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.”