1

Robert H. JensenRobert H. JensenUOP LLCUOP LLC

Innovation Tools for CommercializingProcess Technology

CHEMRAWN XVIOttawa, CanadaAugust 9, 2003

2

AgendaAgenda

BackgroundBackground Technology accomplishments in theTechnology accomplishments in the

Process IndustryProcess Industry UOPsUOPs incentive for innovation incentive for innovation Challenges of the 21Challenges of the 21stst century century

Innovation toolsInnovation tools Gated Technology Delivery ProcessGated Technology Delivery Process Tools for materials innovationTools for materials innovation Tools for process innovationTools for process innovation

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Process Industry BackgroundProcess Industry Background

TThe history of the Process Industry is ahe history of the Process Industry is astory of technical accomplishment andstory of technical accomplishment andinnovation.innovation.

AAchievements during the last centurychievements during the last centuryhave led to both tremendous growthhave led to both tremendous growthand a high level of technicaland a high level of technicalsophistication.sophistication.

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Innovations in the ChemicalInnovations in the ChemicalProcess Industry are SlowingProcess Industry are Slowing

Products

Processes

6060

5050

4040

3030

2020

1010

0019301930 19351935 19401940 19451945 19501950 19551955 19601960 19651965 19701970 19751975 19801980 19851985 19901990

YearYear

Product and process innovations from 1930 to 1985.Product and process innovations from 1930 to 1985.

Inno

vati

ons,

cum

ulat

ive

Inno

vati

ons,

cum

ulat

ive

Source: Chemtech 1995, 25(6), 6.Source: Chemtech 1995, 25(6), 6.

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More Octane Barrels (Yield x RON) via LowerMore Octane Barrels (Yield x RON) via LowerPressure and More Selective CatalystsPressure and More Selective Catalysts

C5+

Yie

ld, L

V-%

PlatformingPlatformingTMTM Technology Technology

Research Octane Number, Clear86 90 94 98 102 106

Theoretical Yield, 8600-9300 OB

90

86

82

78

1950s1960s

1970s 1980s1990s

7200-7400 OB

8500-8600 OB

Approaching Theoretical Yieldof Gasoline from Naphtha

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Fluid Catalytic Cracking TechnologyFluid Catalytic Cracking Technology

Octane Barrel Capacity of FCCOctane Barrel Capacity of FCC

New ReactorNew ReactorConceptsConcepts

Improved ReactionImproved ReactionSystemsSystems

Octane CatalystsOctane Catalysts

Extended RiserExtended Riser

Zeolite CatalystsZeolite Catalysts

AmorphousAmorphousCatalystsCatalysts

6,2006,200

6,0006,000

5,8005,800

5,6005,600

5,4005,400

5,2005,200

5,0005,000

4,8004,80019501950 19601960 19701970 19801980 19901990 19961996

Theoretical Octane BarrelsTheoretical Octane Barrels

Oct

ane

Bar

rels

/ 10

0 B

arre

ls F

eed

Oct

ane

Bar

rels

/ 10

0 B

arre

ls F

eed

More Octane Barrels via More Octane Barrels via ZeoliticZeolitic Catalysts Catalystsand Engineering Improvementsand Engineering Improvements

Approaching TheoreticalYield of Gasoline from

Vacuum Gas Oil

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Top Ten Refining Processes Licensed by UOPTop Ten Refining Processes Licensed by UOPProcess Description No. Units

1 MeroxTM Mercaptan Oxidation 1650

2. PlatformingTM Catalytic Reforming 753

3. UnionfiningTM Hydrotreating 675(VGO, Distillate, Naphtha)

4. Polymerization Poly Gasoline Production 301

5. FCC Catalytic Cracking 212

6. UnicrackingTM Hydrocracking 126

7. Sulfolane BTX Extraction 106

8. HF Alkylation Gasoline Production 105

9. Catalytic Condensation Higher Olefin Production 101

10. Isomerization C5/C6 Isomerization 99

UOP must continue to focus on innovationto meet the challenges of the 21st century.

