Conversion Of Biomass-derived Levulinic Acid Research Articles

Catalytic production of 1,4-pentanediol from lignocellulosic biomass

This review gives a broad overview of the conversion of biomass-derived levulinic acid (LA) and furfural into valuable 1,4-pentanediol (1,4-PDO), which is a degradable polyester monomer.

Hydrodeoxygenation of levulinic acid over Ru-based catalyst: Importance of acidic promoter

Biorefineries are fundamental for sustainable energy. This research explored the conversion of biomass-derived Levulinic acid (LA) into essential compounds γ-valerolactone (GVL) and 1,4-pentanediol (1,4-PDO) using the Ru2.5Mn15Al catalyst. The study underscores the role of Ru incorporation and specific promoters in enhancing catalyst efficiency. The crucial challenge is to destroy the particularly stable ring structure of GVL. The crucial roles of acidity and specific metal species in directing catalytic pathways were revealed by the detailed characterization of the catalyst's textural, acidic, reduction, and electronic properties. They provided valuable insights for sustainable chemical synthesis.

Catalytic Conversion of Levulinic Acid to Pyrrolidone under Mild Conditions with Disordered Mesoporous Silica-Supported Pt Catalyst.

Catalytic conversion of biomass-derived levulinic acid (LA) into high-valued 5-methylpyrrolidones has become an attractive case in studies of biomass utilization. Herein, we developed a disordered mesoporous Pt/MNS catalyst for this reductive amination process under room temperature and atmospheric pressure of hydrogen. The disordered mesoporous structures in support of Pt/MNS catalyst led the formation of highly dispersed Pt species via confinement effect, providing high specific area for enhancing the catalytic sites. With the synergistic effect between highly dispersed Pt species and mesoporous structures, 5-methylpyrrolidones were successfully synthesized from biomass-derived LA and primary amines with high selectivity. Mechanism studies indicated that introducing protonic acid would promote the reductive-amination process, and enamine intermediates could be detected during the in-situ DRIFT tests. Density functional theory (DFT) calculation confirmed that the hydrogenation of enamine intermediate was more accessible than that of imide intermediates, leading the excellent performance of the Pt/MNS catalyst. This work provided a green method to produce 5-methylpyrrolidone and revealed the impact of catalyst structural characteristics on the reaction process.

Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

One-pot conversion of biomass-derived levulinic acid to furanic biofuel 2-methyltetrahydrofuran over bimetallic NiCo/γ-Al2O3 catalysts

The production of furanic biofuel 2-methyltetrahydrofuran (2-MTHF) has been studied by hydrodeoxygenation of biomass-derived levulinic acid (LA) over bimetallic NiCo/γ-Al2O3 catalyst. The contents of Ni and Co in NiCo/γ-Al2O3 were investigated. The Ni5Co25/γ-Al2O3 catalyst gave high activity in hydrodeoxygenation of LA with a 73.4% yield of 2-MTHF under optimal conditions. The crystal phase, valence states, acidity and basicity of catalysts were measured by multiple characterizations to understand the relationships among 2-MTHF yields and catalyst properties. XPS characterization revealed that the number of metal oxides increased on bimetallic catalysts while the reduced metals occupied on monometallic catalysts. The bimetallic catalysts also presented increased acidity than that of monometallic catalysts. These distinct properties were also observed among bimetallic catalysts with different contents of Ni and Co, which were responsible for different performances. Besides, the solvent effect on the structure of 1,4-pentanediol, which was further converted to 2-methyltetrahydrofuran, was disclosed by molecular dynamics simulations.

Facile Synthesis of Nanoarchitectured Hydrotalcite/SBA-15 Composites for the Efficient Conversion of Levulinic Acid to Ethyl Levulinate

In this work, we report the one-pot fabrication of nanoarchitectured hydrotalcite (HT)/SBA-15 composites via a facile in-situ mesoporous templating approach. The characterization studies conferred that the successful incorporation of HT into the SBA-15 mesopores and the formation of composites. These composites showed excellent performance towards the catalytic conversion of biomass-derived levulinic acid (LA) to a biofuel additive ethyl levulinate (EL). The enhancement in the selectivity of EL was observed from 69 to 97% with the incorporation of HT into SBA-15. The experimental results revealed that the catalytic activity of the composites was thoroughly influenced by the density of surface basic sites and surface area. Among all the composites, HTS-2 outperforms the highest EL selectivity of 97.2% with remarkable stability and recyclability.

