Production Of Levulinic Acid Research Articles

Production of levulinic acid from wet microalgae in a biphasic one-pot reaction process

This work addresses the conversion of wet microalgae to levulinic acid (LA) using a one-pot reaction system. Utilizing moisture in microalgae forms a biphasic system with an organic solvent of 1, 2-dichloroethane (DCE) is formed. This system enhances the LA yield by making an acidic environment through the decomposition of DCE in a small quantity and the recovery of products in each aqueous and organic phase. With lipid-rich Nannochloropsis gaditana and carbohydrate-rich Chlorella species, the effects of reaction variables of temperature, water content, and DCE dosage on the LA production were investigated. The LA yield was 30.13 wt% and 28.15 wt% based on the mass of total hexoses (43–47 wt% of convertible hexoses) for the two types of microalgae at 160 °C, while the yield of free fatty acids reached 90.13 w/w% at 180 °C based on the esterifiable lipid. This biphasic system facilitates the forward reaction and the product recovery for concurrent reaction and separation.

The formation of 5-hydroxymethylfurfural and hydrochar during the valorization of biomass using a microwave hydrothermal method

5-Hydroxymethylfurfural (HMF) and levulinic acid (LA) are regarded as value-added platform chemicals that can be derived from biomass waste. However, humins are inevitably produced during valorization processes, reducing the product yields. Previous studies indicated that microwave heating combined with acidic seawater as a reaction medium promotes HMF formation. The present work therefore investigated the relationship between the production of HMF and LA in the liquid phase and that of insoluble humins (that is, hydrochar) under microwave heating in acidic seawater. The selectivities for HMF and LA were found to decrease as the reaction time was increased, as a result of hydrochar formation, and both dehydration and decarboxylation evidently dominated the production of hydrochar in succession. HMF evidently played the most important role in hydrochar formation, and was consumed approximately seven times more rapidly than either fructose or LA. The hydrochar formation mechanism reported herein may be applicable to other similar hydrothermal processes.

Optimization of Levulinic Acid Production from Depithed Sugarcane Bagasse in 1- Ethyl-3-methylimidazolium hydrogen sulfate [EMim][HSO4

In the present study, optimal reaction conditions to produce levulinic acid (LA) from depithed sugarcane bagasse (DSB) using 1-ethyl-3-methylimidazolium hydrogen sulfate [EMim][HSO4] ionic liquid (IL) were investigated. The effect of temperature (100–220 °C), reaction time (2–12 h), and ionic liquid loading (1–4 g) was assessed using response surface methodology based on the Box-Behnken design. The optimum conditions were found to be 100 °C, 7 h, and 4 g of IL, which yielded 54.6% of LA from DSB. The analysis of variance (ANOVA) indicated that the design model was significant at the 95% confidence level. The pareto chart revealed that IL loading had the most significant effect on the production of LA, followed by temperature and reaction time. The P-values also showed that these were the significant model terms. There is a strong correlation between temperature and IL loading. Solvent optimization revealed that the type of solvent used in the LA production has a significant effect on LA yield. Water was used as the control solvent for this study. Methyl isobutyl ketone (MIBK) yielded the highest LA (62%) from all the solvents that were used.

Production of Levulinic Acid from Cellulose and Cellulosic Biomass in Different Catalytic Systems

The reasonable and effective use of lignocellulosic biomass is an important way to solve the current energy crisis. Cellulose is abundant in nature and can be hydrolyzed to a variety of important energy substances and platform compounds—for instance, glucose, 5-hydroxymethylfurfural (HMF), levulinic acid (LA), etc. As a chemical linker between biomass and petroleum processing, LA has become an ideal feedstock for the formation of liquid fuels. At present, some problems such as low yield, high equipment requirements, difficult separation, and serious environmental pollution in the production of LA from cellulose have still not been solved. Thus, a more efficient and green catalytic system of this process for industrial production is highly desired. Herein, we focus on the reaction mechanism, pretreatment, and catalytic systems of LA from cellulose and cellulosic biomass, and a series of existing technologies for producing LA are reviewed. On the other hand, the industrial production of LA is discussed in depth to improve the yield of LA and make the process economical and energy efficient. Additionally, practical suggestions for the enhancement of the stability and efficiency of the catalysts are also proposed. The use of cellulose to produce LA is consistent with the concept of sustainable development, and the dependence on fossil resources will be greatly reduced through the realization of this process route.

