Adsorber, purification system and purification method

Abstract

An adsorber for use in a purification system for cryogenic fluid treatment may include a first layer of adsorbent material and a second layer of adsorbent material within a bed of adsorbent material within the adsorber. The first layer may comprise alumina or other water removal adsorbent material, while the second layer may comprise NaMSX or other suitable molecular sieve adsorbent material. The first layer may be sized to be substantially smaller than the second layer to facilitate a preselected ratio of water adsorption to molecular sieve adsorption such that water may penetrate the first layer to the second layer during purification operations, while the volume of the adsorber may be provided in a much smaller size than conventional designs, utilizing much less adsorbent material in the bed. Embodiments may provide increased purification operational capability, as well as reduced need for adsorbent materials.

Description

Technical Field

[0001] The present invention relates to an adsorber, a pre-purification unit device that can be used in a cryogenic fluid processing system and / or a purification system, an adsorber for purifying air in an air separation system, an air separation system, and methods of making and using the same. Background Art

[0002] Adsorbers are typically found in four different common configurations: vertical, vertical crossflow, horizontal, and radial. Examples of these types of adsorbers can be understood from the disclosures of U.S. Pat. Nos. 4,472,178, 4,541,851, 4,784,672, 5,137,548, 5,232,474, 5,425,240, 5,759,242, 5,846,295, 5,855,650, 5,917,136, 6,086,659, 6,106,593, 6,152,991, 6,506,236, 6,599,347, 6,866,075, 7,022,159, 7,285,154 , No. 7,413,595, No. 8,206,669, No. 8,262,783, No. 8,268,044, No. 8,404,024, No. 8,518,356, No. 8,734,571, No. 8,814,985, No. 9,108,145, No. 9,199,190, No. 9,631,864 and No. 9,731,241, U.S. Patent Application Publication Nos. 2011 / 0206581, 2011 / 0219950, 2019 / 0291078 and 2023 / 0027070, Canadian Patent Publication No. 2,357,276A, and European Patent Publication No. EP1 417 995 A1.

[0003] Temperature swing adsorption (TSA) is often used together with technologies such as pressure swing adsorption (PSA) as a pre-purification for the cryogenic distillation process of air. The function of TSA is to remove components with high freezing points, such as ambient moisture (e.g., water vapor, H 2 O) and carbon dioxide (CO 2 ), which would otherwise freeze in downstream processing, causing operability problems such as plugging. 2 O), hydrocarbons (e.g. methane, CH 4 etc.) and other impurities can also be removed by front-end purification to prevent these impurities from accumulating in downstream processes. Summary of the invention

[0004] Conventionally, adsorbers are designed and operated for purifying air or gas feeds to avoid allowing water to penetrate the moisture removal layer to reach the downstream layer of adsorbent material in the adsorber (if present), thereby avoiding any water from being output from the adsorber within the purified fluid, while also allowing the downstream layer of adsorbent material to remove nitrous oxide, carbon dioxide, and other impurities to form a purified fluid to be output from the adsorber. The removal of water in the initial layer of adsorbent material is generally considered critical so that water penetration therethrough can be avoided so that one or more downstream layers of adsorbent material can effectively remove other target impurities. Conventional designs typically configure beds of adsorbent material and set concentration limits for at least one target impurity (e.g., nitrous oxide and / or carbon dioxide concentration) in the fluid output from a pre-purification unit (PPU) to help ensure that water is prevented from penetrating the open state adsorber and entering downstream equipment, while also preventing other target impurities from exceeding preselected thresholds for entering the downstream equipment.

[0005] We have surprisingly discovered that conventional methods of this type have significant disadvantages and inefficiencies which we believe have not been previously recognized or appreciated. Typically, the moisture removal layer will be designed to be a substantial portion of the bed of adsorbent material in the adsorber for removing moisture. For example, such a layer may be at least 50% of the entire bed of material or of the adsorbent material constituting the bed of adsorbent material. We have surprisingly discovered that such an arrangement utilizes too much water to remove the adsorbent material, which may result in the adsorber being sized much larger than is necessary to accommodate its purification purpose and in significant delays in material layering costs to account for conventional moisture removal designs for the adsorber. It has been surprisingly discovered that such conventional designs have higher manufacturing and operating costs, produce more waste in used materials, result in significantly more costs and regeneration delays in the regeneration of the adsorbent material, and present other disadvantages to the flexible and efficient operation of a system for purifying a fluid feed for cryogenic or other processing.

[0006] Embodiments of our adsorbers, PPUs, apparatus, and methods of making and using the same can provide significant improvements in operational flexibility and operational efficiency compared to conventional designs that were surprisingly found to have such disadvantages. For example, embodiments can allow for the safe and efficient use of smaller sized adsorbers that require the use of less material and have lower capital, maintenance, and operating costs.

[0007] Embodiments may also allow regeneration cycles to take less time and / or incur less operating expense due to the smaller size of adsorbers and adsorbent beds that may be utilized. In addition, embodiments may be easier to maintain by providing simpler filling and removal of adsorbent materials via smaller volumes of material, smaller size adsorbers, and other features. The smaller size of adsorbers that may be utilized may provide for a smaller vessel height and also provide for reduced pressure drop compared to conventional systems, which may further enhance their ability to provide improved operational flexibility and improved efficient operation of larger systems incorporating one or more of our adsorbers.

[0008] Some embodiments of our adsorbers may be provided for use in PPU, cryogenic fluid processing, and other environments, wherein the front end first layer of adsorbent material comprises between 10% and 40% of the total mass of the adsorbent material within the adsorber, and the remaining 90% to 60% of the total mass of the adsorbent bed material comprises a molecular sieve layer of material (e.g., NaLSX, NaMSX, 13X, or other suitable molecular sieve adsorbent material). Even when the fluid is at a temperature between 5°C and 30°C, water is allowed to penetrate the first layer into the second layer during the on-state purification process of the fluid, and such ratio ranges (e.g., a range of 1:9 to 1:1.4 parts of moisture removal adsorbent material layer to molecular sieve adsorbent material layer, a range of 1:9 to 1:4 parts of moisture removal adsorbent material layer to molecular sieve adsorbent material layer, etc.) may still provide the desired purification capacity. Surprisingly, embodiments having this type of ratio range are found to be less expensive to manufacture and operate while also having improved operating flexibility and more efficient operation and a suitable and acceptable level of water removal capability that is comparable to, if not better than, conventional designs having significantly greater water removal layer ratios (e.g., 50% of the bed is water removal layer or more than 50% of the bed is water removal layer) which also require significantly larger adsorbent bed volume layers and larger adsorber vessel sizing.

[0009] Still other embodiments may provide this type of improvement for use in PPU, cryogenic fluid processing, and other environments, where the front end first layer of adsorbent material comprises between 10% and 45% of the total mass of adsorbent material within the adsorber, and the remaining 90% to 55% of the total mass of the adsorbent bed material comprises a molecular sieve layer of material (e.g., NaLSX, CaX, or other suitable molecular sieve adsorbent material). This ratio range may provide the desired purification capacity even when the fluid is at a temperature between 5°C and 30°C, allowing water to penetrate the first layer into the second layer during the on-state purification process of the fluid. It has also been surprisingly found that embodiments having this type of ratio range are less expensive to manufacture and operate, while also having improved operational flexibility and more efficient operation and a suitable and acceptable level of water removal capacity that is comparable to, if not better than, conventional designs having significantly greater water removal layer ratios (e.g., 50% of the bed is water removal layer or more than 50% of the bed is water removal layer), which also require significantly larger adsorbent bed volume layers and larger adsorber vessel sizing.

