EP0631095A2 - Cycle frigorifique et procédé de réglage de la composition du réfrigérant dans le cycle frigorifique - Google Patents
Cycle frigorifique et procédé de réglage de la composition du réfrigérant dans le cycle frigorifique Download PDFInfo
- Publication number
- EP0631095A2 EP0631095A2 EP94109583A EP94109583A EP0631095A2 EP 0631095 A2 EP0631095 A2 EP 0631095A2 EP 94109583 A EP94109583 A EP 94109583A EP 94109583 A EP94109583 A EP 94109583A EP 0631095 A2 EP0631095 A2 EP 0631095A2
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- EP
- European Patent Office
- Prior art keywords
- refrigerant
- refrigeration cycle
- azeotrope
- heat exchanger
- composition
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 260
- 238000005057 refrigeration Methods 0.000 title claims abstract description 185
- 238000000034 method Methods 0.000 title claims description 13
- 239000003507 refrigerant Substances 0.000 claims abstract description 487
- 230000001603 reducing effect Effects 0.000 claims abstract description 17
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 88
- 238000001816 cooling Methods 0.000 claims description 30
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 5
- 230000003247 decreasing effect Effects 0.000 claims description 4
- 230000002159 abnormal effect Effects 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 abstract description 3
- RWRIWBAIICGTTQ-UHFFFAOYSA-N anhydrous difluoromethane Natural products FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 20
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 11
- 238000010586 diagram Methods 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- MVLAISLRRJEXHA-UHFFFAOYSA-L calcium;chloride;fluoride Chemical compound [F-].[Cl-].[Ca+2] MVLAISLRRJEXHA-UHFFFAOYSA-L 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- 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
- F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
- F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
- F25B9/006—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant containing more than one component
-
- 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
- F25B13/00—Compression machines, plants or systems, with reversible cycle
-
- 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
- F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
- F25B2400/13—Economisers
-
- 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
- F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
- F25B2400/16—Receivers
Definitions
- the present invention relates to a refrigeration cycle in which a non-azeotrope refrigerant is used as a working medium. More particularly, the present invention relates to a refrigeration cycle in which the composition ratio of the refrigerant circulating within the refrigeration cycle is controlled and a method of controlling the refrigeration composition ratio of the refrigeration cycle.
- the non-azeotrope refrigerant is a refrigerant in which two or more types of refrigerants having different boiling points are mixed, and has characteristics shown in Fig. 3.
- Fig. 3 is a vapor-liquid equilibrium diagram illustrating characteristics of a non-azeotrope refrigerant in which two types of refrigerants are mixed.
- the horizontal axis indicates the composition ratio X of a refrigerant having a low boiling point, and the vertical axis indicates temperature.
- a saturation vapor line and a saturation liquid line exist in a high temperature region indicated by pressure P H when, for example, pressure is high and when,conversely, pressure is low, these lines exist in a low temperature region indicated by pressure P L .
- a saturation liquid line and a saturation vapor line are determined by the composition thereof.
- X0 denotes the composition ratio of a refrigerant sealed in a refrigeration cycle.
- Points P1 to P4 indicate the typical points of the refrigeration cycle, and point P1 indicates a compressor outlet portion; point P2 indicates a condenser outlet portion; point P3 indicates an evaporator inlet portion; and point P4 indicates a compressor inlet portion.
- Fig. 4 is an illustration of a problem caused by the leakage of a refrigerant to the outside. If liquid leaks, the remaining mixture refrigerant enters the state of X1 in which the ratio of a low boiling-point refrigerant is large; if vapor leaks, the remaining mixture refrigerant enters the state of X2 in which the ratio of a high boiling-point refrigerant is large.
- X0 indicates the composition ratio of a refrigerant which is sealed in initially. If a state in which the composition is X0 is compared with a state in which the composition is X1 at the same pressure, the temperature when the composition is X1 is lower. If, however, a state in which the composition is X0 is compared with a state in which the composition is X2 at the same pressure, the temperature when the composition is X2 is higher.
- Fig. 5 shows general characteristics of a refrigeration cycle with respect to the composition ratio of the low boiling-point refrigerant.
- the composition ratio of the refrigerant remaining within the refrigeration cycle changes from the initial composition ratio, i.e., from the designed composition ratio for the apparatus depending upon leaked portions. Even if there is no leakage to the outside, there is a possibility that the composition ratio of the refrigerant circulating within the refrigeration cycle may vary in the non-steady state of the refrigeration cycle.
- Japanese Patent Unexamined Publication No. 59-129366 discloses that an electrostatic capacitance sensor is used as a means for detecting the composition of a refrigerant circulating within the refrigeration cycle. Further, it is disclosed that the refrigeration cycle comprises a first liquid receiver and a second liquid receiver, an electric heater being disposed in the second liquid receiver. When the outdoor air temperature is low during a heating operation, the electric heater of the second liquid receiver is operated and controlled so that a set refrigerant concentration is reached.
- an apparatus comprising a separator for separating a low-boiling-point refrigerant, a liquid receiver for storing a low-boiling-point refrigerant, and a control valve for returning the refrigerant from the liquid receiver, which apparatus controls the composition of the refrigerant on the basis of the temperature of an element to be cooled.
- a mixture refrigerant composition variable refrigeration cycle in which the upper portion of the liquid receiver is connected to a refrigerant tank and the lower portion of the liquid receiver is connected to the refrigerant tank, which refrigeration cycle comprises a refrigerant tank capable of exchanging heat with a gas pipe through which a heat-source-side heat exchanger is connected to a use-side heat exchanger, a liquid receiver and the like.
