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1.
Angew Chem Int Ed Engl ; 60(3): 1323-1331, 2021 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-33026162

RESUMO

MFI type zeolites with 10-membered-ring pores (ca. 0.55 nm) have the ability to separate p-xylene (ca. 0.58 nm) from its bulkier isomers. Here, we introduced non-zeolitic micropores (ca. 0.6-1.5 nm) and mesopores (ca. 2-7 nm) to a conventional microporous MFI type zeolite membrane, yielding an unprecedented hierarchical membrane structure. The uniform, embedded non-zeolitic pores decreased defect formation considerably and facilitated molecular transport, resulting in high p-xylene perm-selectivity and molar flux. Specifically, compared to a conventional, crack network-containing MFI membranes of similar thickness (ca. 1 µm), the mesoporous MFI membranes showed almost double p-xylene permeance (ca. 1.6±0.4×10-7  mol m-2 s-1 Pa-1 ) and a high p-/o-xylene separation factor (ca. 53.8±7.3 vs. 3.5±0.5 in the conventional MFI membrane) at 225 °C. The embedded non-zeolitic pores allowed for decreasing the separation performance degradation, which was apparently related to coke formation.

2.
Environ Res ; 173: 508-516, 2019 06.
Artigo em Inglês | MEDLINE | ID: mdl-30991175

RESUMO

The adsorption characteristics of four aromatic hydrocarbons (i.e., benzene, toluene, xylene, and styrene) onto ground-activated carbon were investigated both independently and as a mixture of the four at <10 Pa partial pressures (e.g., 0-100 ppm concentration range). The maximum sorption capacities for benzene, toluene, styrene, and xylene were measured both as a sole component and as a mixture (at 10 Pa). In the former, the values were approximately 123, 184, 272, and 238 mg g-1, respectively. In contrast, the latter values were 5, 52, 222, and 248 mg g-1 respectively, showing dramatic reduction in lighter compounds (below C7) relative to heavier ones (above C8). The mechanistic detail of sorption has been explained in terms of Henry's law and Langmuir, Freundlich, Dubinin-Radushkevich, and Elovich isotherm models. The linearized Langmuir adsorption isotherm analysis showed three sorption pressure regions: low (<1 Pa, retrograde), intermediate (1-4 Pa), and high (4-10 Pa). As such, the outcome of this study offers a unique opportunity to acquire detailed information on the dramatic and dynamic effects of the sorptive interaction between competing sorbates, along with a common sorption process between sorbent and sorbate at 298 K.


Assuntos
Hidrocarbonetos , Modelos Químicos , Compostos Orgânicos Voláteis , Adsorção , Benzeno , Tolueno
3.
Angew Chem Int Ed Engl ; 58(51): 18654-18662, 2019 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-31591796

RESUMO

The secondary growth methodology to form zeolite membranes has stringent requirements for homogeneous epitaxial intergrowth of the seed layer and limits the number of accessible high-quality zeolite membranes. Despite previous reports on hetero-epitaxial growth, high-performance zeolite membranes have yet to be reported using this approach. Here, the successful hetero-epitaxial growth of highly siliceous ZSM-58 (DDR-type zeolite) films from a SSZ-13 (CHA-type zeolite) seed layer is reported. The resulting membranes show excellent CO2 perm-selectivities, having maximum CO2 /N2 and CO2 /CH4 separation factors (SFs) as high as about 17 and 279, respectively, at 30 °C. Furthermore, the hybrid membrane maintains the CO2 perm-selectivity in the presence of water vapor (the third main component in both cases), that is, CO2 /N2 SF of about 14 and CO2 /CH4 SF of about 78, respectively, at 50 °C (a representative temperature of both CO2 -containing streams).

