WO2006124578A2 - Procede et appareil de recuperation de gaz anesthesique - Google Patents

Procede et appareil de recuperation de gaz anesthesique Download PDF

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Publication number
WO2006124578A2
WO2006124578A2 PCT/US2006/018416 US2006018416W WO2006124578A2 WO 2006124578 A2 WO2006124578 A2 WO 2006124578A2 US 2006018416 W US2006018416 W US 2006018416W WO 2006124578 A2 WO2006124578 A2 WO 2006124578A2
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WO
WIPO (PCT)
Prior art keywords
gas
waste
chamber
waste anesthetic
gas stream
Prior art date
Application number
PCT/US2006/018416
Other languages
English (en)
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WO2006124578A3 (fr
WO2006124578B1 (fr
Inventor
James M. Berry
Steve Morris
Original Assignee
Anesthetic Gas Reclamation, Llc
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
Priority claimed from US11/266,966 external-priority patent/US7628034B2/en
Priority to CN2006800221563A priority Critical patent/CN101212998B/zh
Priority to KR1020127030743A priority patent/KR101318555B1/ko
Priority to CA2607902A priority patent/CA2607902C/fr
Priority to EP06770274A priority patent/EP1879665A4/fr
Priority to NZ563340A priority patent/NZ563340A/en
Application filed by Anesthetic Gas Reclamation, Llc filed Critical Anesthetic Gas Reclamation, Llc
Priority to AU2006247692A priority patent/AU2006247692B2/en
Priority to KR1020077029106A priority patent/KR101281891B1/ko
Priority to JP2008511400A priority patent/JP4900974B2/ja
Publication of WO2006124578A2 publication Critical patent/WO2006124578A2/fr
Publication of WO2006124578A3 publication Critical patent/WO2006124578A3/fr
Publication of WO2006124578B1 publication Critical patent/WO2006124578B1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M16/00—Devices for influencing the respiratory system of patients by gas treatment, e.g. mouth-to-mouth respiration; Tracheal tubes
    • A61M16/01—Devices for influencing the respiratory system of patients by gas treatment, e.g. mouth-to-mouth respiration; Tracheal tubes specially adapted for anaesthetising
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M16/00—Devices for influencing the respiratory system of patients by gas treatment, e.g. mouth-to-mouth respiration; Tracheal tubes
    • A61M16/0087—Environmental safety or protection means, e.g. preventing explosion
    • A61M16/009—Removing used or expired gases or anaesthetic vapours
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M15/00—Inhalators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M16/00—Devices for influencing the respiratory system of patients by gas treatment, e.g. mouth-to-mouth respiration; Tracheal tubes
    • A61M16/0087—Environmental safety or protection means, e.g. preventing explosion
    • A61M16/009—Removing used or expired gases or anaesthetic vapours
    • A61M16/0093—Removing used or expired gases or anaesthetic vapours by adsorption, absorption or filtration
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B7/00—Respiratory apparatus
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B7/00—Respiratory apparatus
    • A62B7/02—Respiratory apparatus with compressed oxygen or air
    • A62B7/04—Respiratory apparatus with compressed oxygen or air and lung-controlled oxygen or air valves
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2202/00—Special media to be introduced, removed or treated
    • A61M2202/02—Gases
    • A61M2202/0208—Oxygen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2202/00—Special media to be introduced, removed or treated
    • A61M2202/03—Gases in liquid phase, e.g. cryogenic liquids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2205/00—General characteristics of the apparatus
    • A61M2205/36—General characteristics of the apparatus related to heating or cooling
    • A61M2205/3606—General characteristics of the apparatus related to heating or cooling cooled
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2205/00—General characteristics of the apparatus
    • A61M2205/84—General characteristics of the apparatus for treating several patients simultaneously

Definitions

  • This invention concerns the treatment of waste anesthetic gases produced by one or more anesthesia delivery systems of a healthcare or other facility that use inhaled anesthetics for medical, dental, or veterinary purposes.
  • the invention pertains to the removal and reclamation of nitrous oxide, fluoro-ethers, and other halocarbons from a stream of waste anesthetic gases prior to its discharge to the atmosphere.
  • Anesthesia delivery systems in surgical facilities produce significant quantities of waste anesthetic gases.
  • these gases are collected from the patients' exhalation by a dedicated or shared vacuum system.
  • the healthcare facilities typically employ one or more centrally-located vacuum pumps to collect waste gases from individual anesthetizing locations.
  • These vacuum pumps are usually oversized, because they are designed to collect exhaled anesthetics over a wide range of flow rates. Because these pumps operate continuously, the waste anesthetic gas suction system also entrains large amounts of surrounding room air from the anesthetizing locations, significantly diluting the waste anesthetic gases therein.
  • the gas stream is often admixed with additional room air to further dilute it prior to its ejection from the facility.
  • This dilute waste anesthetic gas/air mixture is typically pumped to a location outside of the surgical facility, where it is vented to the open atmosphere.
  • the waste anesthetic gases are generally collected at about 20-30° C with a relative humidity ranging between 10 to 60 percent.
  • the average composition of the waste gases is estimated to be (in volume percent): 25-32 percent oxygen, 60-65 percent nitrogen, 5-10 percent nitrous oxide, and 0.1-0.5 percent volatile halocarbons, including fluoro-ethers, such as isoflurane, desflurane and sevoflurane.
  • the waste anesthetic gas may also contain trace amounts of lubricating oil vapor from the vacuum pumps.
  • waste anesthetic gas halocarbons (similar in composition to Freon-12® and other refrigerants) have been linked to ozone depletion and to a lesser degree, global warming.
  • the halocarbons used in anesthesia (primarily halogenated methyl ethyl ethers) now represent a significant emissions source, because other industrial and commercial halocarbon emissions have been greatly reduced by legislation and other initiatives in recent years.
  • waste anesthetic gas emissions have so far escaped environmental regulation in the United States, legislative initiatives to strictly regulate waste anesthetic gas emissions will likely occur in the near future.
  • U.S. Patent No. 4,259,303 describes the treatment of laughing gas with a catalyst
  • U.S. Patent No. 5,044,363 describes the adsorption of anesthetic gases by charcoal granules
  • U.S. Patent No. 5,759,504 details the destruction of anesthetic gases by heating in the presence of a catalyst
  • U.S. Patent No. 5,928,411 discloses absorption of anesthetic gases by a molecular sieve
  • U.S. Patent No. 6,134,914 describes the separation of xenon from exhaled anesthetic gas.
  • a cryogenic method for scrubbing volatile halocarbons from waste anesthetic gas is disclosed by Berry in U.S. Patent No. 6,729,329, which is incorporated herein by reference.
  • FIG. 1 illustrates a typical waste anesthetic gas reclamation system 10 of prior art for a healthcare facility.
  • the system 10 includes a number of individual anesthetizing stations 15A, 15B, 15C, each having an anesthetizing machine 12A, 12B, 12C which delivers anesthesia to a patient via a mask 14A, 14B, 14C or similar device. Excess anesthetic gases, patients' exhalation, and air are collected at the masks 14 A, 14B, 14C by the anesthetizing machines 12A, 12B, 12C and discharged to a common collection manifold 16.
  • the waste anesthetic gas collection manifold 16 is typically hard plumbed into the healthcare facility, and the anesthetizing machines 12A, 12B, 12C are removably connected to the collection manifold 16 at standard waste anesthetic gas connectors 18A, 18B, 18C, e.g. 19 mm or 30 mm anesthetic connectors.
  • the waste anesthetic gas reclamation system 10 operates at a vacuum pressure which is generated by one or more central vacuum pumps 20.
  • the collected waste gas stream is typically passed through a check valve 35 to a condenser unit 22 consisting of one or more heat exchangers.
  • a source of liquid oxygen, or other suitable heat sink extracts heat from the waste anesthetic stream, condensing the anesthetic gas components.
  • the liquid waste anesthetic condensate is captured in collection vessels 24, and any liquid water condensate is captured in collection vessel 23.
  • the remaining gas stream, stripped of waste anesthetic gas components, passes through a receiver 26B and the vacuum pump(s) 20, and it is then exhausted to the atmosphere outside of the healthcare facility through vent 46.
  • the current methods for scavenging waste anesthetic gases from anesthetizing locations 15A, 15B, 15C in healthcare facilities generally involve drawing high flows of room air into the dedicated or shared vacuum collection manifold 16 to entrain waste anesthetic gases.
  • the collection manifold 16 may also continuously draw in air through a number of idle anesthetizing machines 12A, 12B, 12C.
  • the collection system manifold 16 extracts between 20-30 liters of waste anesthetic gas and/or room air per minute at each anesthetizing location 15A, 15B, 15C.
  • waste anesthetic reclamation system 10 flow rate ranges between 500-1000 1/min. (14-35 scf/min.).
  • a high-flow dilute waste gas system The advantages of a high-flow dilute waste gas system are that the system easily accommodates a wide range of anesthetic exhaust flows, the system is safer because little anesthetic can escape the system, and the system is more trouble-free because little maintenance is required.
  • high-flow systems are energy-intensive, generally requiring large vacuum pumps 20 in order to maintain sufficient suction at a large number of anesthetizing stations 15A, 15B, 15C.
  • vacuum pumps of 100-200 cfm capacity are not uncommon.
  • a low- flow waste anesthetic gas scavenging system which safely concentrates waste anesthetic gases is desirable.
  • a diluted waste anesthetic gas stream is thermally inefficient. Removal of a waste gas component by condensation requires lowering the temperature of the entire flow stream to a point where the partial pressure of the gaseous waste component is equal to or greater than its saturated vapor pressure (at that temperature). Therefore, to cool the large volume of diluted waste anesthetic gas to a temperature below the saturated vapor pressure of its components, a sizeable cooling utility (i.e. a greater quantity of liquid oxygen, liquid nitrogen, etc.) is required.
  • anesthetic gases are highly volatile substances. For a given temperature, they have a higher vapor pressure than the vapor pressure of water and other lower volatile substances. Substances with higher vapor pressures generally require greater cooling to achieve the same or similar condensate recovery as substances with lower vapor pressures. Thus, anesthetic gases need to be cooled to extremely low temperatures, i.e. cryogenic temperatures, in order to recover appreciable amounts of anesthetic as condensate. However, these extremely low temperatures approach, and in many cases, fall below the freeze point of many anesthetics. In such situations, the waste anesthetic gas stream may still contain anesthetic concentrations that could be condensed except for the undesirable freezing of the system. Pressure, in addition to temperature, can greatly influence condensation.
  • Elevating the pressure of the condensation system is advantageous, because it allows condensation to occur at significantly higher temperatures than would otherwise occur at lower operating pressures. This also avoids the risk and problems associated with freezing of the condensate.
  • the most beneficial thermodynamic characteristic is that pressure has a much larger effect on the dew point of the vapor than the freezing point of the liquid.
  • the dew point temperature of a typical anesthetic-laden vapor stream increases with increasing pressure while its freezing point temperature stays relatively constant for varying system pressures.
  • the increased temperature span between the dew point of the vapor and the freeze point of the condensate, due to increases in system pressure, provides greater operational flexibilities for condensation systems. For example, less cryogenic refrigerant is needed to effect the same amount of condensation, because condensation can occur at. higher temperatures. Furthermore, if a more complete separation of the anesthetic from the waste gas stream is desired, the system temperature can be lowered while maintaining an elevated pressure. This permits additional anesthetic to be condensed from the vapor phase without the associated risk of condensate freezing. Thus, a strategy may be developed to achieve the optimum separation of anesthetic by simply adjusting the condensation system pressure relative to the condensation system temperature. Of course, the relative refrigeration versus compression costs should also be considered in any cost optimization strategy.
  • waste anesthetic gas scavenging and reclamation used in hospitals are impractical for use in a small office setting because of their sheer size and expense of operation.
  • Most waste anesthetic gases used in small office settings are simply vented to the atmosphere (or to the operating room) with no treatment and/or attempt to recover the valuable anesthetic components. Therefore, a self-contained waste anesthetic gas scavenging and reclamation system, which will provide the same benefits and/or features as the much larger systems used hospitals and other traditional healthcare facilities, is desirable for these small, discrete office settings.
