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Process NMR Associates
Pulse, Acquire, Control: Ten years of On-Line High Resolution NMR in Refining,
Petrochemical, and Food Manufacturing
Presented By
John Edwards, Ph.D.Process NMR Associates, LLC
Danbury, Connecticut
May 2, 2005ACS Meeting: Mid-Hudson Section
Vassar College, Poughkeepsie
Process NMR Associates
Company: Process NMR Associates, LLC
Founded : 1997
Personnel: 2 Ph.D. Chemists
Background: Analytical and Process Spectroscopy in Petroleum and Petrochemical Industry Process NMR Applications and Support Under Contract to Invensys (1997-2003)Process and Analytical NMR Instrumentation Development
Facilities: 2 Invensys 58 MHz Process MRA Units300 MHz NMR (Liquids)200 MHz NMR (Solids)
Business: Application Development for Process NMR TechnologyProcess NMR Instrumentation DevelopmentAnalytical NMR Services for Commercial and Academic CustomersProcess NMR Database DevelopmentLicensing of Copyrighted NMR Databases and Patented Applications
Process NMR Associates
Presentation Overview
• NMR Basics – Briefly
• Advantages/Disadvantages as a Process Spectroscopy
• Applications1. Reformer Unit Control2. Crude Distillation Unit Control and Optimization3. Naphtha Steam Cracking Control and Optimization
• Application Snippets
Aromaticity – FCC, Base Oil ManufactureStyrene-Butadiene RubbersAromaticsFood
• Conclusion
Process NMR Associates
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
TD-NMRLow Field, FID, Curve-Fitting
Process NMR Associates
TD-NMR PAT Applications+ Tablet hardness / density testing+ Contactless weighing of tablets+ Moisture in powders / tablets+ Moisture in lipophilized proteins+ Total oil / solvent content+ Droplet size distribution of emulsions+ Pore-size of encapsulated liquids
Process NMR Associates
Industrial MRI Applications
Process NMR Associates
TD-NMR - One Sided NMR MOUSE
Process NMR Associates
TD-NMRDownhole Drilling Tool
Process NMR Associates
High Resolution FT-NMRhttp://www.liposcience.com/
Process NMR Associates
High Resolution FT-NMR - MetabonomicsMetabolism Analysis by NMR – Toxicological Screening
Process NMR Associates
Process NMR Associates
Superconducting NMR Systems
Process NMR Associates
High Resolution FT-NMR – Online / in Process
Process NMR Associates
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 ProcessAdvantages: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 > 1000 ppm.Sensitive to Ferro-magnetics.Sample Viscosity Causes Resolution ChangesNon-Hydrogen Containing Species are Not Observed (Exceptions Na, P, F, Al)
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
Process NMR Associates
H2O
Process NMR Associates
Process NMR Associates
Lab and On-Line InstallationsLab Installations
Planned Installations
Equilon, LATosco
BRC
Aramco FPCC
PDVSA Reliance
MotivaFina
EquistarValero Pertamina
BP BASF
Petrochina
AGIP
On-Line Installation - Foods
Invensys Process NMR Installations
Shell
Tnuva
4/29/02
ORLERG
PNAInvensys
Process NMR Associates
Application: Closed Loop Reformer Control
Reformer Capacity: 34,000 Barrels per Day
Control Strategy: Control on MON and Benzene Content
NMR Analysis: 2 Minute Analysis
NMR PLS Outputs: RONMONBenzeneTotal Aromatics
Value Added: Initially - Maximize Benzene Content of Reformate at 1 Wt%Conservatively 4 cents per Barrel (Can Be Much More)
Performance : NMR Available 98%+ For Past 4 YearsModels Updated Once in Past 4 YearsValue Gained From Control $10,000 - $35,000 / Week
Process NMR Associates
Process NMR Associates
Process NMR Associates
Process NMR Associates
Process NMR Associates
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
SEP = 0.33 Octane
Process NMR Associates
Process NMR Associates
Process NMR Associates
Process NMR Associates
Application: Crude Distillation Unit Optimization and Control
Crude Unit Capacity: 180,000 Barrels per Day
Control Strategy: Control on Kero Freeze PointCrude Tower Optimization
NMR Analysis: 15 Minute CycleNMR Results into ROMEO CDU Optimization Package
NMR PLS Outputs: Naphtha – T10, T50, T90, EP Kero – Freeze, FlashCrude – API, Sulfur, TBP (38, 105, 165, 365, 565C)
Value Added: Kero - Approach Freeze Point Limit – Worth $600K/YearCDU Optimization- Conservatively 4 cents per Barrel
Performance : NMR Available 98% 2000-2004
Process NMR Associates
SSC &
MRA
Process NMR Associates
Crude Fast Loop Crude Fast Loop HeaterHeater
Process NMR Associates
MRA Sample System
Crude Brought into NMR at 70C (Crude Fast Loop Heater)
Kerosene and Naphtha Also Brought to NMR at 70C(Sample Heater With PID Control at NMR SSC
All Samples are routed to crude sample return and Pass Through CDU Again
Double Block-and-Bleed and Flushing Protocol to Prevent Cross Contamination of Light Ends With Crude.