[0010] We believe that embodiments can be provided whereby a first layer of adsorbent material can be sized so that water penetrates the first layer into an adjacent downstream second layer of adsorbent material in a bed of adsorbent material within an adsorber, thereby causing water to be preferentially adsorbed by an upstream portion of the second layer. We believe that this can result in other impurities (e.g., CO) that were previously captured by the upstream portion of the second layer of material being removed. 2 and N 2 O) is released, and the downstream portion of the second layer can then more efficiently adsorb the released impurities (e.g., CO 2 and N 2 O) because there is a higher concentration of other impurities in the fluid to be adsorbed in the second layer due to the adsorption of water and the release of other impurities that may occur. We believe that this function can allow the entire second layer to be more effectively used for adsorption of non-water impurities, can allow the first layer material to be more fully used for water adsorption, and can also allow a larger portion of the material in the adsorbent material bed to be fully used for adsorption.

[0011] In a first aspect, an adsorber for a pre-purification unit (PPU) of a cryogenic fluid processing system is provided. The adsorber may include a container connectable between a compressor system and a heat exchanger and a bed of an adsorbent material positioned in the container. The bed may include a first layer of adsorbent material for removing water and a second layer of adsorbent material for removing water and including carbon dioxide (CO 2 ) and nitrous oxide (N 2The bed of adsorbent material may be positioned and configured such that the first layer is positioned adjacent to the second layer such that during purification of a fluid passing through the bed, water penetrates the first layer to the second layer such that the second layer removes the water as well as these other impurities from the fluid to output a purified fluid without water and wherein these other impurities in the purified fluid are equal to or below at least one preselected threshold.

[0012] The fluid may be air or other gas that may pass through a bed of material within the container. The bed of material may be within a chamber defined by the container. The adsorber may be configured as a radial adsorber, a horizontal adsorber, a vertical adsorber, or other types of adsorbers.

[0013] In a second aspect, the fluid may be air or other gas, the first layer may include alumina, activated alumina, or alumina impregnated with potassium salts, and the second layer may include NaMSX, NaLSX, or 13X. Other embodiments may utilize other types of adsorbent materials for the first and second layers, and may be tuned for specific types of feed gases (e.g., specific process gases or feed gases to be provided for downstream processing of the PPU).

[0014] In a third aspect, the first layer can be smaller than the second layer. For example, the first layer can comprise 5 weight percent (wt%) to 25 wt% of the bed, and the second layer can comprise 95 wt% to 75 wt% of the bed. Other embodiments can utilize other types of layer sizing. In some embodiments, the bed can also include additional layers of adsorbent material to account for purification processes that are also desired to occur via the adsorber.

[0015] For example, in some embodiments, the ratio of the mass of adsorbent material in the first layer to the mass of adsorbent material in the second layer within the bed is between 1:9 and 1:5.7. In other embodiments, the ratio of the mass of adsorbent material in the first layer to the mass of adsorbent material in the second layer within the bed is between 1:1.4 and 1:20. Still other embodiments may utilize other types of ratios of the mass of adsorbent material in the first layer to the mass of adsorbent material in the second layer within the bed discussed herein.

[0016] In a fourth aspect, the fluid may be air or an industrial gas stream.The bed may be configured to operate at a temperature range between 5°C and 30°C or other suitable temperature range (eg, between 5°C and 35°C or between 5°C and 25°C, between 0°C and 35°C, etc.).

[0017] In a fifth aspect, the bed of adsorbent material may be configured such that the first layer may comprise alumina, activated alumina, or alumina impregnated with potassium salts, and the second layer may comprise NaMSX, NaLSX, or 13X. Such embodiments may not require or use a third or other additional layer. Other embodiments may utilize at least one additional layer of material.

[0018] In a sixth aspect, the adsorber of the first aspect may include one or more features of the second, third, fourth, and / or fifth aspects discussed above. Other features discussed in the exemplary embodiments shown and described herein may also be included in such embodiments. Therefore, it should be understood that other embodiments may utilize other features or elements.

[0019] In a seventh aspect, a pre-purification system is provided. The pre-purification system may include an embodiment of our adsorber. For example, the pre-purification system may include an adsorber having a container and an adsorbent material bed, the adsorbent material bed comprising a first layer of adsorbent material for removing water and a first layer of adsorbent material for removing water and carbon dioxide (CO 2 ) and nitrous oxide (N 2 The bed of adsorbent material may be positioned and configured so that the first layer is positioned adjacent to the second layer and is sized so that during purification of a fluid passing through the bed, water penetrates the first layer to the second layer so that the second layer removes water as well as CO from the fluid. 2 and N 2 O, to output a purified fluid having no water therein.

[0020] In some embodiments, the fluid may be air or an industrial gas stream, and the purified fluid may have a CO content equal to or lower than a preselected CO 2 Threshold of CO 2 content, and / or the purified fluid may have a content equal to or lower than the preselected N 2 O content threshold N 2 The O content. The threshold value may be any preselected threshold value (eg, less than or equal to 350 ppb or less than or equal to 150 ppb, etc.).

[0021] In the eighth aspect, the first layer may include alumina, activated alumina, or alumina impregnated with potassium salts, and the second layer may include NaMSX, NaLSX, or 13X. Other embodiments may also utilize other materials for the first and second layers.

[0022] In a ninth aspect, the prepurification system can be provided such that the first layer is smaller than the second layer. For example, the first layer can comprise 5 weight percent (wt%) to 25 wt% of the bed, and the second layer can comprise 95 wt% to 75 wt% of the bed.

[0023] In some embodiments, the ratio of the mass of adsorbent material in the first layer to the mass of adsorbent material in the second layer within the bed is between 1:1.4 and 1:20. In other embodiments, the ratio of the mass of adsorbent material in the first layer to the mass of adsorbent material in the second layer within the bed is between 1:9 and 1:5.7. Still other embodiments may utilize different ratios of the mass of adsorbent material in the first layer to the mass of adsorbent material in the second layer within the bed discussed herein.

[0024] In the tenth aspect, the bed may be configured to operate at a temperature range between 5° C. and 30° C. In other embodiments, the bed may be configured to operate at a temperature range between 5° C. and 35° C., between 0° C. and 35° C., or between 5° C. and 25° C. Still other embodiments may utilize beds configured to operate within different temperature ranges.

[0025] In the eleventh aspect, the pre-purification system of the seventh aspect may include one or more features of the eighth aspect, the ninth aspect, and / or the tenth aspect discussed above. Other features discussed in the exemplary embodiments shown and described herein may also be included in such embodiments. Therefore, it should be understood that other embodiments may utilize other features or elements.

[0026] In a twelfth aspect, a process for purifying a fluid for cryogenic processing is provided. The process may include operating an adsorber to receive a fluid for purification. For example, the adsorber may be an embodiment of an adsorber discussed herein. For example, the adsorber may include a bed of adsorbent material, the bed of adsorbent material including a first layer and a second layer located downstream of the first layer. The first layer may include an adsorbent material different from the adsorbent material of the second layer. The process may also include passing the fluid through the bed so that water in the fluid penetrates the first layer to reach the second layer to be adsorbed in the second layer, thereby removing water from the fluid via the second layer. When removing water from the fluid via the second layer, the second layer may also remove CO from the fluid. 2 and N 2 O.

