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WO2017010771A1 - Procédé de régénération de structure métallo-organique - Google Patents

Procédé de régénération de structure métallo-organique Download PDF

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Publication number
WO2017010771A1
WO2017010771A1 PCT/KR2016/007510 KR2016007510W WO2017010771A1 WO 2017010771 A1 WO2017010771 A1 WO 2017010771A1 KR 2016007510 W KR2016007510 W KR 2016007510W WO 2017010771 A1 WO2017010771 A1 WO 2017010771A1
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WO
WIPO (PCT)
Prior art keywords
metal
hkust
organic framework
acid
mof
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Ceased
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PCT/KR2016/007510
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English (en)
Korean (ko)
Inventor
나명수
한승완
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UNIST Academy Industry Research Corp
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UNIST Academy Industry Research Corp
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Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof

Definitions

  • the present invention relates to a method for regenerating a metal-organic framework (M0F).
  • the present invention relates to a method for simply and efficiently regenerating a metal-organic skeleton whose porosity is damaged by water or the like through an acid-base treatment.
  • Metal-organic frameworks have received a lot of attention as potential potential materials for gas separation, storage, and catalysts.
  • M0F-5 has a large pore volume with a large surface area.
  • practical applications are limited due to instability in atmospheric conditions.
  • HKUST Hl see Hong Kong Univers i ty of Science and Techno l ogy- 1; Chui. Et al., Science 1999, 283, 1148-50
  • HKUST-1 is one of the most studied metal-organic frameworks.
  • the hydrothermal stability of HKUST-1 is better than M0F-5, but still poor for continuous use.
  • the present invention provides a method for treating a damaged metal-organic framework (M0F) with an acid; And (2) regenerating the acid-treated metal-organic framework by amide treatment or base treatment.
  • M0F damaged metal-organic framework
  • the damaged metal-organic skeleton can be simply dissolved in strong acid and used for regeneration, the pH of the solution can be adjusted by internal base generation or external base addition, and the regeneration yield is excellent.
  • This method uses damaged metal-organic frameworks as reactions to regenerate at high yields. It is cost effective because it is environmentally friendly and can recycle expensive ligands.
  • the external base addition method is a little more environmentally friendly to the reaction can proceed without using a solvent containing the amide at room temperature, it can be applied to a large scale batch recycling reaction.
  • FIG. 1 is a schematic representation of a method of dissolving a damaged metal-organic framework in accordance with the present invention in a strong acid and regulating by regulating the pH by internal base generation or external base addition.
  • FIG. 2A shows Powder X-Ray Diffraction (PXRD) patterns of M0F-5, damaged M0F-5 and regenerated M0F-5 immediately after synthesis
  • FIG. 2B shows M0F-5, damaged M0F-5 and regenerated postsynthesis. The nitrogen adsorption isotherm of M0F-5 is shown.
  • PXRD Powder X-Ray Diffraction
  • FIG. 3 shows SEM of (a) initial HKUST-KBasolite C300), (b) damaged HKUST-1, (c) HKUST-1 regenerated from nitric acid containing solution, and (d) HKUST-1 regenerated from hydrochloric acid containing solution. It represents an image.
  • Figure 5 shows SEM images of (a) MOF-5 immediately after synthesis, (b) damaged M0F-5, and (c) regenerated M0F-5.
  • FIG. 15 is an SEM image of HKUST-1 regenerated 1 minute after addition of NaOH solution.
  • FIG. 16 is an IR spectrum of HKUST-1 regenerated after 1 minute from addition of NaOH solution.
  • FIG. 17 is the PXRD pattern of initial state HKUST-1 and HKUST-1 regenerated 1 minute after addition of NaOH solution.
  • 19 is an SEM image of HKUST-1 regenerated from a mixture of four different damaged HKUST-1 samples.
  • HKUST-l is an IR spectrum of HKUST-l regenerated from a mixture of initial state HKUST-l and four different damaged HKUST-l samples.
  • FIG. 21 is a PXRD pattern of HKUST-l regenerated from a mixture of initial HKUST-l and four different damaged HKUST-l samples.
  • FIG. 22 shows initial HKUST-l and four different damaged HKUST-l samples. Nitrogen adsorption isotherm of HKUST-1 regenerated from the mixture.
  • the method for regenerating a metal-organic framework comprises the steps of: (1) treating a damaged metal-organic framework (M0F) with an acid; And (2) regenerating the acid treated metal-organic framework by amide treatment or base treatment.
  • M0F damaged metal-organic framework
  • the above steps may be performed sequentially or simultaneously.
  • the damaged metal-organic framework can be regenerated by treatment with an acid and simultaneously with amide treatment or base treatment.
  • Metal-Organic Framework The metal-organic framework (M0F) targeted in the present invention is not particularly limited, and may be, for example, a metal-organic framework having porosity.
