Process NMR - Latest Technology Developments, Reaction Monitoring, Process Control Applications and At-Line Analysis
1. 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
2. Process NMR Associates
250+ Analytical NMR Customers
TTC Labs, Inc.
Process Engineering Excellence
TopNIR Systems
3. Process NMR Associates
High Resolution FT-NMR – Online / in Process
First Generation NMR – 1998
Elbit-ATI/Foxboro NMR
Second Generation NMR – 2003
Qualion
4. Third Generation NMR – Aspect Italia NMR System
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
Lab version
On-Line version
5. Process NMR Associates
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
7. Process NMR Associates
NMR Lock - External 7Li Lock @ 22.5 MHz
Matrix Shimming Performed
by Optimizing FID RMS
Shim DACs Built into the Magnet Enclosure
9. Process NMR Associates
PEG
D
F
E
CH3
C
G
A
300 MHz
H
B
H3C
OH
CH 3
O
P OH
EG
FT-13C
FT-1H
D
A
F
E
C
G
B
H
D
C
I
F
E
CH3
6
5
4
3
H
B
CH3
1
OH
O
58 MHz
A
D
2
G
A
H3 C
7
PE
G
J
E
PEG
H
J
CDCl3
I
B
F
G
PE OH
G
C
A
D
F
C
E
G
H
1 60
1 40
120
10 0
80
60
40
ppm
B
pp m
22. 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)
23. 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%)
RON Validation - April 2001 - April 2002
108
107
106
105
NMR
CFR
104
103
102
101
100
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39
24. Process NMR Associates
Application: Steam Cracking Optimization Installed 2000
Cracker 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 normal-paraffin, iso-paraffin, aromatics, naphthenes
34. 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 Analyzer
2002 -
FCC Unit Analyzer
35. Process NMR Associates
3.0
2.5
2.0
1.5
F
A
C
T
O
R
3
VI 103
1.0
VI 100VI 103
IL
0.5
VI 115
AL
0.0
-0.5
-1.0
Dewaxing
Dearomatization
-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
FACTOR1
Base Oil Manufacturing – NMR Control
20
40
60
80
100
120
140
36. Process NMR Associates
7.00
6.00
5.00
4.00
Acid CH3 Intensity
3.00
Anhydride CH3 Intensity
2.00
1.00
0.00
0:00:00
0:14:24
0:28:48
0:43:12
Process NMR - Latest Technology Developments, Reaction
Monitoring, Process Control Applications and At-Line
Analysis