EP2334994A1 - Compositions et procedes pour l'injection d'agents d'etancheite et/ou siccatifs dans des systemes de climatisation et de refrigeration - Google Patents
Compositions et procedes pour l'injection d'agents d'etancheite et/ou siccatifs dans des systemes de climatisation et de refrigerationInfo
- Publication number
- EP2334994A1 EP2334994A1 EP09812576A EP09812576A EP2334994A1 EP 2334994 A1 EP2334994 A1 EP 2334994A1 EP 09812576 A EP09812576 A EP 09812576A EP 09812576 A EP09812576 A EP 09812576A EP 2334994 A1 EP2334994 A1 EP 2334994A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluid
- air conditioning
- sealant
- viscosity
- refrigerant
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B45/00—Arrangements for charging or discharging refrigerant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/263—Drying gases or vapours by absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/28—Selection of materials for use as drying agents
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B2345/00—Details for charging or discharging refrigerants; Service stations therefor
- F25B2345/001—Charging refrigerant to a cycle
Definitions
- FIG. 1 is a graphic representation of a sealant injection assembly in accordance with a preferred embodiment of the present invention in use with an air conditioning or refrigeration system 1,
- FIG. 2 is a partially exploded perspective view of the assembly of FIG. 1 .
- FIG. 3 is an end view of a fitting and orifice used in the assembly of FIG. 2, and
- FIG. 4 is a cutaway view of a typical single cylinder hermetic compressor.
- a typical hermetically sealed air conditioning or refrigeration system 1 has an evaporator 3, compressor 5, condenser 7 and expansion device 9.
- the system 1 has a "low side" 10 consisting of the part of the system 1 between the expansion device 9 (for example, an orifice 9) and the suction line to the compressor 5.
- the compressor 5 draws in low pressure, low temperature refrigerant in a gaseous state from the "low side" 10.
- the compressor 5 compresses the gaseous refrigerant to a high pressure, high temperature gaseous state that flows to the condenser 7.
- the refrigerant passes through the condenser 7 and is cooled to a liquid state.
- the liquid refrigerant passes through the expansion valve 9, which causes the refrigerant to expand to a low pressure, low pressure temperature gas.
- the evaporator 3 absorbs heat from outside the system 1, and relatively low temperature, low pressure gas is reintroduced to the compressor 5.
- the low side pressure was approx. 77 psig at -the compressor 5, and pressure on the high pressure side of the compressor (the discharge 11) was approx. 256 psig.
- the temperature at the evaporator 3 was approx. 45 0 F and at the condenser approx. 126°F.
- the ambient temperature was approx. 90 0 F.
- the temperature of the gas between the valve 9 and evaporator 3 was approx. 55 0 F.
- the temperature at the compressor 5 discharge 11 was approx. 171 0 F.
- the valve 9 in the test environment had a diameter of approx. 0.059 inches.
- the gas flow rate in the low side between the evaporator 3 and the compressor 5 was approximately 1596 ft/min.
- the diameter of pipe in the low side was nominal 3 ⁇ inch, while the inside diameter of pipe at the discharge was 3/8 inches.
- the test environment was a single phase 2 ton compressor 5.
- Organosilanes cure when in the presence of moisture, such as would occur at the situs of a leak.
- an injection assembly 12 has a vessel 15 containing an organosilane mixture.
- the vessel 15 is a canister 15.
- the mixture is selected for miscibility with the contents of the system 1.
- the system 1 contains a miscible lubricant for lubrication of the compressor 5.
- the system 1 may also have other contents, such as a fluorescent dye for leak detection. It may also contain a chemical dryer to remove moisture from the system 1.
- the inventors have recognized that, in addition to liquid slugging, the introduction of greater concentrations of organosilanes remove lubricants from the compressor 5, resulting in compressor 5 failure.
- the organosilane should be introduced in sufficiently low concentrations and be miscible with the system 1 lubricant to avoid liquid slugging and to maintain sufficient lubricant for proper operation of the compressor 5.
- the organosilane is introduced from vessel 15 to a low side port 17 between the evaporator 3 and compressor 5.
- the organosilane is introduced at a rate that allows the concentration of the organosilane to be diluted sufficiently by the other system 1 contents to prevent liquid slugging and to maintain sufficient concentration of lubricant for proper operation of the compressor 5.
- controlled injection of the organosilane combined with the miscible lubricant is critical when injected at the low side port 17 because of the close proximity between the low-side charging port 17 and compressor 5.
- the organosilane/miscible lubricant mixture enters the compressor 5 along with cool refrigerant vapor it has to first pass by outboard shaft bearing 18. This aids in replacing oil to the outboard bearing which may have been stripped by passing refrigerant.
- the mixture continues on flow path 19a rushing over motor windings (stator 19b, rotor 19c) removing heat from the electric motor.
- compressors and the type of compressor may be reciprocating (piston-cylinder), rotary, scroll, screw or centrifugal. While compressor geometry is critical to the hermetic systems as explained above, general engineering considerations also require control of flow rate, quantity and viscosity of the injected material for the other drives to ensure continued good operation and acceptable compressor life.
- the organosilane can be introduced by many different methods. For example, it can be injected at a very slow rate while the compressor 5 is running continuously. This requires fine control over the injection rate.
- the organosilanes (or a portion thereof) can be injected into a running system 1, followed by a period of time during which the system 1 is stopped.
- the initial use of a running system 1 allows the organosilane to be distributed through the system 1. Stopping the system 1 allows the distributed organosilanes to further mix with the system 1 contents, without forcing areas of high organosilane concentration to flow through the compressor 5 repeatedly. This process can be repeated until all of the organosilane is introduced. Although this may allow for greater rates of introduction, the process would still be slow, and fine control is still required.
- An alternative method of introducing the organosilane is to form an organosilane mixture by pre-diluting the organosilane in a material miscible with the system 1 contents and with the organosilane. This mixture is then introduced into the system 1 using one of the methods discussed above.
- the organosilane is mixed with a lubricant to form the organosilane mixture.
- a lubricant to form the organosilane mixture.
- This has an additional benefit of maintaining lubricant in close proximity to the organosilane at all times.
- the viscosity of the organosilane mixture can be maintained within a selected range.
- Organosilane on its own has a very low viscosity (for example ⁇ 1 cst. at 40 0 C). This in part results in difficulty in controlling the flow of organosilane.
- An additional method of injection would include the use of a fluid injector that can inject the mixture into the working low side system of the unit in small increments, an example include a RevolverTM sold by Cliplight Manufacturing Company of Toronto, Canada.