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Sustainable Development Challenges ofSustainable Development Challenges ofthe 21the 21stst Century for the Refining and Century for the Refining and

Petrochemical IndustryPetrochemical Industrynn Clean FuelsClean Fuels

Cost-effective ways to produce zero sulfur/lownitrogen transportation fuels

Reduction of aromatics and olefins in gasolinewhile maintaining octane

nn Alternatives to Crude OilAlternatives to Crude Oil Natural gas utilization Renewable sources

nn Minimum Environmental ImpactMinimum Environmental Impact Refinery emissions Spent catalyst handling

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AgendaAgenda

BackgroundBackground Technology accomplishments in theTechnology accomplishments in the

Process IndustryProcess Industry UOPsUOPs incentive for innovation incentive for innovation Challenges of the 21Challenges of the 21stst century century

Innovation toolsInnovation tools Gated Technology Delivery ProcessGated Technology Delivery Process Tools for materials innovationTools for materials innovation Tools for process innovationTools for process innovation

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UOPsUOPs Gated Technology Delivery Process Gated Technology Delivery Process

Designed specifically for new product/process developmentDesigned specifically for new product/process developmentRequires technology goals/economic caseRequires technology goals/economic caseRequires gate criteriaRequires gate criteriaIncorporates Six Sigma methodologyIncorporates Six Sigma methodologyFacilitates collaborations with producer-partnersFacilitates collaborations with producer-partners

QualitativeQualitative QuantitativeQuantitative ValidationValidation RealizationRealization

GATESGATES

FirstFirstSuccessfulSuccessful

InstallationInstallation

ProjectProjectSelectionSelection

BusinessBusinessPlanPlan

ApprovalApproval

Full ScaleFull ScaleProductionProductionApprovalApproval

ProductProductLaunchLaunch

ApprovalApproval

CustomerCustomerAcceptanceAcceptance

FinalizedFinalizedTechnologyTechnology

PackagePackage

Business &Business &TechnologyTechnology

DevelopmentDevelopment

IdeaIdeaValidationValidation

IdeaIdeaGenerationGeneration

& Management& Management

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UOP Processes Developed inUOP Processes Developed inCollaboration with OthersCollaboration with Others

Process UOP Partner Application

CyclarTM BP LPG to Aromatics

DetalTM CEPSAFixed Bed Alkylation for Detergent

EthermaxTM Koch EtherificationMTO Norsk Hydro Methanol to OlefinsSunoco/UOP Phenol Process

Sunoco Cumene Oxidation

TatorayTM TorayToluene Transalkylation

ThiopaqTM Spent Caustic Treating

Paques Natural Solutions

Biodesulfurization of Caustic

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AgendaAgenda BackgroundBackground

Technology accomplishments in theTechnology accomplishments in theProcess IndustryProcess Industry

UOPsUOPs incentive for innovation incentive for innovation Challenges of the 21Challenges of the 21stst century century

Innovation toolsInnovation tools Gated Technology Delivery ProcessGated Technology Delivery Process Tools for materials innovationTools for materials innovationNew MaterialsNew MaterialsCombinatorial ChemistryCombinatorial ChemistryAdvanced CharacterizationAdvanced CharacterizationManufacturingManufacturing

Tools for process innovationTools for process innovation

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New Materials InventionMaterials Modification

Rapid Scale-upDiverse Crystallization MethodsDiverse Portfolio of Forming Technologies

Materials Innovation ToolsMaterials Innovation ToolsMaterialsMaterials CombinatorialCombinatorial

ChemistryChemistry

AdvancedAdvanced Characterization CharacterizationManufacturingManufacturing

Active SitesStructure Solution Tool Box

Reaction MechanismsAdsorption Modeling

End-to-EndTM Tool Box

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ZeoliteZeolite Discovery Discoveryand Use By Decadeand Use By Decade

27112661125

KnownStructure TypesDecade

1950-19691970-19791980-19891990-1999Totals

2900490074008200

23,400

U.S. Patents(Composition

or Use)312511

CommercializedStructure Types

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Single

PD

DirectMethods

Modelbuilding

Primary building units(elemental analysis)

Secondary building units(FTIR, NMR, absorption)

Superstructure(PD, ED, HREM)

MolecularModeling

Structure verification(DLS, Rietveld)

Structure Solution Tool Box

Defects(HREM, ED, PD)

Crystals(>1000nm)

Microcrystals(10-1000 nm)

Nanocrystals(

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FTIR

HighRes

TEM

XRD

ElectronDiffraction

TEM

Tools Used to Solve the Structure of UFI

Model vs.TEM

TEM: Unique surface aromatic reactivity

ImagingTEM

Small Crystals

UFI

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Structure Solution of a New Zeolite: UZM-5(IZA 3-letter code UFI)

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Event Beta UZM-5First Synthesized 1967 1999Time to Solve Structure >10 yrs 10 monthsStructure Reported 1988 2002

New Tools Accelerate StructureNew Tools Accelerate StructureSolution of Solution of NanocrystallineNanocrystalline Zeolites Zeolites

Structure provides an understanding ofcatalytic and adsorptive properties

Zeolites offer high acid site density forcatalytic applications (low Si to Al ratio)

Zeolites offer ion-exchange capacity andcompositional diversity for separationapplications