Process NMR Associates
-60
-55
-50
-45
-40
-35
-30
2002
/05/
01
2002
/05/
0220
02/0
5/03
2002
/05/
04
2002
/05/
0520
02/0
5/06
2002
/05/
07
2002
/05/
0820
02/0
5/09
2002
/05/
10
2002
/05/
11
2002
/05/
1220
02/0
5/13
2002
/05/
14
2002
/05/
1520
02/0
5/16
2002
/05/
17
2002
/05/
1820
02/0
5/19
2002
/05/
20
Freeze NfreezeKero Lab v. NMR
Process NMR Associates
Crude Analysis
Process NMR Associates
Process NMR Associates
Process NMR Associates
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
Application: Steam Cracking Optimization
Cracker Facility Capacity: 600,000 Tonnes per Year
Control Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYROOptimization Package
NMR Analysis: 3-4 Minute Cycle (Single Stream)16 Minute Cycle (4 Feed Streams)
NMR PLS Outputs: Naphtha – Detailed PIONAC4-C10 n-paraffin, i-paraffin, aromatics, naphthenes
Value Added: Unit Optimization - $150K /year 4 Units Now Being Optimized ($600K/year)
Performance : NMR Available 98%+ Since August 2000Models Updated in a Limited Manner
Process NMR Associates
Steam Cracker Optimization - Project Timeline Feasibility Performed (30 Samples) – December 1999
Further Model Expansion (90 Samples) – December 1999-March 2000
Online System Installed – April 2000
On-Line Localization and Further Model Expansion (65 Sampes)– May to July 2000
Validation Period – 1 Month 100% Availability Within Specified Accuracy Limit - Aug 2000
System Validated and Accepted – September 2000
Add Validation Period Samples to Models – (Models now contain 215 Samples)
NMR Put on Control (Detailed PIONA into SPYRO Model for Unit Optimization) Oct 2000
Models have been performing relatively untouched (6 parameters updated on 4 occasions) since end of validation period.
