Carbon Catalysts in Biofuel Production: From Furfural to 2-Methylfuran

Salla Jaatinen

Carbon Catalysts in Biofuel Production: From Furfural to 2-Methylfuran

Julkaisun otsikon käännös: Carbon Catalysts in Biofuel Production: from Furfural to 2-Methylfuran

Salla Jaatinen

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Kemikaalien, polttoaineiden ja energian tuottaminen uusiutuvista raaka-aineista on erittäin tärkeää jatkuvasti etenevän ilmastonmuutoksen takia. Yksi vaihtoehto tuottaa kemikaaleja ja polttoaineita on vedyttää uusiutuvaa kemikaalia, furfuraalia. Furfuraalin vedytyksellä voidaan tuottaa useita tuotteita, kuten furfuryylialkoholia ja 2-metyylifuraania (MF). MF:llä on erinomaisia ominaisuuksia korvaamaan bensiinin tuotannossa oktaaniluvun nostajina toimivat fossiiliset vaihtoehdot metyyli-tert-butyyli eetteri ja etyyli-tert-butyyli eetteri. Tällä hetkellä prosessissa käytetty katalyytti on myrkyllinen ja uusia, selektiivisiä vaihtoehtoja tarvitaan. Tässä väitöskirjassa tavoitteena oli tuottaa jalometallittomia ja myrkyttömiä katalyyttivaihtoehtoja MF:n tuotantoon. Katalyytin metallivaihtoehdoiksi valikoitiin siirtymämetallit kupari, nikkeli ja rauta. Reaktio-olosuhteiden optimointi osoitti korkean lämpötilan (230 °C) ja vetypaineen (40 bar) suosivan MF:n tuotantoa. Parhaat tulokset saavutettiin kupari-nikkeli ja kupari-rauta seoksilla, ja jopa 60% MF saanto saavutettiin nestefaasissa panosreaktorissa lyhyessä reaktioajassa (1 - 2 h). Metallikatalyyttien kantajina testattin useita aktiivihiiliä ja mesohuokoista hiilimateriaalia (CMK-3). Valmistettuja katalyyttejä karakterisoitiin useilla menetelmillä, jotta niiden suotuisista ominaisuuksista MF:n valmistuksessa saataisiin tietoa katalyyttien optimointiin. MF:n tuotannon havaittiin tehostuvan pienillä metallipartikkeleilla, pienellä kantajan huokoskoolla ja happamalla kantajalla. Liuottimen sivureaktiot ovat mahdollisia furfuraalin nestefaasivedytyksessä. 2-Propanoli liuotin saattaa reagoida furfuraalin kanssa tarjoten vetyä vedytysreaktioon ja muodostamalla sivutuotteena asetonia. 2-Propanoli saattaa myös reagoida vedyn poiston kautta asetoniksi ja vedyksi. Asetonin muodostumismekanismin havaittiin olevan metalliriippuvainen; kuparilla ja nikkelillä asetoni muodostuu reaktiossa furfuraalin kanssa, kun taas raudalla myös vedyn poistoa tapahtuu. Vedyn liukoisuus reaktiomatriisiin vaikuttaa nestefaasiprosesseihin ja erityisesti prosessien skaalaus suurempaan mittakaavaan tarvitsee tietoa vedyn liukoisuudesta lähtöaineisiin. Vedyn liukoisuuden fur-furaaliin ja 2-propanoliin havaittiin kasvavan lämpötilan (50 - 200 °C) ja paineen (50 - 125 bar) funktiona, vedyn liukoisuus 2-propanoliin oli lähes kolme kertaa korkeampi furfuraaliin verrattuna. Vedyn mooli-osuus esimerkiksi 200 °C:ssa ja 125 bar:ssa oli 2-propanolissa 0.064 ja furfuraalissa 0.038. Liukoisuusdatat mallinnettiin PC-SAFT mallilla ja valittu malli ennusti vedyn liukoisuusdataa hyvin. Tämän väitöskirja tuotti selektiivisen ja nopean katalyytin MF tuotantoon nykyisen katalyytin mahdol-liseksi korvaajaksi, uutta dataa vedyn liukoisuudesta reaktiomatriisiin ja optimoidut hiilikantajaominaisuudet MF tuotantoon.

