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CHEMRAWN XVI Conference
Consultation Forum
Innovation Stage: the way pure to the applied chemistry
Transformation of the old process:Ethylbenzene to Styrene with CO2dilution
CHEMRAWN XVI Conference
Consultation Forum
Innovation Stage: the way pure to the applied chemistry
Transformation of the old process:Transformation of the old process:
EthylbenzeneEthylbenzeneto Styrene with COto Styrene with CO22dilutiondilution
MIN CHE CHON
Chon I nternati onal Co. , Ltd.
MIN CHE CHON
Chon I nternati onal Co. , Ltd.
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Conventional Process for Styrene Production
Drawbacks o f EBD Process w ith Steam
-High energy consumptionduring the condensation of steam
due to high latent heat of water
-Catalyst deactivation in the presence of CO2as a by-product
- The need for high steam-to-ethylbenzene ratio
Worldwide Capacity for Production of Styrene Monomer:more than 20 Mt/year (2.3 Mt/year in Korea)
More than 90%: Ethylbenzene Dehydrogenation with Steam
Commercial Catalyst:Fe2O3-K2O-CeO2 with additives
Role of Steam in Ethylbenzene Dehydro genation (EBD)
- Shift of the equilibrium towards higher conversions
- Supply for heat of reaction with superheated steam
- Decrease of the amount of coke by steam gasification
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Company Capacity Location Starting year Process Licensor
YNCC 140 Yeochon 1986, 1995 Badger Eng.
LG Chemical 330 Yeochon 1990, 1991 Lummus/Monsanto
SK Oxychemical 300 Ulsan 1991 Badger/Mobil/ARCO*
260 Ulsan 1997 ARCO
Dongbu Chemical 210 Ulsan 1978, 1989 Monsanto/Lummus
Samsung GC 590 Daesan 1991, 1996 Badger
Hyundai PC 325 Daesan 1991, 1996 Badger Raytheon
Total 2,155 2.5 Mt/year capacity (Year 2001)
*Dehydrogenation process of MBA (Methyl benzyl alcohol)
Year 1999 (Unit: 1000 T/Y)
Production of Styrene Monomer in Korea
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ProblemsProblems
1. High Energy Consumption by Use of Excess SteamHigh Energy Consumption by Use of Excess Steam
estimated to 10% of production cost
2. Low equilibrium conversion2. Low equilibrium conversionof ethylbenzene to styrene
due to limitation of thermodynamic equilibrium
3. Increase in risk to crack of the reactor and preheater
due to high temperature operation
4. Catalyst deactivation with evaporation of potassium
Suggestion for conventional processSuggestion for conventional process
*New process using carbon dioxide as soft oxidant*New process using carbon dioxide as soft oxidant
Problems of Conventional EBD Process
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Alternative Processes for Styrene Production
Oxidative dehydrogenation with oxygen
; Higher yield by shift of the dehydrogenation equilibrium
Flammable, Need for two catalysts with an oxidation Pd or Pt
2. Selective oxidation of H2from dehydrogenation with O2
;Overcome the contamination of mixing the steam and O2 Need for very selective and stable catalysts for oxidation of H2and
at high temperature
3. Membrane process; Oxidative dehydrogenation avoiding the flammabilityNeed for effective permeability of membrane
4. Oxidative dehydrogenation with carbon dioxide
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SODECO2 Technology DevelopmentSODECOSODECO22Technology DevelopmentTechnology Development
SODECO2 (Styrene from Oxidative Dehydrogenation via CO2):
Styrene Monomer Process via Oxidative Dehydrogenation of Ethylbenzene
using Carbon Dioxide as Soft Oxidant
Source of CO2----- By Product CO2discharged from Petrochemical
Industry
Developed by: Dr. S. E. Park and his group KRICT
CCME(Catalysis Center for Molecular Engineering)
SODECOSODECO22(Styrene from Oxidative Dehydrogenation via CO2):
