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Separation & Purification Laboratory

Prof. Chang-Ha [email protected] http://web.yonsei.ac.kr/Sepapuri

- University of Pittsburgh, Ph. D. (1993)- Merck & Co., Inc., Post Doctoral Fellow (1994)- International Adsorption Society, Director Board (present)

- The 3rd Pacific Basin Conference on Adsorption Science and Technology, Organizing Chairman (2003)

- Korean J. Chem. Eng., Editorial Board (2003-2007)- General direction of Korean Institute of ChemicalEngineers (present)

Research Area- Gas Adsorption Technology

- Adsorption Process: PSA, TSA, VSA - Equilibrium and Kinetics- New Adsorbents

- Membrane Separation: Ceramic & Metal Memb.- SMB(Simulated Moving Bed): Fine Chemicals- Inorganic/Organic Material Synthesis- Supercritical Fluid Technology- CO2 Storage and Conversion- Process Simulations

PSA Process

1. PSA and TSA Processes- H2 recovery from effluent gas: H2 Station, Reformer, FOG, COG, etc- CO2 removal- O2 generation- Air drying

2. Equilibrium & Kinetics- Zeolite, Activated Carbon, Alumina, Silica, CMS, Coal

3. Process Simulation- Dynamic Simulation- Cyclic Process SMB Process

1. New Operating Strategy - Partial Discard- FeedCol- Recycling Partial Discard

2. Separation Process- p-Xylene Separation- Recemic Separation

3. Chromatography- Equilibrium & Kinetics

4. Process Simulation- Dynamic Simulation - Cyclic Process

Gas Adsorption Technology Simulated Moving Bed

1. Membrane Separation- Organic Templating Membrane- Zeolite Membrane- Pd Membrane- Adsorbent/Membrane Hybrid System- Membrane Reactor

2. Gas Separation- H2 Recovery from reforming gas- H2 Recovery from WGSR gas- CO2/CH4 Separation

1. New Adsorbents for Energy- N- and S-compounds removal from fuels- S-compounds removal from natural gas- Mesoporous silica, Magnetite composite, MgOcomposite, Hybrid Silica

2. New Materials for Biotechnology- Functionalized materials- Core/Shell nanoparticles

1. Nanoparticle Synthesis- YAG:Eu3+ Phosphor- Ce3+ ,Eu3+-Codoped YAG Phosphor- LiNi1/3Co1/3Mn1/3O2 cathode2. SCWO Process- NaFeEDTA decomposition- Halogenated compound decomposition- Anti-corrosive Reactor3. Corrosion- Stainless Steel, Hatelloy, Inconel, Titanium, - Metal Surface Analysis4. Hydrocracking of VR5. Cellulose Decomposition

1. CO2 Storage in Coal Seam- CO2 Adsorption Capacity onKorean Coal- CH2 Recovery from Coal Seam- Water effect & SCF2. CO2 Aquifer Storage- Saline Water Capacity for CO2- Sand Stone Adsorption3. CO2 Conversion- Biological Conversion- Biomass Production- Chemical Production

CO2 Storage and Conversion

Supercritical Fluid Technology

InOrg./Org. Material Synthesis

Membrane Separation

Separation & Purification Laboratory

Properties of supercritical water

AD

AD

DPE

DPEPG PPE

DP

DP

PG PPE FP

FP

Feed FeedVent Vent

Product Product

Vent VentFeed Feed

BED 1

BED 1

BED 2

BED 2

AD , adsorption ; DPE , depressurizing pressure equalization ; DP , depressurization ;

PG , purge ; PPE , pressurizing pressure equalization ; FP , Feed pressurization

Cycle sequence of PSA process

Concept : Dual bed• Adsorption/desorption process is exothermic/endothermic

reaction.• Pressure and temperature affect hydrogen separation process.• Heat transfer between inner bed and outer bed in Dual bed raises

efficiency of H2 PSA process.• Dual bed makes PSA compact and efficient

Heat Exchange Pressure Swing Adsorption

Scheme of PSA process

r1

L

(B) Dual bed

Breakthrough Curve H2/CO2/CH4/CO = 69/26/3/2 vol % , Feed rate : 7 LPM , Adsorption pressure : 9atm

time [s]0 200 400 600 800 1000 1200 1400 1600 1800

mol

e fra

ctio

n [-]

0.0

0.2

0.4

0.6

0.8

1.0

COCH4

CO2

H2

Simulation

Tem

pera

ture

[]

