CN118103654A - Method and apparatus for producing argon and oxygen products and method for retrofitting one or more air fractionation facilities - Google Patents

Method and apparatus for producing argon and oxygen products and method for retrofitting one or more air fractionation facilities Download PDF

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Publication number
CN118103654A
CN118103654A CN202280068798.6A CN202280068798A CN118103654A CN 118103654 A CN118103654 A CN 118103654A CN 202280068798 A CN202280068798 A CN 202280068798A CN 118103654 A CN118103654 A CN 118103654A
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China
Prior art keywords
argon
oxygen
separation unit
column
air separation
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CN202280068798.6A
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Chinese (zh)
Inventor
托比亚斯·劳滕施莱格
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Messer LLC
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Linde LLC
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • 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
    • F25J3/04406—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 using a dual pressure main column system
    • F25J3/04412—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 using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • 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
    • 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
    • F25J3/04709—Producing crude argon in a crude argon column as an auxiliary column system in at least a dual pressure main column system
    • F25J3/04715—The auxiliary column system simultaneously produces oxygen
    • 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
    • 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
    • F25J3/04951—Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network
    • F25J3/04963—Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network and inter-connecting equipment within or downstream of the fractionation unit(s)
    • 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
    • F25J3/04969—Retrofitting or revamping of an existing air fractionation unit
    • 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/58—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being argon or crude argon
    • 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/58—Processes or apparatus involving steps for recycling of process streams the recycled stream being argon or crude argon

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

The outlet mixture (E) from the argon discharge column (14) of the air fractionation facility (100) is supplied to and fractionated in a fractionation unit (200) provided separately from the air fractionation facility (100) to obtain an oxygen fraction (GOX, LOX) enriched in oxygen compared to the outlet mixture (E) and an argon fraction (LAR, GAR) enriched in argon compared to the outlet mixture (E). The invention also relates to a corresponding device (1000) and a method for retrofitting one or more air fractionation facilities (100).

Description

Method and apparatus for producing argon and oxygen products and method for retrofitting one or more air fractionation facilities
The present invention relates to a method and an apparatus for the preparation of argon and oxygen products, and a method for retrofitting one or more air separation units according to the preamble of the independent claims.
Background
It is known to prepare air products in liquid or gaseous form by cryogenic air separation in an air separation unit and for example in h. -W.(Editions), industrial Gases Processing, wiley-VCH,2006, in particular section 2.2.5, "Cryogenic Rectification". Unless otherwise defined, the terms used below have the meanings customary in the technical literature.
The air separation unit has a rectifying column device which can be designed differently. In addition to the rectification column for obtaining liquid and/or gaseous nitrogen and/or oxygen (i.e. the rectification column for nitrogen-oxygen separation, which can be combined in particular in known double columns), rectification columns for obtaining other air components, in particular noble gases, or pure oxygen can also be provided.
The rectification columns in a typical rectification column apparatus operate at different pressure levels. Known twin columns have so-called pressure columns (also called higher pressure columns, medium pressure columns or lower columns) and so-called lower pressure columns (also called upper columns). The higher pressure column is generally operated at a pressure in the range of 4 bar to 7 bar, in particular at about 5.3 bar; on the other hand, low pressure columns operate at pressures in the range of generally 1 bar to 2 bar, in particular at about 1.4 bar.
For extracting argon, an air separation unit having a so-called crude argon column and a pure argon column may be used. One example is in(See above) in fig. 2.3A, and is described beginning at page 26, section "Rectification in the Low-pressure, crude and Pure Argon Column" and also beginning at page 29, section "Cryogenic Production of Pure Argon". In a conventional crude argon column, crude argon is extracted and processed in a downstream pure argon column to form pure argon. In principle, for argon extraction, a pure argon column can also be omitted if the rectification column concerned is adapted accordingly. For example, pure argon may be removed from a crude argon column or from a similar rectification column further below the fluid conventionally transferred to the pure argon column, with the portion disposed above the removal point for nitrogen removal.