- the composition ratio of the refrigerant within the refrigeration cycle may vary when the refrigerant leaks out of the refrigeration cycle or during the non-steady operation of the refrigeration cycle.
- the capacity of the refrigeration cycle can be varied by making the composition variable. Therefore, to obtain a high-capacity refrigeration cycle, it is important to control the refrigerant composition ratio within the refrigeration cycle so as to realize a stable operation. There has been a demand for a method of varying this composition ratio inexpensively. Further, it is necessary to use a refrigerant which does not contain chlorine and does not damage the ozone layer, in which a consideration is given to safeguard the earth environment.
- a refrigeration cycle in which a non-azeotrope refrigerant which does not damage the ozone layer is used as a refrigerant, and in which a compressor, a heat-source side heat exchanger, a pressure reducing apparatus, and a use-side heat exchanger are connected in sequence.
- the refrigeration cycle comprises a device, disposed in a pipe portion where a liquid phase is formed, for detecting the composition of a non-azeotrope refrigerant circulating within the refrigeration cycle; a device for varying the composition of a refrigerant having a high-boiling-point refrigerant of the non-azeotropic mixture; a device for varying the composition of a refrigerant having a low-boiling-point refrigerant; and a control apparatus for controlling the devices for varying the composition of the non-azeotropic mixture.
- the composition of the non-azeotrope refrigerant is controlled on the basis of signals from the device for detecting the composition.
- a refrigeration cycle comprising a compressor, a heat-source side heat exchanger, a use-side heat exchanger, and a pressure reducing apparatus, in which a non-azeotrope refrigerant which does not damage the ozone layer is used as the refrigerant.
- the refrigeration cycle comprises a device for detecting the composition of a non-azeotrope refrigerant circulating within the refrigeration cycle; a device for detecting the amount of refrigerant within the refrigeration cycle; and a display device for displaying the composition of the non-azeotrope refrigerant, the amount of refrigerant within the refrigeration cycle, and a refrigerant maintenance operation.
- the composition ratio of a non-azeotrope refrigerant is controlled to a predetermined composition ratio when the non-azeotrope refrigerant is sealed in the refrigeration cycle.
- a composition detecting sensor for detecting the composition of the refrigerant circulating within the refrigeration cycle is disposed in a liquid-state pipe in the refrigeration cycle, it is possible to detect the composition of the mixture refrigerant with a high degree of accuracy. Since control appropriate for the composition ratio in the refrigeration cycle is performed on the basis of the detected composition, a stable operation is possible even when the refrigerant leaks outside and the composition of the refrigerant circulating within the refrigeration cycle is varied from the designed composition of the refrigeration cycle.
- the composition ratio can be controlled to a predetermined composition ratio when a non-azeotrope refrigerant is sealed in the refrigeration cycle, it is possible to reduce variations in the composition ratio during operation. Even when the circulation composition is varied in a non-steady operating state of the refrigeration cycle, it is possible to secure performance and reliability. In addition, it is possible to control the capacity of the refrigeration cycle to capacity commensurate with a cooling or heating load.
- the operation for maintaining the composition of the refrigerant within the refrigeration cycle is considerably simplified.
- Fig. 1 illustrates a refrigeration cycle in which a plurality of indoor machines are connected to one outdoor machine in accordance with a first embodiment of the present invention.
- reference numeral 1 denotes a compressor
- reference numeral 2 denotes an outdoor heat exchanger
- reference numeral 3 denotes an outdoor air blower
- reference numeral 4 denotes a four-way valve
- reference numeral 5 denotes an accumulator
- reference numeral 6 denotes a receiver
- reference numeral 7 denotes an outdoor refrigerant control valve which acts as a pressure reducing mechanism during a heating operation.
- Reference numeral 8 denotes a sensor for detecting the composition of a non-azeotrope refrigerant
- reference numeral 10 denotes a refrigerant tank
- reference numeral 11 denotes a cooling unit
- reference numerals 12, 13 and 14 denote open/close valves
- reference numerals 15, 16 and 17 denote pipes
- reference numerals 91, 92, 93 and 94 denote check valves which constitute an outdoor machine.
- Reference numerals 20a and 20b denote indoor heat exchangers; reference numerals 21a and 21b denote indoor refrigerant control valves which act as a pressure reducing mechanism during a cooling operation; reference numerals 22 and 23 denote refrigerant distribution units; and reference numerals 24 and 25 denote pipes for connecting indoor machines to outdoor machines. The illustration of the indoor air blower is omitted.
- a detecting apparatus in which an electrostatic capacitance sensor 8 for detecting the composition of a non-azeotrope refrigerant is used, and a control apparatus for controlling the open/close valves 12, 13 and 14 are disposed on the outdoor side.
- Fig. 1 the illustration of the control system of the refrigeration cycle is omitted.
- a refrigerant which does not contain chlorine and does not damage the ozone layer is used as the refrigerant.
- HFC32 and HFC134a are used as the non-azeotrope refrigerant will be explained.
- the refrigerant discharged from the compressor flows in the following order: the four-way valve 4 ⁇ the outdoor heat exchanger 2 ⁇ the check valve 93 ⁇ the composition sensor 8 ⁇ the outdoor refrigerant control valve 7 ⁇ the check valve 92 ⁇ the receiver 6.
- the refrigerant is distributed by a refrigerant distribution unit; a part of the refrigerant flows in the order: the indoor refrigerant control valve 21a ⁇ the indoor heat exchanger 20a, and the other flow in the order: the indoor refrigerant control valve 21b ⁇ the indoor heat exchanger 20b.
- the indoor heat exchangers 20a and 20b act as evaporators and a cooling operation is performed.
