bio-processing case study: sampling, monitoring, & control

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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.

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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

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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

Novel gas fermentation technology captures CO-rich

gases and converts the carbon to fuels and chemicals

Making H2 On Demand

LanzaTech can use a Hydrogen free-gas for the production of ethanol

The ethanol molecule contains 6 Hydrogens:

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CO + H2O CO2 + H2

[H2]

• Microbe can make H2 from CO and water as required

• Any CO:H2 ratio can be used Reduces Need for Thermochemical WGS,

Improving Overall C Balance

Feedstock Flexible

Fuel production has been demonstrated with a wide range of available waste gas resources

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H2

CO

Gas Composition

A broad range of CO:H2 ratios can be used by the LanzaTech process

Industrial Flue Gas

e.g. from Steel Mill

Syngas Coal

Municipal Solid Waste (MSW)

Reformed Methane

e.g. Biogas

Biomass

Fuels & Chemicals Gas-to-liquid Conversion

LanzaTech Gas to Liquid Platform

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C4 • BDO • n-Butanol • i-Butanol • Succinic acid

H2 CO CO H2 CO2 CO2

Industrial Syngas: Biomass, Coal, Methane COG, Chemical Power

Native

Synthetic

Engineering Control Chemistry

Customized Catalysts

C2 • Ethanol • Acetic acid

C3 • i-propanol

C5 • Isoprene

Other • PHB • …….

Resources

Product Suite

Product Suite Thermochemical Approaches

Olefins Chemicals Chemical

Intermediates

Hydrocarbon Fuels (diesel, jet, gasoline)

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

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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

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

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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

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

SO2: 500ppm

NOX: 50ppm

Benzene: 0.12 mol% in gas

Toluene: 0.008 mol % in gas

Copper: 100µMol/L

Arsenic: 12μmol/L

Methane: >50% in gas

HCl: Buffered in media

Chromium: (II) 2mMol/L (III) 100mMol/L

Vanadium: 10µMol/L

Bromide: 100µMol/L

Iodide: 50µMol/L

CO2: >50% in gas

N2: >50% in gas

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Goal: Certain gases will contain different impurities; need various on-line low level impurity measurement for different gas feeds

Fermentation System – Bioreactor

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Internal Loop Reactors External Loop Reactors

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

Mass Transfer Estimation

Measure of reactor inlet, Cin, & outlet CO composition determines 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

CL – conc. of gas in liquid C* - gas solubility in liquid kL – overall mass transfer

coefficient aL – specific interfacial area

dtdCL

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

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Goal: singular structure that can be programmed to handle batch start-up, transition to continuous mode, and dynamic transition to steady-state

Artificial neural network

Product Recovery & Waste Water Treatment

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

Product recovery & waste water systems mature technologies with well developed control structures

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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