doped functional materials for new materials and energy applications. The reutilization of halogens facilitates the upcycling of halogen-plastics, but many efforts are needed for mutually beneficial outcomes. Overall, future investigations in the development of copyrolysis and catalyst-driven technologies for upcycling halogen-plastics are highlighted.


Assuntos
Halogênios , Plásticos , Plásticos/química , Pirólise , Reciclagem , Resíduos Sólidos
6.
Environ Sci Technol ; 58(4): 2102-2111, 2024 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-38238255

RESUMO

Waste biomass is one of the promising feedstocks to supply syngas that can be used as fuels, chemicals, reductants, etc. However, the relationship between the component of biomass and the constituent of pyrolysis gas remains unclear. Here, we study the pyrolysis behaviors of various biomasses and reveal the relationship between the biomass components and gas compositions. Further, different pyrolysis gases are applied for the reduction of spent lithium cobalt oxide (LiCoO2) below 500 °C. The pyrolysis gas with a higher concentration of CO has a higher reductivity to convert LiCoO2 to CoO and Li2CO3 with a conversion rate close to 100% in 1 h at 500 °C. The biomass rich in cellulose and with a lower content of lignin tends to produce pyrolysis gas with a high concentration of CO, which comes from the deliberate breakdown of carboxyl, carbonyl, ether, and ester linkages. Moreover, LiCoO2 exerts catalytic functions over the deoxygenation and enhancement of oxygenates and single-ring aromatics. Overall, this paper offers a tailored approach to regulating biomass pyrolysis gases, enabling highly efficient battery recycling and syngas production.


Assuntos
Fontes de Energia Elétrica , Pirólise , Biomassa , Lignina/química , Reciclagem , Gases
7.
Environ Sci Technol ; 58(18): 7826-7837, 2024 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-38653213

RESUMO

The interaction effects between the main components (proteins (P), carbohydrates (C), and lipids (L)) of protein-rich biomass during microwave-assisted pyrolysis were investigated in depth with an exploration of individual pyrolysis and copyrolysis (PC, PL, and CL) of model compounds. The average heating rate of P was higher than those of C and L, and the interactions in all copyrolysis groups reduced the max instant heating rate. The synergistic extent (S) of PC and PL for bio-oil yield was 16.78 and 18.24%, respectively, indicating that the interactions promoted the production of bio-oil. Besides, all of the copyrolysis groups exhibited a synergistic effect on biochar production (S = 19.43-28.24%), while inhibiting the gas generation, with S ranging from -20.17 to -6.09%. Regarding the gaseous products, apart from H2, P, C, and L primarily generated CO2, CO, and CH4, respectively. Regarding bio-oil composition, the interactions occurring within PC, PL, and CL exhibited a significantly synergistic effect (S = 47.81-412.96%) on the formation of N-heterocyclics/amides, amides/nitriles, and acids/esters, respectively. Finally, the favorable applicability of the proposed interaction effects was verified with microalgae. This study offers valuable insights for understanding the microwave-assisted pyrolysis of protein-rich biomass, laying the groundwork for further research and process optimization.


Assuntos
Biomassa , Micro-Ondas , Pirólise , Proteínas/química , Lipídeos/química , Carvão Vegetal/química , Carboidratos/química , Biocombustíveis
8.
Environ Sci Technol ; 58(29): 13047-13055, 2024 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-38977269

RESUMO

Quantification of microplastics in soil is needed to understand their impact and fate in agricultural areas. Often, low sample volume and removal of organic matter (OM) limit representative quantification. We present a method which allows simultaneous quantification of microplastics in homogenized, large environmental samples (>1 g) and tested polyethylene (PE), polyethylene terephthalate (PET), and polystyrene (PS) (200-400 µm) overestimation by fresh and diagenetically altered OM in agricultural soils using a new combination of large-volume pyrolysis adsorption with thermal desorption-gas chromatography-tandem mass spectrometry (TD-GC-MS/MS). Characteristic MS/MS profiles for PE, PET, and PS were derived from plastic pyrolysis and allowed for a new mass separation of PET. Volume-defined standard particles (125 × 125 × 20 µm3) were developed with the respective weight (PE: 0.48 ± 0.12, PET: 0.50 ± 0.10, PS: 0.31 ± 0.08 µg), which can be spiked into solid samples. Diagenetically altered OM contained compounds that could be incorrectly identified as PE and suggest a mathematical correction to account for OM contribution. With a standard addition method, we quantified PS, PET, and PEcorrected in two agricultural soils. This provides a base to simultaneously quantify a variety of microplastics in many environmental matrices and agricultural soil.


