Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
  • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
  • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
  • G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
  • C10G9/18—Apparatus
  • C10G9/20—Tube furnaces
  • C10G9/206—Tube furnaces controlling or regulating the tube furnaces
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F27—FURNACES; KILNS; OVENS; RETORTS
  • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
  • F27D19/00—Arrangements of controlling devices
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F27—FURNACES; KILNS; OVENS; RETORTS
  • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
  • F27D21/00—Arrangement of monitoring devices; Arrangement of safety devices
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F27—FURNACES; KILNS; OVENS; RETORTS
  • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
  • F27D99/00—Subject matter not provided for in other groups of this subclass
  • F27D99/0001—Heating elements or systems
  • F27D99/0033—Heating elements or systems using burners

Definitions

• the instant invention is in the field of methods for the control of excess air in cracker furnace burners.
• the production of olefins by thermally cracking a hydrocarbon material, such as petroleum naphtha, is one of the most important processes in the chemical process industry.
• ABB Corporation reportedly constructed a cracking plant in Port Arthur Texas having a capacity to produce over a million tons of ethylene and propylene per year.
• the cracking process is conducted in a "cracker".
• a cracker usually comprises an enclosure containing tubes and a burner. Heat generated by burning a fuel heats the hydrocarbon material flowing in the tubes so that the hydrocarbon material is thermally cracked to produce, among other things, ethylene and propylene.
• a cracker is comprised of a radiant section and a convection section.
• the burner is positioned in the radiant section so that the tubes positioned in the radiant section are heated primarily by radiant heat emitted from the walls adjacent to the burner.
• the combustion gas from the radiant section is then directed to the convection section where heat from the combustion gas is recoverd to heat tubes positioned in the convection section.
• An oxygen sensor such as a zirconium oxide oxygen sensor, is ordinarily positioned in the cracker between the radiant section and the convection section to facilitate of control the air/fuel ratio of the burner.
• the overall efficiency of the cracker is primarily a function of the amount of excess air present in the firebox and the temperature of the exhaust gas from the cracker.
• the oxygen sensor of a conventional cracker is a "point measurement device", i.e., it measures oxygen at the position where the sensor is located. Such a measurement is not representative of the oxygen concentration in the cracker as a whole.
• Section H4.3 Sensors for Advanced Combustion Systems, Global climate & Energy Project, Stanford University, 2004, by Hanson et al., summarized the development of the tunable near-infrared diode laser and absorption spectroscopy approach for the determination of oxygen, carbon monoxide and oxides of nitrogen in the combustion gas from a coal fired utility boiler, a waste incinerator as well as from jet engines.
• the instant invention is a solution, at least in part, to the above-stated problem of the need for a more reliable and representative analysis of combustion gas from a thermal cracker furnace.
• the instant invention is the application of the tunable near-infrared diode laser and absorption spectroscopy approach for the determination of, for example, oxygen, carbon monoxide and oxides of nitrogen in the combustion gas from a thermal cracker furnace.
• the instant invention is a method for control of the air/fuel ratio of the burners of a thermal cracker comprising the steps of: (a) directing a wavelength modulated beam of near infrared light from a tunable diode laser through combustion gas from the burners to a near infrared light detector to generate a detector signal; (b) analyzing the detector signal for spectroscopic absorption at wavelengths characteristic for an analyte selected from the group consisting of oxygen, carbon monoxide and nitrogen oxide to determine the concentration of the analyte in the combustion gas; and (c) adjusting the air/fuel ratio of the burners (i.e. excess air in the furnace) in response to the concentration of the analyte of step (b).
• Fig. 1 is a schematic side view of a typical thermal cracking furnace 10 for producing olefins
• Fig. 2 is a schematic rear view of the furnace 10 of Fig. 1 schematic rear view of of the furnace 10 of Fig. 1;
• Fig. 3 is a detailed view of a preferred tunable diode laser spectroscopy apparatus for use in the instant invention
• Fig. 4 is a spectra collected using the system of the instant invention showing fine structure absorbance in the wavelength region characteristic for oxygen absorbance of near infrared light generated by a tunable diode laser.
• FIG. 1 shows a schematic side view of a typical thermal cracking furnace 10 for producing olefins including an enclosure 11 having an air inlet 12 and an exhaust outlet 13.
• An air inlet fan 14 provides forced draft through a burner 15.
• An exhaust fan 16 provides an induced draft from the furnace 10.
