Increasing Petrochemicals Project Earnings by Increasing Petrochemicals Project Earnings by Upgrading Steam Cracker C4s and C5sUpgrading Steam Cracker C4s and C5s
Stephen StanleyJose de BarrosFred Gardner
Lummus Technology
1st Indian Oil Petrochemical ConclaveMarch 16, 2012
New Delhi
OutlineOutline
• Today’s presentation will cover C4s and C5s processing routes, including:
– Butadiene Extraction
– Metathesis to produce Propylene from both C4s and C5s Olefins
– Skeletal Isomerization to convert either normal or iso– Skeletal Isomerization to convert either normal or isoC4s and C5s
– Linear and Skeletal Isomerization for increased Butene1 production
– Metathesis and Isomerization to produce Butene 1 and Hexene 1
– Etherification to produce MTBE or TAME
CC22--CC44 Olefins Price HistoryOlefins Price History
3000
3500
4000
4500
5000
$/t
on
ETHYLENE
PROPYLENE
Maximize butadiene yield for highest operating margin
Butadiene prices higher than ethylene and propylene
3
Source ICIS Pricing
0
500
1000
1500
2000
2500
10-Oct-06 28-Apr-07 14-Nov-07 1-Jun-08 18-Dec-08 6-Jul-09 22-Jan-10 10-Aug-10 26-Feb-11 14-Sep-11 1-Apr-12
$/t
on PROPYLENE
Butadiene
1,3 ButadieneProduct
1,2 Butadiene
ExtractiveDistillation Distillation
Raffinate
CrudeC4 Feed
Butadiene
Propyne
C Vapor
Deg
assed
NM
P
s +
NM
P
Process Overview Process Overview –– Butadiene ExtractionButadiene Extraction
1,2 Butadiene
SolventDegassing C4 Acetylenes
C4 Vapor
Deg
assed
NM
P
C 4
s +
NM
P
Butadiene Extraction Market LeadershipButadiene Extraction Market Leadership
• Leading (first quartile) technology in butadiene extraction
• Best solvent: NMP
– Lowest environmental impact, non-corrosive, highest selectivity
• Lowest fouling system• Lowest fouling system
– Operating periods over five years between shutdowns
– Average on-stream factor 8300-8500 hours per year
– Incorporates “popcorn prevention” system
• Commercially proven with 33 operating plants
• Capacities from 65 to 900 MMlb/y
• Commitment to technology improvement
• Ongoing technical support from Lummus and BASF
5
The Solvents: EcoThe Solvents: Eco--Efficiency AnalysisEfficiency Analysis
best0,5
Environm
enta
l Im
pact
NMP process
DMF process
ACN process
1,0
Energy Consumption
Land Use
NMP has lowest environmental
impact and costNMP is less in
all categories
6
worst
1,0
1,50,51,01,5
Costs
Environm
enta
l Im
pact
0,0
0,5 Emissions
Toxicity Potential
Risk Potential
Resources Consumption
Land Use
NMP is the best solvent for butadiene extraction
MethathesisMethathesis Chemistry for Improved Operating MarginChemistry for Improved Operating Margin
• Steam cracker & refinery C4’s & C5’s can be upgraded using metathesis chemistry
• Olefins Conversion Technology (OCT) is the only commercially demonstrated metathesis technology
• Since 2000, Lummus Technology has licensed 37 plants based on the OCT process
– Over 8 million tons of capacity
– More than10% of world’s propylene capacity
• Benefits include:
– Upgrade of C4s & C5’s to high value propylene
– Low CO2 production
– Low utility consumption
– Low capital investment
– Quick project turnarounds
Propylene Selectivity ComparisonPropylene Selectivity Comparison
50
75
100
% PropyleneYield
“By-product”Technologies
