1

Platform molecules and materials from biomass

residues using green chemistry

Dr Duncan Macquarrie

Green Chemistry Centre of Excellence

University of York

Khon Kaen, September 2017

Where are we?

2

York

Green Chemistry Centre of Excellence

3

• £5M purpose-built Centre

with Industrial

Engagement Facility

• Currently at: ~100 Staff

and Students

Activities

4

The Centre’s Activities can be grouped into 4 areas:

• Research

• Industry collaboration

• Education, including

development of teaching

and promotional materials

• Networking with all

chemical stakeholders

5

2. Maximise

incorporation

of materials

7. Use renewables

3. Lower

toxicity4. Design

safer chemicals

12. Accident prevention

11. Monitor and analyse

1. Waste prevention

better than clean-up

5. Don’t use auxiliaries

9. Use

catalysis

8. No

unnecessary

derivatisation

6. Minimise energy

10. Design for

degradation

12 Principles of Green Chemistry

Overview of presentation

• Platform molecules

– Re-inventing petrochemical based products

• Bio-based materials

– Utilising natural porosity and functionality

6

Oil Refining…

Crude Oil

Fuel

Chemicals

Energy

OIL

RE

FIN

ER

Y Plastics

Agro-chemicals

Pharmaceuticals

Nutraceuticals

Solvents

Clothing

Many more……

Asphalt

Current: Fossil-derived Base Chemicals

8

Cru

de o

il, n

atu

ral

ga

s,

co

al

CH4

Naphtha Ethene

Propene

Butenes

Benzene

Toluene

Xylenes

SYN

GASMethanol

FeedstockBase

Chemicals

Example Bulk

Chemicals

Example

Products

ethene oxide

formaldehydemethyl methacrylate

acetic acid

terephthalic acid

styrene

phenol

cyclohexane

aniline

toluene diisocyanate

styrene-butadiene rubber

polybutadiene rubber

polyethene

polyethene oxide

anti-freeze

ethylbenzene

1,2-dichloroethane

propene oxide

vinyl chloride polyvinyl chloride

polypropenepropan-2-ol

nylon

dyes

polyurethanes

polyetheneterephthalate

adhesives

(iso)phthalic acid

polyesters

propandiols

solvents

bisphenol A

polycarbonates

latex

paintsresins

Biorefining…

Fuel

Chemicals

Energy

BIO

RE

FIN

ER

Y Plastics

Agro-chemicals

Pharmaceuticals

Nutraceuticals

Solvents

Clothing

Many more……

Platform

molecules

Materials

Sustainable

catalysts?

Waste Biomass

Platform Molecules replace Base Chemicals

10

BIO

MA

SS

Carbohy

drates

ethanollactic acid

itaconic acid

HMF/CMF

sorbitol

methanol

FeedstockPlatform

Molecules

Key

Derivatives

Bio-based

Products

ethene

formaldehydemethyl methacrylateacetic acid

isosorbide

fumarate

cinnamic acid

levulinates

synthetic rubber

polyethene

polyalkenes

PEG/PEO

NMP

ethene oxide

acrylic acidpropene/butene

polypropene

vanillic acid

nylon

dyes

polyurethanes

adhesives

glycidol

polyesters

solvents

polyethers

polycarbonates

latex

paints

resins

Lignin

Protein

Extracts

Syngas

furfural

unsat. polyesters

vanillinguaiacoleugenol

GluAspProLys

acrylamide

α-pinene

D-limonene(fatty acids)

mannitolPHAs

(glycerol)

antioxidants

surfactants

lubricantsagrichemicals

flavour & fragrance

catalysts

Phe

pharmaceuticalsvarious phenolics

FDCA2,5-dimethylfuran

ZnO-eugenol water soluble polymers

chelators

1,5-pentanediaminemaleate

2-MTHF

terpene oxides

hydroxyacidsepichlorohydrin

Clean Synthesis and Platform Molecules

• Chemicals sustainably

derived from biomass

(bio-PMs)

• Assessment of bio-

based content (14C and

beyond)

• Utilisation of chemicals

derived from waste

• Sustainable catalysts

11

• Alternative reaction

activation (MW, US)

• Alternative solvents

(scCO2, bio-derived, no

solvent)

• Catalysis, ideally

heterogeneous

• Addition reactions rather

than condensation or

elimination

• Flow chemistry

Clean

Synthesis

Sustainable

Chemicals

Bio-Platform Molecules (bio-PMs)

12

2004 - Report by US-DOE to focus research on promising bio-PMs:

We have interest in some other promising bio-PMs:

5-chloromethyl furfural (CMF)

• Bi-phasic reaction

• A range of carbohydrates investigated

• Alternative solvents screened:

13

Green Chem., 15 (2013), 72-75

Tom Farmer

CMF as a bio-PM

14

Green Chem., 15 (2013), 72-75

CMF Lignin – A Free Catalyst

• The waste produced from converting ligno-cellulose

to CMF can be recovered and used as a porous

heterogeneous catalyst

• Texture of surface can be tuned via thermal

treatment (as for Starbons®)