• the interior of the furnace 10 is comprised of three primary portions: the firebox portion 17; the bridge wall portion 18; and the convection portion 19. Combustion gases from the burner 15 are first directed into the firebox portion 17 of the furnace 10, then through the bridge wall portion 18, then through the convection portion 19 and then out of the exhaust outlet 13.
• Feed stream 20 is conducted through tubing 21 to preheat the feed.
• FIG. 1 showing the exterior walls of the firebox portion 17, the bridge wall portion 18 and the convection portion 19.
• a tunable diode laser system 26 is mounted at the bridge wall portion 18 of the furnace 10 so that light from the tunable diode laser of the tunable diode laser system 26 can be shown through the combustion gas flowing through the bridge wall portion 18 to a light detector system 27.
• FIG. 3 therein is shown a more detailed view of the diode laser system 26 and light detector system 27 shown in Fig. 2.
• the system shown in Fig. 3 includes a laser module 37 containing the tunable diode laser.
• a control unit 31 contains the central processing unit programmed for signal processing (to be discussed below in greater detail) as well as the temperature and current control for the tunable diode laser and a user interface and display.
• the control unit may be contained in a separate unit as shown or may be included in one of the other components of the system, e.g. contron unit contained in the transmitter.
• Alignment plate 29 and adjustment rods 30 allow alignment of the laser beam 41.
• the laser beam passes through a window or windows (e.g.
• the windows such as dual sapphire windows 28 may be mounted in a four inch pipe flange 40.
• the space between the windows 28 is purged with 25 Liters per minute of nitrogen at ten pounds per square inch gauge pressure.
• the flange 40 is mounted through the wall of the furnace.
• the laser beam 41 is passed through a window or windows 33 (they maybe dual sapphire or other suitable material such as fused silica) to a near infrared light detector 38.
• the windows 33 may be mounted in a four inch pipe flange 39. The space between the windows 33 is purged with 25 Liters per minute of nitrogen at ten pounds per square inch gauge pressure.
• the flange 39 is mounted through the wall of the furnace. Alignment plate 34 and adjustment rods 35 allow alignment of the detector optics with the laser beam 41.
• Detector electronics 36 are in electrical communication with the control unit 31 by way of cable 37.
• the control unit 31 is also in electrical communication with the process control system 32 for controlling the furnace 10 (by way of electrical cables 38).
• the optical path length of the laser beam 41 is about sixty feet.
• the system shown in Fig. 3 is commercially available from Analytical Specialties of Houston, Texas.
• the system shown in Fig. 3 operates by measuring the amount of laser light that is absorbed (lost) as it travels through the combustion gas. Oxygen, carbon monoxide and nitrogen oxide each have spectral absorption that exhibits unique fine structure. The individual features of the spectra are seen at the high resolution of the tunable diode laser 37.
• the tunable diode laser 37 is modulated (that is scanned or tuned from one wavelength to another) by controlling its input current from the control unit 31.
• Fig. 4 therein is shown a spectrum in the region where oxygen absorbs the modulated beam of near infrared light from the tunable diode laser.
• the absorbance shown in Fig. 4 is proportional to the concentration of oxygen in the combustion gas.
• a carbon monoxide absorbance line near 2333 nanometers is used to determine low parts per million concentration of carbon monoxide.
• a carbon monoxide absorbance line near 1570 is used to determine higher concentrations of carbon monoxide.
• a nitrogen oxide absorbance line near 2740 nanometers is used to determine low to sub parts per million concentration of nitrogen oxide.
• a nitrogen oxide absorbance line near 1800 is used to determine higher concentrations of nitrogen oxide.
• the air/fuel ratio of the burners (excess air in furnace) 15 (which is controlled by the process controller 32 of Fig. 3) can be controlled to optimize the oxygen, carbon monoxide and nitrogen oxide concentrations in the combustion gas in response to the tunable diode laser spectroscopic analysis of oxygen, carbon monoxide and nitrogen oxide outlined above.

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• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Optics & Photonics (AREA)
• Analytical Chemistry (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Thermal Sciences (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• General Physics & Mathematics (AREA)
• Immunology (AREA)
• Pathology (AREA)
• Investigating Or Analysing Materials By Optical Means (AREA)
• Regulation And Control Of Combustion (AREA)

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• 2006
  • 2006-05-09 EP EP06770146A patent/EP1889035A2/de not_active Ceased
  • 2006-05-09 WO PCT/US2006/017977 patent/WO2006124422A2/en not_active Ceased
  • 2006-05-09 JP JP2008512350A patent/JP5142986B2/ja active Active
  • 2006-05-09 CN CN2006800165366A patent/CN101175988B/zh active Active
• 2007
  • 2007-11-02 US US12/735,360 patent/US20110062056A1/en not_active Abandoned

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