adsorption materials and processes for carbon capture from

University of Edinburgh , School of Engineering, Edinburgh SCCS – Scottish Carbon Capture and Storage Centre

Adsorption Materials and Processes for Carbon Capture from Gas-Fired Power Plants – AMPGas

E. Mangano1, E. Shiko1, A. Greenaway3, A. Gibson2, A. Gromov2, M. M. Lozinska3, H. Ahn1, M. C. Ferrari1, H. Yiu4, E. Campbell2, P. A. Wright3, S. Brandani1

1 University of Edinburgh, School of Engineering; 2 University of Edinburgh, School of Chemistry;

3 University of St. Andrews; 4 Heriot-Watt University

EPSRC: EP/J02077X/1

[email protected]

Presentation outline

• The AMPGas project • Novel adsorbents for CO2 capture from flue gas

streams from gas-fired power plants • Ranking of CO2 capacity • ZLC kinetic experiments • CySim adsorption simulator • Ideal Adsorbed Solution Theory revisited • Rotary Wheel Adsorber (RWA) for CO2 capture • LiFi technology

Event name 2

AMPGas Project

Gas CCS Meeting, 25-06-2014 3

Partners:

The University of Edinburgh (Coordinator)

University of St. Andrews Heriot-Watt University

Industrial Partner:

Howden Group Ltd

Other industrial contributions:

Chemviron Carbon; Purolite; Thomas Swan and UOP

AMPGas Project

4

Aims: • Apply a range of experimental techniques to determine equilibrium and

kinetic properties of nanoporous materials, which are being developed for CO2 capture from dilute streams;

• Predict the performance of an integrated adsorption process based on rapid thermal swing;

• Demonstrate the proposed process using a bench scale rotary wheel adsorber.

Materials: Thanks to the expertise of the partners different materials can be tested:

Zeolites (St. Andrews University) Amine-containing MOFs (St. Andrews University) Amine-based Silicas (Heriot-Watt University & St. Andrews University) Amine-containing Carbon and Carbon Nanotubes (University of Edinburgh)

Gas CCS Meeting, 25-06-2014

Cation Gating Zeolites: Flexible, highly selective adsorbents

5

Zeolites containing double 8 membered rings, such as:

ECR-18 RHO

Have been shown to exhibit excellent CO2/N2 selectivity due to a cation gating mechanism:


Reducing hydrophilicity of Cation Gating zeolites

6

Improving performance of zeolitic materials by implementing an hydrophobic shell with long alkyl chain functionalised silanes

SiCl3

Hydrophilic zeolite, deactivated by water

Hydrophobic zeolite, retains high CO2 capacity


Functionalization of Carbon Materials

7

Functionalization of carbon nanotubes with basic amine moieties

MWCNT/agarose aerogel produced by lyophilisation

• Carbon nanotubes can be functionalized for selective carbon capture

• Functionalized CNTs can be utilised to create 3D structures with high specific surface area

• Can be heated ohmically for cyclic regeneration of the adsorbent


Material Preparation Three main types of material prepared: 1. CNTs grafted with a basic amino functionalities 2. Activated carbon grafted with amino functionalities 3. A physical impregnation of amino groups to the surface of two different types of porous carbon

8

Amine Grafted carbon nanotubes (CNT-CO-NHR)

Amine grafted porous carbon

Amine impregnated porous carbon (various loadings)

EDA √ √ √

DETA √ - √

TETA √ √ √

PEI (MW600) √ √ √

PEI (MW10000) √ √ √

PEI (MW750000) √ - -

Linear Triethylenetetramine (TETA):


Development of Novel Experiments

9

An experimental technique should allow us to:

• Rank CO2 capacity of materials rapidly

• Require only small samples

• Interpret the results easily

• Allow to determine kinetics

• Allow to test the materials with water

• Allow to test the materials with SOx and NOx

A properly designed ZLC system can deliver on all of these requirements.


Semi-automated Zero Length Column System

10

Dosing oven

Mass Flow Controllers

ZLC oven

TCD & MS


The ZLC - Advantages

11

•10-15 mg of sample required

•Ranking of new materials

•Adsorption Kinetics

•Effect of impurities Water, SOx, NOx


-100

0

100

200

300

400

500

600

0 200 400 600 800 1000 1200

Time, s

Sig

nal

τ

Full sat. Partial sat.

