Post on 12-Mar-2020
POCA 2POCA 2Implementation of Implementation of NeSSINeSSI for LAMIMS for LAMIMS
MicroReactivityMicroReactivity TestingTesting
High Speed Characterization and Testing High Speed Characterization and Testing of Materialsof Materials
M.J. CohnM.J. CohnUOP LLCUOP LLC
Des Plaines, IL, USADes Plaines, IL, USA
UOP xxxx-1
UOP LLC Who We AreUOP LLC Who We AreWorld’s Largest & Oldest Refining World’s Largest & Oldest Refining and Petrochemical Technology and Petrochemical Technology Licensing OrganizationLicensing OrganizationLeading supplier of catalysts to the Leading supplier of catalysts to the processing industryprocessing industryWorld’s largest supplier of molecular World’s largest supplier of molecular sieve adsorbentssieve adsorbentsRoughly 90years of innovative solutions Roughly 90years of innovative solutions for the hydrocarbon processing industryfor the hydrocarbon processing industryGlobal company with Global company with 12 manufacturing sites12 manufacturing sites
What We DoWhat We DoDevelop technology that Develop technology that provides solutions to provides solutions to problemsproblemsLicense, design, engineer,License, design, engineer,and service process and service process technologytechnologyManufacture and provide Manufacture and provide catalysts, molecular sieves, catalysts, molecular sieves, adsorbents, and specialized adsorbents, and specialized equipmentequipmentTransfer technology to Transfer technology to customers who achieve high customers who achieve high yield of high quality productsyield of high quality products
UOP Sites Around the WorldUOP Sites Around the World
OfficesManufacturing
All Manufacturing Sites are ISO 9002 Registered
UOP Corporate HistoryUOP Corporate History19141914 –– Universal Oil Products formedUniversal Oil Products formed1930’s1930’s –– Sold to major oil companiesSold to major oil companies1940’s1940’s –– Placed in trust to American Chemical Placed in trust to American Chemical
SocietySociety
1950’s1950’s –– Relaunched as a public companyRelaunched as a public company1970’s1970’s –– Acquired by Signal CorporationAcquired by Signal Corporation1980’s1980’s –– Signal merges with Allied Signal merges with Allied
CorporationCorporationUOP merges with Union Carbide’s UOP merges with Union Carbide’s EP&P and CAPS GroupsEP&P and CAPS Groups
1990’s1990’s –– UOP acquires Unocal’s process UOP acquires Unocal’s process technology licensing businesstechnology licensing business
2000’s2000’s –– UOP ownership changes to UOP ownership changes to DOW/HoneywellDOW/Honeywell
World’s Largest TechnologyWorld’s Largest TechnologyLicensing OrganizationLicensing Organization
30,000+ patents, 90% licensable30,000+ patents, 90% licensable70 licensed processes70 licensed processes70 catalysts70 catalystsMolecular sieves adsorbentsMolecular sieves adsorbents30 Engineered products30 Engineered products–– Packaged process units and systemsPackaged process units and systems–– Proprietary equipmentProprietary equipment–– Control systems and instrumentationControl systems and instrumentation
Engineering, technical and training Engineering, technical and training servicesservices
UOP Manufacturing UOP Manufacturing CapabilitiesCapabilities
Catalyst and Adsorbent SupportsCatalyst and Adsorbent Supports–– Metal oxides, including alumina, silica, Metal oxides, including alumina, silica, titaniatitania, zirconia, and clays, zirconia, and clays–– Numerous techniques, including oil dropping, bead forming, Numerous techniques, including oil dropping, bead forming,
extrusion and spray dryingextrusion and spray drying•• Shapes include powders, spheres, and Shapes include powders, spheres, and extrudatesextrudates
Catalytic Component Additions (Catalysts)Catalytic Component Additions (Catalysts)–– Core competency in noble metals, especially salts of platinum anCore competency in noble metals, especially salts of platinum and d
palladiumpalladium–– Comparable strength in base metals, especially oxides and nitratComparable strength in base metals, especially oxides and nitrates of es of
