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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

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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

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Sol-Gel Technologies and their ProductsSol-Gel Technologies and their Products

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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.

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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

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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

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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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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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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

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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.

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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

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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

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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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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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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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Thank-YouThank-You

&&

QuestionsQuestions