Application of NESSI to Modeling Application of NESSI to Modeling and Product /Process Developmentand Product /Process Development

Michelle J. CohnMichelle J. Cohn

uop uop LLCLLC

© 2004 UOP LLC. All Rights Reserved.

UOP LLC Who We AreUOP LLC Who We AreGlobal company with Global company with 11 manufacturing sites 11 manufacturing sites and offices in 25 countriesand offices in 25 countriesMore than 3,600 highly trained More than 3,600 highly trained employeesemployees90 years of innovative solutions 90 years of innovative solutions for the hydrocarbon processing for the hydrocarbon processing industryindustryUOP’s customers are located in UOP’s customers are located in more than 200 countries. more than 200 countries. World’s largest supplier of World’s largest supplier of molecular sieve adsorbentsmolecular sieve adsorbents

What We DoWhat We DoDevelop technology that Develop technology that provides solutions to problemsprovides solutions to problemsLicense, design, engineer,License, design, engineer,and service process technologyand service process technologyDevelop and manufacture Develop and manufacture 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 Research & Development UOP Research & Development ResourcesResources

More than 185 pilot plants (> 60 operating each day)More than 185 pilot plants (> 60 operating each day)

More than 20,000 pilot plantMore than 20,000 pilot plant--days per yeardays per year

Combinatorial chemistry capabilitiesCombinatorial chemistry capabilities

300 million data points generated per day300 million data points generated per day

350,000 laboratory analyses performed per year350,000 laboratory analyses performed per year

Modeling capabilities include: physical, computational Modeling capabilities include: physical, computational fluid dynamics, kinetic, and process simulation fluid dynamics, kinetic, and process simulation (dynamic and steady(dynamic and steady--state)state)

Average annual R&D spending: 8Average annual R&D spending: 8--10% of sales10% of sales

Process Analytical Technology (PAT)Process Analytical Technology (PAT)

PAT in Heterogeneous Catalysis Product and Process Controll

• Continuous composition diversity• Diversity in phase, microstructure, particle characteristics• Diversity in process conditions for all unit operations• Applied to synthesis, preparation, testing and characterization• Requires detailed material characterization

design, monitoring, control and modeling design, monitoring, control and modeling of materials and process conditionsof materials and process conditions

Desired Outcomes from PATDesired Outcomes from PAT

Increased manufacturing and production Increased manufacturing and production efficiencyefficiency

–– Increased product qualityIncreased product quality–– Reduced product variabilityReduced product variability

Increased innovationIncreased innovationReal time lot certification Real time lot certification

Enablers for PATEnablers for PAT

Reactor

Sensor∆T

Time

Online Online ProcessProcess

AnalyticsAnalytics

Data Analysis

ModelBuilding

SamplingFeedbackFeedbackControlControl

NIRNIRFTIRFTIRDLSDLSRAMANRAMAN

UltrasoundUltrasoundLAMIMSLAMIMSMicroMicro--calorimetrycalorimetryFTIRFTIR

NESSI

VTP

A

P.S.

NESSI

High High ThroughputThroughputCharacterization ToolsCharacterization Tools

HT RamanHT RamanActive Site, Active Site, Phase IDPhase ID

LAMIMSLAMIMSReactivityReactivity

IR ThermographyIR ThermographyTPD, AdsorptionTPD, Adsorption

HT Adsorption HT Adsorption Surface Area, PoreSurface Area, PoreSize DistributionSize DistributionFull spectrum of toolsFull spectrum of tools

UltraUltra--fast collection timesfast collection times100100’’s to 1000s to 1000’’s samples /days samples /day

GoalsGoals

Characterization is Key to SuccessCharacterization is Key to SuccessFrom Data From Data

Structure/Function Models Structure/Function Models = Knowledge= Knowledge

HT XRDHT XRDStructural,Structural,Phase IDPhase ID

HT SEMHT SEMMorphology, Particle SizeMorphology, Particle Size

HT XRFHT XRFElementElementAnalysisAnalysis

High Throughput ScreeningLAMIMS

Laser Activated Membrane IntroductionMass Spectrometry

Micro reactivity test Closed environment (realistic catalyst exposure)Very broad temperature application Full QMS product analysis Real world catalysts

The LAMIMS Screening System

System ComponentsLAMIMS reactant delivery systemA 25 watt CO2 barcode writing laserLAMIMS reactorQuadrupole mass spectrometer (QMS)

LAMIMS SystemLAMIMS SystemMeasure of metal sites

Laser heats samplesLaser heats samplesLarge array of samples Large array of samples in reactorin reactorMass spec monitors Mass spec monitors product streamproduct streamDehydrogenation test Dehydrogenation test for metal activityfor metal activityGoal: 1000 samples Goal: 1000 samples tested per day

