Brian Marquardt and Dave Veltkamp Brian Marquardt and Dave Veltkamp

Applied Physics Laboratory /Applied Physics Laboratory /Center for Process Analytical ChemistryCenter for Process Analytical ChemistryUniversity of WashingtonUniversity of WashingtonSeattle, WA 98105 Seattle, WA 98105

Combining Analytical Sensors and NeSSI to Improve Process Understanding

Project Goals and ObjectivesProject Goals and ObjectivesEstablish research platforms integrating Establish research platforms integrating microreactors, NeSSI, and microreactors, NeSSI, and analytical analytical monitoringmonitoring for the multidisciplinary investigation for the multidisciplinary investigation of bio-processing and bio-fuels related of bio-processing and bio-fuels related processes.processes.

These systems will be used to support other These systems will be used to support other CPAC and University projects investigating bio-CPAC and University projects investigating bio-processing, provide opportunities for student processing, provide opportunities for student education, and education, and allow development of allow development of additional instrumentation and techniques for additional instrumentation and techniques for monitoring bio-processesmonitoring bio-processes..

Project Research PlanProject Research PlanTask 1: Task 1: integrate the microreactors with the NeSSI™ integrate the microreactors with the NeSSI™ fluidics system and the analytical monitoring instruments.fluidics system and the analytical monitoring instruments.

Task 2: Task 2: characterize the systems so their properties (i.e., characterize the systems so their properties (i.e., flow, mixing, heat transfer, residence time, etc.) are well flow, mixing, heat transfer, residence time, etc.) are well understood. understood.

Task 3: Task 3: development of the on-line analytical to monitor development of the on-line analytical to monitor the key operational parameters and reaction progress. the key operational parameters and reaction progress.

Task 4: Task 4: development of strategies and implementations development of strategies and implementations for automation and control of the system. for automation and control of the system.

Software and hardware for data and control communication Software and hardware for data and control communication interfaces (hopefully utilizing a Gen II NeSSI™-bus network) will interfaces (hopefully utilizing a Gen II NeSSI™-bus network) will need to be developed and tested.need to be developed and tested.

NeSSI with an Array of Micro-NeSSI with an Array of Micro-Analytical Techniques will Impact Analytical Techniques will Impact

Many IndustriesMany Industries

Process ControlProcess Control

Process Process OptimizationOptimization

Product Product DevelopmentDevelopment

Sensing TechnologiesSensing Technologies

Gas ChromatographyGas Chromatography Thermal Desorption (Thermal Desorption (??))

Dielectric (Dielectric (√√))SpectroscopiesSpectroscopies IR (IR (++)), NIR (, NIR (++)) UV- Vis (UV- Vis (++)) Raman (Raman (√√)) Fluorescence (Fluorescence (++))

Impedance (Impedance (++))Conductivity (Conductivity (√√))Refractive Index (Refractive Index (√√))

Vapochromic SensorsVapochromic Sensors ( (++))GLRSGLRS ( (++))Particle SizingParticle Sizing Light scattering (Light scattering (??) )

TurbidityTurbidity ( (++))pHpH ( (√√))RGARGA ( (++))

Mass SpectrometryMass Spectrometry ( (√√))

LC, SEC, ICLC, SEC, IC ( (++))

Terrahertz Terrahertz ((??))

Corning Microreactor + NeSSICorning Microreactor + NeSSI

Interfacing NeSSI™ to ASI Interfacing NeSSI™ to ASI micromicroFast GCFast GC™™

Complete gas/vapor sensing test platform on the bench top Gas delivery, vapor generation, and blending in NeSSI™ Real time verification of composition using GC and EP-IR

Easily extended to include other analytical and sample treatments

Vapochromic sensor optical cell

GC sipper port

EP-IR gas cell

NeSSI Ballprobe - Raman/NIR/UVNeSSI Ballprobe - Raman/NIR/UV

Agilent NeSSI Dielectric SensorAgilent NeSSI Dielectric Sensor

Cable to Agilent

Network Analyzer

Swagelok 2-Port

Valve Base

Dielectric Probe

Inner Body

O-ring (insid

e)

Outer Body

Exploded View

Close up of

Coaxial Probe

Tip

Liquid Chromatography for NeSSI™Liquid Chromatography for NeSSI™

micromixer

diluent in

column

mobile phase in

sample in

Scott Gilbert, CPAC Visiting ScholarScott Gilbert, CPAC Visiting ScholarCrystal Vision Microsystems LLCCrystal Vision Microsystems LLCAtofluidic Technologies, LLCAtofluidic Technologies, LLC

Split flow approach to samplingSplit flow approach to sampling

-fluidic LC Chip for On-line -fluidic LC Chip for On-line Sample PretreatmentSample Pretreatment

Pulsed electrochemical Pulsed electrochemical

detection (on-chip)detection (on-chip)

Liters per minute

microliters per minute

nanoliters per minute

NeSSI Gas Generation SystemNeSSI Gas Generation System

Features of Circor NeSSI System :1.4 State dilution, able to produce and maintain gas concentrations in ppb range2.Fully automated system, set and forget capability

Automated Circor NeSSI Gas/Vapor System

N2

O2

Mixed Gases

Mass FlowControllers

Vapochromic NeSSI Sensor DesignVapochromic NeSSI Sensor Design

simple designsimple designreversible responsereversible responselow powerlow powerinexpensiveinexpensiveNeSSI compatibleNeSSI compatiblefast response timesfast response timeshigh quantum efficiencyhigh quantum efficiencylong term sensor stabilitylong term sensor stabilitysensitive to a variety of analytessensitive to a variety of analyteslarge number of available large number of available vapochromic compounds (selectivity)vapochromic compounds (selectivity)