Efficient Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Polyoxometalate@Zr-Based Metal-Organic Frameworks: The Synergistic Effect of Bro̷nsted and Lewis Acidic Sites.

Catalytic transformation of levulinic acid (LA) to γ-valerolactone (γ-GVL) is an important route for biomass upgradation. Because both Bro̷nsted and Lewis acidic sites are required in the cascade reaction, herein we fabricate a series of H3PW12O40@Zr-based metal-organic framework (HPW@MOF-808) by a facile impregnation method. The synthesized HPW@MOF-808 is active for the conversion of LA to γ-GVL using isopropanol as a hydrogen donor. Interestingly, with the increase in the HPW loading amount, the yield of γ-GVL increases first and then decreases, and 14%-HPW@MOF-808 gave the highest γ-GVL yield (86%). The excellent catalytic performance was ascribed to the synergistic effect between the accessible Lewis acidic Zr4+ sites in MOF-808 and Bro̷nsted acidic HPW sites. Based on the experimental results, a plausible reaction mechanism was proposed: the Zr4+ sites catalyze the transfer hydrogenation of carbonyl groups and the HPW clusters promote the esterification of LA with isopropanol and lactonization to afford γ-GVL. Moreover, HPW@MOF-808 is resistant to leaching and can be reused for five cycles without significant loss of its catalytic activity.

WO3/Al-HZSM-5 catalysts for effective catalytic conversion of biomass-derived levulinic acid to angelica lactones

WO3/Al-HZSM-5 catalysts for effective catalytic conversion of biomass-derived levulinic acid to angelica lactones

Metal regulating the highly selective synthesis of gamma-valerolactone and valeric biofuels from biomass-derived levulinic acid

Highly selective upgrade of biomass-derived source to biofuels is crucial for the utilization of biomass. Herein, we report a strategy for the highly selective conversion of biomass-derived levulinic acid (LA) to gamma-valerolactone (GVL) or valeric biofuels simply by tuning the used metal Ni or Ru on HZSM-5 support. The catalytic experimental results show that 3 wt% Ni/HZSM-5 catalyst achieves high yield (93.1%) of GVL with negligible formation of pentanoic acid (<1% yield) or pentanoic esters (<1% yield), while 3 wt% Ru/HZSM-5 catalyst exhibits a high yield (85.7%) of pentanoic esters (PE) and pentanoic acid (PA) under the identical conditions. It is found that the introduction of Ru into HZSM-5 would increase the strong acidic sites and enhance the ring-opening of GVL intermediate, promoting the formation of PE and PA. In comparison, 3 wt% Ni/HZSM-5 catalyst shows relative lower acidic sites and negligible ring-opening ability of GVL. The metal effect is further confirmed using GVL and 1, 4-dioxane as substrate, respectively. After that, reaction kinetics are investigated in details and a rational pathway is proposed for the metal effect in deciding the product distribution of LA hydrogenation. This work provides a useful guideline to design proper catalyst for the valorization of biomass resources.

Microwave Irradiation-Enhanced Catalytic Transfer Hydrogenation of Levulinic Acid to γ-Valerolactone Using Ruthenium: A Comparative Study with Conventional Heating Processes

Conversion of biomass-derived levulinic acid to γ-valerolactone (GVL) via catalytic transfer hydrogenation (CTH) using conventional oven heating (COH) is associated with issues, such as long reaction time, and low yield. Microwave irradiation (MWI) appears to be a solution to address these issues as MWI can shorten reaction times and enhance yields. To explore effectiveness of MWI for LA conversion, MWI and COH are compared for LA conversion via CTH catalyzed by a model catalyst, Ru/C. Through investigating the effects of temperature and reaction time, MWI is validated to shorten the reaction time and enhance LA conversion efficiencies in comparison with COH. The optimal condition for the full LA conversion to GVL by Ru/C using MWI is 160 °C for 30 min with 10 mg (Ru/C)/mL (2-PrOH). MWI is also validated to improve conversion of several common levulinate esters (LAEs) to GVL. The regenerated Ru/C can also exhibit almost the same catalytic activity as the pristine Ru/C for LA conversion using MWI. These results indicate that Ru/C is a highly-effective catalyst for LA conversion and MWI can further enhance LA conversion by Ru/C by shortening reaction time and increasing yield of GVL. Thus, MWI is a promising process for enhancing biomass conversion.

