EP1963767A2 - Utilisation des mof pour l'adsorption modulée par la pression - Google Patents

Utilisation des mof pour l'adsorption modulée par la pression

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Publication number
EP1963767A2
EP1963767A2 EP06850287A EP06850287A EP1963767A2 EP 1963767 A2 EP1963767 A2 EP 1963767A2 EP 06850287 A EP06850287 A EP 06850287A EP 06850287 A EP06850287 A EP 06850287A EP 1963767 A2 EP1963767 A2 EP 1963767A2
Authority
EP
European Patent Office
Prior art keywords
adsorption
pressure
adsorbent
desorption
bed
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP06850287A
Other languages
German (de)
English (en)
Other versions
EP1963767A4 (fr
Inventor
Mark M. Davis
John J. Low
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP 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
Application filed by UOP LLC filed Critical UOP LLC
Publication of EP1963767A2 publication Critical patent/EP1963767A2/fr
Publication of EP1963767A4 publication Critical patent/EP1963767A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • 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
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y02P20/156—Methane [CH4]

Definitions

  • the present invention relates to adsorption processes, and more particularly to pressure swing adsorption processes.
  • the process employs metal-organic framework materials having a high porosity and high surface areas, and are useful in the separation of hydrocarbons from hydrogen streams.
  • One technique for separation of one component in a gas from a mixture uses adsorption of one or more components from the mixture onto an adsorbent. This process is further enhanced through pressure swing adsorption (PSA). Pressure swing adsorption entails passing a feedstream over an adsorbent where one, or more, components of the feedstream are selectively adsorbed onto the adsorbent, and where the process of adsorption is performed at a relatively high pressure.
  • PSA pressure swing adsorption
  • the adsorbent is regenerated by reducing the pressure over the adsorbent, and a process of desorption is performed at the relatively low pressure.
  • the desorption process can also be accompanied by the passing of a purge gas having a low concentration of the adsorbate to enhance desorption.
  • the separation of gases from a gas mixture through adsorption in a pressure swing adsorption process is controlled by the pressures used in the process and the capacity of the adsorbent for one, or more, of the components in the gas mixture.
  • the process usually entails a tradeoff between the range in pressure, and the load capacity of the adsorbent for many of the materials used. It is desirable to be able to use materials that can overcome some of these tradeoffs.
  • the invention is a pressure swing adsorption process for removing hydrocarbons from a hydrogen stream.
  • the process passes the hydrogen stream over a metal organic framework material at a high adsorption pressure, generating an effluent stream with a reduced hydrocarbon content.
  • the process then reduces the pressure over the metal organic framework material and releases the hydrocarbon from the material, and generates a stream having hydrocarbons.
  • the process steps are then repeated.
  • the process uses multiple adsorption beds comprising the metal organic framework material and cycles the pressures sequentially through the beds to produce a continuous process.
  • the separation of gases from a gas mixture through adsorption in a pressure swing adsorption process is controlled by the difference between adsorption and desorption pressures and capacity of one of the components in the gas mixture.
  • the process usually entails a tradeoff between the pressure differences and the capacity for many of the materials used.
  • the capacity is the amount of material adsorbed by the adsorbent. It is desirable to be able to use materials that can overcome some of these tradeoffs.
  • pressure swing adsorption a gas made up of at least two constituents, is separated using the differences in selectivity of one of the constituents. Usually, the gas is purified by selectively removing an undesired constituent of the gas.