℃

1 0

2 0

3 0

4 0

5 0

6 01 0 c ms im u la tio n

1 0

2 0

3 0

4 0


1 0

2 0

3 0

4 0


tim e [s ]

0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0 1 4 0 0 1 6 0 0 1 8 0 01 0

2 0

3 0

4 0


time [s]0 200 400 600 800 1000 1200 1400 1600 1800

mol

e fra

ctio

n [-]

0.0

0.2

0.4

0.6

0.8

1.0

COCH4

CO2

H2

Simulation

time [s]

0 200 400 600 800 1000 1200 1400 1600 1800

mol

e fra

ctio

n [-]

0.0

0.2

0.4

0.6

0.8

1.0

COCH4

CO 2

H2

Simulation

2 03 04 05 06 0

in n e r 1 0 cms im u la tion

2 03 04 05 0 o u te r 1 0 cm

s im u la tio n

2 03 04 05 0 o u te r 3 0 cm

s im u la tio n

2 03 04 05 0 o u te r 5 0 cm

s im u la tio n

Tem

pera

ture

[OC

]

2 03 04 05 0 o u te r 7 5 cm

s im u la tio n

tim e [s ]0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0 1 4 0 0 1 6 0 0 1 8 0 0

2 03 04 05 0 in n e r 9 0 cm

s im u la tion

2 03 04 05 06 0

in n e r 1 0 c ms im u la tio n

2 03 04 05 0 o u te r 1 0 c m

s im u la tio n

2 03 04 05 0 o u te r 3 0 c m

s im u la tio n

2 03 04 05 0 o u te r 5 0 c m

s im u la tio n

2 03 04 05 0 o u te r 7 5 c m

s im u la tio n

0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0 1 4 0 0 1 6 0 0 1 8 0 0

2 03 04 05 0 in n e r 9 0 c m

s im u la tio n

Tem

pera

ture

[OC

]

t im e [s ]

< Conventional bed > < Inner bed > < Outer bed >


time [s]0 200 400 600 800 1000 1200 1400 1600 1800

mol

e fra

ctio

n [-]

0.0

0.2

0.4

0.6

0.8

1.0

COCH4

CO2

H2Simulation

time [s]0 200 400 600 800 1000 1200 1400 1600 1800

mol

e fra

ctio

n [-]

0.0

0.2

0.4

0.6

0.8

1.0

COCH4

CO2

H2Simulation

Tem

pera

ture

[]

℃

102030405060

inner 10cmSimulation

1020304050 outer 10cm

Simulation

1020304050 outer 30cm

Simulation

1020304050 outer 50cm

Simulation

1020304050 outer 75cm

Simulation

time [s]0 200 400 600 800 1000 1200 1400 1600 1800

1020304050 inner 90cm

Simulation

Tem

pera

ture

[]

℃

0102030405060

inner 10cmSimulation

1020304050 outer 10cm

Simulation

1020304050 outer 30cm

Simulation

1020304050 outer 50cm

Simulation

1020304050 outer 75cm

Simulation

time [s]0 200 400 600 800 1000 1200 1400 1600 1800

0

20

40 inner 90cmSimulation

Inner with desorption in outer Outer with desorption in inner

• The amount of adsorbent in dual bed is 81% of single bed. • However the breakthrough time in dual bed is longer than that in single bed• The first H2 concentration drop is due to the early breakthrough of CO,CH4 and CO2.• The rolling-up phenomenon of CO and CH4 breakthrough curve is due to competitive adsorption.• Due to the heat exchange effects, the outer bed showed almost isothermal behavior. • Roll-up phenomenon in outer bed is smaller than single bed’s tailing and roll-up.• Heat transfer between adsorption and desorption bed raises efficiency of dual bed.

Breakthrough Curve with Heat ExchangeHeat Exchange Pressure Swing Adsorption

• The separation performance of the Compact PSA was higher than that of a conventional PSA at the same condition.

• Compared to the conventional PSA, the high purity product could be obtained from the Compact PSA with relatively small sacrifice of recovery.

