Hydrogen Production by

Methane Decomposition
using Hydrotalcite Based
Catalyst
Research Proposal Defence
Umair Sikander
(G02960)
Nov 28, 2014
Supervisor: A.P. Dr. Suriati bt Sufian
Co-supervisor: A.P. Dr. Ku Zilati Ku Shaari

Outline
1

Introduction

Problem Statement

Hypothesis

Research Objectives

Literature Review

6 Research Methodology
7 Expected Results
2

INTRODUCTION
Hydrogen is without doubt the best source
of energy available and saying that its
the oldest source of energy is not wrong.
Based on its calorific value Hydrogen is
the best energy source available.
It can be used in combustion engines, as
a propellant, an explosive, a source of
electricity (PEM-Fuel Cells) etc.
0.1Gton of hydrogen is produced
annually, of which 98% is being produced
from fossil fuels by reforming techniques.
3

INTRODUCTION
Methane is the best source material for
Hydrogen
production;
having
highest
Hydrogen-Carbon ratio.
Increasing demand of COx free hydrogen; has
led research towards new green technology
for industrial and automobile applications.
Methane Decomposition (MDe) Process is a
possible candidate as Carbon is the only ByProduct.

CH4

C + 2H2

PROBLEM STATEMENT
High energy requirements since MDe
occurs at 1200oC.
Overall process efficiency is limited to
30-40%
High Carbon deposition on catalyst
surface, reduce active surface area.
Low residence time and hydrodynamic
complexities in MDe Reactors.
Continuous catalyst regeneration
process.
5

HYPOTHESIS
Hydrotalcite is a double layered
structure and is used widely for
synthesis of CNTs and CNFs, proving to
have a high carbon adsorption.
Metallic active sites can be impregnated
on its surface using co-precipitation
methods.
Hydrotalcite based catalyst have been
used for Methane Steam Reforming and
other process of Hydrogen Production.
These attributes make it an ideal
catalyst for Hydrogen Production by MDe

HYPOTHESIS
Fluidized-bed reactors (FBR) and
packed-bed reactors (PBR) are the most
commonly used.
Increase in Pressure Drop, Hi Carbon
deposition, density alterations are major
issues with PBR.
Continuous addition and withdrawl of
solids make FBR more suitable for MDe.
Fluidization in FBR increased heat and
mass transfer rates.
7

OBJECTIVES
Synthesis and characterization of
metallic-HTlcs nano catalyst using soft
synthesis methods.
Analysis of synthesized nano-catalyst for
hydrogen production by MDe.
Development of Kinetic and
Hydrodynamic Modeling Equations
CFD modeling for Fluidized Bed Reactor
Design

LITERATURE REVIEW
Process

Methane decomposition
Hydrocarb process
Steam reforming
Coal gasification with electricity chemical
shift (Westinghouse)
Partial oxidation
High temperature steam electrolysis
Texaco gasification
Coal gasification with high temperature
electrolysis
K-T gasification
Water electrolysis

Total
hydrogen
production
cost in USD
for 100 ft3
2.29
5.82
2.06
4.51
3.12
5.06
4.35
4.43
5.12
6.57

Marban G, Valdes-Sols T. Towards the hydrogen economy? Int J Hydrogen Energy 2007;32:162537

Types of MDe

10

CATALYSTS in MDe
Cu, Fe, Co, Ni, Pt, Pd have been studied
extensively
Minimum reported Temperature for efficient
MDe is 552oC
MDe catalytic activity for the iron group metals
is: Ni>Co>Fe.

Ni/-Al2O3
catalyst have
shown highest
Methane to
Hydrogen
conversion

11

CATALYSTS in MDe
An experimental study for Nicatalyst with loadings
in the 590% range

Venugopal A, Naveen Kumar S, Ashok J, Hari Prasad D, Durga Kumari V, Prasad KBS, et al. Hydrogen production by
12
catalytic decomposition of methane over Ni/SiO2. Int J Hydrogen Energy 2007;32:1782e8.

CATALYST SUPPORT
Comparison between different support materials
for same active surface area

lower the
interaction
between
active and the
support
material
longer the
MDe

Takenaka S, Ogihara H, Yamanaka I, Otsuka K. Decomposition of methane over supported-Ni catalysts: effects of the supports on the catalytic
13
lifetime. Appl Catal A 2001;217:101e10.

Hydrotalcite based Catalysts

14

Reactors in MDe

15

Overview of Literature Survey

Group
Snoeck et al.

Catalyst Used
Ni/-Al2O3

Studies
Optimal Temp range

Findings
High Methane Conversion Efficiency

Avdeeva et al. Cobalt

Qiang Sun et
Iron

Less catalytic Deactivation

Cheaper Material

at lowest Temperature of 650oC

High toxicity, low activity
Low catalytic activity

al.
Venugopal et

Nickel

Effect of temperature

Below 500oC catalytic deactivation

al.
Echegoyen et

Cu doped Ni catalyst Addition of different %ages

al.
Figueiredo

La2O3 doped on Ni-

Gac et al.