- the Cliplight device allows for approximately 0.04 of an ounce to be measured in at any one time. Additional amounts of the mixture depending on the system size could be accurately added. This would be an acceptable method of injection allowing only small amounts of the mixture into the suction gas path and thus preventing possible liquid slugging to the compressor 5.
- a filter 16A could be added, as shown in FIG. 1, to the hose apparatus 16 to filter out any particles injected from the system 1 when charging the canister 15.
- sealants based on organosilanes for refrigeration and air conditioning systems 1 is made possible by control of the rate of introduction and viscosity of the sealant mixture within certain ranges.
- An appropriate choice of organosilane sealant is made to allow effective sealing of small pinhole size leaks in the air conditioning or refrigeration system 1.
- the organosilane is chosen with several criteria in mind.
- the organosilane is miscible in the lubricant fluid; it is typically a monomer, but may contain oligomers, capable of forming a solid polymer with itself or other chosen organosilanes in the presence of moisture under the conditions of the particular application.
- the reaction rate of the organosilane or mixture of organosilanes is sufficient to form an effective seal at the situs of the leak.
- the polymeric seal is chosen to be sufficiently strong to maintain an effective barrier to prevent further leakage of refrigerant from the system 1.
- the organosilanes are chosen to be stable in the absence of moisture, be non-corrosive and otherwise inactive to the components of system 1 and be generally environmentally acceptable. Further, the nature and injected quantity of the organosilanes is chosen, to the extent that it would interfere with the refrigerant and/or lubricant, so that such interference remains consistent with the normal operation of the refrigerant fluid e.g. vaporization and liquefaction characteristics.
- the organosilane is combined with a miscible lubricant at particular ratios to provide the proper mixture viscosity for injection to the refrigerant system 1 to prevent bearing seizure.
- Specific orifice 20 (see FIG. 3) sizes are selected for an apparatus to ensure that the mixture is injected at flow rates required to prevent liquid slugging and subsequent compressor 5 shutdown or failure.
- certain procedures are performed for effective introduction of the mixture. Injection procedures are also described that reduce risk of temporary or catastrophic equipment shutdown. These include allowing the sealant mixture to cool to ambient temperatures before injection. Cooling permits better control over the flow rate of the organosilane component of the mixture.
- Preferred components and compositions for the organosilane include those described in U.S. Patent No. 4,237,172 issued 2 December 1980 to Packo et al under title Sealing Leaks by Polymerization of Volatilized Aminosilane Monomers; United States Patent No.
- Patent No. 5,417,873 issued 23 May 1995 to Packo under title Sealant Containing Partially Hydrolized Tetraalkoxy Silane, for Air Conditioning and Refrigeration Circuits.
- compositions for the organosilane are dependent on the selected criteria from those set out above.
- general nature of the organosilane can be represented as (R 1 )(R 2 )Si(R 3 )(R 4 ) where the preferred nature of the radicals is that
- R 1 is an alkyl radical of 1 -4 carbon atoms or vinyl or -OH
- R 2 is R 1 or ⁇ OR 1 or -NH(R 1 ) or -N(RO 2 or -R 1 NHR 1 NH 2
- R 3 is R 1 or -OR 1 or -NH(Ri) or -N(Ri) 2 or -R 1 NHR 1 NH 2
- R 4 is R 1 or -OR 1 or -NH(R,) or -N(Rj) 2 or -RiNHR 1 NH 2
- oligomers of the monomeric silanes described are the siloxanes:
- R S ,R O or R 7 may be Ri,R 2 ,R 3 or R 4
- This composition was present at about 10% in the organosilane mixture used for experimental purposes where R 5 and Re were -OCH 3 and R 7 was either -CH 3 or vinyl.
- the lubricant is preferably chosen to be miscible with the organosilane mixture at ambient temperatures to provide proper control of the flow.
- Preferred lubricants would include those based on fluids such as polyolesters. Lubricants based on other fluids might be used.
- Those known to be miscible with organosilanes include, for example, mineral oils, alkyl benzenes and polyalkylene glycols.
- Drying agents include, for example, mono- and polyhydric alcohols, including glycols, preferentially mono-, di- and trihydric alcohols, or orthoesters such as orthoformates. While orthoformates are commonly referred to as drying agents, their mode of action is considerably different than that of the alcohols. Alcohols actually form solutions with water so that the water is still present in the system. In the case of materials such as orthoformates or other orthoesters, the water actually takes part in a chemical reaction which transforms the water into other molecular species. Chemicals that react with water in this manner are termed hydrolytes. In the case of orthoesters and other desirable hydrolytic drying agents used in the present invention, the hydrolytic reaction with water forms a fluid that is oil-soluble.
- Hydrolytes used as drying agents are referred to herein as "hydrolytic drying agents".
- hydrolytic drying agents that form (or continue to be) an oil-soluble fluid upon reaction with water include orthoesters (including orthoformates), acetals, epoxides, and carbodiimides.
- Conditioners include, for example, methylene chloride and cyclohexanone.
- Antioxidants include, for example, those based on phenolic and aminic derivatives.
- Corrosion and rust inhibitors include, for example, esters of derivatives from succinic acid.
- Antiwear agents include, for example, sulphur and phosphorus derivatives.
- Metal deactivators include, for example, triazole derivatives.
- Acid and base neutralizers include, for example, buffering agents.
- Detergent additives include, for example, non-ionic detergents.
- Other sealants alternative to or in combination with organosilanes, may also be used. These sealants may consist of polymeric latexes, vinyl acetates, acrylonitriles,epoxide or methacrylates or some combination thereof. The sealant may include alkylene glycol.
- the sealant may contain a catalyst or accelerator.
- the catalyst may contain a copper or cobalt compound.
- the catalyst or accelerator may contain a solubilizer.
- the sealant may contain a filler.
- the filler may be graphite, carbon powder or a polytetrafluoroethylene.
- compositions of the lubricant/organosilane mixture, or the lubricant/hydrolytic drying agent mixture, or the lubricant/organosilane/hydrolytic drying agent mixture are those providing viscosities above a viscosity of 7 cst. when measured at 4O 0 C.
- the choice of this viscosity minimum was determined by experiment as illustrated below in examples 4 to 7. The 40 0 C measurement point is used simply because this is the temperature at which compressor lubricants are typically characterized for viscosity.
- the quantity of organosilane to be added depends on the size of the refrigeration or air conditioning system. This is not due to the size or number leaks in the system. For small leaks, say less than 1/16" in diameter, and a sealant plug 1/16" long, several hundred seals would easily require only an ounce of organosilane.