Styrene Monomer Process via Oxidative Dehydrogenation of Ethylbenzeneusing Carbon Dioxide as Soft Oxidant
Source of CO2----- By Product CO2discharged from Petrochemical
Industry
Developed by: Dr. S. E. Park and his group KRICT
CCME(CatalysisCenter for MolecularEngineering)
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CH2-CH3CH=CH2
H2O+ H2
CH2-CH3CH=CH2
CO2+ H2O
- CO
Ethylbenzene Styrene
New Development in Dehydrogenation
Process using Carbon Dioxide as Soft Oxidant
New Development in Dehydrogenation
Process using Carbon Dioxide as Soft Oxidant
New development
Conventional process
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1. Role of soft oxidant to remove hydrogen as a product
(less dangerous than oxygen)
2. High heat capacity of CO2: 49.1 J/ mol.K at 673K
(37.0 J/mol.K at 673K for H2O and
33.2 J/mol.K at 673K for O2)
3. High selectivity to styrene (97%)
4. Activity Enhancement (high conversion)
5. Equilibrium shift to give lower reaction temperature
6. Cheaper gas than steam or oxygen
Advantages of Carbon Dioxide in Dehydrogenation
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Comparison of Carrier Gases for DehydrogeComparison of Carrier Gases for Dehydroge
nation of Hydrocarbonsnation of Hydrocarbons
Not commercialized
Endothermic
Catalyst deactivation
Low selectivity
Dangerous
Hot spot
Expensive diluent
Highly endothermic
High latent heat
High operation cost
Disadvantage
High selectivity
Activity enhancement
Equilibrium shift
Cheap carrier gas
High activity
Exothermic
Less deactivation
High selectivity
Catalyst stability
Coke resistance
Keeping oxidationstate
Heat capacity
High
(49.1 J/molK at 673K)
Low
(33.2 J/molK at 673K)
Medium
(37.0 J/molK at 673K)
Heat capacity
Soft oxidant
Diluent
Strong oxidant
Not Diluent
Not oxidant
Diluent
Function
Carbon DioxideOxygenSteamCharacteristics
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Characteristics of SODECO2ProcessCharacteristics of SODECO2
Process
1. Direct utilization of CO2as a by-product discharged fr
om petrochemical industry (Self-sufficiency of CO2)
2. Utilization of CO2as soft oxidant to alleviate chemical
equilibrium of ethylbenzene dehydrogenation
3. Selective dehydrogenation process using CO2
(1.5% high in styrene selectivity)
4. Energy saving effect against conventional process
(33% saving effect: 6.5 M dollar for 0.6 Mt-SM/year)5. High activity at lower temperature
(Release of risk in crack of reactor materials)
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Schematic Diagram of SODECO2ProcessSchematic Diagram ofSchematic Diagram of SODECOSODECO22
ProcessProcess
EthtylbenzeneEthtylbenzene
Dehydrogen-ation reactor
Dehydrogen-ation reactor
Product condenser
Product condenser
DistillationDistillation
Benzene/
Toluene mixture
Benzene/
Toluene mixture BTX PlantBTX Plant
Storage tank
for styrene
Storage tank
for styrene
Oxidation proc
ess
Oxidation proc
ess
CO2Oxidant
Discharge
without energy loss
Lower reaction temp.
*Korea Patent Appl. 02-11418 (2002.3.4), EU Patent Appl. 03004382.2 (2002.3.3)
SODECO2(Styrene via Oxidative Dehydrogenation of Ethylbenzene with CO2)
H2OH2O
Off gas
(H2, CO + CO2)
Off gas
(H2, CO + CO2)H2O
H2O Water-gas shift
reactor
Water-gas shift
reactor
MembraneMembraneH2H2
H2/CO2
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Schematic Diagram of SODECO2ProcessSchematic Diagram ofSchematic Diagram of SODECOSODECO22
ProcessProcess
EthtylbenzeneEthtylbenzene
Dehydrogen-ation reactor
Dehydrogen-ation reactor
Product condenser
Product condenser
DistillationDistillation
Benzene/
Toluene mixture
Benzene/
Toluene mixture BTX PlantBTX Plant
Storage tank fo
r styrene
Storage tank fo
r styrene
Oxidation proc
ess
Oxidation proc
ess
CO2Oxidant
Discharge
without energy loss
Lower reaction temp.