4.
J Environ Manage ; 225: 261-271, 2018 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-30096714

RESUMO

Nanotechnology is currently one of the highest priority research fields in many countries due to its immense potentiality and economic impact. Nanotechnology involves the research, development, production, and processing of structures and materials on a nanometer scale in various fields of science, technology, health care, industries, and agriculture. As such, it has contributed to the gradual restructuring of many associated technologies. However, due to the uncertainties and irregularities in shape, size, and chemical compositions, the presence of certain nanomaterials may exert adverse impacts on the environment as well as human health. Concerns have thus been raised about the destiny, transport, and transformation of nanoparticles released into the environment. A critical evaluation of the current states of knowledge regarding the exposure and effects of nanomaterials on the environment and human health is discussed in this review. Recognition on the potential advantages and unintended dangers of nanomaterials to the environment and human health is critically important to pursue their development in the future.


Assuntos
Meio Ambiente , Nanoestruturas , Nanotecnologia , Humanos , Indústrias , Nanopartículas
5.
Environ Geochem Health ; 39(1): 75-88, 2017 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26932558

RESUMO

Permeable reactive barriers (PRBs) have proved to be a promising passive treatment to control groundwater contamination and associated human health risks. This study explored the potential use of low-cost adsorbents as PRBs media and assessed their longevity and risk mitigation against leaching of acidic rainfall through an e-waste recycling site, of which Cu, Zn, and Pb were the major contaminants. Batch adsorption experiments suggested a higher adsorption capacity of inorganic industrial by-products [acid mine drainage sludge (AMDS) and coal fly ash (CFA)] and carbonaceous recycled products [food waste compost (FWC) and wood-derived biochar] compared to natural inorganic minerals (limestone and apatite). Continuous leaching tests of sand columns with 10 wt% low-cost adsorbents were then conducted to mimic the field situation of acidic rainfall infiltration through e-waste-contaminated soils (collected from Qingyuan, China) by using synthetic precipitation leaching procedure (SPLP) solution. In general, Zn leached out first, followed by Cu, and finally delayed breakthrough of Pb. In the worst-case scenario (e.g., at initial concentrations equal to 50-fold of average SPLP result), the columns with limestone, apatite, AMDS, or biochar were effective for a relatively short period of about 20-40 pore volumes of leaching, after which Cu breakthrough caused non-cancer risk concern and later-stage Pb leaching considerably increased both non-cancer and lifetime cancer risk associated with portable use of contaminated water. In contrast, the columns with CFA or FWC successfully mitigated overall risks to an acceptable level for a prolonged period of 100-200 pore volumes. Therefore, with proper selection of low-cost adsorbents (or their mixture), waste-based PRBs is a technically feasible and economically viable solution to mitigate human health risk due to contaminated groundwater at e-waste recycling sites.


Assuntos
Água Subterrânea/química , Reciclagem , Poluentes Químicos da Água/análise , Adsorção , Medição de Risco
6.
Environ Technol ; 36(9-12): 1423-32, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-25424128

RESUMO

There is an increasing interest to recycle greywater for meeting non-portable water demand. However, linear alkylbenzene sulphonates (a form of anionic surfactants) that are commonly found in greywater are less biodegradable at moderate to high concentrations. A fenton-like system is a relatively economic advanced oxidation process that can potentially be used for surfactant degradation in greywater treatment. This study investigated the feasibility of zerovalent iron (ZVI)-mediated Fenton's oxidation of sodium dodecylbenzene sulphonate (SDBS) using Fe0/H2O2 and Fe2+/Fe0/H2O2 systems under a range of operating conditions. For the Fe0/H2O2 binary system, the initial pH value and Fe0 dosage played important roles in final degradation efficiency. For the Fe2+/Fe0/H2O2 ternary systems, a small amount of Fe2+ (0.5-1.7 mM) contributed a synergistic effect to promote iron recycling and SDBS degradation. Approximately, 90% of SDBS mineralization efficiency was accomplished within 15 min at a pH range from 3.0 to 6.5, using 18 mM Fe0 and 15 mM H2O2. However, the removal kinetics was rate-limited by Fe2+ dissolution from the ZVI surfaces. The Fenton-like process of the Fe2+/Fe0/H2O2 ternary system also presents a promising treatment method for synthetic greywater, in which 90% TOC removal was achieved within the first 10 min; 78% COD and 91% BOD5 were achieved after 120 min of reaction.


