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1.
Angew Chem Int Ed Engl ; 63(14): e202319153, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38356309

RESUMO

As a sustainable valorization route, electrochemical glycerol oxidation reaction (GOR) involves in formation of key OH* and selective adsorption/cleavage of C-C(O) intermediates with multi-step electron transfer, thus suffering from high potential and poor formate selectivity for most non-noble-metal-based electrocatalysts. So, it remains challenging to understand the structure-property relationship as well as construct synergistic sites to realize high-activity and high-selectivity GOR. Herein, we successfully achieve dual-high performance with low potentials and superior formate selectivity for GOR by forming synergistic Lewis and Brønsted acid sites in Ni-alloyed Co-based spinel. The optimized NiCo oxide solid-acid electrocatalyst exhibits low reaction potential (1.219 V@10 mA/cm2) and high formate selectivity (94.0 %) toward GOR. In situ electrochemical impedance spectroscopy and pH-dependence measurements show that the Lewis acid centers could accelerate OH* production, while the Brønsted acid centers are proved to facilitate high-selectivity formation of formate. Theoretical calculations reveal that NiCo alloyed oxide shows appropriate d-band center, thus balancing adsorption/desorption of C-O intermediates. This study provides new insights into rationally designing solid-acid electrocatalysts for biomass electro-upcycling.

2.
Small ; 19(9): e2205876, 2023 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-36494175

RESUMO

Electrocatalytic biomass upgrading has proven to be an effective technique for generating value-added products. Herein, the design and development of furfural upgrading using transition-metal borides (MBenes) with simultaneous production of hydrogen are presented. Using density functional theory, the stabilities, selectivities, and activities of 13 MBene candidates are systematically evaluated for furfural upgrading. This research suggests that Fe2 B2 can serve as a promising electrocatalyst for the formation of furoic acid (FAC), with a limiting potential of -0.15 V, and 5-hydroxy-2(5H)-furanone (HFO), with a limiting potential of -0.93 V. Furthermore, Fe2 B2 and Mn2 Fe2 are shown to exhibit favorable limiting potentials of -1.35 and -1.36 V, respectively, for producing 6-hydroxy-2.3-dihydro-6H-pyrano-3-one (HDPO), indicating that they may also serve as electrocatalysts. Based on Sabatier's principle, a descriptor (φ) of material properties is developed for screening catalysts with high catalytic activity considering the electronegativities and d-electron number of metals. Additionally, surface redox potential, electronic properties, and charge-density differences are determined for Fe2 B2 , which is estimated to exhibit high catalytic activity for the oxidation of furfural to FAC and HFO.

3.
Small ; 19(42): e2302271, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37328440

RESUMO

Amine-containing derivatives are important intermediates in drug manufacturing; sustainable synthesis of amine compounds from green carbon-based biomass derivatives has attracted increasing attention, especially the reductive amination of biomass molecules via electrochemical upgrading. To achieve efficient reductive amination of 5-(hydroxymethyl)furfural (HMF) via electrocatalytic biomass upgrading, this work proposes a new HMF biomass upgrading strategy based on metal supported on Mo2 B2 MBene nanosheets using a density functional theory comprehensive study. HMF and methylamine (CH3 CH2 ) can be reduced to 5-(hydroxymethyl) aldiminefurfural (HMMAMF) via electrocatalytic biomass upgrading, which is identified as a promising technology to produce pharmaceutical intermediates. Based on the proposed reaction mechanisms of HMF reductive amination, this work performs a systematic study of HMF amination to HMMAMF using an atomic model simulation method. This study aims to design a high-efficiency catalyst based on Mo2 B2 @TM nanosheets via the reductive amination of 5-HMF and provide insights into the intrinsic relation between thermochemical and material electronic properties and the role of dopant metals. This work establishes the Gibbs free energy profiles of each reaction HMF Biomass Upgrading on Mo2 B2 systems and obtained the limiting potentials of the rate-determining step, which included the kinetic stability of dopants, HMF adsorbability, and the catalytic activity and selectivity of the hydrogen evolution reaction or surface oxidation. Furthermore, charge transfer, d-band center (εd ), and material property (φ) descriptors are applied to establish a linear correlation to determine promising candidate catalysts for reductive amination of HMF. The candidates Mo2 B2 @Cr, Mo2 B2 @Zr, Mo2 B2 @Nb, Mo2 B2 @Ru, Mo2 B2 @Rh, and Mo2 B2 @Os are suitable high-efficiency catalysts for HMF amination. This work may contribute to the experimental application of biomass upgrading catalysts for biomass energy and guide the future development of biomass conversion strategies and utilization.

