Production Of Furfuryl Alcohol Research Articles

Optimization of operating parameters for furfuryl alcohol production in a reactive distillation column using response surface methodology

Furfuryl alcohol is an important platform chemical with a wide range of industrial applications. In this study, the optimization of operating parameters for the production of furfuryl alcohol in a reactive distillation column was investigated using response surface methodology (RSM). The key operating parameters, such as pressure, reflux ratio, feed ratio, and residence time, were examined to determine their influence on the yield of furfuryl alcohol. A Box–Behnken design (BBD) was employed to model the relationships between the process variables and the responses. The optimal operating conditions were determined by maximizing the furfuryl alcohol yield. The results showed that feed ratio and reflux ratio had the most significant impact on the process performance. The optimal operating conditions were found to be a pressure of 0.4 bar, reflux ratio of 5.6 feed ratio of 1, and residence time of 14. Under these conditions, the furfuryl alcohol yield is 99 %.

Conceptual Process Design, Techno-Economics, and Greenhouse Gas Analysis of Furfuryl Alcohol Production via Transfer Hydrogenation

Conceptual Process Design, Techno-Economics, and Greenhouse Gas Analysis of Furfuryl Alcohol Production via Transfer Hydrogenation

Zr-decorated hyper-cross-linked polymers for highly selective upgrading of furfural to furfuryl alcohol

In the present study, the ultra-large specific surface area Zr-decorated hyper-cross-linked polymers (HP) were firstly developed for the catalytic production of furfuryl alcohol (FOL) from furfural (FAL) using isopropanol as both the hydrogen source and solvent. Comprehensive characterizations were performed to uncover the basic physicochemical properties. The as-prepared Zr/HP showed large specific surface area of ∼1000 m2/g, good dispersion of Zr species, plentiful acidity and basicity. 2.5Zr/HP presented the highest activity in the FAL-to-FOL transformation, wherein 97.4 % FAL conversion and 92.9 % FOL yield were achieved within 2 h at 160 °C. The recycling experiments revealed that the as-fabricated Zr-decorated hyper-cross-linked polymers presented good recyclability without significant loss of reactivity even after two consecutive cycles, owing to the strong interaction between hyper-cross-linked polymers and grafted Zr species. Kinetical analysis verified that the activation energy for transfer hydrogenation of FAL could be lowered to a certain degree, especially in the case of lower Zr loadings. More gratifyingly, the Zr-decorated hyper-cross-linked polymers were capable of catalyzing other unsaturated compounds with high conversion rates. In addition, the plausible pathway for the FAL-to-FOL transformation over Zr-decorated hyper-cross-linked polymers was proposed.

Efficient Electrochemical Hydrogenation of Furfural to Furfuryl Alcohol Using an Anion-Exchange Membrane Electrolysis Cell.

The electrochemical hydrogenation (ECH) of furfural (FF) offers a promising pathway for the production of furfuryl alcohol (FA) while aligning with sustainability and environmental considerations. However, this technology has primarily been studied in half-cell configurations operating at high cell voltages and low current densities. Herein, we employ a membrane electrode assembly (MEA) system with an anion-exchange membrane for the ECH of FF and systematically investigate various parameters, including the ionomer content in the cathode catalyst, electrolyte type, electrolyte concentration, and flow rate. Under optimal conditions, our MEA system with non-noble metal-based catalysts exhibits a current density of 30 mA cm-2 with a Faradaic efficiency for FA production of 66% at a cell voltage of 2 V, maintaining operational durability for 5 h. This study highlights the potential of electrochemical FA production for practical applications to realize the decarbonization of the hydrogenation industry.