AD step time [s]

200 220 240 260 280

H2 C

once

ntra

tion

99.0

99.2

99.4

99.6

99.8

100.0

100.2

Inner bedOuter bedSingle bed simul

AD step time [s]

200 220 240 260 280

Rec

over

y [%

]

65

70

75

80

85

Dual bedSingel bed simul

P/F ratio [-]

0.0 0.1 0.2 0.3

H2

Con

cent

ratio

n

86

88

90

92

94

96

98

100

102

Inner bedOuter bedSingle bed simul

P/F ratio [-]

0.0 0.1 0.2 0.3

Rec

over

y [%

]

60

70

80

90

100

Dual bedSingle bed simul

Effect of P/F ratio on Dual Bed(AD step time = 225 s)

Effect of AD step time on Dual Bed(P/F ratio = 0.2)

Process Performance Feed flow rate : 7 LPM , Adsorption pressure : 9 atm


Adsorption Dynamics of a Layered Bed

Breakthrough curves of activated carbon bed, zeolite-5A bed, layered bed (c.r.=0.5)

Effects of Carbon-to-Zeolite Ratio on Layered Bed

Effect of carbon ratio on(a) purity and (b)recovery

At three pressures,Feed rate7 LSTP/min,Purge rate0.7 LSTP/min

At three feed rates,Pressure11 atm,Purge rate0.7 LSTP/min

At three purge rates,Pressure11 atm,Feed rate7 LSTP/min

Effects of Feed Composition on a Layered Bed

0.32 C/Z 0.5 C/Z 0.65 C/Z

C/Z : carbon-to-zeolite ratio.

Breakthrough curves(a) base composition: N2=5.5%(b) higher nitrogen composition: N2=7.5%(c) no nitrogen composition: N2=0.0%

COG (Coke Oven Gas): H2 56.4 %, CH4 26.6 %, CO 8.4 %, N2 5.5 %, CO2 3.1 %

•J.Y Yang and C.H Lee, “Adsorption Dynamics of a Layered Bed PSA for H2Recovery from Coke Oven Gas”, AIChEJournal, June 1998, Vol. 44, No. 6

•C.H. Lee, J.Y. Yang, and H.W. Ahn, “Effects of Carbon-to-Zeolite Ratio on Layered Bed H PSA for Coke Oven Gas”, AIChE Journal, March 1999 Vol. 45, No. 3

•H.W. AHN, J.Y. YANG, C.H. LEE, “Effects of Feed Composition of Coke Oven Gas on a Layered Bed H2 PSA Process”, Adsorption 7: 339–356, 2001

H2 Pressure Swing Adsorption

gasifier

CoalWGSR

Reforming gas

- From gasification of coal- Low H2 fraction- Huge amount of impurities

Experimental and simulated breakthrough curves of a layered bed(AC:Z5A=7:3) under 6.5 bar pressure and 5 LPM feed flow rate

Effect of P/F ratio Effect of adsorption pressure

Two-bed PSA process

Simulation results of four-bed PSA process

Breakthrough curves and Temperature profile

•S. Ahn, M.S. thesis, “2bed/4bed PSA processes for H2 recovery from coal gas “, Yonsei university (2009).

Reforming Gas: H2 38%, CH4 1%, CO 1%, N2 10%, CO2 50%

H2 Pressure Swing Adsorption

• The “FeedCol” operation combines a chromatographic column as a feed column with SMB system to create the “TMB effect”

• The “rectangular pulse input” is introduced to the Feed column, and partially separated feed is injected into the SMB

Modification of SMB configuration “FeedCol” Strategy

FeedCol operation (1+2-2-2-2 system)

• Injection length and injection time are variables to operate the system

• The pre-separated feed improved the separation efficiency even extra adsorbent used in the FeedCol operation

ZoneⅠ ZoneⅡ

ZoneⅢZoneⅣ

QEExtract

QDDesorbent QF

Feed (A+B)

QIPulse

Injectionfor Feed(A+B)

Direction of liquid flow

QRRaffinate

90 1tsw 2tsw 1tsw 2tsw

• H.H. Lee, K.M. Kim and C.H. Lee “Improved performance of simulated moving bed Processes using column-modified feed”,AlChe J., 57(8) (2011) 2036-2053.

Simulated Moving Bed(SMB) ChromatographyDevelopment operating strategy to improve the separation efficiency

• Initial stage of extract and last stage of raffinate in a switching period have huge amount of impurity → Purity can be enhanced by discarding these parts

• However, the other performance parameter were deteriorated from the waste of product in the partial-discard operation

Periodic modulation“Partial-Discard (PD)” and “Recycling Partial-Discard (RPD)” Strategy

Recycling Partial-Discard

• In the Recycling Partial-Discard operation, the discarded portions are recycled as feed to reduce the loss from discarding

• Initial stage of extract and last stage of raffinate are collected to each storage tank and recycled to the last stage and initial stage of feed, respectively

Extract

Raffinate

Direction of fluid

ZoneⅠ ZoneⅡ

ZoneⅢZoneⅣ

FeedDesorbent

1tsw 2tsw

• By applying the recycle concept to PD strategy, the loss of other performance parameters are successfully reduced while the purity can be maximized

• Y.S. Bae and C.H. Lee, “Partial-Discard strategy for obtaning high purity products using simulated moving bed chromatography”, J. of Chromatogr. A. 1122 (2006) 161-173• K.M. Kim, H.H. Lee and C. H. Lee, “Improved Performance of a Simulated Moving Bed Process by a Recycling Method in the Partial-Discard Strategy”, Ind. Eng. Chem. Res., 51(29) (2012) 9835-9849.

