113/12/2017 1

Bio-CO2 value chains for demonstration

NEO-CARBON ENERGY 9th RESEARCHERS’ SEMINAR, 11.12.2017Janne Kärki, VTT

WP3 work during NCE Phase I

Link Link

Altogether 16 individual studies on industry-integrated P2X concepts

Altogether 10 individual studies on enabling framework

Conclusions from Phase I business case studies

• Especially attractive sites for P2X integration are CHP plants and wastewater treatment plants, where heat can be utilised.

• Additionally there are rather good integration opportunities within pulp mills, steel industry and in ammonia production.

• For the 1st applications the best paying capability is offered in transportation fuels.

• Utilisation of at least 1-2 side products (heat, oxygen, steam) for additional revenue is typically required to enable profitability.

Bio-CO2 value chains - project

• Find sustainable new business from biogenic carbon dioxide value chains in Finnish biomass driven industry sectors for:– synthetic fuel production– biogas upgrading– industrial chemicals – other valuable products utilising bio-CO2

• Project schedule: 03.10.2016 - 31.08.2018

• New CO2 capture, purification and utilisation solutions and services– demonstration activites in separate project(s)

Key tasks• WP I: CO2 utilisation

• Review study on different pathways• Case studies in different process environments• Vision on possible value chains

• WP II: CO2 capture & purification• Most potential CO2 capture locations in Central-Finland• Review on CO2 capture & purification in ”utilisation-scale” solutions• Co-operation with possible Finnish technology developers

• Dissemination• www, articles, media, some, etc.• Workshops and a company road-show• Seminar participation

Sustainable new business from biogenic carbon dioxide

13.12.20175

CARBON DIOXIDE, CO2

Mineralisation-Concrete curing

-Aggregates-Mineral carbonation-Precipitated calcium

carbonate (PCC)

Chemical conversion

Biological conversion-Algae cultivation

-Greenhouses-Gas fermentation (e.g. biological methanation)

Polymers-Polycarbonates

-Polyols intermediates

Fuels & chemical

intermediates

Commodity-”Renewable

urea”

Methane (CH4)Formic acid (HCOOH)3

Methanol (CH3OH) 2

Syngas (CO+H2)

Methanol, ethanol..

Gasoline,

olefins...

Gasoline, diesel,

olefins...

MTBE*, DME**

Form-aldehyde

Gasoline

Olefins

Fischer-Tropsch (FT)

+H2

Direct use-Food/beverages

-Industrial gas-Refrigerant

-Working fluid-Solvent

-pH control-Enhanced oil

recovery (EOR)-Enhanced coal

bed methane (ECBM)

*methyl-tert-butyl ether**dimethyl ether

Main CO2 utilisation routes and options

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+H2 +N2+

NOTE: The diagram presents only the most important options for the near-term . There are other routes suchelectrochemical and photochemical routes and hundreds of other possible products.

Vision: New CO2-based production in Central-Finland

13.12.2017Sampo Mäkikouri7

Case study examples

Purpose: study the economic feasibility of CCU processes in different biobased industry sectors

Case 1: Sawmill casea) Methaneb) Methanolc) Formic acid

Case 2: Boosting biogas productiona) Stand-alone biowaste digesterb) Waste-water treatment plant

The cases are generic in nature: they do not represent any actual siteand thus various assumptions regarding e.g. heat demand have been made.

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Why have we chosen these products?

a) Methane (CH4)- Transport fuel sector offers good payment capability- High technology readiness level (TRL8) – demonstrated at relevant scale already

b) Methanol (CH3OH)- Large market: important bulk chemical & chemical intermediate, can also be as fuel- Methanol is used in production of resins/adhesives for wood industry- Methanol is imported to Finland- High technology readiness level (TRL8) – demonstrated at relevant scale already

c) Formic acid (HCOOH)- High-value chemical with low risk of substitution: used e.g. in animal feed,

leather tanning, textile dying and for producing de-icing agents- Theoretically attractive synthesis route from CO2 and H2

(no side-products, CO2+H2 HCOOH)- Currently limited market size &

low technology readiness level (TRL3-5)

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Integration of bio-CCU to the sawmill

• Selected scale is 9 MWe electrolyser corresponding to the Europe’s largest water electrolyser (Woikoski, Kokkola, Finland)

• CO2 is captured from the biomass boiler, which provides the needed heat for the sawmill and produces also district heat

– CO2 is purified to the required specifications– Constant costs of purified CO2 are assumed

• Heat, produced as a side-product of Power-to-X applications, is assumed to be fully utilisable – and also the possible steamdemand of Power-to-X can be covered by the biomass boiler