Selective conversion of furfural to furfuryl alcohol by heterogeneous TiO2 photocatalysis

Selective synthesis of furfuryl alcohol from furfural conversion via semiconductor photocatalytic route has appeared as a promising solution for transforming biomass into high‐value‐added products under mild temperature and pressure conditions. Titanium dioxide (TiO2) photocatalysts were prepared by a simple sol‐gel method followed by a calcination treatment of 500 – 1000 ºC, resulting in materials with distinct physicochemical properties. The photocatalytic efficiency of the TiO2 samples was examined in the selective production of furfuryl alcohol from furfural under UV‐LED irradiation. The influence of various organic solvents, including ethanol, methanol, 2‐propanol, and acetonitrile, was evaluated to optimise the selectivity towards furfuryl alcohol production. Photocatalysts with larger anatase to rutile ratio and increased density of oxygen vacancies (defects) exhibited superior performance for furfuryl alcohol production. The presence of these defects on the catalyst surface leads to a significant enhancement in the photocatalytic efficiency by acting as crucial active sites. Among the TiO2 samples, the highest conversion of furfural into furfuryl alcohol was observed with the TiO2 sample calcined under an air atmosphere at 600 ºC (TiO2‐600), achieving 85% yield and 100% selectivity for furfural after 30 min reaction using ethanol as solvent.

Kinetics and mechanistic insights into selective hydrogenation of furfural to furfuryl alcohol over Ni–Ga intermetallics

AbstractFurfural was mainly used to produce furfuryl alcohol, which is a monomer of furan resins with a global market of ~$0.3 billion/year. Industrial production of furfuryl alcohol is via selective hydrogenation over toxic copper chromate under harsh conditions. Therefore, the search for active and non‐toxic alternatives is highly desired. Here, kinetics studies revealed an inhibitive effect caused by strong furfural adsorption on Ni‐based catalysts, resulting in sites blocking and undesired ring hydrogenation. Such an inhibitive effect can be alleviated over Ni‐Ga intermetallic surfaces by tuning the Ni coordination number, from which the Ni1Ga1 showed markedly enhanced furfuryl alcohol yield (~99%) at milder conditions comparing to the referred Ni catalyst. It is found that isolated Ni sites by Ga on the Ni1Ga1 enabled a tilted adsorption configuration through the carbonyl of furfural. In contrast, the stronger flat‐lying adsorption of furfural was favored on the contiguous Ni sites of the referred catalyst.

Characterization of Potential Dependent Fouling of Cu Electrodes during Electrochemical Hydrogenation and Hydrogenolysis of Furfural in Acid

Furfural (FF) is a platform molecule derived from biomass, that can be electrochemically reduced to produce furfuryl alcohol (FA), a furanic polymer intermediate, and 2-methylfuran (MF), a fuel candidate. On Cu in acidic media, it has been shown that FA and MF are produced via parallel reactions as opposed to a series reaction. Our previous work investigated the reactions for FA and MF production electrochemically with FF concentrations between 10 and 120 mM, showing positive order with respect to FF at low concentrations and zero order rates with respect to FF at higher concentrations. This finding suggesting non-competitive Langmuir-Hinshelwood mechanisms at concentrations of FF between 10 and 120 mM in pH 0 and 1 acidic solutions. At 200 mM concentrations of FF, we have identified fouling on the Cu surface. At moderate potentials, the fouling takes the form of a polymer material, whereas at more negative reduction potentials the fouling takes the form of graphitic coking. Understanding how fouling occurs on Cu electrodes is important in achieving progress towards mitigating or reducing the impact of fouling through reactor setup and catalysts design.In this work, conditions that promote fouling were selected so that the fouling of Cu electrodes could be studied. The conditions were chronoamperometry at -560 or -700 mV RHE, 200 mM FF, 0.5M H2SO4, 20:80 vol% acetonitrile:water, for three hours durations. The Cu electrodes were reused for 3 experiments to further promote fouling and study the impact on the electrochemical performance. We showed that after reuse at -560 mV RHE, a polymeric material formed on the Cu electrode, while when reused at -700 mV RHE the electrode was instead covered in a coke like material. FTIR spectroscopy showed that the polymer formed at -560 mV resembled poly(furfuryl alcohol) while the coking substance showed broad absorbance, expected of coke like materials. To better understand the coke material formed at -700 mV, Raman spectroscopy was used. The material resembled graphitic disorganized carbon, with a D/G band intensity ratio of 0.652.