Simulated Moving Bed(SMB) Chromatography

Hybrid Membrane System

AdsorptionZeolite (Membrane)- micorporous, aluminosilicateminerals- contain many cavities (over 50%)- strong adsorption affinity to polar molecules- possibly adsorb specific non-polar molecules

Activate Carbon (Adsorbent)- the surface area : 300~2500m2/g- the pore size : 30Å(for liquid phase use), 10~25Å(for gas phase use)

L

R inR out

Membrane

Adsorbent

Ceramic MembraneAdvantages Disadvantages

- Long term stability at high temperature

- It has an excellent resistance to harsh environment, such as temperature, pressure and poison

- Inertness to microbiological degradation

-Easy regeneration after fouling

- It is low capital process - Easy catalyst modification

- High capital cost for synthesis- Brittleness- It is difficult to achieve high selectivities in large-scale microporous membranes

- low permeability of the highly selective membranes at medium temperature

- Difficult membrane to module sealing at high temperature

Ceramic Membrane Separation

[1] Jong-Ho Moon, Ji-Han Bae , Youn-Sang Bae, Jong-Tae Chung, and Chang-Ha Lee, Hydrogen separation fromreforming gas using organic templating silica/alumina composite membrane, J. Memb. Sci. 318(2008) 45-55.

Time [sec]

0 100 200 300 400

C/C

0 [ -

]

0.0

0.2

0.4

0.6

0.8

1.0

1.2

4 atmSimulation

AdsorptionAdsorptionPropertiesSingle Gas Permeation

: Transient flux

Multi Component Transient permeation[1]

Pressure[kPa]

100 200 300 400 500 600 700

Mol

e Fl

ux[m

ol/s

ec-m

2 ]

0.0000

0.0005

0.0010

0.0015

High Temperature

Low Temperature

313.15K

GMS+DGM model

348.15K388.15K433.15K473.15K

Single Gas Permeation: Steady State flux

GeometryProperties

PermeationPropertiesPermeationProperties

Characteristics Schematic of Membrane Apparatus


H2/CH4 Binary Component Steady-state permeationIn AMH system [2]

Pressure [kPa]100 200 300 400 500

H2/C

H4 S

epar

atio

n Fa

ctor

[ - ]

100

120

140

160

180

200

30℃

40℃

50℃

(b)

Perm

eatio

n Fl

ux ×

104 [m

ol/m

2 sec]

0.0

0.2

0.4

0.6

0.8

1.030℃

40℃

50℃

Simulation

(a)

Pressure [kPa]100 200 300 400 500

H2/N

2 Sep

arat

ion

Fact

or [

- ]

20

30

40

5030℃

40℃

50℃

Perm

eatio

n Fl

ux ×

105 [m

ol/m

2 sec]

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

30℃

40℃

50℃

Simulation

(a)

(b)

Pressure [kPa]

100 200 300 400 500

H2/C

O S

epar

atio

n Fa

ctor

[ - ]

10

15

20

25

30

35

30℃

40℃

50℃

Perm

eatio

n Fl

ux ×

106 [m

ol/m

2 sec]

1.5

2.0

2.5

3.0

3.5

4.0 30℃

40℃

50℃

Simulation

(a)

(b)

H2/N2 Binary Component Steady-state permeationIn AMH system [2]

H2/CO Binary Component Steady-state permeationIn AMH system [2]

[2] Jong-Ho Moon, Ji-Han Bae, Yun-Jin Han, and Chang-Ha Lee, Adsorbent/Membrane Hybrid (AMH) System for HydrogenSeparation : Synergy Effect between Zeolite 5A and Silica Membrane, J. Memb. Sci. 356(1-2) (2010) 58-69.

Permeation flux of Binary mixtures What’s the Next step?

- To develop an integrated WGS reaction and Palladium alloy membrane separation process at several conditions.

