Intensification Of Conventional Process Industry Through In/On Line Analyses Dr. Ronny McMurray Modcon Systems Ltd / Interline Systems B.V. The Challenges Ahead • The worldwide refining industry has undergone a major transformation in the last decade due to changes in regulatory and market forces, such as fluctuating crude cost, tighter regulation on product quality and refinery emissions, shifting crude quality and fundamental changes in fuel demands • At present, refineries must be flexible enough to respond immediately to crude oil changes and deviations in product demands as a result of the changing global economy. • The required flexibility in the management of a refinery and the complexity of the different processes, crude oils and distillates can only be achieved by stringent monitoring of the quality of the incoming material and the outgoing product streams in each refinery unit. Process Economization Economization of Refinery and Process Industries • • • • Crude Blending – Maximum utilization of low cost and opportunity crudes Crude Distillation – Cut point shifting Secondary Processes – Maximization of the efficiency of consecutive processing units after the CDU Product Blending – Efficient optimized and economic on-line blending Benefit of Process Economization • • • • • • • Reduce giveaways Reduce reprocessing Always in-spec Less time consuming lab analyses Less tank occupation Maximum yield at minimum energy Adjustment of process conditions based on real time analytical data On-Line Process Analyzers ASTM-based discrete analyzers • Best correlation with the laboratory • Long response time • Expensive maintenance Correlative Analyzers (NIR/FTIR, NMR) • Correlation between spectroscopic data and quantified physical properties • Multi-property analysis • Fast response time • Minimal maintenance NMR Process Analytics • Based on alignment of protons in magnetic field • Not limited by transparency of process stream NMR is molecular specific by combination of two major characteristics: Chemical shift Quantified shifting of the signal to a higher frequency according to the chemical nature of neighboring atoms and chemical bond. Hydrogen Concentration Ratio Linear correlation of the concentration of hydrogen atoms with the spectral response of different peaks. Development of Process NMR Systems • Previous NMR process analyzers: high sensitivity towards even minor temperature variations of ± 2 °C • To achieve stable homogeneity of the magnetic field, temperature fluctuations must be isolated from influencing the magnet properties. • Major characteristic of the new 3rd generation: Reduction of the temperature sensitivity to ± 10 °C NMR Process Analyzers Evolution Features Magnet Weight & Size Field strength Bore size Mechanical 2nd Generation 3rd Generation Advantages & Benefits Improvement in the mechanical structure and the overall magnet stability. Better temperature insulation between magnet and the process probe. 170Kg; 35 x 45 x 40 cm 1.47 Tesla (60Mhz for H+) 24mm 34 pieces 170Kg; 40 x 40 x 45 cm 1.47 Tesla (60Mhz for H+) 30mm to 34mm 10 pieces Process Probe Dewar, Stainless steel brazed to Ceramic tube Plain Ceramic pipe Minimized heat transfer between samples and magnet. Better temperature insulation. Increased reliability and robustness. Higher Q (better SNR) Shim Coils 40 copper coils, manually warped and glued onto Aluminum plate. 2 PC boards contain 40 copper coils, fit together as a SHIM cassette Standardized location of the shim coils. Additional thermal insulation. Easy replacement of the SHIM cassette. Elimination of cables & soldering. Hardware 6 Electronic units Plenty of wiring & cables 3 Electronic units Minimal wiring Increased reliability. Overall small foot-print. Software Windows NT Windows XP or 7; New algorithm for standard Models. Fully automated process capacity. Extensive remote diagnostic capabilities. Temperature Susceptibility Environment Fluctuations between streams Must be within : ±1.5°C Should not exceed : ±2.5°C Must be within : ±3°C Should not exceed : ±10°C Enables the analyzer to be applied to any stream, notwithstanding the temperature differences between them. Simpler Sampling System. NMR Analyzer Advantages • Real time, continuous flow-through stream analysis • Applicable to transparent, dense and opaque materials alike • Fundamental Method - Direct Molecular Measurement • Linear Spectral Response across broad range • Direct and Multi-property analysis • Minimal maintenance required • Simple Sample Conditioning required Refinery Applications NIR Location Light Naphtha Kerosene Meroks Treater Diesel Oil Hydrotreater Reformate Catalytic Reforming Jet Fuel Kerosene Diesel Oil Hydrocracked Gasoline Diesel Oil FCC Feed Hydrotreater Vacuum Residuum Visbreaking Asphalt Blowing Asphalt Fluid Catalytic Cracker Alkylation Naphtha Coker Gas Oil Alkylate Hydrotreater FCC Gasoline FCC Gas Oil Catalytic Reforming Hydrotreater Fuel Oil Coker Naphtha Gasoline Blending Hydrotreater Hydrocracker Naphtha Isomerate Isomerization Delayed Coker NMR Location Crude Desalting Heavy Naphtha Vacuum Distillation Crude Oil Blending Atmospheric Distillation Gas Processing Case Study: NMR in Crude Oil Distillation Curve Prepared in cooperation with Aspect Imaging Case Study: Linear Correlation – Crude Oil TBP 350 C 100 NMR Predicted (%) 90 80 70 60 50 40 R² = 0.953 30 20 20 Prepared in cooperation with Aspect Imaging 30 40 50 60 70 Measured (%) 80 90 100 Crude Oil Blending Physical Properties