workshop | beccu

Workshop10.2.2021 @ Zoom

11/02/2021 VTT – beyond the obvious


Workshop agenda13:00 Introduction of the event Jonne Hirvonen / VTT

Session 1: BECCU overview and cost outlook Janne Kärki / VTT

Company reflection Rasmus Pinomaa / The Chemical Industry Federation of Finland

CO2 capture and supply Onni Linjala / VTT

Company reflection Jouko Putkonen / Kleener Power Solutions

Hydrogen supply for BECCU concepts Mikko Lappalainen / VTT

Conversion of CO2 to light olefins Aki Braunschweiler / VTT

Company reflection Antti Pohjoranta / Neste

Polyols and end-products Juha Lehtonen / VTT

Company reflection Soilikki Kotanen / Kiilto

Mid-break

14:30 Market view on CO2 based polymers Pauline Ruiz / Nova

Session 2: Group discussion / Q+A – intro Jonne Hirvonen / VTT

Theme I: End-products Chair: Juha Lehtonen / VTT

Theme II: Processing technologies Chair: Matti Reinikainen / VTT

Theme III: Bio-CO2 capture and hydrogen supply Chair: Timo Leino / VTT

Discussion conclusions Theme chairs / VTT

Event wrap-up Juha Lehtonen / VTT

15:30 Workshop ends


Guidelines for the workshop

Session 1: Presentations and reflections

Please ask questions only in the chat box during Session 1

and/or write them down for discussions in the Session 2

Session 2: Theme group discussions

Free discussion facilitated by theme group leaders

You will be divided into three rooms (if other topic is more favourable, please ask group

hosts to change the room through the chat box)

Joint wrap-up after the discussions in the main session

General: Please keep yourselves muted unless discussing, if possible say your name

and organization. Presentation material will be available: www.beccu.fi/workshop/

Have a nice workshop!

Session 1

will be recorded

http://www.beccu.fi/workshop/


BECCU overview and cost outlook Janne Kärki, VTT

Partner reflection byRasmus Pinomaa

The Chemical Industry Federation of Finland

Session 1:

Performance chemicals and transportation fuels from bio-CO2 and hydrogen

Container scale, easy to transport, easy to connect to

gas streams

H2 SOURCES

CHEMICALS

FUELS

SYNTHESIS

TECHNOLOGIES

CO2 SOURCES

Capturing CO2 and producing new

CO2-based materials with clean hydrogen

will replace fossil resources sustainably!

11/02/2021 VTT – beyond the obvious 7

Parallel Business Finland company projects:

Other funding partner companies benefiting from the project:

VTT’s budget: 2.035 MEUR (co-innovation in total 4.835 MEUR)

Schedule: Jan/2020 – Dec/2021

International co-operation:

Main finance from Business Finland as part of Green Electrification-ecosystem

The BECCU consortium

https://www.globalco2initiative.org/

https://clicinnovation.fi/ecosystems/greene2/

Main objectives of the BECCU project

Perform proof-of-concept for the integrated production of

power & heat, transportation fuels and specialty chemicals based on

utilization of CO2 from bio-based operations and hydrogen from water

electrolysis or industrial processes.

Increase technical readiness levels (TRL) of the studied unit

processes and develop the profitability of the concepts.

Compare selected CO2 utilization concepts (e.g. SNG, methanol) in

contrast to CO2 - based polyol products.

Create new business opportunities throughout the value chain.


Integrated production concepts are needed to enable higher profitability

Versatile polyurethanes in the spotlight

Polyurethane can be used in various long

lifetime applications such as insulation materials Figure: Finnfoam

Polyurethanes are widely used in adhesives

for such applications as woodworking glues Figure: Kiilto

Target chemical products in BECCU project are polyols, including polycarbonate

and polyether polyols, being important raw materials for polyurethanes.

Polyurethanes are used as either flexible or rigid foams (to be used in insulation

materials, footwear, automotive parts etc.) and as adhesives (for such

applications as woodworking glues and in abrasive papers).

Route for chemicals and polymers• The process is based on the production of olefins through reverse water-gas shift

(rWGS) and Fischer-Tropsch (FT) reaction steps.

• The olefins are further converted to epoxides through oxidation reactions by peroxides

and epoxides are polymerized together with CO2 to obtain polyols.

• The yield of C2-C4 olefins is maximized to be used in polyol production and higher

hydrocarbons are utilized as energy carriers (waxes or fuels).

