EP3134197A1 - Adsorption chimique coopérative de gaz acides dans des structures organométalliques fonctionnalisées - Google Patents

Adsorption chimique coopérative de gaz acides dans des structures organométalliques fonctionnalisées

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Publication number
EP3134197A1
EP3134197A1 EP15782401.2A EP15782401A EP3134197A1 EP 3134197 A1 EP3134197 A1 EP 3134197A1 EP 15782401 A EP15782401 A EP 15782401A EP 3134197 A1 EP3134197 A1 EP 3134197A1
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EP
European Patent Office
Prior art keywords
metal
recited
group
ligand
adsorption
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EP15782401.2A
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German (de)
English (en)
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EP3134197A4 (fr
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Jeffrey Long
Thomas Mcdonald
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University of California
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University of California
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Publication of EP3134197A4 publication Critical patent/EP3134197A4/fr
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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
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present technology pertains generally to fluid stream separation schemes and methods for producing metal-organic frameworks, and more particularly to the production and use of metal-organic frameworks with metal atoms that are coord inatively bound to polytopic linkers and ligands that expose basic nitrogen atoms to the pore volumes and the flow of gases.
  • Carbon dioxide generated from the combustion of fossil fuels for heat and electricity production is a major contributor to climate change and ocean acidification.
  • the predicted growth of the global economy and world population in the near future will lead to an increased demand for energy, resulting in even further increases in the concentration of CO2 in the atmosphere.
  • coal and natural gas fired power plants released more than 1 1 .1 gigatons of carbon dioxide in to the atmosphere, which accounts for nearly 30% of total global emissions.
  • Typical flue gas is also released at ambient pressure and at temperatures ranging from about 40°C to 80 °C.
  • the separation of CO 2 from H 2 is also important in the context of two distinct applications: (i) the capture of pre and post combustion CO2 emissions like those produced from coal gasification power plants, and (ii) the purification of hydrogen gas, which is synthesized on large scales annually.
  • Separation of CO 2 from CH 4 is another separation relevant to the purification of natural gas, which can have up to 92% CO2 impurity at its source.
  • Carbon dioxide removal is required for approximately 25% of the natural gas reserves in the United States. Removal of CO2, is typically conducted at pressures between 20 bar and 70 bar with existing processes.
  • Solid adsorbents including zeolites, activated carbons, silicas, and metal-organic frameworks, have received significant attention as
  • zeolites for carbon dioxide capture. Compared to aqueous alkanolamine absorbents, zeolites require significantly less energy input for adsorbent regeneration. However, zeolites have hydrophilic properties that limit their application to separations that do not include water.
  • Activated carbon is another solid adsorbent for carbon dioxide
  • MOFs Metal organic frameworks
  • nanoporous crystalline solids built of metal coordination sites linked by organic molecules show promising properties for gas capture applications. Due to their high surface areas and tunable pore chemistry, the separation capabilities of certain metal-organic frameworks have been shown to meet or exceed those achievable by zeolite or carbon adsorbents.
  • the technology pertains to cooperative chemical adsorption of
  • An acid gas is defined as any gas that can form a covalent bond with an amine or other basic nitrogen group on the ligand or any gas that results in the formation of ammonium with an amine upon adsorption.
  • the methods can work for any gas that is capable of a chemical reaction with an amine including CO 2 , SO 2 , CS 2 , H 2 S, SO 3 , SR 2 , RSH, NO 2 , NO 3 , NO, BR3, and NR 3 etc.
  • This cooperativity results in a large increase in the amount of gas adsorbed with only a small change in adsorption conditions. This is best manifested as a discontinuity (step) in the adsorption isotherm.
  • the metal- organic frameworks for CO 2 adsorption produce an unusually shaped isotherm (the relationship between CO 2 adsorption amount and CO 2 pressure at constant temperature).
  • the first derivative of the isotherm in its functional function form of gas uptake versus pressure) is always positive and its value decreases monotonically as pressure is increased from low pressure to high pressure.
  • the first derivative of the isotherm is also positive. Before the step, the first derivative of the isotherm also decreases;
  • the value of the positive first derivative suddenly increases over a pressure regime. After the step concludes, the first derivative resumes the expected decrease with increasing pressure. It is possible for more than one step to exist in each isotherm.
  • the isotherm step moves to higher pressures at higher temperatures. Unlike other adsorbents, the shape of the isotherm allows the material to adsorb CO 2 more efficiently at higher temperatures. Most adsorbents adsorb CO 2 less efficiently with higher temperatures. Advantages of CO 2 adsorption at higher temperatures include reducing the amount of water adsorbed, reducing the size of the adsorption bed, and reducing the temperature swing of the material between adsorption and regeneration.
  • amine-based adsorbents capture CO 2 or other acid gases and that by understanding the mechanism it has been possible to tune the CO 2 adsorption isotherm to match the step position with the partial pressure of CO 2 in the gas mixture.