US2021/116175 A1 discloses a system and method for argon production in an air separation unit or a bag body having a plurality of cryogenic air separation units. The system and method include a centralized argon purification system disposed in one of the cryogenic air separation units and having an argon column apparatus with one or more argon columns and an argon condenser. The crude argon stream from one or more of the other air separation units is conducted to an argon column apparatus of a centralized argon purification system.
The object of the present invention is to provide improvements in the extraction of argon and oxygen, in particular in assemblies made up of a plurality of air separations, and to provide advantageous measures in order to be able to retrofit corresponding units or unit assemblies, in particular during operation.
Disclosure of Invention
Against this background, the present invention proposes a method and an apparatus for the preparation of argon and oxygen products, and a method for retrofitting one or more air separation units, with the features of the independent claims. The dependent claims and the following description relate to advantageous embodiments of the invention.
The invention makes it possible in particular to adapt the air separation unit during its service life to adapt the changing requirements for the air product. The provision of pure argon and high purity oxygen, which are possible by corresponding adaptations, can particularly cover the need for solar cell manufacturing units.
Because the longer downtime of the retrofit work is often intolerable or intolerable, especially in large air separation units, separate, independent fractionation units (as set forth in the benzene invention context) that can generate both pure argon and high purity oxygen from the argon-rich oxygen-containing gas mixture provide particular benefits. The proposed fractionation unit is not part of the air separation unit of the corresponding composite system as described in US2021/116175 A1 and can thus be retrofitted without stopping the corresponding air separation unit.
Another difference from US2021/116175 A1 is that the argon-rich oxygen-containing gas mixture supplied to the fractionation unit in the context of the present invention has a significantly higher oxygen content of 10 to 20 vol.%, for example about 15 vol.%. This gas mixture is thus subjected to an argon-oxygen separation process in the fractionation unit proposed within the scope of the present invention. In addition to the argon-rich oxygen-containing gas mixture, the fractionation unit proposed within the scope of the invention can be supplied with liquid nitrogen and/or with a small proportion of compressed dry air as operating medium. The aforementioned gas mixture is formed in the air separation unit (or each air separation unit) used as the head gas of the argon discharge column according to the present invention.
"Argon-discharge column" or "empty argon column" is understood to mean a separation column for separating oxygen and argon and not for extracting pure argon product but essentially for discharging argon from a low pressure column, as may be advantageous for separation reasons. In particular, larger air separation units are equipped with corresponding argon discharge columns in order to increase oxygen yield and minimize energy consumption. The head product (also referred to herein as the outlet mixture) of such argon-rejection columns is typically vented to the atmosphere, optionally after heating in the main heat exchanger, because the purity of its components is insufficient for use as a product. The structure of the argon-discharge column is in principle slightly different from that of a conventional crude argon column. However, argon discharge columns typically contain significantly fewer theoretical or actual trays, i.e., less than 40, especially 15 to 30. As in a conventional crude argon column, the bottom region of the argon discharge column is also typically connected to an intermediate point of the lower pressure column.
The present invention relates to both the connection of a single "first" air separation unit to a separate fractionation unit for argon-oxygen separation, and the connection between two or more (e.g., "first" and "second") air separation units and such fractionation units. In the latter, for example, the fraction is removed from one of the air separation units and is mixed in each case with the corresponding fraction from the air separation unit or from the other air separation units. The mixture is then supplied to a fractionation unit. Alternatively, the corresponding fraction may also be separately conveyed to the fractionation unit. In principle, the outlet mixture from the air separation unit may be introduced into a fractionation unit as part of the second air separation unit. Fractionation units disposed separately from any air separation unit are preferred within the scope of the present invention. As regards the fractionation unit, by "separate" from the first (or further) air separation unit in this case is meant that the fractionation unit is accommodated in a partition (cold box) separate from the partition (cold box) of the corresponding air separation unit. Apart from the separate cold box, the separate fractionation unit is preferably at a distance from the air separation unit of at least 20m, preferably at least 50m and for example not more than 2km.
In summary, the present invention proposes a method for providing argon and oxygen products by means of cryogenic air separation, wherein an apparatus is used with an air separation unit or a plurality of air separation units, wherein each air separation unit of the air separation unit or the plurality of air separation units has a main heat exchanger, a rectification column system with a pressure column operating in a pressure range of, for example, 3 to 7 bar, a low pressure column operating in a pressure range of, for example, 1 to 2 bar, and an argon discharge column with less than 40 theoretical trays. The air separation units are not limited at all in their other structural design.