- To test the separation performance by measuring permeation flux of CH4/CO/CO2/H2quaternary mixture


Stress Corrosion Cracking in SCWO

Supercritical water oxidation Anticorrosive SCWO system

fluid discharged from the tube

S.H. Son, J.H. Lee, S.H. Byeon, and C.H. Lee, Surface Chemical Analysis of Corroded Alloys in Subcritical and Supercritical Water Oxidation of 2-Chlorophenol in Continuous Anticorrosive Reactor System ,Ind. Eng. Chem. Res. 2008, 47, 2265-2272

Advantages Disadvantages-High rate decomposition -Shot residence time- complete decomposition- Low temperature - No effluent Nox, Sox, Dioxin

- close system- Minimization of Toxic gas

-Corrosion on system by acid at high temperature and pressure

-Fouling by decreasing solubility of inorganics

- INon-exist of special materials

For corrosion at high temp. and pressure

cross section of the tube wall

Water

NonporousCeramic tube

Metal alloys

Heater

TC

TC

TC

Counteragent

TC

TC

Wastewater (2-CP) Oxidant (H2O2)

Super Critical Water Oxidation

In this study, the effects of metal corrosion on the SCWO of 2-chlorophenol wereinvestigated at subcritical and supercritical conditions by using the anticorrosive SCWOsystem. In addition, to elucidate the corrosion characteristics of the selected metals at bothconditions, a surface chemical analysis of corroded metal alloys was conducted by variousmethods.

0

20

40

60

80

100

0 100 200 300 400 500

Temperature (oC)

Sol

ub

ility

in

wat

er (

Wt

%)

Inorganic

Hydrocarbons

Subcritical Supercritical

Organics Oxygen OxygenOrganics

Water Water

1. Counter agent (NaOH )6. Pressure gauge10. Data saving system14. Heating tape18. Line filter

2. Water7. Check valve11. Pre - heater15. Heating tape controller19.Back pressure regulator

3. Wastewater8. Ball valve12. Heater16. Reactor20. Air/water separator

5. High - pressure pump9. Pressure transducer13. Heater controller17. Condenser (cooling zone)21. Sample tray 22. Thermocouple

4. Oxidant

H.P

H.P

3

8

Gas

H.P

H.P

4

5

7

Gas

1918

12

20

21

16

6

9

11

14

15

22

13

17

10

LiquidH.P

1

P

P

P

H.P

2

P

Counteragent

Water

Wastewater + Oxidant

Nonporousceramictube Metal

alloys

C.-H. Lee et al. / J. of Supercritical Fluids 36 (2005) 59–69


AES montage displays at subcritical and supercritical conditions.

ICP-MS Results of Stainless 316at Subcritical and Supercritical Conditions

Sang-Ha Son et al/ Ind. Eng. Chem. Res., Vol. 47, No. 7, 2008

Corrosion in the subcritical regionBefore corrosion Corrosion in the

supercritical region

Corrosion Phenomena in SCWOStainless 316

S.-H. Son et al. / J. of Supercritical Fluids 44 (2008) 370–378

Corrosion in the subcritical regionBefore corrosion Corrosion in the

supercritical region

AES montage display of the surface of each metal alloy at the subcritical and supercritical conditions (e) and (f) Zirconium 702)

Corrosion Phenomena in SCWOZirconium 702

These figure show the comparison of destruction efficiencies of 2-chlorophenol at bothsubcritical and supercritical conditions with the corrosion of metal alloy. It was evident thatthe corrosion of stainless steel 316 contributed to the improvement of destruction of 2-chlorophenol at both the subcritical and supercritical conditions, compared to the destructionefficiencies without metal corrosion.

Comparison of destruction efficiencies of 2-chlorophenol with corrosion of metal alloys at the subcritical (blank symbols) and supercritical (solid symbols) conditions. (a) Stainless steel 316; (c) Monel K-500.

Sang-Ha Son et al/ Ind. Eng. Chem. Res., Vol. 47, No. 7, 2008


Bio-Catalysis – NSM

HR TEM : scale bar: 5 &10nm

TEM : scale bar: 20 & 50nm

SDS-NSM

S.L. Tie, Y.Q. Lin, H.C. Lee, Y.S. Bae, C.H. Lee, Colloids Surf. A: Physicochem. Eng. Aspects 273 (2006) 75–83.K.M. Ponvel, D.G. Lee, E.J. Woo, I.S. Ahn, C.H. Lee, Korean J. Chem. Eng., 26(1) (2009) 127-130.D.G. Lee, K.M. Ponvel, M. Kim, S.P. Hwang, I.S. Ahn, C.H. Lee, Journal of Molecular Catalysis B: Enzymatic 57 (2009) 62–66.

