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Biobased chemicals
- 1. Biobased Chemicals Presented by S.Rasoulinejad Msc, Microbial Biotechnology Winter 2013-2014
- 2. introduction Bio-based chemicals are derived from renewable feedstock, i.e. all biomass derived from plants, animals or microorganisms (including biological waste from households, agricultural residues, and waste from animals and food/feed production), which can be used in part or as a whole as raw materials for industrial production and energy generation. is important to differentiate between 1st and 2nd generation technology for the production of biofuels and bio-based chemicals. First generations Second generations
- 3. Analysis of markets for bio-based products There is a wide range of bio-based products which could eventually acquire a substantial market acceptance: Fibre based materials (i.e. for construction sector or car industry); Bio-plastics and other bio-polymers; Surfactants; Bio-solvents; Bio-lubricants; Ethanol and other chemicals and chemical building blocks; Pharmaceutical products incl. vaccines; Enzymes; Cosmetics.
- 4. bio-solvents, produced from vegetable oils and from starch progressively replace petrochemical solvents. Solvents mainly part of paintings, inks, varnishes, adhesives etc. Majority of solvents currently petrochemical solvents. Biopolymers, such as polysaccharides (carbohydrates – starch from maize, wheat, and potatoes). Polylactic Acid (PLA), a plastic material derived by fermentation (producing lactic acid) from starches or glucose. Used for food packaging, bags, hygiene products, packaging for biological waste, plant pots, etc. Also composite materials with new qualities; textiles, etc.
- 5. Surfactants lower surface tension of liquids and are used in soaps, detergents, pharmaceuticals, food additives, etc. and for the production of emulsions and foams. They are produced largely from oils. Next generation "biosurfactants" can be produced from algae or bacteria. Biodegradable lubricants made from vegetable oils (and their chemical derivatives) that are non toxic for soil or water. Used as hydraulic oils in areas where high risk of pollution.
- 6. The chemicals of interest are the ones that could potentially serve as building blocks, platforms, for other chemicals and polymers. Glycerol, a by-product of biodiesel production, was used as raw material for the production of propionic acid, 3-hydroxypropionaldehyde (3HPA) and 3hydroxypropionic acid (3HP), while methacrylic acid (MA) was produced from 2-methyl-1,3-propanediol, a by-product of butanediol production. Lactobacillus reuteri was employed as a whole cell biocatalyst for the conversion of glycerol to 3HPA and 3HP in aqueous solution.
- 7. Potato juice, a by-product of potato starch processing, was shown to be a promising, inexpensive nitrogen/vitamin source for the growth of the organism and propionic acid production
- 8. Propionic Acid Production by Microbial Fermentation of Glycerol The main production route of propionic acid is the oxo-synthesis through hydroformylation of ethylene with carbon monoxide yielding the intermediate propionaldehyde, which gives propionic acid on oxidation. It is also obtained as a by-product of the chemical production of acetic acid by liquid phase oxidation of n-butanePresents the current status for propionic acid production from glycerol using propionibacteria in batch/fed-batch operations.
- 9. oxo-synthesis The process typically entails treatment of an alkene with high pressures (between 10 to 100 atmospheres) of carbon monoxide and hydrogen at temperatures between 40 and 200 C. Transition metal catalysts are required)
- 10. microorganisms can produce propionic acid -Veillonella (parvula and alcalescens) -Clostridium propionicum, -Selenomonas (ruminantium and sputigena) -Megashaera -Fusobacterium necrophorum Among them, propionibacteria have been mostly used as hosts for propionic acid production Fig. 3.1 Probionibacteria SEM of P. acidipropionici DSM 4900 grown on glycerolbased medium.
- 11. Fig. 3.2 Propionic acid fermentation pathway The metabolic pathway for propionic acid production from different carbon sources, showing the Wood-Werkman cycle, different intermediates and the metabolic end products. [1] Methylmalonyl-CoA transcarboxylase (pyruvate carboxytransphosphorylase) [2] Malate dehydrogenase [3] Fumarase [4] Succinate dehydrogenase [5]Propionyl-CoA:Succinate CoA transferase [6] Methylmalonyl-CoA mutase (isomerase) [7] Methylmalonyl-CoA racemase [8] Propionaldehyde dehydrogense (Predicted) [9] Alcohol dehydrogenase (Predicted)
- 12. Bio-plastics Existing and emerging bio-based bulk plastics are starch plastics, cellulosic polymers, polylactid acid (PLA), polytrimethylene terephthalate (PTT) from bio-based 1,3-propanediol (PDO), bio-based polyamides (nylon), polyhydroxyalkanoates (PHAs), bio-based polyethylene (PE), polyvinyl chloride (PVC) from bio-based PE, other bio-based thermoplastics (polybutylene terephthalate (PBT), polyphenylene sulphide (PBS), polyethylene terephthalate (PET), polyethylene-co-isosorbide terephthalate polymer (PEIT), further polyesters based on PDO), polyurethane (PUR) from bio-based polyols and bio-based thermosets.