In the air separation unit or in each of the plurality of air separation units, the pressure column is supplied with cooled compressed air, the low pressure column is supplied with a fluid from the pressure column that is enriched in oxygen compared to the cooled compressed air, a transfer mixture comprising 5 to 15% by volume argon and 85 to 95% by volume oxygen and nitrogen is removed from the low pressure column and transferred to the argon-rejection column, and an argon-depleted sump liquid (at least some of which is returned to the low pressure column) and an argon-enriched head gas (at least some of which is discharged from the air separation unit as an outlet mixture) comprising 5 to 20% by volume oxygen and nitrogen compared to the transfer mixture are formed in the argon-rejection column. The transfer mixture is removed from the low pressure column, in particular at or below the so-called argon maximum or argon column belly, as is well known in the art of argon extraction. The sump liquid is fed back in a conventional manner.
According to the invention, at least some of the outlet mixture of the air separation unit or the outlet mixture of the plurality of air separation units is passed to a fractionation unit provided separately from the air separation unit or the plurality of air separation units and fractionated therein to obtain one or more oxygen fractions enriched in oxygen compared to the outlet mixture or the plurality of outlet mixtures and one or more argon fractions enriched in argon compared to the outlet mixture or the plurality of outlet mixtures. The specification "provided separately from the air separation unit or units" is intended to mean in particular a structural implementation according to which the fractionation units provided for obtaining the oxygen fraction and the argon fraction are provided outside a thermally insulated housing containing at least three rectifying columns of the air separation unit and at least one heat exchanger, in particular in separate thermally insulated housings. Each heat-insulating housing is provided in the manner of a known cold box. In addition to the separate cold box, the separate fractionation unit is preferably located at a distance from the air separation unit of at least 20m, preferably at least 50m. In other words, the oxygen fraction and the argon fraction are obtained "outside" the (corresponding) air separation unit, or in a "central" or "centralized" manner for several air separation units of this type.
One aspect of the invention is to extract (in particular high purity) oxygen in addition to the external or concentrated argon production in the sense described above, for which purpose at least one additional rectifying column with a condenser is provided in particular. In other words, the fractionation unit comprises at least two rectification columns each having a head condenser, wherein one of the at least two rectification columns of the fractionation unit is configured for separating mainly or exclusively oxygen from argon and/or nitrogen, and the other or other of the at least two rectification columns of the fractionation unit is configured for separating mainly or exclusively nitrogen from oxygen and/or argon.
According to the invention, the one or more oxygen fractions are or include at least one high purity oxygen fraction having an oxygen content of more than 99.9 vol.%, an argon content of less than 100ppm, and a total hydrocarbon content of less than 100 ppb. At least one high purity oxygen fraction, in particular a liquid high purity fraction and/or a gaseous high purity fraction.
Accordingly, the one or more argon fractions include, inter alia, at least one pure argon fraction having an argon content of more than 99.999 volume percent, a nitrogen content of 0ppm to 2ppm, and an oxygen content of 0ppm to 2ppm, and the at least one pure argon fraction is a liquid pure argon fraction and/or a gaseous pure argon fraction.
The or each outlet fraction comprises 80 to 85% by volume argon, for example about 82% by volume; in particular about 15% by volume of oxygen; and 2 to 5% by volume, for example about 3% by volume, of nitrogen.
An apparatus for providing argon and oxygen products by cryogenic air separation provided in accordance with the present invention includes an air separation unit or units, wherein each air separation unit or units has a rectification column system having a pressure column configured to operate in a pressure range of 3 bar to 7 bar, a low pressure column configured to operate in a pressure range of 1 bar to 2 bar, and an argon discharge column having less than 40 theoretical trays.
