Agro-industrie Recherches et Développements Boris.pdf · Agro-industrie Recherches et...

Agro-industrie Recherches et Développements

SURFACTANTS SURFACTANTS

DERIVED DERIVED

FROM FROM

WHEAT WHEAT

BYPRODUCTSBYPRODUCTS Dr. Boris ESTRINEDr. Boris ESTRINEHead of Green Chemistry DepartmentHead of Green Chemistry Department

b.b.estrineestrine@[email protected] fr

A.R.D.Agro-industrie Recherches & Developpements

CHAMTORGlucose processing plant

C.R.D.Céréales R&D

S.R.D.Sucre R&D

Coopératives Ceréalières :CHAMPAGNE CEREALESCHAMPAGNE COLLIGNY

COHESISCOOPERATIVE AGRICOLE JUNIVILLE

COOPERATIVE AGRICOLE D’ESTERNAYEMC2

NOURICIASCA DE SEZANNE

Production of cosmetic ingredients

20 % 20 %60 %

95 % A.R.D. and SOLIANCE employees5 %

A•R•DAGRO INDUSTRIE RECHERCHES ET DEVELOPPEMENTS

PRODUCTION OF SURFACTANTS FROM CEREAL CO-PRODUCTS BY GREEN CHEMISTRY

LIGNOCELLULOSE

STRAW/BRAN

PHOSPHORYLATIONPYROLYSIS

HEAVY METALRECOVERY

ACTIVATED CARBON

HEMICELLULOSE

PENTOSES

PURIFICATION

SYRUPFERMENTATION

CELLULAR CULTURE(YEAST)

FERMENTATIONETHANOL

(BACTERIE)

FERMENTATIONETHANOL C6 SUGAR

SURFACTANTFATTY alcohols

BIO REFINERY

PAPER RECYCLING

PLANTS

STARCH

FRACTIONATION GLUCOSE

FERMENTATIONPOLYSACCHARIDES

FERMENTATIONETHANOL

(BACTERIA)

CELLULOSE

STRAW

FRACTIONATION

PAPER PASTE

LIGNINE PENTOSES

SEPARATION

LIGNINES

ALTERNATIVE SCHEME

PENTOSES

ORGANIC ACIDS



“Bio-products” from agricultural by-products•Depletion of fossil resources / public consideration for environmental problems

•Need for farmers to envisage changes in European agricultural policy

•Agricultural co-products are available in high quantity and poorly valorised as foodstuff or cattle feed : farmers and agro-industrial firms ask for better added value

•Changes in regulatory affairs for chemicals (REACH)

WHY ?



Surfactants from wheat by-products (bran and straw)• global market volume size about 12 Mill. Tons (2003)

•non ionic surfactant represent around 40% of the market

•mostly used alkyl phenol E.O. : retired from the market for health considerations => place for low cost solutions and polyvalent surfactants (with low hazard and good environmental profile)

•solution of molecules derived from renewable agricultural resources

•agro-food industries generate by-products => biorefineries implemented in the same area

•availability : potential of 5 mill. Tons of sugars available from wheat by-products fractionation (only in France)

WHY ?


•sorbitan esters, sucrose esters, Me-Glu-esters, APGlu…

•sucrose: beet sugar, and glucose: corn or wheat starch =>low prices

Sugar World production (t/year) Price / kgD-sucrose 113 614 000 0,31 €D-glucose 5 000 000 0,60 €D-sorbitol 650 000 0,90 €


NOWADAYS : carbohydrate based surfactants :

Sugar Alkyl Chain

Linking (ester, glycosidic bond)



World production of carbohydrate surfactants (total : 200 000 t/year)

USA40%

Europe20%

Asia25%

Others15%

Only 200000 t/y in a possibility of 5 mill. T/y market volume size ? 1. Price position : ex. APGlucosides (3-4 euros/kg) in comparison with

the 1-2 euros/kg for EO alcohols2. Performance and polyvalence!

NOWADAYS : carbohydrate based surfactants :

Wheat Branand Straw (around 40 euros/t)

Lipophilic tailHydrophilic head

Xylose,Arabinose, Glucose

Hydrogenation of fatty acid tofatty alcohol

Plant oils :Rapeseed, Palm, Coco, Coprah…


Link:glycosidic bond


ARD PHILOSOPHY



WheatWheat

StrawStraw

BranBran StarchStarchHemicellulosesHemicelluloses

DD--GlucoseGlucoseLL--ArabinoseArabinose

DD--XyloseXylose

HydrolysisHydrolysis

HemicellulosesHemicelluloses New APGNew APGHydrolysisHydrolysisLL--ArabinoseArabinose

