Biobased “drop in” bulk chemicals;
“(Meth)Acrylic and Styrenic Monomers from Biomass”
BPM-060 ACTION
BPM Symposium, Wageningen, June 12, 2014
Jacco van Haveren, Jérôme Le Nôtre, Marinella van Leeuwen
BPM-060 ‘ACTION’
Partners:
DSM, BASF, Synbra, GreenICT, WUR-FBR, WUR-BCH
Aim:
To develop scientific and applied knowledge for the generation of
efficient synthesis routes to (meth)acrylic and styrenic monomers
 Biobased PS and PMMA
Intended application area:
Packaging materials, foams, adhesives, coatings, optical fibres
Only subproject within BPM aiming at “drop –in solutions”
Drop-in versus Unique functionality
Drop-in
Unique molecule
Market acceptance
↑↑
↓↓
Speed of introduction
↑↑
↓↓
Fit with existing infrastructure
↑↑ ↔
↔↓
Oil/Feedstock price
sensitivity
↑↑↑
↑
Sustainability
↑↔↓
↑↑↑ ↔
Unique market space
↓↓↓↓
↑↑↑↑
Scalability
↑↑↑
↑↔↓
Legislation (e.g. REACH)
↑↑↑
↑↑↑↓↓↓
Polymers
Polymers made by polycondensation chemistry:
- polyesters e.g. PET, PLA
- polyamides e.g. nylons, aramid fibres
- polyurethanes
Made by radical polymerisation, anionic, cationic
polymerisation:
- polyolefines
- poly(meth)acrylates
- polystyrene
BPM-060 ‘ACTION’
R
Challenges:
- How can we produce styrene and (meth)acrylic acid from biomass?
- What are the biobased feedstocks available?
- Which biotechnological and/or chemical steps are needed?
- Can they be applied to biobased intermediates?
- Is the entire pathway economically viable?
(use of styrene should be avoided for certain products; e.g. unsaturated polyesters
resins- BIOCRES project;- but is less harmful in other applications).
Initial Concept
Amino
Acids
R
BIOMASS
Sugars
2 platform chemicals: Phenylalanine – Itaconic acid
Initial Concept
Use a cross metathesis (ethenolysis) reaction to derive 2
biobased (bulk) chemicals at 100% atom efficiency
Amino Acids (Phe) Platform
Conversion of Protein Biomass into Styrene and Acrylates:
BIOMASS
Bio-ethanol
Waste Stream: DDGS (35%
proteins;150-200€ per ton)
DDGS
Protein Hydrolysis
Amino
Acids
Separation
Deamination
(PAL)
Deamination
(PAL)
Cinnamic acid
in mixture
Purification
Cross-metathesis
Vinasse,
Protamylasse
Styrene
Acrylic acid
Amino Acids (Phe) Platform
Deamination of Phenylalanine:
ammonia lyase
-NH3
Phenylalanine
Cinnamic acid
Phenylalanine Ammonia Lyase (PAL): enzyme naturally present in yeasts
(Rhodotorula glutinis)
Activity, reaction conditions (pH 8-9, T = 25-40 oC), inhibition parameters studied
Study of activity on complex mixtures of amino acids
Amino Acids (Phe) Platform
Enzymatic deamination
- PAL from E. coli more active than R. glutinis
 Km 2.40 mM Phe
 Vmax 0.82 µM CA/min
- no effect of high Phe concentrations on enzyme activity
- ethanol inhibits the reaction
- Product inhibition at [CA]> 5 mM
- Optimum pH: 8 – 8.5
- Optimum Temperature range: 30-37 oC (PAL stable and active for 4 days at 37 oC)
- At 30 oC, volumetric productivity = 2.5-5 kg.m3.h-1
- Cells pre-treatment (Triton X-100)
Amino Acids (Phe) Platform
Enzymatic deamination
Inhibition test reactions with individual amino acids:
influence individual AA on PAL activity
25 mM Phe
6-13 mM of each AA
150 mM Tris pH 8.5
25 µL PAL (20 mg/mL)
1 hr at 30 °C
100
rel. % PAL activity (Phe)
80
60
40
20
0
Phe
Ala Arg Asn Asp Cys Glu Gln Gly His Ile Leu Lys Met Pro Ser Thr Trp Tyr Val
 ca. 25% activity loss
with all AA except Cys
Amino Acids (Phe) Platform
Enzymatic deamination
PAL reaction on protamylasse:
Protamylasse = residual compound from the industrial production of starch from
potatoes
Sample: Avebe (fresh, 02/13)
Composition: complex mixture containing several compounds (DM: 50.3%)
Component
Concentration (g/L)
Amino acids
183.0
Organic acids
135.2
Sugars
142.3
Ash
225.7
 [Phe]= 4-6 g/L, [Cys]= 2-3 g/L
 [Cl-]= 0.5-2.0 g/L
Amino Acids (Phe) Platform
Enzymatic deamination
PAL reaction on protamylasse:
Amino
Acids
PAL
Protamylasse
Conditions: 4-7 days incubation at 30 oC with PAL (20 mg/mL WCW)
Substrate
Reaction time
(days)
mol% cinnamic
acid formed
mol%
p-OH-cinnamic
acid*
P1
4
1.9
0.4
P1
7
3.7
0.9
P2
4
1.4
0.1
P2
7
5.8
1.8
* Tyrosine as substrate
Amino Acids (Phe) Platform
Enzymatic deamination
PAL reaction on protamylasse:
 Results:
up to 5.8% cinnamic acid (and 1.8% p-OH-cinnamic acid) obtained after 7
days.
