WO2017155475A1 - Structure organométallique décorée d'argent pour séparation d'oléfine/alcane - Google Patents

Structure organométallique décorée d'argent pour séparation d'oléfine/alcane Download PDF

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WO2017155475A1
WO2017155475A1 PCT/SG2017/050122 SG2017050122W WO2017155475A1 WO 2017155475 A1 WO2017155475 A1 WO 2017155475A1 SG 2017050122 W SG2017050122 W SG 2017050122W WO 2017155475 A1 WO2017155475 A1 WO 2017155475A1
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organic framework
porous metal
olefin
aromatic compound
nus
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PCT/SG2017/050122
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Dan Zhao
Yuxiang Wang
Zhigang Hu
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National University Of Singapore
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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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • 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
    • 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
    • B01D2256/24—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

Definitions

  • the present disclosure refers generally to the field of olefin/alkane separation, in particular the process of separation using a metal-organic framework.
  • Short chain olefins are one of the most important categories of feedstocks for the chemical industry that could be utilized to synthesize a broad scope of materials ranging from computer parts commonly seen to valuable pharmaceuticals.
  • light olefins are typically obtained from steam cracking of either naphtha or ethane.
  • the separation of this gas mixture in industry is realized by cryogenic distillation, using distillation towers with over 150 trays and operating at 7-28 bar and 183-258K.
  • Such energy intensive process constitutes about 20 % of energy consumption of the whole cracking process whose energy cost is 26-31 GJ/t (in terms of ethylene) for naphtha cracking and 17-21 GJ/t for ethane cracking.
  • a simple modification of the separation process to reduce energy consumption can make a big difference in both cost of production and CO2 emission.
  • MOFs metal-organic frameworks
  • PSA pressure swing adsorption
  • VSA vacuum swing adsorption
  • TSA temperature swing adsorption
  • MOFs metal-organic frameworks
  • MOFs are porous materials constructed from metal-oxygen secondary building blocks and organic linkers bearing various functionalities.
  • MOFs are distinguished candidates for olefin-paraffin adsorption separation owing to their ultrahigh specific surface area, diversified pore size and geometry, and various modification approaches to tune the gas sorption performances.
  • MOFs for olefin-paraffin separation can be divided into two categories according to their selectivities, i.e., alkane-selective MOFs and alkene-selective MOFs.
  • a successful strategy towards alkane-selective MOFs is constructing pore environment judiciously so that paraffins will be preferentially adsorbed in the frameworks thanks to cooperative intramolecular interactions.
  • alkene-selective MOFs apart from the molecular-sieving strategy reported recently, one general guideline is fixing unsaturated metal sites (either as parts of secondary building units or attached functionalities to the bridging ligands) in the MOFs framework.
  • Bloch et al. reported the olefin-paraffin separation ability of FeMOF-74. Olefins introduced into the framework will interact strongly with Fe(II) open sites lined in the one dimensional channels due to the donation of easily polarizable ⁇ bond electrons.
  • the present disclosure refers to a porous metal-organic framework (MOF).
  • the MOF may include a Hafnium or Zirconium metal.
  • the MOF may further include an aromatic compound substituted with at least one carboxylate and optionally with at least one functional group (FG) selected from F, CF 3 , NH 2 , N0 2 , O " , S “ , COO " , SO2 " and PO3 " .
  • the MOF may further include a silver cation, which is complexed to the aromatic compound.
  • the MOF may function as an adsorbent for olefin/alkane separation. It may contain pores in which a mixture of olefin/alkane is directed. These pores, due to an interaction between the silver cation and the double bond of the olefin, may preferentially retain the olefin within the pores, thereby resulting in a separation of the olefin from the alkane.
  • This disclosure presents the synthesis, structural characterizations and gas separation performance of the first hafnium or zirconium based olefin-selective MOF.
  • This Ag(I) decorated MOF exhibits an excellent olefin/alkane separation selectivity of 6 as well as decent recyclability.
  • MHT environmentally-benign hydrothermal
  • PSIE post-synthetic ion exchange
  • the zirconium or hafnium which may be used in this MOF, is substantially non-toxic.
  • the present disclosure refers to method for preparing a porous metal- organic framework as described above.
