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ORGANIC SOLVENTS. Ethanol, acetone, butanol , glycerol Petrochemical industries Due to scarcity of oil and natural gas alternatives for commercial production Use of low cost raw materials (wood, cellulose, starch). ALCOHOL. Chemically manufactured by hydration of ethylene (C2H4)

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slide1

ORGANIC SOLVENTS

Ethanol, acetone, butanol, glycerol

Petrochemical industries

Due to scarcity of oil and natural gas alternatives for commercial production

Use of low cost raw materials (wood, cellulose, starch)

slide2

ALCOHOL

Chemically manufactured by hydration of ethylene (C2H4)

In developing countries microbial fermentation is preferred to cheap raw material available.

Now other countries also realize the potential due to political and economic analysis.

AS A MOTOR FUEL

Green petrol produced using sugar based plants like sugarcane and cassava. The pioneers are Brazil, with several fermentation and distillation plants the 90% of new cars are run on alcohol as a fuel.

slide3

BioAlcohol from Plant Biomass

  • Fermentation produces alcohol
  • Raw materials are
    • STARCHy materials (wheat, rice, maize and potato)
    • CELLULOSic material (wood, agricultural wastes)

Brazil: first country to produce ethanol by large scale yeast fermentation by using sugarcane and cassava

Advantages of ethanol as motor fuel:

less envtal. Pollution, 60%less CO2 as compared to petrol, 65% less Hydrocarbon and 15% less nitric oxide

Flash point (temp. at which substance ignites) is higher (45oC) than petrol (13oC)

Disadvantages

Costlier than petrol

Starting engines in cold difficult

Ethanol may react with Al and Mg to damage containers

Should not pick H2O from air (i.e. highly pure) can cause corrosion of engines and tanks and will not burn

Gasohol: 20% ethanol (has to be highly pure) and 80% petrol (used in USA)

slide4

Ethanol by Fermentation of Micro-organisms

Yeasts: Saccharomyces cerevisae Bacteria: Zymomonas mobilis

Raw material:

Sugary material (molasses, whey, glucose, sucrose)

Starchy materials (wheat, rice, maize, potato, cassava)

Cellulosic material (wood, agricultural wastes)

Pretreatment of raw material:

Depends on type of raw material.

Sugary materials : mild

Cellulosic: extensive acidic or enzyme hydrolysis to release monosaccharide units

PRE TREATMENT: Hydrolysis, clarification, filtration

slide5

RAW MATERIAL

Milled grain

steam

Gelatinized material

PRE TEATMENT

cool

a-amylase

Bacillus amyloliquefaciens

Liquefied material

Glucoamylase

FERMENTATION

Saccharified material

Yeast

Glucose isomerase

Fermentation

Fructose

Alcohol

Industrial production of alcohol and fructose from starch

slide6

STARCH

Hydrolysis

GLUCOSE

Glycolysis

PYRUVATE

pyruvate decarboxylase, TPP, Mg, - CO2

ACETALDEHYDE

Alcohol dehydrogenase, NADH+H+

ETHANOL

ETHANOL FERMENTATION

RAW MATERIAL

PRETREATMENT

STERLIZATION

FERMENTATION

SEPARATION

DISTILLATION

DEHYDRATION

STILLAGE

(wastes

concentration)

USED FOR FUEL,

FEED OR FERTILIZER, SCP, METHANOL

Molasses

pH 4-4.5

21-26oC---30oC

O2 initially

Anaerobic conditions after CO2 produced

Ethanol at high conc inhibits its own synthesis

Eg. Yeasts at 5% alcohol, growth ceases

Zymomonasmobilistolerate 13%

1g glu to 0.511g ethanol (theory)

Pure substrates (glu, lac, suc): 95% conversion rate

Corn starch (industrial grade): 90%

100g pure glucose: 48.5g of ethanol produced, 46.5g CO2, 3.3g glycerol and 1.3g biomass

slide7

Biofuel

Biofuel is defined as solid, liquid or gas fuel derived from recently dead biological material and is distinguished from fossil fuels, which are derived from long dead biological material. Theoretically, biofuels can be produced from any (biological) carbon source

Two common strategies of producing biofuels

One is to grow crops high in sugar (sugar cane, sugar beet, and sweet sorghum) or starch (corn/maize), and then use yeast fermentation to produce ethyl alcohol (ethanol).

The second is to grow plants that contain high amounts of vegetable oil, such as oil palm, soybean, algae, or jatropha. When these oils are heated, their viscosity is reduced, and they can be burned directly in a diesel engine, or they can be chemically processed to produce fuels such as biodiesel.

