CN101346182A - The use of MOFs in pressure swing adsorption - Google Patents

The use of MOFs in pressure swing adsorption Download PDF

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Publication number
CN101346182A
CN101346182A CNA2006800487355A CN200680048735A CN101346182A CN 101346182 A CN101346182 A CN 101346182A CN A2006800487355 A CNA2006800487355 A CN A2006800487355A CN 200680048735 A CN200680048735 A CN 200680048735A CN 101346182 A CN101346182 A CN 101346182A
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adsorbent
pressure
hydrocarbon
mof
adsorption zone
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M·M·戴维斯
J·J·娄
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Honeywell UOP LLC
Universal Oil Products Co
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Universal Oil Products Co
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    • 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]

Abstract

A pressure swing adsorption process for removing light hydrocarbons from a hydrogen stream wherein the process passes the hydrogen stream over a metal organic framework material at a high adsorption pressure, generating an effluent stream with 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. Further, 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.

Description

The application of MOF in pressure oscillating absorption
Background of invention
The present invention relates to adsorption method, and pressure swing adsorption more particularly.This method has been utilized the metal-organic framework materials with high porosity and high surface, and is applicable to separate hydrocarbons from hydrogen stream.
Often one or more components must be separated from admixture of gas to produce purified gases.It can be used for removing impurity or being used for one or more interior components of concentrated gas stream from gas stream.
A kind of be used for the technology that a kind of component is separated from mixture with gas form used one or more components are adsorbed onto adsorbent from mixture.This method is further strengthened by pressure oscillating absorption (PSA).Pressure oscillating absorption requires incoming flow is passed through on adsorbent, and wherein a kind of the or various ingredients of incoming flow selectively is adsorbed on the adsorbent, and wherein carries out this adsorption process under elevated pressures.Make adsorbent reactivation by pressure on the adsorbent is reduced, and under lower pressure, to carry out desorption process.This desorption process also can be attended by the purge gas that feeds the adsorbate with low concentration and finish, and strengthens desorb thus.
By absorption gas is separated from admixture of gas in the pressure swing adsorption, a kind of in admixture of gas capacity of or various ingredients is controlled by the pressure and the adsorbent that use in this method.This method requires pressure limit and adsorbent for trading off between the load capacity of the multiple material that uses usually.Expectation can be used the material that can overcome these some in compromise.
Summary of the invention
The present invention is the pressure swing adsorption that is used for removing from hydrogen stream dealkylation.This method is passed through hydrogen stream on metal-organic framework materials under high adsorptive pressure, produce the outflow logistics of the hydrocarbon content with reduction.Subsequently, this method reduces the pressure on the metal-organic framework materials and discharge hydrocarbon from this material, and generation has the logistics of hydrocarbon.Repeat this processing step subsequently.In a kind of embodiment, this method used a plurality of comprise the adsorbent bed of metal-organic framework materials and make pressure sequentially by bed circulation to form continuous process.
Other purpose of the present invention, embodiment and detailed content can obtain from following detailed description of the present invention.
Figure is the contrast of the absorption of CH4 on carbon and MOF-5.
Detailed Description Of The Invention
By absorption gas is separated from admixture of gas in the pressure swing adsorption, by absorption And a kind of capacity of component is controlled in the difference between the desorption pressures and the admixture of gas. The method is logical Often require pressure difference value and compromise between the capacity of the multiple material that uses. This capacity is absorption The amount of the material of agent absorption. Expectation can be used the material that can overcome these some in compromise.
In the pressure oscillating absorption, utilize a kind of selective difference of component to separate by at least two kinds of component groups The gas that becomes. Usually, by selectively removing the gas group of not expecting this gas of purifying of assigning to. Usually Gas is fed in the absorbing unit under the pressure that raises, and wherein a kind of component is preferentially adsorbed on adsorbent On. A kind of when preferentially being adsorbed, other component also is adsorbed, and expectation is used in the expectation component The adsorbent of absorption aspect with marked difference.
