dominant technology for the propylene production dtp...
TRANSCRIPT
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Dominant Technology for the
Propylene Production(DTPⓇ)Process
N. CHIKAMATSU1 , K. HONDA1, A.OKITA1, J. TAKAHASHI1,
K. OYAMA1, and M. NAKAMURA2
1:JGC Corporation
2:Mitsubishi Chemical Corporation
7th Asian DME Conference
Nov. 2011
Niigata, Japan
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Why propylene?
DTPⓇ Process Features
DTP Ⓡ Demonstration Plant Running
Development Schedule
Contents
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Polypropylene
Acrylic acid
Propylene is an important intermediate product.
Oxo alcohol
Propylene oxide
Acrylonitrile
Cumene Others
World Production
77 million ton-PPY/year
Applications of Propylene
Reference:Economy of Chemical Industry ”Kagaku Keizai”(Mar. 2011)
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20
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60
80
100
120
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014
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Unit:×106 ton
‘08-’14 Increase 4.2%/year
Reference: METI News Release (2010)
World Demand for Propylene W
orl
d D
em
an
d f
or
Pro
pyle
ne
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Conventional Propylene Production Process
Process
Cracking FCC
(Fluid Catalytic Cracking)
Dehydro-
genation Metathesis
Naphtha
Cracker FCC
DCC
[S&W]
OLEFLEX
[UOP]
OCT
[ABB Lummus]
Feedstock Light
Naphtha VGO
85%VGO+
15%VR C3
C2= &
2-C4=
Yield
[wt%]
C2= 29.0 1.0 3.6 - -
C3= 18.0 4.7 22.9 85.0 >90.0
C3=/C2
=
ratio 0.6 4.7 6.4 - -
Production
Ratio[%] 66 32 2
Reference: Journal of Japan Institute of Energy, Inomata (2005)
Almost all propylene is produced from cracking and FCC.
Propylene is by-product of cracking and FCC.
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Ethane Crackers in the Middle East
Country Owner Capacity
[104 ton/year]
Iran
Kharg Petrochemical 50
Amir Kabir Petrochemical 52
Maroon Petrochemical 110
Arvand Petrochemical 100
Arya Sasol Polymer 100
Jam Petrochemical 132
NPC/VPC(No.11) 120
NPC/VPC(No.12) 100
Ilam Petrochemical 32
Saudi
Arabia
Rabigh Refining Petrochemical 130
Tasnee Petrochemical 100
Eastern Petrochemical 130
Yansab 130
Qatar Ras Laffan Ethylene 130
UAE BOUROUGE-Ⅱ 140
Kuwait Equate-Ⅱ 85
Total capacity
for ethylene production:
16 million ton/year
Reference: ENN (2005)
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Product Yield for Feedstock of Cracker
Reference: Journal of Catalysis society of Japan, Suwa(2004)
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10
20
30
40
50
60
Pro
duct Y
ield
[w
t%]
C2 Naphtha VGO
C3=
C2=
Feedstock Ethane Propane Butane Naphtha VGO
C2= Yield 53 40 33 32 22
C3= Yield 1 14 18 16 12
C3 C4
[wt%]
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By-product from naphtha cracking and FCC
Increasing demand (300 million ton/year)
Boom in the construction of ethane crackers
Wild fluctuations in oil prices
Propylene Situation
Expanding of propylene demand-and-supply gap
Diversification of raw materials
Dominant Technology for Propylene production(DTPⓇ)
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+ H2O
+ O2
Natural Gas
Lower Olefins Production from Natural Gas
CH4
C2H6
C3H8
Synthesis
Gas DME
Methanol
Olefins
C2H4
C3H6
DME to
Propylene
Dehydrogenation
Cracking
Methanol to
Olefins
- H2O
- H2
- H2
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CH3OCH3
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Main product: Propylene
By-products: Water,
Ethylene, C4-C6 Olefins,
C1-C4 Paraffins,
C7+ Hydrocarbons
etc.