11.2.2021 VTT – beyond the obvious 11

On economy of CCU pathways

“It is therefore only a

matter of time, before

CCU technologies become

cheaper than today’s

petrochemicals.”


Authors: Michael Carus, Pia Skoczinski, Lara Dammer, Christopher vom Berg, Achim Raschka

and Elke Breitmayer nova-Institute, Hürth(Germany)

Source for figure: https://www.nature.com/articles/s41586-019-1681-6.pdf

*Negative costs mean that the process is profitable under present day assumptions

https://eur03.safelinks.protection.outlook.com/?url=https%3A%2F%2Fwww.nature.com%2Farticles%2Fs41586-019-1681-6.pdf&data=02%7C01%7CJanne.Karki%40vtt.fi%7C854dc121b78b452f928808d799024df3%7C68d6b592500843b59b0423bec4e86cf7%7C0%7C0%7C637146107483469950&sdata=SFys6YDOerP17oDh3hiSyH9pFc5lucIELoT6KlQEPUk%3D&reserved=0

Key parameters in techno-economic calculations for BECCU-polyols production


Inputs Price Outputs Price Other parameters

Electricity (total) 45 €/MWh Polycarbonate polyols calculated Electrolyser electricity input 100 MWe

Hydrogen

peroxide 550 €/t Cyclic carbonates 900 €/t Annual CO2 use 100 kt

CO2 supply 50 €/t By-product heat 20 €/MWhAnnual polyol polycarbonate

production 38 kt

Oxygen 40 €/t Annual plant operation time 8000 h

Total investment cost estimate (20 years and 8% WACC for annuity)

124 M€

Production cost estimate for BECCU-polyols

According to market

information the product price

could be 2500 - 3000 €/t

=> profitable BECCU-

production could be possible

=> payback time (without

taxes and interest) roughly

4 years with 2500 €/t

market price

Note! The estimates are based on assumptions

of several low-TRL technologies that need still

further experimental verification.

Production cost estimate is heavily dependent on the electricity price



Target after the project: Demonstration of olefin production using VTT’s

mobile synthesis unit in an industrial site

More info: beccu.fi

ContactJuha Lehtonen: [email protected] Kärki: [email protected]

VTT Technical Research Centre of Finland Ltd


VTT is one of the largest internationally

networked R&D centres for applied research in

Northern Europe, developing high technology for

sustainable development and creation of new

business opportunities.

CHEMISTRYFROM THE AIR

2

We lower our footprint fromthe operational activities

We grow our handprint, by lowering the global footprint with chemical industry

products and solutions

2

Finland can punch way above its weight!Target small footprint and large handprint. The chemical industry can mitigate climate change globally.

Circular economy

Mineral economy

Fossil economy

Feedstock 2.0In

org

anic

feedst

ock

Org

anic

feedst

ock

Hydrogeneconomy

Bioeconomy

Recyclingeconomy

Resource efficiency

Handprint evolution requires a feedstock revolutionWe lower the global footprint with chemical industry products and solutions.

Fossil / Mineral

Biogenic

Circular

Synthetic

83 %

9 %

8 %

48 %

26 %

24 %

9 %

41 %42 %

2 %8 %

2015 2050

18 Mt

14 Mt

2015 2050

6 Mt

14 Mt

2015

2050

-8 Mt

14 MtCO

2ekv/y

time

4

2 Mt CO2

8 Mt CO2

Future feedstocks in the chemical industry

Energ

y r

eco

very

Circular Recyclates

Oil & minerals

Biomass

H2+ CO

2

Fossil/mineral

Biogenic

Synthetic

PRO

DU

CT M

AN

UFACTU

RIN

G

USE P

HASE

Dis

solv

es

during

the u

sephase

EN

D-O

F-L

IFE

Mechanical and chemical recycling

Sidestreams Reuse

CO2

CO2emissions

CCU

Photo

synth

esi

s

Recy

clin

g

FEED

STO

CK

Atmosphere

CCS

[email protected]

+358 40 586 3705

@RasmusPinomaa

#hiilineutraalikemia

Rasmus Pinomaa

Project Manager

Climate neutral chemistry

For more information contact:


CO2 capture and supplyOnni Linjala, VTT

Partner reflection byJouko Putkonen

Kleener Power Solutions


CO2 CAPTURE AND SUPPLY:

Results from literature review &

pilot-scale carbon capture tests

10.2.2021 – BECCU Mid-Term Workshop

Onni Linjala

CO2 capture in BECCU


CO2 vol-% (in dry gas)