  • a primary object of the invention is to provide an economical system and method for removing fluoro-ethers, nitrous oxide, and other volatile halocarbons from waste anesthetic gases from a surgical or other healthcare facility before such gases are vented to the atmosphere.
  • Another object of the invention is to provide a system and method for substantially preventing atmospheric venting of fluoro-ethers and other volatile halocarbons of waste anesthetic gas while eliminating the need of prior art catalysts, charcoal granules and heating techniques.
  • Another object of the invention is to provide a system and method which reduces anesthetic-related halocarbon emissions from a healthcare facility into the atmosphere by about 99 percent or more.
  • Another object of the invention is to provide a system and method which reclaim and allow re-distillation and/or reuse of a large percentage of the nitrous oxide and/or anesthetic halocarbons used in the facility.
  • Another object of the invention is to provide a system and method which requires minimal additional investment for a healthcare facility to implement.
  • Another object of the invention is to provide an economical system and method which utilizes and enhances existing waste anesthetic gas reclamation systems of healthcare facilities for minimal impact and cost.
  • Another object of the invention is to provide a system and method for separating various removed nitrous oxide, fluoro-ethers, and other volatile halocarbon components based on their physical characteristics, such as their bubble and dew points.
  • Another object of the invention is to provide an economical system and method for increasing the efficacy and efficiency of condensation-type waste anesthetic scavenging systems.
  • Another object of the invention is to provide a flexible system and method for increasing the efficacy and efficiency of condensation-type waste anesthetic scavenging system by operating the system under varying pressures and temperatures.
  • Another object of the invention is to provide a system and method for reclaiming anesthetic gases from a waste anesthetic gas stream which do not require integration with existing waste anesthetic gas reclamation systems of the healthcare facility.
  • Another object of the invention is to provide a system and method for reclaiming anesthetic gases from a waste anesthetic gas stream which minimize reliance on the utility infrastructure and supplies of a healthcare facility.
  • a system and method for the removal of fluoro-ethers, nitrous oxide and volatile halocarbon gas components from waste anesthetic gases which comprise one or more of the following: a low-flow anesthetic gas scavenging unit, a batch-mode frost fractionation process for collecting waste anesthetic gases as frost on the cooling surfaces of a cold trap/fractionator, a compressor with at least one compression stage, and a self-contained unit requiring minimal interfacing with the utility infrastructure and supplies of a healthcare facility.
  • a low-flow scavenging or reclamation system which includes a number of intelligent waste anesthetic gas collection units, one located at each individual anesthetizing machine in a healthcare or surgical facility and fluidly coupled to a combined collection manifold.
  • Each intelligent gas collection unit includes a collection chamber, an exhaust valve to selectively isolate the suction of the collection manifold at the respective anesthetizing station when waste anesthetic gas is not being produced, and associated sensors, circuitry, controls, or mechanisms to operate the exhaust valve.
  • Waste anesthetic gas enters from the anesthetizing machine exhaust into the collection chamber through a standard anesthetic waste-gas connector.
  • a sensitive pressure sensor which is preferably electrically coupled to a solenoid- operated exhaust valve located at the exhaust side of the collection chamber.
  • the pressure measured by the pressure sensor is the difference between the pressure of the collection chamber and the outside ambient air pressure. If the pressure within the collection chamber exceeds ambient pressure, the increased pressure is detected by the pressure sensor, which by control circuitry causes the exhaust valve to open and results in a rapid decrease in collection chamber pressure. As the chamber pressure approaches ambient, the pressure sensor detects the pressure drop and causes the exhaust valve to shut.
  • the collection circuitry is preferably a low voltage direct current circuit, and the exhaust valve is preferably configured as a normally-open valve.
  • a mechanical vacuum breaker and a mechanical relief valve exist in the collection chamber for safety purposes.
  • the pressure detector, exhaust valve, and the circuitry therebetween may optionally be selected and designed to provide a proportional response to pressure changes, so that the exhaust valve opens a small amount for a small pressure rise and a larger amount for a larger pressure rise.
  • the pressure sensor may be pneumatically or mechanically coupled to the exhaust valve for control thereof, and/or the intelligent waste anesthetic gas collection unit may be incorporated into an improved anesthetizing machine instead of integrated with the healthcare facility waste anesthetic gas collection manifold.
  • the improved anesthetizing machine thus includes the anesthetizing machine of prior art and an intelligent waste anesthetic gas collection unit according to an embodiment of the invention.
  • Isolating the collection manifold from entraining room air when no waste anesthetic gas is being produced reduces the average anesthetic scavenging flow by approximately 90 percent, thus reducing the necessary capacity of the vacuum pumps, piping, and associated other hardware.
  • a batch-mode fractionation process which uses cold trap or liquid air trap technology to lower the temperature and pressure of the fluoro-ethers and other anesthetic halocarbons to a point where the vapors collect as frost through desublimation (deposition) onto the cooling surfaces in a cold trap/fractionator.
  • the fluoro-ethers and other anesthetic halocarbon components in the waste anesthetic gas are solidified through refrigeration onto cooling coils in a heat exchanger to remove the components from the effluent gas.
  • the source of refrigeration is preferably liquid oxygen, which is available at surgical facilities, such as hospitals or outpatient clinics, and must generally be warmed for ordinary use.
  • liquefied gases such as liquid nitrogen, etc.
  • the cold trap/fractionator is periodically cycled through a thawing stage during which the cooling surfaces, caked with frost gas components trapped from the waste anesthetic gas passing thereby, are slowly warmed to sequentially separate and collect the trapped components.
  • sufficiently high pressures i.e., typically atmospheric pressure and above
  • the trapped fluoro-ethers and other anesthetic halocarbon components melt and the liquefied components are drained into separate tanks, depending on their physical characteristics.
  • the trapped fluoro- ethers and other anesthetic halocarbon components do not liquefy but rather sublimate directly into the vapor phase.
  • These reclaimed anesthetic vapors are preferably collected via a gaseous anesthetic collection system for further processing. The remainder of the anesthetic gas is preferably vented to atmosphere.
  • a compressor with at least one compression stage is used to elevate the pressure of the waste anesthetic gas stream prior to anesthetic reclamation by condensation.
  • Compression of the waste anesthetic gas to a level above atmospheric pressure is advantageous, because the higher pressure essentially elevates the temperature at which saturation and condensation of the anesthetic gas can occur.
  • compression of the gas above atmospheric pressure allows the same fraction of anesthetic to be removed by condensation at a higher temperature as would otherwise have occurred by condensation at atmospheric pressure and at a lower temperature.
  • a greater fraction of anesthetic may be condensed from the vapor phase as the temperature of the compressed waste anesthetic gas is lowered from this higher temperature.
  • a strategy may be developed to achieve the optimum separation of anesthetic by simply manipulating the condensation system pressure relative to the condensation system temperature. Furthermore, energy and cost saving may be possible when the relative refrigeration versus compression costs are factored into the strategy.
  • a compressor unit consisting of one or more compression stages is located within the waste anesthetic gas scavenger system between the waste anesthetic gas collection unit and the condensation unit.
  • the compressor unit is sized to compress the anesthetic waste gas from the collection unit to a pressure up to 50 psig for subsequent treatment in a condensation system using a refrigerant, i.e. liquid oxygen, liquid nitrogen, etc., supplied by a hospital or other medical, dental, or veterinary facility.
  • the waste anesthetic gas stream is compressed to pressures well above 50 psig to take advantage of attendant increases in separation efficiency and fractional extraction.
  • a separate refrigerant supply for the condenser is desirable in order to avoid the risk of contaminating the healthcare facility's gas supplies should an internal leak within the condenser occur.
  • a self-contained waste anesthetic gas reclamation unit which requires minimal dependence on the utility infrastructure and supplies of a healthcare facility.
  • the unit only requires operational power, a source of waste anesthetic gas, and an atmospheric vent. Therefore, it can be easily accommodated in a small surgical center, such as a physician's office, a small animal clinic, or a dental office.
  • the system/method employs a small refrigeration unit, which cools an intermediate heat transfer
  • the waste anesthetic gas is passed through a multi-stage condenser/heat exchanger wherein heat from the waste anesthetic gas stream is exchanged with the intermediate heat transfer fluid cooled by the small refrigeration unit.
  • the system/method does not depend on liquid oxygen or liquid nitrogen supplies from the healthcare facility in order to provide the necessary cryogenic cooling to the waste anesthetic gas stream.
  • liquid oxygen and/or liquid nitrogen supplied by the healthcare facility could be used in the heat exchanger/condenser as the intermediate heat transfer fluid.
  • Figure 1 illustrates in schematic form a high-flow waste anesthetic gas scavenging and reclamation system of prior art by which fluoro-ethers and other volatile anesthetic gas components are separated from the collected gas stream by condensation before the waste gas stream is vented to the atmosphere;
  • Figure 2 illustrates in schematic form a preferred embodiment of a low-flow waste anesthetic gas reclamation system according to the invention including intelligent waste anesthetic gas collection units which limit air evacuation into the combined vacuum system;
  • FIG 3 is a detailed schematic drawing of an intelligent waste anesthetic gas collection unit of Figure 2 showing a collection chamber at ambient pressure and a pressure detector with associated circuitry to position a solenoid-operated exhaust valve in the shut position;
  • Figure 4 is a detailed schematic drawing of the intelligent waste anesthetic gas collection unit of Figure 3 wherein the collection chamber is at a pressure slightly greater than ambient pressure and the pressure detector and associated circuitry are operating to position the solenoid-operated exhaust valve in the open position;
  • Figure 5 illustrates in schematic form an alternate embodiment of a low-flow waste anesthetic gas reclamation system wherein an intelligent waste anesthetic gas collection unit is combined with an anesthetizing machine of prior art to form an improved anesthetizing machine
  • Figure 6 illustrates in schematic form an alternate embodiment of a low-flow waste anesthetic gas reclamation system useful for retrofitting existing systems wherein intelligent anesthetic gas collection units are separate and distinct from both the collection manifold and from the anesthetizing machine;
  • Figure 7 illustrates in schematic form the process and system by which fluoro-ethers and other volatile halocarbon gas components of waste anesthetic gases are separated therefrom and subsequently fractionated by sequential thawing and collection of the resultant liquid halocarbon prior to venting of the waste anesthetic gases to the atmosphere, using as a heat sink for the process a source of liquefied oxygen;
  • Figure 8 illustrates in schematic form an alternative embodiment including a parallel of two or more cold trap/fractionators
  • Figure 9 illustrates in schematic form an alternative embodiment of the reclamation system of Figure 7 including means to collect trapped components of the waste anesthetic gas which evaporate from the liquid phase or sublime directly into the vapor phase;
  • Figure 10 illustrates in schematic form a preferred embodiment according to the invention of a high-flow waste anesthetic gas reclamation system which includes one or more high-flow waste anesthetic gas collection units, a compressor consisting of one or more compression stages, a single or multiple stage condenser/heat exchanger unit, and an . expansion valve to induce additional anesthetic gas condensation;
  • Figure 11 illustrates in schematic form the process and system by which halocarbon gas components of waste anesthetic gases are liquefied using a source of liquefied oxygen at a healthcare facility for removal of such gas components prior to venting of the waste anesthetic gases to the atmosphere;
  • Figure 12 illustrates in schematic form the process and system by which fluoro-ethers and other volatile halocarbon gas components of waste anesthetic gases are separated therefrom and subsequently fractionated by sequential thawing and collection of the resultant liquid halocarbon prior to venting of the waste anesthetic gases to atmosphere, using as a heat sink for the process a source of liquefied oxygen;
  • Figure 13 illustrates in schematic form a preferred embodiment according to the invention of a low-flow waste anesthetic gas reclamation system which includes one or more low-flow waste anesthetic gas collection units, a compressor consisting of one or more compression stages, a single or multiple stage condenser/heat exchanger unit, and a small turbine to capture the potential energy of the compressed waste gas prior to atmospheric venting;
  • Figure 14 illustrates in schematic form the heat exchanger/condenser of a preferred embodiment of the invention which cools and condenses anesthetic gas components from the waste anesthetic gas stream through countercurrent heat exchange with an intermediate heat transfer fluid that is cooled in a small refrigeration unit;
  • Figure 15 illustrates in schematic form a preferred embodiment of the anesthetic gas reclamation system which includes a low-flow waste anesthetic gas scavenging unit, a compressor consisting of one or more compression stages, a single or multiple stage condenser/heat exchanger unit to remove the anesthetic gas components from the waste anesthetic gas stream, a small refrigeration unit used to cool the heat transfer fluid used as a refrigerant in the condenser, and a small turbine to capture the potential energy of the compressed waste gas prior to atmospheric venting;
  • Figure 16 illustrates in schematic form the process and system by which halocarbon gas components of waste anesthetic gases are liquefied using an intermediate heat transfer fluid to condense those gas components prior to venting of the waste anesthetic gases to the atmosphere
  • Figure 17 illustrates in schematic form the process and system by which fluoro-ethers and other volatile halocarbon gas components of waste anesthetic gases are separated therefrom and subsequently fractionated by sequential thawing and collection of the resultant liquid halocarbon prior to venting of the waste anesthetic gases to atmosphere, using as a heat sink for the process a heat transfer fluid cooled in a separate refrigeration unit; and
  • Figure 18 illustrates in schematic form a preferred embodiment of a self-contained waste anesthetic gas reclamation system which includes a low-flow anesthetic scavenging unit, a compressor, a heat exchanger/condenser to remove the anesthetic gas components from the waste anesthetic gas stream, a small refrigeration unit used to cool the heat transfer fluid used as a refrigerant in the condenser, and an expansion valve to induce additional anesthetic gas condensation.
