WO2001036934A2 - Apparatus and method for collecting and detecting chemicals - Google Patents
Apparatus and method for collecting and detecting chemicals Download PDFInfo
- Publication number
- WO2001036934A2 WO2001036934A2 PCT/US2000/031536 US0031536W WO0136934A2 WO 2001036934 A2 WO2001036934 A2 WO 2001036934A2 US 0031536 W US0031536 W US 0031536W WO 0136934 A2 WO0136934 A2 WO 0136934A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sorbent
- fluid
- chemicals
- sorbent material
- pump
- Prior art date
Links
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
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
Definitions
- the present invention relates to an apparatus for collecting chemical samples, and more specifically, to an apparatus for accumulating a concentration of chemicals over a period of time.
- an apparatus for accumulating a concentration of chemicals over a period of time.
- the presence of toxic chemicals must be detected while their concentrations are below toxic levels. Accordingly, to detect highly toxic chemicals, devices capable of detecting low concentrations within a short period of time are needed.
- One prior art device for detecting low concentrations of chemicals includes a pump such as a diaphragm pump and a preconcentrator tube.
- the pump pumps air through a preconcentrator tube where the chemicals accumulate.
- the preconcentrator tube may comprise a low thermal mass tube that houses a sorbent material.
- the terms "preconcentrator tube” and "sorbent material” are well known in the art and correspond to a tube for accumulating chemicals and a material for sorbi ⁇ g (and, therefore, accumulating the chemicals), respectively.
- a heating element wrapped around the preconcentrator tube is used to heat the sorbent material and thereby desorb the chemicals.
- a single pump is used to pump air through the preconcentrator tube and to a detector. Chemicals in the air accumulate in the sorbent material contained within the preconcentrator tube. The heater on the outside of the preconcentrator tube is activated, and chemicals adsorbed onto the sorbent material are released. The chemicals released from the sorbent material are entrained in the air being pumped to the detector.
- This prior art configuration is simple and low cost. Additionally, this configuration consumes little power in comparison to other prior art designs.
- one drawback of this prior art configuration is that the detector is unable to measure chemicals contained in the air in real-time since a period of time is required to accumulate chemicals in the sorbent material. During the period of time while the chemicals are accumulating within the preconcentrator tube, the user is blind to the presence of toxic chemicals in the air. This period of time may last several minutes. During this time, the user will be exposed to the chemicals, which may be present in toxic levels. Only when heat is applied to the sorbent material are the chemicals released and detected.
- Another disadvantage of this prior art design is that the desorbed chemical must be passed through the entire length of the sorbent material prior to reaching the detector.
- the chemical may react with the sorbent material as it is passed through it. Consequently, a sample of chemical traversing the sorbent material may not accurately reflect the concentration of chemical entering the sorbent material. Additionally, unless the preconcentrator tube is heated for a sufficiently long enough time, all of the chemicals accumulated in the sorbent material will not be released. Again, the sample of chemical released from the sorbent material that reaches the detector may not accurately reflect the concentration of chemical entering the sorbent material. Additionally, the device may exhibit a memory effect in which chemicals remaining in the sorbent material may be released when the preconcentrator tube is heated a subsequent time. Artificially higher levels of chemical may be produced at the detector during this subsequent heating.
- Another prior art configuration employs two pumps, a first pump and a second pump, a three-port three-way valve, a preconcentrator tube, and a detector.
- the three-port three-way valve in the first position, two separate paths are created.
- a first path extends from the first inlet to the preconcentrator tube and from the preconcentrator tube to the first pump.
- a second path extends from the second inlet to the detector and from the detector to the second pump.
- the three-port three-way valve creates a flow path from the second inlet to the preconcentrator tube, from the preconcentrator tube to the detector, and from the detector to the second pump.
- the first pump is subsequently turned off, the three-port three-way valve is switched to the second position, and a heater surrounding the preconcentrator tube is activated. With the heater activated, the chemicals collected in the sorbent material will be released and drawn into the detector by the second pump.
- the three-port three-way valve is in the second position, the direction that the air is pumped through the preconcentrator tube is reversed. Accordingly, all of the chemicals collected in the sorbent material do not have to travel through the sorbent material to reach the detector, thus, lowering the likelihood of a chemical reaction between the chemicals and the sorbent material. Desorption is also more efficient.
- the sorbent material does not need to be heated as long since the chemical does not have to pass through all the sorbent material.
- a further prior art configuration substitutes the three-port three-way valve employed in the second prior art configuration with three single-port three-way valves that are magnetically latched and consume less power than non- magnetically latched valves. Overall power consumption can be reduced by switching to magnetically latched valves. Although the size of three single-port three-way valves is slightly larger than the size of a single three-port three-way valve, the number of batteries required for the three single-port three-way valves is less. Nevertheless, this configuration requires too much space and energy for many field applications.
- an apparatus for detecting one or more chemicals comprises a sorbent element for sorbing the one or more chemicals, a bi-directional pump, and at least one chemical detector.
- the sorbent element has a fluid flow path therethrough.
- the bi-directional pump is connected to pump fluid through the fluid flow path of the sorbent element in a first direction during sorption of the one or more chemicals and to pump fluid through the fluid flow path of the sorbent element in a second direction during desorbtion of the one or more chemicals.
- the at least one chemical detector is connected to receive desorbed chemicals.
- the apparatus may further comprise an enclosed passageway from the bi-directional pump to the sorbent element and from the sorbent element to the chemical detector.
- the sorbent element may comprise a tube having a sorbent material therein.
- an apparatus for detecting one or more chemicals comprises a sorbent element having an inlet and an outlet, a bi-directional pump, and a detector comprising a detector housing containing at least one chemical sensor.
- the sorbent element comprises a sorbent material.
- the bi-directional pump has an intake and a vent. The bi-directional pump is adapted to pump fluid from the intake to the vent when pumping in a first direction and to pump the fluid from the vent to the intake when pumping in a second direction.