  • the method may comprise dissolving an aromatic compound, substituted with at least one carboxylic acid and optionally at least one functional group selected from F, CF3, NH2, NO2, O “ , S “ , COO “ , SO2 “ and PO3 " , and a zirconium or hafnium salt in a solvent mixture of water and an organic acid. It may further include heating the solution to a temperature of 50-200°C for 12-60 h to obtain a solid. Subsequently, the obtained solid and a silver salt may be suspended in a solvent mixture of water and an organic solvent.
  • the method thus described proceeds under modulated hydrothermal synthesis conditions.
  • the method as described above may proceed under mild synthetic conditions. Hence, the method may be scaled-up easily and may be environmentally benign.
  • the present disclosure refers to a product obtained by the method as described above.
  • the present disclosure refers to use of a porous metal-organic framework as described above in the separation of an olefin from an alkane.
  • the present disclosure refers to a process for separating an olefin from an alkane comprising placing a porous metal-organic framework as described above into a container and purging the container with a mixture of an olefin and an alkane, wherein the olefin is preferentially retained within the porous metal-organic framework.
  • the process as described above may allow for recycling of the MOF.
  • the MOF may be re-used in the process several times.
  • the present disclosure refers to a porous metal-organic framework (MOF) comprising a metal.
  • MOF may further include the substituted aromatic compound as disclosed and a silver cation complexed to the aromatic compound.
  • the porous metal-organic framework as described above may have a surface area not exceeding 1,500 cm 2 g "1 .
  • Fig. 1 discloses a schematic illustration of using NUS-6(Hf)-Ag for C2H4/C2H6 separation.
  • Fig. 3 discloses PXRD patterns of NUS-6(Hf) and NUS-6(Hf)-Ag.
  • Fig. 4 discloses 3(a - b) TGA analyses (a) and FT-IR spectra (b) of NUS-6(Hf) (solid line) and NUS-6(Hf)-Ag (dotted line), (c) XPS detailed spectra of Ag 3d of NUS-6(Hf)-Ag (solid line) and NUS-6(Hf) (dotted line), (d) XPS detailed spectra of Ag auger lines NUS-6(Hf) (line structure: - ⁇ ⁇ - ⁇ ) and NUS-6(Hf)-Ag (solid line).
  • Fig. 5 discloses (a) SEM images of NUS-6(Hf). (b) SEM images of NUS-6(Hf)-Ag. The scale bars for (a - b) are 1 ⁇ . The magnification of the 'normal' images in (a) and (b) is 10,000 and the magnified images of (a) and (b) is 43,000. (c - f) EDS mapping of silver (c), sulfur (d), hafnium (e) and oxygen (f) in NUS-6(Hf)-Ag. The selected area for EDS mapping is shown in the inset pictures of (c - f).
  • Fig. 6 discloses N2 sorption isotherms at 77 K (a) and pore size distribution (b) of NUS- 6(Hf) and NUS-6(Hf)-Ag.
  • Fig. 7 discloses (a) C2H4 and C 2 H 6 sorption of NUS-6(Hf) and NUS-6(Hf)-Ag at 298 K. (b) Q st of C2H6 and C2H4 in NUS-6(Hf)-Ag. (c) Comparison of IAST C2H4/C2H6 (1 : 1) adsorption selectivity of NUS-6(Hf)-Ag and NUS-6(Hf) at 298 K. (d) Adsorption cycles of NUS-6(Hf)-Ag.
  • Fig. 7 discloses profile of an equimolar gas mixture of ethane and ethylene on a column packed with NUS-6(Hf)-Ag at ambient condition.
  • Fig. 8 discloses ethylene and ethane isotherms of NUS-6(Hf)-Ag at 298 and 313 K.
  • Fig. 9 discloses IAST selectivity of NUS-6(Hf)-Ag for equimolar ethylene-ethane mixture at 298 and 313 K.
  • Fig. 10 is a schematic illustration of using NUS-6(Hf)-Ag for C2H4/C2H6 separation.
  • Fig. 11 shows an XPS survey of NUS-6(Hf) and NUS-6(Hf)-Ag.
  • Fig. 12 shows (a) XPS survey of UiO-66(Hf)-Ag. (b) XPS detailed spectrum of Ag 3d of UiO-66(Hf)-Ag. (c) XPS detailed spectrum of Ag auger lines of UiO-66(Hf)-Ag.
  • Fig. 13 shows SEM images with different magnification of NUS-6(Hf) treated with HBF4 aqueous solution of the pH value similar to that of the mother solution in PSIE process.