 Proof-of-principle: cinnamic acid can be produced from protamylasse
 Low PAL activity observed:
- low [Phe]: 8 mM (Km = 2.4 mM Phe)
- inhibition by other protamylasse components:
- Cysteine
- Other amino acids
- Salts (Cl-)
- Organic acids (?), sugars (?)
 Future work:
- improve pre-treatments (full oxidation of cysteine, better purification)
- modify reaction parameters (T oC, quantity of PAL, etc.)
Amino Acids (Phe) Platform
Ethenolysis applied to biomass
Conclusion: reaction results into desired products, but catalyst is only moderately
active; not an economically attractive process
Catalyst
Ethylene
DCM, 40 oC, 24 h
Hoveyda-Grubbs 2nd generation
Substrate
(M)
Pethylene
(bar)
Catalyst
(mol%)
Conversion*
(%)
Selectivity**
(%)
0.05
1
12.5
38
60
0.10
1
5.0
29
90
0.10
5
5.0
14
100
0.10
20
5.0
11
100
0.25
20
5.0
4
100
0.50
20
5.0
2
100
Reaction conditions: Reaction time = 24 h, Catalyst = 5 mol% Hoveyda-Grubbs 2nd
generation. *Conversion measured by 1H NMR. **Stilbene appears as by-product.
i) J.P.M. Sanders, J. van Haveren, E.L. Scott, D.S. van Es, J. Le Nôtre, J. Spekreijse,
Int. Pat. Appl. (2011), WO2011/002284A1.
ii) J. Spekreijse, J. Le Nôtre, J. van Haveren, E.L. Scott, J.P.M. Sanders,
Green Chem. 2012, 14, 2747.
Intermediate Conclusions
Amino Acids (Phe) Platform
• The ethenolysis of cinnamic acid (and cinnamate esters) is possible
with close to 100 % selectivity, however, at low conversions and only
with a rather expensive homogeneous catalyst.
• Enzymatic deamination (PAL) is possible in a complex mixture from
waste streams, yet with low activity.
• Alternative approach to ethenolysis desired
Sugars (Itaconic acid) Platform
BIOMASS
Itaconic acid can also be derived chemically from citric acid
Sugars
Fermentation
Esterification
Isomerisation
Cross-metathesis
Itaconic is commercially produced by fermentation
+
Methacrylates
Acrylates
Sugars (Itaconic acid) Platform
Esterification/Isomerisation of itaconic acid:
Sugars (Itaconic acid) Platform
Ethenolysis of mesaconic and citraconic acid ethyl esters:
- Lots of different catalysts and solvents used
- Temperatures: 40 – 110 oC
- Ethylene pressure: 1 – 35 bar
- Reactions performed on citraconate ester, citraconic anhydride, corresponding acids
- No conversion observed!
- Not a viable route to obtain acrylic and methacrylic acid!!
Adapted concept
Decarboxylation of cinnamic
acid
Decarboxylation of itaconic
acid
Conditions?
CO2
Reduced atom efficiency; no coupled production of chemicals needed
Amino Acids (Phe) Platform
Alternative route;
decarboxylation of cinnamic acid
Conditions?
CO2
Thermal decarboxylation:
- without catalyst, 350 oC
- with “catalyst”:
- Cu(I) salts + base, 170-240 oC
- Ag(I) salts + base, 140 oC
Amino Acids (Phe) Platform
Alternative route
5 wt% Pd/C (2.5 mol% Pd)
CO2
oC
H2O, base, 250
40 bar (no initial added pressure)
Time
70.0
60.0
50.0
40.0
Conversion
Styrene
(%)
30.0
'Mass Loss'
20.0
10.0
0.0
0 0:05
0:30
1:00
2:00
Reaction Time
 Reaction works in aqueous basic conditions, compatible with the PAL reaction mixture
Amino Acids (Phe) Platform
Alternative route
Catalyst screening
100.0
2.5
6.5
19.1
90.0
80.0
Reaction conditions:
cinnamic acid (3.0 mmol)
Pd/C (3 mol%)
0.15 M NaOH / iPrOH
stabiliser
29.8
48.6
36.8
70.0
36.3
60.0
97.9
50.0
Other pdts
Styrene
40.0
30.1
67.7
30.0
56.7
44.6
20.0
21.3
10.0
0.0
Cinnamic acid
1.0
1.1
Sugars (Itaconic acid) Platform
Decarboxylation reaction of itaconic acid described in literature:
 Only 1 example, in supercritical water:
CO2
Itaconic acid
NaOH
scH2O
300-350 oC
200-300 bar
Methacrylic acid
40-80% yield
Carlsson et al., Ind. Eng. Chem. Res. 1994, 33, 1989.
