Vision of Micro-Analytics on NeSSI

Transcription

1 Vision of Micro-Analytics on NeSSI Brian Marquardt Ph.D. Charles Branham, Wes Thompson, Thomas Dearing Applied Physics Laboratory / CPAC University of Washington Seattle, WA 98105

2 Process Spectroscopy Applications Pharmaceuticals Food quality and safety Polymers/coatings Fermentation/biotech Cellular/tissue Oil/fuels/petrochemicals Oceanography/environment Challenges Reproducible sampling Background interference

3 Process Challenges Analytical characterization Sampling and screening Data handling Sensor fusing Multi-sensor modeling Process modeling and feed back control Process optimization move toward feed forward control????

4 Spectroscopic Analysis of a Process Possible problems with performing online spectroscopic measurements Bubble formation Solid Formation Phase separation Anything else that you could possibly imagine Most PAT problems are due to sampling not measurement device Need better systems to sample processes!!

5 NeSSI Modular Sampling Systems New Sampling/Sensor Initiative Surface-mount modular component based gas and fluid handling and conditioning systems ISA SP76 interface specification Elastomeric o-ring seals Offer flexibility in design and implementation Allows for optimal positioning of analyzers in a process stream

6 Where Does NeSSI Fit in the Lab Instrument/Sensor Interfaces Design standards make development simpler Reduced toolset to be mastered Reduced sample variability to account for Calibration/validation built-in Consistent physical environment for measurement Stream switching and/or mixing allow generation of standards to match analytical requirements Reaction monitoring Microreactors and continuous flow reactors Batch reactors (with fast loop) Sample Preparation Gas handling (mixing, generation, delivery) Liquid handling (mixing, dilution, conditioning, etc.)

7 NeSSI with an Array of Micro-Analytical Techniques will Impact Many Industries Process Control Process Optimization Product Development

8 At-Line GC s with NeSSI Compatibility ABB Natural GC Agilent 3000 Micro GC Siemens microsam

9 Calidus fast GC from Falcon Analytical

10 Thermo/C2V Fast Micro-GC as well as

11 Applied Analytics Inc. Diode Array OMA-300 A Fiber-optics-diodearray process analyzer For on-line concentration monitoring

12 NeSSI Ballprobe - Raman/NIR/UV Ballprobe Specs. Hastalloy c-276 Ti, SS, Monel Sapphire optic Std. temp range: C Pressure: Barr Matrix Solutions:

13 NeSSI Raman Sampling Block Parker Intraflow NeSSI substrate Sample conditioning to induce backpressure to reduce bubble formation and the heated substrate allows analysis at reactor conditions

14 Kaiser Airhead Raman Gas Probe AirHead TM Probe with compression mount NeSSI interface AirHead TM Probe with NPT- Threaded mount NeSSI interface

15 NeSSI IR Gas Cell

16 microptix NeSSI UV-Vis/NIR Sensor

17 H 2 Scan Adaptation to NeSSI TM Platform Hydrogen specific: 0.5% H2 to 100% H2 v/v Response time (T90) < 30 sec In-line, real-time measurements in process gas streams up to 100 O C Unique models for CO, H 2 S, wet CL mA, RS422 or RS232 serial connectivity Stable results On-site verification and calibration Approved for hazardous locations Intrinsically safe design ATEX certificate granted; UL pending Cost effective to buy / install / maintain Field verification and calibration kit available

18 Astute Sampling System Sampling + Sensors & micro-analyzers GAS TREATMENT COLUMN Astute System with C 2 V Micro GC and H 2 Scan hydrogen analyzer Process

19 Agilent NeSSI Dielectric Sensor Cable to Agilent Network Analyzer Dielectric Probe Inner Body Close up of Coaxial Probe Tip O-ring (inside) Swagelok 2-Port Valve Base Outer Body

20 Mechatest Sampling Solutions NeSSI Liquid Sampler Compliant with ANSI/ISA mm (1.5 in.) footprint. Three Port configuration: Sample Inlet, Bypass and Vent. Quick and safe operation, low dead volume design with bypass. Manual or Automatic sampling In-line Sampling Closed Loop and Emission Free Sampling Easy in operation

21 NeSSI based research and developments at CPAC

22 Vapochromic Oxygen Sensor

23 Calibrated Analog Gas Mixer - 3 stream calibrated mixing with fiber optic oxygen/temperature/humidity sensing

24 Digital Gas Calibration System

25 Digital Calib. Gas Generation System Features of NeSSI System : Fully digital 4 Stage dilution, able to produce and maintain gas concentrations in ppb range Fully automated system, set and forget capability Integrated C2V NeSSI compat. GC Calib, platform for gas sensor dev.

