WO2023250300A1 - Adsorbant pour la séparation d'un flux gazeux - Google Patents

Adsorbant pour la séparation d'un flux gazeux Download PDF

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Publication number
WO2023250300A1
WO2023250300A1 PCT/US2023/068671 US2023068671W WO2023250300A1 WO 2023250300 A1 WO2023250300 A1 WO 2023250300A1 US 2023068671 W US2023068671 W US 2023068671W WO 2023250300 A1 WO2023250300 A1 WO 2023250300A1
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WO
WIPO (PCT)
Prior art keywords
adsorbent
zeolite
exhibits
halloysite clay
weight
Prior art date
Application number
PCT/US2023/068671
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English (en)
Inventor
Patrick Purcell
Kerry C. Weston
Original Assignee
Zeochem Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US17/807,810 external-priority patent/US20220401914A1/en
Application filed by Zeochem Llc filed Critical Zeochem Llc
Publication of WO2023250300A1 publication Critical patent/WO2023250300A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B01D53/0476—Vacuum pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/308—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/12—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen

Definitions

  • the invention is a zeolite adsorbent, which is particularly useful for separation of a gaseous stream.
  • This adsorbent has surprising physical characteristics, such as high tapped bulk density and crush strength, yet also preferably exhibited high capacity, fast kinetics, excellent porosity, and significant pore structure improvements over the prior art.
  • it is suitable for separation and concentration of oxygen by adsorption from a mixed gaseous stream, for example, a gaseous stream composed mainly of nitrogen and oxygen.
  • the adsorbents of this invention are particularly useful for the adsorption and separation of gases .
  • the adsorbent compositions are used in processes for separating O2 from mixtures containing N2, O2 , and other gases by contacting the mixture with an adsorbent composition which selectively adsorbs the N2 with one or more of the less strongly adsorbable components recovered as product .
  • the separation of nitrogen from gas mixtures is the basis for several industrial adsorption processes , including the production of oxygen from air .
  • air is passed through an adsorbent bed having a preference for the adsorption of nitrogen molecules and leaving oxygen and argon (the less strongly adsorbable components) to be produced.
  • the adsorbed nitrogen is then desorbed through a purging step, normally through a change in pressure, including vacuum, and/or through temperature changes to regenerate the adsorbent and the cycle is repeated.
  • a particularly important parameter in evaluating pore structure is hysteresis , which is a factor useful in evaluating pore connectivity .
  • Another important parameter useful for evaluating the adsorption rate of adsorbent is pore di f fusivity ( D p ) for nitrogen, which is a measure of adsorption rate .
  • Conventional agglomerated adsorbents used for such adsorption processes are composed of zeolite powders ( crystallite particles ) , including ion exchanged zeolite powders , depending on the process and binding agent .
  • the binding agent is intended to ensure cohesion of the agglomerated particles , which are generally in the form of beads , pellets , and extrudates .
  • binding agents can also increase overall adsorption capacity of the adsorbent .
  • Certain binding agents , temporary binders , and other processing aids can also fill or otherwise partially plug the particle pores while other binding agents can have an adverse ef fect on the final pore structure , depending on the binding agents ' carrier solvents .
  • the invention includes an adsorbent for separation of a gaseous stream, which adsorbent contains a blend of lithium exchanged zeolite 13X ("L113X” ) , lithium exchanged low silica X zeolite (“LiLSX” ) , and residual halloysite clay .
  • the quantity of the L113X is from about 5 to about 20% of the adsorbent , by weight .
  • the quantity of the LiLSX is from about 80% to about 90% of the adsorbent , by weight .
  • the quantity of the halloysite clay is preferably from about 0 . 1 % to about 5 . 0% of the adsorbent , by weight .
  • This binderless absorbent preferably exhibits high capacity for absorbing gases, fast kinetics, as measured by kinetic tests, and good pore structure characteristics while also preferably exhibiting high crush strength.
  • the binderless adsorbent also exhibits high bulk density, equal to or greater than about 640 g/L, as measured according to DIN/ISO 787.
  • the adsorbent preferably also has improved pore structure with median pore diameter of at least about 5 micron and a fraction of pores that are smaller than or equal to 0.1 micron less than about 6.0%.
  • Said invention also includes a process for the use of the adsorbent for separation of gaseous materials, particularly oxygen from a gas stream.
  • an adsorbent particularly useful for separation by pressure swing adsorption (PSA) , vapor pressure swing adsorption (VPSA) , or temperature swing adsorption (TSA) of a gaseous stream, particularly for separation of O2 from air.
  • PSA pressure swing adsorption
  • VPSA vapor pressure swing adsorption
  • TSA temperature swing adsorption
  • One adsorbent particularly useful for this process is composed of X or Y zeolite crystals, particularly X zeolite.
