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Outline
Introduction: What is
Microbial Desulfurization?
Also known as Biodesulfurization (BDS)
Biological desulfurization process where
microbial catalysts are used to oxidize sulfur
in crude oils
New Regulations
BDS Overview
Increased interest over last 20 years
Desulfurizes wider range of compounds then
conventional hydrodesulfurization (HDS)
Three pathways
Kodama (destructive)
Anaerobic (selective)
4S (specific oxidative)
4S is the most popular/effective
Mechanisms
Kodama Pathway
Sulfur not selectively
cleaved from
dibenzothiopene (DBT)
Carbon-carbon bonds
broken
Metabolize DBTs &
convert to water soluble
compounds
Water soluble products
inhibits further microbial
growth & DBT oxidation
Anaerobic pathway
4S Pathway
Carbon-sulfur bond selectively cleaved
Bacteria Used
4S Pathway Enzymes
DszC Enzyme
45 kDa protein
Catalyzes DBT->DBTO->DBTO2
Step uses oxygen, NADH, and FMNH2 for
activity
DszA Enzyme
50 kDa protein
Transforms sulfone
into sulfinate
o
Step requires
oxygen and NADH
as well
o
Oxygen from
molecular oxygen
DszB Enzyme
40 kDa protein
Final step in the reaction
DszD Enzyme
Uses FMN as a
substrate
Couples the
oxidation of NADH
to substrate
oxidation
Produces FMNH2 to
allow DszC and
DszA to work
Thiopaq
Biogas
Vent air
Refinery Gas
Hydrogen Sulphide
120 Installations World-wide
Reduces to under 25 ppm
Fluctuating Gas Flows
Low maintenance
Ambient Pressures an Temperatures
Benefits of System
More Benefits
Limited utility requirements
Ease of operation. Produced biosulphur is hydrophilic and behaves like a
relatively stable suspension without clogging or other nuisances
Environmentally friendly process based on naturally occurring bacteria
Inherently safe operation:
no free H2S downstream absorber
ambient temperatures for the whole system (solution
temperatures of 25 40 C)
bioreactor and sulphur recovery at atmospheric pressure.
Produced biosulphur is the basis for a range of new agricultural
products designed to act as (ingredients for) liquid fertilizers and liquid
fungicides
Steps of Process
Industrie Eerbek
Netherlands treats water from three
neighboring paper mills
Biogas used to produce electricity
1% to 25 ppm
Thiopaq system was installed in 1993
Hellendoorn, Netherlands
Ice cream waste products converted into electricity
Desulfurized with Thiopaq
40% of factory's energy requirements
Operational 2011
Cargill
Lenzig Ag
McCain
Other Examples
WaterStromen
Hulshof Royal Dutch Tanneries
Weltec BioPowr GmbH
Tempec
Nine Dragons
Smurfit Kappa
Challenges, Advantages
& Current Research
5 Step Process
Production of active resting cells with high
specific activity
Preparation of biphasic system containing oil
fraction, aqueous phase and biocatalyst
BDS of wide range of sulfur compounds at
acceptable rate
Separation of desulfurized oil fraction, recovery
of biocatalyst and return to bioreactor
Efficient wastewater treatment
Major Challenges
Biocatalyst activity improvement
Biocatalyst longevity improvement
Phase contact and separation
Process engineering research
Current Research
Advantages of BDS
Questions?
References
Abin-Fuentes, A., M. E.-S. Mohamed, D. I. C. Wang, and K. L. J. Prather.
"Exploring the Mechanism of Biocatalyst Inhibition in Microbial
Desulfurization." Applied and Environmental Microbiology 79.24
(2013):
7807-817. Web. 6 Feb. 2014.
Mohebali, G., and A. S. Ball. "Biocatalytic Desulfurization (BDS) of
Petrodiesel Fuels."Microbiology 154.8 (2008): 2169-183. Web. 6 Feb.
2014.
Ohshiro, Takashi, and Yoshikazu Izumi. "Microbial Desulfurization of Organic
Sulfur Compounds in Petroleum." Bioscience, Biotechnology, and
Biochemistry 63.1 (1999): 1-9. Web. 6 Feb. 2014.
Paqell | THIOPAQ O&G - Biological Gas Desulpherisation and Sulphur
Recovery | Paqell."Paqell | THIOPAQ O&G - Biological Gas
Desulpherisation and Sulphur Recovery | Paqell. Paqell BV, n.d. Web
Feb. 2014.
Soleimani, M., Bassi, A., and Margaritis, A. 2007. Biodesulfurization of
refractory organic sulfur compounds in fossil fuels. Biotechnol. Adv.
25(6):570-96.
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