introduction to high resolution nmr in process control eas-2007 intro 11-14-0… · process nmr...

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


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


Superconducting NMR Systems


High Resolution FT-NMR – Online / in Process


Relaxation


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


NMR Lock - External 7Li Lock @ 22.5 MHz Shim DACs Built into the Magnet Enclosure

Matrix Shimming Performed by Optimizing FID RMS


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


60 MHz NMR of Alcoholic Beverages

Whiskeys, Vodkas, Gin, Rum

Schnapps

Non Alcoholic Beer

BeersWine

Port

Zoomed CH3 Spectral Region Showing Increasing Alcohol Content



10 9 8 7 6 5 4 3 2 1

1H NMR of Essential Oils


6 5 4 3 2 1

NMR Spectral Differences Between Various Edible Oils

6 5 4 3 2 1 0


Jumping on the Biodiesel Bandwagon


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



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


H2O


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.


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)


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


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


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)


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)


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


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


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


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



Acknowledgements

Paul Giammatteo – PNA

Invensys MRA

Qualion NMR – Israel

Texaco Inc

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