  • FIG 2 schematically illustrates a preferred embodiment of the low-flow waste anesthetic gas collection and reclamation system 11 according to the invention.
  • the reclamation system 11 is nearly identical to the prior art waste reclamation system 10 of Figure 1 described above except for the inclusion of intelligent waste anesthetic gas collection units 3OA, 3OB, 3OC located at or near each anesthetizing station 15A, 15B, 15C in the healthcare facility.
  • the intelligent waste anesthetic gas collection units 3OA, 3OB, 3OC are preferably fluidly coupled within the individual legs of the collection manifold 16 near the standard waste anesthetic gas connectors 18 A, 18B, 18C.
  • Each intelligent gas collection unit 30A, 30B, 30C includes a collection chamber 32A, 32B, 32C, an exhaust valve 34A, 34B, 34C to selectively isolate the suction of the collection manifold 16 at the respective anesthetizing station when waste anesthetic gas is not being produced, and associated sensors, circuitry, controls, or mechanisms to operate the exhaust valve 34A, 34B, 34C.
  • the collection chambers 32 may be rigid, flexible (such as an elastic bag), or a combination of both.
  • Isolating the collection manifold 16 from entraining room air when no waste anesthetic gas is being produced reduces the average anesthetic scavenging flow by approximately 90 percent, thus reducing the necessary capacity of the vacuum pumps, piping, and associated other hardware.
  • waste anesthetic gas flow rate of 500-1000 1/min with the prior art reclamation system 10 of Figure 1 is reduced to 50-100 1/min with the reclamation system 11 of Figure 2 according to the preferred embodiment of the invention.
  • the reclamation system 11 described above requires only the addition of individual intelligent waste anesthetic gas collection units 30A, 30B, 30C to an already existing healthcare waste anesthetic gas reclamation system 10, thus providing a simple and inexpensive means for upgrading current systems.
  • FIG. 3 illustrates an individual intelligent waste anesthetic gas collection unit 30 according to a preferred embodiment of the invention.
  • waste anesthetic gas enters from the anesthetizing machine 12 exhaust into a chamber 32 through a 19 mm, 30 mm, or similar, standard anesthetic waste-gas connector 18.
  • a sensitive pressure sensor 40 electrically coupled to a solenoid-operated exhaust valve 34 located at the exhaust side of the chamber 32.
  • the pressure measured by pressure sensor 40 is the difference between the pressure of chamber 32 and the outside (ambient) air pressure. If the pressure within the chamber 32 rises to slightly above ambient, the increased pressure is detected by the pressure sensor 40, which by control circuitry causes the exhaust valve 34 to open.
  • Opening valve 34 fluidly connects the chamber 32 to the vacuum source in collection manifold 16, resulting in a rapid decrease in pressure in chamber 32.
  • the sensor 40 detects the pressure drop and causes the exhaust valve 34 to close.
  • the intelligent waste anesthetic gas collection unit 30 is powered electrically by a direct current low voltage source 6 to minimize the hazard of fire or explosion.
  • exhaust valve 34 is configured as a normally-open valve, so that if a fault occurs, the exhaust valve 34 will fail open, and the system will, in effect, revert to the a continuous-flow air-dilution scavenging system of prior art.
  • a means of preventing excessive positive or negative pressures being transmitted to the anesthetizing machine 12 is provided in anesthetic waste gas collection unit 30 to assure patient safety.
  • a mechanical vacuum breaker 7 exists in chamber 32 which will be drawn open to restore the pressure to ambient.
  • a mechanical relief valve 8 will open to vent the excess pressure to the atmosphere.
  • the waste anesthetic gas collection unit 30 is preferably constructed of materials which comply with safety standards for use in oxygen-enriched environments.
  • voltage source 6 is preferably wired in series with the switch contacts 5 of pressure detector 40 and with the solenoid 4 of exhaust valve 34.
  • a damping capacitor 9 may optionally be wired in parallel with the exhaust valve solenoid 4.
  • the contacts 5 of pressure detector 40 are closed, and current flows between voltage source 6 and solenoid 4, energizing solenoid 4 and shutting exhaust valve 34.
  • the contacts 5 of pressure detector 40 are opened, thus de-energizing solenoid 4 and allowing exhaust valve 34 to open.
  • the circuitry illustrated in Figures 3 and 4 is of the simplest design, but other more sophisticated circuits may also be used.
  • pressure detector 40 exhaust valve 34, the circuitry therebetween may be selected and designed to provide a proportional response to pressure changes, so that valve 34 opens a small amount for a small pressure rise and a larger amount for a larger pressure rise.
  • suitable means for detecting exhaled breath other than by pressure increases such as by detection of halocarbons, moisture, or flow, may be used.
  • Figure 3 illustrates an electrical circuit coupling pressure sensor 40 and exhaust valve 34
  • the pressure sensor 40 may alternatively be pneumatically or mechanically coupled to exhaust valve 34 for control thereof.
  • the selection and design of mechanical pressure-controlled actuators, mechanically operated valves, pneumatic control circuits, and pneumatically actuated valves is well known in the art; therefore, further discussion is not provided herein.
  • the intelligent waste anesthetic gas collection unit 30 may be incorporated into an improved anesthetizing machine 50 instead of integrated with the healthcare facility waste anesthetic gas collection manifold 16.
  • the improved anesthetizing machine 50 thus includes the anesthetizing machine 12 of prior art and an intelligent waste anesthetic gas collection unit 30 according to an embodiment of the invention as set forth herein.
  • the improved anesthetizing machine 50 is removably coupled to a 19 mm, 30 mm, or similar, standard anesthetic waste-gas connector 18.
  • a healthcare facility having a waste anesthetic gas reclamation system equipped with improved anesthetizing machines 50 at all anesthetizing stations 15 will perform in the same manner as the waste anesthetic gas reclamation system 11 of Figure 2.
  • FIG. 6 illustrates an alternate embodiment where collection units 3OA, 30B, 30C are separate and distinct from both the collection manifold 16 and the anesthetizing machines 12A, 12B, 12C.
  • each collection unit 3OA, 3OB, 3OC removably connects to manifold 16 at a first standard (e.g., 19 mm or 30 mm) anesthetic waste gas connector 18A, 18B, 18C.
  • Each anesthetizing machine 12A, 12B, 12C is in turn removably connected to a second standard anesthetic waste gas connector 19 A, 19B, 19C.
  • FIG. 7 illustrates a preferred embodiment of the batch-mode fractionation process 1 according to the invention for use at a hospital, a surgical facility, or other healthcare facility 110.
  • Waste anesthetic gas is collected and passed through a valve 112 in facility 110 to a waste gas flow line 39.
  • a flow line 27 to supply oxygen to the facility 110 preferably includes a valve 114 to which downstream oxygen service lines inside the hospital 110 are fluidly connected.
  • a source of liquid oxygen is schematically illustrated by tank 120 which preferably exists near the healthcare facility 110.
  • hospitals and other healthcare facilities 110 pass the liquid oxygen through a heat exchanger 122 to raise the temperature of the liquid oxygen (about -193° C) to room temperature (about 25° C) before reaching the facility 110 via flow line 27.
  • liquid oxygen is warmed using heat exchangers 122 located near each tank 120 which expose the liquid oxygen to ambient air temperature.
  • the warmed oxygen gas is then applied by flow line 27 and valve 114 to service lines (not shown) for distribution to the point of patient use within the healthcare facility 110.
  • a cold trap/fractionator 25 which includes an enclosure 130 containing cooling coils 36 therein, serves as a heat exchanger.
  • the internal volume of the cooling coils 36 is fluidly isolated from the remaining volume of the enclosure 130, but the two volumes are thermally/conductively coupled.
  • the cold trap/fractionator 25 promotes heat exchange from waste anesthetic gas in enclosure 130 to liquid oxygen in cooling coils 36.
  • the waste anesthetic gas is provided from the facility 110 by flow line 39, and the liquid oxygen is provided by the liquid oxygen source 120 by flow line 21.
  • Enclosure 130 preferably is of double-walled construction, which provides improved insulation from ambient conditions and thus facilitates heat exchange solely between the waste anesthetic gas and the liquid oxygen.
  • the source flow line 21 for liquid oxygen is preferably fluidly connected to the inlet 47 of the condensing coils 36 by a thermostatic control valve 33.
  • the outlet 48 of the cooling coils is fluidly connected by flow line 126 to flow line 27 for oxygen supply to the facility 110.
  • the existing heat exchanger 122 used to warm the liquid oxygen preferably remains in place fluidly connected in parallel with cold trap/fractionator 25 between liquid oxygen tank 120 and oxygen flow line 27 to warm the oxygen when facility oxygen demand is greater than the demand of the cold trap/fractionator 25, when the cold trap/fractionator 25 is operating in its thaw cycle as described below, or when the cold trap/fractionator 25 is out of service, such as for maintenance or repair.
  • waste anesthetic gas flow line 39 and cut-out valve 112 fluidly connect to collection flow lines (not shown) in the facility 110.
  • waste anesthetic gas flow line 39 is selectively fluidly coupled to an inlet 31 of enclosure 130 or an atmospheric discharge vent 46 by a 3-way bypass valve 29.
  • flow line 39 is directed only to the inlet 31 of enclosure 130 by the 3-way selector valve 29.
  • the waste anesthetic gas flows through enclosure 130 of cold trap/fractionator 25 towards outlet fitting 37, during which gas components are removed by desublimation (deposition) onto the cooling coils 36, and from fitting 37 the waste anesthetic gas flows to the atmosphere via vent 46.
  • the waste anesthetic gas flow line 39 is preferably only directly aligned to the atmospheric discharge vent 46, bypassing the cold trap/fractionator 25, for system maintenance, repair, or when it is desirable for the reclamation system not to be in use.
  • the waste anesthetic gas (generally containing nitrogen, oxygen, nitrous oxide, nitrous oxide, water vapor and fluoro-ethers) generally enters through flow line 39 at about 20-30° C with a relative humidity ranging between 10 to 60 percent.
  • the waste anesthetic gas may also contain trace lubricating oil vapor from the vacuum pumps (not shown).
  • Liquid oxygen (about -193° C) enters the cold trap/fractionator 25 at the inlet 47 to cooling coils 36, while the waste anesthetic gas (about 20-30° C) enters the enclosure 130 of the cold trap/fractionator 25 at inlet fitting 31.
  • This countercurrent heat exchanger arrangement results in a temperature gradient where the top of the cold trap/fractionator 25 is the warmest and where the bottom of the cold trap/fractionator 25 is the coldest.
