Elinor L. Scott

Biomass in the manufacture of industrial products--the use of proteins and amino acids.

The depletion in fossil feedstocks, increasing oil prices, and the ecological problems associated with CO2 emissions are forcing the development of alternative resources for energy, transport fuels, and chemicals: the replacement of fossil resources with CO2 neutral biomass. Allied with this, the conversion of crude oil products utilizes primary products (ethylene, etc.) and their conversion to either materials or (functional) chemicals with the aid of co-reagents such as ammonia and various process steps to introduce functionalities such as -NH2 into the simple structures of the primary products. Conversely, many products found in biomass often contain functionalities. Therefore, it is attractive to exploit this to bypass the use, and preparation of, co-reagents as well as eliminating various process steps by utilizing suitable biomass-based precursors for the production of chemicals. It is the aim of this mini-review to describe the scope of the possibilities to generate current functionalized chemical materials using amino acids from biomass instead of fossil resources, thereby taking advantage of the biomass structure in a more efficient way than solely utilizing biomass for the production of fuels or electricity.

Lignin depolymerisation in supercritical carbon dioxide/acetone/water fluid for the production of aromatic chemicals

Valorisation of lignin plays a key role in further development of lignocellulosic biorefinery processes the production of biofuels and bio-based materials. In the present study, organosolv hardwood and wheat straw lignins were converted in a supercritical fluid consisting of carbon dioxide/acetone/water (300-370°C, 100bar) to a phenolic oil consisting of oligomeric fragments and monomeric aromatic compounds with a total yield of 10-12% based on lignin. These yields are similar to the state-of-the-art technologies such as base-catalysed thermal processes applied for lignin depolymerisation. Addition of formic acid increases the yield of monomeric aromatic species by stabilizing aromatic radicals. Supercritical depolymerisation of wheat straw and hardwood lignin yielded monomeric compounds in different compositions with a maximum yield of 2.0% for syringic acid and 3.6% for syringol, respectively. The results of the present study showed that under the applied conditions competition occurred between lignin depolymerisation and recondensation of fragments.

Immobilised enzymes in biorenewable production

Oils, fats, carbohydrates, lignin, and amino acids are all important raw materials for the production of biorenewables. These compounds already play an important role in everyday life in the form of wood, fabrics, starch, paper and rubber. Enzymatic reactions do, in principle, allow the transformation of these raw materials into biorenewables under mild and sustainable conditions. There are a few examples of processes using immobilised enzymes that are already applied on an industrial scale, such as the production of High-Fructose Corn Syrup, but these are still rather rare. Fortunately, there is a rapid expansion in the research efforts that try to improve this, driven by a combination of economic and ecological reasons. This review focusses on those efforts, by looking at attempts to use fatty acids, carbohydrates, proteins and lignin (and their building blocks), as substrates in the synthesis of biorenewables using immobilised enzymes. Therefore, many examples (390 references) from the recent literature are discussed, in which we look both at the specific reactions as well as to the methods of immobilisation of the enzymes, as the latter are shown to be a crucial factor with respect to stability and reuse. The applications of the renewables produced in this way range from building blocks for the pharmaceutical and polymer industry, transport fuels, to additives for the food industry. A critical evaluation of the relevant factors that need to be improved for large-scale use of these examples is presented in the outlook of this review.

Optimization of the dilute maleic acid pretreatment of wheat straw.

BackgroundIn this study, the dilute maleic acid pretreatment of wheat straw is optimized, using pretreatment time, temperature and maleic acid concentration as design variables. A central composite design was applied to the experimental set up. The response factors used in this study are: (1) glucose benefits from improved enzymatic digestibility of wheat straw solids; (2) xylose benefits from the solubilization of xylan to the liquid phase during the pretreatment; (3) maleic acid replenishment costs; (4) neutralization costs of pretreated material; (5) costs due to furfural production; and (6) heating costs of the input materials. For each response factor, experimental data were fitted mathematically. After data translation to €/Mg dry straw, determining the relative contribution of each response factor, an economic optimization was calculated within the limits of the design variables.ResultsWhen costs are disregarded, an almost complete glucan conversion to glucose can be reached (90% from solids, 7%-10% in liquid), after enzymatic hydrolysis. During the pretreatment, up to 90% of all xylan is converted to monomeric xylose. Taking cost factors into account, the optimal process conditions are: 50 min at 170°C, with 46 mM maleic acid, resulting in a yield of 65 €/Mg (megagram = metric ton) dry straw, consisting of 68 €/Mg glucose benefits (from solids: 85% of all glucan), 17 €/Mg xylose benefits (from liquid: 80% of all xylan), 17 €/Mg maleic acid costs, 2.0 €/Mg heating costs and 0.68 €/Mg NaOH costs. In all but the most severe of the studied conditions, furfural formation was so limited that associated costs are considered negligible.ConclusionsAfter the dilute maleic acid pretreatment and subsequent enzymatic hydrolysis, almost complete conversion of wheat straw glucan and xylan is possible. Taking maleic acid replenishment, heating, neutralization and furfural formation into account, the optimum in the dilute maleic acid pretreatment of wheat straw in this study is 65 €/Mg dry feedstock. This is reached when process conditions are: 50 min at 170°C, with a maleic acid concentration of 46 mM. Maleic acid replenishment is the most important of the studied cost factors.

Fractionation, analysis, and PCA modeling of properties of four technical lignins for prediction of their application potential in binders.