Julkaisun otsikon käännös	Carbon Catalysts in Biofuel Production: from Furfural to 2-Methylfuran
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Valvoja/neuvonantaja	Puurunen, Riikka, Vastuuprofessori Karinen, Reetta, Ohjaaja Lehtonen, Juha, Ohjaaja
Kustantaja	Aalto University
Painoksen ISBN	978-952-60-8445-9
Sähköinen ISBN	978-952-60-8446-6
Tila	Julkaistu - 2019
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

furfuraali
2-metyylifuraani
aktiivihiili
mesohuokoinen hiili
vedytys

YK:n kestävän kehityksen tavoitteet

Tämä tuotos edistää seuraavia kestävän kehityksen tavoitteita:

Pääsy asiakirjaan

http://urn.fi/URN:ISBN:978-952-60-8446-6

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Seitsonen, J. (Manager) & Rissanen, A. (Other)
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@phdthesis{a0a60e1d6df04fa68b6b33c85f68c6de,

title = "Carbon Catalysts in Biofuel Production: From Furfural to 2-Methylfuran",

abstract = "Production of bio-based chemicals, fuels and energy are essential in the current climate environment. Hydrotreatment of renewable platform chemical furfural yields many valuable products, such as furfuryl alcohol and 2-methylfuran (MF). MF has excellent properties for use as a gasoline octane booster to replace current fossil methyl tert-butyl ether and ethyl tert-butyl ether. The current CuCr-catalyst in furfural hydrotreatment is toxic and new and selective catalysts are required. In this dissertation, noble metal free and non-toxic catalysts were prepared for production of MF. Metal catalyst options chosen for this work were copper, nickel and iron. High yields (up to 60%) of MF were achieved with the prepared catalysts in liquid phase batch reactor experiments in short reaction time (1 - 2 h). High temperature (230 °C) and high hydrogen partial pressure (40 bar) were optimal for MF produc-tion, and the most optimal metal combinations were copper-nickel and copper-iron. Active metals were tested in MF production on various activated carbon supports and a mesoporous carbon material (CMK-3). Deep characterization was performed to obtain data of beneficial catalyst characteristics for MF production. Production of MF was enhanced by small metal particle size, small pore volume and higher acidity. These enhancements suppressed the production of competitive products and side reactions, and increased the selectivity towards 2-methylfuran. Solvents may also react in furfural hydrotreatment. The applied 2-propanol can react through catalytic transfer hydrogenation (CTH) offering hydrogen for hydrotreatment reactions and producing acetone. The solvent can also dehydrogenate to acetone and hydrogen. Acetone formation mechanisms were studied with the prepared catalysts. The acetone formation was metal dependent: with nickel and copper acetone formation occurred through CTH while with iron also dehydrogenation took place. Hydrogen solubility in the reaction media is important for the process and especially in scaling up pro-cesses. Hydrogen solubilities in furfural and 2-propanol were measured and observed to increase as a function of temperature (50 - 200 °C) and pressure (50 - 125 bar). Hydrogen solubility in 2-propanol was observed almost three times higher to solubility in furfural. By way of example, at 200 °C and 125 bar hydrogen mole fraction in 2-propanol and furfural was measured to be 0.064 and 0.038 respectively. The solubility data was modelled with PC-SAFT model and the model predicted the hydrogen solubility data well. This dissertation offers a MF selectivity optimized and fast noble metal free catalyst alternative for the current catalyst, new data of hydrogen solubility in the reaction media and optimized carbon support characteristics for the production of MF.",

keywords = "furfural, 2-methylfuran, activated carbon, mesoporous carbon, hydrotreatment, furfuraali, 2-metyylifuraani, aktiivihiili, mesohuokoinen hiili, vedytys, furfural, 2-methylfuran, activated carbon, mesoporous carbon, hydrotreatment",

author = "Salla Jaatinen",

year = "2019",

language = "English",

isbn = "978-952-60-8445-9",

series = "Aalto University publication series DOCTORAL DISSERTATIONS",

publisher = "Aalto University",

number = "41",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Carbon Catalysts in Biofuel Production

