1. Contact Information:
Daniel Accetta
dan.accetta@gmail.com
Sunho Choi
s.choi@neu.edu
Amine loaded Pillared MCM-36 as a platform for CO₂ Capture
Daniel Accetta, Yang Lin, Liah Dukaye, David Hurt, Chris Marsh, Michael Lanzilloti, Christopher Cogswell, Sunho Choi
Northeastern University, 360 Huntington Ave. Boston, MA 02115, USA
Department of Chemical Engineering
AICHE National Conference, Salt Lake City, UT
November 9, 2015
Current CO₂ capture methods are insufficient and environmentally hazardous[1].
Moreover, current Liquid Amine Adsorption methods have the following issues, they are
corrosive to process equipment, hazardous to workers and environment, and require
costly regeneration steps with extra process equipment. Therefore, the goal of our work is
to use porous solid adsorbents loaded with amine groups to improve the capacity of solid
platforms. The creation of porous silicas in the MCM class of frameworks have been
shown to be capable of capturing Carbon Dioxide once loaded with amines[2–5].
However the large pore version of these supports called MCM-36, which is composed of
layers of porous silica staked one on top of the other in the c-axis with silica oxide
supports holding the layers apart has shown capture although at relatively low capacities
We recently published a report on a silica pillared MCM-36 solid loaded with
polyethylenimine, in which a significant decrease in capacity and carbon dioxide diffusion
time was observed upon amine loading[6]. This was attributed to the loss of the porosity
of the solid upon addition of bulky amine groups, leading to significant increases in
diffusion time and decreases in final capacity. In order to attempt to side step this polymer
loading issue, the creation of MCM-36 samples loaded with tetraethylenepentamine as
well as PEI + tetraethylenepentamine has been investigated, and shows significant
increases in capacity over the bare material.
Abstract
Introduction
Methodology
Results
Conclusions
References
Class 1-Molecular
Basket
Class 2-Covalent
Binding
Class 3-
Polymerization
Advantages:
-high CO2 adsorption
capacity
Advantages:
-enhanced stability
-high diffusion rates
Advantages:
-high CO2 adsorption
capacity
-enhanced stability
Disadvantages:
-low diffusion rates
-poor stability
Disadvantages:
-low CO2 adsorption
capacity
Disadvantages:
-low diffusion rates
OOCOOC
Micropores Channel
Large
Gallery
Channels
• CO2 Diffusion in a,b axis through layers
• No Diffusion Possible Between Layers via
c-axis
• Large channels ~ 40 Angstroms
• Small channels ~ 1-20 Angstroms
Step 1
Swelling
Step 2
Pillaring
Step 3
Functionalization
Final Pillared-Amine Structure
Nanosheet Precursor
structure directing agents
Swollen Nanosheet
surfactant molecules
SiO2 pillars
Pillared Nanosheet
amine groups
Swelling
Swollen
Product
Introduction
of Metal
Complex
Hydrolysis
+
Calcination
Pillared
Derivative
[1]S. Choi, J.H. Drese, C.W. Jones, ChemSusChem 2 (2009) 796–854.
[2]W. Klinthong, K. Chao, C. Tan, Ind. Eng. Chem. Res. 52 (2013) 9834–9842.
[3]L.N. Ho, J.P. Pellitero, F. Porcheron, R.J.-M. Pellenq, Langmuir 27 (2011) 8187–97.
[4]M. Gil, I. Tiscornia, Ó. de la Iglesia, R. Mallada, J. Santamaría, Chem. Eng. J. 175 (2011)
291–297.
[5]F. Gao, J. Zhou, Z. Bian, C. Jing, J. Hu, H. Liu, Proc. Inst. Mech. Eng. Part E J. Process
Mech. Eng. 227 (2013) 106–116.
[6]C.F. Cogswell, H. Jiang, J. Ramberger, D. Accetta, R.J. Willey, S. Choi, Langmuir 31 (2015)
4534–4541.
Introduction
of proton
source
Layers
begin to
separate
Successful
introduction
Unsuccessful
introduction
Collision of
layers to form
amorphous solid
Swollen
Product
Protonated
Sample CTAB: Swollen Organic Ligand
TPAOH: Protonation Agent
Results Continued
Figure 2. MCM-36 Synthesis and Impregnation Scheme
Figure 3: Swelling and Pillaring Mechanism to Increase the C-Axis
Figure 1. Introduction of a Chemically Active Pillar
Si
OH
Si
OH
Si
OH
Positive
Cation
Negative
Silanol
Figure 4. X-ray diffraction patterns of (a) MCM-22-P, (b) Swollen MCM-22-P, (c)
MCM-36, (d)MCM-22 zeolite, and (e) 14.5 weight% PEI loaded MCM-36
Figure 5. Nitrogen adsorption isotherms for the samples prepared in this study
TEOS: Metal Complex
0
1
2
3
4
5
6
5 10 15 20 25 30
NormalizedIntensity
Degrees 2 q
(002)
(310)
(101) (102)
(220)(100)
a
b
c
d
e
-50
0
50
100
150
200
250
300
350
400
0 100 200 300 400 500 600 700 800 900
Volume(cc/g)
Pressure (Torr)
MCM-36 Sample A
MCM-36 Sample B
MCM-22
PEI-MCM-2.7
PEI-MCM-3.85
PEI-MCM-3.72
PEI-MCM-7.52
PEI-MCM-14.54
PEI-MCM-16.29
Sample Name
BET Surface
Area m2/g
BJH desorption
pore volume cc/g
BJH Pore Radius
Angstroms Amine weight %
Capture Capacity
(mmol/g)
MCM-36 A 765 0.199 18 0 1.02
MCM-36 B 506 0.178 20.4 0 1.03
1x PEI 14.1 0.0249 18.1 3.97 0.44
10x PEI 28.8 0.0495 16.1 5.12 0.47
25x PEI 21.7 0.0618 18.1 4.99 0.49
40x PEI 18.6 0.132 20.3 8.79 0.62
100x PEI 5 0.0982 18.1 16.6 0.2184
• An optimum loading capacity was obtained for MCM-PEI sorbent
• This represents a point where capture is maximized and diffusion has not
yet completely become blocked
• The MCM-PEI system does not appear to represent a good candidate for
further capture studies due to low capacity once impregnated
• Preliminary results suggest that the use of TEPA as amine leads to
significantly increased capacity because diffusion is not hindered
• Furthermore the addition of TEPA to a PEI loaded sample shows the
ability to regain capacity by impregnation in the small pore space
Sample Name
BET Surface
Area m2/g
BJH
desorption
pore volume
cc/g
BJH Pore
Radius
Angstroms Amine weight %
Capture Capacity
(mmol/g)
MCM-36 506 0.178 20.4 0 1.03
100x PEI 5 0.0982 18.1 16.6 0.2184
MCM-36 B + TEPA - - - 38 2.85
MCM-36 100x PEI +
TEPA - - - 46.02 1.981
Acknowledgments: Dinara
Andirova and Zelong Xie
Figure 7. Summary of amine capture efficiency verse amine weight percent
loaded on each sample
Table 2. Surface characteristics data of MCM-36 compared to MCM with TEPA
obtained via NOVA and TGA analysis
Figure 6.Normalized adsorption half time verse PEI weight percent loaded on
each sample
Table 1. Surface characteristics and PEI weight percent data obtained via NOVA and TGA analysis