- 13. Bio-solvents Solvents are liquids that possess the ability to dissolve, dilute or extract other substances without modifying the chemical composition of the extracted substances or of the solvent itself. There are eight main solvent groups: aromatic hydrocarbons, petroleum-based solvents, alcohols, ketones, esters, ethers, glycol ethers, halogenated hydrocarbons and so-called special solvents.
- 14. Base on their properties, solvents are used as degreasing agents (cleaning of metals, textiles), additives and diluting compounds (paints, varnishes, inks, glues, pesticides), stripping agents (paint, varnish, glue removers) and extraction solvents (perfumes, pharmaceuticals). Biosolvents have applications: plant-protection oils and wetting agents and biofluxing agents. The vast majority of bio-based solvents do not emit volatile organic compounds (VOC) which are harmful to human health.
- 15. Bio-surfactants Surfactants lower the surface tension of liquids, allowing chemicals to mix more easily. Surfactants are usually organic compounds that are amphiphilic, meaning they contain both hydrophobic groups (their tails) and hydrophilic groups (their heads). Bio-surfactants are surfactants in which at least one of the two groups (hydrophilic or hydrophobic) is obtained from plants: they are therefore not necessarily 100% plant-derived.
- 16. Application of bio-surfactants Surfactants are used in many industries such as household detergents, personal care, industrial cleaners, food processing, oleofield chemicals, agricultural chemicals, textiles, emulsion polymerization, paints and coatings, lubricant and fuel additives, metal working, mining chemicals, pulp and paper production, leather processing, etc. The largest end use market for surfactants is household cleaning detergents.
- 17. Raw materials Surfactants are made from oleochemical (bio-based) and/or petrochemical (synthetic) raw materials. Oleochemical surfactants are commonly derived from plant oils such as coconut and palm oils, from plant carbohydrates such as sorbitol, sucrose and glucose or from animal fats such as tallow. In a typical palm plantation, besides the oil and lignocellulosic biomass sources, there is some activity to convert palm oil mill effluent (POME) to high value chemicals and biogas. In the case of corn wet mill and sugar cane plantations, biomass is converted to fuel (mostly bio ethanol) and chemicals such as polyols, acids, and others.
- 20. Platform chemicals Sugars, Oils and other compounds in biomass can be converted into platform chemicals or building blocks directly or as by-products from fuel production processes analogous to the petrochemical industry today.
- 21. Biomass feed stock Intermediat e platform Building blocks Secondry chemicals starch Biobased Syn gas H2 Methan Higher alcohol Mixed alcohols Oxo syntheseis products ....... Ammonia synthesis, hydrogenation products Methyl esters,Formaldehyde, Acetic acid, Dimethylether, Dimethylcarbonate, Methyl amines, MTBE, olefins, Gasoline Olefinhydroformylationproducts: aldehydes, alcohols, acids.... Reagents-building unit Fuel oxygenates Solvents Amines Phenol-formaldehyde resins Plasticizers Polyvinyl acetate Polyvinyl alcohol Industrial transportation Glycerol Lactic Propionic acid ...... Fermentation products, Propylene glycol, malonic, 1,3PDO, diacids, propylalcohol, dialdehyde, epoxides Reagent, propionol, acrylate.... Antifreeze and deicers Emulsifiers textiles Fumaric acid Aceton Malic acid ...... THF, 1,4-Butanediol γ-butyrolactone, pyrrolidones, esters, diamines,4,4-Bionelle, Hydroxybutyricacid Butanediols, butenols..... Green solvents Polypyrrolidones Phthalate polyesters Safe food supply Furfural Xylitol/arabitolitaconic acid Itaconic acid .... Methyl succinatederivatives (see above), unsaturated esters many furan derivatives EG, PG, glycerol, lactate, hydroxyfurans, sugar acids..... Resins, crosslinkers Polyethers Polyhydroxypolyesters Specialty chemical intermediate Communication environment Citric/aconitic acid Lysine Sorbitol ..... 1,5-pentanediol, itaconicderivatives, pyrrolidones, esters, Numerous furan derivatives, succinate, esters, levulinicacid Glycols (EG, PG), glycerol, lactate, isosorbide Caprolactam, diaminoalcohols, 1,5-diaminopentane hemicellul ose cellulose Lignin oil protein Sugers: Glucose Fructose Xylose Lactose Sucrose starch Gallic acid Ferulic acid Direct polymers & gum intermediates Polyurethanes Nylons (polyamides) PEIT polymer Products/uses Recreation housing Health and hygience Phenolics, food additives Poyaminoacids Polysaccharides polyhydroxyalkonoates
- 23. Which Way to Go? Various building block molecules such as 5-hydroxymethylfurfural (HMF), derived from cellulosic biomass, Startup companies such as Segetis: are developing novel chemicals based on levulinic acid for use as replacement solvents and plasticizers. Roquette :has been actively pursuing commercial scale production of isosorbide from sugar feedstock useful in the development of bioplasticizers and bisphenol free polycarobonate resins.
