PIR3502 and PUV3402 Process Photometer

Market Discussion Ethylene and Propylene plants sometimes called Olefins plants Most measurements have traditionally been done by Gas Chromatography in these processes Why Process Filter Photometers? Manufacturing ethylene is an extremely fast process Continuous measurements are very beneficial in controlling a fast process Filter photometers are very reliable Need minimal support No consumables

Applications to be Discussed ABB Hydrogenation Solution Acetylene Methyl Acetylene and Propadiene Ethylene Fractionator Ethane Fractionator Caustic Wash Tower Solution Furnace Decoke

Industrial IT for Acetylene / MAPD Hydrogenation Improve Acetylene / MAPD Hydrogenation Safety, Economic & Environmental Performance Industrial IT for Acetylene / MAPD Hydrogenation

ABB Solution for Hydrogenation in Olefins Plants Leverages already proven measurement capability Feeds to the Hydrogenation reactors of Acetylene to Ethylene and MAPD to Propylene are very variable due to up-stream events Multiwave Photometer provides continuous analysis of the stream feed streams Allows operator to tightly control hydrogen ratio Allows operator to track the ratio changes Minimizes over-hydrogenation Minimizes contaminate breakthrough (acetylene or MAPD) ABB can provide advanced process control in addition if the customer needs it

What is Acetylene / MAPD Hydrogenation ? Key unit operation within Ethylene Plants Removes C2 & C3 acetylenic contaminants from olefin products C2H2 + H2 C2H4 C3H4 + H2 C3H6

Why is Acetylene and MAPD Hydrogenation Important Plants increasingly are using highly variable feedstocks Makes process control more difficult due to fast nature of feedstock composition changes Increased environmental regulations being implemented at the same time the feedstock is becoming more variable Tight control of reaction is critical Over hydrogenation converts ethylene to ethane or propylene to propane (Reduces yield) Under hydrogenation allows acetylene and MAPD break though into the product Immediate flaring of product occurs Acetylene and MAPD are problems in the polyethylene and propylene markets Very expensive event Environmental liability

Industrial IT for Acetylene / MAPD Hydrogenation ABB offers technologies that seamlessly combine to deliver a unique synergistic solution for Acetylene / MAPD Hydrogenation Units Real-time characterization of lead & guard bed feeds real-time, on-line determination of conversion & selectivity Process analytical technology for hydrogen and olefin product quality real-time hydrogen product quality measurements Multivariable control that exploits all of our unique analytical capabilities improved approach based upon the real time availability of lead & guard bed feed composition A complete service portfolio to maintain the performance of the IndustrialIT solution : field services on-line support training & parts / repair Operating companies can obtain a combined analytical & control solution from one vendor delivers unique synergistic benefits enhances unit reliability & selectivity while maintaining safe operation

AAS Solution Components Analytical (budgetary end-user prices) 2 x PIR3502 photometer for lead reactor feed & effluent characterization ($45KUSD) 1 x AO2000- Uras14 analysis of high purity hydrogen stream ($9 - 16KUSD) 1 x PGC2000 Analysis of Guard Reactor effluent ($37 - 40KUSD) Advanced Process Control (budgetary end-user prices) Multivariable, model-predictive control (MVPC) : Meet <1ppm acetylene(s) specification in olefin products while : minimizing hydrogen ratios maximizing throughputs maintaining acceptable catalyst cycle-lengths increasing reactor selectivity to ethylene ( & propylene ) avoiding reactor runaways Upgrade to existing ABB license & platform ($60KUSD) Benefits FEED study of any unit to justify IIT solution ($20KUSD) Implementation of (1 application license, server ) new APC scheme for acetylene hydrogenation unit ($125KUSD)