  • the upper region 60 of the cooling coils 36 of the cold trap/fractionator 25 cools the waste anesthetic gas from about 20° C to about -5° C to extract water vapor as frost on the coils 36.
  • the upper middle region 62 of the cooling coils 36 next cools the waste anesthetic gas to extract sevoflurane at about -60° C by desublimation/deposition onto the coils 36.
  • the lower middle region 63 extracts nitrous oxide by desublimation/deposition at about -90° C
  • the lower region 64 of the cooling coils 36 extracts isoflurane and desflurane between -100° C and -HO 0 C by desublimation/deposition onto the coils 36.
  • Desublimation/deposition of the anesthetic component directly onto coils 36 generally occurs only at low temperatures and pressures.
  • nitrous oxide desublimates/deposits at temperatures and pressures below its triple point of -90°C and 0.88 bar.
  • one or more of the anesthetic components may condense as a liquid and solidify onto coils 36 at a temperature region 62, 63, 64 corresponding to their individual physical characteristics.
  • waste gas mostly nitrogen and oxygen at about -110° C
  • the remainder of waste gas is then exhausted to the atmosphere via line 46 or further processed, for example, by existing catalytic technologies.
  • the liquid oxygen which enters the cold trap/fractionator 25 at about -193° C, exits the cold trap/fractionator 25 at about 0° C.
  • the oxygen may be further warmed by a subsequent process or mixed with warmer oxygen effluent from heat exchanger 122 to reach room temperature or other appropriate temperature for healthcare facility use.
  • the cold trap/fractionator 25 is periodically cycled through a thaw process. During the thaw cycle, the cold trap/fractionator 25 is slowly warmed to about 0° C to defrost the cooling coils 36. Warming is achieved by reducing or securing the flow of liquid oxygen through cooling coils 36 by thermostatic control valve 33 and allowing the cold trap/fractionator 25 to warm to room temperature by heat transfer with its surroundings. In an alternate embodiment, warm oxygen from heat exchanger 122 may be directed through the cooling coils 36 by opening valve 59 to increase the thaw rate. In yet a third embodiment, another fluid (not shown) may be directed through cooling coils 36 to achieve a controlled thaw.
  • the bottom end 57 of enclosure 130 is funnel-shaped and acts as a hopper.
  • the lowest point preferably drains into a 4- way selector valve 58, which in turn is fluidly coupled to three drain tanks 23, 24A, 24B.
  • the solidified anesthetic components melt as removable liquids. Therefore, as the temperature warms past about -100° C, desflurane (melting point of approximately -108° C) and isoflurane (melting point of approximately -103° C) melt from the lower region 64 of cold trap/fractionator 25 and collect in the hopper 57.
  • Selector valve 58 is concurrently aligned to allow the liquid desflurane and isoflurane to gravity feed into the low melting point collection tank 24B.
  • desflurane or isoflurane could be collected in tank 24A with sevoflurane. While the liquid desflurane and isoflurane are preferably collected in the same tank 24B, two separate collection tanks (not shown), one for each component, could also be used.
  • nitrous oxide melts from the lower middle region 63 of cold trap/fractionator 25 and collects in the hopper 57.
  • Selector valve 58 is concurrently aligned to allow the liquid nitrous oxide to gravity feed into mid melting point collection tank 24A.
  • nitrous oxide could be collected in tank 24B with desflurane and/or isoflurane or a separate tank (not shown) could be used to collect the nitrous oxide.
  • the selector valve 58 is positioned to align hopper 57 with the mid melting point collection tank 24A.
  • containers 24 A and 24B may be cooled and/or pressurized to maintain the collected fluoro-ethers at low vapor pressure to minimize evaporative losses.
  • the containers 23, 24A, and 24B may be of any suitable strength and/or capacity, for example, 55 gallon steel drums.
  • the fluoro-ethers are fractionated by desublimation/deposition and/or condensation/solidification as they are removed from the waste anesthetic gas and then discretely recovered by selectively thawing the deposited frosts.
  • this reclamation method and system may also be used to remove other suitable gas components from the waste gas stream.
  • this embodiment describes fractionation of the anesthetic components using three general melting point ranges, a larger number of melting point ranges or selectively narrower melting point ranges may be used as appropriate.
  • waste anesthetic gas mass flow rate via flow line 39 ranges between 500-1,000 1/min (14-35 scf/min) at a less than 2 psig.
  • oxygen gas inflow through flow line 21 to the same large hospital 110 averages 1,000-2,000 1/min (60-100 scf/min) at a pressure of about 50 psig.
  • the cold trap/fractionator 25 is preferably designed and arranged to have a capacity to trap 8 liters (10 kg) of frozen halocarbon gases and 20 liters (20 kg) of frozen water prior to the required thawing cycle.
  • the waste gas system may operate at an increased pressure, for example, up to about 50 psig, for increased efficiency, however, desublimation/deposition of the anesthetic components will probably not be possible at this increased pressure.
  • the reclamation system 1 uses a thermostatically controlled bypass valve 59, in conjunction with the existing heat exchanger 122 and the cold trap/fractionator 25, to maintain optimal oxygen supply temperatures at flow line 27 to the facility 110.
  • a control system (not shown), which comprises flow measurement devices, temperature measurement devices, and/or pressure measurement devices (not shown), is employed to automatically control the setting of thermostatic control valves 33, 59.
  • the control system also contains circuitry to control the thaw cycle, which additionally controls bypass valve 59 and selector valve 58 as appropriate.
  • selection measurement devices and the design and construction of control systems are well known in the art, they are not discussed further herein.
  • U.S. Patent No. 6,134,914 issued to Eschwey et al. and U.S. Patent No. 6,729,329 issued to Berry are incorporated herein by reference.
  • the reclamation system 1 described above requires only three additional components for implementation at most healthcare facilities 110: (1) a cold trap/fractionator 25 located near a source of liquid oxygen 120 and connected thereto, (2) piping to deliver the waste anesthetic gases to the cold trap/fractionator 25, and (3) drain tanks 23, 24A, and 24B to collect water and fractionated liquid halocarbons from the reclamation system 1.
  • a cold trap/fractionator 25 located near a source of liquid oxygen 120 and connected thereto
  • other commonly available liquefied gases such as liquid nitrogen, etc.
  • Piping 39 for anesthetic waste gas delivery to the system 1 can be designed for relatively low pressures, although oxygen content of this stream could be as high as 40-50 percent. However, a high percentage of oxygen in the waste gas flow line 39 requires oxygen-clean installation precautions.
  • All oxygen pathways are preferably grease free and oxygen safe per the National Fire Protection Association standard 99 (NFPA 99).
  • the oxygen pathway through heat exchanger 122 must also be fail safe to allow full oxygen flow to the facility 110.
  • oxygen from tank 120 flows through heat exchanger 122 to flow line 27 and facility 110 during a loss of power while thermostatic bypass valve 33 fails shut to prevent oxygen flow through cold trap/fractionator 25.
  • FIG 8 illustrates an alternative embodiment of the invention.
  • the reclamation system 2 is substantially identical to reclamation system 1 of Figure 7, except that system 2 comprises two cold trap/fractionators 25A, 25B configured in a parallel arrangement.
  • the first cold trap/fractionator 25A is in the thaw cycle
  • the second cold trap/fractionator 25B operates in the cold trap mode, and vice versa.
  • This configuration allows for continuous processing of the anesthetic waste gas.
  • a third cold trap/fractionator (not shown) may be added in parallel for redundancy.
  • each cold trap/fractionator 25A, 25B has its own respective thermostatic control valve 33A, 33B.
  • Each cold trap/fractionator 25A, 25B also has an associated waste gas supply valve 82A, 82B which operate in coordination with waste gas bypass valve 80 to direct waste anesthetic gas flow to the cold trap/fractionator 25A, 25B currently operating in the trap cycle.
  • each cold trap/fractionator 25A, 25B may also have a waste gas vent valve 86 A, 86B.
  • drain valves 84 A, 84B cooperate with selector valve 58 to drain the cold trap/fractionator 25 A, 25B currently operating in the thaw mode.
  • the operation of the reclamation system 2 including the positions of valves 33A, 33B, 82A, 82B, 84A, 84B, 86A, 86B, 58, and 59, is preferably coordinated by a control system (not shown). Because the design and construction of control systems are well known in the art, they are not discussed further herein.
  • Figure 9 illustrates a third embodiment of the invention.
  • one or more of the solidified anesthetic components may sublime directly into the vapor phase.
  • one or more of the solidified anesthetics may evaporate during the thaw cycle, depending on the operational temperature and pressure of the cold trap/fractionator 25.
  • Reclamation system 3 is substantially identical to the reclamation system 1 of Figure 7, except that system 3 is arranged and designed to recapture anesthetic gases trapped from the waste anesthetic gas stream which have sublimed or evaporated during the thawing cycle.
  • reclamation system 3 includes additional equipment, such as a gaseous anesthetic collection tank 24C, a 3-way collection valve 56, an optional vacuum pump 92 and an optional source of nitrogen or other gas 89 with an accompanying isolation valve 90.
  • Collection valve 56, 3-way selector valve 29, and nitrogen isolation valve 90 are all preferably controlled by the control system (not shown) previously described for use with embodiment 1 of Figure 7.
  • control system not shown
  • collection valve 56 is positioned so that outlet fitting 37 is fluidly coupled to the atmospheric discharge vent 46.
  • Waste anesthetic gas enters the cold trap/fractionator 25 through inlet 31, passes over cooling coils 36 to trap water vapor, nitrous oxide, fluoro-ethers, and other volatile halocarbons, and then passes to the atmosphere through outlet 37, nitrous oxide collection valve 56, and vent line 46. Because fluoro-ethers and other halocarbon anesthetics are generally more dense then either nitrogen or oxygen, these sublimated anesthetic gases collect below any existing air (mostly nitrogen and oxygen) in the cold trap/fractionator 25. Thus, during the thaw cycle, these sublimed anesthetic gases collect just above any liquid at the bottom of enclosure 130. Collection valve 56 is aligned so that outlet fitting 37 is fluidly coupled with gaseous anesthetic collection tank 24C. Solid anesthetic components which melt as a liquid, rather than sublime as a vapor, are collected via hopper 57, selector valve 58, and collection tanks 24A, 24B as previously disclosed.
  • Sublimed anesthetic gas is reclaimed by one of several methods.
  • the sublimed anesthetic gas disposed just above any liquid level at the bottom of enclosure 130 may be displaced and collected in tank 24C by using a nitrogen blanket.
  • Nitrogen gas or another suitable blanket gas is allowed to flow through nitrogen isolation valve 90 and into the top of cold trap/fractionator 25 through inlet fitting 31.
  • the 3 -way selector valve 29 is shut to isolate enclosure 130 from vent 46 and waste anesthetic gas entering from facility 110.
  • Nitrogen isolation valve 90 is shut when all of the sublimed anesthetic gas is removed from cold trap/fractionator 25. The remaining nitrogen gas is flushed from cold trap/fractionator 25 through outlet 37, valve 56, and vent 46.
  • the sublimed anesthetic gas disposed just above any liquid level at the bottom of enclosure 130 may be suctioned from cold trap/fractionator 25 and collected in tank 24C by using a vacuum pump 92.
  • the 3-way selector valve 29 is shut to isolate enclosure 130 from vent 46 and waste anesthetic gas entering from facility 110.
  • the vacuum pump 92 draws the sublimed anesthetic gas by suction from the bottom of enclosure 130, through outlet 37, and into collection tank 24C.
  • the operation of vacuum pump 92 ceases and the position of selector valve 56 is reset to prevent flow to tank 24C.
  • Sublimed anesthetic gas may become mixed with other gases within cold trap/fractionator 25 during the thaw cycle, thereby rendering the previously described reclamation methods ineffective. Under these circumstances, additional methods, such as pressure swing adsorption, membrane separation, etc., may be employed to separate the nitrous oxide from these other gases. Various gas-gas separation techniques are well known in the prior art and will not be discussed further herein. By whichever reclamation method, the collected anesthetic gas is preferably processed for reuse.