Assuntos
Agricultura , Cromatografia Gasosa-Espectrometria de Massas , Plásticos , Polietileno , Pirólise , Poluentes do Solo , Solo , Polietileno/química , Solo/química , Poluentes do Solo/análise , Espectrometria de Massas em Tandem , Microplásticos/análise , Polietilenotereftalatos/química , Monitoramento Ambiental/métodos
9.
Environ Res ; 246: 118154, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38218520

RESUMO

The management of plastic waste (PW) has become an indispensable worldwide issue because of the enhanced accumulation and environmental impacts of these waste materials. Thermo-catalytic pyrolysis has been proposed as an emerging technology for the valorization of PW into value-added liquid fuels. This review provides a comprehensive investigation of the latest advances in thermo-catalytic pyrolysis of PW for liquid fuel generation, by emphasizing polyethylene, polypropylene, and polystyrene. To this end, the current strategies of PW management are summarized. The various parameters affecting the thermal pyrolysis of PW (e.g., temperature, residence time, heating rate, pyrolysis medium, and plastic type) are discussed, highlighting their significant influence on feed reactivity, product yield, and carbon number distribution of the pyrolysis process. Optimizing these parameters in the pyrolysis process can ensure highly efficient energy recovery from PW. In comparison with non-catalytic PW pyrolysis, catalytic pyrolysis of PW is considered by discussing mechanisms, reaction pathways, and the performance of various catalysts. It is established that the introduction of either acid or base catalysts shifts PW pyrolysis from the conventional free radical mechanism towards the carbonium ion mechanism, altering its kinetics and pathways. This review also provides an overview of PW pyrolysis practicality for scaling up by describing techno-economic challenges and opportunities, environmental considerations, and presenting future outlooks in this field. Overall, via investigation of the recent research findings, this paper offers valuable insights into the potential of thermo-catalytic pyrolysis as an emerging strategy for PW management and the production of liquid fuels, while also highlighting avenues for further exploration and development.


Assuntos
Poliestirenos , Pirólise , Polienos , Polietileno , Plásticos
10.
Environ Res ; 245: 118016, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38154563

RESUMO

Recovery of carbon fibres and resin from wind turbine blade waste (WTB) composed of carbon fibres (CF)-reinforced unsaturated polyester resin (UPR) has been environmentally challenging due to its complex structure that is not biodegradable and that is rich in highly toxic styrene (main component of UPR). Within this framework, this paper aims to liberate CF and UPR from WTB using a pyrolysis process. The treatment was performed on commercial WTB (CF/UPR) up to 600 °C using a 250 g reactor. The UPR fraction was decomposed into liquid and gaseous phases, while CF remained as a residue. The composition of gaseous phase was monitored during the entire treatment using a digital gas analyser, while gas chromatography-mass spectrometry (GC-MS) was used to characterize the collected liquid phase. CF fraction was collected and exposed to additional oxidation process after treatment at 450 °C for purification propose, then it was analysed using FTIR and SEM-EDX. Finally, the life cycle assessment (LCA) of the CF/UPR pyrolysis was studied using SimaPro software and the results were compared with landfill disposal practices. The pyrolysis results manifested that 500 °C was sufficient for UPR decomposition into styrene-rich oil and gaseous products with yields of 15.23 wt% and 6.83 wt%, respectively, accompanied by 77.93 wt% solid residue including CF. The LCA results showed that pyrolysis with oxidation process has high environmental potential in WTB recycling with significant reduction in several impact categories compared to landfill. However, the pyrolysis scenario revealed several additional environmental burdens related to ecosystems, acidification, Ozone formation, and fine particulate matter formation that must be overcome before upscaling.


