Process NMR Applications

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Process NMR Applications
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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

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Todays markets for process NMR
Refining
Oil and Gas
Water Utilities
Metals Foundry
Petrochemicals
Power
Mining Minerals
Marine
Automotive
Life sciences
Food Beverage
Chemicals
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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
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Process NMR applications in the refinery
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Crude Feed and Distillation
Key application Crude feed distillation
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Why measure crude ?

• In the past...
• 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

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Effects of crude change
Crude feed API variation
Final product upsets
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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

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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
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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

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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
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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.

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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

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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
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CDU feed/distillation real time NMR data
RTO/APC

• Distillation streams
• Octane (RON,MON)
• Specific Gravity _at_ 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 Ar
omaticity API Pred.Yields
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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

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Crude NMR spectrum variability
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Crude Oil chemometrics
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Crude Feed and Distillation
Key application Crude oil blending
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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

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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

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Crude Blending real time NMR data
APC
Optimizer

• Crude
• TBP
• API Gravity
• Water
• Viscosity
• Sulfur
• API Predictive Yields

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Crude Feed and Distillation
Key application FCC Feed and distillation
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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 !

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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

• .

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FCC Feedstock variation vs coke yield
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FCC NMR Solution
APC
Optimizer
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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.

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Crude Feed and Distillation
Key Application Catalytic Reformer
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CCR Effect of feed variability
Variable Feed Hydrogenated heavy naphtha from
CDU Coker Hydrocracker Catcracker spirits
Regenaration
C4s and lighter
Reformer

Butaniser

• Feed variability influences
• Reaction severity
• Benzene precursors (cyclohexane)
• Coking rate

• .

Reformate
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CCR Constraints and control strategy
Variable Feed Hydrogenated heavy Naphtha From
CDU Coker Hydrocracker Catcracker spirits
Regenaration
C4s 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
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CCR NMR solution
Multiple Feed Hydrogenated heavy Naphtha From
CDU Coker Hydrocracker Catcracker spirits
Regenaration
Reformer
C4s and lighter

• Feed
• Distillation
• API Gravity
• PIONA
• S.G.

Butaniser
Reformat RON MON Benzene Aromatics RVP
Distillation

• .

Reformat
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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

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Crude Feed and Distillation
Key application Hydrocracker feed
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Hydrocracker Control goals and parameters

• Control goals
• 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

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Real time NMR data for control
Parameter API Gravity TBP Viscosity Sulfur Anilin
e point Carbon Residue Nitrogen
Control input Yield potential Sulfur
constraints final product Crackability Coking
rate control Catalyst poison
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Crude Feed and Distillation
Key application Product blending
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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
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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

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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

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Naphtha Cracker FeedApplication
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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

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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
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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

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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

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NMR Analyser users


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Nuclear Magnetic Resonance Online Analysis

• Conclusions

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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

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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

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Thank you!

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