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