Anvendelse af enzymer til fremstilling af biobrændsler

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Anvendelse af enzymer til fremstilling af biobrændsler

Anvendelse af enzymer til fremstilling af

biobrændsler

Henrik Lund, Henrik Bisgaard-Frantzen og

Morten Würtz Christensen

Novozymes A/S

Workshop om Biobrændstoffer

Odense, 7. November 2005


Outline of presentation

• Short introduction to enzymes

• Fuel Ethanol

• Market overview, trends and drivers

• Enzyme process development

• Fuel ethanol from cellulose based biomass

• Biodiesel

• Overview of current technology

• What improvements can enzymes potential achieve

• Market overview, trends and drivers

• Biogas

• Where is anaerobic digesters used

• What role does enzymes play in biogas production

• Summary


Short introduction to enzymes

• Enzymes are protein based materials that catalysis the

cleavage or formation of organic compounds

• The reactions are typically conducted at mild conditions

(lower temperature, neutral pH)

• From nature, enzymes are often very substrate specific, but

applying gene technology this can modulated to fit industrial

application

• Enzymes are produced industrial by fermentation and applied

in numerous applications within foods, feed and

technical industries

• Novozymes is the worlds largest producer of industrial

enzymes


Bioethanol


It started in 1933

through Henry Ford


Environmental issues

• Bioethanol is a sustainable and almost CO 2

-neutral energy source

• Bioethanol can replace MTBE as octane booster in gasoline

MTBE (methyl tertiary butyl ether), introduced in 1979 as an oxygenate to replace lead in

gasoline

MTBE has been classified as a “potential carcinogen” and identified as a groundwater

contaminant throughout the USA

10 US states have successfully banned MTBE (e.g. California, New York and Connecticut),

creating a 1.4 billion gallon per year market

• Bioethanol - as a fluid energy source for the transport sector - is so far the

only alternative to gasoline (except from biodiesel and gas)

• Already two type blends of ethanol/gasoline on the market

• blends of 10% ethanol and 90% gasoline = E10

• blends of 85% ethanol and 15% gasoline = E85


Ethanol provides more driving per MJ fossil energy resource

Gasoline:

Oil extraction,

oil transport,

oil refining: 6.8 MJ

6.8 MJ

E85:

Oil extraction,

oil transport,

oil refining: 1 MJ

Driving 1 mile

Corn

growing

0.9 MJ

Transport

of corn

0.1 MJ

Ethanol

production

2 MJ

4.0 MJ


Political issues

• Fuel ethanol will influence:

• Economy

• Stimulates the economic development of the agricultural area

• Benefits the trading balance

• Reduces the Western hemisphere’s fossil energy dependency

• In 2004 alone it is estimated that the ethanol industry expansion will add 22,000

new jobs and more than $15.3 billion to the gross output of the American

economy

• New technology development

• New products with new export opportunities will improve the competitive situation

• International decisions (Kyoto Protocol)

• 5% ethanol substitution will impact the US reduction goal by 13%


Industry size and growth

All Fuel Ethanol 2004

1%

Geographical area

Volume,

million

gallons

Growth, %

p.a.

’04 – ‘05

North America, Total

3800

10%

Europe

125

60%

46%

China

100

35%

50%

Brazil

4100

~5%

Other

50

~15%

Total

8175

8-10%

2%

1%

Worldwide

Value,

million DKK

Growth, %

p.a.

North America Europe ROW Brazil China

Total

58,000

~8%


Many ways to manufacture bioethanol

From sugarcane (Brazil)

From sugar-beets (Europe)

no use of enzymes

Novozymes present market:

The bright future

From starch conversion - USA

China and Europe

corn, wheat, barley

a strongly growing market

usage of enzymes =

1 g protein/gallon

From biomass = cellulose and hemicellulose

from straw

enzymes must be improved.

Usage (starting point) = 100 g

protein/gallon

an international Novozymes

project

”BioEnergy” with research groups

in China, USA (CA, NC) and DK


The principle for all bioethanol production processes are the break down of Starch

to form Fermentable Sugar using various kind of amylases

α-Amylase

α-Amylase

Promozyme

(Fast)

AMG

(Fast)

D-glucose

AMG (Slow)


From starch to bioethanol

• Several process design for bioethanol production exist depending of who,

when and where in the world it takes place

• Wet-milling

– the process for which bioethanol is one product of many. An old

process (start) and expensive process, which also provide many other

products, such as high fructose corn syrup, gluten protein, germ oil

etc.

• Dry-milling

– simple and cheap process developed when the bioethanol demand

exploded during the 1980’’s, using grinded whole corn

• Raw starch hydrolysis

– completely new developed process, which is state of the art within

Biological ethanol manufacturing, combining efficiency and

productivity with the requirement for increasing value of side products

and minimizing environmental issues.


From starch to bioethanol

• Several process design for bioethanol production exist depending of who,

when and where in the world it takes place

• Wet-milling

– the process for which bioethanol is one product of many. An old

process (start) and expensive process, which also provide many other

products, such as high fructose corn syrup, gluten protein, germ oil

etc.

