Product classification

108-29-2

Product Name：2(3H)-Furanone,dihydro-5-methyl-
Molecular Formula：C₅H₈O₂
Purity：99%
Molecular Weight：

Inquiry

Product Details;

CasNo： 108-29-2

Molecular Formula： C₅H₈O₂

Appearance： colorless to pale yellow clear liquid

108-29-2 Properties

Molecular Formula:C5H8O2
Molecular Weight:100.117
Appearance/Colour:colorless to pale yellow clear liquid
Vapor Pressure:0.235mmHg at 25°C
Melting Point:-31 °C(lit.)
Refractive Index:n20/D 1.432(lit.)
Boiling Point:206.624 °C at 760 mmHg
Flash Point:74.98 °C
PSA：26.30000
Density:1.05 g/cm³
LogP:0.71190

108-29-2 Usage

Description

γ-Valerolactone (Item No. 28240) is an analytical reference standard categorized as a prodrug form of γ-hydroxyvaleric acid (GHV; ). This product is intended for research and forensic applications.

Chemical Properties

Colorless liquid. Surface tension 30 dynes/cm (25C), viscosity 2.18 cP (25C), pH (anhydrous): 7. pH (10% solution in distilled water): 4.2. Miscible with water and most organic solvents, resins, waxes, etc.; slightly misciblewith zein, beeswax, petrolatum; immiscible with anhydrous glycerin, glue, casein, arabic gum, and soybean protein. Combustible.

Chemical Properties

γ-Valerolactone has a sweet, herbaceous odor.

Occurrence

Reported found in boiled beef, beef fat, beer, cacao, Swiss cheese, ground and roasted coffee, roasted filberts, milk fat, dried mushroom, peach, roasted peanuts, heated pork fat, black tea and yogurt. Also reported found in peach, strawberry jam, tomato, wheaten bread, Gruyere cheese, heated butter, cooked beef, white wine, red wine, coffee and Bourbon vanilla.

Uses

γ-valerolactone?(GVL) can be used as a green solvent: To transform lignocellulose into furfural using a solid acid catalyst, H-mordenite.To synthesize phosphatidylserine.

Uses

It finds it application as a food additive that is used to improve the taste or odor of a food. It is also used as toiletry fragrances.

Uses

γ-Valerolactone is a naturally occurring chemical found in fruits and is frequently used as a food additive. It can be converted to liquid alkenes which can be used as transportation fuels. γ-Valerolactone is widely used in dye baths (coupling agent), brake fluids, cutting oils, and as solvent for adhesives, insecticides, and lacquers.

Preparation

By reduction of levulinic acid followed by cyclization.

Synthesis Reference(s)

Journal of the American Chemical Society, 112, p. 1286, 1990 DOI: 10.1021/ja00159a082Tetrahedron Letters, 26, p. 5639, 1985 DOI: 10.1016/S0040-4039(01)80907-2The Journal of Organic Chemistry, 50, p. 3930, 1985 DOI: 10.1021/jo00220a053

General Description

γ-Valerolactone has been identified as one of the volatile flavor constituents in mango and honey.

Reactivity Profile

gamma-Valerolactone is an ester. Esters react with acids to liberate heat along with alcohols and acids. Strong oxidizing acids may cause a vigorous reaction that is sufficiently exothermic to ignite the reaction products. Heat is also generated by the interaction of esters with caustic solutions. Flammable hydrogen is generated by mixing esters with alkali metals and hydrides. gamma-Valerolactone is incompatible with strong oxidizers. . gamma-Valerolactone is incompatible with strong oxidizing agents. gamma-Valerolactone is also incompatible with strong acids, strong bases and strong reducing agents. .

Biochem/physiol Actions

Odor at 1%

Safety Profile

Moderately toxic by ingestion. A skin irritant. Mutation data reported. Combustible liquid when exposed to heat or flame; can react with oxidizing materials. To fight fire, use water, foam, CO2, dry chemical. When heated to decomposition it emits acrid smoke and irritating fumes.

Purification Methods

Purify the -lactone by repeated fractional distillation [Boorman & Linstead J Chem Soc 577, 580 1933]. IR: max 1790 (CS2), 1775 (CHCl3) cm-1 [Jones et al. Can J Chem 3 7 2007 1959]. The BF3-complex distils at 110-111o/20mm [Reppe et al. Justus Liebigs Ann Chem 596 179 1955]. It is characterized by conversion to -hydroxy-n-valeramide on treatment with NH3, m 51.5-52o (by slow evaporation of a CHCl3 solution). [Beilstein 17 H 235, 17 I 131, 17 II 288, 17 III/IV 4176, 17/9 V 24.]

InChI:InChI=1/C5H8O2/c1-4-2-3-5(6)7-4/h4H,2-3H2,1H3/t4-/m0/s1

108-29-2 Relevant articles

Selective hydrogenation of levulinic acid to valeric acid and valeric biofuels by a Pt/HMFI catalyst

Kon, Kenichi,Onodera, Wataru,Shimizu, Ken-Ichi

, p. 3227 - 3234 (2014)

We describe one-pot high-yield catalytic pathways for the conversion of levulinic acid (LA) to valeric acid (VA) or valeric acid esters (so-called valeric biofuels) under relatively mild conditions (2 or 8 bar H2, 200 °C). A thorough screening study reveals that a HMFI zeolite-supported Pt metal cluster (Pt/HMFI) with an average cluster size of 1.9 nm shows the highest yield of VA (99%) under solvent-free conditions. The use of ethanol or methanol as solvent changes the selectivity, resulting in 81-84% yields of ethyl valerate (EV) or methyl valerate (MV). Pt/HMFI is also effective for selective formation of valeric acid esters from γVL in alcohols under H2. Kinetics, in situ infrared (IR), and acidity-activity relationship studies show a cooperative mechanism of Pt and Bronsted acid sites of HMFI. VA formation from LA can be driven by Pt-catalyzed hydrogenation of LA to γVL, which undergoes proton-assisted ring-opening by HMFI, followed by Pt-catalyzed hydrogenation. Valeric ester formation from LA is driven by esterification of LA to levulinic ester, which is hydrogenated by Pt. the Partner Organisations 2014.

Maximising opportunities in supercritical chemistry: The continuous conversion of levulinic acid to γ-valerolactone in CO2

Bourne, Richard A.,Stevens, James G.,Ke, Jie,Poliakoff, Martyn

, p. 4632 - 4634 (2007)

Phase behaviour is manipulated during the hydrogenation of aqueous levulinic acid in supercritical CO2 to separate almost pure γ-valerolactone from water and unreacted acid with reduced energy requirements compared to conventional processing. The Royal Society of Chemistry.

-

Austin,A.T.,Howard,J.