- the outlet of the sorbent element is connected to the intake of the bi-directional pump such that the fluid flows from the sorbent material to the bi-directional pump when the pump is pumping in the first direction.
- the inlet of the sorbent element is connected to the detector such that fluid flows from the bi-directional pump to the sensor when the pump is pumping in the second direction.
- the sorbent material may comprise a porous polymer comprising 2,6 diphenyl-p-phenylene oxide.
- the apparatus may further comprise a detector pump having an intake and a vent, wherein the intake of the detector pump is connected to the detector containing the sensor.
- Yet another aspect of the invention comprises a method of detecting one or more chemicals contained in a fluid. This method comprises providing a plurality of flow paths including a first flow path for fluid flow through a sorbent element and a second flow path for fluid flow to at least one chemical detector. The first and second flow paths are connected to respective first and second pumps.
- the fluid containing the one or more chemicals is inputted into an inlet.
- a first portion of the fluid containing the one or more chemicals is flowed from the inlet through the first flow path. At least a portion of the one or more chemicals are thereby collected within the sorbent element.
- a second portion of the fluid containing the one or more chemicals is simultaneously flowed from the inlet through the second flow path to the chemical detector. Fluid is flowed through both of the first and second flow paths without altering the connection of the flow paths with the pumps to deliver the one or more chemicals collected in the sorbent element to the chemical detector.
- the method may further comprise heating the sorbent element to desorb the one or more chemicals collected in the sorbent element.
- An apparatus for collecting and detecting chemicals contained in a fluid comprises an enclosure which provides a fluid pathway for transmitting fluid therethrough.
- the enclosure has two fluid flow ports for allowing fluid to enter and exit the enclosure.
- a sorbent material and a heating element are contained within the enclosure.
- the apparatus further comprises at least one chemical sensor, a first pump, and a second pump.
- the first pump pumps fluid through the enclosure, thereby causing the chemicals to collect on the sorbent material.
- the second pump pumps the chemicals to the chemical sensor.
- the sorbent material may have a cavity therein with the heating element located within the cavity.
- the heating element may be interposed between the enclosure and the sorbent material. This heating element may comprises a resistive film formed on an interior surface of the enclosure.
- a method for collecting and detecting chemicals in a fluid includes providing a sorbent material within an enclosure.
- the sorbent material has exterior walls and the enclosure has interior walls.
- the fluid is introduced into the enclosure thereby collecting the chemicals on the sorbent material.
- Heat is radiated from a source of heat located interior to the interior walls of the enclosure, thereby desorbing the chemicals from the sorbent material.
- the chemicals desorbed from the sorbent material are transferred out of the enclosure and to at least one chemical sensor.
- the method may comprise radiating heat from a source of heat located interior to the exterior walls of the sorbent material.
- FIGURE 1 is a schematic representation of a preferred embodiment of the present invention.
- FIGURE 2A is a fragmented cross-sectional view of a preconcentrator tube depicting a heating element passing through a sorbent material contained within the preconcentrator tube.
- FIGURE 2B is a perspective view of the preconcentrator tube and heating element shown in FIGURE 2A.
- FIGURE 3A is a fragmented cross-sectional view of a preconcentrator tube depicting a heating element comprising a heating element interposed between the preconcentrator tube and a sorbent material contained within the preconcentrator tube.
- FIGURE 3B is a perspective view of the preconcentrator tube and heating element shown in FIGURE 3A.
- FIGURE 4A is a fragmented cross-sectional view of a preconcentrator tube depicting a heating element surrounding the preconcentrator tube.
- FIGURE 4B is a perspective view of the preconcentrator tube and heating element shown in FIGURE 4A.
- FIGURE 5A is a schematic representation of the embodiment shown in FIGURE 1 collecting chemicals in the sorbent material.
- FIGURE 5B is a schematic representation of the embodiment shown in FIGURE 1 desorbing the chemicals from the sorbent material.
- FIGURE 6 is a plot, on axes of Time (in seconds) and Frequency Shift (in hertz), which depicts a sensor output during three cycles of collection and desorption.
- FIGURE 1 An apparatus 10 for detecting chemicals, such as molecules, in accordance with a preferred embodiment of the present invention is shown in FIGURE 1.
- the apparatus 10 has a primary intake 12, which corresponds to a first opening 14 leading into a primary intake passageway 16.
- FIGURE 1 shows a filter 17 inserted in the primary intake passageway 16, which removes unwanted debris.
- the primary intake passageway 16 extends to a preconcentrator element 18 comprising a tube having a front end portion 20 and a rear end portion 22.
- the primary intake passageway 16 is connected to a side 24 of the preconcentrator tube 18 in the front end portion 20.
- the sorbent (i.e. preconcentrator element) 18 in the embodiment shown in FIGURE 1 is in the form of a tube, the present invention is not restricted to the use of a tube as a sorbent element. Chemicals may be accumulated in a chamber having a shape that is not tubular.
- preconcentrator element is defined as a structure, such as a tube, for accumulating chemicals. In the preferred embodiment, such accumulation is achieved by a preconcentrator tube 18 containing a sorbent material 28.
- the sorbent material 28 preferably comprises Tenax® TA 30/60 mesh, which is a porous polymer based on 2,6 diphenyl-p-phenylene oxide developed by AKZO Research Laboratories and which can be obtained from Alltech Associates.
- the sorbent material 28 may be selected from the group consisting of Tenax® GA, Carbosieve, or granulated charcoal.
- any sorbent element 18 may be used to accumulate a concentration of chemicals.
- the sorbent element 18 may comprise a preconcentrator tube having a coated surface to which the chemicals adhere.
- the preconcentrator tube 18 may be cooled to promote adsorption on a surface therein.
- the sorbent element 18 permits fluid to flow therethrough, while collecting chemicals contained within the flowing fluid.
- a bi-directional pump is defined herein as a pump that is capable of pumping fluid in two directions.
