CHEMRAWN
CHEMRAWNXVI
XVIConference
Conference
Consultation
ConsultationForum
Forum
Innovation
InnovationStage:
Stage:the
theway
waypure
puretotothe
theapplied
appliedchemistry
chemistry
Transformation
Transformation of
of the
the old
old process:
process:
Ethylbenzene
Ethylbenzene to
to Styrene
Styrene with
with CO
CO22 dilution
dilution
MIN
MIN CHE
CHE CHON
CHON
Chon
Chon International
International Co.,
Co., Ltd.
Ltd.
Conventional Process for Styrene Production
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 Dehydrogenation (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
Drawbacks of EBD Process with Steam
- High energy consumption during the condensation of steam
due to high latent heat of water
- Catalyst deactivation in the presence of CO2 as a by-product
- The need for high steam-to-ethylbenzene ratio
Production of Styrene Monomer in Korea
Year 1999 (Unit: 1000 T/Y)
Company
Capacity
Location
Starting year
Process Licensor
YNCC
140
Yeochon
1986, 1995
Badger Eng.
LG Chemical
330
Yeochon
SK Oxychemical
300
260
Ulsan
Ulsan
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
1990, 1991
Lummus/Monsanto
1991
1997
Badger/Mobil/ARCO*
ARCO
2.5 Mt/year capacity (Year 2001)
*Dehydrogenation process of MBA (Methyl benzyl alcohol)
Problems of Conventional EBD Process
Problems
1. High Energy Consumption by Use of Excess Steam
– estimated to 10% of production cost
2. Low equilibrium conversion of 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 process
*New process using carbon dioxide as soft oxidant
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 H2 from dehydrogenation with O2
; Overcome the contamination of mixing the steam and O 2
Need for very selective and stable catalysts for oxidation of H2 and
at high temperature
3. Membrane process
; Oxidative dehydrogenation avoiding the flammability
Need for effective permeability of membrane
4. Oxidative dehydrogenation with carbon dioxide
SODECO
SODECO22®
® Technology
Technology Development
Development
SODECO
SODECO2®
2®(Styrene
(Styrenefrom
fromOxidative
OxidativeDehydrogenation
Dehydrogenationvia
viaCO
CO2):
2):
Styrene
StyreneMonomer
MonomerProcess
Processvia
viaOxidative
OxidativeDehydrogenation
Dehydrogenationof
ofEthylbenzene
Ethylbenzene
using
usingCarbon
CarbonDioxide
Dioxideas
asSoft
SoftOxidant
Oxidant
Source
Sourceof
ofCO
CO22---------By
ByProduct
ProductCO
CO22discharged
dischargedfrom
fromPetrochemical
Petrochemical
Industry
Industry
Developed
Developedby:
by: Dr.
Dr.S.
S.E.
E.Park
Parkand
andhis
hisgroup
group KRICT
KRICT
CCME
CCME((Catalysis
CatalysisCenter
Centerfor
forMolecular
MolecularEngineering)
Engineering)
New
NewDevelopment
Developmentin
inDehydrogenation
Dehydrogenation
Process
Processusing
usingCarbon
CarbonDioxide
Dioxideas
asSoft
SoftOxidant
Oxidant
CH2-CH3
H 2O
Ethylbenzene
CH=CH2 + H2
Styrene
Conventional process
CO2
CH2-CH3
CH=CH2 + H2O
- CO
New development
Advantages of Carbon Dioxide in Dehydrogenation
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
Comparison of Carrier Gases for Dehydroge
nation of Hydrocarbons
Characteristics
Steam
Oxygen
Carbon Dioxide
Function
Not oxidant
Diluent
Strong oxidant
Not Diluent
Soft oxidant
Diluent
Heat capacity
Medium
(37.0 J/mol⋅K at 673K)
Low
(33.2 J/mol⋅K at 673K)
High
(49.1 J/mol⋅K at 673K)
Heat capacity
High selectivity
Catalyst stability
Coke resistance
Keeping oxidationstate
High activity
Exothermic
Less deactivation
High selectivity
Activity enhancement
Equilibrium shift
Cheap carrier gas
Disadvantage
Expensive diluent
Highly endothermic
High latent heat
High operation cost
Low selectivity
Dangerous
Hot spot
Not commercialized
Endothermic
Catalyst deactivation
®® Process
Characteristics
of
SODECO
Characteristics of SODECO22 Process
1. Direct utilization of CO2 as a by-product discharged fr
om petrochemical industry (Self-sufficiency of CO2)
2. Utilization of CO2 as 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)
Candidate 1
®
Schematic
Schematic Diagram
Diagram of
ofSODECO
SODECO22® Process
Process
SODECO2®
(Styrene via Oxidative Dehydrogenation of Ethylbenzene with CO2)
HH2 OO
2
Water-gas
Water-gasshift
shift
reactor
reactor
H2/CO2
HH2
2
Membrane
Membrane
Off
Offgas
gas
(H
(H2, ,CO
CO++CO
CO2) )
2
2
Lower reaction temp.