The air separation unit or each of the plurality of air separation units is configured for operation, wherein the pressure column is supplied with cooled compressed air, the low pressure column is supplied with a fluid from the pressure column that is enriched in oxygen compared to the cooled compressed air, a transfer mixture comprising 5 to 15% by volume argon and 85 to 95% by volume oxygen and nitrogen is removed from the low pressure column and transferred to the argon-discharge column, and an argon-depleted sump liquid (at least some of which is returned to the low pressure column) and an argon-enriched head gas (at least some of which is discharged from the air separation unit as an outlet mixture) comprising 10 to 20% by volume oxygen and nitrogen compared to the transfer mixture are formed in the argon-discharge column.
According to the invention, the apparatus has a fractionation unit provided separately from the air separation unit or units, configured to feed at least some of the outlet mixture of the air separation unit or units to the fractionation unit and fractionate it therein to obtain one or more oxygen fractions enriched in oxygen compared to the outlet mixture or mixtures, and one or more argon fractions enriched in argon compared to the outlet mixture or mixtures.
According to the invention, the one or more oxygen fractions are or include at least one high purity oxygen fraction having an oxygen content of more than 99.9 vol.%, an argon content of less than 100ppm, and a total hydrocarbon content of less than 100 ppb. At least one high-purity oxygen fraction, in particular a liquid high-purity oxygen fraction and/or a gaseous high-purity oxygen fraction.
The device according to the invention is especially configured for carrying out the method explained in the embodiments above. Thus, reference is explicitly made to the above description of the method according to the invention and its advantageous embodiments.
The method proposed according to the invention for retrofitting one or more air separation units comprises that one or more air separation units are equipped with a fractionation unit to obtain the device according to the invention as described above, wherein one or more air separation units are equipped with a fractionation unit without interrupting the operation of one or more air separation units for more than two days.
The invention will be described in more detail below with reference to the drawings, which show preferred embodiments of the invention.
Drawings
Fig. 1 shows an air separation unit for use in an apparatus according to an advantageous embodiment of the invention.
Fig. 2 shows an apparatus according to an advantageous embodiment of the invention.
In the drawings, elements that correspond to each other in structure or function are denoted by the same reference numerals, and the description is not repeated for the sake of clarity. The description of the units and the unit components applies in the same way to the corresponding methods and method steps.
Fig. 1 shows an air separation unit, which is shown in a highly simplified manner and is designated as a whole by 100, which can be used in an apparatus according to an advantageous embodiment of the invention.
For a further explanation of the components of the air separation unit 100, which are only briefly discussed below, reference is explicitly made to, for example, the technical literature cited at the outset, in particular fig. 2.3A of Haering (see above) and the relevant explanation. It should be expressly emphasized that the plurality of material flows are not shown and not explained in the illustration in fig. 1 for reasons of generalization and clarity.
In the air separation unit 100, air is sucked via the filter 1 by means of the main air compressor 2 and compressed to a suitable pressure level. The compressed air stream a formed in this way is fed to the rectification column system 10 after being pre-cooled in the pre-cooling unit 3 and after drying and carbon dioxide removal in the pre-cleaning unit 4 in the main heat exchanger 5, optionally after being split into partial streams which are treated differently and possibly cooled differently, further compressed, turbine or throttle relaxed, as shown here by the outlet point.
In the example shown, the rectification column system 10 has a double column comprising a pressure column 11 and a low-pressure column 12, wherein the pressure column 11 and the low-pressure column 12 are connected in a heat exchange manner via a main condenser 13. Furthermore, an argon-discharge column 14 of the type mentioned at the outset is provided, which has a head condenser 15.
At least the pressure column 11 is provided with cooled pressurized atmospheric air of the compressed air stream a. The lower pressure column 12 is provided with an oxygen-enriched fluid compared to the air of the compressed air stream a, which is withdrawn from the pressure column in the form of a material stream B and is sub-cooled in an optional further step shown here at the outlet point, for example a sub-cooling heat exchanger (not shown), some of which is fed directly into the lower pressure column 12 and some of which is used as coolant in the head condenser 15 of the argon-discharge column 14, is then partly evaporated in the process and then fed into the lower pressure column 12 in the form of an evaporation part and a non-evaporation part. The particular type of cooling of the head condenser 15 of the argon discharge column 14 and the process of feeding the material stream B or an oxygen-enriched fluid as compared to the air of the compressed air stream a into the low pressure column 12 is not critical to the invention.