4.
Angew Chem Int Ed Engl ; 62(45): e202311196, 2023 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-37721394

RESUMO

Alanine is widely employed for synthesizing polymers, pharmaceuticals, and agrochemicals. Electrocatalytic coupling of biomass molecules and waste nitrate is attractive for the nitrate removal and alanine production under ambient conditions. However, the reaction efficiency is relatively low due to the activation of the stable substrates, and the coupling of two reactive intermediates remains challenging. Herein, we realize the integrated tandem electrochemical-chemical-electochemical synthesis of alanine from the biomass-derived pyruvic acid (PA) and waste nitrate (NO3 - ) catalyzed by PdCu nano-bead-wires (PdCu NBWs). The overall reaction pathway is demonstrated as a multiple-step catalytic cascade process via coupling the reactive intermediates NH2 OH and PA on the catalyst surface. Interestingly, in this integrated tandem electrochemical-chemical-electrochemical catalytic cascade process, Cu facilitates the electrochemical reduction of nitrate to NH2 OH intermediates, which chemically couple with PA to form the pyruvic oxime, and Pd promotes the electrochemical reduction of pyruvic oxime to the desirable alanine. This work provides a green strategy to convert waste NO3 - to wealth and enriches the substrate scope of renewable biomass feedstocks to produce high-value amino acids.

5.
Angew Chem Int Ed Engl ; 62(37): e202309478, 2023 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-37486710

RESUMO

Electricity-driven organo-oxidations have shown an increasing potential recently. However, oxygen evolution reaction (OER) is the primary competitive reaction, especially under high current densities, which leads to low Faradaic efficiency (FE) of the product and catalyst detachment from the electrode. Here, we report a bimetallic Ni-Cu electrocatalyst supported on Ni foam (Ni-Cu/NF) to passivate the OER process while the oxidation of 5-hydroxymethylfurfural (HMF) is significantly enhanced. A current density of 1000 mA cm-2 can be achieved at 1.50 V vs. reversible hydrogen electrode, and both FE and yield keep close to 100 % over a wide range of potentials. Both experimental results and theoretical calculations reveal that Cu doping impedes the OH* deprotonation to O* and hereby OER process is greatly passivated. Those instructive results provide a new approach to realizing highly efficient biomass upgrading by regulating the OER activity.

6.
Angew Chem Int Ed Engl ; 62(31): e202304852, 2023 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-37278359

RESUMO

The development of a rechargeable battery that can produce valuable chemicals in both electricity storage and generation processes holds great promise for increasing the electron economy and economic value. However, this battery has yet to be explored. Herein, we report a biomass flow battery that generates electricity while producing furoic acid, and store electricity while yielding furfuryl alcohol. The battery is composed of a rhodium-copper (Rh1 Cu) single-atom alloy as anode, a cobalt-doped nickel hydroxide (Co0.2 Ni0.8 (OH)2 ) as cathode, and furfural-containing anolyte. In a full battery evaluation, this battery displays an open circuit voltage (OCV) of 1.29 V and a peak power density up to 107 mW cm-2 , surpassing most catalysis-battery hybrid systems. As a proof-of-concept, we demonstrate that this battery produces 1 kg furoic acid with 0.78 kWh electricity output, and yields 0.62 kg furfuryl alcohol when 1 kWh electricity is stored. This work may shed light on the design of rechargeable batteries with value-added functionality such as chemicals production.

7.
Angew Chem Int Ed Engl ; 61(12): e202115636, 2022 03 14.
Artigo em Inglês | MEDLINE | ID: mdl-34939730

RESUMO

Integrating biomass upgrading and hydrogen production in an electrocatalytic system is attractive both environmentally and in terms of sustainability. Conventional electrolyser systems coupling anodic biosubstrate electrooxidation with hydrogen evolution reaction usually require electricity input. Herein, we describe the development of an electrocatalytic system for simultaneous biomass upgrading, hydrogen production, and electricity generation. In contrast to conventional furfural electrooxidation, the employed low-potential furfural oxidation enabled the hydrogen atom of the aldehyde group to be released as gaseous hydrogen at the anode at a low potential of approximately 0 VRHE (vs. RHE). The integrated electrocatalytic system could generate electricity of about 2 kWh per cubic meter of hydrogen produced. This study may provide a transformative technology to convert electrocatalytic biomass upgrading and hydrogen production from a process requiring electricity input into a process to generate electricity.