0 0.5 1 1.5 2 2.5 3 3.5 4

NH4_NCLi_NCASNCK_NC

Na_(b)CNa_(s)C

K_CNa_NC3.5Na_NC2.6Na_NC2.3Na_NC1.9Na_NC1.3

Na_ NCK_NCLi_NC

Ca_NCNa_C

Na_C1Na_C4

13X

capacity (mmol/g)

13XRHOSTP-ZPAU

Ranking of CO2 capacity for Zeolites (UoStA)

T = 35 °C; PCO2 = 0.1 atm


ZLC Partial loading experiment on Na-Rho (1μm)

13 Gas CCS Meeting, 25-06-2014

R2/D = 167 min

T = 35 °C; PCO2 = 0.1 atm

R2/D = 167 min

T = 35 °C; PCO2 = 0.1 atm

ZLC Partial loading experiment on Na-Rho (1μm)

Partial loading after reg.

Structure seems to open in presence of CO2 and it closes only after regeneration at high temperature


ZLC kinetic experiments on Na-Rho (1μm) – 1% CO2

R2/D = 167 min

1 % experiment BELOW 10% !!!

Evidence of structural change


16

Breakthrough experiment on Rho: CO2/CH4 selectivity

F = 2 ml/min

Ptot = 1 atm

YCO2 = 0 .05

YCH4 = 0.4

Carrier gas: He


Adsorption

Desorption

Complete model

Non-Isothermal: 1T

Non-Isothermal: 2T

Non-Isothermal: 3T

IsothermalNo Pressure drop

Pressure drop No Film

resistance

Film resistance

NoMacropore

MacroporeLDF

MacroporeDiffusion

MicroporeLDF

MicroporeDiffusion

MicroporeEquilibrium

Dusty Gas Model

MS-Surface diffusion

Complete model

Non-Isothermal: 1T

Non-Isothermal: 2T

Non-Isothermal: 3T

IsothermalNo Pressure drop

Pressure drop No Film

resistance

Film resistance

NoMacropore

MacroporeLDF

MacroporeDiffusion

MicroporeLDF

MicroporeDiffusion

MicroporeEquilibrium

Dusty Gas Model

MS-Surface diffusion

Not implemented yet

Adsorption model hierarchy

17

Use the simplest model which accurately describes the adsorption system!

Gas CCS Meeting, 25-06-2014 Dr. Daniel Friedrich

General adsorption cycle simulator

18

Feed Pressurisation

Adsorption

Evacuation

PE

Purge

PE

Column 2

Column 1 Adsorption systems • Multiple adsorption columns • Connected by splitters, mixers,

valves and tanks • Series of cycle steps:

pressurisation, feed, purge, …

Extend column simulation to general adsorption cycles • Modular system with different units: adsorption

columns, valves, splitters, tanks, ... • Arbitrary number and connection of the units • Simulate different cycle configurations by time events,

e.g. switching of valves


Acceleration to cyclic steady state Cyclic Steady State • Many adsorption systems will reach Cyclic Steady State (CSS) • Sequential approach to CSS can be very slow

19

Acceleration schemes • Non-sequential cycle calculation:

epsilon extrapolation algorithm • Interpolation of the starting

conditions • Model and discretisation switch:

node refinement Acceleration by a factor of 10

Friedrich, Ferrari and Brandani: Efficient simulation and acceleration of convergence for a Dual Piston Pressure Swing Adsorption (DP-PSA) system. Industrial & Engineering Chemistry Research, accepted.


Buffer unit for unibed approach

20

•All columns cycle through the same steps •Steps with interaction between two columns

• Output of one column is input of the other column

• Add a buffer unit for each interaction pair •Data in buffer unit is half a cycle out of date •Same result at Cyclic Steady State •Order of magnitude faster


Gas CCS Meeting, 25-06-2014 21

Example of 12 column system: H2 PSA design AD DPE1 DPE2 DPE3 DPE4 PP BD PU PPE4 PPE3 PPE2 PPE1 PR