Microbial and enzymatic conversion of levulinic acid, an alternative building block to fermentable sugars from cellulosic biomass.

Levulinic acid (LA) is an important chemical building block listed among the top 12 value-added chemicals by the United States Department of Energy, and can be obtained through the hydrolysis of lignocellulosic biomass. Using the same approach as in the catalytic production of LA from biomass, catalytic methods to upgrade LA to higher value chemicals have been investigated. Since the discovery of the catabolic genes and enzymes in the LA metabolic pathway, bioconversion of LA into useful chemicals has attracted attention, and can potentially broaden the range of biochemical products derived from cellulosic biomass. With a brief introduction to the LA catabolic pathway in Pseudomonas spp., this review summarizes the current studies on the microbial conversion of LA into bioproducts, including the recent developments to achieve higher yields through genetic engineering of Escherichia coli cells. Three different types of reactions during the enzymatic conversion of LA are also discussed. KEY POINTS: • Levulinic acid is an alternative building block to sugars from cellulosic biomass. • Introduction of levulinic acid bioconversion with natural and engineered microbes. • Initial enzymatic conversion of levulinic acid proceeds via three different pathways. • 4-Hydroxyvalerate is one of the target chemicals for levulinic acid bioconversion.

An efficient method to produce 1,4-pentanediol from the biomass of the algae Chlorella ohadi with levulinic acid as intermediate

Today, the development of innovative methods for production of organic compounds from natural resources is essential topic for many research groups in the worldwide. Levulinic acid is a platform for many important organic processes in the synthesis of natural products, pharmaceuticals, plasticizers, drugs and various other additives. In addition, 1,4-pentanediol which is a product of reduction of levulinic acid, is a valuable raw material in the chemical industry. Here, we report a highly efficient method for the production of levulinic acid from Chlorella ohadi algae using hydrothermal hydrolysis process by using HCl. Our methodology shows that the levulinic acid can be obtained in almost 90% molar yield compared to the glucose in Chlorella ohadi. Finally, we describe a one step reaction for the completely conversion of levulinic acid into 1,4-pentadiol in water using S. cerevisiae yeast as a catalyst.

Levulinic acid production through two-step acidic and thermal treatment of food waste using dilute hydrochloric acid

This research investigated the concept of a two-step acidic and thermal treatment for glucose extraction and levulinic acid (LA) production from food waste using dilute hydrochloric acid (DHA) as a catalyst, and subsequently analyzed the properties of the resulting humins. Glucose extraction was performed under various reaction conditions (reaction temperature range: 120-190 °C, DHA concentration range: 0.2-0.5% v/v); the glucose extraction yield of the acidic treatment step reached 83.17% under the optimal conditions (150 °C in 0.5% DHA). LA production was achieved during the thermal treatment step, which was investigated using two independent experiments to determine the influence of the reaction conditions (reaction time: 5-140min, concentration factor: 1.5-3.0, reaction temperature: 160-190 °C). The LA production process was affected by the concentration factor and the reaction temperature due to the low pH of solution and the rapid reaction rate, respectively. The thermal stability of the humins was highest at a concentration factor of 3.0 because of the 13.07 C/H ratio of the humins.