, p. 3278 - 3284 (1961)

Influence of W on the reduction behaviour and Br?nsted acidity of Ni/TiO2catalyst in the hydrogenation of levulinic acid to valeric acid: Pyridine adsorbed DRIFTS study

Kumar, V. Vijay,Naresh,Deepa,Bhavani, P. Ganga,Nagaraju,Sudhakar,Chary,Venugopal,Tardio,Bhargava

, p. 169 - 176 (2017)

Effect of W on 20 wt%Ni/TiO2catalyst is examined in the hydrogenation of levulinic acid (LA) to valeric acid at ambient H2pressure. The interaction between W and Ni had a significant influence on the hydrogenation activity and product selectivity. The H2-TPR (temperature programmed reduction) results emphasized a shift in Tmaxto very high temperatures due to W species which are in close proximity to Ni particles. The N2O decomposition measurements showed a decrease in N2O uptake with the increase in ‘W’ loadings due to a high ratio of Ni2+/Ni0species at higher tungsten content. X-ray photoelectron spectra (XPS) demonstrated a shift in binding energy to higher owing to a strong interaction between W and Ni particles by the presence of ionic Ni at the near surface region. The ionic Ni species seems to be involved in the conversion of γ-valerolactone (GVL) to valeric acid (VA). Pyridine adsorbed infrared (IR) spectra revealed an enormous increase in surface Br?nsted acidity originated from tungsten interacted Ni/TiO2are the sites responsible for ring opening of GVL to form VA.

Selective and flexible transformation of biomass-derived platform chemicals by a multifunctional catalytic system

Geilen, Frank M. A.,Engendahl, Barhel,Harwardt, Andreas,Marquardt, Wolfgang,Klankermayer, Juergen,Leitner, Walter

, p. 5510 - 5514 (2010)

(Figure Presented) A sustainable supply chain: The controlled transformation of the biomassderived platform compounds levulinic acid (LA) and itaconic acid (IA) into the corresponding lactones, diols, or cyclic ethers (see picture) by using a multifunctional molecular catalyst is described.

Enhanced Production of Γ-Valerolactone with an Internal Source of Hydrogen on Ca-Modified TiO2 Supported Ru Catalysts

Wojciechowska, Joanna,J?drzejczyk, Marcin,Grams, Jacek,Keller, Nicolas,Ruppert, Agnieszka M.

, p. 639 - 650 (2019)

Calcium-modified titania supported Ru catalysts were synthesized and evaluated for the hydrogenation of levulinic acid with formic acid as an internal hydrogen source and water as a green solvent. A new elegant photoassisted method was developed for the synthesis of uniform-size and evenly distributed Ru particles on the titania surface. Compared with the counterpart catalysts prepared by classical wet impregnation, enhanced levulinic acid conversion and γ-valerolactone yield were obtained and further improved through modification of the support by introduction of calcium into the titania support. This synthesis approach resulted in a change of the surface and bulk properties of the support, namely a decrease in the anatase crystallite size and the formation of a new calcium titanate phase. As a consequence, the properties of the catalysts were modified, and smaller ruthenium particles that had stronger interactions with the support were obtained. This affected the strength of the CO adsorption on the catalyst surface and facilitated the reaction performance. The optimum size of Ru particles that allowed for most efficient levulinic acid conversion was established.

Hydrogenation of biomass-derived compounds containing a carbonyl group over a copper-based nanocatalyst: Insight into the origin and influence of surface oxygen vacancies

Hu, Qi,Yang, Lan,Fan, Guoli,Li, Feng

, p. 184 - 195 (2016)

New Mn-containing spinel-supported copper nanocatalysts were directly generated via a Cu-Mn-Al layered double hydroxide precursor route and employed in gas-phase hydrogenation of dimethyl succinate (DMS) to γ-butyrolactone (GBL). It was found that the introduction of manganese into catalyst precursors led to the formation of Mn-containing spinel phases, thereby giving rise to highly dispersive Cu0 nanoparticles and a large number of surface defects (i.e., oxygen vacancies (Ov), Mn2+ species) in reduced catalysts. As-formed copper-based nanocatalysts exhibited exceptional catalytic hydrogenation performance with stability enduring up to 100 h. Such high catalytic efficiency could reasonably be attributed to the surface synergism between Mn2+-Ov-Mn2+ defect structures and active metallic copper species, which controlled the key to hydrogenation related to the adsorption of DMS molecules and following activation of carbonyl groups and the dissociation of hydrogen. Most importantly, such copper-based nanocatalysts displayed great potential applications in the hydrogenations of other biomass-derived compounds containing carbonyl groups (e.g., acetol, levulinic acid, levulinic acid esters, and furfural). The present strategy enables us to tune the surface structures of catalysts for designing new type of copper-based catalysts with significantly enhanced catalytic performance.

Sustainable Strategy Utilizing Biomass: Visible-Light-Mediated Synthesis of γ-Valerolactone

Verma, Sanny,Baig, R. B. Nasir,Nadagouda, Mallikarjuna N.,Varma, Rajender S.

, p. 690 - 693 (2016)

A novel sustainable approach to valued γ-valerolactone was investigated. This approach exploits the visible-light-mediated conversion of biomass-derived levulinic acid by using a bimetallic catalyst on a graphitic carbon nitride, AgPd@g-C3N4. Two on one: A novel approach to γ-valerolactone is described that exploits the visible-light-mediated conversion of biomass-derived levulinic acid by using a bimetallic catalyst on graphitic carbon nitride, AgPd@g-C3N4.

A novel hafnium-graphite oxide catalyst for the Meerwein-Ponndorf-Verley reaction and the activation effect of the solvent

Li, Xiaomin,Du, Zhengjiang,Wu, Yi,Zhen, Yadong,Shao, Rixin,Li, Bingqi,Chen, Chengmeng,Liu, Quansheng,Zhou, Huacong

, p. 9985 - 9995 (2020)

Construction and application of novel hydrogenation catalysts is important for the conversion of carbonyl or aldehyde compounds into alcohols in the field of biomass utilization. In this work, a novel, efficient, and easily prepared hafnium-graphite oxide (Hf-GO) catalyst was constructed via the coordination between Hf4+ and the carboxylic groups in GO. The catalyst was applied into the hydrogenation of biomass derived carbonyl compounds via the Meerwein-Ponndorf-Verley (MPV) reaction. The catalyst gave high efficiency under mild conditions. An interesting phenomenon was found whereby the activity of the catalyst increased gradually in the initial stage during reaction. The solvent, isopropanol, was proved to have an activation effect on the catalyst, and the activation effect varied with different alcohols and temperatures. Further characterizations showed that isopropanol played the activation effect via replacing the residual solvent (DMF) in micro- and mesopores during the preparation process, which was hard to be completely removed by common drying process.

Conversion of biomass-derived levulinate and formate esters into γ-valerolactone over supported gold catalysts

Du, Xian-Long,Bi, Qing-Yuan,Liu, Yong-Mei,Cao, Yong,Fan, Kang-Nian

, p. 1838 - 1843 (2011)

The utilization of biomass has recently attracted tremendous attention as a potential alternative to petroleum for the production of liquid fuels and chemicals. We report an efficient alcohol-mediated reactive extraction strategy by which a hydrophobic mixture of butyl levulinate and formate esters, derived from cellulosic biomass, can be converted to valuable γ-valerolactone (GVL) by a simple supported gold catalyst system without need of an external hydrogen source. The essential role of the supported gold is to facilitate the rapid and selective decomposition of butyl formate to produce a hydrogen stream, which enables the highly effective reduction of butyl levulinate into GVL. This protocol simplifies the recovery and recycling of sulfuric acid, which is used for cellulose deconstruction.

