Integrated approaches in dealing with dilute heterogeneous biomass sources for the production of chemicals

Transcription

1 Integrated approaches in dealing with dilute heterogeneous biomass sources for the production of chemicals Elinor L. Scott, Jurjen Spekreijse Biobased Chemistry and Technology, Wageningen University, The Netherlands , Frontiers in Biorefinery

2 The problem 2

3 Dealing with the problem Simplify and precipitate Use of microorganisms and enzymes to produce well defined molecules/polymers that precipitate Poly(hydroxyalkanoates) Cyanophycin 3

4 Dealing with the problem Simplify and precipitate Use of microorganisms and enzymes to produce well defined molecules/polymers that precipitate Poly(hydroxyalkanoates) Cyanophycin 4

5 Waste water and volatile fatty acids (VFAs) Waste water from the agro-food and paper industries contains volatile fatty acids VFAs are small organic acids (<6 carbon atoms) 400M ton/year paper produced globally Up to 8M ton VFAs Challenges for use Dilute ~0.5 g/l VFA in water Complex mixture 5

6 PHB (Polyhydroxybutyrate) Plasticicumulans acidivorans utilise VFAs to produce PHB Waste water is cleaned and PHB is produced Depending on composition other hydroxyalkanoates may be included. Over 80% of dry weight in PHB L. Marang et al. Bioresour. Technol., 142, 232,

7 Challenges for PHB as material Brittle Degradation temperature close to melting point Polymer processing not trivial Not constant quality Fluctuating feedstock Fluctuating properties 7

8 Advantages PHB as intermediate Insoluble in water Concentrating C from dilute media More defined Instead of mixture of VFAs 8

9 Aim and approach Show that PHB can be used as an intermediate to industrial chemicals Analyse the mechanism behind the conversion of PHB Optimise the conversion of PHB 9

10 Conversion to methyl crotonate Selectivity (%) MC CA M3HB Time (h) Full conversion of PHB 600 mg PHB, 10 ml MeOH, T = 200 o C, p = 8 bar Conversion and selectivity determined by HPLC 10

11 Conversion to methyl crotonate Oligomers Monomers Gases MALDI-TOF: no oligomers detected GC-MS: gases detected (ethylene and propylene) Ethylene, propylene, CO 2 11

12 Conversion to methyl crotonate CA M3HB Selectivity (%) MC CA Selectivity (%) MC M3HB T ( o C) T ( o C) 600 mg starting material, 10 ml MeOH, 6h, p = 8 bar Quantified by HPLC. 12

13 Conversion to methyl crotonate Selectivity (%) MC CA Selectivity (%) MC CA M3HB Temperature ( o C) Pressure (bar) 600 mg PHB, 10 ml MeOH, t = 6 h, left: p = 8 bar, right: T = 200 o C Conversion determined by HPLC. 13

14 Use of intracellular polyhydroxyalkonates (PHA) Comparison of the use of intracellular PHA versus extracellular intracellular materials reduces cost of methyl crotonate >50%* intracellular materials reduces carbon footprint of methyl crotonate >50%*...but does it still react? *: 3.02 /kg to 1.31 /kg and 6.83 kg CO 2 -eq/kg to 3.25 kg CO 2 -eq/kg C. Fernández-Dacosta et al Journal of Cleaner Production, Vol 137, ,

15 Use of intracellular polyhydroxyalkonates (PHA) Sample 3-hydroxyvalerate/ PHA (mol%) PHA/total suspended solids (mass%) MC (mol%) M3HB (mol%) 1 Biomass A CA (mol%) 2 Biomass B Biomass C Biomass D Pure PHB 2 n.a Pure PHBV 20 n.a Reaction of intracellular versus extracellular - similar yields! Reaction conditions: Equivalent of 600 mg PHB, P= 18 bar, t = 6h, T = 200 C, 10 ml methanol.* Average of duplicate experiments. *: influence of <20% water and salts, valerate content and salts have small influences 15

