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Bioenergy-bioproducts. Agenda. Fermentation Xylitol Lignin Products from glycerin, class discussion based on the article. A Historical Perspective. Evidence of fermentation dates to 6,000 BC Egyptians brewed a beer-like substance Mid-1800s Louis Pasteur
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Agenda • Fermentation • Xylitol • Lignin • Products from glycerin, class discussion based on the article
A Historical Perspective Evidence of fermentation dates to 6,000 BC Egyptians brewed a beer-like substance Mid-1800s Louis Pasteur Late 19th - ~1940 Alcohol Fuels WWI Acetone for nitrocellulose WWII Penicillin Production 1970s Oil Embargo Brazil EtOH programs Today Everything’s from Fermentation http://www-bioc.rice.edu/bios576/nih_bioreactor/NDL_Bioreactor%20Page.htm#contents
Food & Beverages Soy Sauce, Pickles Beer & Wine Fuels Ethanol & Butanol Methane Pharmaceuticals Insulin, HGH Enzymes Cellulase, Rennet Organic Acids Lactate, Formate, Succinate Solvents Acetone Vitamins Amino Acids Biochemical Products http://en.wikipedia.org/wiki/File:Succinic-acid-3D-balls.png http://blogs.timesunion.com/saratogaseen/?m=200804 http://www.3dchem.com/molecules.asp?ID=196
Fast-Growing Robust Minimal Product Inhibition High Product Tolerance Easy to Manipulate Safe Degrade Lignocellulosic Material Ferment ALL Resulting Sugars High Rates and Yields The Ideal Microbe http://microbe.wikispaces.com/Microbe
Ethanol Saccharomyces cerevisiae Zymomonas mobilis Thermoanaerobacter BGL1L1 Butanol Clostridium acetobutylicum Escherichia coli C. beijerinkii Lignocellulose Digestion Clostridium thermocellum Microbial Diversity http://blogs.princeton.edu/chm333/f2006/biomass/bioethanol/06_major_issue_biobutanol/ http://www.bath.ac.uk/bio-sci/research/profiles/wheals-a.html http://www.nrel.gov/data/pix/searchpix.cgi?getrec=3308686&display_type=verbose
Media/Feedstock http://en.wikipedia.org/wiki/Industrial_fermentation
Simple Few steps Fast/short residence time Actual yield = theoretical yield High productivity Recoverable catalyst (the cells) Easily separable culture The Ideal Process
Controls pH Temperature Agitation Headspace Composition Pressure Volume Residence Time Bioreactor Breakdown http://www.abe.ufl.edu/%7Echyn/age4660/lect/lect_21/lect_21.htm
Problems • Baker’s cannot utilize five carbon sugars to produce ethanol • Genetically modified microorganisms (E.coli KO11, Z.mobilis, P.stipitis) • have diverse nutrient requirements • not as robust as baker’s yeast • cannot tolerate/metabolize inhibitors generated during pretreatment • For biomass to ethanol process to be economically feasible it has to produce high value co-products
Inhibitors • 5 groups of inhibitors • Released during pretreatment and hydrolysis • Acetic acid and extractives • By-products of pretreatment and hydrolysis • HMFs and furfurals, formic acid • Lignin degradation products • Aromatic compounds • Fermentation products • Ethanol, acetic acid, glycerol, lactic acid • Metals released from equipment
Xylitol (1) • Sweetener • as sweet as sucrose • 40% less calories (suitable for diabetics, does not use insulin to be metabolized) • Recommended for oral health • teeth hardening • antimicrobial properties (causes bacteria to lose the ability to adhere to the tooth stunting the cavity causing process)
Xylitol (2) • Feels and tastes exactly like sugar and leaves no unpleasant aftertaste • Currently produced via chemical way • acid hydrolysis • hydrogenation and purification (expensive) • Uses: • natural sweetener • chewing gun • tooth paste
Xylitol (3) Imagine eating guilt xylitol-sweetened brownies or knowing that xylitol-sweetened chewing gum is preventing cavities and gum disease. With xylitol, you can now have your sweet tooth and treat it, too!
