addedvalue of homogeneous, heterogenousand ... 2013 - jl dubois arkema... · addedvalue of...

1

Added value of Homogeneous,

Heterogenous and Enzymatic Catalysts in

Biorefineries

Jean-Luc DUBOIS

Scientific Director

Arkema is a member of the European Biorefinery / technology Projects

Arkema received the 2013 Award from the European BiomassIndustry Association for its merits in advanced biomass processing

OPTICO

OPTICO

2 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress

Arkema’s Existing Biorefineries

4 Vegetable Oil-based

1 Wood-based

11 % of Turnover (700 M€)

Arkema’s Renewable Products have technical advantages

2

Fatty Nitriles & Amines

Feuchy

Epoxidized Linseed& soybean Oils,

Terpenes

Blooming Prairie

Casda

Castor Oil-BasedPA MonomersSebacic Acid

Marseille St Menet

Castor Oil basedPolyamide Monomer

Coating Solutions

Wood-basedActivated Carbons

Parentis

Vegetable Oil based


Fatty Acid ProfileSource: « Lexicon of Lipid Nutrition », Pure Appl. Chem., Vol 73, N°°°°4, PP 685-744, 2001 and Oleon datasheets + internal data

0% 20% 40% 60% 80% 100%

DH12C

Coconut

Palm Kernel

Babassu

CASTOR

Tallow

Olive

Palm

Lard

Honesty

Safflower (high oleic)

Crambe

Rapeseed HIGH erucic

Lesquerella fendleri

Groundnut

Rapeseed low erucic

Canola

Jatropha

Corn

Cotton seed

Camelina

Soya bean

Walnut

Sunflower

Linseed

Safflower (high linoleic)

Content (wt %)

Saturated

Monounsaturated

Polyunsaturated

Castor


Ricinoleic Acid based

Renewable polymers

C7

C8

Amino

Acid

C11

DiAmine

DiAcid

C10

PA THT

PA HT

Bio-composites

2 Octanol derivatives

Castor

plants

Castor

seeds

Castor

oil

Glycerol

Casda’s Biorefinery

Marseille’s Biorefinery

O

HO

OH

85-90 %

PA 10.10PA 10.XPA X.10

PA11


Value to the customer

● High flexibility

● Low water absorption

● Chemical resistance

● Impact resistance

● Low density

● Easy tube extrusion processing

Market opportunities & drivers

● Transportation

– Lightweight materials for metal replacement

● Energy (off shore)

– Non conventional oil recovery

● Consumer goods (sports, cosmetics)

– Increasing standard of living

Main end-markets

5

Specialty polyamides market


Selective Enzymatic Extraction of Ricinoleic Acid

from Castor Oil

Collaboration with C. Bourlieu, B. Barea, E. Dubreucq, P. VilleneuveUMR IATE, Montpellier, France

Ingénierie des Agropolymères et Technologies Émergentes


RRR : 71.0 % (p/p)

ROR : 7.2 % (p/p)91 %

1,3-diricinoleoyle-2-

oleoyle-sn-glycerol

RLR : 6.6 % (p/p)

95 % 1,3-diricinoleoyle-2-

lineleoyle-sn-glycerol

RPR : 1.6 % (p/p)


palmitoyle-sn-glycerol

RRLinolenic : 0.15 % (p/p)

RSR : 1.1 % (p/p)


steroyle-sn-glycerol

RRRR (estolide): 0.45 % (p/p)

RRLesquerolate :

0.67 % (p/p)

OH

O

O

O

C

O

(CH2)7

(CH2)7

(CH2)7

C

OC

O9

11 13

OH

OH

Triacylglycerols identified in Castor Oil

R: C18:1, OH – P: C16:0 - S: C18:0 – O: C18:1 – L: C18:2

(Lin & Arcinas, 2005; Lin et al., 2006; Weber et al., 2006 )


0102030405060708090

100T

aux

de c

onve

rsio

n (%

)

0 0.5 2 4 6 8 24

Temps (Heure)

RA

LA

OA

MethRA

MethLA

MethOA

Test in methanolysis of Castor Oil

Methanol/Castor Oil : 1.5:1 in 3 methanol additions (3*1.5:1 at 0, 2 & 4 Hr)

Legend : RA = ricinoleic acid, LA = Linoleic acid, OA = Oleic acidMethRA = Methyl ricinoleate, MethLA =Methyl linoleate, MethOA = Methyl oleate

Results on Castor Oil

Time scale (Hr)

WO2010/100366 : Jean-Luc DUBOIS, Claire BOURLIEU- LACANAL, Jéröme LECOMTE, Eric DUBREUCQ, Pierre VILLENEUVE.