  • the metal-organic framework is M0F-5 (IRM0F-1), HKUST-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF- 8, IRMOF-9, IRMOF-10, IRMOF-ll, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, M0F-74 (Mg), M0F-74 (Fe), M0F- 74 (Co), M0F-74 (Ni), M0F-74 (Zn), MOF-14, MOF-177, MOF—508, UMCM-1, DUT-9, UiO-BPY, UiO-67, ZrMOF-BIPY And UiO-68, MOF-802, MOF-804, MOF-805, MOF-806, and MOF-808.
  • the specific structure (composition) of the metal-organic framework is M0
  • IRMOF-5 Zn40 (BDC-0C5Hn) 3
  • IRM0F-7 Zn 4 0 (BDOC 4 H 4 ) 3
  • MOF-177 Zn 4 0 (BTB) 2
  • MOF-508 Zn 2 (BDC) 2 (BPY)
  • DC BDC- (OH) 2 2, 5-d i hydroxy- 1, 4-benzened i carboxy 1 at e
  • the damaged metal-organic framework may be at least one of the various metal-organic frameworks exemplified above.
  • the damaged metal-organic framework refers to a metal-organic framework that has been degraded or degraded, or deteriorated or deteriorated.
  • the damaged metal-organic framework is water, steam, hydrochloric acid, nitric acid, sulfuric acid phosphoric acid, acetic acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, acetone, carbon tetrachloride, chloroform, dichloromethane, dimethylacetamide, diethylformamide, dimethyl sulfoxide And metal-organic frameworks damaged by sides, benzene, toluene, methanol, ethane, propanol, isopropyl alcohol and the like.
  • the damaged metal-organic framework may comprise a metal-organic framework damaged by water or steam.
  • the damaged metal-organic framework has a porosity and / or BET specific surface area of 99% or less, 90% or less, 80% or less, compared to the metal-organic framework in its initial state immediately after synthesis from the raw material. It can mean a metal-organic framework that is 70% or less.
  • Acid Treatment This step is a step of treating the damaged metal-organic framework (M0F) with an acid.
  • the type of acid used in this step is not particularly limited, but is preferably a strong acid.
  • nitric acid (HN0 3 ), hydrochloric acid (HC1), acetic acid, formic acid, hydrofluoric acid and the like can be used as the acid.
  • the metal-organic framework is generally weak to acids because it is composed of ligands containing carboxyl groups, and the metal-organic frameworks damaged by water are also composed of ligands containing metal ions and carboxyl groups and can be easily dissolved by addition of strong acids. . Damaged metal-organic frameworks contain the same stoichiometric ratios of metal ions and ligands as the metal-organic frameworks before they are damaged. Conditions similar to those required for synthesis.
  • the acid treatment can be carried out in a solvent, for example by adding a solvent and / or an acid to the damaged metal-organic framework.
  • the acid treatment is performed by treating the damaged metal-organic framework with d- 3 alcohol, water, dimethylformamide, acetone, carbon tetrachloride, chloroform, dichloromethane, dimethylacetamide, diethylformamide, dimethylsulfoxide, It may be carried out by stirring in benzene, toluene, or a mixed solvent thereof.
  • Base conditions reaction regeneration reaction
  • This step is a step of regenerating the acid-treated metal-organic framework by amide treatment or base treatment.
  • the regeneration step can be formed in two ways: (i) internal base production (ie in situ pathway) or (ii) external base addition (ie ex situ pathway). Regeneration reaction through internal base generation
  • the regenerating step by treating with amide may include stirring the acid treated metal-organic framework in an amide solvent under a temperature condition of 60 to 150 ° C.
  • the reaction temperature during the amide treatment may be 70 to 120 ° C if more limited.
  • the basic solvent may be added in an amount of 0.75 to 1.25 equivalents, 0.75 to 1.1 equivalents, and 0.9 to 1.1 equivalents based on 1 equivalent of the acid.
  • the basic solvent may be added in an amount of 0.75 to 1 equivalent based on 1 equivalent of the acid.
  • 1 equivalent of base to 1 equivalent of acid means an amount corresponding to the number of moles of base that can neutralize the amount of 1 mole of acid.
  • Nonstoichiometric Reaction may be a non-stoichiometric reaction in terms of the ratio of metal and ligand.
  • the regeneration reaction i.e., the amide treatment or the base treatment can be carried out in the above in s i tu or ex s i tu route after further addition of metal ions to the acid treated metal-organic framework.
  • the addition amount of the metal ions is not particularly limited, but for example, 1 to 50% ⁇ 10 to 40%, or 1 to 30% of the number of moles of metal ions contained in the acid-treated metal-organic framework solution Moles of metal ions can be added.
  • Regenerated Metal-Organic Skeletal The regenerated metal-organic framework, which has undergone more than one step, is prepared in contrast to the metal-organic framework before damage (the initial metal-organic framework just after synthesis from the raw material). Porosity and BET specific surface area of more than% can be recovered.
  • the regenerated metal-organic framework can recover porosity of at least 90%, at least 95% and even at least 98% relative to the metal-organic framework prior to damage.
  • Ethanol was purchased from B & J.
  • Powder X-ray diffraction was performed using Bruker D2 PHASER.
