1. Process NMR Applications

2. Applications: Distinct NMR Analyzer Features
Non-invasive analytical
technology
Electronic, not optical
Absolute measurement
technique, no zero or
referencing
Ability to analyze dark and
opaque samples
High temperature/wide flow-
through probe for highly
viscous samples
Limited filtering of sample
required
Robust models due to highly resolved
quality spectra, structural information
Limited calibration data: short time-to-profit
No moving parts inside – reduced
maintenance

3. Today’s markets for process NMR
Refining
Oil and Gas
Water & Utilities
Metals & Foundry
Petrochemicals
Power
Mining & Minerals
Marine
Automotive
Life sciences
Food & Beverage
Chemicals

4. Future new markets for Process NMR
Refining
Oil and Gas
Water & Utilities
Metals & Foundry
Petrochemicals
Power
Mining & Minerals
Marine
Automotive
Life sciences
Food & Beverage
Chemicals

5. Process NMR applications in the refinery

6. Crude Feed and Distillation
Key application: Crude feed & distillation
Crude Feed and Distillation

7. Why measure crude ? In the past... The market today:
Little variation, constant supply of
same crude
Refineries were designed for
stable feed
Advance control mainly on the
CDU run-down products:
feed-back control only
The market today:
Increased competition & drive
to maximize profits
Buying of low-cost crude
(heavier types)
Buying on spot markets
High variability in offered crude
quality
Refineries today must cope with
this variation in order to ensure
profitability

8. Effects of crude change
Crude feed API variation
Final product upsets

9. Effect of crude quality variation on CDU
Optimal cut points affected
Product quality control risks
Feed rate is slowed down and not maximized
Energy consumption not optimal
Risk of violating the process equipments constraints

10. CDU transition issues
With each crude transition, crude feed rate is reduced due to:
Column flooding issues
Heat shock risks on exchanger
Allow feedback control
Throughput
Crude 2
HEAVY Crude 1
Settle
Ramp
Switch
HEAVY
Crude 1
Lost Throughput
Time

11. CDU Feed variability: Control strategies
Feed Switch Control:
Avoid unit upset whenever crude transition occurs via process control compensation
Crude Feed Blending:
For those refiners having access to constant crude supplies from fields via pipeline / large tank farms
Blend crude to a constant or known feed

12. Traditional Crude CDU control
laboratory TBP
analysis
1/day
Crude-Assay
information
On-line model
CDU
Gas / LPG / Gasoline
Off-line
planning
model
Light Naphtha
Heavy Naphtha Kerosene
Light Gas Oil
Heavy Gas Oil
Residue
Online inferential feedback every 15 minutes

13. Crude Assay Data Crude has a wide range of properties/qualities
API Gravity
Sulfur
Pour points
Water, nickel, vanadium, salts
API gravity is not the only factor affecting crude processing behavior. It can also be affected by other parameters.
(low API Gravity crude with low wax content and vice versa)
The quality of crude of the same name can vary over time.

14. Problems with crude assay data
The crude assay data may be old
Every crude tank has a heel of mixed crudes received earlier
Crude in a tank will settle:
– Compatibility
– Solubility
– Stratification
A crude switch (normally 7 to 8 hours) results in an unknown blend of the old and new crude in the pipeline

15. CDU feed/distillation optimization & control
APC
Optimizer
Cut point optimization
Product quality control
Feed rate maximization
Optimize energy consumption
Avoid the risk of violating the
process equipments constraints
Real time crude feed NMR data allows the optimizer to determine APC set-points for :

16. CDU feed/distillation real time NMR data
RTO/APC
Distillation streams
Octane (RON,MON)
Specific 15C
Density
RVP
Naphthalene Content
PIONA
Viscosity
Pour Point
Cetane Index
Flash point
Cloud point
Freeze point
Distillation
Feed
API Gravity
TBP
Sulfur Content
Water
TAN
Aromaticity
API Pred.Yields

17. Benefits from real time CDU NMR data
Commercial benefits
Supply chain optimization
Expand flexibility in feed stock selection
Crude purchasing agents can strategically buy feed stock on the spot market
Crude Assay correction for refinery accounting
Operational benefits ($0.06 savings per barrel* – client documented)
Feed-forward control for distillation column controller (APC, RTO)
Improved higher value product yields
Maximizing unit throughput - 70% recovery of potential lost throughput due to instability
Improved performance of downstream units
NMR analyzer benefits
Improvement in analyzer availability
Reduction in maintenance costs
Reduce number of analyzers
Unique ability to provide all control/APC properties with one analyzer