Very fast enzymaticReaction �� 0.5 hr

Con

vers

ion

Rat

e

(%

, by

acid

type

initi

ally

in

trig

lyce

ride

“in-planta” Catalysis for the production of methyl ricinoleate

Reactive seed crushing on Castor Seeds

PROCESS INTENSIFICATION

Objective: Produce at the same time Castor Oil Methyl Ester, Glycerin

and a detoxified Castor Meal without ricin and allergens

Provide a technology for the seed producer, to deliver higher value

products (esters and seed meal)

Collaborative development with VALAGRO

Acknowledgement to ADEME for financial support


Reactive seed crushing process

Crushing

Steam

Extraction

Refining

Methyl EsterFAME

Solvent (Methanol)

Glycerine

Crushing

Steam

Extraction

Refining

Methyl EsterFAME

Solvent (Methanol)

Glycerine

+ <catalyst>


Product Analysis

< 12 wt %

<0.5

<0.2 wt %

<0.2 wt %

<0.8 wt %

-

Biodiesel

EN14214

0.8

1.2

3.5

3.5

90.6

0.3

99.6

nd

0.03

0.33

0.36

~90

0.6

Test 09E30-4

Seeds Acidity mg KOH/g

0.6

0.9

2.3

3.3

91.5

0.57

99.1

nd

0.1

0.7

0.8

Analysis of an ester from

conv. process

-Esters Yield

≥≥≥≥ 98.5Ratio [MR/(MR+ glycerides)]

-Triglycerides, %

-Monoglycerides, %

-Diglycerides, %

0.8 – 1.1Palmitic C16:0

0.7 - 1.0Stearic C18:0

4.1- 4.7Linoleic C18:2

2.0 – 3.3Oleic C18:1

85.0 – 89.0Ricinoleic C18:1, OH (MR)

Fatty Esters Profile

≤≤≤≤ 0.3Acidity Index, mg KOH/g

≤≤≤≤1.0Glycerides (%)

TARGET ARKEMA


Detoxification. Ricin and Allergen (CB-1A)Special acknowledgement to Dr Xiaohua He, Western Regional Research Center, USDA,

Albany, USA for “blind” testing seed meals and confirming our results. JL Dubois, A Piccirilli, J

Magne, X. He, Industrial Crops and Products, 43 (2013) 194-199.

1,6 10-4

2,4 10-4

> 4 10-4*

> 4 10-4*

Active Ricin (%)

99.99%2.2 ××××10-4100°°°°C/4h120°°°°C / 4h100°°°°C / 16hContinuous fixed bed process

99.95%8.6 ××××10-4-120°°°°C / 4h100°°°°C / 16hContinuous fixed bed process

94.50%0.01-120°°°°C / 4h100°°°°C / 16hBatch process, agitated bed

-1.8---Defatted flakes (60°C, 10h)

Ricinereduction

(%)

Ricin (%)Final Drying

(T°C, h)

Solventremoval

T°C/(h)

Drying

T°C/(h)

Seed/Seed meal

Immunologic Assay + Mass spectrometry test done by CEA (Saclay)

Continuous fixed bed process

Continuous fixed bed process

Defatted flakes (60°°°°C, 10h)

Seed/Seed meal

non allergenic at 10%> 2000120°C, 4h

non allergenic at 10%> 2000150°C, 4h

Allergenic at 10%300< DL50 < 2000*

(*mortality 100%)

-

Cutaneous sensitvity test

(Local Lymph Node Assay)

Accute toxicity on rats (DL50, mg/kg)

Final Drying(T°C, h)

* Value above the saturation limit of the method** + additional drying at 100°C, 4 h


The Triple Effect

� Reduce CAPEX� Smaller number of pieces of equipment

� Reduce OPEX�Reduce maintenance, labor and processing cost

� Detoxify�Reduced toxicity of the Seed Meal

Also contributed to this work

● ADEME financial support to project RICHARB

● Jacques BARBIER, Antoine PICCIRILLI, Julien MAGNE (Valagro)

WO2010/076527, Jean-Luc DUBOIS, Julien MAGNE, Jacqu es BARBIER, Antoine PICCIRILLIWO2010/084276, Jean-Luc DUBOIS, Antoine PICCIRILLI, Jacques BARBIER, Julien MAGNEWO2011/092430, (Jatropha seeds) Jean-Luc DUBOIS, Jul ine MAGNE, Anoine PICCIRILLI…

14

Metathesis of Vegetable Oils for

Aminoacids production

Xiaowei Miao, Raluca Malacea, Cedric Fischmeister, Christian Bruneau, Pierre Dixneuf