  • the gaseous anesthetic collection means of reclamation system 3 ( Figure 9) is incorporated in the multiple cold trap/fractionators 25A, 25B of reclamation system 2 ( Figure 8).
  • Figure 10 illustrates a preferred embodiment of a high-flow waste anesthetic gas collection and reclamation system 200 having a compressor with at least one stage to elevate the pressure of the waste anesthetic gas prior to anesthetic reclamation by condensation.
  • the reclamation system 200 is similar to the previously described prior art waste anesthetic gas reclamation system 10 of Figure 1 except for the inclusion of an expansion valve 43 and one or more compression stages provided by a compressor 42.
  • Compressor 42 is preferably disposed between the waste anesthetic gas collection units 15A, 15B, 15C and the condenser 22.
  • Expansion valve 43 is preferably disposed between the condenser 22 and the receiver 45.
  • waste anesthetic gas collection manifold 16 is typically hard plumbed into the healthcare facility, and the anesthetizing machines 12A, 12B, 12C are removably connected to the collection manifold 16 at standard waste anesthetic gas connectors 18A, 18B, 18C, e.g. 19 mm or 30 mm anesthetic connectors.
  • the waste anesthetic gas collection manifold 16 operates at a slight vacuum pressure, e.g. 5 cm, which is generated by compressor 42. From the collection manifold 16, the collected waste anesthetic gases are passed through a check valve 35 into the first stage of a single stage or multiple stage compressor 42.
  • the compressor 42 is sized to compress the anesthetic waste gas from the collection units 15A, 15B, 15C to a pressure up to 50 psig for subsequent treatment in a condensation unit 22. Pressures above 50 psig are preferable in order to take advantage of attendant increases in separation efficiency and fractional extraction.
  • Multistage compressors are used to avoid the problems associated with high compression ratios, such as high discharge temperatures and increased mechanical breakdowns. As a result, compressor manufacturers recommend a compression ratio of no more than 10:1, especially for low-temperature applications. Multistage compressors can also be more economical than single stage compressors because of the attendant power cost savings attributable to compression stages having smaller compression ratios. However, the compressor 42 of system 200 needs only a single compression stage, because a compression ratio of no more than 10: 1 is anticipated.
  • the condenser 22 preferably uses a liquid oxygen, liquid nitrogen, or similar refrigerant obtained from the common supply of these liquefied gases normally available at a hospital or other medical, dental, or veterinary facility. If the waste anesthetic gas is compressed above the facility's gas supply pressure (e.g. 50 psig), then contamination of the common refrigerant supply with waste anesthetic is possible should an internal leak occur within the condenser unit 22. In an alternative preferred embodiment, the waste anesthetic gas stream is compressed to pressures well above 50 psig to take advantage of the attendant increases in separation efficiency and fractional extraction.
  • the waste anesthetic gas stream is compressed to pressures well above 50 psig to take advantage of the attendant increases in separation efficiency and fractional extraction.
  • the waste anesthetic gas flows through a collection vessel or receiver 26A which allows any liquid condensed due to compression to be removed and separated from the compressed waste anesthetic gas stream.
  • any water vapor in the gas stream should be removed to prevent freezing of the liquid water condensate in the condenser 22.
  • a preferred method to remove water vapor from the waste anesthetic gas stream is to use a first condenser stage 222A ( Figure 11), however, alternative water removal processes (not shown) may be employed, such as desiccation, adsorption, filtration, semi-permeable or hydrophobic membranes, etc. These various gas drying methods may be used at any point prior to the condensation of the anesthetic gases, including before the compression stage.
  • the compressed waste anesthetic gas stream is then cooled in a single or multiple stage condenser 22 such that the temperature of the nitrous oxide and other anesthetic halocarbons are lowered to a point where the vapors either condense as a removal liquid on the condenser coils 236B ( Figure 11) or collect as frost on the condenser coils 136 ( Figure 12).
  • the temperature and pressure at which the condensation process is conducted controls whether the anesthetic gas components are condensed as a removable liquid or deposited as a frost.
  • the remaining waste gas (mainly composed of entrained air) may be vented to the atmosphere 46.
  • the compressed waste gas is first passed through an expansion valve 43 and a receiver 45 prior to atmospheric venting 46.
  • the expansion valve 43 reduces the compressed waste gas to atmospheric pressure and further cools the compressed waste gas via the Joule- Thompson effect. Any additional anesthetic components in the waste gas may be condensed through Joule-Thompson adiabatic expansion. These anesthetic condensates are collected in the receiver 45 prior to the atmospheric discharge 46 of the waste gas.
  • the compressed waste gas is first throttled through a small turbine 44 ( Figure 13) or similar device and a receiver 45 prior to atmospheric release 46 ( Figure 13) in order to capture the potential energy of the compressed waste gas.
  • the captured energy may then be used to power the compressor 42 or supply other energy requirements of the method and system.
  • Any anesthetic components condensed by expansion of the waste gas in turbine 44 are likewise collected in the receiver 45 prior to the atmospheric discharge 46 of the waste gas.
  • heat integration of the cooled waste gas with streams to be cooled may reduce the overall cooling utility of the method and system.
  • compression of the waste anesthetic gas stream causes the temperature of the gas stream to increase.
  • the cooled waste gas stream to be vented 46 could be used to cool this compressed waste anesthetic gas stream prior to condensation in order to reduce the overall refrigerant requirement of the heat exchanger/condenser 22.
  • a condenser unit 22 which includes first and second condensers 222A and 222B.
  • the outlet line 221 for liquid oxygen from supply tank 220 is fluidly connected to the condensing coils 236B of the second vessel 222B.
  • the outlet of condensing coils 236B is fluidly connected via flow line 225 to the inlet of coils 236A of first vessel 222A.
  • the outlet of coils 236A is fluidly connected via flow line 227 to valve 214 and flow lines connected thereto (not shown) of the healthcare facility.
  • a flow line 239 connects the waste anesthetic gas flow lines from receiver 26A ( Figures 10 and 13) of the healthcare facility to an inlet of heat exchanger/condenser 222A.
  • the temperature of oxygen flowing at the inlet of the coils 236A is controlled thermostatically by valve 233 such that the temperature of the oxygen supply at valve 214 is approximately room temperature, i.e. about 25 0 C.
  • the waste anesthetic gas enters heat exchanger/condenser 222A via flow line 239 at an elevated temperature due to compression.
  • the compressed waste anesthetic gas enters at the top or entrance of heat exchanger/condenser 222A and passes downward over coils 236A wherein it exchanges heat with the liquid oxygen flowing countercurrently through the coils 236A.
  • Water vapor in the compressed waste anesthetic gas condenses to liquid water at a specific temperature (above 0 0 C), which is dependent upon the pressure of the compressed waste anesthetic gas stream.
  • the liquid water then falls by gravity to tank 23 for storage and removal.
  • the cooled compressed gas near the bottom of vessel 222A is conducted via flow line 241 to the top or entrance of heat exchanger/condenser 222B where it is applied at a temperature greater than 0 0 C.
  • the cooled compressed gas applied to the top of heat exchanger/condenser 222B passes over coils 236B wherein it exchanges heat with the liquid oxygen flowing countercurrently through the coils 236B.
  • the oxygen from flow line 221 enters the coils 236B at a temperature of approximately -150 0 C and leaves the coils 236B via flow line 225 at an increased temperature.
  • an intermediate bypass valve 235 may be provided in line 221 to bring the temperature in line 225 at the inlet of coils 236A to approximately 0 0 C.
  • the temperature of the compressed waste anesthetic gas from flow line 241 is lowered while passing over the coils 236B such that the halocarbons of the waste gas are liquefied and discharged into a collection tank 24.
  • the remainder of the compressed waste gas i.e., those components which are not harmful to the atmosphere, are vented to the atmosphere via flow line 46, throttled through an expansion valve 43 ( Figure 10) to induce additional anesthetic condensation, throttled through a small turbine 44 ( Figure 13) to capture the potential energy of the compressed gas, or subjected to further processing by existing catalytic techniques (not shown).
  • FIG. 12 generally illustrates the system and method of the ' co- pending patent application, which has been modified for an entering compressed waste anesthetic gas stream.
  • this second system and method of waste anesthetic reclamation is not as significantly affected by increases in the pressure of the waste anesthetic gas stream.
  • a condenser unit 22 consisting of a cold trap/fractionator 125 is provided with cooling coils 136 therein.
  • the outlet line 121 for liquid oxygen from supply tank 120 is fluidly connected to the condensing coils 136 of cold trap/fractionator 125.
  • the flow of oxygen at the inlet of the coils 136 is controlled thermostatically by valve 133.
  • the existing heat exchanger 122 used to warm the liquid oxygen, preferably remains in place fluidly connected in parallel with cold trap/fractionator 125 between liquid oxygen tank 120 and oxygen flow line 127 to warm the oxygen when the cold trap/fractionator 125 does not keep pace with facility oxygen demand, is operating in its thaw cycle as described below, or is out of service, for maintenance or repair, for example.
  • Valve 129 normally remains closed when heat exchanger 122 is not in use.
  • the oxygen from flow line 121 enters the coils 136 at a temperature of approximately -150 0 C and leaves the coils 136 at approximately 0° C.
  • Oxygen intended for use by the healthcare facility may be further warmed by a subsequent process or mixed with warmer oxygen effluent from heat exchanger 122 to reach room temperature or an appropriate temperature.
  • the outlet of coils 136 is fluidly connected via flow line 127 to valve 114 and flow lines connected thereto (not shown) of the healthcare facility.
  • a flow line 139 connects the waste anesthetic gas flow lines from receiver 26A ( Figures 10 and 13) of the healthcare facility to an inlet 131 of heat exchanger/condenser 125.
  • the temperature of the waste anesthetic gas enters heat exchanger/condenser 125 via flow line 139 at an elevated temperature due to compression.
  • the compressed waste anesthetic gas enters at the top or entrance 131 of heat exchanger/condenser 125 and passes downward over coils 136 wherein it exchanges heat with the liquid oxygen flowing countercurrently through the coils 136.
  • the waste anesthetic gas leaves the heat exchanger/condenser 125 through fitting 137 and is purged to the atmosphere via flow line 46.
  • This countercurrent heat exchanger arrangement results in a temperature gradient where the top of the cold trap/fractionator 125 is the warmest and where the bottom of the cold trap/fractionator 125 is the coldest.
  • the upper region 160 of the cooling coils 136 of the cold trap/fractionator 125 cools the compressed waste anesthetic gas to a temperature of approximately -5 0 C to extract water vapor as frost on the coils 136.
  • the upper middle region 162 of the cooling coils 136 next cools the compressed waste anesthetic gas to a temperature of approximately -60 0 C which allows sevoflurane to condense and solidify onto the coils 136.
  • the lower middle region 163 extracts nitrous oxide by condensation and solidification at a temperature of approximately -90 °C
  • the lower region 164 of the cooling coils 136 extracts isoflurane and desflurane by condensation and solidification onto the coils 136 at the lowest temperature (between approximately -100 0 C and -110 0 C).
  • heat exchanger/condenser 125 is operated under low pressure (i.e. vacuum pressure)
  • the anesthetic components may be desublimated/deposited directly onto coils 136 without first entering a liquid phase.
  • the cold trap/fractionator 125 is periodically cycled through a thaw process in order to defrost the cooling coils 136. Thawing of coils 136 is effectuated by reducing or prohibiting the flow of liquid oxygen therethrough by thermostatic control valve 133. This allows the cold trap/fractionator 125 to warm to room temperature through heat transfer with its ambient surroundings.
  • warmed oxygen from heat exchanger . 122 may be partially or completely directed through the cooling coils 136 by simultaneously opening valve 159 and closing valves 133, 154.
  • another fluid (not shown) may be directed through cooling coils 136 to achieve a controlled thaw.
  • a funnel-shaped hopper 157 forms the lowest point of heat exchanger/condenser 125 and preferably drains into a 4-way selector valve 158, which in turn is fluidly coupled to anesthetic collection tanks 24A, 24B and a water collection tank 23.
