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Methyl methacrylate The principal application, consuming approximately 80% of the MMA, is the manufacture of polymethyl methacrylate acrylic plastics (PMMA). Methyl methacrylate is also used for the production of the co-polymer methyl methacrylate-butadiene- styrene (MBS), used as a modifier for PVC. Lucite International is the world's leading supplier of Methyl Methacrylate (MMA). Methacrylates polymerize easily to form resins and polymers with excellent performance characteristics including exceptional optical clarity, strength and durability - especially in aggressive all weather or corrosive environments. They can also be co- polymerized with other monomers to form a broader range of products typically used for paints, coatings and adhesives. Lucite has developed Alpha which is a two-stage, high-yield patented process route to MMA that liberates the industry from its traditional dependence on Acetone, Hydrocyanic acid and Isobutylene. Developed and piloted over a 12-year period, the Company's first world-scale Alpha plant in Singapore was commissioned in 2008 and is now fully operational. It has a capacity of 120kte per annum. The ALPHA technology uses ethylene, methanol and carbon monoxide as readily available and potential biobased raw materials. In addition Alpha has benefits regarding cost (advantage of around 40% over conventional MMA technology) and lower capital investment and variable costs and low environmental impact (76). Other C4 based building blocks Several other C4 based building blocks are currently used at scales around 100 kton/year and up. Important examples are 1,4-butanediol (formed from succinic acid), tetrahydrofuran (THF, from succinic acid), and 1,4-butanediamine (formed from succinic acid). Another interesting building block is (R)-3- hydroxybutyric acid. This building block can be produced by the (enzymatic) hydrolysis of the biosynthesized PHB or via direct biosynthesis routes (117). 9.5 C5 containing compounds Furfural Furfural is one of the members of the Furanics class, which also encompass a group of molecules which include 5- hydroxymethylfurfural, 2,5-furandicarboxylic acid and 2,5- dimethylfuran. The chemical dehydration of five carbon carbohydrates such as xylose and arabinose yields furfural. Furfural is an established chemical product with a static market. World production of furfural has been estimated at around 200,000 tonnes per annum of which 60-70% is used for the production of furfuryl alcohol (58, 92). Its production has rapidly declined in the developed world, while production is increasing in developing regions. China is the world’s principal producer of furfural, followed by the Dominican Republic. It is anticipated that furfural production will increase in the upcoming years probably lowering its costs and making traditional and new outlets of furfural economically attractive again (92). Levulinic acid Levulinic acid can be produced by acid treatment of starch or the C6-carbohydrates in lignocellulosic biomass via the hydration of HMF, an intermediate in this reaction. A side product of this reaction is formic acid which is produced in equimolar amounts. It is also possible to obtain levulinic acid from the five carbon carbohydrates in hemicellulose (e.g. xylose, arabinose) by addition of a reduction step (via furfuryl alcohol) subsequent to the acid treatment. Levulinic acid has been promoted as an important biorefinery building block due to its high yield from six carbon carbohydrates (15). The U.S. company Segetis is commercialising levulinic ketals for a variety of applications (62). Levulinic acid contains two reactive functional groups that allow a great number of synthetic transformations. Figure 12 below shows a number of interesting derivates of Levulinic acid. 22 Figure 12. Chemicals derived from levulinic acid. The Biofine process is commercialised by Maine BioProducts (MBP) and the process works by “cracking” any lignocellulosic feedstock under the influence of dilute mineral acid and moderate temperature, with a novel dual reactor design that allows high throughput and high yields. The cellulose fraction is broken down to form levulinic acid and formic acid as co- product. The hemicellulose fraction is cracked to furfural, which can be delivered as a product, or upgraded to levulinic acid. The lignin, along with some degraded cellulose and hemicellulose and any inerts, comes out of the process as a carbon-rich char mixture which is combusted to produce power for the process and for export (72). Isoprene / Farnesene (Biohydrocarbons) The fermentation of carbohydrates to biohydrocarbons is the latest wave of targets for bio-based chemical production. This opportunity is in part due to the recent advances in synthetic biology which is allowing industry to design microbes for the production of a new range of molecules. Isoprene is a five carbon hydrocarbon used primarily in the production of polyisoprene rubber, styrenic thermoplastic elastomer block copolymers and butyl rubber. Isoprene is found in products ranging from surgical gloves to car tyres. Isoprene has a market value of $1-2 billion. The production of isoprene from renewable resources (BioIsopreneTM) is the target of a joint venture between the Goodyear Tire and Rubber Company and the biotechnology company Genencor (55). Using development samples of BioIsopreneTM from Genencor, Goodyear have produced a synthetic rubber for incorporation in a concept tyre demonstrating the equivalence of BioIsopreneTM with petroleum derived isoprene (56).PDF Image | Bio-based Chemicals Value Added Products from Biorefineries
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