Assuntos
Benzenossulfonatos/química , Peróxido de Hidrogênio/química , Ferro/química , Compostos Orgânicos/isolamento & purificação , Purificação da Água , Análise da Demanda Biológica de Oxigênio , Catálise
7.
J Am Chem Soc ; 136(22): 7961-71, 2014 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-24813064

RESUMO

As a subset of the metal-organic frameworks, zeolitic imidazolate frameworks (ZIFs) have potential use in practical separations as a result of flexible yet reliable control over their pore sizes along with their chemical and thermal stabilities. Among many ZIF materials, we explored the effect of thermal treatments on the ZIF-7 structure, known for its promising characteristics toward H2 separations; the pore sizes of ZIF-7 (0.29 nm) are desirable for molecular sieving, favoring H2 (0.289 nm) over CO2 (0.33 nm). Although thermogravimetric analysis indicated that ZIF-7 is thermally stabile up to ~400 °C, the structural transition of ZIF-7 to an intermediate phase (as indicated by X-ray analysis) was observed under air as guest molecules were removed. The transition was further continued at higher temperatures, eventually leading toward the zinc oxide phase. Three types of ZIF-7 with differing shapes and sizes (~100 nm spherical, ~400 nm rhombic-dodecahedral, and ~1300 nm rod-shaped) were employed to elucidate (1) thermal structural transitions while considering kinetically relevant processes and (2) discrepancies in the N2 physisorption and CO2 adsorption isotherms. The largest rod-shaped ZIF-7 particles showed a delayed thermal structural transition toward the stable zinc oxide phase. The CO2 adsorption behaviors of the three ZIF-7s, despite their identical crystal structures, suggested minute differences in the pore structures; in particular, the smaller spherical ZIF-7 particles provided reversible CO2 adsorption isotherms at ~30-75 °C, a typical temperature range of flue gases from coal-fired power plants, in contrast to the larger rhombic-dodecahedral and rod-shaped ZIF-7 particles, which exhibited hysteretic CO2 adsorption/desorption behavior.


Assuntos
Dióxido de Carbono/química , Imidazóis/química , Zeolitas/química , Adsorção , Cromatografia em Gel , Hidrogênio/química , Termodinâmica
8.
Chempluschem ; : e202400389, 2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-39016313

RESUMO

The circular economy represents an economic model that prioritizes sustainability and resource efficiency, aiming to minimize waste minimization, promote reuse, and close material loops. This Special Collection highlights recent advancements in green chemistry, catalysis, and waste valorization, fields critical for achieving sustainable practices and resource efficiency within a circular economy. Researchers from the Asia-Pacific region, Europe, South America, and North America have contributed to designing sustainable chemical processes that minimize environmental impact. These efforts involve developing efficient reactions to reduce waste generation and resource depletion. Additionally, this Special Collection showcases examples of effective catalysts with the potential to enhance resource conservation and circularity and convert waste and biomass materials into valuable products.

9.
Adv Sci (Weinh) ; : e2403128, 2024 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-38868919

RESUMO

Methylcyclohexane (MCH) dehydrogenation is an equilibrium-limited reaction that requires high temperatures (>300 °C) for complete conversion. However, high-temperature operation can degrade catalytic activity and produce unwanted side products. Thus, a hybrid zeolite membrane (Z) is prepared on the inner surface of a tubular support and used it as a wall in a membrane reactor (MR) configuration. Pt/C catalysts is packed diluted with quartz sand inside the Z-coated tube and applied the MR for MCH dehydrogenation at low temperatures (190-250 °C). Z showed a remarkable H2-permselectivity in the presence of both toluene and MCH, yielding separation factors over 350. The Z-based MR achieved higher MCH conversion (75.3% ± 0.8% at 220 °C) than the conventional packed-bed reactor (56.4% ± 0.3%) and the equilibrium state (53.2%), owing to the selective removal of H2 through Z. In summary, the hybrid zeolite MR enhances MCH dehydrogenation at low temperatures by overcoming thermodynamic limitations and improves the catalytic performance and product selectivity of the reaction.