- 24. In the case of bio plasticizers reFlexTM 100 thermal stability, and improved plasticization efficiency butyl benzyl phthalate [BBP] diisononylcyclohexane-1, 2 dicarboxylate (DINCH)
- 26. This is very true for bio products such as bio ethylene derived from sugar cane or bio 1, 3 propane diol that are targeted to replace corresponding petroleum derived products.
- 28. Pathways to Building Blocks from Sugars
- 29. industrial Corrosion inhibitors, dust control, boiler water treatment, gas purification, emission abatement, specialty lubricants, hoses, seals transportation Fuels, Oxygenates, Anti-freeze, Wiper fluids molded plastics, Car seats, Belts hoses, Bumpers, corrosion inhibitors textiles Carpets, Fibers,fabric, Coatings, Foam cushions,uphols tery,drapes, Lycra, spandex Safe food supply Food packing, Presevatives, Fertilizers, Pesticides, beverage bottles, Appliances, Beverage can coating, vitamins environment communication Water chemicals, Flocculants, Chelators, cleaners and detergents Molded plastics, Computer casings, Optical fiber coating,liquid crystal displays, pens, pencils, inks, Dyes, Paper products housing Paints, Resins, Siding, Insulation, Cements, Coatings, Varnishes, Flame retardents, Adhesives, carpeting recreation Health and hygience Footgear, Protectives equipment, Camera and film, Bicycle parts & tires, Wet suits, Tapes-CD’sDVD’s, Golf equipment, Camping gear,boats Plastic eyeglasses, Cosmetics, Detergents, Pharmaceuticals , Suntan lotion, Medical-dental product, aspirin Figure 3 – Analogous Model of aBiobasedProduct Flow-chart for BiomassFeedstocks
- 30. Sugar-based platform. Platforms based on sugars (Werpy, et al., 2004) have been deployed to create acids such as succinic acid and convert the acid to high value chemicals such as: 2- pyrrolidone, 1, 4 butane diol, tetra hydrofuran and others.
- 33. Polyethylene terephthalate PET Polybutylene terephthalate and PBT
- 34. Chemical Economics Handbook® (CEH)
- 36. Solar cells for sustainable production of methanol from CO2 In the BIOCOMET project, The researchers simulate the photosynthesis process in plant cells by manufacturing biomethanol on a large-scale, using solar cells for the purpose. (Bio)methanol is used as a raw material for making plastics (including bioplastics) and also in fuels (for biodiesel and for the fuel additive MTBE). This project is part of the BioSolar Cells programme and enables Wageningen UR Food & Biobased Research to contribute to the Biobased Economy.
- 37. Tulip compounds for production of biobased polymers Tulips produce tulipaline and tuliposides. These compounds play a role in the protective mechanisms of the plant and also fight bacteria, fungi and insects. Also, the compounds are suitable as building blocks for the production of plastics
- 38. Producing hydrogen from biomass Hydrogen is a promising fuel for the future biomass may be used as a raw material, the conversion to electricity is extremely efficient, and hydrogen does not contribute to the production of CO2. Up to the present, residual materials from the food industry, potato steam peels, molasses, wheat bran, and barley straw have all been studied for their potential as biomass. Eventually, cultivated biomass such as sugar beets and sweet sorghum will also be added to this list.
- 39. Fermentations About Wageningen UR The core of biochemical hydrogen production consists of two consecutive fermentations : During the first fermentation, when they reach 70ºC, thermophilic (heat-loving) bacteria convert the substrate to hydrogen, CO2 and organic acids. During the following fermentation, with the aid of light energy, bacteria convert the organic acids to hydrogen and CO2. This makes it possible to raise the efficiency level of the hydrogen production as high as 75%.
