Furan Chemistry Research Articles

Effective extraction of larch holocellulose with alkaline deep eutectic solvent and production of furan chemicals with the coordination of temperature-controlled polyoxometalates and metal salt in biphasic system.

This study focused on extracting holocellulose from Changbai larch waste, which is rich in hexose and beneficial for furan chemicals production. Various alkaline deep eutectic solvents (DESs) was applied in the extraction of holocellulose. DES composed of lysine (Lys) and 2-aminoethanol (MEA) with strong alkalinity had a superior ability to remove lignin, and the purity of holocellulose could reach 82.7%. Consequently, a double-acid system formed by a temperature-controlled polyoxometalates catalyst (ChnH3-nPW12, n=1, 2, 3,) prepared by choline chloride (ChCl) and phosphotungstic acid (H3PW12O40) and different metal salts were used in the hydrolysis of holocellulose to 5-hydroxymethylfurfural (HMF) and 2-furaldehyde (FF) in a two-phase system of water and organic solvent. The yields of HMF and FF reached 43.5% and 78.2%, respectively, when ChH2PW12 and AlCl3 were employed under the conditions of 10mL water/methyl isobutyl ketone (MIBK) (1:9, V:V), 9h, and 150°C. ChH2PW12is easy to recycle and can be used up to 5 times. This study offers a novel strategy to retain as much hemicellulose as possible to achieve holocellulose by alkaline DESs, and the one-pot process by the coordination of polyoxometalates and metal salt provides a simultaneous production of high-value furan chemicals from larch waste.

On the chemistry of furfuryl alcohol polymerization: A review

AbstractThis review dives into the intricate chemistry of furfuryl alcohol (FA) polymerization, a critical process for producing FA‐based resins (oligomers and polymers). Despite over a century of studies, the complexity of FA resinification continues to intrigue scientists, engendering extensive discourses. The inherent complexity and heterogeneity of FA resins have thwarted attempts to propose a universally applicable structural elucidation, prompting the investigation of numerous proposed mechanisms. Drawing upon an extensive corpus of literature, we survey various proposed mechanisms and representative structural attributes of a range of FA polymeric systems. The insights from a rich tapestry of experimental evidence collectively illuminate the manifold intermediates and pathways that characterize various FA polymerization techniques. A critical appraisal of prevailing debates and counterarguments offers a nuanced perspective on the diverse facets of FA polymerization chemistry. Moreover, this work underscores the latent potential of biobased chemistry, from the perspective of furan chemistry, as a potent catalyst for driving the essential objectives of de‐fossilization and sustainability within the chemical and materials industries. Subsequently, it provides valuable insights into the present state of knowledge on FA polymerization, thereby serving as a vanguard for delineating future research trajectories in this captivating field.

Efficient production of hydroxymethyl-2-furfurylamine by chemoenzymatic cascade catalysis of bread waste in a sustainable approach

In this study, efficient and sustainable conversion of waste bread (WB) to 5-hydroxymethyl-2-furoamine (HMFA) was achieved in a cascade reaction in betaine:malonic acid (B:MA) − water. 5-HMF (30.3 wt% yield) was synthesized from WB (40.0 g/L) in B:MA − water (B:MA, 18 wt%) in 45 min at 190 °C. By using the newly created recombinant E. coli HNILGD-AlaDH cells expressing L-alanine dehydrogenase (AlaDH) and ω-transaminase mutant HNILGD as biocatalyst, the WB-valorized 5-HMF was biologically aminated into HMFA in a high yield (92.1%) at 35 °C for 12 h through in situ removal of the amino transfer by-products of the amine donor, greatly reducing amine donor dosage (from D-Ala/5-HMF = 16/1 to D-Ala/5-HMF = 2/1, mol/mol) and improving the productivity of HMFA (0.282 g HMFA per g WB). This two-step chemical-enzymatic cascade reaction strategy with B:MA and HNILGD-AlaDH whole-cell provides a new idea for the chemoenzymatic synthesis of valuable furan chemicals from waste biomass.