[0027] In the thirteenth aspect, the temperature of the fluid may be between 5°C and 30°C or other suitable temperature ranges (eg, a temperature range between 5°C and 35°C, between 0°C and 35°C, or between 5°C and 25°C, etc.).

[0028] In the fourteenth aspect, the first layer can comprise alumina, activated alumina, or alumina impregnated with a potassium salt, and the second layer can comprise NaMSX, NaLSX, or 13X.

[0029] In the fifteenth aspect, the second layer may be larger than the first layer. For example, the first layer used in the process may comprise 5 weight percent (wt%) to 25 wt% of the bed, and the second layer used in the process may comprise 95 wt% to 75 wt% of the bed.

[0030] In some embodiments, the ratio of the mass of adsorbent material in the first layer to the mass of adsorbent material in the second layer within the bed is between 1:1.4 and 1:20. In other embodiments, the ratio of the mass of adsorbent material in the first layer to the mass of adsorbent material in the second layer within the bed is between 1:9 and 1:5.7. Still other embodiments may utilize different ratios of the mass of adsorbent material in the first layer to the mass of adsorbent material in the second layer within the bed discussed herein.

[0031] In the sixteenth aspect, the process may further include outputting the purified fluid for cryogenic treatment, such that the purified fluid is free of water and has a CO concentration equal to or lower than a preselected CO concentration. 2 Threshold of CO 2 content, and / or the purified fluid has a content equal to or lower than the preselected N 2 O content threshold N 2 The O content. The threshold value may be any suitable preselected threshold value (eg, less than or equal to 350 ppb or less than or equal to 150 ppb, etc.).

[0032] In the seventeenth aspect, the process of the twelfth aspect may include one or more features of the thirteenth, fourteenth, fifteenth, and / or sixteenth aspects discussed above. Other features discussed in the exemplary embodiments of the processes shown and described herein may also be included in such embodiments. Therefore, it should be understood that other embodiments may utilize other features or elements.

[0033] Additional details, objects, and advantages of our cryogenic fluid processing systems, air separation systems, adsorbers, prepurification systems utilizing one or more adsorbers, and methods of making and using the same will become apparent as the following description of certain exemplary embodiments of the invention proceeds. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Exemplary embodiments of cryogenic fluid processing systems, air separation systems, adsorbers, prepurification systems utilizing one or more adsorbers, and methods of making and using the same are shown in the accompanying drawings included with the accompanying drawings. It should be understood that like reference numerals used in the drawings identify like components.

[0035] Figure 1 Schematic diagram of a first exemplary embodiment of a pre-purification unit (PPU) of the pre-purification system 3.

[0036] Figure 2 is a schematic diagram of a first exemplary embodiment of an adsorber 20 that may be included in the PPU 17 of the pre-purification system 3 .

[0037] Figure 3 is a schematic diagram of a second exemplary embodiment of an adsorber 20 that may be included in the PPU 17 of the pre-purification system 3 .

[0038] Figure 4 Graph showing results from an evaluation of an exemplary embodiment of our adsorber used in a pre-purification process for cryogenic fluid applications.

[0039] Figure 5 Graph showing results from an evaluation of an exemplary embodiment of our adsorber used in a pre-purification process for cryogenic fluid applications.

[0040] Figure 6 Graph showing results from an evaluation of an exemplary embodiment of our adsorber used in a pre-purification process for cryogenic fluid applications.

[0041] Figure 7 Graph showing results from an evaluation of an exemplary embodiment of our adsorber used in a pre-purification process for cryogenic fluid applications for an operating pressure of 15 bar.

[0042] Figure 8 A schematic diagram of a first exemplary embodiment of a cryogenic fluid processing facility having an air separation unit (ASU) utilizing a first exemplary embodiment of a pre-purification system 3 positioned to purify an air stream for feeding to an air separation column assembly 4 for separating the air into oxygen and / or nitrogen streams and other streams (e.g., at least one waste stream and / or an argon stream, etc.).

[0043] Fig. 9 is a flow chart showing an exemplary embodiment of a process for purifying a fluid stream for cryogenic fluid processing. Embodiments of the PPU 17 and cryogenic fluid processing equipment may be configured to utilize this exemplary embodiment of the process. DETAILED DESCRIPTION

[0044] Figure 1 An exemplary pre-purification system 3 is shown that includes a pre-purification unit (PPU) 17. The PPU 17 of the pre-purification system 3 may include a plurality of adsorbers 20. Each adsorber 20 of the PPU 17 may include an adsorbent material layer that may remove a plurality of target elements from a compressed feed to be fed to the PPU 17 for purification via adsorption (e.g., exposure to an adsorbent material that may include an alumina layer, a catalyst material layer, or other suitable adsorbent material layer). The adsorbers of the PPU 17 may include a first adsorbent 17a and a second adsorbent 17b. The first adsorbent 17a and the second adsorbent 17b may each be configured as a vertical adsorbent, a horizontal adsorbent, or other type of adsorbent (e.g., a vertical cross-flow adsorbent or a radial adsorbent, etc.). In some arrangements, the adsorbent may be configured such that a feed stream enters from the bottom or adsorbent vessel and an output stream exits from the top or vessel, or such that a feed stream enters from the bottom or vessel and an output stream exits from the bottom of the vessel.

[0045] The PPU 17 may utilize an arrangement of adsorbers 20 so that they are configured to utilize a temperature swing adsorption process and / or a pressure swing adsorption process. Figure 2 and Figure 3 An illustrative embodiment of an adsorber 20 that may be used with the PPU 17 is shown.

[0046] The first adsorber 17a and the second adsorber 17b of the PPU 17 may be arranged within the PPU 17 so that they operate in parallel, so that while the first adsorber 17a is in operation to perform a purification process by adsorbing a target material from a fluid fed to the PPU 17, the second adsorber 17b may be shut down so that it may be thermally regenerated to regenerate the adsorbent material bed 20b of the adsorber 20. When in a shut down state, the adsorber may not receive a fluid for fluid purification.

[0047] While the second adsorber 17b is in operation to perform a purification process by adsorbing the target material from the air fed to the PPU 17, the first adsorber 17a may be shut down so that it may be thermally regenerated to regenerate the adsorbent material bed 20b of the adsorber 20.

[0048] The regeneration gas stream may be fed to the idle adsorber of the PPU 17 to regenerate the adsorber material by heating the adsorber material so that the impurities adsorbed therein are released and output from the adsorber via the regeneration gas. The output regeneration gas may be discharged to the atmosphere or otherwise disposed of.

[0049] It should be understood that when the adsorber 20 is in an off-line state, it may undergo a regeneration process to regenerate one or more layers of adsorbent material within the adsorber. When returned to an on-line state, the adsorber may operate with improved efficiency due to the regeneration of the adsorbent material, as the regeneration of the material may return the material to a condition close to or at its original state for adsorbing a target material from a fluid stream.

[0050] The PPU 17 can be configured so that the fluid input to the first adsorber or the second adsorber is changed (e.g., via a valve position change, etc.) to switch the parallel adsorbers between their operating and shut-down states (e.g., when the first adsorber is operating, the second adsorber can be shut down, and vice versa). The regeneration gas flow RGF (at Figure 2 and Figure 3 ) may be via a low pressure (LP) column (e.g., Figure 8 The gas may be obtained from the waste stream output from the LP column 11a) shown in FIG. 1 , or may be gas from another source in the plant or ASU system.

