WO2023033133A1 - 空気分離装置用アルゴン塔および空気分離装置 - Google Patents
空気分離装置用アルゴン塔および空気分離装置 Download PDFInfo
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- WO2023033133A1 WO2023033133A1 PCT/JP2022/033062 JP2022033062W WO2023033133A1 WO 2023033133 A1 WO2023033133 A1 WO 2023033133A1 JP 2022033062 W JP2022033062 W JP 2022033062W WO 2023033133 A1 WO2023033133 A1 WO 2023033133A1
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- Prior art keywords
- argon
- column
- bed
- beds
- length
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 title claims abstract description 348
- 229910052786 argon Inorganic materials 0.000 title claims abstract description 174
- 238000000926 separation method Methods 0.000 title claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 42
- 239000007788 liquid Substances 0.000 description 31
- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 238000010586 diagram Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 150000001485 argon Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- 230000001174 ascending effect Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010992 reflux Methods 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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04642—Recovering noble gases from air
- F25J3/04648—Recovering noble gases from air argon
- F25J3/04654—Producing crude argon in a crude argon column
- F25J3/04666—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system
- F25J3/04672—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser
- F25J3/04678—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser cooled by oxygen enriched liquid from high pressure column bottoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/16—Fractionating columns in which vapour bubbles through liquid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
-
- 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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04642—Recovering noble gases from air
- F25J3/04648—Recovering noble gases from air argon
- F25J3/04654—Producing crude argon in a crude argon column
- F25J3/04666—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system
- F25J3/04672—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser
- F25J3/04703—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser being arranged in more than one vessel
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04642—Recovering noble gases from air
- F25J3/04648—Recovering noble gases from air argon
- F25J3/04721—Producing pure argon, e.g. recovered from a crude argon column
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04642—Recovering noble gases from air
- F25J3/04648—Recovering noble gases from air argon
- F25J3/04721—Producing pure argon, e.g. recovered from a crude argon column
- F25J3/04727—Producing pure argon, e.g. recovered from a crude argon column using an auxiliary pure argon column for nitrogen rejection
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
- F25J3/04872—Vertical layout of cold equipments within in the cold box, e.g. columns, heat exchangers etc.
- F25J3/04878—Side by side arrangement of multiple vessels in a main column system, wherein the vessels are normally mounted one upon the other or forming different sections of the same column
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
- F25J3/04896—Details of columns, e.g. internals, inlet/outlet devices
- F25J3/04909—Structured packings
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
- F25J3/04896—Details of columns, e.g. internals, inlet/outlet devices
- F25J3/04927—Liquid or gas distribution devices
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
- F25J2235/50—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being oxygen
Definitions
- the present invention relates to an argon column for an air separation device and an air separation device.
- a typical air separation unit is equipped with a high-pressure distillation column, a low-pressure distillation column, and an argon column as distillation columns.
- argon is industrially extracted, an air separation apparatus that employs a structured packed column using structured packing as the argon column is used, and compressed air is used as a raw material, and a side-cut feed (argon purity around 10%) is used from the middle stage of the low pressure column. , oxygen around 90%, nitrogen around 100 ppm) is rectified in an argon column. This results in high purity product argon.
- the argon concentration at the top of the argon column is 98% to 99.999% or more (oxygen purity of about 1 ppm).
- the packing is vertically divided by a certain length for the purpose of preventing drift of descending liquid in the distillation column and maintaining distillation performance.
- the filling in each section is called a bed, and its length is called a bed length.
- a liquid distributor and a collector (hereinafter referred to as "internal") for remixing and redistributing the descending liquid are installed between the partitioned beds in the distillation column.
- Patent Literature 1 discloses an argon column with seven beds, all of which have the same bed length.
- Patent Document 2 discloses an argon column in which the bed length of the bottom layer is short and the bed length of the other beds is equal in order to prevent deterioration of performance among the beds stacked in the vertical direction.
- Patent Documents 1 and 2 do not disclose a technique for reducing the height of the argon tower.
- the present invention provides an argon column for an air separation device and an air separation device as follows.
- a structured packed column using a structured packing which is used in an air separation unit comprising a high pressure column, a low pressure column, and an argon column, in which product argon is obtained from a fluid supplied from the middle stage of the low pressure column as a raw material.
- an argon tower having an upper section and a lower section; the upper section and the lower section have equal bed lengths within the same section; The upper section length is 72% or less of the total bed length,
- An argon column for an air separation unit wherein the upper bed length is at least 1.25 times the lower bed length.
- the number of beds in the upper section is 1 or more;
- An air separation device comprising the argon column for an air separation device according to any one of [1] to [4].