VSM

Ox-NSM Amino Acid coated- NSM SDS-NSM

a : Ox-NSM, b : Leu-NSM, c : reference NSM

SDS-NSM

ABS-NSM

ABS-NSM

Surface modified NSM(Nano Size Magnetite)

Leu-NSMOx-NSM ABS-NSM

S.L. Tie, H.C. Lee Y.S. Bae, M.B. Kim, K.T. Lee, C.H. Lee, Colloids and Surfaces A: Physicochem. Eng. Aspects 293 (2007) 278–285.S.H. Lim, E.J. Woo, H.J. Lee, C.H. Lee, Applied Catalysis B: Environmental 85 (2008) 71–76.E.J. Woo, K.M. Ponvel, I.S. Ahn, C.H. Lee, J. Mater. Chem. 20 (2010) 1511–1515.K.M. Ponvel, C.H. Lee, J. Phys. Chem. A MATCHEMPHYS-D-09-03162R1

TEM & HR-TEM & SEM image

VSM

(a) NSM particles(b) NSM-MCF

(a) magnetic nanoparticles(b) magnetic core/shellNSM and Si-NSM-1

A : Ox-NSMB : Ox-Fe3O4@SiO2 C : Fe3O4/Fe@SiO2D : Fe2O3/Fe@SiO2

A : Ox-NSM B : Ox-Fe3O4@SiO2 C : Fe3O4/Fe@SiO2 D : Fe2O3/Fe@SiO2

(a) MCM-41 (b) NSM (c) and (d) Si-NSM-1

(a) and (b) : magnetic nanoparticles(c) and (d) : magnetic/silica nanoparticles

(a) NSM (b) and (c) MCF (d) and (e) NSM-MCF

Bio-Catalysis – Magmetite silicaMagnetite Silica Composite

• Toxic chemical in gas phase present a hazard to the environment.

• They are very stable molecules, they are hard to destroy and can persistin the atmosphere for long periods of time.

• Natural gas streams and crude oil streams contain H2S, which is verytoxic, hazardous, and corrosive.

• MgO is an exceptionally important material, with uses in catalysis, toxicwaste remediation, or as an additive in refractory, paint, andsuperconducting products, as well as fundamental and application studies.

• Ultrafine metal oxide particles have found use as bactericides,adsorbents, and, specifically, catalysts.

• MgO in particular has shown great promise as destructive adsorbent fortoxic chemical agents.

The purpose of this work is to study the adsorptive properties of MgO.Through high surface area of these materials, we would try to improvethe adsorptive capacity, affinity and selectivity toward toxic chemical ingas phase.

Magnesium Oxide Nano-Particles

- Mg(OH)2 - MgO

- MgO

- MgO- Mg(OH)2

Aerogel Hydrothermal

Polyol thermolysis

1) Chem. Mater. 1991, 3 , 175-181. / MgO Surface area : 522 m2/g2) Y. Qian, Chem. Mater, 2001, 13, 435. / MgO Size : 20~50 nm, Surface area : 143 m2/g3) T. Vasudevan, Nanotechnoloy, 2007, 18, 225601. / MgO Size : ~10 nm, Surface area : 112 m2/g

1) 2)

3)

Magnesium Oxide Nano-ParticlesTEM images

XRD : MgO

The purpose of this work is tostudy the adsorption propertiesof Lithium (Li) modifiedmesoporous silica adsorbentstoward nitrogen and sulfurcompounds in fuels and gas.

0 3 6 9 12 150

10

20

30

40

N

itrog

en R

emov

al (%

)

Adsorbent dose (mg/ml)

Si-Zr YSP-Li MCF-Li

a)

0 3 6 9 12 150

10

20

30

40

50

Nitr

ogen

Rem

oval

(%)

Adsorbent dose (mg/ml)

Si-Zr YSP-Li MCF-Li

b)

0 100 200 300 400 500 2736 28800

5

10

15

20

25

30

35

40

a)

YSP-Li MCF-Li Si-Zr

Time (min)

Nitr

ogen

Rem

oval

(%)

0 100 200 300 400 500 2000 2500 30000

10

20

30

40

Nitr

ogen

Rem

oval

(%)

Time (min)

YSP-Li MCF-Li Si-Zr

a)

1 2 30

10

20

30

40

50

1st adsorption at 15 oC Readsorption After MIBK Readsorption After Toluene

Nitr

ogen

Rem

oval

(%)

YSP-Li MCF-LiSi-Zr

a)