- a bi-directional pump 30 shown in FIGURE 1 as having an intake 32 and a vent 34 can pump air from the intake to the vent or from the vent to the intake.
- the bi-directional pump 30 comprises a rotary vane pump.
- Other types of bi-directional pumps 30 that can be used in accordance with the present invention include blowers and positive displacement pumps.
- the bi-directional pump 30 preferably is capable of pumping air at a flow rate in the range between 25 and 2000 standard cubic centimeters/minute (seem). Most preferably, the bi-directional pump 30 is capable of pumping air at a flow rate in the range between 200 and 1000 seem.
- the rearend portion 22 of the preconcentrator tube 18 is connected to an intake 32 on the a bi-directional pump 30 by a passageway 36.
- a first flow meter 38 and a first scrubber 40 are disposed in the passageway 36 connecting the preconcentrator tube 18 to the bi-directional pump 30.
- a flow meter measures the flow of air passing through it or other properties related to flow, e.g., rate of flow.
- a scrubber is defined herein in accordance with its conventional usage to be a filter for purifying a fluid.
- the first flow meter 38 comprises a bi-directional flow meter, i.e., a flow meter capable of measuring flow passing over a single pathway in either of two directions.
- the first flow meter 38 preferably can measure the flow of air from the preconcentrator tube 18 to the bi-directional pump 30 and can measure the flow of air from the pump to the preconcentrator tube.
- an exhaust line 42 extending from the bi-directional pump 30 has an outlet opening 44, which preferably vents to the ambient atmosphere.
- a second scrubber 46 is disposed in the exhaust line 42.
- both the first scrubber 40 and the second scrubber 46 are comprises of the same material as the sorbent material 28 contained within the preconcentrator tube 18.
- the first scrubber 40 as well as the second scrubber 46 may contain Tenax®
- a detector 50 comprises a housing 52 having an entrance orifice 54 and an exit orifice 56.
- the detector housing 52 preferably contains a sensor array 58 comprising a plurality of sensors capable of sensing the chemicals to be detected. Alternatively, the housing 52 may contain a single sensor.
- the sensor array 58 of the preferred embodiment preferably comprises a plurality of surface acoustic wave
- the detector 50 may comprise other chemical detectors including, e.g., a gas chromatograph, an ion mobility spectrometer, or a mass spectrometer.
- a separate passageway 62 connects the exit orifice 56 of the housing 52 of the detector 50 to an intake 66 of a detector pump 64 having a vent 68.
- the detector pump 64 preferably is capable of pumping air at a flow rate in the range between 50 and 500 standard cubic centimeters/minute (seem) and vents to ambient air.
- a second flow meter 70 is disposed in the passageway 62 between the detector 50 to the detector pump 64.
- Each of the passageways, the primary intake passageway 16, the passageway 36 connecting the preconcentrator tube 18 to the bi-directional pump 30, the exhaust passageway 42 extending from the bi-directional pump, the passageway 48 connecting the primary intake passageway to the detector 50, and the passageway 62 connecting the detector to the detector pump 64 may, in accordance with the present invention, be formed by tubes.
- the passageways 16, 36, 42, 48, 62 may have shapes other than tubular.
- the passageways 16, 36, 42, 48, 62 may be formed as integrated flow circuits that are part of a manifold.
- FIGURE 1 depicts a heater 72 and a temperature sensor 74 in thermal contact with the preconcentrator tube 18 and the sorbent material 28.
- An electronic controller 76 is electrically connected to a power supply 78, which is electrically connected to the heater 72, the bi-directional pump 30, and the detector pump 64.
- the first flow meter 38, the second flow meter 70, and temperature sensor 74 are also electrically connected to the controller 76.
- a detector unit 80 is comprised of the detector 50, the second flow meter 70, the detector pump 64, the electronic controller 76 and the power supply 78.
- the preconcentrator tube 18, the first flow meter 38, and the bi-directional pump 30 are electrically connected to the detector unit 80.
- a detector unit 80 and a sample acquisition device for obtaining a gaseous sample from a surface which may be employed in conjunction with the preferred embodiment of the present invention, is disclosed in the application of William D. Bowers, Serial No. 09/151 ,743, filed on September 11, 1998, entitled "Pulsed Air Sampler,” which is hereby incorporated by reference.
- the heater 72 has a heating element 82 that extends into the preconcentrator tube 18 from the end 26 of the tube.
- the heating element 82 extends through a central, elongated, longitudinal cavity in the sorbent material 28.
- the heating element 82 shown in FIGURES 2A and 2B comprises a film 85 that is formed on the exterior surface of a ceramic tube 84.
- the film 85 covers at least that portion of the ceramic tube 84 that extends into the longitudinal cavity of the sorbent material 28.
- the film 85 has a primary surface 88 which is juxtaposed with and in substantial contact with the sorbent material 28.
- the portion of the ceramic tube 84 not covered with the film 85 is a no heat zone that does not generate heat.
- this film 85 comprises a material, which when deposited, forms a resistive film. More specifically, this film 85 may comprise material selected from the group consisting of indium tin oxide (ITO) films and printed resistive ink films used in the semiconductor industry.
- ITO indium tin oxide
- This film 85 may also comprise a vapor deposited film, a thick film, or a thin film.
- the ceramic tube 84 may comprise aluminum oxide.
- the sorbent material 28 is secured inside 90 the preconcentrator tube 18 with retainer screens 92a, 92b.
- One of the retainer screens 92a is mounted on the ceramic tube 84 while the other retainer screen 92b is attached to an inside wall 94 of the preconcentrator tube 18.
- the sorbent material 28 has a size such that it contacts the inside wall 94 of the preconcentrator tube 18 as shown in FIGURE 2A.
- FIGURES 3A and 3B depict the heating element 82 interposed between the preconcentrator tube 18 and the sorbent material 28.
- This heating element 82 is situated so as to surround the sorbent material 28.