*Korea Patent Appl. 02-11418 (2002.3.4), EU Patent Appl. 03004382.2 (2002.3.3)
SODECO2(Styrene via Oxidative Dehydrogenation of Ethylbenzene with CO2)
H2H2
H2OH2O
Off gas
(CO + CO2)
Off gas
(CO + CO2) MembraneMembraneO2
O2
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Schematic Diagram of SODECO2ProcessSchematic Diagram ofSchematic Diagram of SODECOSODECO22
ProcessProcess
EthtylbenzeneEthtylbenzene
Dehydrogen-ation reactor
Dehydrogen-ation reactor
Product condenser
Product condenser
DistillationDistillation
Benzene/
Toluene mixture
Benzene/
Toluene mixture BTX PlantBTX Plant
Storage tank
for styrene
Storage tank
for styrene
Oxidation proc
ess
Oxidation proc
ess
CO2Oxidant
Discharge
without energy loss
Lower reaction temp.
*Korea Patent Appl. 02-11418 (2002.3.4), EU Patent Appl. 03004382.2 (2002.3.3)
SODECO2(Styrene via Oxidative Dehydrogenation of Ethylbenzene with CO2)
H2OH2O
Off gas
(H2, CO + CO2)
Off gas
(H2, CO + CO2)O2
O2 PrOx react
or
PrOx react
or
MembraneMembraneH2H2
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Development of Commercial EBD catalystsDevelopment of Commercial EBD catalysts
Generation
Main Component
Chemical PromoterTextual Promoter
Selectivity Promoter
Others (Binder, etc.)
1st (~1960)
Fe/K
-
Ca
2nd (~1980)
Fe/K
Ce
W,Cu
-
Ca
3rd (~2000)
Fe/K
Ce, Ce-Zr
Mg
Mo
Ca
Cr
SODECO2
New Catalyst for EB dehydro-g
enation with CO
2as an oxidant
KRICT
> 65 ~ 80
aStyrene yield, %
Function
Commercial catalysts
Catalytic Activitya
-
< 55
BASF/Shell
55 ~ 60
NGC, etc.
60 ~ 65
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Catalyst for SODECO2ProcessCatalyst for SODECO2
Process
Function
Active Phase
Activity Promoter
Stability Promoter
Structural stabilizer
Catalyst Support
Component
Fe3O4 V2O5
Mn -
Mo Sb
Ca ,Mg Mg
Promoted-Al2O3, ZrO2
C i f l i f
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Catalyst
Temperature (oC)
Pressure (atm)
Space velocity
(LHSV, h-1)
Carrier/EB (molar)
Styrene yield (%)Styrene selectivity (%)
Catalyst lifetime
Others
Commercial (steam)Commercial (steam)
SOR: 625-575(600)
EOR: 655-605(630)
0.750.75-1.0
8-12
60-6694.0-96.5
2 years
Only H2product
COCO22-EBD-EBD
SOR: 525 575
EOR: not fixed
0.75
1.0
2-10
55 6597.0 98.0
?
X(CO2) = 40-45%
CO/H2 = 1.0-1.5
Comparison of catalytic performance
between commercial and CO2-SM catalyst
Comparison of catalytic performance
between commercial and CO2-SM catalyst
SOR : Start-of-run; EOR : End-of-run
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Mi cro(Lab. )Bench Pi l ot F (i n. ) 3/ 81/ 2 2 Reactor l ength(f t. ) 13 4 Catal yst vol ume 15ml
500ml 4 l i ter Shape of catal yst granul e
Microactivity Test Unit Bench-scale Mini Pilot
Scal e-up Study vof SODECO2 Processf romLab to Mi ni Pi l ot
Scal e- up Study vof SODECO2 Processf romLab to Mi ni Pi l ot
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Equipment
CO2Feed
EB Feed
Pre-heater
Temperature
control
Productanalysis
Micro uint
Mass flow controller
Cylinder gas (R-grade)
Syringe pump
Preheating
Zone
Single heating zone
Gas component; on-lined GC(TCD)
Liq. component;
Condensed to
GC(FID)
Bench scale
Mass flow controller
Cylinder gas (R-grade)
LC pump
Pre-heater (electric) wi
th mixer
5-zoned heater
with PID controller
Gas component; on-lined GC(TCD)
Liq. component;
Condensed to
GC(FID)
Mini Pilot
Mass flow controller
CO2from EG/EO Plant
LC pump
Pre-heater (electric)
with mixer
5-zoned heater
with PID controller
Gas component; on-lined GC(TCD)
Liq. component;