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nn Reduced time for catalystReduced time for catalystdiscovery and processdiscovery and processdevelopmentdevelopment Increased probability ofIncreased probability of

successsuccess

Increased throughput ofIncreased throughput oftechnologytechnologycommercializationscommercializations

nn Stronger patent positionStronger patent position

Impact of Combinatorial ChemistryImpact of Combinatorial ChemistryC

ash

Flow

($)

Cas

h Fl

ow ($

)

Time (yrs)Time (yrs)

Technology CommercializationTechnology Commercialization

CombiCombi ConventionalConventional00

Reduced Risk forBreakthrough Programs

Reduced Risk forBreakthrough Programs

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Fully Integrated SystemsFully Integrated SystemsSignificant Increase in ThroughputSignificant Increase in Throughput

End-to-End-to-EndEndTMTM Combinatorial System Combinatorial System

Pretreatment:Pretreatment:ReductionReduction

Combinatorial Synthesis:Combinatorial Synthesis:One-shot synthesis ofOne-shot synthesis oflibraries of materiallibraries of materialss

Post Post SynSyn Processing: Processing:Ion Exchange,Ion Exchange,

Metals AdditionMetals Addition

Finishing Step:Finishing Step:Oxidation, Steaming,Oxidation, Steaming,

OxychlorinationOxychlorination

2-5Leads

Screening:Screening:Parallel screeningParallel screening

of catalytic formulationsof catalytic formulations

100sIdeas

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CombiCombi Target: New Paraffin Target: New ParaffinIsomerizationIsomerization Catalyst Catalyst

nn CC5 5 IsomerizationIsomerization

nn CC6 6 IsomerizationIsomerization

nn Ring OpeningRing Opening

nn-Pentane-Pentane61.761.7

ii-Pentane-Pentane93.593.5

nn-Hexane-Hexane31.031.0

2, 2 DMB2, 2 DMB9494

2, 3 DMB2, 3 DMB105105

oror

2 MP2 MP74.474.4

3 MP3 MP75.575.5

Values areValues areblending RONblending RON

BenzeneBenzene120120

CyclohexaneCyclohexane8484

HH22

MethylMethylCyclopentaneCyclopentane

9696

nn-Hexane-Hexane31.031.0

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Commercial Commercial IsomIsom Catalysts Catalysts

7575

7676

7777

7878

7979

8080

8181

8282

8383

8484

100100 150150 200200 250250 300300Temperature Temperature ((C)C)

CC55+

RO

N C

alcu

late

d+

RO

N C

alcu

late

d

Zeolitic Zeolitic Sulfated Zirconia Sulfated Zirconia

Chlorided Alumina Chlorided Alumina

CC55/C/C66 Isomerization Catalysts Isomerization CatalystsActivity ComparisonActivity Comparison

nnFormation of high octaneFormation of high octaneproducts favored by lowproducts favored by lowtemperature.temperature.nnTwo classes ofTwo classes of

commercial isomcommercial isomcatalysts exist:catalysts exist:

ChloridedChlorided alumina catalyst: alumina catalyst:most active; reactormost active; reactorsystem is highest capitalsystem is highest capitalinvestmentinvestment

Sulfated zirconia andSulfated zirconia andzeoliticzeolitic:: lower activity; lower activity;reactor system is lowerreactor system is lowercapital costcapital cost

Market Need: higher activityMarket Need: higher activitycatalyst for use in lowercatalyst for use in lowercapital reactor systemcapital reactor system

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Post-Synthesis Post-Synthesis CombiCombiProcessing and FinishingProcessing and Finishing

B Level(16)

L1 L4 L3L2

Modifiers(16)

M1 M4 M3M2

A Level(4)

5 876

Temp(32)

T2T1

Modifiers(64)

M5M6

Temp(128)

BulkSupport

BBranch

Binary Modifiers(128)

T2T1

Process Variables(1152)

Noble MetalAddition &

FinalTreatment

Noble MetalAddition &

FinalTreatment

M5 M1 M6M8

M8M7

CombiCombi Screening for Rapid Screening for RapidIdentification of Catalyst LeadsIdentification of Catalyst Leads

Prototypes are a SignificantImprovement to Reference

0

10

20

30

40

50

60

70

95% ReferenceBand

1 2 3WHSV / hr-1

Yie

ld /

%

MeetsTarget

> 5% YieldImprovement

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Pilot Plant Testing Confirms Combi LeadsPilot Plant Testing Confirms Combi Leads

CombinatorialCombinatorial512512 Catalysts / 5 weeks

ConventionalConventional271 271 Catalysts / 3 years

Fig

ure

Of

Mer

itCombi #3

CommercialReference

Ref #2

Temperature (C)(C)