16 Conclusions step 1 Reaction occurs via thermolysis followed by esterification Optimisation 6 hours 200 o C 18 bar 60% MC and 10% CA Use of intracellular material Ca. 50% MC and 5% CA 16

17 Aim and approach 17

18 Ethenolysis Hoveyda Grubbs 2 nd generation 18

19 Ethenolysis v Self Metathesis 19

20 Ethenolysis v Self Metathesis High pressures of ethylene commonly used to prevent self-metathesis.* * S. C. Marinescu et al. JACS, 131, 10840,

21 Ethenolysis Methyl crotonate is not reactive towards self-metathesis 21

22 Ethenolysis Conversion (%) Pressure (ethylene, bar) 0.5M methyl crotonate, 5 mol% HG-2 as catalyst, DCM, 40 o C, 24 h. Conversion measured by Crotonate/acrylate ratio by 1 H-NMR 99+% selective 22

23 Ethenolysis J. Scholz et al. Adv. Synth. Catal., 353, 2701,

24 Conclusion PHB to chemicals PHB can be used as an intermediate to obtain biobased monomers from waste water Intracellular PHA can also be used Reduction in costs Reduction in carbon footprint Conversion: 100% Selectivity: 60% (extracellular) ca. 50% (intracellular) Conversion: 50% Selectivity: 100% 24

25 Acknowledgement STW users committee Dr. ir. R. Kleerebezem, TU Delft Dr. ir. M.C. Cuéllar Soares, TU Delft Dr. ir. C.A. Ramirez, University Utrecht PTG Eindhoven NNZ bv AVEBE UA Corbion Purac DSM Innovation Center Attero Bioclear BV Biobased Chemistry and Technology, Wageningen University 25

26 Conclusion PHB to chemicals PHB can be used as an intermediate to obtain biobased monomers from waste water Intracellular PHA can also be used Reduction in costs Reduction in carbon footprint Conversion: 100% Selectivity: 60% (extracellular) ca. 50% (intracellular) Conversion: 50% Selectivity: 100% 26

27 Conversion of PHB in methanol with varying amounts of methanol. P=39 bar Reaction conditions: 0.6 g PHB per 10 ml MeOH, t = 6 hours, pressure build-up of up to 39 bar, for 10 and 20 ml nitrogen gas was added to reach 39 bar. Average of duplicate experiments. a) p = 7 bar. 27

28 28

29 Conversion to methyl crotonate MC Loss (%) T ( o C) 600 mg MC, 10 ml MeOH, 6h, p = 8 bar Quantified by HPLC. 29

30 Thermolysis mechanism N. Grassie et al. Polym. Degrad. Stab., 6, 127,

31 Pressure optimisation Selectivity (%) MC CA M3HB Pressure (bar) 600 mg PHB, 10 ml MeOH, t = 6 h, left: p = 8 bar, right: T = 200 o C Conversion determined by HPLC. 31

32 Pressure optimisation Selectivity (%) MC CA M3HB Pressure (bar) 600 mg PHB, 10 ml MeOH, t = 6 h, left: p = 8 bar, right: T = 200 o C Conversion determined by HPLC. 32

33 Pressure optimisation Selectivity (%) MC CA M3HB Pressure (bar) 600 mg PHB, 10 ml MeOH, t = 6 h, left: p = 8 bar, right: T = 200 o C Conversion determined by HPLC. 33

34 Dealing with the problem Simplify and precipitate Use of microorganisms and enzymes to produce well defined molecules/polymers that precipitate Poly(hydroxyalkanoates) Cyanophycin 34

35 Cyanophycin Polymer: aspartic acid backbone and arginine side chains Mainly in cyanobacteria as nitrogen and energy reserve Granule: 35% (wt/wt) Steinle et al Agentschap.NL, WUR (NL), University of Munster (D), AVEBE (NL), Cosun (NL), ECN (NL) 35

36 Konst et al 36