Goran Jovanovic Oregon State University School of Chemical, Biological, and Environmental Engineering

Sweet Spot of Microtechnology In Affiliation With:

MBI Microproducts Breakthrough Institute

ONAMI Oregon Nanoscience And Microtechnologies Institute

goran.jovanovic@oregonstate.edu

Microreactor Technologies for Production of Advanced Liquid Biofuels

The study, development, and application of devices whose operation is based on the scale of 1-100 microns.

Microtechnology

(A human hair is approximately 100 microns thick.

Image source: http://www.flickr.com/photos/thestarshine/69591402/

goran.jovanovic@oregonstate.edu

Nature has selected the micro scale for the realization of many biological processes.

Leaf Alveoli Kidney

Nature’s Microtechnology

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What is Microtechnology Good For?

•  Production of information lab-on-chip

•  Production of services pacemaker kidney dialyzer

•  Production of energy and bulk material chemicals fuel upgrade biofuels nanoparticles

goran.jovanovic@oregonstate.edu

•  Microreactors for Biodiesel Production •  Microreactors for Production H2O2 •  Microreactor for Desulphurization of Fuels •  Microseparators for Liquid-Liquid Extraction •  Microreactors for Production of Veins and Arteries •  Microscale-Based Blood Oxygenation •  Microreactor for Destruction of Toxic Waste •  Microtechnology-Based Water Desalination •  Microsensor for Detection of Human Pathogens in Food and Water •  Microtechnology-Based Hydrogen Storage •  Microtechnology-Based Gas-to-Liquid FT Process 5

•  Microreactors for Biodiesel Production •  Microreactors for Production H2O2 •  Microreactor for Desulphurization of Fuels •  Microseparators for Liquid-Liquid Extraction •  Microreactors for Production of Veins and Arteries •  Microscale-Based Blood Oxygenation •  Microreactor for Destruction of Toxic Waste •  Microtechnology-Based Water Desalination •  Microsensor for Detection of Human Pathogens in Food and Water •  Microtechnology-Based Hydrogen Storage •  Microtechnology-Based Gas-to-Liquid FT Process

goran.jovanovic@oregonstate.edu

Hydrogenation of bio-oils

H2 H2 H2

H2

H2

H2

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Transesterification of bio-oils

CH3OH CH3OH CH3OH

Biodiesel Biodiesel Biodiesel

TG DG MG k3

k−3⎯ →⎯← ⎯⎯ Glycerol

k2

k−2⎯ →⎯← ⎯⎯

k1

k−1⎯ →⎯← ⎯⎯

Micro-Scale Reactors

First MECS micro-reactor, OSU 1999

goran.jovanovic@oregonstate.edu

Flow separator

Teflon spacer Quartz window

Gasket

Plate

Microreactors

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Microreactors

Biodiesel Phase

Microreactor

Glycerol Phase

Syringe Pump

Stock solution of methanol with dissolved NaOH in 10 ml syringe

ON/OFF

Soybean Oil in 60 ml syringe

Experimental Setup

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Various Views - Biodiesel Microreactor

Methanol

Crude Oil

Glycerol

Heating Fluid

Biodiesel

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Reaction Channels Oil Inlet Manifold

Oil/Glycerol Phase Separation Chamber

Oil/Biodiesel Phase Outlet to Second Stage

Glycerol Outlet

Methanol Inlets

Single Stage Biodiesel Microreactor

goran.jovanovic@oregonstate.edu

Two Stage Biodiesel Microreactor

First Stage Product Glycerol Stream

Second Stage Product Biodiesel Outlet First Stage

Oil Inlet

Second Stage Methanol Inlet

Second Stage Product Glycerol Stream

Heating Fluid Inlet/Outlet

First State Methanol Inlet

Second Stage

First Stage Methanol Crude Oil Glycerol

Heating Fluid

Biodiesel

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Exploded View - Biodiesel Microreactor

Second Stage

First Stage

Oil Inlet/Manifold First Stage Methanol Inlet/Manifold

First Stage Reaction Channels First Stage Product Glycerol Outlet

Fluid Driven Thermal Plate

First State Separation Chamber

First Stage Oil Phase Outlet

Second Stage Oil Phase Manifold

Second State Separation Chamber

Second Stage Methanol Inlet/Manifold

Second Stage Reaction Channels

Second Stage Product Glycerol Outlet Second Stage

Product Biodiesel Outlet

Heating Fluid Inlet/Outlet

Methanol Crude Oil Glycerol

Heating Fluid

Biodiesel

goran.jovanovic@oregonstate.edu

Micro-Reactor Design

Major design consideration was to preserve the gas-liquid segmented flow in the microchannels. The solution chosen was to implement a single, long microchannel on a horizontal plane that wraps back and forth on a single plate (It could be used as a device with multiple, parallel channels).