- the heating element 82 shown in FIGURES 3A and 3B comprises a film formed between the preconcentrator tube 18 and the sorbent material 28.
- this film may comprise a material, which when deposited, forms a resistive film. More specifically, this film may comprise material selected from the group consisting of indium tin oxide (ITO) films and printed resistive ink films used in the semiconductor industry.
- This film may also comprise a vapor deposited film, a thick film, or a thin film.
- ITO indium tin oxide
- the heating element 82 shown in FIGURES 3A and 3B has a first surface 96 which is in contact with and is juxtaposed with the sorbent material 28.
- a second surface 98, opposite to the first surface 96, is juxtaposed with and contacts the inside wall of the tube 18.
- the preconcentrator tube 18 depicted in FIGURES 3A and 3B preferably comprises a ceramic. More preferably, the preconcentrator tube 18 comprises a ceramic having low thermal mass (or low mass). Most preferably, the preconcentrator tube 18 also has a low specific heat so as to enable rapid heating and cooling of the preconcentrator tube.
- the sorbent material 28 is secured inside 90 the preconcentrator tube 18 with a retainer screens 92a, 92b.
- each of the retainer screens 92a, 92b is affixed to the inside wall 94 of the preconcentrator tube 18.
- FIGURES 4A and 4B depict the preconcentrator tube 18 with the heating element 82 wrapped around it. This heating element 82 is situated so as to surround the preconcentrator tube 18.
- the heater 72 shown in FIGURES 4A and 4B comprises a thin foil heater.
- a thin foil heater is shown in
- FIGURES 4A and 4B other heaters 72 that heat the sorbent material 28 from outside the preconcentrator tube 18 may be employed.
- a current could be passed through a wire wrapped around the preconcentrator tube 18.
- a wire wound heater comprising heater wire with insulation wound around the wire could be used.
- the heating element 82 for the foil heater shown in FIGURES 4A and 4B has a first primary surface 102 which is not in contact with but faces the sorbent material 28.
- a second primary surface 104, opposite to the first surface 102, is neither in contact with nor facing the sorbent material 28.
- the heating element 82 also has end surfaces 106, perpendicular to the first and second primary surfaces 102, 104, which are not in contact nor facing the sorbent material 28.
- the preconcentrator tube 18 depicted in FIGURES 4A and 4B preferably comprises a metal, and more preferable low thermal mass metal. Low thermal mass can be achieved with low mass; accordingly, a preconcentrator tube 18 having thin walls may be advantageously employed.
- FIGURE 4A also shows each of the retainer screens 92a, 92b affixed to the inside wall 94 of the preconcentrator tube 18 and the sorbent material 28 extending to the inside walls of the preconcentrator tube.
- the heating element 82 can be either within the sorbent material 28 or outside the sorbent material. However, a heating element 82 within the sorbent material 28 provides more even heating therein. Additionally, heating from within the sorbent material 28 is more efficient and faster. When the heating element 82 is contained within the sorbent material 28, most of the surface area of the heating element will face and be in contact with the sorbent material. Accordingly, less heat is lost by being radiated or conducted away from the sorbent material 28.
- the heating element 82 shown in FIGURES 2A-2B is more efficient than the foil heater shown in
- FIGURES 4A-4B because more of the surface area on the heating element is usable for transferring heat to the sorbent material 28.
- a substantial portion of the primary surface 88 of the heating element 82 depicted in FIGURES 2A-2B is in contact with or facing the sorbent material 28. Heat, thus, can be transferred to the sorbent material 28 by conduction or radiation through the primary surface 88.
- the first primary surface 102 of the foil heater depicted in FIGURES 4A-4B faces the sorbent material 28, the second primary surface 104 does not; and the second primary surface is the same size as the first primary surface.
- the first primary surface 102 of the foil heater does not participate in the direct transfer of heat to the sorbent material 28.
- Only the first primary surface 102 of the foil heater directs thermal energy to the sorbent material 28.
- the end surfaces 106 of the foil heater depicted in FIGURES 2A-2B do not directly transfer heat to the sorbent material 28 since they neither faces nor contact the sorbent material.
- the heating element 82 shown in FIGURES 2A-2B is more efficient than the heating element in FIGURES 4A-4B. For example, less heat is radiated away from the sorbent material 28. Additionally, the heating element 82 in FIGURES 2A-2B is directly in contact with the sorbent material 28 while the heater foil shown in FIGURES 4A-4B is not.
- FIGURES 3A-3B is also more efficient than the heating element in FIGURES 4A- 4B.
- the heating element 82 in FIGURES 3A-3B has a first surface 96 that is in direct contact with and faces the sorbent material 28 whereas the thin foil heater in FIGURES 4A-4B is not in direct contact with the sorbent element.
- FIGURES 5A and 5B depicts the operation of the embodiment shown in FIGURE 1.
- FIGURE 5A illustrates a first mode of operation, the collection mode, wherein chemicals are collected in the sorbent material 28.
- FIGURE 5B depicts a second mode of operation, the desorption mode, wherein chemicals collected on the sorbent material are desorbed from it.
- the bi-directional pump 30 In the collection mode, chemicals such as molecules are collected on the sorbent material 28 by activating the bi directional pump 30 such that air is pulled into the primary intake 12 and through the preconcentrator tube 18. This air is exhausted out the vent 34 of the bi-directional pump 30. To cause the air to flow from the intake 12 through the preconcentrator tube 18, the bi-directional pump 30 operates in a first direction, herein designated as the forward direction.
- FIGURE 5A shows arrows 108, 110, which represent the flow of air into the primary intake 12 and through the primary intake passageway 16.
- the air drawn into the primary intake 12 passes through the first filter 17, which removes unwanted debris from the air, thereby preventing this unwanted debris from accumulating on the sorbent material 28.
- the air travels from the primary intake passageway 16 into the preconcentrator tube 18 as indicated by another arrow 112.