DD--XyloseXylose

GLYCOSYLATIONGLYCOSYLATION

Corn Corn or or WheatWheat

StarchStarch DD--GlucoseGlucoseHydrolysisHydrolysis

APGAPGGLYCOSYLATIONGLYCOSYLATION

Classical route for the preparation of APG

New approach developed by A.R.D. for new agro-surfactants

Green chemistry for green surfactants => free of solvent Glycosylation

O

OOHO

OHHOROH, H+

H2ODP


0

20

40

60

80

Wheat straw De-starched wheatbran

Wheat bran

L-arabinose D-xylose D-glucose D-galactose et D-mannose Dioses

Natural distribution of sugars : depending vegetable origin and process


PENTOSES FROM HEMICELLULOSES

Chromatography techniques allows easy separation and pure sugar

manufacturing for tailored made

surfactants

PRODUCTION OF SURFACTANTS FROM CEREAL CO-PRODUCTS BY GREEN CHEMISTRY A•R•D

AGRO INDUSTRIE RECHERCHES ET DEVELOPPEMENTS

WHEAT BRANWashing

DESTARCHED BRANAcid hydrolysis at 130°C

BRAN HYDROLYSATELiming

LIMED HYDROLYSATEFiltre-pressing

NEUTRALISED JUICECationic & anionic exchange

DEMINERALISED JUICEConcentration

BRAN PENTOSE SYRUP

WHEAT BRANWashing

DESTARCHED BRANEnzymic hydrolysis

BRAN HYDROLYSATEDecantation & centrifugation

TROUBLE BRAN JUICEUltrafiltration

BRAN PERMEATEChromatography

BRAN PENTOSE FRACTIONConcentration

BRAN PENTOSE SYRUP

Thermo-chemical Enzymic

FRACTIONATIONPROCESSES



Sugars evolution in processed bran

0

10

20

30

40

50

60

70

80

90

100

Wheat bran Destarched bran Bran hydrolysate Limed hydrolysate Neutralised juice Demineralised juice Bran pentose syrup

% of purity

Glucose

Xylose

ArabinoseSum

Total sugars Free sugars

Syrup contentGlucose: 19%Xylose: 47%Arabinose: 27%Galactose: 2%DP2: 1,8%Ashes : 0,2%Proteins: 0,8%Others: 1%

THERMOCHEMICAL PROCESS

HYDROLYSIS



Treatment T°C + Acid Enzymes

StrengthHigh yield

Very low DP amount

SpecificityCost of

purification DP present

Weakness Degradation products

Medium yield

COMPARISON OF THE 2 PROCESSES

0102030405060708090

100

0 60 120 180 240 300

time (mn)

Res

idua

l sug

ars

(%)

D-glucoseD-xyloseL-arabinose


Advantages in carrying out a sugars blend glycosidation :

1) pentoses show an higher chemical reactivity

2) synergetic effect between pentoses and glucose, is increasing reaction kinetics

3) avoid sugars separation steps

4) grafting occurs below 120°C


ADVANTAGES OF BRAN SUGARS

Polymerization degree of alkyl glycosides

1,4

1,11

2,2

1,51,4

0

0,5

1

1,5

2

2,5

Alkyl Glucosides Alkyl Xylosides Alkyl Arabinosides

DP

DP min DP max


DP range is influencing the properties of surfactants ⇒ Large scale of properties (similar to surfactants derived from ethylene oxide)


ADVANTAGES OF PENTOSES


EmulsifiersEmulsifiers

Washing or foaming Washing or foaming surfactantssurfactants

SolubilizerSolubilizer,, plasticizerplasticizer, , etc.etc.

14 to 22 carbons (Ex palm oil)

8 to 14 carbons (Ex palm kernel oil or coprah)

4 to 8 carbons (i.e. Fusel oil)

Various length of fatty chain

Mix of cleaning, foaming, detergent powers depending on the chain length and the compositions of sugar syrups.


INFLUENCE OF FATTY ALCOHOLS



0

20

40

60

80

100

0 0,05 0,1 0,2 0,3

NaCl content (%)

Res

idua

l em

ulsi

on (%

) Wheat BranGlycosides

Glycosidesderived fromglucose

Salts and pH stability > Classical Glucosides or EO Alcohols

Viscosity adjustments…

Applications: cream, milk for cosmetics / agrochemicals…

Neither thickener, nor co-emulsifier have been added for the test.

