WO1994027135A1 - Sampling and analysis system and method - Google Patents

Sampling and analysis system and method Download PDF

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Publication number
WO1994027135A1
WO1994027135A1 PCT/US1993/004712 US9304712W WO9427135A1 WO 1994027135 A1 WO1994027135 A1 WO 1994027135A1 US 9304712 W US9304712 W US 9304712W WO 9427135 A1 WO9427135 A1 WO 9427135A1
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WIPO (PCT)
Prior art keywords
sample
stream
analysis
probe
upstream
Prior art date
Application number
PCT/US1993/004712
Other languages
French (fr)
Inventor
Steven M. Maggard
James H. Higginbotham
Joseph H. Walker
Original Assignee
Ashland Oil, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ashland Oil, Inc. filed Critical Ashland Oil, Inc.
Priority to PCT/US1993/004712 priority Critical patent/WO1994027135A1/en
Priority to AU43809/93A priority patent/AU4380993A/en
Publication of WO1994027135A1 publication Critical patent/WO1994027135A1/en
Priority to KR1019940704679A priority patent/KR950702270A/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/10—Devices for withdrawing samples in the liquid or fluent state
    • G01N1/20—Devices for withdrawing samples in the liquid or fluent state for flowing or falling materials
    • G01N1/2035—Devices for withdrawing samples in the liquid or fluent state for flowing or falling materials by deviating part of a fluid stream, e.g. by drawing-off or tapping
    • 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
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
    • 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
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2829—Mixtures of fuels
    • 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
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/03—Cuvette constructions
    • G01N21/05—Flow-through cuvettes
    • G01N2021/054—Bubble trap; Debubbling