• Dry-milling

– simple and cheap process developed when the bioethanol demand

exploded during the 1980’s, using grinded whole corn

• Raw starch hydrolysis

– completely new developed process, which is state of the art within

Biological ethanol manufacturing, combining efficiency and

productivity with the requirement for increasing value of side products

and minimizing environmental issues.


From starch to bioethanol

• Several process design for bioethanol production exist depending of who,

when and where in the world it takes place

• Wet-milling

– the process for which bioethanol is one product of many. An old

process (start) and expensive process, which also provide many other

products, such as high fructose corn syrup, gluten protein, germ oil

etc.

• Dry-milling

– simple and cheap process developed when the bioethanol demand

exploded during the 1980’’s, using grinded whole corn

• Raw starch hydrolysis

– completely new developed process, which is state of the art within

Biological ethanol manufacturing, combining efficiency and

productivity with the requirement for increasing value of side products

and minimizing environmental issues.


The addition of enzymes enable also a lot of other benefits than

just starch hydrolysis

• Viscosity reduction

• Reduce energy consumption

• Increase ethanol yields

• Reduce content of residual starch in the by product

(“Dry Distillers Grains”)

• Increase fermentation efficiency and rate

• Increase production capacity


Summary - Enzymes for Fuel Ethanol

production and Process Improvements

α-amylase

Liquefaction and Dextrinisation of Starch

Glucoamylase and Pullulanase

Saccharification of Dextrins

Viscosity reducing enzymes

Reduces viscosity by break down of non starch polysaccharides (NSP)

Protease

Provides yeast nutrition, and improve yeast efficiency


The future is in lignocellulosic biomass

The cellulosic biomass conversion industry doesn`t exist today but

• …present production is approximately 180

million tons/year

• Conservative estimates suggest that

biomass in the USA is sufficient to support

between 80 and 115 billion litres

ethanol/year

• This corresponds to a US gasoline

substitution of 15-20%...

• …but available corn stover (logistics) is

estimated at one-third of the total biomass

• So, if just 15% of available US corn stover

is processed, it would make 1.5 billion

gallons of fuel ethanol


What is the problem in utilising the corn stover

• The challenge is due to

• the structure of the fibres that are part of the plant

”skeleton”. The fibres have a very compact structure

and are very difficult to degrade

• the many different enzymes needed to conduct a

significant degradation of fibres


Cost comparison after recent achievements:

Grain vs. biomass in USD/gallon ethanol

January 2004

$7,00

USD/gallon EtOH produced

$6,00

$5,00

$4,00

$3,00

$2,00

$1,00

Biomass

Enzymes

Depreciation of capital

Total

$0,00

Starch

Cellulose

1999

Cellulose new

Source: NREL economic model 1999 and Novozymes


Biodiesel


The first bio based fuel was vegetable oil

At the 1900 Paris Exposition,

Rudolph Diesel presented his

new combustion engine….

It was fueled by 100% peanut oil !!


Biodiesel – Introduction

• Fossil diesel replacement based on renewable resources

• Fatty acid methyl esters from vegetable and animal lipids

• Raw materials varies from refined oil to recycled cooking

oil/rendering fats/deodorization distillate from vegetable oil

refineries

• Biodiesel process technology applied in production depends

on free fatty acid (FFA) concentration in raw material

• No commercial scale enzyme process has been developed

yet


Enzyme catalyzed biodiesel process

OOC

OOC

OOC

+

COOH

Lipase

Methanol, Water

COOCH

H 3

C

3 Glycerol, Water, Lipase

8

+


Source: Lurgi Engineering


Biodiesel – Current Process Technology

• High amounts of FFA (> 0.2%) in rawaterial requires

additional precaution

• Acid-catalyzed pre-esterification is required prior to alkaline

catalyzed esterification to avoid soap formation

• Sulfuric acid creates salt problems in glycerol recovery

• Larger excess of methanol is needed in acid-cat. process

• Acid conditions are corrosive to process equipment

Industrial need for flexible biodiesel process

technology, which can accept high FFA-feed stocks

with a minimal of pre-processes and recovery processes


Fatty acid distillates from palm oil refining

Laboratory scale

• Water: 25% (based on oil); methanol: 1.5 molar eq. to FFA

• Reaction temperature: 50°C

Palm oil fatty acids distillates (89 % FFA) (50C)

Conversion (%)

90

80

70

60

50

40

30

20

10

0

NS 81020 30LU/g

NS 81022 500 LU/g

NS 81006 500 LU/g

NS 81023 500 LU/g

0 5 10 15 20 25 30

Time [hr]


Rape seed oil

Low water content, stepwise methanol addition

• Methanol: 1.43 molar eq. to FA Water: 5.2% (based on oil)