  • the surface morphology of these crystals resembled that of NUS-6(Hf)-Ag, suggesting that the rugged surface of the NUS-6(Hf)-Ag crystals may originate from the etching of HBF 4 generated in situ during the ion-exchange process.
  • Fig. 14 shows an EDS spectrum of NUS-6(Hf)-Ag.
  • Fig. 15 shows C2H4 (circle) and C2H6 (square) sorption isotherms of UiO-66(Hf)-Ag
  • Fig. 16 shows C 2 H 4 and C 2 H 6 sorption isotherms of NUS-6(Hf) and NUS-6(Hf)-Ag at
  • Fig. 17 shows the Qst of C 2 H 4 and C 2 H 6 in NUS-6(Hf).
  • Fig. 18 shows (a) N2 sorption isotherm at 77 K of NUS-6(Hf)-Ag after 8 cycles of C 2 H 4 sorption tests (filled, adsorption; open, desorption). (b) XRD pattern of NUS-6(Hf)-Ag after 8 cycles of C2H sorption tests.
  • Fig. 19 shows Breakthrough curves of C 2 H 4 and C2H6 running through a bypass gas line.
  • the dead volume time of the gas mixture was hence calculated to be 466.9 s.
  • Fig. 20 shows typical desorption curves of NUS-6(Hf)-Ag under the condition of 20 seem He flow at room temperature.
  • Fig. 21 shows the 2 nd (a) and 3 rd (b) C 2 H 4 /C 2 H 6 breakthrough curve of NUS-6(Hf)-Ag column.
  • Fig. 22 shows (a) XRD pattern of NUS-6(Hf)-Ag after breakthrough experiment, (b) XPS detailed spectra of Ag 3d. (c) Auger spectrum of Ag of NUS-6(Hf)-Ag after breakthrough experiment.
  • the M4N5N5 line was located at 1133.0 eV and 3ds/ 2 was located at 368.2 eV, leading to a modified auger parameter equal to 721.8 eV.
  • the metal-organic framework may comprise a Hafnium or Zirconium metal; an aromatic compound substituted with at least one carboxylate and optionally with at least one functional group selected from F, CF3, Nth, NO2, O “ , S “ , COO “ , SO2 “ and PO3 “ ; and a silver cation complexed to the aromatic compound.
  • the MOF be microporous and/or mesoporous.
  • the MOF may have a hierarchical micro/meso-porous nature. This micro/meso-porous nature may result in a stepwise adsorption behavior with adsorption-desorption hysteresis (shown in Fig. 6b).
  • the pore width of the pores may be less than about 100 nm, or less than about 50 nm, or less than about 40 nm, or less than about 30 nm.
  • the MOF, having the silver cation complexed to it has the same characteristics in terms of porosity and crystallinity as the MOF without the silver cation complexed to it.
  • the particles formed from the MOF may have a size of about 0.5 to about 3 ⁇ , or about 0.5 to about 2 ⁇ , or about 0.7 to about 1.5 ⁇ , or about 0.7 to about 1.2 ⁇ , or about 1 ⁇ . A small portion of the particles may possess quasi-octahedral shapes.
  • the surface of the MOF may be adorned with grooves and cavities. The distribution of silver, the anionic functional group, hafnium or zirconium and oxygen within the MOF may be even.
  • hafnium or zirconium may be non-toxic and/or environmentally-benign. Further advantageously, the use of hafnium or zirconium may result in strong bonds of the metal to the carboxylate functionality of the substituted aromatic compound.
  • the hafnium or zirconium may be in the oxidation state +4 in the MOF.
  • the periodic assembly of the atoms may form a cell, which may lead to the MOF.
  • the pores may be embedded in this cell (shown in Fig. 2).
  • the cell may contain Bronsted acid and Lewis acid sites.
  • the substituted aromatic compound to be used in this disclosure may be selected from benzene, 1, 3, 5-triphenyl-benzene, benzo-tris-thiophene, triazine, 2, 4, 6-tribenzene and 1, 3, 5, - trinaphthyl benzene.
  • the substituted aromatic compound may provide an electron-rich aromatic pi electron density, enabling the silver cation to be complexed thereto.
  • the substituted aromatic compound to be used in this disclosure may contain at least one carboxylate, optionally at least two carboxylates.