Production of furan chemicals from contaminated biomass using hydrothermal-assisted activated persulfate strategy: Exploring the critical role of heavy metals on products

Sustainable disposal of heavy metal contaminated biomass has always been a challenging task. Here, a strategy was proposed for directly producing valuable 5-hydroxymethylfurfural (HMF) and furfural (FF) from contaminated biomass through hydrothermal-assisted persulfate activation strategy. The optimal yields were obtained at 18.6 and 22.5 wt% for HMF and FF, respectively. The hydrothermal process promoted the release of Fe, Mn, Cu, Zn, and Cr from biomass into the liquid phase and then activated peroxymonosulfate (PMS) to destroy the lignocellulose structure and increase the accessible of cellulose and hemicellulose. Meanwhile, the metal and acidic environment provided by the reaction system act as natural catalysts to synergistically promote the production of HMF and FF. The controlled experiments revealed that Fe, Mn, Zn, and Cr played a major role in biomass conversion during this process. Moreover, possible reaction mechanisms and pathways were explored through quenching tests and density functional theory calculations. This study provides a simple pretreatment and promising valorization strategy for the sustainable utilization of heavy metal-contaminated biomass.

Efficient synthesis of furfurylamine from biomass via a hybrid strategy in an EaCl:Gly-water medium.

The objective of this work was to develop an efficient approach for chemoenzymatically transforming biomass to furfurylamine by bridging chemocatalysis and biocatalysis in a deep eutectic solvent of EaCl:Gly-water. Using hydroxyapatite (HAP) as support, heterogeneous catalyst SO4 2-/SnO2-HAP was synthesized for transforming lignocellulosic biomass into furfural using organic acid as a co-catalyst. The turnover frequency (TOF) was correlated with the pKa value of the used organic acid. Corncob was transformed by oxalic acid (pKa = 1.25) (0.4wt%) plus SO4 2-/SnO2-HAP (2.0wt%) to produce furfural with a yield of 48.2% and a TOF of 6.33 h-1 in water. In deep eutectic solvent EaCl:Gly-water (1:2, v/v), co-catalysis with SO4 2-/SnO2-HAP and oxalic acid was utilized to transform corncob, rice straw, reed leaf, and sugarcane bagasse for the production of furfural with the yield of 42.4%-59.3% (based on the xylan content) at 180°C after 10min. The formed furfural could be efficiently aminated to furfurylamine with E. coli CCZU-XLS160 cells in the presence of NH4Cl (as an amine donor). As a result of the biological amination of furfural derived from corncob, rice straw, reed leaf, and sugarcane bagasse for 24h, the yields of furfurylamine reached >99%, with a productivity of 0.31-0.43g furfurylamine per g xylan. In EaCl:Gly-water, an efficient chemoenzymatic catalysis strategy was employed to valorize lignocellulosic biomass into valuable furan chemicals.

Integrated experimental and DFT analysis on the efficient and green upgrading of agroforestry biomass derived furan chemicals over NiMoO4-CNTs-CF electrocatalyst with bi-catalytic sites

Agroforestry biomass derived Furfural (FUR) and 5-hydroxymethylfurfural (HMF) have attracted considerable attention which could be converted to high-value fuel additives and fine chemicals. However, it still remains a hot issue to exploit more efficient and greener means for the conversion of furan aldehyde under moderate conditions. Herein, electro-catalysis driven by electricity without hazardous oxidants have been proven to be a promising and powerful tool. Meanwhile, NiMoO4-CNTs-CF was demonstrated to be effective and durable electrocatalyst with bi-catalytic sites. At 96.98% and 93.78% yield of furoic acid (FA) and 2,5-furandicarboxylic acid (FDCA), the faradaic efficiency for FA and FDCA could reach 95.47% and 89.42%, respectively. Detailed studies revealed that the electrical conductivity, charge density and electron transfer on the electrode surface were remarkably improved. The FA yield maintained over 90% after five successive cycles, demonstrated that this electrocatalyst could exhibit highly durable stability during the conversion. Density functional theory (DFT) calculations revealed that the synergistic effect of Ni and Mo could improve the electrocatalytic oxidation activity and selectivity of NiMoO4-CNTs-CF electrocatalyst. It significantly made up for the insufficient and incomplete single metal catalytic mechanism in the previous works. This finding provided an innovative and feasible way to synthesize high-value furan-based chemicals derived from the renewable resources, which would significantly benefit food, pharmacy and chemical industry.

Conditions to Control Furan Ring Opening during Furfuryl Alcohol Polymerization.