  • the gas is typically fed into an adsorption unit at an elevated pressure, where one of the constituents is preferentially adsorbed onto an adsorbent. While one constituent is preferentially adsorbed, other constituents are also adsorbed, and it is desired to use adsorbents that have significant differences in the adsorption of the desired constituents.
  • the adsorbent is regenerated through reversing the adsorption process to desorb the constituents. This is done by changing the conditions of the adsorbent environment through reducing the pressure.
  • the gas feed to the adsorption unit is stopped, and the adsorption unit is depressurized.
  • the gas feed is stopped when the adsorption unit is near or at capacity for the adsorbent with the desired constituent.
  • the adsorption unit is depressurized to a specified level where the adsorbed constituents desorb generating a desorbent stream that is relatively rich in the constituent that is more strongly adsorbed onto the adsorbent.
  • the desorption process can use an inert gas, or a non- hydrocarbon gas to facilitate the desorption process.
  • the desorption gas is passed over the adsorbent to remove the adsorbed constituents as they desorb from the adsorbent.
  • the desorption gas is passed over the adsorbent in a direction opposite the direction of the feed gas to regenerate the adsorbent.
  • An aspect of a pressure swing adsorption system is the isotherm for adsorbing a component in a gas dictates the operating pressures and loading onto the adsorbent. Most materials have an isotherm, wherein the saturation limit is rapidly approached, and then there is a small incremental improvement in adsorption for a relatively large increase in pressure.
  • the working capacity of an adsorbent is defined as difference in the amount of the adsorbed components on the adsorbent between the adsorption pressure and the desorption, or regeneration, pressure. Lowering the regeneration pressure can increase the capacity of the adsorbent for selectively removing a component from a gas, but the effluent stream from the regeneration step may need to be recompressed.
  • a lower regeneration pressure increases the recompression costs.
  • adsorbents that are suitable. The selection is dependent upon the feed gas constituents and other factors generally known to those skilled in the art. In general, suitable adsorbents include molecular sieves, silica gels, activated carbons, activated aluminas, and other porous metal oxides. When purifying methane containing streams, the methane is often adsorbed along with the impurities that one wishes to remove. The choice of adsorbent presents problems in selecting an adsorbent that has the greatest differential in adsorption between hydrogen and selected impurities, especially light hydrocarbons such as methane and ethane.
  • the search is for a high permeability material that also has a high capacity for use in a pressure swing adsorber. This means a material with a very high surface area and a high porosity. It is desired to increase the loading of the adsorbent, while minimizing recompression requirements. This translates to higher desorption pressures.
  • One embodiment of the invention is a process using pressure swing adsorption to remove methane and other light hydrocarbon compounds, such as ethane, from a hydrogen feedstream.
  • the process comprises passing a hydrogen feedstream having hydrocarbons over an adsorbent in an adsorption zone, and at a temperature and pressure sufficient to adsorb a portion of the hydrocarbons.
  • the remaining gases in the feedstream becomes an effluent stream having a reduced hydrocarbon content.
  • the adsorbent in the process is a material known as a metal organic framework (MOF), and has a high surface area and high porosity. The surface area of the material is greater than 1500 m 2 /gm.
  • MOF metal organic framework
  • the pressure in the adsorption zone is then reduced to a pressure for desorbing the hydrocarbons, and generates a desorption effluent stream having an enriched hydrocarbon content.
  • the effluent stream will have an increased methane content, as methane is the primary light hydrocarbon in the hydrogen feedstream.
  • Other light hydrocarbons include ethane, propane, butanes, and small amounts of other hydrocarbons.
  • the process during desorption can include passing a carbon dioxide lean purge gas over the adsorbent.
