CN110075805A - A kind of normal temperature preparation method of the metal-organic framework materials of Preferential adsorption ethane - Google Patents
A kind of normal temperature preparation method of the metal-organic framework materials of Preferential adsorption ethane Download PDFInfo
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- CN110075805A CN110075805A CN201910380349.5A CN201910380349A CN110075805A CN 110075805 A CN110075805 A CN 110075805A CN 201910380349 A CN201910380349 A CN 201910380349A CN 110075805 A CN110075805 A CN 110075805A
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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
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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
- 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]
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- 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)
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- 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
Abstract
The invention discloses a kind of normal temperature preparation methods of the metal-organic framework materials of Preferential adsorption ethane.Method includes the following steps: zinc oxide and six hydration copper tetrafluoroborates are dispersed in water and ethyl alcohol；Quinoline-5-carboxylic acid is dispersed in N,N-dimethylformamide；Above-mentioned solution is mixed, gained mixed solution is placed in be stirred at room temperature；Solid product is obtained by filtration in solution after stirring, by purifying, drying, vacuum activating, obtains the metal-organic framework materials of Preferential adsorption ethane.The present invention is prepared for the metal-organic framework materials with good paraffin selectivity at normal temperature, reduces the synthesis energy consumption of material, and material prepared has good ethylene-ethane gas absorption separating property at normal temperatures and pressures.The material can from ethylene-ethane gaseous mixture Preferential adsorption ethane, in addition to this, which also has good steam stability, be directly exposed in air after 40 days still have good crystalline structure.
Description
Technical field
The present invention relates to the adsorption and separation material of ethylene-ethane, in particular to a kind of metal-of Preferential adsorption ethane is organic
The normal temperature preparation method of framework material.
Background technique
Ethylene is one of the chemical products having the call in the world, is occupied an important position in national economy, is weighing apparatus
Measure the one of the important signs that of a national oil development of chemical industry level.Ethylene mostlys come from cracking petroleum hydrocarbon gas, but its often with
Ethane forms admixture of gas.Traditional low temperature distillation technology ethylene purification usually requires 120-180 column plate, and energy consumption accounts for polymerization
The 85% of grade production cost of ethylene.Therefore, the method that ethylene-ethane is efficiently separated under development room temperature normal pressure is very necessary.A variety of
In new separation technology, ADSORPTION IN A FIXED BED lock out operation convenience, facility are simply, it can be achieved that the chemical separation process of high energy efficiency.
Adsorbent is the core of adsorption separation technology, traditional adsorption materials such as commercial sieves, active carbon, active carbon molecular sieve
Material and metal organic frame (Metal-Organic Frameworks, MOFs) have been used in the purification application of alkene.But
It is the usual Preferential adsorption alkene of these adsorbent materials, and needs that ability is desorbed in alkene in continuous adsorption-desorption cycle
The alkene of polymer grade purity is obtained, this will generate additional energy consumption.In addition, MOFs is mostly by solvent-thermal method in high temperature
It is prepared under high pressure.Such as M2(dobdc) material needs 120 DEG C to heat and react obtained for 24 hours, is the very high mistake of energy consumption
Journey significantly increases the application cost of adsorption separation technology.Therefore the MOFs normal temperature synthesis method of research high energy efficiency is used to prepare
Chemical adsorbing separation material with paraffin selectivity is very important.
Summary of the invention
The present invention overcomes the deficiencies of the prior art and provide a kind of the normal of the metal-organic framework materials of Preferential adsorption ethane
Warm preparation method.
The purpose of the present invention is achieved through the following technical solutions:
A kind of normal temperature preparation method of the metal-organic framework materials of Preferential adsorption ethane, comprising the following steps:
(1) zinc oxide and six hydration copper tetrafluoroborates are dispersed in the mixed liquor of water and ethyl alcohol；
(2) quinoline-5-carboxylic acid is dispersed in N,N-dimethylformamide；
(3) step (1) solution is poured into step (2), gained mixed solution is placed in and is stirred at room temperature；
(4) solid product is obtained by filtration in the solution after step (3) stirring, by purifying, drying, vacuum activating, obtained
The metal-organic framework materials of Preferential adsorption ethane.
