Research activities at research group of Applied Chemistry and Process Chemistry

Research activities at research group of Applied Chemistry and Process Chemistry LuTek Final Seminar 9.5.2012 Pekka Tynjälä, PhD

Content of the presentation Advanced catalytic oxidation processes in (waste)water treatment Research on lithium ion battery chemicals and chemical precipitation Catalytic conversion of biomass to fuels and valuables

Advanced catalytic oxidation processes in (waste)water treatment CeO 2 Pt/ZrO 2 Pt/CeO 2 Al 2 O 3 Pt/Al 2O 3

Advanced catalytic oxidation processes in (waste)water treatment Researchers in our group: M.Sc. (Chem.) Hanna Runtti M.Sc. (Eng.) Laura Rahikka M.Sc. (Chem.) Tero Luukkonen M.Sc. (Chem.) Emma Tolonen M.Sc. (Chem.) Anne Heponiemi Senior researchers: D.Sc. Pekka Tynjälä D.Sc. Jaakko Rämö (advisor) D.Sc. Tauno Kuokkanen (advisor) PhD Sylvain Keav (advisor) Ass prof Rachid Brahmi (advisor) Prof. Ulla Lassi Main projects on that topic : Moniwater/Tekes Valokata/Tekes AOPI/Academy of Finland, 2012 2016 Teollisuuden jätevesien käsittely, 2009 2012 Several projects with industry

Advanced oxidation processes in water/wastewater treatment Industrial collaboration: Cabb Oy (Kemfine), Kemira, Snellman, Eskopuu, UPM Kymmene, Stora Enso, JP Analysis, Yara, Sachtleben Pigments, PAC Solution, Rautaruukki, Outokumpu, Talvivaara, Keliber, Gasek, Arizona Chemical etc. Some significant references: Heponiemi et al., (2011) Topics in Catal. 54: 1034 1041. Luukkonen et al., (2012) PowerPlant Chemistry 14(2): 112 119. Heponiemi & Lassi, (2012) Advanced oxidation processes in industry, accepted for publication. Rahikka et al. (2012) Ce Zr mixed oxides in the catalytic wet air oxidation, manuscript.

Research on lithium ion battery chemicals and chemical precipitation

Akkumateriaalien tutkimusinfrastruktuurin kehittäminen (AKKU)

Tavoitteet (1) Rakentaa ja käyttöönottaa akkukemikaalien tutkimusympäristö (sähkökem. ominaisuudet) (2) Tutkimuslaboratorion toiminnan käynnistäminen (3) Litiumklusteri innovaatioympäristön toimintaedellytysten parantaminen ja yhteistyön tiivistäminen (4) Alueen akkuteknologia ja materiaaliosaamisen lisääminen (5) Tutkimuslaitos teollisuus yhteistyön vahvistaminen (6) Luoda edellytykset kansallisesti ja kansainvälisesti kilpailukykyiselle akkukemikaalien tutkimus ja tuotekehitystoiminnalle Keski Pohjanmaalla

Research on lithium ion battery chemicals Researchers in our group: M.Sc. (Chem.) Siru Tuomaala M.Sc. (Eng.) Samuli Räsänen (defence 2012) M.Sc. (Eng.) Juho Välikangas M.Sc. (Geol.) Pekka Tanskanen B.Sc. Toni Kauppinen B.Sc. Minna Jokinen Main projects on that topic : LITIUM/Tekes 2008 2010 IMPOLI/Tekes 2010 2012 LITHIUM/Academy of Finland (under evaluation) NANOLI/Teknologiateollisuus foundation, 2013 NOFALI/Tekes 2012 2014 Several projects with industry Senior researchers: D.Sc. Pekka Tynjälä (advisor) D.Sc. Tao Hu (advisor) D.Sc. Tauno Kuokkanen (advisor) Prof. Ulla Lassi Several industrial advisors Kuva: Siru Tuomaala 2010

AKKU- Odotettavissa olevat tulokset Hankkeen päättyessä litiumklusteri innovaatioympäristön käytössä on moderni laitteistokokonaisuus akkukemikaalien testaukseen ja kennojen valmistukseen Osaajaresurssit akkumateriaalien testaukseen ja uutta osaamista ko. aihealueen ympärillä.

Akkututkimus Elektrodin valmistus Aktiivinen elektrodimateriaali + sidosaine + grafiitti + liuotin Sekoitus & viskositeetin määritys Elektrodimateriaalin valmistus Päällystys virrankeräimelle Kuivaus Kalanterointi (puristus)

Akkututkimus Kennon valmistus & testaus Elektrodin leikkaus Kennon kasaus Kennon sulkeminen Testaus

Catalytic conversion of biomass to fuels and valuables

Catalytic conversion of biomass to fuels and valuables Researchers in our group: Main projects on that topic : M.Sc. (Chem.) Jana Holm M.Sc. (Chem.) Henrik Romar M.Sc. (Chem.) Audrey Hernoux M.Sc. (Chem.) Kirsi Partanen M.Sc. (Chem.) Sari Kilpimaa M.Sc. B. Wikman (coordinator) M.Sc. Riikka Lahti Senior researchers: Ass. Prof. Jean Marc Leveque D.Sc. Tero Tuuttila (advisor) Prof. Ulla Lassi Several industrial advisors HighBio/Interreg Nord IVA, 2008 2011 Catalytic conversion of biomass to biofuels (Fortum foundation 2009 2012) Biomass to fuels and chemicals (application) SusFuFlex/Academy of Finland HighBio2/Interreg Nord IVA, 2011 2013 Catalytic conversion of sugars to 5 HMF (Fortum foundation 2012 2015) ForestRefine, BotniaAtlantica 2012 2014 ComBiCat/Tekes (under evaluation) Greenhouse 2011 2013 NanoCatalysts/Tekes (under evaluation) Projects with industry

