Division of Energy Systems ResearchEnergy Process System Lab.

A Study of Carbon Dioxide Adsorption Performance by the A Study of Carbon Dioxide Adsorption Performance by the Ion Exchange of ZeoliteIon Exchange of Zeolite--13X13X

Ajou University , South KoreaAjou University , South Korea

HyungHyung--Teak KimTeak Kim

Energy Process System Lab.ContentsContents

IntroductionI

Experimental II

Results and discussionIII

ConclusionIV

Energy Process System Lab.

The syngas produced from the wastes can be utilized

as fuel in the gas engine for electricity generation which

has higher efficiency or feedstock in C-1 chemistry to

produce useful chemical raw materials.

CO2 must be separated from

the gas mixture of CO2, CO,

H2 to produce medium-Btu

syngas mainly composed of

CO and H2

Prepared sorbents are conducted with CO2 adsorption/desorption experiments in

the lab-scale reactor with various conditions.

Zeolite samples which are ion exchanged with Li+, Na+, K+, Ca2+ are also experimented for

adsorption/desorption characteristic.

IntroductionIntroduction

Energy Process System Lab.IntroductionIntroduction

Earth average temperature℉

Global warming Global warming that that threaten threaten lifelife!!!!

U.S National Climatic Data Center 2001

Energy Process System Lab.Introduction Introduction (CO2 Capture)(CO2 Capture)

AdsorptionComparatively simple design

Good for high concentration of CO2 gas

No corrosion

No wastewater

Energy Process System Lab.Introduction Introduction (CO2 Regeneration)(CO2 Regeneration)

Concept of carbon dioxide Concept of carbon dioxide

adsorption/desorption process adsorption/desorption process

Desorption system

Desorption system

Desorption system

Adsorption system

Adsorption system Adsorption system

Energy Process System Lab.

J – 13X Na2O 19.5981MgO 0Al2O3 32.1969SiO2 46.734Cl 0.40919

K2O 0.46303CaO 0.52764TiO2 0

Fe2O3 0CuO 0.07107

XRF (X-Ray Fluorescence)

In this research, used zeolite 13X of

Jishim tec.

Main ingredients of adsorbent is Na2O,

Al2O3, SiO2

(단위:wt%)

Materials(1) Materials(1) ; Zeolite13X

Energy Process System Lab.

BET analysis result BET analysis result

Bet area(m2/g)

Pore volume(cc/g)

Pore size(Å)

Zeolite 13X(Jishim) 863.2 0.4608 4.6071

Powder surface

Sample cell

LN2

Gas in (N2, Ar,Kr)

Sample powder

Gas outgas molecules(N2,Ar,Kr) Principle of

BET method

- Physisorption by

Van der Waals f

orce at low te

mperature

Materials(2) Materials(2) ; Zeolite13X

Energy Process System Lab.

TSA

Exhaust gas

Process flow diagram of adsorption /desorption reactor

Experiments (1) Experiments (1) ; ; reactor

Energy Process System Lab.Experiments (2)Experiments (2) ; Hydrothermal methodMaterials Description

Ingredient ofSynthesis

Zeolite 13X Basic materialNacl, KCl, CaCl2, LiCl Ion exchange of aqueous solutions

Bentonite((Al,Mg)2Si4O10(OH)2∙4H2O)

Inorganic bonding agent

Methyl cellulose Organic bonding agentH2O Solvent

Methods Description

Sequentialsynthesis methods

Ion exchange • Ion exchange of aqueous solutions is injected using the nozzle and mixing with zeolite in reactor. 60℃, 1atm, 12hr

Dry • 120℃, 1atm, 2hr

Synthesis • Bentonite, Methyl cellulose and H2O are mixed• 60℃, 1atm, 1hrDry • 120℃, 1atm, 2hr

Calcine • 650℃, 1atm,2hr• 5℃/min

Applying instruments Mixer, Heat mental, Furnace, Vacuum Desiccator

Energy Process System Lab.