The transfer mixture comprising the above components is removed from the low-pressure column 12 via a side outlet at the so-called argon belly and transferred to the argon-discharge column 14 in the form of a material stream C. Cryogenic rectification in argon discharge column 14 results in the formation of an argon-depleted liquid sump liquid (which is returned to lower pressure column 12 as stream D) as compared to the transfer mixture, and head gas (which is withdrawn as stream E as the non-condensed portion of the argon-enriched oxygen-containing outlet mixture in head condenser 15 of argon discharge column 14). Reference is explicitly made to the above explanation of the components and the relative contents of the outlet mixture. The outlet mixture E is heated in the main heat exchanger 5 to about ambient temperature, in particular to 250K to 350K, more particularly to 260 to 320K.
Fig. 2 shows a highly simplified device, generally designated 1000, according to one embodiment of the invention. In the example illustrated here, the device 1000 comprises two air separation units, for example but not necessarily of the type shown in fig. 1, and therefore is also denoted here as 100. The components thereof, namely the filter 1, the main air compressor 2, the pre-cooling unit 3, the pre-cleaning unit 3, the main heat exchanger 5 and the rectification column system 10 (the latter is shown here in a common frame), and the argon-rich oxygen-containing outlet mixture of the material flow E (which outlet mixture is discharged from the argon discharge column 14, in particular via the main heat exchanger 5, as shown above) have been explained.
In the apparatus 1000, the hot material streams E are now combined to form a combined stream F, which is compressed in the compressor unit 20 and then supplied to the fractionation unit 200. In fractionation unit 200, the argon-rich oxygen-containing outlet mixture of material stream E or aggregate stream F is separated to obtain (in the example illustrated herein) a gaseous high purity oxygen fraction (UHP-) GOX, a liquid high purity oxygen fraction (UHP-) LOX, a gaseous argon fraction GAR, and a liquid high purity oxygen fraction LAR, particularly by cryogenic rectification.
In the example illustrated herein (but this is in principle optional), the fractionation unit 200 is supplied with a liquid nitrogen stream G and a compressed air stream H from one or both of the air separation units 100.
As shown here in very simplified form, the fractionation unit 200 comprises at least two rectification columns 210, 220 each having a head condenser (not shown separately), wherein one of the at least two rectification columns 210, 220 of the fractionation unit 200 is configured for separating mainly or exclusively oxygen from argon and/or nitrogen and the other or the other of the at least two rectification columns 210, 220 of the fractionation unit 200 is configured for separating mainly or exclusively nitrogen from oxygen and/or argon. Alternatively, the columns 210, 220 may be designed as in EP 299364B1 (columns 10 and 23), for example. The combined stream is then introduced into the lower region of the first column 210 (10 in EP 299364B 1). At an intermediate point, a liquid stream is removed from the first column 210 and fed to the head of the second column 220 (23 in EP 299364B 1). At the bottom of the second column 220, high purity oxygen is withdrawn, and at the top of the first column 210, argon containing little oxygen is withdrawn. In addition, a conventional pure argon column may be provided in which the oxygen-free argon is still nitrogen-free.
The second column 220 may also be omitted if the material stream E/F is completely hydrocarbon free. Instead, the first tower then extends downwards and is provided with bottom heating. The high purity oxygen product is then withdrawn at the bottom of the first column.
Gaseous nitrogen is typically used as the heat transfer medium and heat transfer fluid for heating and cooling the column in fractionation unit 200. If the air separation unit or one of the air separation units is arranged spatially close to the fractionation unit 200, it is alternatively or additionally possible for the dry air to branch off from the feed air of the corresponding air separation unit. Of course, if available, drying pressure from another source may also be used; ; compressed air or another external drying gas.