Assuntos
Ecossistema , Pirólise , Fibra de Carbono , Poliésteres , Estireno , Carbono
11.
Environ Res ; 243: 117835, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38052358

RESUMO

In Greece, there is no organized practice in agricultural and animal wastes management. Their exploitation is still set aside, due mainly to economic reasons and lack of incentives for their efficient utilization. Therefore, in the present work a technoeconomic assessment for the environmentally friendly useful exploitation of biomass residues produced in the Prefectures of Ilia and Achaia (Western Greece) for the generation of energy by an integrated anaerobic digestion (AD)-pyrolysis processing plant was carried out. The processed biomass of the AD unit is corn residues and cattle manure, while the feedstock of pyrolysis unit is olive tree prunings. The residues will be transferred to collection areas by field tractors. Then an integrated harvester is used and afterwards, the residues are discharged from the lifting bin of the harvester to trucks and are transported to the processing unit. The total fixed capital for a capacity of 328,716 t/y is equal to 11.5 M€, while the initial working capital is equal to 2.1 M€. The total operational cost of this investment is estimated at 18.3 M€/y, the projected revenues amount to 21.4 M€/y and the net profit is equal to 3.1 M€/y. The return on investment is estimated at 23% and the payback period becomes equal to 4.4 years. From the sensitivity analysis becomes apparent that the capacity, the incentive cost, the fuel price, the products price and the total fixed capital affect significantly the investment characteristics of the proposed AD-pyrolysis processing unit. The amount of the expected profit is considered quite significant, and the evaluation criteria (return on investment and payback period) advocate for a more detailed examination of the investment plan, in the direction of undertaking the project.


Assuntos
Biocombustíveis , Pirólise , Animais , Bovinos , Biomassa , Anaerobiose , Esterco
12.
Environ Res ; 242: 117614, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-37996005

RESUMO

Waste-to-energy conversion presents a pivotal strategy for mitigating the energy crisis and curbing environmental pollution. Pyrolysis is a widely embraced thermochemical approach for transforming waste into valuable energy resources. This study delves into the co-pyrolysis of terrestrial biomass (potato peel) and marine biomass (Sargassum angastifolium) to optimize the quantity and quality of the resultant bio-oil and biochar. Initially, thermogravimetric analysis was conducted at varying heating rates (5, 20, and 50 °C/min) to elucidate the thermal degradation behavior of individual samples. Subsequently, comprehensive analyses employing FTIR, XRD, XRF, BET, FE-SEM, and GC-MS were employed to assess the composition and morphology of pyrolysis products. Results demonstrated an augmented bio-oil yield in mixed samples, with the highest yield of 27.1 wt% attained in a composition comprising 75% potato peel and 25% Sargassum angastifolium. As confirmed by GC-MS analysis, mixed samples exhibited reduced acidity, particularly evident in the bio-oil produced from a 75% Sargassum angastifolium blend, which exhibited approximately half the original acidity. FTIR analysis revealed key functional groups on the biochar surface, including O-H, CO, and C-O moieties. XRD and XRF analyses indicated the presence of alkali and alkaline earth metals in the biochar, while BET analysis showed a surface area ranging from 0.64 to 1.60 m2/g. The favorable characteristics of the products highlight the efficacy and cost-effectiveness of co-pyrolyzing terrestrial and marine biomass for the generation of biofuels and value-added commodities.


Assuntos
Carvão Vegetal , Óleos de Plantas , Polifenóis , Alga Marinha , Solanum tuberosum , Biocombustíveis , Pirólise , Biomassa , Temperatura Alta
13.
Environ Res ; 246: 118129, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38211718

RESUMO

The depletion of finite fossil fuel reserves and the severe environmental degradation resulting from human activities have compelled the expeditious development and application of sustainable waste to energy technologies. To encapsulate energy and environment in sustainability paradigm, bio waste based energy production is need to be forged in organic bio refinery setup. According to world bioenergy association, biomass can cover 50 % of the primary energy demand of the world. Therefore, the present study focuses on reforming the energy mix for a clean energy generation, where, sample composition of cotton stalk was acidified in dilute (5% wt.) hydrochloric acid (HCL) for analyzing material burnout patterns in biomass conversion systems utilized in organic bio refinery sector. Advanced thermochemical burning technique, which includes pyrolysis and combustion was applied at four different leaching times from 0 to 180 min under nitrogen environment from 0 °C to 500 °C and air from 500 °C to 900 °C, respectively. Different analyses including proximate, ultimate, gross calorific value (GCV), thermos-gravimetric, kinetic, XRD, FTIR, SEM-EDS were used for analyzing the degradation of demineralized cotton stalk at different treatment rates. Proximate study demonstrated that cotton stalk leaching for 180 min has efficiently infused HCL, leading in a significant increase in fixed carbon and higher heating value of 20.23 % and 12.48%, respectively, as well as a reduction in carbon footprint of around 54.80%. The findings of proximate was validated by GCV analysis and CHNS analysis as value of carbon and hydrogen has shown increasing behavior with the time delay in demineralization Thermo-gravimetric and derivative thermo-gravimetric data analyses shows an increasing trend of conversion efficiency, with the maximum increase of 98 % reported for sample 3H.TT.DEM. XRD characterization has reported 23° to 25° angle for all the observed peaks. Sample 3H.TT.DEM has shown maximum angle inclination along with matured crystalline peak. The latter observations has been validated by FTIR spectroscopy as sample 3H.TT.DEM has reported maximum O-H group formation. Sample 3H.TT.DEM has reported lowest activation energy of 139.51 kJ*mole-1 and lowest reactivity of 0.000293649%*min 0C, due to moderate and stable reactiveness. In SEM examination, increment in pore size and number of pores within the structural matrix of cotton stalk was observed with the enhancement in acidulation process. Furthermore, in EDS analysis, 3H.TT.DEM has shown most balanced distribution of the elements. In this research, sustainable transformation of biomass is envisioned to improve the waste bio refinery system, significantly contributing to the achievement of Sustainable Development Goals 7, 12 and 13.