  • Infrared spectra were measured using a ThermoFisher Scientifc iS10 FT—IR spectrometer.
  • HKUST-1 was prepared according to the prior art (S. Xiang et al., J. Am. Chem. Soc. 2009, 131, 12415.).
  • Preparation Example 2 Preparation of Damaged Metal-Organic Skeletal
  • 0.2 mL of a 70% nitric acid solution was prepared with 50 mL of DEF, and 0.25 g of the damaged MOF-5 obtained in Preparation Example 2-1 was dissolved therein.
  • Example 2 Regeneration of HKUST-1 Through Internal Base Production
  • lOmL of 1M nitric acid solution or 1M hydrochloric acid solution, and DMF / EtOH / 3 ⁇ 40 (2: 2 : 1, v / v / v) 50mL was added stirring.
  • the reaction solution was stored for 1 day at 70 ° C. Obon.
  • the solvent was replaced several times for 2 days with DMF and acetone. Samples were dried for 1 day at 120 ° C. in vacuum.
  • the recovery yield was 0.87 g (87%) with nitric acid and 0.70 g (70%) with hydrochloric acid.
  • Example 4 HKUST-1 Regeneration from Mixtures of Different Damage Samples 8.0 g of the mixture of damaged samples obtained in Preparation Example 2-3 was prepared using a 1M HC1 solution.
  • Example 1 Analysis of Regenerated M0F-5 Through Internal Base Production
  • the damaged M0F-5 sample was dissolved in nitric acid solution and M0F-5 was regenerated to the initial state through solvent heat reaction with DEF. .
  • Example 2 Analysis of HKUST-1 Regenerated by Internal Base Production
  • the damaged HKUST-1 was dissolved in a strong acid solution and then subjected to solvent thermal reaction in a mixed solvent of DMF / EtOH / 3 ⁇ 40 to measure the micrometer size.
  • HKUST-1 crystals were obtained (see FIGS. 3 and 7 and 8).
  • Nitrogen adsorption, etc. of HKUST-1 was the same as the initial state HKUST-1 (see Fig. 9).
  • the BET specific surface area of the reproduced HKUST-1 samples (1820 or 1840 m 2 / g) was the same as the specific surface area of the initial state HKUST-1 (1840 m 2 / g).
  • recovery yield there was a slight difference depending on the type of acid. Specifically, the recovery yield of nitric acid treated HKUST-1 reached about 9OT, and hydrochloric acid. The recovery yield of treated HKUST-1 was found to be about 70%.
  • Example 3 Analysis of HKUST-1 Regenerated by External Base Addition
  • HKUST-1 was added only outside the base, without using an amide solvent. Damaged HKUST-1 was regenerated by adjusting to a pH suitable for network structure formation.
  • HKUST-1 The IR spectrum of HKUST-1 regenerated by external base addition was the same as the initial state HKUST-1 (see FIG. 10).
  • the damaged HKUST-1 was first dissolved using a strong acid solution such as HC1 solution, and an appropriate amount of NaOH solution was added to adjust the pH of the solution. .
  • HKUST-1 could be regenerated (see FIG. 11).
  • the PXRD pattern of HKUST-1 regenerated by adding 0.775 equivalents of base per equivalent of acid was the same as that of HKUST-1 in the initial state (see FIG. 4A), and the porosity of the regenerated HKUST-1 was also in the initial state.
  • the recovery rate of HKUST-1 was only 38%.
  • the base was added in the same amount, the recovery yield of regenerated HKUST-1 reached a very high value of 87%.
  • HKUST-1 was difficult to regenerate.
  • the PXRD pattern of the crystal product obtained by adding 1.25 equivalents of sodium hydroxide to 1 equivalent of acid was different from that of HKUST-1 in the initial state.
  • the BET specific surface area calculated from the nitrogen adsorption line and the like of the crystal product was only 270 m 2 / g.
  • the dimensions of HKUST-1 crystals regenerated by external base addition are much smaller than those of HKUST— regenerated by internal base generation, the BET specific surface area of these regenerated HKUST-1 are all independent of the regeneration procedure. Same as the initial HKUST-1.
  • the HKUST-1 Unlike the restoration of the M0F-5, which is affected by the type of acid, the HKUST-1
  • HKUST-1 can be regenerated from a solution in which damaged HKUST-1 is dissolved in nitric acid (see FIGS. 12-14).
  • the crystalline HKUST-1 could be recovered in about 92% yield (see FIG. 19).
  • the regenerated HKUST-1 was compared with the initial state of HKUST-1 through IR spectra, PXRD and nitrogen adsorption tests (see FIGS. 20 to 22).
  • the PXRD pattern and IR spectrum of the regenerated HKUST-1 were identical to those of the initial HKUST-1, and the porosity of the regenerated HKUST-1 was comparable to that of the initial HKUST-1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé pour régénérer simplement et efficacement une structure métallo-organique (MOF), qui a une porosité endommagée par l'eau ou analogue, par traitement acide-base, le procédé comprenant les étapes suivantes : traiter une structure métallo-organique endommagée avec un acide ; et régénérer la structure métallo-organique traitée à l'acide à l'aide d'un traitement amide ou d'un traitement de base. Selon le procédé, la structure métallo-organique endommagée peut être utilisée pour une régénération en étant simplement dissoute dans un acide puissant ; le pH d'une solution peut être réglé en formant une base interne et en ajoutant une base externe ; et le rendement de régénération est excellent.
PCT/KR2016/007510 2015-07-13 2016-07-11 Procédé de régénération de structure métallo-organique Ceased WO2017010771A1 (fr)