Dehydrogen-at
Dehydrogen-at
ion
ionreactor
reactor
Product
Product conde
conde
nser
nser
HH2 OO
2
without energy loss
CO 2
Oxidant
Discharge
Oxidation
Oxidationproc
proc
ess
ess
Distillation
Distillation
Storage
Storagetank
tank
for
styrene
for styrene
Benzene/
Benzene/
Toluene
Toluenemixture
mixture
BTX
BTXPlant
Plant
Ethtylbenzene
Ethtylbenzene
*Korea Patent Appl. 02-11418 (2002.3.4), EU Patent Appl. 03004382.2 (2002.3.3)
Candidate 2
®
Schematic
Schematic Diagram
Diagram of
ofSODECO
SODECO22® Process
Process
SODECO2®
(Styrene via Oxidative Dehydrogenation of Ethylbenzene with CO2)
Off
Offgas
gas
(CO
+
(CO +CO
CO2) )
OO2
2
2
Membrane
Membrane
HH2
2
Product
Product conde
conde
nser
nser
HH2 OO
2
Lower reaction temp.
Dehydrogen-at
Dehydrogen-at
ion
ionreactor
reactor
without energy loss
CO 2
Oxidant
Ethtylbenzene
Ethtylbenzene
Distillation
Distillation
Storage
Storagetank
tankfo
fo
rrstyrene
styrene
Benzene/
Benzene/
Toluene
Toluenemixture
mixture
BTX
BTXPlant
Plant
Discharge
Oxidation
Oxidationproc
proc
ess
ess
*Korea Patent Appl. 02-11418 (2002.3.4), EU Patent Appl. 03004382.2 (2002.3.3)
Candidate 3
®
Schematic
Schematic Diagram
Diagram of
ofSODECO
SODECO22® Process
Process
SODECO2®
(Styrene via Oxidative Dehydrogenation of Ethylbenzene with CO2)
OO2
2
PrOx
PrOxreact
react
or
or
Off
Offgas
gas
(H
(H2, ,CO
CO++CO
CO2) )
2
2
Lower reaction temp.
HH2
2
Membrane
Membrane
Dehydrogen-at
Dehydrogen-at
ion
ionreactor
reactor
Product
Product conde
conde
nser
nser
HH2 OO
2
without energy loss
CO 2
Oxidant
Discharge
Oxidation
Oxidationproc
proc
ess
ess
Distillation
Distillation
Storage
Storagetank
tank
for
styrene
for styrene
Benzene/
Benzene/
Toluene
Toluenemixture
mixture
BTX
BTXPlant
Plant
Ethtylbenzene
Ethtylbenzene
*Korea Patent Appl. 02-11418 (2002.3.4), EU Patent Appl. 03004382.2 (2002.3.3)
Development
Development of
of Commercial
Commercial EBD
EBD catalysts
catalysts
Generation
Function
Main Component
1st (~1960)
2nd (~1980)
3rd (~2000)
Fe/K
Fe/K
Fe/K
Ce
Ce, Ce-Zr
W,Cu
Mg
Chemical Promoter
Textual Promoter
Cr
SODECO2 ®
New Catalyst fo
r EB dehydro-g
enation with CO
2 as an oxidant
Selectivity Promoter
-
-
Mo
Others (Binder, etc.)
Ca
Ca
Ca
Commercial catalysts
-
BASF/Shell
NGC, etc.
