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Studies of the Catalytic Conversions of Bio-Oils Obtained by Pyrolytic Decomposition of Non-Edible Biomaterials. Ferenc Lónyi. Institute of Materials and Environmental Chemistry Research Centre for Natural Sciences Hungarian Academy of Sciences. Biomass conversion. Product. Biomass.

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slide1

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

Ferenc Lónyi

Institute of Materials and Environmental Chemistry

Research Centre for Natural Sciences

Hungarian Academy of Sciences

slide2

Biomass conversion

Product

Biomass

Conversion

- Diversity

- Seasonal and disseminated occurrence

  • 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

Liquid fuel

- biodiesel

- ”green” diesel

- FT fuel

- lower alcohols

Produces

- vegetable oil

- algae oil

- energy plants

Biological

- aerobic and anaerobic fermentation

- enzymatic hydrolysis

Chemical (catalytic)

-transesterification of oils

- hydrorefining of oils

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

gasification of pyrolysis oil to

H2/CO mixture

Pipeline gas

- bio-methane

  • Wastes
  • - lignocellulosic
  • - communal
  • - industrial
  • animal
  • by-products
  • Thermal
  • - combustion
  • - gasification
  • Pyrolysis
  • (CO2 negative)

Electric energy

- fuel cell

- Gas turbine/generator

- Gas engine/generator

slide3

Pyrolysis

Char

(~35 wt%)

Pyrolysis gas

(~65 wt%)

Biomass

(e.g. Meat and Bone Meal)

~85 %-a

condensable

Pyrolysis (~450 – 500 0C)

Pyrolysis oil

  • Not suitable as fuel:
  • relatively low energy density
  • - chemical instability
  • corrosivity
  • immiscible with conventional fuels
  • environmentally hazardous
  • emission (e.g. NOx)

Reforming is needed!

slide4

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%: 60

H, wt% 7

O, wt% 32

N, wt% 1

-----------------------------------------

Density (kg/dm3): 1.12

Heating value (MJ/kg) 21.3

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

C, wt%: 74

H, wt% 12

O, wt% 5

N, wt% 9

-----------------------------------------

Density (kg/dm3): 0.97

Heating value (MJ/kg) 36.5

  • Reforming:
  • - Catalytic steam reforming to H2/COmixture
  • Catalytic cracking and decarboxylation
  • Catalytic esterification
  • Reforming:
  • - Catalytic steam reforming to H2/COmixture
  • 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
slide5

Catalytic steam reforming of pyrolysis oils

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

CO + H2O CO2 + H2 [2]

[1] highly endotherm

[2] slightly exotherm

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

slide7

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

Pyrolysis oil from MBM

Hydrocarbon fuel

+ H2

+ NH3(+H2O)

catalyst

N-compounds: aliphatic nitriles, amines and amides

slide8

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

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

Conversion

Ammonia

Conversion, Yield, mol%

Propane

Ammonia

Selectivity, mol%

Propane

Temperature, oC

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