  • the CO 2 binding involves breaking a nitrogen-element bond, where the element is not hydrogen. All other amine-based adsorbents are understood to bind CO 2 by breaking a nitrogen-hydrogen bond.
  • the CO 2 adsorption isotherm step position is related to the metal-amine bond strength. This is not how other amine-based CO 2 adsorbents work. It is possible to match the step position to the concentration of gas for removal of an acid gas, particularly CO 2 , by changing the strength of metal-amine bond in the framework. Adsorbent stability is also increased by changing metal-amine bond strength.
  • the composition of the porous adsorbent preferably a metal-organic framework
  • the temperature of adsorption the temperature of adsorption
  • the pressure of the adsorptive the composition of the gas mixture
  • the entropy of the gas mixture the manner in which the material was previously treated.
  • the amount of non-target gases (H 2 O, SO 2 , N 2 , etc.) that are adsorbed can be reduced by changing the substituent's on the diamine.
  • Adsorbent stability can be increased by using amines with boiling points above regeneration temperature of the adsorbent (i.e. using less volatile amines).
  • the framework family has a functionalized surface having two adjacent amines wherein an ammonium is formed from one amine and a carbamate is formed from the other amine.
  • the metal-organic frameworks have a functionalized pore surface having adjacent amine adsorption sites that adsorb at least one CO 2 molecule. Adsorption sites adapt a regular, and repeating orientation. The new orientation allows each site to contribute to the adsorption of two or more CO 2 molecules. Adsorption also occurs without a significant change in the volume of the adsorbent.
  • chemical adsorption method is provided using a metal-organic framework that has functionalized surface locations with two adjacent amines.
  • An ammonium is formed from one of the amines and a carbamate is formed from the other amine and a CO 2 molecule is adsorbed with the adjacent amines.
  • the two adjacent adsorption sites are a subset of a plurality of adsorption sites where cooperativity occurs and the amines adsorb CO 2 at the same time and form chains or aggregates of ammonium carbamate. These chains of ammonium carbamate extend along the surface of the metal-organic framework in at least one direction.
  • Carbon dioxide adsorption applications include: removing CO 2 from outside air; removing CO 2 from air people breath; removing CO 2 as a greenhouse gas from the emissions of power plants; removing CO 2 from natural gas; removing CO 2 from oxygen; sensor for the presence of CO 2 ; using the heat of adsorption for making heat; and the use of the adsorbent as a heat pump.
  • FIG. 1 is a schematic flow diagram of a method of gas separations according to one embodiment of the technology.
  • FIG. 2A is an idealized adsorption isotherm with a typical Langmuir- type isotherm shape.
  • FIG. 2B is a step shaped isotherm of one embodiment of the present technology.
  • FIG. 3A through FIG. 3C depicts the mechanism for CO 2 adsorption at three neighboring M-mmen sites within an infinite one-dimensional chain of such sites running along the crystallographic c axis of a mmen- M 2 (dobpdc) compound.
  • Simultaneous proton transfer and nucleophilic attack of N on a CO2 molecule forms an ammonium carbamate species that destabilizes the amine coordinated at the next metal site, initiating the cooperative adsorption of CO2 by a chain reaction.
  • FIG. 4 depicts CO 2 adsorption isotherms at 40°C shown on a linear scale for ⁇ , ⁇ '-dimethylethylenediamine derivatives of Mg 2 (dobpdc), Mn 2 (dobpdc), Fe2(dobpdc), Co2(dobpdc), and Zn 2 (dobpdc).
  • FIG. 5 depicts CO2 adsorption isotherms at 40°C shown on a
  • FIG. 6 depicts CO2 adsorption isotherms at 40°C shown on a
  • the difference in the isotherm step position is attributable to changes in the metal-amine bond strength differences between Mg and Co.
  • FIG. 7 depicts CO2 adsorption isotherms at 40°C shown on a
  • FIG. 8 depicts CO 2 adsorption isotherms at 100 °C shown on a
  • FIG. 9 depicts CO2 adsorption isotherms at 25 °C shown on a
  • FIG. 10 depicts CO2 adsorption isotherms at 120 °C shown on a logarithmic scale for ethylenediamine, N-methylethylenediamine, and ⁇ , ⁇ '- dimethylethylenediamine derivatives of Mg 2 (dobpdc).
  • the difference in the isotherm step position is attributable to increasing the strength of interaction between the amine and CO2 that form the carbamate or increasing the strength of the ammonium carbamate interaction can overcome the increased metal-amine bond strength associated with primary amines.
  • FIG. 1 1 depicts CO2 adsorption isotherms at 50 °C shown on a
  • FIG. 12 depicts CO 2 adsorption isotherms at 120 °C shown on a logarithmic scale for ethylenediamine, 1 ,2-diaminopropane, and 1 ,2- diaminocyclohexane derivatives of Mg 2 (dobpdc).
