Evaporation Characteristics of a Liquid Bio-Fuel from Chicken Litter

Erik Tolonen
Dept. of Mechanical Engineering, University of Ottawa, Ottawa, Ont.

Introduction:
Bio-fuels can be produced from a variety of agricultural wastes and can provide many benefits:

Renewable source of energy and fuels Means of disposal of waste Source of bio-products and raw materials Reduce use of food crops for fuel

Introduction:
Pyrolysis is the process of converting solid combustible material into liquid bio-fuels and gases:

Heating of biomass to temperatures of approximately 200

oC

to 500 oC without oxygen

Fast Pyrolysis: Very short residence time (~1 sec.) Vapors rapidly quenched to form a liquid Gases flared

Introduction:
Bio-oil is a renewable fuel produced by the pyrolysis of waste bio-mass. However, it has considerable drawbacks which makes its use difficult:

Phase separation Contains oxygen which lowers the heating value High viscosity Acidic Polymerization Combustion residues

Introduction:
Agriculture Canada has been involved in a project to upgrade raw bio-oil to produce higher quality fuels and bioproducts:

Upgraded fuels Food additives Medical precursors for drugs and medicines Industrial chemicals

Production:
Dried raw chicken litter underwent thermochemical conversion in a packed bed fast pyrolysis reactor. The resulting product was a viscous dark fluid.

Stirred bed of stainless steel shot provided heat transfer to

the biomass

Reactor conditions maintained at 375 oC, 1 atm with

feeding rate of 1 g/sec.

Residence time of ~ 1 sec. Vapors condensed in a cold wall condenser

Packed Bed Reactor: Biomass

Introduction:
Auger
Reactor Vessel Bed Material Stir Bar Heating Element

Motor

Volatile Gases

Water Jacket Condenser

Liquids

Production:
Raw bio-oil contains two phases: an oil based fraction (heavy) which contains hydrocarbons and a water based fraction (light) containing dissolved compounds.

Phase separation occurred after the sample was allowed to

sit for 24 hours

The light fraction was separated from the heavy fraction

by decanting; a small amount of water remained dissolved in the heavy fraction

The heavy fraction was retained for further processing

Production:

Light Fraction

Heavy Fraction

Production:
The heavy fraction contains high levels of oxygen which lowers its heating value. To remove this microwave solvent extraction and column chromatography was used.

Microwave solvent extraction reduced the oxygen

concentration from 25% to 5%

Column chromatography was used to separate

hydrocarbons from the microwaved sample

Removal of water from the sample The fraction produced was a clear liquid with a slight odor

Production:
Raw Bio-oil Upgraded Bio-oil

Analysis:
Py-FIMS is a powerful method for the determination of compounds with high molecular masses.

Sample heated in a quartz furnace at a linear rate A high electric field ionizes the vapors Mass spectrometry analyses the ions produced Suitable for long chain hydrocarbons and large molecules Produces soft ionization, molecular ions without
fragmenting the molecules

Analysis:
Main Compound Families Identified
Paraffins CnH2n+2

Alkenes

CH2=CH-(CH2)n-CH3

Fatty Acids

CH3-(CH2)n-COOH

AlkyBenzenes

A-(CH2)n-CH3

Diols

OH-(CH2)n-OH

Analysis:
Main Compound Families Identified
Family: Paraffins Alkenes Fatty Acids Alky-Benzene Diols Other Percent: 24.2% 30.3% 13.0% 16.0% 12.0% 5.0%

Droplet Experiments
Experiments were performed on individual droplets using a moving furnace technique:

Droplets were suspended on a quartz fibre or a

thermocouple

A video camera was used to record the change in the

droplet size with time

Droplet diameter and temperature could be compared

with a droplet evaporation model

Nitrogen atmosphere prevented droplet ignition

Droplet Experiments

Droplet Experiments
A fine wire thermocouple with a cement bead was used to suspend a fuel droplet for some experiments. This allowed the determination of the droplet temperature as it evaporated.

Provides an approximate distillation curve to fit

composition for the preliminary model

Compared with the model using Py-FIMS data

Computational Model
Classical droplet evaporation theory:

quasi-steady state heat and mass transfer closely coupled constant transport properties constant pressure Td no chemical reactions

Tinf Vapor Flux rs Heat Flux

Computational Model
Classical droplet evaporation theory: d2: (mm2) Heating Vaporization d2s,0 T: (C)

T, boil

tv t: (s) t: (s) Temperature history for single component fuel only

tv

Computational Model
A continuous thermodynamics model was developed to predict the history of the fuel drops as they underwent evaporation:

The fuel contains multiple chemical families and

numerous components, it doesnt behave as a pure fuel

Each family of compounds is represented by a distribution

function characterized by its mean and standard deviation

The mean and standard deviation for for each family was
determined from Py-FIMS data of the sample

Computational Model
Continuous thermodynamics:

Describes complex mixtures by means of probability

density function

Computational Model
Gamma distribution function used to model each chemical
group, has been used successfully for conventional fuels

Chicken litter bio-oil has much higher boiling

temperatures then conventional fuels
Fuel: Initial Boiling Point (IBP) Final Boiling Point (FBP)

Refined Bio-oil
Diesel

460 oC
170 oC

530 oC
370 oC

Gasoline

37 oC

204 oC

Computational Model
The fuel was modeled using five groups with the
following distribution properties
Family: Paraffins Alkenes Composition: 24.2% 30.3% Mean: (kg/kmol) 380.0 380.0 Deviation: (kg/kmol) 40.0 50.0

Fatty Acids
Alky-Benzene Diols Other

13.0%
16.0% 12.0% 5.0%

390.0
380.0 390.0 -

20.0
40.0 20.0 -

Computational Model
Continuous Thermodynamics Model:

Governing equations for vapor phase (continuity, species,

energy) for one component, then integrated over
distribution function

Transport equations for distribution moments Analytical solution for gas phase concentrations and
temperatures

Numerical solution in time of droplet energy and mass

balance to get changing temperature and composition

Results:

Results:
Droplet Residue - 500 oC

Results:
Droplet Fibre Experiments 600 oC

0.0 sec

1.0 sec

2.0 sec

3.0 sec

4.0 sec

5.0 sec

6.0 sec

7.0 sec

Results:
Droplet Thermocouple Experiments 600 oC

0.0 0.0 sec sec

1.0 1.0 sec sec

2.0 2.0 sec sec

3.0 3.0 sec sec

4.0 sec sec 4.0

5.0 sec sec 5.0

6.0 sec sec 6.0

7.0 sec sec 7.0

Results:
Droplet Diameter Variation with Time 500 oC

Results:
Droplet Diameter Variation with Time 600 oC

Results:
Droplet Diameter Variation with Time 700 oC

Results:
Droplet Temperature Variation with Time

400 oC 300 oC

Results:
Droplet Temperature Variation with Time

600 oC 500 oC

Results:
Droplet Temperature Variation with Time 800 oC 700 oC

Conclusions:
Raw bio-oil was successfully upgraded into a higher quality fuel:

Composed of long chain hydrocarbon and related

compounds with a heating value comparable to conventional fuels

Temperature and evaporation results agree with

predictions of the model

Internal boiling was observed and residue formed by

pyrolysis during evaporation

Thank you:
This project would not have been possible without the support of the following people:

Dr. William Hallett - The University of Ottawa

Dr. Carlos Monreal - Agriculture Canada Dr. Peter Fransham - ABRITech Inc.

Dr. Gerald Jandl - The University of Rostock, Germany

Partial funding provided by NSERC

Any Questions?