- the rapidity with which a leak will seal depends on delivering an effective quantity of the sealant to the situs of the leak. This latter consideration, experience in automotive applications, and general practical considerations such as the size of the injection apparatus, suggest that injections of between 1/8 and 1 oz. of organosilanes are sufficient for most applications, with larger systems requiring the larger amount. In addition, it has been found that injections up to a maximum of 10% of the lubricant quantity in the system are recommended due to concerns with injection of liquid into the low side in proximity to the compressor 5.
- organosilane is combined with a miscible lubricant.
- the quantity of lubricant mixed with the organosilane is determined by considerations of first, providing adequate lubrication as the fluid enters the compressor 5 as has been previously described and second, of producing limited effect on the final lubricant viscosity, preferably no more than 10% reduction, once the organosilane has been distributed throughout the system.
- the desired viscosity of the lubricant/organosilane mixture can be achieved by varying the ratio of the two or by adjusting the viscosity of the lubricant.
- Organosilanes of interest generally have very low viscosities ( ⁇ 1 cst. @ 40 C) while lubricants of interest are much higher in viscosity (10 to 220 cst. or more @ 40 C).
- the effect of the injected mixture on the final lubricant mixture depends on the injected viscosity as well as both the viscosity and quantity of oil in the system.
- Table 1 provides information on the range of characteristics of typical refrigeration and air conditioning systems. As described previously, the systems in Table 1 cover the range of compressor drives and types. The methods and considerations outlined in herein apply to all such systems.
- *1 ton represents approximately 12,000BTU
- ⁇ L , ⁇ 2 are the viscosities of components 1 and 2 and
- C is a constant dependent on the nature of the components.
- Equation 1 can be rearranged to give the final viscosity of the mixture as:
- ⁇ fina i is the final viscosity of the sump mixture after injection of the sealant mixture
- Xj n J 1 is the mole fraction of injected material in the final sump mixture
- Xsump is the mole fraction of the original sump oil in the final sump mixture
- Hinj, ⁇ sump are the viscosities of the injected material and original sump oil respectively
- Equation 2 is a constant dependent on the nature of the components.
- Equation 3 provides a basis for determining the desired viscosity and quantity limits on the injected material.
- Equation 3 can be adjusted based on any selected limit on final viscosity other than the 90% of original sump viscosity used here.
- Fr is the desired fraction of the original sump oil viscosity to be maintained.
- Line 3 similarly shows that injecting 1/8 of an ounce of organosilane in 1 ounce of the lubricant/organosilane mix into such a system using a 32 cst. lubricant rather than the 10 cst. mix of Line 2 would produce a sump viscosity of 29.9 cst. This is above the suggested 29 cst. limit for this lubricant and would be an acceptable formulation.
- Rows 4 and 5 show information for systems using a 32 cst. lubricant and having a sump capacity of 30 ounces. Up to about 1/ 5 of an ounce of organosilane can be injected while still maintaining an injected viscosity of at least 7 cst.
- Rows 8, 9, and 10 indicate the diminishing effect of larger sump size with various injections compared to the previous rows, allowing up to 3/5 of an ounce of organosilane to be injected while still maintaining final viscosity above 29 cst.
- Rows 11 and 12 give information for systems using 46 or 68 cst. lubricants in the sump.
- An example of the use of this computational technique is the determination of acceptable combinations, ratios and amounts of lubricant and organosilane to be injected by consideration of the system characteristics exhibited in Table 1. For example if a small unit with a 10 oz. sump contains 32 cst. lubricant, what should be the composition of the injected material using a 32 cst. lubricant and an organosilane mix? With 1 ounce injected, the maximum amount of organosilanes used here is calculated to be 0.175 of an ounce with the injected mixture having a viscosity of 12 cst. and the system lubricant having a final viscosity of 29 cst.
- Table 3 gives examples of situations where the viscosity limit of lubricant (32 cst)/organosilane mix needs to be controlled above the minimum viscosity requirement of 7 cst. dependent on the total amount injected.
- the lubricant/organosilane mixture should be at a minimum viscosity of 12 cst. at 40 C which correspond to less than 0.175 oz. of organosilane in the 1 oz. of material injected.
- Equations 1-4 allow calculation of acceptable mixtures of lubricant and organosilane to be used for any specific situation in terms of the size of the unit (oil capacity) and viscosity of the sump oil.
- the minimum ratio of lubricant to organosilane is predetermined by the minimum allowable injected viscosity and the individual viscosities of the lubricant and organosilane in the injected mixture.
- the viscosity of mixtures relate exponentially to component viscosities and in ratios dependent on mole fractions rather than simple weight fractions.
- the molecular nature of the lubricant affects the relation between viscosity and molecular weight so that the examples presented here are not to be taken as representing the only possible trends.
- Some systems operate with a lubricating subsystem that is independent of the refrigerant. In this case, organosilanes alone are injected into the refrigerant circuit.
- organosilanes alone in systems where the lubricant is carried by a miscible refrigerant.
- the organosilane alone, or in a mix with lubricant can be injected into the high side of a refrigeration system while the unit is operating up to a maximum of 6% per minute of the systems total oil content.
- a system with a 50 oz oil capacity could be injected up to a rate of 3 oz/ min. of organosilanes.
- the quantity injected remains limited by the foregoing based on limits to reduction in sump viscosity.
- injection of the lubricant/organosilane mixture is accomplished through the use of a sealed canister 15 and a coupling hose assembly 16 that is first fitted to the canister 15 and then to the inactive refrigeration system 1 through an injection port 17 on the low-pressure side of the compressor 5.
- the canister 15 can be pressurized before the canister 15 is sealed.
- the pressure in the canister 15 causes the sealant mixture to enter the system 1 when the canister is opened, there is fluid connection to the system 1, and the system 1 is running to cause "low side" 10 pressures to drop.
- the canister 15 was not pre-pressurized as will be explained below; however, a charged pressure of 100 psig was found to be acceptable for allowing the sealant mixture to enter the system 1 in the test environment, where the low side pressure was 77 psig as mentioned previously.
- the sealed canister 15 can have a pressure near, at or below ambient.
- the canister 15 can be charged (pressurized) using the system 1 pressure. First the system 1 is turned off and pressure within the system 1 is allowed to equalize. In the test environment, this results in an overall system 1 pressure of approximately 100 psig.
- the canister 15 can have a pressure near, at or below ambient.
- the canister 15 can be charged (pressurized) using the system 1 pressure. First the system 1 is turned off and pressure within the system 1 is allowed to equalize. In the test environment, this results in an overall system 1 pressure of approximately 100 psig.
- the canister 15 is at a pressure of about 20 inches of mercury vacuum.
- the vacuum is a result of packaging processes that ensure much of the air is removed from the canister 15 before it is sealed.