  • the process can be carried out by either passing the adsorbent bed through a high pressure adsorption zone, and then moving the adsorbent bed to a low pressure desorption zone, such as occurs with an adsorbent wheel in a rotating drum adsorber.
  • the process can also be carried out by alternately pressurizing the adsorbent bed and passing the feedstream over the bed, and depressurizing the adsorbent bed and passing a purge gas over the bed.
  • These processes are improved and made continuous by using a sequence of at least two adsorbent beds, wherein the beds are cycled through the adsorption and desorption steps in a sequential manner to provide a continuous operation.
  • the process of cycling the adsorbent beds comprises pressurizing a first adsorbent bed to an adsorption pressure and flowing the feedstream over the first adsorbent bed, while depressurizing a second adsorbent bed to a desorption pressure and flowing a purge stream over the second adsorbent bed.
  • the process can be further smoothed with respect to pressure changes by additional beds, wherein intermediate beds are pressurized or depressurized before switching flows.
  • the feedstream is passed over the adsorbent, in a first adsorbent zone, at the highest pressure of the process, with the hydrocarbons adsorbed, generating a hydrocarbon depleted hydrogen stream.
  • the hydrocarbon depleted hydrogen discharges from the adsorption zone so that hydrocarbon adsorption front is formed in the zone at the hydrogen feedstream inlet end and progressively moves toward the outlet.
  • the adsorption zone is sized to produce a hydrogen gas product with a hydrocarbon concentration less than 1% by volume.
  • the feedstream to the adsorbent unit is terminated when either the hydrocarbon adsorption front is at a predetermined point in the adsorption unit, or when there is an increase in the hydrocarbon in the hydrogen stream to above a predetermined value.
  • the feedstream is then terminated to the first adsorption zone, and directed to a second adsorption zone.
  • the first adsorption zone is depressurized and a purge gas is passed through the first adsorption zone to regenerate the adsorbent in the first adsorption zone.
  • the purge gas preferably flows in a counter current direction relative to the flow of the feedstream in the adsorption zones to remove the hydrocarbons in the reverse direction that they were adsorbed.
  • the first zone When the first zone has been regenerated, it is repressurized to the pressure level for the feedstream, the feedstream is switched to the first zone, and the second adsorption zone is depressurized and regenerated with a purge gas at regeneration conditions, and the process cycle is repeated.
  • the operating conditions for the pressure swing adsorption process include adsorption pressures from 2 MPa (20 atms.) to 5 MPa (50 aims.).
  • the desorption pressure is in a range from 1 kPa (1 atm) to 1.5 MPa (15 atms.), with a preferred range from 500 kPa (5 atm) to 1 MPa (10 atms.).
  • the desorption step is preferably operated at a pressure sufficient to minimize recompressing the desorption effluent stream.
  • the adsorbent needs to be thermally stable for a range of temperatures, and operation is at temperatures between 0 0 C to
  • the process can further comprise passing a purge stream at desorption conditions over the adsorbent to facilitate the desorption of the hydrocarbons.
  • the desorbent effluent stream can be recompressed and directed to a fuel system. It is preferred to desorb the adsorbate at moderate pressures to minimize repressurization of the desorbent effluent stream.
  • a repressurized desorbed hydrocarbon stream can be used as a fuel gas.
  • New materials have been found to have good properties for adsorption separation. These materials are MOFs, or metal-organic framework materials. MOFs have very high surface areas per unit volumes, and have very high porosities.
  • MOFs are a new generation of porous materials which have a crystalline structure comprising repeating units having a metal or metal oxide with a positive charge and organic units having a balancing counter charge. MOFs provide for pore sizes that can be controlled with the choice of organic structural unit, where larger organic structural units can provide for larger pore sizes. The capacity and adsorption characteristics for a given gas is dependent on the materials in the MOF, as well as the size of the pores created. Structures and building units for MOFs can be found in US 2005/0192175 published on September 1, 2005 and WO 2002/088148 published on November 7, 2002, both of which are incorporated by reference in their entireties.
