IMPROVED GLYCERIN QUALITY

VIA SOLID CATALYST

TRANSESTERIFICATION TECHNOLOGY:
THE ESTERFIP-H PROCESS
Michel Bloch - Axens

Bio-Oil International Conference, Vigo, February 2006

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Agenda

A few words about us

The Esterfip-H new heterogeneous catalyst process

Principles
Process Scheme
Comparison with homogeneous catalysis
Commercial status

Conclusions

Institut Franais du Ptrole

from the Well to the Wheel

Independent Industrial R&D center

E&P, Refining & Petrochemicals, Engines & Energy
1730 peoples on 2 main locations (Paris Lyon)

IFP-Lyon in a few figures

630 employees (81% of them

in R&D)

50% of IFP's R&D staff

> 170 pilot units, mock-ups

& test benches

Institut Franais du Ptrole

from the Well to the Wheel

Refining & Petrochemicals

Develop clean and economical processes &
products for the production of current & future
fuels (and petrochemicals bases) from Oil, Gas,
Coal & Biomass.
Commercialisation through subsidiaries such as
AXENS

Axens

Benchmark technology and service

provider to the hydrocarbon industries

Axens enhances customer performance

through innovative technical solutions

Innovative processes, catalysts,

adsorbents, equipment and services,
backed by nearly fifty years of
commercial success

Axens is a fully owned subsidiary of IFP

ISO 9001 (2000)

Certified since 1996

Global Network

Calvert City
Princeton
Savannah

Moscow
Beijing
Tokyo

Houston

Caracas

Offices
Manufacturing Sites
Agencies
Tech Service

Rueil-Malmaison
(Headquarters)
Lyons, Solaize
Salindres
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Catalyst Manufacturing Facility

Salindres, France

IFP/Axens: a Pioneer in Biofuels Technologies

1992:

First biodiesel plant started-up

1993:

First MTBE converted to ETBE

1996:

First ETBE plant started-up

2006:

First solid catalyst biodiesel plant

Esterfip Process Milestones

1984 Lab research initiated

1987-1989: Pilot operations for homogeneous process Esterfip

Preliminary trials and operating conditions screening

Process validation

Methyl ester production for captive fleet tests

1992 Start-up of first Esterfip industrial plant for Sofiproteol at
Compigne (France) - Initial capacity = 20 000 t/y
1997 Debottlenecking of Compigne unit
(Present capacity = 100 000 t/y)
2002 Development of heterogeneous process Esterfip-H
2004 Selection of Esterfip-H by Sofiproteol for its new plant in Ste
(France) with a capacity of 160,000 t/y

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Trans-Esterification Reaction
A Three-Step, Catalytic, Reversible Reaction
Vegetable Oil

Methanol

CH2 OCOR1

Methyl-Esters
(Biodiesel)

Glycerin

R1COOCH3

CH2 OH

Catalyst

CH OCOR2 + 3 CH3OH

R2COOCH3 + CH

CH2 OCOR3

R3COOCH3

OH

CH2 OH

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Esterfip-H Reaction
NaOH
or
NaOMe

R-COO-CH2
R-COO-CH
R-COO-CH2
+
Heterogeneous
Homogeneous
CH3-OH
Catalyst

Glycerin

CH3-OH
R-COO-CH3
HO-CH2
HO-CH
HO-CH2

NaO-CH2
HO-CH
HO-CH2

Neutralization
Step
Glycerin

Biodiesel
+ CH3ONa
+ R-COONa

Aqueous
HCl

HO-CH2
HO-CH + R-COOH +
Fatty Acids
HO-CH2

MeOH
H 2O
NaCl
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Heterogeneous Esterfip-H
Methanol
Partially
Refined
Vegetable
Oil

Mineral
Acid
Solid
Catalyst
Reactor
Reactor

Biodiesel
(Diester)
Settler

Neutralization
Washing

Evaporation

Catalyst
Mineral
Acid

Glycerin
Glycerin
Purification

Fatty Acids
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Esterfip-H
Simplified Process Flow Diagram
Partial
Evap.

Partial
Evap.

Methyl Esters
Full
Evap.

R1

R2

Methanol

Vegetable
Oil

> 98%
Glycerin

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Glycerin quality (wt %)

Homogeneous

Esterfip - H

80

98

balance

0.5

Organic compound

1.2

1.2

Methanol

0.3

0.3

Glycerol
Water

Salts

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Homogeneous vs. Heterogeneous

Homogeneous
Maximum yield, 99.5%
Glycerin quality
Complex separation &
purification steps
Salt and aqueous wastes
Consumption of chemicals
Mild conditions T & P
Low MeOH/oil ratio

Heterogeneous
Yield above 100%
Glycerin quality
Simple separation & purification
steps
No waste stream
No Consumption of chemicals
Lower Catalytic cost
T & P conditions more severe
Higher MeOH/oil ratio

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Esterfip-H - 1st Commercial Reference

New plant in Ste,

France

Capacity: 160,000 tons

per year

To be commissioned in
the Q1 2006

Ste

Selected by Diester Industrie

(Europes largest producer)

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Conclusions

Axens / IFP

Over 10 years of experience in biodiesel

production technologies

Ongoing research and development in the field

of vegetable oil esterification

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Conclusions
Esterfip-H is IFP/Axens answer to
the growing biodiesel demand

High biodiesel yield

High glycerol quality
Green process (no waste)
Simplified operations (no chemicals handling)

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Thank you!
www.axens.net

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