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Mesoporous Melamine-Formaldehyde Resins as Efficient Heterogeneous Catalyst for Continuous Synthesis of Cyclic Carbonates from Epoxides and gaseous CO2
Umeå universitet, Teknisk-naturvetenskapliga fakulteten, Kemiska institutionen.
Umeå universitet, Teknisk-naturvetenskapliga fakulteten, Kemiska institutionen.
Umeå universitet, Teknisk-naturvetenskapliga fakulteten, Kemiska institutionen.
Division of Materials Science, Luleå University of Technology, Luleå, Sweden.
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2020 (Engelska)Ingår i: ACS Sustainable Chemistry and Engineering, E-ISSN 2168-0485, Vol. 8, nr 34, s. 12852-12869Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Herein we report the application of inexpensive mesoporous melamine-formaldehyde resins (MMFR and MMFR250) obtained by a novel template-free and organosolvent-free hydrothermal method as efficient heterogeneous catalysts for direct synthesis of cyclic carbonates from CO2 and epoxides (epichlorohydrin, butylene oxide and styrene oxide). The catalytic activity of the melamine resins was attributed to the abundant Lewis basic N-sites capable of activating CO2 molecules. Based on CO2-Temperature programmed desorption, the concentration of surface basic sites for MMFR and MMFR250 were estimated to be 172 and 56 µmol/g, while the activation energy of CO2 desorption (strength of basic sites) were calculated to be 92.1 and 64.5 kJ/mol. We also observed considerable differences in the catalytic activity and stability of polymeric catalysts in batch and in continuous-flow mode; due to the existence of a synergism between adsorption of CO2 and cyclic carbonates (poison). Our experiments also revealed important role of catalyst surface chemistry and CO2 partial pressure upon catalyst poisoning. Nevertheless, owing to their unique properties (large specific surface area, large mesoporous and CO2 basicity) melamine resins presented excellent activity (turnover frequency 207-2147 h-1), selectivity (>99%) for carbonation of epoxides with CO2 (20 bar initial CO2 or CO2:epoxide mole ratio ~1.5) under solvent-free and co-catalyst-free conditions at 100-120 oC. Most importantly, these low-cost polymeric catalysts were reusable and demonstrated exceptional stability in a flow reactor (tested upto 13 days time on stream, weight hourly space velocity 0.26-1.91 h-1) for continuous cyclic carbonate production from gaseous CO2 with different epoxides (conversion 76-100% and selectivity >99%) under industrially relevant conditions (120 oC, 13 bar, solvent-free/co-catalyst-free) confirming their superiority over the previously reported catalytic materials.

Ort, förlag, år, upplaga, sidor
American Chemical Society (ACS), 2020. Vol. 8, nr 34, s. 12852-12869
Nyckelord [en]
mesoporous melamine-formaldehydepolymers, solid amines, CO2 utilization, cyclic carbonates, activation-deactivation, fixed-bed reactor
Nationell ämneskategori
Annan kemiteknik Kemiska processer Organisk kemi Annan kemi Materialkemi
Identifikatorer
URN: urn:nbn:se:umu:diva-173936DOI: 10.1021/acssuschemeng.0c03123ISI: 000567778600015Scopus ID: 2-s2.0-85092356817OAI: oai:DiVA.org:umu-173936DiVA, id: diva2:1457011
Projekt
Bio4Energy
Forskningsfinansiär
Bio4EnergyVetenskapsrådet, 2016-04090KempestiftelsernaKnut och Alice Wallenbergs StiftelseTillgänglig från: 2020-08-10 Skapad: 2020-08-10 Senast uppdaterad: 2023-03-23Bibliografiskt granskad
Ingår i avhandling
1. Development of nitrogen-containing materials for capture and catalytic conversion of carbon dioxide to value-added chemicals
Öppna denna publikation i ny flik eller fönster >>Development of nitrogen-containing materials for capture and catalytic conversion of carbon dioxide to value-added chemicals
2021 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