tungsten, cobalt, nickel, and molybdenumtungsten, cobalt, nickel, and molybdenum–– Understanding and use of Understanding and use of ofof catalytic modifiers, attenuators, and catalytic modifiers, attenuators, and
extenders extenders
Catalyst ProcessingCatalyst Processing–– Noble and base metal loading (solutions, spray, coNoble and base metal loading (solutions, spray, co--mull, IX)mull, IX)–– Drying and activation by oxidationDrying and activation by oxidation–– Reduction capacity for noble metal productsReduction capacity for noble metal products
UOP Engineering UOP Engineering CompetenciesCompetencies
Process design developmentProcess design developmentProcess SynthesisProcess SynthesisCost estimating (capital, operating)Cost estimating (capital, operating)Ability to integrate process and mechanical systemsAbility to integrate process and mechanical systems–– Reactors/regenerators and internalsReactors/regenerators and internals
Reaction systemsReaction systems–– Select most appropriate system for task Select most appropriate system for task
Solids circulationSolids circulationSpecialized unit operationsSpecialized unit operations–– Low Low dpdp heaters/exchangers, high pressure heatersheaters/exchangers, high pressure heaters
Thermodynamics and process modeling Thermodynamics and process modeling
UOP Research & Development UOP Research & Development ResourcesResources
More than 185 pilot plants,> 60 operating each dayMore than 185 pilot plants,> 60 operating each dayMore than 20,000 pilot plantMore than 20,000 pilot plant--days per yeardays per yearCombinatorial chemistry capabilitiesCombinatorial chemistry capabilities300 million data points generated per day300 million data points generated per day350,000 laboratory analyses performed per year350,000 laboratory analyses performed per yearModeling Capabilities include: physical, Modeling Capabilities include: physical, computational fluid dynamics, kinetic and process computational fluid dynamics, kinetic and process simulations (dynamic and steadysimulations (dynamic and steady--state)state)Average Annual R&D Spending: 8Average Annual R&D Spending: 8--10% of Sales10% of Sales
Key Research and Development Key Research and Development CompetenciesCompetencies
Catalyst / Adsorbents Reactors• Noble, base metal and super acid
catalysts• Molecular sieves, metal
oxides, pillared clays• Binding, forming, oil dropping,
extrusion, wash coating• Molecular modeling• Surface science and
characterization
• Fixed and radial flow• Temp controlled reactor (TCR)• Fluidized, transport, slurry,
trickle, and ebullated bed• Bubble column reactor• Hybrid reaction / distillation• Hybrid reaction / adsorption• Batch / continuous modeling
Commercialization• Exploratory R & D• Pilot plant facilities• Kinetics measurement and analysis• Risk management• Scale-up engineering• Novel hardware design• Catalyst and adsorbent manufacture
Separations• Adsorptive separations• Polymeric membranes• Pressure swing adsorption• Temperature swing adsorption• Solvent extraction• Distillation trays / tubes
Active SitesActive Sites
XPSXPSXX--ray Adsorptionray Adsorption
–– XANESXANES–– EXAFSEXAFS–– InIn--situ situ
XANES/EXAFSXANES/EXAFS
Gas AdsorptionGas Adsorption–– TPRTPR–– NH3 TPDNH3 TPD–– TMP NMRTMP NMR
IR and RAMANIR and RAMANSpecialty XSpecialty X--ray ray FluorescenceFluorescence
StructuralStructural
Powder XPowder X--ray Diffractionray Diffraction–– High tempHigh temp
Specialty XSpecialty X--Ray Ray DiffractionDiffraction
–– Microbeam Microbeam analysisanalysis
MetallurgyMetallurgyMicroscopyMicroscopy
–– SEMSEM–– Low Vacuum SEMLow Vacuum SEM–– TEMTEM–– STEMSTEM–– AFMAFM–– OpticalOptical
NMR solids & liquidsNMR solids & liquids
Reactivity Adsorption Reactivity Adsorption MechanismMechanism
High Temperature High Temperature CalorimetryCalorimetryDiffusionDiffusionMicroreactorsMicroreactorsSpecialty Specialty MicroreactorsMicroreactors
–– TEOMTEOM–– TSRTSR–– SSITKASSITKA–– TAPTAP–– Isotopic Isotopic
LabelingLabeling
Where we are planningto apply NeSSI
Advanced CharacterizationAdvanced Characterization