Highly selective catalytic transfer hydrogenation of biomass derived furfural to furfural alcohol over Zr/SBA-15 catalysts

The effective utilization of furfural (FU) from biomass for the production of furfuryl alcohol (FOL) is becoming increasingly important due to the versatility of FOL production of valuable chemicals. This study reports a highly efficient approach for in-situ hydrothermal methods to prepare SBA-15 (SB) and x% Zr/SBA-15 (ZSB) composite catalysts with different weight percentages (x = 1, 3, and 5 wt.%). The prepared bare and most active catalysts were analyzed by XRD, FT-IR, FE-SEM, EDS, and TEM. Characterization studies showed that Zr species were present and uniformly distributed in the SB framework. All the prepared materials were used for liquid phase catalytic transfer hydrogenation (CTH) of FU with isopropanol (2-PrOH) at atmospheric N2 pressure (1 atm) under mild reaction conditions. The 3ZSB catalyst showed excellent conversion of FU (100 %) and remarkably high selectivity for FOL (97 %). To achieve the highest possible conversion of FU with high selectivity to the desired products, the experimental parameters such as reaction temperature, hydrogen donor, time, molar ratio, and catalyst weight were optimized. The reusability of the most active 3ZSB composite catalysts was also tested for up to six sequences. Moreover, no significant change in catalytic performance was observed. In this study, a green, efficient, and sustainable process for the catalytic synthesis of FOL using biomass-derived FU is presented. This process is of great importance in promoting the sustainable use of biomass resources.

Chemobiocatalytic transformation of biomass-derived D-xylose into furfuryl alcohol in a sustainable reaction system

The feasibility of chemobiocatalytic production of furfuryl alcohol from biomass-derived D-xylose was investigated using a tandem catalysis with deep eutectic solvent betaine:benzenesulfonic acid (DES BE:BA) and recombinant Escherichia coli DCF cell. The DES BE:BA (2.5 wt%) was applied to catalyze D-xylose under 170 °C for 0.5 h, resulting in a furfural yield of 51.1%. Consequently, recombinant Escherichia coli DCF fully transformed D-xylose-derived furfural to furfuryl alcohol in DES BE:BA-water under pH 7.5 and 40 °C using HCOONa as cosubstrate. This eco-friendly chemobiocatalytic strategy was successfully applied for transforming D-xylose to furfuryl alcohol in DES BE:BA-water.

Mechanistic Changes with Applied Potential in Cu Fouling during Furfural Electrochemical Hydrogenation and Hydrogenolysis

CO2 emissions are generated in the chemical industry by factors such as the generation of reactants, including hydrogen, as well as in heating of the reactors. Electrochemical methods can avoid the need for externally provided hydrogen by generating required protons in-situ from the electrolyte, and can be more easily coupled with renewable electricity than their thermocatalytic counterparts. Therefore, to assist in the mitigation of CO2 emissions, electrochemical processes can be used. Furfural is a biomass-derived platform molecule that can be electrochemically reacted to form several species of interest including fine chemicals and fuels. Furfuryl alcohol, the hydrogenation product, is one fine chemical of interest used to make furanic molds or resins. The hydrogenolysis product of furfural, 2-methylfuran, has been identified as a fuel additive. The electrochemical hydrogenation and hydrogenolysis over Cu catalysts in acidic media allows for the parallel production of furfuryl alcohol and 2-methylfuran. During the electrochemical hydrogenation and hydrogenolysis of furfural over Cu in acidic electrolyte, the Cu catalyst will become covered in carbonaceous material with use. This fouling changes with applied potential, with a polymeric material being formed at -560 mV RHE while at -700mV a non-polymeric carbonaceous material is formed on the Cu. In both cases, the fouling leads to deactivation of the catalyst. In this work, Cu metal foils were intentionally fouled to study the mechanisms that led to catalyst fouling to provide insights into possible mitigation techniques.A semi batch reactor was used in which the Cu working electrode was recycled to further foul the catalyst. The catholyte had 200 mM furfural and 0.5 M H2SO4 in a 80:20 vol% water:acetonitrile co-solvent. The Cu electrode was recycled thrice with fresh electrolytes each time. After use at -560 mV RHE a polymer formed on the surface; FTIR of the fouled surface showed consistent spectra as poly(furfuryl alcohol). At -700 mV RHE, no polymer was found, however a carbonaceous layer was found. XPS was used to better distinguish between the carbonaceous fouling that occurred at different applied potentials.