KRICT
< 55
55 ~ 60
60 ~ 65
> 65 ~ 80
Catalytic Activitya
aStyrene
yield, %
®® Process
Catalyst
for
SODECO
Catalyst for SODECO22 Process
Function
Component
Active Phase
Fe3O4
V2O5
Activity Promoter
Mn
-
Stability Promoter
Mo
Sb
Structural stabilizer
Ca ,Mg
Mg
Catalyst Support
Promoted-Al2O3, ZrO2
Comparison
Comparison of
of catalytic
catalytic performance
performance
between
between commercial
commercial and
and CO
CO22-SM
-SM catalyst
catalyst
Commercial (steam)
CO2-EBD
SOR: 625-575(600)
SOR: 525 – 575
EOR: 655-605(630)
EOR: not fixed
0.75
0.75
0.75-1.0
1.0
Carrier/EB (molar)
8-12
2-10
Styrene yield (%)
60-66
55 – 65
94.0-96.5
97.0 – 98.0
2 years
?
X(CO 2) = 40-45%
CO/H2 = 1.0-1.5
Catalyst
Temperature (oC)
Pressure (atm)
Space velocity
(LHSV, h -1)
Styrene selectivity (%)
Catalyst lifetime
Others
Only H2 product
SOR : Start-of-run; EOR : End-of-run
Scale-up
Scale-up Study
Study vof
vof SODECO
SODECO22®
® Process
Process
from
from Lab
Lab to
to Mini
Mini Pilot
Pilot
Microactivity Test Unit
Bench
Micro(Lab.)
Pilot
F (in.)
2
length(ft.)
4
1/2
Reactor
3
Catalyst volume
500ml
Shape of catalyst
spheroid
Mini Pilot
Bench-scale
3/8
1
15ml
4 liter
Tablet
granule
(F=1mm)
(F=3mm)
Characteristics
Characteristics of
of Reactor
Reactor Systems
Systems
Micro uint
CO2 Feed
Mass flow controller
Cylinder gas (R-grade)
EB Feed
Syringe pump
LC pump
LC pump
Preheating
Zone
Pre-heater (electric) wi
th mixer
Pre-heater (electric)
with mixer
Single heating zone
5-zoned heater
with PID controller
5-zoned heater
with PID controller
Gas component;
on-lined GC(TCD)
Liq. component;
Condensed to
GC(FID)
Gas component;
on-lined GC(TCD)
Liq. component;
Condensed to
GC(FID)
Pre-heater
Temperature
control
Product
analysis
Gas component;
on-lined GC(TCD)
Liq. component;
Condensed to
GC(FID)
Bench scale
Mini Pilot
Equipment
Mass flow controller
Mass flow controller
Cylinder gas (R-grade) CO2 from EG/EO Plant
Bench
Bench Scale
Scale Unit
Unit for
for Ethylbenzene
Ethylbenzene De
De
hydrogenation
hydrogenation with
with CO
CO22
•
•
•
Design SM Production Capacity : 2.5 Ton / yr
Catalyst volume = 500 ml Shape :spheroid (Φ=3mm)
Design SM Production Capacity : 2.5 Ton / yr
Catalyst volume = 500 ml Shape :spheroid (F=3mm)
LHSV = 1.0 h-1, CO2/EB = 5/1, 50% yield @ 560oC
LHSV = 1.0 h-1, CO2/EB = 5/1, 50% yield @ 560oC
®
SM
SM Production
Production via
viaSODECO
SODECO22® Process
Process
@
@ Pilot-scale
Pilot-scale system
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,
CO2 Conv.= 42% @ 560oC (Dual 4 Tubes of Bench scale)
Comparison
Comparison of
of economical
economical properties
properties
for
for EBD
EBD processes
processes
Basis for calculation : 0.6Mt-SM/yr
SODECO2®
Conventional
Temperature(oC)
560
600
SM Selectivity(%)
96.5
95.0
Economic effect
Loss of latent heat
Cost for
super-heated steam
Energy saving
Total
$ 2.7 M
66 %
100%
$ 17 M
$ 6.6M
$ 9.3 M
Project Financing
üCritical Technology-21 Program
Greenhouuse Gas Research Center
Financed by the Ministry of Science and Technology
üSGC Daesan Petrochemical Complex
Pilot Scale Demonstration Unit for Catalyst Performance Test
ü Key to Success
Scale-up Technology of Catalyst
Stable Enough for industrial Application
Related
Related Publications
Publications
? 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 application
- 4 Patents of Korea
? Research Papers
Environ. Challenge and Greenhouse Control in 21C, Green Chem (2003), Catal. Today,(2003),
Res. Chem, Intermed, 28, 461,(2002), Catal. Commun., 3, 227 (2002); Appl. Organomet.