18. Crude NMR spectrum variability

19. Crude Oil chemometrics

20. Crude Feed and Distillation
Key application: Crude oil blending
Crude Feed and Distillation

21. Crude blending controls goals
APC
Optimizer
Accurate monitoring of different crude feed blending-streams’
composition allows precise and ultimate crude blend
Expensive good crudes can be mixed with cheap low quality
crudes and still achieve desired properties or quality
Maximizing profit

22. Benefits of crude blend control
Improved CDU stability and throughput
Improved overall refinery throughput
Better performance of downstream units
e.g. P/A ratio effect on BTX CCR output
Final product quality improvement
Reduction energy costs
Better crude change management
2-3 % refinery operating margin gain

23. Crude Blending real time NMR data
APC
Optimizer
Crude
TBP
API Gravity
Water
Viscosity
Sulfur
API Predictive Yields

24. Crude Feed and Distillation
Key application: FCC Feed and distillation
Crude Feed and Distillation

25. FCC Feed – why measure ? Why perform FCC measurement online?
Critical to success of closed-loop
real-time optimization projects.
Feed characterization is critical in
determining:
Catalyst coking rate
(coking precursors)
Sulfur constraints
Potential catalyst poisons
Today, FCC feed becomes variable in quality and has regular quality shifts:
Varying crude gives varying FCC feed
Crude moves towards heavy and less sweet
Can the VDU provide enough feed ?
Is it more economical to buy feed on the open market ?
If well controlled, the FCC is the biggest money maker
However, reliable online measurement on FCC feed was traditionally not available !

26. FCC Feed variability effects
Variable FCC Feed
Atmospheric Residue
Vacuum Gasoil
Visbreaker VGO
Coker VGO
Regenaration
Reactor
Distillation Products
C3/C4
Gasoline
Heavy Naphtha
Light Cycle oil (LCO)
Heavy Cycle oils (HCO)
Varying FCC Feed qualities
can influence :
• Filling of plant constraints
• Product quality
• Product yields
• Unit throughput
• Regenerator operation
• Wet gas compressor operation
• Energy consumption
Fractionator .

27. FCC Feedstock variation vs coke yield
Varying feedstock quality will upset equilibrium between reactor and
Regenerator, hence preventing the operator from reaching optimal operation.
By monitoring FCC feedstock quality in real time, the operator can operate
the process more comfortably.
Coke Yield
Regenerator Variables
Regenerator Heat Balance
Regenerator Temperature
Catalyst / Oil Ratio
Residual Coke on Catalyst
Feedstock Quality
Catalyst Activity
Reactor Temperature (In / Out)
Reactor Pressure
Reactor Variables

28. FCC NMR Solution
APC
Optimizer

29. FCC Feed real time data and control benefits
FCCU controls and optimization include feed preparation, the reactor/regenerator, the main fractionator, the wet gas compressor, and the downstream gas plant.
Typical operating objectives are
• Maximizing unit capacity
• Maintaining product quality while maximizing yields of most valuable products
• Optimizing energy utilization
• Controlling conversion
• Improving safety and reliability via operational stability
Total economic benefit can approach $0.30/bbl feed.

30. Crude Feed and Distillation
Key Application :Catalytic Reformer
Crude Feed and Distillation

31. CCR – Effect of feed variability
Variable Feed
Hydrogenated heavy naphtha from CDU
Coker
Hydrocracker
Catcracker spirits
Regenaration
C4’s and lighter
Reformer
Feed variability influences
Reaction severity
Benzene precursors (cyclohexane)
Coking rate
Butaniser .
Reformate

32. CCR – Constraints and control strategy
Variable Feed
Hydrogenated heavy Naphtha
From CDU
Coker
Hydrocracker
Catcracker spirits
Regenaration
C4’s and lighter
Reformer
Product constraints
Octane Number
Aromatics
Benzene
RVP
Butaniser
Control Strategy
Maximize Octane
Reduce variation in Octane and RVP
Maximize catalyst life (coking rate )
Push against units constraints
Minimize energy cost .
Reformat