CMF

Water

Immiscible

Solvent

Aq. HCl

“CMF lignin”

CatalystΔ

H2O EtOHLignocellulose

H2SO4

LA EL

ChemSusChem, 8, 2015, 24, 4172–4179

Tabitha Petchey

Platform molecules from protein waste

• Proteins exist in several food-related waste streams

• Breakdown to amino acids

• Decarboxylate:

16

Microwave-assisted / isophorone catalysed

17

15mins 200W MW

propanol solvent

65% yield

Isophorone recovered

Yann Li

Sustainable Solvent Selection Service

18

Andy Hunt, James Sherwood

Solvent property mapping

19

Aprotic solvents

Amines

Dipolar aprotics

ChlorinatedHydrocarbon

Nitro

Ethers Ester Ketones

Nitriles

Cyrene - a bio-based dipolar aprotic

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Levoglucosenone CyreneBiomassStep 1 Step 2

Green Chem., DOI: 10.1039/C7GC00112F

ChemSusChem, 9(24), 3503-3512.

2,2,5,5-Tetramethyltetrahydrofuran (TMTHF)

✓ Replacement for non-polar solvents

✓ Inherently non-peroxide forming

✓ Clean synthetic route

✓ Potentially bio-based

✓ Comparable solvent performance to toluene

A. J. Hunt et al., Green Chemistry, 2017, accepted.

• The lack of any α-protons to

the ether means that

TMTHF is non-peroxide

forming and is therefore

suitable for use a solvent in

radical polymerisations (see

right)

• The lone pair of e-s on the O

are sterically protected by

the four methyl groups so

TMTHF behaves less like

and ether and more like

toluene

Andy Hunt,

Fergal Byrne

22

Silica based chemistries

• A “simple” catalyst for a “simple” reaction

– Amide formation from acid and amine is one of the most

problematic and highest priority reactions identified by ACS

Green Chemistry Institute Pharmaceutical Round Table

– Good yields with 10wt% chromatographic silica

– Product crystallises directly.

– Catalyst completely reusable

– Catalyst not a dehydrating agent

R OH

O

R'NH

2

R NH

O

R H2O+ +

Chem. Comm., (2009), 2562-2564

700 °C

K60 silica

James Comerford, Lyndsey Ledingham, Tabitha Petchey

SBA’s – Mesoporous Silicas

23

Arkivoc, vii (2012), 282-293

• Activated structured silica (SBAs) superior to

standard K60 – further advancing our own

technology

– 5%wt activated SBA gives comparable yields to 20%wt

activated K60

SBA’s in Flow

24

Arkivoc, vii (2012), 282-293

continous flow,

toluene solvent

• Excellent applicability for catalyst in flow reaction

• Flow facilitates scale-up

• Cymene (from orange peel) also very good solvent

Structured Silica from Ash – Bio-MCMs

• Burning of biomass in power stations leaves bio-ash

• Bio-ash used to form bio-derived structured silica

• Improving the sustainability of heterogeneous catalysts

• Utilisation of waste for catalyst formation

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Green Chem., 15 (2013), 1203-1210

Emma Cooper

Jennie Dodson

Starbons – tunable mesoporous materials

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• Now being produced in multi-kg/day scale

• Registered company currently being bought

from the University

• 3 Patents and over 20 research articles

• Current customers Merck and Trio Healthcare

• Scale-up development through Porous4App

H2020 commercialisation grant

Enhanced CO2 capture by waste-derived mesoporous carbons. Angewandte Chemie, 55, 9173

Treatment of laundrette wastewater using Starbon and Fenton’s reagent. J Env Sci and Health, 51(11), 974

Revisiting the structure of mesoporous α-D-polysaccharide gels. ChemSusChem. 9(3), 280-288.

Cinthia Mena Duran, Mario De bruyn,

Xiao Wu, Vitaliy Budarin Andy Hunt, and many more

Starbon process

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Starting materials can include starch present in waste food, e.g. - Potato peelings- Waste maize (corn) starch- Waste grain or wheat starch- Pectin from orange peel- Alginate from seaweed

Processing

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RoboQbo processor

Ca. 15kg / hour

This project has received funding from the European

Union’s Horizon 2020 research and innovation program

under grant agreement No 686163

Processing

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Freeze dryer – ca. 1.5kg/day

Textural properties

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Succinic acid

Sucrose

1.1 nm

Sucrose

Methylene Blue

1.5 nm

Metal Complex

Catalyst. 2 nm

Activated carbon (Norit)

Average diameter 0.45 nm

Mesopore volume 0.25 ml/g

BET Surface area 800 m2/g

Mesopore surface

area

60 m2/g

Starbon-300

Average diameter 5.0 nm

Mesopore volume 0.65 ml/g

BET Surface area 310 m2/g

Mesopore surface

area

190 m2/g

Succinic acid

0.5 nm

0.45 nm 5.0 nm

Applications

31 31

• Recovery of precious metals from waste streams through reductive adsorption (Starbon® R Series)

• Purification, in particular removal of harmful organics and heavy metals to purify water and clean up waste streams (Starbon® P Series)

• Separation of complex mixtures for production and analysis with Starbon® as the stationary phase in chromatographic systems (Starbon® S Series)

• Catalysis of bio-refinery downstream processes including esterification reactions in aqueous systems (Starbon® C Series)

• Catalysis using adsorbed metal complexes and nanoparticles

• As a hybrid with mixed metal oxides for energy storage

Next generation Starbons ?