Anthropogenic carbon dioxide (CO2) emissions have become a critical environmental issue because a large amount of CO2 releasing into the atmosphere, particularly from the massive use of fossil fuels, is the major factor promoting the global warming and climate change. To mitigate the CO2 emissions, Carbon Capture, Utilization and Storage (CCUS) can be one of important solutions. Inspired by the CCUS approach, the aims of this thesis are to develop materials for CO2 capture (Papers I, II) and conversion of CO2 to value-added chemicals (Papers III, IV) such as dimethyl carbonate (DMC) and cyclic carbonates (CCs). The main idea is to focus on nitrogen-containing materials because basic nitrogen sites can increase the chemical affinity towards CO2, which is a weak Lewis acid gas.

In practice, aqueous monoethanolamine (aq MEA) is widely used to capture CO2 from flue gases in CCUS projects. However, this solvent suffers from several major drawbacks such as high energy consumption for regeneration of MEA, degradation and evaporation. In Paper I, aq pentaethylenehexamine (PEHA) was proposed as an alternative solvent for chemical absorption of CO2. A comprehensive study was performed, including the influence of water content on CO2 capacity, chemical composition of absorption products, viscosities before and after absorption, regeneration of PEHA, correlation between CO2 capacity with Kamlet-Taft parameters, comparison with aq MEA. In Paper II, aq PEHA was further studied for CO2 capture from bio-syngas resulting from pilot-scale gasification of biomass to investigate the influence of other compositions on the capture performance. Additionally, this solvent was simultaneously used as a reagent for chemical pretreatment of biomass to investigate the influence of pretreatment on biomass gasification and CO2 capture.

The conversion of captured CO2 to value-added chemicals gains increasing attentions in both academia and industry because CO2 represents a renewable, virtually inexhaustible, and nontoxic building block. In addition, this approach can provide economic incentives for CO2 capture facilities by selling their captured CO2 to other interested users or by benefiting from their own additional facilities using the CO2. In Paper III, 1,8-diazabicyclo[2.2.2]undec-7-ene (DBU) was used to capture and subsequent conversion of CO2 to DMC at ambient conditions. In Paper IV, mesoporous melamine-formaldehyde resins were prepared, characterized and studied as heterogeneous catalysts for synthesis of CCs from epoxides and CO2. These low-cost polymeric catalysts were reusable and demonstrated excellent performance in a flow reactor under industrially relevant conditions (120 °C, 13 bar, solvent-free/co-catalyst-free).

Applications of ionic liquids (ILs) in capture and conversion of CO2 to organic carbonates were briefly reviewed in Paper V (mini review). The viscosity of ILs for CO2 capture and the mechanism involved in the CO2 binding were also discussed.

In conclusion, this thesis will hopefully contribute to the sustainable development of society in the fields of reducing anthropogenic CO2 emissions and production of chemicals.

Ort, förlag, år, upplaga, sidor
Umeå: Umeå University, 2021. s. 79
Nyckelord
CCUS, PEHA, DBU, mesoporous melamine-formaldehyde, DMC, cyclic carbonate, flow reactor
Nationell ämneskategori
Annan kemiteknik Naturvetenskap
Forskningsämne
fysikalisk kemi; hållbar utveckling
Identifikatorer
urn:nbn:se:umu:diva-181614 (URN)978-91-7855-503-1 (ISBN)978-91-7855-504-8 (ISBN)
Disputation
2021-04-23, KBC Glasburen, Department of Chemistry, Umeå, 10:00 (Engelska)
Opponent
Handledare
Tillgänglig från: 2021-04-01 Skapad: 2021-03-19 Senast uppdaterad: 2021-03-19Bibliografiskt granskad

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Bui, Thai Q.Konwar, Lakhya JyotiSamikannu, AjaikumarMikkola, Jyri-Pekka

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