- the argon column for air separation apparatuses of this invention can reduce the column height of a distillation column, without reducing distillation performance.
- the air separation device of the present invention can be downsized without lowering the distillation performance.
- FIG. 3 is a cross-sectional view of an argon tower for an air separation device, which is a comparative example of the present invention
- 1 is a schematic diagram of an air separation device that is an embodiment to which the present invention is applied
- FIG. 4 is a schematic diagram of an air separation device that is another embodiment to which the present invention is applied. It is a figure which shows the result of the simulation of an experimental example. It is a figure which shows the result of the simulation of an experimental example.
- FIG. 1 shown in FIG. 1 is a cross-sectional view of an argon tower 11 for an air separation apparatus, which is the first embodiment of the present invention.
- an argon column for an air separation device hereinafter also simply referred to as "argon column" 11 of the present embodiment is used in an air separation device comprising a high pressure column, a low pressure column, and an argon column. .
- the argon column 11 of the present embodiment is a regular packed column using a regular packing (bed), and the gas-liquid countercurrent contact in the column causes a side-cut feed from the middle stage of the low-pressure column.
- the argon column 11 has three upper beds 2u, three lower beds 2l, and internals 5 between the beds. That is, the argon column 11 of this embodiment has six beds in total. In the argon column 11, each bed and the inner internals 5 are alternately stacked in the axial direction (vertical direction).
- Beds 2u and 2l are liquid-gas contact media for mass transfer operations.
- the beds 2u and 2l are not particularly limited as long as they are media that promote gas-liquid contact.
- Known beds can be applied as the beds 2u and 2l.
- the inner internal 5 is configured with a liquid distributor 3 and a collector 4 . Also, in the inner internal 5 , the collector 4 is positioned above the liquid distributor 3 .
- the liquid distributor 3 has a function of remixing the liquid to make the liquid composition uniform and then distributing the liquid.
- the liquid descending from the bottom of the bed positioned above the liquid distributor 3 (hereinafter also simply referred to as "descending liquid") can be uniformly distributed to the bed positioned below the liquid distributor 3.
- the structure of the liquid distributor 3 is not particularly limited as long as it can collect and remix liquids. Those with distributed holes can be applied.
- the collector 4 collects the liquid flowing down from the bottom of each bed in the argon column 11 above the liquid distributor 3, and the gas rising toward the bottom of each bed (hereinafter also simply referred to as “rising gas”). It has the function of ventilating the
- the structure of the collector 4 is not particularly limited as long as it has the functions described above.
- a gas mainly containing oxygen and argon is supplied to the bottom of the argon tower 11 and becomes rising gas rising in the tower.
- the ascending gas is liquefied by an overhead condenser (not shown), flows down as a reflux liquid to the bed 2u located at the top, and is continuously brought into gas-liquid contact with the ascending gas for distillation.
- the liquid that has flowed down from the bottom of the bed is collected by the collector 4, distributed uniformly by the liquid distributor 3, flows down the respective beds 2u and 2l, is collected by the collector 4, and is then collected by the liquid distributor 3 again. is distributed evenly again by and flows down to the beds 2l, 2u located below.
- argon is concentrated at the top of the column to a concentration that satisfies product specifications, and an oxygen-enriched liquid containing argon is sent back to the low-pressure column from the bottom as a side feed.
- the oxygen concentration in the product argon is preferably 10 ppm or less.
- FIG. 1 is a cross-sectional view showing the configuration of the argon tower of the prior art (Patent Document 1 mentioned above).
- the conventional argon column 111 there are four beds 2u positioned on the upper side, three beds 2l positioned on the lower side, and internal interconnects positioned between the beds. Null 5 is provided. That is, the conventional argon column 111 has seven total beds. In the argon column 111, each bed and the inner internals 5 are alternately stacked in the axial direction (vertical direction).
- the bed lengths of the beds 2u (1A) and 2l (1A) are all equal.
- the height of the distillation column is suppressed while maintaining the distillation performance.
- the argon column 11 of the present embodiment is provided with three beds 2u located on the upper side and three beds 2l located on the lower side. It is That is, the argon column 11 of this embodiment has six beds in total. In the argon column 11 of this embodiment, the beds 2u have the same bed length, and the beds 2l have the same bed length. Moreover, in the argon column 11 of this embodiment, the bed length of the bed 2u is longer than the bed length of the bed 2l. Furthermore, in the argon column 11 of this embodiment, the total number of internals 5 is five, which is one less than the conventional argon column 111 . With such a configuration, in the argon column 11 of the present embodiment, compared to the conventional argon column 111, the distillation performance is not lowered by one, and the installation space of the internal internal 5 is reduced by one. height can be further reduced.