Stabilization of cobalt catalysts by embedment for efficient production of valeric biofuel

Sun, Peng,Gao, Guang,Zhao, Zelun,Xia, Chungu,Li, Fuwei

, p. 4136 - 4142 (2014)

We herein report, for the first time, a bifunctional base-metal catalyst (Co@HZSM-5) that acts as an efficient alternative to noble-metal catalysts (e.g., Pt, Ru) for the conversion of levulinic acid into valeric biofuel under batch and fixed-bed reactor conditions. The cobalt nanoparticles were embedded in HZSM-5 crystals and catalyzed the sequential hydrogenations of the ketone and alkene functional groups; meanwhile, the acidic zeolite catalyzed the ring opening of the γ-valerolactone intermediate. Although base metals (e.g., Co) are abundant and inexpensive, their sintering and/or leaching under liquid-phase conditions always lead to the irreversible deactivation of the catalyst. In this system, the embedment structure stabilizes the nanoparticles, and Co@HZSM-5 could be used up to eight times. This work provides a practical clue toward the stabilization of base-metal catalysts and will inspire the development of large-scale biorefinery.

Selective, Heterogeneous Oxidation of Alcohols and Diols with Potassium Permanganate

Jefford, Charles W.,Wang, Ying

, p. 634 - 635 (1988)

Primary alcohols can be conveniently oxidized to carboxylic acids using solid KMnO4/CuSO4*5H2O/KOH in an organic solvent; 1,4- and 1,5-diols can be selectively oxidized to the corresponding lactones using appropriate mixtures of KMnO4/CuSO4*5H2O without added base.

-

Mosher,Preiss

, p. 5605 (1953)

Domino reaction catalyzed by zeolites with Br?nsted and Lewis acid sites for the production of γ-valerolactone from furfural

Bui, Linh,Luo, Helen,Gunther, William R.,Román-Leshkov, Yuriy

, p. 8022 - 8025 (2013)

Take the straight path: Furfural was converted into γ-valerolactone (GVL) through sequential transfer-hydrogenation and hydrolysis reactions catalyzed by zeolites with Lewis and Br?nsted acid sites (see picture). Together, Zr-Beta and Al-MFI nanosheets generated GVL in 78 % yield without the use of precious metals or molecular H2. This system offers an attractive streamlined strategy for the production of GVL from biomass-derived molecules. Copyright

Synergy between the metal nanoparticles and the support for the hydrogenation of functionalized carboxylic acids to diols on Ru/TiO2

Primo, Ana,Concepcion, Patricia,Corma, Avelino

, p. 3613 - 3615 (2011)

Ruthenium nanoparticles supported on titania are over three times more active than conventional ruthenium on carbon for the hydrogenation of lactic acid. This superior catalytic activity can be due to a combined action of small ruthenium nanoparticles and the titania support.

Efficient Synthesis of Furfuryl Alcohol and 2-Methylfuran from Furfural over Mineral-Derived Cu/ZnO Catalysts

Yang, Xiaohai,Xiang, Xiaomin,Chen, Hongmei,Zheng, Hongyan,Li, Yong-Wang,Zhu, Yulei

, p. 3023 - 3030 (2017)

Two kinds of typical mineral-derived Cu/ZnO catalysts consisting of aurichalcite and zincian malachite were introduced for furfural hydrogenation to furfuryl alcohol (FOL) and 2-methylfuran (2-MF) in a fixed-bed reactor. Under proper reaction conditions, high yields of FOL (above 99 %) and 2-MF (94.5 %) could be obtained over the aurichalcite Cu/ZnO catalyst (AC-CZ), whereas the best yield of 2-MF was only 76.9 % (0.5 h?1) over the zincian malachite Cu/ZnO catalyst (ZM-CZ). The normalized productivity of 2-MF was 43.5 mol kgCu ?1 h?1 and 17.4 mol kgCu ?1 h?1 for AC-CZ and ZM-CZ, respectively (LHSV=1.5 h?1). The catalysts were characterized by XRD analysis, Raman spectra, CO IR spectroscopy, H2 temperature-programmed reduction, N2O titration, NH3 temperature-programmed desorption, and X-ray photoelectron spectroscopy. The far better performance of AC-CZ in furfural hydrogenation was ascribed to its higher dispersion of copper species, superior copper surface area, better surface acidity distribution, and stronger Cu0–ZnO synergy. In addition, the surface acidity of the catalysts seemed to have a higher influence on 2-MF production than the Cu surface area, but the optimal balance of both factors still needs to be investigated systematically.

RANEY Ni catalyzed transfer hydrogenation of levulinate esters to γ-valerolactone at room temperature

Yang, Zhen,Huang, Yao-Bing,Guo, Qing-Xiang,Fu, Yao

, p. 5328 - 5330 (2013)

A catalytic transfer hydrogenation process was developed for the production of γ-valerolactone (GVL) from ethyl levulinate (EL) and a H-donor at room temperature. Ethyl levulinate was almost quantitatively converted to γ-valerolactone. Further, a two step process for producing GVL from biomass derived platform molecules was also reported. The Royal Society of Chemistry 2013.

Ruthenium-Promoted Acceptorless and Oxidant-Free Lactone Synthesis in Aqueous Medium

Bhatia, Anita,Kannan, Muthukumar,Muthaiah, Senthilkumar

, p. 721 - 725 (2019)

Ruthenium-catalyzed formation of lactones from diols in aqueous medium has been demonstrated. 1,3,5-Triazaphosphaadamantane (PTA) included water-soluble ruthenium complexes [RuCl 2 (PPh 3)(2,6-Py-(CH 2 -PTA) 2 ]·2Br and [RuCl 2 (PPh 3) 2 (2-PyCH 2 PTA)]·Br in the presence of KOH were found to be efficient for the synthesis of lactones from diols. The reported synthetic protocol is green as it uses water as solvent, avoids the use of any hydrogen acceptor/oxidant, and produces hydrogen as the only side product. Mechanistic studies revealed that lactone formation involved aldehyde intermediate and followed dehydrogenative pathway.

Single pot conversion of furfuryl alcohol to levulinic esters and γ-valerolactone in the presence of sulfonic acid functionalized ILs and metal catalysts

Hengne, Amol M.,Kamble, Sumit B.,Rode, Chandrashekhar V.

, p. 2540 - 2547 (2013)

Ionic liquids functionalized with acidic anions, HSO4, ClSO 3H, PTSA, TFA (MIm), HSO4 and TFA (NMP) were found to efficiently (99% conversion) catalyze the alcoholysis of furfuryl alcohol (FAL) in the presence of methanol, ethanol, n-butanol and isopropyl alcohol (IPA) to the corresponding levulinic acid esters under mild temperature (90-130 °C) conditions. The extended alkyl chain length of [MIm] using 1,4-butane sultone enhanced the Bronsted acidity of [BMIm-SH][HSO4] catalyst resulting into the highest selectivity of >95% to Me-LA. An increase in both temperature and catalyst concentration increased the furfuryl alcohol conversion and selectivity to levulinate esters. In contrast, an increase in the substrate concentration from 5 to 15% caused a decrease in Me-LA selectivity due to accumulation of intermediate ethers of furfuryl alcohol. Using a combination of [BMIm-SH][HSO4] and 5% Ru/C catalyst, direct conversion of FAL to γ-valerolactone (GVL) is shown for the first time. A complete conversion of FAL with the highest selectivity of 68% to GVL could be achieved under optimum conditions while higher Ru loading enhanced the GVL selectivity to 94% in the hydrogenation step of this tandem approach. Our catalyst system could be efficiently recycled five times retaining the original activity and selectivity levels.

