Optimizing levulinic acid from cellulose catalyzed by HY-zeolite immobilized ionic liquid (HY-IL) using response surface methodology (original) (raw)
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Industrial Crops and Products, 2019
This work is a continuation and extension of previously published study on the conversions of oil palm empty fruit bunch and mesocarp fiber biomass to levulinic acid and ethyl levulinate via an eco-friendly indium trichloride-1-methylimidazolium hydrogen sulfate (Tiong et al., 2017). Herein, a response surface methodology based on a central composite design method was used to optimise the operating conditions of the conversions. The conversions consisted of a two-sequential steps, that is, depolymerisation to levulinic acid, followed by esterification to ethyl levulinate. The optimum depolymerisation occurred at 177°C in 4.8 h with 0.15 mmol indium trichloride in ionic liquids-to-biomass ratio of 6.6:1 (w/w) and 22.7% (w/w) of water, whilst esterification was at 105°C in 12.2 h with ethanol to substrate ratio of 7.2:1 (v/v). The maximum levulinic acid yields of 17.7% and 18.4%, and the subsequent ethyl levulinate yields of 18.7% and 20.1% were achieved from the conversions of oil palm empty fruit bunch and mesocarp fiber biomass, respectively. LA and EL efficiencies were > 63% for both biomass conversions. The ionic liquids could be recycled up to three consecutive runs with a minimal loss of < 25% of ethyl levulinate yield. This study highlighted the potential of proposed ionic liquids for biorefinery processing of renewable feedstock in a greener and sustainable approach.
Efficient conversion of lignocellulosic biomass to levulinic acid using acidic ionic liquids
Carbohydrate polymers, 2018
In the present research work, dicationic ionic liquids, containing 1,4-bis(3-methylimidazolium-1-yl) butane ([C4(Mim)2]) cation with counter anions [(2HSO4)(H2SO4)0], [(2HSO4)(H2SO4)2] and [(2HSO4)(H2SO4)4] were synthesised. ILs structures were confirmed using 1H NMR spectroscopy. Thermal stability, Hammett acidity, density and viscosity of ILs were determined. Various types of lignocellulosic biomass such as rubber wood, palm oil frond, bamboo and rice husk were converted into levulinic acid (LA). Among the synthesized ionic liquids, [C4(Mim)2][(2HSO4)(H2SO4)4] showed higher % yield of LA up to 47.52 from bamboo biomass at 110°C for 60min, which is the better yield at low temperature and short time compared to previous reports. Surface morphology, surface functional groups and thermal stability of bamboo before and after conversion into LA were studied using SEM, FTIR and TGA analysis, respectively. This one-pot production of LA from agro-waste will open new opportunity for the con...
Renewable Energy, 2019
This study investigated the kinetic and thermodynamic studies of oil palm mesocarp fiber cellulose conversion to levulinic acid and upgrading to ethyl levulinate via an eco-friendly Bronsted-Lewis acidic ionic liquid, that is, indium trichloride-1-methylimidazolium hydrogen sulfate (InCl 3-[HMIM][HSO 4 ]). The conversion reactions, i.e. cellulose depolymerisation to levulinic acid, and the subsequent upgrading esterification to ethyl levulinate, were conducted at a temperature range of 135e175 C and 65e105 C, respectively. Pseudo-homogeneous kinetic models were adapted to evaluate the best reaction order. The results indicate that both reactions followed the pseudo-homogeneous first-order kinetic models. Relative low activation energies of 56.5 kJ mol À1 and 28.1 kJ mol À1 were obtained for the cellulose depolymerisation, and the subsequent upgrading esterification, respectively, implying a higher energy and catalytic efficiency system. The first-order rate constants were calculated to analyse the thermodynamic activation parameters. The Gibbs free energy of activation for the cellulose depolymerisation, and the subsequent upgrading esterification were þ115.5 kJ mol À1 and þ90.3 kJ mol À1 respectively, which were relatively lower than the previous works that used various type of catalysts. These kinetic and thermodynamic parameters provide insights to the oil palm mesocarp fiber cellulose conversion to levulinic acid and ethyl levulinate via the proposed eco-friendly ionic liquids.