Exploring the hydrogenation of furfural in the liquid phase by high-throughput screening of commercial catalysts: Effects of temperature, solvents, and promoters on the production of 2-methylfuran

2-methylfuran from the hydrogenation of furfural could be a viable green route to get synthetic gasoline or to be used as a blending fuel. However, it is currently produced as a by-product during the gas phase production of furfuryl alcohol using Cu catalysts, presenting fairly low productivities, while due to the complexity of the reaction, other more active metals lead mostly to by-products. Recently, solvents and promoters have been demonstrated to be useful for tuning the kinetics of the reaction. Here, to speed up the industrialization of 2-methylfuran, 48 commercial catalysts, involving the use of Cu, Ni, Co, Ir, Pt, Pd, Rh, Ru, and Re on several supports and different metallic loadings, were tested employing a high-throughput approach in the liquid phase at 60, 120 and 180 °C, using ethyl acetate, chlorobenzene, ethyl acetate, n-heptane and two mixed solvents involving a 0.5 w.t. % CHCl3/n-heptane and a 20 w.t. % isopropanol/n-heptane mixture. Among the selected catalysts, the top performing ones, in order of importance, were Ir/C, allowing up to 89 % 2-methylfuran yields, followed by Ni/Al2O3 in the presence of chlorine as a promoter, and Cu/ZnO/Al2O3. Besides relations between the achieved yields, active metal loadings, and support effects, useful correlations have been investigated between activity, selectivity, and solvents polarity.

Discovery of new strains for furfural degradation using adaptive laboratory evolution in Saccharomyces cerevisiae

In industrial production, the excessive discharge of furfural can pose harm to soil microorganisms, aquatic animals and plants, as well as humans. Therefore, it is crucial to develop efficient and cost-effective methods for degrading furfural in the environment. Currently, the use of Saccharomyces cerevisiae for furfural degradation in water has shown effectiveness, but there is a need to explore improved efficiency and tolerance in S. cerevisiae for this purpose. In this study, we isolated and evolved highly efficient furfural degradation strains, namely YBA_08 and F60C. These strains exhibited remarkable capabilities, degrading 59% and 99% furfural in the YPD medium after 72 h of incubation, significantly higher than the 31% achieved by the model strain S288C. Through analysis of the efficient degradation mechanism in the evolutionary strain F60C, we discovered a 326% increase in the total amount of NADH and NADPH. This increase likely promotes faster furfural degradation through intracellular aldehyde reductases. Moreover, the decrease in NADPH content led to a 406% increase in glutathione content at the background level, which protects cells from damage caused by reactive oxygen species. Mutations and differential expression related to cell cycle and cell wall synthesis were observed, enabling cell survival in the presence of furfural and facilitating rapid furfural degradation and growth recovery. Based on these findings, it is speculated that strains YBA_08 and F60C have the potential to contribute to furfural degradation in water and the production of furfuryl alcohol, ethanol, and FDCA in biorefinery processes.

Kinetics study of the selective hydrogenation of furfural to furfuryl alcohol over CuAl2O4 spinel catalyst

The catalytic hydrogenation of furfural is an important process that produce value-added furfural derivatives, especially furfuryl alcohol. In this work, the kinetics of the catalytic furfural hydrogenation over copper aluminate spinel (CuAl2O4) was studied in a batch-type reactor under various reaction parameters including the stirring speed, initial furfural concentration, H2 pressure, and reaction temperature. The CuAl2O4 catalyst showed excellent performance in furfuryl alcohol production as the furfural conversion could reach 100% and the furfuryl alcohol yield was >98%. The furfural concentration and the reaction temperature were found to significantly impact on the reaction rate, while other parameters showed less contributions leading to a flexible operation window. It was determined that the reaction rate expression followed the equation r = kCfurfural0.335 with the apparent activation energy of 44.6 kJ/mol. The developed kinetic model for hydrogenation of furfural to furfuryl alcohol were in good agreement with the experimental results. The kinetic model presented here could be useful for process design and scale-up of the hydrogenation reactor in the industrial application.