Effect of SiO2 support properties on the performance of Cu-SiO2 catalysts for the hydrogenation of levulinic acid to gamma valerolactone using formic acid as a hydrogen source

Lomate, Samadhan,Sultana, Asima,Fujitani, Tadahiro

, p. 3073 - 3083 (2017)

Vapor phase catalytic transfer hydrogenation of aqueous levulinic acid (LA) with formic acid (FA) as a hydrogen source was carried out over copper loaded on to several SiO2 supports having different physicochemical properties. The SiO2 supports and Cu-SiO2 catalysts with different support properties were characterized by XRD, TPR, XPS, NH3-TPD and UV-vis techniques to evaluate the copper species and its interaction with the support. The SiO2 support alone showed lower LA conversion and low selectivity to GVL whereas Cu-SiO2 catalysts were found to show high conversion and selectivity to the desired product with formic acid as the hydrogen source. The difference in the activities and product selectivity among different copper supported silica appears to be a complex function of acidity and the nature of copper species in the Cu-SiO2 catalysts. No direct correlation was observed between a specific catalyst property such as acidity and pore size, and the performance of the Cu-SiO2 catalysts. From the characterization, it appears that the species responsible for higher activity and selectivity to GVL are monomeric partially oxidized copper species in a strong interaction with the support in combination with a higher number of acid sites, both of which are present in Cu-SiO2-Q6. Cu-SiO2-Q6 showed the highest conversion and selectivity of 66 and 81%, respectively, under optimized conditions.

Direct catalytic transformation of biomass derivatives into biofuel component γ-valerolactone with magnetic nickel-zirconium nanoparticles

Li, Hu,Fang, Zhen,Yang, Song

, p. 135 - 142 (2016)

A series of mixed oxide nanoparticles were prepared by a coprecipitation method and characterized by many techniques. Nickel-zirconium oxide catalysts and their partially reduced magnetic counterparts were highly efficient in the direct transformation of biomass derivatives, including ethyl levulinate, fructose, glucose, cellobiose, and carboxymethyl cellulose, into γ-valerolactone (GVL) without the use of an external hydrogen source, producing a maximum GVL yield of 95.2 % at 200 °C for 3 h with hydrogen-reduced magnetic Zr5Ni5 nanoparticles (-1 h-1). Moreover, the magnetic Zr5Ni5 nanoparticles were conveniently recovered by means of a magnet for five cycles with almost constant activity. Attractive separation: Acid-base bifunctional NiZr nanocatalysts with strong magnetism show high activity and reusability in the transformation of biomass derivatives, including EL, fructose, glucose, cellobiose, and carboxymethyl cellulose, into γ-valerolactone (GVL) with 95.2 % yield and 98 % selectivity (see figure).

Selective hydrogenation of levulinic acid to γ-valerolactone using in situ generated ruthenium nanoparticles derived from Ru-NHC complexes

Tay, Boon Ying,Wang, Cun,Phua, Pim Huat,Stubbs, Ludger Paul,Huynh, Han Vinh

, p. 3558 - 3563 (2016)

Hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was studied by using mono- and bidentate p-cymene ruthenium(ii) N-heterocyclic carbene (NHC) complexes as catalyst precursors. In water, all complexes were found to be reduced in situ to form ruthenium nanoparticles (RuNPs) with a high hydrogenation activity. In organic solvents, complexes with monodentate NHC ligands also formed nanoparticles, while complexes with bidentate ligands gave rise to stable homogeneous catalysts with moderate hydrogenation activities.

High-yield production of levulinic acid from cellulose and its upgrading to γ-valerolactone

Ding, Daqian,Wang, Jianjian,Xi, Jinxu,Liu, Xiaohui,Lu, Guanzhong,Wang, Yanqin

, p. 3846 - 3853 (2014)

Direct catalytic conversion of cellulose to levulinic acid (LA) by niobium-based solid acids and further upgrading to γ-valerolactone (GVL) on a Ru/C catalyst were realized through sequential reactions in a reactor. Firstly, using aluminium-modified mesoporous niobium phosphate as a catalyst, cellulose can be directly converted to LA with as high as 52.9% yield in aqueous solution, even in the presence of the Ru/C catalyst. To the best of our knowledge, this is the best result over a heterogeneous catalyst so far. It was found that the type of acid (Lewis and Bronsted acids) and acid strength had an influence on the yield of LA; the doping of aluminium can enhance the strong Lewis and Bronsted acids, especially the strong Lewis acid, thus resulting in the increase of LA yield from cellulose as well as from glucose and HMF. Such an enhancement by a Lewis acid on LA yield from HMF was further confirmed by adding lanthanum trifluoroacetate [(TfO)3La], a strong Lewis acid, in the catalytic system (HCl, (TfO)3H, niobium phosphate), indicating that a suitable ratio of Lewis/Bronsted acid is important for higher selectivity to LA from HMF, as well as from cellulose. Then, after replacing N2 with H2, the generated LA in the reaction mixture can be directly converted to γ-valerolactone through hydrogenation over the Ru/C catalyst without further separation of LA. This journal is the Partner Organisations 2014.

-

Austin,A.T.,Howard,J.

, p. 3284 - 3289 (1961)

Simple and efficient conversion of cellulose to γ-valerolactone through an integrated alcoholysis/transfer hydrogenation system using Ru and aluminium sulfate catalysts

Huang, Yao-Bing,Yang, Tao,Luo, Yu-Jia,Liu, An-Feng,Zhou, Yi-Han,Pan, Hui,Wang, Fei

, p. 6252 - 6262 (2018)

The direct conversion of cellulose to specific chemicals represents an important but challenging area that attracts much attention. In this study, we report, for the first time, a one-step conversion of cellulose to γ-valerolactone (GVL), a platform molecule with multiple applications, by integrating alcoholysis and transfer hydrogenation systems over mixed metal salt and Ru catalysts without external hydrogenation. A maximum GVL yield of 51.2% was obtained at 180 °C for 70 min reaction time with microwave heating. The metal salt effectively catalyzed cellulose alcoholysis to generate levulinate in isopropanol, which was also the hydrogen donor for the subsequent catalytic transfer hydrogenation of levulinate to GVL over the Ru/ZrO2 catalyst. It was found that the types of metal center and support material had a significant influence on the reactivity of the catalyst for the catalytic transfer hydrogenation (CTH) reaction, i.e., concerning the existence of sulfuric acid species and water in the reaction system. Microwave heating was demonstrated to be an effective method for cellulose-to-GVL conversion as compared to conventional oil heating, through drastically reducing the reaction time and avoiding decomposition of the reagents. The catalysts were successfully recycled and reused with high reactivity. Finally, the system was also applied to the synthesis of GVL from real biomass, demonstrating the high applicability and potential of the catalytic system for industrial production.

