Using Enzymes for Cost Efficient Biodiesel Production

T. Balle, P.M. Nielsen, S.Träff, A.Rancke-Madsen, Hans Christian Holm

Novozymes A/S, Denmark

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Agenda

Novozymes solutions for

oils and fats processing

Our BioFAME process

The enzyme reaction

Large scale industrial experience

with Used Cooking Oil

PFAD conversion

Summary

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World leader in industrial enzymes & microorganisms and market leader in all industries where present

13-14% of revenue invested in R&D

R&D activities in 5 countries

Enzyme production in Brazil, China, Denmark, India and USA

More than 6,500 granted or pending patents

43 new products launched during the last 5 years

Enzymes for industrial use Market size ~ 4-5 Billion USD

Novozymes 47%

DuPont Danisco

21%

DSM 6%

Others 26%

Novozymes in brief

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Current & Developing Enzyme applications in oils and fats processing

Enzymatic degumming

Enzymatic Interesterification

Ester synthesis Speciality fats for nutritional use

Removal of gums to ensure yield stability, & quality

Change in fat melting properties for margarine and shortenings

Bio-diesel, oleochemicals, speciality esters and FAEE

Synthesis of omega 3 & similar products for healthy nutrition

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More than 100 Plants World-Wide use Novozymes enzymatic solutions to improve their oil & fats processing

Enzymatic Degumming plants Enzymatic Interesterification plants

Synthesis and modification plants Pilot biodiesel plants

Our BioFAME process is transesterification and esterification followed by polishing

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Economical benefits for the Novozymes BioFAME process are based on

Feedstock flexibility

Process oils independent of the FFA content

Enable use of lower cost raw materials

Glycerin is pure

Technical grade glycerin can be sold at high value

Energy consumption

Significantly lower methanol rectification costs

Low methanol surplus dosed

Methanol is re-used with glycerin-water phase

Re-use wet methanol

No need to dry the oil feedstock

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We will be cost competitive to chemical processes on high quality substrates like soybean, rapeseed and palm oils.

We are already competitive on high FFA substrates

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Alkaline wash reduce free fatty acids and glycerides and make final biodiesel meet specifications.

The soap stock is acidified and sent back – i.e. no yield loss

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0

0,5

1

1,5

2

2,5

3

Before CW After CW

% in

FA

ME TG

DG

MG

FFA

BG = 0.17%

BG = 0.10%

The enzyme works at the oil/water interface

Mixing is important – we need a an emulsion with a large surface area between oil and glycerin/water phases

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Oil/FAME

Glycerin/water

Mixing

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Glycerides + MeOH glycerides/glycerin + FAME

Glycerides + H2O glycerides/glycerin + FFA

FFA + MeOH FAME + H2O

Reaction at interface

Enzyme process works well with any content of free fatty acids

Increased process robustness and economy are obtained by using a liquid enzyme formulation.

Most previous enzyme work for biodiesel has used Novozyme 435, why change enzyme?

.

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Callera Trans Novozym 435

Reaction with glycerides Yes Slow with TG

Requires water Yes No

Formulation Liquid Immobilized

Re-uses required Few – low risk Many – high risk

With the liquid enzyme we have a cost efficient and low risk enzymatic process

A cost competitive process requires a high enzyme productivity.

Factors influencing enzyme productivity and reuse:

Loss due to high methanol concentration or too high temperatures

Mineral acid in oil – easily adjusted by ppm addition of NaOH

High soap content in oil

Physical loss

Glycerin phase

(FAME phase)

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3 phases after BioFAME FAME Emulsion Clear glycerin

Re-using the enzyme for 3 batches of Used Cooking Oil 1% Callera Trans, 35C, 3% water, 1.5eqv MeOH

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We end at around 2% free fatty acids and 1% bound glycerides. Key issue with used cooking oil is the content of polymerized glycerides

New focus on making BioFAME from Crude palm oil and PFAD

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0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4

% F

FA

Time (hours)

0.10%

0.20%

0.50%

PFAD: 55°C/ 0.1-0.5% NS40085/0% Water/5% Glycerol/0.8 Eqv Methanol

First step 7 hour reaction

% FAME % FFA % NC

84.9 5.72 4.21

Reaction conditions: 1% NS40085/55°C/7hour reaction time, ~12% glycerol. Methanol, 1.2 EQV (NC= Not converted comprised of partial glycerides, sterols etc)

For PFAD we will need more than 1 process step as the water formed from reacting of free fatty acids need to be removed. This proces is being optimized in the laboratory.

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Alternatives to the alkaline wash are under development one process uses an enzymatic polishing reaction to reduce free fatty acids and glycerides

Time (hours)

% FFA

Cycle 1 Cycle 2

0 5.32 1.33

2 1.44 0.58

4 1.46 0.54

6 1.33 0.6

1/1.5% NS40079 + 6% MeOH split dosing, 60 °C, drying of FAME & enzyme between cycles

Initial results from the laboratory are quite promising

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Tsinghua China – Hunan plant

Lipase-mediated industrial scale production of biodiesel (20,000t/y) put

into operation Dec 8, 2006. Initially in a process with t-butanol;

Now restarting in solvent free process

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Final product

Blue Sun - USA. 3 enzyme reactors of 300 m3 each

Started early 2013

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Viesel Biofuels – Florida USA

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BioFAME process operating since January 2013 in 250 tons scale producing biodiesel in spec. (ASTM) from used cooking oil

Bound glycerides, FFA and FAME in spec (ASTM)

> 99% purity of glycerol obtained by glycerin bleed-off after 1st batch

The Novozymes BioFAME process is now been scaled up at several partner plants to collect experience/data for processing different qualities of oil feed-stocks. Broader launch in 2014.

PFAD is the next substrate to be investigated and promising results are being obtained using esterase enzymes

Final polishing is critical and new enzyme formulations/technologies are under development

Enzymes can help you improve process yield and product quality

Thank you for your attention

SUMMARY

Conclusion: Increase MeOH and decrease H2O

But there are limitations:

MeOH: The enzyme is sensible to high MeOH concentrations in the glycerin phase Keep it relatively low to prevent inactivation

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13% MeOH in glycerin 16%

1% H2O in reactor 3%

H2O: The Callera Trans requires some H2O but it impacts equilibrium = FFA after reaction Keep it relatively low to limit FFA after reaction

BioFAME process generates more profit than Chemical processes

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US$ per ton biodiesel

Chemical Transesterification 0.25% FFA in feed-stock

Chemical Esterification and Transesterification ≈ 0.25-7% FFA

BioFAME ≈ 0-7% FFA

Greenfield plant capacity: 1000 Tons Biodiesel/day

*Feed-stock cost: $1100/ton, Methanol cost: $450/ton, Biodiesel sales value: $1250/ton

Depreciation 11 14 11

Yield% 98 100 100

Catalyst 26 24 25-50

Utilities 9 17 3-5.5

Effluent 0 3 1

Other costs 1178 1156 1157

Total costs 1224 1214 1196-1222

Glycerin value 17 17 38

Profit 43 53 64-91