Definitions

  • the present invention relates to the field of on-stream analysis, particularly to sampling systems designed to provide stable samples; e.g. of gasoline to an analyzer; e.g., a near-infrared analyzer, commonly class 250, subclass 343 or 341.
  • an analyzer e.g., a near-infrared analyzer, commonly class 250, subclass 343 or 341.
  • U.S. 4,575,488 and U. S. 3,961,898 each use an on-line analysis instrument with a debubbler upstream to separate bubbles deliberatel added between sequential samples.
  • An NIR sampling system designed to provide a stable gasoline sample stream to an NIR analyzer.
  • Preferred design elements include a temperature-controlled stream moving through an inverted coalescer whereby gas bubbles are removed through an overhead stream. Elevated pressure is used to reduce degassing as well.
  • One or more prototype fuels can be injected to calibrate the instrument and prove accuracy before and/or after analysis of a sample.
  • the present invention is useful for the preferred NIR fiberoptic probes and other NIR probes, but can also be used for salt plates, quartz curettes, and heavy metal fluorides; e.g., zirconium fluorides and for other methods of analysis; e.g., colorimetry and infrared.
  • Figure 1 is a schematic diagram of a preferred sample conditioning system according to the present invention.
  • Figure 2 is a typical gasoline blending system showing various components and particularly showing line 30 leading to analyzer 25 which line 30 is also shown in Figure 1.
  • Figure 3 is an elevation view of the rack and closed cabinet showing the components of the invention in place and also shown in side view in Figure 3A.
  • Figure 4 is a side view of the rack and open cabinet showing the interior elements in place.
  • Figure 5 is a detail of the inner cabinet of Figure 4.
  • Figure 6 is a detail of the NIR sample assembly and connection to the fiberoptic cable.
  • Figure 7 is a correlation curve of real octane (ASTM/2699/2700) versus octane measured by NIR octane, showing lower line correlating only a single point and an upper line correlating by two points the entire range.)
  • the apparatus of the present invention consists of the following major components:
  • Sample supply means 20 comprising an adduction probe, a control valve and relatively small diameter (for minimum hold-up) tubing (preferably stainless steel) for withdrawing the sample from the stream to be analyzed.
  • Optional purge means 50 comprising an inward gas (preferably nitrogen) supply and valves and pressure gauges for permitting the purging of the entire system to clear liquids from the system for maintenance purposes.
  • an inward gas preferably nitrogen
  • Optional sample filter means 70 for removing particulates from the sample said means preferably comprising a self-cleaning, continuous filter means, such as "Swirlklean", Model No. II, manufactured by Collins Products Company of Livingston, Texas, together with suitable pressure gauges, flow indicators, valving and tubing.
  • a self-cleaning, continuous filter means such as "Swirlklean", Model No. II, manufactured by Collins Products Company of Livingston, Texas, together with suitable pressure gauges, flow indicators, valving and tubing.
  • Sample temperature controller means 90 comprising an inlet temperature indicator, a temperature controller, such as Filtrine, Model No. PC-50AXP-1LH, manufactured by Filtrine Manufacturing Company of Harrisville, New Hampshire for controlling the temperature of the sample to the preferred temperature range preferably in the room-temperature range, most preferably approximately 18°-25°C (65°-75°F) and additionally comprising suitable drain valves, outgoing temperature indicator, pressure indicator, and the like.
  • a temperature controller such as Filtrine, Model No. PC-50AXP-1LH, manufactured by Filtrine Manufacturing Company of Harrisville, New Hampshire for controlling the temperature of the sample to the preferred temperature range preferably in the room-temperature range, most preferably approximately 18°-25°C (65°-75°F) and additionally comprising suitable drain valves, outgoing temperature indicator, pressure indicator, and the like.
  • Degassing means 110 comprising a coalesscer, such as the Balston Model No. 45S6, manufactured by Balston Inc. of Lexington, Massachusetts and suitable flow indicators for ratioing the flow through the analysis probe means 130 or back to the sample return means 150.
  • a coalesscer such as the Balston Model No. 45S6, manufactured by Balston Inc. of Lexington, Massachusetts and suitable flow indicators for ratioing the flow through the analysis probe means 130 or back to the sample return means 150.
  • Analysis probe means 130 manufactured by NIRSystems Division of Perstorp Analytical, Inc., Model OL-5050 of Silver Springs, Maryland, comprising a chamber for introducing an analytical probe, preferably a near-infrared fiberoptic probe, pressure indicating means, back pressure regulator valve, and the like.
  • Sample return means 150 comprising means for collecting both streams from the degasser means and from the degasser means and from the sample filter into a header, which in turn feeds to the strea from which the sample was originally taken by sample supply means 20, but at a point having lower pressure.
  • the probe sees a clean, degassed sample of controlled temperature and pressure free from particulate matter.
  • Use of small diameter tubing preferably less than one inch, more preferably less than one-half inch, and most preferably three-eighths and one-quarter inch, insures timely delivery of the sample with minimum hold up because of fast flow through the entire sample conditioning system.
  • Figure 2 shows the location of the sample conditioning system.
  • the sample conditioning system is installed along with the "at-line" or "on-line” analyzer 25, also described in U. S. Patent 4,963,745, to S. M. Maggard and assigned to the assignee of the present invention.
  • sample supply means 20 includes eductio probe 29 which removes a sample from the approximate midpoint of the main process line and delivers it through sample block valve 34 into line 30, also shown in Figure 2.
  • Line 30 continues through purge supply means 50 which comprises a nitrogen source, a nitrogen contro valve 54, a sample block valve 56, pressure indicator 58, and enters sample filter means 70 which comprises a "Swirlklean" filter 72 (described above) having a capacity of about one gallon/minute. After this sample filter 72, the sample flows through a bypass filter 72 to remove solids from liquid using a small pore membrane on the filtrate side, along with a high speed bypass to provide continuous self-cleaning.
  • sample flows past pressure indicator 74 and continues on to sample temperature control means 90 with particulates being removed at the bottom via line 76 which flows through flow indicator 78, flow control valve 80 and process block valve 82.