0 % 10 % 20 % 30 % 40 % 50 % 60 % 70 % 80 % 90 % 100 %

BIOMASS COMBUSTION

OXYGEN ENRICHED COMBUSTION

OXYCOMBUSTION

SYNGAS VIA GASIFICATION

ETHANOL FERMENTATION

RAW BIOGAS

In BECCU the scope of CO2 capture has focused on:

• post-combustion capture from biogenic flue gases (e.g. combustion processes)

• raw biogas purification

• Biogenic CO2 emissions are targeted for climate benefit

• Multiple sources of biogenic CO2 are available in energy production and industrial sector


Technology Energy requirement per

captured CO2 tonne

Capture cost per CO2 tonne

Solid fuel Gaseous fuel

Liquid absorbents MEA 3.3–3.7 GJ 1 44 € 2 64 € 2

PZ+AMP 2.5 2; 3.2 GJ 3 34 € 2 56 € 2

KS-1 2.6 GJ 4 $59 5 -

KS-21 2.6 GJ 6 $55 5 -

CANSOLV 2.3 7 - -

Multi-phase

absorbents

Aq. NH3 2.5 GJ 8 $53 8 -

CAP 2.2 GJ 9 - -

UNO MK 3 2.0–2.5 GJ 10 $45 11 -

Hot-CAP 1.8 GJ 12 - -

DMX <2.5 GJ 13 39 € 2 -

Water-lean

solvents

eCO2Sol 2.3 GJ 14 $47 15 -

2.0 GJ (exp.) 14

Solid adsorbents PSA >2.3 GJ 2 $40 16 -

VSA 1.7 GJ 17 - -

VeloxoTherm 1.5 GJ 18 41 € 2 -

Membranes MTR Polaris 1.0 GJ 19 47 € 2 80 € 2

$30 (exp.) 20

Hybrid systems Membrane-sorbent - $36 2 -

Electrochemical

separation

NGCC-MCFC

hybrid-cycle

- - 34 € 21

Oxyfuel processes Allam cycle - - 34 € 2

Ref: 1) GCCSI in Svendsen 2014; 2) IEAGHG 2019a; 3) Rabensteiner et al. 2016; 4) Yagi et al. in IEAGHG 2019a; 5) Carroll 2017;

6) Tanaka et al. 2018; 7) Singh & Stéphenne 2014; 8) Li et al. 2016; 9) Augustsson et al. 2017; 10) Smith et al. 2014; 11) UNO 2014;

12) Lu et al. 2014; 13) Broutin et al. 2017; 14) Zhou et al. 2018; 15) Lail 2016; 16) Ritter et al. 2015; 17) Krishnamurthy et al. 2014;

18) CCJ 2011; 19) Baker et al. 2018; 20) Merkel 2018; 21) IEAGHG 2019b

Literature review on CO2 capture

KEY TAKES

• Numerous different technologies are being developed

• Many large-scale demonstration projects are currently taking place

or planned for near-future

• The most mature post-combustion capture technologies reach

capture costs at around 34 – 80 €/tCO2

• Approaching capture cost of 30 €/tCO2

CONTENT

• Biogenic CO2 sources

• Overview on CO2 capture, treatment, transportation and utilization

• State-of-the-art and emerging post-combustion CO2 capture

technologies

Pilot-scale carbon capture tests


Technology Enhanced water scrubbing Enhanced soda scrubbing Kleener-liquid

Capture method Physical absorption Chemical absorption Chemical absorption

Capture solvent Water Aquaeuos sodium carbonate (Na2CO3) A novel ash-based capture solution

Equipment Bubble-type absorption column VTT’s novel ejector technology VTT’s ejector technology used in the pilot tests

Advantages

• No chemicals or additives used

• Low-cost capture solvent (regular water)

• No solvent-based emissions

• Fully-electric → good control and adjustability

• Good CO2 absorption capacity

• Low-cost absorbent (soda)


• Can utilize waste heat in solvent regeneration

• Good CO2 absorption capacity

• Supporting circular economy via ash utilization


• Can utilize waste heat in solvent regeneration

VTT’s pilot-scale ejector equipmentVTT’s container (left) and CarbonReUse’s container (right)

Pilot-scale carbon capture tests


Week CO2 source Tested technologies Test objectives

#36 Synthetic gas mixturesVTT Soda

CarbonReUse

- Verifying proper function of test equipment

- Testing capture performance with modifiable gas compositions

#37 Pine chips (flue gas)