Adsorbent is by oppositely regenerating adsorption process, thus with the component desorb.This is by the carrying out of the condition of reduction pressure change adsorbent environment.At the appointed time or under the condition, stop gas feed, and absorbing unit is reduced pressure to absorbing unit.Preferably, the capacity that is in the adsorbent with desired components when absorbing unit down or stop gas feed when neighbouring.With the absorbing unit specified level that reduces pressure, wherein adsorbed components desorb produces and is rich in the stronger desorb logistics that is adsorbed on the component on the adsorbent relatively.This desorption process can use the gas of inert gas or nonhydrocarbon to promote this desorption process.With desorption gas on adsorbent by to remove the absorbed component of desorb from adsorbent.Preferably, stripping gas is passed through on adsorbent with the direction relative with the direction of feeding gas, make adsorbent reactivation thus.
The one side of pressure oscillating absorption system is thermoisopleth (isotherm) the control operation pressure of component in the adsorbed gas and the heap(ed) capacity on the adsorbent.Most of materials have thermoisopleth, the limit that wherein reaches capacity apace, and have little improvement for bigger pressure increase subsequently.The displacement volume of adsorbent is defined as between adsorptive pressure and desorb or the regeneration pressure difference of the amount of adsorbed components on the adsorbent.Reduce regeneration pressure and can improve adsorbent for the capacity of selectively from gas, removing component, but the outflow logistics in the regeneration step of may must pressurizeing again.But the regeneration pressure of reduction has increased the cost that pressurizes again.
In the pressure oscillating absorption, there is the suitable adsorbent of many classes.Feed gas constituents and those skilled in the art known other factors is usually depended in selection.Usually, Shi Yi adsorbent comprises molecular sieve, silica gel, activated carbon, activated alumina and other porous metal oxide.When purifying contained the logistics of methane, methane often was adsorbed with the impurity that hope is removed.Adsorbent be chosen in the problem of selecting to have proposed to have between hydrogen and selected impurity, particularly light hydrocarbon such as methane and the ethane adsorbent aspect of maximum adsorption power difference.
In order to overcome compromise and to improve PSA, the high osmosis material that also has the high power capacity that is used for the pressure oscillating absorber is studied.Its implication is the material with very high surface area and high porosity.Expectation increases the heap(ed) capacity of adsorbent, and pressurization demand is again minimized.This means higher desorption pressures.
One embodiment of the present invention are the method for utilizing pressure oscillating absorption to remove methane and other light hydrocarbon compounds such as ethane from the hydrogen incoming flow.This method comprises that the hydrogen incoming flow that will have hydrocarbon is passed through on the adsorbent in adsorption zone, and adsorbs under the temperature and pressure of a part of hydrocarbon being enough to.Residual gas in the incoming flow becomes the outflow logistics of the hydrocarbon content with reduction.Adsorbent in this method is the material that is known as organometallic skeletal (MOF), and has high surface and high porosity.The surface area of this material is greater than 1500m 2/ gm.Subsequently the pressure in the adsorption zone is reduced to the pressure that is used for the hydrocarbon desorb, and produces the outflow logistics of hydrocarbon content with enrichment.This outflow logistics will have the methane content of increase, because methane is light hydrocarbon main in the hydrogen incoming flow.Other light hydrocarbon comprises ethane, propane, butane and a spot of other hydro carbons.This method is passed through poor carbon dioxide purge gas can comprising during the desorb on adsorbent.
This method can by or with adsorbent bed among the high pressure adsorption zone by, and adsorbent bed is moved to the low pressure desorption zone carry out subsequently, for example adopt the adsorbent wheel in the cylinder absorber to carry out.This method also can by alternatively pressurize adsorbent bed and with incoming flow in bed by and will reduce pressure adsorbent bed and with purge gas in bed by carrying out.