  • the substituted aromatic compound to be used in this disclosure may additionally contain Lewis acid sites which may form additional complexes with the olefin. The complexation of the olefin to either the silver cation or the Lewis acid sites of the substituted aromatic compound may provide a synergistic effect.
  • the substituted aromatic compound may be selected from a compound represented as Formula (I):
  • n is an integer selected from 0 to 4.
  • FG is a functional group as defined above.
  • the functional group may be anionic, optionally selected from the group consisting of O “ , S “ , COO “ , S0 2 - and ⁇ 0 3 " .
  • the substituted aromatic compound may be selected from a compound represented as Formula (la):
  • the substituted aromatic compound may alternatively be selected from a compound represented as Formula (lb):
  • n is an integer from 0 to 3, wherein m + n ⁇ 6; and FG is as defined above.
  • the anionic functional group may be a sulfate anion.
  • the silver cation may be complexed to the sulfate moiety.
  • the silver cation may additionally be complexed to the electron-rich aromatic pi electron density.
  • the substituted aromatic compound may be represented as in Formula (la) and n may be 1.
  • the substituted aromatic compound may be selected from 2-sulfo terephthalic acid.
  • the silver cation may have an oxidation state of Ag(I).
  • the bondings between the silver (I) cation and the olefin in the separation process may be based on a two orbital overlaps.
  • the ⁇ components of these bondings are formed by the overlap of the full ⁇ molecular orbitals of the olefins with the vacant outmost s orbitals of the silver metal.
  • ⁇ components result from the backdonation of electrons from the outer full d orbitals of Ag(I) to the vacant ⁇ * orbitals of olefins.
  • the silver cation may be present in about 5-30 atomic %, preferably in about 8-20 atomic%, more preferably in about 10-15 atomic % of the aromatic compound. In embodiments where there is one anionic functional group within the substituted aromatic compound, the silver cation may therefore be present in about 5-30 atomic %, preferably in about 8-20 atomic %, more preferably in about 10-15 atomic % of the functional group. In one example, the silver cation is present in about 13% of the functional group.
  • the metal-organic framework may have a large surface area. A typical limit for this large surface area may be a surface area of not exceeding 1,500 cm 2 g "1 .
  • the porous metal-organic framework may have a surface area of about 500 - 1,500 cm 2 g "1 , optionally of about 800 - 1,400 cm 2 g "1 , or of about 1,000 - 1,200 cm 2 g "1 .
  • the porous metal-organic framework may be crystalline.
  • the MOF as disclosed herein may retain its crystallinity during the method of production, or it may be only slightly reduced.
  • a method for preparing a porous metal-organic framework comprising i) dissolving an aromatic compound precursor, substituted with at least one carboxylic acid and optionally at least one functional group selected from F, CF3, Nth, NO2, O “ , S “ , COO “ , SO2 “ and PO3 " , and a zirconium or hafnium salt in a solvent mixture of water and an organic acid, heating the solution to a temperature of 50-200°C for 12-60 h to obtain a solid,
  • the method may use water as a co-solvent. Further advantageously, due to the use of hafnium or zirconium, the method of making the MOF may be producing less toxic side products or intermediates and reduce the exposure to hazardous materials.
  • the molar ratio between the substituted aromatic compound precursor and the zirconium or hafnium salt may be approximately 2: 1 to 1 :2, more preferably 1.5: 1 to 1 : 1.5, most preferably approximately 1 : 1 ( ⁇ 10%, optionally ⁇ 5%).
  • the volume ratio between the water and the organic acid may be approximately 3: 1 to 1 : 1, more preferably 2: 1 to 1.2: 1, most preferably approximately 1.5: 1 ( ⁇ 10%, optionally ⁇ 5%).
  • the aromatic compound precursor may be represented by the following Formula (II):
  • n is an integer selected from 1 to 3;
  • n is an integer selected from 0 to 4.
  • FG is a functional group as defined above.
  • the substituted aromatic compound precursor may be selected from a compound represented as Formula (Ha):
  • the substituted aromatic compound precursor may alternatively be selected from a compound represented as Formula (lib):
  • n is an integer from 0 to 3, wherein m + n ⁇ 6; and FG is as defined above.
  • the functional group may be defined as in the first aspect.
  • the zirconium or hafnium salt may be selected from a zirconium or hafnium halogen salt. Alternatively, it may be a zirconium or hafnium nitrate salt.
  • a zirconium or hafnium halogen salt may be selected from fluoride, chloride and bromide salt. In one example, it may be chloride salt.