• Aims:

• Simpler process

• Better particle size/shape control

• Better mechanical strength

➢ Carbon Silica Composites

➢ Silica provides control of physical properties and mechanical

strength

➢ Carbon layer provides the chemical functionality

32

Tengyao Jiang

Konstantina Sotiriou

Collaboration with

Khon Kaen University

Material preparation

33

Characterisation

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0.0 0.2 0.4 0.6 0.8 1.0

silica

300

500

800

Vo

lum

e A

dso

rbe

d (

cm3/g

ST

P)

Relative Pressure (P/Po)

Fig. 6 N2 adsorption / desorption

isotherm plots of silica KS60 and CSCs.

Material BET surface area

(m2 g-1)

Pore volume

(cm3 g-1)

Pore diameter

(nm)

Carbon layer thickness

(nm)

Silica K60 467 0.80 6.7 -

CSC 300 321 0.32 4.4 1.15

CSC 500 380 0.39 4.5 1.10

CSC 800 1056 1.22 4.8 0.95

Table 1. Textural properties of silica K60 and CSCs.

Type IV Isotherms.

Nitrogen adsorption/ desorption porosimetry

Metal adsorbency

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Selectivity related to reduction of metals

Capacity of adsorbents

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0

10

20

30

40

50

60

70

80

90

100

% R

em

ova

l

Initial Concentration / mg L-1

CSC300

CSC 500

CSC 800

500 300 150 100 50

25

Lignin – a potential source or aromatics

37

Biomass processing damages lignin – can we

isolate lignin in a more accessible state?

Long Zhou

Vitaliy Budarin

Jiajun Fan

MW hydrothermal deconstruction

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Solid-state NMR 13C CP-MAS

Pyrolysis GCMS

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Summary

• Holistic approach to biomass utilisation

– Polysaccharides to platform molecules

– Polysaccharides to functional materials

– Lignin as catalyst and as raw material for aromatics

– Inorganics (silica) also utilised as matrices for catalysts and

adsorbents

40

Thanks to :

41

EPSRC, EU FP7 & H2020, Royal Society, GSK,

Pfizer, Conacyt

Towards a seaweed biorefinery

42

Hamnavoe, Shetland,

October 2011Ascophyllum Nodosum

Yuan Yuan

Biorefinery schematic

43

43

Ascophyllum Nodosum

Solid residue

Solid residue

Solid residue

Solid residue (biochar)

Pre extraction: water

then aq. ethanolPre-extraction fractions

Fucoidan extraction

Fucoidan (precipitated)

+

Supernatant

Alginate extractionAlginate precipitated

+

Supernatant

High T hydrolysis Sugars bioethanol

Microwave Chemistry

Fucoidans as antioxidants

44

0.00%

5.00%

10.00%

15.00%

20.00%

25.00%

5 min 15 min 30 min 3*3 h

DP

PH

ra

dic

al

sca

ven

gin

g

effe

ct

(%)

Extraction time

150 °C

120 °C

90 °C

Conventional

Ferricyanide (III) to ferricyanide (II)

DPPH scavenging

Yuan and Macquarrie, Carb. Polym. 2015 129 101-107

Fermentation of sugars

45

0.00

2.00

4.00

6.00

8.00

10.00

12.00

0 12 24 36 48 60 72 84

Su

ga

r co

nce

ntr

ati

on

(g

/L)

Time (h)

Gal

Glu

Man

-5.00%

5.00%

15.00%

25.00%

35.00%

45.00%

55.00%

65.00%

0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

0 20 40 60 80

Eth

an

ol

percen

t th

eo

reti

ca

l y

ield

(%

)

Con

cen

trati

on

(g

/L)

Time (h)

Ethanol

concentration

Ethanol yield

Biochar as a solid fuel

46

％ C % H % N HHVa (MJ/kg) EDb Mass yield EYc %

Raw seaweed 36.26 4.86 0.84 13.73 / / /

Biorefinery 51.05 5.29 1.87 21.23 1.55 21.44 33.23

Fucoidan extraction

only

39.91 5.50 1.68 15.42 1.12 50.04 56.04

Alginate extraction only 41.47 5.55 1.34 16.65 1.21 39.82 48.18

Hydrolysis only 54.05 5.7 1.6 22.93 1.67 33.23 55.49

HHV almost as high as direct hydrolysis residues,

but also gain alginates and fucoidans

Yuan and Macquarrie ACS Sust. Chem. Eng., (2015) 3 1359-1365