- Hose assembly 16 is evacuated and then the canister 15 seal is broken using a can-tapper 21 that is built into the hose assembly 16 in such a way that refrigerant mix from the system 1 is allowed into the canister 15 until pressures are stabilized, and the canister 15 is charged.
- the can-tapper 21 has a manually operated valve (see valve handle 25 below) for fluid connection (open) and fluid disconnection (closed) of the canister 15 from the system 1.
- the can-tapper 21 is also a fitting for sealed fluid connection to the canister 15, typically by way of compatible threads in the can-tapper and on the canister 15, and corresponding seals, such as a rubber gasket or an o-ring.
- canister 15 contents to the refrigerant system 1 is controlled to a maximum flow rate of about 6 cc/sec which in the preferred embodiment is obtained through the use of orifice 20 having a maximum diameter of about 0.06 in.
- a maximum flow rate of about 6 cc/sec which in the preferred embodiment is obtained through the use of orifice 20 having a maximum diameter of about 0.06 in.
- Figure 2 One such arrangement is shown in Figure 2.
- the minimum orifice size should be about 0.02 inches in diameter to avoid orifice plugging due to contamination from particles from system 1 as the canister 15 is charged.
- This minimum restriction could be removed by the inclusion of a filter, such as filter 16A of FIG. 1, in the injection hose between the fitting 22 and the injection port 17.
- the orifice 20 is located within fitting 22 of FIG. 2. In the test environment an orifice of 0.0292 inches diameter was successful.
- the hose assembly 16 has a hose 23 between the can-tapper 21 and the fitting 22.
- the action of filling the canister 15 with refrigerant upon tapping the canister 15 and opening a valve in the tapper 21 causes the canister 15 and its contents to heat to temperatures well above ambient. Temperatures of 135 0 F were encountered in tests. This may affect the flow rate of the organosilane as it enters the system 1.
- the canister 15 is fluidly disconnected after charging and the system 1 is run. Then the canister 15 is again fluidly connected to the system 1. This allows the system 1 to achieve full low side 10 pressure that will best allow the sealant mixture to enter the system 1.
- the canister 15 should be allowed to cool to at or near ambient temperature while still fluidly connected to the non-running system 1. If not, then charge in the canister 15 may be lost as pressure will drop with the temperature in a closed canister 15.
- the contents of the canister 15 should enter the cooler suction gas stream with as close to ambient temperature of the system 1 as possible so as not to effect the volume of the cooler gas going to the compressor 5.
- a compressor 5 generally requires at least a four percent return of oil to maintain adequate lubrication on metal-to-metal surfaces.
- a residential system 1 operating at a suction pressure of 70 psig will typically have a corresponding evaporator 3 saturation temperature of 41 degrees F. If the system 1 is operating satisfactorily then the actual suction line 10 temperature should be approximately 51 degrees F. This is due to an extra 10 degrees of superheat picked up during the expansion.
- the primary reason for inverting the canister is to simplify the procedure for the technician. If the technician forgets to invert the canister before injection into the air-conditioning unit (see 10. below) then the transfer of the mixture would not be successful because of the gas on top and the heavier liquid residing on the bottom of the can.
- the connection to the low-side charging port is made with the canister inverted for charging and injection as one-step. This also limits stressing the hose assembly by changing position while under pressure. Having the gas first pass through the mixture also helps to mix the contents of the mixture if possible stratification occurred between the organosilane and the miscible lubricant.
- a canister was used with approximate dimensions of 5 cm. diameter and 10 cm height and this contained about 89 cc (3 oz.) of a lubricant/organosilane mix.
- the canister 15 filled with refrigerant and inverted at ambient conditions, this would produce a lower column of liquid about 4.5 cm. high covered with a gaseous column of refrigerant 5.5 cm. in height.
- the pressure exerted by the refrigerant was around 120 psi and this was then injected into a system operating at 66 psi. Thus the driving force for injection of the liquid phase into the system was about 54 psi.
- ⁇ P is the differential pressure
- p is the fluid density
- units below 1 ton should require about 1/8 - l/4oz. of organosilane and larger units 1 A -1 oz.
- the total quantities of the mixture will also depend on the practicality of the details of the injection system being used. The viscosity of the mixture and the quantity of organosilane can be adjusted within these general guidelines.
- the general test apparatus is shown schematically in Figure 2 and represents the basic components of a typical refrigeration system 1.
- a refrigerant gas (R-22 was used in the test environment; however, R 134a and other refrigerants could also be used) is circulated by means of a hermetically sealed electric motor and compressor 5.
- the gas is condensed to liquid by means of a condenser 7; the liquid passes through valve 9 and then through an evaporator 3 where the liquid is regenerated to a gas accompanied by the desired cooling effect.
- the gas then returns to the compressor 5 for repeating cycles of the process.
- a test was performed using a 0.029 in. orifice 20 to inject a 3 fl. oz. mixture consisting of 3 parts of a commercial polyolester refrigeration compressor 5 oil and 1 part of an organosilane sealant such that the mixture had a viscosity of 8 cst. @ 4O 0 C.
- the oil capacity of the single phase hermetically sealed 2 ton system 1 was 55 oz.
- the system 1 was injected with the organosilane/oil mixture with no change in amperage of the motor, indicating no liquid slugging.
- the system 1 was run successfully for 12 days until shut down deliberately.
- a start/stop test was run with 60 start/stops over a 3 1 A hr. period. This is a severe test due to the surge of electricity required to start the spinning of the rotor of the motor and also due to some initial loss of oil from the inboard bearing at each start. The test was successful with no change in operating variables and the system 1 ran for an additional 13 days with excellent operation until it was deliberately shut down.
- Controlled rate of introduction of the organosilane/oil mix was investigated as a variable.
- the hose assembly shown in Figure 2 was used to introduce mixtures into a 2 ton refrigeration system 1 fitted with an oversized 2 1 A ton condenser 7.
- the can-tapper 21 at one end of the hose seals and punctures a canister 15 containing the sealant.
- the fitting 22 at the other end is attached to the refrigeration system 1 and low-side port 17 is opened to allow the sealant mixture to enter the refrigeration system 1 through an orifice 20.
- the size of this orifice 20 affects the injection rate of the sealant.
- a capillary tube was used to control introduction of the sealant.
- An orifice 20 size of 0.055 in. was found to allow successful introduction of the sealant into the above refrigeration system 1.
- the system 1 ran for 18 days with no change in operating variables before it was deliberately shut down.