Combinatorial ChemistryCombinatorial ChemistryVision:Vision: Utilize combinatorial tools and Utilize combinatorial tools and methods to reduce cycle time for new methods to reduce cycle time for new product invention product invention andand commercializationcommercialization..Implication:Implication: Invent and implement Invent and implement combinatorial tools and methods that combinatorial tools and methods that effectively link combi scale to pilot and effectively link combi scale to pilot and commercial scalescommercial scales–– Sample preparation is representativeSample preparation is representative–– Screening tests are predictiveScreening tests are predictive
CombiCombi MicroMicro PilotPilot DemoDemo CommercialCommercial
ScalableScalablePredictivePredictive
Combinatorial VisionCombinatorial Vision
1 2 3
DiscoveryDiscovery ResearchResearch(1000s of ideas)(1000s of ideas)
FocusFocus ResearchResearch(100s of ideas)(100s of ideas)
Successful Successful CommercialCommercialOperationOperation(1 prototype)(1 prototype)
Catalyst PreparationCatalyst PreparationCatalyst TestingCatalyst Testing
ModelingModelingInformaticsInformatics
Process DevelopmentProcess Development(2(2--5 leads)5 leads)
Combi is a Step in theTechnology Delivery Process
Enablers of Combinatorial CharacterizationEnablers of Combinatorial CharacterizationEfficient ways of materials synthesisEfficient ways of materials synthesisParallel preparation of experimental catalystsParallel preparation of experimental catalystsAvailability and development of highAvailability and development of high--speed speed characterization toolscharacterization toolsParallel and high throughput testing of Parallel and high throughput testing of catalytic propertiescatalytic propertiesData analysis techniques Data analysis techniques -- informaticsinformatics
Accelerated processes of discovery andAccelerated processes of discovery andtechnology deliverytechnology delivery
Combinatorial CapabilitiesCombinatorial Capabilities
Catalyst Catalyst Preparation
ModularModularInterchangeableInterchangeableStandStand--alonealoneFlexible
Preparation
Reactor Reactor AssayAssay
Material SynthesisMaterial Synthesis
CharacterizationCharacterization
Data AnalysisData Analysis
Flexible
Heat Treatment Heat Treatment UnitUnit
LAMIMSLAMIMS(Laser activated membrane (Laser activated membrane
introduction mass spectrometry)introduction mass spectrometry)Micro reactivity TestMicro reactivity TestClosed environment (realistic catalyst exposure Closed environment (realistic catalyst exposure history)history)No moving partsNo moving partsVery broad temperature applicationVery broad temperature applicationFull QMS product analysisFull QMS product analysisReal world catalystsReal world catalystsStateState--ofof--art catalyst as standard (universal rankingart catalyst as standard (universal ranking))
The LAMIMS Screening System
•LAMIMS reactant delivery system
•A 25 watt CO2barcode writing laser
•LAMIMS reactor
•Quadrupole mass spectrometer (QMS)
LAMIMS ReactorLAMIMS Reactor
Diffusion layer
Silicone rubber
Al Flow Distributor
Stainless Steel Frit
ZnSe Window
Catalyst Spot
Carbon paper is overlaid upon the membraneCarbon paper is overlaid upon the membrane–– Heat dissipater protecting polymer Heat dissipater protecting polymer
membranemembrane
Catalyst array is deposited upon the carbon paperCatalyst array is deposited upon the carbon paperEntire reactor is heated to base temperatureEntire reactor is heated to base temperatureLaser tuning of catalyst spot temperatureLaser tuning of catalyst spot temperatureQMS analysis of product distributionQMS analysis of product distribution
Sample Inlet
Catalyst Spot
To QMA
Silicone Rubber Membrane
Heat Cartridge Well
Tripod Base
ZnSe window
Al toothed flow distributor
Reactor
Methylcyclohexane (MCH) Methylcyclohexane (MCH) dehydrogenationdehydrogenation
CH3 CH3 + 3 H2
tolueneMCH
MCH Conversion to toluene is a measure of metal reactivity
Data from Reactor SystemData from Reactor SystemForty five Pt (0.2%) catalysts. Forty five Pt (0.2%) catalysts.