- 40. Thanks for you attention
Notas del editor
- Distinction is based on therenewable feedstock: 1st generation technology uses food components, such asvegetable oils, sugar and grain or animal fats, whereas 2nd generation refers tonon-food biomass, i.e. energy crops, waste biomass or agricultural residues.
- Lactobacillus reuteri was employed as a whole cell biocatalyst for the conversion of glycerol to3HPA and 3HP in aqueous solution.
- As well, propionic acid is integrated in cellulose acetate propionate (CAP) plastics, which are used for the manufacture of textiles, fibres, and reverse osmosis membranes.هم چنین ، پروپیونیک اسیدی که اینگره هستش در سلولز استات پروپیونات پلاستیک، که استفاده میشه برای ساخت منسوجات، فیبر ها و غشاهای ریورس اسمزیسit is also used in the production of anti-arthritic and antibiotic drug preparations, herbicides, flavours and perfumesIt can be converted to acrylates which are used in paints, resins and other products (Hasegawa et al. (1982) showed the possibility of conversion of propionic acid to 3HP, another important platform chemical, using a mutant strain of Candida rugosa)همین طور در تولید آنتی بیوتیک، ضد درد مفاصل و آماده سازی برخی دارو ها، علف کش ها، طعم ها ( اسانس ها) و عطر هاهمین طور می تونه کانورت بشه به آکریلات ( پروپنوعات ؛ نمک یا استری از پروپنوییک اسید ) که در نقاشی ، رزین ها و سایر تولیدات ( هسگاوا در سال 1982 نشان داد که احتمال تبدیل پروپیونیک اسید به 3-هیدروکسی...... با استفاده از یک گونهی موتانت شده ی کاندیدا روگوسا)
- میکرو اورگانیسم هایی که توانایی تولید پروپیونیک اسید دارند:Propionibacteria are Gram-positive, non-spore پروپیون باکتری ، باکتری گرم مثبت ، بدون اسپورforming, non-motile, facultative anaerobic, حرکت ندارد،بی هوازی های گوناگونpleomorphic, rod-like microorganisms (Fig. 3.1) چند شکلی ،میله ای شکل همون طور که در شکل مشخص شده[71]. Based on their natural habitat, بر اساس زیستگاه طبیعیشون این باکتری تقسیم بندی میشه:propionibacteria are classified into: classical انواعی که از محصولات لبنی مانند شیر و پنیر جدا میشن(dairy) propionibacteria isolated from cheese andmilk and include P. freudenreichii, P. jensenii, P. مثل:پ.فرئودنریچی،پ.جنسی،پ.توئنی،پ.اسیدیپروپیونیک،پ.کوکوئیدسthoenii, P. acidipropionici, P. coccoides, P.cyclohexanicum, and cutaneous propionibacteriaisolated from human skin and include P. acnes,P. avidum and P. granulosum [71]. Besidepropionic acid, propionibacteria also produce a علاوه بر پروپیونیک اسید که پروپیونیک باکتری تولید می کند یکسری مواد صنعتی دیگه هم تولید می کنه مثل number of other industrially important productsincluding vitamin B12, trehalose, bacteriocins and exopolysaccharides [72-75] ویتامین ب12،ترهالوز،باکتریوسین و اگزو پلی ساکاریدها( پلی مری با وزن مولکولیه The whole cells of propionibacteria are even used/or can be potentially used as زیاد که از باقی مانده قند ها تشکیل میشه و توسط باکتری به محیط پیرامون ترشح starter cultures in cheese manufacture, unicellular protein for animal feed, تمامی می تونند یا پتانسیل اینکه به عنوان استاتر در پنیر استفاده کنند، مواد افزودنی leavening additive for baking, and in preparation of ensilage [71]. برای نان و و و و .....