  • the difference in the isotherm step position and number of steps is attributable to changing the nature of alkyl groups on the alkyl bridge that connects the two diamines.
  • FIG. 13A depicts CO 2 adsorption isotherms at 40°C shown on a logarithmic scale for ⁇ , ⁇ '-dimethylethylenediamine derivatives of
  • FIG. 13B depicts isosteric heats of adsorption calculations indicating nearly identical heats of CO 2 adsorption onto the ⁇ , ⁇ '- dimethylethylenediamine derivatives of Mg 2 (dobpdc) and Mn 2 (dobpdc). Differences in CO 2 step position are thus associated with entropic effects associated with translational, vibrational, and rotational motions of the diamines prior to CO2 adsorption.
  • FIG. 14 depicts H 2 O adsorption isotherms at 40 °C shown on a linear scale for N,N-dimethylethylenediamine, ⁇ , ⁇ -diethylethylenediamine, and ⁇ , ⁇ -diisopropylethylenediamine derivatives of Mg 2 (dobpdc).
  • the difference in the amount of water adsorbed at a particular pressure is attributable to using alkyl groups of various sizes to reduce the amount of pore space available for non-acid gas molecules to adsorb.
  • FIG. 1 For illustrative purposes, embodiments of the apparatus and methods for gas separations are generally shown.
  • One embodiment of the technology is described generally in FIG. 1 to illustrate the methods. It will be appreciated that the methods may vary as to the specific steps and sequence and the apparatus may vary as to structural details without departing from the basic concepts as disclosed herein.
  • the method steps are merely exemplary of the order that these steps may occur. The steps may occur in any order that is desired, such that it still performs the goals of the claimed technology.
  • FIG. 1 one method 10 for separating acid gases from a stream of gases using functionalized porous frameworks with controlled step-shaped isotherms is generally shown.
  • the apparatus configuration and separation conditions can be optimized for gas separation capacity, temperature and pressure swings and regeneration energy.
  • Typical separations include pre- combustion feedstock gas separations such as the removal of carbon dioxide from natural gas, digester gas, or syngas as well as post
  • combustion separations such as flue gas streams.
  • the selection of the type of framework or particular framework can account for the composition of the gases to be treated and the temperature and pressure at the time of presentation to the separator.
  • the regeneration energy and temperature swing requirements and framework cost, stability and reactivity can also be considered in the selection of the framework configuration and the functionalizing ligands.
  • the framework that is selected at block 20 is prepared at block 30 of FIG. 1 .
  • the preferred frameworks for acid gas separations are porous metal-organic framework compositions of metal atoms coord inatively bound to polytopic organic linkers that have pores whose dimensions that permit the flow of gases and have interior surfaces that expose coordinatively unsaturated metal ions.
  • the framework is further functionalized with ligands that are bound to the coordinatively unsaturated metal ions that expose basic nitrogen atoms to the pore volumes.
  • Ligands are prepared and the framework is functionalized at block 40.
  • the preferred frameworks that are prepared at block 30 are metal organic frameworks that have metal atoms in an oxidation state appropriate to binding with both a polytopic linker and basic nitrogen ligand elements.
  • the metal is one or more atoms selected from the group Al, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Sc, Ti, V, and Zn.
  • Mg 2 (dobpdc), Mn 2 (dobpdc), Fe 2 (dobpdc), Co 2 (dobpdc), and Zn 2 (dobpdc) are shown in FIG. 4 and FIG. 5 respectively.
  • the structure of the metal organic framework is determined in part by the rigid or semi-rigid polytopic organic linkers that are used in its formation.
  • Preferred polytopic linker molecules include aromatic
  • the polytopic linker is composed of one or more linkers selected from the group: 1 ,3,5-benzenetripyrazolate; 1 ,3,5- benzenetrisinazoiate; 1 ,3,5-benzenetristetrazolate, 1 ,3,5- benzenetricarboxylate; 1 ,4-benzenedicarboxy!ate; and 2,5-dioxido-1 ,4- benzenedicarboxylate.
  • the linkers containing at least two cyclic rings, two carboxylate groups, and two oxido groups such as 4,4'-dioxido- 3,3'-biphenyldicarboxylate and 4'-4"-dioxido-3',3"-terphenyldicarboxylate.
  • the framework has a metal is selected from the group Ca, Fe, Mn, Cu, Co, Ni, Cr, or Cd and the polytopic liker is 1 ,3,5-benzenetripyrazolate.
  • the metal is selected from the group Ca, Fe, Mn, Cu, Co, Ni, Cr, or Cd and the polytopic linker is 1 ,3,5-benzenetristetrazolate.
  • the metal is selected from the group Cr, Mn, Fe, Co, Ni, or Cu and the polytopic linker is 1 ,3,5-benzenetristriazolate.
