Process NMR Applications

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

Today’s markets for process NMR

Refining

Metals & Foundry

Power

Marine

Oil and Gas

Water & Utilities

Petrochemicals

Life sciences

Chemicals

Mining & Minerals

Automotive

Food & Beverage

Future new markets for Process NMR

Refining

Metals & Foundry

Power

Marine

Oil and Gas

Water & Utilities

Petrochemicals

Life sciences

Chemicals

Mining & Minerals

Automotive

Food & Beverage

Process NMR applications in the refinery

Crude Feed and Distillation

Key application: Crude feed & distillation

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

Effects of crude change

Crude feed API variation

Final product upsets

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

Crude 2HEAVY Crude 1

Settle

Ramp

Ramp SwitchHEAVY Crude 1

Crude 2

Lost Throughput

Time

CDU transition issues

Throughput

With each crude transition, crude feed rate is reduced due to: Column flooding issues Heat shock risks on exchanger Allow feedback control

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

Traditional Crude CDU control

Residue

Light Naphtha

Heavy

Naphtha

Kerosene

Light Gas Oil

Heavy Gas Oil

Gas / LPG / Gasoline

laboratory TBPanalysis

1/day

laboratory TBPanalysis

1/day

Crude-Assayinformation

Crude-Assayinformation On-line modelOn-line model

Off-line planning

model

Off-line planning

model

Online inferential feedback every 15 minutes

CDU

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.

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

CDU feed/distillation optimization & control

OptimizerOptimizer

APCAPC

Real time crude feed NMR data allows the optimizer to determine APC set-points for :

• Cut point optimization• Product quality control• Feed rate maximization• Optimize energy consumption• Avoid the risk of violating the process equipments constraints

CDU feed/distillation real time NMR data

Distillation streams

Octane (RON,MON)Specific Gravity @ 15CDensityRVPNaphthalene ContentPIONAViscosityPour Point

Cetane Index

Flash point

Cloud point

Freeze point

Distillation

RTO/APC

Feed API GravityTBPSulfur ContentWaterTANAromaticityAPI Pred.Yields

Benefits from real time CDU NMR data

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

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

Crude Feed and Distillation

Key application: Crude oil blending

Crude blending controls goals

APCAPC

OptimizerOptimizer

• 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

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

Crude Blending real time NMR data

APCAPC

OptimizerOptimizer

Crude

TBP

API Gravity

Water

Viscosity

Sulfur

API Predictive Yields

Crude Feed and Distillation

Key application: FCC Feed and distillation

FCC Feed – why measure ?

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 !

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

FCC Feed variability effectsVariable FCC Feed

Atmospheric ResidueVacuum GasoilVisbreaker VGOCoker VGO

Reacto

rR

eacto

r

.

Fractio

nato

r

Reg

en

aration

Distillation Products

C3/C4GasolineHeavy NaphthaLight 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

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 operatethe process more comfortably.

Coke Yield

Regenerator Variables

Regenerator Heat BalanceRegenerator TemperatureCatalyst / Oil RatioResidual Coke on Catalyst

Feedstock QualityCatalyst ActivityReactor Temperature (In / Out)Residual Coke on CatalystReactor PressureCatalyst / Oil Ratio

Reactor Variables

FCC NMR Solution

APC

Optimizer

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.

Crude Feed and Distillation

Key Application :Catalytic Reformer

CCR – Effect of feed variability

Variable Feed

Hydrogenated heavy naphtha from CDUCokerHydrocrackerCatcracker spirits

Refo

rmer

Refo

rmer

.

Bu

taniser

Reg

en

aration

Reformate

C4’s and lighter

Feed variability influences Reaction severity Benzene precursors

(cyclohexane) Coking rate

CCR – NMR solution

Multiple Feed

Hydrogenated heavy NaphthaFrom CDUCokerHydrocrackerCatcracker spirits

Refo

rmer

Refo

rmer

.

Bu

taniser

Reg

en

aration

Reformat

C4’s and lighter

Feed

Distillation

API Gravity

PIONA

S.G.

Reformat RON MON Benzene Aromatics RVP Distillation

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

Crude Feed and Distillation

Key application : Hydrocracker feed

Hydrocracker – Control goals and parameters

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

Control goals maximize profits by making best ratio

of gasoline/distillate production (season dependent)

maximize throughput with minimal energy

Real time NMR data for control

Parameter

API Gravity

TBP

Viscosity

Sulfur

Aniline point

Carbon Residue

Nitrogen

Control input

Yield potential Sulfur constraints final productCrackabilityCoking rate control Catalyst poison

Crude Feed and Distillation

Key application :Product blending

Product blender control

Optimiser

Digital Blender

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

Product Blending Analysis

RONMOND86E200 & E300AromaticsBenzeneOxygenatesMTBETAMEETBE

RONMOND86E200 & E300AromaticsBenzeneOxygenatesMTBETAMEETBE

Methanol

Ethanol

API Gravity

Flash Pt.

Cloud Pt.

Pour Pt.

Freeze Pt.

Cetane Index

Viscosity

Optimizer

Digital Blender

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

Naphtha Cracker FeedApplication

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

Naphtha Cracker – Why measure feed ?

Application Naphtha Cracker Feed

Naphtha Feed

PIONA

Distillation

Sulfur

API Gravity

Specific Gravity

Density

Detailed Hydrocarbons

Cyclopentane

Cyclohexane

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

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

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

NMR Analyser users

Nuclear Magnetic Resonance Online Analysis

Conclusions

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

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

Thank you!

Contact us:QUALION NMR  ANALYZERS Advanced Technology CenterBuilding 22, P.O.B. 15017 Haifa 31905Israel  Tel:  (+972) 4-855 1161Fax:  (+972) 4-855 1162Email:  info@qualion-nmr.comWeb:  www.qualion-nmr.com