10.
Chempluschem ; 88(7): e202300157, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37263976

RESUMO

Utilizing renewable energy to hydrogenate carbon dioxide into fuels eliminates massive CO2 emissions from the atmosphere and diminishes our need for using fossil fuels. This review presents the most recent developments for designing heterogeneous catalysts for the hydrogenation of CO2 to formate, methanol, and C2+ hydrocarbons. Thermodynamic challenges and mechanistic insights are discussed, providing a strong foundation to propose a suitable catalyst. The main body of this review focuses on nanostructured catalysts for constructing efficient heterogeneous systems. The most important factors affecting catalytic performance are highlighted, including active metals, supports and promoters that can potentially be used. The summary of the results and the outlook are presented in the final section. During the past few decades, heterogeneous CO2 hydrogenation has gained much attention and made tremendous progress. Thus, many highly efficient catalysts have been studied to discover their active sites and provide mechanistic insights. This paper summarizes recent advances in CO2 hydrogenation and its conversion into various hydrocarbons such as formate, methanol, and C2+ products. As for formate production, Au and Ru nanocatalysts show superior activity. However, considering the catalyst cost, Cu-based catalysts have an excellent prospect for methanol production, among other catalysts. Ultra-small nanoparticles and nanoclusters appear promising to provide highly active cost-effective catalysts. A growing number of researchers are investigating the possibility of directly synthesizing C2+ products through CO2 hydrogenation. The major challenge in producing heavy hydrocarbons is breaking the ASF limitations, which have been achieved over bifunctional catalysts using zeolites. Using suitable support and promoter can lead to a superior activity, ascribed to structural, electronic, and chemical promotional effects.


Assuntos
Dióxido de Carbono , Metanol , Hidrogenação , Formiatos
11.
Nanomaterials (Basel) ; 13(24)2023 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-38133017

RESUMO

Preserving ultrasmall sizes of metal particles is a key challenge in the study of heterogeneous metal-based catalysis. Confining the ultrasmall metal clusters in a well-defined crystalline porous zeolite has emerged as a promising approach to stabilize these metal species. Successful encapsulation can be achieved by the addition of ligated metal complexes to zeolite synthesis gel before hydrothermal synthesis. However, controlling the metal particle size during post-reduction treatment remains a major challenge in this approach. Herein, an in situ incorporation strategy of pre-made atomically precise gold clusters within Na-LTA zeolite was established for the first time. With the assistance of mercaptosilane ligands, the gold clusters were successfully incorporated within the Na-LTA without premature precipitation and metal aggregation during the synthesis. We have demonstrated that the confinement of gold clusters within the zeolite framework offers high stability against sintering, leading to superior CO oxidation catalytic performance (up to 12 h at 30 °C, with a space velocity of 3000 mL g-1 h-1).

12.
Biotechnol Adv ; 67: 108181, 2023 10.
Artigo em Inglês | MEDLINE | ID: mdl-37268152

RESUMO

The sustainable utilization of biochar produced from biomass waste could substantially promote the development of carbon neutrality and a circular economy. Due to their cost-effectiveness, multiple functionalities, tailorable porous structure, and thermal stability, biochar-based catalysts play a vital role in sustainable biorefineries and environmental protection, contributing to a positive, planet-level impact. This review provides an overview of emerging synthesis routes for multifunctional biochar-based catalysts. It discusses recent advances in biorefinery and pollutant degradation in air, soil, and water, providing deeper and more comprehensive information of the catalysts, such as physicochemical properties and surface chemistry. The catalytic performance and deactivation mechanisms under different catalytic systems were critically reviewed, providing new insights into developing efficient and practical biochar-based catalysts for large-scale use in various applications. Machine learning (ML)-based predictions and inverse design have addressed the innovation of biochar-based catalysts with high-performance applications, as ML efficiently predicts the properties and performance of biochar, interprets the underlying mechanisms and complicated relationships, and guides biochar synthesis. Finally, environmental benefit and economic feasibility assessments are proposed for science-based guidelines for industries and policymakers. With concerted effort, upgrading biomass waste into high-performance catalysts for biorefinery and environmental protection could reduce environmental pollution, increase energy safety, and achieve sustainable biomass management, all of which are beneficial for attaining several of the United Nations Sustainable Development Goals (UN SDGs) and Environmental, Social and Governance (ESG).