  • the zirconium or hafnium of the respective salt may have an oxidation state of +4.
  • the organic acid may be a carboxylic acid.
  • the carboxylic acid may be selected from the group consisting of formic acid, acetic acid or propionic acid. In one example, it may be acetic acid.
  • the reaction temperature in step i) may be in the range of about 40 °C to about 200 °C, about 40 °C to about 100 °C, about 40 °C to about 120 °C, about 40 °C to about 140 °C, about 40 °C to about 160 °C, about 40 °C to about 180 °C, about 60 °C to about 80 °C, about 60 °C to about 100 °C, about 60 °C to about 120 °C, about 60 °C to about 140 °C, about 60 °C to about 160 °C, about 60 °C to about 180 °C, about 60 °C to about 200 °C, about 80 °C to about 100 °C, about 80 °C to about 120 °C, about 80 °C to about 140 °C, about 80 °C to about 160 °C, about 80 °C to about 180 ° or, about 80 °C to about 200 °C.
  • the boiling point of the solvent mixture may be
  • the duration of reaction step i) may be in the range of about 8 hours to about 48 hours, about 8 hours to about 40 hours, about 8 hours to about 36 hours, about 8 hours to about 30 hours, about 12 hours to about 48 hours, about 12 hours to about 44 hours, about 12 hours to about 36 hours, about 12 hours to about 24 hours or about 18 hours to about 24 hours.
  • the obtained solid is washed with an organic solvent.
  • the organic solvent may be a polar protic solvent. It may be preferably an alcohol, optionally selected from the group consisting of methanol, ethanol or isopropanol. In one example, it may be methanol.
  • the organic solvent may be water-soluble. As such, it may be selected from the group consisting of methanol, ethanol, acetone, tetrahydrofuran, dimethylformamide and acetonitrile. In one embodiment, it may be acetonitrile.
  • the volume ratio between the water and the organic solvent in step ii) may be approximately 2: 1 to 1 :2, more preferably 1.5: 1 to 1 : 1.5, most preferably approximately 1 : 1 ( ⁇ 10%, optionally ⁇ 5%).
  • step ii) may be conducted under darkness. In some embodiments, step ii) may be repeated. In preferred embodiments, step ii) may be conducted three times. In some embodiments, step ii) may be conducted under room temperature. In some embodiments, the reaction time in step ii) may be in the range of about 8 hours to about 48 hours, about 8 hours to about 40 hours, about 8 hours to about 36 hours, about 8 hours to about 30 hours, about 12 hours to about 48 hours, about 12 hours to about 44 hours, about 12 hours to about 36 hours, about 12 hours to about 24 hours or about 12 hours to about 16 hours.
  • a porous metal-organic framework as disclosed in the first or the third aspect in the separation of an olefin from an alkane.
  • a process for separating an olefin from an alkane comprising placing a porous metal-organic framework as disclosed in the first or the third aspect into a container and purging the container with a mixture of an olefin and an alkane, wherein the olefin is preferentially retained within the porous metal-organic framework.
  • Fig. 1 the process as disclosed above is shown schematically.
  • an ethylene/ethane mixture left side is provided to the MOF (center) and on the right side, only the ethane exits.
  • the ethylene is retained within the MOF.
  • the process of using the MOF as disclosed herein may reduce the exposure to hazardous chemicals as compared with other MOF's.
  • the process may be a pressure swing adsorption process.
  • This pressure swing adsorption (PSA) process may be defined as a process which relies on the fact that under high pressure, gases tend to be attracted to solid surfaces, or "adsorbed". The higher the pressure, the more gas is adsorbed. When the pressure is reduced, the gas is released, or desorbed. PSA processes can be used to separate gases in a mixture because different gases tend to be attracted to different solid surfaces more or less strongly. In some embodiments, the olefin /alkane mixture may therefore be in the gaseous state.
  • the porous metal-organic framework is recyclable.
  • the MOF may be able to undergo the adsorption-desorption separation process of olefins and alkanes at least 3, 5 or 8 times.
  • the MOF as disclosed herein may experience no decrease in specific surface area or crystallinity after at least 3, 5 or 8 cycles of adsorption-desorption.
  • the olefin / alkane mixture to be supplied in the process may be in a molar ratio of 2: 1 to 1 :2, more preferably 1.5: 1 to 1 : 1.5, most preferably approximately 1 : 1 ( ⁇ 10%, optionally ⁇ 5%).