Cu
Magnesia doping

increased rapidly
3% doping shows better Methane

of Cu
Effect of Lanthanide doping

Conversion
Shows better results of doping over

Effect of Magnesia doping

Ni-Cu catalyst as compared to Ni

Stronger adsorption sites initially,

over different

non-linear catalytic activity.

Venugopal et

catalyst
Ni/SiO2

Ni loadings in 5-90% range

MDe increased till 30% Ni loading

al.
Aielo et al.

70%Ni-10%Cu-

Effects of different loading

Addition of Fe increases catalyst

Jang et al.

10%Fe/Al2O3
Fe supported on

%ages
Effects of support on Fe

stability till Temp of 750oC

Rapid deactivation below 7500C,

Alumina

catalyst

high Methane conversion for

Ammendola et Cu supported on

Effect of support on Cu

100min
90% methane conversion but for

al.

catalyst

5% diluted Methane and only for 90

Alumina

minutes

16

Overview of Literature Survey

Continued
Group
Suelves et al.

Li et al.
Ermakova et

Catalyst Used

Studies

Findings

Carbon black and

Comparison between two

Carbon black shows better

activated Carbon

types of catalyst

conversion and activated carbon

Catalytic activity tests

rapidly deactivates
Catalyst easily reduced between

Effects of Silica support

500-750oC
Yield drops due to formation of

Effects of different support

metallic silicates
Lower the interaction between

materials

support and Ni, higher the yield

Ni/-Al2O3
Ni & Fe on SiO2

al.
Takenaka et al. Ni over various
supports

17

Methodology

18

Methodology
Synthesis of Metallic HT based
catalyst

After 12hr aging

Precipitates
washed
and dried
for 12hr

Continuous stirring

Calcination at 1100K for 1day

19

Methodology
Characterization of
Characterization
Catalyst
Technique

Analysis

FE-SEM

Surface Morphology will be measured by

examining the topography using FE-SEM.

FTIR Analysis

To measure the functional group attachment.

To measure the thermal stability of catalyst,

TGA

as high temperature is required for methane

decomposition.
To measure the crystallinity of catalyst and

XRD Analysis

to investigate the molecular structure.

Catalyst structure uniformity and surface

XPS analysis

adsorption

will

be

analyzed

using

XPS

analysis.
20

Methodology
H2 production by MDe in Fluidized Reactor

Effect of Temperature
Pressure Drop
Carbon deposition
Extent of Reaction
Catalyst regeneration
21

Methodology
CFD studies for optimal reactor
Design
ANSYS FLUENT will be used
Dual sub-modeling approach
Euler-Euler based two fluid
Model
Isothermal reactor system

22

Methodology
MFIX Model by NETL, USA for Hydrodynamics
For reaction kinetics, Gidaspow theory for
Granular Flow
Reaction Mechanism developed by Muradov
(CH4)g (CH3)a + (H)a (1)
(CH3)a (CH2)a + (H)a (2)
(CH2)a (CH)a + (H)a
(3)
(CH)a (C)a + (H)a (4)
n(C)a 1/n(Cn)c
(5)
2(H)a (H2)g
(6).

23

Methodology
Develop Reactor
Geometry & Meshing
using Gambit
Define Physical
properties (Euler-Euler
Two phase Flow)

Modify
Kinetic/Hydrodyna
mic Model
According
to
Experimen
tal/Reporte
d Data

Incorporate Gidaspow
Kinetic Model and MFIX
Hydrodynamic Model

Set
Boundary
Conditions
Modify Mesh size
or B.C.

NO

YES

Initialize

Converge

NO

Optimized
Reactor
Design
YES
24

In a Nut-Shell

25

Expected Results
A green future fuel (Hydrogen)
production technology.
Potential catalytic nanomaterials for
hydrogen production.
Optimized fluidized reactor design for
hydrogen production.

26

Gantt Chart
Fist Year
3 years

2nd Year

Semester 2 (Jan 2015)

Semester1 (July
2014)

Task

10 11 12

3RD Year

Semester 3 (July

Semester 4 (Jan

Semester 5 (July

2015)

2016)

2016)

10 11 12

Semester 6 (Jan 2016)

5

10 11

12

Literature
Review
Ordering of
Chemicals
Synthesis of
Catalyst
Characterizat
ion of
Catalyst
Hydrogen
production
Studies
Post
production
Characterizat
ion

R E A C T O R

M O D E L I

N G

Developing
Modeling Eq
CFD
Modeling
Thesis
Writing &
Submission

27

Thank You
Q&A

28