• There is no demand for oxygen at site:– In optimistic scenarios, it is assumed that some revenue can be

generated from O2

– In conservative scenarios oxygen is assumed to be vented

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CO2

Simplified block diagramsFormic acid synthesis

• Chemical conversion of CO2 and H2 via homogenous catalysis

• 105 bar & ~90 °C, ruthenium- and phosphino-based catalysts• Tertiary amine for adduct-formation and polar solvent (methanol-water)• Steam required for separation of solvent and amine from the product

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Electrolysis=67% LHV)

Synthesisconv.H2=63%

conv.CO2=98%

Stripping of solvent

(methanol)

Liquid-liquidseparation of

catalysts

Reactive distillation

(separation and purificationof FA from amine-adduct)

Electricity& gridservice

Steam

Heat

Water H2

CO2O2

Formic acid (85%)

Amine

Amine+catalysts

Methanol

FA-adductFree amineCatalystsMethanol

FA-adductMethanol

Amine FA-Amine adduct Formic acid

Perez-Fortes&Tzimas (2016). Technoeconomic and environmental evaluation of CO2 utilisation for fuel production – Synthesis of methanol and formic acid, Joint Research Centre, Report EUR 27629 EN, 86 p.

3.7 MW

3060 kg/h

1440 kg/h

181 kg/h

1620 kg/h

2540 kg/h

8.5 MW

~1/5 Eastman/Taminco’sOulu plant

Economic feasibility evaluationHourly plant operation model for P2X processes

• The NCE-model is based on mass and energy balances calculated from given efficiencies and chemical conversion rates, losses etc. for each process

• Main input variables: – Price/values of process inputs and outputs

• Hourly electricity prices, constant price for others– CAPEX and O&M costs– Economic parameters (e.g. WACC, lifetime)

• Results:– Cost and income structures– Profit, EBIT, EBITDA, Payback period, IRR and

levelised cost of product (taxes not considered)– Operation mode distribution (full load, FCR, stand-by)

• Sensitivity:– Optimistic and conservative scenarios for market values– Sensitivity towards main variables

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CAPEX of the main processes• Total investment costs are scaled from the reference size specific costs according to equation:

Cost = Reference cost ×Capacity

Reference capacity

• OPEX:

[1] BioCat Project Final Report[2] Same as [1] but assuming 30% cost reduction for pure CO2 feed[3] Derived from Perez-Fortes&Tzimas (2016)

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Referencespecific costs

Referencecapacity Scaling factor

Alkalineelectrolyser (eff. 67% LHV)

1000 k€/MWe 9 MWe 0.93

Chemical methanation 1000 k€/MWSNG 5 MWSNG 0.67

Biologicalmethanation (raw biogas as feed)

730 k€/MWSNG[1]

5 MWSNG[1]

0.40[1]

Biologicalmethanation(pure CO2 asfeed)

510 k€/MWSNG[2]

5 MWSNG[2]

0.40 [2]

Methanol synthesis 1000 k€/MWMeOH 5 MWMeOH 0.67

Formic acid synthesis

5400 k€/(tFA/h) [3]

1.5 tFA/h[3] 0.67

WACC 6%, 20 years

Installation/project cost of 15% is added to costs

9 MWe plants:SNG & MeOH ~18 M€Formic acid ~27 M€

2 MWe plantSNG ~5 M€ (biol.methanation)

*NOTE: in case of formic acid synthesis – which is a net consumer of heat+steam– the higher values for heat and steam (€/MWh) are actually decreasing the competitiveness

Market parametersOptimistic scenario Conservative scenario

Products • SNG 80 €/MWh• MeOH 100 €/MWh• Formic acid 700 €/t

• SNG 60 €/MWh• MeOH 70 €/MWh• Formic acid 600 €/t

Electricity spot pricescenario

• Finland 2016 80% (avg. price 25.6 €/MWh)

• Extra price variation±30%

• Finland 2016 (avg. price 32.0 €/MWh)

Electricity transmission + net taxes 11 €/MWh 11 €/MWh

FCR scenario Finland 2016 fixed(17.4 €/MW, h)

Finland 2016 fixed(17.4 €/MW, h)

CO2 capture+purification 30 €/tCO2 50 €/tCO2

O2 utilisation 50 €/tO2 0 €/tO2

Heat utilisation* 30 €/MWh 20 €/MWh

Steam utilisation* 30 €/MWh 20 €/MWh

Investment subsidy 30% 0%

Biogas pumpprice today~80 €/MWh(VAT0%)

