Non-conventional renewable resources for the production of ... · biomass resources for bioethanol production in India The scope of study (cont…) • Generation of data on feasibility

Non-conventional renewable resources for

the production of biofuels

Ashok Pandey

Centre for Biofuels

National Institute for Interdisciplinary Science and Technology

Council of Scientific and Industrial Research

Trivandrum, India

CSIR NETWORK

2

-1st Generation of biofuels: ethanol from sugar, corn,

molasses, starchy biomass, etc

- 2nd Generation of biofuels: biodiesel from vegetable

oils and bioethanol from lignocellulosic biomass

- 3rd Generation of biofuels: algal biofuels

- 4th Generation of biofuels: biohydrogen

-1st Generation of biofuels: ethanol from sugar, corn,

molasses, starchy biomass, etc

-

- 3rd Generation of biofuels: algal biofuels

- 4th Generation of biofuels: biohydrogen

2nd Generation of biofuels: bioethanol

Environmental Benefits of Biofuels

The main benefits of biofuels are environmental .

Emissions – Biofuels produce fewer carbon emissions than fossil fuels, thereby

reducing air pollution, greenhouse gasses, and toxins.

Sustainability – Biofuels offer an renewable and sustainable alternative. Crops can be

grown continuously, and can easily be expanded to accommodate growing demand for

fuel.

Base Ingredients – Many of the feedstock for biofuels are considered "waste"

products, such byproducts of agriculture and even municipal solid waste. Turning

these products into an energy source helps in waste management in addition to energy

generation

Biodegradation – Since biofuels are made with biodegradable matter, they are less

toxic than fossil fuels. Biofuels present much less of a health and environmental

hazard. They can be cleaned up more easily and much quicker, reducing expenses

involved.

Less Strain on the Earth – Digging for oil and coal, which is found buried deep in the

earth's crust, causes a strain on the earth itself. From the dangers of coal mining to oil

spills and the possible connection of earthquakes to drilling, seeking fossil fuels can

be dangerous business. Biofuels would reduce these risks completely.

Reduction in GHG emissions

• Major environmental benefit of biofuels is in

the reduction of GHG emissions

• GHG emissions of a biofuel depends on the

energy used in growing and harvesting the

feedstock, as well as the energy used to

produce the fuel

• On a full fuel-cycle basis, corn ethanol has the

potential to reduce GHG emissions by as much

as 52% over petroleum-based fuels.

• Ethanol made from cellulosic biomass has the

potential to reduce greenhouse gas emissions

by as much as 86%

• Biofuels have the added benefit of providing a

"carbon sink." As crops grow to produce the

feedstock for making the biofuel, they absorb

carbon dioxide from the atmosphere.

Emission Low-level Blends (i.e., E10) High-level Blends (i.e.,

E85)

Carbon Monoxide (CO) 25-30% decrease 25-30% decrease

Carbon Dioxide (CO2) 10% decrease Up to 100% decrease

(E100)

Nitrogen Oxides (NOx) 5% increase or decrease Up to 20% decrease

Volatile Organic Carbons (VOC's):

Exhaust

Evaporative

7% decrease

No change (in Canada)

30% or more decrease

Decrease

Sulfur Dioxide (SO2) and

Particulate Matter

Decrease Significant decrease

Aldehydes 30-50% increase (but

negligible due to catalytic

converter)

Insufficient data

Aromatics (Benzene and

Butadiene)

Decrease More than 50%

decrease

Reductions in Emission in Ethanol Blends of Gasoline

Source : Canadian Renewable Fuels

Association

• Ethanol naturally biodegrades in soil and water without leaving harmful residues

in the environment. Ethanol when used instead of MTBE as a petrol oxygenate

eliminates the release of the toxic and carcinogenic MTBE into environment

• Production of ethanol fuel requires less fossil energy than its petroleum-based

counterpart. Cellulosic ethanol requires only ten percent of the fossil energy

required to deliver a gallon of liquid transportation fuel on an energy equivalent

basis compared to gasoline.