- the dotted line shown in FIG. 1A and the dotted line shown in FIG. Define the upper section as the upper section and the lower section as the lower section.
- the upper end of the bed located on the third stage from the bottom of the conventional argon column 111 is defined as the reference, the section above it is defined as the upper section, and the section below it is defined as the lower section.
- the bed located in the upper section is defined as an upper bed 2u, and the bed located in the lower section is defined as a lower bed 2l.
- the sum of the bed lengths in the argon column is the "total bed length”
- the sum of the bed lengths of the upper bed 2u located in the upper section is the “upper section length”
- the sum of the bed lengths of the lower bed 2l located in the lower section are respectively defined as “lower section length”.
- the argon column 11 of this embodiment consists of an upper section and a lower section, and both the upper section and the lower section have the same bed length within the same section, the upper section has 3 beds, and the lower section has 3 beds.
- the number of beds in the section is 3.
- the position (height) of the lower section of the argon tower 11 of this embodiment is the same as the position (height) of the lower section of the conventional argon tower 111 .
- the number of beds in the lower section of the argon column 11 of this embodiment and the number of beds in the lower section of the conventional argon column 111 are both three. That is, the argon column 11 of this embodiment and the conventional argon column 111 have the same bed length of the lower bed 2l and the same lower section length.
- the argon column 11 of this embodiment and the conventional argon column 111 are different in both the bed length of the upper bed 2u and the upper section length (the argon column 11 is longer).
- the upper section length is 72% or less of the total bed length, and the upper bed length is 1.25 times or more the lower bed length.
- the argon column 11 has an upper section length of 72% or less of the total bed length, and the upper bed length is 1.25 times or more of the lower bed length, so that the distillation performance is improved.
- the total number of beds can be reduced without degradation, the total number of internals associated with the beds can also be reduced, and the argon column can be realized with a reduced height of the distillation column by limiting the increase in upper section length.
- FIG. 1 is a cross-sectional view showing the configuration of an argon tower 12 that is a modification of the present embodiment.
- the dotted line shown in FIG. 1(C) is the position that defines the top of the third bed from the bottom in the conventional argon column 111 shown in FIG. 1(A).
- the argon column 12 has five beds in total.
- the beds 2u (1C) have the same bed length
- the beds 2l (1C) have the same bed length.
- the bed length of the bed 2u (1C) is longer than the bed length of the bed 2l (1C).
- the total number of internals 5 in the argon column 12 is four, one less than the argon column 11 described above.
- the argon column 12 consists of an upper section and a lower section, and both the upper section and the lower section have equal bed lengths within the same section, the number of beds in the upper section is 2, and the number of beds in the lower section is is 3.
- the position (height) of the lower section of the modified argon column 12 is the same as the position (height) of the lower section of the conventional argon column 111 and the argon column 11 of the above-described embodiment.
- the modified argon column 12, the argon column 11 of the embodiment described above, and the conventional argon column 111 all have three beds in the lower section.
- the argon column 12 of the modified example, the argon column 11 of the embodiment described above, and the conventional argon column 111 all have the same bed length of the lower bed 2l and the same lower section length.
- the argon tower 12 of the modified example, the argon tower 11 of the embodiment described above, and the conventional argon tower 111 are all different in the bed length of the upper bed 2u and the upper section length.
- the argon column 12 has an upper section length of 72% or less of the total bed length.
- the argon column 12 has an upper bed length that is 1.25 times or greater than the lower bed length.
- FIGS. 2A to 2C are cross-sectional views showing the configuration of an argon tower that is a modification of the present embodiment.
- the dotted lines shown in FIGS. 2A to 2C are positions defining the upper side of the second bed from the bottom in the conventional argon column 111 shown in FIG. 1A.
- beds 2u (2A) to 2u (2C) are arranged in the upper part of the tower. There are 4 beds, and two beds 2l are located below. That is, the argon columns 21, 22, 23 have 4-6 total beds. In the argon columns 21, 22, 23, the beds 2u(2A) to 2u(2C) have the same bed length, and the beds 2l(2A) to 2l(2C) have the same bed length. Further, in the argon columns 21, 22, 23, the bed lengths of the beds 2u (2A) to 2u (2C) are longer than the bed lengths of the beds 2l (2A) to 2l (2C).
- the total number of internals 5 in the argon columns 21, 22, 23 is 5, 4, 3, respectively, which is less than the total number (6) of the internals 5 in the conventional argon column 111 described above.
- the column height can be further reduced without deteriorating the distillation performance compared to the conventional argon column 111.
- the argon columns 21, 22, 23 consist of an upper section and a lower section, the upper section and the lower section both have equal bed lengths within the same section, and the number of beds in the upper section is 2 to 4.