In situ generated Ni(0)@boehmite from NiAl-LDH: An efficient catalyst for selective hydrogenation of biomass derived levulinic acid to Γ-valerolactone

Gundekari, Sreedhar,Srinivasan, Kannan

, p. 40 - 43 (2017)

We report in situ generation of Ni(0)@boehmite from NiAl-layered double hydroxide (LDH) under reaction conditions which showed superior catalytic activity in the hydrogenation of levulinic acid (LA) to γ-valerolactone (Gvl) with quantitative yield in aqueous medium. Formation of Ni(0)@boehmite in course of the reaction was confirmed by PXRD, TEM, TGA and FT-IR. This catalyst shows superior conversion compared to a series of simple Ni based homogeneous as well as heterogeneous catalysts. The Ni(0)@boehmite catalyst is recyclable, and active even at higher concentrations of LA (25 wt%).

-

Nikishin et al.

, (1976)

Transfer hydrogenation of ethyl levulinate to γ-valerolactone catalyzed by iron complexes

Dai, Nan,Shang, Rui,Fu, Mingchen,Fu, Yao

, p. 405 - 408 (2015)

Conversion of biomass-derived ethyl levulinate to γ-valerolactone is realized by using homogeneous iron-catalyzed transfer hydrogenation (CTH). By utilizing Casey's catalyst and cheap isopropanol as hydrogen source, γ-valerolactone can be generated in 95% yield. Addition of catalytic amount of base is important to achieve good yield.

Porous Organic Zirconium Phosphonate as Efficient Catalysts for the Catalytic Transfer Hydrogenation of Ethyl Levulinate to γ-Valerolactone without External Hydrogen

Wang, Jianjia,Wang, Ruiying,Zi, Huimin,Wang, Haijun,Xia, Yongmei,Liu, Xiang

, p. 750 - 759 (2018)

Organic hybrid zirconium phosphonate materials (ZrATMP, ZrEDTMPS, ZrDTPMPA, and ZrHEDP) were synthesized through reaction of organic phosphonic acid sodium salt and ZrOCl2 in water, which exhibited high catalytic activity on the conversion of ethyl levulinate (EL) to γ-valerolactone (GVL) in the presence of isopropanol. The obtained catalysts were characterized by FT-IR, TGA, XRD, BET, XPS, ICP-AES, SEM, TEM, NH3-TPD, and CO2-TPD. The results demonstrate that the number of acid sites and basic sites between the layers of the catalysts play a very important role in promoting the conversion of EL to GVL and that the functional groups that exist in phosphates could regulate the number of acid and basic sites. Meanwhile, the catalysts could be easily separated from the reaction system and reused at least five times without any obvious decrease in activity or selectivity.

Water-promoted hydrogenation of levulinic acid to γ-valerolactone on supported ruthenium catalyst

Tan, Jingjing,Cui, Jinglei,Deng, Tiansheng,Cui, Xiaojing,Ding, Guoqiang,Zhu, Yulei,Li, Yongwang

, p. 508 - 512 (2015)

A highly efficient and green process for the hydrogenation of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) has been developed. GVL was obtained in a yield of 99.9mol-% with a turnover frequency as high as 7676h-1 in aqueous medium by using a Ru/TiO2 catalyst under mild reaction conditions (70-°C). The strong interaction between Ru and TiO2 facilitated both the dispersion of Ru nanoparticles and the stability of the catalyst. In addition, as solvent, water participated in the hydrogenation of LA, which was confirmed by an isotope- labeling experiment with D (D2O). Specifically, the H atom(s) in water took part in the hydrogenation of the C=O group of LA, which promoted the catalytic activity and GVL yield remarkably. Water of catalysis: Water promotes the hydrogenation of levulinic acid to γ-valerolactone on a supported ruthenium catalyst with a γ-valerolactone yield of 99.9mol-% at 70-°C.

γ-valerolactone ring-opening and decarboxylation over SiO 2/Al2O3 in the presence of water

Bond, Jesse Q.,Martin Alonso, David,West, Ryan M.,Dumesic, James A.

, p. 16291 - 16298 (2010)

γ-Valerolactone (GVL) has been identified as a promising, sustainable platform molecule that can be produced from lignocellulosic biomass. The chemical flexibility of GVL has allowed the development of a variety of processes to prepare renewable fuels and chemicals. In the present work involving a combination of computational and experimental studies, we explore the factors governing the ring-opening of GVL to produce pentenoic acid isomers, as well as their subsequent decarboxylation over acid catalysts or hydrogenation over metal catalysts. The ring-opening of GVL has shown to be a reversible reaction, while both the decarboxylation and hydrogenation reactions are irreversible and kinetically controlled under the conditions studied (temperatures from about 500 to 650 K). The most significant contributor to lactone reactivity toward ring-opening is the size of the ring, with γ- lactones being more stable and less readily opened than δ- and ε-analogues. We have observed that the presence of either a C=C double bond or a lactone (which opens to form a C=C double bond) is necessary for appreciable rates of decarboxylation to occur. Olefinic acids exhibit higher rates of decarboxylation than the corresponding lactones, suggesting that the decarboxylation of alkene acids provides a lower energy pathway to olefin production than the direct decarboxylation of lactones. We observe lower rates of decarboxylation as the chain length of alkene acids increases; however, acrylic acid (3-carbon atoms) does not undergo decarboxylation at the conditions tested. These observations suggest that particular double bond configurations yield the highest rates of decarboxylation. Specifically, we suggest that the formation of a secondary carbenium ion in the β position leads to high reactivity for decarboxylation. Such an intermediate can be formed from 2- or 3-alkene acids which have at least four carbon atoms.

MPV reduction of ethyl levulinate to γ-valerolactone by the biomass-derived chitosan-supported Zr catalyst

Wang, Tianlong,Xu, Hai,He, Jianghua,Zhang, Yuetao

, p. 14686 - 14694 (2020)

Herein, we used the biopolymer chitosan as a support to synthesize a biomass-derived catalyst (chitosan-Zr) to achieve GVL in 97% yield from MPV reduction of EL, by using isopropanol as a hydrogen source. The catalyst system is also applicable to the reduction of various organic compounds with carbonyl groups. Additionally, we have proposed a possible mechanism for this reaction based on the systematic investigation towards the reaction. Moreover, the recycle and reuse experiment showed that this chitosan-Zr exhibited long-life catalytic performance and can maintain its high catalytic performance even after five runs of recycle and reuse experiments.