- the refrigerant discharged from the compressor flows in the following order: the four-way valve 4 ⁇ the pipe 24 ⁇ the distribution unit 22.
- a part of the refrigerant flows in the order: the indoor heat exchanger 20a ⁇ the indoor refrigerant control valve 21a, and the other flow in the order: the indoor heat exchanger 20b ⁇ the indoor refrigerant control valve 21b.
- the indoor heat exchangers 20a and 20b act as condensers and a heating operation is performed.
- a cooling unit 11 is a double-pipe heat exchanger.
- the open/close valves 12 and 13 are opened.
- the liquid in the bottom of the receiver 6 flows out through the open/close valve 12, and the liquid is formed into a low-temperature refrigerant by the pressure reducing effect of the open/close valve 12 and guided into the inner pipe of the cooling unit 11.
- gas inside the receiver 6 flows out through the open/close valve 13 and is guided into the outer pipe of the cooling unit 11.
- the low-temperature refrigerant gas of the inner pipe exchanges heat with the gas of the outer pipe, and the low-temperature refrigerant is gasified and guided into the accumulator 5 through the pipe 15.
- the condensed liquefied refrigerant of the outer pipe is guided into the refrigerant storage tank 10.
- the open/close valves 12 and 13 are closed. The above operation and effect make it possible to store the liquid refrigerant in the refrigerant storage tank 10.
- the open/close valve 14 is opened so that the liquid refrigerant can be discharged to the accumulator 5 through the pipe 15.
- composition varying effect will be explained below.
- Fig. 6 illustrates changes of the state of the refrigerant in a refrigerant passage from the condenser to the receiver when a non-azeotrope refrigerant is used as a thermal medium.
- the horizontal axis indicates the composition ratio X of the low-boiling-point refrigerant, i.e., HFC32, and the vertical axis indicates temperature, with pressure being constant.
- the composition ratio X0 indicates the composition ratio of the refrigerant sealed in the refrigeration cycle.
- Point A indicates the state of the inlet of the condenser; point B indicates the condensation start point; point C indicates the state of the inside of the receiver; and point D indicates the state of the outlet of the cooling unit.
- Point C indicates that the flow rate of the liquid is very small.
- Point E indicates the liquid state inside the receiver, and the composition ratio of HFC32 is X1.
- Point F indicates the gas state, and the composition ratio of HFC32 is X g . It can be seen that the composition ratio of gas at point F is greater than the composition ratio X0 of the refrigerant sealed in the refrigeration cycle, and the composition ratio in the refrigeration cycle can be varied by taking out gas.
- a gas refrigerant having a large composition ratio of HFC32 taken out from the upper portion of the receiver 6 is liquefied in the cooling unit 11 and stored in the tank 10.
- the composition ratio of the refrigerant within the refrigeration cycle becomes smaller than X0.
- the composition ratio of the refrigerant within the refrigeration cycle is smaller than X0, it is possible to return the refrigerant having a large composition ratio of HFC32 to the refrigeration cycle by opening the open/close valve 14.
- the refrigerant composition ratio in the main refrigeration cycle can be varied by taking out or returning the gas refrigerant inside the receiver.
- HFC32, HFC125 and HFC134a the boiling points of HFC32 and HFC125 are higher than that of HFC134a, and therefore the present invention utilizing the difference between the boiling points of mixed refrigerants may be applied.
- HFC32 and HFC125 exhibit azeotropic characteristics which can be regarded as a single refrigerant, and the above-described mixture refrigerant can be assumed as a mixture refrigerant of the azeotrope refrigerant of HFC32 and HFC125, and HFC134a.
- the composition varying function of the present invention may be exhibited for a mixture refrigerant of HFC32, HFC125 and HFC134a.
- Fig. 8 is a sectional view of the electrostatic capacitance type composition detecting sensor 8 shown in Fig. 1.
- reference numeral 53 denotes an outer tube electrode
- reference numeral 54 denotes an inner tube electrode, both of which are hollow tubes.
- the inner tube electrode 54 is fixed at its both ends by stoppers 55a and 55b in which a circular groove is provided in the central portion of the outer tube electrode 53.
- the outer diameter of the stoppers 55a and 55b is nearly the same as the inner diameter of the outer tube electrode 53, and the side opposite to the inner tube electrode holding side is fixed by the refrigerant introduction pipe 59 having an outer diameter nearly the same as the inner diameter of the outer tube electrode 53.
- the refrigerant introduction pipe 59 is fixed to the outer tube electrode 53.
- the inner tube electrode 54 is fixed to the central portion of the outer tube electrode 53.
- An outer-tube electrode signal line 56 and an inner-tube electrode signal line 57 are connected to the outer tube electrode 53 and the inner tube electrode 54 in order to detect an electrostatic capacitance value.
- a signal line guide tube 58 e.g., a hermetic terminal
- for guiding the inner-tube electrode signal line 57 to the outside of the outer tube electrode 53 and for preventing the refrigerant inside from escaping to the outside, are disposed outside the inner-tube electrode signal line 57.
- At least one through passage having a size smaller than the inner diameter of the inner tube electrode 54 is disposed in the central portion thereof, and at least one passage for the refrigerant is disposed at a place between the inner tube electrode 54 and the outer tube electrode 53, so that the flow of the mixture refrigerant flowing through the inside is not obstructed.
- Fig. 9 illustrates the relationship between the composition ratio of the refrigerant and the electrostatic capacitance value when the electrostatic capacitance sensor is used.