EMULSIFIERS: Long tail APP for self emulsifying base: up to 47 % APG in starting alcohol (without distillation!) Non EO surfactant, no cloud point, low cost formulation

4000

6000

8000

10000

12000

14000

16000

0,00% 0,10% 0,20% 0,30% 0,40% 0,50% 0,60%Percentage of salt (NaCl)

Bro

okfie

ld (c

yl3,

spe

ed 1

2)


PRODUCTION OF NEW SURFACTANTS FROM CEREAL CO-PRODUCTS BY GREEN CHEMISTRY

LiquidLiquid self emulsifying base: Impossible with glucoside derivatives; the near-zero energy emulsification. Non EO surfactant for Mini-emulsions / Oily emulsifying concentrates / Sprayable emulsions for detergents/cosmetics and agrochemicals…

[0,5µm] emulsion area

Bluish emulsions

APP 1APP 1

APP 2APP 2 APP 3APP 3

0

5

10

15

20

25

30

0,11 0,15 0,2 0,26 0,34 0,45

µm

% N

D [4,3] = 0,2 µm



Foaming / Washing propertiesFoaming / Washing properties: Efficiency, Effectiveness of middle tail length APP for hard surface cleaning

• High micellisation speed

• Low surface tension: (γCMC = 25,5 à 27 mN/m)

• synergistic compatibilities

1

10

100

1000

10000

7 9 11 13

nbre de C

CM

C (m

g/l)

XylosidesGlucosides

air

eau

γ(mN/m)

log CCMC



Contact angle (°) Teflon Paraffin

Water 104 96

APGlu 62 55

PentosidesPentosides 5151 4141

Reduction in the contact angles on

hydrophobic surfaces

ARD Pentosides >> APglucoside

Wetting propertiesWetting properties:

Highly effective detergents and agrochemicals



Drift under controlDrift under control : :

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

Xyl C8

Xyl C10

Xyl C12

APG 8/10

Triton X114

5 ms5séq.

Efficiency of short middle to short tail

pentosides

Control size of the drops and

avoids the rebounds



Striking differences with APG in two phases diagramsStriking differences with APG in two phases diagrams:

Protection and control release of thermo-sensible cosmetics or phyto-ingredients

SPHERULITESSPHERULITESSPHERULITESSPHERULITES



DPHO O

O

R1

R2

Wheat bran & wheat strawBy-products of cereal industry

Hydrophylic head

Ramified lipophilic tail

3-méthyl-1-butanol(alcool isoamylique)

HOHO

2-méthyl-1-butanolHO

OHO

OHOH

OH

D-Glucose

HOO

OHOH

HO

D-Xylose ou L-Arabinose

R1=H , R 2=Me ou R 1=Me , R 2=H

SOLUBILIZER : short tail APP

Fusel oilBy products of sugar (ethanol) industry



0

500

1000

1500

2000

2500

3000

SDS APG 8/10 APG 8/10 + GluC4 Solubilzer ARD

So

lub

iliz

ing

po

wer

(%/

SD

S)

Strong solubilizing power



Solubilization of perfumesSolubilization of perfumesSolubilizers tested

PerfumesA.R.D. Cremophor

RH 40 Transcutol ORAMIX BG14 AG 6206 Tween 20

Lemon (Huber the Nose 19-11454) 5,8 - 7,2 4,3 > 28,7 > 15,0 > 17,2 nd

Pine OSF France 34230 5,0 5,0 > 26,0 > 13,7 > 13,8 5,0

Grapefruit OSF France 4,1 5,3 > 26,6 > 12,0 > 12,0 4,0

Mint OSF France 20636 2,6 5,1 > 25,5 > 9,5 > 9,5 2,6

Peach OSF France 20668 5,1 7,6 > 25,0 9,5 9,5 5,0

Solubilizer/perfume (g/g) until complete solubilization in water

Efficiency with essential oils, cosmetic ingredients (α-bisabolol…)



Environmental considerations

0

1 0

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8 9 10 1 1 12 1 3 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

J ours

% d

e b

iod

égra

dat

ion

S odium Acetate

ARD

LAS

• Ultimate biodegradability along EOCD 301F

• Favorable eco-toxicity



Environmental considerations• Smooth surfactants

MUCOUS MEMBRANE

VERY SLIGHT

ARD SLIGHT

IRRITATION LAS + APG

LES + APG LAS SAS Laurylethersulphate LAS + protein Lauryl sulphate

Lauryl sulphate SAS + APG + betaines LES + protein

IRRITANT SKIN COMPATIBILITY VERY IRRITANT IRRITANT NOT/LITTLE IRRITANT Zein or patch test

Nonionics Laurylsulphate

+ betaines

RBC & DRAIZE TEST

Betaines

LAS + proteins SAS + APG

soap

Sulfosucc Quats

Protein condensates



CONCLUSIONS

1. Renewable raw materials for low cost surfactants2. Co-products from the patented process could be valorised3. Low energy consumption process (<90°C with pentoses to >110°C with Glu)4. High biodegradability according to OECD 301F, equal to sodium acetate5. Not irritant product (RBC and Zein test), especially for skin6. Broad range of applications



Wheat APP

SOLIANCE

Avena fatua Galium aparine



Thank you for attention

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