Levulinic acid production

Chang, C., Cen, P. and Ma X. 2007. Levulinic Acid Production from Wheat Straw. Biores. Technol., 98, 1448-1453. 

Direct conversion of cellulose in an unpurifled state has been shown in the case of levulinic acid production. Production of levulinic acid as a high-yield direct product of controlled acid hydrolysis of cellulose is an exception to the complex product slate typically produced from biomass feedstocks. While the levulinic acid is only derived from the cellulose portion of the biomass and other components end up as byproducts, technology has now been demonstrated for recovery of the levulinic acid product at yields and purity sufiident to generate market interest". Based on related research developments, levulinic acid may prove to be an important building block for... 

Chang C, Cen P, Ma X (2007) Levulinic acid production from wheat straw. Bioresour Technol 98 1448-1453... 

Fang Q, Hanna MA (2002) Experimental studies for levulinic acid production from whole kernel grain sorghum. Bioresour Technol 81 187-192... 

A deaminase deficiency would block heme and uroporphyrin I production. It is unlikely that such a deficiency exists in acute intermittent porphyria because there is no reduction in the amount of heme protein synthesized in the liver. Uroporphyrin I production is slightly increased. Thus, an increase in amino levulinic acid production is the only explanation for the development of acute intermittent porphyria. 

Fitzpatrick, S. Personal communication regarding potential levulinic acid production costs based on Biofine technology. Biofine Corporation, 2004, South Glens Falls, NY. 

Galletti, A.M.R., Antonetti, C., De Luise, V., Licursi, D., Nassi, N., 2012. Levulinic acid production ft om waste biomass. BioResources 7,1824-1835. 

Formic acid is made in equimolar amounts and other C6-based processes for levulinic acid production. It is largely produced as a value-adding coproduct. 

Cha, J.Y., Haima, M. A., 2002. Levulinic acid production based on extrusion and pressurized batch reaction. Industrial Crops and Products 16 (2), 109-118. 

In the acid hydrolysis process (79—81), wood is treated with concentrated or dilute acid solution to produce a lignin-rich residue and a Hquor containing sugars, organic acids, furfural, and other chemicals. The process is adaptable to all species and all forms of wood waste. The Hquor can be concentrated to a molasses for animal feed (82), used as a substrate for fermentation to ethanol or yeast (82), or dehydrated to furfural and levulinic acid (83—86). Attempts have been made to obtain marketable products from the lignin residue (87) rather than using it as a fuel, but currently only carbohydrate-derived products appear practical. 

When levulinic acid (CH3CCH2CH2CO2H) was hydrogenated at high pressure over a nickel catalyst at 220°C, a single product, C5Hg02, was isolated in 94% yield. This compound lacks hydroxyl absorption in its IR spectrum and does not immediately liberate carbon dioxide on being shaken with sodium bicarbonate. What is a reasonable structure for the compound ... 

Lactic acid and levulinic acid are two key intermediates prepared from carbohydrates [7]. Lipinsky [7] compared the properties of the lactide copolymers [130] obtained from lactic acid with those of polystyrene and polyvinyl chloride (see Scheme 4 and Table 5) and showed that the lactide polymer can effectively replace the synthetics if the cost of production of lactic acid is made viable. Poly(lactic acid) and poly(l-lactide) have been shown to be good candidates for biodegradeable biomaterials. Tsuji [131] and Kaspercejk [132] have recently reported studies concerning their microstructure and morphology. 

The photo-Kolbe reaction is the decarboxylation of carboxylic acids at tow voltage under irradiation at semiconductor anodes (TiO ), that are partially doped with metals, e.g. platinum [343, 344]. On semiconductor powders the dominant product is a hydrocarbon by substitution of the carboxylate group for hydrogen (Eq. 41), whereas on an n-TiOj single crystal in the oxidation of acetic acid the formation of ethane besides methane could be observed [345, 346]. Dependent on the kind of semiconductor, the adsorbed metal, and the pH of the solution the extent of alkyl coupling versus reduction to the hydrocarbon can be controlled to some extent [346]. The intermediacy of alkyl radicals has been demonstrated by ESR-spectroscopy [347], that of the alkyl anion by deuterium incorporation [344]. With vicinal diacids the mono- or bisdecarboxylation can be controlled by the light flux [348]. Adipic acid yielded butane [349] with levulinic acid the products of decarboxylation, methyl ethyl-... 