- Fig. 9 illustrates measured values obtained when HFC134a is used as a high boiling-point refrigerant and HFC32 is used as a low boiling-point refrigerant from among the mixture refrigerant and they are sealed in the composition ratio detecting sensor shown in Fig. 8 as gas and liquid, respectively.
- the horizontal axis indicates the composition ratio of the HFC32, and the vertical axis indicates the electrostatic capacitance value which is an output from the composition ratio detecting sensor 8.
- a comparison of the electrostatic capacitance value of gas of each refrigerant with that of liquid of each refrigerant shows that the liquid refrigerant has a larger value, and the difference between the electrostatic capacitance value of gas and that of liquid is large, in particular, in the HFC134a. This indicates that the electrostatic capacitance value varies when the dryness of the refrigerant varies.
- a comparison between the electrostatic capacitance values of HFC134a and HFC32 shows that HFC32 has a larger electrostatic capacitance value for both liquid and gas. This indicates that only a gas or liquid refrigerant exists in the composition ratio detecting sensor 8, and when the composition of the refrigerant varies, the electrostatic capacitance value varies.
- the composition ratio detecting sensor 8 since the inside of the composition ratio detecting sensor 8 enters a two-phase state of gas and liquid, the electrostatic capacitance value varies due to the dryness of the refrigerant in addition to the composition ratio of the mixture refrigerant, it becomes impossible to detect the composition ratio. Therefore, when the composition ratio of the mixture refrigerant is detected by using the composition ratio detecting sensor 8, it is necessary to dispose the composition ratio detecting sensor 8 in a portion where the refrigerant is always gas or liquid in the refrigeration cycle. In this embodiment, since the check valves 91 to 94 are arranged, the refrigerant passing through the composition ratio detecting sensor 8 is in a liquid state. Means other than the electrostatic capacitance type may be used for the composition ratio detecting means.
- Fig. 10 is a flowchart illustrating a method of controlling the refrigeration cycle shown in Fig. 1.
- the composition ratio is determined on the basis of a signal from the composition ratio detecting sensor 8.
- a check is made to determine whether the detected composition ratio X is greater than the composition ratio X0 of the refrigerant sealed in the refrigeration cycle.
- the open/close valves 12 and 13 are opened.
- the open/close valves 12 and 13 are closed.
- composition of the refrigerant within the refrigeration cycle to X0 or thereabouts, making it possible to prevent the pressure on the high pressure side from abnormally increasing and making a stable operation possible. Since the composition ratio of the non-azeotrope refrigerant can be varied, it becomes possible to vary the heating and cooling capacity as shown in Fig. 3.
- FIG. 11 A second embodiment of a refrigeration cycle in accordance with the present invention is shown in Fig. 11.
- Fig. 11 also shows a refrigeration cycle in which the composition ratio of a non-azeotrope refrigerant is variable, and principally the amount of a high-boiling-point refrigerant is varied.
- Components in Fig. 11 having the same reference numerals as those in Fig. 1 designate identical components.
- reference numeral 30 denotes a refrigerant tank; reference numerals 31 and 32 denote open/close valves; and reference numerals 33 and 34 denote pipes.
- the direction of flow of the refrigerant during heating and cooling operations is the same as in Fig. 1. It is possible to make the liquid refrigerant in the bottom portion of the accumulator 5 flow out to a tank 30 via an open/close valve 31 and to make the refrigerant in the tank 30 return to the main refrigeration cycle via the open/close valve 32.
- Fig. 12 shows changes of the refrigerant in a system from the evaporator to the accumulator 5.
- the horizontal axis indicates the composition ratio X of the low-boiling-point refrigerant, i.e., HFC32, and the vertical axis indicates temperature, with pressure being constant.
- the temperature of saturation vapor is different from that of saturation liquid even at the same pressure as shown in the figure.
- X0 indicates the composition ratio of HFC32 in the refrigerant sealed in the refrigeration cycle.
- Point G indicates the inlet state of the evaporator
- point H indicates the state inside the accumulator 5. Since the refrigerant inside the accumulator 5 has been passed through the evaporator, the dryness of the refrigerant is great, and point H is close to the vapor line. Therefore, the states of liquid and gas at point H are indicated by points J and I. At point J, the high-boiling-point refrigerant composition ratio of HFC134a is high, and at point I, the composition ratio of the low-boiling-point refrigerant approaches X0.
- the liquid refrigerant can be stored in the accumulator 5 by increasing the opening of the indoor refrigerant control valve 21a or 21b in the case of a cooling operation.
- Fig. 13 is a flowchart for controlling the refrigeration cycle shown in Fig. 11.
- the composition ratio is determined on the basis of a signal from the composition sensor.
- a check is made to determine whether the detected composition ratio X is greater than the composition ratio X0 of the refrigerant sealed in the refrigeration cycle.
- the open/close valve 32 is opened.
- the open/close valve 32 is closed.
- the open/close valve 31 is opened.
- the open/close valve 14 is closed. ⁇ is the tolerance.
- composition of the refrigerant within the refrigeration cycle to X0 or thereabouts, making a stable operation possible. Since the composition ratio of the non-azeotrope refrigerant can be varied, it becomes possible to vary the heating and cooling capacity as shown in Fig. 3.
- Fig. 14 also shows a refrigeration cycle in which the composition ratio of the non-azeotrope refrigerant can be varied, and the functions of the embodiment shown in Figs. 1 and 11 are integrated.
- Components in Fig. 14 having the same reference numerals as those in Fig. 11 designate identical components.
- Reference numeral 40 denotes a refrigerant tank; reference numerals 41 and 43 denote open/close valves; and reference numerals 42 and 44 denote pipes.
