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Home , Black liquor, Chemrec

Advanced and chemicals from (and renewable electricity) Rikard Gebart Division of Energy Science Luleå/Piteå Outline

• Forest industry • Black liquor • The LTU Green Fuels demo plant • Combination with electrolysis • Field testing of bio-DME and bio- • Conclusions Chemical pulping

Wood chips Chemical fibers supply pulping

Pulping liquor Black liquor regeneration concentration

• Highly optimised and large scale process • Typical mill size 500 000 – 1 000 000 ton pulp per year • Corresponds to 1 000 000 – 2 000 000 ton pulp per year • Black liquor energy flow rate ≈ 200 – 400 MW per plant Black liquor is an excellent gasification fuel • Very high alkali content, 20-30% water • Very reactive, catalyzed by Na – Gasification possible at 1000 C – Very little soot and tar • Very important – it is a liquid that can be pumped Gasification reactivity Lab scale experiments @ 1000 °C

Saw dust Black liquor Black Liquor Energy in Europe Approx: 20 000 MW Black Liquor = clusters of mills together having a large boiler capacity

= important single mill Some 65 large plants Black liquor gasification to MeOH

Wood chips Chemical Pulp fibers supply pulping

Pulping liquor Liquid fuel Black liquor regeneration gasification concentration

O2 Air separation unit (ASU)

Synthesis gas MeOH synthesis cleaning

• Recovery boiler can be replaced with a gasifier • Need to increase supply of low grade to maintain energy balance • Small increase in energy use in lime kiln for regeneration of cooking chemicals The Black Liquor Gasifier

BLACK LIQUOR

COOLING OXYGEN AND WATER ATOMIZING MEDIA

GAS COOLER COOL,LOW TAR, LOW SOOT SYNTHESIS GAS REACTOR RAW GAS

QUENCH

GREEN LIQUOR

WEAK CONDENSATE WASH Carlsson, P., ”Large scale experiments and modeling of black liquor gasification”, PhD thesis, Luleå University of Technology, 2011 Jafri, Y., ”Entrained flow gasification of black liquor and ”, LicEng thesis, Luleå 8 University of Technology, 2016 8 The LTU Green Fuels demo plant

Investment 300 MSEK

Pilot gasification Pilot methanol + DME Field testing 3 MW, 20 t DS/d 4 t/d methanol/DME Volvo Trucks DME >28 000 h since 2005 >12 000 h since 2011 8 trucks, >1 500 000 km Recovery of cooking chemicals without difficulties DME and methanol in Is run in 3 week campaigns 24/7, high availability industrial applications

• The plant was built by Chemrec in several collaborative research projects since 2004 • In 2013 the plant and staff was transferred to Luleå University of Technology 9 Next improvement – combine with electrolysis

Wood chips Chemical Pulp fibers supply pulping

Pulping liquor Liquid fuel Black liquor regeneration gasification concentration

Off-site fast Residual O2 pyrolysis biomass On-site Renewable electrolysis power H2 Synthesis gas MeOH cleaning synthesis

• Elimination of CO-shift and ASU, lower CAPEX and lower specific OPEX

• Push methanol synthesis to convert all CO2 10 • Works with both partial and full stream of black liquor Efficiency for the new electrofuel process

• More than a doubling of capacity compared to gasification only • Needs a lot of renewable power • Same production cost as gasification only (with current power price) 11 Very high carbon efficiency

Base case

New process

• Doubling of carbon efficiency compared to gasification only • Almost all carbon is bound in methanol, the rest is recycled 12 Process economics for BioDME

• Estimated necessary sales price with 15% IRR: 70-90 €/MWh* • Typical plant size: 150 000 ton DME per year • Flexible output of methanol or DME • Methanol can be upgraded with MTG to gasoline that satisfies the current gasoline standard

* Carvalo, L., ”Opportunities to broaden biomass feedstocks in thermochemical conversion technologies”, PhD thesis, Luleå University of Technology, 2018 Andersson, J., ”Systems analysis of chemicals production via integrated entrained flow biomass gasification”, PhD thesis, Luleå University of Technology, 2016 13 Demonstration of bio-DME and bio-methanol production

14 The BioDME project

• Demonstration of new once-through methanol technology • Demonstration of integrated fuel production from black liquor at • BioDME demonstrated as diesel substitute • BioDME project partners:

15 Cumulative BioDME production

1000

900 BioDME project LTU Biosyngas Program 800

700

600

500

400

300 Produced BioDME,ton

200

100

0 jul.12 jul.13 jul.14 okt.12 okt.13 okt.14 jan.12 jun.12 jan.13 jun.13 jan.14 jun.14 jan.15 feb.12 feb.13 feb.14 feb.15 apr.12 apr.13 apr.14 apr.15 dec.11 maj.12 sep.12 nov.12 dec.12 maj.13 sep.13 nov.13 dec.13 maj.14 sep.14 nov.14 dec.14 maj.15 aug.12 aug.13 aug.14 mar.12 mar.13 mar.14 mar.15

More than 1000 ton DME + MeOH was produced until May 2016

(1) Landalv, I.; Gebart, R.; et al., “Two years experience of the BioDME project - A complete wood to wheel concept”, Environ. Prog. Sustain. Energy, 2014, 33 (3), 744–750. 16 Development of filling stations

17 Field test with HD trucks in commercial operation

18 Volvo field test 8 trucks, 2013-01-01 to 2015-01-31

(1000 Km) Status Target 2015-01-31 June 2014 Total mileage 1 550 1 400 1 truck 328 250

Extended field test

19 Field testing of bio-methanol

• Passenger car > 20 000 km with M56 • Speedway motorcycle with M100 • Drag racing car with M100 • Pilot boat (converted diesel engine) • 50 ton bio-MeOH supplied as catalyst to bio-diesel production

20 Conclusions • Black liquor is an important biomass resource and an excellent gasification fuel • Black liquor gasification is a mature process after more than 28 000 hours of operation • Combination of gasification and electrolysis – Eliminates the need for an ASU – More than doubles the potential of black liquor and bio-oil • Co-gasification of black liquor and bio-oil* – benefits from the catalytic effect of the black liquor – Increases the potential of black liquor with at least 50% • BioDME has been demonstrated in heavy duty trucks in commercial operation for more than 1 500 000 km – Low soot, Nox and GHG performance – Excellent well-to-wheel efficiency * Slides not shown today Thank you for your attention! Catalytic co-gasification – hitchhike on black liquor reactivity

Low heating value High reactivity

Mixing Efficient gasification?

Other biomass

Pyrolysis oil High heating value residue Low reactivity Forest fuel etc. Validation of co-gasification concept

Small modification of the pilot Summary of co-gasification • First attempt spring 2015 • Operation 1100 h, app. 170 ton PO • Operation 900 h with metanol/DME

• Up to 20% PO; 3,5 MWth • No difference in green liquor quality • Robust operation, no technical difficulties Co-gasification in pilot scale

Energy efficiency gasification Temperature sensitivity 50 80 2.5

45 70 2 CGE ) Svartlut 15% PO 40 60 1.5

H2 35 50 1 %CH4 in in %CH4 % of syngas of % CO 30 2 40 0.5

CO basisfree(sulfur CGE % 25 30 0 1000 1020 1040 1060 1080 1100 20 20 BL 10% PO 15% PO 20% PO Reactor temperature (C)

1.3% CH4 1.5% N2 1.4% H2S 114 ppm C6H6 11 ppm C2-C3 Co-gasification: energy balance 0% PO 25% PO 50% PO

69% incremental efficiency PO to MeOH

Andersson, J., Lundgren, J., Furusjö, E., & Landälv, I. (2015). Co-gasification of pyrolysis oil and black liquor for methanol production. Fuel, 158, 451–459. https://doi.org/10.1016/j.fuel.2015.05.044 Forest industry Source: Biomassaflöden i svensk skogsnäring 2004, by-products in Per Olov Nilsson. Rapport 23-2006 Skogsstyrelsen ISSN 1100-0295

*Million tons dry biomass Forest industry Source: Biomassaflöden i svensk by-products in skogsnäring 2004, Per Olov Nilsson. Rapport 23-2006 Sweden /2 Skogsstyrelsen ISSN 1100-0295

*Million tons dry biomass

Gasification of biomass

Fuels & Chemicals

Felling residues

Black liquor Fuels & Chemicals gasification Durable containment materials: The key to gasification of high alkali fuels

29 Source: Ingvar Landälv, LTU