26 Gas Calib. System LabView Control Program Perform automated DoE calibration runs input and log sensor, reference, temperature and pressure feeds System designed for full digital (plug and play) performance as h/w matures

27 Sensor response to O 2 Gas Predicted O 2 % replicates at each concentration Concentration range: 0-100% Oxygen R 2 = 0.990, 3 PC RMSEC = Intensity (counts) 0% 100 % Calculated O 2 % 60 Wavelength (nm)

28 Response Time of Oxygen Gas Sensor 1 Nitrogen Relative Intensity % 98msec 95% 10msec 3 Replicates Averaged Air Compound/ Polymer VCS/Teflon PtTFPP/PS Mean Response Time of Exchanges between O 2, N 2, Air (T 95% ) 16 ms 39 sec % 32msec 95% 7msec 3 replicates Averaged Oxygen PtTFPP/PTFEM 19 sec Time(msec) Yeh, T.S., et al., Sensor and Actuators B, 2006, 119, 701.

29 Sensor Response for O 2 in Solution Predicted Oxygen Concentration(micromol/liter) R 2 = Latent Variables RMSEC = Bias = e replicates at each concentration Concentration range: 1 μmol/l - 55 μmol/l Measured Oxygen Concentration(micromol/liter) 1 μmol/l = 32.5 ppb Realative Intensity μmol/l 55 μmol/l Wavelength(nm)

30 Response Time of Dissolved O 2 Sensor 1 Nitrogen Relative Intensity % 8sec 95% 5sec 3 Replicates Averaged Air 100% 6sec 95% 2sec 3 replicates Averaged Oxygen Compound/ polymer VCS/Teflon Most other Oxygen Sensors Mean Response Time of Exchanges between O 2, N 2, Air (T 95% ) 3.7 s 30 s Time(sec) Loloee. R., et al., IEEE Sensors, 2007, 1404.

31 Modular NeSSI Oxygen Gas Sensor 1/16 in bifurcated fiber optic fiber 1/16 to 1/8 in Swagelok union Sensor Body Fiber optic ferrule with plastic housing Close up of Outer Body Tip Vapochromic Tip Exploded View Agilent NeSSI Mount

32 Raman Filtration/Sampling Sys

33 Fast Loop Fermenter. Sampler

34 Hydrolysate Ferm. 8 hours Polyfit ROI Fluorescence

35 3-D Plot of Polyfit Raman Data Ethanol Intensity (Arb. Units) 800 Glucose 900 Raman Shift (cm -1 ) Sample

36 Fermenter Sampler Increased analytical capability Filter biomass Representative sample Cleaning? Dead space? Sterilize?

37 Permeation Apparatus - CPAC inspired and Parker built prototype permeation apparatus - Currently, used to generate calibrated organic vapor samples for sensor testing - Vapor calibration NeSSI system with Kaiser Airhead gas probe for analysis

38 IR of Ethanol Vapor Flow Data Signal Intensity /Au Wavelength /Microns

39 Ethanol Calib. against flow rate R 2 = Latent Variables RMSEC = Bias = e-015 Samples/Scores Plot Y Predicted Y Measured 1

40 IR Ethanol Vapor Spectra vs T 16 x C 20C 25C 30C 35C 40C 10 Signal Intensity /Au Wavelength /Microns

41 Ethanol Calib. Temp change R 2 = Latent Variables RMSEC = Bias = 0 Samples/Scores Plot of Multiple SPC files 35 Y Predicted Y Measured 1

42 Controlled Chemical Synthesis - NeSSI flow management system (P, T, flow sensors, backpressure, filter) - NeSSI analytic sampling system (mulit probe Raman, IR, NIR, RI, Density, )

43 Synthesis Sampling and Control - Early stage development of NeSSI centric reactor control and analysis system for new chemical reaction development, optimization and controlled production

44 NeSSI Sampling System for Reactor Raman Probe monitor clean bypass Property of Brian Marquardt, Univ. of Washington

45 3D Plot of Raman Reaction Data GC Results (%) Test R-OH 2EHCF R-Cl Carbonate Dimer Ch. 1 Toluene Chloroformate Toluene Property of Brian Marquardt, Univ. of Washington

46 Acknowledgments Center for Process Analytical Chemistry Vendors who provided slides Parker U.S. Food and Drug Administration Corning Glass Kaiser Optical Systems La Maison Européenne des Procédés Innovants (MEPI )