Assuntos
Carbono , Carvão Vegetal , Carvão Vegetal/química , Solo , Biomassa
13.
ACS Appl Mater Interfaces ; 14(2): 2893-2907, 2022 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-34985249

RESUMO

Biogas is an environmentally friendly and sustainable energy resource that can substitute or complement conventional fossil fuels. For practical uses, biogas upgrading, mainly through the effective separation of CO2 (0.33 nm) and CH4 (0.38 nm), is required to meet the approximately 90-95% purity of CH4, while CO2 should be concomitantly purified. In this study, a high CO2 perm-selective zeolite membrane was synthesized by heteroepitaxially growing a chabazite (CHA) zeolite seed layer with a synthetic precursor that allowed the formation of all-silica deca-dodecasil 3 rhombohedral (DDR) zeolite (with a pore size of 0.36 × 0.44 nm2). The resulting hydrophobic DDR@CHA hybrid membrane on an asymmetric α-Al2O3 tube was thin (ca. 2 µm) and continuous, thus providing both high flux and permselectivity for CO2 irrespective of the presence or absence of water vapor (the third largest component in the biogas streams). To the best of our knowledge, the CO2 permeance of (2.9 ± 0.3) × 10-7 mol m-2 s-1 Pa-1 and CO2/CH4 separation factor of ca. 274 ± 73 at a saturated water vapor partial pressure of ca. 12 kPa at 50 °C have the highest CO2/CH4 separation performance yet achieved. Furthermore, we explored the membrane module properties of the hybrid membrane in terms of the recovery and purity of both CO2 and CH4 under dry and wet conditions. Despite the high intrinsic membrane properties of the current hybrid membrane, reflected by the high permeance and SF, the corresponding module properties indicated that high-performance separation of CO2 and CH4 for the desired biogas upgrading was achieved at a limited processing capacity. This supports the importance of understanding the correlation between the membrane and module properties, as this will provide guidance for the optimal operating conditions.


Assuntos
Materiais Biocompatíveis/química , Reatores Biológicos , Dióxido de Carbono/isolamento & purificação , Metano/isolamento & purificação , Zeolitas/química , Dióxido de Carbono/química , Teste de Materiais , Metano/química , Tamanho da Partícula
14.
Environ Pollut ; 279: 116899, 2021 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-33743438

RESUMO

Development of non-noble metal cluster catalysts, aiming at concurrently high activity and stability, for emission control systems has been challenging because of sintering and overcoating of clusters on the support. In this work, we reported the role of well-dispersed copper nanoclusters supported on TiO2 in CO oxidation under industrially relevant operating conditions. The catalyst containing 0.15 wt% Cu on TiO2 (0.15 CT) exhibited a high dispersion (59.1%), a large specific surface area (381 m2/gCu), a small particle size (1.77 nm), and abundant active sites (75.8% Cu2O). The CO oxidation activity measured by the turnover frequency (TOF) was found to be enhanced from 0.60 × 10-3 to 3.22 × 10-3 molCO·molCu-1·s-1 as the copper loading decreased from 5 to 0.15 wt%. A CO conversion of approximately 60% was still observed in the supported cluster catalyst with a Cu loading of 5 wt% at 240 °C. No deactivation was observed for catalysts with low copper loading (0.15 and 0.30 CT) after 8 h of time-on-stream, which compares favorably with less stable Au cluster-based catalysts reported in the literature. In contrast, catalysts with high copper loading (0.75 and 5 CT) showed deactivation over time, which was ascribed to the increase in copper particle size due to metal cluster agglomeration. This study elucidated the size-activity threshold of TiO2-supported Cu cluster catalysts. It also demonstrated the potential of the supported Cu cluster catalyst at a typical temperature range of diesel engines at light-load. The supported Cu cluster catalyst could be a promising alternative to noble metal cluster catalysts for emission control systems.