Pink yeast • Novel, naturally occurring, robust yeast from genus Rhodotorula selected from poplar trees • Tolerant of (and capable of metabolizing) high concentrations of fermentation inhibitors • Rapidly and effectively utilizes both hexose and pentose sugars PTD3 5-C & 6-C sugars • Ethanol • Xylitol
How do we do it? Fermentation Synthetic sugars or hydrolysate Flasks Sugar, ethanol, xylitol analysis HPLC
Mixed synthetic sugars Experimental Yields: Xylitol: 70% Ethanol: 84% 6C EtOH 5C XOH
PTD3 in steam exploded hardwood and softwood mixture Experimental Yields: Xylitol: 68% Ethanol: 100% 5C EtOH XOH 6C
Xylitol-conclusions • Yes, Pink yeast is able to efficiently utilize 5 and 6C to produce lots of ethanol and xylitol • Glucose 85% EOH • Galactose 86% EOH • Mannose 94% EOH • Xylose 64% XOH • Arabionse 29% XOH
Lignin • 3-dimensional phenolic polymer • Complex structure • Composes ~15-40% of lignocellulosic biomass • 2nd most abundant natural polymer Sakakibara
Lignin: current use • In Kraft pulping, lignin is recovered in black liquor • 50 million metric tons produced annually worldwide • ~95% of this is incinerated for thermal electrical energy • Burning generates an average fuel value of 23.4 MJ/kg
Arboform • A lignin-based thermoplastic • Made from a mixture of lignin, plant fibers, and waxes • Developed by German company Tecnaro in 1998 • Appearance and some physical properties similar to wood • Moldable like plastic
Arboform: chemical properties • Pelletized mixture of lignin, fine fibers of wood, hemp or flax, and wax • Up to 50% lignin • Liquifies at temperatures as low as 170°C • Polypropylene: ~160°C • Polyethylene: 105-120°C • Polystyrene: ~240°C • Thermally stable up to 105°C • Can be injection molded similar to conventional plastic
Arboform: physical properties • Better molding capabilities than plastic • Irregular fiber orientation resists warping • Flooring & building material • Good acoustic properties (speakers & musical instruments) • Currently 300 metric tons produced annually
Disadvantages: Some forms are not water resistant Requires removal of sulfur Cost: $1.60/lb, compared with less than $1/lb for polypropylene Arboform: pros and cons • Advantages: • Completely biodegradable • Can be burned after use • Not made from crude oil • At least as strong as plastic
An alternative to plastic? • More than 100 million metric tons of plastics originating from crude oil are produced annually (worldwide) • The pacific trash vortex is twice the size of Texas, reaches 300 feet below sea level, and 90% of it is plastic
Lignosulfonates • Lignosulfonates is the name for a product containing sulfonated lignin and other wood chemicals. • Mainly from the acid sulfite process. • A small amount from sulfonated kraft lignin. • Before becoming lignosulfonates (marketable product), this material (spent sulfite liquor) is “cleaned up”. • Pulping chemicals are removed. • Sometimes non lignin compounds (sugars, etc) are removed chemically, biologically, or through physical methods. • Often the lignin is chemically modified. • Product is concentrated to a molasses thickness product or to a powder.
Lignosulfonates-uses • Dispersant • Concrete, Dyes, Gypsum wallboard • Binder • Road dust control, animal feed • Emulsifier (think an oil and vinegar salad dressing). • Emulsions are finely dispersed drops of oil or wax in water. • Lignin acts a s stabilizer in the emulsion. • Chelating agent • Oil Well Drilling Fluids, Micronutrient Fertilizers • Raw material for chemical production • Vanillin (softwood)
Concrete dispersant • Concrete is made up of 3 ingredients: cement, sand, and aggregate. • Water is mixed in to make a workable slurry and to harden the concrete. • By using a dispersant like lignosulfonates, less water can be used to get the same viscosity slurry. This makes stronger concrete. Image borrowed from JimRadfprd.com
Dye dispersant • Dyes used to dye cloth are water insoluble. • In order to dye cloth, dye particles are dispersed in water. What this means are the dye particles are small enough that they pretty much act like they are dissolved. A dispersant keep them apart so they don’t get big and sink. Sulfonated lignins do this very well. After dying, the lignin is washed out.
Dusty roads are considered a health hazard by the government and thus dust control is mandated Dust can be controlled with water, lignosulfonates or calcium chloride. Binding-dust control
Binding-dust control • Lignosulfonates cause the particles to pack closer together and also to adhere. • This process forms a dust “free” and also more stable road.
Pellet binder • The natural stickiness of lignosulfonates help them function as a pellet binder; it helps hold the material together.
Glycerin and products • Class discussion
Acknowledgements “Bioenergy Lab” on Alcatraz At the 31st Symposium on Biotechnology for Fuels and Chemicals