- Refrigerant - 134A Charge - 105g AMPS - 1.1
- Unit GE with Matsushita SB30C50GAU6 compressor Refrigerant 134A Charge 1.59 ounces
- the typical procedure used to inject mixtures into the refrigeration system 1 involves opening the canister 15 containing the oil/organosilane mixture to a low pressure port 17 just prior to the non-operating compressor 5.
- the mixture is at a pressure near 20 inches of mercury vacuum before opening to the refrigerant system 1 which is typically near 100 psig.
- the entry of the refrigerant into the mixture in the canister 15 causes a heating effect and raises the canister 15 and contents to about 25°C above ambient.
- Single phase systems 1 are particularly susceptible to this effect since entry of the hot mixture into the refrigeration system 1 would cause momentary heating of the suction vapor and a decrease in the vapor's density. This in turn affects the ability of the vapor to cool the motor and other mechanical parts.
- Example orthoesters may be one or some of trimethylorthoformate (TMOF), trimethylorthoacetate (TMOA), triethylorthoformate (TEOF), triethylorthoacetate (TEOA). Triisopropylorthoformate (TIPOF), or triisopropylorthoacetate (TIPOA).
- TMOF trimethylorthoformate
- TMOA trimethylorthoacetate
- TEOF triethylorthoformate
- TEOA triethylorthoacetate
- TIPOF Triisopropylorthoformate
- TIPOA triisopropylorthoacetate
- other orthoformates with an aryl substituent such as triethylorthobenzoate (TEOB) may be used.
- the present methods describe a series of options in which the orthoformate is efficiently added after system charging to remove accumulated water during operation of the system. Addition of a refrigeration base oil/orthoformate composition as an initial charge is impractical. The presence of a minimum amount of base oil such as polyester is required to provide sufficient lubrication for the system. Replacing base oil on the initial charge with significant amounts of orthoester sacrifices the required lubrication performance. Adding ineffectually small amounts of the orthoester in an initial charge limits the water reduction performance of the orthoester component.
- the present methods of adding orthoester and other additives allow customized addition of hydrolyte to the particular system. The present methods also ensure that the orthoesters are mixed throughout the a/c or refrigeration system and not added only to the oil sump. This ensures reaction with water wherever it is present throughout the a/c or refrigeration system.
- the orthoformate may be introduced into the a/c or refrigeration system alone or in combination with other additives by one of a variety of techniques such as for example from a vacuum packed canister, a pressurized refrigerant can, a syringe or piston operating device, or from an in-line canister, for example using the methods otherwise described herein for injection of additives.
- One method of introducing the orthoformate includes introducing the orthoformate at a time prior to the injection of another additive that is unstable in the presence of moisture followed by injection of the other additive at a time before it is known that the orthoformate is fully reacted with moisture in the system.
- This can include for example the organosilane sealants previously described herein. It can also include dye and dye mixtures typically injected for use in leak detection as previously described herein. Such dyes may include perylene or napthalimide for example.
- the dye may be carried in a lubricant, such as those described previously, such lubricants can be reactive with moisture.
- polyolester is often utilized as a lubricant and can be unstable in the presence of moisture.
- orthoformates generally react more quickly with moisture than organosilanes, and the dye and dye mixtures typically utilized in air conditioning and refrigerant systems. This allows the orthoester to be injected at the same time.
- the orthoesters can be included together with the other moisture reactive additive (sealant) in a single vessel for contemporaneous injection into the system. Since the orthoester reacts with water before the organosilane, the formation of deleterious silicone polymers within the system is avoided.
- the orthoformate or other orthoester can be injected into the system at a time prior to the injection of the other additive followed by injection of the other additive at a time before it is known that the orthoformate is fully reacted with moisture in the system.
- the other additive can be injected immediately after or contemporaneously with the orthoformate.
- a technician uses a hose connected to the system to inject the orthoformate
- the technician could use the same hose for injection of the other additive immediately thereafter while leaving the hose connected to the system.
- Undesired reaction of additives with moisture within an air conditioning or refrigeration system can be deleterious to the system for at least some of the reasons discussed previously.
- undesired reaction of an organosilane away from a leak site can reduce the effective amount of the sealant for reaction at a leak site.
- sealant such as organosilane
- sealant is often injected in amounts far greater than are required for leak sealing in a moisture-free system. This can be seen for example when sealant is found in oil sludge when a system is opened up for examination, hi addition to requiring additional sealant undesired reactions of sealant with moisture can result in contamination of the system, such as might cause blockages and otherwise reduce the efficiency of the system.
- Undesired reaction of dye and/or carrying lubricant can cause the formation of crystal and gel-like substances within the system. Such substances can also cause blockages or otherwise negatively affect the operation of the system.
- orthoformates or other orthoesters react with moisture the result is typically a liquid that is soluble in oil typically found in air conditioning and refrigeration systems.
- Some non-orthoformate drying agents that have been used in air conditioning systems can themselves react with moisture to form globs that trap particulate and can lead to blockages.
- Similar viscosity and time of injection requirements can be applied to the addition of orthoesters and other drying agents that provide or remain fluid after reaction with water. These requirements can also be applied to the addition of mixtures of orthoesters and sealing agents, or mixtures of orthoesters, sealing agents, and other desired additives such as indicator dyes.
- an orthoformate, or a mix of orthoformate and organosilane, or a mix of orthoformate, organosilane, and indicator dye can be mixed with an ISO 32 grade refrigeration compressor oil, for example, in a ratio to maintain a total mixture viscosity above 7 cSt.
- Compressor oils of other viscosity grades may be used and the composition of the oil may be mineral, polyalkylene glycol, polyolester, or polyalpholef ⁇ n subject only to the requirement that the orthoester is soluble in the compressor oil at the selected ratio.
- the orthoester may be injected as a pure compound or as a solution in the presence of other useful additives.
- the orthoester can be included with compressor oil and organosilane sealant compounds as discussed previously.
- the mixture ratios can be such that the injected materials have a viscosity minimum of 7 cSt at 40 C and the mixture is of a single phase.
- Orthoesters may be selected subject to the requirements above.
- Preferred orthoesters may be one or some of trimethylorthoformate (TMOF), trimethylorthoacetate (TMOA), triethylorthoformate (TEOF), triethylorthoacetate (TEOA).
- TIPOF triisopropylorthoformate
- TIPOA triisopropylorthoacetate
- TEOB triethylorthobenzoate
- Catalytic effects can be useful in improving the amount of water consumed by a given orthoformate, although it is typically not necessary to use a catalyst.
- a catalyst As an example an sulfonated macroreticular solid acid catalyst can be used. This may be used by including the catalyst in a canister in line with the circulating refrigerant medium or as a side-stream.