BioEnergy Research, 2014
Cellulose can be converted to a mixture of ethyl levulinate and levulinic acid by heating with a Brönsted acidic ionic liquid catalyst in aqueous ethanol medium in a one-pot operation under mild conditions. The highest ethyl levulinate yield of 19.0 % was obtained for a reaction carried out at 170°C for 12 h in water-ethanol medium containing 38.5 % water and using 1-(1-propylsulfonic)-3methylimidazolium chloride as the catalyst. The levulinic acid yields continue to increase with increasing water content up to about 54 % water in aqueous ethanol for reactions carried out at 150°C for 48 h, and the highest levulinic acid yield was 23.7 %. The acidic, ionic liquid catalyst used can be efficiently recovered (96 %) from the water phase with negligible contamination, and the stability of the catalyst was confirmed by comparison of the 1 H NMR spectrum of the recovered catalyst with fresh catalyst.
Catalytic Conversion of Glucose to Levulinic Acid Using Zeolite Immobilized Ionic Liquid as Catalyst
2016
Concerns towards diminishing fossil resources compel the chemical industry to explore alternatives for basic chemical productions. Carbohydrates derived biomass are promising alternatives for sustainable supply of fuels and valuable chemicals due to their abundant and relatively inexpensive properties. Carbohydrate such as glucose is a compound from which various bio-based chemicals can be derived. Among those chemicals, levulinic acid (LA) has received significant attention as platform chemicals for synthesizing a broad range of bio-based fuels. The conversion of carbohydrates to LA have been conducted in water in the presence of various catalysts, including homogeneous and heterogeneous catalysts. In this study, a new zeolite immobilized ionic liquid (HY-IL) catalyst has been explored for catalytic conversion of glucose to LA. The catalyst was prepared by immobilizing an acidic ionic liquid; 1,4 methylsulfonic acid imidazolium tetrachloroaluminate ([MSIM][AlCl4]) into HY zeolite w...
Conversion of Biomass and Its Derivatives to Levulinic Acid and Levulinate Esters via Ionic Liquids
Industrial & Engineering Chemistry Research, 2018
Biomass has emerged as an abundant and relatively low cost carbon resource alternative to 2 fossil fuel resources in the sustainable production of specialty chemicals and biofuel. Levulinic 3 acid is an attractive platform chemical. Upgrading of levulinic acid produces levulinate esters, 4 which serve as a transportation fuel and fuel additive. The present review focuses on the 5 development of sustainable conversion of biomass into levulinic acid and levulinate esters via 6 ionic liquids dual solvent-catalysts. The synthesis routes of levulinic acid and levulinate esters, and 7 the corresponding ionic liquids are introduced. The biomass pretreament, as well as the 8 conversions of lignocellulosic biomass and their derivatives into levulinic acid and levulinate 9 esters, are detailed in relation to the catalytic role, properties and performance of acidic ionic 10 liquids. Finally, the operating conditions affecting the ionic liquids catalytic conversions are 11 discussed as part of a comprehensive review of this topic.
Conversion of Oil Palm Biomass to Ethyl Levulinate via Ionic Liquids
Chemical Engineering Transactions, 2017
Biomass is a potential renewable feedstock that can be used as a replacement for fossil resources. A variety of high end chemicals have been produced from biomass including ethyl levulinate, which is a viable biofuel for diesel engines. In this study, the capability of three types of imidazolium based ionic liquids (ILs) catalysts, i.e., 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]) and 1-methylimidazolium hydrogen sulfate ([HMIM][HSO4]) to convert oil palm empty fruit bunch (OPEFB) and oil palm mesocarp fiber (OPMF) biomass to ethyl levulinate were compared. The procedure entailed a sequential reaction of depolymerisation of biomass at 160 °C for 3 hours, followed by an esterification at 90 °C for 12 h in excess ethanol, with ILs-to-biomass ratio of 5 : 1 by weight and 20 wt% water. It was demonstrated that only the last two acidic [HSO4]- counteranion based ILs are able to convert the biomass to ethyl levulinate. Mon...
Globally, the effects of climate change due to natural sources and human activities that releases greenhouse gases has led to a greater need for a sustainable and renewable resource called biomass. In South Africa (KwaZulu-Natal) there is an excess of sugarcane bagasse (SB) therefore this study was undertaken using SB. SB was valorised to replace chemicals obtained from fossil fuel processing. Levulinic acid (LA) was identified by the National Renewable Energy Laboratory (NREL) as a chemical that can be produced from biomass. LA is a platform chemical therefore many compounds are produced from LA hence in this work three LA derivatives namely diphenolic acid (DPA), γ-valerolactone (GVL) and ethyl levulinate (EL) production were studied. The main purpose of this work was to optimize the production of LA from depithed sugarcane bagasse (DSB) using ionic liquids (ILs), which are environment benign compared to sulfuric acid which is currently used in commercial production of LA from bio...