- the air entering the preconcentrator tube 18 flows through the sorbent material 28 which traps chemicals 1 14 therein.
- the first flow meter 38 measures the flow or rate of flow through the preconcentrator tube 18 and through the sorbent material 28.
- Electrical connection to the controller 76 enables the first flow meter 38 tq provide feedback to regulate the rate at which the bi-directional pump 30 passes air through the preconcentrator tube 18. More specifically, the first flow meter 38 outputs a signal indicative of the flow or flow rate through the preconcentrator tube 18 enabling the controller 76 to adjust the pump rate of the bi-directional pump 30 accordingly.
- the controller 76 will set the power from the power supply 78 that is directed to the bi-directional pump 30, thus, controlling the rate that the bi- directional pumps the air through the sorbent material 28.
- the bi-directional pump may also have a tachometer that measures and outputs pump speed (e.g., revolutions/minute). This tachometer can, therefore, provide feedback for controlling the flow rates as well as provide general diagnostics information.
- the number density of chemicals 114 collected on the sorbent material 28 is a function of the chemical nature of the sorbent, the concentration of the chemicals in the air, and the total volume of air pumped through the sorbent material.
- the total volume of air pumped through the sorbent material depends on the flow rate of the air through the sorbent material 28 and the length of time the air passes through the sorbent material. Higher flow rates through the sorbent material 28 mean shorter the times required for collecting a sufficient number density of chemicals for detection. Accordingly, high flow rates through the sorbent material are preferred. These flow rates may range between 25 and 2000 standard cubic centimeters/minute (seem), and more preferably, between 200 and 1000 seem. Most preferably, the maximum flow rate provided by the bi-directional pump 30 is employed during the collection mode.
- Arrows 116b, 116c on two sides of the first scrubber 40 illustrate the passage of the air through a first scrubber prior to entering the bi-directional pump 30.
- the first scrubber 40 filters out any chemicals that would otherwise reach the bi-directional pump 30.
- the first scrubber 40 preferably comprises sorbent material that will trap the type of chemicals to be detected at the detector 50. Without the first scrubber 40, these chemicals would reach and contaminate the bi-directional pump 30. As a result, some of these chemicals might be ejected by the bi-directional pump 30 back into the passageway 36 between the preconcentrator tube 18 and the bidirectional pump whenever bi-directional pump pumps in the reverse direction. These chemicals would then flow through the preconcentrator tube 18 and into the detector 50, creating an artificially high reading by the detector.
- the air in passageway 36 between the preconcentrator tube 18 and the bidirectional pump 30 is pumped through the first scrubber 40 when in the collection mode. Chemicals are trapped in the sorbent material in the first scrubber 40 and do not reach the bi-directional pump 30.
- the bi-directional pump 30 After passing through the first scrubber 40, the air moves into the bi-directional pump 30.
- the bi-directional pump 30 provides the pumping power to transfer the air from the primary intake 12 and through the preconcetrator tube 18.
- the bi-directional pump 30 is shown in FIGURE 5A as a rotary vane pump.
- An arrow 118 indicates the motion of the rotor and vanes 120 in the bi-directional pump 30 when the apparatus 10 for detecting chemicals operates in the collection mode.
- the air drawn into the bi-directional pump 30 is expelled out the vent 34 of the bi-directional pump and into the exhaust line 42.
- the air passes through the second scrubber 46 as illustrated by two arrows 122a, 122b on two sides of the second scrubber 46.
- Another arrow 124 represents the air being discharged from the opening 44 in exhaust line 42.
- the detector pump 64 samples air drawn in the primary intake 12 to detect the presence of the chemicals in real-time. In particular, a portion of the air entering the primary intake 12 and passing through the primary intake passageway 16 is drawn by the detector pump 64 into the passageway 48 between the primary intake passageway and the detector 50. Arrows 126 indicate the flow of air from the primary intake passageway 16, through the passageway 48 between the primary intake passageway and the detector 50 and to the detector. The air enters the detector 50 through the entrance orifice 54 and passes over the sensor array 58. The sensor array 58 detects the presence the chemicals to be detected and outputs a signal, which is communicated to the user of the apparatus 10.
- the air passing over the sensor array 58 exits the detector 50 through the exit orifice 56 and enters the passageway 62 between the detector 50 and the detector pump 64 as indicated by another arrow 128.
- the air proceeds through the second flow meter 70 to the detector pump 64.
- the air is drawn into the intake 66 of the detector pump 64 and expelled out the vent 68 of the detector pump.
- the detector pump 64 provides the pumping power to draw a portion of the air from the primary intake passageway 16 to the detector 50 while the second flow meter 70 measures the flow or rate of flow through the detector. Electrical connection of the second flow meter 70 to the controller 76 enables the second flow meter to provide feedback to regulate the rate at which the detector pump 64 passes air through the detector 50.
- the second flow meter 70 outputs a signal indicative of the flow or flow rate through the detector 50, thereby enabling the controller 76 to set the power from the power supply 78 that is directed to the detector pump 64.
- the apparatus 10 for detecting chemicals is shifted from the collection mode to the desorption mode.
- chemicals 114 collected on the sorbent material 28 are d ⁇ sorbed by activating the heater 72 while air is pumped from the exhaust line 42 of the bi-directional 30 and through the preconcentrator tube 18.
- the bi-directional pump 30 is switched from pumping in the first direction (i.e.
- FIGURE 5B depicts the operation of the apparatus for detecting chemicals in the desorption mode. Air is drawn into the opening 44 in the exhaust line 42. This air is pumped through the exhaust line 42 to the bi-directional pump 30. Before reaching the bi-directional pump 30, the air passes through the second scrubber 46 as illustrated by two arrows 130a, 130b.
- the second scrubber 46 removes unwanted chemicals from the air entering the exhaust line 42, thereby preventing these unwanted chemicals from entering the bi-directional pump 30.
