Emerging Research and Opportunities in Chemicals and Fuels

Carson MeredithProfessor & Associate Chair

School of Chemical & Biomolecular Engineering

Faculty Carsten Sievers Chris Jones Ryan Lively

Andy Bommarius Matthew Realff Pradeep Agrawal Rachel Chen

Carsten Sievers

Catalytic Routes for Sustainable Production of Fuels

and Chemicals

Synthesis Process Development

Surface Reactions

Characteri-zation

Tailored active sites

Water-tolerant

solid acid

Multi-functional catalysts

Acidity / Basicity

Metal particles

Porosity

Crystalinity

In-situ spectro-scopy

Inter-mediates

Reaction pathways

Catalytic reactions

Reactor design

De-activation

SieversObjectives: Understand pathways of catalyst deactivation in hot

liquid water Elucidate influence of biomass-derived feedstocks on

stability of solid catalysts Improving hydrothermal stability using protective

coatings and additives

Approaches: Kinetic studies on transformations of solid catalysts in

hot water and solutions of oxygenates Physicochemical characterization (N2 physisorption,

XRD, TEM, SEM, IR, NMR, XPS, titration) Development of synthesis techniques for improving

hydrothermal stability Performance studies with stabilized catalysts

2θ / °

ppm

ppm

t / h

t / h

PtAl3+ + H2O ↔ H+

O

H+ +H2

Cl

H

OH

Al

Stability of Solid Catalysts in Hot Water

H1

C1

O3

H2

H3H4

H5

H6

H7

H8

C2C3

O1

O2

O4

Al1Al2

SieversObjectives: Understand surface interactions of biomass-derived

oxygenates in aqueous media Identify intermediates and reaction pathways for

aqueous phase reforming, hydrodeoxygenation, etc. Quantify rates of individual reaction steps Identify active sites

Approaches: IR spectroscopy NMR spectroscopy Liquid phase adsorption isotherms Inelastic neutron scattering Raman spectroscopy DFT calculations (with David Sholl)

Glycerol on γ-Al2O3

ATR IR setup for in-situ studies in liquid phase under flow conditions

Feed InletEffluent

N2 Inlet

IR InletIR Outlet

TC

Heating Element

Gasket

Window

IRE

Surface Chemistry of Oxygenates in Water

Agrawal / SieversObjectives: Understand the influence of morphology and

specific active sites on kinetics of gasification at high pressure (5-20 atm)

Develop kinetic models for gasification at high pressure

Investigate synergistic effective in co-gasification of biomass and coal

Approaches: Preparation of char samples in a pressurized

entrained flow gasifier (see picture) Characterization of char morphologies and

active sites for gasification Kinetic studies on gasification and pyrolysis by

TGA/DSC Modeling of gasification kinetics

Collector

ReactorSection

FlowStraightener

Injector

Preheater

Pressure Seals

Gasification and Pyrolysis of Biomass

Chris Jones

Cellulose

Glucose Hydroxymethylfurfural

Current Project Areas:

1. Catalytic conversion of hydroxylmethylfurfural and furfural into chemicals

2. Application of nanofibrillated cellulose as a catalyst support

Valorization of Cellulose

OOOH

cat

H2

OOHOH

HOOH OH

HMF THFDM 126-HTcat

H2

cat

HOOH

cat

HOOH

cat

HO

O O

cat

cat

NH3NH

O

12-DH-HE

1-H-HE

16-DHH

caprolactone caprolactam

Jones

Develop catalysts and conditions to convert HMF into monomer for important polymers (polyesters, nylons, polyolefins)

Nanocrystalline Cellulose as an Organocatalyst Support

• Many enzymes work by cooperative acid-base catalysis

• Develop cellulose-supported amines as cooperative acid-basecatalysts for HMF conversion into biofuels

HMF Conversion to Monomers for Polymers

Funded by RBI Ph.D. Fellowship

Bommarius / Realff

Feedstocks Pretreatment Enzymatic degradation Sugars Fermentation Biofuels

Innovative chemical and biological pretreatments for lignocellulosic materials for downstream biological conversion.

Cellulose Pretreatment

Endoglucanases (I, II), Cellobiohydrolases (I, II) β-glucosidase

0

6

12

18

24

0 16 32 48 64 80 96

t (h)

100

75

50

25

0

Con

vers

ion

(%)

Ionic liquids

Subsituted imidazoles

EMIMAc

1-MI HMI DMI

Chemical pretreatment

GoalEnhance enzymatic efficiency on lignocellulosic biomass for biofuel applicationsMajor challenges• Feedstock recalcitrance • High enzyme cost

Rachel ChenCellulose

Cellodextrins(DP2~7)Cellobiose

Glucose

PTS System for Cellobiose & Glucose

Cellodextrin bindingABC transport

Cellodextrin(DP)Cellodextrin Phosphorylase

Cellodextrin(DP-1) + Glucose-1-P

Glucose-6-P

Biofuels

Biofuels

Cellulases

Cellulases

Cellulases

Glycolysis

Glucose-6-P

Native assimilation pathway

Cellobiose-P

Pi

Inner-membrane

Outer-membranePeriplasm

Cytoplasm

Metabolic engineering of E. coli

Ryan Lively Low-energy pre-purification strategies

5.5Å a

aMayoral A, Carey T, Anderson PA, Diaz I. Micropor. Mesopor. Mater. 2013, 166(1), p. 117

Super-hydrophobic molecular sieves

0 1 2 3 4 51

10

100 1-butanol 1-propanol 2-propanol ethanol

alcohol conc., liquid phase (mol%)

ZIF-8 Sor

ptio

n se

lect

ivity

, q p ( )

Zeolites Metal-organic frameworks

Highest EtOH/H2O sorption selectivity in the literature

Matthew Realff

Mobile Processing Systems

Pyrolysis System Design

e.g. Diesel from syngas

Hydrodeoxygenation

Design cost-effective solutions considering logistics and process costs

Biorefinery Logistics Supply Chain Network Design