• Korean Journal of Chemical Engineering
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• v.35 no.11
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• pp.2232-2240
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• 2018

We applied methanesulfonic acid (MSA) as a green catalyst to produce levulinic acid (LA) from monomeric sugars. To optimize reaction factors and assess the effect of reciprocal interactions, a statistical experimental design was applied. Optimized result of 40.7% LA yield was obtained under the following conditions: 60 g/L galactose, 0.4 M MSA at $188^{\circ}C$ for 26.7 min. On the other hand, 66.1% LA yield was achieved under 60 g/L fructose and 0.4 M MSA at $188^{\circ}C$ for 36 min conditions. For the effect of combined severity factor on the LA yield from galactose, the LA yield showed a peaked pattern, which was linearly increased until a CSF 3.2 and then diminished with a high CSF. Moreover, it was closely fitted to a non-linear Gaussian peak pattern with a high regression value of 0.989. These results suggest that MSA and galactose, derived from marine red macro-algae, can potentially be applied for the conversion into platform chemicals.

• Analytical Science and Technology
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• v.30 no.5
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• pp.295-302
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• 2017

This study presents a method validation for extraction and quantitative analysis of levulinic acid in soy sacues using high performance liquid chromatograph-photodiode array detector (HPLC-PDA). The levulinic acid in samples were extracted with distilled water, and then purified with C18 Sep-Pak cartridge. The calibration curves showed good linearity (R > 0.999) in a relatively wide concentration range ($2.5-400{\mu}g/mL$). Mean recoveries and relative standard deviation (RSD) of levulinic acid spiked in soy sauce samples at different spiking levels ($2.5-400{\mu}g/mL$; 6 point). Recoveries were 87.58-97.26 % with RSD less than 15 %, and limit of detection (LOD) and limit of quantification (LOQ) were 0.64 and $1.64{\mu}g/mL$, respectively. According to monitoring result with the established method, levulinic acid was found in 43 of 59 domestic commercial soy sauces, soy sauce based sauces and seasoned meats. The contamination levels were 0.44-1.23 mg/mL for soy sauces, 0.03-0.83 mg/mL for soy sauce based sauces and 8.43-38.94 mg/mL for seasoned meats. The results indicated to be rapidly and accurately qualifying levulinic acid and can be used as a suitable quality control method for soy sauce and soy sauce related commodities.

• Korean Chemical Engineering Research
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• v.60 no.2
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• pp.193-201
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• 2022

5-HMF(5-Hydroxymethylfurfural) and LA(levulinic acid) derived from biomass are green platform chemicals, which have a wide of potential applications as biofules and biochemicals. In this study, the kinetics of LA formation from glucose decomposition with various concentration of sulfuric acid at different temperature was investigated. The experiments were performed in a broad temperature (140-200 ℃), using H₂SO₄ (1-3 wt%) as the catalyst. Glucose solution was made by dissolving 1 g of glucose in 10 ml of H₂SO₄ solution. The reactions rates increased with temperature and the activation energy showed a similar tendency to previous reported values. Reaction time for maximum concentration of 5-HMF decreased as the temperature increased. Furthermore, the decomposition of 5-HMF was fast as the acid concentration increased. Reaction time to reach maximum concentration of levulinic acid was reduced as the acid concentration increased. Continuing to raise the temperature decreased the maximum concentration of levulinic acid and increased the amount of humins. On the basis of results, kinetic parameters help to understand mechanism of LA and 5-HMF. In addition, this study provides useful information to achieve high concentration of LA and 5-HMF from biomass.