Improve these methods and realize continuous process by the sequence of using at least two adsorbent beds, bed is circulated so that continued operation to be provided in a sequential manner by absorption and desorption procedure.This comprises the process of adsorbent bed circulation and first adsorbent bed is pressurized to adsorptive pressure and incoming flow is flowed on first adsorbent bed, and desorption pressures and purge flow is flowed on second adsorbent bed simultaneously reduces pressure second adsorbent bed to.Forward incoming flow and purge flow to second adsorbent bed and first adsorbent bed respectively, and second adsorbent bed is pressurized to adsorptive pressure and incoming flow is flowed on second adsorbent bed, desorption pressures and purge flow is flowed on first adsorbent bed simultaneously reduces pressure first adsorbent bed to.This method can further change pressure by extra bed and seamlessly transit, and wherein before conversion is flowed intermediate bed is pressurizeed or decompression.
Being used for reducing in the method for hydrogen incoming flow hydrocarbon content and particularly methane, incoming flow is passed through on adsorbent in first adsorption zone, under the maximum pressure of this method, hydrocarbon is adsorbed thus, produces the hydrogen stream that reduces hydrocarbon.The hydrogen stream of this minimizing hydrocarbon is discharged from adsorption zone, makes to form hydrocarbon absorption cutting edge of a knife or a sword (front) also gradually towards the outlet motion in hydrogen incoming flow porch in this district.Preferably, make this adsorption zone size to fit to make the hydrogen gas product of hydrocarbon concentration less than 1 volume %.When hydrocarbon absorption cutting edge of a knife or a sword is in the absorbing unit predetermined point or the increase of hydrocarbon is higher than predetermined value in hydrogen flows, stop the incoming flow of this absorbing unit.Stop the incoming flow of first adsorption zone subsequently, and import second adsorption zone.With first adsorption zone decompression and purge gas is passed through from first adsorption zone, thus in first adsorption zone with adsorbent reactivation.This purge gas preferably flows on the direction of the mobile convection current of incoming flow in respect to adsorption zone, removes hydrocarbon thus on the rightabout of absorption.
When making the regeneration of first district, with its stress level that is pressurized to incoming flow again, make incoming flow forward first district to, and with decompression of second adsorption zone and employing purge gas regeneration under regeneration condition, and repeat this process cycles.
The operating condition of pressure swing adsorption comprises the adsorptive pressure of 2MPa (20atm.)～5MPa (50atm.).The desorption pressures scope is 1kPa (1atm.)～1.5MPa (15atm.), and preferable range is 500kPa (5atm.)～1MPa (10atm.).This desorption procedure is preferably operated being enough to make again pressing and desorption to flow out under the minimized pressure of logistics.Adsorbent must be heat-staple in the certain temperature range, and operates under 0 ℃～400 ℃ temperature.
This method may further include, and purge flow is passed through on adsorbent to promote the desorb of hydrocarbon under desorption condition.Desorb can be flowed out logistics pressurizes and imports in the fuel system.Preferably make adsorbate desorb under middle pressure, the pressurization again that logistics is flowed out in desorb is minimized.The hydrocarbon stream of Jia Ya desorb can be used as fuel gas again.
Found to have the new material of the superperformance that is used for adsorbing separation.These materials are MOF, perhaps metal-organic framework materials.MOF has high surface areas per unit volumes, and has high porosity.MOF is the porous material of a new generation, and it has crystal structure, comprises repetitive with positively charged metal or metal oxide and the organic unit to electric charge with balance.The hole dimension that MOF provides the selection that can adopt the organic structure unit to control, wherein bigger organic structure unit can provide bigger hole dimension.Depend on the material among the MOF and the size in the hole that forms for the capacity of specific gas and characterization of adsorption.The structure of MOF and formation unit can find among the disclosed WO 2002/088148 on September 1st, 2005 disclosed US 2005/0192175 and on November 7th, 2002, and the two all is incorporated herein by reference.