Assuntos
Carbono , Nitrogênio , Humanos , Biomassa , Nitrogênio/análise , Pirólise , Biocombustíveis/análise
14.
Environ Res ; 245: 118076, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38160977

RESUMO

Owing to the ever-increasing generation of plastic waste, the need to develop environmentally friendly disposal methods has increased. This study explored the potential of waste plastic straw to generate valuable light olefins and monocyclic aromatic hydrocarbons (MAHs) via catalytic pyrolysis using high-silica zeolite-based catalysts. HZSM-5 (SiO2/Al2O3:200) exhibited superior performance, yielding more light olefins (49.8 wt%) and a higher MAH content than Hbeta (300). This was attributed to the increased acidity and proper shape selectivity. HZSM-5 displayed better coking resistance (0.7 wt%) than Hbeta (4.4 wt%) by impeding secondary reactions, limiting coke precursor formation. The use of HZSM-5 (80) resulted in higher MAHs and lower light olefins than HZSM-5 (200) because of its higher acidity. Incorporation of Co into HZSM-5 (200) marginally lowered light olefin yield (to 44.0 wt%) while notably enhancing MAH production and boosting propene selectivity within the olefin composition. These observations are attributed to the well-balanced coexistence of Lewis and Brønsted acid sites, which stimulated the carbonium ion mechanism and induced H-transfer, cyclization, Diels-alder, and dehydrogenation reactions. The catalytic pyrolysis of plastic straw over high-silica and metal-loaded HZSM-5 catalysts has been suggested as an efficient and sustainable method for transforming plastic waste materials into valuable light olefins and MAHs.


Assuntos
Hidrocarbonetos Aromáticos , Zeolitas , Dióxido de Silício , Pirólise , Temperatura Alta , Biomassa , Alcenos , Catálise , Hidrocarbonetos
15.
Environ Res ; 248: 118205, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38242421

RESUMO

This paper presents a techno-economic analysis (TEA) of six (6) scenarios of the kraft lignin catalytic (CFP) and thermal (TFP) fast pyrolysis towards the production of high value-added chemicals (HVACs) and electric energy, based on experimental data from our previous work. ASPEN PLUS was used to simulate the proposed plants/scenarios and retrofitted custom-based economic models that were developed in Microsoft EXCEL. The results showed that scenarios 1 and 2 in which the produced bio-oil is used as fuel for electricity production are the most cost-deficient. On the other hand, scenarios 3 and 6 that utilize the light bio-oil fraction to recover distinct HVACs, along with the use of heavier fractions for electricity production, have showed a significant investment viability, since profitability measures are high. Furthermore, scenarios 4 and 5 that refer to the recovery of mixtures (fractions) of HVACs, are considered an intermediate investment option due to the reduced cost of separation. All the proposed scenarios have a substantial total capital investment (TCI) which ranges from 135 MM€ (scenario 4) to 380 MM€ (scenario 6) with a Lang factor of 6.08, which shows that the CAPEX results are within reason. As far as the comparison of lignin CFP and TFP goes, it is shown that lignin CFP leads to the production of aromatic and phenolic monomers which have a substantial market value, while TFP can lead to important value-added chemicals with a lower OPEX than CFP. A target of return of investment (ROI) of 32% has been set for the selling prices of the HVACs. In summary, this study aims at listing and assessing a set of economic indicators for industrial size plants that use lignin CFP and TFP towards the production of high value-added chemicals and energy production and to provide simulation data for comparative analysis of three bio-oil separation methods, i.e. distillation, liquid-liquid extraction and moving bed chromatography.


