Normal butanol bio-process production

Normal butanol bio-process production

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Instroductionbio-fuelBio alcoholsBiodieselbiogas and solid biofuelsSeveral Bio-Fuel are categorized below based on their physical and chemical properties.

Bioethanol

Biobutanol (biogasoline)Several primary alcohols, such as methanol, ethanol, butanol, etc., have been considered to be biofuel candidates because of their similar physical and chemical properties to gasoline.

Instroductionbio-fuel

As shown in the following chart, renewable energy occupied 19.1% of global final energy consumption, and biofuels shared 50% of consumed renewable energy in 2015.Renewable 2015 global state report

Properties of bio alcohols GasolineMethanolEthanolNormal ButanolEnergy Density (MJ/L)321619.629.2Air-Fuel Ratio14.66.5911.2Heat of vaporazation (MJ/Kg)0.361.20.920.43Research Octan number91-9913612996Motor octan Number81-8910410278

Economic and environmental assessment of n-butanol production in an integrated first and second generation sugarcane biorefinery: Fermentative versus catalytic routes

Properties ofBiobutanol

Normal butanol contains a longer hydrocarbon chain being more similar to gasoline (both are hydrophobic) It is capable of performing better for an engines cold start. higher energy content, lower volatility, higher boiling point, and does not readily adsorb moisture. The Reid vapor pressure of n-butanol is 7.5 times lower than that of ethanol high octane rating makes the alcohol more suitable to be used in internal combustion engines. Biobutanol is considered the next generation biofuel due to many advantages over ethanol. Among these:

Microbial ethanol production: Experimental study and multivariate evaluation

Application ofNormal butanolColourless, mobile solvent of medium volatility and a Feedstock for syntheses.

Solvent for dyes.

Extractant in the production of drugs and natural substances such as antibiotics, hormones, vitamins, alkaloids and camphor.

Additive in polishes and cleaners.

Solubilizer in the textile industry, such as additive in spinning baths or carrier for colouring plastics.

Feedstock for the production of glycol ethers.

Starting material for various butyl monocarboxylates.

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Global Demands forn-Butanol About half of the production of pure n-Butanol and its derivate is used as solvents in the coatings industry. The advantage here is that n-butanol prevents blushing of certain coatings when they dry under humid conditions.

Normal butanol has a projected global market of 5 million tonnes in 2018.

China34%America25%Europe24%

DisadvantagesLow Productivity yield:

This low concentration is because butanol is toxic to microorganisms that rarely tolerate more than 2% butanol.

High substrate cost

High Separation cost

Butanol istoxicat a rate of 20g per liter.

Biodiversity : A large amount of arable land is required to grow crops. This could see some natural habitats destroyed including rainforests.

Alcohol based fuel are not compatible with some fuel system component.

123Separation and purification of biobutanol during bioconversion of biomass

Production of BioButanol

Fermentation ofBiobutanol Butanol fermentation, also referred to asalcoholic fermentation, is a biological process in which sugars such asglucose,fructose, andsucroseare converted into cellular energy. The Butanol fermentation process feeds fundamentally has similar process as an ethanol process.

The process is called ABE fermentation.

ABE FermentationUses bacterial fermentation to form Acetone, Butanol and Ethanol from sugar.Developed by Chaim Weizmann during World War 1.Anaerobic process.It produces solvents in 3:6:1 ratio where 3 parts acetone, 6 part butanol and 1 part ethanol are produced.Uses the strain of bacteria genus Clostridia. Clostridium acetobutylicum is generally used.

Production of acetonebutanolethanol (ABE) in a continuous flow bioreactor using degermed corn and Clostridium beijerinckii

History One of the oldest industrial fermentation processes one of the oldest industrial fermentation processes known, ranking second in scale only to ethanol fermentation by yeast.

Producing high quantities of acetone was so important during WW1, because of its usage as cordite in British military.