  • desflurane melting point of approximately -108° C at atmospheric pressure
  • isoflurane melting point of approximately -103° C at atmospheric pressure
  • Selector valve 158 is concurrently aligned to allow the liquid desflurane and isoflurane to gravity feed into one of the collection tanks 24A, 24B. As the cold trap/fractionator continues to warm above -90 0 C, the trapped nitrous oxide melts from the lower middle region 163 of cold trap/fractionator 125 and collects in the hopper 157. Selector valve 158 is concurrently aligned to allow the liquid nitrous oxide to gravity feed into one of the collection tanks 24 A, 24B. As the temperature warms further still above -65 0 C, sevoflurane (melting point of approximately -67° C at atmospheric pressure) melts from the upper middle region 162 of the cooling coils 136 and collects in the hopper 157.
  • Selector valve 158 is concurrently aligned to allow the liquid sevoflurane to gravity feed into one of the collection tanks 24 A, 24B. Likewise, as the cold trap/fractionator 125 continues to warm, the water vapor frost will melt above 0 0 C from the upper region 160 and be channeled by selector valve 158 into the water collection tank 23. By this method, the fluoro-ethers are fractionated as they are removed from the waste anesthetic gas.
  • Figure 13 illustrates a low-flow waste anesthetic gas collection and reclamation system 500 according to an alternative preferred embodiment of the invention for use in a hospital, surgical, dental, veterinary, or other healthcare facility.
  • the reclamation system 500 is the same as the previously described reclamation system 200 of Figure 10 except for the replacement of expansion valve 43 with turbine 44 and the inclusion of intelligent waste anesthetic gas collection units 3OA, 3OB, 3OC located at or near each anesthetizing station 15A, 15B, 15C in the healthcare facility.
  • the intelligent waste anesthetic gas collection units 3OA, 3OB, 3OC are preferably fluidly coupled within the individual legs of the collection manifold 16 near the standard waste anesthetic gas connectors 18A, 18B, 18C.
  • Each intelligent gas collection unit 3OA, 3OB, 3OC includes a collection chamber 32A, 32B, 32C, an exhaust valve 34A, 34B, 34C to selectively isolate the suction of the collection manifold 16 at the respective anesthetizing station when waste anesthetic gas is not being produced, and associated pressure sensors 4OA, 4OB, 4OC, circuitry, controls, or mechanisms to operate the exhaust valve 34A, 34B, 34C.
  • the collection chambers 32A, 32B, 32C may be rigid, flexible (such as an elastic bag), or a combination of both.
  • waste anesthetic gas enters from the anesthetizing machine 12A, 12B, 12C exhaust into chamber 32A, 32B, 32C through a 19 mm, 30 mm, or similar standard anesthetic waste-gas connector 18A, 18B, 18C.
  • a sensitive pressure sensor 4OA, 4OB, 4OC electrically coupled to a solenoid-operated exhaust valve 34A, 34B, 34C located at the exhaust side of the chamber 32A, 32B, 32C.
  • the pressure measured by pressure sensor 4OA, 4OB, 4OC is the difference between the pressure of chamber 32A, 32B, 32C and the outside (ambient) air pressure.
  • the pressure sensor 4OA, 4OB, 4OC which by control circuitry causes the exhaust valve 34A, 34B, 34C to open. Opening valve 34A, 34B, 34C fluidly connects the chamber 32A, 32B, 32C to the vacuum source in collection manifold 16, resulting in a rapid decrease in pressure in chamber 32A, 32B, 32C.
  • the sensor 4OA, 4OB, 4OC detects the pressure drop and causes the exhaust valve 34A, 34B, 34C to close.
  • the waste anesthetic gas collection manifold 16 operates at a slight vacuum pressure, e.g. 5 cm, which is generated by compressor 42. Therefore, isolating the collection manifold 16 from entraining room air when no waste anesthetic gas is being produced reduces the average anesthetic scavenging flow by approximately 90 percent and subsequently reduces the necessary capacity of the compressor 42, heat exchanger/condenser 22, piping, and associated other hardware.
  • waste anesthetic gas flow rate of 500-1000 1/min with the prior art reclamation system 10 of Figure 1 is reduced to 50-100 1/min with the reclamation system 500 of Figure 13.
  • a low-flow scavenging system provides a more efficient means of waste anesthetic gas recovery through condensation, because a smaller volume of gas has to be cooled to the condensation temperatures of the individual anesthetic gases.
  • the collected waste gas stream is passed through a check valve 35 to compressor 42.
  • Compressor 42 has a single compression stage sized to elevate the pressure of the anesthetic waste gas from collection units 3OA, 3OB, 3OC to a pressure above atmospheric pressure for subsequent treatment in a condensation unit 22.
  • the waste anesthetic gas flows through a collection vessel or receiver 26A which allows any liquid condensed due to compression to be removed and separated from the compressed waste anesthetic gas stream.
  • the compressed waste anesthetic gas stream is then cooled in a multi-stage condenser 22 such that the temperature of the nitrous oxide and other anesthetic halocarbons are lowered to a point where the vapors condense on the condenser coils 236B ( Figure 11) as a removal liquid (see disclosure with respect to Figure 11).
  • a single stage cold trap/fractionator 125 Figure 12
  • the temperature and pressure at which the condensation process is conducted controls whether the anesthetic gas components are condensed as a removable liquid or deposited as a frost.
  • the liquid anesthetic condensate is captured in a collection container 24A, 24B and the liquid water condensate is captured in a collection container 23.
  • the compressed waste gas is preferably first throttled through a small turbine 44 or similar device prior to atmospheric release 46 in order to capture the potential energy of the compressed waste gas.
  • the captured energy may then be used to power the compressor 42 or supply other energy requirements of the method and system. Reducing the pressure of the compressed work anesthetic gas stream through turbine 44 may induce additional condensation of anesthetic components. Therefore, receiver 45 is provided to collect these anesthetic condensate prior to atmospheric discharge 46 of the remaining waste gas.
  • a preferred embodiment of the self-contained waste anesthetic gas reclamation system is arranged and designed to operate with minimal reliance on the utility infrastructure and supplies of a healthcare facility. Unlike other systems which require liquid oxygen and/or liquid nitrogen supplied by the healthcare facility to condense the gaseous anesthetic components, the system disclosed herein requires only the availability of mechanical or electrical power for operation. Moreover, the present system simply needs an atmospheric vent to discharge the waste, gases void of their anesthetic components and does not need an extensive waste air handling system. Thus, the preferred embodiment is comparatively self- contained and can be easily accommodated within a physician's office, veterinary clinic ⁇ or dental office. [Larger, more conventional waste anesthetic gas reclamation systems, such as those traditionally used in hospitals, would be impractical in these settings because of their sheer size and expense.]
  • FIG 14 illustrates the heat exchanger/condenser 222 of a preferred embodiment of the invention which cools and condenses anesthetic gas components from the waste anesthetic gas stream through countercurrent heat exchange with, an intermediate heat transfer fluid.
  • the heat transfer fluid such as DuPont Suva® 95 or a similar ultra-low temperature refrigerant, is subsequently cooled using a conventional, electrically or mechanically powered refrigeration unit 270 prior to being returned to the heat exchanger/condenser 222.
  • the use of a separate refrigeration unit 270 to cool a heat transfer fluid or refrigerant eliminates the need for liquid nitrogen and/or liquid oxygen to be supplied by the healthcare facility.
  • DuPont Suva® 95 is the preferred refrigerant, because it is the industry standard for use in medical freezers and other very low temperature applications (between -40 0 C and -101 0 C), has significantly lower compressor discharge temperatures which allow greater system reliability and compressor longevity, and is an environmentally friendly refrigerant.
  • the heat transfer fluid flows through coils 236 of heat exchanger/condenser 222 and evaporates as it absorbs heat from the anesthetic gas components condensing on the outer surface of coils 236.
  • the intermediate heat transfer fluid is then cooled through a conventional vapor-compression process using a one or more refrigeration stages.
  • the saturated (or slightly superheated) heat transfer fluid, now at least partially evaporated, is compressed in a compressor 272 to a higher pressure.
  • the compression causes the heat transfer fluid to become superheated (i.e. achieve a higher temperature than the saturation temperature of the fluid at the elevated pressure) at the outlet of the compressor 272.
  • the superheated fluid is subsequently cooled and condensed in a heat exchanger/condenser 274 using a suitable coolant, preferably air.
  • a suitable coolant preferably air.
  • the condensed fluid at elevated pressure is then throttled through an expansion valve 276 to a lower pressure.
  • the heat transfer fluid consisting mainly of liquid and low quality vapor, is once again ready to absorb heat from the condensing anesthetic gas components in the heat exchanger/condenser 222.
  • a cryogenic refrigeration unit may be used to cool an intermediate heat transfer fluid to even lower temperatures (i.e. well below -73 0 C) than can be achieved with conventional refrigeration systems.
  • a cryogenically-cooled heat transfer fluid is used to cool and condense these anesthetic components as previously disclosed.
  • Cryogenic refrigeration processes such as the simple Linde or Joule-Thompson cycle, are well known in the prior art and will not be further discussed herein.
  • FIG 15 illustrates a low-flow waste anesthetic gas collection and reclamation system 300 according to a preferred embodiment of the invention for use in a physician's office, dental office, small animal clinic or other healthcare facility.
  • the reclamation system 300 is similar to the previously described prior art waste anesthetic gas reclamation system 10 of Figure 1 except for the inclusion of a small turbine 344, one or more compression stages provided by a compressor 342, and intelligent waste anesthetic gas collection unit 330 located at or near an anesthetizing station 315 in the healthcare facility.
  • Compressor 342 is preferably disposed between the intelligent waste anesthetic gas collection unit 330 and the condenser 322.
  • Small turbine 344 is preferably disposed between the condenser 322 and the atmospheric vent 346.
  • the intelligent waste anesthetic gas collection unit 330 is preferably fluidly coupled to the collection intake 316 near the standard waste anesthetic gas connector 318.
  • the intelligent gas collection unit 330 includes a collection chamber 332, an exhaust valve 334 to selectively isolate the suction of the collection intake 316 at the respective anesthetizing station when waste anesthetic gas is not being produced, and associated pressure sensor 340, circuitry, controls, or mechanisms to operate the exhaust valve 334.
  • the collection chamber 332 may be rigid, flexible (such as an elastic bag), or a combination of both.
  • waste anesthetic gas enters from the anesthetizing machine 312 exhaust into chamber 332 through a 19 mm, 30 mm, or similar standard anesthetic waste- gas connector 318.
  • a sensitive pressure sensor 340 electrically coupled to a solenoid-operated exhaust valve 334 located at the exhaust side of the chamber 332.
  • the pressure measured by pressure sensor 340 is the difference between the pressure of chamber 332 and the outside (ambient) air pressure. If the pressure within the chamber 332 rises to slightly above ambient, the increased pressure is detected by the pressure sensor 340 which by control circuitry causes the exhaust valve 334 to open. Opening valve 334 fluidly connects the chamber 332 to the vacuum source in collection intake 316, resulting in a rapid decrease in pressure in chamber 332. As the chamber pressure approaches ambient, the sensor 340 detects the pressure drop and causes the exhaust valve 334 to close.
  • the waste anesthetic gas collection intake 316 operates at a slight vacuum pressure, e.g. 5 cm, which is generated by compressor 342. If a compressor 342 is not used in system 300, then a vacuum pump (not shown) will need to be disposed between collection intake 316 and atmospheric vent 346 in order to generate the slight vacuum pressure in collection intake 316. Preventing the collection intake 316 from entraining room air when no waste anesthetic gas is being produced reduces the average anesthetic scavenging flow by approximately 90 percent and subsequently reduces the necessary capacity of the compressor 342, heat exchanger/condenser 322, piping, and other associated hardware (not shown).
  • waste anesthetic gas flow rate of 500-1000 1/min can be expected using the prior art reclamation system 10 of Figure 1.
  • a low-flow scavenging system would reduce this anesthetic gas flow rate to 50-100 1/min.
  • the system 300 shown in Figure 15, for implementation in smaller healthcare facilities, is designed for an anesthetic gas flow rate of 1-20 1/min. Nevertheless, a low-flow scavenging system provides a more efficient means of waste anesthetic gas recovery through condensation whatever the anesthetic gas flow rate, because a smaller volume of gas has to be cooled to the condensation temperatures of the individual anesthetic gases.