• Reaction temperature: 40°C

Yield , Methyl ester

100%

90%

80%

70%

60%

50%

40%

30%

20%

Dosa ge e f f e c t of NS 8 10 0 6 on Bi odi e se l P r oduc t i on

Ra pe se e d oi l 17 7 g, wa t e r 10 ml , M e OH st e pwi se

5ml MeOH wer e added

80000 LU

40000 LU

20000 LU

10000 LU

5000 LU

10%

0%

0 2 4 6 8 10 12 14 16 18 20 22 24

hour s


Potential benefits of enzymatic biodiesel process

• Raw material flexibility

• No pre-esterification process required

• Enzymatic degumming and transesterification in one step

• Easier recovery operation

• No catalyst to neutralize

• No salts in glycerol phase

• No salt deposit during glycerol recovery

• Can be used both with methanol and ethanol

• water content in alcohol or oil is no issue

• No handling of chemical catalyst

• Improved occupational health environment


Biodiesel Market Overview, Trend and Drivers

Region

Volume

2003

(1000 ton)

Growth

(%)

CAGR

Volume

2008

(1000 ton)

Volume

2015

(1000 ton)

Europe (+15)

1434

35

6430*

North

America

116

44

499

China

50

5000**

SEA


300*

Brazil

0

645*

TOTAL

1600

7574

*) Assuming at least B5 rule implemented in countries

**) Assuming Chinese governmental incentive towards biodiesel

• Europe is leading the industry…with Germany as the main driver

• World wide diesel consumption for transportation (2001): 640 mio ton

• Assuming B5 rule: 32 mio ton biodiesel potential (world wide in 01’)


Biodiesel Market Overview, Trends and Drivers

Trends: Biodiesel will influence …

• the raw material flow of vegetable oil

• the market for glycerol (market prices declining)

• further development of crops for non-edible oil

(e.g. Jatropha tree) and higher oil yielding crops

• the motor companies to develop new and effective diesel engines

(VW and General Motors are active in this process)

• the discontinuities within sustainable fuel process development

- will biodiesel continue when Biomass-to-liquid process is ready

Drivers:

• Political decisions to move into biodiesel

• EU directive (5.75% biofuel)

• High oil prices

• Large fraction of EU car park is diesel engine based (>40%)


Increasing methane yield in anaerobic biogas digester

Enzymatic degradation of complex polymer structures

• Manure (pig, cattle)

• Impact on agriculture livestock quota

• Impact on general water quality (”vandmiljøplan 3”)

• Municipal sludge

• Decreasing residual sludge digistate

• Dewatering of sludge

• Energy Crops (e.g. corn stover, clover grass)

• Driver: High electricity cost

(Germany, Austria)


Influence of different enzymes on methane yield in the process

of biodegradation

ENZYME Type Final products

Lipase 1

Cellulase 1

Cellulase 2

Lipase

Cellulase

Cellulase

Fatty acids and

glycerine

Monosacharide

(Glucose)

Monosacharide

(Glucose)

Methane yield

Increasement / decreasement

(%)

Maize Grass

+18 +40

+3 +38

+12 +67

Protrease 2 Protease Peptides -3 -5

Mixture of 8

enzymes

Mixture Mixture +4 14

In collaboration with University of Vienna


Summary

• Bioethanol

• Several industrial enzymatic processes in place

• Increasing growth in this segment and main driver in Novozymes

endeavor within Biofuels

• US has been the leading area, EU and China are following strongly

• Ethanol from lignocellulose will be the future challenge

• Biodiesel

• Enzyme process under development (=> pilot)

• Market is there and EU is by far the industry leader

• Future raw material supply will be a subject for discussion and

agricultural policy makers

• Biogas

• Enzyme business is its in infancy for the municipal segment

• Enzyme processes under development for both manure and energy

crops


Summary

• Bioethanol

• Several industrial enzymatic processes in place

• Increasing growth in this segment and main driver in Novozymes

endeavor within Biofuels

• US has been the leading area, EU and China are following strongly

• Ethanol from lignocellulose will be the future challenge

• Biodiesel

• Enzyme process under development (=> pilot)

• Market is there and EU is by far the industry leader

• Future raw material supply will be a subject for discussion and

agricultural policy makers

• Biogas

• Enzyme business is its in infancy for the municipal segment

• Enzyme processes under development for both manure and energy

crops


Summary

• Bioethanol

• Several industrial enzymatic processes in place

• Increasing growth in this segment and main driver in Novozymes

endeavor within Biofuels

• US has been the leading area, EU and China are following strongly

• Ethanol from lignocellulose will be the future challenge

• Biodiesel

• Enzyme process under development (=> pilot)

• Market is there and EU is by far the industry leader

• Future raw material supply will be a subject for discussion and

agricultural policy makers

• Biogas

• Enzyme business is its in infancy for the municipal segment

• Enzyme processes under development for both manure and energy

crops


Going forward…

• Novozymes strives to develop biological solutions for

global needs

• Collaboration with the various stakeholders (raw material

supplier, processors, biofuel marketers) is important

• However, local initiatives will be important to

demonstrate feasibility of new processes based on

different raw materials

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