Edwards EAS-2007 Intro 11-14-07

8/14/2019 Edwards EAS-2007 Intro 11-14-07

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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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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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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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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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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



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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


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



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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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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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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)


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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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



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Acknowledgements

Paul Giammatteo PNA

Invensys MRA

Qualion NMR Israel

Texaco Inc

Edwards EAS-2007 Intro 11-14-07

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