- the refrigerant tank 40 is formed integral with the accumulator 5 as shown in Fig. 14, so that heat can be exchanged between the refrigerant tank 40 and the accumulator 5.
- the gas refrigerant inside the receiver 6 can be condensed and liquefied by making the liquid refrigerant flow into the tank 40 via the open/close valve 41 and exchanging heat with the accumulator 5. It is also possible to make the liquid refrigerant in the bottom portion of the tank 40 flow out into the accumulator 5 via the open/close valve 43 so that the liquid refrigerant is returned to the main refrigeration cycle. Therefore, by opening the open/close valve 41, it is possible to release gas having a large composition ratio of HFC32 from the main refrigeration cycle and decrease the composition ratio of HFC32. On the other hand, by opening the open/close valve 43, it is possible to release the liquid refrigerant having a large composition ratio of HFC134a from the main refrigeration cycle and decrease the composition ratio of HFC134a.
- Fig. 15 is a detailed view of the receiver 6, the accumulator 5 and the tank 40, all of which are shown in Fig. 14.
- Components in Fig. 15 having the same reference numerals as those in Fig. 14 designate identical components.
- a pipe 34 through which the accumulator 5 is connected to the compressor 1 is formed into a U-shape inside the accumulator 5, and the end portion thereof is open in the upper portion of the accumulator 5.
- a hole 36 for returning oil circulating within the refrigeration cycle is disposed in the bottommost portion of the U-shape, and a hole 35 for making a part of gas flow out is disposed in the topmost portion of the U-shape.
- a pipe 42 and the open/close valve 41 are connected to each other at an appropriate position in the upper portion of the receiver 6 and at an appropriate position in the upper portion of the refrigerant tank 40. Further, a pipe 44 and the open/close valve 43 are connected to each other at appropriate positions of the lower portion of the accumulator 5 and the refrigerant tank 40.
- the refrigerant tank 40 is formed integral in the lower portion of the accumulator 5 in Fig. 15, the refrigerant tank 40 may be arranged in any way if heat can be exchanged between the accumulator 5 and the refrigerant tank 40.
- Fig. 16 is a flowchart for controlling the refrigeration cycle shown in Fig. 14.
- the composition ratio is determined on the basis of a signal from the composition ratio detecting sensor.
- a check is made to determine whether the detected composition ratio X is greater than the composition ratio X0 of the refrigerant sealed in the refrigeration cycle.
- the open/close valve 41 is opened.
- the open/close valve 41 is closed.
- the open/close valve 43 is opened.
- reference numeral 1 denotes a compressor
- reference numeral 2 denotes an outdoor heat exchanger
- reference numeral 3 denotes an outdoor air blower
- reference numeral 4 denotes a four-way valve
- reference numeral 5 denotes an accumulator
- reference numeral 6 denotes a receiver
- reference numeral 7 denotes an outdoor refrigerant control valve
- reference numeral 8 denotes a sensor for detecting the composition ratio of a non-azeotrope refrigerant
- reference numerals 91, 92, 93 and 94 denote check valves which are disposed in outdoor machines.
- the electrostatic capacitance sensor 8 for detecting the composition ratio of the non-azeotrope refrigerant
- the electrostatic capacitance type liquid level sensor 60 for detecting the liquid level of the refrigerant
- a liquid-level detection apparatus for detecting the liquid level of the refrigerant
- a computation apparatus for computing the composition of a refrigerant a computation apparatus for computing the amount of the refrigerant
- a display apparatus for displaying the display apparatus.
- the indoor heat exchangers 20a and 20b act as evaporators, and a cooling operation is performed.
- the refrigerant discharged from the compressor flows in the order: the four-way valve 4 ⁇ the pipe 24 ⁇ the distribution unit 22.
- a part of the refrigerant flows in the order: the indoor heat exchanger 20a ⁇ the indoor refrigerant control valve 21a, and the other flows in the order: the indoor heat exchanger 20b ⁇ the indoor refrigerant control valve 21b.
- the refrigeration cycle constructed as described above it is possible to easily maintain the refrigeration cycle even when the refrigerant sealed in the refrigeration cycle leaks outside and the composition ratio of the non-azeotrope refrigerant varies. More specifically, it is possible to selectively display the amount of refrigerant within the refrigeration cycle, the composition ratio of the refrigerant, a display of whether the type and amount of the refrigerant are normal or not, the type of the refrigerant to be added, and the amount of the refrigerant to be added, facilitating a maintenance operation to a greater extent.
- Fig. 18 shows an example in which a valve 61 for sealing in a refrigerant is added to the refrigeration cycle shown in Fig. 17.
- the valve 61 is disposed on the inlet side of the accumulator 5 of the refrigeration cycle.
- Reference numeral 62 denotes a bomb for a low-boiling-point refrigerant; and reference numeral 63 denotes a bomb for a high-boiling-point refrigerant.
- the low-boiling-point refrigerant bomb 62 is connected to the refrigerant sealing-in valve 61 and the refrigerant is sealed in when the refrigerant to be added is a low-boiling-point refrigerant.
- the refrigerant to be added is a high-boiling-point refrigerant, there is a case in which the pressure in the refrigerant bomb is lower than that inside the refrigeration cycle.
- Fig. 20 illustrates the internal state of the refrigerant bomb 64.
- Gas having the composition at point K and liquid having the composition at point L in the figure coexist inside the refrigerant bomb 64. Therefore, it is possible to take out a refrigerant having a large composition ratio of a low-boiling-point refrigerant by taking out gas, and by taking out liquid, it is possible to take out a refrigerant having a large composition ratio of a high-boiling-point refrigerant.
