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Information for New Graduate StudentsF ll 2010
Engineering and Chemistry forFall 2010
Engineering and Chemistry for Sustainable Technologygy
Charles A Eckert and Charles L LiottaCharles A. Eckert and Charles L. LiottaSchool of Chemical & Bimolecular Engineering
School of Chemistry and BiochemistrySchool of Chemistry and BiochemistrySpecialty Separations CenterG i T h Atl tGeorgia Tech, Atlanta
1
“Sustainable” is not just hugging ahugging a
tree…
2
It’s getting everyone to hug a treeIt s getting everyone to hug a tree
3
Chemical Engineering and Chemistryg g y21-Year Collaboration
• Jointl Directed PhD St dents• Jointly Directed PhD Students49 Completed12 In Progress12 In Progress
• ~50 Joint ResearchGrantsGrants
• ~250 Publications and Presentationsand Presentations
• 2004 Presidential Green ChemistryGreen Chemistry Challenge Award 4
Current Group – ChEs and Chemists • Students – All Co-AdvisedStudents – All Co-Advised
PhD Candidates: Ryan Hart, Ali Fahdel, Greg Marus, Emily Nixon, Kyle Flack, Swetha Sivaswamy, Olga Dzenis, Will , y , y, g ,Heaner, Mike Mojica, Amy Rohan, Jackson Switzer, Wilmarie Medina Undergraduates (9 at present)Undergraduates (9 at present)
• Staff Senior Scientists and Postdoctorals – Pamela Pollet, BethSenior Scientists and Postdoctorals Pamela Pollet, Beth Cope, Rani Jha, Manjusha Verma, Elizabeth Biddinger, Manish TalrejaCoordinator, Deborah BabykinCoordinator, Deborah Babykin
• Other CollaboratorsOther GT Students and Faculty S d d l O h i i iStudents and Faculty at Other UniversitiesIndustry Partners 5
We Work TogetherWe Work Together• Each Problem Has a TeamEach Problem Has a Team
Multilevel, Multidisciplinary• Each Person Is on MultipleEach Person Is on Multiple
Teams• AdvantagesAdvantages
Not All Problems Are FourYears
Facilitates CommunicationsAble to Do High Risk, High Return Research Michelle Kassner, PhD ChBE, 2008,
Chevron; Tori Blausucci, PhD ChBE. 2009. ExxonMobil6
What Do We Do – and Why?y• Tunable Solvents
Supercritcal FluidsNearcritical FluidsGas Expanded Fluids
• Smart Solvents• Advantages
BenignBenignBetter Transport PropertiesFaclile Downstream Processing
Ryan Hart, 4th Year PhD Student, ChBE
Faclile Downstream Processing7
Examples of Sustainable Technology• Goals
Environmentally Benigny gCost-Effective
• Energy Applicationsgy ppCO2 Recovery from Flue GasBenign Harvesting of Tar Sands and Oil Shale
• Green PharmaceuticalsHeather Patrick PhD ChBEContinuous Reactions for Pharma
Benign Reactions in Nearcritical WaterC li R i S i
Heather Patrick, PhD ChBE, 2000, Emory University
Coupling Reaction + SeparationsHomogeneous Catalyst Recycle 8
Example: Smart Solvent Replacement for Supersolvent DMSOfor Supersolvent -- DMSO
• Product Isolation from DMSOAdd water, precipitateExtract with another organic
• Problems with DMSO Removal S
O
• Problems with DMSO RemovalIsolation is product dependent.Contaminated aqueous waste
CH3H3CDimethyl sulfoxideq
No solvent recycling• Smart Solvent – Changes Properties on Command
As good as DMSODecomposes into Volatile Fragments on CommandEasy to RemoveEasy to RemoveCan be Reformed and Recycled Later 9
DMSO-like Solvent Has “Built-In” RecyclePipyrlene SulfonePipyrlene Sulfone
S
O
+ SO2
m.p. = –12 °C b.p. = 42 °C -10 °CO
• Solvent Properties Comparable to DMSO • T-Based Switch Decomposition ~110°CT-Based Switch, Decomposition ~110 C• Reaction is Reversible
ilib i d d• Equilibrium and Rates Are Good10
Potential Process CycleExtraction or Reaction with Smart Solvent
R R iReverse ReactionReformulatesPolar, High-
ReturnReformed
SolventBleed GaseousSolvent Fragmentsg
Boiling Solvent From Separator
SolventDecomposes toLow-Boiling
Dissolution or Reaction Occursin Polar High-
Feed
i hdLow BoilingFragments
in Polar, HighBoiling Solvent
WithdrawProduct
11
Example: Reversible Ionic LiquidsCO S h R b H
NR N
R HCO2 Switch, Reverse by Heat
N
N N
N
N NMeOH
1 atm. CO2N N
