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Process NMR Associates
Introduction to High Resolution NMR in Process Control
Presented By
John Edwards, Ph.D.
Process NMR Associates, LLC
Danbury, Connecticut
November 14, 2007
Eastern Analytical Symposium, Somerset, New Jersey
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Process NMR Associates
Presentation Overview
NMR Basics Briefly
Process NMR / Benchtop NMR Technology
Advantages/Disadvantages as a Process Spectroscopy for Real-Time Anlaysis
Timeline of NMR Application Development
Process NMR Applications
Conclusions
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Superconducting NMR Systems
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High Resolution FT-NMR Online / in Process
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Relaxation
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Permanent Magnet Technology
Halbach Magnet Designs
Multiple Matched Magnet Segments.Physically Brought Together to Form
Condensed Magnetic Field of 1.35 Tesla
N S
Mechanical Shims ObtainRough Bo Homogeneity
N S
Electrical ShimGradients
N S
Current Passed
Through WireGradients Creates
Shaped MagneticFields That areUsed to Straighten
Field Lines
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Process NMR Associates
Why Shim? NMR Imaging (MRI)
N SH2O
H2OH2O
Good ShimHomogeneous Field
FT
H2O Should Give One
Resonance if Shim is Good
NMR Spectroscopy
N S
H2O
H2OH2O
Bad ShimInhomogeneous Field
FT
Bad Shim or 3 DifferentH-Types?
Eg. H2O in NMR Tube Eg. H2O in Human Body
H2O
H2OH2O
N S
Head
Field Lines
With DifferentBo
FT Computer ObtainsSpatial Location of
H2O in Head
Computer Generates
Image Based onWater Location
In MRI Large Shimsare Utilized toDistort the MagneticField in a Known
Manner in Order toMake the H2O PeakPosition SpatiallyDependent
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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
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pp m1234567
CH3
CH3
CH3
O
OH
A
B
C
D E F
G
H
A
F
B
CG
H
D E
PEG OH
PEG
ppm40608010012 01 401 60
CH3
CH3
CH3
O
OH
A
B
C
D E F
G
H
I J
HI
J
DE
F
A
B
G
C
PEG
CDCl3
FT-13C FT-1H
300 MHz
A
F
B
C
GH
D E
PEG O H
PEG
58 MHz
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Process NMR Associates
60 MHz NMR of Alcoholic Beverages
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Whiskeys, Vodkas, Gin, Rum
Schnapps
Non Alcoholic Beer
BeersWine
Port
Zoomed CH3 Spectral Region
Showing Increasing Alcohol Content
Process NMR Associates
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10 9 8 7 6 5 4 3 2 1
1H NMR of Essential Oils
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6 5 4 3 2 1
NMR Spectral Differences Between Various Edible Oils
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6 5 4 3 2 1 0
Process NMR Associates
Jumping on the Biodiesel Bandwagon
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10 9 8 7 6 5 4 3 2 1 0
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Olefin
Ester-Me
Diesel Aromatics
10 9 8 7 6 5 4 3 2 1 010 9 8 7 6 5 4 3 2 1 0
Biodiesel Diesel Blends B0, B5, B15, B20, B100
Process NMR Associates
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H-Types Observed in a Gasoline 1H NMR Spectrum
8 7 6 5 4 3 2 1 0
CH
R
R
H
H
R
H
R
H
R
H
H
R
CH2CH3
CH3
CH3
PPM
Oxygenate
H-Types Observed in a Gasoline 1H NMR Spectrum
8 7 6 5 4 3 2 1 0
CH
R
R
H
H
R
H
R
H
R
H
H
R
CH2CH3
CH3
CH3
PPM
Oxygenate8 7 6 5 4 3 2 1 0
CH
R
R
H
H
R
R
H
H
R
H
R
H
R
H
H
R
R
H
R
H
R
H
H
R
R
H
H
R
CH2CH3
CH3CH3
CH3
PPM
Oxygenate
ppm12345678
300 MHz 1H NMR of Gasoline
CH3
CH2
CH
CH3
-CH2AromaticsEthanol
Alkenes
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H2O
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NMR Innovations Developed to Bring NMR On-Line
Permanent Magnet Stability and Design
Shimming Protocols
Flow-Through Probe Technology
Post Processing Developments
Robust auto-phasing routines
Frequency Domain Averaging
Post-processing monitoring of each constituent spectrum
for heavy stream analyses where sediment/rust may be present.