Assuntos
Eletricidade , Furaldeído , Biomassa , Eletrodos , Hidrogênio
8.
Angew Chem Int Ed Engl ; 61(37): e202209849, 2022 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-35876073

RESUMO

Electrochemical reduction of biomass-derived 5-hydroxymethylfurfural (HMF) represents an elegant route toward sustainable value-added chemicals production that circumvents the use of fossil fuel and hydrogen. However, the reaction efficiency is hampered by the high voltage and low activity of electrodes (Cu, Bi, Pb). Herein, we report a Ru1 Cu single-atom alloy (SAA) catalyst with isolated Ru atoms on Cu nanowires that exhibits an electrochemical reduction of HMF to 2,5-dihydroxymethylfuran (DHMF) with promoted productivity (0.47 vs. 0.08 mmol cm-2 h-1 ) and faradic efficiency (FE) (85.6 vs. 71.3 %) at -0.3 V (vs. RHE) compared with Cu counterpart. More importantly, the FE (87.5 %) is largely retained at high HMF concentration (100 mM). Kinetic studies by using combined electrochemical techniques suggest disparate mechanisms over Ru1 Cu and Cu, revealing that single-atom Ru promotes the dissociation of water to produce H* species that effectively react with HMF via an electrocatalytic hydrogenation (ECH) mechanism.


Assuntos
Ligas , Furaldeído , Furaldeído/análogos & derivados , Hidrogenação , Cinética
9.
Angew Chem Int Ed Engl ; 61(19): e202200211, 2022 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-35170172

RESUMO

The biomass-derived alcohol oxidation reaction (BDAOR) holds great promise for sustainable production of chemicals. However, selective electrooxidation of alcohols to value-added aldehyde compounds is still challenging. Herein, we report the electrocatalytic BDAORs to selectively produce aldehydes using single-atom ruthenium on nickel oxide (Ru1 -NiO) as a catalyst in the neutral medium. For electrooxidation of 5-hydroxymethylfurfural (HMF), Ru1 -NiO exhibits a low potential of 1.283 V at 10 mA cm-2 , and an optimal 2,5-diformylfuran (DFF) selectivity of 90 %. Experimental studies reveal that the neutral electrolyte plays a critical role in achieving a high aldehyde selectivity, and the single-atom Ru boosts HMF oxidation in the neutral medium by promoting water dissociation to afford OH*. Furthermore, Ru1 -NiO can be extended to selective electrooxidation of a series of biomass-derived alcohols to corresponding aldehydes, which are conventionally difficult to obtain in the alkaline medium.

10.
Angew Chem Int Ed Engl ; 60(37): 20253-20258, 2021 09 06.
Artigo em Inglês | MEDLINE | ID: mdl-34173309

RESUMO

High-entropy oxides (HEOs), a new concept of entropy stabilization, exhibit unique structures and fascinating properties, and are thus important class of materials with significant technological potential. However, the conventional high-temperature synthesis techniques tend to afford micron-scale HEOs with low surface area, and the catalytic activity of available HEOs is still far from satisfactory because of their limited exposed active sites and poor intrinsic activity. Here we report a low-temperature plasma strategy for preparing defect-rich HEOs nanosheets with high surface area, and for the first time employ them for 5-hydroxymethylfurfural (HMF) electrooxidation. Owing to the nanosheets structure, abundant oxygen vacancies, and high surface area, the quinary (FeCrCoNiCu)3 O4 nanosheets deliver improved activity for HMF oxidation with lower onset potential and faster kinetics, outperforming that of HEOs prepared by high-temperature method. Our method opens new opportunities for synthesizing nanostructured HEOs with great potential applications.