Production of Furfuryl Alcohol from Corncob Catalyzed By CCZU-KF Cell Via Chemoenzymatic Approach

In this work, the hybrid route of chemo-catalysis and bio-catalysis were used to chemoenzymatically catalyze corncob to produce furfuryl alcohol via sequential conversion with solid acid catalyst at 180 ℃ for 10 min, and E. coli CCZU-KF whole-cell biocatalyst at 35 ℃ for 72 h in 10 vol% choline chloride system. The yield of furfuryl alcohol was 97.7%. This work successfully demonstrated the green and efficient synthesis of furfuryl alcohol production from biomass via chemoenzymatic approach.

Synthesis of Alumina Supported Pt-SnO2 Hybrid Nanostructures by In Situ Transformation of PtSn Alloy Nanoparticles and Their Application as Highly Efficient Catalysts for Selective Hydrogenation of Furfural

In this work, PtSn alloy nanoparticles were synthesized by coreduction of Pt and Sn precursors by ethylene glycol in the presence of stabilizing agents and then were in situ transformed into Pt-SnO2 hybrid nanostructures on alumina supports by calcination. Relative to Pt/Al2O3, Pt1-(SnO2)0.3/Al2O3 demonstrates improved catalytic efficiency for furfuryl alcohol production by furfural hydrogenation. Under the H2 pressure of 1.0 MPa, 100 °C, 3.0 h, and furfural/Pt molar ratio of 1435/1, the furfuryl alcohol yields could approach 98.2%. The enhancement of catalytic performance of the Pt-SnO2/Al2O3 could be ascribed to the formation of the close contact Pt-SnO2 interfaces, which is highly active for furfural hydrogenation due to the synergistic effect between Pt and SnO2.

Selective Furfuryl Alcohol Production from Furfural via Bio-Electrocatalysis

The catalytic reduction of renewable furfural into furfuryl alcohol for various applications is in the ascendant. Nonetheless, the conventional chemo-catalysis hydrogenation of furfural always suffers from poor selectivity, harsh conditions, and expensive catalysts. Herein, to overcome the serious technical barriers of conventional furfuryl alcohol production, an alternative bio-electrocatalytic hydrogenation system was established under mild and neutral conditions, where the dissolved cofactor (NADH) and the alcohol dehydrogenase (ADH) participated in a tandem reaction driven by the electron from a novel Rh (III) complex fixed cathode. Under the optimized conditions, 81.5% of furfural alcohol selectivity can be realized at −0.43 V vs. RHE. This contribution presents a ‘green’ and promising route for the valorization of furfural and other biomass compounds.

Theoretical study on the hydrogenation of furfural for furfuryl alcohol production over low Ni modified Cu catalysts

Cu-based catalysts are efficient for the upgrading of biomass-derived furfural (FF) to produce furfuryl alcohol (FOL), and a low amount of Ni doping is promising to improve the catalytic performance. Herein, Cu (111), Cu7Ni (111), and Cu3Ni (111) catalyst models were constructed. Density functional theory (DFT) calculations were applied to explore the effects of Ni on the FF hydrogenation mechanism by analyzing the FF adsorption configurations, adsorption energies, electronic structures of the adsorbed FF and the catalyst surfaces, as well as reaction pathways and energy barriers of FF hydrogenation. Ni doping promotes the charge transfer between the catalyst surface and FF, thus enhancing the adsorption capacity of the catalyst. The H2 dissociation ability can also be enhanced by the Ni modification. In the initial hydrogenation process, the aldehyde group of the adsorbed FF is easy to hydrogenate and thus contributing to the selective production of FOL. With the increase of the Ni amount, the competitiveness of the hydroxyalkyl intermediate (F–CHOH) involved pathway increases according to the gradually widened energy barrier gaps among the competing pathways. All in all, the Cu3Ni (111) catalyst has the best hydrogenation activity with an energy barrier of 8.99 kJ/mol.

