Synthesis and Characterization of

Catalysts for BiofuelsKen Andrzejewski

Marian High School

NDRET 2012

“Engineering a More Sustainable Energy Future”

Center for Sustainable Energy at Notre Dame

P.I.: Dr. Jason Hicks

Graduate Student Mentor: Greg Neumann

Fossil fuels -nonrenewable resources -consumed at a tremendous rate -will eventually disappear -necessary to explore options to replace or enhance

the use of these fuels with renewable sourcesPlants

-naturally produce the structural organic compounds cellulose, hemicellulose and lignin

-large amounts of these materials are discarded or burnt as waste whenever crops are harvested

-potential energy sources, if we can develop a method to capture that energy

Catalytic Upgrading

Lignocellulosic Biomass Fine

Chemicals

FuelsWhy lignocellulosic biomass?-Abundant, with potential to decrease CO2 emissions-Quantity of fossil fuels is finite=Through catalytic conversion these biomass molecules can be converted to platform fuels and chemicals that can be dropped into current refineries

Slide courtesy of Greg Neumann

Cellu

losi

c Bi

omas

sSyn Gas

(CO + H2)

Bio-Oils

Aqueous Sugars

Lignin

Hydrogen

Methanol

Alkanes

Gasificatio

n

Fischer-

TropschMethanol Syn

Water-Gas Shift

Pyrolysis

Liquefaction

Hydrolysis

Used for Process Heat

Dehydroxygenation

Zeolite Upgrading

Aqueous Phase Processing

Liquid Fuels & Chemicals

Liquid Fuels & Chemicals

Ethanol

Aromatic Hydrocarbons

Liquid Alkanes or Hydrogen

Dehydration

Fermentation

Strategies for Upgrading Biomass

Graphic by Greg Neumann

Naturally occurring crystalline materialsShape SelectiveSolid Acid MaterialMFI structure selectively

produces aromatic hydrocarbons

. D. H. Olson,” G. T. Kokotailo, S. L. Lawton,J. Phys. Chem. 1981, 85, 2238-2243Gaertner, C. A.; Serrano-Ruiz, J. C.; Braden, D. J.; Dumesic, J. A., I&ECR 2010, 49 (13), 6027-6033.- Slide courtesy of Greg Neumann

Catalyst Design

Zeolite Catalysts

Larger PoresAllow larger molecules to fitMaintain selectivity of shape selective microporous

structure

Representations of ZSM-5 structural framework

Experimental and molecular simulation studies of a ZSM-5-MCM-41 micro-mesoporous molecular sieve

Microporous and Mesoporous Materials, Volume 118, Issues 1–3, 1 February 2009, Pages 396-402Chen Huiyong, Xi Hongxia, Cai Xianying, Qian Yu

Zeolite structure type MFI (example: Zeolite ZSM-5).

Teaching Materials that Matter: An Interactive, Multi-media Module on Zeolites in General ChemistryAmy H. Roy, Rachel R. Broudy, Scott M. Auerbach and Department of Chemistry, University of Massachusetts, Amherst, MA 01003-4510, vining@chem.umass.eduWilliam J. Vining*

The Chemical Educator, Vol. 4, No. 3, S1430-4171(99)03300-2, 10.1007/s00897990300a, © 1999 Springer-Verlag New York, Inc.

Synthesis of Zeolite HZSM-5 Catalyst

Various chemicals (Polymer F-127, Tri-Methyl Benzene, Aluminum Isopropoxide, Tetra-ethyl Orthosilicate, Tetra-n-propylammonium Hydroxide, DI Water) were combined in proportion in stages that involved heating, stirring and steaming.

This process takes 7-8 days.Produced 4 sample stocks of HZSM-5These were further prepared by calcination

Samples were analyzed using Physisorption

-pore size

-catalyst surface area

•As my synthesized samples were forming, previously synthesized samples were used to pyrolyze a feedstock.•Small quantities were measured and inserted into quartz pyrotubes Loading Quartz tube for pyrolysis

•Samples were pyrolyzed in the pyroprobe and analyzed for organic compounds harvested by the catalyst using the GC/MS.•Throughout my time in the lab, the method for GC/MS analysis was modified and improved, as this whole process is currently in developmental stages.