Example - Hydrogen : Acetylene Ratio Control

Hydrogen : Acetylene Ratio Control - Common Problems The majority of units run with poor hydrogen : acetylene ratio control resulting in : lower reaction selectivity leading to reduced olefin gains ( or net losses ) acetylene slippage causing off-specification product & flaring closer approaches to “runaway” conditions higher “green-oil” production with increased regeneration frequency & shorter catalyst life product downgrades to ethane (or propane) with associated recycle costs Poor ratio control is further deteriorated by rapid feed compositional changes acetylene content heavy ends from upstream fractionation upsets neither occurrence detected fast enough by conventional GC analyzers During plant upsets, operators tend to ramp up to excessive H2 addition rates to maintain on-specification product leads to extremely high olefin losses greatly reduced selectivity usually held in this condition for longer than the duration of the initial incident

ABB Solution ABB multivariable control technology driven by our unique capability of real-time feed & mid-bed stream characterization Feeds to lead & guard beds are characterized in real-time with a continuous process photometer providing a true hydrogen demand picture leading to optimum ratio control Inherently more effective than traditional approaches that rely on slow feedback from gas chromatographs As part of a wider multivariable control scheme, this approach leads to improvements in olefin yields compared to baseline traditional APC performance Plant upsets are smoothly managed eliminate operator “over hydrogenation” for excessive periods

Benefits of ABB approach to Hydrogen : Acetylene Ratio control Setting hydrogen addition rates based upon real-time characterization of lead & guard bed feeds offers several advantages over conventional approaches Average H2 : Acetylene ratios are lowered even in those operations that have already implemented advanced process control in an attempt to improve baseline performance Flaring incidents are reduced as the H2 ratio is maintained consistently without analyzer dead time effects, resulting in higher availability of on-spec product annualized savings associated with reduced flaring are $0.5 - 1 M* (depending on baseline converter performance) Ethylene yields are increased due to improvements in olefin selectivity across the beds implementation of traditional APC can improve olefin yields ( as a percentage of feed ) by up to 0.5% the enhanced ABB approach can improve olefin yield gain by an additional 0.2%. this results in average benefits of $1 – 1.5 M* per annum ethane recycle costs are also reduced * Billion pounds per year facility

Benefits of ABB approach to Hydrogen : Acetylene Ratio control Less frequent approaches to runaway conditions as precise hydrogen ratio control avoids “over hydrogenation” and rapid ethylene consumption Plants can finally realize the expected gains of recent investments in state of the art catalysts exploit catalyst capability for low H2 : acetylene ratios avoid operating “ on the safe side” Reduce green oil formation & the need for large inlet temperature increases to maintain unit conversion reduce regeneration frequency & improve catalyst life track catalyst performance throughout the operating cycle Maintain optimum ratio control during plant upsets real-time determination of acetylenes & “heavies” avoid operator initiated “over hydrogenation” for excessive periods Summary For many years, operators have considered improved hydrogen ratio control limited by measurement and control capability ABB can now deliver this approach in a single analytical-control package

Analytical Measurements The Backbone of the Solution!

Acetylene Converters: Lead Bed Inlet Measurements: 0-2% Acetylene 0-30% Ethane 0-2% Propylene 0-100% Ethylene Process Benefits Fast acetylene analysis on the acetylene converter inlet Provides feed forward control for the hydrogen addition to the inlet of the lead bed Traditionally done with Gas Chromatography (3-6 minute analysis time) Additional measurements provide additional information for control of over hydrogenation and thermal runaway Benefits provided by Multiwave PIR 3502 Multi-component capability allows for all measurements on one analyzer PIR 3502 can compensate for the spectral interferences from the other stream components Continuous online measurement for optimum control of a very fast process

Acetylene Converters: Guard Bed Inlet (Midbed) Measurements: 0-0.5% Acetylene 0-30% Ethane 0-100% Ethylene Process Control Benefits Fast acetylene analysis on the acetylene converter guard bed inlet Provides feedback control to the lead bed Provides feedforward control for hydrogen feed to the guard bed Traditionally done with Gas Chromatography (3-6 minute analysis time) Additional measurements provide additional information for control of over-hydrogenation and thermal runaway Benefits provided by Multiwave PIR 3502 Multi-component capability allows for all measurements on one analyzer PIR 3502 can compensate for the spectral interferences from the other stream components Continuous online measurement for optimum control of a very fast process