Vapochromic NeSSI Sensor DesignVapochromic NeSSI Sensor Design

Fiber optic cable to Ocean Optics

Spectrometer

Swagelok 2-Port

Valve Base

Fiber-optic

Probe(405 nm LED)

Inner Body

O-ring (insid

e)

Outer Body

Exploded View

Close up of Outer Body Tip

VapochromicTip

Development of a Micro-NMR System

NMR spectrum of a 3 micro liter NMR spectrum of a 3 micro liter water sample using a RF micro-coilwater sample using a RF micro-coilM. McCarthy, UC Davis

Other potential Other potential commercial analyzers for commercial analyzers for

NeSSI/microreactor NeSSI/microreactor project project

C2V fast micro-GCC2V fast micro-GC

http://www.c2v.nl/

At-Line GC’s with NeSSI Compat.At-Line GC’s with NeSSI Compat.ABB Natural GC

Siemens microSAM

Agilent 3000 M

icro GC

Applied Analytics Inc. Diode Array Applied Analytics Inc. Diode Array

OMA-300 OMA-300 A  Fiber-optics-diode-A  Fiber-optics-diode-array process analyzerarray process analyzerFor on-line concentration For on-line concentration monitoringmonitoring

Applied Analytics Microspec IRApplied Analytics Microspec IR

FEATURESFEATURES

Ideal for monitoring Ideal for monitoring PPM PPM level level WATER WATER in various solventsin various solvents

In stream quantitative measurementsIn stream quantitative measurements

Contains no moving parts andContains no moving parts and

Extremely robust allowing for Extremely robust allowing for installations in process stream installations in process stream environmentsenvironments

Replaces analyzers such as process Replaces analyzers such as process spectrometers in the process plant.spectrometers in the process plant.

NeSSI™ IR Gas CellNeSSI™ IR Gas Cell

NeSSI Compatible Spectroscopic Cell NeSSI Compatible Spectroscopic Cell Axiom Analytical, Inc.Axiom Analytical, Inc.

Currently AvailableCurrently Available

FFV Series Transmission Cells (Near-IR, UV-Visible) FNL-120 UV-Visible ATR Cell

In DevelopmentIn Development Raman Cells (Single- and Multi-pass)

Possible DevelopmentPossible Development Diffuse Reflectance Cells (For turbid liquids) Mid-IR ATR Cells

Courtesy of Mike DoyleAxiom Analytical, Inc.

NeSSI Project DeliverablesNeSSI Project DeliverablesIntegrate NeSSI, microreactors and Integrate NeSSI, microreactors and analyticsanalytics

Develop and publish the NeSSI Gen III specificationDevelop and publish the NeSSI Gen III specification

Continue development of interfaces for Continue development of interfaces for analytical instrumentationanalytical instrumentation liquid sample vaporizer using nanoliter volume inkjet-type liquid sample vaporizer using nanoliter volume inkjet-type

injectors and heated carrier streaminjectors and heated carrier streamDirect liquid injection to GCDirect liquid injection to GC

Direct liquid injection to Mass specDirect liquid injection to Mass spec Likely will need to generalize Scott Gilbert’s dilution Likely will need to generalize Scott Gilbert’s dilution

stream devicestream deviceOn-board dilutant (solvent) storage reservoirsOn-board dilutant (solvent) storage reservoirs

Pneumatic pumping (piston/syringe pump) Pneumatic pumping (piston/syringe pump)

Analytical-on-NeSSI Gen III Spec.Analytical-on-NeSSI Gen III Spec.Work with Sponsors, Vendors, End-usersWork with Sponsors, Vendors, End-users Draft at Fall 2008 CPAC MeetingDraft at Fall 2008 CPAC Meeting Final at SpringFinal at Spring 2009 CPAC Meeting 2009 CPAC Meeting

Goal is to provide analytical developers Goal is to provide analytical developers with a clear idea of what they must design with a clear idea of what they must design to and what they can expect from NeSSIto and what they can expect from NeSSI Compendium of parametersCompendium of parameters Example reference systemsExample reference systems

Generally useful to extend application base of Generally useful to extend application base of NeSSINeSSI

Typical info for the Gen lll SpecTypical info for the Gen lll Spec

Application operational setting rangesApplication operational setting ranges

Available sample conditioning optionsAvailable sample conditioning options

Power budget limits and example Power budget limits and example calculationcalculation

Communication protocols, messages, and Communication protocols, messages, and ratesrates Much of this work will be performed with the Much of this work will be performed with the

help of Bruce Finlayson's senior project help of Bruce Finlayson's senior project students and from our work at CPACstudents and from our work at CPAC

AcknowledgmentsAcknowledgmentsCenter for Process Analytical ChemistryCenter for Process Analytical Chemistry

CPAC Post-doc – Tom DearingCPAC Post-doc – Tom Dearing

Students – Charles Branham and Wes Thompson, UWStudents – Charles Branham and Wes Thompson, UW

Vendors who provided slidesVendors who provided slides

Professor Kent Mann, Univ. of MinnesotaProfessor Kent Mann, Univ. of Minnesota

Scott Gilbert – UW Visiting scholarScott Gilbert – UW Visiting scholar

Swagelok, Parker and Circor Swagelok, Parker and Circor

ABB, Agilent, Aspectrics, Honeywell, ExxonMobilABB, Agilent, Aspectrics, Honeywell, ExxonMobil