33. CCR – NMR solution . Reformer Butaniser C4’s and lighter Reformat
Multiple Feed
Hydrogenated heavy Naphtha
From CDU
Coker
Hydrocracker
Catcracker spirits
Regenaration
Reformer
C4’s and lighter
Feed
Distillation
API Gravity
PIONA
S.G.
Butaniser
Reformat
RON
MON
Benzene
Aromatics
RVP
Distillation .
Reformat

34. Benefits of CCR Application
Operational benefits
$0.04 per barrel* – client documented
Benefits of NMR Analyzer technology
Reduce number of analyzers
Reduce maintenance costs
Reduce product giveaways
Minimal Modeling effort application
Fast online time
Simple integration
*When coupled with APC / RTO

35. Crude Feed and Distillation
Key application : Hydrocracker feed
Crude Feed and Distillation

36. Hydrocracker – Control goals and parameters
maximize profits by making best ratio of gasoline/distillate production (season dependent)
maximize throughput with minimal energy
Control parameters
Heater controls
Charge and conversion control
(bed temprature and hydrogen )
Fractionator control
H2 purity and H2/Oil control
Benefits reported up to 30 c/bbl

37. Real time NMR data for control
Parameter
API Gravity
TBP
Viscosity
Sulfur
Aniline point
Carbon Residue
Nitrogen
Control input
Yield potential
Sulfur constraints final product
Crackability
Coking rate control
Catalyst poison

38. Crude Feed and Distillation
Key application :Product blending
Crude Feed and Distillation

39. Product blender control
Feedforward control for component quality variation
Feedback control for product quality variations
Quality integration of product and component tanks
Projected product qualities at blend header
Digital
Blender
Optimiser

40. Product Blending Analysis
Digital Blender
Optimizer
RON
MON
D86
E200 & E300
Aromatics
Benzene
Oxygenates
MTBE
TAME
ETBE
Methanol
Ethanol
API Gravity
Flash Pt.
Cloud Pt.
Pour Pt.
Freeze Pt.
Cetane Index
Viscosity

41. Benefits of NMR in product blending
Significant reduction in maintenance costs by replacing multiple analyzers
Eliminate operator bias and errors in lab sampling
Minimal Modeling effort application
Linear models allow extrapolation
Simple integration and quick results

42. Naphtha Cracker Feed Application

43. Naphtha Cracker – Why measure feed ?
Naphtha quality variability
Crude changes in refinery
Spot-market opportunity naphthas
Changes in the refinery processes
Potential benefits of real time data
Allow real feed-forward control
Keep furnaces and coils at optimal severity and production
Operate close to plant constraints

44. Application Naphtha Cracker Feed
Naphtha Feed
PIONA
Distillation
Sulfur
API Gravity
Specific Gravity
Density
Detailed Hydrocarbons
Cyclopentane
Cyclohexane
Methyl-cyclopentane
Methyl-cyclohexane
Benzene
Toluene
Ethylbenzene
Xylenes
Hydrogen
Viscosity
Cycle time : 2 min

45. Naphtha cracker feed analysis: benefits
Increase throughput and push for equipment constraints
Better naphtha feedstock management
Increase yields on higher valued olefins
Reduce energy consumption
Modeling benefits for RTO
Increase furnace run times (coking)/manage run-lengths

46. Analytical benefits Single instrument for multiple components
Fast response time (2 min)
Low maintenance
Non-optical and non intrusive
No regular solvent cleaning
Absolute measurement, no zero, no referencing
Robust models based on linear response and good spectral resolution
No-moving parts
Wide 7 mm flow-through cell

47. NMR Analyser users

48. Nuclear Magnetic Resonance Online Analysis
Conclusions

49. The NMR Analyzer advantage - control
Real time, accurate stream analysis
Reduction in response time from Lab allows tighter control (e.g. PIONA in seconds)
Multi-property analysis and increased information regarding stream matrix to allow better management decisions (molecular management)
Avoid errors in stream analysis
Measurements are reliable and done online in real time
Eliminates data entry errors from Lab input

50. The NMR Analyzer advantage - analytical
Simple sample conditioning required
No water removal
Coarse or limited filtering to protect valve seats
Linear Spectral Response across broad range
Models can be extrapolated accurately
Multi-property analysis replaces conventional analyzers and provide much faster results
Minimal maintenance required
No moving parts in sensor
Fast track project execution with conceptual study, basic design and reduced client risk
Useful initial results after commissioning
Project payback in less than one year

51. Thank you!
Contact us:
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