- Samples were prepared in approximately 40 gram batches by measuring the desired amount of water into a vial, adding compressor oils and then adding the orthoformate and any additional chemicals. Typically 1 wt % water was used since this amount is insoluble in compressor oils and represents a severe test of the invention. Samples were shaken periodically over several days with observations made on the reaction mixtures over this time period. At the end of the test period, water content of the solution or mixture determination by the Karl-Fischer method, ASTM D6304.
- a 5200 BTU window style air conditioner was modified to include al6 cu.in. sealed liquid line drier and isolation valves with bypass piping for on line change outs.
- Two liquid moisture indicators were integrated into the circuit for observing moisture levels as low, medium or high as shown by colour changes from pink through green.
- the unit was put into service under constant load at an ambient temperature of 70F/21.1C. Normal operating conditions for the unit typically result in 68 psig suction pressure and a 220 discharge pressure. The following procedures demonstrated the efficacy of orthoesters in water removal from this unit.
- a canister may contain simply a drying agent such as TEOF.
- the size of the canister may be variable. It has been found that a canister containing about 29.6 ml (about 1 ounce) of TEOF is appropriate for 300-18,000 BTU systems of Table 1 to remove up to 2 ml of moisture. For larger systems having potentially more moisture more than one canister can be used, if desired.
- a canister for a 300- 18,000 BTU system can include 29.6 ml of total contents made up of 21 ml of TEOF, 7.4 ml of lubricant and organosilane sealant mixture, and 1.2 ml of leak detection dye mixture, such as for example a napthalmide and polyolester oil mixture.
- An example sealant mixture is sold as HVACR TM by Cliplight Manufacturing Company of Toronto, Canada.
- An example dye mixture is sold as Cliplight AC Universal TM dye by Cliplight Manufacturing Company of Toronto, Canada.
- a canister for a 18,000-60,000 BTU system can include 88.6 ml of total contents made up of 29.6 ml of TEOF, 56.6 ml of lubricant and organosilane sealant mixture, and 2.4 ml of leak detection dye mixture, such as for example a napthalmide and polyolester oil mixture.
- An example sealant mixture is sold as HVACR TM by Cliplight Manufacturing Company of Toronto, Canada.
- An example dye mixture is sold as Cliplight AC Universal TM dye by Cliplight Manufacturing Company of Toronto, Canada.
- a canister can include 44.30 ml of total contents made up of 14.7 ml of TEOF, 28.4 ml of lubricant and organosilane sealant mixture, and 1.2 ml of leak detection dye mixture, such as for example a napthalmide and polyolester oil mixture.
- An example sealant mixture is sold as SUPERSEAL TM by Cliplight Manufacturing Company of Toronto, Canada.
- An example dye mixture is sold as Cliplight AC Universal TM dye by Cliplight Manufacturing Company of Toronto, Canada.
- a canister can be sold as a kit, either with instructions for use, or in combination with a hose for attaching the canister to the refrigerant stream of an air conditioning or refrigeration system.
- the above combinations are example embodiments only.
- the above combinations are example embodiments of a "total" solution in that a hydrolyte drying agent is provided in combination with an organosilane sealant and a leak detection dye.
- the hydrolyte drying agent is used to dry the system to improve system operation generally in addition to preparing it for improved effectiveness of the sealant and the dye.
- an orthoformate hydrolyte drying agent could also be provided together with a dye or dye mixture or, alternatively, with a sealant mixture.
- An orthoformate hydrolyte drying agent can be mixed with a dye or dye mixture, or with a sealant mixture, to stabilize the dye and dye mixture, and the sealant mixture, for storage prior to injection into a system.
- Dyes and dye mixtures containing components that react with moisture have been found in some circumstances to react over time in storage.
- a relatively small amount of an orthoformate can be utilized in the container. The amount need only be enough to react with any possible amount of anticipated moisture in the dye, dye mixture or sealant mixture. Again, the orthoformate drying agent will react more quickly with moisture than the dye, dye mixture or sealant mixture.
- the above methods and devices involving the utilization of orthoesters can increase performance and stability of organosilane mixtures when used separately or combined with dyes, such as for example perylene and naphthalimide dyes and lubricants by reducing air conditioning and refrigeration system moisture content.
- dyes such as for example perylene and naphthalimide dyes and lubricants
- a lesser, or optimized, amount of organosilane, or dye can be used in an air conditioning and refrigeration system while allowing greater potential for chemical productivity performance and stability while on route to its intended target.
- Increased chemical reaction can result in more work done because of decreased reaction with internal residual moisture as is the case of chemical solutions which form a solid polymer, gels or crystallize when coming in contact with water.
- Moisture laden air can enter systems in manufacturing or when being serviced or when loss of system refrigerant creates a lower than atmospheric condition on the suction side of the compressor which results in drawing air containing a moisture content into the system while in operation.
- organosilanes where the intended purpose is to react with atmospheric moisture externally at the point of a refrigerant leak forming a solid polymer the performance of the reaction can be affected by internal moisture contents within the system away from the leak situs.
- the volume of organosilanes has been found to be increased to offset premature reaction with internal system moisture.
- the pre polymerization has been found to reduce the amount of chemical performance reaching the intended purpose while possibly leaving residual polymer particulate as in the case of a high system moisture content internally causing a potential blockage and mechanical breakdown.
- moisture reactive dyes such as perylene and naphthalimide
- a simulate reaction to internal moisture occurs.
- the dyes when coming in contact with internal system moisture will begin to form gels and in some cases will solidify forming a crystallized substance.
- This by product of the reaction to internal system moisture will also as in the case of the organosilanes cause a blockage to refrigerant flow and eventually result in a mechanical breakdown.
- Critical blockages will usually form at the expansion valves and in capillary tubes, reducing refrigeration effect and ultimately causing a catastrophic mechanical failure.
- Liquid line driers can also be installed to help remove small amounts of moisture.
- the primary objective of these driers is to help with the removal of particulate and sludge.
- Embodiments of the methods and devices described herein can provide an alternative method for water removal by chemically reacting with water to transform it to a more benign product. Such a chemical reactant reduces water content in the system without requiring removal of refrigerant or application of a deep vacuum.
- embodiments of the methods and devices described herein can be used to enhance the ability of chemicals which react to water for a specific purpose or become unstable when in contact with water by including orthoformates for the removal of water from air conditioning or refrigeration systems to enhance the potential of organosilanes and dyes, such as for example perylene and naphthalimide, lubricating oils, or the combination of them as a mixture.
- these applications can be introduced to a system at the time of manufacturing or servicing of a refrigerant free system or to operating refrigeration or air conditioning systems which have absorbed water from the environment.