Acetylene Converter Applications Lead Bed Inlet Measure Component: Acetylene 0-2% Ethane 0-30% Propylene 0-2% Ethylene 0-100% Stream Composition: Acetylene 1% Methane 0.2% Propane 0.2% Propylene 0.5% Ethane 25% Ethylene Balance Guard Bed Inlet Measure Component: Acetylene 0-0.5% Ethane 0-30% Ethylene 0-100% Stream Composition: Acetylene 0.2% Methane 0.2% Propane 0.2% Propylene 0.5% Ethane 25% Ethylene Balance

Acetylene Converter: Spectra REFERENCE ETHYLENE COMP. % TRANSMISSION ETHANE MEASURE BLACK: 70% ETHANE BLUE: 100% ETHYLENE RED: 10% ACETYLENE ACETYLENE MEASURE WAVENUBER (CM-1)

Acetylene Converter: Measurement Precision Acetylene will have significant interference from Ethane Uncompensated 30% Ethane would cause about a 8% of Full Scale error (0.12% Acetylene) Using the compensation capability of most filter photometers will reduce this affect by approximately 10X – 15X or less than 1% of Full Scale error (<0.015% Acetylene) Acetylene will have small interference from Ethylene Uncompensated the 100% Ethylene would cause about a 2% interference (0.03% Acetylene) Using interference compensation the ethylene interference would be reduced to about 0.2% of full scale error (0.003% Acetylene) Ethane measurement is interference free from the other stream components

MAPD Converters: Lead Bed Inlet Measurements 0-2% Methyl Acetylene 0-2% Propadiene 0-2% MAPD 0-10% Propane 0-2% Butadiene Process Control Benefits Fast MAPD analysis on the converter lead bed inlet improves converter control and efficiency Provides feedback control to the lead bed Traditionally done with Gas Chromatography (10-13 minute analysis time) Additional measurements provide additional information for control of over-hydrogenation and thermal runaway Benefits provided by Multiwave PIR 3502 Multi-component capability allows for all measurements on one analyzer PIR 3502 can compensate for the spectral interferences from the other stream components Continuous online measurement for optimum control of a very fast process Cell design allows for the sample to be run at pressure and then returned to process

MAPD Converters: Guard Bed Inlet Measurements 0-0.5% Methyl Acetylene 0-0.5% Propadiene 0-0.5% MAPD 0-10% Propane Process Control Benefits Fast MAPD analysis on the converter lead bed inlet improves converter control and efficiency Provides feedback control to the lead bed Provides feedforward control for hydrogen feed to the guard bed Traditionally done with Gas Chromatography (10-13 minute analysis time) Additional measurements provide additional information for control of over-hydrogenation and thermal runaway Benefits provided by Multiwave PIR 3502 Multi-component capability allows for all measurements on one analyzer PIR 3502 can compensate for the spectral interferences from the other stream components Continuous online measurement for optimum control of a very fast process Cell design allows for the sample to be run at pressure and then returned to process

MAPD Converters: Applications Inlet Application Measure Components: 0-2% Methyl Acetylene 0-2% Propadiene 0-2% MA + PD 0-10% Propane 0-2% Butadiene Stream Composition: Methyl Acetylene 1% Propadiene 1% Ethylene 0.4% Propane 6% Propylene Balance Mid-Bed Applications Measure Components: 0-0.5% Methyl Acetylene 0-0.5% Propadiene 0-0.5% MA + PD 0-10% Propane Stream Composition: Methyl Acetylene 0.2% Propadiene 0.2% Ethylene 0.4% Propane 6% Propylene Balance

MAPD Converter: Spectra REFERENCE % TRANSMISSION PROPYLENE COMP. BLACK: 15% PROPADIENE BLUE: 100% PROPYLENE RED: 7% METHYL ACETYLENE PROPADIENE MEASURE WAVENUMBER (CM-1) METHYL ACETYLENE MEASURE