  • the pressure of the process may be at approximately 1 atm in the adsorption cycle.
  • the temperature may be room temperature.
  • olefin / alkane co-adsorption selectivity may be about 3-6, about 4-5, or about 4.4.
  • the olefin and the alkane in the above process may be selected from aliphatic carbon compounds, preferably wherein the aliphatic carbon compounds are selected from Ci-8alkanes and C2-8alkenes.
  • the olefin may be selected from C2-salkenes, more preferably from ethane and propene, and the alkane may be selected from Ci-salkanes, more preferably from ethane and propane.
  • the retaining of the olefin may be based on the interaction of the ⁇ orbitals of the olefin with the s orbitals of the silver cation and the d orbitals of the silver cation to the vacant ⁇ * orbitals of olefins.
  • porous metal-organic framework comprising
  • the metal in the sixth aspect may be selected from a group III, IV, V, VI, X and a group
  • the metal is selected from titanium, zirconium, hafnium, vanadium, chromium, molybdenum, scandium, lead, palladium and cerium.
  • the substituted aromatic compound of the sixth aspect may be defined as in the first aspect.
  • reagents were obtained from commercial suppliers and used without further purification.
  • Field-emission scanning electron microscope (FE-SEM) analyses were conducted on an FEI Quanta 600 SEM (20 kV) equipped with an energy dispersive spectrometer (EDS, Oxford Instruments, 80 mm 2 detector). Samples were treated via Pt sputtering before observation.
  • Thermogravimetric analysis was performed using a Shimadzu DTG-60AH thermal analyzer under a N 2 (100 mL min "1 ) with a heating rate of 10 °C min "1 .
  • FTIR spectra were obtained with a Bio-Rad FTS-3500 ARX FTIR Spectrometer.
  • X-ray photoelectron spectroscopy (XPS) experiments were carried out using a monochromatic Al Ka radiation (1486.6 eV) at 15 kV as the excitation source.
  • Elemental analyses for carbon, hydrogen, nitrogen and sulfur were performed by Elementar vario MICRO cube, while metal contents analyses were conducted by an Inductively Coupled Plasma-Optical Emission Spectrometer (ICP- OES, Perkin Elmer Optima 5300DV). Bed porosity is determined by Mercury Intrusion Porosimetry Micromeritics Autopore III 9420.
  • MOF precursors NUS-6(Hf) or UiO-66(Hf), 500 mg, before activation
  • AgBF 4 2.5 g, 12.8 mmol
  • Breakthrough set up is shown in Fig. 10.
  • the adsorption bed is purged with 20 seem He flow for three days for activation.
  • an equimolar mixture of C2H4 and C2H6 is purged into the bed with a flow rate of 2 seem.
  • the gas composition at the exit of the column is determined by mass spectrometry and the flow rate of each component is calibrated by an internal reference Ar flow that has a flow rate of 4.5 seem.
  • the mean residence time of gas components and the gas uptake of the packed adsorbent are calculated using equation (1), where Fo is the gas molar flow rate at the inlet, F is the gas molar flow rate at the outlet, L is the bed length, vo is the interstitial velocity, ⁇ is the bed porosity, co is the inlet gas concentration and qo is the corresponding gas concentration in the adsorbent. Breakthrough selectivity is calculated using equation 2),
  • Zr/Hf MOFs are well known for their ultrahigh thermal stability and chemical resistivity owing to the robust Zr/Hf-0 bonds. Nevertheless, few research efforts have been put into the development of Zr/Hf based MOFs to separate short chain olefin molecules from the paraffin counterparts of the same carbon number. With the strategy of the introduction of unsaturated open metal sites borne in mind, Zr/Hf MOFs were designed and synthesized that can preferentially adsorb ethylene. Recently, Hf MOFs (NUS-6(Hf)) containing sulfonic groups were prepared through modulated hydrothermal (MHT) method.
  • MHT modulated hydrothermal
  • the sulfonic acid groups in NUS-6(Hf) are ideal anchors for fixing Ag(I) and the Lewis acid sites on the secondary building blocks (SBU) which may be active sites to complex with ethylene. Without being bound to theory, it is speculated that these functionalities may work synergistically to endow the MOF with capability to selectively adsorb ethylene.
  • TGA Thermogravimetric analyses indicates that thermostability of the NUS-6(Hf) is well preserved after PSIE (Fig. 4a).