The chemistry of biomass-derived furans is particularly sensitive to ring openings. These side reactions occur during furfuryl alcohol polymerization. In this work, the furan ring-opening was controlled by changing polymerization conditions, such as varying the type of acidic initiator or the water content. The degree of open structures (DOS) was determined by quantifying the formed carbonyl species by means of quantitative 19F NMR and potentiometric titration. The progress of polymerization and ring opening were monitored by DSC and FT-IR spectroscopy. The presence of additional water is more determining on ring opening than the nature of the acidic initiator. Qualitative structural assessment by means of 13C NMR and FT-IR shows that, depending on the employed conditions, poly(furfuryl alcohol) samples can be classified in two groups. Indeed, either more ester or more ketone side groups are formed as a result of side ring opening reactions. The absence of additional water during FA polymerization preferentially leads to opened structures in the PFA bearing more ester moieties.

Production of Bulk Chemicals with Biocatalysis: Drivers and Challenges Reflected in Recent Industrial Granted Patents (2015-2020).

The application of biocatalysis and White Biotechnology tools in chemical areas concerning the production of bulk compounds and other related low-added value products (with high volumes) has been gaining importance in recent years. The expected drivers of biocatalysis for these sectors are energy savings, regioselectivity (leading to cleaner products), the possibility of using thermolabile substrates, as well as the generation of less by-products and manageable wastes. This paper explores some recent industrial granted patents related to biocatalysis and bulk chemicals. Several patents have been identified in fields such as biodiesel and esterification reactions, and sugar or furan chemistry. Overall, innovative strategies involve the identification of novel enzymes, the set-up of improved immobilization methods, as well as novel reactor designs that can offer improved performances and economics. The reported examples indicate that biocatalysis can certainly offer opportunities for these areas as well, far from the typical pharmaceutical and fine chemical applications often reported in the literature.

The processing-module assembly strategy for continuous bio-oxidation of furan chemicals by integrated and coupled biotechnology

We designed a technology to combined biotechnology, chemical and electrochemical techniques to achieve furoic acid bio-production from bio-toxic furfural.

AVA Biochem, Pioneer in Industrial Biobased Furan Chemistry.

Swiss-based AVA Biochem AG is the global leader in the industrial production and sale of the bio-based platform chemical 5-hydroxymethylfurfural (5-HMF), a renewable and non-toxic alternative to a range of petroleum-based materials. 5-HMF has a broad range of applications in the chemical, pharmaceutical and food industries. Since 2014 AVA Biochem has been producing high-purity 5-HMF for research purposes and specialty chemicals markets, as well as technical-grade 5-HMF for bulk chemistry applications. AVA Biochem's own R&D department also develops the downstream chemistry of 5-HMF and thus opens the door to biobased furan chemistry on an industrial scale.

Effective selectivity conversion of glucose to furan chemicals in the aqueous deep eutectic solvent

This work demonstrated a smart route of biomass-derived glucose conversion in a biphasic aqueous deep eutectic solvent (DES), which was formed by glucose, ChCl, water, and co-solvent EtAc. Four kinds of value-added furan chemicals, including 5-Hydroxymethylfurfural (HMF), 5-(Acetyloxy) methyl furfural (AMF), 5-Chloromethylfurfural (CMF) and 5-Ethoxymethylfurfural (EMF) were successfully synthesized through a single-step reaction by monitoring the reaction conditions. High yield to 73.2% furan products, including 52.9% of HMF and 17.5% of AMF was obtained from a high concentration of glucose under mild conditions. Moreover, the produced furan mixture could further be converted into other useful chemicals, 2,5-furan dicarboxylic acid (FDCA) and 2,5-dimethyl furan (DMF), directly through simple oxidation and hydrogenation methods, respectively. This study suggested a sustainable synthetic pathway from abundant biomass glucose to furan products and value-added chemicals in the presence of completely green material and catalysts, which showed advantages for the industrial application.

Bioconversion of 5-Hydroxymethylfurfural (HMF) to 2,5-Furandicarboxylic Acid (FDCA) by a Native Obligate Aerobic Bacterium, Acinetobacter calcoaceticus NL14.