MAPD Converter: Measurement Precision Propadiene will have a significant interference from Propylene Uncompensated 100% Propylene would cause about a 7% of Full Scale error (0.14% Propadiene) Using the interference compensation capability will reduce this affect by approximately 10X – 15X or less than 0.7% of Full Scale error (<0.014% Propadiene) Methyl Acetylene will have a small interference from Propylene Uncompensated the 100% Propylene would cause about a –0.7% of full scale interference (0.014% Methyl Acetylene) Using interference compensation the propylene interference would be reduced to about 0.07% of full scale error (0.0014% Methyl Acetylene)

Other Multiwave Applications in Olefins Plants

Ethylene Fractionator Measurement: 0-30% Ethylene Process Benefits Purification part of the process Ethylene is removed from the ethane Fast analysis time important for the control of the fractionator tower Benefits provided by Multiwave Analysis can be made at elevated pressure so sample can be returned to the process Provides continuous analysis Precise measurement Reliable Analyzer

Ethylene Fractionator: Application Measurement: Ethylene 0-35% Stream Composition: Ethylene 20% Propylene 3% Propane 3% Ethane Balance

Ethylene Fractionator: Spectra % TRANSMISSION REFERENCE ETHYLENE MEASURE BLACK: 100% ETHANE RED: 25% ETHYLENE BLUE: 5% PROPYLENE WAVENUMBER (CM-1)

Ethylene Fractionator: Measurement Precision Very easy measurement for a filter photometer No interferences Expected precision ± 0.5% of full scale

Benefits Provide by Multiwave Ethane Fractionator Measurement: 0-30% Ethane Process Benefits Purification part of the process Ethane is removed from the ethylene Fast analysis important for the control of the fractionator tower Benefits Provide by Multiwave Analysis can be made at elevated pressure so sample can be returned to the process Provides continuous analysis Precise measurement Reliable Analyzer

Ethane Fractionator: Application Measurement: Ethane 0-30% Stream Composition: Ethane 10% Methane Trace Ethylene Balance

Ethane Fractionator: Spectra REFERENCE % TRASMISSION BLACK: 35% ETHANE RED: 100% ETHYLENE ETHANE MEASURE WAVENUMBER (CM-1)

Ethane Fractionator: Measurement Precision Very easy measurement for a filter photometer No interferences Expected precision ± 0.5% of full scale

Caustic Wash Tower Solution Application (Page 1) Measurement: 0-10% Sodium Hydroxide Process Benefits Sodium hydroxide used to remove carbon dioxide from the furnace outlet streams Scrubbing solution must have excess caustic at all times to prevent carbon dioxide from going to other parts of the process A fast and accurate sodium hydroxide measurement allows the wash tower to be operated at lower excess caustic when controlled with an analyzer with cycle times Operation cost savings by running at lower excess caustic

Caustic Wash Tower Solution Application (Page 2) Benefits Provided by Multiwave Precise and continuous measurement allows operation at lower excess cost Can compensate for interferences As carbon dioxide is removed from the process gas sodium carbonate builds up in the scrubbing solution Sodium carbonate will interfere with the caustic measurement if it is not compensated Isolated sample cell can be heated to help keep salts in solution Cell can be made from Hastelloy C to handle the corrosive stream Can provide timed flush for the SHS and cell with water by use of the zero benchmark functions Can withstand some bubbles from the non-dissolved light hydrocarbons that get through the degasser in the SHS No reagents to periodically replace Low maintenance Only one moving part

Caustic Wash Tower Solution Application Measurement: Sodium Hydroxide 0-10% Stream Composition: Sodium Hydroxide 5% Sodium Carbonate 1% Dissolved Hydrocarbons 0.1% Water Balance

