Griffin LanzaTech - 20 July 2011 MAS

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Bio-Processing Case Study:

Sampling, Monitoring, & Control for


Gas Fermentation to Fuel & Chemicals

Derek Griffin

CPAC Summer Institute


20 July, 2011
University of Washington

© 2011 LanzaTech Inc. All rights reserved.


The LanzaTech Process

Novel gas fermentation


technology captures CO-rich
gases and converts the carbon
to fuels and chemicals

Gas feed stream

Gas reception Compression Fermentation Recovery Product


tank

• Gases are sole source of energy


• Production of fuels and chemicals
• Potential to make material impact on the future energy pool (>100s of billions of gallons
per year)
• Completely outside of the food value chain
• Biofuel and carbon capture technology solution

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Making H2 On Demand

 LanzaTech can use a Hydrogen free-gas for the


production of ethanol

 The ethanol molecule contains 6 Hydrogens:

CO + H2O CO2 + H2

[H2]

• Microbe can make H2 from CO and


water as required
Reduces Need for • Any CO:H2 ratio can be used
Thermochemical WGS,
Improving Overall C Balance
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Feedstock Flexible
Gas
Composition
Industrial Fuels & Chemicals
Flue Gas
e.g. from Steel Mill Gas-to-liquid Conversion
CO
Syngas
Coal
Municipal Solid
Waste (MSW)

Reformed Methane
e.g. Biogas
H2

Biomass

A broad range of CO:H2 ratios can


be used by the LanzaTech process

 Fuel production has been demonstrated with


a wide range of available waste gas resources
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LanzaTech Gas to Liquid Platform
Resources CO H2 H2 CO2 CO2
CO
Industrial Syngas: Biomass, Coal, Methane COG, Chemical Power

Native
Customized Engineering
Control
Catalysts
Synthetic Chemistry

C2 C3 C4 C5 Other
• Ethanol • i-propanol • BDO • Isoprene • PHB
Product Suite • Acetic acid • n-Butanol • …….
• i-Butanol
• Succinic acid
Thermochemical Approaches
Hydrocarbon Fuels
Product Suite (diesel, jet, Chemical Chemicals
gasoline) Intermediates Olefins

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Process Overview

 3 Main Sections to LanzaTech Process


– Gas Conditioning
– Anaerobic Gas Fermentation
– Product Recovery

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Gas Conditioning & Clean-up

 Key Measurements:
– Inlet gas composition – On-line Gas Chromatography (GC)
• Measure CO, CO2, N2, H2, CH4, O2, & H2S
– Gas temperature and pressure
– Gas flowrate

 Bioreactor system operates at 8-10 bar


– Low pressure gases require up to 4 compression trains
– Compression sizing and design based on inlet gas flowrate, pressure, and overall
composition
– Need to account for pressure drop through deoxygentation and gas-cleanup

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Deoxygenation

 Anaerobic fermentation requires reduced


oxygen content O2 levels < 100
ppm
– Deoxygenation vessel size, temperature, and
residence time based on gas flowrate, inlet O2
level, and catalyst activity
 Continuous gas streams require accurate O2
measurement in and out of deoxygenation bed
– Simple feed-forward and feed-back control can
be used for changes in inlet and outlet gas
respectively

 Some gas streams are intermittent (steel mill BOF gas)


requiring gas holder(s)
– Improved process robustness with multiple gas holders that
can be tested for O2 & contaminant levels before using gas
as fermentation feed
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Gas Clean-up

 LanzaTech process can tolerate high levels


of impurities so extensive gas cleanup may
not be necessary
– Microbes tolerant to H2S up to 2%
• Can be measured by GC
– Currently testing BTEX up to 500 ppm in
laboratory
– Contaminant testing currently performed
off-line to measure levels of BTEX, HCN,
NH3, etc..
 Microbes require low level of sulfur in
fermentation broth
– Inlet gas may provide sulfur in form of H2S
eliminating requirement for sulur
component in media preparation