2,5-Furandicarboxylic acid (FDCA), one of the top biomass-based platform chemical, is highly promising for resins and polymers, and it can be prepared from the bio-oxidation of hydroxymethyl furfural (HMF), which can be obtained mainly from lignocellulosic glucose that has a high production potential from not edible biomass.A native strain, Acinetobacter calcoaceticus NL14, that could convert HMF into FDCA is used for combining degradation and fermentation by consolidated bioprocessing (CBP). In this study, it was observed that the initial HMF concentration and pH neutralizer played important roles in the bioconversion of HMF, 5g/L of HMF could be converted by 100% within 48h with 0.5g/L sodium carbonate (Na2CO3) with the production of 0.31g/L FDCA. Extra glucose and hydrogen peroxide (H2O2) addition could further promote the production of FDCA to 0.54g/L with 100% HMF conversion and a higher conversion rate. This report could provide a potential native bacterium for furan chemicals bioconversion and bioelimination, especially for FDCA bioproduction.

OH chemistry of non-methane organic gases (NMOGs) emitted from laboratory and ambient biomass burning smoke: evaluating the influence of furans and oxygenated aromatics on ozone and secondary NMOG formation

Abstract. Chamber oxidation experiments conducted at the Fire Sciences Laboratory in 2016 are evaluated to identify important chemical processes contributing to the hydroxy radical (OH) chemistry of biomass burning non-methane organic gases (NMOGs). Based on the decay of primary carbon measured by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS), it is confirmed that furans and oxygenated aromatics are among the NMOGs emitted from western United States fuel types with the highest reactivities towards OH. The oxidation processes and formation of secondary NMOG masses measured by PTR-ToF-MS and iodide-clustering time-of-flight chemical ionization mass spectrometry (I-CIMS) is interpreted using a box model employing a modified version of the Master Chemical Mechanism (v. 3.3.1) that includes the OH oxidation of furan, 2-methylfuran, 2,5-dimethylfuran, furfural, 5-methylfurfural, and guaiacol. The model supports the assignment of major PTR-ToF-MS and I-CIMS signals to a series of anhydrides and hydroxy furanones formed primarily through furan chemistry. This mechanism is applied to a Lagrangian box model used previously to model a real biomass burning plume. The customized mechanism reproduces the decay of furans and oxygenated aromatics and the formation of secondary NMOGs, such as maleic anhydride. Based on model simulations conducted with and without furans, it is estimated that furans contributed up to 10 % of ozone and over 90 % of maleic anhydride formed within the first 4 h of oxidation. It is shown that maleic anhydride is present in a biomass burning plume transported over several days, which demonstrates the utility of anhydrides as markers for aged biomass burning plumes.

Catalytic oxidation of carbohydrates into organic acids and furan chemicals.

A wide variety of commodity chemicals can be produced from the catalytic oxidation of carbohydrates or carbohydrate derived molecules including formic acid, acetic acid, glycolic acid, gluconic acid, glucaric acid, malonic acid, oxalic acid, 2,5-diformylfuran (DFF), 5-hydroxymethyl-2-furancarboxylic acid (HFCA), 5-formyl-2-furancarboxylic acid (FFCA), and 2,5-furandicarboxylic acid (FDCA). This review will highlight the recent research progress in the development of new routes for the production of organic acids and furan compounds via catalytic oxidation reactions. Particular attention will be paid to these one-pot reactions with the requirements of an acidic site and a metal site. For the one-pot transformation of cellobiose or lignocellulose into gluconic acid, these reactions were performed via a one-step strategy using a single catalyst containing an acidic site and a metal site. However, a two-step strategy was adopted for the oxidative transformation of carbohydrates into DFF or FDCA in order to avoid the oxidation of the carbohydrates. The first step was performed for the dehydration of carbohydrates into 5-hydroxylmethylfuran (HMF) in the presence of an acid catalyst, and the second step was performed for the oxidation of HMF into DFF or FDCA with a metal catalyst.

Problemi gospodarenja otpadom u Kanadi

The article considers the problem of the waste (communal, industrial, dangerous, and radioactive one) removing in the territory of Canada. The danger from dioxin and furan chemicals to which the government of the developed industrial countries pay more attention, has been stressed out. Radioactive waste problem grows up, as much because of big quantities of exhausting gasses, that much because of their storing location problems.

ChemInform Abstract: One‐Pot Conversion of Carbohydrates into Furan Derivatives via Furfural and 5‐Hydroxylmethylfurfural as Intermediates

AbstractReview: 125 refs.

One-Pot Conversion of Carbohydrates into Furan Derivatives via Furfural and 5-Hydroxylmethylfurfural as Intermediates.

