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U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Ch
emic
alC
hem
ical
& P
roce
ss E
ng
inee
rin
g &
Pro
cess
En
gin
eeri
ng
Novel Material for the Separation of Novel Material for the Separation of Mixtures of Carbon Dioxide and Mixtures of Carbon Dioxide and
NitrogenNitrogen
Mohamed A. M. ElsayedMohamed A. M. Elsayed
Supervisors : Prof. P. J. Hall & Dr. M. J. HeslopSupervisors : Prof. P. J. Hall & Dr. M. J. Heslop
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Ch
emic
alC
hem
ical
& P
roce
ss E
ng
inee
rin
g &
Pro
cess
En
gin
eeri
ng
IntroductionIntroduction
POROUS POROUS CARBONCARBON
Naturally occurring carbonaceous material
Physical or chemical activation Polymer precursorPolymer precursor
Fewer minerals impurities & controlled Fewer minerals impurities & controlled pore structure pore structure
PyrolysisPyrolysis
Sol-gel processSol-gel process
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Ch
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& P
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g &
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Sol-Gel Technologies and their ProductsSol-Gel Technologies and their Products
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Ch
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alC
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& P
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ng
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OBJECTIVESOBJECTIVES
First stageFirst stage
1- 1- further developing and modifying resorcinol formaldehyde sol-gel further developing and modifying resorcinol formaldehyde sol-gel synthesis procedure to make high surface area carbon xerogels synthesis procedure to make high surface area carbon xerogels with a controlled pore structure. with a controlled pore structure.
2- Studying factor affecting on the texture properties and characteristics 2- Studying factor affecting on the texture properties and characteristics of the produced material. of the produced material.
4 - Using different techniques for characterization and analysis 4 - Using different techniques for characterization and analysis (BET, TPD, FTIR, TGA, XRD, SEM, etc…)(BET, TPD, FTIR, TGA, XRD, SEM, etc…)
Second stageSecond stage
3- Further chemical impregnation to produce nitrogen-enriched carbon 3- Further chemical impregnation to produce nitrogen-enriched carbon xerogelsxerogels
1-Investigation of full binary isotherms for CO1-Investigation of full binary isotherms for CO22 and N and N22 from composition from composition
and flow-rate transient times in chromatographic columnsand flow-rate transient times in chromatographic columns
2- Studying factor affecting on the selectivity of CO2- Studying factor affecting on the selectivity of CO22 and N and N22.
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Ch
emic
alC
hem
ical
& P
roce
ss E
ng
inee
rin
g &
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cess
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Experimental Experimental
Resin synthesis RF-xerogels Carbon xerogels
Active carbon xerogels
Carbon characterization
N2 adsorption-desorption techniques
Drying Pyrolysis
Co2 gasification
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
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Ch
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Result and discussion
Resin analysisResin analysis
Ultimate and Proximate analyses using Elemental and Ultimate and Proximate analyses using Elemental and Thermogravimetric analyzer respectively Thermogravimetric analyzer respectively
Nomenclature
Ultimate (wt% dry-ash-free basis ) Proximate (wt% )
C H N O Moisture Volatile Fixed carbon
Ash
RF-MEA RF-DEARF-MDEARF-NH4HCO3
RF-K2CO3
RF-Na2CO3
62.9864.7364.6764.4763.0472.90
5.455.245.634.865.126.00
0.420.350.310.320.000.00
31.1529.6829.4030.3731.8421.10
4.6643.3972.4792.4472.2923.530
61.79652.30863.73357.13350.43849.675
33.29343.06034.00739.70545.17346.155
000000
R/F= 0.5 and R/C = 300 by mole PH=6 and R/W = 0.25 g/cm3
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Ch
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& P
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Thermogravimetric analysis of a dried resorcinol-Thermogravimetric analysis of a dried resorcinol-formaldehyde gelformaldehyde gel
30
40
50
60
70
80
90
100
110
-0.8
-0.6
-0.4
-0.2
0
0.2
0 200 400 600 800 1000 1200
RF-K2CO
3
RF-MDEARF-Na
2CO
3
RF-MEARF-NH
4HCO
3
RF-DEA
Derivative
Weig
ht L
oss (
% )
Deriv
ative
We
ight %
( %/m
in)
Temperature ( 0C)
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NIVERSITY OF TRATHCLYDE
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FTIR spectra for the synthesis resins with different FTIR spectra for the synthesis resins with different type of catalytic species type of catalytic species
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0cm-1
%T
RF-Na2co3
RF-K2CO3
RF-MEA
RF-NH4HCO3
RF-MDEA
RF-DEA
-OH
-CH2-aromatic
amides & amines
lactamenitrile
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NIVERSITY OF TRATHCLYDE
IN GLASGOW
THE
Ch
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alC
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& P
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ng
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cess
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CarbonCarbon xerogelsxerogels characterization by BET.characterization by BET.
