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Application of Filter Photometers in the Production of Ethylene and Propylene

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Application of Filter Photometers in the Production of Ethylene and Propylene Analytical Products Sales Engineering Application of Filter Photometers in the Production of Ethylene and Propylene SC7-66-403 Gary D. Brewer APPLICATION OF FILTER PHOTOMETERS IN THE PRODUCTION OF ETHYLENE AND PROPYLENE Gary D. Brewer Product Manager, Photometers ABB Inc. 843 N. Jefferson St. Lewisburg, WV 24901 KEYWORDS Photometer, Infrared Spectroscopy, IR, Near Infrared Spectroscopy, NIR, Ultraviolet Spectroscopy, UV, Ethylene, Propylene ABSTRACT There have been several successful applications of process filter photometers in ethylene plants throughout the world. The process of manufacturing ethylene is extremely fast; therefore, the continuous measurements provided by filter photometers allow for a fast response to process changes for better control and process optimization. The capability of the current generation of filter photometers to use several analytical wavelengths to compensate for spectral interferences have allowed their use in measurements that previously could not be done by photometers. The high reliability and simplicity of filter photometers make them a valuable tool in the process control of an olefins plant. Applications in the IR and NIR spectral regions in both the vapor and liquid phases will be discussed to demonstrate their capabilities and benefits in this manufacturing process. Applications that will be discussed include the measurement of acetylene and ethane at the acetylene converters and the measurement of methyl acetylene and propadiene (MAPD) at the MAPD converters can be measured on a single infrared photometer. Applications at the caustic wash tower and the measurement of carbon dioxide at the furnace decoke will also be discussed. INTRODUCTION Ethylene is one of the highest volume chemicals produced in the world. It is used in the manufacturing of other chemicals such as: polyethylene, ethylene dichloride, vinyl chloride, polyvinyl chloride, ethylene glycol, ethylene oxide, etc… Approximately 50% of ethylene produced comes from the cracking of ethane/propane from natural gas and the rest from naphtha and gas oil. The cracking of ethane is an extremely fast process with any individual molecule being in the pyrolysis reactor from 100 milliseconds to a few seconds.(1) Therefore fast measurements are required to control and optimize the process. Filter photometers in the infrared, near infrared, visible, and ultraviolet spectral regions have been used in the hydrocarbon processing industries for many years and have proven to be very robust and easy to maintain. They are normally less expensive than spectrophotometers that are designed for operation in a process environment. A filter photometer uses narrow band pass optical filters for its wavelength selection and thus works with discrete parts of the spectrum.(2) Figure 1 shows a comparison of a full spectrum scan of butane and water along with the filters that would be used to make the measurements on a filter photometer. It demonstrates how photometers work with discrete parts instead of the full spectrum. Process filter photometers are available that measure only single components in liquid or vapor streams or that can measure multiple components in liquid or vapor streams. Some are designed to work with extracting and conditioning the sample and some are designed to utilize fiber optic probes for in-situ measurements. In most designs the reference signal goes through the same optical path as the measure signal and are ratioed. This provides several benefits that make them very stable and reliable in a process analysis: Minimizes drift from source, filter and detector aging Minimizes drift from cell window obstructions Minimizes effect of some particulates in a gas or liquid sample Minimizes effect of some bubbles in a liquid sample N WATER VAPOR SPECTRUM FILTER SSIO SPECTRA BUTANE SPECTRUM % TRANSMI WAVELENGTH (NM) FIGURE 1 –NEAR INFRARED SPECTRA OF BUTANE, WATER VAPOR AND FILTERS APPLICATIONS ACETYLENE CONVERTERS Measuring acetylene and sometimes ethane with a fast analysis in the inlet stream to the acetylene converters allows for better control of the converter operation. A typical acetylene converter application is as follows: Measure Components: Stream Composition: Acetylene 0-1.5% Acetylene 1% Ethane 0-30% Ethane 25% Methane 0.2% Propane 0.5% Propylene 0.3% Ethylene Balance Figure 2 shows that 3333 wavenumbers (cm-1) is a feasible wavelength for measuring acetylene, 2700 cm-1 is a suitable wavelength for measure ethane, and 2500 cm-1 is a feasible reference wavelength. The spectra also indicate that the acetylene measurement will have some interference from both ethane and ethylene. The ethane measurement will not