 Recent patent by Lucite Int. UK Ltd: WO2012/069812A1:
Continuous flow reactor at T = 250-350 oC and P = 200 bar
[itaconic acid] = 65 g/L
[NaOH] = 0.5 M
Reaction time < 10 min
 19-58% yield
BPM ACTION; screening catalysts in order to perform reaction
at (much) milder temperatures
Sugars (Itaconic acid) Platform
Catalyst screening:
Reaction conditions: itaconic acid (400 mg, 3.0 mmol), 0.15 M NaOH (20 mL), 250 oC
(40 bar built-up pressure), 1 h.
Sugars (Itaconic acid) Platform
Reactions with Pt/Al2O3, effect of temperature:
Reaction conditions: itaconic acid (400 mg, 3.0 mmol),
0.15 M NaOH (20 mL), 1 h.
Sugars (Itaconic acid) Platform
Reactions starting from citric acid:
Decarboxylation procedure
- CO2
BIOMASS
Sugars
Decarboxylation procedure
- H2O, - 2 CO2
Sugars (Itaconic acid) Platform
Reactions starting from citric acid:
Conditions
Conversion
citric acid
Itaconic acid
Mesaconic
acid
Citraconic
acid
Methacrylic
acid
Others
Carlsson
100
35.0
16.0
25.0
6.0
18.0
WUR
99.6
4.0
10.5
4.5
41
46.1
-
Carlsson et al., Ind. Eng. Chem. Res. 1994, 33, 1989:
NaOH, 320 oC, 200 bar, 1 min  100% conversion, 6% MAA selectivity
WUR process:
0.15 M NaOH, Pt/Al2O3 cat., 250 oC, 40 bar, 1 h  100% conversion, 41% MAA selectivity
Sugars (Itaconic acid) Platform
Cost estimation of the production of MAA from citric acid:
Data for calculation:
Metal
Platinum
Palladium
Ruthenium
Compound or process step
Pure citric acid
Impure citric acid
NaOH
Heat (150250 oC)
Purification MAA (distillation, bp=161 oC)
Price (euro/kg)
37600
19320
2340
Price (euro/metric ton)
800
600
200
50-100
50-100
 recyclable, assuming 0.001wt% loss
 ca. 50 euros/t of MAA
Overall conclusions
Overall Conclusions –
Future Plans
-
Itaconic acid (citric acid) and phenylalanine are potential platform
chemicals.
-
Styrene can be derived from phenyl alanine rich agricultural side
streams
-
Itaconic acid and citric acid can be converted very effectively into
methacrylic acid; patent application filed
-
Several industrial partners already indicated an interest in further R&D
work
Output; Public Presentations
Oral communications:
 NCCC
 BPM Symposium (2x)
Poster: “Application of metathesis to produce biobased styrene and
acrylates”
 BPM Symposium, Wageningen (2x).
 An Innovative Truth IV (Congres over duurzame ICT & Energie),
June 20, 2012, Utrecht.
 “Catalysis for Clean Energy and Sustainable Chemistry”
Conference, June 27-29 2012, Madrid (Spain).
 “20th International Symposium on Olefin Metathesis” – ISOM XX,
July 14-19 2013, Nara (Japan).
Output; Publications
Patent:
 “Bio-derived olefin synthesis.”
J.P.M. Sanders, J. van Haveren, E. Scott, D.S. van Es, J. Le Nôtre, J. Spekreijse, PCT
Int. Appl. 2011, WO 2011002284 A1 (EP 2448903).
Patent application:
 “Process for the production of methacrylic acid.”
J. Le Nôtre, E.L. Scott, J. van Haveren, EP Appl. EP13181709.0 (26/08/13).
Full papers:
 “Simultaneous production of biobased styrene and acrylates using ethenolysis.” J.
Spekreijse, J. Le Nôtre, J. van Haveren, E.L. Scott, J.P.M. Sanders, Green Chem.
2012, 14, 2747.
 “Synthesis of biobased methacrylic acid by decarboxylation of itaconic acid and citric
acid catalysed by transition metal solid catalysts.” J. Le Nôtre, S.C.M. Witte van Dijk, J.
van Haveren, E.L. Scott, J.P.M. Sanders, Chemsuschem; accepted for publication.
 “Production of biobased styrene from agro-industrial rest streams via a one-pot
enzymatic deamination and transition metal catalysed decarboxylation in water.” M.B.
van Leeuwen, J. Le Nôtre, S.C.M. Witte-van Dijk, C.G. Boeriu, E.L. Scott, J. van
Haveren, J.P.M. Sanders, manuscript in preparation.
Acknowledgements
Biobased Commodity Chemicals Group
Biobased Products Group
Dr. Jérôme le Nôtre
Ing. Marinella van Leeuwen
Prof. Dr. Johan Sanders
Dr. Ir. Carmen Boeriu
Dr. Elinor L. Scott
Susan Witte
Questions?