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CN-122028978-A - Adsorbent material, adsorption system and adsorption process for hydrogen recovery

CN122028978ACN 122028978 ACN122028978 ACN 122028978ACN-122028978-A

Abstract

An adsorption system having at least one adsorber retaining a bed of adsorbent material may be configured to provide enhanced purification at a relatively low cost of hydrogen or helium gas. Embodiments may utilize an activated carbon layer between at least one upstream layer and at least one downstream layer. The activated carbon layer may include activated carbon may have a preselected Surface Area (SA), bulk density, total Open Pore Volume (TOPV), and/or TOPV to surface area ratio (TOPV/SA).

Inventors

  • J. A. Taka
  • J.R. Hufton
  • T.C. GORDON
  • G.C.Liu
  • Virbhadra S.J.

Assignees

  • 气体产品与化学公司

Dates

Publication Date
20260512
Application Date
20241031
Priority Date
20231103

Claims (20)

  1. 1. An adsorber for an adsorption system, the adsorber comprising: a vessel positionable to receive a fluid to purify the fluid, the vessel having a bed of adsorbent material; The adsorbent material bed includes an activated carbon layer comprising activated carbon, the activated carbon of the activated carbon layer having: (i) A Surface Area (SA) in the range of 380 m 2 /g to 750 m 2 /g, and (Ii) The ratio of total open cell volume (TOPV) to SA (TOPV/SA) has a value greater than 0.59 nm and less than 0.83 nm.
  2. 2. The adsorber of claim 1 wherein the activated carbon of the activated carbon layer further has: (iii) Carbon dioxide (CO 2) isosceles heat of adsorption at a surface coverage of 0.5 mmol/g capable of less than or equal to 23.39 kilojoules per mole (kJ/mol), and (Iv) TOPV of 0.53 cubic centimeters per gram (cc/g) or less, and Wherein the activated carbon layer has a bulk density greater than or equal to 0.60 grams per cubic centimeter (g/cc).
  3. 3. The adsorber of claim 2 wherein the activated carbon of the activated carbon layer further has: (v) Particle sizes range between 1 millimeter (mm) in diameter and 5 mm mm in diameter.
  4. 4. The adsorber of claim 1 wherein the adsorption system is a Pressure Swing Adsorption (PSA) system.
  5. 5. The adsorber of claim 1 wherein the activated carbon layer has a bulk density of between 0.53 grams per cubic centimeter (g/cc) and 0.62 g/cc.
  6. 6. The adsorber of claim 5 wherein the activated carbon further has: Carbon dioxide (CO 2) isosceles heat of adsorption at a surface coverage of 0.5 millimoles per gram (mmol/g) capable of being less than or equal to 23.39 kilojoules per mole (kJ/mol) and greater than 0 kJ/mol, and/or TOPV between 0.50 cubic centimeters per gram (cc/g) and 0.40 cc/g.
  7. 7. The adsorber of claim 5 wherein the activated carbon further has: Carbon dioxide (CO 2) isosceles heat of adsorption at a surface coverage of 0.5 millimoles per gram (mmol/g) capable of being less than or equal to 23.39 kilojoules per mole (kJ/mol) and greater than 0 kJ/mol, and/or TOPV between 0.45 cubic centimeters per gram (cc/g) and 0.62 cc/g.
  8. 8. The adsorber of claim 1 wherein the activated carbon further has a TOPV of between 0.40 cubic centimeters per gram (cc/g) and 0.50 cc/g.
  9. 9. The adsorber of claim 1 wherein the bed of adsorbent material further has at least one downstream layer positioned downstream of the activated carbon layer, the bed of adsorbent material having only a single activated carbon layer, the single activated carbon layer being the activated carbon layer.
  10. 10. The adsorber of claim 1 wherein the bed of adsorbent material further has at least one downstream layer positioned downstream of the activated carbon layer and at least one upstream layer positioned upstream of the activated carbon layer, the bed of adsorbent material having only a single activated carbon layer, the single activated carbon layer being the activated carbon layer.
  11. 11. The adsorber of claim 1 wherein the bed of adsorbent material is configured to purify a feed fluid stream of hydrogen having a hydrogen content of less than 79 volume percent (vol-%) to output a purified fluid stream having a hydrogen content of greater than or equal to 95 vol-%.
  12. 12. An adsorption system, the adsorption system comprising: At least one adsorber according to claim 1.
  13. 13. A method for adsorption, the method comprising: Positioning a bed of adsorbent material within a vessel of an adsorber, the bed of adsorbent material comprising an activated carbon layer comprising activated carbon having: (i) A Surface Area (SA) in the range of 380 m 2 /g to 750 m 2 /g, and (Ii) A ratio of total open cell volume (TOPV) to SA (TOPV/SA) having a value greater than 0.59 nm and less than 0.83 nm; passing a feed fluid stream through the bed of adsorbent material to purify the feed fluid; after the feed fluid stream has passed through the bed of adsorbent material, a purified fluid stream is output from the vessel.
  14. 14. The method of claim 13, wherein the feed fluid has a hydrogen content of less than 79 volume percent (vol%) to output a purified fluid stream having a hydrogen content of greater than or equal to 95 vol%.
  15. 15. The method of claim 14, wherein the activated carbon further has: (iii) Carbon dioxide (CO 2) isosceles heat of adsorption at a surface coverage of 0.5 millimoles per gram (mmol/g) capable of being less than or equal to 23.39 kilojoules per mole (kJ/mol) and greater than 0 kJ/mol, and (Iv) TOPV of 0.53 cubic centimeters per gram (cc/g) or less, and Wherein the activated carbon layer has a bulk density greater than or equal to 0.60 grams per cubic centimeter (g/cc).
  16. 16. The method of claim 14, wherein the activated carbon further has: (iii) Particle sizes range between 1 millimeter (mm) in diameter and 5mm mm in diameter.
  17. 17. The method of claim 14, wherein the activated carbon layer further has a bulk density of between 0.53 grams/cubic centimeter (g/cc) and 0.62 g/cc.
  18. 18. The method of claim 17, wherein the activated carbon further has: (iii) Carbon dioxide (CO 2) isosceles heat of adsorption at a surface coverage of 0.5 millimoles per gram (mmol/g) capable of being less than or equal to 23.39 kilojoules per mole (kJ/mol) and greater than 0 kJ/mol, and/or (Iv) TOPV between 0.50 cubic centimeters per gram (cc/g) and 0.40 cc/g.
  19. 19. The method of claim 17, wherein the activated carbon further has: (iii) Carbon dioxide (CO 2) isosceles heat of adsorption at a surface coverage of 0.5 millimoles per gram (mmol/g) capable of being less than or equal to 23.39 kilojoules per mole (kJ/mol) and greater than 0 kJ/mol, and/or (Iv) TOPV between 0.45 cubic centimeters per gram (cc/g) and 0.62 cc/g.
  20. 20. The method of claim 14, wherein the activated carbon further has a TOPV of between 0.40 cubic centimeters per gram (cc/g) and 0.50 cc/g.

