Process NMR Associates Process NMR - Latest Technology Developments, Reaction Monitoring, Process Control Applications and At-Line Analysis Presented By John Edwards, Ph.D. Process NMR Associates, LLC Danbury, Connecticut May 7, 2012 CPAC Spring Meeting, Seattle, WA
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Process NMR Associates
Process NMR - Latest Technology Developments,
Reaction Monitoring, Process Control Applications
and At-Line Analysis
Presented By
John Edwards, Ph.D.
Process NMR Associates, LLC
Danbury, Connecticut
May 7, 2012
CPAC Spring Meeting, Seattle, WA
TTC Labs, Inc.
Process Engineering Excellence
Process NMR Associates
TopNIR Systems
250+ Analytical NMR Customers
Process NMR Associates
High Resolution FT-NMR – Online / in Process
First Generation NMR – 1998 Elbit-ATI/Foxboro NMR Second Generation NMR – 2003
Qualion
Lab version
On-Line version
New magnet design – 30mm bore size
• The amount of magnetic pieces that assemble the magnet reduced from 34 to 10. Reduction in
Mechanical Complexity
• Bore size of the magnet was increased to 30 mm - improve temperature susceptibility
• Improved temperature and shim stability.
New Digital Spectrometer Design - reduces footprint, improves signal processing capabilities
Probe - Improved Probe Q for Higher Sensitivity.
Software – Windows 7 – Improved Chemometric Capabilities
Third Generation NMR – Aspect Italia NMR System
New magnet design solves the problem of:
Long term and short term Stability
Temperature sensitivity
State of the Art electronics:
Smaller foot-print
40 Shim coils on 2 single PCB
Integrated PCB for Shim & Heater Control
Digital RF & Acquisition –
improve SNR
New concept of Process Probe:
Entire sample pipe through
without contact with the system
Much better temperature
insulation
Higher Q (better sensitivity)
New Software:
Includes new algorithm for
standard and global Models
Fully automated process capacity
Extensive remote diagnostic capabilities
New Magnet System
Process NMR Associates
NMR Sample System and Placement
Process NMR Associates
Process NMR Associates
NMR Lock - External 7Li Lock @ 22.5 MHz Shim DACs Built into the Magnet Enclosure
Matrix Shimming Performed
by Optimizing FID RMS
Process NMR Associates
Process NMR Associates
p p m1234567
CH3
CH3
CH3
O
OH
A
B
C
D E F
G
H
A
F
B
CG
H
D E
PEG OH
PEG
p p m4 06 08 01 0 01 2 01 4 01 6 0
CH3
CH3
CH3
O
OH
A
B
C
D E F
G
H
I J
H
IJ
DE
F
A
B
G
C
PEG
CDCl3
FT-13C FT-1H
300 MHz
A
F
B
C
G
H
D E
PEG OH
PEG
58 MHz
Process NMR Associates
ppm 1 2 3 4 5 6 7 8
300 MHz
CH3
CH2
CH
a-CH3
a-CH2
Aromatics Ethanol
Alkenes
60 MHz
Gasoline 1H NMR
Process NMR Associates
Gasoline Parameters:
Octane Numbers
Distillation Properties (T10, T50, T90)
Benzene Content (wt%)
Total Aromatics (Wt%)
Total Olefins (Wt%)
Total Saturates (Wt%)
Oxygenates (Wt%)
Reid Vapor Pressure
Process NMR Associates
Diesel Fuels
Biodiesels
Ethyl-benzene
Diethyl-benzene
Vinegar an Alcohol Fermentation
Process NMR Associates
Advantages and Disadvantages of NMR Applied to Process Control
Advantages:
Non-Optical Spectroscopy
No Spectral Temperature Dependence
Minimal Sampling Requirements
Spectral Response to Sample Chemistry is Linear
Chemical Regions of NMR Spectra are Orthogonal
Entire Volume is Sampled by the RF Experiment
Water is in Distinct Region and can be digitally removed
Detailed Hydrocarbon information is readily observed.
Fundamental Chemical Information Can be Derived Directly from Spectrum.
Colored/Black Samples Readily Observed Without Impact
Disadvantages:
Solids Cannot be Observed in a Liquid Stream
Individual Molecular Component Sensitivity Not Observed Directly in the Spectrum.
Low Sensitivity to Impurities – Quantitative > 500 ppm.
Sensitive to Ferromagnetics.
Sample Viscosity Causes Decrease in Resolution
Non-Hydrogen Containing Species are Not Observed (Exceptions Na, P, F, Al)
Process NMR Associates
Application: Closed Loop Reformer Control - Installed 1998 Reformer Capacity: 34,000 Barrels per Day
Control Strategy: Control on MON and Benzene Content
NMR Analysis: 2 Minute Analysis
NMR PLS Outputs: RON, MON, Benzene (Wt%) Total Aromatics (Wt%)