  • Another embodiment has a framework where the metal is selected from the group Cd, Fe, Al, Cr, Ti, Sc or V and the polytopic linker is 1 ,3,5- benzenetriscarboxylate or 1 ,4-benzenedicarboxylate.
  • Yet another framework has metal selected from the group Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn and the polytopic linker is 2,5- dioxido-1 ,4-benzenedicarboxylate.
  • Another preferred framework has a metal selected from the group Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn and the polytopic ligand is 4,4'-dioxidobiphenyl-3,3'-dicarboxylate.
  • the functionalizing ligand that is selected and prepared at block 40 of FIG. 1 preferably has an amine that will expose basic nitrogen atoms within the pore volume when bound to the metal organic framework.
  • the basic nitrogen ligand is a primary, secondary, or tertiary alkylamine. In another embodiment, the basic nitrogen ligand is a primary or secondary imine.
  • the preferred functionalizing ligand prepared at block 40 is a diamine.
  • Suitable ligand diamines include: ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, 1 ,2-propanediamine, 2,3-butanediamine, 1 ,2-diamino-2-methylpropane, N- boc-ethylenediamine, N-ethylethylenediamine, ⁇ , ⁇ '- diethylpropylenediamine, ⁇ , ⁇ -diethylethylenediamine, N- isopropylethylenediamine, ⁇ , ⁇ '-diisopropylethylenediannine, N- isopropylpropylenediamine, ⁇ , ⁇ '-diisopropylpropylenediannine, ⁇ , ⁇ '- diisopropylethylenediamine, , N-methylethylenediamine, ⁇ , ⁇ '- dimethylethylenediannine, N-methylpropylenediamine, ⁇ , ⁇ '- dimethyl
  • ⁇ , ⁇ , ⁇ ', ⁇ '-tetrannethylpropylenediannine diethylenetriamine, 2-(2- aminoethyoxy)ethylannine, dipropylenetriamine, 1 ,2-diaminocyclohexane, piperazine, and ths(2-aminoethyl)amine.
  • Other ligands include 2- (Diisopropylphosphino)ethylamine N-methylethanolamine, and
  • the mechanism can work for separating any acid gas that can chemically react with an amine including CO2, SO2, CS2, H 2 S, SO3 SR 2 , RSH, NO 2 , NO 3 , NO, BR 3 and NR 3 .
  • a diamine or polyamine ligand is particularly preferred.
  • the metal-organic framework is particularly preferred.
  • composition has adjacent amine groups where exposure to CO2 results in reversible formation of an ammonium carbamate complex from pairs of adjacent amines.
  • adjacent amine groups have basic nitrogen atoms separated by less than 1 nm. This proximity allows a proton transfer to occur. For example CO2 binding of this type is not achieved without proton transfer from one amine to the next to form an ammonium carbamate ion pair.
  • the formation of a first ammonium carbamate complex lowers energetic barriers that enable subsequent complexes to be formed under the same conditions of temperature and pressure.
  • separations is a framework formed from a 4,4'-dioxidobiphenyl-3,3'- dicarboxylate polytopic ligand and a basic nitrogen ligand of ⁇ , ⁇ '- dimethylethylenediamine and the metal is selected from the group Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn.
  • the frameworks that are prepared at blocks 30 and 40 are tunable phase-change adsorbents that permit the cooperative chemical adsorption of carbon dioxide and other acid gases in metal-organic frameworks for efficient gas separations and capture.
  • adsorption for example, produce an unusually shaped isotherm (the relationship between CO2 adsorption amount and CO2 pressure at constant temperature) that gives these materials excellent properties. It was found that the reason for the isotherm shape is the mechanism by which the acid gas is adsorbed. The amine ligand which was previously bonded to a metal-organic framework is reorganized. The reorganization is dependent on the metal of the framework. The mechanism is general to metal sites with closely spaced amines (or other atoms) coordinated to them. Unlike other adsorbents, the shape of the isotherm allows the material to adsorb CO2 more efficiently at higher temperatures as most adsorbents adsorb CO2 less efficiently with higher temperatures.
  • FIG. 2A depicts variations in idealized CO2 adsorption behavior with temperature for a classical microporous adsorbent showing the usual Langmuir-type isotherm shape. This can be compared with the isotherm shape of FIG. 2B of the phase-change adsorbent showing a step-shaped (sometimes referred to as 'S-shaped') isotherm.
  • 2B indicates the working capacity (that is, the amount of gas removed) for a separation performed using a temperature swing adsorption process in which selective adsorption occurs at P ads and Tiow and desorption is performed at P de s and T high for a classical adsorbent or T m edium for the phase change adsorbent described herein.
  • FIG. 2A and FIG. 2B illustrates the extraordinary advantages
  • adsorbent exhibiting step-shaped isotherms in a temperature swing adsorption process versus the Langmuir-type isotherms observed for most microporous adsorbents.
  • 0W ) is contacted with the adsorbent, which selectively adsorbs a large amount of CO 2 .