“On-purpose”Technologies
8
0
25
50Yield
Relative Investment
OCT is low cost on-purpose
Olefins Conversion Technology EconomicsOlefins Conversion Technology Economics
Traditional OCT feed sources: Steam cracker
and FCC
Ref: CMAI
on-purpose propylene production
option
9
Ethylene Ethylene ButeneButene MetathesisMetathesis
Main Metathesis Reaction
OCT upgrades lower cost butenes 0.74 ton C4 ���� 1 ton propylene
10
1 moleEthylene+
1 moleButene-2
2 molesPropylene=
Ethylene/Pentene MetathesisEthylene/Pentene Metathesis
Main Metathesis Reaction
Propylene
+Ethylene
+
11
Butene-1
Propylene
+
Pentene-2
Ethylene
+
+
Butenes Ethylene Propylene
Value added by OCTValue added by OCT
> $52 million/year for a 150 kta OCT
Butenes0.74 ton
Ethylene0.31 ton
Propylene1.00 ton
$550/ton $1100/ton $1100/ton
Catalyst + Utilities $30/ton
$350/ton upgrade
Ethylene/Pentene OCTEthylene/Pentene OCT
• Steam cracker C5s typically hydrogenated to olefins or paraffins and recycled to cracking heaters
• After selective hydrogenation, C5s can now be fed to OCT as additional feedstock
13
Ethylene + propylene yield increases by 2.5 Ethylene + propylene yield increases by 2.5 times compared to crackingtimes compared to cracking
Improved Margins Improved Margins –– CC44/C/C55 OCTOCT
$15
$20
$25 $22
$17
US
Mil
lio
n $
Expected payback less than 2 years
$0
$5
$10
Gross
Margin Net Margin
US
Mil
lio
n $
14
Value Added to C4 only OCT
Ethylene Feed
Propylene Product
Lights PurgeRecycle Ethylene
OCT Reactor Ethylene Column Propylene ColumnGuard Bed
OCT Process Scheme a Simple ProcessOCT Process Scheme a Simple Process
Ultra-high purity propylene >99.9+%
C4 & C5 Feed C4 PlusC4 & C5 Recycle
15
No superfractionators required
Energy-neutral reaction
Fixed bed
reactor
CDCDIsisIsis ProcessProcess
• CDIsis isomerizes both isobutene & isopenteneto normal butene & pentene to increase OCU feed
• CDIsis unit, integrated with OCT, is an effective way of converting low-value isobutene & isopentene to ultimately high-value propylene isopentene to ultimately high-value propylene product
16
Chemistry Chemistry
• Chemistry:
– Olefin skeletal isomerization
– Equilibrium reaction
• Can go both ways
• Temperature sets equilibrium distribution
17
Isobutene
Butene-2
Butene-1
~
CDCDIsisIsisSMSM Skeletal Isomerization of IsobuteneSkeletal Isomerization of Isobutene
CD-DeIB®
Conventional Processing
OCT
Isobutene/Isobutane to Cracking
Propylene
Ethylene
Mixed C4sOlefins
~
Poor Crackingselectivity
18
Cracking
Mixed C4sOlefins CDCD--DeIBDeIB OCTOCT
~
Propylene
CDCDIsisIsisIsobutaneIsobutene
~Ethylene
Adds up to 60% more propylene production
CDIsis Unit for more Propylene
CDCDIsisIsis Unit Integrated with OCTUnit Integrated with OCT
255 kta
Mixed C4s
CC44 Treating and Treating and Selective Selective
HydrogenationHydrogenation
CDCD--DeIBDeIB
UnitUnit
H2
78 kta Isobutane/ Isobutene purge
34 kta
Ethylene
OCT Unit100 kta
Propylene
Product
43 kta
C4+ By-product
i-C4s
CDCDIsisIsis Unit Integrated with OCTUnit Integrated with OCT
255 kta
Mixed C4s
H2
CC44 Treating and Treating and Selective Selective
HydrogenationHydrogenation
CDCD--DeIBDeIB
UnitUnit
Fractionator Bottoms Product
Same CSame C44 feedfeed
78 kta Isobutane/ Isobutene purge
CDIsis
Unit