  • NUS-6(Hf) and NUS-6(Hf)-Ag in this study were characterized by field-emission scanning electron microscopy (FE-SEM) (Fig. 5). Different from the octahedral shape of NUS-6(Hf) prepared by similar MHT method reported previously, most NUS-6(Hf) nanoparticles synthesized in this study exhibit irregular shape (Fig. 5a). Closer inspection reveals agglomeration of small particles and that only a small portion of particles possess quasi-octahedral habit (Fig. 5a, inlet figure). As for NUS-6(Hf)-Ag, the size of the particles basically remain unchanged after PSM (Fig. 5b).
  • NUS-6(Hf)-Ag is adorned with grooves and cavities (Fig. 5b, inlet figure), possibly due to the etching by HBF 4 generated during ion exchange treatment (Fig. 13).
  • EDS energy- dispersive spectroscopy
  • Fig. 5c-5f The inductively coupled plasma-optical emission spectroscopy (ICP-OES) together with elemental analysis shows that approximately 13% of sulfonic groups are attached to Ag(I).
  • ICP-OES inductively coupled plasma-optical emission spectroscopy
  • the Brunauer-Emmett-Teller (BET) surface area of NUS-6(Hf) was determined to be 1194.3 cm 2 g "1 , while NUS-6(Hf)-Ag has a BET surface area of 1027 cm 2 g "1 .
  • This decline in surface area could be attributed to the loading of Ag(I) into the framework and slight loss of crystallinity.
  • the N2 adsorption isotherm of NUS-6(Hf)-Ag shows a steep lifting, most likely due to condensation of N2 on the rugged external surface (Fig. 6a).
  • Quenched solid density functional theories (QSDFT) model indicates that the pore size distribution of the MOF slightly shifts to left hand side after PSIE, but the overall profile remains unchanged (Fig. 6b).
  • Such gas sorption characterizations prove that the porosity and crystallinity of the NUS-6(Hf) is well maintained after PSIE.
  • NUS-6(Hf)-Ag shows a C2H4 uptake of 2.02 mmol g "1 (Fig. 7b), 50 % higher than the uptake of C2H6.
  • the soar of C2H4 isotherm of NUS-6(Hf)-Ag at low pressure range indicates a strengthened framework-guest interaction, which suggests the important role of Ag(I) in enhancing the selectivity for C2H4.
  • UiO-66(Hf)-Ag Compared with NUS-6(Hf)-Ag, UiO-66(Hf)-Ag has very marginal gas adsorption preference towards either C2H4 or C2H6 as UiO-66(Hf) does (Figure 15), which further confirms that sulfonic groups play a vital role in enriching Ag(I) inside the MOF structure.
  • IAST Ideal adsorbed solution theory
  • the selectivity is as high as 6.0 at 100 kPa, not only far exceeding the one of NUS-6(Hf) (0.955), but also surpassing HKUST-1 (3.6), zeolite 5A (4.5), MgMOF-74 (5.6), PCN-16 (2.8) and NOTT-102 (3).
  • HKUST-1 3.6
  • zeolite 5A 4.5
  • MgMOF-74 5.6
  • PCN-16 2.8
  • NOTT-102 NOTT-102
  • NUS-6(Hf)-Ag in separating C2H4 and C2H6.
  • a 50/50 ethylene/ethane mixture was purged through a 14 cm, 1 ⁇ 4' column packed with 750 mg NUS-6(Hf)-Ag with a volumetric flow rate of 2 seem (standard cubic centimeter per minute).
  • the C2H6 breakthrough curve proceeded to an additional roll up.
  • the specific capacity of C2H4 and C2H6 of NUS-6(Hf)-Ag calculated from this breakthrough experiment was determined to be 0.72 mmol/g and 0.16 mmol/g, respectively.
  • the decline in both adsorption capacity and selectivity indicates the competitive adsorption of C2H4 and C2H6 during breakthrough.
  • the difference in crystal qualities of samples prepared in different batches for breakthrough experiments may be another reason for the discrepancy between single gas sorption analysis and binary gas breakthrough experiments.
  • recyclability is another dimension to fully evaluate adsorbents' capabilities in industrial C2H4/C2H6 separation.