- the refrigerant is taken out from the valve 65 in Fig. 19 when a low-boiling-point refrigerant is sealed in, and a refrigerant is taken out from the valve 67 in Fig. 19 when a high-boiling-point refrigerant is sealed in.
- the detection display apparatus 80 is provided, in addition to the electrostatic capacitance sensor 85, with a computation apparatus for computing the composition of a refrigerant and a display apparatus for displaying the composition thereof.
- a computation apparatus for computing the composition of a refrigerant and a display apparatus for displaying the composition thereof.
- HFC32 and HFC134a are used as the non-azeotrope refrigerant.
- the refrigerant discharged from the compressor flows in the following order: the four-way valve 4 ⁇ the outdoor heat exchanger 2 ⁇ the check valve 93 ⁇ the outdoor refrigerant control valve 7 ⁇ the check valve 92 ⁇ the receiver 6.
- the refrigerant is distributed by the distribution unit 23.
- a part of the refrigerant flows in the order: the indoor refrigerant control valve 21a ⁇ the indoor heat exchanger 20a, and the other flows in the order: the indoor refrigerant control valve 21b ⁇ the indoor heat exchanger 20b. They merge in the distribution unit 22, flow in the order: the pipe 24 ⁇ the four-way valve 4 ⁇ the accumulator 5, and return to the compressor.
- the indoor heat exchangers 20a and 20b act as evaporators, and a cooling operation is performed.
- the refrigerant discharged from the compressor flows in the following order: the four-way valve 4 ⁇ the pipe 24 ⁇ the distribution unit 22.
- a part of the refrigerant flows in the order: the indoor heat exchanger 20a ⁇ the indoor refrigerant control valve 21a, and the other flows in the order: the indoor heat exchanger 20b ⁇ the indoor refrigerant control valve 21b.
- the indoor heat exchangers 20a and 20b act as condensers, and a heating operation is performed.
- the sensor 85 of the detection display apparatus 80 is connected between the open/close valves 83 and 84, and the refrigerant is made to flow through the sensor 85 while a cooling or heating operation is being performed.
- a refrigerant take-out section for detecting the composition of the refrigerant is disposed in the refrigeration cycle, and the composition ratio can be detected by the detection display apparatus 80 which is disposed separately from the refrigeration cycle system. As a result, there is no need to dispose a composition ratio sensor in the refrigeration cycle, and therefore the refrigeration cycle can be constructed at a low cost.
- the cycle is evacuated to a vacuum by a vacuum pump, and then refrigerants may be sealed in according to the descending order of their boiling points, each by a predetermined amount.
- refrigerants may be sealed in according to the descending order of their boiling points, each by a predetermined amount.
- the present invention it is possible to vary the composition ratio of the refrigerant within the refrigeration cycle in which a non-azeotrope refrigerant is sealed in by using an inexpensive apparatus and to stabilize the composition ratio of the non-azeotrope refrigerant.
- composition ratio of the refrigerant within the refrigeration cycle in which a non-azeotrope refrigerant is sealed in can be detected and since the amount of refrigerant within the refrigeration cycle can be detected, it becomes possible to display types of refrigerants to be added and deleted and the amount of the refrigerant to be added and deleted, greatly facilitating the operation of maintaining the refrigerant of the refrigeration cycle.
- composition ratio of the refrigerant sealed in the refrigeration cycle is controlled, a highly efficient operation of the refrigeration cycle is possible.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Compression-Type Refrigeration Machines With Reversible Cycles (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98101094A EP0838643B1 (fr) | 1993-06-24 | 1994-06-21 | Cycle frigorifique utilisant un frigorigène non-azéotropique |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP153246/93 | 1993-06-24 | ||
| JP15324693 | 1993-06-24 | ||
| JP15324693A JPH0712411A (ja) | 1993-06-24 | 1993-06-24 | 冷凍サイクルおよび冷凍サイクルの冷媒組成比制御方法 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98101094A Division EP0838643B1 (fr) | 1993-06-24 | 1994-06-21 | Cycle frigorifique utilisant un frigorigène non-azéotropique |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0631095A2 true EP0631095A2 (fr) | 1994-12-28 |
| EP0631095A3 EP0631095A3 (fr) | 1995-03-01 |
| EP0631095B1 EP0631095B1 (fr) | 2000-01-12 |
Family
ID=15558261
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19940109583 Expired - Lifetime EP0631095B1 (fr) | 1993-06-24 | 1994-06-21 | Procédé de chargement d'un réfrigérant non-azéotrope et de réglage de la composition du réfrigérant dans un cycle frigorifique |
