Process NMR Associates The Overlooked Spectroscopy NMR and

Process NMR Associates The Overlooked Spectroscopy NMR and Process Analytical Technology Presented By John Edwards, Ph. D. Process NMR Associates, LLC Danbury, Connecticut December 1, 2004 NYSAS Meeting, Wanaque, NJ

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 NMR Instrumentation Development Facilities: 2 Invensys 58 MHz Process MRA Units 300 MHz NMR (Liquids) 200 MHz NMR (Solids) Business: Application Development for Process NMR Technology Process NMR Instrumentation Development Analytical NMR Services for Commercial and Academic Customers Process NMR Database Development Licensing of Copyrighted NMR Databases and Patented Applications

Process NMR Associates Invensys Process NMR Installations BASF BRC BP AGIP PNA Equilon, LA Invensys Tnuva ERG ORL Tosco Aramco PDVSA Motiva Fina Equistar Valero 4/29/02 Petrochina FPCC Reliance Shell Pertamina Lab Installations Lab and On-Line Installations Planned Installations On-Line Installation - Foods

Process NMR Associates Presentation Overview • NMR Basics – Briefly • Advantages/Disadvantages as a Process Spectroscopy • Applications 1. Reformer Unit Control 2. Crude Distillation Unit Control and Optimization 3. Naphtha Steam Cracking Control and Optimization • Application Snippets Aromaticity – FCC, Base Oil Manufacture Styrene-Butadiene Rubbers Aromatics Food • Conclusion

Process NMR Associates

Process NMR Associates

Process NMR Associates

Process NMR Associates

Process NMR Associates NMR Spectroscopy Why Shim? NMR Imaging (MRI) Example : H 2 O in Line Example : H 2 O in Human Body Head N H 2 O FT S Bad Shim Inhomogeneous Field N H 2 O S Good Shim Homogeneous Field Bad Shim or 3 Different H-Types? FT H 2 O Should Give One Resonance if Shim is Good H 2 O N H 2 O FT In MRI Large Shims are Utilized to Distort the Magnetic Field in a Known Manner in Order to Make the H 2 O Peak Position Spatially Dependent S Field Lines With Different Bo Computer Obtains Spatial Location of H 2 O in Head Computer Generates Image Based on Water Location

Process NMR Associates TD-NMR Low Field, FID, Curve-Fitting 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-NMR Downhole Drilling Tool

Process NMR Associates High Resolution FT-NMR http: //www. liposcience. com/

Process NMR Associates High Resolution FT-NMR - Metabonomics Metabolism Analysis by NMR – Toxicological Screening

Process NMR Associates

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 spectrum for heavy stream analyses where sediment/rust may be present.

Process NMR Associates Advantages and Disadvantages of NMR Applied to Process 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 > 1000 ppm. Sensitive to Ferro-magnetics. Sample Viscosity Causes Resolution Changes Non-Hydrogen Containing Species are Not Observed (Exceptions Na, P, F, Al)

Process NMR Associates

Process NMR Associates H 2 O

Process NMR Associates

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: RON MON Benzene Total 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 Years Models Updated Once in Past 4 Years Value Gained From Control $10, 000 - $35, 000 / Week

Process NMR Associates

Process NMR Associates

Process NMR Associates

Process NMR Associates

Process NMR Associates 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 Point Crude Tower Optimization NMR Analysis: 15 Minute Cycle NMR Results into ROMEO CDU Optimization Package NMR PLS Outputs: Naphtha – T 10, T 50, T 90, EP Kero – Freeze, Flash Crude – API, Sulfur, TBP (38, 105, 165, 365, 565 C) Value Added: Kero - Approach Freeze Point Limit – Worth $600 K/Year CDU Optimization- Conservatively 4 cents per Barrel Performance : NMR Available 98% 2000 -2004

Process NMR Associates SSC & MRA

Process NMR Associates Crude Fast Loop Heater

Process NMR Associates MRA Sample System § Crude Brought into NMR at 70 C (Crude Fast Loop Heater) § Kerosene and Naphtha Also Brought to NMR at 70 C (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

Process NMR Associates Crude Analysis

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Process NMR Associates Crude Reconciliation

Process NMR Associates Application: Steam Cracking Optimization Cracker Facility Capacity: 600, 000 Tonnes per Year Control Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYRO Optimization Package NMR Analysis: 3 -4 Minute Cycle (Single Stream) 16 Minute Cycle (4 Feed Streams) NMR PLS Outputs: Naphtha – Detailed PIONA C 4 -C 10 n-paraffin, i-paraffin, aromatics, naphthenes Value Added: Unit Optimization - $150 K /year 4 Units Now Being Optimized ($600 K/year) Performance : NMR Available 98%+ Since August 2000 Models 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