The material that is used for this method comprise have multiple metal, MOF that metal oxide, metal cluster (metalcluster) or metal oxide cluster (metal oxide cluster) constitute the unit, hereinafter be called metal and constitute the unit, wherein metal is selected from transition metal and the beryllium in the periodic table.Preferred metals is drawn together zinc (Zn), cadmium (Cd), mercury (Hg) and beryllium (Be).Metal constitutes the unit and connects to form loose structure by organic compound, wherein be used to connect the organic compound that adjacent metal constitutes the unit and comprise 1,3,5-benzene three benzoic ethers (1,3,5-benzenedicarboxylate, BTB), 1,4-benzene dicarboxylic acid ester (1,4-benzenedicarboxylate, BDC), cyclobutyl 1,4-benzene dicarboxylic acid ester (cyclobutyl1,4-benzenedicarboxylate, CB BDC), 2-amino 1, (2-amino 1 for 4-benzene dicarboxylic acid ester, 4-benzenedicarboxylate, H2N BDC), tetrahydrochysene pyrene 2,7-dicarboxylic ester (tetrahydropyrenedicarboxylate, HPDC), terphenyl dicarboxylic ester (terphenyl dicarboxylate, TPDC), 2, and 6-naphthalene dicarboxylic acids ester (2,6-naphthalene dicarboxylate, 2,6-NDC), pyrene 2, (pyrene 2,7-dicarboxylate for the 7-dicarboxylic ester, PDC), the diphenyl dicarboxylic acid ester (biphenyl dicarboxylate, BDC), the any dicarboxylate compounds that perhaps has phenyl.
The improved concrete material that is presented at the absorption property aspect has the loose structure of three-dimensional extension and comprises: have general formula Zn 4O (1,3,5-benzene three benzoic ethers) 3Material MOF-177, have general formula Zn 4O (1,4-benzene dicarboxylic acid ester) 3Material MOF-5 (being also known as IRMOF-1), have general formula Zn 4O (cyclobutyl 1,4-benzene dicarboxylic acid ester) 3Material IRMOF-6, have general formula Zn 4O (2-amino 1,4-benzene dicarboxylic acid ester) 3Material IRMOF-3 and have general formula Zn 4O (terphenyl dicarboxylic ester) 3, or Zn 4O (tetrahydrochysene pyrene 2,7-dicarboxylic ester) 3Material IRMOF-11, have general formula Zn 4O (2,6-naphthalene dicarboxylic acids ester) 3Material IRMOF-8.
These materials are owing to high surface has high power capacity, and have favourable thermoisopleth, and wherein adsorbent discharges a large amount of adsorbates under the middle pressure of about 5atm. (0.5MPa).
Embodiment
Use metallic organic framework to improve from comprising hydrogen (H 2) the high pressure logistics in remove methane (CH 4) and other light hydrocarbon.In this particular example, this is that high useless the pressure used, and wherein waste gas stream is imported in the fuel system.By adsorbent is regenerated under middle pressure, owing to there is significant saving in required the pressurization again of reducing.Fuel system is usually in 4atm～7atm (operation under the pressure of 400kPa～700kPa).Among this embodiment, main impurity is methane, and in the PSA system adsorption activity of MOF-5 and the activity of activated carbon is contrasted.Shown the thermoisopleth of methane on the adsorbent among the figure, used basis as the pound methane/every cubic feet of adsorbent bed.The methane dividing potential drop of incoming flow is 20atm, and it is adsorbed under the pressure of 5atm subsequently.The heap(ed) capacity of activated carbon and MOF is respectively 1.05 and 2.15lbs-CH 4/ ft 3MOF is shown as the load capacity greater than the twice of carbon.In order to increase the carbon heap(ed) capacity, desorption pressures can be reduced to 1atm, the heap(ed) capacity on the carbon is 1.8 as a result.The low pressure that is used for carbon must be accompanied by and be used for the methane that discharges during the pressing and desorption stage again and turn back to the remarkable increase of the energy consumption aspect of fuel system pressure methane is flowed out logistics.
An aspect of of the present present invention is the combination that obtains changing nemaline material of isothermal or material, make capacity-pressure curve can not increase and stop gradually (taper off), but when pressure increases, still keep significant capacity increase in the normal operation range of pressure oscillating absorber with pressure.MOF provides some this abilities.
