Valorisation of wheat bran into surfactant molecules by Caroline - PowerPoint PPT Presentation

Valorisation of wheat bran into surfactant molecules by Caroline Rémond (INRA/URCA FARE), Magali Deleu (ULiège), Yamini Satyawali (VITO) Representing the ValBran consortium www.valbran.eu Facebook page: @Valbiom @interregFranceWallonieVlaanderen #ValBran LinkedIn & Twitter: ValBiom asbl #ValBran Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 1

Interreg France ‐ Wallonie ‐ Vlaanderen ONDERZOEK EN INNOVATIE RECHERCHE ET INNOVATION 1. Versterken van het onderzoek en de innovatie van de grensoverschrijdende zone in de strategische sectoren en de sectoren met een sterke complementariteit | Accroissement de la recherche et de l’innovation de la zone transfrontalière dans les secteurs stratégiques et les secteurs à forte complémentarité 2. Grotere overdracht en verspreiding van goede praktijken in de strategische sectoren en de sectoren met een sterke complementariteit in de grensoverschrijdende zone | Accroissement du transfert et de la diffusion des bonnes pratiques innovante dans les secteurs stratégiques et à forte complémentarité de la zone transfrontalière Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 2

Alkyl glycosides and sugar esters, non ‐ ionic surfactants of interest Non ‐ ionic surfactants ≈ 50 % of the total surfactant market in Europe Growing interest for surfactants from renewable ressources: biodegradability, non toxic for humans and environment Al Alkyl kyl poly polygly glycoside ides (A (APG PG) Appyclean TM (Wheatoleo), World market: 100,000 T/year Oramix TM , Montanov TM Emulsifiers, foaming agents, wetting agents for (Seppic), … cosmetics, detergents, phytosanitary Sugar ester Sug ers CrodestaTM (Croda), World market: 10,000 T/year products from Sisterna, … Emulsifiers for cosmetics and food Chemically produced : limited degree of polymerization (DP) for the glycon part which impacts hydrophilic ‐ lipophilic balance, generation of undesirable molecules 3

Alkyl glycosides and sugar esters, non ‐ ionic surfactants of interest Wheat bran valorisation into surfactants • Wheat bran , agricultural co ‐ product from Cellulose milling industries and 1G bioethanol industries Xylans • Main use: food (fibers) and feed Enzymatic processes environmentally friendly Enzymatic processes environmentally friendly Enzymatic • • Cellulose and xylans fractionation Cellulose and xylans fractionation hydrolysis • • Functionalization of sugars from fractionation Functionalization of sugars from fractionation glucose xylose Surfactants for high added ‐ value applications Cosmetics, food… Enzymatic functionalization Fatty acid, alcohol Wheat bran residues (+ cellulases ‐ hemicellulases): feed Alkyl glycosides or sugar esters Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 4

Partners Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 5

Overview of the project Cosmetics, phytosanitaries, food ‐ feed additives, detergents 6

Enzymatic synthesis of alkyl xylosides Enzymatic transglycosylation Wheat bran yl  ‐ D ‐ xyl Ex Example: ample: sy synthesis of pen pentyl xylosi sides des No pretreatment xylanase xylanase pentan ‐ 1 ‐ ol / H 2 O 48h, 50 ° C Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 7

Enzymatic synthesis of alkyl xylosides • Synthesis efficient with wheat bran from Bi Biow owanz anze (Wanze, Belgium) and from ADM ADM (Pomacle Bazancourt, France) • Op Optim timization tion of of the the tr transgly ansglycosyla lation tion reaction action conditions: nditions: Pentyl  ‐ D ‐ xylosides : 4.9 4.9 g/ g/L • mg pentyl  ‐ D ‐ xylosides / g xylans present in wheat bran 450 450 mg  equivalent to transglycosylation performed from commercial xylans Ochs et al. Green Chem., 2011, 13, 2380 Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 8

Enzymatic synthesis of alkyl xylosides • Up ‐ sc Up scalin aling of the the re reaction in a 2 lit liter ers react eactor or  same yields of transglycosylation Reaction efficient for the synthesis of alkyl  ‐ D ‐ xylosides with C chain • chain lenghts from C3 to lengh to C10 C10 (propan ‐ 1 ‐ ol to decan ‐ 1 ‐ ol) Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 9

Properties of the pentyl xylosides Surf Surface ace ‐ activ active pr properti operties es  Capacity to decrease the surface tension (  CAC )  Aggregation behaviour: Critical aggregation concentration (CAC) (CAC,  CAC ) 10 Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019