Results - Sawmill case

LCOP = Levelised cost of product, €/MWh for SNG and MeOH, €/kg for formic acid

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• Formic acid case is highly profitable even with conservative market parameterswhile SNG & MeOH are clearly unfeasible

– SNG and MeOH would require the product to have roughly a double value to break-even

• With optimistic assumptions SNG is just about profitable, while MeOH cangenerate somewhat more profit

k€/ak€/ak€/ayears

€/MWh or €/kg

80 €/MWh 100 €/MWh 0.70 €/kg 60 €/MWh 70 €/MWh 0.60 €/kgAssumed valueof product:

Optimistic scenario Conservative scenario

ResultsSawmill case – Formic acid sensitivity study

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• There is a lot of uncertainty with formic acid case due to low TRL– Highest uncertainly for catalyst costs especially for the catalyst consumption

as the process has not been piloted yet

8-fold increase in catalyst costs or the decrease of product value from 600 ~400 €/t, would makeformic acid case unfeasible

k€/ak€/ak€/ayears

€/kg

Referencevalue was0.6 €/kg

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Results are described in more detail in:

Sampo Mäkikouri, Markus Hurskainen, Janne Kärki, Eemeli Tsupari, Eija Alakangas, Cyril Bajamundi (2017). INTEGRATED UTILISATION PATHWAYS FOR BIOGENIC CARBON DIOXIDE IN BIOMASS DRIVEN INDUSTRY SECTORS

http://www.vtt.fi/sites/BioCO2/PublishingImages/tiedotteet/5BO.4.4_paper.pdf

See also:www.vtt.fi/sites/BioCO2/

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From desktop studies to action…

Kestävää kasvua ja työtä-ohjelma

Project: Demonstration of bio-CO2products with novel research platform

Kestävää kasvua ja työtä-ohjelma

Key objective

Demonstrate utilization of biobased CO2 as a raw material for • synthetic transportation fuels• boosting bio-SNG production• or industrial

chemicals/products

Schedule 01.09.2017 - 31.7.2019

Kestävää kasvua ja työtä-ohjelma

Targeted research platform

Investment on mobile hydrogen production unit will be made and it will be integrated with existing VTT’s synthesis unit and industrial CO2 streams

Kestävää kasvua ja työtä-ohjelma

Demos

Demonstrations with the developed platform will be conducted within e.g. bio-product mill or in bioethanol or biogas production

Kestävää kasvua ja työtä-ohjelma

Mobile synthesis until (MOBSU)

CO2

H2

MOBSU is a multipurpose synthesis unit for CO2 upgrading to energy carriers and chemicals which can be transported on-site where CO2 emissions and energy are available.

- Control room- Process area- Gas alarms and safety system- Gas analysis

PRODUCTS:- WAXES AND LIQUID HYDROCARBONS- SYNTHETIC NATURAL GAS- METHANOL

Kestävää kasvua ja työtä-ohjelma

Electrolyser investmentCompetitive bidding process:

(31/08/2017) 23 Target Companies(26/10/2017) 16 Contacted Companies(01/11/2017) 9 Companies Logged-in to Claudia System(13/11/2017) 2 Companies submitted tenders(30/11/2017) Decision was approved, published in Claudia

End of May Expected Delivery

Kestävää kasvua ja työtä-ohjelma

Electrolyser - Main Features

Giner ELX Electrolyser:• Proton Exchange Membrane (PEM)

electrolyser• Production of 4 Nm3/h with 55 bar

output and 50 bar storage pressure• Nominal power ~20 kW• Hydrogen purity is 99.999 % • Housed in standard 10ft shipping

container Giner ELX PEM electrolyser in an IP55 container

Kestävää kasvua ja työtä-ohjelma

Electrolyser - Key Components

Kestävää kasvua ja työtä-ohjelma

CO2 capture options

Ville Laitinen

CarbonReUse Finland Oy- Possible co-operation between projects

Biogas or other biogenic processes- Utilisation of existing CO2

Kestävää kasvua ja työtä-ohjelma

Stages of the project1. Investment for H2 production (PEM, 4 m3/h, turn-key)

2. Integration analysis of H2 production with different CO2 sourcesand synthesis unit

3. Demonstration activities:

a. SNG production in biogas processes

b. Liquid and solid hydrocarbons within biogenic CO2 sources, e.g bio-CHP or bioethanol production

4. Feasibility studies of different products and markets

5. Business opportunity analyses

6. Dissemination and company activation

Kestävää kasvua ja työtä-ohjelma

Thank you for your attention!

janne.karki@vtt.fi

www.vtt.fi/sites/bioeconomyplus