AD DPE1 DPE2 DPE3 DPE4 PP BD PU PPE4 PPE3 PPE2 PPE1 PR

PPE1 PR AD DPE1 DPE2 DPE3 DPE4 PP BD PU PPE4 PPE3 PPE2

PPE3 PPE2 PPE1 PR AD DPE1 DPE2 DPE3 DPE4 PP BD PU PPE4

PU PPE4 PPE3 PPE2 PPE1 PR AD DPE1 DPE2 DPE3 DPE4 PP BD PU

PU PPE4 PPE3 PPE2 PPE1 PR AD DPE1 DPE2 DPE3 DPE4 PP BD PU

BD PU PPE4 PPE3 PPE2 PPE1 PR AD DPE1 DPE2 DPE3 DPE4 PP

PP BD PU PPE4 PPE3 PPE2 PPE1 PR AD DPE1 DPE2 DPE3 DPE4 PP

PP BD PU PPE4 PPE3 PPE2 PPE1 PR AD DPE1 DPE2 DPE3 DPE4

DPE3 DPE4 PP BD PU PPE4 PPE3 PPE2 PPE1 PR AD DPE1 DPE2

DPE1 DPE2 DPE3 DPE4 PP BD PU PPE4 PPE3 PPE2 PPE1 PR AD

AD DPE1 DPE2 DPE3 DPE4 PP BD PU PPE4 PPE3 PPE2 PPE1 PR AD

AD DPE1 DPE2 DPE3 DPE4 PP BD PU PPE4 PPE3 PPE2 PPE1 PR AD

Luberti et al., Design of a H2 PSA for cogeneration of ultrapure hydrogen and power at an advanced integrated gasification combined cycle with pre-combustion capture, Adsorption J., 20, 511-524, 2014.

Mauro Luberti

The Ideal Adsorbed Solution (IAS) Theory


• IAS theory (Myers and Prausnitz, 1965) is used to predict multicomponent adsorption systems.

• Several algorithms are available to solve the problem

• There appears to be a lack of understanding of the conditions which guarantee convergence to the physically correct solution.

• Inconsistencies in the reported computational effort required

Spr

eadi

ng P

ress

ure

Equilibrium Pressure

2

p01 p0

2p

1A

X

B

C D

AX = y2

BX = y1

CX = x2

DX = x1

π

ABXBy =1 AB

AXy =2

CDCXx =2CD

XDx =1

IAST - Summary


• We have NC equilibrium equations

• We can impose

• So if we know gas phase pressure and composition we can solve for the spreading pressure and the mole fractions.

• We then calculate the total amount adsorbed

• The final equation needed is

∑=i i

i

nx

n 01

( ) iii PPx =π0

∑=i

ix1

∫=Π=P

S dppq

RTA

0

0π


IAST – Solution nested loop

• From the NC equilibrium equations

• Summing over all components – This equation can be solved numerically for Π

– At each iteration and for each component P0 has to be calculated from – NOTE this function increases monotonically with P0 so can be solved numerically

starting from any sufficiently small initial guess value of P0

( )PP

yxi

ii Π= 0

( ) 01 0 =Π

−= ∑i i

i

PyPf

00

0

=−Π ∫P

dppq


IAST – Solution nested loop

• There are very recent claims that the method is unstable

IAST algorithms


Different algorithms have been proposed to solve the IAST problem:

• Nested-Loop using Newton’s method (Myers & Valenzuela, 1986)

• FastIAS (O’ Brien & Myers, 1985 & 1988) in which the system of Nc equations is solved by solving the corresponding Jacobian matrix with non-zero elements only in the diagonal and the last row

• Landa et al. (2013) algorithm in which the problem is solved by integrating a system of Nc ODEs

We have demonstrated that N-L and the FastIAS can be extended to all types of isotherms and proposed initial guess strategies that always guarantee convergence of the algorithms