Ruthenium p-cymene complexes with α-diimine ligands as catalytic precursors for the transfer hydrogenation of ethyl levulinate to γ-valerolactone

Biancalana, Lorenzo,Fulignati, Sara,Antonetti, Claudia,Zacchini, Stefano,Provinciali, Giacomo,Pampaloni, Guido,Raspolli Galletti, Anna Maria,Marchetti, Fabio

, p. 17574 - 17586 (2018)

The ruthenium compounds [(η6-p-cymene)RuCl{κ2N-(HCNR)2}]NO3 (R = 4-C6H4Me, [1]NO3; 4-C6H4OH, [2]NO3; C6H11═Cy, [3]NO3; 4-C6H10OH, [4]NO3; tBu, [5]NO3) were prepared in high yields from [(p-cymene)RuCl2]2, AgNO3 and the appropriate α-diimine. Compounds [2]PF6 and [4]PF6 were obtained by a straightforward reaction of [(η6-p-cymene)RuCl(MeCN)0.66]PF6, [6]PF6, with α-diimine, whereas [4]BPh4 was obtained by metathesis between [4]NO3 and NaBPh4. All the ruthenium products were characterized by analytical methods, IR, NMR and UV-Vis spectroscopy; in addition, the structure of [1]NO3 was ascertained by an X-ray diffraction study. Compounds [1-4]NO3, [4]PF6 and [4]BPh4 were investigated as catalytic precursors in the transfer hydrogenation reaction of ethyl levulinate to γ-valerolactone in isopropanol solution under microwave irradiation. [4]BPh4 was revealed to be the best catalytic precursor, affording γ-valerolactone in 62% yield under optimized experimental conditions.

Conversion of levulinic acid and formic acid into γ-valerolactone over heterogeneous catalysts

Deng, Li,Zhao, Yan,Li, Jiang,Fu, Yao,Liao, Bing,Guo, Qing-Xiang

, p. 1172 - 1175 (2010)

LA Lacers: The conversion of levulinic acid (LA) to γ-valerolactone is catalyzed by heterogeneous catalysts without using the external H2. Ru-P/SiO2 has been demonstrated to be a bifunctional catalyst giving a yield of 96 %. Through a two-step process, excellent performance can be achieved in eight recycling runs. Moreover, no hazardous 2-Me-THF is produced during the process. Copyright

An efficient and reusable bimetallic Ni3Fe NPs@C catalyst for selective hydrogenation of biomass-derived levulinic acid to Γ-valerolactone

Wang, Haojie,Chen, Chun,Zhang, Haimin,Wang, Guozhong,Zhao, Huijun

, p. 1599 - 1607 (2018)

Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity, selectivity and stability in catalytical conversion. Herein, we report a facile one-pot carbothermal route to in-situ controllable synthesize heterogeneous bimetallic Ni3Fe NPs@C nanocatalyst. The X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and N2 adsorption-description results reveal that the Ni3Fe alloy nanoparticles are evenly embedded in carbon matrix. The as-prepared Ni3Fe NPs@C catalyst shows excellent selective hydrogenation catalytic performance toward the conversion of levulinic acid (LA) to γ-valerolactone (GVL) via both direct hydrogenation (DH) and transfer hydrogenation (TH). In DH of LA, the bimetallic catalyst achieved a 93.8% LA conversion efficiency with a 95.5% GVL selectivity and 38.2 mmol g?1 h?1 GVL productivity (under 130 °C, 2MPa H2 within 2 h), which are 6 and 40 times in comparison with monometallic Ni NPs@C and Fe NPs@C catalysts, respectively. In addition, the identical catalyst displayed a full conversion of LA with almost 100% GVL selectivity and 167.1 mmol g?1 h?1 GVL productivity at 180 °C within 0.5 h in TH of LA. Under optimal reaction conditions, the DH and TH catalytic performance of 500-Ni3Fe NPs@C(3:1) catalyst for converting LA to GVL is comparable to the state-of-the-art noble-based catalysts. The demonstrated capability of bimetallic catalyst design approach to introduce dual-catalytic functionality for DH and TH reactions could be adoptable for other catalysis processes.

Vapor-phase hydrogenation of levulinic acid to Γ-valerolactone over Cu-Ni bimetallic catalysts

Yoshida, Rei,Sun, Daolai,Yamada, Yasuhiro,Sato, Satoshi,Hutchings, Graham J.

, p. 79 - 82 (2017)

Vapor-phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was performed over SiO2-supported Cu-Ni bimetallic catalysts with different Cu/Ni weight ratios under ambient H2 pressure. Characterization of the catalysts was carried out using powder X-ray diffraction, temperature-programmed reduction and thermogravimetric analysis. In contrast to the monometallic catalysts i.e. Ni/SiO2 and Cu/SiO2, the Cu-Ni/SiO2 bimetallic catalyst with a Cu/Ni weight ratio of 6/14 exhibits an excellent catalytic activity, and gave a GVL yield higher than 99% with a productivity of 1.64kgGVLkgcat.?1h?1 at 250°C and at a high WHSV of 1.65h?1 for 50h.

Transfer hydrogenation of methyl levulinate into gamma-valerolactone, 1,4-pentanediol, and 1-pentanol over Cu-ZrO2 catalyst under solvothermal conditions

Yang, Yongquan,Xu, Xingliang,Zou, Weijian,Yue, Huijuan,Tian, Ge,Feng, Shouhua

, p. 50 - 53 (2016)

Diverse products were obtained from transfer hydrogenation of methyl levulinate (ML) by adjusting different factors under solvothermal conditions. Excellent yields of gamma-valerolactone (GVL, 75%), 1,4-pentanediol (1,4-PDO, 39%), and 1-pentanol (1-PAO, 13.8%) could be obtained using zirconium-supported copper catalyst calcined at 550 °C and under optimal conditions.

Boosting levulinic acid hydrogenation to value-added 1,4-pentanediol using microwave-assisted gold catalysis

Bucciol,Tabasso,Grillo,Menegazzo,Signoretto,Manzoli,Cravotto

, p. 267 - 277 (2019)

Microwave (MW) -assisted levulinic acid (LA) hydrogenation has been performed over two gold catalysts (commercial 1 wt% Au/TiO2 by AUROlite and 2.5 wt% Au/ZrO2, prepared using deposition-precipitation). MW-assisted LA hydrogenation was carried out in water and in solvent-free conditions via (i) H-transfer and (ii) molecular H2. Au/TiO2 promoted complete LA conversion and the further reduction of the produced GVL to 1,4-pentanediol (1,4-PDO) in the presence of 50 bar H2 at 150 °C (4-hour reaction). Interestingly, selectivity to 1,4-PDO was complete at 200 °C. Extended characterisation highlighted the cooperative role played by the gold nanoparticles and the support, onto which activated hydrogen atoms spillover to react with LA. This results in the remarkable activity of Au/TiO2. Both catalysts showed structural and morphological stability under reaction conditions. It was possible to reactivate the Au/TiO2 catalyst by MW-assisted oxidation, paving the way for catalyst recycling directly inside the MW reactor.

Aqueous Hydrogenation of Levulinic Acid to 1,4-Pentanediol over Mo-Modified Ru/Activated Carbon Catalyst

Cui, Jinglei,Tan, Jingjing,Zhu, Yulei,Cheng, Fangqin

, p. 1316 - 1320 (2018)

A highly efficient and green process was developed for direct conversion of levulinic acid into 1,4-pentanediol over Mo-modified Ru/activated carbon (AC) catalyst in a continuous fixed-bed reactor. The Ru–MoOx/AC catalyst was found to be efficient for the aqueous-phase hydrogenation of levulinic acid to 1,4-pentanediol, whereby a high yield (96.7 mol %) of 1,4-pentanediol was obtained under mild reaction conditions (70 °C, 4 MPa H2).

Selective Levulinic Acid Hydrogenation in the Presence of Hybrid Dendrimer-Based Catalysts. Part I: Monometallic

Maximov, Anton L.,Zolotukhina, Anna V.,Mamedli, Adila A.,Kulikov, Leonid A.,Karakhanov, Edward A.