- the second scrubber 46 preferably comprises sorbent material that will trap the type of chemicals to be detected at the detector 50. Chemicals are trapped in the sorbent material in the second scrubber 46 and never reach the bi-directional pump 30. Accordingly, these unwanted chemicals will not flow through the preconcentrator tube 18 and into the detector 50, affecting the output of the detector.
- the air in the exhaust line 42 proceeds to the bi-directional pump 30 where it drawn into the vent 34 on the bi-directional pump.
- the bi-directional pump 30 pushes this air out of the intake 32 of the bi-directional pump and into the passageway 36 connecting the bi-directional pump with the preconcentrator tube 18.
- the bidirectional pump 30 provides the pumping power to draw air from the opening 44 in the exhaust line 42 and force the air through the preconcetrator tube 18.
- the bi-directional pump 30 is shown in FIGURE 5B as a rotary vane pump.
- An arrow 132 indicates the motion of the rotor and vanes 120 in the bi-directional pump 30 when the apparatus 10 for detecting chemicals operates in the desorption mode.
- the bi-directional pump 30 is a rotary vane pump
- the polarity of the voltage supplied by the power supply 78 to the bi-directional pump is reversed. Switching polarity causes the rotor and vanes 120 to spin in an opposite direction.
- FIGURE 5B depicts the air passing through the first scrubber 40, which filters out any chemicals released by the bi-directional pump 30. Such chemicals are trapped in the sorbent material in the first scrubber 40 and do not reach the preconcentrator tube 18 or the detector 50.
- the air after passing through the first scrubber 40, continues on through the first flow meter 38, which measures the flow or rate of flow through the preconcentrator tube 18 and through the sorbent material 28. Electrical connection to the controller 76 enables the first flow meter 38 to provide feedback to regulate the rate at which the bi-directional pump 30 passes air through the preconcentrator tube 18. The air travels from the passageway 36 connecting the bi-directional pump 30 to the preconcentrator tube
- the heater 72 is activated when the apparatus 10 is in the desorption mode so as to provide energy to cause the chemicals 114 collected in the sorbent material 28 to be desorbed into the air flowing through the preconcentrator tube 18. These chemicals 114, once desorbed, are carried away by the air flowing through the preconcentrator tube 18 as illustrated by an arrow 136 at the front of the preconcentrator tube shown in FIGURE 5B.
- Power is supplied to the heater 72 by the power supply 78, which is regulated by feedback from the temperature sensor 74.
- the temperature sensor 74 in thermal contact with the sorbent material 28 through the preconcentrator tube 18, sends a signal to the controller 76, which then adjusts the amount of power from the power supply 78 that is delivered to the heater 72.
- the heater 72 heats the sorbent material 18 to a temperature in the range between about 70°C and 250°C (200°C for Tenax®) to desorb chemicals therefrom.
- the temperature controller 76 is programmed to raise the temperature of the sorbent material 28 in stages, holding the temperature at a number of temperature setpoints prior to reaching the temperature at which the chemicals to be detected are desorbed from the sorbent material.
- a small amount of the chemical may be mixed with a large number of background chemicals. These background chemicals can be present in concentrations that are several orders of magnitude higher than the chemicals of interest. If the preconcentrator tube 18 is heated in a single step to a temperature at which all of the chemicals to be detected are desorbed from the sorbent material, the background chemicals may be released with the chemicals of interest. The release of the background chemicals creates "chemical noise," that is, the detector 50 must be able to distinguish the presence of the chemicals to be detected from the background chemicals.
- the ability to distinguish the chemicals of interest from other chemicals can be improved by separating the times at which different chemicals are desorbed from the sorbent material 28.
- the temperature of the sorbent material 28 can be raised in stages, being held for a period of time at one or more temperatures lower than the temperature at which the chemicals to be detected are desorbed from the sorbent material.
- the high concentrations of background chemicals will then reach the detector at a different time as the chemicals to be detected.
- the preconcentrator tube 18 can be heated first to a temperature lower than the temperature at which the non-volatile toxic chemical is desorbed, then to the temperature at which the non-volatile toxic chemical is desorbed.
- the background chemicals with low volatility are thereby first driven off the sorbent material 28. Accordingly, chemical noise at the detector 50 is reduced at the point in time when the non-volatile toxic chemical reaches the detector.
- the chemicals 114 once desorbed from the sorbent material 28, are carried away by the air flowing through the preconcentrator tube 18 into the primary intake passageway 16. Pumping power to push the air out the preconcentrator tube 18 and into the primary intake passageway 16, is provided by the bi-directional pump 30.
- the detector pump 64 continues to draw air into the detector 50 while the apparatus 10 for detecting chemicals is in the desorption mode. Consequently, air being pumped through the preconcentrator tube 18 and into the primary intake passageway 16 is directed into the passageway 48 connecting the primary intake passageway to the detector 50. Arrows 138 indicate the flow of air from the primary intake passageway 16 into the passageway between the primary intake passageway and the detector 50. The air then enters the detector 50 and passes over the sensor array 58. The sensor array 58 detects the presence the chemicals and outputs a signal, which is communicated to the user of the apparatus 10, preferably after some processing.
- the detector pump 64 provides the pumping power to draw the air from the primary intake passageway 16 to the detector 50.
- the second flow meter 70 measures the flow or rate of flow through the detector 50 and provides feedback to the controller 76.
- the controller 76 is used to regulate the rate at which the detector pump 64 passes air through the detector 50.
- the bi-directional pump 30 pumps the air through the preconcentrator tube 18 at a rate that is about equal to the rate at which the detector pump 64 pumps air to the detector 50. If the flow rate of air through the preconcentrator tube 18 exceeds the flow rate of air to the detector 50, some air passing through the preconcentrator tube will not enter the passageway 48 connecting the primary intake passageway 16 to the detector 50. Instead, some air will escape through the primary intake 12. Accordingly, some of the chemicals to be detected will not reach the detector 50 for detection. In contrast, if the flow rate of air to the detector 50 exceeds the flow rate of air through the preconcentrator tube 18, additional air drawn in through the primary intake 12 will reach the detector, diluting the concentration of chemicals 114 released from the preconcentrator tube.