Condensed to
GC(FID)
Characteristics of Reactor SystemsCharacteristics of Reactor Systems
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Desi gn SMProducti on Capaci ty : 2.5 Ton / yr Catal yst vol ume = 500 ml Shape :spheroi d (F=3mm) LHSV = 1.0 h-1, CO2/EB = 5/1, 50%yield @ 560oC
Design SM Production Capacity : 2.5 Ton / yr
Catalyst volume = 500 ml Shape :spheroid ( =3mm)
LHSV = 1.0 h-1, CO2/EB = 5/1, 50% yield @ 560oC
Bench Scal e Uni t f or Ethyl benzene Dehydrogenati on wi th CO2
Bench Scal e Uni t f or Ethyl benzene Dehydrogenati on wi th CO2
SM Production via SODECO Process
SM Production viaSM Production via SODECOSODECO22 ProcessProcess
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SM Production via SODECO2Process
@ Pilot-scale system
SM Production viaSM Production via SODECOSODECO22 ProcessProcess
@ Pilot-scale system@ Pilot-scale system
Annual SM Production : 20 Ton / yr
Catalyst volume = 4 L; Shape: Tablet (5 x 3 mm)
P = 0.75 atm, LHSV = 1.0 h-1, CO2/EB = 5/1,
CO2Conv.= 42% @ 560oC (Dual 4 Tubes of Bench scale)
C i f i l i
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Comparison of economical propertiesfor EBD processes
Comparison of economical propertiesfor EBD processes
Conventional
600
95.0
100%
$ 17 M
Basis for calculation : 0.6Mt-SM/yr
Temperature(oC)
SM Selectivity(%)
Economic effect
Loss of latent heat
Cost for
super-heated steamEnergy saving
Total
SODECO2
560
96.5
$ 2.7 M
66 %
$ 6.6M
$ 9.3 M
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Key to SuccessKey to Success Scale-up Technology of Catalyst
Stable Enough for industrial Application
Project FinancingProject Financing
Critical Technology-21 ProgramCritical Technology-21 ProgramGreenhouuse Gas Research Center
Financed by the Ministry of Science and Technology
SGCSGC DaesanDaesanPetrochemical ComplexPetrochemical Complex
Pilot Scale Demonstration Unit for Catalyst Performance Test
R l d P bli i
Related Publications
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? Patents
-Catalyst for Dehydrogenating Aromatic Hydrocarbons with Carbon Dioxide, U.S. Patent 6,
034,032, U.S.Patent 6,037,511(2000).
-Dehydrogenation of Alkylaromatic Hydrocarbons using Carbon Dioxide as Soft Oxidant 2
003-13139(Korea), 2003-057644(Japan), 03004382.2 (Europe), U.S. Patent under appli cation
-4 Patents of Korea
? Research Papers
Environ. Chall enge and Greenhouse Control in 21C,Green Chem (2003), Catal . Today,(2003),
Res. Chem, I ntermed, 28, 461,(2002), Catal . Commun., 3, 227(2002); Appl . Organomet.
Chem., 14, 815 (2001); J. Catal. ,195, 1 (2000); Catal. L ett.,65, 75 (2000); Catal . Lett.,69, 93
(2000); Res. Chem. Intermed., 25(5), 411 (1999); Chem. Lett., (10), 1063 (1998) etc.
? Presentations
ACS Keynote Lecture(2001), ACS Fuel Chem. Div. (1996), ACS Fuel Chem. Div. (2002),
5th,6th, 7thI nt.Conf .Carbon Dioxide Uti l . (1999, 2001, 2003)
Related PublicationsRelated Publications
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Dr. Sang-Eun Park
Affiliation: Korea Research Institute of Chemical Technology
E-mail:[email protected]
Dr. Sang-Dr. Sang-EunEunParkPark
Affiliation: Korea Research Institute of Chemical Technology
E-mail:[email protected]
Senior Researcher
to
Director
KRICT1987-present
Visiting
Researcher
Dept. of Chemistry,
KAIST
1987-1987
Post Doc.Researcher
Associate
Dept. of Chemistry,
Texas A&M Univ.
1984-1986
Chemical Engineeri
ng Design Process
Development
Chief ResearcherCentral Research In
st. Of Chon Enginee
ring Co.