- the number of beds in the lower section is two.
- the positions (heights) of the lower sections of the modified argon columns 21 , 22 , 23 are the same as the position (height) of the lower section of the conventional argon column 111 .
- the number of beds in the lower section of the modified argon columns 21, 22, 23 and the conventional argon column 111 is two. That is, the modified argon columns 21, 22, 23 and the conventional argon column 111 have the same bed length of the lower bed 2l and the same lower section length.
- the argon columns 21, 22, 23 of the modified examples and the conventional argon column 111 differ in the bed length of the upper bed 2u and the upper section length. Also, the argon columns 21, 22, 23 have an upper section length of 72% or less of the total bed length. Furthermore, the argon columns 21, 22, and 23 have upper bed lengths greater than or equal to 1.25 times lower bed lengths.
- the argon column 11 of this embodiment it consists of an upper section and a lower section, and both the upper section and the lower section have the same bed length in the same section, and the number of beds in the upper section is 3, the number of beds in the lower section is 3, the upper section length is no more than 72% of the total bed length, and the upper bed length is no less than 1.25 times the lower bed length.
- the total number of internal internals 5 can be reduced by one compared to the total number (6) of internal internals 5 of the conventional argon column 111 while suppressing an increase in the length of the upper section.
- the argon column 11 of the present embodiment can reduce the height of the distillation column without reducing the distillation performance. can be suppressed further.
- the distillation performance is not reduced, The height of the distillation column can be further reduced.
- FIG. 4 is a schematic diagram showing the configuration of an air separation device 100 that is an embodiment to which the present invention is applied.
- the air separation device 100 of the present embodiment includes an argon column 10 divided into two at an arbitrary position inside a cold box (cooling box) 150, a high pressure distillation column (high pressure column) 20 , a low-pressure distillation column (low-pressure column) 30 and a high-purity argon distillation column 40 .
- the air separation device 100 of the present embodiment by applying the argon column 11 of the embodiment described above as the argon column 10, it is possible to reduce the height of the distillation column, and the cold It is possible to make the box 150 compact (that is, downsize the entire device).
- the technical scope of the present invention is not limited to the above embodiments, and various modifications can be made without departing from the gist of the present invention.
- the argon column 11 may be used without being divided, or the argon column 11 may be divided into two or more and used.
- the dividing position at this time is not limited to the boundary between the upper section and the lower section.
- the case where the number of upper beds 2u constituting the upper section is 2 to 3 has been described as an example, but the present invention is not limited to this. That is, when the number of the lower beds 2l constituting the lower section is two or three, the number of the upper beds 2u constituting the upper section may be one.
- the argon column is not limited to collecting the product from the top of the column. As shown in FIG. may be taken. In this case, one argon column need not have both the upper section and the section 101 where the separation is performed at the upper part.
- the argon column with the upper section and the argon column containing the section performing the separation at the upper portion 101 may be separate.
- the product argon from the upper section of the argon column 11 is further introduced into the high-purity argon column. no. If the nitrogen composition is 500 ppm or less, preferably 50 ppm or less, more preferably 1 ppm or less, there is no need to install a high-purity argon column.
- FIGS. 3A to 3C are cross-sectional views showing the configuration of an argon tower that is a comparative example of the present invention.
- the dotted lines shown in FIGS. 3A to 3C are positions defining the top of the first bed from the bottom in the conventional argon column 111 shown in FIG. 1A.
- the beds 2u (3A) to 2u (3C) have the same bed length, and the beds 2l (3A) to 2l (3C) have the same length as the conventional argon column 111.
- Bed length is equal to bed 2l (1A).
- the bed lengths of the beds 2u (3A) to 2u (3C) are longer than the bed lengths of the beds 2l (3A) to 2l (3C).
- the total number of internals 5 of the argon columns 31, 32, 33 are 4, 3, 2, respectively, which is less than the total number of internals 5 (6) of the conventional argon column 111 described above.
- the argon columns 31, 32, and 33 of the comparative examples consist of an upper section and a lower section, and both the upper section and the lower section have equal bed lengths within the same section, and the number of beds in the upper section is two. ⁇ 4 and the number of beds in the lower section is 1 each.
- the distillation performance was calculated from the gas-liquid flow state in the argon column (flow rate distribution of the gas-liquid in the cross section of the column).
- the flow rate distribution takes into consideration the tendency of the liquid to gather on the column wall, and the local gas-liquid ratio at that time is used to calculate the distillation performance.
- the effect of reducing the number of beds is calculated assuming perfect liquid mixing.
- Figs. 1 to 3 show filling forms for each condition.