• New & Renewable Energy
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• v.19 no.4
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• pp.11-19
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• 2023

Levulinic acid (LA) derived from cellulosic biomass, serves a crucial intermediate that can be used in various chemical conversions. This study focused on optimizing the production of LA using two types of pretreated rice husk (de-ashed and delignificated cellulosic biomass) in a batch reaction system through catalytic conversion with sulfuric acid. To determine the optimal conditions, the conversions of glucose and α-cellulose were examined to compare the effects of pretreatment on the rice husk. The experimental parameters covered a broad spectrum, including temperatures ranging from 140℃ to 200℃, a reaction time was up to 600 minutes, and a substrate to catalyst (acid solution) ratio of 100 g/L. The highest LA yield was 44.8%, achieved from de-ashed rice husk with 3.0 wt.% of sulfuric acid at 180℃ and with a reaction time of 180 minutes. In the case of the delignificated rice husk, a LA yield of 43.6% was obtained with 3.0 wt.% of sulfuric acid at 200℃ and with reaction time of 30 minutes.

• Journal of the Korean Wood Science and Technology
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• v.43 no.6
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• pp.838-850
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• 2015

In this study, dilute acid pretreatment was operated using small-diameter Quercus mongolica for evaluating the yield change of furfural and levulinic acid depending on pretreatment factors. The dilute acid pretreatment was conducted depending on reaction temperature ($140-180^{\circ}C$), reaction time (10-30 min), and sulfuric acid concentration (0-2%, w/w). Then, glucose, XMG (xylose + mannose + galactose), furfural, and levulinic acid contents in the liquid hydrolyzate were measured and analyzed after pretreatment. Glucose content increased to 16.02% as reaction temperature, reaction time, and sulfuric acid concentration increased, but it decreased at the sulfuric acid concentration of 2% (reaction temperature: > $170^{\circ}C$, reaction time: > 20 min). On the other hand, reaction temperature had a strong influenced on XMG content, and XMG content decreased to 1.63% through increasing of reaction temperature and sulfuric acid concentration, but XMG content was less affected by changes of reaction time. Furfural content increased with the increase of reaction temperature, reaction time, and sulfuric acid concentration, and maximum furfural content was 7.61% (reaction temperature: $180^{\circ}C$, reaction time: 20 min, sulfuric acid concentration: 1%) based on a weight of raw material, while furfural content was dropped in more severe condition than in maximum furfural content condition. Levulinic acid content also increased with higher reaction temperature, reaction time, and sulfuric acid concentration. Especially, the sharp increase of levulinic acid content was observed above $170^{\circ}C$, and maximum levulinic acid content was 10.98% (reaction temperature: $180^{\circ}C$, reaction time: 30 min, sulfuric acid concentration: 2%). However, less than 1% of furfural and levulinic acid content was obtained in non-acidic catalyst condition that in whole conditions of reaction temperature and reaction time.

• Korean Chemical Engineering Research
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• v.58 no.2
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• pp.293-300
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• 2020

Eucheuma spinosum, red macro-algae, contains carrageenan as the major polysaccharide and is commercially produced in Indonesia, Malaysia, Philippines, China and Tanzania. In this study, E. spinosum was converted to sugar and platform chemicals (5-HMF, levulinic acid, formic acid) via FeCl₃-catalytic hydrothermal reaction. In addition, statistical methodology (3-level 3-factor Box-Behnken design) was applied to optimize and evaluate the effects of reaction factors (reaction temperature, catalyst concentration and reaction time). As a result of optimization, the concentration of 5-HMF was obtained to be 2.96 g/L at 160 ℃, 0.4 M FeCl₃ and 10 min. Optimal conditions of levulinic and formic acids were determined at 200 ℃, 0.6 M FeCl₃ and 30 min, and the concentrations were obtained to be 4.26 g/L and 3.77 g/L, respectively.

• Journal of Microbiology and Biotechnology
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• v.32 no.1
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• pp.110-116
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• 2022