- the flow rate of air passing through the preconcentrator tube 18, which carries the chemicals 114 out of the sorbent material 28 should be about equal to the flow rate of air to the detector 50.
- the first and second flow meters 38, 70 can be used to provide feedback to the controller 76, to thereby match the rate of flow of air through the preconcentrator tube 18 with the rate of flow of air to the detector 50.
- the pressure at the preconcentrator tube 18 could be matched with the pressure at the detector 50. For the foregoing reasons, the measurements made by the detector 50 will be most accurate when the pressure at the preconcentrator tube 18 is approximately equal to the pressure at the detector 50.
- FIGURE 6 illustrates the reproducability of measurements obtained using the apparatus 10 depicted in FIGURE 1 with a SAW sensor as the detector 50.
- a SAW sensor outputs an oscillating signal having a frequency that shifts when chemicals are adsorbed onto the sensor. This frequency shift, in hertz, is plotted over time, in seconds, to track the output of the SAW sensor during three cycles of collection and desorption.
- the intervals when the detector pump 64 pumps air across the detector 50 while chemicals collect in the preconcentrator tube 18 correspond to three periods of time T réelle T 2 , T 3 .
- the SAW sensor output during these three periods Tsammlung T 2 , T 3 is relatively small, i.e., in the range of between 40 to 100 Hz.
- peaks 140 results with the release of the chemicals 114 during desorption.
- the magnitude of the peaks is fairly reproduceable, 560, 580, and 580 Hz, respectively, indicating that chemicals are not randomly released from the preconcentrator tube 18, the first and second scrubbers 40, 46 nor the bi-directional pump 30 during desorption.
- the preferred embodiment is described as detecting chemicals contained in air, separate embodiments of the invention may be used to detect chemicals in other fluids. Additionally, the apparatus 10 may be employed to detect the presence of chemicals other than molecules, such as sub-micron, neutrally charged chemicals or chemicals in the form of aerosols.
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Materials By The Use Of Ultrasonic Waves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001538773A JP2003515122A (en) | 1999-11-17 | 2000-11-17 | Apparatus and method for collecting and detecting chemicals |
EP00991394A EP1232380A2 (en) | 1999-11-17 | 2000-11-17 | Preconcentrator for chemical detection |
AU32627/01A AU3262701A (en) | 1999-11-17 | 2000-11-17 | Preconcentrator for chemical detection |
IL14945700A IL149457A (en) | 1999-11-17 | 2000-11-17 | Apparatus and method for collecting and detecting chemicals |
CA002391452A CA2391452A1 (en) | 1999-11-17 | 2000-11-17 | Apparatus and method for collecting and detecting chemicals |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/437,422 | 1999-11-17 | ||
US09/437,422 US6656738B1 (en) | 1999-11-17 | 1999-11-17 | Internal heater for preconcentrator |
US09/441,734 US6455003B1 (en) | 1999-11-17 | 1999-11-17 | Preconcentrator for chemical detection |
US09/441,734 | 1999-11-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001036934A2 true WO2001036934A2 (en) | 2001-05-25 |
WO2001036934A3 WO2001036934A3 (en) | 2002-02-14 |
Family
ID=27031313
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/031536 WO2001036934A2 (en) | 1999-11-17 | 2000-11-17 | Apparatus and method for collecting and detecting chemicals |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1232380A2 (en) |
JP (1) | JP2003515122A (en) |
AU (1) | AU3262701A (en) |
CA (1) | CA2391452A1 (en) |
IL (1) | IL149457A (en) |
WO (1) | WO2001036934A2 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004061405A (en) * | 2002-07-31 | 2004-02-26 | Horiba Ltd | Apparatus and method for analyzing gas |
JP2006515673A (en) * | 2002-09-27 | 2006-06-01 | ハネウェル・インターナショナル・インコーポレーテッド | Phase micro analyzer |
WO2006083999A1 (en) * | 2005-02-02 | 2006-08-10 | Bae Systems Integrated Defense Solutions, Inc. | Surface acoustic wave sensors with fluid inlet and mounting structure |
WO2007030205A1 (en) * | 2005-09-07 | 2007-03-15 | Microsensor Systems, Inc. | System, apparatus and method for concentrating chemical vapors |
US7449050B2 (en) | 2005-12-29 | 2008-11-11 | Microsensor Systems, Inc. | System, apparatus and method for concentrating chemical vapors |
CZ302757B6 (en) * | 2005-12-08 | 2011-10-19 | Ústav analytické chemie AV CR, v.v.i. | Bismuth pre-concentration process for determining thereof by atomic absorption spectrometry method |
CN103217330A (en) * | 2013-04-09 | 2013-07-24 | 安徽省安光环境光学工程技术研究中心有限公司 | Device for separating atmospheric particulates on line |
US9581566B2 (en) | 2012-01-13 | 2017-02-28 | Panasonic Healthcare Holdings Co., Ltd. | Biological sample measurement device |
CN112543866A (en) * | 2018-08-08 | 2021-03-23 | 松下电器产业株式会社 | Detection method, control system, detection system, and program for detection device |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6442997B1 (en) * | 2001-10-01 | 2002-09-03 | Lockheed Martin Corporation | Ram-air sample collection device for a chemical warfare agent sensor |
US7208123B2 (en) * | 2002-06-24 | 2007-04-24 | Particle Measuring Systems, Inc. | Molecular contamination monitoring system and method |
GB0606346D0 (en) * | 2006-03-30 | 2006-05-10 | Smiths Group Plc | Preconcentrator and detector apparatus |
GB201314252D0 (en) * | 2013-08-08 | 2013-09-25 | Smiths Detection Watford Ltd | Apparatus and method |
EP3523620A4 (en) * | 2016-10-10 | 2020-06-10 | PerkinElmer Health Sciences, Inc. | Sampling pumps and closed loop control of sampling pumps to load traps |