Chem., 14, 815 (2001); J. Catal., 195, 1 (2000); Catal. Lett., 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, 7 th Int.Conf.Carbon Dioxide Util. (1999, 2001, 2003)
Dr.
Eun Park
Dr. SangSang-Eun
Park
Affiliation:
Affiliation:Korea
KoreaResearch
ResearchInstitute
InstituteofofChemical
ChemicalTechnology
Technology
E-mail:[email protected]
E-mail:[email protected]
Year
Organization
Title
Others
1977-1984
Central Research In
st. Of Chon Enginee
ring Co.
Chief Researcher
Chemical Engineeri
ng Design Process
Development
1984-1986
Dept. of Chemistry,
Texas A&M Univ.
Researcher
Associate
Post Doc.
1987-1987
Dept. of Chemistry,
KAIST
Visiting
Researcher
1987-present
KRICT
Senior Researcher
to
Director
PFD
PFDfor
forConventional
ConventionalStyrene
StyreneMonomer
MonomerProcess
Process
Off-gas
Reactor
R1
~560oC
Bz,Tol
Styrene
R2
~0.7atm
Ethylbenzene
Recycle
H2 O/HC
Steam
Crude
SM
~630oC ~1atm
Mixer
Heater
C1
C2
C3
Column
Ethylbenzene
Condensate
C4
Styrene
Residue
*Energy cost for superheated steam: 15 M dollar for 0.6 Mt-SM/year capacity
Lummus/UOP
Lummus/UOP Classic
Classic SMTM
SMTM Process
Process
®® Process
PFD
of
SODECO
PFD of SODECO22 Process
H2
Scrubber
Stripper
Recycle Gas
Compressor
2
H 2,H2O
CO 2
Stripper
Reactor
H2, CO CO
Absorber
CO2
Steam
(From OSBL)
To BTX
Process co
ndensate
K2CO 3
Furnace
Finishing Column
EB
EB Column
BT Column
G-W-HC
separator
Stripper
CO2 PW
B-Reactor
A-Reactor
EB Recycle
Residue
Condensate
Lummus/UOP-SMART Process;
(Styrene Monomer Advanced Reheat Technology)
The SMART SM™ process combines oxidative reheat technology with adiabatic dehydrogen
ation 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 r
eheater and reducing superheated steam requirements.
UOP-SMART
UOP-SMART Process
Process
Ethylbenzene
dehydrogenation
Styrene
Steam
Hydrogen
Hydrogen oxidation
Light ends
Hydrogen oxidation
Heater
Product
Separation
Recycle ethylbenzene/hydrogen
Ethylbenzene
Purity
Purity of
of CO
CO22by-product
by-product from
from
Ethylene
Ethylene Oxide
Oxide (EO)
(EO) Process
Process
Component
Case1
Case2
CO2
99.46%
99.9%
H2O
0.51%
-
O2
50ppm
100ppm
N2
50ppm
100ppm
Methane
-
300ppm
Ethylene
140ppm
200ppm
Ethane
80ppm
100ppm
*Separation of EO and CO 2 through absorption process to purify EO product
Catalytic
Catalytic Activity
Activity in
in EBD
EBD with
with CO
CO22 in
in Bench-scale
Bench-scale
100
EB Conv. (%)
60
80
40
Temp. = 560oC, LHSV = 1.0 h-1
Wcat = 15 g, CO 2/EB = 5.4/1.0
60
20
0
0
SM Select. (%)
80
Catalyst: Fe-V-Sb-Mg-Al
100
200
300
400
Time-on-stream (h)
500
40
SM
SMProduction
Production
EB
EBFeeding
Feeding: :30cc/hr
30cc/hr
SM
SMYield
Yield: :~~60%
60%
SM
Production
SM Production==370g/day
370g/day
New
New CO
CO22-EBD
-EBDcatalyst
catalystvs.
vs.Commercial
Commercialsteam-EBD
steam-EBDcatalyst
catalyst
100
New CO 2-EBD cat
CO 2
Styrene Yield (%)
80
Commercial Steam-EBD cat
60
40
steam
Equilibrium (CO2)
Equilibrium (steam)
Catalyst (CO2)
Ce-K-Fe2O3 (steam)
20
0
500
Reaction condition:
P = 0.75 atm, LHSV = 1.0 h-1,
CO 2/EB = 5/1 (CO 2 Cat.)