- h u be the length of the upper bed and h l be the length of the lower bed in the vertical direction of the bed 2u or the bed 2l.
- HU be the upper section length and HL be the lower section length.
- FIG. 1 shows an argon column with 3 lower beds
- FIG. 2 shows 2 lower beds
- FIG. 3 shows 1 lower bed, all of which have the same lower bed length h1 .
- Argon column (A) shown in each figure (Fig. 1 (A): 3 lower beds and 4 upper beds, Fig. 2 (A): 2 lower beds and 4 upper beds, Fig. 3 (A): When the number of lower beds is 1 and the number of upper beds is 4), the upper section length HUA that satisfies the concentration specification (oxygen 1 ppm) at the top of the column, and when the upper beds are changed from 4 beds (A) to 2 beds (C) in each figure , an upper section length HUC that satisfies the same overhead oxygen concentration specification was calculated.
- the raw material composition supplied to the lower section is the same under all conditions.
- the vertical axis indicates the section length difference between (A) and (C) in each figure as the numerator
- the denominator indicates the ratio of the section length difference between (A) and (C) in FIG. and is defined by the following equation (1).
- the horizontal axis indicates the ratio of the upper section length to the total bed length (the sum of the upper section length and the lower section length) in (C) of each figure, and is defined by the following equation (2) .
- Fig. 7 shows the relationship between the total bed length of (B) and (C), in which the number of beds is reduced in Figs. 1 and 2, in which the upper section length to the total bed length is 72% or less, and the upper bed length to the lower bed length. is shown.
- the horizontal axis indicates the upper bed length/lower bed length in (B) or (C) of each figure, which is defined by the following equation (3).
- the vertical axis indicates the ratio with the total bed length of (A) in each figure as the denominator and the total bed length of (B) or (C) as the numerator, and is defined by the following formula (4).
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Abstract
Description
なお、蒸留塔内には、区切られたベッド間に、下降液を再混合・再分配するための液分配器やコレクタ(以下、「内部インターナル」(internal)と呼ぶ)が設置される。
また、特許文献2には、鉛直方向に積んだベッドのうち、性能低下を防止する為に最下層のベッドのベッド長が短く、その他のベッドのベッド長が等しいアルゴン塔が開示されている。
[1] 高圧塔、低圧塔、及びアルゴン塔を備える空気分離装置に用いられる、規則充填物を利用した規則充填塔であり、前記低圧塔の中段から供給される流体を原料として製品アルゴンを得るアルゴン塔であって、
上部セクションと下部セクションとを有し、
前記上部セクションおよび前記下部セクションは、同じセクション内でいずれも等しいベッド長であり、