1977-1984
OthersTitleOrganizationYear
PFD for Conventional Styrene Monomer Process
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ReactorR1 R2
Steam
Ethylbenzene
Bz,Tol
Ethylbenzene
Recycle
Styrene
StyreneResiduCondensate
Off-gas
Column
C1 C2 C3 C4
H2O/HC
CrudeSM
Mixer
Heater
~630oC
~560oC
~1atm
~0.7atm
PFD for Conventional Styrene Monomer ProcessPFD for Conventional Styrene Monomer Process
*Energy cost for superheated steam: 15 M dollar for 0.6 Mt-SM/year capacity
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Lummus/UOP Classic SMTM ProcessLummus/UOP Classic SMTM Process
PFD of SODECO2Process
PFD ofPFD of SODECOSODECO22ProcessProcess
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222H2
Recycle GasCompressor
CO2 PW
Furnace
A-Reactor
B-Reactor
EB
Stripper
Stripper
S
tripper
Scrubb
er
Reactor
G-W-HC
separator
G-W-HC
separator
To BTX
EB Recycle
BTColumn
E
BColumn
Fin
ishingColumn
Residue
Ab
sorber
Condensate
CO2
H2, CO CO
2
K2CO3Process co
ndensate
Steam(From OSBL)
H2,H2O
CO2
Lummus/UOP-SMART Process;
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(Styrene Monomer Advanced Reheat Technology)
The SMART SM process combines oxidative reheat technology with adiabatic dehydrogenation technology to produce high purity (99.85 wt% minimum) styrene monomer (SM) from e
thylbenzene.
This results in EB conversion of more than 80%, as well as eliminating the costly interstage reheater and reducing superheated steam requirements.
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UOP-SMART ProcessUOP-SMART Process
Product
Separation
Heater
Ethylbenzene
Recycle ethylbenzene/hydrogen
Hydrogen oxidation
Hydrogen oxidation
Ethylbenzenedehydrogenation
Light ends
Styrene
Hydrogen Steam
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CO2 99.46% 99.9%
H2O 0.51% -O2 50ppm 100ppm
N2 50ppm 100ppm
Methane - 300ppm
Ethylene 140ppm 200ppm
Ethane 80ppm 100ppm
Component Case1 Case2
*Separation of EO and CO2through absorption process to purify EO product
Purity of CO2by-product from
Ethylene Oxide (EO) Process
Purity of CO2by-product from
Ethylene Oxide (EO) Process
C t l ti A ti it i EBD ith CO i B h l
Catalytic Activity in EBD with COCatalytic Activity in EBD with CO in Bench scalein Bench scale
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0 100 200 300 400 5000
20
40
60
80
EBCo
nv.(%)
Time-on-stream (h)
40
60
80
100
SMSe
lect.(%)
Temp. = 560oC, LHSV = 1.0 h-1
Wcat= 15 g, CO2/EB = 5.4/1.0
Catalyst: Fe-V-Sb-Mg-Al
Catalytic Activity in EBD with CO2in Bench-scaleCatalytic Activity in EBD with COCatalytic Activity in EBD with CO22in Bench-scalein Bench-scale
SM Production EB Feeding : 30cc/hr
SM Yield : ~ 60%
SM Production = 370g/day
SM ProductionSM Production EB Feeding : 30cc/hr
SM Yield : ~ 60%
SM Production = 370g/day
New CO EBD catalyst vs Commercial steam EBD catalyst
New CO2-EBD catalyst vs Commercial steam-EBD catalyst
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Lowering reaction temperature (up to 50oC) due to alleviation of
chemical equilibrium with carbon dioxide
SM Production : 20 M-t/Yr (SM Yield = 65% @ 560oC)
500 550 600 6500
20
40
60
80
100
Styr
eneYield(%)
Reaction Temp. (oC)
Equilibrium (CO2)Equilibrium (steam)
Catalyst (CO2)
Ce-K-Fe2O
3(steam)
CO2
steam
Commercial Steam-EBD cat
New CO2-EBD cat
Reaction condition:
P = 0.75 atm, LHSV = 1.0 h-1,
CO2/EB = 5/1 (CO2Cat.)
CO2Conv.= 42% @ 560oC
H2O/EB = 10/1 (Steam Cat.)