CO 2 Conv.= 42% @ 560oC
H2 O/EB = 10/1 (Steam Cat.)
Catalyst volume = 4 L
550
600
650
o
Reaction Temp. ( C)
Lowering reaction temperature (up to 50 oC) due to alleviation of
chemical equilibrium with carbon dioxide
SM Production : 20 M-t/Yr (SM Yield = 65% @ 560oC)
* Korea Patent Appl. 02-11418 (2002.3.4), EU Patent Appl. 03004382.2 (2002.3.3)
Comparison
Comparisonof
ofstyrene
styreneyields
yieldsin
insteam-EB
steam-EB
DD and
and CO
CO22-EBD
-EBD catalysts
catalysts
H2O
N2
Styrene Yield (%)
80
CO2
Catalyst
Catalyst ::
Fe-V-Sb-Mg-Al
Fe-V-Sb-Mg-Al
60
CO2
H2O
40
N2
N2
CO2
H2O
20
Commercial
(K2O-Fe2O3)
Reaction
Reactionconditions:
conditions:
o
Temp.
=
Temp. =600
600oC,
C,
-1
LHSV
LHSV==1.0
1.0hh -1
HH2O(N
)/EB = 8/1;
2O(N22)/EB = 8/1;
CO
CO22/EB
/EB==5.4/1
5.4/1
CCME-SM1
Catalyst
*US Patent 6,037,511(2000) for catalyst; US Patent 6,034,032 (2000) for process
Simplified
Simplified Reaction
Reaction Equations
Equations of
of EB
EB Dehydrogenation
Dehydrogenation
®®and conventional
via
SODECO
via SODECO22 and conventional
Oxidative Dehydrogenation of EB via SODECO2 ® Process
CO2
[ ]*
CO + [O]s
C6H5CH2CH3 + [O]s
C6H5CH=CH2 + H2O
C6H5CH2CH3 + CO2
C6H5CH=CH2 + CO + H2O
[ ]* : a surface vacancy
[O]s: a lattice oxygen atom
Simple Dehydrogenation of EB with Steam
C6H5CH2CH3
Steam
C6H5CH=CH2 + H2
Mechanism
Mechanismfor
forOxidative
OxidativeDehydrogenation
Dehydrogenationof
ofEB
EBwith
withCO
CO22
over
overIron-oxide
Iron-oxidecatalyst
catalyst
+ H2
+ CO + H2O
H2
Fe3 O4 Spinel
Fe3+
[O]
CO2
Fe2+
Support
Support
Simple Dehydrogenation
Oxidative Dehydrogenation
S.-E. Park et.al. , AIChE 2000 Spring Meeting, Atlanta, GA, Mar. 9 - 12, 2000.
SODECO2® Technology Development
®
SODECO
SODECO22®(Styrene
(Styrenefrom
fromOxidative
OxidativeDehydrogenation
Dehydrogenationvia
viaCO
CO2):
2):
New
Newprocess
processfor
forstyrene
styreneproduction
productionwith
withCO
CO22discharged
dischargedfrom
fromoxidation
oxidationpp
rocess
rocess
Discharge
Dischargeof
of0.556
0.556tone
toneof
ofcarbon
carbondioxide
dioxideper
per11tone
toneof
ofethylene
ethyleneoxide
oxide(EO)
(EO)
Purity
Purityof
ofCO
CO22as
asaaby-product
by-productof
ofEO
EOprocess:
process:>>99%
99%(Others:
(Others:0.5%
0.5%H2O
H2Oaa
nd
ndless
lessthan
than300
300ppm
ppmof
ofC1
C1and
andC2
C2hydrocarbons)
hydrocarbons)
Production
Productionof
ofEO:
EO:600,000
600,000t/year
t/yearin
inKorea
Korea(CO
(CO22330,000
330,000t/year
t/yearin
inEO
EOproc
proc
ess)
ess)
Creation of New Chemical Industry by Utilization of
Carbon Dioxide Discharged from Chemical Process
CO2 mitigation
Replacing steam
Energy saving
CO2 as a by
-product in i
ndustry
w/o purification
Polymerization
CO2 utilization
Petrochemical industry
(styrene monomer)
Processing
Catalyst
Iron oxide waste
Iron mill
Polystyrene