前記上部セクション長は、総ベッド長の72%以下であり、
上部ベッド長は、下部ベッド長の1.25倍以上である、空気分離装置用アルゴン塔。
[2] 前記上部セクションのベッド数は、1以上であり、
前記下部セクションのベッド数は、2以上である、[1]に記載の空気分離装置用アルゴン塔。
[3] 製品アルゴン中の酸素濃度が10ppm以下である、[1]または[2]に記載の空気分離装置用アルゴン塔。
[4] 鉛直方向に2以上に分割された、[1]乃至[3]のいずれかに記載の空気分離装置用アルゴン塔。
[5] [1]乃至[4]のいずれかに記載の空気分離装置用アルゴン塔を備える、空気分離装置。
また、本発明の空気分離装置は、蒸留性能を低下させることなく、小型化できる。
先ず、本発明を適用した一実施形態である空気分離装置用アルゴン塔の構成について、図面を参照しながら説明する。図1中に示す(B)は、本発明の第一実施形態である、空気分離装置用アルゴン塔11の断面図である。
図1(B)に示すように、本実施形態の空気分離装置用アルゴン塔(以下、単に「アルゴン塔」ともいう)11は、高圧塔、低圧塔、及びアルゴン塔を備える空気分離装置に用いる。具体的には、本実施形態のアルゴン塔11は、規則充填物(ベッド)を用いる規則充填塔であり、塔内で気液が向流接触することにより、低圧塔の中段からサイドカットしたフィードを原料にして製品アルゴンを得る蒸留塔である。
アルゴン塔11の塔内には、上側に位置する3つのベッド2uと、下側に位置する3つのベッド2lと、各ベッド間に位置する内部インターナル5とが設けられている。すなわち、本実施形態のアルゴン塔11は、ベッド総数が6つである。また、アルゴン塔11の塔内には、軸方向(鉛直方向)に、各ベッドと内部インターナル5とが交互に積層されている。
先ず、図1(B)に示すアルゴン塔11では、主に酸素とアルゴンとを含むガスがアルゴン塔11の塔底部に供給され、塔内を上昇する上昇ガスとなる。
上昇ガスは、図示略の塔頂コンデンサにより液化され、還流液として、最上部に位置するベッド2uに流下し、上昇ガスと連続的に気液接触して蒸留が行われる。ベッドの底部から流下した液は、コレクタ4により集液された後、液分配器3により均一に分配されて各ベッド2u,2lを流下し、コレクタ4に集められたのち、再び液分配器3によって再度均一に分配されて、下方に位置するベッド2l,2uに流下する。
本実施形態のアルゴン塔11では、製品アルゴン中の酸素濃度は、10ppm以下であることが好ましい。
図1(A)に示すように、従来のアルゴン塔111の塔内には、上側に位置する4つのベッド2uと、下側に位置する3つのベッド2lと、各ベッド間に位置する内部インターナル5とが設けられている。すなわち、従来のアルゴン塔111は、ベッド総数が7つである。また、アルゴン塔111の塔内には、軸方向(鉛直方向)に、各ベッドと内部インターナル5とが交互に積層されている。
また、従来のアルゴン塔111では、ベッド2u(1A)及びベッド2l(1A)のベッド長(アルゴン塔の軸方向のベッドの長さ)が全て等しい。
このような構成により、従来のアルゴン塔111では、蒸留性能を維持しつつ、蒸留塔の高さを抑えている。
なお、本実施形態のアルゴン塔11では、ベッド2u相互のベッド長が等しく、ベッド2l相互のベッド長も等しい。
また、本実施形態のアルゴン塔11では、ベッド2uのベッド長は、ベッド2lのベッド長よりも長い。
さらに、本実施形態のアルゴン塔11では、内部インターナル5の総数が5つであり、従来のアルゴン塔111よりも1つ少ない。
このような構成により、本実施形態のアルゴン塔11では、従来のアルゴン塔111と比較して、蒸留性能を低下させることなく、1つ削減された内部インターナル5の設置スペースの影響により蒸留塔の高さをより抑えることができる。
また、上部セクションに位置するベッドを上部ベッド2u、下部セクションに位置するベッドを下部ベッド2lと定義する。
さらに、アルゴン塔内のベッド長の和を「総ベッド長」、上部セクションに位置する上部ベッド2uのベッド長の和を「上部セクション長」、下部セクションに位置する下部ベッド2lのベッド長の和を「下部セクション長」と、それぞれ定義する。
なお、本実施形態のアルゴン塔11の下部セクションの位置(高さ)は、従来のアルゴン塔111の下部セクションの位置(高さ)と同じである。また、本実施形態のアルゴン塔11の下部セクションのベッド数、および従来のアルゴン塔111の下部セクションのベッド数は、いずれも3である。すなわち、本実施形態のアルゴン塔11と従来のアルゴン塔111とは、下部ベッド2lのベッド長、及び下部セクション長がいずれも等しい。一方、本実施形態のアルゴン塔11と従来のアルゴン塔111とは、上部ベッド2uのベッド長、及び上部セクション長がいずれも異なる(いずれもアルゴン塔11の方が長い)。
後述する実施例において説明するように、アルゴン塔11は、上部セクション長が総ベッド長の72%以下であり、上部ベッド長が下部ベッド長の1.25倍以上であることにより、蒸留性能を低下させることなくベッド総数を削減でき、ベッドに伴う内部インターナルの総数も減らすことができ、上部セクション長の増加を抑えることで、蒸留塔の高さを抑えたアルゴン塔を実現できる。
次に、上述した本実施形態のアルゴン塔11の変形例について、説明する。
図1中に示す(C)は、本実施形態の変形例であるアルゴン塔12の構成を示す断面図である。ここで、図1(C)中に示す点線は、図1(A)に示す従来のアルゴン塔111において、下から3段目のベッドの上方を定義する位置である。
アルゴン塔12では、ベッド2u(1C)は、相互にベッド長が等しく、ベッド2l(1C)は、相互にベッド長が等しい。