  • the collected waste gas stream is passed through a check valve 335 to a compressor unit 342.
  • the compressor 342 is sized to compress the anesthetic waste gas from the collection unit 330 to a pressure above atmospheric pressure for subsequent treatment in a condensation unit 322. Pressures above 50 psig are preferable in order to take advantage of attendant increases in separation efficiency and fractional extraction.
  • Multistage compressors are used to avoid the problems associated with high compression ratios, such as high discharge temperatures and increased mechanical breakdowns. As a result, compressor manufacturers recommend a compression ratio of no more than 10:1, especially for low-temperature applications. Multistage compressors can also be more economical than single stage compressors because of the attendant power cost savings attributable to compression stages having smaller compression ratios. However, the compressor 342 of system 300 needs only a single compression stage, because a compression ratio of no more than 10: 1 is anticipated.
  • the waste anesthetic gas flows through a collection vessel or receiver 326 which allows any liquid condensed due to compression to be removed and separated from the compressed waste anesthetic gas stream.
  • any water vapor in the gas stream should be removed to prevent freezing of the liquid water condensate in the condenser 322.
  • a preferred method to remove water vapor from the waste anesthetic gas stream is to use a first condenser stage 422A ( Figure 16), however, alternative water removal processes (not shown) may be employed, such as desiccation, adsorption, filtration, semi-permeable or hydrophobic membranes, etc.
  • These various gas drying methods may be used at any point prior to the condensation of the anesthetic gases, including before the compression stage.
  • the compressed waste anesthetic gas stream is then cooled in a single or multiple stage condenser 322 such that the temperature of the nitrous oxide and other anesthetic halocarbons are lowered to a point where the vapors either condense on the condenser coils 436B ( Figure 16) as a removal liquid or collect as frost on the condenser coils 536 ( Figure 17).
  • the temperature and pressure at which the condensation process is conducted controls whether the anesthetic gas components are condensed as a removable liquid or deposit as a frost.
  • a condenser 322 with at least two stages 422A, 422B ( Figure 16) is preferred.
  • the first stage 422 A ( Figure 16) is used to remove water vapor from the waste anesthetic gas stream while subsequent stages 422B ( Figure 16) are used to condense the anesthetics.
  • the liquid anesthetic condensates (un-fractionated) are collected in container 324 and the liquid water condensate is collected in container 323, both of which are regularly drained.
  • a dedicated heat transfer fluid which flows through the coils 436A, 436B, 536 ( Figures 16 and 17) of condenser 322, is used to cool and condense the anesthetic waste gas components.
  • the heat transfer fluid such as DuPont Suva® 95 or a similar ultra-low temperature refrigerant, is subsequently cooled using a conventional, electrically powered refrigeration unit 370 prior to being returned to the heat exchanger/condenser 322.
  • the intermediate heat transfer fluid is cooled through a conventional vapor-compression process using a one or more refrigeration stages.
  • the use of a separate refrigeration unit 370 to cool a heat transfer fluid or refrigerant eliminates the need for liquid nitrogen and/or liquid oxygen to be supplied by the healthcare facility.
  • liquid oxygen, liquid nitrogen, or a similar refrigerant obtained from the common supply of these liquefied gases normally available at a hospital or other medical, dental, or veterinary facility could be used in place of the dedicated heat transfer fluid.
  • the waste anesthetic gas is compressed above the facility's gas supply pressure (e.g. 50 psig)
  • contamination of the common refrigerant supply with waste anesthetic is possible should an internal leak occur within the condenser unit 322. Therefore, when using liquid oxygen, liquid nitrogen, or a similar refrigerant, a separate supply source is recommended for waste anesthetic gas pressures above 50 psig in order to avoid the risk of contaminating the common gas supplies of the healthcare facility with waste anesthetic gas.
  • the remaining waste gas (mainly composed of entrained air) may be vented to the atmosphere 346. More preferably, however, the compressed waste gas is first throttled through a small turbine 344 or similar device prior to atmospheric release 346 in order to capture the potential energy of the compressed waste gas. The captured energy may then be used to power the compressor 342 or supply other energy requirements of the method and system. Additional anesthetic components in the waste gas may also be condensed by expansion in the turbine 344. These anesthetic condensates are collected in receiver 345 prior to the atmospheric discharge 346 of the waste gas.
  • heat integration of the cooled waste gas with streams to be cooled may reduce the overall cooling utility of the method and system.
  • compression of the waste anesthetic gas stream causes the temperature of the gas stream to increase.
  • the cooled waste gas stream to be vented 346 could be used to cool this compressed waste anesthetic gas stream prior to condensation in order to reduce the overall refrigerant requirement of the heat exchanger/condenser 322.
  • a condenser unit 422 which includes first and second condensers 422A and 422B.
  • the outlet line 421 for cooled heat transfer fluid from refrigeration unit 270 ( Figure 14) is fluidly connected to the condensing coils 436B of the second vessel 422B.
  • the outlet of condensing coils 436B is fluidly connected via flow line 425 to the inlet of coils 436A of first vessel 422A.
  • the outlet of coils 436A is fluidly connected via flow line 427 to the inlet of small refrigeration unit 270 ( Figure 14).
  • a flow line 439 connects the waste anesthetic gas flow lines from receiver 326, 626 ( Figures 15 and 18) of the healthcare facility to an inlet of heat exchanger/condenser 422.
  • the waste anesthetic gas enters heat exchanger/condenser 422 via flow line 439 at an elevated temperature due to compression.
  • the compressed waste anesthetic gas enters at the top or entrance of heat exchanger/condenser 422A and passes downward over coils 436A wherein it exchanges heat with the heat transfer fluid flowing countercurrently through the coils 436A.
  • Water vapor in the compressed waste anesthetic gas condenses to liquid water at a specific temperature (above 0 0 C), which is dependent upon the pressure of the compressed waste anesthetic gas stream.
  • the liquid water then falls by gravity to tank 423 for storage and removal.
  • the cooled compressed gas near the bottom of vessel 422A is conducted via flow line 441 to the top or entrance of heat exchanger/condenser 422B where it is applied at a temperature greater than 0 0 C.
  • the cooled compressed gas applied to the top of heat exchanger/condenser 422B passes over coils 436B wherein it exchanges heat with the heat transfer fluid flowing countercurrently through the coils 436B.
  • the heat transfer fluid from flow line 421 enters the coils 436B at a temperature of approximately -90 0 C and leaves the coils 436B via flow line 425 at an increased temperature.
  • an intermediate bypass valve 437 may be provided in line 421 to bring the temperature in line 425 at the inlet of coils 436A to approximately 0 0 C.
  • the temperature of the compressed waste anesthetic gas from flow line 441 is lowered while passing over the coils 436B such that the halocarbons of the waste gas are liquefied and discharged into a collection tank 424.
  • the remainder of the compressed waste gas i.e., those components which are not harmful to the atmosphere, are preferably throttled through a small turbine 344 ( Figure 15) to capture the potential energy of the compressed gas.
  • these compressed waste gases may be vented to the atmosphere via flow line 446, throttled through an expansion valve 643 ( Figure 18) to induce additional anesthetic condensation, or subjected to further processing by existing catalytic techniques (not shown).
  • FIG 17 generally illustrates the system and method of the ' co-pending patent application, which has been modified to accommodate an entering compressed waste anesthetic gas stream as well as the replacement of liquid oxygen by a dedicated heat transfer fluid, such as Suva® 95 or a similar ultra-low temperature refrigerant.
  • a dedicated heat transfer fluid such as Suva® 95 or a similar ultra-low temperature refrigerant.
  • this second waste anesthetic recovery method is not as significantly affected by increases in the pressure of the waste anesthetic gas stream.
  • a cold trap/fractionator or condenser unit 522 is provided with cooling coils 536 therein.
  • the outlet line 521 for cooled heat transfer fluid from refrigeration unit 570 is fluidly connected to the condensing coils 536 of cold trap/fractionator 522.
  • the flow of cooled heat transfer fluid at the inlet of the coils 536 is controlled thermostatically by valve 533.
  • the cooled heat transfer fluid from flow line 521 enters the coils 536 at a temperature of approximately -90 0 C and leaves the coils 536 at approximately 0° C.
  • the outlet of coils 536 is fluidly connected via flow line 527 to the inlet of the small refrigeration unit 570.
  • a flow line 539 connects the waste anesthetic gas flow lines from receiver 326, 626 ( Figures 15 and 18) of the healthcare facility to an inlet 531 of heat exchanger/condenser 522.
  • the temperature of the waste anesthetic gas enters heat exchanger/condenser 522 via flow line 539 at an elevated temperature due to compression.
  • the compressed waste anesthetic gas enters at the top or entrance 531 of heat exchanger/condenser 522 and passes downward over coils 536 wherein it exchanges heat with the heat transfer fluid flowing countercurrently through the coils 536.
  • the waste gas leaves the heat exchanger/condenser 522 through fitting 537 and is purged to the atmosphere via flow line 546.
  • This countercurrent heat exchanger arrangement results in a temperature gradient where the top of the cold trap/fractionator 522 is the warmest and where the bottom of the cold trap/fractionator 522 is the coldest.
  • the upper region 560 of the cooling coils 536 of the cold trap/fractionator 522 cools the compressed waste anesthetic gas to a temperature of approximately -5 0 C to extract water vapor as frost on the coils 536.
  • the middle region 562, 563 of the cooling coils 536 next cools the compressed waste anesthetic gas to a temperature of approximately -60 0 C which allows sevoflurane to condense and solidify onto the coils 536.
  • the lower region 564 extracts nitrous oxide by condensation and solidification at a temperature of approximately -90 0 C.
  • heat exchanger/condenser 522 is operated under low pressure (i.e. vacuum pressure)
  • the anesthetic components may be desublimated/deposited directly onto coils 536 without first entering a liquid phase.
  • the waste anesthetic gas contains isoflurane (melting point of approximately - 103° C) and/or desflurane (melting point of approximately -108° C)
  • a cryogenically cooled heat transfer fluid or liquefied gas such as liquid oxygen or liquid nitrogen, will be required to condense and solidify these anesthetic components onto the lower region 564 of coils 536.
  • the remainder of the compressed waste gas i.e., those components which are not harmful to the atmosphere, are preferably throttled through a small turbine 344 (Figure 15) to capture the potential energy of the compressed gas.
  • these compressed waste gases may be vented to the atmosphere via flow line 546, throttled through an expansion valve 643 ( Figure 18) to induce additional anesthetic condensation, or subjected to further processing by existing catalytic techniques (not shown).
  • the cold trap/fractionator 522 is periodically cycled through a thaw process in order to defrost the cooling coils 536. Thawing of coils 536 is effectuated by reducing or prohibiting the flow of heat transfer fluid therethrough by thermostatic control valve 533. This allows the cold trap/fractionator 522 to warm to room temperature through heat transfer with its surroundings at ambient temperature. In an alternative embodiment, another fluid (not shown) may be directed through cooling coils 536 to achieve a controlled thaw.
  • a funnel-shaped hopper 557 forms the lowest point of heat exchanger/condenser 522 and preferably drains into a 4-way selector valve 558, which in turn is fluidly coupled to anesthetic collection tanks 524A, 524B and a water collection tank 523.
  • a 4-way selector valve 558 which in turn is fluidly coupled to anesthetic collection tanks 524A, 524B and a water collection tank 523.
  • nitrous oxide melts from the lower region 564 of cold trap/fractionator 522 and collects in the hopper 557.
  • Selector valve 558 is concurrently aligned to allow the liquid nitrous oxide to gravity feed into one of the collection tanks 524 A, 524B.
  • sevoflurane melts from the middle region 562, 563 of the cooling coils 536 and collects in the hopper 557.
  • Selector valve 558 is concurrently aligned to allow the liquid sevoflurane to gravity feed into a second collection tank 524 A, 524B.
  • the water vapor frost will melt above 0 0 C from the upper region 560 and be channeled by selector valve 558 into the water collection tank 523.