Claims (15)

1. A method for providing argon and oxygen products by cryogenic air separation, wherein an apparatus (1000) is used with a first air separation unit (100), the first air separation unit (100) having a main heat exchanger (5), a rectification column system (10) with a pressure column (11), a low pressure column (12) and an argon-discharge column (14) with less than 40 theoretical trays, in the first air separation unit (100), the pressure column (11) is supplied with cooled compressed air (a), the low pressure column (12) is supplied with a fluid (B) from the pressure column (11) that is enriched in comparison with the cooled compressed air (a), a transfer mixture (C) comprising 5 to 15% by volume argon and 85 to 95% by volume oxygen is withdrawn from the low pressure column (12), the transfer mixture is transferred to the argon-discharge column (14), and an argon-depleted liquid and an argon-containing head (14) containing 5 to 20% by volume oxygen in comparison with the transfer mixture is formed in the argon-discharge column (12) as a heated air-discharge-head (E) in the at least one of the main heat exchanger(s), the outlet(s) is formed in the at least some of the outlet of the argon-discharge-tank(s) and the outlet(s) is heated, at least some of the heated outlet mixture (E) of the first air separation unit (100) is supplied to a fractionation unit (200) provided separately from the first air separation unit (100) and fractionated therein to obtain an oxygen fraction (GOX, LOX) enriched in oxygen compared to the outlet mixture (E) and an argon fraction (LAR, GAR) enriched in argon compared to the outlet mixture (E).
2. The method according to claim 1, wherein the oxygen fraction (GOX, LOX) is formed from a high purity oxygen fraction having an oxygen content of more than 99.999 volume%, an argon content of less than 5ppm, and a total hydrocarbon content of less than 5 ppb.
3. The method according to claim 1 or claim 2, wherein the outlet mixture (E) is heated to about ambient temperature, in particular to 250K to 350K, in the main heat exchanger (5).
4. A method according to claim 3, wherein the heated outlet mixture (E) is supplied to the separate fractionation unit (200) at about ambient temperature, in particular at a temperature of 250K to 350K.
5. The method according to any of the preceding claims, wherein the apparatus (1000) further comprises a second air separation unit (100), wherein the second air separation unit (100) has a rectifying column system (10) with a pressure column (11), a low pressure column (12) and an argon-discharge column (14) with less than 40 theoretical trays, wherein in the second air separation unit (100) the pressure column (11) is supplied with cooled compressed air (a), the low pressure column (12) is supplied with a fluid (B) enriched with oxygen from the pressure column (11) compared to the cooled compressed air (a), a transfer mixture (C) comprising 5 to 15% by volume argon and 85 to 95% by volume oxygen is withdrawn from the low pressure column (12), the transfer mixture is transferred to the argon-discharge column (14), and a sump liquid depleted of argon and an argon-enriched head gas comprising 5 to 20% by volume oxygen is formed in the argon-discharge column (14) as a heated air mixture in at least some of the second sump (E), and wherein the heat exchange mixture is returned from the second sump (100) to the outlet of the heat exchanger (E), and at least some of the heated outlet mixture (E) of the second air separation unit (100) is supplied to the fractionation unit (200) also formed separately from the second air separation unit.
6. The method according to any of the preceding claims, wherein the pressure column (11) of the first and/or second air separation unit is operated in a pressure range from 3 bar to 7 bar and the low pressure column (12) of the first and/or second air separation unit is operated in a pressure range from 1 bar to 2 bar.
7. Process according to any one of the preceding claims, wherein the oxygen-enriched oxygen fraction (GOX, LOX) is a liquid high purity oxygen fraction (LOX) and/or a gaseous high purity oxygen fraction (GOX).
8. The method according to any of the preceding claims, wherein the one or more argon fractions (GAR, LAR) are or comprise at least one pure argon fraction having an argon content of more than 99.999 vol%, a nitrogen content of 0 to 2ppm and an oxygen content of 0 to 2ppm.
9. The method of claim 8, wherein the at least one pure argon fraction is a liquid pure argon fraction (LAR) and/or a gaseous pure argon fraction (GAR).
10. A process according to any one of the preceding claims, wherein the or each outlet mixture (E) comprises 80 to 85% by volume argon and 2 to 5% by volume nitrogen.