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 Wt% Process NMR Associates Cyclopentane GC NMR Date

Process NMR Associates

Process NMR Associates 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 and Mixed Naphtha/Gas Oil Blend Operation Parameter n-c 4 n-c 5 n-c 6 n-c 7 n-c 8 n-c 9 n-c 10 Total n-paraffin I-c 4 I-c 5 i-C 6 i-C 7 i-C 8 i-C 9 i-C 10 i-C 11 Total I-paraffin cyclopentane me-cyclopentane Cyclohexane Methylcyclohexane Other C 7 -Nap c 8 -Nap c 9 -Nap c 10 -Nap Total Naphthenes Benzene Toluene Ethylbenzene Xylenes C 9 - Arom C 10 -arom Total Aromatics R 0. 9340 0. 9761 0. 9616 0. 9840 0. 9882 0. 9918 0. 9716 0. 9840 0. 8765 0. 9834 0. 9865 0. 9119 0. 9800 0. 9905 0. 9866 0. 9613 0. 9617 0. 9821 0. 9937 0. 9940 0. 9872 0. 9025 0. 9713 0. 9892 0. 8950 0. 9794 0. 9950 0. 9920 0. 9902 0. 9951 0. 9875 0. 9586 0. 9967 Std Dev Mean Dev 0. 52 0. 067 0. 73 -0. 004 0. 73 -0. 093 0. 33 -0. 032 0. 29 -0. 008 0. 18 -0. 003 0. 13 0. 022 0. 81 0. 013 0. 07 0. 001 0. 76 0. 043 0. 59 -0. 050 0. 46 -0. 015 0. 42 -0. 035 0. 26 0. 010 0. 24 0. 013 0. 08 -0. 007 0. 81 -0. 011 0. 14 -0. 004 0. 23 -0. 018 0. 26 0. 034 0. 29 0. 001 0. 32 -0. 052 0. 36 0. 002 0. 28 0. 026 0. 06 -0. 001 0. 83 0. 019 0. 10 0. 006 0. 17 0. 007 0. 04 0. 002 0. 14 0. 003 0. 16 0. 006 0. 07 0. 001 0. 31 0. 022

Process NMR Associates Application Snippets

Process NMR Associates FCC, RCC, Hydrotreating, Base Oil Manufacture Carbon Aromaticity Correlation Between Carbon Aromaticity and Refractive Index 50 45 40 35 30 25 20 15 10 5 0 1. 4000 1. 4500 1. 5000 1. 5500 Refractive Index 1. 6000 Why Measure Refractive Index When NMR Allows the Carbon Aromaticity to be Obtained Directly?

Process NMR Associates

Process NMR Associates Process Samples

Process NMR Associates Monomer Ratios

Process NMR Associates Selective Vinylidene Synthesis

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Process NMR Associates Process NMR – Dairy 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: R 2 > 0. 96 error <1 wt%

0 Process NMR Associates CH 2 Process NMR Butter - before phase separation Butter Water CH 3 CH and alpha to olefins Cis/trans olefins 10 8 6 4 2 0 CH 2 -2 Butter - after phase separation CH and alpha to olefins CH 3 Cis/trans olefins 10 8 6 4 2 0 -2

Process NMR Associates 15 10 Regular Block Regular Tub Light Fat-Free Water Saturated fat and protein Carbohydrates Unsaturated fat region and sugars 5 0 20 40 60 80 100 Overlay of 4 Cream Cheese Products 120 140

Process NMR Associates Process NMR – 23 Na Monitoring of Sodium Content in Food

Process NMR Associates Process NMR – Alcoholic Beverages Whiskeys, Vodkas, Gin, Rum 80000 Lower Alcohol Liquors 60000 Port 40000 Wine Beers Non Alcoholic Beer 20000 7750 7800 7850 7900 7950 8000 8050 8100 0 6600 6800 7000 7200 7400 7600 7800 8000 8200

Process NMR Associates Process NMR – “Fruit” Juices 100000 Exchangable carbohydrate hydroxyls and H 2 O (Peak moves depending on carbohydrate concentration). 80000 60000 Carbohydrates 40000 20000 0 7000 7200 7400 7600 7800 8000

Process NMR Associates Conclusion High 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