DTP Reaction
Zeolite catalyst
CH3OH
Methanol DME
C3H6
Propylene
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Advantages of DTPⓇ Catalyst
Typical
MFI
Catalyst
DTPⓇ
Catalyst
Proprietary MFI type Zeolite (ZSM-5) Catalyst
High Propylene Selectivity
Stable Performance at High Temperature
Feed : DME
Feature
of DTPⓇ
Catalyst
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Hydrocarbon
Recycle
DTP
Reactor
Dehydration
Reactor
Feed:
Methanol
Water Gasoline
LPG
Propylene
Separation
Unit
Water
Separator
Compressor
C1-C2
C4-C6
Light gas
DME
+Steam
2,500 t/d 760 t/d (254,000 t/y)
DTPⓇ Process Flow
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Joint Development of JGC Corporation and
Mitsubishi Chemical Corporation
Simple Fixed-bed Adiabatic Reactor
Catalyst Regeneration by Combustion of Coke
High Propylene Yield (70%) by Recycling
By-Products
Optional Co-Feed of C4 Olefins from
Naphtha Cracker / FCC
DTPⓇ Process Features
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Constructed in Mitsubishi Chemical’s Mizushima Plant
Operation Started in August 2010
DTPⓇ Demonstration Plant
This demonstration is subsidized by NEDO.
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DTPⓇ Demonstration Plant Features
Identical Reaction Conditions to Those of
Commercial Scale Design
Actual C4-C6 By-Products Recycling to
DTP Ⓡ Reactor
Reactor Switching for Regeneration
Optional Co-Feed of C4 Olefins from
Naphtha Cracker
Confirmation of State of Products
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Hydrocarbon
Recycle Feed:
Methanol
Water Gasoline
LPG
Propylene
C4-C6
Light gas
DME
+Steam
70 %
Example of Running Data of the Demonstration Plant
Feed:
C4 Olefin
3 %
3 %
16 %
8 % Purge
Selectivity = Total Carbons of each effluent / Total carbons of methanol and C4 olefins as feed
High Selectivity for Propylene
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Example of Running Data of the Demonstration Plant
Propylene Yield = Total Carbons of propylene product / Total carbons of methanol and C4 olefin as feed
0
10
20
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60
70
80
90
100
Pro
pyl
en
e Y
ield
[%]
Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7
Propylene Yield: approximately 70%
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Example of Running Data of the Demonstration Plant
Repeat of Reaction and Regeneration Successfully
0
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90
100
0 10 20 30 40 50 60
Days
Pro
pyle
ne Y
ield
[%
]
React. Reg. React. Reg. React. Reg.
Propylene Yield : Calculated according to
products from reactor A
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Confirmation of State of Products
Products from Demonstration Plant
Propylene mixture Water Gasoline
Analyzed and evaluated each product
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Confirmation of State of Catalyst
Fresh
Catalyst
Degraded
Catalyst
Regenerated
Catalyst
Coke on Degraded Catalyst Eliminated Sufficiently
Catalysts from DTP Reactor of Demonstration Plant
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Propylene Production via Methanol Derived from Natural Gas
in Gas-Producing Countries
Propylene Production with the Use of Both Methanol and
Ineffectively Utilized C4 Olefins from Naphtha Cracker
DTPⓇ Process Applications
Natural Gas Propylene
MeOH / DME
C4 Olefins
Propylene
Ethylene
MeOH / DME
Naphtha
Cracker
DTPⓇ
DTPⓇ
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Process MTO MTP DTP
Company UOP /
Hydro Lurgi
JGC /
Mitsubishi Chemical
Catalyst modified SAPO-34 modified ZSM-5 modified ZSM-5
Process description
Reactor system Fluidized bed Fixed bed Fixed bed
Regeneration Continuous Batch mode Batch mode
Recycle no Olefin and Water Olefin and Paraffin
Conversion [%] 99.6 >99 >99.9
Operation Conditions
Temp. [deg-C] 350-550 425 450-550
Pressure[bar-G] 1-3 1.5 2.0
Olefin Yields[wt%] - - -
Ethylene 48-31 - -
Propylene 34-45 65 >70
Comparison with Competitive Processes
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2007 2008 2009 2010 2011 2012 2013 2014
R&D activity
Equipment Scale
Marketing
Catalyst Improvement
Labo. Reactor(2 g/d)
Bench Plant (5 kg/d)
Demonstration Plant
License Promotion
Commercialization Planning
DTPⓇ Process Development Schedule
Process Improvement
Catalyst Development
Process Development
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Thank You
for
Your Attention !
Contact:
Dr. Nobuyasu Chikamatsu
JGC Corporation
e-mail: [email protected]