The plate is 267mm X 187mm in size and made from 0.5mm thick (316) stainless steel.

The overall channel length is 16,740mm

−1Sc

dNTG

dt at  wall

= ′′k CH2CTG

at  wall mol

mcat2 s

⎡

⎣⎢

⎤

⎦⎥Reaction Rate:

Reactant-H2 Phase 1 Reactant TG

and intermediates

Catalyst

d1 d2

d3 d4

Fluid input hole

Catalyst deposition hole

Alignment hole (for bonding)

Hole for clamp bolt

Installed Micro-Reactor Assembly

Input tube

Output tube

Thermal

insulation

Hydrothermal Treatment of Plate Microreactor in Heated Enclosure

Ci

CTGo

Residence Time [min]

Triglycerides

Diglycerides

Monoglycerides Fatty Acids Alkanes

Groups of Laminae create one

“Block-Stage”

Integrated and Parallel processing

2m

1m

Advantages of Microtechnology

•  Advantages arising from Fundamental Phenomena;

•  Advantages arising from Parallel Architecture;

•  Advantages arising from Commercial Applications;

•  Advantages in the area of Safety and Security.

goran.jovanovic@oregonstate.edu

Fundamental Advantages of Microtechnology

•  Intensification of Heat and Mass Transport - Small scale - Short time of mass and heat transport (τ =l2/D) •  Reduced Size - 10-100 times reduction in hardware volume over conventional technology; - 5-50 times reduction in hardware mass; - Shifts size-energy trade-offs toward higher efficiency; - Able to integrate heat exchanges with reactors and separators simplifying processes. •  Large surface to volume ratio (105-108 m2/m3) •  Changes chemical product distribution

Large surface to volume ratio (105-108 m2/m3)

goran.jovanovic@oregonstate.edu

•  Low Pressure Drop Reduces power for pumps, fans, and blowers;

•  Gravity independence Gravity effect diminish to surface and hydrodynamics forces as size of channels decreases;

•  High Degree of Reaction Control Minimizing unwanted environmental and side reactions; Minimize unwanted reversible reactions; Enables processing of very energetic reactants; Intensification of chemical kinetics (the last frontier in mass transport)

•  Extremely High Quench Rates Small reactant volumes mean less mass or energy required to quench; Extremely rapid heat transport enables fast thermal discharge.

Fundamental Advantages of Microtechnology

goran.jovanovic@oregonstate.edu

Advantages of Microtechnology-Parallel Architecture

•  Fast screening of materials, catalyst and processes •  Flexibility in capacity and in design

- Provides for deployment at wide range of scales; - Facilitates gradual expansion of capacity as scale of operations grows by adding more modules;

•  Operating robustness and controllability - Enhances reliability, allowing problems to be isolated and repaired.

•  Mass Production of Microscale Components - Microlamination process enables mass production; - Bonded stacks can contain multiple processes; - Multiple processes in a single device reduces field assembly and

testing.

Flexibility in capacity and in design

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Commercial Advantages of Microtechnology •  Lower capital investment; •  Lower operating cost; •  Faster transfer of research to commercial production; •  Earlier start of production at lower cost - Reduces life-cycle costs through early testing at implementation scale;

•  Easier scale up (numbering -up) to production capacity; •  Distributed technology implementation (distributed production);

•  Integration of micro-technologies with other systems; •  Lower cost of transportation of material and energy; •  Replacing batch with continuous processes.

Distributed technology implementation (distributed production);

Integration of micro-technologies with other systems;

goran.jovanovic@oregonstate.edu

goran.jovanovic@oregonstate.edu

Safety and Security Advantages

•  Small channel inhibits flame/explosion front propagation;

•  Small volumes translate to low energy content stored;

•  Smaller volume less hazardous materials in the process.

Large surface to volume ratio

Flexibility in capacity and

design

Distributed production

Integration with other systems

Sweet Spot

Sweet Spot of Microtechnology

goran.jovanovic@oregonstate.edu

goran@engr.orst.edu

People. Ideas. Innovation.

Thank you for your attention!