Butanol was an only unwanted byproduct.

A sectioned British 18 pounder field gun shrapnel round, World War I, with bound string to simulate the appearance of the original cordite propellant

Butanol became a more important product after the war.

industrial ABE fermentation declined rapidly after the 1950s as a result of the cheaper petrochemical production of butanol.

The chemical process was mostly based on aldol condensation of acetaldehydes, followed later by dehydration and then hydrogenation of croton aldehyde. With this fast growing industrial discovery also known as the Oxo synthesis, the fermentation processes were abandoned.

The chemical route did not last for a long time until rise in crude oil prices when industrial ABE fermentation facilities started to emerge again in China and Brazil.

Clostridiaacetobutylicum

Clostridia are a large class of microorganisms that were traditionally grouped together based on the characteristic look of the family of cells.

The word Clostridium is derived from the Greek word Kloster meaning spindle.

Obligate anaerobic microorganisms.

Spore forming.

They possess wide substrate utilization ability and can use many types of carbon sources ranging from glucose, sucrose, lactose, xylose, xylan, starch and glycerol.

There are 4 particular species of clostridia Clostridium acetobutylicum, C. beijirinckii, C.saccharobutylicum and C. saccharoper butylacetonium.

Metabolic engineering of Clostridium acetobutylicum: recentadvances to improve butanol productionTina Lu tke-Eversloh and Hubert Bahl

Preparation of CBS Fermentation mediumTrace Metal Solution:EDTACalcium ChlorideZinc Sulphate Ferrous SulphateBoric AcidManganese ChlorideSodium MolybdateCupric ChlorideCopper SulphatePottasium Iodide

Adjust pH at 4.00 with NaOH, autoclave and store at 4 C

Central Bureau Seer (CBS) medium is synthetically designed for anaerobic growth of the bacteria by TU Delft, Netherlands. CBS medium comprises of 3 solutions:

Preparation of CBS Fermentation mediumVitamin Solution : Dissolve 25mg d Biotin in 0.1 M NaOH.Add 400ml water and adjust the ph to 6.5.Add the following: P-Amino Benzoic AcidNicotinic acidCa- panthanoatePyrodixine, HClThiamine, HClAdjust pH to 6.5 and add m-Inositol.Adjust pH to 6.5 and transfer it into an autoclave reagent bottle at 4 C.

The metabolic pathway

Glucose is catabolized to pyruvate via the EmbdenMeyerhofParnas pathway and acetyl-CoA is primarily formed by the pyruvate: ferredoxin oxidoreductase.

Under certain growth conditions, such as pH values >5 and iron limitation, lactate can be the major fermentation product.

Acetate is synthesized via phosphotransacetylase and acetate kinase reactions with the latter reaction providing ATP.

For the biosynthesis of butyrate, two molecules of acetylCoA are condensed to acetoacetyl-CoA, followed by a reduction to butyryl-CoA, which is then converted to butyrate via phosphotransbutyrylase and butyrate kinase reactions with ATP generation.

As a reaction to the significant decrease of the pH in the culture, which may destroy the essential proton gradient across the membrane, C. acetobutylicum switches its metabolism from acidogenesis to solventogenesis.

The metabolic pathway

Acetate and butyrate are reassimilated to their corresponding CoA derivatives catalyzed by the acetoacetyl-CoA: acyl-CoA transferase, with acetoacetyl-CoA as the CoA donor.

Particularly when reducing equivalents are limiting, acetoacetate is decarboxylated to acetone in order to drive the transferase reaction by acetoacetate removal.

Butyraldehyde and butanol dehyrdogenase activities, which can be provided by different dehydrogenases, convert butyryl-CoA to butyraldehyde and finally to butanol.

the role of the different alcohol dehydrogenases and their regulation still remains to be elucidated.