Valorization of thermochemical conversion of lipid-extracted microalgae to levulinic acid

Scenedesmus obliquus, a green microalga of the class Chlorophyceae, has been used to produce biofuels. However, limited research has been reported on platform chemicals that use microalgae as biomass to replace fossil sources. This paper reports on the investigation of levulinic acid (LA) production from lipid-extracted S. obliquus with an acid-catalyzed thermochemical conversion using a statistical experimental approach. For the reaction factors, the highest effect on LA yield resulted from catalyst concentration. The optimized LA yield of 45.63 wt% (70.7 mol%) was achieved with 5 wt% lipid-extracted microalgae and reaction factors of 0.85 M HCl as a catalyst at 180 °C for 10 min. Also, the LA yield as a function of the combined severity factor followed a sigmoid curve. High LA yield resulted from combined severity factors greater than 3.4. These results indicate that the production of platform chemicals may be possible using microalgae feedstocks and thermochemical conversion.

Optimisation of glucose and levulinic acid production from the cellulose fraction of giant reed (Arundo donax L.) performed in the presence of ferric chloride under microwave heating

A two-step exploitation of the giant reed cellulose to glucose and levulinic acid, after the complete removal of the hemicellulose fraction, was investigated using FeCl3 as catalyst. In the first step, the microwave-assisted hydrolysis of cellulose to glucose was optimised by response surface methodology analysis, considering the effect of temperature, reaction time and catalyst amount. Under the optimised reaction conditions, the glucose yield was 39.9 mol%. The cellulose-rich residue was also converted by enzymatic hydrolysis, achieving the glucose yield of 39.8 mol%. The exhausted residue deriving from the chemical hydrolysis was further converted to levulinic acid by microwave treatment at harsher reaction conditions. The maximum levulinic acid yield was 64.3 mol%. On the whole, this cascade approach ensured an extensive and sustainable exploitation of the C6 carbohydrates to glucose and levulinic acid, corresponding to about 70 mol% of glucan converted to these valuable bioproducts in the two steps.

Clean Production of Levulinic Acid from Fructose and Glucose in Salt Water by Heterogeneous Catalytic Dehydration.

Levulinic acid (LA) is considered to be one of the promising organic bio-platform chemicals and intermediates for the synthesis of fuels, chemicals, and polymers. In the present study, heterogeneous catalytic dehydration of hexose sugars, fructose and glucose, using a strong cation exchange resin (hydrogen form) as an acid catalyst, was performed to produce LA in an aqueous medium. The effect of salts such as NaCl, KCl, CaCl2, Na2CO3, and Na2SO4 in the medium on the rate of sugar conversion and LA yield was evaluated. Under optimum reaction conditions, 10% (w/w) fructose was dehydrated to LA (with 74.6% yield) in 10% (w/w) NaCl aqueous solution in 24 h at 110 °C using the catalyst at 30% (w/w sugar). Even 10% (w/w) glucose monohydrate was directly dehydrated to LA (with 70.7% yield) under similar conditions but at 145 °C. This study shows that the salts enhance the rate of catalytic dehydration in the order of Cl– > CO32– > SO42–. Thus, the combination of high sugar concentration and heterogeneous catalysis in an aqueous system under relatively mild conditions could provide a high-yielding and sustainable process for bio-based LA production.

Microwave‐assisted synthesis of levulinic acid from low‐cost, sustainable feedstocks using organic acids as green catalysts

AbstractBACKGROUNDModern day scientific endeavour strives towards global sustainability through the smart utilisation of renewable resources as base materials for chemicals. Until now, the most common commercial process to produce levulinic acid (a mass‐produced platform chemical) depends on a two‐stage mineral acid‐catalysed reaction, which generates harmful environmental waste. In this work, an environmentally friendly levulinic acid production route using less harmful organic acids assisted by microwave heating from biomass feedstocks is reported for the first time.RESULTSUsing aluminum sulfate as a green Lewis acid catalyst and seven organic acids, levulinic acid was successfully produced from barley straw under microwave heating, with maleic acid giving the highest catalytic conversion. A Response Surface Methodology (RSM) approach was used to rapidly and effectively examine the effect of five reaction variables on the productivity of the levulinic acid. A wide range of different biomass wastes (barley straw, brewery waste, olive cake, spent tea leaves and potato, tomato, and mandarin peels) were subsequently screened to produce the levulinic acid. The highest yield of 86 wt% based on cellulose content from mandarin peel (a value comparable to a lengthier ‘non‐green’ route) was achieved under the following optimized reaction conditions: 180 °C, 38 min, 2 M maleic acid concentration, 0.1 g Al2(SO4)3 and 1:22 biomass: maleic acid ratio (g mL−1).CONCLUSIONSThe proposed method is a promising new route towards the green, high yield production of levulinic acid from a variety of agricultural and household lignocellulosic biomass wastes, without the need for pre‐treatment. © 2020 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Technical-economic Analysis of Processes for the Production of Levulinic Acid

