Octane Enhancers from Crop Oils

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Octane Enhancers from Crop Oils Wayne Seames,
Principal Investigator Professor of Chemical
Engineering University of North Dakota Skip
Byrnes, FAA Technical Monitor
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Octane Enhancers from Crop Oils Project
Objectives

• To generate octane enhancers for 100LL AvGas
• Make compatible for blending with alkylate
• Meet all 100LL specifications
• To extend the petroleum fuel supply using
  renewable source blendstock
• To reduce or eliminate the need for
  tetraethyl lead additives as an octane booster

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Octane Enhancers from Crop Oils

• Senior Personnel
• Wayne Seames, Professor, Chem Eng
• Darrin Muggli, Professor, Chem Eng
• Alena Kubatova, Assistant Professor, Chemistry
• Michael Mann, Professor, Chem Eng

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OUR VISION THE CROP OIL REFINERY

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OUR VISION THE CROP OIL REFINERY

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Octane Enhancers from Crop Oils Process Flow
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Octane Enhancers from Crop Oils Project Tasks

• Optimize aromatics rich organic liquid product
  (OLP) via catalytic cracking in progress
• Demonstrate feasibility to alkylate some of the
  aromatics to improve volatility, octane, and
  freeze point - complete
• Develop process at lab-scale and assess
  feasibility in progress
• Set up small engine testing system in progress
• Make 100 Octane AvGas samples and test in
  progress
• Generate sufficient quantities of AvGas for
  engine testing post project task

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Octane Enhancers from Crop Oils Optimization of
an aromatics-rich organic liquid product (OLP)
Results Doped HZSM-5 increased yield of
aromatics-rich OLP significantly
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Octane Enhancers from Crop Oils Optimization of
an aromatics-rich organic liquid product (OLP)

• Results Doped HZSM-5 increased concentration of
  aromatics in the OLP significantly

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Octane Enhancers from Crop Oils Optimization of
an aromatics-rich organic liquid product (OLP)

• A detailed study was conducted to evaluate how
  important factors affect OLP yield. Factors found
  to be significant were
• Reaction Time
• Reaction Temperature
• Catalyst Amount

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Octane Enhancers from Crop Oils Optimization of
an aromatics-rich organic liquid product (OLP)

• A detailed study was conducted to evaluate how
  important factors affect coke (tars) formation.
  The same factors were found to be significant
• Reaction Time
• Reaction Temperature
• Catalyst Amount

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Octane Enhancers from Crop Oils Optimization of
an aromatics-rich organic liquid product (OLP)

• Optimal conditions further refined with doped
  HZSM-5

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• Octane Enhancers from Crop Oils
• Barriers to Success

• Coke formation on catalyst reduces carbon
  by-products and increases complexity of process
• Aromatics specification meet it or get a
  waiver?
• Spec due to high volatility of benzene and
  toluene
• Heavy aromatics have low volatility and do not
  have the same level of inhalation hazard as
  benzene and toluene
• Blendstock Quality
• Balance between processing costs versus handling
  and blending costs
• Make very high octane concentrate?

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Octane Enhancers from Crop Oils Aromatics rich
organic liquid product (OLP)

• Barriers to Success
• Coke formation on catalyst
• Nanocatalyst development in progress
• Generation of aromatics without catalyst
• From light ends olefins in progress
• From OLP olefins scheduled

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Octane Enhancers from Crop Oils Nanocatalyst
development Reforming olefins from light ends
RESULTS Using the doped nanoHZSM-5 catalyst, a
high fraction of propylene was converted into
aromatics.
Compared to standard HZSM-5, coke formation was
substantially lower.
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Octane Enhancers from Crop Oils Feedstock
Flexibility

• Work performed at Cal Poly Pomona by
  undergraduates to expose them to research as a
  possible career path
• Objective Crack a variety of crop oils and
  compare organic liquid product yield and
  composition

10 Oils Processed Soybean, Canola, High Oleic
Canola, Cottonseed, Corn, Cuphea, Linseed,
Camelina, Crambe, and Juncea
From left to right Elfira Sidharta, David
Rodriguez, Elizabeth Scott
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Octane Enhancers from Crop Oils Feedstock
Flexibility

• Experiments - in progress
• Analytical work - in July when samples received
  at UND
• Correlations of yield/composition to feedstock
  composition - in August

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Octane Enhancers from Crop Oils Very High Octane
Concentrate

• APPROACH
• Remove the benzene/toluene from the organic
  liquid product, then convert into heavy aromatics
  and cycloparaffins
• Extractive distillation with sulfolane is
  demonstrated process in similar applications
• Start with model compounds
• Benzene extraction at UND
• Toluene extraction at CPP

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Octane Enhancers from Crop Oils CPP Toluene
Extraction Study
Procedure Toluene mixed with hexane, then mixed
together with sulfolane either with or without
water. Then the organic and aqueous phases are
separated.
From left to right Lawrence Hadipranoto, Ken
Nguyen and Steven Castaneda

• Experiments complete
• Analytical at UND in progress

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Octane Enhancers from Crop Oils UND Benzene
Extraction

• Similar experiments to those at CPP being
  performed at UND for benzene in hexane and
  extraction with sulfolane in progress
• Aromatic rich OLP being generated in sufficient
  quantities to perform small scale extraction
  tests in progress
• Aromatic rich OLP will be generated in larger
  quantities to perform lab-scale extractive
  distillation tests next fall

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Octane Enhancers from Crop Oils Other Work In
Progress/Planned

• Generating sufficient quantities of aromatics
  rich OLP to
• Convert to heavy aromatics and cycloparaffins
• Test octane number and other key AvGas properties
• Blend with alkylate to make 100 Octane AvGas
  meeting all key specifications
• Further develop doped nanoHZSM-5 catalyst for low
  coke aromatics production
• Research the feasibility of converting olefins
  from high olefin OLP into aromatics-rich OLP and
  then into AvGas
• Eliminates need for catalyst
• Increases yield of carbon co-products
• Allows co-production with other co-products
  currently developed for commercialization such as
  short chain fatty acids, jet fuel, and diesel
  fuel

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Octane Enhancers from Crop Oils Other Work In
Progress/Planned

• Set up AvGas engine test system
• Rotak 912 4 stroke aircraft engine
• Operational test stand
• Load by dynamometer
• 0.4 liters/min fuel consumption
• Generate sufficient aromatics-rich OLP, then
  AvGas to run engine tests
• Process depends on results of OLP rich olefins to
  aromatics tests
• Requires bench-scale production by adapting
  existing bench scale jet fuel production unit

Existing Diesel On Test Stand
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Octane Enhancers from Crop Oils Co-Funded by
Bayer Crop Science