Assuntos
Cobre , Titânio , Catálise , Oxirredução
15.
Bioresour Technol ; 297: 122488, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31796381

RESUMO

Metal clusters and nanoparticles, which have been used to tune the acidity of zeolite support, are beneficial for promoting the catalytic performance of various reaction processes, including biomass conversion. However, catalytic instabilities resulting from metal coalescence, sintering and leaching are major problems that need to be resolved. Therefore, metal encapsulation within the zeolite structure has been proposed as a feasible solution for this issue, particularly for biomass conversions that require high temperatures. In this current review, recent developments in metal confinement techniques are described along with experimental examples of biomass upgrading reactions. The present and future perspectives of zeolite-encapsulated metal catalysts in biomass conversions are also given.


Assuntos
Zeolitas , Biomassa , Catálise , Temperatura Alta , Metais
16.
J Hazard Mater ; 384: 121161, 2020 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-31629599

RESUMO

Mesoporous ZSM-5 (MFI) zeolite was synthesized by using bacterial cellulose-derived activated carbon (BC-AC500) with a high surface area as a hard template. Different ratios of BC-AC500 and zeolite precursor gel were prepared in a Teflon-lined autoclave and crystallized at 180 °C for 48 h in a rotating oven. The physicochemical properties of the samples were characterized by x-ray diffraction (XRD), scanning/transmission electron microscopies (SEM/TEM), and N2 physisorption techniques. It was found that the mesoporous ZSM-5 zeolites have a specific surface area of 184-190 m2/g, a high mesopore volume of 0.120-0.956 ml/g and a wide pore size distribution ranging from 5 to 100 nm with a maximum at approximately 25.3 nm. The successfully made mesoporous ZSM-5 was tested as an adsorbent for formaldehyde adsorption in batch mode. The mesoporous ZSM-5 zeolite made from bacterial cellulose-derived activated carbon showed significantly faster adsorption kinetics than conventional ZSM-5 (0.0081 vs. 0.0007 g/mg min, respectively). The prepared material has an adsorption capacity of 98 mg/g and is highly reusable. The reported mesoporous ZSM-5 zeolites can be deployed for the rapid removal of toxic organics from wastewater when urgently needed, e.g., under breakthrough conditions.


Assuntos
Formaldeído/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Zeolitas/química , Adsorção , Bactérias , Carbono , Celulose
17.
Sci Total Environ ; 704: 135414, 2020 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-31810693

RESUMO

Efficient conversion of food waste to value-added products necessitates the development of high-performance heterogeneous catalysts. This study evaluated the use of Al2O3 as a low-cost and abundant support material for fabricating Lewis acid catalysts, i.e., through the in-situ doping of Cu, Ni, Co, and Zr into Al2O3 followed by calcination. The characterisation results show that all catalysts were mainly amorphous. In particular, adding the transition metals to the Al2O3 matrix resulted in the increase of acidity and meso-/micro-pores. The catalysts were evaluated in the conversion of glucose, which can be easily derived from starch-rich food waste (e.g., bread waste) via hydrolysis, to fructose in biorefinery. The results indicate that the Ni-doped Al2O3 (Al-Ni-C) achieved the highest fructose yield (19 mol%) and selectivity (59 mol%) under heating at 170 °C for 20 min, of which the performance falls into the range reported in literature. In contrast, the Zr-doped Al2O3 (Al-Zr-C) presented the lowest fructose selectivity despite the highest glucose conversion, meaning that the catalyst was relatively active towards the side reactions of glucose and intermediates. The porosity and acidity, modified via metal impregnation, were deduced as the determinants of the catalytic performance. It is noteworthy that the importance of these parameters may vary in a relative sense and the limiting factor could shift from one parameter to another. Therefore, evaluating physicochemical properties as a whole, instead of the unilateral improvement of a single parameter, is encouraged to leverage each functionality for cost-effectiveness. This study provides insights into the structure-performance relationships to promote advance in catalyst design serving a sustainable food waste biorefinery.