- Some embodiments can include the introduction of ortho formates in a non-acidic environment into a refrigeration or air conditioning system with subsequent reduction of water content through hydrolysis.
- Some embodiments provide for the use of specific catalytic media and specific orthoformates to provide up to enhance the reduction of the amount of water.
- Thhis may include the use of acidic or basic macroreticular ion exchange resins, such as acid ion exchange resins to enhance the reactivity of water with orthoformates beyond a 1 :1 molar ratio of water and orthoformate.
- the resins may be all or part of a filtering device as part of the a/c or refrigeration system.
- Neutralizing media may be introduced into air conditioning and refrigeration systems with said orthoformates.
- Some embodiments provide for introduction of orthoformates into refrigeration and air conditioning systems in combination with refrigerant compressor oils. Some embodiments provide a method to remove reaction products from the resultant mixture after reaction of the water. Removal of reaction products of orthoformates and water by partial or full recovery of the system refrigerant can be performed for example by a) shutting down the system to allow pressure in the a/c or refrigeration system to equalize and sufficient time for the compressor oil to migrate back to the sump, and b) using a small positive displacement pump or vacuumed vessel attached to the suction charging valve to remove the lighter reaction products from the sump.
- orthoformates are part of the refrigeration oil/refrigerant composition originally installed in the air conditioning or refrigeration system or as part of a retrofit process during system service.
- injection of the orthoformate alone or in useful mixtures with other additives can, for example, be accomplished by one of several methods such as introduction from a vacuum packed can into the low side charging valve of the system while in operation, introduction of the contents from a pressurized refrigerant can into the low or high side charging valve, introduction of the contents from a vacuum packed can into the high or low side charging valve on a system which has had the refrigerant recovered and is in vacuum, injection of contents from a syringe or piston operating device (vessel) utilizing modulated positive displacement into low or high side charging valve when the machine is operating or not operating, inject of the contents using an inline canister into the high or low side charging ports.
- introduction from a vacuum packed can into the low side charging valve of the system while in operation introduction of the contents from a pressurized refrigerant can into the low or high side charging
- a method of maintaining an air conditioning or refrigeration system charged and pressurized with a system fluid comprising a refrigerant comprising: (a) introducing into the system fluid, a maintenance fluid containing a hydrolytic drying agent which maintains a fluid form upon hydrolytic reaction with water, and having a maintenance fluid viscosity; and (b) causing the system to distribute said maintenance fluid throughout the system fluid.
- the method further comprises c) determining if the system fluid continues to indicate the existence of water in the system, and, if so, then repeating a), b), and c).
- the hydrolytic drying agent is introduced into the system fluid at a controlled rate.
- the hydrolytic drying agent forms or maintains an oil-soluble form after reacting with water.
- the hydrolytic drying agent is an orthoester.
- the orthoester is selected from the group consisting of trimethylorthoformate, trimethylorthoacetate, triethylorthoformate, triethylorthoacetate, triisopropylorthoformate, triisopropylorthoacetate, and triethylorthobenzoate.
- the maintenance fluid viscosity is selected such that, after said maintenance fluid is introduced, a sump viscosity of a sump mixture of the air conditioning or refrigeration system is affected by less than a 10% reduction.
- a controlled rate of introduction of the maintenance fluid is selected to avoid liquid slugging and to maintain sufficient lubricant for proper operation of the compressor.
- the controlled rate is less than 6% (by volume) of a total oil content of the system per minute. [00151] According to a further aspect, the controlled rate is less than 6cc/second.
- the maintenance fluid viscosity is selected such that, when said maintenance fluid is introduced, a sump viscosity of a sump mixture of the air conditioning or refrigeration system does not fall below 29 cst at 4O 0 C.
- the maintenance fluid viscosity is not less than 7 cst at 4O 0 C.
- the maintenance fluid further comprises a sealant.
- the sealant is an organosilane.
- the maintenance fluid further comprises a refrigerant.
- the maintenance fluid further comprises an indicator dye.
- the indicator dye is a fluorescent dye.
- the method further comprises (c) introducing into the system fluid, simultaneously with step (a) or (b), shortly after step (a), or shortly after step (b), a sealant fluid comprising a sealant and having a sealant fluid viscosity; and (d) causing the system to distribute said sealant fluid throughout the system fluid.
- the sealant fluid is introduced at a second controlled rate.
- the maintenance fluid viscosity and the sealant fluid viscosity are selected such that, when said sealant fluid is introduced, a sum viscosity of a sump mixture of the air conditioning or refrigeration system is affected by less than a 10% reduction.
- a controlled rate of introduction of the maintenance fluid and a second controlled rate of introduction of the sealant fluid are selected to avoid liquid slugging and to maintain sufficient lubricant for proper operation of the compressor.
- the controlled rate and the second controlled rate combine to less than 6% (by volume) of a total oil content of the system per minute.
- the controlled rate and the second controlled rate combine to less than 6cc/second.
- the maintenance fluid viscosity and the sealant fluid viscosity are selected such that, when said sealant fluid is introduced, a sump viscosity of a sump mixture of the air conditioning or refrigeration system does not decrease below 29 cst at 4O 0 C.
- the sealant fluid viscosity is not less than 7 cst at 4O 0 C.
- the method further comprises (c) passing said hydrolytic drying agent through a filter/dryer comprising a solid catalyst.
- the solid catalyst is selected from the group consisting of a solid acid catalyst and a solid basic catalyst.
- the solid catalyst is a macroreticular ion exchange resin.
- the macroreticular ion exchange resin is Amberlyst
- the filter/dryer also contains a filter drying medium.
- the filter drying medium is selected from the group consisting of any one or more of alumina, charcoal and molecular sieves, either in separate layers or admixed with said ion exchange resin.
- a device for use in maintaining an air conditioning or refrigeration system comprising: (a) a sealed vessel adapted to receive a hose assembly forming, at a proximal end, a sealed fluid connection to a refrigerant fluid of the system, and having at a distal end, a receiving unit for the vessel, and (b) in the sealed vessel: : (i) a fluid containing a hydrolytic drying agent which maintains a fluid form upon reaction with water, and (ii) a sealant.
- the hydrolytic drying agent is an orthoester.
- the orthoester is selected from the group consisting of trimethylorthoformate, trimethylorthoacetate, triethylorthoformate, triethylorthoacetate, triisopropylorthoformate, triisopropylorthoacetate, and triethylorthobenzoate.
- the sealant is an organosilane.
- the fluid has a viscosity of not less than 7 cst.
- the fluid further comprises an indicator dye.
- the indicator dye is a fluorescent dye.