  • Preferred are one or more type zeolite X which incorporate cations, such as Li, Ca, K, Na, Ag, and mixtures thereof, particularly Li, wherein one embodiment is a zeolite X containing Li cations.
  • the S1O2/A12O3 ratio is preferably less than 15, in one embodiment less than 5, and in another embodiment less than or equal to 2.5.
  • a particularly alternative embodiment has a S1O2/A12O3 ratio of from about 1.9 to about 2.3.
  • the halloysite clay has a tubular shape with a length from about 0.5 - 2.0 micron and a diameter of about 50 - 100 nm.
  • the blended product is kneaded, granulated, and shaped into a preferred shaped product. It can be formed into beads, extrudates and/or spray dried microspheres and in one embodiment, it is formed into beads.
  • the resulting product is then dried at a temperature from about 100°C to 400°C. After drying it is calcined at a temperature from about 500 to about 700°C to produce a shaped LSX/halloysite clay blended product.
  • the LSX/halloysite clay blended product is then treated with a caustic solution that converts a significant portion of the halloysite clay into a zeolite 13X.
  • a caustic solution that converts a significant portion of the halloysite clay into a zeolite 13X.
  • from about 60 to about 95% or more, by weight, of the halloysite clay is converted into a zeolite 13X.
  • the process of caustically digesting the halloysite clay material occurs at a temperature of about 80°C utilizing a caustic solution.
  • the caustic solution contains primarily sodium hydroxide and potassium hydroxide.
  • the caustic solution is substantially sodium hydroxide. Utilization of substantially sodium hydroxide for the caustic treatment results in production of substantially more of the zeolite 13X from the halloysite clay.
  • Other combinations of hydroxides and other materials can be utilized to modify the final composition of the adsorbent.
  • the product is lithium-exchanged at least about 90%, in one embodiment at least about 95%, and in another embodiment at least about 98% to produce the final adsorbent.
  • the final adsorbent includes from about 80 to about 90%, by weight, LiLSX and from about 5% to about 20%, by weight, of L113X with the remaining quantity being residual halloysite clay in an amount from about 0.1 to about 5%, by weight.
  • Also present in the final composition of the adsorbent after the conversion may be oxides of any of the following elements alone or in combination: Al, Si, Ba, Li, Na, K, Mg, Ca, Fe, Ti, Y and Zr, along with other residual components.
  • the preferred adsorbent preferably utilized a kaolin clay as the binder that, when converted into a zeolite, has the same composition as that of the primary zeolite that is utilized for the desired adsorption process.
  • caustic digestion of a kaolin clay generally produces a low silica LiX zeolite.
  • Applicant has discovered that a surprisingly useful adsorbent can be produced that contains both LiLSX zeolite and L113X zeolite along with a quantity of residual halloysite clay.
  • the adsorbent produced by this process has enhanced physical characteristics over those of prior art adsorbents.
  • the adsorbent exhibits tapped bulk density of at least about 640 g/L measured by DIN/ISO 787 and crush strength of at least about 8 N/mm.
  • the disclosed adsorbent composition has high strength and high crush strength as well as low porosity and has a surprisingly fast nitrogen uptake rate which can be attributed to the characteristics of the pore structure.
  • pore diffusivity (D p ) for nitrogen greater than 5.0 x 10 ⁇ 6 m 2 /s.
  • D p pore diffusivity
  • This high pore diffusivity (D p ) for nitrogen is surprising, especially considering the physical characteristics of the adsorbent particles.
  • This disclosure of pore diffusivity (D p ) is determined based on nitrogen pore diffusivity, when measured at 1.5 bar and 300K, as described, for example, in US Patent No. 6,500,234 B2, US Patent No. 6,790,260 B2, and US Patent No. 9,486,732 B2.
  • a low silica zeolite X (2.0 silica/alumina ratio) is mixed with a halloysite clay in a ratio of about 85/15 zeolite to clay, by weight. This mixture is then formed into spheres and calcined. These calcined particles are then introduced to a hot ( ⁇ 90C) sodium hydroxide solution for several hours to convert the clay into 13X zeolite. The particles are then washed with water to remove excess caustic, and then the particles undergo a lithium ion exchange to at least about 95%.
  • the quantity of the lithium exchanged low silica zeolite X is 85%, the quantity of the lithium exchanged zeolite 13X is 12%, and the quantity of the residual halloysite clay is 3%.
  • a shaped adsorbent containing lithium exchanged low silica X zeolite with an attapulgite binder as described in columns 3-8 of US Patent No. 7,300,899.
  • a binderless shaped adsorbent obtained from Tosoh which contains LiLSX with a commercial name of NSA -700.
  • Comparative Sample 5 (C-5) A binderless shaped adsorbent obtained from Hanchang, which contains LiLSX.
  • Inventive Example 1 are compared with adsorbents of Comparative Samples C-l, C-2, C-3, C-4, and C-5.
  • inventive adsorbent composition containing a combination of LiX and L113X with residual halloysite clay has the best combination of both physical characteristics and pore structure, including median pore diameter, lower percentage of pores that are less than 0.1 pm, improved hysteresis factor and higher pore di f fusivity for nitrogen . Notwithstanding these improved characteristics , the inventive composition also contained a higher tapped bulk density and greater crushing strength than the comparative examples .