Description

Adsorbent material, adsorption system and adsorption process for hydrogen recovery Cross Reference to Related Applications The present application claims priority from U.S. non-provisional application Ser. No. 18/501,068, filed on 3/11/2023, and incorporated herein by reference. Technical Field The present innovation relates to adsorbent materials, adsorption systems, adsorption processes, adsorbers, and methods of making and using the same for purifying a hydrogen product stream. Background Adsorbers typically come in four different common configurations, vertical cross-flow, horizontal, and radial. Examples of adsorbers, adsorption systems, and adsorbent materials that may be used for adsorbers may be found in U.S. Pat. nos. 3,176,444, 3,430,418, 3,564,816, 3,986,849, no. 4,541,851, no. first, second, third, fourth, fifth, sixth, seventh, eighth, and eighth first, second, third, fourth, fifth, sixth, seventh, eighth, and eighth U.S. patent application publication nos. 2011/0206581, 2011/0219950, 2019/0291078 and 2023/0027070, canadian patent publication No. 2,357,276A, chinese patent publication No. CN a and european patent publication No. EP 1 417 995 A1. Temperature Swing Adsorption (TSA), pressure swing adsorption (VSA), pressure Swing Adsorption (PSA), and pressure swing vacuum adsorption (PVSA) are adsorbent systems that can be used in different types of purification systems. For example, PSA systems are used to recover and purify gaseous products, such as hydrogen. Disclosure of Invention We have determined that PSA systems are often difficult to proficiently purify hydrogen (H2) from feed streams having relatively low hydrogen content. For example, when the hydrogen in the feed to be treated is less than 80 volume percent (vol%), PSA systems may typically need to have a relatively large bed of adsorbent material for purifying the feed to form a suitable hydrogen product gas. This can result in high capital cost equipment for the PSA system and the large operating costs associated with low H2 recovery. In some cases, due to such complexity, it may not be desirable to use a PSA system for low hydrogen content feeds. This may reduce the design flexibility of providing a hydrogen product stream for different applications that may form a relatively low hydrogen content stream for purification. We have developed embodiments for adsorbent materials, adsorbers, and adsorption systems that can be configured for processing relatively low hydrogen content feeds (e.g., feeds having less than 80% hydrogen by volume). Embodiments may help reduce adsorber size by providing an adsorbent bed of improved efficiency for such applications, and may also allow the adsorption system to be more widely suited for different hydrogen purification processing applications. For example, some embodiments may be adapted to provide improved productivity in generating hydrogen from a feed by providing an increase in the rate of hydrogen generated per volume unit of adsorbent material (e.g., the rate of hydrogen generated per cubic meter of adsorbent bed material per hour). This type of improvement may allow for the use of smaller size adsorbers, which may reduce capital costs associated with available adsorber equipment. In the case of retrofit, higher H2 production rates may result in more revenue generated from the H2 sales. Embodiments may also provide improved recovery of hydrogen, which may allow for less fuel to be used to make a given amount of hydrogen (e.g., reduce the amount of natural gas required for producing hydrogen from a Steam Methane Reforming (SMR) process, etc.). Improved recovery of hydrogen may help reduce fuel usage, as well as reduce carbon dioxide emissions associated with producing hydrogen gas in such processes. In some embodiments, the bed of adsorbent material may suitably comprise multiple layers. Such beds may include a single layer of activated carbon adsorbent material positioned between at least one upstream layer of adsorbent material and at least one downstream layer of adsorbent material. The adsorbent material of the upstream and downstream layers may be other types of adsorbent materials. For example, in some embodiments, the bed may include an alumina layer positioned upstream of the activated carbon layer for moisture removal (e.g., water removal), and a layer of zeolite material may be positioned downstream of the activated carbon layer for carbon monoxide (CO), nitrogen (N2), and/or methane (CH 4) removal. In such configurations, the activated carbon layer may be sized for removal of carbon dioxide and a portion of the methane in the feed. As another example, some embodiments may utilize a bed comprising an alumina layer and a silica layer positioned upstream of an activated carbon layer for removing water and heavy hydrocarbons (hydrocarbons having four or more carbons), and a zeolite layer positioned downstream of the activated carbon layer for removing methane and nitrogen or removing c