Measurable in Process Streams: IBP, T(10), T(50), T(90), TBP, ), API Gravity, Water, Viscosity, Sulfur, API, Yields, TAN Benefit of NMR in on-Line Crude Oil Blending • Material in-spec throughout entire blending process • Instantaneous production of the blend by on line adjustment of feed based on real time analytical data • Allows crude cost reduction by maximum incorporation of heavy/opportunity crudes. • Allows rapid availability of the product • No large occupation of mixing tanks, low space requirements • Rapid response to fluctuations in raw materials • Reduction of costly giveaways • On-Line Sulfur and TAN optimization • High production capacity – no lag time due to timeconsuming laboratory analyses CRUDE A CRUDE B CRUDE C BLENDING CONTROL UNIT CRUDE BLEND Benefit by On-line NMR controlled Blending In Tank Crude 1 1 hours Crude 2 4 hours Crude 3 2 hours Mixing 24 hours Lab 1.5 hours Re processing 12 hours Lab Final 1.5 hours LOAD Production Time about 32-44 hours In Line TANK Crude 1 Crude 2 Crude 3 7 hours Static Mixer NMR Production Time about 7 hours In Spec Integrated NMR-based Blending Solution If a 200,000 barrels per day refinery can increase average sulphur from 3.0 to 3.2 and the average API can be lowered from 22 to 20, then the crude savings is estimated to be $10 million (based on World Bank 2004 data) Crude Distillation Unit, Physical Properties Measurable in Process Streams: Density, API, IBP, FBP, T10%, T90%, RVP, flash point, pour point, cloud point, freezing point, cetane, number, PONA, benzene, naphthenes, paraffins, olefines, aromatic, Sulfur and water. • • • • • Naphtha, kerosene and light gasoil are measurable by NIR and NMR. NIR is sensitive to crude switching, while NMR is not! Heavy process streams like HAGO, LVGO, HVGO, residues and crude oils are opaque and cannot continuously be measured by NIR/FTIR or discrete analyzers, but only be by NMR. NMR process analyzers allows full process monitoring of incoming crude and entire range of distillates. NMR provides real time analytical data for process optimization Benefit NMR in Crude Distillation NMR Benefits: • On line monitoring of the crude oil quality allows on line adjustment of process parameters, based on real time analytical data. • Reduces influence caused by crude switching. It enables to execute real time process adjustments. • on-line monitoring crude and distillate enables accurate determination of both upper (T90% - FBP) and lower (T10% IBP) distillation points enables accurate cut point. Result • Increased distillation capacity • Increased CDU yield • Reduced energy consumption • Less production (storage) less valued distillates Case study: NMR in CDU Crude Monitoring Streams Crude Kero VGO IBP °C Parameters Sulfur, Density, Water, Distillation Freeze point Distillation at 150 °C Sulphur % Lab NMR Upper limit Lower Limit Refinery A Capacity 14 million tons crude oil Marginal Improvement $ 3000 K Case Study 2: NMR in CDU Distillates Streams KERO LVGO HAGO LAGO Parameters Freeze points Distillation Refinery B Capacity 4.5 million tons crude oil Marginal Improvement $ 1000 K Fluid Catalitic Cracking – FCC Physical Properties Measurable in Process Streams: Distillation, Gravity, Water, Viscosity, Sulfur, aromaticity, concarbons, basic Nitrogen, asphaltenes, refractive index, paraffins, naphtalenes, carbon aromaticity, carbon naphthenicity, carbon parafinicity. Benefit: • Majority of process streams are opaque and best measured by NMR. • Full control of feed and product streams by NMR enables optimization of the reaction and fractionator. • Increases product yield and reduces catalyst recycling, and reduces energy. Chemical Industries • Raw materials, intermediate compounds and final products have distinguishable NMR spectra. • NMR enables to quantify the presence of each of them, and the chemical properties of the process stream, notwithstanding whether transparent or opaque. • Water does not disturb the measurement – significant signal. Benefit: • Chemical reactions can be followed up by monitoring the chemical conversion of raw materials to the final product, through their intermediates. • This enables to change process conditions, to increase the chemical yield and preventing unnecessary processing time. Case Study - Reaction Monitoring H+ NMR Process Analyzer - MOD 8000 • The unique MOD 8000 NMR process analyzers have been introduced in response to the need by crude oil blenders and refineries to on-line quantify physical quality properties in process streams, notwithstanding whether transparent or opaque. • NMR process analyzers reduces the need to invest in multiple sets of different analyzers. All analyses are performed by one analyzer in one single measurement. • NMR process analyzers correlate between linear spectral response and quantified values of physical properties, by using chemometrics. NMR Benefit in Process Intensification • • • • • • • • • Maximum process yield required products Product always in-spec! Increases production capacity of required products Reduces energy and catalyst consumption Reduces reprocessing, storage of semi-final products, giveaways or off spec products Reduces space for multiple analyzer systems – one analyzer for many physical quality parameters Reduced time consuming laboratory analyses Prevents lag time between laboratory results and real time analyses Real time process control allows on line process optimization THANK YOU
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