  • the adsorbent is heated to liberate pure CO 2 with a partial pressure of P d es, and is then reused for subsequent adsorption/desorption cycles.
  • P d s low pressure
  • the steepness of the isotherm gradually diminishes as the temperature increases, necessitating a high desorption temperature to achieve a significant working capacity for a separation.
  • a phase-change adsorbent of the type described here (FIG. 2B)
  • the position of the isotherm step shifts dramatically to higher pressures as the temperature increases, such that a large working capacity can be achieved with only a small increase in temperature.
  • the CO 2 adsorption isotherm can be tuned to match the step position with the partial pressure of CO 2 in the gas mixture. For an efficient carbon capture process, one would ideally create a phase-change adsorbent with a large vertical step positioned just below the partial pressure of CO 2 in the flue gas.
  • the CO 2 adsorption isotherm step position is primarily related to the metal-amine bond strength. Manipulation of the bond strength will allow control over the isotherm step positions that are shown in FIG. 2B.
  • the metal-heteroatom (particularly metal- amine) bond strength, and therefore CO 2 step position can be adjusted by changing the identity of the metal in the framework.
  • the metal- heteroatom bond strength, and therefore the CO 2 step position can be adjusted by changing the identity of the heteroatom.
  • Mg 2 (dobpdc) can be functionalized with two isomers of dimethylethylenediamine. N,N- dimethylethylenediamine (one primary amine and one tertiary amine
  • Mg 2 (dobpdc) can be functionalized with a series of
  • the alkyl group of the secondary amine was varied to include N- methylethylenediamine, N-ethylethylenediamine, and N- isopropylethylenediamine.
  • the step position of the methyl group containing material occurs before the step position of the ethyl group-containing compound.
  • the step position of the ethyl group occurs between the isopropyl containing material.
  • Metal-heteroatom bond strength, and therefore CO 2 step position can also be adjusted by changing the identity of the substituents on the heteroatom.
  • metal-amine bond strength, and therefore CO 2 step position can be adjusted by changing identity of the amine steric and/or electronic properties. As shown in FIG. 7, the difference in the isotherm step position is attributable to changes in the metal-amine bond owing to changes in the steric and electronic properties of the amine that is bonded to the metal site.
  • Mg 2 (dobpdc) can be functionalized ⁇ , ⁇ '- dimethylethylenediamine and ⁇ , ⁇ '-dimethylpropylenediamine.
  • the position and number of steps in the isotherm can be changed since the orientation and energetics of the ammonium carbamate changes.
  • FIG. 1 1 depicts CO2 adsorption isotherms at 50 °C shown on a logarithmic scale for ⁇ , ⁇ '- dimethylethylenediamine and ⁇ , ⁇ '-dimethylpropylenediamine derivatives of Mg 2 (dobpdc). The difference in the isotherm step position and number of steps is attributable to changing the length of the bridge between the two diamines.
  • Mg 2 (dobpdc) can be functionalized 1 ,2-diaminopropane and 1 ,2- diaminocyclohexane.
  • the position of the steps is shifted versus ethylenediamine due to energy differences created by the steric bulk.
  • FIG. 12 depicts CO2 adsorption isotherms at 120 °C shown on a logarithmic scale for ethylenediamine, 1 ,2-diaminopropane, and 1 ,2-diaminocyclohexane derivatives of Mg 2 (dobpdc).
  • the difference in the isotherm step position and number of steps is attributable to changing the nature of alkyl groups on the alkyl bridge that connects the two diamines.
  • the step is associated with a large change in entropy that occurs when disordered amines and CO2 become organized into chains.
  • the initial entropy of the framework is related to the strength of the metal-amine bond and to what extent the diamine can move with translation, vibrational, and rotational degrees of freedom.
  • two adsorbents can have steps in different positions despite very similar heats of adsorption owing to entropy differences between the materials. This is exemplified by Mg 2 (dobpdc) and Mn 2 (dobpdc) which possess nearly identical heats of adsorption but different step positions related to the extent that amines are dynamic on the pore surfaces. See FIG. 13A and FIG. 13B.
  • the differences in CO2 step position are thus associated with entropic effects associated with the translational, vibrational, and rotational motions of the diamines prior to CO 2 adsorption.
  • the strength of the C-N bond in a carbamate and the strength of the N-H bond of the ammonium can be changed by altering the steric and/or electronics of the amine.
  • the strength of the ionic interactions between the ammonium and carbamate can also be changed by altering the sterics and/or electronics of both amines.
  • the strength of the carbamate-metal bond can also be changed by changing the identity of the metal.
  • Mg 2 (dobpdc) can be functionalized ethylenediamine, N-methylethylenediamine, and ⁇ , ⁇ '-dimethylethylenediamine.