Nowadays most of energy supply and chemicals are produced from fossil fuels. However, environmental concerns like global warming, depletion of non-renewable resources and pollution, force to search for more sustainable alternative feedstocks. In this framework, the valorization of renewable resources is currently one of the most promising strategies for the next future. In particular, the use of biomass is ranked first for production of chemicals. One of the most attractive compounds that can be obtained from lignocellulosic biomass is Levulinic acid (LA). The present work analyses, from a technical, economic and safety standpoint, the valorization of waste biomass (OPEFB, oil palm empty fruit bunch) to LA with different methodologies. Energy demand of the plant and the separation efficiency are evaluated carrying out process simulations by the commercial software Aspen HYSYS V10. The obtained results allowed an economic analysis of the alternatives, based on the evaluation of investment and main operating costs. The alternatives were screened on the basis of net present value (NPV) of costs. Safety performance was investigated by an inherent safety assessment method. This considered toxic dispersion and fire scenarios, calculating the damage distances associated with the potential outcomes of an accident and allowing for the evaluation of a potential hazard index for each main process equipment. The choice of the optimal layout configuration for the production of LA in early phases of design allowed to address, in a time and cost-effective way, further design activities in reducing the energy demand and ensuring potentially safer plants making the whole process more sustainable.

Kinetic insights into the lignocellulosic biomass-based levulinic acid production by a mechanistic model

In this work, a mechanistic model was developed to simulate the kinetics of the production of levulinic acid (LA) from sugarcane bagasse (SCB), rice husk (RH) and soybean straw (SS). The production of LA from those agro-industrial wastes followed the methodology of biorefining in three stages. Experimental data from the third stage (catalytic depolymerization of cellulose) obtained under a wide range of operating conditions were used to estimate the parameters of the model. An optimization procedure based on a genetic algorithm was used to determine the optimal parameter values. The prediction of the concentrations of glucose, 5-HMF and LA using the mechanistic model was particularly accurate, as demonstrated by R2 and RMSE. Thereby, a satisfactory concordance was reached between the high yields of LA of 61.1 mol%, 67.7 mol% and 61.4 mol% calculated by the model, and the experimental yields of 60.5 ± 2.1 mol%, 65.2 ± 2.9 mol% and 61.5 ± 4.0 mol% (under optimum conditions of 190 °C, 7.0% w/v of H2SO4, 75 min) for SCB, RH and SS, respectively. The biorefining of the agro-industrial wastes under optimum operating conditions allowed a satisfactory catalytic depolymerization of cellulose, regardless of the degree of crystallinity. The estimation of yields led to suggesting a strategy from the point of view of process synthesis and design, integrating SCB, RH and SS to supply their off-season and, thus, to ensure the supply of raw materials in the production of LA.

Challenges to Levulinic Acid and Humins Valuation in the Sugarcane Bagasse Biorefinery Concept

