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i nnova t i ve env i ronmenta l so lu t i ons
Valorization of Biofuel By-products
Shawn Samborsky1, Salman Safari2, Daniel Alessi2*
1KBL Environmental Ltd., 2University of Alberta
*alessi@ualberta.ca
Introduction
Privately owned and Northern company founded in Yellowknife, Northwest
Territories
Conventional activities include waste management, soil treatment and
environmental consulting
Reputation for innovation
Lifecycle management for wastes produced in bioindustrial processes
Leveraging research and cost savings toward waste valorization
Biofuels char case study
Lifecycle management
Waste produced in virtually all industrial sectors
Can be overlooked but needs consideration in context of overall project
Potentially very expensive
Opportunity in Waste
Even with very good planning inefficiencies exist
Leverage optimization toward greater problem solving
Applied research can be a valuable tool
Leveraged funding can help
Case Study – Biofuels Company
Produced char as by-product
Impacted with PAHs (particularly naphthalene)
Requires hazardous waste receiving facility
Approach
Review handling methods and identify inefficiencies
Provide solutions for reduced cost
Use savings to drive research which further reduces cost
Leverage cash and in-kind inputs toward grant funding (NSERC and MITACS)
Optimized equipmentNegotiated rates
Funded Research Waste Declassification Funded Research Waste Valorization
Operations change Cost savingsCost savings Operations change
Handling methods
Right sized bins and trucks
Negotiated best possible rates with disposal facilities
Optimized transport
Leveraged Funding
Saved ~30% on disposal and handling expenses
Used a portion to apply as in cash funding for MITACS internship
Added in-kind funding
Leveraged inputs toward NSERC
$18,000 becomes $50,000
Research
Literature review for best candidate technologies
Laboratory experiments for proof of concept
Intensive experimentation and condition optimization for best candidate technology
Developed new environmental analysis surrogate to replace costly TCLP
procedure
Validated methods with commercial lab
Selected treatments
Solvent extraction using ethanol.
Organophilic sorbents such as modified clay with quaternary amine.
Thermal desorption.
In-house Toxicity Characteristic
Leaching Procedure (TCLP)
Extraction fluid: Acetic acid diluted by DI water, pH~4.9.
0.75 g sample in 15 ml extraction fluid, mixed for 18 hours at 30 rpm.
Centrifugation at ~1500 g for 10 min and analysis of aliquots of supernatant.
Naphthalene concertation measurement:
UV-Vis Fluorescence Spectroscopy: naphthalene excitation wavelength: 272 nm,
naphthalene emission wavelength: 330 nm.
0
100000
200000
300000
400000
500000
600000
700000
800000
300 350 400 450
Co
un
ts/S
ec
Wavelength (nm)
0.1 ppm0.5 ppm1 ppm5 ppm
Char characteristics
C H N O S Ash
Concentration
(%)17.0±0.5 5.6±0.5 <0.2 44.3±0.8 <0.2 33
0
10
20
30
40
50
60
70
80
90
100
0 200 400 600 800
Mas
s (%
)
T (ºC)
Air
N2
Thermogravimetric analysis (TGA) of the char:
~45% water,
~8.6% volatile organic content
~8.4% fixed carbon
Scanning electron microscopy micrograph of the char.
Si Al Mg Ca Fe K
Concentration
(%)7.1±0.4 3.0±0.2 0.50±0.03 4.9±0.3 1.5±0.1 0.50±0.03
Solvent extraction
Agitating char in ethanol (10% and 40% (w/v)) for 30 hours.
Centrifugation followed by TCLP on solvent treated char.
The required volume of ethanol is too high.
char-controlChar/ethanol
(40% w/v)
Char/ethanol
(10% w/v)
Naphthalene in
leachate (ppm)6.40±0.05 4.2±0.4 1.42±0.05
Organophilic sorbent
Organo clay® courtesy of CETCO, USA, with 25-33% quaternary amine loading.
Magnetic organo clay was prepared by in situ growth of magnetite nanoparticles on the clay.
Running TCLP on mixtures of biochar and sorbents at different ratios.
Regenerating magnetic organo clay by heating it at 200 ˚C for 30 min.
Transmission electron microscopy micrograph of magnetic organo clay.
specific surface
area (m2g-1)pore volume (cm3g-1) Pore size (nm)
Organo clay 0.4 0.004 7.8
Magnetic organo clay 17.0 0.055 7.5
Organophilic sorbent: TCLP results
0
1
2
3
4
5
6
7
0.00 0.20 0.40 0.60 0.80 1.00
Nap
hth
alen
e co
nce
ntra
tio
n in
leac
hat
e (p
pm
)
Sorbent/char ratio
Organo clay
Magnetic Organo clay
0
10
20
30
40
50
60
70
80
90
100
Organo clay Magnetic Organo clay Regenerated MagneticOrgano clay
Nap
hth
alen
e R
emo
val (
%)
(sorbent/char ratio: 1/1)
Thermal desorption
Heat treatment of char samples under ventilation.
TCLP on treated samples
Temperature effect
Desorption time effect
Leachable naphthalene (ppm) Char(control) Char (120 ˚C)
After 2 hours
Char (200 ˚C)
After 2 hours
In-house TCLP 7.2±0.1 1.3±0.05 0.1±0.01
Commercial lab 10 NA 0.027
Leachable naphthalene (ppm) Char (200 ˚C)
After 30 min
Char (200 ˚C)
After 1 hour
Char (200 ˚C)
After 2 hours
In-house TCLP 0.38±0.01 0.1±0.01 0.1±0.01
Before after
desorption
Real time chemical analysis of offgas:
TGA-FTIR
0
0.1
0.2
0.3
0.4
500 1500 2500 3500
Ab
so
rba
nc
e
Wavenumber (cm-1)
Naphthalene
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
500 1500 2500 3500
Ab
so
rba
nc
e
Wavenumber (cm-1)
Naphthalene
Beginning of 200 ˚C
After 30 min at
200 ˚C
Next Phase
Pilot scale testing
Procure equipment for declassification
Leverage further costs savings toward waste valorization of char materials
Conclusions
Lifecycle analysis of clean tech facilities is crucial
Operational details can yield funds for research
Applied research and provide significant savings as well as derive higher value for
waste materials
i nnova t i ve env i ronmenta l so lu t i ons
Thank you and Acknowledgements
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