[0051] For at least some embodiments, the regeneration gas flow RGF may pass through the vessels of the absorber 20 along a flow path that is opposite to the fluid flow path through the vessels of the adsorber when the adsorber is in an on-stream state. For such embodiments, the inlet of the vessel may serve as the outlet for the regeneration gas during the on-stream state, and the outlet of the vessel may serve as the inlet for the regeneration gas during the off-stream state.

[0052] Each adsorber 20 (e.g., first adsorber 17a, second adsorber 17b, etc.) of PPU 17 may include a bed 20b of adsorbent material held within a container that includes one or more layers of adsorbent material. The first adsorbent layer of the first bed 21 of adsorbent material may be configured via composition, layer thickness, particle size, pore volume, density, and / or chemical structure (e.g., how cations are attached to the zeolite framework), etc., to selectively remove ambient moisture and may also remove CO. 2 and / or other impurities, and the second adsorption layer of the first bed 20b can be configured via composition, layer thickness, particle size, pore volume, density, and / or chemical structure (e.g., how cations are attached to the zeolite framework), etc., to selectively remove CO from the compressed air fed to the PPU 17 when the adsorber 20 is in operation. 2 、N 2 O, heavy hydrocarbons and / or other fluid components.

[0053] By passing a compressed fluid (e.g., a compressed gas) through the adsorbent bed 20b of the operating adsorber of the PPU 17, undesirable components in the fluid stream (such as ambient moisture, CO 2 、N 2 O, hydrogen, carbon monoxide, heavy hydrocarbon components, etc.) can be completely or partially removed. The purified fluid can be output from the PPU 17 to feed a cryogenic fluid processing system (e.g., ASU system 1, etc.) or other equipment processing system.

[0054] Figure 2 and Figure 3 An example is shown of how a fluid stream may enter the vessel of an adsorber 20 as an inlet feed 23 to contact a first layer 21 of adsorbent material within a bed 20a of adsorbent material. The fluid may then pass through a second layer 22 of adsorbent bed 20b. The adsorbent material of the second layer 22 may be different from the adsorbent material of the first layer 21. The purified fluid may then be output as a purified fluid stream 25 via an outlet of the adsorber 20.

[0055] The first layer 21 may be considered a water removal layer or a moisture removal layer. The first layer 21 may also be considered a front layer because it may be positioned to first contact the fluid to be purified when the adsorber is in an in-service state condition for fluid purification (which may also be referred to as an on-state condition or an on-state position). Examples of adsorbent materials that may be included in the first layer 21 include aluminum oxide (Al2O3). 2 O 3 ), activated alumina or activated alumina impregnated with potassium salt.

[0056] The second layer 22 may be considered a molecular sieve layer. The second layer 22 may also be considered a back-end layer because it may be positioned to contact the fluid to be purified after the fluid has passed through the first layer 21 when the adsorber is in an on-state condition for fluid purification. Examples of adsorbent materials that may be included in the second layer 22 include NaMSX, CaX, 13X, NaX, NaLSX, or other suitable molecular sieve layer adsorbent materials that may promote CO 2 、N 2 O. Any moisture (e.g., water) may be intentionally allowed to be adsorbed through the first layer 21 discussed herein (e.g., core-shell adsorbent material or alumina / zeolite mixture of adsorbent material, etc.). The adsorbent material of the second layer 22 may also be configured to remove other impurities (e.g., hydrocarbons, etc.).

[0057] Conventionally, the adsorber 20 is designed and operated in a PPU to avoid allowing water to penetrate the moisture removal layer to reach the downstream layer (if present), or to exit the adsorber, where the water is in the purified fluid. This need to avoid water from exiting the PPU is generally to avoid freezing of the water in downstream processing, which can lead to serious and expensive repair problems (e.g., equipment failure, plugging, etc.). Conventional designs typically configure a bed of adsorbent material 20b and set limits on the concentration of nitrous oxide and / or carbon dioxide in the fluid exiting the PPU to help ensure that water is prevented from penetrating the water removal layer of the adsorber, and that undesirable concentrations of nitrous oxide and carbon dioxide are prevented from exiting the adsorber for an open state, to avoid, for example, such impurities from entering downstream equipment.

[0058] We have surprisingly discovered that conventional approaches of this type have significant disadvantages and inefficiencies that result in conventional adsorbers unnecessarily utilizing large beds of adsorbent material with sized for the moisture removal layer, which is oversized due to concerns about water penetration through the adsorber into downstream equipment. For example, it has been surprisingly discovered that the water removal layer or moisture removal layer in the first layer 21 material can account for 10% to 20% of the total volume or mass of the adsorbent material bed 20b and provide sufficient water adsorption to provide a long-lived adsorbent material bed 20b that is capable of preventing water penetration from the adsorber 20 while also removing suitable levels of nitrous oxide and carbon dioxide from the fluid to be treated. Furthermore, it has been surprisingly discovered that such conditions exist for a large operating temperature range for the adsorber 20, which can be in the range of, for example, 5°C to 30°C or 5°C to 25°C.

[0059] Figure 4 Shown is a graph reflecting evaluation work we performed on an exemplary embodiment of our adsorber, wherein a nitrous oxide concentration of 105 parts per billion (ppb) in the adsorber outlet stream was the control setting for adsorber operation in the evaluations performed. Figure 4The graph of FIG. 1 shows exemplary adsorption layer mass ratios for a temperature operating range of 5° C. to 30° C. (and a range of 5° C. to 25° C.) where the first layer 21 comprises alumina and the second layer 22 comprises NaMSX (line with triangular data point markers) or 13X (solid line with circular data point markers). It was surprisingly found that as the temperature increased within this range, from 5° C. to 25° C., the mass percentage of alumina could be maintained at about 20 weight percent (wt%) and 13X could be maintained at 80 wt% of the total mass of the adsorption bed 20b. It was also surprisingly found that as the temperature increased within the operating temperature range of 5° C. to 30° C., the mass percentage of alumina could be maintained at 25 wt% to 15 wt%, while the mass of NaMSX could be maintained at 75 wt% to 85 wt% of the total mass of the adsorption bed 20b.

[0060] Figure 5 A graph reflecting additional evaluation work we have performed on exemplary embodiments of our adsorber is shown, showing exemplary adsorption layer mass ratios for a temperature operating range of 5°C to 30°C (as well as a range of 5°C to 25°C), where the first layer 21 comprises alumina and the second layer 22 comprises NaMSX (line with asterisk* data point markers) or 13X (line with triangle data point markers). A nitrous oxide concentration of 105 ppb in the adsorber outlet stream was the control setting for adsorber operation in the evaluations performed. It was surprisingly found that as the temperature increased within this range, from 5°C to 25°C, the mass percentage of alumina could be maintained at about 20 weight percent (wt%), and 13X could be maintained at 80 wt% of the total mass of the adsorbent bed 20b. It was also surprisingly found that as the temperature increased within the operating temperature range of 5°C to 30°C, the mass percentage of alumina could be maintained at 25 wt% to 15 wt%, and the mass of NaMSX could be maintained at 75 wt% to 85 wt% of the total mass of the adsorbent bed 20b. It was also surprisingly found that from 5°C to 20°C, the NaMSX second layer 22 can be maintained at 75 wt% of the total mass of the adsorbent bed 20b, and the alumina first layer 21 can be maintained at 25 wt%.

