1

Source: Jos D. Figueroa, National Energy Technology Laboratory (NETL), USDOE

Slide 2
Chemical Looping Technology Improvements
through PI

Current project objectives are to:

1. What are the efficiencies for CLC technology integrated within
generating facilities
2. Hydrodynamics - Identify gas-solid handling systems to improve
integration of key solids handling
3. To investigate reactor choice used for oxide particles fluidisation
4. Methods for intensifying reduction and oxidation reactions

(Fluidised Beds might not be the best technology to carry out

solid-gas reactions)
Slide 3
 Chemical Looping Combustion
Reactions:

- Fuel reactor

(2n + m)MyOx + CnH2m (2n + m)MyOx1 + mH2O + nCO2

- Air reactor

MyOx1 + 1/2 O2(air) MyOx + (air : N2 + unreacted O2)

4
Aim:
Aspen Plus
To develop a fluidised bed model for CLC inspired by a model proposed for FCC
(to replace the Gibbs reactor model, largely used in the literature of CLC)

Issues considered:

Adequate contact time between fuel and air and solid oxygen carrier to achieve
maximum conversion

Size of the two reactors

Adequate solid inventory

Adequate molar flowrate ratio between air and fuel

6
 Aspen Plus Implementation
The red-ox reaction of NiO/Ni supported by bentonite is investigated.

The fuel reactant is pure methane and the oxidising agent is air.

Within the fuel reactor the specific reduction reaction is:

CH4 + 4NiO CO2 + 2H2O + 4Ni

While within the riser the specific oxidation reaction is:

O2 + 2Ni 2NiO

The un-reacted core model was applied and the controlling step for both oxidation
and reduction reactions is the kinetic step

7
 Aspen Plus implementation
Fuel reactor: bubbling regime
Two phase theory: bubble phase with low content of solids and emulsion phase characterised by
perfect mixing of gas and solids

Reactor axially divided into several sections consisting a PFR representing the gas flow through
the bubbles and a CSTR representing the gas flow through the emulsion

Gas mass transfer between bubble and emulsion phase occurs at the exit of the each stages between
the outlet streams

External calculator block in Excel defines the operating conditions of the feed
External calculator and transfer blocks to implement the mass transfer terms
External FORTRAN subroutines used to implement the reactions
8
 Aspen Plus implementation
Air reactor: fast fluidisation regime
Axial distribution of solid particles

Reactor split into a lower and an upper region, the dense and lean phase respectively

One CSTR models the dense phase

Three CSTRs model the upper region characterised by three different mean void fraction

External calculator block in Excel is used to define the operating conditions of the feed
External FORTRAN subroutines are used to implement the reactions

9
Results: Bubbling Bed Model

10
 Results: Bubbling bed model

Conversion increases with the number of stages

The comparison with data from the literature shows that 5 stages give
the conversion observed

Gibbs reactor does not consider gas by-pass in the bubble phase: this
explains the higher conversion

A sensitivity analysis was carried out to find the minimum solid

inventory to achieve more than 90% in methane conversion; this was
found t be 92.5%.

11
Results: Riser Model

12
 Results: Riser model

The set of parameters to achieve a conversion of solid that allows the

circulations of solid particles between air and fuel reactor in steady state
condition was found:

Uo [m/sec] DR [m] HR [m] Lm [m] Ks [m/sec] Fair/FCH4

1.79 0.8 3.5 0.25 4.41E-04 1.25

13
 Conclusions

The model takes into account hydrodynamics and kinetics

The main process variables can be estimated (e.g. diameter and height of
the two beds, solid inventory, molar flowrate ratios)

The model shows higher accuracy than a Gibbs reactor (it considers the
gas bypass through the bubble phase)

The system can be implemented into the full power plant system to
calculate the process thermal efficiency and attempt economic analysis
and LCA.

14
 CDF Studies
CFD studies on the Bubbling bed (Fuel) reactor show the issues in creating a workable
bed condition

27.2 s 36.8 s

17.0 s 39.9 s 20.5 s 32.0 s

2s 2s 2s

Simulation Exp. Simulation Exp. Simulation

Exp.

Group A/B Group B Group D

dp=125 micron dp=350 micron dp=800 micron
Increasing particle size (decreasing IPF)

Slide 15
 Process Intensification
Gas-Solid fluidised beds remain an attractive method for use in chemical
and processing industries. However, there are several intrinsic weaknesses
and issues including:

Bubbling bubble formation cause some gas to bypass fluidised particles,

resulting in lower gas-solids contact
Elutriation eventuating in loss of reactants, occasional pollutants (hence
need for cyclone). This is exacerbated in larger scale CFBs operated in
turbulent regime to maintain throughput
Scale-up - does not come easily
Large scale - reactor with tall cyclone leads to low mobility and compactness
leading towards higher capital and running costs
Umf the need to match Umf values for the oxidiser and reducer to ensure
effective fluidisation and throughput

Slide 16
 Future work
Integration of Aspen Plus with CFD modelling to study the gas bypass and the
whole efficiency of the process

CLC Process Intensification

17