Levulinic acid (LA) is currently one of the most promising chemicals derived from biomass. However, its large-scale production is hampered by the challenges in biomass hydrolysis and the poor selectivity due to the formation of humins (HUs). This study addresses these challenges using the biorefinery concept of biomass fractionation. A three-step process (pretreatment, delignification, and acid-catalyzed conversion) was optimized to produce LA from SCB considering the yield (YLA), efficiency (ELA), and concentration of LA (CLA) as functions of temperature, reaction time, acid concentration, and solids loading. By means of a multi-response optimization, values of YLA (20.9 ± 1.25 g/100gISF-D), ELA (37.5 ± 2.24 mol%), and CLA (25.1 ± 1.50 g/L) were obtained at 180 °C, 75 min, 7.0% w/v H2SO4, and 12.0% w/v of solids loading. Six scenarios for production of LA were analyzed in terms of yields of LA, HUs, lignin, and other sugar-derived products considering one-, two-, or three-step processes. The economic analysis indicated that the three-step scenario delivers better economic figures given that other valuable biomass fractions (hemicellulosic sugars and lignin) are better used and contribute to the overall economic performance of the process. The results also demonstrate the burden of HUs in the economics of the process because it was shown that the largest production of LA is also linked to the largest formation of HUs, which does not necessarily yield the best economic results. These findings indicate the importance of added value by-products for the profitable production of LA in biorefineries.

Optimization of Levulinic acid production from groundnut shell using Taguchi orthogonal array design

The exploitation of lignocellulosic biomass is receiving an increasing attention due to its renewability, abundance and low price value, and can be converted into various valuable platform compounds such as furfural, lactic acid, formic acid and levulinic acid. Among these products, levulinic acid (LA) is the main compound of biomass hydrolysis, which has been classified by the United States Department of Energy as one of the top-12 promising building blocks. This work reported the transformation of groundnut shell into LA. The production of LA was carried out in a 50 cm3 Teflon lined stainless steel reactor. The LA produced was extracted from the aqueous mixture using ethyl acetate, about 1g of sodium sulphate anhydrous were added to remove the water in the organic layer after the aqueous layer was drained and then heated at a temperature of about 78 oC for the solvent to evaporate and LA was the residue. The production process was optimized using a Taguchi orthogonal array design, with optimum yield of 74.54 % at reaction conditions of temperature (180 °C), time (3.5 h), and acid concentration (0.3 M). The FT-IR spectrum of the produced LA showed absorption at about 1705.13 cm-1 and 3039.91 cm-1 indicating the conjugated carbonyl and the hydroxyl of carboxylic acid functional group. It was recommended that high yields of LA can be achieved across a range of optimization variables as long as two out of the three conditions are met: high acid catalyst concentration, long reaction time or high temperature within the range tested, as LA is relatively stable once formed. Moreover, the results obtained revealed that groundnut shell could be a potential substrate for levulinic acid production.
 Keywords: Groundnut shell, Levulinic acid, Optimization, Hydrolysis, Taguchi design.

Catalytic Conversion of Carbohydrate Biomass in Ionic Liquids to 5-Hydroxymethyl Furfural and Levulinic Acid: A Review

The projections of ionic liquids as green solvents in chemical processes have increased in recent years. Ionic liquid is a versatile chemical with various applications. The aim of this review is to present a comprehensive perspective of ionic liquid for processing carbohydrate biomass by considering the recent progress in this field. Special attention is given to the application of ionic liquids for the production of 5-hydroxymethyl furfural (5-HMF) and levulinic acid (LA). Factors affecting the catalytic conversion of carbohydrate biomass in ionic liquid and the mechanisms of 5-HMF and LA production are also presented. In addition, the recyclability of the ionic liquid for carbohydrate biomass processing is discussed. The viewpoint for the application of functionalized ionic liquid as potential green solvent and catalyst is also highlighted. Future studies pertinent to carbohydrate biomass conversion in ionic liquids to 5-HMF and LA could use this review for selecting the appropriate reaction conditions required to achieve their specific goals. Besides, combination of technologies from ionic liquids and biomass processing strategies for the production of various fuels and value-added chemicals can be comprehended for applications in a lignocellulosic biorefinery.