  • the materials of use for this process include MOFs with a plurality of metal, metal oxide, metal cluster or metal oxide cluster building units, hereinafter referred to as metal building units, where the metal is selected from the transition metals in the periodic table, and beryllium.
  • metal building units where the metal is selected from the transition metals in the periodic table, and beryllium.
  • Preferred metals include zinc (Zn), cadmium (Cd), mercury (Hg), and beryllium (Be).
  • the metal building units are linked by organic compounds to form a porous structure, where the organic compounds for linking the adjacent metal building units include 1,3,5- benzenetribenzoate (BTB); 1 ,4-benzenedicarboxylate (BDC); cyclobutyl 1,4- benzenedicarboxylate (CB BDC); 2-amino 1,4 benzenedicarboxylate (H2N BDC); tetrahydropyrene 2,7-dicarboxylate (HPDC); terphenyl dicarboxylate (TPDC); 2,6 naphthalene dicarboxylate (2,6-NDC); pyrene 2,7-dicarboxylate (PDC); biphenyl dicarboxylate (BDC); or any dicarboxylate having phenyl compounds.
  • BTB 1,3,5- benzenetribenzoate
  • BDC 1 ,4-benzenedicarboxylate
  • CB BDC cyclobutyl 1,4- benzenedi
  • Specific materials that show improvement in adsorption properties have a three- dimensional extended porous structure and include: MOF- 177, a material having a general formula of Zn 4 O(1, 3, 5-benzenetribenzoate) 2 ; MOF-5, also known as IRMOF-I, a material having a general formula of Zn 4 O(1, 4-benzenedicarboxylate) 3 ; IRMOF-6, a material having a general formula of Zn 4 ⁇ (cyclobutyl 1,4-benzenedicarboxylate); IRMOF-3, a material having a general formula of Zri 4 O(2-amino 1,4 benzenedicarboxylate) 3 ; and IRMOF-11, a material having a general formula of Zn 4 O (terphenyl dicarboxylate) 3 ,or ZrL t O ⁇ etrahydropyrene 2,7- dicarboxylate) 3 ; and IRMOF-8, a material having a general formula of Z
  • the use of a metal organic framework improves the removal of methane (CH 4 ) and other light hydrocarbons from a high pressure stream comprising hydrogen (H 2 ).
  • this is a high waste pressure application where the waste gas stream is directed to a fuel system.
  • the fuel systems are typically operated at pressures from 4 atm to 7 atm (400 kPa to 700 kPa).
  • the primary impurity is methane
  • the adsorbent activity of MOF-5 is compared with the activity of activated carbon in a PSA system.
  • the isotherms for methane over the adsorbents are shown in the Figure using the basis of lbs of methane per cubic foot of adsorbent bed.
  • the feed stream has a methane partial pressure of 20 atm which is then desorbed at a pressure of 5 atm.
  • the loadings for the activated carbon and the MOF-5 are 1.05 and 2.15 lbs-CH 4 /ft 3 , respectively.
  • the MOF-5 exhibits a loading capacity of more than double that of carbon.
  • the desorption pressure can be reduced to 1 atm, with a resulting loading on the carbon of 1.8.
  • the low pressure used for carbon must be accompanied with a significant increase in power usage to recompress the methane released during the desorption stage to return the methane effluent stream to a fuel system pressure.
  • One aspect of the invention is to have a material, or combination of materials, that changes the shape of the isotherm, so that the capacity-pressure curve does not taper off as pressure increases, but still retains significant capacity increases as the pressure is increased over the normal operating ranges for a pressure swing adsorber.
  • MOFs provide some of this capability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé d'adsorption modulée par la pression utilisant des matériaux MOF (Metal Organic Framework), c'est-à-dire à réseaux organométalliques, pour l'élimination de composés d'hydrocarbures légers d'un courant d'hydrogène gazeux.
EP06850287A 2005-12-21 2006-12-13 Utilisation des mof pour l'adsorption modulée par la pression Withdrawn EP1963767A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US75257405P 2005-12-21 2005-12-21
PCT/US2006/062042 WO2007111739A2 (fr) 2005-12-21 2006-12-13 Utilisation des mof pour l'adsorption modulée par la pression