C12H22O11+H2O + invertase 2 C6H12O6

C6H12O6+ Zymase C4H9OH + 2CO2 + H2OThe biphasic metabolism of C. acetobutylicum is tightly associated with different growth stages, that is exponentially growing cells mainly produce acetic and butyric acid, while acetone and butanol are formed by stationary cells After entering the stationary phase, cells start to synthesize granulose as intracellular storage compound, and these clostridial stage cells can be microscopically distinguished from vegetative cells. However, the regulatory mechanisms of granulose formation and re-utilization are not known. Subsequently, the sporulation process is initiated and the granulose granula presumably serve as energy and carbon source for endospore formation

Economic optimization

Feed stockSeparation uniteAlcoholchemical route

Typical Feed stocks First Generation Biofuel

First-generation bio-butanol requires a relatively simpleprocess to be produced mostly afforded by fermentation of mostlyhexose sugars. These sugars are derived through hydrolysis ofstarch-rich crops such as maize, wheat, rice and cassava. Prior touse, the raw materials (grains) are usually hydrolysed intodextrose, which can be subsequently bio-converted into glucoseusing glucoamylase enzyme

Second generation Biofuel

-Biofuels from different agricultural residues and part of theplant biomass are often termed second generation .-Lignocellulosic materials are associated with low cost, sufficiently abundance and usually generate low net greenhouse emissions.-Second generation liquid biofuelsare generally produced by two fundamentally different approaches i.e. biological or thermochemical processing, due to their structural complexity.

Third generation Biofuel

Algae has increasingly became one of the promising feedstock,arising from its vast availability. It is categorized as a thirdgeneration feedstock.

First generation biofuelsFirst generation biofuelsClostrudium SpeciousYieldProductivity g/L.hg/Lg/gCassava StarchC.beijerinckityrobutyricum6.660.180.96

GlucoseC.acetobutylicum CICC 80120.13

Cassava flourC.acetobutylicum DP 217 5.7430.76

Oil palm sapC.acetobutylicum DSM 1731 14.40.35

Fermentation Condition pH=5 and T=37 degree Celsius

Separation Unite One important problem associated to the biobutanol production is the separation process, because there is involved an azeotrope in the mixture acetone-butanol-ethanol obtained from the fermentation process.

The main strategies identified for the separation of this mixture are adsorption, pervaporation, gas striping, membrane distillation and liquid-liquid extraction.

It should be noted that adsorption has lower energy requirements but it is subjected to fouling, and its recovery and selectivity is low. On the other hand, pervaporation offers a selective separation of organics from water; however, more development is needed in the membranes to improve the recovery ratio.

Separation UniteGas striping does not suffer from clogging or fouling by biomass, nevertheless this process leads insufficient recovery of solvents.

Membrane distillation shows high selectivity for solvents, but also its membrane suffers from clogging and fouling which reduces the recovery rate.

Liquid-liquid extraction (LLE) has high selectivity and great potential in separation of biobutanol from ABE fermentation due to biobutanol is more hydrophobic than other biofuels and the concentration is lower. But it consume a lot of energy. Should be optimized.

Separation and purification of biobutanol during bioconversion of biomass

AlcoholChemicalRoute

dyhidrogenationAdol CondensationHydrogenationThe first liquid phase reaction is the dehydrogenation of ethanol to form acetaldehydes.Adol condensation use to produce a b-hydroxyaldehyde or b-hydroxyketone.The subsequent step after aldol-condensation is hydrogenation of aldol-adducts to increase their solubility in the aqueous phase.

gas phase of ethanol reaction over a zeolite catalyst to synthesize butanol.

Butamax Advanced Biofuels, a joint venture of BP and DuPont, has developed an innovative biobutanol production technology offering a low-cost, high-value drop-in biofuel for global transportation fuels supply. Butamax technology is designed to convert the sugars from various biomass feedstocks, including corn and sugarcane, into biobutanol using existing biofuel production facilities.

Butamax Gevo Press Release 08-24-15

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