11.
Angew Chem Int Ed Engl ; 60(42): 22908-22914, 2021 10 11.
Artigo em Inglês | MEDLINE | ID: mdl-34405508

RESUMO

Nickel hydroxide (Ni(OH)2 ) is a promising electrocatalyst for the 5-hydroxymethylfurfural oxidation reaction (HMFOR) and the dehydronated intermediates Ni(OH)O species are proved to be active sites for HMFOR. In this study, Ni(OH)2 is modified by platinum to adjust the electronic structure and the current density of HMFOR improves 8.2 times at the Pt/Ni(OH)2 electrode compared with that on Ni(OH)2 electrode. Operando methods reveal that the introduction of Pt optimized the redox property of Ni(OH)2 and accelerate the formation of Ni(OH)O during the catalytic process. Theoretical studies demonstrate that the enhanced Ni(OH)O formation kinetics originates from the reduced dehydrogenation energy of Ni(OH)2 . The product analysis and transition state simulation prove that the Pt also reduces adsorption energy of HMF with optimized adsorption behavior as Pt can act as the adsorption site of HMF. Overall, this work here provides a strategy to design an efficient and universal nickel-based catalyst for HMF electro-oxidation, which can also be extended to other Ni-based catalysts such as Ni(HCO3 )2 and NiO.


Assuntos
Furaldeído/análogos & derivados , Hidróxidos/química , Níquel/química , Platina/química , Adsorção , Biomassa , Catálise , Furaldeído/química , Cinética , Nanopartículas Metálicas/química , Oxirredução , Análise Espectral Raman
12.
Chemistry ; 24(69): 18258-18270, 2018 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-30125404

RESUMO

The continuous advance in exploring renewable energy resources such as solar and wind will certainly alleviate our reliance on limited fossil reserves. However, the sustainable development of mankind demands not only energy but also carbon-based chemical goods. Unfortunately, exploitation of renewable energy resources like solar and wind will not lead to any carbon-based chemicals. The only sustainable and green carbon source is biomass, the scale of annual production of which has an immense potential to complement that of fossil-derived carbons. To utilize biomass in economically effective ways, many catalytic processes have been investigated. Among various strategies of biomass refinery, electrocatalytic upgrading stands out as an attractive option because of its benign operation conditions, high energy efficiency, and convenient control on production rate and selectivity using electrochemical parameters. This Minireview showcases several electrocatalytic systems for both reductive and oxidative upgrading of representative biomass-derived intermediate compounds, including 5-hydroxymethylfurfural, furfural, levulinic acid, glycerol, and sorbitol to different value-added products. The catalytic routes and mechanisms of each biomass-derived platform compound are discussed and compared. In order to be feasible for large-scale applications, low-cost composition and preparation of electrocatalysts are mandatory and will be emphasized. Finally, our personal perspective on the current challenges and future directions of electrocatalytic biomass upgrading is presented.

13.
Angew Chem Int Ed Engl ; 55(34): 9913-7, 2016 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-27417546

RESUMO

As an environmentally friendly approach to generate H2 , electrocatalytic water splitting has attracted worldwide interest. However, its broad employment has been inhibited by costly catalysts and low energy conversion efficiency, mainly due to the sluggish anodic half reaction, the O2 evolution reaction (OER), whose product O2 is not of significant value. Herein, we report an efficient strategy to replace OER with a thermodynamically more favorable reaction, the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), catalyzed by 3D Ni2 P nanoparticle arrays on nickel foam (Ni2 P NPA/NF). HMF is one of the primary dehydration intermediates of raw biomass and FDCA is of many industrial applications. As a bifunctional electrocatalyst, Ni2 P NPA/NF is not only active for HMF oxidation but also competent for H2 evolution. In fact, a two-electrode electrolyzer employing Ni2 P NPA/NF for simultaneous H2 and FDCA production required a voltage at least 200 mV smaller compared with pure water splitting to achieve the same current density, as well as exhibiting robust stability and nearly unity Faradaic efficiencies.

14.
J Colloid Interface Sci ; 657: 438-448, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38061227

RESUMO

Electrochemical oxidation of biomass-based 5-hydroxymethylfurfural (HMF) is an effective approach for achieving the high-value products of 2,5-furandicarboxylic acid (FDCA). However, the restricted formation of high-valence metal active species for electrocatalysts results in a sluggish kinetic process of HMF oxidation reaction (HMFOR). Herein, we fabricated the Ni3+-rich cross-linked α-Ni(OH)2 nanosheets for accelerating the HMFOR through an anion-mediated strategy. It is identified that the Cl- ions with strong penetrability replace a portion of lattice oxygen atoms in α-Ni(OH)2 to form Ni-Cl bonds, contributing to breaking the inherent lattice order and generating a special Ni3+-rich structure. Owing to the promoted adsorption and accelerated oxidation of hydroxyl and aldehyde groups by the affluent Ni3+ active species, the large oxidation current density of 116.5 mA cm-2 and HMFOR kinetic constant of 0.067 min-1 has been achieved at 1.45 V (vs. RHE). By analyzing the oxidation products, the FDCA yield and Faradic efficiency are both higher than 99.25 % and 99.36 % for five successive determinations. Therefore, this work provides an insightful anion-mediated strategy for designing high-performance electrocatalysts for biomass conversion application.