In the above method, step (1) specifically:
Dehydrated alcohol (EtOH) and water (H is added in six hydration copper tetrafluoroborates and zinc oxide2O) ultrasound 5 in mixed solution
It is uniformly mixed within~30 minutes, the six hydration copper tetrafluoroborate and zinc oxide molar ratio are 3:1~1:1；EtOH and H2O molar ratio
For 50:1~2:1.
In the above method, step (2) specifically:
It is evenly dispersed by ultrasound 5~30 minutes in quinoline-5-carboxylic acid addition N,N-dimethylformamide (DMF) solution；Institute
Stating quinoline-5-carboxylic acid and six hydration copper tetrafluoroborate molar ratios is 3:1~1:1；N,N-dimethylformamide and dehydrated alcohol
Molar ratio is 3:1~1:1.
In the above method, step (3) specifically: step (1) solution is poured into step (2) solution, gained is mixed molten
Liquid is placed in be stirred at room temperature, when stirring a length of 15min~for 24 hours.
In the above method, step (4) specifically: solid product is obtained by filtration in the solution after step (3) stirring, process is pure
Change, dry, vacuum activating, obtains the metal-organic framework materials of Preferential adsorption ethane；The filtering obtained solid product, first
It is rinsed 2-5 times using 20mL~60mL n,N-Dimethylformamide, reuses 12~72h of soaked in absolute ethyl alcohol, every 6~18h is more
Change a dehydrated alcohol；Impregnating terminates to filter place the product in 70~180 DEG C of vacuum drying 4~18h of activation, the gold activated
Category-organic framework material.
Compared with prior art, the present invention has the following advantages and beneficial effects:
The present invention is prepared for the metal-organic framework materials with good paraffin selectivity at normal temperature, reduces material
Synthesis energy consumption, material prepared has good ethylene-ethane gas absorption separating property at normal temperatures and pressures.The material can
The Preferential adsorption ethane from ethylene-ethane gaseous mixture, in addition to this, the material also have good steam stability, directly exposure
Still there is after 40 days good crystalline structure in air.
Detailed description of the invention
Fig. 1 is the ethylene-ethane adsorption isotherm map (25 DEG C) that embodiment 1,2,3 prepares material.
Fig. 2 is the XRD characterization figure that embodiment 1,2,3 prepares material.
Fig. 3 is that embodiment 1,2,3 prepares the material exposure XRD diagram after 40 days in air.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
11.745mg zinc oxide (0.145mmol) and 0.1g six are hydrated copper tetrafluoroborate (0.29mmol) to be added to
0.15mL H2In the mixed solution of O and 6mL dehydrated alcohol, ultrasonic 5min obtained solution A.0.1g quinoline-5-carboxylic acid is added to
Ultrasound 5min obtained solution B in 6mL DMF solution.Solution A is poured into solution B and is mixed, is placed in and stirs 1h at room temperature, filters and divides
From.Obtained solid product is rinsed 3 times using DMF, ethyl alcohol is reused and carries out immersion 48h, every 12h replaces an ethyl alcohol.It impregnates
After filter, place the product in 8h is dried in vacuo at 120 DEG C, obtain product.
Embodiment 2
23.49mg zinc oxide (0.29mmol) and 0.1g six are hydrated copper tetrafluoroborate (0.29mmol) and are added to 0.15mL
H2In the mixed solution of O and 6mL dehydrated alcohol, ultrasonic 5min obtained solution A.0.1g quinoline-5-carboxylic acid is added to 6mL DMF
Ultrasound 5min obtained solution B in solution.Solution A is poured into solution B and is mixed, is placed in and stirs 12h at room temperature, filters separation.It will
Obtained solid product is rinsed 3 times using DMF, is reused ethyl alcohol and is carried out immersion 48h, every 12h replaces an ethyl alcohol.After immersion
It filters, place the product in 8h is dried in vacuo at 120 DEG C, obtains product.