98+% Availability September 2000 – September 2004
March 2002 – Three Further Feed-Streams Added to NMR
Process NMR Associates
Process NMR Associates
Process NMR Associates
Process NMR Associates
Process NMR Associates
Cyclopentane
5/17
5/24
5/31 6/7 6/14
6/21
6/28 7/5 7/12
7/19
7/26 8/2 8/9 8/16
8/23
8/30 9/6
Date
Wt% GC
NMR
Process NMR Associates
Process NMR Associates
Parameter R Std Dev Mean Devn-c4 0.9340 0.52 0.067n-c5 0.9761 0.73 -0.004n-c6 0.9616 0.73 -0.093n-c7 0.9840 0.33 -0.032n-c8 0.9882 0.29 -0.008n-c9 0.9918 0.18 -0.003n-c10 0.9716 0.13 0.022Total n-paraffin 0.9840 0.81 0.013I-c4 0.8765 0.07 0.001I-c5 0.9834 0.76 0.043i-C6 0.9865 0.59 -0.050i-C7 0.9119 0.46 -0.015i-C8 0.9800 0.42 -0.035i-C9 0.9905 0.26 0.010i-C10 0.9866 0.24 0.013i-C11 0.9613 0.08 -0.007Total I-paraffin 0.9617 0.81 -0.011cyclopentane 0.9821 0.14 -0.004me-cyclopentane 0.9937 0.23 -0.018Cyclohexane 0.9940 0.26 0.034Methylcyclohexane 0.9872 0.29 0.001Other C7-Nap 0.9025 0.32 -0.052c8-Nap 0.9713 0.36 0.002c9-Nap 0.9892 0.28 0.026c10-Nap 0.8950 0.06 -0.001Total Naphthenes 0.9794 0.83 0.019Benzene 0.9950 0.10 0.006Toluene 0.9920 0.17 0.007Ethylbenzene 0.9902 0.04 0.002Xylenes 0.9951 0.14 0.003C9 - Arom 0.9875 0.16 0.006C10-arom 0.9586 0.07 0.001Total Aromatics 0.9967 0.31 0.022
Single PLS Model for Each GC Component
Low Model Maintenance
SPYRO Optimization and APC Utilize Real Time Analysis
4 Crackers Now Covered by 1 NMR
Multiple GC Analyzers Replaced Reduced Maintenance
Reduced Laboratory Participation
Other Installations:Expanding Model Base to Cover Gas Oils andMixed Naphtha/Gas Oil Blend Operation
Process NMR Associates
0
5
10
15
20
25
20 40 60 80 100 120 140
Arbitrary Y / Arbitrary X Overlay Z-Zoom CURSOR
File #16 = RFYOG33 9/7/00 2:40 PM Res=None
Foxboro NMR SPC File.
Milk
Half and Half
Light Cream
Sour Cream
Reduced Fat Yogurt
Strawberry Yogurt
Block Cream Cheese
Tub Cream Cheese
Light Cream Cheese
Fat Free Cream Cheese
Margarine
Butter
Water and Fat Content models were built using all products listed. All products
were purchased from a local supermarket.
Water and fat contents (weight percent) were estimated using food label
information only.
Initial model results: R2 > 0.96
error <1 wt%
Process NMR – Dairy
Process NMR Associates
010 8 6 4 2 0 -2
Butter - before phase separation
Cis/trans olefins
CH and alpha
to olefins
Water
CH2
CH3
10 8 6 4 2 0 -2
Cis/trans olefins
CH and alpha
to olefins
CH2
CH3
Butter - after phase separation
Process NMR
Butter
Process NMR Associates
0
5
10
15
20 40 60 80 100 120 140
0
5
10
15
20 40 60 80 100 120 140
Water
Unsaturated fat regionCarbohydrates
and sugars
Saturated fat and protein
Overlay of 4 Cream Cheese Products
Regular BlockRegular TubLightFat-Free
Process NMR Associates
Process NMR – 23Na Monitoring of Sodium Content in Food
0
20000
40000
60000
80000
6600 6800 7000 7200 7400 7600 7800 8000 8200
0
20000
40000
60000
80000
6600 6800 7000 7200 7400 7600 7800 8000 8200
7750 7800 7850 7900 7950 8000 8050 8100 7750 7800 7850 7900 7950 8000 8050 8100
Whiskeys, Vodkas, Gin, Rum
Lower Alcohol Liquors
Non Alcoholic Beer
BeersWine
Port
Process NMR Associates
Process NMR – Alcoholic Beverages
0
20000
40000
60000
80000
100000
7000 7200 7400 7600 7800 8000
0
20000
40000
60000
80000
100000
7000 7200 7400 7600 7800 8000
Exchangable carbohydrate hydroxylsand H2O (Peak moves depending oncarbohydrate concentration).
Carbohydrates
Process NMR Associates
Process NMR – “Fruit” Juices
Process NMR Associates
ConclusionHigh Resolution FT-NMR has
Left the Research Laboratory…. and is Arriving in a Process
Near You!
See Further Information at http://www.process-nmr.com
Process NMR Associates
Acknowledgements
Paul Giammatteo – PNA
Tony Van Poyenbroeck – Cardoen Technology, Belgium
Our NMR Customers