54 kta
Ethylene
Up to 60% more CUp to 60% more C33--
~50% more butenes~50% more butenes
OCT Unit160 kta
Propylene
Product
49 kta
C4+ By-product
Improved Margins Improved Margins
Expected payback less than 2 years
OCT Integrated with CDIsis Unit
21
2 years
CDCDIsisIsis/OCT Integration /OCT Integration –– SummarySummary
• CDIsis process is commercially proven
• Simple process, flowsheet and reactor operation similar to OCT unit
• CDIsis unit integration would increase the net margin by about US$25 million for unit expanded from 100 to 160 ktafrom 100 to 160 kta
• Pay-out in less than 2 years
22
CPT Chemistry for 1CPT Chemistry for 1--ButeneButene
• Isomerization technology for 1-Butene
Isomerization
• Equilibrium conversion ~20%
• No side reactions
• Energy neutral
2-Butene 1-Butene
• Proven C4 feed treatment system to insure isom catalyst performance
• Maximized heat interchange for low energy input reaction system
• Simple reactor design
CPT CPT ButeneButene IsomerizationIsomerization
• Simple reactor design
• Spare reactors for continuous operation
• Regeneration system included for catalysts and adsorbents
• Proven energy-efficient Sulzer heat pump recovery system (Butene fractionation)
4Butene
Fractionator
Product Pump
Raffinate-2
1-ButeneIsobutylene
must be removed to
meet specification
Butane content sets recycle and
fractionation energy
CPT CPT ButeneButene IsomerizationIsomerization Process Flow DiagramProcess Flow Diagram
Isomerization
Reactor
Feed Pump
Reflux Pump
Raffinate-3
To LPG storageFuel
Isomerization
Treater
CW
SulzerHeat Pump
FractionationSystem
+ CH3-OH
CH3
CH3
CH2C CH3
CH3
CH3
C O CH3
∆ ∆ ∆ ∆ Hr = - 8.5 - 9.5 Kcal / mol
MTBEMTBE
isobutene MTBE
Amberlyst
Methanol
Ethers Process ChemistryEthers Process Chemistry
isobutene MTBEMethanol
+ C2H5-OH
CH3
CH3
CH2C CH3
CH3
CH3
C O C2H5
∆ ∆ ∆ ∆ Hr = - 8.5 - 9.5 Kcal / mol
ETBEETBE
isobutene ETBE
Amberlyst
Ethanol
Achieving Very High ConversionAchieving Very High Conversion
Conventional System
• Reaction followed by separation of product
• followed by reaction followed by another separation
• …….
• More separation steps increase capital cost
• Very high conversion cannot be achieved economically• Very high conversion cannot be achieved economically
What is Catalytic Distillation?What is Catalytic Distillation?
Process Simplification by...
Combining reaction and distillation in one single operation
CONVENTIONAL SYSTEM CD SYSTEM
Fixed Bed Reactor Fractionator CD Column
Achieving Very High ConversionAchieving Very High Conversion
CD System
• Very high conversion can be achieved economically
CDModules
Catalytic DistillationCatalytic Distillation
Similar to Structured Packing
Contains Catalyst Inside the Packing
Typical Typical CDCDMtbeMtbe SchemeScheme
C4 Feed
Methanol
C4/Methanol
C4 Raffinate
Catalytic
DistillationPrimary
Reactor
Methanol
Extraction
Methanol
Recovery
Water
MTBE
• Upgrading both steam cracker & refinery C4’s and C5’s can enhance profitability
• Butadiene Extraction
• OCT
• CPT
ConclusionConclusion
• MTBE/ETBE
• Lummus supplies all technologies and can therefore optimize upgrading the C4’s and C5’s
Increased Project Earning will result
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