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KR10-2015-0099344 2015-07-13
KR1020150099344A KR101676442B1 (ko) 2015-07-13 2015-07-13 금속-유기 골격체의 재생방법

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CN111111784B (zh) * 2019-12-12 2022-09-13 广东省石油与精细化工研究院 一种UiO-67包裹Co催化剂及其制备方法和应用
KR102874192B1 (ko) 2020-03-31 2025-10-21 누맷 테크놀로지스, 인코포레이티드 변형된 금속 유기 프레임워크(mof) 조성물, 이의 제조 방법 및 사용 방법
AU2021248803B2 (en) * 2020-03-31 2024-10-24 Numat Technologies Inc. Activated amino containing metal organic framework (MOF) compositions, process of making and process of use thereof
CN113075313B (zh) * 2021-03-22 2022-09-30 武汉海关技术中心 一种测定环境水体和鱼类中的喹诺酮类药物的方法
KR20250099824A (ko) 2023-12-26 2025-07-03 국립창원대학교 산학협력단 금속-유기 골격체의 재생방법 및 재생시스템

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MAJANO, GERARDO ET AL.: "Solvent-mediated Reconstruction of the Metal-organic Framework HKUST-1 (Cu3(BTC)2", ADVANCED FUNCTIONAL MATERIALS, vol. 24, no. 25, 2014, pages 3855 - 3865, XP001590247 *
RAGANATI, F. ET AL.: "C02 Capture Performance of HKUST-1 in a Sound Assisted Fluidized Bed", CHEMICAL ENGINEERING JOURNAL, vol. 239, 2014, pages 75 - 86, XP055348634 *
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