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)

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.
 BioAlcohol from Plant Biomass
•Fermentation produces alcohol

•Raw materials are

1. STARCHy materials (wheat, rice, maize and potato)
2. 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 (45 oC) than
petrol (13 C)
o

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)
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
RAW MATERIAL Milled grain
steam

Gelatinized material
PRE TEATMENT cool
a-amylase
Liquefied material Bacillus amyloliquefaciens
Glucoamylase

Saccharified material FERMENTATION

Yeast
Glucose isomerase

Fructose Fermentation

Alcohol

Industrial production of alcohol and fructose from starch

 STARCH
ETHANOL FERMENTATION Hydrolysis
GLUCOSE
RAW MATERIAL Molasses Glycolysis
PYRUVATE
pH 4-4.5
pyruvate
21-26oC---30oC
PRETREATMENT decarboxylase, TPP, Mg, -
O2 initially CO2
ACETALDEHYDE
Anaerobic conditions
Alcohol
STERLIZATION after CO2 produced dehydrogenase, NADH+H+
ETHANOL

FERMENTATION
Ethanol at high conc inhibits its own
SEPARATION synthesis
Eg. Yeasts at 5% alcohol, growth ceases
DISTILLATION Zymomonas mobilis tolerate 13%

DEHYDRATION 1g glu to 0.511g ethanol (theory)

Pure substrates (glu, lac, suc): 95%
conversion rate
STILLAGE Corn starch (industrial grade): 90%
(wastes 100g pure glucose: 48.5g of ethanol
concentration) produced, 46.5g CO2, 3.3g glycerol and
1.3g biomass
USED FOR FUEL,
FEED OR FERTILIZER, SCP, METHANOL
 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.
 Agricultural products specifically grown for biofuel

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

rapeseed, wheat and sugar beet primarily in Europe;
sugar cane in Brazil;
palm oil and miscanthus in 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.
 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

Ethanol producing microorganisms Glucose

Saccharomyces cerevisiae
Glycolysis
S. carlsbergensis
Yeast

Kluyeromyces fragilis TCA cycle Pyruvate

CO2
Candida tropicalis
Acetaldehyde
Bacteria

Zymomonas mobilis NADH NAD+

Clostridium thermocellum Ethanol
Vegetable oil Plant with sugar Plant with starch Plant with ligno-
(sugarcane) (maize, potato, cellulose
cassava)

treatment

Hydrolysis Gasification

Esterification Synthetic
Dehydration catalysis

PURIFIED OIL BIODIESEL BIOETHANOL BIOMETHANOL

Bioethanol from LignoCellulosic waste
 Clostridium acetobutylicum
ACETONE AND BUTANOL C. butyricum

Acetone used in manufacture of nitrocellulose for explosives

wood hydrolysates, molasses, starch, sucrose

Acetyl COA
Glucose b-hydroxy-
Acetyl COA Acetoacetyl CoA b-methyl glutaryl
Pyruvate CoA
b-hydroxybutyl CoA Acetyl COA
Acetoacetic acid
Acetyl CoA
Crotonyl CoA
Acetone
Acetyl PO4
Butyryl CoA
Butyric Acid Isopropanol
Acetic acid
Butanol

Nowadays acetone and butanol are by products of petroleum industry

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

Phase I: rapid growth, acetic acid, butyric acid, titratable

acidity, pH5.2

Phase II: incr in acetone, butanol decr 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.
GLYCEROL

• Starting material for manufacture of explosives

• Produced by saponification of fats and oils.

• Chemically synthesized from propylene or propane

 PRODUCTION Produced by yeast during alcoholic fermentation
Sodium bisulfite blocks blocks alcohol production and
large scale glycerol production
2-3 days Glucose
50% yield
Fructose 1,6 bisPO4

Glyald 3 PO4 DHAPO4

DHAP
Pyruvate dehydrogenase
Glyald 3 PO4

Acetaldehyde
ACETALD.
SULFITE Sodium CH2-OH GLYCEROL
COMPLEX bisulfite
blocks CH-OH
Ethanol
CH2-OH
Sodium sulfite +CO2 ---> Sod bisulfite
 PRODUCTION from alga and bacteria

Dunalielia salina in 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 subtilis capable of converting glucose to glycerol, ethanol,

Lactic acid, butanediol
Produces high yield at anaerobic conditions despite being an aerobic MO