KR102156728B1 (en) * | 2019-01-09 | 2020-09-16 | (주)바이오니아 | Surface Heater-bonded sample concentration tube, analyzing apparatus including the same and analysis method using the same |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4584887A (en) * | 1984-10-10 | 1986-04-29 | The United States Of America As Represented By The Administrator Of The National Aeronautics & Space Administration | Solid sorbent air sampler |
GB2250633A (en) * | 1990-10-31 | 1992-06-10 | Extrel Corp | Preconcentrating gas samples for analysis |
-
2000
- 2000-11-17 EP EP00991394A patent/EP1232380A2/en not_active Withdrawn
- 2000-11-17 JP JP2001538773A patent/JP2003515122A/en active Pending
- 2000-11-17 AU AU32627/01A patent/AU3262701A/en not_active Abandoned
- 2000-11-17 IL IL14945700A patent/IL149457A/en not_active IP Right Cessation
- 2000-11-17 CA CA002391452A patent/CA2391452A1/en not_active Abandoned
- 2000-11-17 WO PCT/US2000/031536 patent/WO2001036934A2/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4584887A (en) * | 1984-10-10 | 1986-04-29 | The United States Of America As Represented By The Administrator Of The National Aeronautics & Space Administration | Solid sorbent air sampler |
GB2250633A (en) * | 1990-10-31 | 1992-06-10 | Extrel Corp | Preconcentrating gas samples for analysis |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004061405A (en) * | 2002-07-31 | 2004-02-26 | Horiba Ltd | Apparatus and method for analyzing gas |
JP2006515673A (en) * | 2002-09-27 | 2006-06-01 | ハネウェル・インターナショナル・インコーポレーテッド | Phase micro analyzer |
WO2006083999A1 (en) * | 2005-02-02 | 2006-08-10 | Bae Systems Integrated Defense Solutions, Inc. | Surface acoustic wave sensors with fluid inlet and mounting structure |
US7327068B2 (en) | 2005-02-02 | 2008-02-05 | Bae Systems Information And Electronic Systems Integration Inc. | Sensors and related devices and methods |
WO2007030205A1 (en) * | 2005-09-07 | 2007-03-15 | Microsensor Systems, Inc. | System, apparatus and method for concentrating chemical vapors |
CZ302757B6 (en) * | 2005-12-08 | 2011-10-19 | Ústav analytické chemie AV CR, v.v.i. | Bismuth pre-concentration process for determining thereof by atomic absorption spectrometry method |
US7449050B2 (en) | 2005-12-29 | 2008-11-11 | Microsensor Systems, Inc. | System, apparatus and method for concentrating chemical vapors |
US9581566B2 (en) | 2012-01-13 | 2017-02-28 | Panasonic Healthcare Holdings Co., Ltd. | Biological sample measurement device |
CN103217330A (en) * | 2013-04-09 | 2013-07-24 | 安徽省安光环境光学工程技术研究中心有限公司 | Device for separating atmospheric particulates on line |
CN112543866A (en) * | 2018-08-08 | 2021-03-23 | 松下电器产业株式会社 | Detection method, control system, detection system, and program for detection device |
Also Published As
Publication number | Publication date |
---|---|
JP2003515122A (en) | 2003-04-22 |
CA2391452A1 (en) | 2001-05-25 |
IL149457A (en) | 2005-05-17 |
EP1232380A2 (en) | 2002-08-21 |
IL149457A0 (en) | 2002-11-10 |
WO2001036934A3 (en) | 2002-02-14 |
AU3262701A (en) | 2001-05-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6455003B1 (en) | Preconcentrator for chemical detection | |
US6656738B1 (en) | Internal heater for preconcentrator | |
WO2001036934A2 (en) | Apparatus and method for collecting and detecting chemicals | |
US8302458B2 (en) | Portable analytical system for detecting organic chemicals in water | |
US7449050B2 (en) | System, apparatus and method for concentrating chemical vapors | |
US7841244B2 (en) | Apparatus and method for mobile collection of atmospheric sample for chemical analysis | |
US6378385B1 (en) | Pulsed air sampler | |
US4759210A (en) | Apparatus for gas-monitoring and method of conducting same | |
TWI592658B (en) | Gas analysis apparatus,gas analysis system and gas analysis method | |
US7197949B2 (en) | Meso sniffer: a device and method for active gas sampling using alternating flow | |
US20090090196A1 (en) | Preconcentrator and Detector Apparatus | |
WO2007030205A1 (en) | System, apparatus and method for concentrating chemical vapors | |
US8062610B2 (en) | Apparatus and methods for use in concentration of gas and particle-laden gas flows | |
WO2011031559A1 (en) | Preconcentrating a sample | |
US7244288B2 (en) | Pulsed vapor desorber | |
RU2146811C1 (en) | Technique of ecological monitoring of organic compounds and device for its realization | |
US20110214482A1 (en) | Large volume analyte preconcentrator | |
EP1062504A1 (en) | A valveless gas chromatographic system with pulsed injection and temperature programmed elution | |
JP4100607B2 (en) | Gas analyzer and gas analysis method | |
GB2618073A (en) | Detector inlet and method | |
GB2624900A (en) | Detector inlet apparatus and method | |
JPH1010101A (en) | Pre-concentrator collector for detecting minute amount of gaseous chemical substance | |
SE517834C2 (en) | Apparatus for detection of an analyte in air |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ CZ DE DE DK DK DM DZ EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
AK | Designated states |
Kind code of ref document: A3 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ CZ DE DE DK DK DM DZ EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
WWE | Wipo information: entry into national phase |
Ref document number: 149457 Country of ref document: IL |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2391452 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 2001 538773 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2000991394 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2000991394 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2000991394 Country of ref document: EP |