Other Benefits

Fossil Energy spent per Btu of Fuel Produced [BTUs]

Process Stage Corn Stover Corn w/ Co product Forest - Woody Residue

Gasoline

Feedstock 0.08 0.12 0.10 0.04

Transportation 0.01 0.03 0.05 0.01

Refinery 0.00 0.57 0.05 0.16

Distribution 0.02 0.02 0.02 0.01

End Use 0.00 0.00 0.00 1.00

Total 0.11 0.74 0.22 1.21

Source -NREL

Employment –Jobs ranging from farming to production to transportation

would be created with the development of biofuels.

Decreased Dependence on Foreign Products – Almost every country is

capable of producing biofuels, albeit some with help from more developed

countries. There's no doubt that fuel independence increases domestic

security and self-dependence.

Cost – While the initial cost of integrating biofuels into current uses may be

high, once that is addressed, the use of biofuels would be much less

expensive than traditional fuel. Since production of biofuel material is also

controllable, the fluctuations in price will be minimal as compared to

petroleum

Greater Profits for Farmers – When biofuels are made from crops, the

farmers who grow these foods benefit as the prices of their crops increase to

keep up with demand. This could help farmers all over the world, who have

traditionally struggled to earn a fair wage for all of the work involved in their

trade.

Other Benefits

Availability of feedstocks in India?

Availability of feedstocks in India?

For the purpose of understanding the feasibility and sustainability

of producing biofuels from biomass in India,

a clear understanding of the production, current uses and excess

availability (‘surplus’) of biomass was needed.

Further, the storage, transportation and procurement practices

of such biomass resources also need to be understood.

NIIST-TIFAC study on the sustainable availability of potent

biomass resources for bioethanol production in India

The scope of study

• Identification of top biomass resources available in India with state-

wise/geographical distribution.

• Assessment of the total quantity of biomass generation (state-wise

and national)

• Assessment of current consumption of the identified biomass

resources and usage pattern (state-wise and national).

• Assessment of current practices in storage and transport, if existing

for agro-residues/biomass resources.

NIIST-TIFAC study on the sustainable availability of potent

biomass resources for bioethanol production in India

The scope of study (cont…)

• Generation of data on feasibility of collecting the feedstock other

than agro-residues (inclusive of forest biomass resources such as

bamboo and pine needles, and aquatic biomass such as water

hyacinth). Estimates on the cost of collection, drying (if applicable as

in the case of water hyacinth), storage and transport have to be

prepared.

• Cost assessment for the biomass when procured at small-scale and

at large-scale.

NIIST-TIFAC study on the sustainable availability of potent

biomass resources for bioethanol production in India

The scope of study (cont…)

• Identification of major locations in the country with highest

concentration of the 5-6 feedstocks.

• Sources of procurement of biomass and agro-residues.

NIIST study on the sustainable availability of potent biomass

resources for bioethanol production in India

Primary data sources

Secondary data sources

National scale

More than 90% of the cereal crop

residues are used domestically !

Surplus residues are sufficient to

support projected demand for 2020 even

with the most pessimistic conversion

figures (Projected Demand for 2017 at 10%

Blending = 2.2 Billion L)

NIIST-TIFAC survey

report, 2009

Agro residue Annual

Availability

(MMT)

Cellulose

(%)

Alcohol -

Theoretical

Max

(Billion L)

Alcohol -

Estimated @35%

efficiency

(Billion L)

Rice Straw 8.9 33 2.11 0.737

Wheat Straw* 9.1 33 2.15 0.754

Bagasse 6.4 40 1.84 0.643

Corn Stover* 1.1 35 0.28 0.097

Sugar Cane Tops 79.5 35 19.96 6.985

Chili PHR 0.5 47 0.17 0.059

Cotton PHR 11.4 31 2.53 0.887

Bamboo 3.3 42 0.99 0.348

TOTAL 30.03 10.51

Identification of feedstock to work-on

Liquid fuel from water hyacinth

Water hyacinth (Eichhornia) is a free-floating perennial aquatic plant native

to tropical and sub-tropical South America.

One of the fastest growing plants known and labeled as one of the worst

invasive plants in the world.

• Two parent plants produced 30 offspring after 23 days, and 1,200 at the

end of four months.

• Weight gains of 4.8% per day.