T2 - From Furfural to 2-Methylfuran

AU - Jaatinen, Salla

PY - 2019

Y1 - 2019

N2 - Production of bio-based chemicals, fuels and energy are essential in the current climate environment. Hydrotreatment of renewable platform chemical furfural yields many valuable products, such as furfuryl alcohol and 2-methylfuran (MF). MF has excellent properties for use as a gasoline octane booster to replace current fossil methyl tert-butyl ether and ethyl tert-butyl ether. The current CuCr-catalyst in furfural hydrotreatment is toxic and new and selective catalysts are required. In this dissertation, noble metal free and non-toxic catalysts were prepared for production of MF. Metal catalyst options chosen for this work were copper, nickel and iron. High yields (up to 60%) of MF were achieved with the prepared catalysts in liquid phase batch reactor experiments in short reaction time (1 - 2 h). High temperature (230 °C) and high hydrogen partial pressure (40 bar) were optimal for MF produc-tion, and the most optimal metal combinations were copper-nickel and copper-iron. Active metals were tested in MF production on various activated carbon supports and a mesoporous carbon material (CMK-3). Deep characterization was performed to obtain data of beneficial catalyst characteristics for MF production. Production of MF was enhanced by small metal particle size, small pore volume and higher acidity. These enhancements suppressed the production of competitive products and side reactions, and increased the selectivity towards 2-methylfuran. Solvents may also react in furfural hydrotreatment. The applied 2-propanol can react through catalytic transfer hydrogenation (CTH) offering hydrogen for hydrotreatment reactions and producing acetone. The solvent can also dehydrogenate to acetone and hydrogen. Acetone formation mechanisms were studied with the prepared catalysts. The acetone formation was metal dependent: with nickel and copper acetone formation occurred through CTH while with iron also dehydrogenation took place. Hydrogen solubility in the reaction media is important for the process and especially in scaling up pro-cesses. Hydrogen solubilities in furfural and 2-propanol were measured and observed to increase as a function of temperature (50 - 200 °C) and pressure (50 - 125 bar). Hydrogen solubility in 2-propanol was observed almost three times higher to solubility in furfural. By way of example, at 200 °C and 125 bar hydrogen mole fraction in 2-propanol and furfural was measured to be 0.064 and 0.038 respectively. The solubility data was modelled with PC-SAFT model and the model predicted the hydrogen solubility data well. This dissertation offers a MF selectivity optimized and fast noble metal free catalyst alternative for the current catalyst, new data of hydrogen solubility in the reaction media and optimized carbon support characteristics for the production of MF.

AB - Production of bio-based chemicals, fuels and energy are essential in the current climate environment. Hydrotreatment of renewable platform chemical furfural yields many valuable products, such as furfuryl alcohol and 2-methylfuran (MF). MF has excellent properties for use as a gasoline octane booster to replace current fossil methyl tert-butyl ether and ethyl tert-butyl ether. The current CuCr-catalyst in furfural hydrotreatment is toxic and new and selective catalysts are required. In this dissertation, noble metal free and non-toxic catalysts were prepared for production of MF. Metal catalyst options chosen for this work were copper, nickel and iron. High yields (up to 60%) of MF were achieved with the prepared catalysts in liquid phase batch reactor experiments in short reaction time (1 - 2 h). High temperature (230 °C) and high hydrogen partial pressure (40 bar) were optimal for MF produc-tion, and the most optimal metal combinations were copper-nickel and copper-iron. Active metals were tested in MF production on various activated carbon supports and a mesoporous carbon material (CMK-3). Deep characterization was performed to obtain data of beneficial catalyst characteristics for MF production. Production of MF was enhanced by small metal particle size, small pore volume and higher acidity. These enhancements suppressed the production of competitive products and side reactions, and increased the selectivity towards 2-methylfuran. Solvents may also react in furfural hydrotreatment. The applied 2-propanol can react through catalytic transfer hydrogenation (CTH) offering hydrogen for hydrotreatment reactions and producing acetone. The solvent can also dehydrogenate to acetone and hydrogen. Acetone formation mechanisms were studied with the prepared catalysts. The acetone formation was metal dependent: with nickel and copper acetone formation occurred through CTH while with iron also dehydrogenation took place. Hydrogen solubility in the reaction media is important for the process and especially in scaling up pro-cesses. Hydrogen solubilities in furfural and 2-propanol were measured and observed to increase as a function of temperature (50 - 200 °C) and pressure (50 - 125 bar). Hydrogen solubility in 2-propanol was observed almost three times higher to solubility in furfural. By way of example, at 200 °C and 125 bar hydrogen mole fraction in 2-propanol and furfural was measured to be 0.064 and 0.038 respectively. The solubility data was modelled with PC-SAFT model and the model predicted the hydrogen solubility data well. This dissertation offers a MF selectivity optimized and fast noble metal free catalyst alternative for the current catalyst, new data of hydrogen solubility in the reaction media and optimized carbon support characteristics for the production of MF.

KW - furfural

KW - 2-methylfuran

KW - activated carbon

KW - mesoporous carbon

KW - hydrotreatment

KW - furfuraali

KW - 2-metyylifuraani

KW - aktiivihiili

KW - mesohuokoinen hiili

KW - vedytys

KW - furfural

KW - 2-methylfuran

KW - activated carbon

KW - mesoporous carbon

KW - hydrotreatment

M3 - Doctoral Thesis

SN - 978-952-60-8445-9

T3 - Aalto University publication series DOCTORAL DISSERTATIONS

PB - Aalto University

ER -

Carbon Catalysts in Biofuel Production: From Furfural to 2-Methylfuran

Abstrakti

Tutkimusalat

YK:n kestävän kehityksen tavoitteet

Pääsy asiakirjaan

Sormenjälki

Laitteet

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