Assuntos
Lignina , Óleos de Plantas , Polifenóis , Pirólise , Lignina/química , Biocombustíveis , Biomassa
16.
Environ Res ; 247: 118169, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38244973

RESUMO

The current study presents for the first time how recovered carbon black (rCB) obtained directly from the industrial-scale end-of-life tires (ELTs) pyrolysis sector is applied as a precursor for activated carbons (ACs) with application in CO2 capture. The rCB shows better physical characteristics, including density and carbon structure, as well as chemical properties, such as a consistent composition and low impurity concentration, in comparison to the pyrolytic char. Potassium hydroxide and air in combination with heat treatment (500-900 °C) were applied as agents for the conventional chemical and physical activation of the material. The ACs were tested for their potential to capture CO2. Ultimate and proximate analysis, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), Raman spectroscopy, thermogravimetric analysis (TGA), and N2/CO2 gas adsorption/desorption isotherms were used as material characterization methods. Analysis revealed that KOH-activated carbon at 900 °C (AC-900K) exhibited the highest surface area and a pore volume that increased 6 and 3 times compared to pristine rCB. Moreover, the AC-900K possessed a well-developed dual porosity, corresponding to the 22% and 78% of micropore and mesopore volume, respectively. At 0 °C and 25 °C, AC-900K also showed a CO2 adsorption capacity equal to 30.90 cm3/g and 20.53 cm3/g at 1 bar, along with stable cyclic regeneration after 10 cycles. The high dependence of CO2 uptake on the micropore volume at width below 0.7-0.8 nm was identified. The selectivity towards CO2 in relation to N2 reached high values of 350.91 (CO2/N2 binary mixture) and 59.70 (15% CO2/85% N2).


Assuntos
Carvão Vegetal , Hidróxidos , Compostos de Potássio , Fuligem , Carvão Vegetal/química , Dióxido de Carbono/química , Espectroscopia de Infravermelho com Transformada de Fourier , Pirólise , Adsorção
17.
Environ Res ; 242: 117566, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-37977274

RESUMO

In this study, cow dung biomass was converted into biochar (BC). BC900 was obtained through one-step pyrolysis at 900 °C, while BC700-900 and BC900-700 were obtained via two-step pyrolysis at temperature ranges of 700-900 °C and 900-700 °C, respectively. The primary objective was to investigate the adsorption performance and application value of BCs for tetracycline (TC) in water. The samples underwent characterization using scanning electron microscopy and mapping analysis, Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. Subsequently, the effects of reaction time, adsorbent dosage, temperature, pH, and ionic strength were analyzed. Based on the fitting results of adsorption kinetics, the pyrolytic BCs exhibited a better fit with the pseudo-secondary kinetic model. The adsorption isotherm indicated monolayer adsorption on the surface of the adsorbents, with maximum adsorption capacities of 158.93 mg/g for BC900-700, 150.15 mg/g for BC700-900, and 142.56 mg/g for BC900, respectively. Furthermore, results from simulated wastewater and regeneration experiments demonstrated that BC900-700 exhibited not only excellent adsorption performance in wastewater but also remarkable regeneration capabilities. The two-step pyrolysis BCs in this study displayed a higher adsorption capacity compared to the one-step pyrolysis BCs in practical applications. These findings provide insights for further exploring the adsorption mechanism and optimizing the process.


Assuntos
Carvão Vegetal , Águas Residuárias , Poluentes Químicos da Água , Adsorção , Pirólise , Água , Poluentes Químicos da Água/química , Tetraciclina , Antibacterianos , Cinética , Espectroscopia de Infravermelho com Transformada de Fourier
18.
Environ Res ; 248: 118282, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38295974

RESUMO

The escalating consumer demand for crabs results in a growing amount of waste, including shells, claws, and other non-edible parts. The resulting crab shell waste (CSW) is disposed of via incineration or landfills which causes environmental pollution. CSW represents a potential biological resource that can be transformed into valuable resources via pyrolysis technique. In this study, microwave pyrolysis of CSW using self-purging, vacuum, and steam activation techniques was examined to determine the biochar production yield and its performance in treating palm oil mill effluent (POME). The biochar produced through microwave pyrolysis exhibits yields ranging from 50 to 61 wt%, showing a hard texture, low volatile matter content (≤34.1 wt%), and high fixed carbon content (≥58.3 wt%). The KOH-activated biochar demonstrated a surface area of up to 177 m2/g that is predominantly composed of mesopores, providing a good amount of adsorption sites for use as adsorbent. The biochar activated with steam removed 8.3 mg/g of BOD and 42 mg/g of COD from POME. The results demonstrate that microwave pyrolysis of CSW is a promising technology to produce high-quality biochar as an adsorbent for POME treatment.