Ion-exchange furnace

Experiments (3)Experiments (3)

The adsorbent of Zeolite 13x is dissolved in NaCl,KCl,CaCl2,LiCl and H2O, and

the mixture is dehydrated for 12 hour . Then, the production is added in the

solution of Bentonite ((Al,Mg)2Si4O10(OH)2∙4H2O)and methyl cellulose, and

dried for about 2 hour. At last, the dried product is calcined at 923K

(wi th the temperature gradient 5℃/min) to obtain Zeol i te adsorbent .

; Ion-exchange method

Zeolite 13x

Energy Process System Lab.Experiments (4)Experiments (4)

Materials Description

Ingredient ofSynthesis

Zeolite 13X of ion-exchange Basic material

H2O Solvent

Methods Description

Sequentialsynthesis methods

Mixing • Zeolite 13X, H2O is mixed and kneaded

Extrusion • Adsorbent of pellet type is produced using extruder

Dry • 120℃, 1atm, 2hr

Calcine • 650℃, 1atm, 5hr• 5℃/min

Applying instruments Extruder, Heat mental Furnace

; Extrusion method

Energy Process System Lab.Experiments (5)Experiments (5)

ion exchanged Zeolite 13x Extrusion

Adsorbent of pellet type

The adsorbent mixture of zeolite 13x and H2O are extruded to cylindrical

shaped form by an extrurder. At last, the product is calcined at 873K (with the

temperature gradient 5°C/min) to obtain Zeolite adsorbent.

Energy Process System Lab.Results and discussion(3)Results and discussion(3)

XRD (X-Ray Diffraction) analysis result

Rigaku company D/MAX 2500U/PC Analysis condition : nitrogen condition

13X-Na13X-Ca13X-K13X-Li

Energy Process System Lab.

12hr Ion exchange (ppm)Ca K Li Na Al

13X-Ca 46800 20250 3408013X- K 80520 26230 961413X-Na 77410 3237013X-Li 17100 36170 76330

13X-Ca 13X-K 13X-Na13X-Li

Results and discussion(4)Results and discussion(4)ICP(Inductively Coupled Plasma) analysis result

Most alkali metallic ionshows high

concentration except Li

Energy Process System Lab.

CO2-TPD analysis result

Results and discussion(6)Results and discussion(6)

Pretreatment : 30℃ to 300℃(10℃/min), at 300℃ for 30min with He(flow rate=50cc/min)

Adsorption: at 25℃ for 30min with 10%CO2/He(flow rate=50cc/min)

Sweeping : at 25℃ for 30min with He(flow rate=50cc/min)

Desorption: 25℃ to 400℃(10℃/min), at 400℃ for 1 hr with He(flow rate=50cc/min)

Sample(g) Flow rate(ml/min, min)Set point

(℃)

SPHolding

time(min)

adsorption amount(cm3/g)

13X-Na 0.0798 50.10, 30 400 60 26.0409

13X-Ca 0.0887 50.11, 30 400 60 19.7837

13X-K 0.0920 50.15, 30 400 60 17.5778

13X-Li 0.0887 50.16, 30 400 60 16.3974

Energy Process System Lab.Results and discussion(7)Results and discussion(7)

XRD (X-Ray Diffraction) analysis result

4hr 1M4hr 3M12hr 1M12hr 3M24hr 1M24hr 3M

Rigaku company D/MAX 2500 U/PC Analysis condition : nitrogen condition

Energy Process System Lab.Results and discussion(8)Results and discussion(8)Comparison of CO2 adsorption performance

CO2 adsorption per unit mass of adsorbent mg CO2/ g

Energy Process System Lab.ConclusionConclusion

To enhance CO2 absorption capacity, ion-exchange solution such as NaCl,

KCl, LiCl and CaCl2 is used with Zeolite 13X with 12hr time period. Zeolite 13X

with NaCl ion-exchanged shows the highest adsorption quantity.

Structure of Zeolite adsorbent with ion exchanged of different aqueous

solution represents no big change. While changing the concentration and

exposed time of aqueous solution during the ion-exchange process, structure of

the adsorption was not transformed.

The CO2 adsorption amount had not changed greatly with NaCl molarity but

changed with exposure time.

Energy Process System Lab.AcknowledgmentAcknowledgment

This work is supported through the research fund of

next-generation, new environmental technology program,

which is sponsored by the Ministry of Environment,

Korean government.

Energy Process System Lab.

Thank you for your attention!!Thank you for your attention!!