Assuntos
Óxido de Alumínio/química , Alimentos , Eliminação de Resíduos/métodos , Resíduos , Glucose , Concentração de Íons de Hidrogênio , Hidrólise , Metais/química , Porosidade
18.
Bioresour Technol ; 298: 122544, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31838242

RESUMO

Lignocellulosic wastes constitute a significant portion of the municipal solid waste, which should be valorised for the synthesis of value-added chemicals to achieve circular bioeconomy. This study evaluates the use of γ-valerolactone (GVL) and acetone as green co-solvents to produce levulinic acid (LA) from lignocellulosic paper towel waste at different temperatures using dilute H2SO4. At the highest reaction temperature (200 °C), H2O-only system achieved ~15 Cmol% of LA at maximum. while GVL/H2O and acetone/H2O co-solvent systems enhanced the depolymerisation of paper towel waste and the subsequent conversion to LA, with the highest yield amounted to ~32 Cmol%. Acetone/H2O solvent system generated ~17 Cmol% LA at a lower temperature (180 °C), while higher temperature induced polymerisation of soluble sugars and intermediates, hindering further conversion to LA. In contrast, the availability of soluble sugars was higher in the GVL/H2O system, which favoured the production of LA at higher temperatures.


Assuntos
Ácidos Levulínicos , Lignina , Solventes , Temperatura
19.
Chemosphere ; 226: 924-933, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31509922

RESUMO

-While sulfate radical (SO4-)-based processes are useful to degrade acetaminophen (ACE), studies of using peroxymonosulfate (PMS) to degrade ACE are quite limited. In addition, although Co is validated as the most effective metal for activating PMS, very few Co catalysts have been developed and investigated for activating PMS to degrade ACE. Since carbon is a promising substrate to support Co nanoparticles (NPs) to form Co/carbon composite catalysts, most existing carbon substrates require delicate fabrications. As biochar is an easy-to-obtain but versatile carbon material, pyrolysis of Co/lignin affords an advantageous Co-impregnated biochar (CoIB) as an attractive catalyst for PMS activation. Specifically, as CO2 substitutes N2 as a reaction medium for pyrolysis of Co/lignin, the syngas production from pyrolysis can be substantially improved and a magnetic CoIB is afforded. This CoIB consists of evenly-distributed Co nanoparticles (NPs) impregnated in carbon matrices of biochar, and possesses several superior characteristics, such as high porosity, large surface area and magnetism, enabling CoIB a promising catalyst for activating PMS to degrade ACE. CoIB also shows a much higher catalytic activity of PMS activation than CoIBN2, and Co3O4 for degrading ACE. CoIB is also recyclable for activating PMS to effectively degrade ACE for multiple cycles. The ACE degradation pathway by this CoIB-activated PMS is proposed according to the degradation products. These findings validate that CoIB is assuredly an advantageous heterogeneous catalyst, which can be easily prepared from pyrolysis of Co/lignin in CO2 with concomitant enhanced syngas production for effectively activating PMS to degrade ACE.


Assuntos
Acetaminofen/química , Dióxido de Carbono/química , Carvão Vegetal/química , Cobalto/química , Lignina/química , Peróxidos/química , Pirólise , Catálise
20.
J Hazard Mater ; 374: 365-371, 2019 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-31028915

RESUMO

CO2 capture is projected as one of the pragmatic approaches to deal with the global warming phenomenon. Adsorption-based CO2 capture is considered an economically attractive option to reduce CO2 emission. The success of the adsorption-based capture primarily relies on adsorbents and thus a variety of adsorbents have been investigated in the literature. We here report a high surface area (210.2 m2/g) exfoliated Ni-Al LDH nanoplatelet as a promising candidate for CO2 capture at an intermediate temperature of 200 °C applicable to integrated gasification combined cycle (IGCC) and sorption enhanced water gas shift (SEWGS) reactions. The materials were well characterized by PXRD, TGA, FTIR, TEM, ICP-OES, and N2 adsorption surface area, and pore size distribution techniques. A unique nanoflower morphology comprising of exfoliated LDH platelets of ca. 5 layer thickness was obtained. The CO2 capture capacity (0.66 mmol/g) of the exfoliated Ni-Al LDH nanoplatelet is comparable to that of the widely reported Mg-Al LDH-derived mixed oxides and MgO-based adsorbents. Provided that Ni-Al and other transition metal LDH materials are known to exhibit superior catalytic properties for CO2 methanation, this work could pave the way for development of dual-functional materials for CO2 capture and conversion.

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