また、アルゴン塔12では、ベッド2u(1C)のベッド長は、ベッド2l(1C)のベッド長よりも長い。
さらに、アルゴン塔12の内部インターナル5の総数は4つであり、上述したアルゴン塔11よりも1つ少ない。
このような構成により、本実施形態の変形例であるアルゴン塔12では、上述したアルゴン塔11と比較して、蒸留性能を低下させることなく、蒸留塔の高さをさらに抑えることができる。
なお、変形例のアルゴン塔12の下部セクションの位置(高さ)は、従来のアルゴン塔111、及び上述した実施形態のアルゴン塔11の下部セクションの位置(高さ)と同じである。また、変形例のアルゴン塔12、上述した実施形態のアルゴン塔11、および従来のアルゴン塔111の下部セクションのベッド数は、いずれも3である。すなわち、変形例のアルゴン塔12、上述した実施形態のアルゴン塔11、および従来のアルゴン塔111は、下部ベッド2lのベッド長、及び下部セクション長がいずれも等しい。一方、変形例のアルゴン塔12、上述した実施形態のアルゴン塔11、および従来のアルゴン塔111は、上部ベッド2uのベッド長、及び上部セクション長がいずれも異なる。
また、アルゴン塔12は、上部セクション長が総ベッド長の72%以下である。
さらに、アルゴン塔12は、上部ベッド長が下部ベッド長の1.25倍以上である。
図2中に示す(A)~(C)は、本実施形態の変形例であるアルゴン塔の構成を示す断面図である。ここで、図2(A)~(C)中に示す点線は、図1(A)に示す従来のアルゴン塔111において、下から2段目のベッドの上方を定義する位置である。
アルゴン塔21,22,23では、各ベッド2u(2A)~2u(2C)は、相互にベッド長が等しく、各ベッド2l(2A)~2l(2C)は、相互にベッド長が等しい。
また、アルゴン塔21,22,23では、ベッド2u(2A)~2u(2C)のベッド長は、ベッド2l(2A)~2l(2C)のベッド長よりもそれぞれ長い。
さらに、アルゴン塔21,22,23の内部インターナル5の総数はそれぞれ5,4,3であり、上述した従来のアルゴン塔111の内部インターナル5の総数(6つ)よりも少ない。
このような構成により、本実施形態の変形例であるアルゴン塔21,22,23では、従来のアルゴン塔111と比較して、蒸留性能を低下させることなく、塔高をさらに抑えることができる。
なお、変形例のアルゴン塔21,22,23の下部セクションの位置(高さ)は、従来のアルゴン塔111の下部セクションの位置(高さ)と同じである。また、変形例のアルゴン塔21,22,23、および従来のアルゴン塔111の下部セクションのベッド数は、いずれも2である。すなわち、変形例のアルゴン塔21,22,23、および従来のアルゴン塔111は、下部ベッド2lのベッド長、及び下部セクション長がいずれも等しい。一方、変形例のアルゴン塔21,22,23、および従来のアルゴン塔111は、上部ベッド2uのベッド長、及び上部セクション長がいずれも異なる。
また、アルゴン塔21,22,23は、上部セクション長が総ベッド長の72%以下である。
さらに、アルゴン塔21,22,23は、上部ベッド長が下部ベッド長の1.25倍以上である。
図4は、本発明を適用した一実施形態である空気分離装置100の構成を示す模式図である。
図3中に示す(A)~(C)は、本発明の比較例であるアルゴン塔の構成を示す断面図である。ここで、図3(A)~(C)中に示す点線は、図1(A)に示す従来のアルゴン塔111において、下から1段目のベッドの上方を定義する位置である。
また、アルゴン塔31,32,33では、ベッド2u(3A)~2u(3C)のベッド長は、ベッド2l(3A)~2l(3C)のベッド長よりもそれぞれ長い。
さらに、アルゴン塔31,32,33の内部インターナル5の総数はそれぞれ4,3,2であり、上述した従来のアルゴン塔111の内部インターナル5の総数(6つ)よりも少ない。
図1~3において、上部ベッド数を4から2(各図の(A)から(C))に削減した場合に、内部インターナル5の総数が減るため、アルゴン塔の塔高を抑えられる。一方で、上部ベッド数を削減すると、蒸留性能の低下を補うために上部セクションに余分にベッドを充填する必要があるため、充填長が長くなる。そこで、図1~3において、上部ベッド数を4から2(各図の(A)から(C))に削減した場合、総ベッド長に対する上部セクション長の割合と、追加ベッド長の割合との関係を検証した。
上部セクション長が総ベッド長の72%以下になる、アルゴンが濃縮していく領域においては、下部ベッド長hlに対する上部ベッド長huの比についても最適値があることを見出した。
図1および図2において、上部ベッド数を3から2(各図の(B)から(C))に削減するときの、総ベッド長の割合と、下部ベッド長hlに対する上部ベッド長huの割合との関係を検証した。
図7において、横軸は、各図の(B)または(C)における上部ベッド長/下部ベッド長を示しており、以下の式(3)で定義される。
2l、2l(1A)、2l(1B)、2l(1C)、2l(2A)、2l(2B)、2l(2C)、2l(3A)、2l(3B)、2l(3C):下部ベッド
3:液分配器
4:コレクタ
5:内部インターナル
10、11、12、21、22、23、31、32、33、111:空気分離装置用アルゴン塔(アルゴン塔)
20:高圧蒸留塔(高圧塔)
30:低圧蒸留塔(低圧塔)
40:高純度アルゴン蒸留塔
100:空気分離装置
150:コールドボックス(保冷箱)
Claims (5)
- 高圧塔、低圧塔、及びアルゴン塔を備える空気分離装置に用いられる、規則充填物を利用した規則充填塔であり、前記低圧塔の中段から供給される流体を原料として製品アルゴンを得るアルゴン塔であって、