Ionic Liquids as Solvents for Catalytic Conversion of Lignocellulosic Feedstocks
2012
The deconstruction and upgrading of lignocellulosic biomass dissolved in ionic liquids was studied as a potential alternative route to products traditionally synthesized from petroleum. While domestic biomass is a cheaper, lower carbon emission, alternative feedstock to petroleum, its utilization requires the selective deconstruction of the biopolymer to monomeric sugars and upgrading of the sugars to higher value products. Since biomass is soluble in ionic liquids, there is the opportunity to do both the deconstruction and secondary upgrading using "one-pot" homogeneous catalysis. The primary focus of this work was to understand the kinetics of both biomass deconstruction and secondary sugar chemistry in ionic liquids. Biomass is a complex collection of molecule that consists of three primary components, cellulose, hemicellulose, and lignin. Since cellulose is the primary component, accounting for roughly 45 wt% of the raw biomass on a dry basis, initial studies aimed to understand the hydrolysis of dissolved cellulose to its sugar residue glucose. Using microcrystalline Avicel cellulose as a model, the rate laws and activation energies of cellulose hydrolysis and glucose dehydration were determined in the ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]). No evidence of oligosaccharides was observed, suggesting that hydrolysis occurs preferentially at chain ends and is irreversible. Gradually adding water to the reaction solution, so as not to precipitate cellulose but also limit the secondary dehydration of the resulting glucose to 5-hydroxymethyl furfural (5-HMF), significantly increased glucose yield and limited production of degradation products (humins). Several mechanisms were proposed to explain the effects of water, and possible routes to humin formation. While understanding the reactivity of model compounds is important to the development of biomass conversion technologies, it is critical to understand how the components of biomass react in their native form. An investigation was carried out to compare the reactivity of cellulose and hemicellulose model compounds to both pretreated and miscanthus grass in 1-ethyl-3methylimidazolium chloride ([Emim][Cl]). Activation energies of model compounds were compared with the native component in raw biomass. Significant rate decreases in hydrolysis of the cellulosic and hemicellulosic Table of Contents List of Figures .
Biomass Conversion and Biorefinery, 2021
Oil palm biomass, which is abundantly available in Malaysia, has many types of applications in various industries. In this study, oil palm frond (OPF) was liquefied with 1-butyl-3-methylimidazole hydrogen sulfate ([BMIM][HSO 4 ]) ionic liquid (IL) at optimum conditions. The liquefied OPF-ionic liquid (LOPF-IL) was mixed with furfural at a ratio of 0.8 (w/w), water-tofeedstock ratio of 0.125 (w/w), and sulfuric acid loading of 0.5 mL at 100°C for 1 h to form a gel. Carbon cryogel liquefied oil palm frond (CCOPF) was prepared using a freeze-dryer followed by calcination. CCOPF was further characterized using N 2 sorption, NH 3-TPD, TGA, XRD, FTIR, and FESEM to determine its physical and chemical properties. The thermally stable CCOPF exhibited a large total surface area (578 m 2 /g) and high total acidity (17.6 mmol/g). Next, CCOPF was tested for levulinic acid catalytic esterification by varying the parameters including ethanol-to-levulinic acid molar ratio, catalyst loading, and reaction time at 78°C. At the optimum conditions, the conversion of levulinic acid and ethyl levulinate yield was 70.9 and 71.7 mol%, respectively. CCOPF was reusable up to five runs with no significant conversion drop. Accordingly, CCOPF is conferred as a potential biomass-derived acid catalyst for ethyl levulinate production. Keywords Oil palm frond. Biomass. Liquefaction. 1-Butyl-3-methylimidazole hydrogen sulfate. Carbon cryogel. Ethyl levulinate Highlights • Liquefaction of oil palm frond with [BMIM][HSO 4 ] ionic liquid yielded LOPF-IL mixture. • Synthesis of carbon cryogel liquefied OPF (CCOPF) from LOPF-IL and furfural. • Good surface properties and high thermal stability are exhibited by microspherical CCOPF. • Esterification of levulinic acid is conducted over biomass-derived CCOPF catalyst.