Jean-Luc Dubois, Jean-Luc Couturier


Route selected: Cross metathesis

Mechanism described by Yves Chauvin

R1

R1

R2

R2

+

R2R1

+

R1 R2

[M=]

Ru

NMesMesN

Cl

Cl PPPPhhhhPPPPCCCCyyyy3333

Homogeneous Catalystex. Grubbs II

MR

MR2

R2R1

R1 R1

M

R1

MR2

MR2

R1R1

R1

RR1 R2

R1 R1

R2

R1

R2

R2


Arkema’s Renewable Long Chain Polyamides

Butadiene

Polyamide-12

Lactame-12

CDT

Castor Oil

Polyamide-11

Amino-11

Undecenoic Acid

Polyamide-10.10

Diamine-10

Sebacic Acid Undecenoic ME

Polyamide-12

Amino-12

Undecenenitrile

Acrylonitrile

MethylAcrylate


Oil

Unsaturated fatty acid derivatives as precursors

to polyamides through metathesis

ϖ-unsaturated fatty nitrile / ester

METATHESIS

HYDROGENATION

(CH2)8

N

O

O

N

N

(CH2)8

O

O

O

(CH2)8

N

O

+

+

NH2

(CH2)11

O

O

O O

(CH2)8

WO2010/055273, Jean-Luc DUBOIS & WO2010/089512, Jea n-Luc DUBOISX Miao, C Fischmeister, P Dixneuf, C Bruneau, JL Du bois, JL Couturier, Green Chemistry, 2012

High TurnOverNumbers

18

Glycerol conversion to Acrolein and Acrylic Acid

Collaborations with:

Pr Hölderich, RWTH Aachen

Pr Ueda, Hokkaido University

Pr Patience, Ecole Polytechnique de Montréal

WO06/087083 Jean-Luc DUBOIS, C DUQUENNE, W HOLDERIC HWO07/090990 Jean-Luc DUBOISWO07/090991 Jean-Luc DUBOISWO08/087315 Jean-Luc DUBOIS, Gregory PATIENCEAnd more than 30 other patent applications filed


Acrolein/ Acrylic Acid: ARKEMA’s Project

Acrolein and Acrylic acid are currently produced from propylene (Petroleum).

Double internal dehydration of Glycerol leads to Acrolein which is further oxidized to Acrylic acid

Acrolein/AcrylicAcid Unit

Crude Glycerol

Thermal Oxidizer

Acrolein or Acrylic acid

Tank

Tank

Wastes: salts…

Separation

OH

OH

OHCH2

O

+ 2H2O CH2O

OH

Methionine

Fine Chemicals/Fragrances

Polyacrylate= dispersing agents for minerals Superabsorbants


Environmentally Friendly Process:

Avoid scenarios of past accidentsTarget: develop a new process for on-site Acrolein production (PROXI-plants) to avoid storage and transportation of a highly toxic Chemical.

Pierre Bénite, France. July 10, 1976.

Taft, USA/ December 10, 1982.

Major contamination of the Rhône River, during clean-up of a train tank367 Tons dead fish

Explosion of a Storage facility17000 people evacuated


Cradle to gate analysis

Acrolein ex propylene: 3190 kg CO2/t

Acrolein ex glycerol: Target 980 kg/t

Acrylic acid ex Propylene: 950 kg CO2/t

Acrylic Acid ex glycerol: target 0 kg/t

Diesel Blend

Vegetable Oil

MethanolTransesterification

MethanolTransesterification

BiodieselDiesel

CO2Plant growth = consumption of atmospheric CO2

GlycerineAcrolein/ Acrylic Acid

Done within the Glyvalacr Project sponsored by Ademe


12 Principles of Green Chemistry

1. Prevent waste �� We use a waste

2. Design safer Chemicals and Products �� Drop in

3. Design less hasardous chemical synthesis �� Process for on-site production

4. Use Renewable feedstocks �� Glycerol

5. Use catalysts not stoichiometric reagents ��Heterogeneous Catalyst

6. Avoid Chemical derivatives �� Direct route

7. Maximize atom economy �� C3 to C3

8. Use safer solvents and reaction conditions �� no solvent, safer process

9. Increase Energy effciency �� Translated into CO2 balance

10. Design Chemicals and products to degrade after use �� return plant-based CO2 to the atmosphere

11. Analyse in Real time to prevent pollution �� Target = on-time consumption

12. Minimize the potential for accidents �� Avoid transportation and storage

23

Thank you

for your attention

………………………………………………………………………………………….........

………………………………………………………………………………………….........24

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