Selective conversion of biomass-derived levulinic acid to ethyl levulinate catalyzed by metal organic framework (MOF)-supported polyoxometalates

The esterification of levulinic acid (LA) and ethanol into ethyl levulinate is an attractive biomass conversion process since the product EL has wide applications as food additive, fragrance and fuel. Herein, a metal-organic framework (MOF)-supported phosphomolybdic acid [Cu-BTC][HPM] was synthesized with 1,3,5-Benzenetricarboxylic acid, copper nitrate and phosphomolybdic acid in a one-step process at ambient temperature. The synthesized [Cu-BTC][HPM] was used for the catalytic esterification of levulinic acid to EL in ethanol, and showed excellent activity with a high EL yield close to 100% at 120 °C for 6 h, which should be ascribed to the uniform dispersion of HPM embedded in the MOF. The [Cu-BTC][HPM] catalyst could keep stable crystal structure and active component contents, and thus exhibited good stability in recycling process.

Preparation of valeric acid and valerate esters from biomass-derived levulinic acid using metal triflates + Pd/C

The selective conversion of biomass-derived levulinic acid to produce valeric acid and valerate esters was successfully performed in the presence of H2, in which metal triflates and Pd/C were used as the catalysts.

Catalytic conversion of biomass-derived levulinic acid into alcohols over nanoporous Ru catalyst

1,4-pentanediol or monohydric alcohol were achieved with high selectivity from levulinic acid under relatively mild conditions using nanoporous Ru.

Conversion of levulinic acid into alkyl levulinates: Using lipase immobilized on meso-molding three-dimensional macroporous organosilica as catalyst

For conversion of biomass-derived levulinic acid into alkyl levulinates, a novel kind of lipase-based biocatalyst was prepared through immobilized lipase B from C. antarctica (CALB) on organosilica material with highly ordered 3D macroporous organosilica frameworks and a 2D hexagonal meso-structure (named 3DOM/m-OS) for the first time. The catalytic performance of the immobilized lipase (NER@3DOM/m-OS) was investigated. NER@3DOM/m-OS was used as biocatalyst to catalyze the esterification reaction between levulinic acid (LA) and n-butanol. Under optimized reaction conditions, 74.59% of ester yield was achieved after 12h of reaction. NER@3DOM/m-OS was also used to production of other alkyl levulinates, the ester yields increased to 84.51% (octyl levulinate) and 91.14% (dodecyl levulinate), respectively. When NER@3DOM/m-OS was used repeatedly in batch reactions, the ester yields of n-butyl, octyl, and dodecyl levulinate could retain 46.18%, 82.33% and 81.25% after 9 reaction cycles, respectively, which was better than commercial lipase Novozym 435 under the same condition.

New Method for Highly Efficient Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone in Water without Precious Metal Catalysts

γ-Valerolactone (GVL) is receiving increasing attention because of its significant characteristics of an ideal sustainable liquid fuel. In this work, a novel and nonprecious metal catalytic method of the hydrogenation of biomass-derived levulinic acid (LA) into GVL by water splitting is first reported. Commercially available nonprecious metals of Fe, Ni, Cu, Cr, and Mo exhibited significantly catalytic activities in the hydrogenation of LA into GVL. Over 90% yield of GVL from LA can be obtained at a relatively low temperature of 180 °C, and an excellent 98% yield of GVL was achieved over the Fe catalyst at 250 °C. Catalyst Fe is stable and still keeps the high catalytic activity after recycles. The extraordinary catalytic activity of the general Fe powder is probably because of the role of hot water and also a synergistic role of the Fe and ZnO or Zn/ZnO. Also, the reactor wall of a reactor made of the stainless steel material acted as a significant catalyst, and a considerably high GVL yield of 56% can b...

Highly efficient conversion of biomass-derived levulinic acid into γ-valerolactone over Ni/MgO catalyst

Hydrogenation of levulinic acid (LA) was investigated with Ni/MgO for the production of γ-valerolactone (GVL).

Conversion of levulinic acid into γ-valerolactone using Fe3(CO)12: mimicking a biorefinery setting by exploiting crude liquors from biomass acid hydrolysis.

The conversion of biomass-derived levulinic acid (LA) into gamma-valerolactone (GVL) using formic acid (FA) and Fe3(CO)12 as the catalyst precursor was achieved in 92% yield. To mimic a biorefinery setting, crude liquor (containing 20% LA) from the acid hydrolysis of sugarcane biomass in a pilot plant facility was directly converted into GVL in good yield (50%), without the need for isolating LA.