Caustic Wash Tower Solution: Spectra BLACK: 100% WATER RED: 15% NaOH IN WATER BLUE: 5% Na2CO3 IN WATER SODIUM CARBONATE COMPENSATION % TRASMISSION REFERENCE SODIUM HYDROXIDE MEASURE WAVENUMBER (CM-1)

Caustic Wash Tower: Measurement Precision Sodium hydroxide measurement will have a significant interference from sodium carbonate Uncompensated 1.5% sodium carbonate will cause a 10% of full scale interference (1% sodium hydroxide) Using interference compensation the interference would be expected to be reduced to less than ± 1% of full scale (± 0.1% sodium hydroxide) Testing on installed analyzers has shown the interference to be less than ± 0.5% of full scale (± 0.05% sodium hydroxide)

Caustic Wash Tower Feed Measurement: 0-200 ppm Carbon Dioxide Stream Composition: 30-500 ppm Carbon Dioxide 200-500 ppm Carbon Monoxide 30-45% Hydrogen 5-9% Methane 30-40% Ethylene 15-35% Ethane 0.2-1% Propylene 0.1-0.5% Propane 0.1-0.5% 1,3 Butadiene

Caustic Wash Tower Overhead Measurement: 0-2000 ppm Carbon Monoxide Stream Composition: 2-4% Water Vapor 30-500 ppm Carbon Dioxide 200-500 ppm Carbon Monoxide 30-45% Hydrogen 5-9% Methane 30-40% Ethylene 15-35% Ethane 0.2-1% Propylene 0.1-0.5% Propane 0.1-0.5% 1,3 Butadiene

Furnace Decoke Measurement: 0- 15% Carbon Dioxide Process Benefits Pyrolysis reactors have a carbon build up from the cracking of the feedstock Carbon build up reduces the heat transfer which reduces the cracking efficiency Periodically need to remove the carbonaceous material Done by injecting steam in combination with heat converts the carbon to carbon dioxide Monitoring the decrease in CO2 concentration during decoke: Optimizes the operation Minimizes time and utilities spent on decoking

Furnace Decoke Benefits Provided by Multiwave Straight forward spectroscopic measurement Difficult to provide representative sample to analyzer Sample contains high particulate loading Sample contains free water droplets Water vapor concentrations vary between 35 to 90% Successful approach has been to use a reflux sampler to remove the particulate and free water prior to the Multiwave Located at process line Cools the sample to condense the water Condensed water then removes the particulate Particulate and condensed water go back into process line Heated sample cell and optics not damaged if water break through occurs from DRS upset Very reliable analyzer Low Maintenance

Dynamic Reflux Sampler (DRS2170)

DRS: Principle of Operation Primary sample conditioning occurs in a virtually in-situ fashion with the DRS approach. Condensable components are removed and are used to support particulate removal before they can present problems in the sample transport system’s downstream components and the analyzer. The DRS is essentially a fixed temperature distillation derived from the need to remove water as a condensable component from low boiling point gases. Cooling is provided by way of a vortex cooler controlled by an electronic temperature controller.

Furnace Decoke: Application Measurement: Carbon Dioxide 0-15% Stream Composition: Carbon Dioxide 10% Carbon Monoxide 5% Water 8% Oxygen 17% Nitrogen Balance

Furnace Decoke: Spectra % TRANSMISSION REFERENCE BLACK: 1% CARBON DIOXIDE RED: 5% CARBON MONOXIDE BLUE: 2% WATER VAPOR CARBON DIOXIDE MEASURE WAVENUMBER (CM-1)

Furnace Decoke: Measurement Precision Very easy measurement for a filter photometer No interferences Expected precision ± 0.5% of full scale

Conclusions PIR3502 Process Photometers can be used to provide several fast and continuous measurements in the manufacturing of ethylene and propylene Inlet to the Acetylene converters Mid-bed in the Acetylene converters Inlet to the MAPD converters Mid-bed in the MAPD converters Ethylene fractionator tower Ethane fractionator tower Caustic wash tower Furnace Decoke