Effect of changing catalyst species and the catalyst ratios.Effect of changing catalyst species and the catalyst ratios.
100
120
140
160
180
200
220
100
200
300
400
500
600
700
800
900
0 0.2 0.4 0.6 0.8 1
RF-MEARF-MDEARF-DEARF-NH4HCO3RF-K2CO3
RF-Na2CO3
Vol
ume
Ads
orbe
d (
cm3/g
ST
P)
Relative Pressure (P/P0)
100
200
300
400
500
600
700
800
0 0.2 0.4 0.6 0.8 1
RF-MEA100
RF-MEA50
RF-MEA200
RF-MEA300
Vol
ume
Ads
orbe
d (
cm3/g
ST
P)
Relative Pressure (P/P0)
(b)
(a) R/C= 300 by mole with different type of catalytic species
(b) MEA was used as a catalyst with different R/C ratio
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
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Ch
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Characteristic pore properties of RF carbon xerogelsCharacteristic pore properties of RF carbon xerogels
Nomenclature
R/C SBETa
(m2/g)
Vtb
( cm3/g)
Vmicc
(cm3/g)
Vmesd
(cm3/g)
Dpe
(nm)
Volume fraction %
% micro % meso
RF-Na2CO3
RF-K2CO3
RF-NH4 HCO3
RF-MEARF-DEARF-MDEA
RF-MEARF-MEARF-MEARF-MEA
300300300300300300
50100200300
672436496488444485
652600546484
1.2580.3370.2320.2380.2080.229
1.1270.5630.4460.229
0.3040.2000.2290.2260.2050.224
0.2950.2950.2510.224
0.9540.1370.0030.0120.0030.005
0.8320.2680.1950.005
7.4763.0891.8701.9521.8761.893
6.9143.4523.2651.899
24.259.398.794.998.597.8
26.252.456.397.8
75.840.71.305.101.502.20
73.847.643.72.20
a Specific surface area determined from the BET equation.bTotal pore volume.
cMicropore volume determine by Horvath-Kawazoe equation.dMesopore volume .
eMean pore diameter.
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
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Ch
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Pore size distribution of the RF carbon xerogels Pore size distribution of the RF carbon xerogels
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
1 10 100 1000
RF-MEA100
RF-MEA50
RF-MEA200
RF-MEA300
Incr
emen
tal P
ore
Vol
ume
(cm
3/g
)
Pore Diameter ,(nm)
(b)
(a) R/C= 300 by mole with different type of catalytic species
(b) MEA was used as a catalyst with different R/C ratio
0
0.0005
0.001
0.0015
0.002
0.0025
0.003
0
0.1
0.2
0.3
0.4
0.5
RF-MEARF-DEARF-MDEARF-NH4HCO3
RF-Na2CO3
RF-K2CO3
1 10 100 1000
Incr
emen
tal P
ore
Vol
ume
(cm
3/g
)
(a)
Pore Diameter ,(nm)
R/F=0.5 by mole and R/W=0.25 g/cm3
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
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Ch
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Effect of R/W on porous structure of carbon xerogels.Effect of R/W on porous structure of carbon xerogels.
