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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
5 03 0 c ms im u la tio n
1 0
2 0
3 0
4 0
5 05 0 c ms 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 01 0
2 0
3 0
4 0
5 07 5 c ms im u la tio n
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 >
Heat Exchange Pressure Swing Adsorption
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
Heat Exchange Pressure Swing Adsorption
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
Ceramic Membrane Separation
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
Ceramic Membrane Separation
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
Super Critical Water Oxidation
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
Super Critical Water Oxidation
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