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Process NMR Applications

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Presentation on theme: "Process NMR Applications"— Presentation transcript:

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

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: QUALION NMR  ANALYZERS   Advanced Technology Center Building 22, P.O.B Haifa 31905 Israel    Tel:  (+972) Fax:  (+972)   Web: 

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