Cu/CuOx@C for efficient selective transfer hydrogenation of furfural to furfuryl alcohol with formic acid

AbstractBackgroundCatalytic transfer hydrogenation has been increasingly employed as an effective and safe method for biomass upgrading; however, relying on biomass‐derived formic acid (FA) as hydrogen source has rarely been studied, especially in the production of furfuryl alcohol (FOL) from biomass‐derived furfural (FF) via selective hydrogenation, which is challenging due to diverse unsaturated groups. Herein, in situ encapsulation and stabilization of Cu/CuOx in a porous carbon matrix (Cu/CuOx@C) was reported for the first time and applied in the hydrogenation of FF to FOL with FA.ResultsVarious analytical techniques were used to characterize the effect of pyrolysis temperature on Cu/CuOx@C, since the temperature can be adjusted to control the reduction of the catalyst to give different Cu0/Cun+ ratios. The optimal catalyst Cu/CuOx@C‐450 gave a 99.1% FF conversion and 98% FOL selectivity under suitable reaction conditions, exhibiting excellent activity that was even better than those of noble metal catalysts. Further, density functional theory calculations were used to reveal the effect of Cu species on FA decomposition and final catalytic performance.ConclusionThe catalytic activity of Cu/CuOx@C was influenced by the pyrolysis temperature of the catalyst precursor, and its good performance was mainly attributed to a high dispersion of accessible catalytic Cu/CuOx nanoparticles on the porous carbon and to an appropriate Cu0/Cun+ ratio. © 2022 Society of Chemical Industry (SCI).

Defect-engineered MOF-808 with highly exposed Zr sites as highly efficient catalysts for catalytic transfer hydrogenation of furfural

The highly efficient production of furfuryl alcohol (FFA) from biomass-derived furfural (FFR) is attracting increasing attention due to its wide application in the production of value-added chemicals. Zr-based MOF-808 is promising for liquid catalytic transfer hydrogenation (CTH) of FFR to FFA in terms of possessing a great number of Lewis-acid sites. Herein, a series of defective MOF-808 (Dx-MOF-808) samples were prepared via a competitive coordination-removal strategy by modulating with benzoic acid (HBC). HBC was introduced as the temporary ligand for competing with formal ligand 1,3,5-benzenetricarboxylic acid (H3BTC) to coordinate with metal clusters and then it was removed with methanol to obtain the Dx-MOF-808. The results showed that HBC serves not only as a temporary ligand participating in the synthesis of MOF-808 to obtain defective structure but also as a modulator controlling the particle size by terminating the growth of crystals. By changing the amount of HBC addition, the degree of ligand deficiency and the number of exposed Zr sites can be well regulated. Especially, excellent performance of FFR conversion (99%), FFA selectivity (94.4%) and FFA formation rate (48.6 mmol·g−1·h−1) was achieved over D40-MOF-808 sample with 2-propanol as a hydrogen donor under mild conditions (90 °C, 2 h), ranking it the best among the reported catalysts. Detailed characterizations proved that the high activity of D40-MOF-808 was jointly influenced by the high surface area, the high content of exposed Zr metal sites and ligand deficiency.

Solvent effects in integrated reaction-separation process of liquid-phase hydrogenation of furfural to furfuryl alcohol over CuAl2O4 catalysts

Selective hydrogenation of furfural to furfuryl alcohol over CuAl2O4 catalysts is studied in a batch reactor using a range of solvents of varying chemical properties. We find that the reactions in branched alcohols provide higher furfuryl alcohol yields compared to linear alcohols. Besides, the reactions performed in nonane and decane provide excellent furfuryl alcohol yields of 96%. In situ FTIR analysis indicates that the carbonyl group of furfural is preferentially adsorbed leading to such high catalyst performance. Importantly, the efficient production of furfuryl alcohol in immiscible solvents minimizing downstream process is achieved in this integrative reaction-separation concept.