Example 1: Dual-site Langmuir

27

1

10

100

Ratio

of e

xecu

tion

time 10 kPa

Nested loop

Landa et al. 2013

FastIAS avg. time = 1.3e-4 s

1

10

100

Ratio

of e

xecu

tion

time 100 kPa

Nested loopLanda et al. 2013FastIAS avg. time = 2e-4 s

1

10

100

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Ratio

of e

xecu

tion

ime

Y1

1000 kPa

Nested loopLanda et al. 2013FastIAS avg. time = 2.6e-4 s


28

1

10

100

1000

Exec

utio

n tim

e ra

tio 10 kPa


1

10

100

1000

Exec

utio

n tim

e ra

tio

100 kPa


1

10

100

1000

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Exec

utio

n tim

e ra

tio

Y1

1000 kPa

Nested loop

Landa et al. 2013

FastIAS avg. time = 4.5e-5 s

Example 2: Dual-site Langmuir starting from previous Pi0


Example 3: 10 components system

29

Component, i qisat (mol/kg) bi (kPa-1) σi (-) yi

1 5 0.01 1.2 0.1

2 3 0.006 1.1 0.01

3 4 0.0009 0.8 0.01

4 2 0.01 1.2 0.05

5 3.5 0.005 1 0.2

6 4 0.001 1.1 0.2

7 2 0.015 1.2 0.1

8 2.5 0.001 1.15 0.2

9 4 0.0001 1 0.02

10 5.5 0.006 1 0.11

𝑞𝑞𝑖𝑖 𝑃𝑃𝑖𝑖0 = 𝑞𝑞𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠𝑏𝑏𝑖𝑖𝑃𝑃𝑖𝑖0

1 + 𝑏𝑏𝑖𝑖𝑃𝑃𝑖𝑖0+σ𝑖𝑖2𝑏𝑏𝑖𝑖𝑃𝑃𝑖𝑖0 1 − 𝑏𝑏𝑖𝑖𝑃𝑃𝑖𝑖0

2 1 + 𝑏𝑏𝑖𝑖𝑃𝑃𝑖𝑖03

FastIAS > 10 times faster than Landa et al. and 4 times faster than N-L

Ptot = 300 kPa


IAST – solution nested loop for all isotherms

30

0

10

20

30

40

50

0 50 100

q

P

Type II

0

10

20

30

40

50

0 50 100

q

P

Type III

Type IV

0

10

20

30

0 50 100

q

P

0

10

20

30

0 50 100

q

P

Type V

𝑑𝑑2𝑔𝑔𝑖𝑖𝑑𝑑𝑃𝑃𝑖𝑖0

2 =1𝑃𝑃𝑖𝑖0

𝑑𝑑𝑞𝑞𝑖𝑖0

𝑑𝑑𝑃𝑃𝑖𝑖0−𝑞𝑞𝑖𝑖0

𝑃𝑃𝑖𝑖0

𝑑𝑑𝑞𝑞𝑖𝑖0

𝑑𝑑𝑃𝑃𝑖𝑖0=𝑞𝑞𝑖𝑖0

𝑃𝑃𝑖𝑖0

Dashed lines


Rotary Wheel Adsorber for carbon capture – Advantages

31

• Can treat large volumes of gas

• Lower capital cost (no multiple columns, piping , valves, etc…)

• Efficient heat integration

• Low pressure drop

• Can perform rapid temperature swings

• Thermal cycles of few minutes: 10 times faster than traditional TSA in fixed bed

• Significant reduction of the size of the capture plant

Due to very low concentration of CO2 thermal swing adsorption is required for rapid regeneration of the adsorbent. A properly designed rotary wheel adsorber:


Bench scale Rotary Wheel Adsorber for carbon capture

32

• 12-columns rotary system

• Up to 24 thermocouples (2 per column)

• Large amount of data to be sent in real time

• Max. rotational speed 1 rpm

• Regeneration using electrical heating elements

• One of the first LiFi communication on moving elements

• Real time computer for data acquisition and control of the system


RWA concept - system control

33

Slip rings for H-E

60 W AC motor 0 - 1 rpm

NI – CRIO real time computer

MFC Gas

D-P transducers

LED ring TC data + position

LiFi receiver


34

Preliminary simulations

TRI-PE-MCM-41

P = 0.05 bar

Adapting Cysim cycle simulator for the simulation of a base case study:

Adsorbent : TRI-PE-MCM-41(Y. Belmabkhout, et al., 2010)

Feed: 5% CO2 in N2

Adsorption time: 1 min 35 °C

Heating time: 3 min

F = 200 cc/min


35

Preliminary simulations


36

Real rotary system


LiFi – how does it work?

37

Time

Intensity

1 1 1 1 0 0 0 0 0

On

Off

Spectrum:

• Unregulated (free)

• Huge

• Safe

Existing Infrastructure

Inexpensive devices

Gas CCS Meeting, 25-06-2014 Prof. Harald Haas, Dr. Stefan Videv

Recent ‘hero’ demonstrations

38

3.5 Gbps from single color LED at 5 mW

1.1 Gbps at 10 m at 5 mW

5 mW

Gas CCS Meeting, 25-06-2014 Prof. Harald Haas, Dr. Stefan Videv

Conclusions • Several materials have been developed and tested using different

techniques (ZLC, TGA, Breakthrough)

• Some of the amine-based carbons show a clear chemisorption process

• Some of the zeolitic frameworks show evidence of structural modification associated to presence of CO2

• We extended the IAST methods to all types of isotherms and made the N-L and FastIAS more robust algorithms to be included in CySim

• A novel bench scale rotary wheel adsorber has bee designed and is being built at the UoE

• CySim is being modified to predict the performance of the bench scale prototype

• A novel LiFi communication system (one of the first on moving elements) is being developed for the data acquisition in the RWA 39 Gas CCS Meeting, 25-06-2014

Acknowledgments


We gratefully acknowledge EPSRC for funding the AMPGas project (EP/J02077X/1)

adsorption materials and processes for carbon capture from

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