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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 StreamIndividual 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)
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Process NMR Associates
Online NMR Applications Timeline
1993 - Development of Laboratory Based process NMR Methodologies
1995 - BTU Analysis of Refinery Fuel Gas
1995 - Sulfuric Acid Strength in Emulsion Zone of Stratco Acid Alkylation Unit
1999 - Diesel Blending System
1999 - Reformer Control System
2000 - Naphtha Cracker Feed Analyzer Full GC PIONA
2000 - Crude Unit Analyzer
2000 - Crude Blending System
2001 - Gasoline Blending System,
2001 - Base Oil Manufacturing Anaylzer
2002 - FCC Unit Analyzer
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Application: Steam Cracking Optimization Installed 2000Cracker Facility Capacity: 600,000 Tonnes per Year
Control Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYRO Optimization
NMR Analysis: 3-4 Minute Cycle (Single Stream)
NMR PLS Outputs: Naphtha Detailed PIONA
C4-C10 n-paraffin, i-paraffin, aromatics, naphthenes
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Application: Crude Distillation Unit Optimization and Control Installed 2001Crude Unit Capacity: 180,000 Barrels per Day
Control Strategy: Control on Kero Freeze Point and Crude Tower Optimization
NMR Analysis: 15 Minute Cycle - NMR Results into ROMEO CDU Optimization
NMR PLS Outputs: Naphtha T10, T50, T90, EP - D86 Distillation
Kero Freeze, Flash
Crude API, Sulfur, TBP (38, 105, 165, 365, 565C)
Process NMR Associates
Kero Freeze Lab Vs NMR
-65
-60
-55
-50
-45
-40
2002
/05/01
2002
/05/03
2002
/05/05
2002
/05/07
2002
/05/09
2002
/05/
11
2002
/05/
13
2002
/05/
15
2002
/05/
17
2002
/05/
19
Lab Freeze (DegC)NMR Freeze (DegC)
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Crude Adjustment
0
10
20
30
40
50
60
70
80
90
10 0
-150 50 250 450 650 850 1050
CutPoint Deg C
W
T%Yield
Before
After
NMR
CrudeCrude
ReconciliationReconciliation
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Units Problem Faced by NMR Spectroscopy for Process Control
NMR Spectrum Reveals: Orthogonal Distinction of Proton Chemical Types
Quantified in Units that are: Atomic% Hydrogen
Reaction Monitoring Chemical Shift Resolved Peaks or Peak Ratios Can be Monitored
What the Engineer Wants: Historically Derived Analysis Units for Chemical Properties..GC or MS - Wt % or Vol % - (Which are Molecularly Incorrect Numbers)
Chemometrics is Required to Produce Values for Chemical Properties in the Units Desired
by the Control Community. Long term many chemical property control variables could be
controlled directly from the NMR spectral variance in the appropriate chemical shift area.
Long Term Direction is to Control Directly from the NMR Spectrum
Base Oil Manufacturing Process An Example of Using NMR and PCA Based Control
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Process NMR Associates
1.00
3.03
SF: 75.43 MHz SW: 50000.00 Hz AQ: 0.48 seconds TD: 65536 points Scale units: ppm
Aromatics Paraffins
13C NMR Spectrum
Area under aromatic
peaks corresponds to
carbon aromaticity
Correlate to 60 MHz
Process 1H NMR Using PLS Regression
0
0 15 30 45
0
15
0 15 30 45
1
2345 6
7
8
9
10
1112
13
141516
17
18
19
2021
22
232425
26
27
2829303132
3334
3536373839
40
41
42
43
44
45464748
4950
51
52
5354
55
56
5758
59
60
6162
63
64
65
66
676869
70
71
72
73
7475
76
0
30
45
0 15 30 45
Actual Aromaticity (13C)
PredictedAromaticity(1H)
0
2
4
6
8
10
12
0 20 40 60 80 100 120 140 160 180
PLS
Model
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PCA Analysis Performed on Base Oil Samples
VI 103
FACTOR1
FACT
OR3
IL
VI 115
VI 103
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.01.5
2.0
2.5
3.0
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
Dewaxing
Dearomatization
VI 100
AL
Process NMR Associates
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Acknowledgements
Paul Giammatteo PNA
Invensys MRA
Qualion NMR Israel
Texaco Inc
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