1 2 30

10

20

30

40

50 1st adsorption at 45 oC Readsorption After MIBK Readsorption After Toluene

N

itrog

en R

emov

al (%

)

Si-Zr MCF-LiYSP-Li

b)

[1] Youn-Sang Bae, Min-Bae Kim, Hyun-Jung Lee, and Chang-Ha Lee, “Adsorptive Denitrogenation of Light Gas Oil by Silica-Zirconia Cogel”, AIChE Journal 52, (2006), 510-521.[2] Jun-Mi Kwon, Jong-Ho Moon, Youn-Sang Bae, Dong-Geun Lee, Hyun-Chul Sohn, Chang-Ha Lee, "Adsorptive Desulfurization and Denitrogenation of Refinery Fuels by Mesoporous Silica Adsorbents," ChemSusChem,1 (2008) 307-309.

The effect of adsorbentconcentration on nitrogencompounds uptake at 15 °C(a) and 45 °C (b) for 48 h(80 rpm) in fuel.

Kinetic of nitrogen compoundsadsorption at 15°C (a) and45°C (b) (adsorbentconcentration – 10mg/ml,stirring speed – 80 rpm).

Effect of recovering sorbentsby 5 ml of Toluene or MIBKat (a) 15°C and (b) 45°C(adsorbent concentration –10mg/ml, stirring speed at80 rpm) for 24 h and 48 hfor first adsorption (withfuel).

TEM images of (a,b) MCF-Liand (c,d) YSP-Li.

Results: According toadsorption capacity, adsorptionrate and regeneration, the Li-modified silica adsorbents (YSP-Li and MCF-Li) were better thanSi-Zr cogel for diesel fueldenitrogenation. The adsorptioncapacity of YSP-Li was lesssensitive to the appliedtemperature and itsregeneration ability wasexcellent.

Lithium modified mesoporous silica for denitrogen of raw diesel fuel RHDS DSL

CH

4

CH

3 SH

MFC

Mixturetank

RTD

TC

Filter

PG

PG

To GC

HeaterSorbent

0 100 200 300 400 5000,0

0,2

0,4

0,6

0,8

1,0

0 50 100 150 200 2500,0

0,5

1,0

1,5

2,0

C/C

0

Time, min

Dimethyl disulfide Methylmercaptan

C/C

0

Time, min

Adsorption Readsorption

Desorption at 100C0

a)

0 100 200 300 400 500 600 700 8000,0

0,2

0,4

0,6

0,8

1,0

0 50 100 150 2000,0

0,5

1,0

1,5

2,0

2,5

C/C

0

Time, min

Methylmercaptan Dimethyl disulfideC

/C0

Time, min

Adsorption Readsorption

Desorption 100C0

b)

0 20 40 60 80 100 120 140 1600,0

0,2

0,4

0,6

0,8

1,0

C/C

0

Time, min

c) Adsorption at 50C0

[3] Seol-Hee Lim, Eun-Ji Woo, Hyunjoo Lee, Chang-Ha Lee "Synthesis of magnetite–mesoporous silica composites as adsorbents fordesulfurization from natural gas," Applied Catalysis B: Environmental, In Press, 2008.

Breakthrough curves of methylmercaptan on YSP-Li (a) and MCF-Li(b) at 25C°, and YSP-Li at 50C° (c) (activated at 150C°) anddesorption curve of methylmercaptan and dimethyl disulide from YSP-Li (a) and MCF-Li (b) at 100C°. Gas mixture flow rate – 50 ml/min.The concentration of methylmercaptan in gas mixture was 291ppm.

Adsorbentmass 0.3g Column diameter 7mm

Gas flow rate 50ml/min Column length 50mm

Lithium modified mesoporous silica for desulfurization of natural gas

• Petroleum vacuum residue (VR) consist mainly hydrocarbons with high boiling points and contains much higher portions of asphaltenes as well as much higher concentrations of sulfur, nitrogen, heavy metal (vanadium, nickel) compared with the conventional crude oils.

• The processes that convert these residues into low boiling , value-added products, less concentrations of heterocyclic species and metals are called residue upgrading processes.

• Advantage of upgrading VR in supercritical hydrocarbon solvent process:+ Mild operating temperature (about 390-420oC) + Improve the diffusion rate , enhance coke extraction, retard coke deposition at the

supercritical hydrocarbon solvent state.+ The combination between activated carbon and hydrocarbon solvent make the

“hydrogen – shuttling” mechanism would enhance solvent effect significantly.