| EP98101094A Expired - Lifetime EP0838643B1 (fr) | 1993-06-24 | 1994-06-21 | Cycle frigorifique utilisant un frigorigène non-azéotropique |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98101094A Expired - Lifetime EP0838643B1 (fr) | 1993-06-24 | 1994-06-21 | Cycle frigorifique utilisant un frigorigène non-azéotropique |
Country Status (3)
| Country | Link |
|---|---|
| EP (2) | EP0631095B1 (fr) |
| JP (1) | JPH0712411A (fr) |
| DE (2) | DE69432489T2 (fr) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0693663A3 (fr) * | 1994-07-21 | 1996-12-18 | Mitsubishi Electric Corp | Appareil de détection d'information de commande pour un appareil de conditionnement d'air frigorifique à frigorigène non-azéotrope |
| EP0715134A3 (fr) * | 1994-11-29 | 1998-01-21 | Sanyo Electric Co. Ltd | Cycle frigorifique |
| EP0685692A3 (fr) * | 1994-05-30 | 1998-06-17 | Mitsubishi Denki Kabushiki Kaisha | Système de circulation de réfrigérant |
| EP0750166A3 (fr) * | 1995-06-23 | 1998-11-18 | Mitsubishi Denki Kabushiki Kaisha | Système de circulation de frigorigène |
| US5927087A (en) * | 1994-11-29 | 1999-07-27 | Ishikawa; Atuyumi | Refrigerating cycle |
| EP0854326A3 (fr) * | 1997-01-21 | 2000-07-12 | Mitsubishi Denki Kabushiki Kaisha | Installation frigorifique ou de conditionnement d'air |
| EP0732551A3 (fr) * | 1995-03-15 | 2001-02-28 | Kabushiki Kaisha Toshiba | Commande pour une installation de climatisation |
| EP0898128A3 (fr) * | 1997-08-22 | 2001-09-05 | Carrier Corporation | Pompe à chaleur à compression internement étagée et à fluide frigorigène variable |
| EP0898133A3 (fr) * | 1997-08-20 | 2001-11-07 | Mitsubishi Denki Kabushiki Kaisha | Appareil frigorifique et de conditionnement d'air et procédé pour déterminer la composition de fluide frigorigène d'un appareil frigorifique et de conditionnement d'air |
| EP1293735A3 (fr) * | 2001-09-12 | 2003-05-28 | Mitsubishi Denki Kabushiki Kaisha | Circuit de réfrigérant |
| WO2009147172A1 (fr) * | 2008-06-05 | 2009-12-10 | Alstom Technology Ltd. | Système de refroidissement multi-réfrigérant avec aménagements pour le réglage de la composition du réfrigérant |
| EP1553365A3 (fr) * | 2004-01-06 | 2012-06-20 | Samsung Electronics Co., Ltd. | Installation de climatisation |
| EP2722617A4 (fr) * | 2011-06-16 | 2014-11-05 | Mitsubishi Electric Corp | Dispositif de conditionnement d'air |
| US20240110736A1 (en) * | 2022-09-30 | 2024-04-04 | Hill Phoenix, Inc. | Co2 refrigeration system with multiple receivers |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002081777A (ja) | 2000-09-08 | 2002-03-22 | Hitachi Ltd | 冷凍サイクル |
| GB2511670B (en) * | 2011-12-22 | 2018-01-31 | Mitsubishi Electric Corp | Refrigeration cycle device |
| KR102477524B1 (ko) * | 2018-01-26 | 2022-12-15 | 엘지전자 주식회사 | 공기조화기 |
| NO344169B1 (en) * | 2018-06-04 | 2019-09-30 | Waertsilae Gas Solutions Norway As | Method and system for storage and transport of liquefied petroleum gases |
| JP7258106B2 (ja) * | 2018-06-29 | 2023-04-14 | 三菱電機株式会社 | 冷凍サイクル装置 |
| FR3111193B1 (fr) | 2020-06-04 | 2023-06-16 | Commissariat Energie Atomique | Procédé de détermination de l’évolution de la composition circulante d’un fluide de travail |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3668882A (en) * | 1970-04-29 | 1972-06-13 | Exxon Research Engineering Co | Refrigeration inventory control |
| JPS59129366A (ja) * | 1983-01-11 | 1984-07-25 | 株式会社日立製作所 | 冷凍装置 |
| DE3406588A1 (de) * | 1984-02-23 | 1985-08-29 | Siemens AG, 1000 Berlin und 8000 München | Waermepumpe mit nichtazeotropen kaeltegemischen, insbesondere fuer eine raumheizung eines wohnhauses |
| JPS61213554A (ja) | 1985-03-20 | 1986-09-22 | 松下電器産業株式会社 | 冷凍サイクルの冷媒比率可変制御装置 |
| KR890004867B1 (ko) * | 1985-03-25 | 1989-11-30 | 마쯔시다덴기산교 가부시기가이샤 | 열펌프장치 |
| US4624112A (en) * | 1985-08-26 | 1986-11-25 | Murray Corporation | Automotive air conditioner charging station with over-ride controls |
| US4700549A (en) * | 1986-06-11 | 1987-10-20 | Sundstrand Corporation | On-board refrigerant charging system |
| US4913714A (en) * | 1987-08-03 | 1990-04-03 | Nippondenso Co., Ltd. | Automotive air conditioner |
| JPH0833254B2 (ja) | 1987-08-29 | 1996-03-29 | ダイキン工業株式会社 | ヒ−トポンプシステム |
| JPH01273959A (ja) * | 1988-04-25 | 1989-11-01 | Nippon Denso Co Ltd | 車両用空気調和機 |
| US4972676A (en) * | 1988-12-23 | 1990-11-27 | Kabushiki Kaisha Toshiba | Refrigeration cycle apparatus having refrigerant separating system with pressure swing adsorption |
| US5012651A (en) * | 1988-12-28 | 1991-05-07 | Matsushita Electric Industrial Co., Ltd. | Heat pump apparatus |
| US5062275A (en) * | 1989-03-09 | 1991-11-05 | Nippondenso Co., Ltd. | Automotive air conditioner |