上部セクションと下部セクションとを有し、
前記上部セクションおよび前記下部セクションは、同じセクション内でいずれも等しいベッド長であり、
前記上部セクション長は、総ベッド長の72%以下であり、
上部ベッド長は、下部ベッド長の1.25倍以上である、空気分離装置用アルゴン塔。 - 前記上部セクションのベッド数は、1以上であり、
前記下部セクションのベッド数は、2以上である、請求項1に記載の空気分離装置用アルゴン塔。 - 製品アルゴン中の酸素濃度が10ppm以下である、請求項1または2に記載の空気分離装置用アルゴン塔。
- 鉛直方向に2以上に分割された、請求項1乃至3のいずれか一項に記載の空気分離装置用アルゴン塔。
- 請求項1乃至4のいずれか一項に記載の空気分離装置用アルゴン塔を備える、空気分離装置。
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JPH07155585A (ja) * | 1993-12-08 | 1995-06-20 | Hitachi Ltd | 充填物及び空気分離装置 |
JP2000249464A (ja) * | 1998-12-28 | 2000-09-14 | Nippon Sanso Corp | 気液接触装置、空気液化分離装置、およびガス分離方法 |
JP2000337766A (ja) | 1999-05-21 | 2000-12-08 | Boc Group Inc:The | 蒸留方法および蒸留塔 |
JP2004251569A (ja) * | 2003-02-21 | 2004-09-09 | Hitachi Ltd | 深冷空気分離装置 |
JP2010046616A (ja) * | 2008-08-22 | 2010-03-04 | Taiyo Nippon Sanso Corp | 気液接触装置 |
JP2010210151A (ja) * | 2009-03-10 | 2010-09-24 | Taiyo Nippon Sanso Corp | 粗アルゴン塔 |
JP2011206681A (ja) | 2010-03-30 | 2011-10-20 | Taiyo Nippon Sanso Corp | 液分配器 |
JP2016059888A (ja) | 2014-09-19 | 2016-04-25 | 大陽日酸株式会社 | 規則充填物 |
JP6257656B2 (ja) | 2013-03-06 | 2018-01-10 | リンデ アクチエンゲゼルシャフトLinde Aktiengesellschaft | 空気分離装置、アルゴンを含有する生成物を獲得する方法、及び、空気分離装置を建造する方法 |
JP2020026898A (ja) * | 2018-08-09 | 2020-02-20 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | 空気分離装置 |
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- 2022-09-02 WO PCT/JP2022/033062 patent/WO2023033133A1/ja active Application Filing
- 2022-09-02 JP JP2023545688A patent/JPWO2023033133A1/ja active Pending
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JPH07155585A (ja) * | 1993-12-08 | 1995-06-20 | Hitachi Ltd | 充填物及び空気分離装置 |
JP2000249464A (ja) * | 1998-12-28 | 2000-09-14 | Nippon Sanso Corp | 気液接触装置、空気液化分離装置、およびガス分離方法 |
JP2000337766A (ja) | 1999-05-21 | 2000-12-08 | Boc Group Inc:The | 蒸留方法および蒸留塔 |
JP2004251569A (ja) * | 2003-02-21 | 2004-09-09 | Hitachi Ltd | 深冷空気分離装置 |
JP2010046616A (ja) * | 2008-08-22 | 2010-03-04 | Taiyo Nippon Sanso Corp | 気液接触装置 |
JP2010210151A (ja) * | 2009-03-10 | 2010-09-24 | Taiyo Nippon Sanso Corp | 粗アルゴン塔 |
JP2011206681A (ja) | 2010-03-30 | 2011-10-20 | Taiyo Nippon Sanso Corp | 液分配器 |
JP6257656B2 (ja) | 2013-03-06 | 2018-01-10 | リンデ アクチエンゲゼルシャフトLinde Aktiengesellschaft | 空気分離装置、アルゴンを含有する生成物を獲得する方法、及び、空気分離装置を建造する方法 |
JP2016059888A (ja) | 2014-09-19 | 2016-04-25 | 大陽日酸株式会社 | 規則充填物 |
JP2020026898A (ja) * | 2018-08-09 | 2020-02-20 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | 空気分離装置 |
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