CH3

Metal

CH3

H23+

MCH Toluene

To QMSPorous inlet

barrier

Reactant Gas Inlet

Gas out

Laser Beam

Fenix Laser Marker

tested per day

Sample Inlet

Catalyst Spot

To QMA

Silicone Rubber Membrane

Heat Cartridge Well

Tripod Base

ZnSe window

Al toothed flow distributor

Reactor

Data from Reactor System45 samples

Applying NeSSI TechnologyApplying NeSSI Technology

Honeywell sensorsParker Hannifin Intraflow substrate and componentsGO pressure regulatorsParker valves and actuatorsBrooks mass flow controllers

Used Ethernet and DeviceNet networks and commercially available Gen I LabView software on PC for configuration, control, data and diagnosticsProved the need for low power small size actuators and valvesExceptional diagnostic, control, and data collection capabilities Remote monitoring and control via standard internet tools Fast and easy configuration using LabView

Overview of SystemOverview of System

MFC

MFC

MFC

Cell

Laser

Vent

Nitrogen

Argon

Hydrogen

Neslab

Safety Enclosure

HT

-60

3

LAMIMS Flow System

MS

vent

vent

vent

cell

vent

Laser

MFC-20010( 0 -200 ccm)

0 - 250 PSI

0 - 250 PSI

NC

0 - 250 PSI

2005

KV-2006

PCV-

2007

PI-2008PSV-

2009 PCV-

20012

PI-2011 CK-

20013

KV

-201

4

NC

KV-4001

KV-4005

CK-4006

VP-4007

KV

-400

8

PSV-4011

HT-4014

LA-4015

CON-

5011

vent

MFC-10010 ( 0 -200

ccm)

0 - 250PSI

NC

0 - 250 PSI

NC

HV-1005 KV-1006PCV-1007

PI-1008PSV-

1009PI-1011

PCV-

1012

CK-1013KV-1014

CON- 6001

Set at 250 PSI

Set at 7 PSIG

Set at 250 PSI

Set at 250 PSI

CK-4017

AL-

5016

CK-4018

PI-4020

Vent

Vent

0 - 15 PSI

PI-7010

04

Safety enclosure

House Nitrogen gas

Argon gas

cylinder

House Hydrogen gasvent

MFC-30010 ( 0 -250 ccm)

0 - 250 PSI

0 - 250 PSI

HV-3005

HV-

KV-3006

PCV-

3007

PI-3008PSV-

3009PI-3011

PCV-

3012

CK-3013

NC

KV

-301

4

NC

PSV-4004

ISC-

4009

V-5002

TE

-5

00

4

CON-

5009

CON-

5010

refil vessell

0 - 600 PSI

0 - 600 PSI

HV-2001PI-2003

HV-3001PCV-

3002

PI-3003

0 - 600 PSI

HV-1001 PCV-

1002

PI-1003

0 - 600 PSI

To TSR

system

PUR-10

Set at 250 PSI0 - 600 PSI

PUR-2004

Neslab

Set at 250 PSI

PSV-2000

Optional

To TSR

system

Corridor area

Automated System ComponentsDescriptionDescription##

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

Pressure IndicatorsPressure Indicators6 6

24VDC bellows sealed 24VDC bellows sealed valvesvalves

6 6

Back Pressure RegulatorsBack Pressure Regulators33

Device Net Flow controllersDevice Net Flow controllers33

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 Lab View Automation software completedLab View Automation 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

Desired Outcomes from PAT and Desired Outcomes from PAT and NESSINESSI

Increased manufacturing and process Increased manufacturing and process efficiencyefficiency

–– Increased qualityIncreased quality–– Reduced variabilityReduced variability

Increased innovationIncreased innovationReal time certificationReal time certification

PAT SummaryPAT Summary

Technology and industry needs are Technology and industry needs are converging for PAT and NESSIconverging for PAT and NESSI

–– InIn--situ measurementssitu measurements–– Sensor integrationSensor integration–– Computational capacity and methodsComputational capacity and methods

Demonstrated success in refining and Demonstrated success in refining and petrochemicalspetrochemicalsOpportunities for crossOpportunities for cross--industry industry fertilizationfertilization

NESSINESSIPATPAT

AdvancedAdvancedCharacterizationCharacterization InformaticsInformatics

SummarySummary

Enabling Step Changes In Technology Enabling Step Changes In Technology

Innovation and growth driven by enabler toolboxInnovation and growth driven by enabler toolboxOpportunities PAT and NESSIOpportunities PAT and NESSI

–– Seek enhanced understanding of process variables and Seek enhanced understanding of process variables and relationship to performancerelationship to performance

Enabling technologies cut across industriesEnabling technologies cut across industries

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.”