have any significant interference. If ethane is not measured a 2700 cm-1 wavelength filter will be needed to compensate for this interference and a 2075 cm-1 wavelength can be used to compensate for the ethylene interference. Without compensation the acetylene measurement would have about an 8% of full-scale interference from ethane and a 1% of full-scale interference from ethylene. On filter photometers additional wavelengths that pick up the absorbance from an interfering compound and using linear regression to compensate for the interference normally reduces the interference by a factor between 10X to 15X and therefore the acetylene measurement precision would be approximately ±1% of full scale (±0.02% Acetylene). N SSIO % TRANSMI WAVELENGTH (NM) FIGURE 2 – INFRARED SPECTRA OF ACEYTLENE, ETHYLENE & ETHANE MAPD CONVERTERS Measuring methyl acetylene and propadiene with a fast analysis in the inlet stream to the MAPD converters allows for better control of the converter operation. A typical MAPD converter stream is: Measured Components: Stream Composition: Methyl Acetylene 0-2% Methyl Acetylene 1% Propadiene 0-2% Propadiene 1% Ethylene 0.4% Propane 6% Propylene Balance Figure 3 shows that 3333 cm-1 is a feasible wavelength to measure methyl acetylene, 1960 cm-1 is a suitable wavelength to measure propadiene and 2500 cm-1 is an acceptable wavelength to use as a reference. Figure 2 shows that propylene has a small absorbance at the reference wavelength and also at the propadiene measure wavelength and therefore this interference will need to be compensated for. The propylene spectrum in Figure 2 indicates that 1850 cm-1 will be a good wavelength to use for the propylene interference compensation. If the propylene interference were not compensated, then 100% propylene would create a 7% of full-scale error on the propadiene measurement and about a –0.7% of full-scale error on the methyl acetylene measurement. After compensation by using the propylene filter above and linear regression the interference will be reduced to less than ±0.7% of full scale (±0.014% propadiene) on the propadiene channel and to less than ±0.07% of full scale (±0.0014% methyl acetylene) on the methyl acetylene channel. There is benefit to the process control for a fast analysis of methyl acetylene and propadiene on the outlet of the MAPD converters. The required ranges of 0-200 ppm methyl acetylene and 0-200 ppm propadiene are too low for most filter photometers to provide a reliable analysis. N SSIO BLACK: 15% PROPADIENE % TRANSMI BLUE: 100% PROPYLENE RED: 7% METHYL ACETYLENE -1 WAVENUMBER (CM ) FIGURE 3 – INFRARED SPECTRA OF METHYL ACETYLENE, PROPADIENE, AND PROYLENE ETHYLENE FRACTIONATOR The ethylene fractionator (splitter) is where the ethylene is the purification part of the process where the desired product, ethylene, is removed from the ethane. The filter photometer provides a fast analysis time that allows for optimal control of a fractionator tower. A typical stream of an ethylene fractionator tower is: Measure Components: Stream Composition: Ethylene 0-35% Ethylene 20% Propylene 3% Propane 3% Ethane Balance Figure 4 shows that 1905 cm-1 is feasible wavelength to measure ethylene and 1961 cm-1 is suitable for a reference wavelength. The spectra show that the other stream components do not absorb at these wavelengths and therefore interference compensation will not be needed. N SSIO % TRANSMI BLACK: 100% ETHANE RED: 25% ETHYLENE BLUE: 5% PROPYLENE WAVENUMBER (CM-1) FIGURE 4 – INFRARED SPECTRA OF ETHANE, ETHYLENE, PROPANE, AND PROPYLENE ETHANE FRACTIONATOR In the ethane fractionator tower the ethane is removed from the process stream and is returned to a pyrolysis furnace for conversion into ethylene. The fast measurement of ethane allows for optimum control of the fractionator. A typical stream at the ethane fractionator is: Measured Components: Stream Composition: Ethane 0-30% Ethane 10% Methane Trace Ethylene Balance Figure 5 shows that 2775 cm-1 is a suitable wavelength to measure the ethane and 2500 cm-1 will work well as a reference wavelength. Since this is essentially a binary stream there are not any spectral interferences to deal with and is a straightforward measurement. N SSIO % TRANSMI BLACK: 35% ETHANE RED: 100% ETHYLENE WAVENUMBER (CM-1) FIGURE 5 – INFRARED SPECTRA OF ETHANE AND ETHYLENE CAUSTIC WASH TOWER SOLUTION ANALYSIS The caustic wash tower uses a sodium hydroxide solution to remove the carbon dioxide from the hydrocarbon stream out of the furnaces. The solution must contain excess caustic at all times to prevent the carbon dioxide in the sample from proceeding to other parts of process. A fast and accurate analysis of the sodium hydroxide content of the solution allows the wash tower to be operated at lower excess caustic concentrations and thus a reduction in operation cost and maintenance. Measure Components: Stream
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