11. An apparatus (1000) for providing argon and oxygen products by cryogenic air separation, the apparatus comprising a first air separation unit (100) having a main heat exchanger (5), a rectifying column system (10) having a pressure column (11) configured to operate in a pressure range of 3 to 7 bar, a low pressure column (12) configured to operate in a pressure range of 1 to 2 bar, and an argon rejection column (14) having less than 40 theoretical trays, the first air separation unit (100) having a feed air line for feeding cooled compressed air (a) into the pressure column (11) and a feed oxygen line for conveying an oxygen-enriched fluid (B) from the pressure column (11) into the low pressure column (12) compared to the cooled compressed air (a), a transfer mixture (C) comprising 5 to 15% by volume argon and 85 to 95% by volume oxygen is withdrawn from the low pressure column (12) and transferred to the argon separation unit (5) as an argon separation unit (5) and an argon separation unit (5) is provided as an outlet for the argon separation unit (100) having a main separation air outlet (20%) from the argon separation unit (14), and is configured to convey at least some of the outlet mixture (E) of the air separation unit (100) from the outlet line to the fractionation unit and to fractionate it therein to obtain an oxygen fraction (GOX, LOX) enriched in oxygen compared to the outlet mixture (E) and an argon fraction (LAR, GAR) enriched in argon compared to the outlet mixture (E).
12. The apparatus of claim 11, wherein the fractionation unit (200) is configured to obtain the oxygen fraction (GOX, LOX) as a high purity oxygen fraction having an oxygen content of more than 99.999 vol%, an argon content of less than 5ppm, and a total hydrocarbon content of less than 5 ppb.
13. The apparatus according to claim 11 or claim 12, further comprising a second air separation unit (100), wherein the second air separation unit (100) comprises a main heat exchanger (5), a rectifying column system (10) having a pressure column (11) configured to operate in a pressure range of 3 to 7 bar, a low pressure column (12) configured to operate in a pressure range of 1 to 2 bar, and an argon-discharge column (14) having less than 40 theoretical trays, wherein the second air separation unit (100) has a feed air line for feeding cooled compressed air (a) into the pressure column (11) and a feed oxygen line for conveying an oxygen-enriched fluid (B) from the pressure column (11) to the low pressure column (12) compared to the cooled compressed air (a), a transfer mixture (C) comprising 5 to 15% by volume argon and 85 to 95% by volume oxygen is withdrawn from the low pressure column (12) and transferred from the low pressure column (12) to the argon-discharge column (14) for transferring the argon-enriched air to the main heat exchanger (5) via the argon-discharge line (5) from the argon-discharge unit (14), wherein the apparatus is configured to transfer at least some of the outlet mixture (E) of the air separation unit (100) from the outlet line to a fractionation unit (200) also formed separately from the second air separation unit (100).
14. A method for retrofitting one or more air separation units (100), characterized in that the first air separation unit (100) is configured with a separate fractionation unit (200) to obtain the apparatus according to any one of claims 11 to 13.
15. The method according to claim 14, wherein the first air separation unit (100) is equipped with the fractionation unit (200) without interrupting the operation of the first air separation unit (100) for more than two days.
CN202280068798.6A 2021-11-10 2022-11-02 Method and apparatus for producing argon and oxygen products and method for retrofitting one or more air fractionation facilities Pending CN118103654A (en)

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DE3722746A1 (en) 1987-07-09 1989-01-19 Linde Ag METHOD AND DEVICE FOR AIR DISASSEMBLY BY RECTIFICATION
US20090320520A1 (en) * 2008-06-30 2009-12-31 David Ross Parsnick Nitrogen liquefier retrofit for an air separation plant
JP6427359B2 (en) * 2014-08-12 2018-11-21 神鋼エア・ウォーター・クライオプラント株式会社 Method and apparatus for producing ultra-high purity oxygen
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US10066871B2 (en) * 2015-07-31 2018-09-04 Praxair Technology, Inc. Method and apparatus for argon rejection and recovery
US11713921B2 (en) 2019-10-17 2023-08-01 Praxair Technology, Inc. System and method for the production of argon in an air separation plant facility or enclave having multiple cryogenic air separation units
CN113739515B (en) * 2021-09-06 2022-10-21 乔治洛德方法研究和开发液化空气有限公司 Method and device for extracting high-purity liquid argon through rich argon

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