Polyhydroxyalkanoates (PHAs) are emerging as alternatives to plastics by replacing fossil fuels with renewable raw substrates. Herein, we present the construction of engineered Escherichia coli strains to produce short-chain-length PHAs (scl-PHAs), including the monomers 4-hydroxyvalerate (4HV) and 3-hydroxyvalerate (3HV) produced from levulinic acid (LA). First, an E. coli strain expressing genes (lvaEDABC) from the LA metabolic pathway of Pseudomonas putida KT2440 was constructed to generate 4HV-CoA and 3HV-CoA. Second, both PhaAB enzymes from Cupriavidus necator H16 were expressed to supply 3-hydroxybutyrate (3HB)-CoA from acetyl-CoA. Finally, PHA synthase (PhaC_Cv) from Chromobacterium violaceum was introduced for the subsequent polymerization of these three monomers. The resulting E. coli strains produced four PHAs (w/w% of dry cell weight): 9.1 wt% P(4HV), 1.7 wt% P(3HV-co-4HV), 24.2 wt% P(3HB-co-4HV), and 35.6 wt% P(3HB-co-3HV-co-4HV).

• Korean Journal of Microbiology
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• v.38 no.2
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• pp.144-151
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• 2002

For elucidating the relationship between the biosynthetic pathways for polyhydroxyslkanoates (PHAs) and 5-aminolevulinic acid (ALA), culture conditions for the production of these two biomaterials by Rhodopseudomonas sp. KCTC 1437 were investigated. Of the carbon substrates tested, acetic acid was the best carbon source for cell growth and PHA biosynthesis. When succinic acid was added as a co-substrate into culture medium, cell growth and PHA production were greatly increased up to 2.5 g/ι and 73% of dry cell weight, respectively. The PHA obtained from the carbon substrates tested was homopolyester of 3-hydroxybutyrate, while valeric acid was only effective for the production of copolyester consisting of 3-hydroxybutyrate and 3-hydroxyvalerate. Anaerobic light culture condition was better for PHA production and cell growth than anaerobic dark or aerobic dark culture condition. The organism was capable of synthesizing ALA when glycine and succinic acid were added to the culture medium. ALA was produced to ca.400 mg/ι when levulinic acid, soccinic acid, and glycine were repeatedly added with a reductant (sodim thioglycolate). However, the presence of glycine, levulinic acid and sodium glycolate inhibited the cell growth and the conversion of carbon substrates to PHA. From these results it is apparent that the production yields of PHA and ALA could not be increased simultaneously because the optimal conditions for the production of PHA and ALA are opposed to each other.

• Journal of the Korea Organic Resources Recycling Association
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• v.5 no.1
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• pp.63-69
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• 1997

The role of L-glutamic acid, a precursor of $C_5$ ALA biosynthetic pathway, on the production of 5-aminolevulinic acid (ALA) has been described in cells of Rhodospirillum rubrum N-1. To the Lascelles basal medium the addition of both 30 mM L-glutamicacid and 20 mM levulinic acid (LA) provided to increase the extracellular ALA yield up to 40 fold (76 mg/l). By the addition of both 60 mM glycine and succinic acid, precursorsof $C_4$ ALA biosynthetic pathway, at middle log phase of cell growth ALA yield was increased 27 fold (52 mg/l) although the celt growth was inhibited to a certain extent.

• Journal of Microbiology
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• v.39 no.1
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• pp.79-82
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• 2001

The influence of levulinic acid (LA) on the production of copolyester consisting of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) by Ralstonia eutropha was investigated. Addition of LA into the culture medium greatly increased the molar fraction of 3HV in the copolyester, indicating that LA can be utilized as a precursor of 3HV. In shake flask culture, the 3HV content in the copolyester increased from 7 to 75 mol% by adding 0.5 to 4.0 g/L LA to the medium containing fructose syrup as a main carbon source. A maximal copolyester concentration of 3.6 g/L (69% of dry cell weight) was achieved with a 3HV content of 40 mo1% in a jar fermentor culture containing 4.0 g/L of LA. When LA (total concentration, 4 g/L) was added repeatedly into a fermentor culture to maintain its concentration at a low level, the copolyester content and the 3HV yield from LA reached up to 85% of dry cell weight and 5.0 g/g, respectively, which were significantly higher than those when the same concentration of the LA was supplied al1 at once. The present results indicated that LA is more effective than propionate or valerate as a cosubstrate fur the production of copolyesters with varying molar fractions of 3HV by R. eutropha.