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