Recently, there has been growing interest in the transformation of renewable biomass into value-added fuels and chemicals. The catalytic conversion of naturally abundant carbohydrates can generate two-important furan chemicals: 5-hydroxymethylfurfural (HMF) from C6 carbohydrates and furfural from C5 carbohydrates. Both HMF and furfural have received great interest as precursors in the synthesis of commodity chemicals and liquid fuels. In recent years, a trend has emerged to integrate sequential catalytic processes involving multistep reactions for the direct one-pot transformation of carbohydrates into the aimed fuels and chemicals. One-pot reactions have remarkably unique and environmentally friendly benefits, including the fact that isolation and purification of intermediate compounds can be avoided. Herein, the present article aims to review recent advances in the one-pot conversion of carbohydrates into furan derivatives via furfural and HMF as intermediates. Special attention will be paid to the catalytic systems, mechanistic insight, reaction pathways, and catalyst stability. It is expected that this review will guide researchers to develop effective catalytic systems for the one-pot transformation of carbohydrates into furan derivatives.

Solid acid catalyzed synthesis of furans from carbohydrates

ABSTRACTThe alternative feedstock, biomass (particularly lignocelluloses), having the profuse availability, is promising for the synthesis of several value-added chemicals which are currently obtained from fossil feedstock. In this article, the synthesis of two extremely significant furan chemicals viz. furfural and 5-hydroxymethylfurfural (HMF) are discussed. In the synthesis of furans from biomass, numerous challenges, i.e., use of edible sugars as substrates, selectivity to furans, their isolation in pure form, reuse of catalyst, environmental issues, etc., are perceived and in the recent past researchers tried to resolve those by developing advance methodologies. This article comprehensively summarizes the latest progress made in the above-mentioned areas and also provides commentary on the analyses of results, rationale for observed activity and mechanisms, etc. It also discusses future aspects of this work.

Exploring the Chemistry of Furans: Synthesis of Functionalized Bis(furan‐2‐yl)methanes and 1,6‐Dihydropyridazines

AbstractThe reactivity of 2,2‐bis(furan‐2‐yl)propane towards nitroso‐ and azoalkenes was explored. The expected hetero‐Diels–Alder adducts, 4a,7a‐dihydro‐4H‐furo[2,3‐e][1,2]oxazines and 4a,7a‐dihydrofuro[3,2‐c]pyridazines, were obtained in good yield. The furo‐oxazines were easily converted into the corresponding bis(furan‐2‐yl)methanes bearing an open‐chain oxime. Interestingly, the synthesized furo‐pyridazines showed a different chemical behavior. In the presence of HCl, they underwent a rearrangement giving 6‐(2‐oxobutyl)‐1,6‐dihydropyridazine derivatives in a process having as its key step a furan ring‐opening reaction. The synthesis of 4a,7a‐dihydrofuro[3,2‐c]pyridazines from 2‐methylfuran and the subsequent acid‐catalysed rearrangement to the corresponding 6‐(2‐oxopropyl)‐1,6‐dihydropyridazines was also achieved.

One-flow syntheses of diverse heterocyclic furan chemicals directly from fructose via tandem transformation platform

The sustainable green chemistry associated with lignocellulosic biomass is of current interest for producing various chemical feedstocks via multi-step transformation processes. Here we introduce a chemical platform system for the multicomponent cascade transformation of natural lignocellulosic biomass resources. We demonstrate the concept by developing an integrated continuous two-step microfluidic system as a tandem transformation platform for direct conversion of fructose to diverse furan chemicals with excellent yields up to 99% via decarbonylation, etherification, oxidation and hydrogenolysis of a 5-hydroxymethylfurfural (HMF) intermediate. A sequential two-step process is utilized to complete the dehydration of fructose in the surface acid catalyst at 150 °C for 6 min, which is followed by the four types of HMF conversion in a binary or ternary phase to produce furfuryl alcohol (94% yield), 5-ethoxymethylfurfural (99%), 2,5-diformylfuran (82%) and 2,5-dimethylfuran (90%) with magnetic-based heterogeneous catalysts at 70–150 °C for 6–60 min. This innovative tandem microfluidic platform enables precise control of the reaction temperature and time for each individual biomass conversion step in a one-flow manner with no separation and purification steps for intermediates and catalysts.