Publications (2)

Publication Number Publication Date
EP1963767A2 true EP1963767A2 (fr) 2008-09-03
EP1963767A4 EP1963767A4 (fr) 2010-03-03

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP06850287A Withdrawn EP1963767A4 (fr) 2005-12-21 2006-12-13 Utilisation des mof pour l'adsorption modulée par la pression

Country Status (7)

Country Link
EP (1) EP1963767A4 (fr)
CN (1) CN101346182A (fr)
AU (1) AU2006340775A1 (fr)
CA (1) CA2633676C (fr)
NZ (1) NZ569159A (fr)
WO (1) WO2007111739A2 (fr)
ZA (1) ZA200805557B (fr)

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WO2008140788A1 (fr) 2007-05-11 2008-11-20 The Regents Of The University Of California Séparation de gaz d'adsorption de gaz multi-composants
EP2167511A4 (fr) 2007-07-17 2010-12-22 Univ California Préparation de structures zéolithiques fonctionnalisées
EP2190662B1 (fr) 2007-09-25 2018-12-26 The Regents of The University of California Structures organométalliques biocompatibles et comestibles
US8946454B2 (en) 2008-06-05 2015-02-03 The Regents Of The University Of California Chemical framework compositions and methods of use
WO2010080618A2 (fr) 2008-12-18 2010-07-15 The Regents Of The University Of California Matrices poreuses réactives
US20110277767A1 (en) * 2008-12-18 2011-11-17 The Regents Of The University Of California Metal organic frameworks (mofs) for air purification
US8480955B2 (en) 2008-12-29 2013-07-09 The Regents Of The University Of California Gas sensor incorporating a porous framework
EP2382043A1 (fr) 2009-01-15 2011-11-02 The Regents of the University of California Structure organométallique conductrice
EP2384237A1 (fr) 2009-02-02 2011-11-09 The Regents of The University of California Capture d'oxyde d'éthylène réversible dans des structures poreuses
JP5698229B2 (ja) 2009-06-19 2015-04-08 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニアＴｈｅ Ｒｅｇｅｎｔｓ Ｏｆ Ｔｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｃａｌｉｆｏｒｎｉａ 錯体混合リガンド開骨格材料
EP2437867A4 (fr) 2009-06-19 2012-12-05 Univ California Capture du dioxyde de carbone, et son stockage par utilisation de cadres ouverts
US8841471B2 (en) 2009-09-25 2014-09-23 The Regents Of The University Of California Open metal organic frameworks with exceptional surface area and high gas storage capacity
US9102609B2 (en) 2010-07-20 2015-08-11 The Regents Of The University Of California Functionalization of organic molecules using metal-organic frameworks (MOFS) as catalysts
BR112013007140A2 (pt) 2010-09-27 2016-06-14 Univ California estrutura orgânica covalente condutora, exibidor flexível, semicondutor, dispositivo de armazenagem de gás, e, sensor químico
MX2013008390A (es) 2011-01-21 2013-08-12 Univ California Preparacion de estructuras de metal-triazolato.
RU2013140772A (ru) 2011-02-04 2015-03-10 Те Риджентс Оф Те Юниверсити Оф Калифорния Получение каркасных структур на основе пирокатехолятов металлов
US9078922B2 (en) 2011-10-13 2015-07-14 The Regents Of The University Of California Metal-organic frameworks with exceptionally large pore aperatures
WO2015127033A1 (fr) 2014-02-19 2015-08-27 The Regents Of The University Of California Ossatures organometalliques resistantes aux acides, aux solvants et a la chaleur
EP3074405A2 (fr) 2014-03-18 2016-10-05 The Regents of the University of California Matériaux mésoscopiques constitués de super-réseaux ordonnés de réseaux métal-organiques microporeux
WO2015195179A2 (fr) 2014-03-28 2015-12-23 The Regents Of The University Of California Réseaux métal-organiques comprenant une pluralité de sbu avec différents ions métalliques et/ou une pluralité de ligands de liaison organique avec différents groupes fonctionnels
KR20180087369A (ko) 2015-11-27 2018-08-01 더 리젠츠 오브 더 유니버시티 오브 캘리포니아 제올라이트 이미다졸레이트 프레임워크
RU2607735C1 (ru) * 2015-12-02 2017-01-10 Леонид Федорович Шестиперстов Разделение многокомпонентных газовых смесей способом короткоцикловой безнагревной адсорбции с трехэтапным извлечением целевого газа высокой чистоты
US10315152B2 (en) 2017-06-08 2019-06-11 DK Engineering Consulting LLC Method and system for pressure swing adsorption
CN113830735B (zh) * 2021-11-23 2022-07-12 清华大学 碳氢燃料重整中温净化制氢方法、设备和燃料电池供能系统

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CULP J T ET AL: "Hydrogen storage on porous coordination polymers" MATERIALS SCIENCE AND TECHNOLOGY (MATERIALS SCIENCE AND TECHNOLOGY 2005 CONFERENCE - 20050925 TO 20050928 - PITTSBURGH, PA),, vol. 3, 25 September 2005 (2005-09-25), pages 31-41, XP009128243 ISBN: 978-0-87339-645-5 *
FLETCHER ET AL: "Flexibility in metal-organic framework materials: Impact on sorption properties" JOURNAL OF SOLID STATE CHEMISTRY, ORLANDO, FL, US, vol. 178, no. 8, 1 August 2005 (2005-08-01), pages 2491-2510, XP005027299 ISSN: 0022-4596 *
See also references of WO2007111739A2 *

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ZA200805557B (en) 2009-12-30
CN101346182A (zh) 2009-01-14
WO2007111739B1 (fr) 2008-03-06
EP1963767A4 (fr) 2010-03-03
AU2006340775A1 (en) 2007-10-04
CA2633676A1 (fr) 2007-10-04
WO2007111739A2 (fr) 2007-10-04
CA2633676C (fr) 2014-07-29
WO2007111739A3 (fr) 2007-12-21
NZ569159A (en) 2010-11-26

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