VTT Soda

CarbonReUse

Kleener-liquid

- Post-combustion capture in realistic flue gas conditions

- Comparing performance of the technologies

#38 Washed straw (flue gas)VTT Soda

CarbonReUse


- Comparing performance of the technologies

- Effect of another biomass type on capture performance

#40Spruce bark (flue gas)

Raw biogasVTT Soda


- Effect of a third biomass type on capture performance

- Performance of VTT’s soda process in biogas purification

Pine chips

Washed straw pellets

Spruce bark

Raw biogas from Metener

Results from the pilot-tests


CarbonReUse Kleener VTT Soda

Synthetic gas 15 vol-% CO2 95.1 - 96.7

Synthetic gas 30 vol-% CO2 98.3 - -

Pine chips (flue gas) 97.1 94.2 95.9

Washed straw (flue gas) 96.0 - 96.6

Spruce bark (flue gas) - - 96.5

Raw biogas - - 93.6

CarbonReUse Kleener VTT Soda

Synthetic gas 15 vol-% CO2 74 - 83–86

Synthetic gas 30 vol-% CO2 86 - -

Pine chips (flue gas) 72–76 69–71 74–79

Washed straw (flue gas) 64–70 - 78–83

Spruce bark (flue gas) - - 88-90

Raw biogas - - 97–98

Mean purity of the captured CO2 [vol-% in dry gas]

Capture rate [%] (calculated via mass balances)

Conclusions:

• All tested technologies were proven functional in post-combustion carbon capture at realistic conditions.

• Technical performance of the tested technologies are promising and in align with other carbon capture technologies at development-scale.

Company Presentation

Ash Handling & CO2 Recovery

Ash handling

Power plant Kleener-Nutri

Process water

Bottom ash Kleener-Terra

Fly ash

Kleener-Envi

CIRCULAR

ECONOMY

Water

CO2 recovery

Flue gasesCO2

Ecosystem of the circular economy

Shipping

Biomass Power Plants

Equipment manufacturing

Metal processing industry

Construction industry

Cement industry

Fertilizer industry

Logistics

Fuel processing

Synfuels and chemical industry raw material

Coal Power Plants

Cement industry

Biomass Power Plants

NG Power Plants

Biomass Power Plant ASH HANDLING

The ash from the biomass power plant is processed by a method patented by Kleener so that metals and heavy metals are separated from other available recycled products such as silicates and dry substances. Thus, the reuse of recycled products is not restricted because the products no longer contain substances that restrict their use. Furthermore, nutrients for plants can be separated in the process to be used either as a fertilizer raw material or CO2 recovery solvent.

BIOMASS POWER PLANTFLY & BOTTOM ASH

ASH HANDLING

Metal processing industry


Cement industry

KLEENER LIQUID

CO2 RECOVERYCO2 recovery process uses Kleener liquid produced in the ash handling process. Using a formula from nature, Kleener liquid mixed with water offers 150 times better CO2 absorption than water alone. Combined with Kleener technology it makes a system for CO2 recovery from flue gases much cheaper than any other known technologies.


CCS = Carbon Capture and SequestrationCCU= Carbon Capture and Use

RECOVERED CO2

KLEENER LIQUID

Full Scale Ash Handling Station in KajaaniStart-up Q4/2021

Container CO2 Recovery Equipment

CO2 Recovery Testing Unit, VTTTests in June & September 2020

• Kleener-Envi combined with

VTT’s ejector technology

• License agreement to be signed

Outstanding CO2 Recovery

Performance

0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%

C O 2 C A P T U R E C O S T

E N E R G Y C O N S U M P T I O N

C A P E X

E Q U I P M E N T S I Z E

AMINE KLEENER

By all measures, the system utilizing advanced Kleener absorption technology, regeneration technology, and Kleener liquid simplifies the process leading to lower equipment and operating costs compared to the most used amine-based solutions.

29 € / t CO2

60 € / t CO2

2,6 GJ / t CO2

4,6 GJ / t CO2

Kleener system performance values calculated to be comparable with results of: “The CO2stCap Project” : Sintef et al.