Embodiment 3
11.745mg zinc oxide (0.145mmol) and 0.1g six are hydrated copper tetrafluoroborate (0.29mmol) to be added to
0.15mL H2In the mixed solution of O and 6mL dehydrated alcohol, ultrasonic 5min obtained solution A.0.1g quinoline-5-carboxylic acid is added to
Ultrasound 5min obtained solution B in 6mL DMF solution.Solution A is poured into solution B and is mixed, is placed in and stirs 12h at room temperature, is filtered
Separation.Obtained solid product is rinsed 3 times using DMF, ethyl alcohol is reused and carries out immersion 48h, every 12h replaces an ethyl alcohol.Leaching
It is filtered after bubble, place the product in 8h is dried in vacuo at 120 DEG C, obtains product.
The metal-organic framework materials of Preferential adsorption ethane obtained by various embodiments of the present invention, ethylene-ethane, C1~
C3 gas absorption performance and characterization result are as follows:
(1) ethylene-ethane gas absorption performance measures
Adsorption instrument, which is mostly used, using Micromeritics 3Flex full function tests embodiment 1 prepared by the present invention, real
Example 2, the ethylene-ethane Adsorption Isotherms in embodiment 3 are applied, result is as shown in Figure 1.
As can be seen from the figure the metal-organic framework materials of three Preferential adsorption ethane prepared by the present invention, can be from
Preferential adsorption ethane in ethylene-ethane gaseous mixture, and there is good ethylene-ethane separation selectivity.
(2) XRD characterization is analyzed
Implementation prepared by the present invention is tested using the full-automatic X-ray diffractometer of the D8-ADVANCE type of German Bruker company
Example 1, embodiment 2,3 material of embodiment XRD spectra, their characteristic peaks within the scope of 2 θ=5 °~50 ° are as shown in Figure 2.
Fig. 3 shows the metal-organic framework materials of Preferential adsorption ethane prepared by three examples, 2 θ~10.1 ° ±
0.1 °, 15.7 ° ± 0.1 °, 18.4 ° ± 0.1 ° and 20.4 ° ± 0.1 ° shows apparent characteristic peak.Show it with good
Crystal framework structure.
(3) steam stability
Implementation prepared by the present invention is tested using the full-automatic X-ray diffractometer of the D8-ADVANCE type of German Bruker company
Example 1, embodiment 2,3 material of embodiment expose the XRD spectra after 40 days in air, they are within the scope of 2 θ=5 °~50 °
Characteristic peak is as shown in Figure 3.
Fig. 3 shows the metal-organic framework materials of Preferential adsorption ethane prepared by three examples, is being exposed to air
In after 40 days, people shows well at 2 θ~10.1 ° ± 0.1 °, 15.7 ° ± 0.1 °, 18.4 ° ± 0.1 ° and 20.4 ° ± 0.1 °
Characteristic peak.Show that it is being exposed in air after 40 days, still there is good crystalline structure, there is good steam to stablize
Property.
(4) pore structure characterizes
Embodiment 1 prepared by the present invention, real is tested using ASAP2010 specific surface area and distribution of pores structural test machines
Apply example 2,3 material of embodiment at 196K using CO2The pore structure of gas test, test result are as shown in table 1.
Table 1
(note: SBET aFor BET specific surface area；SLangmuir bFor Langmuir specific surface area；PVcFor Kong Rong.)
Table 1 shows in a certain range, with the increase of stirring duration, the material specific surface area of invention preparation and hole
Appearance can also increase therewith.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (5)
1. a kind of normal temperature preparation method of the metal-organic framework materials of Preferential adsorption ethane, which is characterized in that including following step
It is rapid:
(1) zinc oxide and six hydration copper tetrafluoroborates are dispersed in the mixed liquor of water and ethyl alcohol；
(2) quinoline-5-carboxylic acid is dispersed in N,N-dimethylformamide；
(3) step (1) solution is poured into step (2), gained mixed solution is placed in and is stirred at room temperature；
(4) solid product is obtained by filtration in the solution after step (3) stirring, by purifying, drying, vacuum activating, obtained preferential
Adsorb the metal-organic framework materials of ethane.