  • FIG. 10 depicts CO2 adsorption isotherms at 120 °C shown on a logarithmic scale for ethylenediamine, N-methylethylenediamine, and ⁇ , ⁇ '- dimethylethylenediamine derivatives of Mg 2 (dobpdc).
  • the difference in the isotherm step position is attributable to increasing the strength of interaction between the amine and CO2 that form the carbamate or increasing the strength of the ammonium carbamate interaction can overcome the increased metal-amine bond strength associated with primary amines.
  • the step of the adsorbent containing all primary amines occurs prior to the step of the adsorbent containing one primary and one secondary amine.
  • the step of the adsorbent containing one secondary amine occurs before the step of the adsorbent containing two secondary amines.
  • Mg 2 (dobpdc) can be functionalized with a series of
  • diamines containing one primary amine and one tertiary amine containing one primary amine and one tertiary amine.
  • the identity of the alkyl groups on the tertiary amines can be varied to include N,N- dimethylethylenediamine, ⁇ , ⁇ -diethylethylenediamine, and N,N- diisopropylethylenediamine. Due to the reduced steric bulk of the primary amine, the primary amine is expected to coordinate to the metal cation in all three cases. Because of the presence of hydrogen atoms on only the primary amine, the carbamate must form on the primary amine end of the diamine while ammonium must form of the carbamate end of the diamine.
  • the step position of the dimethyl containing adsorbent occurs before the step of the diethyl containing adsorbent.
  • the step of the diethyl containing adsorbent occurs before the step of the diisopropyl containing compound.
  • FIG. 9 depicts CO2 adsorption isotherms at 25 °C shown on a
  • the adsorption properties can also be changed by altering the
  • the adsorption of acid gases is related to the interaction of multiple amines with acid gases to cooperatively adsorb molecules. Other non-acid gases do not adsorb via cooperative mechanisms including H 2 O, N 2 , and hydrocarbons (including but not limited to CH ).
  • H 2 O, N 2 , and hydrocarbons including but not limited to CH .
  • the surface area available for other gases to adsorb onto can be changed without altering the volumetric capacity of the adsorbent for acid gases such as CO 2 .
  • variations of the amine sterics can be used to increase or decrease the amount of other gases adsorbed onto other accessible pore spaces.
  • the adsorption of acid gases, especially CO2 occurs via insertion of CO2 into the metal-amine bonds to form carbamates.
  • the rate of adsorbent degradation can be controlled by changing the strength of the metal-amine bond, such that stronger bonds will reduce amine volatility.
  • heavier amines will generally exhibit increased boiling points.
  • inclusion of steric groups can be used to decrease amine volatility such that the boiling point of the pure amine will be a higher temperature than the optimum adsorbent regeneration temperature.
  • the difference in the amount of water adsorbed at a particular pressure is attributable to using alkyl groups of various sizes to reduce the amount of pore space available for non-acid gas molecules to adsorb as shown in FIG. 14.
  • a mixture stream of gases can be exposed to the solid-phase material for separation at block 50 of FIG. 1 to produce a gaseous stream depleted in CO2 and a solid-phase
  • composition enriched in CO2 or other acid gas The separation conditions as well as the composition of the solid-phase material are also controlled to optimize the separations at block 50.
  • the solid-phase composition enriched in acid gas is
  • the location of the isotherm step should be shifted to lower pressures. This can be accomplished by varying the relative strength of the amine-CO2 and amine-MOF interactions.
  • a higher pressure step is more advantageous than a lower pressure step. This can be accomplished by varying the relative strength of the amine-CO 2 and amine-MOF interactions as well.
  • the amine may be chosen to allow for regeneration to occur under vacuum or pressurized conditions.
  • an adsorbent with a step at a higher pressure over a lower pressure is desirable. This can be accomplished by varying the relative strength of the amine-CO 2 and amine- MOF interactions.
  • the entropy the amines have on the surface of the framework can be changed. This can be accomplished by changing the rate of diamine exchange, which is dependent on the strength of the metal-amine bond and varies for each metal.
  • Adsorption is favorable when the free energy of the phase containing ordered chains of ammonium carbamate is lower in energy than the configuration that allows for adsorption to occur via non-cooperative processes. This is related to the enthalpy of adsorption, the entropy of the solid phase and the entropy of the gas phase.
  • optimum adsorption and desorption conditions can be controlled by altering the entropy of the gas phase surrounding the adsorbent.
  • the entropy of the gas mixture can be changed by varying the temperature of the gas phase, the pressure of the gas phase, or the composition of the gas phase.
  • the presence of multiple gases during desorption can be used to decrease the temperature of desorption owing to the increased entropy of the mixed gas phase during the desorption process.
  • H 4 dobpdc 27.4 mg, 0.10 mmol was added to a 20-ml glass scintillation vial and Mg(NOs) 2 -6 H 2 O (64.0 mg, 0.25 mmol), and 10 ml of mixed solvent (55:45 MeOH:DMF) were subsequently added.