  • the column was kept at ambient temperature and flushed with a 20 seem He flow (Fig. 20). Similar with the results (Fig. 7d) of consecutive adsorption- desorption test conducted on the gas sorption analyzer, the column packed with NUS-6(Hf)-Ag demonstrated decent recyclability under mild activation conditions. For the following two more adsorption desorption breakthrough cycles conducted after regeneration (Fig.
  • Corrected residence time is equal to corresponding residence time minus dead volume time.
  • NUS-6(Hf)-Ag will be a competitive material candidate for C2H4/C2H6 adsorption separation. Future work on optimizing the column regeneration condition to reduce the regeneration time will be helpful for evaluation of the full potential of NUS-6(Hf)-Ag in practical industrial scenario.

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Abstract

L'invention concerne une structure organométallique poreuse comprenant un métal de zirconium ou hafnium ; un composé aromatique substitué par au moins un carboxylate et éventuellement par au moins un groupe fonctionnel choisi parmi F, CF3, NH2, NO2, O-, S-, COO-, SO2 - et PO3 - ; et un cation d'argent complexé au composé aromatique. L'invention concerne également un procédé de préparation d'une structure organométallique poreuse telle que définie ci-dessus, consistant à : i) dissoudre un composé aromatique, substitué par au moins un carboxylate et éventuellement au moins un groupe fonctionnel choisi parmi F, CF3, NH2, NO2, O-, S-, COO-, SO2 - et PO3 -, et un sel de zirconium ou hafnium dans un mélange de solvants d'eau et d'un acide organique, à chauffer la solution à une température entre 50 et 200 °C pendant 12 à 60 heures pour obtenir un solide, ii) à mettre en suspension le solide obtenu et un sel d'argent dans un mélange de solvants d'eau et d'un solvant organique. L'invention concerne également un procédé de séparation d'une oléfine et d'un alcane, le procédé consistant à placer une structure organométallique poreuse telle que définie ci-dessus dans un récipient et à purger le récipient avec un mélange d'une oléfine et d'un alcane, l'oléfine étant de préférence retenue dans la structure organométallique poreuse.
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CN110982084A (zh) * 2019-12-10 2020-04-10 北京工业大学 一种基于最短卟啉羧酸配体的锆的金属有机骨架材料和制备及其应用
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CN115739190A (zh) * 2022-11-14 2023-03-07 江南大学 一种植酸金属络合物催化剂及其制备方法与应用

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CN109239246B (zh) * 2018-09-06 2020-06-26 天津商业大学 用金属有机骨架模板法制备多孔钛胶的固相萃取分析方法
CN109239246A (zh) * 2018-09-06 2019-01-18 天津商业大学 用金属有机骨架模板法制备多孔钛胶的固相萃取分析方法
CN110982084B (zh) * 2019-12-10 2021-05-14 北京工业大学 一种基于最短卟啉羧酸配体的锆的金属有机骨架材料和制备及其应用
CN110982084A (zh) * 2019-12-10 2020-04-10 北京工业大学 一种基于最短卟啉羧酸配体的锆的金属有机骨架材料和制备及其应用
CN111495328A (zh) * 2020-04-24 2020-08-07 太原理工大学 方酸钙的氨改性方法及其在乙烯乙烷高效分离中的应用
CN111495328B (zh) * 2020-04-24 2022-05-17 太原理工大学 方酸钙的氨改性方法及其在乙烯乙烷高效分离中的应用
CN111394730A (zh) * 2020-04-29 2020-07-10 Tcl华星光电技术有限公司 蚀刻液再生装置及蚀刻液再生方法
CN112480421A (zh) * 2020-11-09 2021-03-12 武汉理工大学 一种溶剂诱导海胆状MOFs的合成方法
CN112480421B (zh) * 2020-11-09 2023-12-05 武汉理工大学 一种溶剂诱导海胆状MOFs的合成方法
CN113181881A (zh) * 2021-04-29 2021-07-30 郑州大学 一种新型ZIF-8@Ag配合物核壳结构杂化材料及其制备方法和应用
CN113181881B (zh) * 2021-04-29 2023-04-14 郑州大学 一种ZIF-8@Ag配合物核壳结构杂化材料及其制备方法和应用
CN115739190A (zh) * 2022-11-14 2023-03-07 江南大学 一种植酸金属络合物催化剂及其制备方法与应用
CN115739190B (zh) * 2022-11-14 2024-02-13 江南大学 一种植酸金属络合物催化剂及其制备方法与应用

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