Wood and its byproducts can also be converted into biofuels such as woodgas, methanol or ethanol fuel. It is also possible to make cellulosic ethanol from non-edible plant parts, but this can be difficult to accomplish economically.

slide8

Agricultural products specifically grown for biofuel

Corn, switchgrass, and soybeans, primarily in the United States;

rapeseed, wheat and sugar beetprimarily in Europe;

sugar cane in Brazil;

palm oil and miscanthusin South-East Asia;

sorghum and cassava in China;

jatropha in India.

Hemp has also been proven to work as a biofuel.

Biodegradable outputs from industry, agriculture, forestry and households can be used for biofuel production, either using anaerobic digestion to produce biogas, or using second generation biofuels; examples include straw, timber, manure, rice husks, sewage, and food waste.

Biomass can come from waste plant material. The use of biomass fuels can therefore contribute to waste management as well as fuel security and help to prevent climate change, though alone they are not a comprehensive solution to these problems.

slide9

Ethanol producing microorganisms

Glucose

Saccharomyces cerevisiae

S. carlsbergensis

Kluyeromyces fragilis

Candida tropicalis

Zymomonas mobilis

Clostridium thermocellum

Glycolysis

Yeast

TCA cycle

Pyruvate

CO2

Acetaldehyde

NADH

NAD+

Bacteria

Ethanol

Bioethanol

Can be used as a replacement to petrol for automobiles

1930s in USA ethanol was produced from maize at 20% conc to produce gasohol called AGROL

In UK gasoholwas markted by Cleaveland Oil Company undr name DISCOL till 1960s until petrol became available and cheaper.

Large scale production was started in 1975 in Brazil follwed by USA in 1978

slide10

Vegetable oil

Plant with sugar

(sugarcane)

Plant with starch

(maize, potato, cassava)

Plant with ligno-cellulose

treatment

Hydrolysis

Gasification

Synthetic

catalysis

Esterification

Dehydration

BIODIESEL

PURIFIED OIL

BIOETHANOL

BIOMETHANOL

slide12

Clostridium acetobutylicum

C. butyricum

ACETONE AND BUTANOL

Acetone used in manufacture of nitrocellulose for explosives

wood hydrolysates, molasses, starch, sucrose

Acetyl COA

Glucose

Pyruvate

Acetyl CoA

Acetyl PO4

Acetic acid

b-hydroxy-

b-methyl glutarylCoA

Acetoacetic acid

Acetone

Isopropanol

AcetoacetylCoA

b-hydroxybutylCoA

Crotonyl CoA

ButyrylCoA

Butyric Acid

Butanol

Acetyl COA

Acetyl COA

Nowadays acetone and butanol are by products of petroleum industry

Fermentation is discontinued

slide13

Raw material: molasses, ammonium sulphate, Ca CO3, corn steep liquor, gassed with CO2, starting pH 5.8-6.0, 34oC, 36h

PRODUCTION

Phase I: rapid growth, acetic acid, butyric acid, titratable acidity, pH5.2

Phase II: incr in acetone, butanoldecr in acidity (acid break)

Phase III: decr in solvent production and no incr in pH

Contamination: absolute sterile conditions are required, bacteriophages and Lactobacilli cn be contaminants

Product yield: 30% carbohyd. Gets converted. With molasses 7:3 butane acetone and corn medium 6:3. Production of butanol is influened by its toxicity…more than 13.5% conc is toxic.

Recovery: acetone and butanol recovered by continuous distillation and fractionation. Leftover residue is used as animal feed after drying.

slide14

GLYCEROL

  • Starting material for manufacture of explosives
  • Produced by saponification of fats and oils.
  • Chemically synthesized from propylene or propane
slide15

Produced by yeast during alcoholic fermentation

Sodium bisulfite blocks blocks alcohol production and large scale glycerol production

PRODUCTION

2-3 days

50% yield

Glucose

Fructose 1,6 bisPO4

Glyald 3 PO4

Pyruvate

Acetaldehyde

Ethanol

DHAPO4

Glyald 3 PO4

GLYCEROL

DHAP

dehydrogenase

ACETALD. SULFITE COMPLEX

Sodium bisulfite blocks

CH2-OH

CH-OH

CH2-OH

Sodium sulfite +CO2 ---> Sod bisulfite

slide16

PRODUCTION from alga and bacteria

Dunalieliasalinain Israel, lives in high salt envt and synthesizes glycerol to balance osmotic pressure of hypersaline lakes.

When surrounding salt is more more intracellular solutes (glycerol)

When surrounding salt conc is reduced, glycerol is exxcreted out into medium

Bacillus subtiliscapable of converting glucose to glycerol, ethanol,

Lactic acid, butanediol

Produces high yield at anaerobic conditions despite being an aerobic MO