15.
Fundam Res ; 4(1): 69-76, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38933839

RESUMO

The electrochemical oxidation of biomass molecules coupling with hydrogen production is a promising strategy to obtain both green energy and value-added chemicals; however, this strategy is limited by the competing oxygen evolution reactions and high energy consumption. Herein, we report a hierarchical CoNi layered double hydroxides (LDHs) electrocatalyst with abundant Ni vacancies for the efficient anodic oxidation of 5-hydroxymethylfurfural (HMF) and cathodic hydrogen evolution. The unique hierarchical nanosheet structure and Ni vacancies provide outstanding activity and selectivity toward several biomass molecules because of the finely regulated electronic structure and highly-exposed active sites. In particular, a high faradaic efficiency (FE) at a high current density (99% at 100 mA cm-2) is achieved for HMF oxidation, and a two-electrode electrolyzer is assembled based on the Ni vacancies-enriched LDH, which realized a continuous synthesis of highly-pure 2,5-furandicarboxylic acid products with high yields (95%) and FE (90%).

16.
Sci Bull (Beijing) ; 69(18): 2870-2880, 2024 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-38942696

RESUMO

Electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a sustainable strategy to produce bio-based plastic monomer, is always conducted in a high-concentration alkaline solution (1.0 mol L-1 KOH) for high activity. However, such high concentration of alkali poses challenges including HMF degradation and high operation costs associated with product separation. Herein, we report a single-atom-ruthenium supported on Co3O4 (Ru1-Co3O4) as a catalyst that works efficiently in a low-concentration alkaline electrolyte (0.1 mol L-1 KOH), exhibiting a low potential of 1.191 V versus a reversible hydrogen electrode to achieve 10 mA cm-2 in 0.1 mol L-1 KOH, which outperforms previous catalysts. Electrochemical studies demonstrate that single-atom-Ru significantly enhances hydroxyl (OH-) adsorption with insufficient OH- supply, thus improving HMF oxidation. To showcase the potential of Ru1-Co3O4 catalyst, we demonstrate its high efficiency in a flow reactor under industrially relevant conditions. Eventually, techno-economic analysis shows that substitution of the conventional 1.0 mol L-1 KOH with 0.1 mol L-1 KOH electrolyte may significantly reduce the minimum selling price of FDCA by 21.0%. This work demonstrates an efficient catalyst design for electrooxidation of biomass working without using strong alkaline electrolyte that may contribute to more economic biomass electro-valorization.

17.
ChemSusChem ; 16(17): e202300685, 2023 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-37477393

RESUMO

To date the electroactive species of selective aldehyde oxidation to carboxylates at gold electrodes is usually assumed to be the diolate. It forms with high concentration only in very alkaline electrolytes, when OH- binds to the carbonyl carbon atom. Accordingly, the electrochemical upgrading of biomass-derived aldehydes to carboxylates is believed to be limited to very alkaline electrolytes at many electrode materials. However, OH- -induced aldehyde decomposition in these electrolytes prevents application of electrochemical aldehyde oxidation for the sustainable upgrading of biomass to value-added chemicals at industrial scale. Here, we demonstrate the successful oxidation of aliphatic aldehydes at a rotating gold electrode at pH 12, where only 1 % of the aldehyde resides as the diolate species. This concentration is too small to account for the observed current, which shows that also other aldehyde species (i. e., the geminal diol and the non-hydrated aldehyde) are electroactive. This insight allows developing strategies to omit aldehyde decomposition while achieving high current densities for the selective aldehyde oxidation, making its future industrial application viable.

