Markus Antonietti, Max Braun, Davide Esposito,

Valerio Molinari

Max Planck Institute of Colloids and Interfaces

Research Campus Golm, D-14424 Potsdam

Hydrothermal reforming of Biomass:

Using all components of wood for new materials

Aronsborg, Sweden

2018

A closer look: the „great garbage patches“

www.strangesounds.org www.io9.com www. bodhisurfschool.com

An even closer look: plastic accumulation in animals

www.wikipedia.org www.coastalcare.org

www. plastictides.wordpress.com www. plungediving.com.au

Even more closer look: endocrine disruptors

www.wikipedia.org www.greenliving.about.com www.youtube.com www. Integrative-pediatricsonline.com

Sustainable processes2020/2025 !

Bloomberg:the innovations will be driven by

philantropes/cities/companies !!

New solutions/system integrations

best based on biological resources

biomimetic approaches

New biobased monomers and polymers using

biofunctionality

Materials designed even for misuse

The chance: biobased economy the misrelation of product and waste

Biomass: is it a scalable ressource

• annual world oil production 4 km3

• annual world terrestrial biomass growth 120 km3

• 6,7 % of biomass sufficient to compensate for crude oil

• 11 % of biomass already part of farming cycles

• Side products are a natural choice for chemistry

• sugar 380 $ /t, recycled paper 100 $/t, pulpwood 28 $/t,

biomass waste: transport only..

Hydrothermal Carbonization,

a Sol-Gel Chemistry of Carbon

a technique to turn wet plant material

into monomers

into polymers

into carbonaceous materials

all in water

colloid and interface chemistry

Carbon efficiency ≈ 1

Friedrich Bergius described 1913

the elemental steps of HTC

HTC

works via dehydration of carbohydrates

-at 180 °C – 200 °C

-for 2 – 16 h´s

-C6H12O6 __ C6H6O3 + 3 H2O C6H2O + 5 H2O -quite cheap ( ca. 0.40 €/kg starch, 200 €/t

biomass)

-leads to useful nanostructures

-with useful interface chemistry

-„the dispersion polymerization of carbon“

Carbonaceous structures to be made:

(all from glucose/starch/biomass)

O

H

HO

H

HO

H

OH

OHHH

OH

- 3 H2O O

O

H

HO

Glucose C6H12O6 5-HMF C6H6O3

Diels-Alder reactions

towards Phenol-Resins

Disproportionation/Polymerization

towards polyfuranes

Aldol Polycondensation towards

polyaldehydes

„Avalanche“ model of molecular chemistry

Ion Exchange Resin for water purification

from sugar waste

O

HOH OH

H

H

OH

OH

H

O

H

O

OH

COOH

O O

OH

OH

OH

+180-200 C°

O

O

OHOH

OH

H

-3H2O

-H2O

OHOH

O

OH

OHOH

O

OH

-H2O

O

HOH OH

H

H

OH

OH

H

O

H

O

OH

COOH

O O

OH

OH

OH

+180-200 C°

O

O

OHOH

OH

H

-3H2O

-H2O

OHOH

O

OH

OHOH

O

OH

-H2O

carbonization

1µm1µm

1µm1µm

a) b)

c) d)

1µm1µm1µm1µm

1µm1µm1µm1µm

a) b)

c) d)

0 200 400 600 800 10000

50

100

150

200

250

300

350

400

Equil

ibri

um

concentr

ati

on o

n C

arb

on, qe, m

g/g

Equilibrium solution concentration, Ce, mg/L

Pure-C

1AcA-C

2AcA-C

5AcA-C

10AcA-C

15

Replication of polystyrene latex nanoparticles

SBET=367 m2/g

Vpore=0.58 ml/g

SBET=39 m2/g

Vpore=0.01 ml/g

After removal of latex:

Hydrophilic carbon capsules:

Does HTC also work with (german)

waste biomass? industrial biomass waste: sugar beets (5Mt),

rapeseed straw (20 Mt), waste water sludges

(10 Mt), orange peels (2Mt) etc.

(And can we make plastics out of it ?)

A pilot plants, in cooperation with the MaxPlanck Society

A video: 1 kg/sec…

Biochar and „Terra Preta“: C- polymers as soil conditioner

www. biochar-international.org

„classical“ reaction engineering

Bilder: Dank an Dr Heiko Pieplow

Global Soil degradation

Source: FAO

Formation of bicontinous nanosponges

On molecular and nanoscale:

no biotexture left

From Hydrothermal Carbonization

to Hydrothermal refining

„top cut“ 0.1 %

(e.g.patchoulol)

„medium cut“

30 % platform chemicals

e.g. lactic acid, xylene, green solvents

„base cut“

70 % „fertility, fuels and energy“

e.g. methane, coal, fertilizer and

humic matter

Hot water processing of biomass: a commodity..

The X-Presso-Refinery

www.amazon.com

A pilot plant movie

good for ca. 10000 t/year…

Aqueous HTR-processes

provide new platform chemicals

Lactid

Acid

Gamma-

butyrolacton

HTR = hydrothermal reforming/digestion

p-xylene

Hydrothremal digestion of sugars/cellulose to lactic acid

LEVULINIC ACID AND

METHYLENE-Γ-VALEROLACTONE

31

Di = 160 nm (DLS)

Mw = 2 * 105 g/mol

Levulinic Acid g-Valerolactone Methylene-g-Valerolactone

Methyl Methacrylate From Cellulose,

Paper and Milled

Wood

The Idea: Converting Cellulose based Biomass

or Waste into sustainable Plastics

Dr. Klaus Tauer,. Chunxiang Wie.