Inlet
OutletTol
uene
Pro
duct
ion
The vision…The vision…
Lab Automation using NeSSILab Automation using NeSSI
Used Ethernet and DeviceNet networks and commercially available Used Ethernet and DeviceNet networks and commercially available Gen I Gen I productsproductsLabViewLabView software on PC for configuration, control, data and diagnosticssoftware on PC for configuration, control, data and diagnosticsProved the need for low power small size actuators and valvesProved the need for low power small size actuators and valvesExceptional diagnostic, control, and data collection capabilitieExceptional diagnostic, control, and data collection capabilities s Remote monitoring and control via standard internet toolsRemote monitoring and control via standard internet toolsFast and easy configuration using Fast and easy configuration using LabViewLabView
•Honeywell sensors
• Parker Hannifin Intraflowsubstrate and components
• GO pressure regulators
• Parker valves and actuators
• Brooks mass flow controllers
System Overview
HT
-603
House Nitrogen gas
LAMIMS Flow System
MS
vent
vent
cell
vent
Laser
MFC-20010( 0 -200 ccm)
0 - 250 PSI
0 - 250 PSI
0 - 250 PSI
HV-2005 PCV-2007
PI-2008PSV-2009 PCV-
20012
PI-2011 CK-20013
NC
KV-4005
CK-4006
VP-4007
KV
-400
8
PSV-4011
HT-4014
LA-4015
CON-
vent
MFC-10010 ( 0 -200ccm)
0 - 250PSI
NC
0 - 250 PSI
NC
HV-1005 KV-1006PCV-1007
PI-1008PSV-1009
PI-1011
PCV-1012
CK-1013KV-1014
0 - 600 PSI
HV-2001PI-2003
CON- 6001
Set at 250 PSI
Set at 250 PSI
Set at 250 PSI
CK-4017
AL-5016
CK-4018
0 - 600 PSI
PI-4020
Vent0 - 15 PSI
PI-7010
HV-1001 PCV-1002
PI-1003
0 - 600 PSI
To TSRsystem
PUR-1004Set at 250 PSI
PSV-2000
Safety enclosure
MFC
MFC
MFC
Cell
Laser
Vent
Nitrogen
Argon
Hydrogen
Neslab
Safety Enclosure
Overall
Detailedvent
Argon gascylinder
House Hydrogen gasvent
NC
MFC-30010 ( 0 -250 ccm)
0 - 250 PSI
0 - 250 PSI
HV-3005
KV-2006
KV-3006
PCV-3007
PI-3008PSV-3009
PI-3011
PCV-3012
CK-3013
KV
- 2014
NC
KV
-3014
NC
KV-4001
PSV-4004
ISC-4009
CON-5009
CON-5010
5011Optional
Vent
V-5002
TE
-5
00
4
refil vessell
0 - 600 PSI
HV-3001PCV-3002
PI-3003
Set at 250 PSI
Set at 7 PSIG
0 - 600 PSI
PUR-2004
Neslab
Corridor area
To TSRsystem
Automated System Components
4 port two position valves4 port two position valves22
3 port two position valve3 port two position valve11
Pressure reducing Pressure reducing regulatorsregulators
3 3
Honeywell Pressure Honeywell Pressure IndicatorsIndicators
6 6
24VDC bellows sealed 24VDC bellows sealed valvesvalves
6 6
Back Pressure Back Pressure RegulatorsRegulators
33
Device Net Flow Device Net Flow controllerscontrollers
33
LABVIEW SCREEN
LAMIMS Gas Handling SystemConstruction and Demonstration Accelerated with NeSSI
Mass Spectrometer installed Mass Spectrometer installed Laser installedLaser installedNESSI gas manifold installed NESSI gas manifold installed Automation software completedAutomation software completedSafety review completedSafety review completed
baselinebaseline+10%+10%Manifold costManifold cost4months4months2months2monthsPersonnel timePersonnel time6 months6 months4months4monthsElapsed timeElapsed timeTypicalTypicalW/W/NeSSINeSSIResourcesResources