Assuntos
Braquiúros , Carvão Vegetal , Animais , Óleo de Palmeira , Micro-Ondas , Pirólise , Vapor , Resíduos Industriais/análise
19.
Environ Res ; 250: 118376, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38354891

RESUMO

Antibiotic mycelial dreg (AMD) has been categorized as hazardous waste due to the high residual hazardous contaminants. Inappropriate management and disposal of AMD can cause potential environmental and ecological risks. In this study, the potential of pleuromutilin mycelial dreg (PMD) as a novel feedstock for preparing tetracycline hydrochloride (TC) adsorbent was explored to achieve safe management of PMD. The results suggested that residual hazardous contaminants were completely eliminated after pyrolysis. With the increase of pyrolysis temperature, the yields, H/C, O/C, (O + N)/C, and pore size in PMD-derived biochars (PMD-BCs) decreased, while BET surface area and pore volume increased, resulting in the higher stability of the PMD-BCs prepared from higher temperatures. The TC adsorption of the PMD-BCs increased from 27.3 to 46.9 mg/g with the increase of the pyrolysis temperature. Surprisingly, pH value had a strong impact on the TC adsorption, the adsorption capacity of BC-450 increased from 6.5 to 71.1 mg/g when the solution pH value increased from 2 to 10. Lewis acid-base interaction, pore filling, π-π interaction, hydrophobic interaction, and charge-assisted hydrogen bond (CAHB) are considered to drive the adsorption. This work provides a novel pathway for the concurrent detoxification and reutilization of AMD.


Assuntos
Antibacterianos , Carvão Vegetal , Carvão Vegetal/química , Adsorção , Tetraciclina/química , Temperatura Baixa , Micélio , Pirólise
20.
Environ Res ; 249: 118388, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38331149

RESUMO

Nowadays, the scarcity of energy resources is promoting the search for alternative energy sources, boosting interest in the use of forest lignocellulosic residue in the energy sector. In this study, the focus is on the energy recovery from two lignocellulosic residues originated during the pruning of ornamental trees (Horse Chestnut, CI, and False Acacia, FA). Both conventional and flash pyrolysis techniques were applied. The experimental pyrolysis variables were obtained from the study of the thermal behaviour of the pruning residues in thermogravimetric analysis. It was carried out under 5 heating rates and kinetic parameters were estimated using Flynn-Wall-Ozawa method. Results denoted higher maximum mass loss rate values for the same release temperature regions under FA experiments. Also, FA samples had lower final residues for the processes. However, activation energy values were so close for both species. FA was also linked to the faster reactions according frequency factor outcomes. Conventional pyrolysis of pruning residues was carried out in a horizontal oven of original design at a heating rate of 25 °C/min, at 750 °C and 60 min of permanence at that temperature; flash pyrolysis was tested in that oven at 750 and 850 °C. In these pyrolysis processes, three fractions were obtained: bio-char, bio-oil and gas. The physicochemical attributes of the bio-chars suggested their potential utility as biofuels (28.4-29.8 MJ/kg), adsorbent precursors or soil additives. Conventional pyrolysis bio-oils had a dominant monoaromatic hydrocarbons nature, with phenols being the most abundant (≥60%), while flash bio-oils contain mainly polycyclic aromatic hydrocarbons. Conventional pyrolysis gases contained up to 60 vol% of CO2; flash pyrolysis gases had high combustible gas content (CO, CH4, H2) and a low CO2 content (<25 vol%). As a result, their calorific value (18.06 MJ/kg) exhibited a threefold increase compared to the gas produced through conventional pyrolysis (6.04 MJ/kg).


Assuntos
Biocombustíveis , Biomassa , Pirólise , Biocombustíveis/análise , Acacia/química , Corylus/química , Termogravimetria , Árvores
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