[0061] Figure 6A graph reflecting additional evaluation work we have performed on an exemplary embodiment of our adsorber configured for temperature swing pressure swing adsorption (TPSA) is shown, showing exemplary adsorption layer mass ratios for a temperature operating range of 5°C to 30°C (as well as a range of 5°C to 25°C) where the first layer 21 comprises alumina and the second layer 22 comprises NaMSX (line with asterisk* data point markers), 13X (line with triangle data point markers), or NaLSX (line with circle data points). A nitrous oxide concentration of 105 ppb in the adsorber outlet stream was the control setting for adsorber operation in the evaluations performed. It was also surprisingly found that as the temperature increased over the operating temperature range of 5°C to 30°C, the mass percentage of alumina could be maintained at 25 wt% to 30 wt%, while the masses of NaMSX and 13X could each be maintained at 75 wt% to 70 wt% of the total mass of the adsorbent bed 20b. It has also been surprisingly found that from 5°C to 30°C, the NaMSX second layer 22 can be maintained at a weight percentage between 65 wt% and 75 wt% of the total mass of the adsorbent bed 20b, and the alumina first layer 21 is maintained such that it is between 25 wt% and 35 wt%.

[0062] Figure 7 Yet another graph reflecting additional evaluation work we performed on an exemplary embodiment of our adsorber at an operating pressure of 15 bar is shown, the graph showing exemplary adsorption layer mass ratios for a temperature operating range of 5°C to 30°C (as well as a range of 5°C to 25°C) where the first layer 21 comprises alumina (solid line with triangular data point markers) and the second layer 22 comprises 13X (dashed line with triangular data point markers). A nitrous oxide concentration of 105 ppb in the adsorber outlet stream was the control setting for adsorber operation in the evaluations performed. Surprisingly, it was found that as the temperature increased over the operating temperature range of 5°C to 30°C, the mass percentage of alumina could be maintained at 5 wt% to 10 wt%, while the mass of 13X could be maintained at 95 wt% to 90 wt% of the total mass of the adsorbent bed 20b.

[0063] Based on the evaluations performed, it was surprisingly determined that suitable adsorbers can be provided for PPU operation purposes, with adsorbers having a surprisingly small proportion of water adsorbed layer compared to the downstream molecular sieve layer. In some embodiments, for an operating temperature range of 5°C to 30°C, the ratio of the mass of water adsorbed (e.g., alumina) material to the mass of molecular sieve adsorbed (e.g., 13X or NaMSX or NaLSX) can range from 1:20 to 1:10 or 1:9 to 1:4. In some configurations and embodiments, for an operating temperature range of 5°C to 30°C, this range can be 1:4 or can be in the range of a ratio of 1:1.4 to 1:5.7. In other embodiments, for an operating temperature range of 5°C to 30°C, the ratio of the mass of water adsorbed (e.g., alumina) material to the mass of molecular sieve adsorbed (e.g., 13X or NaMSX or NaLSX) can range from 1:20, between 1:20 and 1:10, can be 1:9, or can be 1:9 to 1:5.7.

[0064] For the embodiments of the adsorbent material bed 20b, it was found that the adsorbent material volume concentration ratio has a similar range. For example, in some embodiments, for the operating temperature range of 5°C to 30°C for the adsorbent material bed 20b, the ratio of the volume percent (vol%) of the water adsorbent (e.g., alumina) material layer (e.g., first layer material 21) to the vol% of the molecular sieve adsorbent (e.g., 13X or NaLSX or NaMSX) layer (e.g., second layer material 22) can be in the range of 1:1.4 to 1:4 (e.g., this ratio can be 1:4, 1:3, or between 1:1.4 and 1:4, etc.).

[0065] Some embodiments of the adsorber 20 may be provided such that no third nitrous oxide removal layer of any type is required downstream of the second layer 22. Such embodiments may be provided with only two layers of adsorbent material.

[0066] It has been discovered that embodiments of adsorber 20 that can use alumina as the first layer adsorbent material 21 and NaMSX as the second layer adsorbent material 22, wherein the first layer is about 20 vol% to about 20 wt% of the entire bed 20b, and NaMSX is about 80 vol% to about 80 wt% of the entire bed 20b (e.g., NaMSX is 75 wt% to 85 wt% of the bed 20b and 75 vol% to 85 vol% as the second layer 22, and alumina is the remainder of the bed as the first layer 21) provide a significant reduction in overall adsorbent bed volume requirements, and provide water removal, CO removal, and 2 Remove and N 2 O removal, which avoids water penetration of the adsorber, and based on evaluations of examples of our adsorber used in PPU 17 embodiments, for a preselected purification operation cycle time of at least 2 hours (and between 2 hours and 4 hours), only CO is allowed to2 and N 2 O breaks through at or below a preselected threshold. Some embodiments may be provided with such a configuration so that between 14% and 40% volume reduction may be provided for sizing of the adsorber compared to conventional designs.

[0067] In evaluations of embodiments of our adsorber 20 having a first layer 21 of relatively small overall size of bed 20b (e.g., no more than 30% of the size of the bed and more than 5% or 10% of the size of bend 20b) and a second layer 22 of large overall size of the bed (e.g., at least 70% of the size of bed 20b and no more than 90% or 95% of the overall size of bed 20b), it was found that allowing water to penetrate the first layer 21 to adsorb within the second layer 22 provides an unexpected benefit that results in more efficient utilization of the adsorption capacity of the entire bed 20b while still preventing water from penetrating the adsorber without detracting from the ability of the second layer to remove sufficient levels of N from the fluid fed to the adsorber 20. 2 O and CO 2 Because water entering the second layer 22 may have a previously unforeseen effect on the adsorbent material, it was found that this unexpected and surprising event would occur.

[0068] For example, we believe that water penetration through the first layer 21 into the second layer 22 may result in water being preferentially adsorbed by the upstream portion of the second layer 22, which may result in the CO previously captured by the material being 2 and N 2 O is released. The downstream portion of the second layer 22 can then more efficiently adsorb the released CO 2 and N 2 O, because there is a higher concentration of CO in the fluid to be adsorbed in the second layer due to the adsorption of water and possible release of other impurities 2 and N 2 O. This allows the entire second layer 22 to be more effectively used to adsorb non-water impurities (e.g., CO 2 and N 2 O) and allows a greater portion of the material within bed 20b to be fully utilized for adsorption.

[0069] For example, as it relates to improved utilization of bed 20b, the entire first layer 21 can be more effectively utilized because water is allowed to penetrate the layer. This allows the downstream portion of the first layer 21 to be fully utilized or more fully utilized for adsorption compared to conventional designs that prevent water from penetrating the first front layer. In addition, the second layer 22 can be more fully utilized as described above, so that a larger area of ​​the second layer 22 is more fully utilized for adsorption of impurities (e.g., water, CO 2 and N 2 O), which also allows a larger area of ​​the second layer 22 to be more fully utilized for adsorption compared to conventional designs.

[0070] Figure 8 An exemplary apparatus 1 that may be configured for an exemplary process of cryogenic fluid processing is shown. Embodiments of the apparatus 1 may utilize embodiments of the PPU 17 and / or one or more adsorbers 20 discussed above. For example, Figure 8 Embodiments of the invention may be configured as equipment that may include a cryogenic fluid processing system (e.g., an air separation unit (ASU) system 1). The ASU system 1 may be configured as a cryogenic air distillation system for producing one or more output streams to provide one or more desired products (e.g., oxygen and / or liquid oxygen and / or nitrogen and / or liquid nitrogen and / or argon and / or liquid argon and / or other fluid streams, etc.). In some embodiments, the ASU system 1 may be an equipment. In other embodiments, the equipment may include the ASU system 1 as a component of a larger facility. For example, the equipment including the ASU system 1 may be an industrial power plant, a large manufacturing facility, or other type of equipment. Embodiments of the equipment or ASU system 1 may utilize a controller to help monitor and / or control the operation of the equipment and / or ASU system 1.