18.
Adv Sci (Weinh) ; 10(4): e2205540, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36480314

RESUMO

The conversion of biomass is a favorable alternative to the fossil energy route to solve the energy crisis and environmental pollution. As one of the most versatile platform compounds, 5-hydroxymethylfural (HMF) can be transformed to various value-added chemicals via electrolysis combining with renewable energy. Here, the recent advances in electrochemical oxidation of HMF, from reaction mechanism to reactor design are reviewed. First, the reaction mechanism and pathway are summarized systematically. Second, the parameters easy to be ignored are emphasized and discussed. Then, the electrocatalysts are reviewed comprehensively for different products and the reactors are introduced. Finally, future efforts on exploring reaction mechanism, electrocatalysts, and reactor are prospected. This review provides a deeper understanding of mechanism for electrochemical oxidation of HMF, the design of electrocatalyst and reactor, which is expected to promote the economical and efficient electrochemical conversion of biomass for industrial applications.

19.
Environ Sci Pollut Res Int ; 30(4): 8790-8808, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-35655013

RESUMO

The objective of this study is to compare the environmental and social performance of two small-scale avocado biorefineries implanted in a rural zone in the North of Colombia. Two small-scale biorefineries were proposed. Small-B1 addressed to produce avocado oil and animal feed, and Small-B2 focused on the guacamole production. The environmental analysis was done by applying the life cycle assessment methodology. Then, agronomic information and process simulation were required to complete the analysis. Moreover, the water footprint of the avocado crops was estimated. Both biorefineries were compared with the direct avocados production and commercialization. The social assessment was achieved by the estimation of quantitative indicators related to wages, jobs, and working hours. The agricultural carbon and water footprints of the creole avocado crop were 0.59 kg CO2-eq/kg and 2.13 m3/kg. In the same way, Small-B1 and Small-B2 obtained a carbon and water footprints of 8.99 kg CO2-eq/kg and 6.63 m3/kg and 0.72 kg CO2-eq/kg and 1.38 m3/kg, respectively. The hotspots of the creole avocado crop are related to the use of fertilizers and fungicides. Then, new strategies should be implemented to reduce the farmer's dependency. The social analysis exhibit a high resilience of the Small-B1 biorefinery since a salary increase to worker about 50% can be proposed. In addition, the installation of this biorefinery can create more than ten jobs. A disjunction was found between the economic, environmental, and social analyses. Thus, the need to establish a multidimensional strategy to design sustainable biorefineries is presented.


Assuntos
Persea , Animais , Colômbia , Dióxido de Carbono , Mudança Social , Água , Estágios do Ciclo de Vida
20.
Front Chem ; 11: 1067488, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36742037

RESUMO

Refiners around the globe are either considering or are actively replacing a portion of their crude oil inputs originating from fossil sources with alternative sources, including recycled materials (plastics, urban waste, mixed solid waste) and renewable materials (bio-mass waste, vegetable oils). In this paper, we explore such replacement, specifically focusing on the fluid catalytic cracking (FCC) operation. Five pyrolysis oils, obtained from municipal solid waste (MSW) and biogenic material (olive stones/pits), were fully characterized and tested at 10% loading against a standard fluid catalytic cracking (FCC) vacuum gasoil (VGO) feed in a bench scale reactor using an industrially available fluid catalytic cracking catalyst based on ultrastable Y zeolite to simulate fluid catalytic cracking co-processing. Despite having unique feed properties, including high Conradson carbon (e.g., up to 19.41 wt%), water (e.g., up to 5.7 wt%), and contaminants (e.g., up to 227 ppm Cl) in some cases, the five pyrolysis oils gave similar yield patterns as vacuum gasoil. Gasoline was slightly (ca. 1 wt%) higher in all cases and LPG slightly (ca. 1 wt%) lower. Olefinicity in the LPG streams were unchanged, bottoms and light cycle oil (LCO) showed no significant changes, while dry gas was slightly (up to -0.2 wt%) lower. Coke selectivity was also unchanged (maximum -7.7 wt%, relatively), suggesting minimal to no heat balance concerns when co-processing in an industrial fluid catalytic cracking unit. The results demonstrate the applicability of municipal solid waste and biogenic originating pyrolysis oils into a refinery. A catalyst design concept is explored, based on higher rare Earth oxide exchange and/or utilization of ZSM-5 zeolite, that would further minimize the impacts of replacing fossil oils with pyrolysis oils, namely one that shifts the 1% higher gasoline into LPG.

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