Introduction

Goal of Work

In this work, we investigate the effectiveness of various kinds of catalysts and hydrocarbon solvents in the upgrading of VDU-VR at supercritical condition in a batch reactor.

[1] D.S.Scott, D. Radlein, J. Piskorz, P. Majerski, Th.J.W deBruijn. Fuel 80 (2001) 1087-1099.[2] Chunbao Xu, Shawn Hamilton, Adiel Mallik, Mainak Gosh, Energy & Fuels, 21, (2007),3490-3498.

Upgrading of Vacuum Residue(VR) in SCF

hydro-carbon solvent

CatalystT: 400oC

H2

Figure2. SimDis analysis plot

Figure 1. Schematic diagram of the experiment apparatus.

naph

tha

solven

t

kerosene

distillate

Heavy oil

Pitch

These peaks of kerosene , naphtha which were appears in DimDis analysis plot were proved that the carbon –carbon bonding of VR were cleaved under supercritical fluid condition

Figure3. Boiling point distribution plot

The fractions of naphtha, kerosene and distillates, which is shown in the boiling distribution plot, were generated by the VR upgrading reaction

Upgrading of Vacuum Residue(VR) in SCF

0.74K379ppm

Increasing CO2 atmospheric concentration &global surface temperature

Themogravimetryanalyzer

Automatic High Pressure Gas Adsorption Analyzer

Experimental Apparatus

High pressure gravimetric analyzer

-Establishment of Database for CO2Sequestration

-Measurement/Evaluation of CO2 storage capacity in Coal Bed & Deep Saline Formations

-Optimization of CO2storage process design

Geological Storage Option

The Geological Storage of CO2

Dry coal plate’s diameter change of CO2adsorption at 318.15 K[1]

High pressure CO2/CH4 mixture gas preferential sorption measurement on dry coal at 318.15K[2]

Adsorption and desorption of CH4 and CO2on dry coal and wetted coal at 338.15K[2]

M-DR and M-DR+k fitting of CO2 adsorption at 338.15K[2]

Pure CO2 & CH4 Adsorption on Coal

Mixture gas Adsorption on Coal

[1] Junwei He, “High pressure adsorption of CO2 on coal”, M.S. thesis, Yonsei University(2009).[2] Yao Shi, “High pressure adsorption and desorption behaviors of CH4 and CO2/CH4 mixture on coal”, M.S. thesis, Yonsei University(2010).

Texture of sample Coal

[1]

Model Fitting Properties of Sandstone

The Geological Storage of CO2

Renewable and available essentially for all countries.Contains negligible sulphur, nitrogen and metal contents.Does not result in a net increase in the CO2 concentration in the atmosphere.

Biomass:

Wood is the preferred raw material for biomass conversion based on resource

and process evaluations.

Lignocellulose consists mainly of:Cellulose (35–50%)Hemicellulose (20–35%)Lignin (5–25%)

Problem of conversion: Lignocellulose

Structure of cellulose (chain conformation) (left) and Lignin (right)

Biomass Fuel with Supercritical Solvent

1 – Reactor, 300ml.2 – Heater3 – Stirrer4 – Thermocouple5 – Cover of reactor

PH2

1234

5

6

8

79Supercritical fluids provide unique

transport properties:• Gas-like diffusivity• Liquid-like properties• Have the ability to dissolve materials notnormally soluble in either liquid or gaseousphase of the solvent. Therefore it promotes thegasification/ liquefaction reactions.• Acid and sulfur containing groups on thesurface have been found to be an effectivecatalyst for cellulose liquefaction.[1]

The purpose of this work:• Study decomposition pathways of microcrystalline cellulose, lignin and lignocellulose in various solvents at sub- and supercritical conditions.• Check the catalytic ability of surface modified magnetic nanoparticles. [2,3]

• Combine with technology of VR upgrading.

6 – Safety valve7 – Pressure gauge8 – Motor9 – Digital Pressure Gauge

[1] Da-ming Lai, Li Deng, Jiang Li, Bing Liao, Qing-xiang Guo, and Yao Fu, ChemSusChem 4 (2011) 55–58.[2] Seol-Hee Lim, Eun-Ji Woo, Hyunjoo Lee, Chang-Ha Lee, Appl Catal B: 85 (2008) 71–76.[3] Kanagasabai Muruganandam Ponvel, Yo-Han Kim, Chang-Ha Lee, Mat Chem Phys 122 (2010) 397–401.

Reactor for biomass conversion

Biomass Fuel with Supercritical Solvent

separation & purification laboratoryweb.yonsei.ac.kr/sepapuri/htm/progressing_projects.pdf-...

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