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Process NMR Associates
Introduction to High Resolution NMR in Process Control
Presented By
John Edwards, Ph.D.
Process NMR Associates, LLCDanbury, Connecticut
November 14, 2007Eastern Analytical Symposium, Somerset, New Jersey
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
Process NMR Associates
High Resolution FT-NMR – Online / in Process
Process NMR Associates
Process NMR Associates
Relaxation
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Permanent Magnet TechnologyHalbach 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 PassedThrough WireGradients CreatesShaped MagneticFields That areUsed to “Straighten”Field Lines
Process NMR AssociatesWhy Shim? NMR Imaging (MRI)
N SH2O
H2OH2O
Good Shim Homogeneous Field
FT
H2O Should Give OneResonance if Shim is Good
NMR Spectroscopy
N SH2O
H2OH2O
Bad Shim Inhomogeneous Field
FT
Bad Shim or 3 Different H-Types?
Eg. H2O in NMR Tube Eg. H2O in Human Body
H2OH2OH2O
N S
HeadField Lines
With DifferentBo
FTComputer ObtainsSpatial Location of H2O in Head
Computer GeneratesImage Based onWater Location
In MRI Large Shimsare Utilized toDistort the MagneticField in a Known Manner in Order to Make the H2O Peak Position Spatially Dependent
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
pp m1234567
CH3
CH3
CH3
O
OHA
B
C
D E F
G
H
A
F
B
CG
H
D E
PEG OH
PEG
ppm4060801001201 401 60
CH3
CH3
CH3
O
OHA
B
C
D E F
G
H
I J
HI
J
D E
F
A
B
G
C
PEG
CDCl3
FT-13C FT-1H
300 MHz
A
F
B
C
GH
D E
PEG OH
PEG
58 MHz
Process NMR Associates
60 MHz NMR of Alcoholic Beverages
Whiskeys, Vodkas, Gin, Rum
Schnapps
Non Alcoholic Beer
BeersWine
Port
Zoomed CH3 Spectral Region Showing Increasing Alcohol Content
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Process NMR Associates
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
6 5 4 3 2 1 0
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Jumping on the Biodiesel Bandwagon
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10 9 8 7 6 5 4 3 2 1 0
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
Process NMR Associates
H-Types Observed in a Gasoline 1H NMR Spectrum
8 7 6 5 4 3 2 1 0
CH
RR
HH
R
H
R
H
R
H
HR
CH2CH3
CH3
CH3
PPMOxygenate
H-Types Observed in a Gasoline 1H NMR Spectrum
8 7 6 5 4 3 2 1 0
CH
RR
HH
R
H
R
H
R
H
HR
CH2CH3
CH3
CH3
PPMOxygenate
8 7 6 5 4 3 2 1 0
CH
RR
HH
RR
HH
R
H
R
H
R
H
HR
R
H
R
H
R
H
HR
R
H
HR
CH2CH3
CH3CH3
CH3
PPMOxygenate
ppm12345678
300 MHz 1H NMR of Gasoline
CH3
CH2
CH
α−CH3
α-CH2AromaticsEthanol
Alkenes
Process NMR Associates
Process NMR Associates
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 spectrumfor heavy stream analyses where sediment/rust may be present.
Process NMR Associates
Advantages and Disadvantages of NMR Applied to Process ControlAdvantages:Non-Optical SpectroscopyNo Spectral Temperature DependenceMinimal Sampling RequirementsSpectral Response to Sample Chemistry is LinearChemical Regions of NMR Spectra are OrthogonalEntire Volume is Sampled by the RF ExperimentWater is in Distinct Region and can be digitally removedDetailed 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 ResolutionNon-Hydrogen Containing Species are Not Observed (Exceptions Na, P, F, Al)
Process NMR Associates
Online NMR Applications Timeline1993 - 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
Process NMR Associates
Application: Steam Cracking Optimization Installed 2000Cracker Facility Capacity: 600,000 Tonnes per YearControl Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYRO OptimizationNMR 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: Closed Loop Reformer Control Installed 1998Reformer Capacity: 34,000 Barrels per DayControl Strategy: Control on MON and Benzene ContentNMR Analysis: 2 Minute AnalysisNMR PLS Outputs: RON, MON, Benzene (Wt%) Total Aromatics (Wt%)
RON Validation - April 2001 - April 2002
100
101
102
103
104
105
106
107
108
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39
NMRCFR
Application: Crude Distillation Unit Optimization and Control Installed 2001Crude Unit Capacity: 180,000 Barrels per DayControl 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, FlashCrude – API, Sulfur, TBP (38, 105, 165, 365, 565C)
Process NMR Associates
Kero Freeze Lab Vs NMR
-65
-60
-55
-50
-45
-4020
02/05
/0120
02/05
/0320
02/05
/0520
02/05
/0720
02/05
/0920
02/05
/1120
02/05
/1320
02/05
/1520
02/05
/1720
02/05
/19
Lab Freeze (DegC) NMR Freeze (DegC)
Process NMR Associates
Process NMR Associates
Crude Adjustment
0
10
20
30
40
50
60
70
80
90
100
-150 50 250 450 650 850 1050
CutPoint Deg C
WT%
Yie
ld
BeforeAfterNMR
Crude Crude ReconciliationReconciliation
Process NMR Associates
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
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
00 15 30 45
0
15
0 15 30 45
12
345 6
7
8
9
10
1112
13
141516
1718
19
2021
22
232425
26
27
2829303132
333435
36373839
40
41
42
43
44
45464748
4950
51
52
5354
55
56
5758
5960
6162
63
64
6566
676869
70
71
72
73
7475
76
0
30
45
0 15 30 45
Actual Aromaticity (13C)
Pred
icte
d A
rom
atic
ity (1 H
)
0
2
4
6
8
10
12
0 20 40 60 80 100 120 140 160 180
PLSModel
Process NMR Associates
Process NMR Associates
20 40 60 80 100 120 140
Dearomatization and De-Waxing
Base Oil Manufacturing Process
Key Parameters: Carbon Aromaticity, Paraffinicity, Naphthenicity
Typical Spectra
PCA Analysis Performed on Base Oil Samples
VI 103
FACTOR1
FACTOR3
ILVI 115
VI 103
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
DewaxingDearomatization
VI 100
AL
Process NMR Associates
Process NMR Associates
Acknowledgements
Paul Giammatteo – PNA
Invensys MRA
Qualion NMR – Israel
Texaco Inc
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