- The type and the degree of reduction (γ) of the carbon source influences the انواع درجه ی عدد کاهش برای منبع کربن تاثیر میذاره الگو های متابولیکی به دست امدpattern of metabolic by-products obtained [76]. With the majority of carbon با اکثریت منبع کربن شامل گلوکز ، لاکتوز ، زایلوز، سوکروزو لاکتات، استیک اسید به sources including glucose, lactose, xylose, sucrose and lactate, acetic acid is عنوان مادهی جانبی اصلی تولید شده به حساب میاد در حالیکه گلیسرول درست مقابل obtained as a major by-product (Eq8, 9)1. Glycerol, in contrast, این هستش که منجر به به یک الگوی همو پروپیونات فرمنتیشن میشه با بازده بالاtriggers ahomopropionate fermentation pattern leading to a high propionate yield (Eq10)[52, 77-79]. Since glycerol is more reduced than other carbon sources, its گلیسرول نسبت به سایر منابع کربن بیشتر کاهش می یابد ،conversion to pyruvate generates higher amount of reducing equivalents, drivingthe metabolic flux towards propionic acid to achieve the required co-factor balance.Glucose, on the other hand, generates lower amount of reducing equivalents, and در حالیکه گلوکز کمترین میزان کاهش رو داره و علاوه بر این تولید استاتhence acetate production is preferred as a source for ATP, yielding higher cell ترجیح داده میشه به عنوان منبع برای انرژِی، ابزدهی و دنسیت تولیدdensity. Consequently, the molar ratio of propionic acid to acetic acid (PA/AA) is در نتیجه ، نسبت پروپیونیک اسید به استیک اسید به طور زیادی تحت اثر منبع کربن greatly affected by the carbon source and could vary between 2:1 when lactate is هستش و می تونه متفاوت باشه بین 2و 1در حالیکه لاکتات استفاده میشه utilized to 30:1 in case of glycerol [77]. 30:1 در مورد گلیسرول. Most propionibacteria can cover their own needs of vitamins, except for biotin اکثر پروپیون باکتری ها می تونند نیاز های خودشون رو بر طرف کنن ( ویتامین جز برای (vitamin B7) and pantothenic acid (vitamin B5) that should be supplementeبیوتین ب7 و پنتوتنیک اسید ب5 که باید
- Raw materialsThe starting raw materials are usually sugars or starches, partially also recycled materials from foodor wood processing. Algae based resin production has also been announced to be commercialised bythe end of 2010.
- Raw materialsBiosolvents can be entirely or partially plant-based. Examples of bio-solvents are soy methyl ester(soy oil esterified with methanol), lactate esters (fermentation derived lactic acid reacted withmethanol or ethanol) and D-Limonene (extracted from citrus rinds).
- Whole crop biorefineryIn a whole crop biorefinery, grain and straw fractions are processed into a portfolio of end products. Abengoa Bioenergy is commissioning the first commercial-scale whole crop biorefiner plant in Spain, daily processing 70 tons of agricultural residues (wheat, barley straw) to produce annually over fivemillion litres of fuel grade ethanol.Marine biorefineryThe global primary biomass production is equally divided between terrestrial and aquatic systems. So far, policies have focused mainly on terrestrial biomass, little attention being devoted to marine sources like microalgae and macroalgae and their derivatives. Algae can, depending on species and growingconditions, accumulate significant amounts of oils, carbohydrates, starch and vitamins. (Source: Langeveld et al.19)
- The twelve sugar-based building blocks are: 1,4-succinic, fumaric and malic acids, 2,5- furan dicarboxylic acid, 3-hydroxy propionic acid, aspartic acid, glucaric acid, glutamic acid, itaconic acid, levulinic acid, 3-hydroxybutyrolactone, glycerol, sorbitol and xylitol/arabinitol. The list was derived by examining the potential markets for the building blocks and their derivatives and the technical complexity of the synthesis pathways. Utrecht University et al 13 report and the FROPTOP program identified a larger list of viable bulk organic chemicals from biomass by application of ‘white biotechnology’, i.e. industrial biocatalysis.
- From ligninAnother product from biomass based processes is lignin18. At the moment it is mainly used to produce process heat by combustion or in animal feeds although around 1 million tonnes of lignin polymers are traded as chemicals. However, lignin also has the potential to be a chemical feedstock 18. Lignin can be used as a carbon source by gasification producing syngas (carbon monoxide/ hydrogen), which can be transformed into methanol, dimethyl ether, olefins and mixed alcohols (ethanol and higher value alcohol chemicals). In addition lignin can be converted into aromatic hydrocarbon products that can be used commercially (e.g. phenol or vanillin)27. The single most important group of plastic precursors, for which bio-based alternatives are still missing, are aromaticcompounds. Lignin could be an answer to this need even though it is structurally very complex and diverse, making the production of aromatic compounds from biomass a major challenge.
- PBT (Polybutylene terephthalate) and PET (Polyethylene terephthalate)
- (researchers from Wageningen UR Food & Biobased Research and Plant Research International, part of Wageningen UR, together with biomethanol producer BioMCN from Delfzijl, are all working on the development of a sustainable production of methanol from CO2.)