, p. 222 - 233 (2018)

Hybrid Ru-containing catalysts, based on poly(propylene imine) (PPI) dendrimers, immobilized in silica pores, were synthesized and characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The synthesized Ru catalysts proved their efficiency in the selective hydrogenation of levulinic acid and its esters at 80 °C, 30 bar of H2, and 50 % volume substrate concentration in water. Quantitative yields of γ-valerolactone were obtained for both micro- and mesoporous Ru catalysts within 2 h with catalytic activity as high as 1610 h?1. The reaction rate and selectivity on γ-valerolactone were found to depend on several factors such as carrier structure, temperature, presence of water, and substrate/Ru ratio. The novelty of these hybrid materials is the presence of both weak acid (SiO2) and organic base centers (dendrimer amino groups), enhancing the dispersion of Ru nanoparticles. The presence of amino groups in the catalyst stabilizes the Ru nanoparticles during the synthesis and promotes the adsorption of levulinic acid on the surface of Ru nanoparticles during the reaction. Synthesized hybrid Ru catalysts can be reused several times without significant loss of activity.

Ruthenium and Iridium Dipyridylamine Catalysts for the Efficient Synthesis of γ-Valerolactone by Transfer Hydrogenation of Levulinic Acid

Wang, Shengdong,Dorcet, Vincent,Roisnel, Thierry,Bruneau, Christian,Fischmeister, Cédric

, p. 708 - 713 (2017)

The selective and efficient transfer hydrogenation of levulinic acid into γ-valerolactone was performed with new ruthenium and iridium catalysts bearing dipyridylamine (dpa) ligands. Reactions were performed in the presence of formic acid and triethylamine using catalyst loading as low as 0.05 mol % with a ruthenium complex (turnover number = 1980). Recyclability of a ruthenium catalyst was demonstrated by running 6 consecutive reactions in almost quantitative yields.

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

Metzker, Gustavo,Burtoloso, Antonio C. B.

, p. 14199 - 14202 (2015)

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.

Efficient, solvent-free hydrogenation of α-angelica lactone catalysed by Ru/C at atmospheric pressure and room temperature

Al-Shaal, Mohammad G.,Hausoul, Peter J. C.,Palkovits, Regina

, p. 10206 - 10209 (2014)

The hydrogenation of α-angelica lactone was investigated over Ru/C. A mild protocol was developed, which resulted in full conversion and 96% selectivity toward γ-valerolactone. The reaction network was investigated and α-angelica lactone was employed in the one-pot conversion into 2-methyltetrahydrofuran, demonstrating its superiority as a platform molecule in potential biorefinery schemes. This journal is the Partner Organisations 2014.

Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium-based metal-organic frameworks

Valekar, Anil H.,Cho, Kyung-Ho,Chitale, Sachin K.,Hong, Do-Young,Cha, Ga-Young,Lee, U-Hwang,Hwang, Dong Won,Serre, Christian,Chang, Jong-San,Hwang, Young Kyu

, p. 4542 - 4552 (2016)

A series of highly crystalline, porous, zirconium-based metal-organic frameworks (Zr-MOFs) with different ligand functionalities and porosities were applied for catalytic transfer hydrogenation of ethyl levulinate (EL) to form γ-valerolactone (GVL), using isopropanol as a hydrogen donor. The roles of the ligand functionality and the metal center of the Zr-MOFs were identified and reaction parameters optimized, for selective production of GVL. The maximum yield of GVL (up to 92.7%) was achieved in 2 h at 200 °C with UiO-66(Zr). Interestingly, zirconium trimesate (MOF-808) emerged as the most suitable candidate, with the highest GVL formation rate (94.4 μmol g-1 min-1) among the catalysts tested at 130 °C. It was also found to be effective in conversion of EL to GVL in an open system using the solvent refluxing method. Both the catalysts (UiO-66(Zr) and MOF-808) were recycled at least five times under their specified reaction conditions without a notable change in catalytic activity and product selectivity. Fresh and recycled catalysts were characterized in detail using X-ray powder diffraction (XRD), N2 adsorption-desorption, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) in order to understand the stability and structural changes that occurred in the catalysts. Finally, a plausible reaction mechanism was presented on the basis of active sites present in catalysts confirmed by characterization results.

-

Taylor,Close

, (1925)

Production of gamma-valerolactone from sugarcane bagasse over TiO2-supported platinum and acid-activated bentonite as a co-catalyst

Putro, Jindrayani N.,Kurniawan, Alfin,Soetaredjo, Felycia E.,Lin, Shi-Yow,Ju, Yi-Hsu,Ismadji, Suryadi

, p. 41285 - 41299 (2015)

Nowadays, biomass utilization has become the center of attention for researchers worldwide and is driven by the depletion of global petroleum supplies for the production of energy and valuable chemicals while easing the atmospheric CO2 burden. We propose here a green strategy for transforming sugarcane bagasse into gamma-valerolactone (GVL), an attractive platform molecule that can be further converted into a variety of chemical derivatives for wide use in industrial applications. Our recent strategy involves the solid acid-catalyzed hydrothermal conversion of cellulose and hemicellulose derived from biomass to give an aqueous solution comprising levulinic acid (LA), followed by catalytic hydrogenation of LA to GVL. Native and acid-activated bentonites were used as solid acid catalysts to promote hydrothermal conversion of cellulose and hemicellulose. The maximum achievable yield of LA was 159.17 mg per gram of oven-dried biomass for 60 min reaction at 473.2 K in the presence of a 2% acid-activated bentonite catalyst. Catalytic hydrogenation reactions of LA to GVL over 1% Pt@TiO2 and acid-activated bentonite as a co-catalyst were performed at temperatures of 393.2-473.2 K and residence times of 120-360 min. The combined solid catalyst gave an attractive performance with respect to LA conversion (～100%) and GVL selectivity (95%) under milder reaction conditions in comparison to 1% Pt@TiO2 without an acid co-catalyst. The spent catalyst could be reused for five consecutive hydrogenation cycles with a marginal decrease in the catalytic activity and GVL selectivity. Coke formation was believed to be the main cause of catalyst poisoning and calcination of the spent catalyst under a stream of pure oxygen at 723.2 K was applied for removing coke deposits from the active catalyst sites, thus restoring the catalytic performance.

Acid-Functionalized Mesoporous Carbon: An Efficient Support for Ruthenium-Catalyzed γ-Valerolactone Production

Villa, Alberto,Schiavoni, Marco,Chan-Thaw, Carine E.,Fulvio, Pasquale F.,Mayes, Richard T.,Dai, Sheng,More, Karren L.,Veith, Gabriel M.,Prati, Laura

, p. 2520 - 2528 (2015)

The hydrogenation of levulinic acid has been studied using Ru supported on ordered mesoporous carbons (OMCs) prepared by soft-templating. P- and S-containing acid groups were introduced by postsynthetic functionalization before the addition of 1 Ru by incipient wetness impregnation. These functionalities and the reaction conditions mediate the activity and selectivity of the levulinic acid hydrogenation. The presence of S-containing groups (Ru/OMC-S and Ru/OMC-P/S) deactivates the Ru catalysts strongly, whereas the presence of P-containing groups (Ru/OMC-P) enhances the activity compared to that of pristine Ru/OMC. Under mild conditions (70C and 7bar H2) the catalyst shows high selectivity to γ-valerolactone (GVL; >95) and high stability on recycling. However, under more severe conditions (200C and pH2=40bar) Ru/OMC-P is particularly able to promote GVL ring-opening and the consecutive hydrogenation to pentanoic acid.

