innovation tools for commercializing process technology
TRANSCRIPT
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Robert H. JensenRobert H. JensenUOP LLCUOP LLC
Innovation Tools for CommercializingProcess Technology
CHEMRAWN XVIOttawa, CanadaAugust 9, 2003
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AgendaAgenda
§§ BackgroundBackground•• Technology accomplishments in theTechnology accomplishments in the
Process IndustryProcess Industry•• UOP’sUOP’s 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•• UOP’sUOP’s 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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UOP’sUOP’s Gated Technology Delivery Process Gated Technology Delivery Process
§§Designed specifically for new product/process developmentDesigned specifically for new product/process development§§Requires technology goals/economic caseRequires technology goals/economic case§§Requires gate criteriaRequires gate criteria§§Incorporates Six Sigma methodologyIncorporates Six Sigma methodology§§Facilitates 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
•• UOP’sUOP’s 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 innovationüüNew MaterialsNew MaterialsüüCombinatorial ChemistryCombinatorial ChemistryüüAdvanced CharacterizationAdvanced CharacterizationüüManufacturingManufacturing
•• Tools for process innovationTools for process innovation
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üNew Materials InventionüMaterials Modification
Rapid Scale-upDiverse Crystallization MethodsDiverse Portfolio of Forming Technologies
Materials Innovation ToolsMaterials Innovation ToolsMaterialsMaterials CombinatorialCombinatorial
ChemistryChemistry
AdvancedAdvanced Characterization CharacterizationManufacturingManufacturing
Active SitesüStructure Solution Tool Box
Reaction MechanismsAdsorption Modeling
üEnd-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(<10nm)
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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 Systems••Significant 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 ((ººC)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)
M5
M6
Temp(128)
BulkSupport
BBranch
Binary Modifiers(128)
T2T1
Process Variables(1152)
Noble MetalAddition &
FinalTreatment
Noble MetalAddition &
FinalTreatment
M5 M1 M6M8
M8
M7
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 (ºC)(ºC)
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 (ººC)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
•• UOP’sUOP’s 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 innovationüüExperimental dataExperimental dataüüEngineering technologyEngineering technologyüüSeparationsSeparationsüüModelingModeling
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ModelingModeling üReactor SystemsüKinetic ModelingüCold 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
üPilot 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
Directio
n of R
eactor
Inten
sificat
ion
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 innovationüMaterialsüCombinatorial ChemistryüAdvanced CharacterizationüManufacturing
• Tools for process innovationüExperimental dataüEngineering technologyüSeparationsüModeling