From: https://www.slideshare.net/SappiHouston/basics-of-wood-pulp-and-paper-november-2012

Today missing: hemicellulose

LIGNIN DEPOLYMERIZATION: A CLOSER LOOK

V. Molinari, C. Giordano, M. Antonietti, D. Esposito, J. Am. Chem. Soc. 2014, 5, 1758.

Model studies on di-aryl

compounds.

Reaction are performed using a

fixed-bed reactor.

Mono-Aromatics

aliphatic

Poly-Aromatics

Reaction on real lignin

Development of Heterogeneous catalysts

Some Use of Catecholes

Uruchiol

but also: protein glue, mussel adhesives, binds from minerals to carbohydrates, some creative polymer chemistry to do…

Japan China

Wood-Remixes

Disintegrate wood into fragments:

- Cellulose micro/nanofibrils

- Lignin

- (hemicelluloses)

Remix it with polymers, flame retarders, minerals, antifungals

Any density (not only MDF)

Type of micro/nano fiberboard, but lignin glued

Any pore structure

Perception and eco-acceptance of wood (all natural)

Easy preparation:Kitchen Materials

Controlled density: 0,1 – 1 kg/L

Easy to shape

Real

waffle

Lig

nin

w

affle

Climbing wall as qualitative test

Conventional shelf Max load: 10 Kg

Tested load: 70 Kg

Fibres are highly packed to sustain great mechanical

stress

4 µm

„Super-Wood“ ? - Fire - Water - Fungi/Termites - All in a thermoset process ?

The phloem: pressure tight tubes

Water repelling wood… with lignin !

Flame retardance ?

0 100 200 300 400 500 600

0

20

40

60

80

100

Mass/%

T (°C)

= degraded orgsolv coating

= orgsolv coating

- A chemical and a physical effect - Clay, phosphates

Biofuel-Molecules: „3rd generation“

1. Generation: food-fuel competition 2. Generation: bioethanol from non edibles: highly inefficient 3. Generation: lignobiomass, chemical, highly efficient

sugar, here fructose HMF dimethylfuran

29.3 MJ/l (EtOH: 21.3) 101 Octan

non-water miscible

Potential efficiency: 0.93 (best bioethanol: 0.4 – 0.5)

Integrated continuous flow system

Combination of 2 steps: Direct connection of solid acid column to HCUBE (flow rates similar) (Combination of both catalysts – mixed column)

Amberlyst 15

Ni@WC

110°C 30bar 0,25ml/min

150°C 30bar 0,25ml/min

1.)

2.)

Fructose in EtOH and FA

HMF in EtOH and FA

DMF in EtOH and FA

1. Amberlyst 15

2. Ni@WC

Similar microfluidic project Nature 2015

Ours: ease, bigger scale

1. Solid acid cat: Fructose in EtOH with Formic acid

6 8 10 12

-1000000

0

1000000

2000000

3000000

4000000

5000000

6000000

7000000

8000000

9000000

10000000

11000000

12000000

13000000

14000000

dirt

abundance[-

]

time[min]

Amberlyst 15

fru etoh fa 110°C 1,0ml/min

fru etoh fa 110°C 0,8ml/min

fru etoh fa 110°C 0,5ml/min

fru etoh fa 110°C 0,2ml/min

fru etoh fa 110°C 0,1ml/min

dirt

2. Integrated continuous flow system

Combination of 2 steps: Direct connection of solid acid column to HCUBE (flow rates similar) (Combination of both catalysts – mixed column)

Fructose in EtOH and FA

HMF in EtOH and FA

DMF in EtOH and FA

1. Amberlyst 15

2. Ni@WC

2 4 6 8 10 12 14

0

500000

1000000

1500000

2000000

2500000

3000000

abundance[-

]

time[min]

Direct Combination

Amberlyst 15 110 30 0,25

Ni@Wc 150 30 0,25

Amberlyst 110 30 0,25

Ni@WC 150 30 0,25

HMF derivative

2 4 6 8 10 12 14

-500000

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

abundance[-

]

time[min]

Evaporation of product stream

Amberlyst 15 + Ni@WC

in EtOh

2 4 6 8 10 12 14

0

1000000

2000000

3000000

4000000

abundance[-

]time[min]

Pure Combi product of Amberlyst 15 and Ni@WC

2 4 6 8 10 12 14

0

1000000

2000000

3000000

4000000

5000000

6000000

7000000

abundance[-

]time[min]

Evaporation product

yellow liquid left in bottom part

DMF and EtOH are evaporating easily Yellow liquid stays inside flask

80% conversion In mL Contiflow

and

44% 56%

Rotavap separation (whole process)

Selectivity very high!

110°C 30bar 0,25ml/min

150°C 30bar 0,25ml/min

0

0,01

0,02

0,03

0,04

0,05

1 2 3 4 5 6 7

con

cen

trat

ion

[M]

time[h]

DMF production over time

Ethyl levulinate production over time

7 h long term run

small drop of conversion over time:

Nickel leaching!?

Conclusion

o Hydrothermal Carbonisation: Carbon from biomass

o biocarbon as carbon sink: artificial humic matter

o heat insulation, catalyst supports, nanomaterials

o hydrothermal reforming und refining: (new) monomers and

polymers from biomass

o remixed wood: a tool to understand chemical variation

(“retrosynthesis”)

o New biofuel/biosolvent processes