  • Figure 18 illustrates a waste anesthetic gas scavenging and reclamation system 600 according to a preferred embodiment of the invention for use in a physician's office, dental office, small animal clinic or other healthcare facility.
  • the reclamation system 600 is similar to the previously described waste anesthetic gas reclamation system 300 of Figure 15 in that system 600, like system 300, only requires operational power (not shown), a source flow 615 of anesthetic waste gases, and an atmospheric vent 646. Additionally, however, system 600 is arranged and designed to be a compact, self-contained unit in order to facilitate its placement in a patient's room in proximity with an anesthetizing machine 612.
  • system 600 is a packaged unit 602 which occupies a total volume of approximately one cubic foot.
  • System 600 includes a heat exchanger/condenser 622 which cools and condenses anesthetic gas components from the waste anesthetic gas stream through countercurrent heat exchange with an intermediate heat transfer fluid that is cooled in a small refrigeration unit 670.
  • system 600 may include a small compressor 642 and receiver 626, and/or an expansion valve 643 (or a small turbine 344 ( Figure 15)) and receiver 645.
  • system 600 may incorporate a low-flow anesthetic waste gas collection unit 630.
  • system 600 includes a compressor 642 and receiver 626 as well as an expansion valve 643 and receiver 645.
  • the waste anesthetic gas collection and reclamation system 600 couples via an attachable flow line 606 to an existing high-flow 615 or more preferably, a low-flow 630 waste anesthetic gas collection unit.
  • the waste anesthetic gas collection intake 616 operates at a slight vacuum pressure, e.g. 5 cm, generated by a compressor 642, which is preferably disposed between intake 616 and the heat exchanger/condenser 622. From collection intake 616, the collected waste gas stream is passed through a check valve 635 to compressor 642.
  • Compressor 642 has a single compression stage sized to elevate the pressure of the anesthetic waste gas from collection unit 615, 630 to a pressure above atmospheric pressure for subsequent treatment in a condensation unit 622.
  • the waste anesthetic gas flows through a collection vessel or receiver 626 which allows any liquid condensed due to compression to be removed and separated from the compressed waste anesthetic gas stream.
  • the compressed waste anesthetic gas stream is then cooled in a multi-stage condenser 622 such that the temperature of the nitrous oxide and other anesthetic halocarbons are lowered to a point where the vapors condense on the condenser coils 436B ( Figure 16) as a removal liquid (see disclosure with respect to Figure 16).
  • a single stage condenser 522 ( Figure 17) could be used to condense and collect the vapors as a frost on condenser coils 536 ( Figure 17) (see disclosure with respect to Figure 17).
  • the temperature and pressure at which the condensation process is conducted controls whether the anesthetic gas components are condensed as a removable liquid or deposited as a frost.
  • a condenser 622 with at least two stages 422A, 422B ( Figure 16) is preferred.
  • the first stage 422A ( Figure 16) is used to remove water vapor from the waste anesthetic gas stream while the second stage 422B ( Figure 16) is used to condense the anesthetics.
  • the liquid anesthetic condensates (un-fractionated) are collected in small volume (i.e. one liter) container 624 and the liquid water condensate is collected in small volume (i.e. one liter) container 623, both of which are regularly drained.
  • a dedicated heat transfer fluid which flows through the coils 436 A, 436B, 536 ( Figures 16 and 17) of condenser 622, is used to cool and condense the anesthetic waste gas components.
  • the heat transfer fluid such as DuPont Suva® 95 or a similar ultra-low temperature refrigerant, is subsequently cooled using a conventional, electrically powered refrigeration unit 670 prior to being returned to the heat exchanger/condenser 622.
  • the intermediate heat transfer fluid is cooled through a conventional vapor-compression process using a one or more refrigeration stages.
  • the use of a separate refrigeration unit 670 to cool a heat transfer fluid or refrigerant eliminates the need for liquid nitrogen and/or liquid oxygen to be supplied by the healthcare facility.
  • liquid oxygen, liquid nitrogen, or a similar refrigerant obtained from the common supply of these liquefied gases normally available at a hospital or other medical, dental, or veterinary facility could be used in place of the dedicated heat transfer fluid.
  • the remaining compressed waste gases (mainly composed of entrained air) are preferably passed through an expansion valve 643 and a receiver 645 prior to atmospheric venting 646.
  • the expansion valve 643 reduces the compressed waste gas to atmospheric pressure and further cools the waste gas via the Joule-Thompson effect. Additional anesthetic components remaining in the waste gas may be condensed through Joule-Thompson adiabatic expansion. These anesthetic condensates are collected in the receiver 645 prior to the atmospheric discharge 646 of the waste gas.
  • the cooled waste gas to be vented 646 is then preferably used to cool the entering compressed waste anesthetic gas stream of flow line 639 in a countercurrent heat exchanger 680. This reduces the refrigerant requirement of the heat exchanger/condenser 622, and thus, the overall operational cost of the system 600.
  • the waste gases, throttled through valve 643 and warmed in exchanger 680, are vented through an attachable flow line 637 to an existing atmospheric vent 646 at the healthcare facility.

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Abstract

La présente invention se rapporte à un procédé et à un appareil permettant de récupérer et de séparer des constituants d'un gaz anesthésique des déchets de gaz anesthésique destinés à être purgés d'un établissement de soins. Le procédé et l'appareil de récupération de gaz anesthésique de type par condensation selon l'invention comprennent les modes de réalisation préférés suivants : une unité de piégeage de gaz anesthésique à écoulement faible, un processus de fractionnement de givre permettant de recueillir les déchets de gaz anesthésique sous forme de givre sur les surfaces de refroidissement d'un piège à froid/fractionnateur, un compresseur doté d'au moins un étage de compression, et une unité autonome nécessitant un interfaçage minimal avec l'infrastructure de l'installation et les approvisionnements de l'établissement de soins.
PCT/US2006/018416 2005-05-13 2006-05-11 Procede et appareil de recuperation de gaz anesthesique WO2006124578A2 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP2008511400A JP4900974B2 (ja) 2005-05-13 2006-05-11 麻酔ガス再生方法および装置
KR1020127030743A KR101318555B1 (ko) 2005-05-13 2006-05-11 마취가스 재생 방법 및 장치
CA2607902A CA2607902C (fr) 2005-05-13 2006-05-11 Procede et appareil de recuperation de gaz anesthesique
EP06770274A EP1879665A4 (fr) 2005-05-13 2006-05-11 Procede et appareil de recuperation de gaz anesthesique
NZ563340A NZ563340A (en) 2005-05-13 2006-05-11 Receiving waste anesthetic gas in a chamber which is sent to a vacuum manifold on detection of the gas
CN2006800221563A CN101212998B (zh) 2005-05-13 2006-05-11 麻醉气体回收方法及装置
AU2006247692A AU2006247692B2 (en) 2005-05-13 2006-05-11 Method and apparatus for anesthetic gas reclamation
KR1020077029106A KR101281891B1 (ko) 2005-05-13 2006-05-11 마취가스 재생 방법 및 장치

Applications Claiming Priority (6)

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US68064405P 2005-05-13 2005-05-13
US60/680,644 2005-05-13
US68224905P 2005-05-18 2005-05-18
US60/682,249 2005-05-18
US11/266,966 US7628034B2 (en) 2005-05-13 2005-11-04 Method of low flow anesthetic gas scavenging and dynamic collection apparatus therefor
US11/266,966 2005-11-04

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WO2006124578A3 WO2006124578A3 (fr) 2007-11-22
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WO2008119223A1 (fr) * 2007-03-30 2008-10-09 Hong Kong Applied Science & Technology Research Institute Co., Ltd. Estimation de canal ofdm/ofdma
EP2016968A1 (fr) * 2007-07-16 2009-01-21 Mil'S Dispositif d'aspiration de gaz d'anesthésie
FR2920095A1 (fr) * 2007-08-20 2009-02-27 Mil S Soc Par Actions Simplifi Dispositif de raccordement relie a une source de depression et destine au raccordement d'une conduite d'aspiration
WO2010071538A1 (fr) * 2008-12-18 2010-06-24 Nordic Gas Cleaning Ab Appareil et procédé de traitement de gaz
WO2011075033A1 (fr) * 2009-12-14 2011-06-23 Nordic Gas Cleaning Ab Unité de décomposition éliminant un composant gazeux indésirable dans un courant de gaz
DE102011012125A1 (de) 2011-02-23 2012-08-23 Dräger Medical GmbH Narkosegasfortleitungsvorrichtung für ein Anästhesiegerät
US8267081B2 (en) 2009-02-20 2012-09-18 Baxter International Inc. Inhaled anesthetic agent therapy and delivery system
WO2012128695A1 (fr) * 2011-03-24 2012-09-27 Nordic Gas Cleaning Ab Appareil pour la décomposition de l'oxyde nitreux dans un courant gazeux
US9622683B2 (en) 2012-07-11 2017-04-18 Financial Consultants Llc Device for evacuating and/or monitoring gas leaking from a patient during surgery or anesthetization
CN114538392A (zh) * 2021-12-22 2022-05-27 合肥雅美娜环境医疗设备有限公司 一种治疗仪治疗气再利用结构

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CN108319185A (zh) * 2017-12-20 2018-07-24 北京航天计量测试技术研究所 气路二级安全冗余装置
TWI725362B (zh) * 2018-12-10 2021-04-21 李守雄 冷凍空調系統清洗裝置
CN115451646A (zh) * 2022-10-14 2022-12-09 散裂中子源科学中心 一种冷却系统或设备的排水干燥系统

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008119223A1 (fr) * 2007-03-30 2008-10-09 Hong Kong Applied Science & Technology Research Institute Co., Ltd. Estimation de canal ofdm/ofdma
EP2016968A1 (fr) * 2007-07-16 2009-01-21 Mil'S Dispositif d'aspiration de gaz d'anesthésie
FR2918896A1 (fr) * 2007-07-16 2009-01-23 Mil S Soc Par Actions Simplifi Dispositif d'aspiration de gaz d'anesthesie
FR2920095A1 (fr) * 2007-08-20 2009-02-27 Mil S Soc Par Actions Simplifi Dispositif de raccordement relie a une source de depression et destine au raccordement d'une conduite d'aspiration
WO2010071538A1 (fr) * 2008-12-18 2010-06-24 Nordic Gas Cleaning Ab Appareil et procédé de traitement de gaz
US8267081B2 (en) 2009-02-20 2012-09-18 Baxter International Inc. Inhaled anesthetic agent therapy and delivery system
WO2011075033A1 (fr) * 2009-12-14 2011-06-23 Nordic Gas Cleaning Ab Unité de décomposition éliminant un composant gazeux indésirable dans un courant de gaz
DE102011012125A1 (de) 2011-02-23 2012-08-23 Dräger Medical GmbH Narkosegasfortleitungsvorrichtung für ein Anästhesiegerät
WO2012128695A1 (fr) * 2011-03-24 2012-09-27 Nordic Gas Cleaning Ab Appareil pour la décomposition de l'oxyde nitreux dans un courant gazeux
US9622683B2 (en) 2012-07-11 2017-04-18 Financial Consultants Llc Device for evacuating and/or monitoring gas leaking from a patient during surgery or anesthetization
CN114538392A (zh) * 2021-12-22 2022-05-27 合肥雅美娜环境医疗设备有限公司 一种治疗仪治疗气再利用结构

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CA2607902C (fr) 2015-11-24
JP4900974B2 (ja) 2012-03-21
NZ563340A (en) 2011-03-31
EP1879665A4 (fr) 2012-03-07
WO2006124578A3 (fr) 2007-11-22
CN101212998A (zh) 2008-07-02
CN101212998B (zh) 2012-06-13
KR20080033166A (ko) 2008-04-16
CA2607902A1 (fr) 2006-11-23
AU2006247692A1 (en) 2006-11-23
JP2008539978A (ja) 2008-11-20
EP1879665A2 (fr) 2008-01-23
WO2006124578B1 (fr) 2008-02-21
KR20130006699A (ko) 2013-01-17
AU2006247692B2 (en) 2011-08-25
KR101318555B1 (ko) 2013-10-16
KR101281891B1 (ko) 2013-07-08

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