Properties of the pentyl xylosides Surface ‐ active properties ‐ Results Pentyl  -D- CAC (mg.L -1 )  CAC (mN/m) xylosides mixture Literature (Bouxin et al. , 2010) From WB 1 3089 59 Octyl  /  ‐ D ‐ xylosides DP1 : CMC = 950 mg.L ‐ 1 From WB 2 2150 39 • Poor surface ‐ active properties – longer alkyl chain (C8 or C10) • But potential hydrotrope properties (under investigation) Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 11

Enzymatic synthesis of sugar esters 1 st step : production of glucose and xylose hydrolysates from wheat bran Wheat bran D ‐ glucose D ‐ xylose Enzymatic No pretreatment hydrolysis + H 2 O, 50 ° C No additives According to enzyme loading and reaction duration: Wheat bran from BIO BIOWANZE 50 to 100% of glucose and xylose released (Wanze, BE) and from ADM ADM (Pomacle ‐ Bazancourt, FR) Hydrolysate rich in glucose and xylose Starch and wheat bran residues Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 12

Enzymatic synthesis of sugar esters 1 st step : production of glucose and xylose hydrolysates from wheat bran Scientific and technological lock: recalcitrance properties of wheat bran Prescribed solution: Room Temperature Ionic liquid (RTIL) pretreatment prior enzymatic hydrolysis Optimization of conditions pretreatment by PLS ‐ Surface Response Design Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 13

Enzymatic synthesis of sugar esters 1 st step : production of glucose and xylose hydrolysates from wheat bran Response surface plots of sugar (A: glucose, B: xylose) release after enzymatic hydrolysis Optimal conditions of pretreatment: diluted ‐ [C2mim][OAc] in water (10 % v/v) at 150 °C for 40 min Competitive yields achieved: Y glucose = 83 % and Y xylose = 95 % Araya ‐ Farias et al . (2019). Frontiers in Chemistry. 7:585 Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 14

Enzymatic synthesis of sugar esters 2 nd step : production of sugar esters from glucose and xylose hydrolysates Example: synthesis of laurate glucose and xylose esters D ‐ glucose D ‐ xylose O O Lipase O HO + HO OH OH Methyl laurate or lauric acid 2M2B, molecular sieves Sugars conversion: 80 80 ‐ 100% 100% • • Modulation of glc glc ester ers an and xyl xyl ester ers ra ratios and and of of mo mono no ‐ and and di dies esters ratios according to D ‐ glc/D ‐ xyl ratio (hydrolysate) and reaction conditions ra • (Trans)esterification efficient with fatty acids and fatty acids esters with C chain chain leng enght from C8 to to C18 C18 Méline et al . Enz. Microbial. Technol. 2018 Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 15

Properties of the sugar esters Surface ‐ active properties  Structure ‐ activity relationships of purified molecules from (trans)esterification reactions XC8 Xylose octanoate monoester Number of alkyl chains X(C8)2 Xylose octanoate diester Ester link XC12 Xylose laurate monoester Length of alkyl chains XC14 Xylose myristate monoester XC18 Xylose stearate monoester Xylose 1 or 2 chains X2C12 Di-Xylose laurate monoester 1 → 4 8 → 18 C X3C12 Tri-Xylose laurate monoester Number of xylose residues X4C12 Tetra-Xylose laurate monoester Xylo-oligosaccharides laurate XyC12 monoesters Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 16

Properties of the sugar esters Surface ‐ active properties  Structure ‐ activity relationships of purified molecules ‐ Results Length of alkyl chains Number of alkyl chains Number of xylose residues 500 500 500 400 400 400 CAC (mg.L ‐ 1 ) CAC (mg.L ‐ 1 ) CAC (mg.L ‐ 1 ) 300 300 300 200 200 200 The best candidate: 100 100 100 0 0 0 XC12 X2C12 X3C12 X4C12 XyC12 XC8 XC12 XC14 XC18 XC8 X(C8)2 50 50 50  CAC (mN/m) 40  CAC (mN/m) 40  CAC (mN/m) 40 30 30 30 X(C8)2 20 20 20 Xylose octanoate diester 10 10 10 0 0 0 XC8 XC12 XC14 XC18 XC12 X2C12 X3C12 X4C12 XyC12 XC8 X(C8)2 Middle chain length Two alkyl chains Limited number of xylose residues Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 17

Properties of the sugar esters Surf Surface ace ‐ acti active pr properties operties  Structure ‐ activity relationships of mixtures from (trans)esterification reactions obtained from wheat bran D-glc and D-xyl lauryl esters mixture CAC (mg.L -1 )  CAC (mN/m) 44.4 24.4 Mixture with mono-esters mainly 48.3 27.5 Mixture with di-esters mainly Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 18

Properties of the sugar esters Potential as antibacterial agent  Permeabilization of bacterial plasma membrane Ghent, Bio Base Europe Pilot Plant ‐ 7.11.2019 19