Another method for preparing pyrrole rings is by Ugi-type three-component condensation (Scheme 6.184). In the protocol published by Tye and Whittaker [345], levulinic acid was reacted with two different isonitriles and four amine building blocks (1.5 equivalents) to provide a set of eight pyrrole derivatives. While the previously published protocol at room temperature required a reaction time of up to 48 h and provided only moderate product yields, the microwave method (100 °C, 30 min) optimized by a Design of Experiments (DoE) approach (see Section 5.3.4), led to high yields of the desired lactams for most of the examples studied. 

Key products obtained from the fermentation of glucose are levulinic acid and 5-hydroxymethyl-2-furfural (Scheme 1.1). 

A variety of cyclic products have been prepared from educts containing carbonyl as well as carboxylic groups. Thus, Hanusch-Kompa and Ugi prepared a large number of five-membered cyclic gamma-lactam compounds like 44 from levulinic acid. Other carbonylic acids can lead to compounds like 45, which is made from phthalaldehyde acid, valine methylester, and tert-butylisocyanide. The products like 46 and 47 can result from the U-4CR and further cyclization. 

Levulinic acid and formic acid are end products of the acidic and thermal decomposition of lignocellulosic material, their multistep formation from the hexoses contained therein proceeding through hydroxymethylfurfural (HMF) as the key intermediate, while the hemicellulosic part, mostly xylans, produces furfural.A commercially viable fractionation technology for the specific... 

Biorefinery includes fractionation for separation of primary refinery products. The fractionation refers to the conversion of wood into its constituent components (cellulose, hemicelluloses and lignin). Processes include steam explosion, aqueous separation and hot water systems. Commercial products of biomass fractionation include levulinic acid, xylitol and alcohols. Figure 3.3 shows the fractionation of wood and chemicals from wood. 

Thermolysis of D-fructose in acid solution provides 11 and 2-(2-hydrox-yacetyl)furan (44) as major products. Earlier work had established the presence of 44 in the product mixtures obtained after acid-catalyzed dehydrations of D-glucose and sucrose. Eleven other products were identified in the D-fructose reaction-mixture, including formic acid, acetic acid, 2-furaldehyde, levulinic acid, 2-acetyl-3-hydroxyfuran (isomaltol), and 4-hydroxy-2-(hydroxymethyl)-5-methyl-3(2//)-furanone (59). Acetic acid and formic acid can be formed by an acid-catalyzed decomposition of 2-acetyl-3-hydroxyfuran, whereas levulinic acid is a degradation prod-uct of 11. 2,3-Dihydro-3,5-dihydroxy-6-methyl-4//-pyran-4-one has also been isolated after acid treatment of D-fructose.The pyranone is a dehydration product of the pyranose form of l-deoxy-D-eo f o-2,3-hexodiulose. In aqueous acid seems to be the major reaction product of the pyranone. 

It is interesting to note that a similar scheme for making synthetic rubber was put forward many years ago. This Heinemann synthetic rubber process was essentially the production of levulinic acid from starch, its conversion with phosphorus pentasulfide into methylthiophene (XXXVII), which is reduced to 1,3-pentadiene. 

Levulinic acid, acting in its lactone form (XXXII) undergoes dehydration and two products have been obtained, - and /3-angelica lactones, (XXXVIII) and (XXXIX), respectively. a-Angelica lactone has been found to polymerize to a tacky resin by the catalytic agency of boron trifluoride. 

In 2008, Xiuyang et al. made an in-depth experimental study on the glucose decomposition in High Temperature Liquid Water (HTLW) from 180 to 220°C [73]. Interestingly, at 220°C, 100% of glucose was consumed within 90 min without addition of any catalyst. Analysis of the crude revealed that the main products of the reaction were HMF, levulinic acid, humic matter, and two unidentified soluble compounds. The maximum yield of HMF was obtained after 30 min of reaction (32%). 

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