Selective hydrogenation of biomass derived substrates using ionic liquid-stabilized ruthenium nanoparticles

Julis, Jennifer,Hoelscher, Markus,Leitner, Walter

, p. 1634 - 1639 (2010)

Ionic liquid-stabilized ruthenium nanoparticles with an average size between 2-3 nm are very active catalysts for the hydrogenation of biomass derived substrates. Their catalytic performance complements that of classic homogeneous and heterogeneous ruthenium catalysts.

The transfer hydrogenation of high concentration levulinic acid to γ-valerolactone catalyzed by glucose phosphate carbamide zirconium

Chen, Shuainan,Fu, Zaihui,Jiang, Dabo,Liu, Yachun,Wan, Feifei,Yang, Bo,Zhang, Chao,Zhang, Huanhuan,Zhang, Qiao,Zhu, Jiekun

, p. 3428 - 3438 (2021)

Zr-Based catalysts have been extensively applied in Meerwein-Ponndorf-Verley type catalytic transfer hydrogenation (CTH) reactions, but they are easily deactivated in the CTH conversion of high concentrations of levulinic acid (LA) to γ-valerolactone (γ-GVL). This work discloses that by using cheap glucose and ZrCl4as two main raw materials, glucose phosphate carbamide zirconium (GluPC-Zr) is easily synthesized at large scale and low costviaa simple two-step conversion. The constructed GluPC-Zr has enhanced Lewis acid-base properties and good porosity, thus exhibiting outstanding activity for the CTH reactions of LA or its esters with isopropanol (IPA), providing 95-98% γ-GVL yields. Because of the excellent esterification performance of the introduced acidic phosphate groups, GluPC-Zr also works well at high LA concentrations, achieving a much higher turnover frequency (TOF, 8.2 mmol γ-GVL per g catalyst per h) than previously reported Zr-based catalysts (TOF, 0.2-2.4). And it shows excellent reusability in the reaction of LA with IPA, still providingca.95% γ-GVL yield after the seventh cycle run. This work provides a preferential esterification strategy for LA to hamper catalyst deactivation, which is of special significance for the large-scale production of γ-GVL from biomass-derived LA and a low-cost GluPC-Zr catalyst.

Ru-decorated N-doped carbon nanoflakes for selective hydrogenation of levulinic acid to γ-valerolactone and quinoline to tetrahydroquinoline with HCOOH in water

Chauhan, Arzoo,Kar, Ashish Kumar,Srivastava, Rajendra

, (2022/03/27)

The effective dissociation of biomass-derived formic acid, as a sustainable hydrogen source, in water is explored for the hydrogenation of levulinic acid (LA) and quinoline. Ru decorated carbon nanoflakes prepared by carboreduction (in Ar/H2 atmosphere) of Ru containing N-doped carbon were used as catalysts. The successful formation of Ru-decorated N-doped carbons was confirmed by numerous spectroscopic tools. The catalyst exhibited outstanding activity and selectivity for the hydrogenation of LA and quinoline using formic acid as a hydrogen donor in water under mild conditions. The catalyst afforded 99.8% LA conversion and 100% selectivity for γ-valerolactone (GVL), whereas 99.8% quinoline conversion and 93% selectivity for 1,2,3,4-tetrahydroquinoline (THQ) were obtained. Recycling experiments suggested that the catalyst was stable even after the 5 cycles. Various controlled experiments and characterizations were conducted to demonstrate the structure-activity relations and suggest plausible reaction mechanisms for the hydrogenation of LA and quinoline. The exploration of formic acid as a sustainable H2 source and the development of metal decorated N-doped carbons for hydrogenation of LA and quinoline will be fascinating to catalysis researchers and industrialists.

Sustainable metal-lignosulfonate catalyst for efficient catalytic transfer hydrogenation of levulinic acid to γ-valerolactone

Liao, Peizhen,Liu, Qiying,Lu, Luying,Ma, Longlong,Wang, Chenguang,Wu, Jingcheng,Xu, Tianyi,Zhang, Xinghua,Zhu, Yuting

, (2022/03/15)

Production of γ-valerolactone (GVL) from biomass-derived platform levulinic acid (LA) via catalytic transfer hydrogenation (CTH) over renewable lignosulfonate-derived catalyst is reported herein. Lignosulfonate-derived catalysts were prepared by assembled Zr-metals with sodium lignosulfonate (LigS) derived from the industry paper waste. The resulting Zr-LigS catalyst exhibited excellent catalytic performance in 92.5% GVL yield under mild conditions. With the combination of detail catalyst characterizations, catalytic performance of the Zr-LigS catalyst, in-situ ATR-FTIR and poisoning experiments, the hydrothermal treatment of Zr4+ and LigS resulted in the formation of basic sites, which contributed significantly to the CTH reaction. Kinetic experiments demonstrated that the activation energy was as low as 41.9 kJ/mol. Furthermore, isotopic labeling experiments suggested that the β-H in isopropanol is transferred to the C[dbnd]O bond of LA by the formation of six-membered intermediates on the basic sites, which is the rate-determining step.

Photo-Thermo-Dual Catalysis of Levulinic Acid and Levulinate Ester to γ-Valerolactone

Bunrit, Anon,Butburee, Teera,Liu, Meijiang,Huang, Zhipeng,Meeporn, Keerati,Phawa, Chaiyasit,Zhang, Jian,Kuboon, Sanchai,Liu, Huifang,Faungnawakij, Kajornsak,Wang, Feng

, p. 1677 - 1685 (2022/01/28)

Herein, we developed photo-Thermo-dual catalytic strategies for the production of γ-valerolactone (GVL) from levulinic acid (LA) and its ester using platinum-loaded TiO2 as a dual-functional catalyst. Both catalytic systems were evaluated under mild reaction conditions. In the photocatalysis system, a base plays crucial roles in the conversion of LA and EL to GVL. The control experiments reveal that plausible mechanistic pathways of both systems proceed via the hydrogenation of the ketone group of LA to the corresponding alcohol as a major intermediate followed by a subsequent cyclization step to GVL. This dual-functional catalyst provides alternative strategies for the conversion of LA and its ester into GVL, which could pave the way for biomass utilization in a more effective and practical manner.

Renewable bio-based routes to γ-valerolactone in the presence of hafnium nanocrystalline or hierarchical microcrystalline zeotype catalysts

Antunes, Margarida M.,Fernandes, Auguste,Pillinger, Martyn,Ribeiro, Filipa,Silva, Andreia F.,Valente, Anabela A.

, p. 56 - 71 (2022/01/19)

Different renewable bio-based routes leading to the versatile bioproduct γ-valerolactone (GVL) were studied in integrated fashions, starting from furfural (Fur), α-angelica lactone (AnL) and levulinic acid (LA), in the presence of multifunctional hafnium-