• It grows very fast and duplicates each seven days with an annual

productivity between 930 and 2,900 tons per hectare.

Characteristics

• Mat forming, floating plant

• Spongy, waxy and glossy leaves

• 95% water, has a fibrous tissue

• Remove nutrients directly from water

• Reproduction includes

• Sexual-- seeds

• Asexual– over wintering stems and the creation of daughter plants

– Disrupts commercial and recreational use of waterways

– Much like algae their deaths lead to anoxic conditions

Water hyacinth - major ecological and economic

problem in this century

World-wide distribution of Eichhornia crassipes

Ref : GIC 2006

• The first step adopted for the solution of this problem was control by

known methods.

• Many years ago, various kinds of herbicides such as Dalapon, Diquat, and

others were used in some places.

• The ecological problems created by these herbicides were obvious.

• The water could not be used for irrigation or human consumption for long

periods of time, and the fauna in the eco-system were seriously affected

Control measures – Not a successful story

Chemical control

• Biological control of the hyacinth has been studied with several kinds of

animal viruses, bacteria, fungi, herbivorous fish such as grass carp and

tilapia, ducks, geese, turtles, snails, and other animals.

• However, the results have been disappointing, perhaps because of

defense mechanisms in the plants.

Biological control

The advantages of water hyacinth as a source of fuel are:

• It is abundantly and freely available

• Its production takes up no extra land

• It saves wood, which is increasingly scarce and precious

• Overall, it does not increase atmospheric carbon dioxide

• The biomass consists of more than 50% cellulose and hemicellulose

• Production on a larger scale creates more local jobs than other renewable

systems of a comparable size

• Use in this way can be a substantial contribution to its control

There are, of course, two major difficulties:

• The problems of harvesting and handling large volumes of water hyacinth

• The high water content of water hyacinth

Water hyacinth biomass as a source for liquid and gaseous

fuel production

Water hyacinth biomass as a source for liquid and gaseous fuel

production - The concept and approach

The conceptual biorefinery is built on two platforms

1. Sugar Platform which uses biochemical conversion of biomass to fermentable

sugars, followed by subsequent fermentation to yield useful products.

2. Thermo-chemical platform where biomass is gasified using thermo-chemical

reactions to generate fuels and the byproducts are utilized.

Sugar Platform ( Biochemical)

Thermochemical /

Syngas ( H2, CO) platform

Combined

Heat & Power Bioethanol

Sugar

Feed stocks

Clean Gas

Residues

Water hyacinth biomass as a source for liquid and gaseous

fuel production - Sugar Platform

Lignocellulosic biomass to ethanol technology –Challenges

• Availability

• Sustainability

• Cost

• Selection of

feedstock

• Infrastructure

• Collection

• Storage

• Composition

• Variability

• What is the best

method of

pretreatment

• Acid or Alkali

• Conc. of treatment

agent, biomass

loading

• Treatment

conditions

• Change in

composition

• Susceptibility to

hydrolysis

• Recovery of lignin

• Hydrolysis

conditions

• Enzyme and

Biomass

loading, Time

• Better enzyme

cocktails

• Reduce cost of

production

• Sugar

Concentration

methods

• Analysis of

inhibitors

• Better sugar

conversion

and alcohol

production

• Detoxification

of

hydrolysates

• C5

fermentation#

• Best

conditions for

fermentation

• SSF , Co-

fermentation

• Improving

Ethanol

recovery

• Dewatering of

ethanol

• Storage

• Transportatio

n

pretreatment Processed

Biomass Fermentable

sugars Ethanol

Lignin to energy Sugars to

products

Alcohol

fermenting

microbes

Cellulases

Hemicellulases

21.03%

33.65% 12.05%

18%

14%

Cellulose Hemicellulose

Lignin Ash

Others

Composition

Pretreatment

Pretreatment can be the most expensive

process in biomass-to-fuels conversion but it

has great potential for improvements in

efficiency and lowering of costs through further

research and development.