Catalyst volume = 4 L
New CO2-EBD catalyst vs. Commercial steam-EBD catalystNew CO2 EBD catalyst vs. Commercial steam EBD catalyst
* Korea Patent Appl. 02-11418 (2002.3.4), EU Patent Appl. 03004382.2 (2002.3.3)
Comparison of styrene yields in steam EB
Comparison of styrene yields in steam-EB
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Comparison of styrene yields in steam-EB
D and CO2-EBD catalysts
Comparison of styrene yields in steam EB
D and CO2-EBD catalysts
Reaction conditions:
Temp. = 600oC, LHSV = 1.0 h-1
H2O(N2)/EB = 8/1; CO2/EB = 5.4/1
Reaction conditions:
Temp. = 600oC, LHSV = 1.0 h-1
H2O(N2)/EB = 8/1;
CO2/EB = 5.4/120
40
60
80
H2ON2
CO2
StyreneYie
ld(%)
Catalyst
Commercial(K2O-Fe2O3)
CCME-SM1
CO2
N2N2
CO2
H2O
H2O
*US Patent 6,037,511(2000) for catalyst; US Patent 6,034,032 (2000) for process
Catalyst : Fe-V-Sb-Mg-Al
Catalyst : Fe-V-Sb-Mg-Al
Simplified Reaction Equations of EB Dehydrogenation
Simplified Reaction Equations of EB Dehydrogenation
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[ ]* : a surface vacancy
[O]s: a lattice oxygen atom
Simplified Reaction Equations of EB Dehydrogenation
via SODECO2and conventional
Simplified Reaction Equations of EB Dehydrogenation
via SODECO2and conventional
C6H5CH2CH3+ [O]s C6H5CH=CH2 + H2O
Oxidat iveDehyd rogenat ion of EB v ia SODECO2Process
CO2 CO + [O]s[ ]*
C6H5CH2CH3+ CO2 C6H5CH=CH2+ CO+ H2O
C6H5CH2CH3 C6H5CH=CH2+ H2
SimpleDehyd rogenation o f EB w i th Steam
Steam
Mechanism for Oxidative Dehydrogenation of EB with CO2
Mechanism for Oxidative Dehydrogenation of EB with COMechanism for Oxidative Dehydrogenation of EB with CO22
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Support
CO2
Fe2+Fe3+
Simp le Dehydrogenation Oxidative Dehydro genation
[O]
H2
Support
+ CO + H2O+ H2
Fe3O4Spinel
Mechanism for Oxidative Dehydrogenation of EB with CO2over Iron-oxide catalyst
y g 22over Iron-oxide catalystover Iron-oxide catalyst
S.-E. Park et.al. , AIChE 2000 Spring Meeting, Atlanta, GA, Mar. 9 - 12, 2000.
SODECOSODECO T h l D l t
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SODECOSODECO22Technology Development
SODECO2(Styrene from Oxidative Dehydrogenation via CO2):
New process for styrene production with CO2discharged from oxidation p
rocess
Discharge of 0.556 tone of carbon dioxide per 1 tone of ethylene oxide (EO)
Purity of CO2as a by-product of EO process: > 99% (Others: 0.5% H2O a
nd less than 300 ppm of C1 and C2 hydrocarbons)
Production of EO: 600,000 t/year in Korea (CO2
330,000 t/year in EO proc
ess)
SODECOSODECO22(Styrene from Oxidative Dehydrogenation via CO2):
New process for styrene production with CO2discharged from oxidation p
rocess
Discharge of 0.556 tone of carbon dioxide per 1 tone of ethylene oxide (EO)
Purity of CO2as a by-product of EO process: > 99% (Others: 0.5% H2O a
nd less than 300 ppm of C1 and C2 hydrocarbons)
Production of EO: 600,000 t/year in Korea (CO2330,000 t/year in EO proc
ess)
Creation of New Chemical Industry by Utilization of
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Creation of New Chemical Industry by Utilization of
Carbon Dioxide Discharged from Chemical Process
Petrochemical industry
(styrene monomer)
Polystyrene
CO2mitigation
Replacing steam
Energy saving
CO2utilization
Polymerizationw/o purification
CO2as a by
-product in i
ndustry
Iron mill
Iron oxide wasteCatalyst
Processing