Studies of the Catalytic Conversions of Bio-Oils Obtained by Pyrolytic Decomposition of Non-Edible

BiomaterialsFerenc Lónyi

Institute of Materials and Environmental ChemistryResearch Centre for Natural SciencesHungarian Academy of Sciences

Biomass conversion

- Diversity- Seasonal and

disseminated occurrence

Biomass Conversion Product

- Near to the location of biomass generation - Using the best conversion technology (economy and

product requirement)

- Locally used energy (heat or electric)

- Transportable energy- Intermediates and

chemicals

Produces- vegetable oil- algae oil- energy plants

Biological- aerobic and anaerobic

fermentation- enzymatic hydrolysis

Thermal- combustion- gasification- Pyrolysis (CO2 negative)

Chemical (catalytic)- transesterification of oils

- hydrorefining of oils- processing the products of other conversions, e.g.

gasification of pyrolysis oil to

H2/CO mixture

Wastes- lignocellulosic- communal- industrial- animal by-products

Electric energy- fuel cell- Gas turbine/generator- Gas engine/generator

Pipeline gas- bio-methane

Liquid fuel- biodiesel - ”green” diesel- FT fuel- lower alcohols

Pyrolysis

Biomass(e.g. Meat and Bone Meal)

Pyrolysis (~450 – 500 0C)

Char (~35 wt%)

Pyrolysis gas (~65 wt%)

Pyrolysis oil

~85 %-a condensable

Not suitable as fuel:- relatively low energy density- chemical instability- corrosivity- immiscible with conventional fuels - environmentally hazardous

emission (e.g. NOx)

Reforming is needed !

Composition of pyrolysis oils

Pyrolysis oil of plant origin(e.g. from agricultural and forestry residues)

Pyrolysis oil of animal origin *

(e.g. from meat and bone meal (MBM))

C, wt%: 60H, wt% 7O, wt% 32N, wt% 1-----------------------------------------Density (kg/dm3): 1.12Heating value (MJ/kg) 21.3

(Zhang et al., Bioresource Technology 96 (2005) 545

C, wt%: 74H, wt% 12O, wt% 5N, wt% 9-----------------------------------------Density (kg/dm3): 0.97Heating value (MJ/kg) 36.5

Reforming:- Catalytic steam reforming to H2/CO mixture- Catalytic cracking and decarboxylation- Catalytic esterification

Reforming:- Catalytic steam reforming to H2/CO mixture- Hydrotreating (heteroatom removal)

- ~20 million tons of animal by-products in the EU 27 countries- environmentally dangerous waste (microbiological re- and trans-contamination)- incineration is not favored (fly ash, emission of furans, dioxins and NOx) → pyrolysis

*

Catalytic steam reforming of pyrolysis oils

CxHyNvOz + xH2O → xCO + (y/2+x-z)H2 + (v/2)N2 [1]

CO + H2O CO2 + H2 [2]

Products: H2,CO,CO2,N2, (CH4)

[1] highly endotherm[2] slightly exotherm

CatalystT a,0C

WHSV b,h-1 S/C c TOS d,

hXC.

e,wt%

Ni/K/ 750 8 (0.8) 5 7 97.9

γ-Al2O3f 750 4 (0.4) 5 35 >99

M-1 f

750 18 (0.8) 5 13 94.0

750 9 (0.4) 5 19 >99

700 9 (0.4) 5 24 >99

M-2 f700 9 (0.8) 5 11 >99

700 4.5 (0.4) 5 16 >99

M-2 g

700 9 (0.8) 5 12 >99

700 4.5 (0.4) 5 18 >99

700 4.5 (0.4) 3 23 >99

CatalystT a,0C

WHSV b,h-1 S/C c TOS d,

hXC.

e,wt%

Ni/K/ 750 8 (0.8) 5 7 97.9

γ-Al2O3f 750 4 (0.4) 5 35 >99

M-1 f

750 18 (0.8) 5 13 94.0

750 9 (0.4) 5 19 >99

700 9 (0.4) 5 24 >99

M-2 f700 9 (0.8) 5 11 >99

700 4.5 (0.4) 5 16 >99

M-2 g

700 9 (0.8) 5 12 >99

700 4.5 (0.4) 5 18 >99

700 4.5 (0.4) 3 23 >99

Product distribution[%]

H2 55-60

N2 10-15

CO 5-10

CH4 3-5

CO2 15-20

Product distribution[%]

H2 55-60

N2 10-15

CO 5-10

CH4 3-5

CO2 15-20

a Reaction temperature (the dolomite guard bed was kept always at 800°C). b Weight hourly space velocity based on the weight of the Ni-catalyst, not including the weight of the cordierite support (the values in parenthesis are the WHSV for the dolomite guard bed). c Steam to carbon molar ratio of the feed. d Time on stream. e Carbon conversion. f Catalyst was pre-reduced in H2 at 500°C. g The catalyst was used without pre-reduction.

Catalytic steam reforming of pyrolysis oil obtained from MBM

Catalytic hydrotreating of pyrolysis oils

CxHyNvOz + nH2 → CxH2x+2 + zH2O + vNH3

(heteroatom removal via HDO and HDN)

Unattractive process for pyrolysis oils of plant origin:- high H2 demand due to the high oxygen content (>30 wt%)

- useless H2O is formed as by-product

Feasible process for pyrolysis oils of animal origin:- relatively low H2 demand

- valuable NH3 is formed as by-product

N-compounds: aliphatic nitriles, amines and amides

Pyrolysis oil from MBM

+ H2

catalyst

Hydrocarbon fuel

+ NH3 (+H2O)

0

20

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200 250 300 350 4000

20

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Konv

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Hoza

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Ni2P/Szilikagél, WHSV= 1h-1, p= 30 bar

Szele

ktivit

ás, m

ol%

Hõmérséklet, °C

Konverzió

Ammónia

Propán

DPA

TPA

Ammónia

Propán

DPA

TPA

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200 250 300 350 4000

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Konv

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Ni2P/Szilikagél, WHSV= 1h-1, p= 30 bar

Szele

ktivit

ás, m

ol%

Hõmérséklet, °C

Konverzió

Ammónia

Propán

DPA

TPA

Ammónia

Propán

DPA

TPA

Catalytic hydrodenitrogenation (HDN) of propyl-amine model compound (preliminary experiment)

Ni2P/silicagel, WHSV= 1 h-1, p= 30 bar

Con

vers

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Yie

ld, m

ol%

Sel

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Conversion

Ammonia

Ammonia

Propane

Propane

Temperature, oC