  • the vial was sealed with a PTFE-lined cap and placed in a 2 cm deep well plate on a 393 K hot plate. After 12 h a white powder formed on the bottom and walls of the vial.
  • the reaction mixture was then decanted and the remaining powder was soaked in DMF at 343 K for 12 hours, after which the solvent was decanted and replaced with fresh DMF. This process was repeated 6 times over the course of 3 days.
  • the solvent was switched to MeOH and the process repeated until by infrared spectroscopy the amide stretch of DMF was no longer apparent.
  • the solid was then collected by filtration and fully desolvated by heating under dynamic vacuum ( ⁇ 10 pbar) at 523 K for 24 h to afford 23.3 mg (0.073 mmol), 73% of Mg 2 (dobpdc).
  • the generator was set at 40 kV and 40 mA, due to the oxygen sensitivity of Fe 2 (dobpdc) and mmen- Fe 2 (dobpdc), X-ray diffraction patterns were collected in sealed glass capillaries placed on the powder stage.
  • Infrared spectra were collected on a Perkin-Elmer Spectrum 400 equipped with an attenuated total reflectance (ATR) accessory.
  • Thermogravimetric analysis (TGA) was carried out at a ramp rate of 2 °C/min in a nitrogen flow with a TA Instruments Q5000. Elemental analyses for C, H, and N were performed at the Microanalytical Laboratory of the University of California, Berkeley.
  • the second O atom of the carbamate had a close interaction of 2.61 (9)A ° with the N atom of a neighboring mmen, resulting in chains of ammonium carbamate running along the crystallographic c axis of the structure.
  • the observed ammonium carbamate N...O distance was similar to the distance of 2.66-2.72A " in a single crystal of puremmen-CO 2 (methyl (2-(methylammonio) ethyl) carbamate). This well-ordered chain structure was maintained at 295 K, as determined from a full Rietveld refinement against data collected at this temperature.
  • the adsorption of CO2 at ambient temperatures is associated with a structural transition to form an extended chain structure held together by ion pairing between the metal- bound carbamate units and the outstretched ammonium group of a neighboring mmen molecule.
  • the foregoing structural information enabled the formulation of a detailed mechanism for the adsorption of CO 2 in phase-change adsorbents of the type mmen-M 2 (dobpdc).
  • the uncoordinated amine of a mmen molecule acts as a strong base to remove the acidic proton from the metal-bound amine of a neighboring mmen molecule.
  • Deprotonation occurs only in the presence of CO 2 , such that simultaneous nucleophilic addition of CO2 results in the formation of a carbamate with an associated ammonium countercation.
  • the mechanism of CO2 adsorption suggests that variation of the metal amine bond strength should provide a method of manipulating the isotherm step position.
  • the step position varies in the order Mg ⁇ Mn ⁇ Fe ⁇ Zn ⁇ Co, in good agreement with the published series for octahedral metal complex stabilities.
  • the lack of a step for the Ni compound, even at very high pressures is attributable to the exceptional stability of the Ni-mmen bond, which prevents carbamate insertion from taking place under the conditions surveyed.
  • Effective adsorbents for carbon capture must possess large working capacities for processes occurring at temperatures above 40 °C and at CO2 partial pressures near 0.15 bar for coal flue gas or near 0.05 bar for a natural gas flue stream.
  • the location of the isotherm steps for the Mg and Mn compounds makes them better suited for this application than the Fe, Co or Zn compounds, which are better suited for separations from gas mixtures with higher CO2 concentrations.
  • adsorption isobars were collected under dynamic gas flow.
  • Phase change adsorbents showed very large working capacities when used in temperature swing adsorption processes.
  • mmen- Mg 2 (dobpdc) to give a working capacity in excess of 13 wt%, the material must simply swing between 100 °C and 150 °C.
  • the working capacity of mmen-Mn 2 (dobpdc) was in excess of 10 wt% when cycled between 70 and 120 °C.
  • 15% CO2 in N 2 was flowed over the samples during the cooling phase, whereas 100% CO 2 was used during heating phases.
  • phase-change adsorbents In contrast to aqueous amine absorbents that use heat exchangers to save sensible energy costs, the greater working capacities and smaller temperature swings of phase-change adsorbents allow more economical processes to be developed for a high-enthalpy adsorbent without the use of a heat exchanger. Because phase-change adsorbents saturate with CO2 at their transition point, it is not necessary for adsorption to occur at the lowest possible temperature. Whereas we previously showed thatmmen- Mg 2 (dobpdc) can operate effectively under standard flue gas adsorption conditions (40 °C).
  • Adsorbing CO2 at elevated temperatures affords several additional process benefits besides directly decreasing sorbent regeneration energy.
  • overcoming the competitive adsorption of water vapor, which is present in flue gas at high concentrations presents a serious challenge for solid adsorbents.