Jouko Putkonen

Tel. +358 400 624856

[email protected]

www.kleener.fi

mailto:[email protected]


http://www.kleener.fi/


Hydrogen supply for BECCU conceptsMikko Lappalainen, VTT

WP1.4 Hydrogensupply for BECCU concepts



State-of-the-art and future view


IRENA 2020 Hydrogen Europe 2020

New publications

2021 Green Hydrogen kick-off

https://irena.org/-/media/Files/IRENA/Agency/Publication/2020/Dec/IRENA_Green_hydrogen_cost_2020.pdf

https://hydrogeneurope.eu/index.php/node/1691


State-of-the-art and future electrolyser KPIs

Alkaline PEM SOEC

SOTA 2050 SOTA 2050 SOTA 2050

System electrical

efficiency

(kWh/kg H2)

50 – 78 < 45 50 – 83 < 45 45 – 50 < 40

Stack lifetime (h) 60 000 100 000 50 000 – 80 000 100 000 – 120 000 < 20 000 80 000

Operating

temperature (°C)70 – 90 > 90 50 – 80 80 700 – 850 < 600

CAPEX system

(USD/kWe)500 – 1000 < 200 700 – 1400 < 200 > 2000 < 300

Wide range in system CAPEX is due to cost dependency on the scale and scope of delivery

IRENA 2020

https://irena.org/-/media/Files/IRENA/Agency/Publication/2020/Dec/IRENA_Green_hydrogen_cost_2020.pdf


Electrolyser production cost reduction

through:• Manufacturing volume

• Increased automation

• Stack design and assembly

• Balance of Plant cost reductions

ITM began with 350 MW production line

which will be increased to 700 MW and

1 GW. Second factory could be 2 GW

Nel will install first 500 MW production line

and capacity will be added as needed

aiming to 2 GW

Electrolyser production cost

ITM

Nel

“Today 900 €/kW at 10 MW systems and

in next three years 570 €/kW at 100 MW”

ITM Power

“…green hydrogen with levelised cost of

1.5 $/kg by 2025 based on large scale

facility”

https://www.rechargenews.com/transition/green-hydrogen-itm-power-s-new-gigafactory-will-cut-costs-of-electrolysers-by-almost-40-/2-1-948190

https://www.rechargenews.com/transition/nel-to-slash-cost-of-electrolysers-by-75-with-green-hydrogen-at-same-price-as-fossil-h2-by-2025/2-1-949219


Hydrogen cost comparison for BECCU

Low cost renewable

electricity is needed

Electrolyser features• Efficiency

• CAPEX (capacity)

• Full load hours

By-product values• Oxygen

• Heat

CO2 emission allowance


Current view on hydrogen projects

Cumulative planned PtH projects 2020 – 2040

Hydrogen Europe 2020

European Hydrogen strategy• 2024: 6 GW

• 2030: 40 GW

Current demand for grey hydrogen -

mainly for oil refining and ammonia

fertilizer - is equivalent to 140 GW

of electrolysis in Europe alone

Renewable energy availability for

electrolysers

https://hydrogeneurope.eu/index.php/node/1691


Hydrogen strategiesPublished strategies

Strategies in development

2020 (40 GW)

… and more to come

2020 (25 GW)

2020 (5 GW)

2018 (6.5 GW)

2020 (3 – 4 GW)

2020 (2 – 2.5 GW)

2020 (4 GW)

2019

2020

2019

2020

Publish year (electrolyser capacity target by 2030)


By-product hydrogen utilisation


By-product hydrogen is attractive due to

relatively high purity and surplus capacity

Current utilisation:• A fuel in boiler for steam and heat production

• HCl production

• Merchant (sold to other users)

• Vented into air

By-product H2 for BECCU concepts

Company Plant Hydrogen output

Annual

hydrogen

production

Annual hydrogen

surplus

(estimate)

Hydrogen

production

process

Use of hydrogen

t/h MWH2 t/a t/a

Kemira

Chemicals

Äetsä

NaClO30.81 27 6 000 1 500

Chlorate

electrolysis

Fuel in CHP boiler,

Feedstock in fine

chemical

production

Joutseno

NaClO3

NaOH

1.49 508500

2 0002 200

Chlorate +

chlor-alkali

electrolysis

Fuel in CHP boiler,

HCl production,

Sold to Woikoski


Fischer-Tropsch (FT) synthesis and

reverse-water-gas-shift reaction based

on catalytic partial oxidiation of H2/CO2

feed (CPOX/rWGS)

In-situ biogas upgrading to biomethane

BECCU concepts for by-product H2

utilisation

11/02/2021

Mikko Lappalainen

[email protected]

@VTTFinland www.vtt.fi

https://www.beccu.fi/


Conversion of CO2 to light olefinsAki Braunschweiler, VTT

Partner reflection byAntti Pohjoranta, Neste

Conversion of CO2 to light olefins


Aki Braunschweiler

Two step process from CO2 to lightolefins

CO2 + H2

IRON

CATALYZED

FT

(ALPHA-)

