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