  • Amine-based solid adsorbents fare better than those using a purely physical adsorption mechanism, because they are known to retain their affinity for CO 2 under humid conditions.
  • the physical adsorption of water on non-amine binding sites increases the overall regeneration energy of the material.
  • the mmen-Mg 2 (dobpdc) also adsorbed nearly 90% less water at 100 °C than at 40 °C.
  • the energy penalty associated with desorbing co-adsorbed water can be substantially decreased by performing CO2 adsorption at a high temperature, obviating the need for strict flue gas dehumidification.
  • No changes to the CO2 adsorption isotherm were apparent after exposure to water at 40 °C or 100 °C, indicating the stability of the mmen-Mg 2 (dobpdc) in the presence of water vapor even at high temperatures.
  • a method for acid gas separations comprising: (a) determining concentration of an acid gas from a stream of a mixture of gases; (b) preparing a porous metal organic framework of metal atoms bound to polytopic organic linkers; (c) selecting basic nitrogen ligands capable of binding with unsaturated metal ions of the organic framework with a binding strength; (d) binding the basic nitrogen ligands to
  • mixture contains at least one of the following gases CO2, SO2, CS2, H 2 S, SO 3 , SR 2 , RSH, NO 2 , NO 3 , NO, BR3, NR 3 where R is an organic moiety.
  • metal atoms of the framework are atoms selected from the group of atoms consisting of Al, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Sc, Ti, V, and Zn.
  • the polytopic linker is selected from the group 1 ,3,5-benzenetripyrazoiate, 1 ,3,5- benzenetristriazoiate, 1 ,3,5-berszersetristetrazoiate, 1 ,3,5- benzenetricarboxylate, 1 ,4-benzenedicarboxylate; 2,5-dioxido-1 ,4- benzenedicarboxylate, 4,4'-dioxidobiphenyl-3 ! 3 , -dicarboxy!ate and 4'-4"- dioxido-3',3"-terphenyldicarboxylate.
  • the basic nitrogen ligand is an alkylamine selected from the group of a primary, secondary, or tertiary alkylamine.
  • the method comprising: (a) providing a porous metal-organic framework; (b) functionalizing pore surfaces with a plurality of ligands producing two adjacent amines that define adjacent adsorption sites; and (c) adsorbing acid gas molecules with the adjacent amine adsorption sites;
  • the ligand is an alkylamine selected from the group of a primary, secondary, or tertiary alkylamine.
  • a porous metal-organic framework composition for acid gas separations comprising:(a) a plurality of metal atoms bound to polytopic organic linkers forming a porous metal-organic framework; and (b) a plurality of ligands bound to coord inatively unsaturated metal ions that expose nitrogen atoms to pore volumes of the framework; (c) wherein a stepped isotherm is produced upon contact with a stream of mixed gases.
  • composition of any preceding embodiment, wherein the metal atoms of the framework are atoms selected from the group of atoms consisting of Al, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Sc, Ti, V, and Zn.
  • composition of any preceding embodiment, wherein the polytopic linker is selected from the group 1 ,3,5-benzenetripyrazoiate,
  • composition of any preceding embodiment, wherein the metal is selected from the group of Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni,
  • Cu and Zn and the polytopic ligand is 2, 5-dioxido-1 ,4- benzenedicarboxylate.
  • composition of any preceding embodiment, wherein the metal is selected from the group of Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni,
  • Cu, and Zn and the polytopic linker is 4,4'-dioxidobiphenyl-3,3'- dicarboxylate.

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Abstract

L'invention concerne un système et un procédé pour des séparations de gaz acides à l'aide de structures poreuses d'atomes de métal liées de manière coordinative à des lieurs polytopique qui sont fonctionnalisés à l'aide de ligands d'azote basique qui exposent des atomes d'azote aux volumes de pores formant des sites d'adsorption. Des ligands d'azote basique adjacents sur la structure organométallique peuvent former un ammonium à partir d'un ligand et un carbamate à partir de l'autre. La formation d'une paire de carbamate d'ammonium influe sur la formation de carbamate d'ammonium sur des sites d'adsorption adjacents. L'adsorption de gaz acide aux sites d'adsorption forme des agrégats liés de manière covalente de plus d'une paire d'ions de carbamate d'ammonium. L'isotherme d'adsorption de gaz acide peuvent être réglée afin de correspondre à la position de plateau avec la pression partielle de gaz acide dans le flux de mélange de gaz à travers la manipulation de la force de liaison métal-ligand par sélection du ligand, du métal et des matériaux de lieur polytopique.
EP15782401.2A 2014-04-22 2015-04-22 Adsorption chimique coopérative de gaz acides dans des structures organométalliques fonctionnalisées Pending EP3134197A4 (fr)

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CN109201009B (zh) * 2018-11-22 2021-10-29 天津工业大学 负载偶氮的光敏铬金属有机骨架多孔材料的制备和应用

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