Strategy for biological co-production of levulinic acid and polyhydroxyalkanoates by using mixed microbial cultures fed with synthetic hemicellulose hydrolysate

Hemicellulose hydrolysates (HH), which could be an interesting carbon source to feed mixed microbial cultures (MMC) able to accumulate high value-added compounds. This research focused on the evaluation of a culture strategy to achieve the simultaneous biological production of Levulinic Acid (LA) and Polyhydroxyalcanoates (PHA) by MMC fed with a synthetic HH (SHH). The culture strategy involves the use of sequential batch reactors (SBR) to select microorganisms capable of producing LA and PHA. This work proved that the cultivation strategy used allowed the biological production of LA, reaching 37%w/w when the SHH was composed of 85% pentoses. In addition, the simultaneous biological production of LA and PHB was possible when the SHH was enriched with acetate (45% pentoses − 50% acetate). Finally, this study showed that the composition of the SHH impacts directly on the selected microorganism genus and the type and quantity of the value-added compounds obtained.

Sustainability assessment of levulinic acid and succinic acid production from empty fruit bunch

Empty fruit bunch (EFB) generated as waste in plantation mill activities in Malaysia is a potential biomass feedstock of biorefinery for fuels and chemicals production. Levulinic acid and succinic acid, two out of 12 chemical building blocks identified by Department of Energy (DOE) to be used in synthesis of high-value materials, can be produced from biochemical conversion of the EFB. This paper evaluates sustainability assessment of EFB to levulinic acid and succinic acid. The assessments include net present value (NPV), global warming potential (GWP), and Hazard identification and ranking (HIRA) to cater for economic, environment, and safety performances, respectively. The results show that the levulinic acid production is more economically attractive than succinic acid production. The environmental impact quantification reveals that the levulinic acid has lower GWP score of 6.3 kgCO2-eq/kg levulinic acid than succinic acid with 11.2 kgCO2-eq/kg succinic acid. Meanwhile, the succinic acid production is inherently safer than levulinic acid production due to its less severe operating conditions.

Valorization of Sugarcane Bagasse to a Platform Chemical (Levulinic Acid) Catalysed by 1-Butyl-2,3-dimethylimidazolium Tetrafluoroborate ([BMMim][BF4

The Biofine process is the currently used method for the industrial production of levulinic acid (LA) from biomass. In this process sulfuric acid is used to catalyze the reaction, the former is a corrosive and toxic catalyst. In this work, an environmental friendly catalyst: 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BMMim][BF4]) was used to optimize the LA production from depithed sugarcane bagasse (DSB). The Box–Behnken design (response surface methodology) was used to design the set of experiments with three variables, namely, time, temperature and catalyst loading. The optimum condition for water as a solvent was 100 °C, 7 h and 4 g of a catalyst which yielded a maximum amount of 44.8% of LA from DSB. When different solvents were investigated at the optimum condition for LA production, methyl isobutyl ketone (MIBK) was the best solvent (54.2%). This study also showed that [BMMim][BF4] is capable of theoretically producing 62.1% of LA. The reusability study showed that [BMMim][BF4] can be used for up to four times without losing it activity.

Kinetic Studies and Optimization of Heterogeneous Catalytic Oxidation Processes for the Green Biorefinery of Wood

In the present work, a kinetic study and optimization of the process of spruce wood peroxide oxidation in “acetic acid–water” medium in the presence of suspended TiO2 catalyst at temperatures 70–100 °C were accomplished for the first time. The effect of wood species and organic solvent nature on the features of the processes of catalytic peroxide fractionation of wood biomass on microcrystalline cellulose and soluble organic products from lignin and hemicelluloses is described. Solid products of wood peroxide oxidation were characterized by FTIR, XRD, SEM, solid state 13C CP-MAS NMR and soluble products were identified by GC–MS. The experimental optimization of the process of birch wood oxidation by oxygen in “water–alkaline” medium in the presence of suspended Cu(OH)2 catalyst was carried out at temperature range 160–180 °C. The scheme of biorefinery of birch wood, based on catalytic oxidative fractionation of wood biomass with the production of pentosans, vanillin, syringaldehyde and levulinic acid was developed. The resulting products are in demand in many areas, including food, pharmaceutical, chemical, cosmetic industries, synthesis of new functional and biodegradable polymers.