Combi #1

Combi #2

25

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New, New, CombiCombi-Developed-DevelopedPI-242PI-242TMTM Catalyst Catalyst

7575

7676

7777

7878

7979

8080

8181

8282

8383

8484

100100 150150 200200 250250 300300

Temperature (Temperature (C)C)

CC55+

RO

N+

RO

N

Zeolitic

Sulfated Zirconia

Chlorided Alumina

PI-242 Catalyst

nn PI-242PI-242TMTM catalyst catalystdeveloped fromdeveloped fromcombicombi formulation formulation

nn Higher activity thanHigher activity thansulfated zirconia orsulfated zirconia orzeoliticzeolitic

nn Simple drop-in intoSimple drop-in intolowest capital reactorlowest capital reactorsystemsystem

CC55/C/C66 Isomerization Catalysts Isomerization CatalystsActivity ComparisonActivity Comparison

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AgendaAgenda BackgroundBackground

Technology accomplishments in theTechnology accomplishments in theProcess IndustryProcess Industry

UOPsUOPs incentive for innovation incentive for innovation Challenges of the 21Challenges of the 21stst century century

Innovation toolsInnovation tools Gated Technology Delivery ProcessGated Technology Delivery Process Tools for materials innovationTools for materials innovation Tools for process innovationTools for process innovationExperimental dataExperimental dataEngineering technologyEngineering technologySeparationsSeparationsModelingModeling

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ModelingModeling Reactor SystemsKinetic ModelingCold Flow Modeling Computational Fluid Dynamics

Experimental DataExperimental Data Engineering TechnologyEngineering Technology

SeparationsSeparations

AdsorbentsAdsorption Systems

Membranes

Core skillsInstrumentation

and ControlProcess Flowsheeting

and Design

Process Innovation ToolsProcess Innovation Tools

Pilot Plants Analysis Informatics

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Reactor Design OptionsReactor Design Options

Tubular ReactorTubular Reactor

Downflow Downflow AdiabaticAdiabatic

Radial-FlowRadial-FlowAdiabaticAdiabatic

Fluidized-BedFluidized-BedReactorReactor

UOP 2868-5c

PressurePressureDropDrop

TemperatureTemperature

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Reactor Design from Kinetic Modeling

Years

Rea

ctio

n K

inet

ics

Tim

e C

onst

ant

Seconds MonthsDaysHoursMinutes

m-seconds

seconds

minutes

hours

VaporRiserFCC

FixedFluid Bed

MTO Moving-BedRadial Flow

CCR Platforming,Oleflex, Cyclar

Fixed-Bed Radial FlowSR Platforming, Pacol

Cyclic FixedBed Axial Flow

Detal

Fixed-BedAxial Flow

Hydrocracking

CirculatingLiquid Riser

Alkylene

EbulatingBed

Direct

ion of

React

or Int

ensific

ation

Catalyst Deactivation Time Constant

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Reactor Design for Reactor Design for AlkyleneAlkylene Process Process

nn Process requirements:Process requirements:

Short contact timeShort contact time

Rapid disengagementRapid disengagement

Frequent regenerationFrequent regeneration

nn Solution: circulatingSolution: circulating

liquid riser reactorliquid riser reactor

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FluidizationTesting in

Alkylene ColdFlow Model

RTD studies Catalyst density Catalyst attrition Distributor design

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AlkyleneAlkylene Process Process

LiquidLiquidTransportTransportReactorReactor

Iso-CIso-C44/H/H22

Iso-CIso-C44RecycleRecycle

AlkylateAlkylateLPGLPGFractionationFractionation

SectionSection

Olefin FeedOlefin Feed

nn Uses solid catalystUses solid catalystnn No acid soluble oilNo acid soluble oilnn No corrosionNo corrosion

nn Reduced maintenanceReduced maintenancenn Higher yieldsHigher yields

Innovation Tools:Innovation Tools: Novel Catalyst Novel Catalyst Unique Reactor Design Unique Reactor Design Cold Flow Modeling Cold Flow Modeling Computational Fluid Dynamics Computational Fluid Dynamics

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SummarySummary The Process Industry must focus on innovationThe Process Industry must focus on innovation

to meet the challenges of the 21to meet the challenges of the 21stst century century

Innovation tools can accelerate the delivery ofInnovation tools can accelerate the delivery ofnew process technologynew process technology

A Gated Technology Delivery Process Tools for materials innovationMaterialsCombinatorial ChemistryAdvanced CharacterizationManufacturing

Tools for process innovationExperimental dataEngineering technologySeparationsModeling