  • sample temperature controller 96 which is a prepackaged sample heater/chiller utilizing a high speed single pass flow design for heating/cooling liquids, Model No. PC50AXP-1LH, manufactured by Filtrine Manufacturing Co., and having a capacity of approximately 5 liters/minute, and set for a set point of approximately 24° C (75° F), and exits through block valve 98, pressure indicator 102, temperature indicator 104, which is provided with suitable drain valves for maintenance.
  • the stream flowing from sample temperature controller means 90 into degasser means 110 continues into the degasser 112, a stainless steel filter with replaceable filter elements for removing high solids content from liquids, and exits as a bypass stream 114 which contains most or all of the bubbles entrained into the stream entering the degasser and which flows through flow indicator 118, needle flow control valve 120, block valve 122 into sample return 150.
  • all flow meters are preferably armored, rather than glass or plastic. Particularly preferred is a metallic rotameter with a magnetic follower for flow indication.
  • the other stream from degasser 112 is the debubbled stream 116 which flows through pressure indicator 124, flow control valve 126, flow indicator 128, and through analytical probe chamber 131.
  • the NIR probe chamber 131 manufactured by
  • NIRSystems is a 3"x 3"x 2" block of 304 series stainless steel with 1/2" 316 series stainless steel Swagloc tube fittings for sample inlet and outlet, and a 3/4" 316 series stainless steel Swagloc tube fitting to attach the fiberoptic holder.
  • the analytical probe chamber 131 contains a conventional fiberoptic or other probe for near-infrared or other analytical instrument and permits clean, temperature controlled, particle fee, debubbled flow past that probe for accurate consistent measurement of the analytical properties being measured.
  • the strea continues through pressure indicator 132,back pressure regulator valve 134, block valve 136, and into sample return header 138 which has pressure indicator 139 and block valve 142 (located directly on the main process line) and flows back into the process line at a point somewhat downstream from sample supply means 20 and at a lower pressure than at the sample supply means.
  • the protofuel injection system 85 comprises automatic valve 86 and protofuel sources A and B, which can be alternatively injected into the sample feed line in place of the sample taken from the sample supply 32.
  • Protofuel is a suitable fuel of carefully determined octane (analyzed by ASTM 2699 and/or 2700, preferably by a number of different labs so that the average can be used).
  • the calibration of the system can be checked and standardized for exact accuracy. Stability can also be checked by repeated injection of protofuels.
  • two separate protofuels are made available so that protofuel A can be injected and then followed sequentially by injection of protofuel B. This provides two points of different octane as shown in Figure 7.
  • the lower correlation line shows a correlation only at a single point as determined by only a single prototype
  • the upper correlation line shows a correlation at all points over the entire range as determined by two or more prototype fuels being injected, a substantial improvement over the one-point correlation line because it fixes the correlation curve so that it correlates with values obtained by the ASTM standard knock-engine method, over the entire octane range.
  • the correlation curve need not be a straight line, though a straight line has been found to be an excellent approximation, based on extensive commercial use.
  • FIG. 3 the external appearance of a preferred commercial embodiment of the invention for Division II, Class 2, Area Specification For Flammable Hydrocarbon Service, depicts stainless steel cabinet 300 displaying internal temperature on thermometer 302 with temperature being controlled by air conditioner/heater 304 and conduit connections 306 being provided for RS232 connection (direct or via modem) to a personal computer (PC - not shown) displaying the octane and other variables measured by NIR. External power enters through conduit 308 to the interior of the box. (This system ca readily be upgraded to a Division I, Class 1 rating by providing fail-safe automatic shutdown in case of failure of air conditioning, cabinet purging or other critical components.)
  • Z-Purge pressure regulators 310 and 312 regulate the purge air pressure and flow into the cabinet as required by National Electrical
  • FIG. 4 shows cabinet 300 with its door open revealing inner NIR instrument cabinet 400 shown in further detail in Figure 5, lamp 402 which provides illumination through fiberoptic reference cable 404 and fiberoptic sample cable 406.
  • Auxiliary power 408 protects the system electrically and provides and internal voltage regulator plus uninterruptable power supply.
  • Auxiliary power 408 provides a steady 110 volts to transformer 410 which in turn provides 200 volt power supply to the NIR instrument and to auxiliary 12 volt power supply for the lamp 402.
  • the lamp enclosure 402 also includes a solenoid-operated shutter which alternates illumination through the reference fiberoptic cable 404 and then sequentially, through the sample fiberoptic cable 406.
  • Cables 406 and 404 are held respectively by machined metal block alignment holders 428 and 430 which direct their beams fixedly into monochromator which disperses the light into different orders of the spectrum and into different wavelengths.
  • the monochromator 432 receives, first, the sample fiberoptic light beam 434 and then the reference fiberoptic light beam 436.
  • the sample fiberoptic light beam is conducted by a cable to the sample, and thence reflected back through cable 406 before entering monochromator 432.
  • This instrument arrangement is called "Post Dispersive Transflectance Measurement". (The sampling system could, of course, operate with other types of NIR, infrared, colorimetric or other instrument schemes.)
  • the order sorter filter 438 also contains a new set of wavelength standards and functions to determine the order in which the wavelengths from the diffraction envelope focus on the detector 440 which outputs an electrical signal to transmission amplifier 442 which passes through various electrical circuits to the housed in 444 and 446, and thence to motherboard 450 which outputs a signal to the PC and/or the process control computer (not shown).
  • This signal preferably meets the standards of RS232 for compatibility with other equipment.
  • Probe chamber 130, Model DL-6500 or OL-5000, and the connected NIR Analyzer are manufactured by NIRSystems, of Silver Springs, Maryland.
  • the PAIRS NIR analysis system by Perkin-Elmer is expected to also be suitable when available in 1992.
  • compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variations of these compositions, methods, or embodiments are readily apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein.
  • the order of debubbler and temperature control is not critical, though debubbling is preferably downstream of temperature controller.