1) Production of highly digestible solids that

enhances sugar yields during enzyme

hydrolysis

2) Avoiding the degradation of sugars including

those derived from hemicellulose

3) Minimizing the formation of inhibitors for

subsequent fermentation steps

4) Recovery of lignin for conversion into valuable

co-products

5) To be cost effective by minimizing heat and

power requirements

Typical goals of pretreatment

Process flow in water hyacinth biomass to ethanol

Drying

Dried

Screening profile of different acids on pretreatment of water hyacinth

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

H2SO4 HCl Acetic acid Formic acid

Red

ucin

g s

ug

ar

(g/g

)

Different pretreatment agents

Parameters – Optimum condition Reducing Sugar (g/g)

Acids H2SO4 0.327 ± 0.0049

H2SO4 concentration 4% 0.342 ± 0.0021

Solid loading 10% 0.342 ± 0.0049

Temperature 1210C 0.348 ± 0.0014

Incubation time 75 minutes 0.356 ± 0.0035

Optimum conditions for acid

pretreatment of water hyacinth

Effect of different acid on sugar

yield

Structural analysis of native and acid pretreated water hyacinth

SEM

XRD

FTIR

Optimum conditions for hydrolysis of acid pretreated

water hyacinth

Parameters Optimum conditions Reducing Sugar (g/g)

Incubation time 24 hours 0.487 ± 0.0070

Biomass loading 12.5% 0.671 ± 0.0063

Type of surfactant Triton X-100 0.685 ± 0.0028

Surfactant concentration

(Triton X-100)

0.1% 0.689 ± 0.0098

Enzyme concentration 70 FPU 0.723 ± 0.0070

Fermentation efficiency of sulphuric acid pretreated water hyacinth

Maximum ethanol concentration of 0.292 (% w/v) was obtained after

fermentation using 2% H2SO4 pretreated and saccharified water hyacinth.

The overall efficiency of the process is 59.3%.

Conclusions

• Water Hyacinth has been observed as a potential biomass for the production

of bioethanol.

• Most of the hemicellulose present in the biomass could be recovered in

soluble form by 4% sulphuric aicd pretreatment at 10% (w/w) solid loading

with pretreatment temperature at 121 degree Celsius for 75 minutes.

• Fermentation of enzymatically treated biomass hydrolysate with

Saccharomyces cerevisiae resulted a final ethanol yield of 0.292% (w/v).

To be inaugurated today - 23rd April 2012

Alkali pretreatment scheme Acid pretreatment scheme

Lab to plant: Design of process-flows and volumes

Raw

Biomass

Milled

Biomass

Acid/Alkali

Preprn tank

Dilute

Acid

Dilute

Alkali

Buffer Enzym

e

Nauta

mixer

H2O tank

Neutralization

reactor

Vibra

Sifter

Plate &Frame

Filter

Hold

Tank

Hold

Tank

Solid fraction

Pretreated

Biomass

Hydrolysis

Reactor

Hold

Tank

Pentose rich fraction

Continuous

centrifuge

Continuous

centrifuge

Waste solid

discharge

Sugar

concentrator

(RO)

Hold

Tank

Fermente

r

Seed

Fermente

r

Hold

Tank

Distillation

still

Distillation

Column

Condensate

hold

Ethanol

Hold

Molecular

Sieve Dehydrated

Ethanol

The Bioethanol Pilot Plant

Pilot plant

Acknowledgements

Naturol Bioenergy,

Hyderabad

Godavari Biorefinery,

Sameerwadi Kerala State Bamboo

Corporation

CSIR-NCL , Pune; CSIR-IICT, Hyderabad; EPFL, Switzerland; HTBS, Pune;

Scigenics India Pvt Ltd, Chennai

MAPs Enzymes Pvt

Ltd

Our partners, collaborators and facilitators

Department of Science & Technology

Government of India CSIR

Dr Rajeev K Sukumaran, Dr K Madhavan Nampoothiri, Dr P Binod,

Dr R Sindhu, Vikram Surender, M Kiran Kumar, Vani Sankar,

Dr Reeta Rani Singhania, KU Janu, M Kuttiraja, Preeti Varghese, Sandhya

VarierKP Rajasree, Abraham Mathew, Aravind Madhavan, Gincy Marina

Mathew, Mr PN Sivankutty Nair, Mr Prakash KM, Dr Vijayalakshmi Amma

Acknowledgements

The Organizers