OLEFINS

RHODIUM

CATALYZED

RWGS

• Step 1: Reverse Water Gas Shift (RWGS)

CO2 + H2 Synthesis gas (CO + H2) and water

• Step 2: Fischer Tropsch synthesis (FT)

CO + 2H2 Hydrocarbons

• FT process conditions determine the quality of the hydrocarbons

• Light olefins = alkenes with two to five carbon atoms


https://pixabay.com/fi/photos/auringonlasku-jalostamon-teollisuus-2165885/

Fischer Tropsch invented in 1925,

first commercalized in 1936

First coal to liquid, later gas to liquid

Current big industrial operators

Sasol, Shell, Qatar Petroleum

No industrial plants utilizing

biomass or CO2

RWGS not as commerzialied

Industrial operators


Research at VTT

Research in the BECCU project

• Laboratory

experiments

• Process

optimization

• Deep learning

model

Results and upcoming experiments

RWGS tested and functioning well

Suitable FT catalyst not yet found

Gas circulation system to be

implemented

Part of the product gas recycled

back to RWGS

Bio-CO2 feed to be tested

Modeling

Objectives for 2021

• Full implementation of the laboratory

equipment

• Maximizing the selectivity to light

olefins

• Modeling the system with AI Deep

Learning model or with a kinetic

model


https://pixabay.com/fi/photos/arrow-kohde-napakymppi-tavoite-2886223/

Aki Braunschweiler

[email protected]

+358 40167 9457

@VTTFinland www.vtt.fi

BECCU commentary

Antti Pohjoranta, Technology manager, Neste renewable hydrogen & power-to-x, 2020-02-10, BECCU mid-term workshop

64

65

Reduced

CO2 emission

Waste heat

to use

Low-GHG

products

Introducing

green

hydrogen

Green hydrogen &

H2 tradings

CO2 to permanent

storage (CCS)

CO2 utilization

(CCU)

Carbon

capture

H2

Renewable

hydrogen units

Carbon capture and

storage/utilization (CCU/S)

Power-to-Liquid (PtL)

new circular hydrocarbons

e-crude

Renewable

electricity

Carbon capture and utilization with renewable hydrogen are key elements in refinery transformation towards circularity

Thank you

66

[email protected]


Polyols and end-productsJuha Lehtonen, VTT

Partner reflection bySoilikki Kotanen, Kiilto

Polyols and End-products

Juha Lehtonen, Adina Anghelescu-Hakala, Sari Rautiainen, Riitta Mahlberg, Pauliina Pitkänen


Route for chemicals and polymers• The process is based on the production of olefins through reverse water-gas shift

(rWGS) and Fischer-Tropsch (FT) reaction steps

• The olefins are further converted to epoxides through oxidation reactions by peroxides

and epoxides are polymerized together with CO2 to obtain polyols

• The yield of C2-C4 olefins is maximized to be used in polyol production and higher

hydrocarbons are utilized as energy carriers (waxes or fuels)


Polyols from mixed C2-C4 olefins

11/02/2021 70

Mixed olefins Mixed epoxidesPolyols from mixed

epoxides


Epoxidation

• Epoxidation of mixed C2-C4 alkenes and fatty acids

• The reactions will be performed in gas-liquid system applying

different solvents

• Co-operation with ÅA via two MSc theses (prof. Tapio Salmi)

Polyol synthesis

• Polyols will be synthesized applying mixtures of Ethylene oxide

(EO), propylene oxide (PO), butane oxide (BO)

• Experiment for the synthesis of polyether polyols will be

performed in parallel with polycarbonate polyol synthesis

• Epoxidized fatty acids will be studied as co-feed for polyol

syntheses

Epoxidation and polyol synthesis R&D


Polyurethanes

• Mixed C2-C4 polycarbonate and polyether polyols will be

tested for different rigid and flexible foam and other

polyurethane formulations together with company partners

• Application testing of polyurethanes will be performed for

selected applications

Non-isocyanate polyurethanes (NIPUs)

• Cyclic polycarbonates obtained as by-product from

polycarbonate polyol synthesis will be separated and applied

to produce non-isocyanate polyurethanes

• Targeted polyurethane formulations and applications will be

planned together with company partners

…to polyurethanes and NIPUs


Epoxidation studies • Experimental work at VTT ongoing

• ÅA 1st Master’s thesis being finalised

• ÅA 2nd thesis started in Jan

Heterogeneous catalyst preparation at VTT

Patenting ongoing on mixture epoxidation

Epoxidation status


Polyols

Polyol synthesis status

Focus of the task is development of polycarbonates polyols produced by

copolymerisation of CO2 with mixtures of epoxides EO/PO/BO

Work has been started with copolymerization of BO using a heterogeneous

catalyst

Adjustment of the molecular weight of polycarbonate polyols by:

• Variation of starter polyol content

• Reaction conditions

• Samples characterization: GPC, NMR, DSC


Properties of produced polyol polycarbonates

76

Sample

Starting materials GPC (CHCl3) DSC, 2nd Heating

Epoxide DiolDiol

(mol%)Mn Mw Mp PDI

Tg,

(°C)

Cp

(J g-1 K-1)

BECCU-1 BO 1,4-Butanediol 10.0 56 106 49 1.87 - -




BECCU-5,

2nd purif.BO

-- 183 320 586 050 707 430 3.19 -2,7±0,4 0,32±0,06

BECCU-6,

2nd purif.BO 1,4-Butanediol 0.12 122 370 299 010 177 150 2.44 -29,8±0,8 0,51±0,14

BECCU-9,

2nd purif.BO 1,4-Butanediol 0.5 70 600 302 860 295 540 4.28 -33,0 0,35

BECCU-10 PO 1,4-Butanediol 1.1 848 1 627 1.91 ongoing

Next steps – polycarbonate polyols


Continue the experiments on copolymerisation of CO2 with epoxybutane (BO)

using a heterogeneous catalyst Optimisation of reaction conditions for adjusting the molecular weight

Samples characterisation: DSC, NMR and GPC

Selection of the samples for:

o Preparation of polyurethane materials at VTT

o Application tests with the companies

Copolymerisation experiments with propylene oxide (PO) using the same

catalyst

Copolymerisation using PO/BO mixture of epoxides


Polyurethanes

Polyurethane materials from polyol polycarbonates

• Poly(carbonate-urethane) materials based on polycarbonate polyols are prepared by coupling reaction

with a diisocyanate (t.ex.MDI)

• Reversible urethane groups are introduced in block copolymers containing hard segments (isocyanate

chain extender) and soft domains (polycarbonate polyol) which enlarge also the molar mass.

• Experimental plan:o Test different molar ratio NCO/OH

o Solvent or no solvent

o Catalyst applied

o Parameters: reaction time, temperature.

Purification: - Precipitation of the product in diethyl ether,

drying, stored in the fridge

Characterisation: FTIR, NMR, GPC, DSC, TGA

Sample code Mn Mw MP PDI

BECCU-6 53 470 234 400 220 180 4.38

BECCU-6_PU.1, 20 min 102 660 360 360 194 180 3.51

BECCU-6_PU.1, 40 min 101 420 354 210 209 370 3.49

NIPU routes

Reaction conditions

Intermediate Reagent Reaction conditions

Intermediate/final NIPU Reaction conditions

Intermediate/final NIPU

Cyclic polycarbonates + diamines

CO2, cat.

130oC, 30h, 1 MPa

70oC, 15

min

150oC, 4h

NIPU with secondary OH-groups

+ NIPU with primary OH-groups

Self-condensation of dihydroxyurethanes: starting with ethylene carbonate and diamine

(CH2)2O ethylene oxide

CO2, [(C6H5)3P]2Ni

ethylene carbonate

DMSO,

60oC, 24h

dihydroxyurethane

Bu2SnO (10%), xylene

145-150oC, 6h

-

polyurethane

yield in N2 71% yield in air 57%

Self-condensation of dihydroxyethanes: starting with aminoalcohols and ethylene carbonate

(CH2)2O ethylene oxide

CO2, [(C6H5)3P]2Ni

ethylene carbonate

RT, CH2Cl2

dihydroxyethane

Bu2Sn(OCH

3)2

xylene

160-170oC, 4h

Task 3.4 Non-isocyanate polyurethanes (NIPUs)

Preparation of NIPUs using model/commercial compounds

Datta, J. & Wloch, M. 2016. Polym. Bull. 73: 1459-1496.

Polycondensation of dihydroxyurethanes: starting with diamines + ethylene carbonate

Ethylene carbonate

Dihydroxyurethane

Melt phase,

60oC, 3h

Parameters strongly affecting

the outcome of the

polymerization:

o Reaction temperature

o Reaction time

o Amount of the catalyst

Experiments with hexamethylenediamine and

ethylene carbonate have been started.

