Understanding Chemistry in the IH2®

Process

Dhairya Mehta1, Vikrant Urade1, Laxmi Narasimhan1,

Madhusudhan Rao1 and Alan Del Paggio2

1Shell India Markets Pvt. Ltd, Shell Technology Centre Bangalore, India

2CRI Catalyst Company LP, Houston, TX

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Outline

• Introduction to the IH2® Process

• Overarching Chemistry of the IH2® Process

• First-Stage Catalytic Hydropyrolysis

• Second-Stage Catalytic Hydroconversion

• Summary

Exports

Biogenic CO2

High Pressure Steam

BioChar

Hydrocarbon Fuel

NH3 Fertilizer Concentrate

S Fertilizer

Lock

Hoppers

Bulk Operations

Siz

ed &

Drie

d

1st S

tag

e R

eacto

r

Hyd

rop

yro

lysis

2n

d Sta

ge

Re

acto

r

Hyd

roco

nve

rsio

n

Cyclones

Bio

Ch

ar R

em

ove

d

BioChar

Lig

ht G

as

Phase

Separation

Wa

ter

Gas

Clean Up

Water

Clean Up

Distillation

SMR Renewable H2

Gasoline

Jet

Diesel

IH2® Process Schematic

Overarching Chemistry of the IH2® Process

Cellulose

Hemicellulose

Lignin

IH2® Process

Representative lipid from microalgae

Overarching Chemistry of the IH2® Process

IH2® Process PET

Representative plastic

1st Stage Reactor - Bubbling fluidized bed

• Biomass Oxygenated vapors Hydrocarbons

• Multiple reactions occurring simultaneously

• Devolatilization – Solid to Vapors (Endothermic)

• Catalytic Hydrodeoxygenation – Vapors contacted with catalyst

to produce hydrocarbons (Exothermic)

• Estimated heat of reaction = -960 BTU/lb-biomass

1st Stage Liquid Properties

Wood Hydrocarbon Liquid

%O 43.9 3.3

%C 49.7 85.7

%H 5.8 11.0

S/ ppm 300 273

TAN - 2.3

Density/ g ml-1 0.2 0.864

% Deoxygenation - 92.5

• >90% deoxygenation accomplished in the first stage itself

1st Stage Liquid Properties

• Product distribution extends only up to C20, no

compounds heavier than diesel

Polar Extract Comprises Mainly Phenolics

• Derived from the

lignin component of

wood

• Phenol the only

remaining oxygen

functionality

• Methoxy group

deoxygenated

1st Stage Proposed Kinetic Model

ACTIVE BIOMASS

BIOMASS

CHAR

OXYGENATED INTERMEDIATES +

GAS

GAS

ν12.GASOLINE + ν22.DIESEL + νhH2O

k1

k4

k2

k3

k5 k6

ν11.GASOLINE + ν21.DIESEL + νX COX

Broido-Shafizadeh Mechanism for devolatilization

Devolatilization Kinetics Experimental Results

Progress of Deoxygenation from the 1st

to the 2nd Stage

Wood 1st stage 2nd stage

%O 43.9 3.3 BDL

%C 49.7 85.7 88.0

%H 5.8 11.0 12.0

S/ ppm 300 273 9

TAN - 2.3 <0.01

Density/ g ml-1 0.2 0.864 0.832

% Deoxygenation - 92.5 >99.5%

• >99.5% deoxygenation accomplished in 2nd

stage

• Significant reduction in ‘S’ content of the

hydrocarbon liquid

2nd Stage Liquid Analysis DHA Showing Composition of Gasoline/Kero Fraction

Distinct peaks at

• C5: From Hemicellulose?

• C6: From Cellulose?

• C9: From Lignin?

• C12: Dimers or C-C concatenation

• C7 and Below: Naphthenes

• C8 and Above: Aromatics

Summary

• Devolatilization

Rate of devolatilization and char yield are dependent on

temperature

Operating temperature of 1st stage reactor determined by

devolatilization

Summary

• Devolatilization

• 1st Stage Catalytic Hydrodeoxygenation

>90% deoxygenation accomplished

Naphthenes and aromatics are the major species among

hydrocarbons

Lignin-derived phenolics are the only remaining oxygenate

species

Summary

• Devolatilization

• 1st Stage Catalytic Hydrodeoxygenation

• 2nd Stage Catalytic Hydroconversion

Oxygen below detectable limit

Naphthenes and aromatics major constituents of liquid product

Sulfur content down to <10 ppm

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