Bio-based organic acids

In this paper, we focus on synthesis and application of esters of bio-based organic acids. Organic acid esters are used or have potential for use in many industrial and consumer applications including solvents, paint strippers, surfactants, fragrances, and fuel stabilizers2. The chemicals used in these... 

TABLE 1.1 Conversion Pathways, Derivatives, and Potential Applications of Bio-based Organic Acids... 

The development of bio-based succinic acid production was carried out as the NEDO (New Energy and Industrial Technology Development Organization, an implementing agency of METI in Japan) project from 2004 to 2006, and the possibility of bio-based materials was confirmed. 

The second economic parameter which has high impact on the bio-based succinic acid market is the availability of succinic acid and the demand for succinic acid-based products. Currently the market is evolving very rapidly. For several years bio-based succinic acid was on the future portfolio of only a few companies. The plans for industrial production were still very vague as most of the companies were in the phase of research and development. Meanwhile production organisms and processes have been developed and tested in several pilot plants and in the last 2 years a number of press releases mapped several of the major players (Table 16.2) in the surprisingly fast-growing market of bio-based succinic acid. 

HMF is an important versatile sugar derivative and is a key intermediate between bio-based carbohydrate chemistry and petroleum based industrial organic chemistry (1, 2). The most coimnon feedstock for HMF is fructose and reactions are carried out in water-based solvent systems using acid catalysis (3,4). HMF is unstable in water at low pH and breaks down to form levulinic acid and formic acid, resulting in an expensive HMF recovery process. In strongly polar organic co-solvents, such as dimethylsulfoxide (DMSO), levuhnic acid formation is reduced and HMF yields are improved (5). 

The potential for industrial biotech has been broadly recognized and chemical and biotech companies are starting to move into this space and grow their presence. In fact, about five percent of the estimated USD 1.2 trillion total chemical sales already depend on biotech. The global market for bio-based ethanol alone is worth USD 15 billion other basic organic molecules such as citric acid (USD two billion) and lactic acid are produced by fermentation, and so are all but three amino acids (approx. USD four billion) various basic, advanced and active pharmaceutical ingredients produced by the fine chemical industry are worth USD 7.5 billion the attractive enzyme market has reached USD two billion in... 

It is evident from Figure 1.3 that formaldehyde, dioxane, organic acids, acetonitrile and THF are not desirable solvents. THF and formaldehyde are significant outliers on this last graph because of their particularly poor performance under one of the assessment methods. Methanol, ethanol and methyl acetate are preferred solvents based on their EHS assessment. Heptane, hexane and diethyl ether are preferred based on LCA. However, it must be noted that the LCA was performed based on petrochemical production of the solvents and if the first group of solvents was bio-sourced, perhaps these three solvents... 

Becker, J., Lange, A., Fabarius, ]., and Wittmaim, C. (2015) Xop value platform chemicals bio-based production of organic acids. Curr. Opin. Biotechnol, 36, 168—175. 

The book is organized in several chapters and deals with the most important biopolymer classes like the different polysaccharides (starch, cellulose, chitin), lignin, proteins and (polyhydroxy alkanoates) as raw materials for bio-based plastics, as well as with materials derived from bio-based monomers like lipids, poly(lactic acid), polyesters, polyamides and polyolefines. Additional chapters on general topics - the market and availability of renewable raw materials, the importance of bio-based content and the aspect of biodegradability - provide important information related to all bio-based polymer classes. 

The disadvantages of using mineral acids such as concentrated HCl or H2SO4 to hydrolyse biomass is that they are toxic, corrosive, hazardous and difficult to recycle. The use of heterogeneous solid acids can ease product separation and provide better catalyst recyclability. For example, mesoporous transition metal oxides have been used in biomass transformations. " Polymer-based acids have been employed for the hydrolysis of various organic substrates. " In particular, carbon-based solid acids made by sulfonation of carbonized polymers, such as the solid acid shown in Figure 7.7, have shown promise. Sulfonated bio-char has been similarly used. ... 

Wieschalka S, Blombach B, Bott M, Eikmanns BJ. (2013). Bio-based production of organic acids with Corynebacterium glutamicum. Microb Biotechnol, 6, 87-102. 

Succinic acid can be produced by anaerobic fermentation of several wild-type strains Anaerobiospirillum, Propionibacterium, Escherichia,Pec-tinas. Succinie aeid is eonsidered as one of the major bio-based platform ehemieals (Figure 1.9). Its applieations are foreseen as well in commodity chemicals (THF, hydrojgrsuccinimide etc.), as organic acids (malic, fumaric, itaconic etc.) or polymers (polybutylene succinate, PBS). ... 

Other widely used ion-exclusion columns for the analysis of organic acids in combination with carbohydrates and alcohols are Aminex HPX-87 H (Bio-Rad, Hercules, CA, USA) and Rezex ROA (Phenomenex, Torrance, CA, USA), which are typically operated at elevated temperatures for optimal resolution. Both column substrates are totally sidfonated poly(styrene-co-divinyl-benzene)-based resins with a degree of cross-linking of 8% that slightly differ in particle size. Figure 5.7 illustrates the better resolution and peak shapes with less fronting effects for organic acid analysis on the Rezex ROA colunrn in comparison to the Aminex HPX-87H, while the overall analysis times are comparable. 

---