Next steps – Polyurethane and NIPU


Preparation of PU using produced polyol polycarbonates and MDI isocyanate

NIPU trials using ethylene carbonate and hexamethylenediamine

Characterisation including: FTIR, NMR, GPC and DSC

Soilikki Kotanen / Kiilto RDI

Company Reflection

We arehere to stay

We are a family of around 1000 Kiiltonians.

8,4% of ourpersonnel workin RDI.

In 2020 we had net sales of

294 M€.

20802028

CARBON NEUTRAL BY VISION IN1919

We operate close to our customers in

11 countries, with production in

4 of them ( ).

CONSTRUCTION

We operate in four business areas

INDUSTRIAL ADHESIVES

AND FIREPROOFING

PROFESSIONAL

HYGIENE

CONSUMER GOODS

Our Promise to the Environment guides all our actions

We use less fossil and virgin raw

material and reduce waste every year.

We enable our customers to minimise their

environmental footprint.

We reduce the use of fossil and virgin

packaging material every year.

European ResponsibleCare Award 2019

All our companyoperations will be

carbon neutralby 2028.

Industrial bondingsolutionsKiilto has reactive polyurethane adhesives for industrial bonding solutions.

Polyols are used as raw materials in them.Woodworking

Structuralbonding

Kiilto will investigate to replace fossil polyols with polyols synthetized by VTT. Samples to be tested in adhesive formulations and in application tests.

Kiilto has reseach on isocyanate free polyurethanes and these raw material options will also be tested in lab scale in Kiilto lab.

www.kiilto.com

Short break – we will continue at 14:30

Coming up:

Market view on CO2 based polymers Pauline Ruiz, Nova Institute

Session 2: Group discussionsYour input, facilitated by VTT experts



Market view on CO2 based polymersPauline Ruiz, Nova Institute

BECCU-project workshop - online

Pauline Ruiz, 10th February 2021

100 pages of a comprehensive overview of the

different production routes of CO2-basedpolymers that are developed and

commercialised

A total of more than 40 companies andresearch projects are presented

– 4 –

PEC: Polyethylene carbonate, PPC: Polypropylene carbonate, PBC: Polybutylene carbonate, PEPC: poly(ethylene-co-propylene) carbonate, PPCHC: poly(propylene-co-cyclohexene) carbonate

Asahi Kasei and various under their licenses

various 750,000 Aromatic polycarbonates

Covestro Germany 5,000Polycarbonates polyols for

polyurethanes

Empower Materials United States 500PPC, PEC, PCHC, PPCHC,

PBC

Jiangsu Zhongke Jinlong-CAS Chemical

China 10,000 PPC polyols

Jilin Boda New Materials China 50,000 PPC or PEC

Inner Mongolia Mengxi High-Tech

GroupChina 3,000 PPC, PEPC, PPCHC

Saudi Aramco (formerly Novomer) United States 5,000 PPC, PEC

Taizhou BangFeng Plastic China 30,000 PPC

Nanyang Zhongju Tianguan -

Tianguan GroupChina 5,000 PPC

ca. 850 kt/a of CO2-based polymers already

produced

– 6 –

Nordic Blue Crude is

commercial plant for CO2-

based diesel, kerosene,

naphtha, and wax.

Source: Holen, G. and Bruknapp, R. 2019: Nordic Blue Crude, 100% Carbon Neutral, Disrupt or be disrupted. Presentation at 7th Conference on Carbon Dioxide as Feedstock for Fuels,

Chemistry and Polymers, 2020-03-21, Cologne,

Germany

– 7 –

LanzaTech’s Commercial,

Pilot Stage and Immediate

Target Products

Source: Mihalcea, C. 2019: Unique Process to Convert CO2 into Isopropanol and Acetone. Presentation at 2019-03-20, Cologne, Germany.

Register now and get one of the limited spots. www.renewable-carbon.eu/events/polymer-session/

– 8 –

http://www.renewable-carbon.eu/events/polymer-session/

Contact: Mr. Dominik Vogt, +49 (0) 2233 48 14 49, [email protected]

All conferences at www.bio-based.eu


http://www.bio-based.eu/

Sustainability

M. Sc Pauline Ruiz

+49 (0) 2233 48 [email protected]

Polymer science

Life cycle assessment

Sustainable chemistry


Session 2:

Group discussion

Theme I: End-productsChair: Juha Lehtonen, VTT

Theme II: Processing technologiesChair: Matti Reinikainen, VTT

Theme III: Bio-CO2 capture and hydrogen supplyChair: Timo Leino, VTT


www.beccu.fi

Thank you for participating!

http://www.beccu.fi/

workshop | beccu

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