[0071] The ASU system 1 may be configured to include a pre-purification system 3 configured to purify an intake stream of air to remove impurities from the air, which is fed to an air separation tower assembly 4 to separate the air into one or more fluid product streams and one or more fluid waste streams. The one or more product streams may include at least one nitrogen stream and / or at least one oxygen stream, and may also include one or more argon streams or other air components. The air separation tower assembly 4 may also output one or more fluid waste streams. The waste streams may be discharged into the atmosphere and / or used in one or more other equipment processes.

[0072] The air separation tower assembly 4 may include a multi-tower assembly 11 including a low-pressure tower 11a positioned above a high-pressure tower 11b. In a multi-tower tower arrangement, a reboiler-condenser 11c may be positioned between the high-pressure tower 11b and the low-pressure tower 11a. The high-pressure tower 11b may be considered as the first tower of the multi-tower assembly, which operates at the highest pressure of the towers of the multi-tower tower assembly. For example, a high-pressure (HP) tower 11b may operate at a pressure higher than the operating pressure of a low-pressure (LP) tower 11a, which may be considered as the second tower of the multi-tower assembly.

[0073] In some embodiments, LP column 11a may operate at a pressure between 1.1 atm and 5 atm, between 1.1 atm and 3 atm, or at a pressure greater than 1 bar and less than 5 bar, and HP column 11b may operate at a pressure between 4.5 atm and 15 atm, or at a pressure greater than 4 bar and less than 15 bar.

[0074] from Figure 1 and Figure 8As can be best understood in FIG. 1 , an intake stream 10 of air or industrial gas may pass through a compressor system 13 to compress the fluid to a higher preselected pressure. The pressurized fluid may be output from the compressor system 13 and fed to a prepurification unit (PPU) 17 of the prepurification system 3 via a compressed fluid feed conduit. The PPU 17 may be configured to purify the compressed fluid stream output from the compressor system 13 to remove impurities from the fluid (e.g., water and other impurities as described above). For example, the PPU 17 may be configured as an adsorption system designed to remove undesirable impurities such as, for example, carbon dioxide (CO 2 ) from the fluid. 2 ), carbon monoxide (CO), water (H 2 O) and nitrous oxide (N 2 O). The PPU 17 may be configured for pressure swing adsorption (PSA), temperature swing adsorption (TSA), or temperature swing pressure swing adsorption (TPSA).

[0075] An optional PPU pre-cooler 14 may be positioned between the compressor system 13 and the PPU 17 to cool the compressed fluid to a preselected PPU temperature or a temperature within a PPU temperature range before the compressed fluid is fed to the PPU 17. The PPU pre-cooler 14 may be (or include) a chiller, a mechanical chiller, an absorption chiller, or a heat exchanger that receives a cooling medium for cooling the fluid.

[0076] Purified compressed fluid may be output from the PPU 17 (e.g., as the purified fluid stream 25 discussed above) and fed to the main heat exchanger 29 via a heat exchanger feed conduit. Prior to being fed to the main heat exchanger 29, the purified fluid may be fed from the PPU 17 to a booster compressor 18 for further compressing at least a portion of the purified fluid output from the PPU 17 to a higher pressure. In such embodiments, all of the compressed purified fluid output from the PPU 17 may undergo further compression, or the stream may be split such that a first portion of the purified fluid output from the PPU 17 is fed directly to the main heat exchanger 29, while a second portion of the purified fluid output from the PPU 17 is fed to the booster compressor 18 to undergo further compression to a higher pressure before the second portion is fed to the main heat exchanger 29. The booster compressor feed conduit and the booster compressor output conduit may be arranged to facilitate feeding of fluid from the PPU 17 to the booster compressor 18 , and output of further compressed fluid from the booster compressor 18 to the main heat exchanger 29 .

[0077] In other embodiments, booster compressor 18 may not be utilized, and the entire purified fluid output from PPU 17 may be fed to main heat exchanger 29 via the main heat exchanger feed conduit.

[0078] The main heat exchanger 29 may be configured to cool the compressed purified fluid output from the PPU 17. Cooling may be provided via one or more fluid streams output from the air separation tower assembly 4. For example, one or more streams of nitrogen fluid and / or oxygen fluid may be output from the air separation tower assembly 4, and thus one or more fluid streams pass through the main heat exchanger 29 to serve as a cooling medium for cooling the compressed purified fluid output from the PPU. The fluid streams from the air separation tower assembly 4 may include at least one nitrogen stream and at least one oxygen stream (e.g., a liquid oxygen stream, LOX). When these fluid streams output from the air separation tower assembly 4 pass through the main heat exchanger 29, these fluid streams may be warmed by the compressed purified fluid. For example, in an embodiment where a LOX stream is fed to the main heat exchanger 29 as a cooling medium, the LOX stream may be heated so that it is output from the main heat exchanger 29 as a gaseous oxygen stream (GOX).

[0079] The cooled purified fluid can be output from the main heat exchanger 29 for being fed to the air separation tower assembly 4 via at least one air separation tower assembly feed conduit. The first portion of the compressed purified air can be fed to the HP tower 11b of the air separation tower assembly 4. A portion of the first portion can be diverted therefrom to form a third portion of the feed fluid. The third portion can be output from the main heat exchanger 29 and fed to the expander 31 to reduce the pressure of the third portion and also reduce the temperature of the portion of the fluid for feeding to the LP tower 11a. Then, the third portion of the air can be fed from the expander 31 to the LP tower 11a of the air separation tower assembly 4 via the expander LP feed conduit positioned between the expander 31 and the low pressure (LP) tower 11a.

[0080] A second portion of the compressed and purified fluid (a portion that may be further compressed via booster compressor 18) may be output from main heat exchanger 29 and also fed to LP column 11a. That being said, in embodiments that do not utilize booster compressor 18, this second portion of the fluid may not be present. In such embodiments, if a third portion of the fluid fed to expander 31 via a split of the first portion of the compressed purified fluid fed to main heat exchanger 29 is utilized, this third portion may be considered the second portion of the fluid rather than the third portion.

[0081] HP column 11b may be positioned and configured to process a cooled first portion of the purified and pressurized fluid fed to HP column 11b to form a first HP nitrogen-rich vapor stream that is fed to first reboiler-condenser 11c. In some embodiments, the HP nitrogen-rich vapor stream may comprise 100 volume percent to 99 volume percent (vol%) nitrogen, or at least 95 vol% nitrogen.

[0082] HP tower 11b can also form a first HP oxygen-rich stream. The HP oxygen-rich stream can be a fluid that is a liquid, a vapor, or a combination of a liquid and a vapor. In some embodiments, the HP oxygen-rich stream can include 30 vol% to 40 vol% oxygen and 1 vol% to 3 vol% argon, and the balance nitrogen (e.g., 69 vol% to 57 vol% nitrogen).

[0083] The first HP nitrogen-rich vapor stream may be fed to a reboiler-condenser 11c to form an HP condensate stream, which may be split into a plurality of portions via a conduit arrangement including at least one valve or other splitting mechanism. For example, a first portion of the HP condensate stream may be output from the first reboiler-condenser 11c and subsequently recycled back to the HP column 11b as an HP reflux stream via an HP reflux stream conduit.