Though adopted the preferred implementation of being thought at present to describe the present invention, should be understood that the present invention is defined in disclosed embodiment, but should cover various improvement and equivalent arrangements included within the scope of claims.
Claims (according to the modification of the 19th of treaty)
1, a kind of pressure swing adsorption that is used for removing from the hydrogen incoming flow dealkylation comprises:
(a) in adsorption zone under the temperature and adsorptive pressure that are enough to adsorb at least a portion hydrocarbon component in this incoming flow, the incoming flow that comprises hydrogen and at least a hydrocarbon component is passed through on adsorbent, wherein this adsorbent comprises metallic organic framework (MOF) material, and produce the outflow hydrogen stream of the hydrocarbon content with reduction thus, continuation reaches its adsorption capacity by a period of time up to this adsorbent with this incoming flow substantially on adsorbent;
(b) pressure in the adsorption zone is reduced to desorption pressures and continues to be enough to that therefrom logistics is flowed out in the time of desorb and the desorb of regaining the hydrocarbon content with enrichment with at least a portion hydrocarbon; With adsorption zone is pressurized to again adsorptive pressure and repeating step (a) and (b).
2, the method for claim 1, it passes through purge flow during further being included in desorption procedure on adsorbent.
3, claim 1 or 2 method, wherein this adsorption zone comprises a plurality of adsorbent beds that comprise adsorbent, and makes adsorbent bed pass through adsorptive pressure and desorption pressures circulates in a sequential manner.
4, the method for claim 3 wherein makes the process of adsorbent bed circulation comprise adsorbent bed is passed through among adsorption zone and desorption zone.
5, the method for claim 3 wherein makes the process of adsorbent bed circulation comprise: be pressurized to adsorptive pressure with first, simultaneously with second desorption pressures that reduces pressure; To flow and forward second and forward first to from second from first; Be pressurized to adsorptive pressure with second, simultaneously with first desorption pressures that reduces pressure.
6, each method in the claim 1～2, it further comprises: be enough to adsorb under the temperature and pressure that flows out at least a portion hydrocarbon in the logistics, the outflow logistics is passed through among second adsorption zone, wherein this adsorption zone has the adsorbent that comprises metallic organic framework (MOF) material, and produces the second outflow logistics of the hydrocarbon content with reduction thus; Be enough at least a portion hydrocarbon therefrom under the desorption pressures of desorb with the pressure in the adsorption zone is reduced to, and fetch the desorb effluent of hydrocarbon content with enrichment.
7, each method in the claim 1～2, wherein this MOF comprises the metal-organic framework that system forms, it has multiple metal, metal oxide, metal cluster or metal oxide cluster and constitutes the unit, with the organic compound that is connected adjacent formation unit, wherein this connection compound comprises linear dicarboxylic acid's ester of the phenyl with at least one replacement.
8, each method in the claim 1～2, wherein this MOF is selected from and has general formula Zn 4O (1,4-benzene dicarboxylic acid ester) 3Material MOF-5, have general formula Zn 4O (cyclobutyl 1,4-benzene dicarboxylic acid ester) 3Material IRMOF-6, have general formula Zn 4O (2-amino 1,4-benzene dicarboxylic acid ester) 3Material IRMOF-3 and have general formula Zn 4O (terphenyl dicarboxylic ester) 3, or Zn 4O (tetrahydrochysene pyrene 2,7-dicarboxylic ester) 3Material IRMOF-11, have general formula Zn 4O (2,6-naphthalene dicarboxylic acids ester) 3Material IRMOF-8, have general formula Zn 4O (1,3,5-benzene three benzoic ethers) 3Material MOF-177 and composition thereof.
9, the process of claim 1 wherein that operating temperature is 0 ℃～400 ℃, adsorptive pressure is 2MPa (20atm.)～5MPa (50atm.), and desorption pressures is 100kPa (1atm.)～1.5MPa (15atm.).
10, each method in the claim 1～2, it comprises that further logistics is flowed out in desorb pressurizes again.