O2COMe
2
N2 CO2
2
Non-polar Ionic
Li id
CO2
pLiquid LiquidN2 or heat
12
Process: Claisen-Schmidt Reaction and Separation Using Smart Ionic LiquidSeparation Using Smart Ionic Liquid
1- Pentane,MeOH;4h
OO
MeOH;MgSO4
2-CO2
4h, 80oC
O
O
H+
2
REACTION SEPARATION
+ H 2O
4h, 80oC80oC
REFORMATIONRECYCLE
TMBG Ionic Liquid Pentane 13
CO2 Recovery from Power Plants 2 y fUsing Single-Component Silyl RevILs
• Dual Mechanism Solvent AbsorptionChemical Absorptionp
By Reaction of CO2 with RevILs
Physical AbsorptionBy Dissolution of CO2 in RevILs
• Increases Capacityp yBetter Separation with Less Energy Penalty
14
Assay Both Thermodynamics and Rates i h Si l P Di d ATR IR C llwith Single-Pass Diamond ATR IR Cell
• Ample Adsorption in Single Pass• Custom Cell, Small Volume – No Transport
Limitations • Temperature-Controlled• Rapid and Accuratep
15
Multifaceted Approach: Discovery and UseSynthesis of Amine
Precursors
Investigation of New MoleculeThermodynamicInvestigation ofPhysical Properties
New Molecule Characterization
Thermodynamic Properties
Structure-Property Analysis and Simulationand Simulation
Design and Application to Coal-Fired Power Plants 16
ASPEN Flow SheetSimulation Results
• Industry Standard Design Software
Simulation Results$ per ton of CO2 removed
Fixed Costs 4.50Regeneration 3.61Software
• Permits Process Alternatives
gEnergy (Steam)
Electricity 4.06Cooling Water 0.87Alternatives,
Optimization• Calculates Flows, Rates,
Materials 2.16Total 15.20
C cu es ows, es,Energy, Economics
17
RevILs for Harvesting Hydrocarbons f T S d /Oil Sh lfrom Tar Sands/Oil Shale
• Domestic Resources O• Domestic Resources • Built-in Separation R NH2 R NH3
CO N
H
R
• Reuse of Solvent• Superior to Current
Molecular Liquid
Ionic Liquidp
Technology
PentanePentaneRevIL 18
Nearcritical Water: A Benign SolventNearcritical Water: A Benign Solvent• Research Partner: Lilly K• Water at 250-350º C
Like Acetone
−+ +⎯⎯ →← OHHKOH W2
Dissolves both Salts and Organics
• Natural Acid (Base) -12
-11
Natural Acid (Base)Catalyzes ReactionsEliminates Waste
14
-13lo
g K
w275ºC
• Facile ProcessingHomogeneous Reactions
-15
-14
0 100 200 300 400ReactionsSeparation by Cooling
0 100 200 300 400Temperature, ºC
19
FriedelFriedel--Crafts ReactionsCrafts ReactionsFriedelFriedel--Crafts ReactionsCrafts Reactions• Traditional Methods
Excess Lewis Acid• Nearcritical Water
No Added AcidAcid or Alkyl Chloride CorrosiveMust Neutralize
Carboxylic Acid or AlcoholSelf-NeutralizingFacile SeparationMust Neutralize
Waste SaltsFacile SeparationZero Waste Salts
OH OH OH
+ H3C C
CH3
CH3
OH +C(CH3)3Water
+ H2O
OH
+ H3C CO
OH
+ H2OWater
C(CH3)3
OHOH OH
CH3C O
20
Gas-Expanded Liquids (GXLs)Gas Expanded Liquids (GXLs)Tunable Organic-CO2 Mixtures
GASGAS• Good Organic Solvents
Miscible with CO
Liquid
Miscible with CO2
• Solubility is Pressure T bl
Liquid
Liquid
Liquid• Solvent properties are
pressure tunable
Tunable
LiquidLiquid pressure tunable• Separation by
DepressurizationAdd CO2
Depressurization21
Homogeneous Catalyst Recycle with GXLsHomogeneous Catalyst Recycle with GXLs
• Homogeneous CatalystsHomogeneous CatalystsSelectivity, RatesAsymmetric Synthesisy yDifficult to Reuse
• ParadigmHomogeneous ReactionChange Phase Behavior f S tifor Separation
• “Designer” Solvents“D i ” C t l t• “Designer” Catalysts
Megan Donaldson, PhD ChBE 2008, Dow; Nicole Hess, BS ChBE 2008, Berkeley
CO2 Induced Immiscibility:2 yOrganic Aqueous Tunable Solvents (OATS)
+ CO • Homogeneous Reaction+ CO2 • Homogeneous ReactionOrganic/Aqueous SolutionAmbient Pressure
Vapor VaporAmbient Pressure
• CO2 Induces Phase Split • GXL P S l t f
Organic
H2O
GXL
Aqueous
• GXL Poor Solvent forIonic CatalystsE2
CatalystAqueousCatalyst
Enzymes• Decant, Depressurize
C l R l- CO2
Catalyst RecycleProduct Purification 23
Homogeneous Catalysis with OATSHomogeneous Catalysis with OATSHomogeneous Catalysis with OATSHomogeneous Catalysis with OATSBiocatalyst Recycle and Product PurificationBiocatalyst Recycle and Product Purification