Abstract

L'invention concerne un adsorbant zéolitique pour la séparation de l'oxygène d'un flux gazeux. L'adsorbant est un mélange d'une zéolite échangée au lithium 13X, d'une zéolite X à faible teneur en silice échangée au lithium et d'une argile halloysite. L'invention concerne également un procédé de fabrication de l'adsorbant zéolitique. L'invention concerne en outre un procédé de production d'oxygène à partir d'un flux gazeux à l'aide de l'adsorbant zéolitique.
PCT/US2023/068671 2022-06-20 2023-06-19 Adsorbant pour la séparation d'un flux gazeux WO2023250300A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17/807,810 US20220401914A1 (en) 2021-06-21 2022-06-20 Binderless adsorbent for separation of a gaseous stream
US17/807,810 2022-06-20

Publications (1)

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WO2023250300A1 true WO2023250300A1 (fr) 2023-12-28

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PCT/US2023/068671 WO2023250300A1 (fr) 2022-06-20 2023-06-19 Adsorbant pour la séparation d'un flux gazeux

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5203887A (en) * 1991-12-11 1993-04-20 Praxair Technology, Inc. Adsorbent beds for pressure swing adsorption operations
US6425940B1 (en) 1998-02-27 2002-07-30 Praxair Technology, Inc. Advanced adsorbent for PSA
US6500234B1 (en) 1998-02-27 2002-12-31 Praxair Technology, Inc. Rate-enhanced gas separation
US6616732B1 (en) * 1999-10-05 2003-09-09 Ceca, S.A. Zeolite adsorbents, method for obtaining them and their use for removing carbonates from a gas stream
US6790260B2 (en) 2000-12-20 2004-09-14 Praxair Technology, Inc. Enhanced rate PSA process
US7300899B2 (en) 2002-01-22 2007-11-27 Zeochem, Llc Lithium exchanged zeolite X adsorbent blends
US9050582B2 (en) 2012-06-22 2015-06-09 Praxair Technology, Inc. Adsorbent compositions
US20190388871A1 (en) * 2016-12-02 2019-12-26 Arkema France Zeolite adsorbent material, method of preparation and use for non-cryogenic separation of industrial gases

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5203887A (en) * 1991-12-11 1993-04-20 Praxair Technology, Inc. Adsorbent beds for pressure swing adsorption operations
US6425940B1 (en) 1998-02-27 2002-07-30 Praxair Technology, Inc. Advanced adsorbent for PSA
US6500234B1 (en) 1998-02-27 2002-12-31 Praxair Technology, Inc. Rate-enhanced gas separation
US6616732B1 (en) * 1999-10-05 2003-09-09 Ceca, S.A. Zeolite adsorbents, method for obtaining them and their use for removing carbonates from a gas stream
US6790260B2 (en) 2000-12-20 2004-09-14 Praxair Technology, Inc. Enhanced rate PSA process
US7300899B2 (en) 2002-01-22 2007-11-27 Zeochem, Llc Lithium exchanged zeolite X adsorbent blends
US9050582B2 (en) 2012-06-22 2015-06-09 Praxair Technology, Inc. Adsorbent compositions
US9486732B2 (en) 2012-06-22 2016-11-08 Praxair Technology, Inc. Adsorbent compositions
US20190388871A1 (en) * 2016-12-02 2019-12-26 Arkema France Zeolite adsorbent material, method of preparation and use for non-cryogenic separation of industrial gases

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Nanosized Tubular Clay Minerals - Halloysite and Imogolite; Developments in clay science , ISSN 1572-4352 ; volume 7", vol. 7, 1 January 2016, ELSEVIER, NL, ISBN: 978-0-08-100293-3, article H. YANG ET AL: "Physicochemical Properties of Halloysite", pages: 67 - 91, XP055622277, DOI: 10.1016/B978-0-08-100293-3.00004-2 *

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