Abstract Functional properties of technical lignins need to be characterized in more detail to become a higher added value renewable raw material for the chemical industry. The suitability of a lignin from different plants or trees obtained by different technical processes can only be predicted for selected applications, such as binders, if reliable analytical data are available. In the present paper, structure dependent properties of four industrial lignins were analyzed before and after successive organic solvent extractions. The lignins have been fractionated according to their molar mass by these solvents extractions. Kraft and soda lignins were shown to have different molar mass distributions and chemical compositions. Lignin carbohydrate complexes are most recalcitrant for extraction with organic solvents. These poorly soluble complexes can consist of up to 34% of carbohydrates in soda lignins. Modeling by principle component analysis (PCA) was performed aiming at prediction of the application potential of different lignins for binder production. The lignins and their fractions could be classified in different clusters based on their properties, which are structure dependent. Kraft softwood lignins show the highest potential for plywood binder application followed by hardwood soda lignin and the fractions of Sarkanda grass soda lignin with medium molar mass. Expectedly, the softwood lignins contain the highest number of reactive sites in ortho positions to the phenolic OH group. Moreover, these lignins have a low level of impurities and medium molar mass.

Assessment of technological options and economical feasibility for cyanophycin biopolymer and high-value amino acid production

Major transitions can be expected within the next few decades aiming at the reduction of pollution and global warming and at energy saving measures. For these purposes, new sustainable biorefinery concepts will be needed that will replace the traditional mineral oil-based synthesis of specialty and bulk chemicals. An important group of these chemicals are those that comprise N-functionalities. Many plant components contained in biomass rest or waste stream fractions contain these N-functionalities in proteins and free amino acids that can be used as starting materials for the synthesis of biopolymers and chemicals. This paper describes the economic and technological feasibility for cyanophycin production by fermentation of the potato waste stream Protamylasse™ or directly in plants and its subsequent conversion to a number of N-containing bulk chemicals.

Deoxygenation of biobased molecules by decarboxylation and decarbonylation – a review on the role of heterogeneous, homogeneous and bio-catalysis

Use of biomass is crucial for a sustainable supply of chemicals and fuels for future generations. Compared to fossil feedstocks, biomass is more functionalized and requires defunctionalisation to make it suitable for use. Deoxygenation is an important method of defunctionalisation. While thermal deoxygenation is possible, high energy input and lower reaction selectivity makes it less suitable for producing the desired chemicals and fuels. Catalytic deoxygenation is more successful by lowering the activation energy of the reaction, and when designed correctly, is more selective. Catalytic deoxygenation can be performed in various ways. Here we focus on decarboxylation and decarbonylation. There are several classes of catalysts: heterogeneous, homogeneous, bio- and organocatalysts and all have limitations. Homogeneous catalysts generally have superior selectivity and specificity but separation from the reaction is cumbersome. Heterogeneous catalysts are more readily isolated and can be utilised at high temperatures, however they have lower selectivity in complex reaction mixtures. While bio-catalysts can operate at ambient temperatures, the volumetric productivity is lower. Therefore it is not always apparent in advance which catalyst is the most suitable in terms of conversion and selectivity under optimal process conditions. Here we compare classes of catalysts for the decarboxylation and decarbonylation of biobased molecules and discuss their limitations and advantages. We mainly focus on the activity of the catalysts and find there is a strong correlation between specific activity (turn over frequency) and temperature for metal based catalysts (homogeneous or heterogeneous). Thus one is not more active than the other at the same temperature. Alternatively, enzymes have a higher turnover frequency but drawbacks (low volumetric productivity) should be overcome.

Synthesis of biobased N-methylpyrrolidone by one-pot cyclization and methylation of γ-aminobutyric acid

N-Methylpyrrolidone (NMP) is an industrial solvent that is currently based on fossil resources. In order to prepare it in a biobased way, the possibility to synthesize NMP from γ-aminobutyric acid (GABA) was investigated, since GABA can be obtained from glutamic acid, an amino acid that is present in many plant proteins. Cyclization of GABA to 2-pyrrolidone and subsequent methylation of 2-pyrrolidone to NMP was achieved in a one-pot procedure, using methanol as the methylating agent and a halogen salt (i.e. ammonium bromide) as a catalyst. A selectivity above 90% was achieved, as well as a high conversion. Methylation of 2-pyrrolidone could also be done with dimethyl carbonate, but then the selectivity for NMP was less (67%).

A study on the applicability of L-aspartate α-decarboxylase in the biobased production of nitrogen containing chemicals

β-Alanine could serve as an intermediate in the biobased production of nitrogen containing chemicals from L-aspartic acid. Following the biorefinery concept, L-aspartic acid could become widely available from biomass waste streams via the nitrogen storage polypeptide cyanophycin. Since α-decarboxylation of L-aspartic acid is difficult to perform chemically, the applicability of Escherichia coliL-aspartate α-decarboxylase (EC 4.1.1.11) (ADC) for the production of β-alanine was studied. With an increasing activity up to 90 °C and maintaining its activity upon storage for 24 hours at 60 °C, ADC showed a remarkably high thermostability. ADC has an optimum at pH 7.5 and starts to lose activity upon storage below pH 6. An inhibiting effect by β-alanine was not observed. Immobilization on Sepabeads EC-EP and EC-HFA epoxy supports did not result in an increased thermostability, but did improve operational stability. Nonetheless, enzyme inactivation occurs during catalysis, probably caused by irreversible transamination of the catalytically essential pyruvoyl group.

Biobased synthesis of acrylonitrile from glutamic acid

Glutamic acid was transformed into acrylonitrile in a two step procedure involving an oxidative decarboxylation in water to 3-cyanopropanoic acid followed by a decarbonylation-elimination reaction using a palladium catalyst.