Installation Went Very WellInstallation Went Very WellList of Minor IssuesList of Minor Issues
The check valves were ordered with a 1psi cracking The check valves were ordered with a 1psi cracking pressure.pressure. However, the check valves were delivered with a much However, the check valves were delivered with a much higher cracking pressure.higher cracking pressure. This was corrected the following day by This was corrected the following day by ordering new springs for the check valves.ordering new springs for the check valves.All the block valves and the mass flow controller for the nitrogAll the block valves and the mass flow controller for the nitrogen en line were specified to be normally opened.line were specified to be normally opened. They all were delivered They all were delivered normally closed.normally closed. A “simple” nitrogen line (needle valve and block A “simple” nitrogen line (needle valve and block valve) added to correct this safety issuevalve) added to correct this safety issueAll the connections to the All the connections to the NeslabNeslab fourfour--way valve (KVway valve (KV--4001) and to 4001) and to the vent fourthe vent four--way valve (KVway valve (KV--4005) were incorrectly installed.4005) were incorrectly installed. We We had to take apart most of the had to take apart most of the NeSSINeSSI system to correct this. system to correct this. Original design to put all electronics modules (Original design to put all electronics modules (labviewlabview field point field point modules, power supply, modules, power supply, etcetc.) inside an enclosure. .) inside an enclosure. The The NeSSINeSSIsystem arrived without such an enclosure, and all the electronicsystem arrived without such an enclosure, and all the electronics s parts were exposed to the outside, including the 110V cables.parts were exposed to the outside, including the 110V cables.The Brooks mass flow controllers failed to communicate The Brooks mass flow controllers failed to communicate ((DeviceNetDeviceNet communication) correctly with the automation communication) correctly with the automation software.software. Falaah resolved this issue with Brooks. Falaah resolved this issue with Brooks.
“Overall the “Overall the NeSSINeSSI system performs wellsystem performs well
AcknowledgmentsAcknowledgmentsEugene Smotkin, IIT, UPREugene Smotkin, IIT, UPR--RPRPRenxuan Liu, NuVant Systems Inc., currently GTIRenxuan Liu, NuVant Systems Inc., currently GTIYongtaeYongtae Kim, IITKim, IITDoug Galloway, UOP Doug Galloway, UOP Richard R. Willis, UOPRichard R. Willis, UOPFalaah Falih, UOP Falaah Falih, UOP Robert J. Allen, UOPRobert J. Allen, UOPMichael J. McCall, UOPMichael J. McCall, UOPJose A. Rodriguez, UPRJose A. Rodriguez, UPR--RPRPAmit Amit NayarNayar, IIT, IITJohn Mosher, HoneywellJohn Mosher, HoneywellRobert Nickels, HoneywellRobert Nickels, HoneywellSteve Doe, Parker HannifinSteve Doe, Parker Hannifin
A portion of this work was performed under the support of the U.S. Department of Commerce, National Institute of Standards and Technology, Advanced Technology Program, Cooperative Agreement 70NANB9H3035.”