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Abstract

A NIR sampling system designed to provide a stable gasoline sample stream to a NIR analyzer. Preferred design elements include a temperature-controlled stream moving through an inverted coalescer whereby gas bubbles are removed through an overhead stream. Elevated pressure is used to reduce degassing as well. One or more prototype fuels can be injected to calibrate the instrument and prove accuracy before and/or after analysis of a sample.

Description

SAMPLING AND ANALYSIS SYSTEM AND METHOD
Cross Reference to Related Application
U.S. Patent Application Serial No. 506,391, filed April 9, 1990, (Attorney Docket No. 6362AUS) relates to the general field of the present invention.
Background of the Invention
1. Field of the Invention:
The present invention relates to the field of on-stream analysis, particularly to sampling systems designed to provide stable samples; e.g. of gasoline to an analyzer; e.g., a near-infrared analyzer, commonly class 250, subclass 343 or 341.
2. Description of the Prior Art
U.S. 4,575,488 and U. S. 3,961,898 each use an on-line analysis instrument with a debubbler upstream to separate bubbles deliberatel added between sequential samples.
U.S. 4,963,745 to Maggard et al. (Docket No. 6353AUS) determines research, motor, and pump octane by infrared absorbance.
Summary of the Invention
1. General Statement of the Invention:
An NIR sampling system designed to provide a stable gasoline sample stream to an NIR analyzer. Preferred design elements include a temperature-controlled stream moving through an inverted coalescer whereby gas bubbles are removed through an overhead stream. Elevated pressure is used to reduce degassing as well. One or more prototype fuels can be injected to calibrate the instrument and prove accuracy before and/or after analysis of a sample.
2. Utility of the Invention
The present invention is useful for the preferred NIR fiberoptic probes and other NIR probes, but can also be used for salt plates, quartz curettes, and heavy metal fluorides; e.g., zirconium fluorides and for other methods of analysis; e.g., colorimetry and infrared.
Brief Description of the Drawings
Figure 1 is a schematic diagram of a preferred sample conditioning system according to the present invention.
Figure 2 is a typical gasoline blending system showing various components and particularly showing line 30 leading to analyzer 25 which line 30 is also shown in Figure 1.
Figure 3 is an elevation view of the rack and closed cabinet showing the components of the invention in place and also shown in side view in Figure 3A.
Figure 4 is a side view of the rack and open cabinet showing the interior elements in place. Figure 5 is a detail of the inner cabinet of Figure 4.
Figure 6 is a detail of the NIR sample assembly and connection to the fiberoptic cable.
Figure 7 is a correlation curve of real octane (ASTM/2699/2700) versus octane measured by NIR octane, showing lower line correlating only a single point and an upper line correlating by two points the entire range.)
Description of the Preferred Embodiments
In preferred embodiments, the apparatus of the present invention consists of the following major components:
Sample supply means 20 comprising an adduction probe, a control valve and relatively small diameter (for minimum hold-up) tubing (preferably stainless steel) for withdrawing the sample from the stream to be analyzed.
Optional purge means 50 comprising an inward gas (preferably nitrogen) supply and valves and pressure gauges for permitting the purging of the entire system to clear liquids from the system for maintenance purposes.
Optional sample filter means 70 for removing particulates from the sample, said means preferably comprising a self-cleaning, continuous filter means, such as "Swirlklean", Model No. II, manufactured by Collins Products Company of Livingston, Texas, together with suitable pressure gauges, flow indicators, valving and tubing.
Sample temperature controller means 90 comprising an inlet temperature indicator, a temperature controller, such as Filtrine, Model No. PC-50AXP-1LH, manufactured by Filtrine Manufacturing Company of Harrisville, New Hampshire for controlling the temperature of the sample to the preferred temperature range preferably in the room-temperature range, most preferably approximately 18°-25°C (65°-75°F) and additionally comprising suitable drain valves, outgoing temperature indicator, pressure indicator, and the like.
Degassing means 110 comprising a coalesscer, such as the Balston Model No. 45S6, manufactured by Balston Inc. of Lexington, Massachusetts and suitable flow indicators for ratioing the flow through the analysis probe means 130 or back to the sample return means 150.
Analysis probe means 130, manufactured by NIRSystems Division of Perstorp Analytical, Inc., Model OL-5050 of Silver Springs, Maryland, comprising a chamber for introducing an analytical probe, preferably a near-infrared fiberoptic probe, pressure indicating means, back pressure regulator valve, and the like. Sample return means 150 comprising means for collecting both streams from the degasser means and from the degasser means and from the sample filter into a header, which in turn feeds to the strea from which the sample was originally taken by sample supply means 20, but at a point having lower pressure.
