Microbial Desulfurization

CHBE446: Process Economics and Design 2

6 February 2014
Heather Cook
Savannah Green
Dave Weglein
Mike Wellen

Outline

Introduction & History

Mechanisms
Current Uses in Industry
Major Challenges & Advantages
Current Research

Introduction: What is
Microbial Desulfurization?
Also known as Biodesulfurization (BDS)
Biological desulfurization process where
microbial catalysts are used to oxidize sulfur
in crude oils

Introduction: Why is BDS

important?
Combustion of sulfur compounds leads to
production of sulfur oxides
High concentrations of sulfur oxides in the
atmosphere can lead to health issues such as
asthma, bronchial irritation, and lung cancer

Ability to desulfurize compounds that are

recalcitrant to the current standard
technology in the oil industry (Abin-Fuentes,
et al)

New Regulations

Sulfur content in crude oil ranges from

0.03% - 7.89%

Many crude oils are increasing in sulfur content

Clean Air Act Amendments introduced by

EPA in 1990 to restrict sulfur concentrations
in fuels

Reduce annual SO2 emissions

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

Anaerobic strain can degrade some of DBT

Products: biphenyl & H2S
Makes this a selective pathway
Advantage:
o Oxidation of hydrocarbons to undesired compounds
is minimal
Disadvantage:
o Reduced caloric content in fuel
o Specific activity for most isolated strains are
insignificant for alkylated DBTs
o

4S Pathway
Carbon-sulfur bond selectively cleaved

Bacteria Used

4S Pathway Enzymes

Reaction is energy-intensive and needs

cellular metabolism

The 4S pathway involves sequential

oxidation of the sulfur part and cleaving of
the CS bonds
Four main enzymes used in the 4S pathway

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

Uses FMH2 as cosubstrate

Step requires
oxygen and NADH
as well
o

Oxygen from
molecular oxygen

DszB Enzyme

40 kDa protein
Final step in the reaction

Rate limiting step

o

Present in cells in smaller amount in cytoplasm

DszD Enzyme

Uses FMN as a
substrate
Couples the
oxidation of NADH
to substrate
oxidation
Produces FMNH2 to
allow DszC and
DszA to work

Currents Uses in Industry

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

Produces Elemental Sulfur

Benefits of System

Deep H2S removal and recovery as elemental S, extremely low

SO2 emissions are achieved

Special costly equipment such as burners and reboilers are not

required. The regeneration and sulphur recovery section always
operate at atmospheric pressure and ambient temperature

Reliability of a natural process coupled with the efficiency of

dedicated engineering

Simple process configuration- and control with stable operation

Expensive chemicals such as those required for liquid redox

processes are not required. Only sodium hydroxide and
nutrients are needed

Broad and flexible operating range with short system start-up

times

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

Sulfide rich solution loaded to flash drum

Loaded to bioreactor
Lean solution returned to absorber
Elemental Sulfur seperated out
Bioreactor contents are recycled over settler
Concentrated slurry dewatered in centrifuge
Filtrate is cycled back
Small slipstream of clear solvent

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

Ben & Jerrys

Hellendoorn, Netherlands
Ice cream waste products converted into electricity
Desulfurized with Thiopaq
40% of factory's energy requirements
Operational 2011

Cargill

Starch processing company

Sulfate rich water treated with anaerobic bioreactor

Lenzig Ag

Viscose Fiber Production

2009 produced 568,600 tonnes

Produces range of secondary compounds

Some streams need to be discharged.

SULFATEQ system installed in 2002

McCain

Potato processing company

Receives biogas from anaerobic water treatment and
solids digester
To prevent corrosion of gas engine, Thiopaq converts
hydrogen sulfide to elemental sulfur
Longer life for gas engine.

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

Reduction in biocatalyst activity associated

with the generation of the end product (2hydroxybiphenyl)
Increase of bacterial desulfurization rate
through identification of certain genes
Overexpression of FMN reductase
Change in host strain for dsz genes

Advantages of BDS

Requires less energy and hydrogen

Operates at ambient temperature and
pressure with high selectivity
Decreased energy costs
Low emissions
No generation of undesired products

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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