CO2 In CO2 OutCO2 Recycle
Liq.-Liq.Separation
Homog.Biocatalysis
DrugPurification
Reactants Products
Aqueous/Enzyme Recycle
Organic Solvent Recycle
24
OATS for Hydroformalation Reactionf y fHCORhL3
CO, H2, 120oC, 20bar O
H
• Water-soluble catalyst O HOctene isomersy• Rh catalyst is expensive- minimal loss necessary• Industrial process for propyleneIndustrial process for propylene• Mass transfer inhibited for larger olefins• THF improves solubility SO3NaTHF improves solubility• TON improved 50 – 100 Fold• Isomer distribution
P SO3Na
• Isomer distribution
NaO3S25
OATS for Biocatalytic Synthesis andOATS for Biocatalytic Synthesis and Purification of Hydrophobic Drugs
• Enantioselective Biocatalysis Water Insoluble SubstratesFacile Product Isolation and
James Brown, PhD, ChBE, 2000, ExxonMobil; Jason Hallett, PhD, ChBE,
2002, Imperial College, LondonFacile Product Isolation and Catalyst Recycle
• OATS MixtureBenign Alternative for OrganicsHigher EnantioselectivityHi h Effi iHigher EfficiencyHigher Stability of EnzymesFacile Purification ofFacile Purification of Pharmaceuticals
26
Biocatalytic Synthesis of Chiral Alcoholsy y fNADH-dependent enzymatic reduction of
less ater sol ble ketonesHO HO
ADH
less-water soluble ketones
NADH+H NAD+
FDHHCOOHCO2
FDH
Enzymes: ADH (alcohol dehydrogenase), FDH (formate dehydrogenase); ( y g );Cofactor: NAD(H) — hydrogen transfer agents;Buffer: 0.1 M ammonia formate, pH ≈ 6.5 27
Typical Projects: Recent GrantsTypical Projects: Recent Grants• NSF, Application of
Reversible Ionic Liquids • DOE and ConocoPhillips, CO2
CaptureCoupling Reactions and SeparationsJoint with German Partner, P f L it A h
Single-Component Reversible Ionic LiquidsSilylation
Prof. Leitner, Aachen• AMPAC, Many Topics
High Energy Materials
Molecular Design • Dow, Polymer Modification
Silyl SubstituentsNovel Routes to PharmaSpecialty ChemicalsFlow Reactors
yEffect of CO2
• Lilly, Applications to Pharmaceuticals
Heterogeneous Catalysis• Corning
Flow Reactors for Pharma
Pharmaceuticals DMSO SubstituteReactions in NCW
• PRF Smart Solvents forFlow Reactors for PharmaAlso with AMPAC
• PRF, Smart Solvents for Nanoparticles
28
Finishing the DegreeFinishing the Degree• Interviewing A full time job• Interviewing -- A full-time job• Connections and
RecommendationsRecommendations• Average time for PhD = 4.3
yearsyears• Typical Pattern
∼1/3 Academic Employment1/3 Academic Employment ∼2/3 Industrial Employment
Greg Marus, 4th year PhD Student, ChBE
Recent PhDs from Research GroupIn Chemistry and Chemical EngineeringIn Chemistry and Chemical Engineering
• 2007Charu Panday SW Research
• 2009Tori Blasucci – ExxonMobilCharu Panday, SW Research
Susanta Samanta, MillikenLiz Hill, Rohm & Haas
Tori Blasucci ExxonMobilKristin Kitagawa – BASF
• 2010Liz Hill, Rohm & HaasLaura Draucker, EPAEjae John, U. Trinidad
Hillary Huttenhower – Pratt and Whitney
Jack Ford, U. Kansas • 2008
Ryan Hart -- ExponentAli Fadhel -- TBD
John Gohres – EvonikMegan Donaldson – Dow Reagan Charney – Law FirmMichelle Kassner – Chevron
Decision Process – Pick a Group p
• Research Goals • We SeekEducationSatisfaction
TeamworkMultidisciplinary Satisfaction
Personal GrowthY Sh ld S k
p yApproachMolecular Viewpoint• You Should Seek
Enthusiasm
pPhD degreeExperiment and
MotivationCreativity
Experiment and ModelingEnthusiasm, Motivation,Creativity Enthusiasm, Motivation, and Creativity 31
If You Might Be Interested in Joining UsIf You Might Be Interested in Joining Us
• Talk to the ProfessorsTalk to the ProfessorsChuck Eckert, 2206 ES&T, 4-7070
Coordinator, Deborah Babykin, 2301 ES&T, 4-3690Coo d ato , ebo a aby , 30 S& , 3690
Charlie Liotta, 2201B MS&E, 5-3111Coordinator, Michele Yeager, 2201C MS&E , 4-8222, g , ,
• Talk to the StudentsAll in the NW Wing Level 2 ES&TAll in the NW Wing, Level 2, ES&TGo in any office and ask for a tour
• Come to o r Gro p Meetings• Come to our Group Meetings32
33