Biobased industrial chemicals from glutamic acid

In dit onderzoek is op zoek gegaan naar routes om van glutaminezuur vier producten te maken die van waarde zijn voor de industrie, die nu uit olie gemaakt worden. Dat zijn grondstoffen voor allerlei soorten kunststof, zoals nylon en rubbers. Het onderzoek laat zien dat alle vier die producten inderdaad gemaakt kunnen worden uit glutaminezuur. Vervolgens is niet alleen gekeken naar de manier waarop dat zou kunnen, maar ook naar de praktische uitvoerbaarheid, de economische haalbaarheid en de impact op het milieu. Daarbij bleek dat er voor twee van de vier producten nog verbeteringen nodig zijn om te kunnen concurreren met de productie uit olie, maar dat de andere twee industrieel haalbaar kunnen zijn. Productie daarvan uit glutaminezuur vermindert onze afhankelijkheid van fossiele brandstoffen en is beter voor het milieu

Availability of protein-derived amino acids as feedstock for the production of bio-based chemicals

This review describes different potential sources for amino acids that could be used for the production of bulk chemicals in a biorefinery, such as agricultural byproduct streams. Volumes at which these sources and the amino acids therein are available were determined, and the most interesting amino acids in terms of their potential available quantity were identified. The investigated sources are maize and wheat DDGS, sugarcane vinasse and its leaves, sugar beet vinasse and its leaves, cassava leaves, press cakes of rapeseed, sunflower, soybean, palm oil and Jatropha, animal slaughter waste, microalgae, macroalgae, grass and alfalfa. It can be concluded that there are enough sources available to produce bio-based chemicals such as N-methylpyrrolidone with a market sizes around 100 kt per year from amino acids. Bulk chemicals such as acrylonitrile can partly be replaced in the future by their bio-based equivalent, depending on the amounts of biofuels that will be produced in the future. However, it is still necessary to find cost-effective methods for the isolation of amino acids from the discussed source

Synthesis of biobased N-methylpyrrolidone by one-pot cyclization and methylation of c-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 -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%)

Environmental comparison of biobased chemicals from glutamic acid with their petrochemical equivalents

Glutamic acid is an important constituent of waste streams from biofuels production. It is an interesting starting material for the synthesis of biobased chemicals, thereby decreasing the dependency on fossil fuels. The objective of this paper was to compare the environmental impact of four biobased chemicals from glutamic acid with their petrochemical equivalents, i.e. N-methylpyrrolidone (NMP), N-vinylpyrrolidone (NVP), acrylonitrile (ACN), and succinonitrile (SCN). A consequential life cycle assessment was performed, wherein glutamic acid was obtained from sugarbeet vinasse. The removed glutamic acid was substituted with cane molasses and ureum. The comparison between the four biobased and petrochemical products showed that for NMP and NVP the biobased version had less impact on the environment, while for ACN and SCN the petrochemical version had less impact on the environment. For the latter two an optimized scenario was computed, which showed that the process for SCN can be improved to a level at which it can compete with the petrochemical process. For biobased ACN large improvements are required to make it competitive with its petrochemical equivalent. The results of this LCA and the research preceding it also show that glutamic acid can be a building block for a variety of molecules that are currently produced from petrochemical resources. Currently, most methods to produce biobased products are biotechnological processes based on sugar, but this paper demonstrates that the use of amino acids from low-value byproducts can certainly be a method as well. Keywords: biobased chemicals, biorefinery, glutamic acid, life cycle assessment, system expansio

Techno-economic assessment of the production of bio-based chemicals from glutamic acid

In this review, possible process steps for the production of bio-based industrial chemicals from glutamic acid are described, including a techno-economic assessment of all processes. The products under investigation were those that were shown to be synthesized from glutamic acid on lab-scale, namely N-methylpyrrolidone (NMP), N-vinylpyrrolidone (NVP), succinonitrile, and acrylonitrile. The goal was not only to assess the economic feasibility at this stage, but mainly to discover where is the most potential for improvements in these processes, in order to direct future research. The techno-economic assessment leads to the conclusion that the production of NMP and NVP is the most feasible both in terms of technology and economy. Bio-based acrylonitrile and succinonitrile do not seem very profitable under the current process configurations. Especially the acrylonitrile process shows very high costs in relation to the possible gains. Further optimization is necessary, but a clear direction where the optimization should be aimed could be derived from the assessment, and was provided in the discussion of the processes. The main point to optimize was the reaction of glutamic acid with sodium hypochlorite, a bottleneck in both the acrylonitrile and the succinonitrile process

The application of glutamic acid alpha-decarboxylase for the valorization of glutamic acid

Glutamic acid is an important constituent of waste streams from biofuels production. It is an interesting starting material for the synthesis of nitrogen containing bulk chemicals, thereby decreasing the dependency on fossil fuels. On the pathway from glutamic acid to a range of molecules, the decarboxylation of glutamic acid to -aminobutyric acid (GABA) is an important reaction. This reaction, catalyzed by the enzyme glutamic acid -decarboxylase (GAD) was studied on a gram scale. In this study, GAD was immobilized on Eupergit and in calcium alginate and its operational stability was determined in a buffer free system, using various reactor configurations. Immobilization was shown to increase the GAD stability. The conditions for the highest GABA production per gram of enzyme were determined by extrapolation of enzyme stability data. At 30 °C in a fed batch process this results in an average volumetric productivity of 35 kg m-3 hr-1. The cost of using GAD immobilized in calcium alginate was estimated as 5 per metric ton of product. Furthermore it was shown that the cofactor pyridoxal-5-phosphate (PLP) could be regenerated by the addition of a small amount of -ketoglutaric acid to the reactor. In conclusion the application of immobilized GAD in a fed batch reactor was shown to be a scalable process for the industrial production of GABA from glutamic acid. Graphical abstract image for this article (ID: b913741f

Synthesis of Biobased Succinonitrile from Glutamic Acid and Glutamine

Succinonitrile is the precursor of 1,4-diaminobutane, which is used for the industrial production of polyamides. This paper describes the synthesis of biobased succinonitrile from glutamic acid and glutamine, amino acids that are abundantly present in many plant proteins. Synthesis of the intermediate 3-cyanopropanoic amide was achieved from glutamic acid 5-methyl ester in an 86 mol¿% yield and from glutamine in a 56 mol¿% yield. 3-Cyanopropanoic acid can be converted into succinonitrile, with a selectivity close to 100¿% and a 62¿% conversion, by making use of a palladium(II)-catalyzed equilibrium reaction with acetonitrile. Thus, a new route to produce biobased 1,4-diaminobutane has been discovered