Catalytic conversion of biomass-derived levulinic acid into γ-valerolactone using iridium nanoparticles supported on carbon nanotubes

A new method has been developed for the catalytic conversion of biomass-derived levulinic acid (LA) into γ-valerolactone (GVL) with molecular hydrogen (H 2 ) using a series of heterogeneous noble metal catalysts. Excellent yields of the GVL were obtained under mild reaction conditions of 50°C and 2 MPa of H 2 using iridium nanoparticles supported on carbon nanotubes (Ir/CNT). It is noteworthy that the reaction proceeded smoothly in the presence of formic acid (FA, co-produced with LA in equimolar amounts during the acid-mediated hydrolysis of lignocellulosic biomass). Furthermore, the FA remained intact, highlighting the practical advantages of this process for the convenient and cost-effective processing of a biomass-derived LA/FA solution. The method is effective for the simultaneous production of GVL and FA from a wide variety of renewable biomass resources. 以碳纳米管(CNTs)担载Ir纳米粒子为催化剂进行生物质基平台化合物乙酰丙酸(LA)选择加氢制备γ-戊内酯(GVL)的研究, 并利用X射线衍射、X射线光电子能谱和透射电镜表征了使用前后的Ir/CNT催化剂, 探讨了影响LA催化加氢制GVL反应性能的因素和该反应的可能路径. 结果表明, 与Ru, Rh和Pd等传统铂族金属相比, Ir/CNT催化剂不但可在温和条件下(50 °C, 2.0 MPa, H 2 )实现LA至GVL的完全转化, 且可对多类直接源于生物质水解的含等量LA/甲酸的“真实”体系实现GVL的高效选择合成. Iridium nanoparticles supported on carbon nanotubes have been used as a highly efficient catalyst for the hydrogenation of biomass-derived levulinic acid to γ-valerolactone (GVL) in the presence of formic acid. The GVL was obtained in an excellent yield of 96% at an operating temperature of 50°C.

Catalytic conversion of biomass-derived levulinic acid to valerate esters as oxygenated fuels using supported ruthenium catalysts

The development of the catalytic conversion of biomass-based platform molecules into oxygenated fuel molecules is of great significance in order to reduce the dependence on fossil resources and to solve environmental problems. Alkyl valerate esters were proven to have the potential to be renewable additives of gasoline and diesel. In this work, we studied the hydrogenation of levulinic acid (LA) to valerate esters over supported Ru catalysts, and found that the acidity was an important factor for the catalyst performance. A bifunctional catalyst Ru/SBA-SO3H was developed as an active catalyst, and a highest yield of 94% to ethyl valerate (EV) was achieved. The catalyst was characterized by nitrogen adsorption/desorption methods, X-ray power diffraction (XRD), transmission electron spectroscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The effects of reaction conditions were comprehensively investigated and probable reaction pathways were proposed and verified. The conversion of LA to various alkyl valerate esters can also be catalyzed by the bifunctional catalyst. In addition, supported Cu and Ni catalysts were also screened under similar reaction conditions as Ru-based catalysts, and the combination of Ni/SBA-15 and SBA-SO3H exhibited activity for the conversion of LA to EV.

A sulfuric acid management strategy for the production of liquid hydrocarbon fuels via catalytic conversion of biomass-derived levulinic acid

In this study, we first develop an integrated strategy for the catalytic conversion of lignocellulose into liquid fuels based on the production of levulinic acid (LA) followed by its hydrogenation to γ-valerolactone (GVL). Our integrated strategy involves a novel catalytic conversion process employing alkylphenol-based separation to extract LA from the sulfuric acid containing aqueous solution following the sulfuric acid catalyzed deconstruction of cellulose. To minimize utility consumption, we perform heat integration, while the remaining heating requirement is satisfied by the combustion of residual biomass. Hot combustion gases are also used to generate electricity, which meets the electricity requirement of the process, while the excess electricity is sold to the grid. We perform a technoeconomic analysis for the alkylphenol-based strategy and compare its economics with a previously reported strategy, in which butyl acetate was used as an extractive solvent to separate GVL from sulfuric acid following the LA hydrogenation step. With some improvements in the process configuration, the alkylphenol strategy leads to a minimum selling price (MSP) of $4.40 per gallon of gasoline equivalent (GGE) for compatible biofuel components, whereas the butyl acetate strategy leads to a MSP of $4.68 per GGE. We show that the alkylphenol strategy becomes a significantly better choice when the catalyst lifetime for the hydrogenation of LA becomes less than 6 months.