[0084] A second portion of the HP condensate stream may be output from the reboiler-condenser 11c and then fed to the cryocooler 35 via a cryocooler feed conduit. The cryocooler 35 may be a heat exchanger that may cool the second portion of the HP condensate stream so that the second portion is at a lower temperature suitable for feeding to the LP column 11a as a nitrogen-rich LP feed, which is fed to the LP column 11a via a nitrogen-rich LP feed conduit extending from the cryocooler 35 to the LP column 11a. The second portion of the HP condensate stream may be reduced in pressure for feeding to the LP column (e.g., via a valve of the nitrogen-rich LP feed conduit extending from the cryocooler 35 and / or via another type of pressure reducing mechanism included in this conduit). The nitrogen-rich LP feed may be a substantially nitrogen-rich liquid feed (e.g., completely liquid, at least 90 vol% liquid, at least 80 vol% liquid, etc.).

[0085] The first HP oxygen-rich stream may be fed to a cryogenic cooler 35 (not shown) for cooling. Alternatively, the first HP oxygen-rich stream may forgo such cooling via the cryogenic cooler 35. In some embodiments, the first HP oxygen-rich stream may pass through an HP oxygen-rich stream conduit extending from HP tower 11b, the HP oxygen-rich stream conduit being configured such that the HP oxygen-rich stream output from HP tower 11b may be reduced in pressure via a pressure reducing mechanism (e.g., an expander, a valve, etc.), and then fed to LP tower 11a as a substantially liquid oxygen-rich feed entering LP tower 11a.

[0086] Reflux for LP column 11a may be provided via a nitrogen-rich LP feed fed to LP column 11a via a nitrogen-rich LP feed conduit extending from cryogenic cooler 35 to LP column 11a. As discussed above, the nitrogen-rich LP feed may be formed via a second portion of the HP condensate stream output from reboiler-condenser 11c. There may be additional liquid provided via one or more of the oxygen-rich feeds fed to LP column 11a.

[0087] Rising vapor or column boils for LP column 11a may also be formed via reboiler-condenser 11c and may be fed to LP column 11a such that the vapor (or gas) within LP column 11a flows countercurrently to the liquid fed to LP column 11a (e.g., nitrogen-rich LP feed flows downward as rising vapor flows upward in LP column 11a, etc.).

[0088] LP tower 11a is operable to output a plurality of separated fluid streams. Some of these fluid streams may be considered nitrogen waste streams (e.g., at least one nitrogen-rich waste stream) of fluids primarily composed of nitrogen gas and / or liquid nitrogen. For example, LP tower 11a is operable to output an upper vapor waste stream and a first LP oxygen-rich liquid stream. In at least some embodiments, LP tower 11a may also output a top nitrogen-rich vapor output stream (not shown), a first argon-rich vapor stream (not shown), and one or more other output streams.

[0089] An upper vapor waste stream may be output from the LP column 11a and fed to the cryocooler 35 for use as a cooling medium for cooling a second portion of the HP condensate stream output from the reboiler-condenser 11c and fed to the cryocooler 35 via a cryocooler feed conduit. This waste vapor stream may then be output from the cryocooler 35 and fed to the main heat exchanger 29 for use as a cooling medium therein before being output from the main heat exchanger 29 as a waste stream which may be vented to the atmosphere or otherwise used in equipment that may be connected to the ASU system 1 (e.g., for mixing with flue gas or passing through another heat exchanger for subsequent use in equipment, etc.).

[0090] The first LP oxygen-rich liquid stream output from LP column 11a may be fed to a pump 37 to increase the pressure of the stream before it is fed to main heat exchanger 29 for use as a cooling medium. In some embodiments as described above, the warm oxygen-rich stream may be output from the main heat exchanger as a GOX stream.

[0091] As discussed above, embodiments of the PPU 17 utilizing embodiments of our adsorber 20 may allow the ASU system 1 to operate more efficiently while also avoiding undesirable levels of impurities from entering equipment downstream of the PPU. For example, embodiments of the PPU 17 may be operated such that an open state of the PPU 17 adsorber 20 is able to remove all of the water from the compressed fluid fed to the PPU for purification, and may remove sufficient N 2 O and CO 2 , making CO 2 Equal to or less than 1 ppm CO in the output purified fluid 2 or other pre-selected CO 2 The content threshold, and N 2O is equal to or less than 350 parts per billion (ppb) or other preselected N in the output purified fluid 2 The PPU 17 can be controlled and operated so that when CO in the output fluid is detected, 2 and / or N 2 When the O content is equal to or sufficiently close to the preselected impurity threshold content level, the open state adsorber is switched to a closed state condition (which may also be referred to as a shutdown state or shutdown condition) to be regenerated via a regeneration flow, while the closed state adsorber is switched to an open state to receive a compressed fluid to purify the fluid. As discussed above, the cycle of the open state adsorber and the closed state adsorber may occur repeatedly. In some embodiments, the cycle time of the open state and closed state cycle may be between 2 hours and 8 hours, greater than 1 hour and less than 8 hours, between 1 hour and 6 hours, between 4 hours and 6 hours, or other time periods.

[0092] Fig. 9 An exemplary process for purifying a fluid stream for cryogenic fluid processing is shown. The embodiments of the PPU 17 and cryogenic fluid processing equipment discussed above may be configured to utilize this exemplary embodiment of the process.

[0093] like Fig. 9 As shown, the first step S1 of the process may include filling the vessel of adsorber 20 to have a bed 20b of adsorbent material including a first layer 21 and a second layer 22. The first layer may include alumina and the second layer may include a suitable molecular sieve adsorbent material (e.g., 13X, NaMSX, NaLSX).

[0094] In a second step S2, the adsorber 20 with the formed bed 20b may be positioned to receive a fluid to purify the fluid for subsequent cryogenic processing. For example, the adsorber may be included in the PPU 17 of the pre-purification system 3.

[0095] In a third step S3, the adsorber 20 may be operated so that it receives a fluid to be purified. The adsorber 20 may be operated so that water in the received fluid passes through or penetrates the first layer 21 upstream of the second layer 22, so that some of the water in the fluid enters the second layer 22 to be adsorbed by the second layer 22, while no water flows out of the adsorber 20. As the fluid passes through the second layer 22, other impurities in the fluid to be purified may be removed via adsorption using the adsorbent material of the second layer 22. These other impurities adsorbed by the second layer 22 may include, for example, CO 2 as discussed above. 2 and N 2 O.

[0096] In a fourth step S4, the adsorption capacity of the bed 20b may be detected as meeting or being at a preselected level for switching the adsorber 20 to an off-state condition for regeneration of the adsorbent material bed 20b as discussed above. Such detection may be performed after one or more hours of operation (e.g., 2 hours to 8 hours of operation, 2 hours to 6 hours of operation, 4 hours to 6 hours of operation, at least 3 hours of operation and less than or equal to 8 hours of operation, every 8 hours of operation, every 6 hours of operation, every 2 hours of operation, etc.). Detection may be provided via at least one concentration sensor or other sensor that monitors the concentration of one or more impurities (e.g., N 2 O and / or CO 2 The controller may receive data from one or more sensors to automatically control valves or other components to facilitate the switching of the adsorber 20 of the PPU 17 between its open state and closed state.

[0097] In the fifth step S5, the regeneration gas flow RGF may enter the closed state adsorber 20 to heat the adsorbent material, release the adsorbed impurities from the material, so that the adsorbent material can be regenerated for subsequent purification purposes, and the adsorber 20 may be returned to the open state condition. Then, after the adsorber currently in the open state condition reaches the adsorption capacity limit predefined or preselected by the operator, the adsorber 20 may be switched to the open state condition.