New, innovative and sustainable transportation fuels (SusFuFlex)

Introduction SusFuFlex project focuses on the production of higher bioalcohols and other compounds suitable as oxygenates (e.g. butanol, pentanol, mixed alcohols). The main aims are: 1) To study old and novel procedures for microbiological production of biobutanol, higher alcohols and oxygenates as fossil fuel substitutes 2) To develop and optimize catalytic materials and chemical (catalytic) reaction pathways in the production of bioalcohols and other bio-derived compounds 3) To conduct a sustainability analysis of the processes to be developed, to analyze the atom economy of the new processes and to make a preliminary economical analysis, and 4) To integrate the processes and know-how developed by the research groups.

Why higher alcohols as transportation fuels? Table 1. Fuel properties of gasoline, diesel and C1 C5 alcohols. Fuel Energy Air-to- RON* MON** Water density fuel solubility (MJ/l) ratio (%) Gasoline 32 14.6 91-99 81-89 negligible Diesel 35.5 (60 to 100 - - Negligible on idle) 14.7 n-pentanol 27.8 11.68 Low Low 0% n-butanol 29.2 11.12 96 78 7% Ethanol 19.6 8.94 130 96 100% Methanol 16 6.43 136 104 100% *) RON = research octane number, **) MON = motor octane number Butanol, pentanol and mixed alcohols are also less corrosive than ethanol They can be used for replacing fossil fuels in existing combustion engines Higher alcohols can be distributed via the existing pipelines (low vapour pressure) They can be produced in an industrial scale

Microbial approach in biobutanol production Pre-treatment of biomass Raw materials -lignocellulosic (pulp mill sludges) and starch-based biomass as a carbon source or -a low-value by-product from food industry, e.g. cheese whey, a by-product from lactose purification, potato peels Fermentation of sugars to alcohols Solvent recovery, recycling of IL

Summary of results The pre treatment of lignocellulosics biomass to fermentable sugars is a challenging task Based on the results, fiber sludge (as a carbon source) will be potential for fermentation process high sugar concentration enough low amount of impurities IL residues low Other sludges might also be potential for biofuel production

CATALYTIC CONVERSION OF BIOMASS INTO TRANSPORTATION FUELS AIM OF THE RESEARCH Development of novel, chemical (catalytic) reaction pathways for the production of butanol and higher bioalcohols. M.Sc. (Chem.) Audrey Hernoux MAIN FIELDS OF THE RESEARCH Evaluation of former and novel procedures for chemical production of butanol Chemical degradation of biomass to obtain intermediate product(s) Development and optimization of catalytic reactions for the production of butanoland higher alcohols Catalyst synthesis and characterization Alcohol(s) synthesis over heterogeneous catalyzed reactions Sustainability analysis and evaluation of atom economy of the new processes The research will be carried out as a Joint Project with prof. Jean Marc Leveque, Université de Savoié, France. It is funded by Fortum foundation, 2009 2012.

Catalytic conversion of sugars to 5 HMF Kirsi Partanen: A part of D.Sc. Thesis

A value chain for forest biomass 27

HIGHBIO INTERREG NORD 2008 2011 Refining of new products and raw materials by gasification of biomass Possibilities Example of energy and material integration in the greenhouse 28

References HOLM, J., ASIKKALA, J. & LASSI, U. (2009) Cellulose fractionation from real sludge samples through ionic liquid [BMIM]Cl, Chemical Engineering Transactions vol. 17, 1645 1650. ROMAR, H., LAHTI, R, TYNJÄLÄ, P. & LASSI, U. (2011) Co and Fe catalysed Fischer Tropsch synthesis in biofuel production, Topics in Catalysis, vol. 54, 1302 1308. HOLM, J., ROMAR, H., LAHTI, R., LASSI, U. & LAJUNEN, M. (2012) Enzyme and acid catalysed hydrolysis of fibre sludge in [BMIM]Cl and [AMIM]Cl ionic liquids, revised for publication in Catalysis Today. KILPIMAA,S., KUOKKANEN, T. & LASSI, U. (2011) Physical and chemicals properties of wood ash from burning and gasification processes. The Journal of Solid Waste technology and Management, 879 887. HERNOUX, A., LEVEQUE, J M, LASSI, U., BOISSEAU, S. & MARAIS, M F. (2012) Conversion of a non water soluble potato starch waste into reducing sugars under non conventional technologies, manuscript

References KILPIMAA,S., KUOKKANEN, T. & LASSI, U. (2012) Chemical and leaching properties of wood ash from burning and gasification processes, submitted for publication in Waste Management. HOLM, J.& LASSI, U. (2011) Ionic liquids in the pretreatment of lignocellulosic biomass, In: Ionic Liquids, Theory and Applications (ed.xx), InTech publishing, 987 953 7619 X X, Chapter 24, pp. 545 560. HERNOUX, A., LEVEQUE, J M, LASSI, U., BOISSEAU, S. & MARAIS, M F. (2011) Catalytic conversion of biomass into transportation fuel, In: Proceedings of GPE 3 rd International Congress Green Process Engineering, December 6 8, Kuala Lumpur, Malaysia, (oral presentation, refereed conference publication)

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