According to the invention, the probe sees a clean, degassed sample of controlled temperature and pressure free from particulate matter. Use of small diameter tubing, preferably less than one inch, more preferably less than one-half inch, and most preferably three-eighths and one-quarter inch, insures timely delivery of the sample with minimum hold up because of fast flow through the entire sample conditioning system.
Figure 2 shows the location of the sample conditioning system.
The sample conditioning system is installed along with the "at-line" or "on-line" analyzer 25, also described in U. S. Patent 4,963,745, to S. M. Maggard and assigned to the assignee of the present invention.
EXAMPLE
Referring to Figure 1, sample supply means 20 includes eductio probe 29 which removes a sample from the approximate midpoint of the main process line and delivers it through sample block valve 34 into line 30, also shown in Figure 2. Line 30 continues through purge supply means 50 which comprises a nitrogen source, a nitrogen contro valve 54, a sample block valve 56, pressure indicator 58, and enters sample filter means 70 which comprises a "Swirlklean" filter 72 (described above) having a capacity of about one gallon/minute. After this sample filter 72, the sample flows through a bypass filter 72 to remove solids from liquid using a small pore membrane on the filtrate side, along with a high speed bypass to provide continuous self-cleaning. After this filter 72 having removed particles larger than one micron, preferably 0.45 micron, the sample flows past pressure indicator 74 and continues on to sample temperature control means 90 with particulates being removed at the bottom via line 76 which flows through flow indicator 78, flow control valve 80 and process block valve 82.
Continuing with the filtered stream 84 flowing into the sample temperature controller means 90, the stream flows past block valve 92, temperature indicator 94 into sample temperature controller 96 which is a prepackaged sample heater/chiller utilizing a high speed single pass flow design for heating/cooling liquids, Model No. PC50AXP-1LH, manufactured by Filtrine Manufacturing Co., and having a capacity of approximately 5 liters/minute, and set for a set point of approximately 24° C (75° F), and exits through block valve 98, pressure indicator 102, temperature indicator 104, which is provided with suitable drain valves for maintenance.
The stream flowing from sample temperature controller means 90 into degasser means 110 continues into the degasser 112, a stainless steel filter with replaceable filter elements for removing high solids content from liquids, and exits as a bypass stream 114 which contains most or all of the bubbles entrained into the stream entering the degasser and which flows through flow indicator 118, needle flow control valve 120, block valve 122 into sample return 150.
Because of flammability and explosion hazard in gasoline service, all flow meters are preferably armored, rather than glass or plastic. Particularly preferred is a metallic rotameter with a magnetic follower for flow indication. The other stream from degasser 112 is the debubbled stream 116 which flows through pressure indicator 124, flow control valve 126, flow indicator 128, and through analytical probe chamber 131. The NIR probe chamber 131, manufactured by
NIRSystems is a 3"x 3"x 2" block of 304 series stainless steel with 1/2" 316 series stainless steel Swagloc tube fittings for sample inlet and outlet, and a 3/4" 316 series stainless steel Swagloc tube fitting to attach the fiberoptic holder. The analytical probe chamber 131 contains a conventional fiberoptic or other probe for near-infrared or other analytical instrument and permits clean, temperature controlled, particle fee, debubbled flow past that probe for accurate consistent measurement of the analytical properties being measured. The strea continues through pressure indicator 132,back pressure regulator valve 134, block valve 136, and into sample return header 138 which has pressure indicator 139 and block valve 142 (located directly on the main process line) and flows back into the process line at a point somewhat downstream from sample supply means 20 and at a lower pressure than at the sample supply means.
The protofuel injection system 85 comprises automatic valve 86 and protofuel sources A and B, which can be alternatively injected into the sample feed line in place of the sample taken from the sample supply 32. Protofuel is a suitable fuel of carefully determined octane (analyzed by ASTM 2699 and/or 2700, preferably by a number of different labs so that the average can be used). By injecting protofuel into the system periodically, the calibration of the system can be checked and standardized for exact accuracy. Stability can also be checked by repeated injection of protofuels. Preferably, two separate protofuels are made available so that protofuel A can be injected and then followed sequentially by injection of protofuel B. This provides two points of different octane as shown in Figure 7.