- a charged, pressurized air conditioning or refrigeration system having: a compressor, a high side, a low side, and a refrigerant fluid having a refrigerant and travelling from the high side to the low side and back; a canister, containing a maintenance fluid comprising a hydrolytic drying agent which maintains a fluid form upon reaction with water; a hose assembly having a manually operated valve, and forming, at a proximal end, a sealed fluid connection to the refrigerant fluid, and having, at a distal end, a receiving unit for the canister; said distal end capable of puncturing or otherwise opening said canister to form a fluid connection between the maintenance fluid and the refrigerant fluid.
- the hydrolytic drying agent is an orthoester.
- the orthoester is selected from the group consisting of trimethylorthoformate, trimethylorthoacetate, triethylorthoformate, triethylorthoacetate, triisopropylorthoformate, triisopropylorthoacetate, and triethylorthobenzoate.
- the maintenance fluid also comprises a sealant.
- the sealant is an organosilane.
- the air conditioning or refrigeration system further comprises a can tapper for puncturing or otherwise opening said canister.
- the air conditioning or refrigeration system further comprises a flow rate controller which controls or restricts the maximum flow rate of the maintenance fluid into the refrigerant fluid.
- the flow rate controller is an orifice.
- the fluid connection is formed between the maintenance fluid and the refrigerant fluid, the maintenance fluid flows into the maintenance fluid at a maximum flow rate of 6 cc/second.
- the air conditioning or refrigeration system further comprises a filter/dryer canister, comprising a solid catalyst, through which the refrigerant fluid travels.
- the solid catalyst is selected from the group consisting of a solid acidic catalyst and a solid basic catalyst.
- the solid catalyst is a macroreticular ion exchange resin.
- the resin is Amberlyst 15.
- the filter/dryer canister also contains a filter drying medium.
- the filter drying medium is selected from the group consisting of any one or more of alumina, charcoal, and molecular sieves, either in separate layers or admixed with said catalyst.
- kits comprising: the device of claim 31; a hose assembly capable of forming, at a proximal end, a sealed fluid connection between an inside of the hose assembly and a refrigerant fluid in an air conditioning or refrigeration system, and capable of attaching, at a distal end, to the vessel, said distal end capable of puncturing or otherwise opening said vessel to form a fluid connection between the inside of the hose and the fluid.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Lubricants (AREA)
- Sealing Material Composition (AREA)
Abstract
Applications Claiming Priority (2)
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US9620808P | 2008-09-11 | 2008-09-11 | |
PCT/CA2009/001264 WO2010028493A1 (fr) | 2008-09-11 | 2009-09-11 | Compositions et procédés pour l'injection d'agents d’étanchéité et/ou siccatifs dans des systèmes de climatisation et de réfrigération |
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EP2334994A1 true EP2334994A1 (fr) | 2011-06-22 |
EP2334994A4 EP2334994A4 (fr) | 2013-11-06 |
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EP09812576.8A Withdrawn EP2334994A4 (fr) | 2008-09-11 | 2009-09-11 | Compositions et procedes pour l'injection d'agents d'etancheite et/ou siccatifs dans des systemes de climatisation et de refrigeration |
Country Status (3)
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EP (1) | EP2334994A4 (fr) |
CA (1) | CA2736909A1 (fr) |
WO (1) | WO2010028493A1 (fr) |
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WO2010122150A1 (fr) * | 2009-04-23 | 2010-10-28 | Vtu Holding Gmbh | Procédé de déshydratation d'un liquide ionique |
WO2014161088A1 (fr) | 2013-04-02 | 2014-10-09 | Brasscorp Limited | Neutralisation et élimination améliorées d'acides dans des systèmes de chauffage, ventilation et conditionnement d'air (cvca) en utilisant des agents anti-hygroscopiques |
Citations (7)
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US5015782A (en) * | 1987-12-08 | 1991-05-14 | Mobil Oil Corporation | Ether production |
EP0580308A1 (fr) * | 1992-07-04 | 1994-01-26 | Kao Corporation | Composition de fluide de travail pour machine de réfrigération |
US5436356A (en) * | 1993-02-09 | 1995-07-25 | Shell Oil Company | Carbonylation process |
WO1996034067A1 (fr) * | 1995-04-24 | 1996-10-31 | Silicon Resources, Inc. | Compositions et procedes permettant de deshydrater, de passiver et de rendre etanche des systemes |
US20020189265A1 (en) * | 2001-03-08 | 2002-12-19 | Ferris James E. | Apparatus, methods and compositions for placing additive fluids into a refrigerant circuit |
CA2469966A1 (fr) * | 2004-06-04 | 2005-12-04 | Brasscorp Limited | Compose et methodes d'injection de produits d'etancheite dans des systemes de conditionnement d'air et de refrigeration |
US20050268642A1 (en) * | 2004-06-04 | 2005-12-08 | Paul Appler | Composition and methods for injection of sealants into air conditioning and refrigeration systems |
-
2009
- 2009-09-11 EP EP09812576.8A patent/EP2334994A4/fr not_active Withdrawn
- 2009-09-11 WO PCT/CA2009/001264 patent/WO2010028493A1/fr active Application Filing
- 2009-09-11 CA CA2736909A patent/CA2736909A1/fr active Pending
Patent Citations (7)
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US5015782A (en) * | 1987-12-08 | 1991-05-14 | Mobil Oil Corporation | Ether production |
EP0580308A1 (fr) * | 1992-07-04 | 1994-01-26 | Kao Corporation | Composition de fluide de travail pour machine de réfrigération |
US5436356A (en) * | 1993-02-09 | 1995-07-25 | Shell Oil Company | Carbonylation process |
WO1996034067A1 (fr) * | 1995-04-24 | 1996-10-31 | Silicon Resources, Inc. | Compositions et procedes permettant de deshydrater, de passiver et de rendre etanche des systemes |
US20020189265A1 (en) * | 2001-03-08 | 2002-12-19 | Ferris James E. | Apparatus, methods and compositions for placing additive fluids into a refrigerant circuit |
CA2469966A1 (fr) * | 2004-06-04 | 2005-12-04 | Brasscorp Limited | Compose et methodes d'injection de produits d'etancheite dans des systemes de conditionnement d'air et de refrigeration |
US20050268642A1 (en) * | 2004-06-04 | 2005-12-08 | Paul Appler | Composition and methods for injection of sealants into air conditioning and refrigeration systems |
Non-Patent Citations (1)
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See also references of WO2010028493A1 * |
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Publication number | Publication date |
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WO2010028493A1 (fr) | 2010-03-18 |
EP2334994A4 (fr) | 2013-11-06 |
CA2736909A1 (fr) | 2010-03-18 |
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