[0098] It should be appreciated that embodiments of the process may allow for significant benefits as described above. For example, embodiments may allow for improved and greater utilization of the material of bed 20b, while also allowing for the use of smaller sized adsorbers for the purification process as discussed above. In addition, as discussed above, the efficiency of bed 20b regeneration and filling of the vessels of adsorber 20 to form the bed may be improved.

[0099] It should be understood that the embodiments explicitly shown and discussed herein may be modified to meet a specific set of design goals or a specific set of design criteria. For example, the arrangement of valves, pipes and other conduit elements (e.g., conduit connection mechanisms, tubes, seals, etc.) used to interconnect different units of the equipment for fluid communication of fluid flows between different units may be arranged to meet a specific equipment layout design that takes into account the available area of ​​the equipment, the sizing equipment of the equipment, and other design considerations. As another example, the flow rate, pressure, and temperature of the fluid through the adsorber and through other equipment elements may be varied to take into account different equipment design configurations and other design criteria. As yet another example, the material composition of the different structural components used for the adsorber 20, PPU 17, and ASU system 1 may be any type of suitable material that may be required to meet a specific set of design criteria. For example, in some contemplated embodiments, some embodiments may utilize at least one third layer and / or one or more other additional layers of adsorbent material. In addition, embodiments may be used in conjunction with any type of adsorber container (radial, vertical, horizontal, vertical cross flow, etc.) for PPU 17.

[0100] It should be understood that embodiments of the ASU system 1 may be configured as an air separation plant or incorporated into another type of plant in which at least one adsorber 20 may be utilized. The plant, adsorption system, PPU 17, and adsorber 20 may each be configured to include process control elements positioned and configured to monitor and control operations (e.g., temperature and pressure sensors, flow sensors, an automated process control system having at least one workstation including a processor, non-volatile memory, and at least one transceiver for communicating with the sensor elements, valves, and a controller for providing a user interface for the automated process control system that may be executed at the workstation and / or another computer device of the plant, etc.).

[0101] As another example, it is contemplated that certain features described separately or as part of an embodiment may be combined with other separately described features or parts of other embodiments. Thus, the elements and actions of the various embodiments described herein may be combined to provide further embodiments. Thus, although certain illustrative embodiments of adsorbers, adsorption systems, PPUs, apparatus having adsorption systems utilizing one or more of the adsorbers, ASU systems, cryogenic fluid processing systems, and methods of making and using the same have been shown and described above, it should be clearly understood that the invention is not limited thereto, but may be otherwise variously implemented and practiced within the scope of the following claims.

Claims

1. An adsorber for a pre-purification unit (PPU) of a cryogenic fluid processing system, comprising: a container connectable between the compressor system and the heat exchanger; a bed of adsorbent material positioned in the vessel, the bed comprising a first layer of adsorbent material for removing water and a second layer of adsorbent material for removing water and other impurities including carbon dioxide (CO2) and nitrous oxide (N2O); The bed of adsorbent material is positioned and configured so that the first layer is positioned adjacent to the second layer so that during purification of a fluid passing through the bed, water penetrates the first layer to the second layer so that the second layer removes water and the other impurities from the fluid to output a purified fluid without water, and the other impurities are equal to or below at least one preselected threshold.

2. The adsorber according to claim 1, wherein the fluid is air or other gas, the first layer comprises alumina, activated alumina or alumina impregnated with potassium salt, and the second layer comprises NaMSX, NaLSX or 13X.

3. The adsorber of claim 2, wherein the first layer comprises 5 weight percent (wt%) to 25 wt% of the bed, and the second layer comprises 95 wt% to 75 wt% of the bed.

4. The adsorber of claim 1, wherein the fluid is air or an industrial gas stream and the bed is configured to operate at a temperature range between 5°C and 30°C.

5. The adsorber of claim 1, wherein the first layer comprises alumina, activated alumina, or alumina impregnated with a potassium salt, and the second layer comprises NaMSX, NaLSX, or 13X. The adsorber of claim 1 , wherein the first layer is smaller than the second layer.

7. The adsorber of claim 1, wherein the ratio of the mass of the adsorbent material of the first layer to the mass of the adsorbent material of the second layer in the bed is between 1:9 and 1:5.

7.

8. The adsorber of claim 1, wherein the ratio of the mass of the adsorbent material of the first layer to the mass of the adsorbent material of the second layer in the bed is between 1:1.4 and 1:

20.

9. A pre-purification system comprising: an adsorber having a container having a bed of adsorbent material including a first layer of adsorbent material for removing water and a second layer of adsorbent material for removing water as well as carbon dioxide (CO2) and nitrous oxide (N2O); The bed of adsorbent material is positioned and configured so that the first layer is positioned adjacent to the second layer, and is sized so that during purification of a fluid passing through the bed, water penetrates the first layer to reach the second layer, so that the second layer removes water as well as CO2 and N2O from the fluid to output a purified fluid without water therein.

10. The pre-purification system of claim 9, wherein the fluid is air or an industrial gas stream, and the purified fluid has a CO2 content equal to or below a preselected CO2 content threshold, and / or the purified fluid has a N2O content equal to or below a preselected N2O content threshold.

11. The prepurification system of claim 9, wherein the first layer comprises alumina, activated alumina, or alumina impregnated with a potassium salt, and the second layer comprises NaMSX, NaLSX, or 13X.

12. The prepurification system of claim 9, wherein the first layer comprises 5 weight percent (wt%) to 25 wt% of the bed, and the second layer comprises 95 wt% to 75 wt% of the bed.

13. The pre-purification system of claim 9, wherein the bed is configured to operate at a temperature range between 5°C and 30°C.

14. The prepurification system of claim 9, wherein the bed is configured such that a third layer is not utilized, the first layer comprises alumina, activated alumina, or alumina impregnated with a potassium salt, and the second layer comprises NaMSX, NaLSX, or 13X.

15. The prepurification system of claim 9, wherein the ratio of the mass of the adsorbent material of the first layer to the mass of the adsorbent material of the second layer within the bed is between 1:1.4 and 1:

20.

16. The prepurification system of claim 9, wherein the ratio of the mass of the adsorbent material of the first layer to the mass of the adsorbent material of the second layer in the bed is between 1:9 and 1:5.

7.

17. The pre-purification system of claim 9, wherein the first layer is smaller than the second layer.

18. A process for purifying a fluid for cryogenic processing, comprising: an adsorber operated to receive a fluid for purification, the adsorber having a bed of adsorbent material including a first layer and a second layer downstream of the first layer, the first layer comprising an adsorbent material different from the adsorbent material of the second layer; as well as The fluid is passed through the bed so that water in the fluid penetrates the first layer to reach the second layer for adsorption in the second layer to remove water from the fluid through the second layer. When water is removed from the fluid through the second layer, the second layer also removes carbon dioxide (CO2) and nitrous oxide (N2O) from the fluid.

19. The process of claim 18, wherein the temperature of the fluid is between 5°C and 30°C, the first layer comprises alumina, activated alumina, or alumina impregnated with potassium salts, and the second layer comprises NaMSX, NaLSX, or 13X; and The second layer is larger than the first layer.

20. The process of claim 18, comprising outputting the purified fluid for cryogenic processing such that the purified fluid has no water therein and has a CO2 content equal to or below a preselected CO2 content threshold, and / or the purified fluid has a N2O content equal to or below a preselected N2O content threshold.

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