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Contaminants

The addition of multiple potentially toxic, Gases, Metal Ions


and organic contaminants have been tested off-line:

 H2S: 2% in gas feed  Chromium: (II) 2mMol/L


 SO2: 500ppm (III) 100mMol/L
 NOX: 50ppm
 Benzene: 0.12 mol% in gas  Vanadium: 10µMol/L
 Toluene: 0.008 mol % in gas  Bromide: 100µMol/L
 Copper: 100µMol/L  Iodide: 50µMol/L

 Arsenic: 12μmol/L  CO2: >50% in gas

 Methane: >50% in gas  N2 : >50% in gas

 HCl: Buffered in media

 Goal: Certain gases will contain different impurities; need various


on-line low level impurity measurement for different gas feeds 10
Fermentation System – Bioreactor

 Air-lift bioreactors are commonly


used for fermentation over
stirred tank reactors
– Gas well mixed
– Homogeneous 3-phase
mixture
– No agitator or stirrer,
minimal cell shear & lower
power consumption
– Pressure difference between
riser and downcomer aids in
fluid circulation
– Fewer internal moving parts
= better sterilization
Internal Loop Reactors External Loop Reactors

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Mass Transfer Estimation

 CL – conc. of gas in liquid


 C* - gas solubility in liquid
 kL – overall mass transfer
coefficient
 aL – specific interfacial area

dC L
 Measure of reactor inlet, Cin, & outlet CO composition determines
dt
 Gas solubility, C*, depends on headspace pressure & reactor
temperature which are monitored and controlled
 Other variables that contribute to G/L mass transfer
– Gas/liquid holdup
– Bubble size/number distribution effects aL
– Gas velocity (mean residence time) effects boundary layer and kL
– Mixing times & Turbulent/Laminar Flow also effects kL 12
Potential Control Structures
 Multiple inputs/outputs & complicated process model
combining 3-phase bioreactor hydrodynamics and microbial
reaction system
– Numerous unique bioreactor ‘scenarios’ and overall system
non-linearity eliminate use of simple feedback control
 Model predictive control requires extensive data-base covering
all possible ‘scenarios’
 Fuzzy Logic – apply a ‘truth value’ to
variables in different scenarios
 Neural Net - more complex, adaptive,
computational model. Can be taught or
trained on various scenarios

 Goal: singular structure that can be


programmed to handle batch start-up, Artificial neural network
transition to continuous mode, and dynamic
transition to steady-state 13
Product Recovery & Waste Water Treatment

Product recovery &


waste water systems
mature technologies
with well developed
control structures

1. Broth concentration measured entering recovery section


2. Metabolites leaving product recovery measured entering water treatment
3. Nutrients and metabolites measured in water recycle to media preparation
– Need to be able to accurately measure low levels of salts & minerals

 Anhydrous ethanol product, waste water purge, & biomass purge also
monitored to ensure within target specifications 14
Media Preparation

 Continuous media preparation requires inputs from gas stream


composition and nutrient concentration in water recycle
 Water treatment & gas flow is continuous while media is prepared
in batches
 Currently Investigating dissolved O2 measurement in media
– Requires costly in-situ monitor that can measure ppb levels
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Summary

 LanzaTech’s gas fermentation technology differs from


conventional biological fermentation processes due to gasesous
feedstock and G/L mass transfer issue of nearly insoluble gases

 Conventional sampling, monitoring, and control can be achieved


for gas conditioning and product recovery sections
 Biggest challenge surrounds bioreactor
– In-situ measurements of G/L ratio, dissolved CO, metabolite &
nutrient concentrations are current challenges
– Numerous inputs & outputs based on biological system requires
detailed process model & complicated control structure
– Bioreactor & microbial behavior can drastically change depending
on microbe, gas feed, and/or metabolites produced requiring unique
process models and control schemes

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 Questions & Comments:
[email protected]

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