| US5056329A (en) * | 1990-06-25 | 1991-10-15 | Battelle Memorial Institute | Heat pump systems |
| US5186012A (en) * | 1991-09-24 | 1993-02-16 | Institute Of Gas Technology | Refrigerant composition control system for use in heat pumps using non-azeotropic refrigerant mixtures |
| JP2764489B2 (ja) * | 1991-10-29 | 1998-06-11 | 株式会社荏原製作所 | 冷凍装置用冷媒及び該冷媒を用いる冷凍装置 |
| JP3178103B2 (ja) * | 1992-08-31 | 2001-06-18 | 株式会社日立製作所 | 冷凍サイクル |
| DE4230818A1 (de) * | 1992-09-15 | 1994-03-17 | Fritz Egger Gmbh | Verfahren und Einrichtung zur Leistungsregelung einer Kompressions-Wärmepumpe und/oder Kältemaschine |
-
1993
- 1993-06-24 JP JP15324693A patent/JPH0712411A/ja active Pending
-
1994
- 1994-06-21 DE DE1994632489 patent/DE69432489T2/de not_active Expired - Fee Related
- 1994-06-21 DE DE1994622551 patent/DE69422551T2/de not_active Expired - Fee Related
- 1994-06-21 EP EP19940109583 patent/EP0631095B1/fr not_active Expired - Lifetime
- 1994-06-21 EP EP98101094A patent/EP0838643B1/fr not_active Expired - Lifetime
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0685692A3 (fr) * | 1994-05-30 | 1998-06-17 | Mitsubishi Denki Kabushiki Kaisha | Système de circulation de réfrigérant |
| US5987907A (en) * | 1994-05-30 | 1999-11-23 | Mitsubishi Denki Kabushiki Kaisha | Refrigerant circulating system |
| US6032473A (en) * | 1994-05-30 | 2000-03-07 | Mitsubishi Denki Kabushiki Kaisha | Refrigerant circulating system |
| EP0854331A3 (fr) * | 1994-07-21 | 2000-08-30 | Mitsubishi Denki Kabushiki Kaisha | Appareil de détection d'information de commande pour un appareil de conditionnement d'air frigorifique à frigorigène non-azéotrope |
| AU683385B2 (en) * | 1994-07-21 | 1997-11-06 | Mitsubishi Denki Kabushiki Kaisha | Control-information detecting apparatus for a refrigeration air-conditioner using a non-azeotrope refrigerant |
| EP0854329A3 (fr) * | 1994-07-21 | 2000-08-30 | Mitsubishi Denki Kabushiki Kaisha | Appareil de détection d'information de commande pour appareil de conditionnement d'air frigorifique à frigorigène non-azéotrope |
| EP0853221A3 (fr) * | 1994-07-21 | 2000-08-30 | Mitsubishi Denki Kabushiki Kaisha | Appareil de détection d'information de commande pour un appareil de conditionnement d'air frigorifique à frigorigène non-azéotrope |
| EP0693663A3 (fr) * | 1994-07-21 | 1996-12-18 | Mitsubishi Electric Corp | Appareil de détection d'information de commande pour un appareil de conditionnement d'air frigorifique à frigorigène non-azéotrope |
| EP0854330A3 (fr) * | 1994-07-21 | 2000-08-30 | Mitsubishi Denki Kabushiki Kaisha | Appareil de détection d'information de commande pour un appareil de conditionnement d'air frigorifique à frigorigène non-azéotrope |
| US5927087A (en) * | 1994-11-29 | 1999-07-27 | Ishikawa; Atuyumi | Refrigerating cycle |
| EP0715134A3 (fr) * | 1994-11-29 | 1998-01-21 | Sanyo Electric Co. Ltd | Cycle frigorifique |
| EP0732551A3 (fr) * | 1995-03-15 | 2001-02-28 | Kabushiki Kaisha Toshiba | Commande pour une installation de climatisation |
| EP0750166A3 (fr) * | 1995-06-23 | 1998-11-18 | Mitsubishi Denki Kabushiki Kaisha | Système de circulation de frigorigène |
| EP0854326A3 (fr) * | 1997-01-21 | 2000-07-12 | Mitsubishi Denki Kabushiki Kaisha | Installation frigorifique ou de conditionnement d'air |
| EP0898133A3 (fr) * | 1997-08-20 | 2001-11-07 | Mitsubishi Denki Kabushiki Kaisha | Appareil frigorifique et de conditionnement d'air et procédé pour déterminer la composition de fluide frigorigène d'un appareil frigorifique et de conditionnement d'air |
| EP0898128A3 (fr) * | 1997-08-22 | 2001-09-05 | Carrier Corporation | Pompe à chaleur à compression internement étagée et à fluide frigorigène variable |
| EP1293735A3 (fr) * | 2001-09-12 | 2003-05-28 | Mitsubishi Denki Kabushiki Kaisha | Circuit de réfrigérant |
| EP1553365A3 (fr) * | 2004-01-06 | 2012-06-20 | Samsung Electronics Co., Ltd. | Installation de climatisation |
| WO2009147172A1 (fr) * | 2008-06-05 | 2009-12-10 | Alstom Technology Ltd. | Système de refroidissement multi-réfrigérant avec aménagements pour le réglage de la composition du réfrigérant |
| EP2722617A4 (fr) * | 2011-06-16 | 2014-11-05 | Mitsubishi Electric Corp | Dispositif de conditionnement d'air |
| US20240110736A1 (en) * | 2022-09-30 | 2024-04-04 | Hill Phoenix, Inc. | Co2 refrigeration system with multiple receivers |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69422551T2 (de) | 2000-08-03 |
| EP0838643A2 (fr) | 1998-04-29 |
| JPH0712411A (ja) | 1995-01-17 |
| DE69432489T2 (de) | 2004-02-12 |
| DE69432489D1 (de) | 2003-05-15 |
| EP0838643B1 (fr) | 2003-04-09 |
| EP0631095A3 (fr) | 1995-03-01 |
| EP0838643A3 (fr) | 2000-11-15 |
| EP0631095B1 (fr) | 2000-01-12 |
| DE69422551D1 (de) | 2000-02-17 |
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