Note that the lower correlation line shows a correlation only at a single point as determined by only a single prototype, whereas the upper correlation line shows a correlation at all points over the entire range as determined by two or more prototype fuels being injected, a substantial improvement over the one-point correlation line because it fixes the correlation curve so that it correlates with values obtained by the ASTM standard knock-engine method, over the entire octane range. Where three or more prototype fuels are analyzed, the correlation curve need not be a straight line, though a straight line has been found to be an excellent approximation, based on extensive commercial use.
Referring to Figure 3, the external appearance of a preferred commercial embodiment of the invention for Division II, Class 2, Area Specification For Flammable Hydrocarbon Service, depicts stainless steel cabinet 300 displaying internal temperature on thermometer 302 with temperature being controlled by air conditioner/heater 304 and conduit connections 306 being provided for RS232 connection (direct or via modem) to a personal computer (PC - not shown) displaying the octane and other variables measured by NIR. External power enters through conduit 308 to the interior of the box. (This system ca readily be upgraded to a Division I, Class 1 rating by providing fail-safe automatic shutdown in case of failure of air conditioning, cabinet purging or other critical components.)
Z-Purge pressure regulators 310 and 312 regulate the purge air pressure and flow into the cabinet as required by National Electrical
Code, Class I, Division 2, for the electronics box 400 and for the lamp source box 402, respectively. Bypass flow meter 118 and 128 measure the flow as shown schematically in Figure 1. Degasser 112 eliminates bubbles as also shown schematically in Figure 1. Sample temperature controller 90 houses the components shown under that number in
Figure 1.
Figure 4 shows cabinet 300 with its door open revealing inner NIR instrument cabinet 400 shown in further detail in Figure 5, lamp 402 which provides illumination through fiberoptic reference cable 404 and fiberoptic sample cable 406. Auxiliary power 408 protects the system electrically and provides and internal voltage regulator plus uninterruptable power supply. Auxiliary power 408 provides a steady 110 volts to transformer 410 which in turn provides 200 volt power supply to the NIR instrument and to auxiliary 12 volt power supply for the lamp 402. The lamp enclosure 402 also includes a solenoid-operated shutter which alternates illumination through the reference fiberoptic cable 404 and then sequentially, through the sample fiberoptic cable 406.
Cables 406 and 404 are held respectively by machined metal block alignment holders 428 and 430 which direct their beams fixedly into monochromator which disperses the light into different orders of the spectrum and into different wavelengths. Thus the monochromator 432 receives, first, the sample fiberoptic light beam 434 and then the reference fiberoptic light beam 436. The sample fiberoptic light beam is conducted by a cable to the sample, and thence reflected back through cable 406 before entering monochromator 432. This instrument arrangement is called "Post Dispersive Transflectance Measurement". (The sampling system could, of course, operate with other types of NIR, infrared, colorimetric or other instrument schemes.)
The order sorter filter 438 also contains a new set of wavelength standards and functions to determine the order in which the wavelengths from the diffraction envelope focus on the detector 440 which outputs an electrical signal to transmission amplifier 442 which passes through various electrical circuits to the housed in 444 and 446, and thence to motherboard 450 which outputs a signal to the PC and/or the process control computer (not shown). This signal preferably meets the standards of RS232 for compatibility with other equipment. Probe chamber 130, Model DL-6500 or OL-5000, and the connected NIR Analyzer are manufactured by NIRSystems, of Silver Springs, Maryland. The PAIRS NIR analysis system by Perkin-Elmer is expected to also be suitable when available in 1992.
Modifications Specific compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variations of these compositions, methods, or embodiments are readily apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein. For example, the order of debubbler and temperature control is not critical, though debubbling is preferably downstream of temperature controller. Also, the techniques of copending USSN 698,411 (6379AUS) can be used in conjunction with the protofuel injection by utilizing as at least one of the protofuels a mixture of known amounts of pure hydrocarbon components having octane values calculated from results obtained from a calibrated NIR instrument so that the numbers previously determined for said components can be compared with the numbers obtained by analysis by the system under calibration.
Reference made in the above specification is intended to result in such patents or literature being expressly incorporated herein by reference including any patents or other literature references cited within such references. What is claimed is:

Claims

1. A sample conditioning system comprising in combination:
Sample supply means 20; Sample filter means 70;
Sample temperature controller means 90; Degassing means 110; Analysis probe holder means 130; and Sample return means 150.
2. A system according to Claim 1 wherein said degassing means 110 comprises a degasser 112 feeding a degassed stream to an analytical probe chamber 130 and outputting a second stream 114 comprising substantially all the bubbles entrained in the incoming stream to be sampled, said second stream being bypassed around said sample probe chamber and returned to the stream being sampled.
3. A system for the analysis of hydrocarbons by near-infrared absorption comprising in combination:
A. a near infrared spectrophotometer operably connected to measure;
B. at least two sources of reference liquid hydrocarbon mixtures of predetermined property and predetermined near infrared absorption, said sources communicating with; C. prototype injection means for automatically periodically injecting one of said reference hydrocarbon mixtures of predetermined property into said infrared spectrophotometer to provide a correlation curve or line reference for calibration of said system over a range.
4. A system according to Claim 3, wherein said prototype injection means comprises means for injecting a plurality of reference fuels having different predetermined properties.
5. A system according to Claim 4, wherein at least one of said prototypes comprises a mixture of known pure hydrocarbons in known amounts.
6. A system according to Claim 4 wherein said predetermined property comprise octane or cetane.
7. A system according to Claim 10 wherein the analysis probe holder contains a fiber optic probe.
8. A system according to Claim 7 wherein the fiber optic probe is adapted for post dispersive transflectance measurement.
9. A system according to Claim 3 wherein the system is substantially enclosed in hermetic cabinets having cabinet purging means.
10. A system according to Claim 3 additionally comprising in combination the following elements in fluid communication:
A. Sample supply means (20); upstream of the following which are connected in series B. Sample filter means (70); and
C. Sample temperature controller means (90); and
D. Degassing means (110); all upstream of
E. Analysis probe holder means (130); connected upstream of F. Sample return means (150).
11. A system according to Claim 10 wherein said degassing means 110 comprises a degasser 112 feeding a degassed stream to an analytical probe chamber 130 and outputting a second stream 114 comprising substantially all the bubbles entrained in the incoming stream to be sampled, said second stream being bypassed around said analysis probe holder and returned to the stream being sampled.
12. A system for the analysis of hydrocarbons by infrared absorption, the improvement comprising in combination providing the following elements in fluid communication:
A. sample supply means; upstream of
B. sample temperature controller means; and
C. degassing means; both upstream of D. analysis probe holder means containing a fiber optic probe adapted for post dispersive transflectance measurement and operably connected to an infrared spectrophotometer;
E. prototype injection means for automatically periodically injecting one of at least two hydrocarbon mixtures of predetermined property into said system to provide a reference for calibration of said system over a range;
F. a plurality of sources of said hydrocarbon mixtures of predetermined property operably connected to feed said prototype injection means.
13. A system according to Claim 12 comprising an on-line system analyzing liquid fuels to determine octane.
14. A system according to Claim 12 wherein said hydrocarbon is a liquid fuel and said property comprises octane or cetane.
PCT/US1993/004712 1993-05-03 1993-05-17 Sampling and analysis system and method WO1994027135A1 (en)

Priority Applications (3)

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PCT/US1993/004712 WO1994027135A1 (en) 1993-05-17 1993-05-17 Sampling and analysis system and method
AU43809/93A AU4380993A (en) 1993-05-17 1993-05-17 Sampling and analysis system and method
KR1019940704679A KR950702270A (en) 1993-05-03 1994-12-22 Compact conterbalancing system for sectional doors

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US7012255B2 (en) 2002-05-20 2006-03-14 General Electric Company Method of measuring the concentration of hydroperoxides of alkylaromatic hydrocarbons

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WO2003100395A1 (en) * 2002-05-20 2003-12-04 General Electric Company Method of measuring the concentration of hydroperoxides of alkylaromatic hydrocarbons
US7012255B2 (en) 2002-05-20 2006-03-14 General Electric Company Method of measuring the concentration of hydroperoxides of alkylaromatic hydrocarbons

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