PyroprobeGas Chromatograph/Mass

Spectrometer (GC/MS)

Results:

AcetoneAcetaldehydeBenzeneCarbon MonoxideCarbon DioxideEthyl BenzeneFurans

IndaneMethyl NaphthaleneNaphthalenePhenolTrimethyl BenzeneTolueneXylene

Classroom Application

• Without the expensive instrumentation, it is not possible to repeat the lab work in a high school situation.•Since the focus of the research is the harnessing of energy from feedstock materials, we can use a lab that demonstrates the amount of energy contained in various fuel sources.

Measuring the Caloric Value of Various Fuels

Student Sheet 

The Purpose of this investigation is to determine how much energy is contained within different plant-based materials and chemicals which may typically be considered as waste

materials. These materials are sometimes referred to as feedstocks.  

Pre-lab (Day 1):In groups of 4: Discuss the terms Fuel and Energy. How are they related? What makes a material a good

fuel? What types of energy are there? Where is energy found? How can we determine how much energy is found within a given fuel sample?

Where does most of our energy come from for everyday needs? Why are we concerned about energy?

Discuss – Are heat and temperature the same thing? Explain your answer. Brainstorm and create a list of potential ‘waste’ fuel substances. Remember that the list

you put together should be materials that are readily attainable. When we have a finalized list, you will need to obtain/bring in the fuel materials your group has chosen.

Share with the class the results of the above steps. Complete the standard pre-lab write-up for this experiment. 

Calorimeter setup(Drawing courtesy of Nevin Longenecker – John Adams High School)

thermometer

stopper

Test tube

Fuel sample

Cork holder

Water

Soda can

Possible calorimeter set ups

http://www.flinnsci.com/store/Scripts/prodView.asp?idproduct=14881

Home-made Calorimeter

(photo courtesy of Nevin Longenecker)

Commercially available food calorimeter (Flinn Scientific)

Data TableType of Fuel

Mass of Fuel

Start Temp.

End Temp.

Temp. Change

Calories of Fuel Sample

Calories per gram

Calories per 100 grams

Kcal per 100 grams

Questions:Which fuel sample had the highest caloric

energy per gram? Which had the least? What explanation can you offer for the different values?

Where is this energy found within the fuel samples?

Energy in this lab is released in two forms. What are they?

What are some possible ways (other than burning) we might be able to harness the ‘leftover’ energy in feedstock substances?

Standards addressed:Chemistry:SCI.C.6 2010 - ThermochemistryRecognize that chemical reactions result in either the

release or absorption of energy.(C.6.1, C.6.2, C.6.3)Apply the law of conservation of energy. (C.6.4)

Biology:SCI.B.3 2010 - Matter Cycles and Energy TransferDescribe how the sun’s energy is captured and used to

construct sugar molecules that can be used as a form of energy or serve as building blocks of organic molecules. (B.3.1, B.3.2, B.3.3) Diagram how matter and energy cycle through an ecosystem. (B.3.4, B.3.5)

Pyrolysis Lab – in developmentPyrolysis of waste organic feedstocks to

form potential aromatic hydrocarbon materials

Technically torrefaction since temperature doesn’t really exceed 320 degrees C.

Solids are heated without oxygen (total vacuum)

‘Bio-oil’ vaporizes from solid and condenses back to liquid

Products are bio-oil (basically liquid smoke) and char (which may be condensed to charcoal)

Torrefaction/Pyrolysis SetupVacuum

pump

Ice Bath

Heat source

Fuel source

Tygon Tubing

First pyrolysis set up using Erlenmeyer flask and a hot plate. This worked, but flask was too large and there was a fear of the flask breaking due to heat.

Refined pyrolysis set up using Round Bottom flask and heating mantle. This produced results within 10 minutes of heating and took about 40 minutes to complete.

Final Run Setup

This is why coffee is bad for you:

Further ideas:In the future, I would like to test the bio oils using the

Vernier mini-GC probeware to see if the composition of the material can be determined.

http://www.vernier.com/products/sensors/gc-mini/

Thanks to:

Dr. Jason HicksGreg NeumannDallas RenselNick McNamaraThe rest of the Hicks Lab

Group

Nevin LongeneckerUniversity of Notre DameND RETcSENDRebecca Hicks & Jenny Frech2012 RET participants

Questions?