100
200
300
400
500
600
700
800
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
SBET
Smic
S BE
T [ m
2 / g
]
R/W [ g / cc]
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
Vt [cm3/g]
Vmic
[ cm3/g]
V [
cm3
/g]
R/W [ g / cc]
R/F=0.5, R/C= 100, PH=6 and MEA as a catalyst
(a) BET surface area and surface area of micropores
(b) Total and micropores volume
U S
NIVERSITY OF TRATHCLYDE
IN GLASGOW
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Effect of pH on the on porous structure of carbon xerogelsEffect of pH on the on porous structure of carbon xerogels
200
300
400
500
600
700
800
3 4 5 6 7 8
SBET
Smic
S BE
T [ m
2 / g
]
pH
0
0.2
0.4
0.6
0.8
1
1.2
3 4 5 6 7 8
Vt [cm3/g]
Vmic
[ cm3/g]
V [
cm3/g
]
pH
R/F=0.5 R/C=100 by mole, R/W=0.25 g/cm3 and MEA as a catalyst.
(a) BET surface area and surface area of micropores
(b) Total and micropores volume
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NIVERSITY OF TRATHCLYDE
IN GLASGOW
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Ch
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Effect of degree of Burn-off.Effect of degree of Burn-off.
0
500
1000
1500
2000
2500
3000
0
0.5
1
1.5
2
2.5
3
0 20 40 60 80 100
SBET
(m2 / g ) Vt ( cm3/g)
Vmic
( cm3/g)
BE
T s
urf
ace
are
a (
m2 /g
)
To
tal pore
volu
me
( cm 3/g
)
Burn-off (wt%)
R/F=0.5 R/C=100 by mole, R/W=0.25 g/cm3 and MEA as a catalyst.
Variation of the BET surface area, pore volume and micropore volume with the burn off level of carbon xerogels gasified in CO2 at 900°C
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NIVERSITY OF TRATHCLYDE
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Structural characterization with scanning electron Structural characterization with scanning electron
microscopymicroscopy analysis.analysis.
SEM images of cross-section of (a) and (b) samples synthesized under condition pH=6, R/C=300 and R/W=0.25 before and after pyrolysis respectively (c) and (d) carbon xerogels synthesized under condition pH=6, R/C=100 and R/W=0.25 with 0 % and 37% burn-off respectively. (All the samples were prepared using MEA as catalyst)
(a) (b)
( c ) (d)
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ConclusionConclusion
Microporous carbons with high porosity and surface area can be prepared from Microporous carbons with high porosity and surface area can be prepared from Resorcinol-Formaldehyde resinsResorcinol-Formaldehyde resins
The samples evolve from micro-mesoporous solid (RF-NaThe samples evolve from micro-mesoporous solid (RF-Na22COCO33: combination of : combination of
types I and IV isotherms) with 24.2% micropore to an exclusively microporous types I and IV isotherms) with 24.2% micropore to an exclusively microporous material (RF-NHmaterial (RF-NH44HCOHCO33: type I isotherm) with 98.7% micropore. : type I isotherm) with 98.7% micropore.
It is possible to tailor the morphology of these materials by varying the initial It is possible to tailor the morphology of these materials by varying the initial pH of the precursor’s solution in a narrow rangepH of the precursor’s solution in a narrow range
FTIR study shows that samples prepared by MEA, DEA, MDEA and NHFTIR study shows that samples prepared by MEA, DEA, MDEA and NH44HCOHCO33
contain nitrogenated functional groups contain nitrogenated functional groups
High surface area (> 2890 mHigh surface area (> 2890 m22/g) can be obtained at high burn off levels /g) can be obtained at high burn off levels (>75%). (>75%).
These porous materials with these functional groups are being expected as These porous materials with these functional groups are being expected as suitable candidates for acidic gas capture like COsuitable candidates for acidic gas capture like CO22 and SO and SO22, which will be , which will be
studied in the next stage. studied in the next stage.
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NIVERSITY OF TRATHCLYDE
IN GLASGOW
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Thank-YouThank-You
&&
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