Process NMR Associates Detailed Hydrocarbon Analyses of Naphtha by On-Line NMR Integration of Real-Time NMR Feed Analysis With Advanced Process Control and Optimization Presented By John Edwards, Ph.D. Process NMR Associates, LLC Danbury, Connecticut November 21, 2002 Eastern Analytical Symposium, Somerset, New Jersey
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Process NMR Associates
Detailed Hydrocarbon Analyses of Naphthaby On-Line NMR
Integration of Real-Time NMR Feed AnalysisWith Advanced Process Control and Optimization
Presented ByJohn Edwards, Ph.D.
Process NMR Associates, LLCDanbury, Connecticut
November 21, 2002Eastern Analytical Symposium, Somerset, New Jersey
Process NMR Associates
Presentation Overview
• Process NMR Associates, LLC – Business Profile
• NMR Basics – Very Briefly
• Advantages/Disadvantages of NMR as a Process Spectroscopy
• Applications
1. Naphtha Steam Cracking Control and Optimization
2. Reformer Unit Control
• Conclusion
Process NMR Associates
Company: Process NMR Associates, LLC
Founded : 1997
Personnel: 2 Ph.D. Chemists
Background: Analytical and Process Spectroscopy in Petroleum and Petrochemical (Texaco Inc.)
Business: Application Development for Invensys Process MRAAnalytical NMR Services for Commercial and AcademicCustomers
Process NMR Associates
Process NMR Associates
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 dependence under optimal conditionsMinimal sampling requirementsSpectral response to sample chemistry is linearChemical regions of NMR spectra are orthogonalEntire volume is sampled by the NMR 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 or black samples are readily observed
Disadvantages:Solids cannot be observedIndividual molecular components 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
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
Application: Steam Cracking Optimization
Cracker Facility Capacity: 600,000 Tonnes per Year
Control Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYROOptimization Package (Technip/KTI) and APC
Other Projects require D86 and D2887 Distillation and Density
Value Added: Unit Optimization - $150K /year 4 Units Now Being Optimized ($600K/year)ROI 6-8 Months
Performance : NMR Available 99%+ Since May 2000Models Updated in a Limited Manner
Plant Issues :
Crackers produce 600,000 tonnes of ethylene per year
365 Days of Production per year with turnaround every third year
Strategic Requirements : Naphtha purchased with widely varying feed specification
Need:
Cracker Feed Characterization for APC and Optimization
APC Requirements: Monitor feed characteristics to minimize lost production due to high number of feed transitions:
Simplistically: 1) Heavier naphtha can violate coil outlet temperatures leading to coking or tube wall damage
2) Lighter naphtha can exceed downstream compressor loading
Optimization Requirements: Detailed PIONA analysis allows conditions to be optimized for optimum ethylene/propylene/butyleneproduction based on market conditions.
Process NMR Associates
Process NMR Associates
Distillate
Furnace
Steam
Separation
C2-C3Fractionator
C4+Fractionator
Light Gas Oils
Naphtha
NMR
Optimizer
APC
Steam Ratio
Feed FlowRate
CoilOutlet Temp
Economic Data : Feed/Product Values
PossibleNMR
Steam Cracking Process
EquistarBASF-Antwerpen
Petrochina
Ethylene
Propylene
Butylene
LN
MN-HN
BASF-Ludwigshaven
Process NMR Associates
38.1937.4633.26Total iso-Paraffin
0.0500.2iso-C11
0.650.11.47iso-C10
1.840.52.45iso-C9
3.602.154.03iso-C8
7.105.335.8iso-C7
13.4813.499.05iso-C6
11.0515.519.86iso-C5
0.420.380.4iso-C4
37.7739.0833.08Total n-Paraffin
0.140.020.46n-C10
1.000.191.7n-C9
2.030.952.9n-C8
4.443.494.7n-C7
10.9210.57.97n-C6
15.9619.3711.73n-C5
3.284.533.46n-C4
Naphtha C
Naphtha B
Naphtha AComponent
0.030.120.3Total Olefins
5.503.3210Total Aromatics
0.0400.11Arom-C10
0.360.041.07Arom-C9
1.330.622.87Xylenes
0.210.070.55Ethyl-Benzene
1.791.233.15Toluene
1.771.362.25Benzene
18.3820.0223.36Total Naphthenes
0.0200.04Nap-C10
1.730.612.92Nap-C9
2.341.823.44Nap-C8
2.783.363.26Other Nap-C7
3.233.064.98Methylcyclohexane
3.133.823.77Cyclohexane
4.015.153.82Methylcyclopentane
1.142.21.13Cyclopentane
Naphtha C
Naphtha B
Naphtha AComponent
TYPICAL NAPHTHA
Process NMR Associates
Naphtha 1 Naphtha 2 Naphtha 3Conversion (%) 81.5 94.2 92.0Outlet Temperature (K) 1053 1073 1073Steam/Feed Ratio 0.5 0.5 0.75
Feasibility Performed (30 Samples) – December 1999
Further Off-Line Model Expansion (90 Samples) – December 1999-March 2000
Online System Installed – April 2000
On-Line Localization and Further Model Expansion (65 Samples)– 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 of 32 updated on 4 occasions) since end of validation period. Models updated in limited manner 5 times in 2 years.
99+% Availability September 2000 – May 2002
March 2002 – Three Further Feed-Streams Added to NMR – No model updates required.
Other Installations:Expanding Model Base to Cover Gas Oils andMixed Naphtha/Gas Oil Blend OperationModel base to be developed for NMR analyzer on gaseous products of naphtha cracker.
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
Tal Cohen – Foxboro NMR Israel
Tony Van Poyenbroeck – Cardoen Technology, Belgium