Claims (10)

1, a kind of pressure swing adsorption that is used for removing from the hydrogen incoming flow dealkylation comprises:
(a) in adsorption zone under the temperature and adsorptive pressure that are enough to adsorb at least a portion hydrocarbon component in this incoming flow, the incoming flow that comprises hydrogen and at least a hydrocarbon component is passed through on adsorbent, wherein this adsorbent comprises metallic organic framework (MOF) material, and produce the outflow hydrogen stream of the hydrocarbon content with reduction thus, continuation reaches its adsorption capacity by a period of time up to this adsorbent with this incoming flow substantially on adsorbent;
(b) pressure in the adsorption zone is reduced to desorption pressures and continues to be enough to that therefrom logistics is flowed out in the time of desorb and the desorb of regaining the hydrocarbon content with enrichment with at least a portion hydrocarbon; With adsorption zone is pressurized to again adsorptive pressure and repeating step (a) and (b).
2, the method for claim 1, it passes through purge flow during further being included in desorption procedure on adsorbent.
3, claim 1 or 2 method, wherein this adsorption zone comprises a plurality of adsorbent beds that comprise adsorbent, and makes adsorbent bed pass through adsorptive pressure and desorption pressures circulates in a sequential manner.
4, the method for claim 3 wherein makes the process of adsorbent bed circulation comprise adsorbent bed is passed through among adsorption zone and desorption zone.
5, the method for claim 3 wherein makes the process of adsorbent bed circulation comprise: be pressurized to adsorptive pressure with first, simultaneously with second desorption pressures that reduces pressure; To flow and forward second and forward first to from second from first; Be pressurized to adsorptive pressure with second, simultaneously with first desorption pressures that reduces pressure.
6, each method in the claim 1～5, it further comprises: be enough to adsorb under the temperature and pressure that flows out at least a portion hydrocarbon in the logistics, the outflow logistics is passed through among second adsorption zone, wherein this adsorption zone has the adsorbent that comprises metallic organic framework (MOF) material, and produces the second outflow logistics of the hydrocarbon content with reduction thus; Be enough at least a portion hydrocarbon therefrom under the desorption pressures of desorb with the pressure in the adsorption zone is reduced to, and fetch the desorb effluent of hydrocarbon content with enrichment.
7, each method in the claim 1～6, wherein this MOF comprises the metal-organic framework that system forms, it has multiple metal, metal oxide, metal cluster or metal oxide cluster and constitutes the unit, with the organic compound that is connected adjacent formation unit, wherein this connection compound comprises linear dicarboxylic acid's ester of the phenyl with at least one replacement.
8, each method in the claim 1～7, wherein this MOF is selected from and has general formula Zn 4O (1,4-benzene dicarboxylic acid ester) 3Material MOF-5, have general formula Zn 4O (cyclobutyl 1,4-benzene dicarboxylic acid ester) 3Material IRMOF-6, have general formula Zn 4O (2-amino 1,4-benzene dicarboxylic acid ester) 3Material IRMOF-3 and have general formula Zn 4O (terphenyl dicarboxylic ester) 3, or Zn 4O (tetrahydrochysene pyrene 2,7-dicarboxylic ester) 3Material IRMOF-11, have general formula Zn 4O (2,6-naphthalene dicarboxylic acids ester) 3Material IRMOF-8, have general formula Zn 4O (1,3,5-benzene three benzoic ethers) 3Material MOF-177 and composition thereof.
9, the process of claim 1 wherein that operating temperature is 0 ℃～400 ℃, adsorptive pressure is 2MPa (20atm.)～5MPa (50atm.), and desorption pressures is 100kPa (1atm.)～1.5MPa (15atm.).
10, each method in the claim 1～9, it comprises that further logistics is flowed out in desorb pressurizes again.
CNA2006800487355A 2005-12-21 2006-12-13 The use of MOFs in pressure swing adsorption Pending CN101346182A (en)

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US60/752,574 2005-12-21

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WO (1) WO2007111739A2 (en)
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