2. the normal temperature preparation method of the metal-organic framework materials of Preferential adsorption ethane, feature exist according to claim 1
In step (1) specifically:
Dehydrated alcohol (EtOH) and water (H is added in six hydration copper tetrafluoroborates and zinc oxide2O) 5 ~ 30 points of ultrasound in mixed solution
Clock is uniformly mixed, and the six hydration copper tetrafluoroborate and zinc oxide molar ratio are 3:1 ~ 1:1；EtOH and H2O molar ratio be 50:1 ~
2:1。
3. the normal temperature preparation method of the metal-organic framework materials of Preferential adsorption ethane, feature exist according to claim 1
In step (2) specifically:
It is evenly dispersed by ultrasound 5 ~ 30 minutes in quinoline-5-carboxylic acid addition N,N-dimethylformamide (DMF) solution；The quinoline
Quinoline -5- carboxylic acid and six hydration copper tetrafluoroborate molar ratios are 3:1 ~ 1:1；The molar ratio of N,N-dimethylformamide and dehydrated alcohol
For 3:1 ~ 1:1.
4. the normal temperature preparation method of the metal-organic framework materials of Preferential adsorption ethane, feature exist according to claim 1
In step (3) specifically: step (1) solution is poured into step (2) solution, gained mixed solution is placed in and is stirred at room temperature,
The h of a length of 15min ~ 24 when the stirring.
5. the normal temperature preparation method of the metal-organic framework materials of Preferential adsorption ethane, feature exist according to claim 1
In step (4) specifically: solid product is obtained by filtration in the solution after step (3) stirring, it is living by purifying, drying, vacuum
Change, obtains the metal-organic framework materials of Preferential adsorption ethane；The filtering obtained solid product first uses the mL of 20 mL ~ 60
N,N-Dimethylformamide is rinsed 2-5 times, and 12 ~ 72 h of soaked in absolute ethyl alcohol is reused, and every 6 ~ 18h replaces a dehydrated alcohol；
Impregnating terminates to filter place the product in 70 ~ 180 DEG C of vacuum drying 4 ~ 18 h of activation, the metal-organic framework material activated
Material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938213A (en) * | 2019-12-19 | 2020-03-31 | 北京工业大学 | Preparation method of copper-based microporous metal organic framework material and gas separation application thereof |
| CN113583252A (en) * | 2021-08-16 | 2021-11-02 | 大连理工大学盘锦产业技术研究院 | Microporous metal organic framework Cu (Qc)2Preparation method of (1) |
| CN115044050A (en) * | 2022-05-25 | 2022-09-13 | 华南理工大学 | Metal organic framework-organic molecular chain covalent modification material preferentially adsorbing alkane and preparation method thereof |
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| WO2017223046A1 (en) * | 2016-06-20 | 2017-12-28 | North Carolina State University | Metal-organic frameworks and methods of making and use thereof |
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2019
- 2019-05-08 CN CN201910380349.5A patent/CN110075805A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017223046A1 (en) * | 2016-06-20 | 2017-12-28 | North Carolina State University | Metal-organic frameworks and methods of making and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| JUNJIE ZHAO ET AL: "Facile Conversion of Hydroxy Double Salts to Metal−Organic Frameworks Using Metal Oxide Particles and Atomic Layer Deposition Thin-Film Templates", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938213A (en) * | 2019-12-19 | 2020-03-31 | 北京工业大学 | Preparation method of copper-based microporous metal organic framework material and gas separation application thereof |
| CN110938213B (en) * | 2019-12-19 | 2021-05-07 | 北京工业大学 | Preparation method of copper-based microporous metal organic framework material and gas separation application thereof |
| CN113583252A (en) * | 2021-08-16 | 2021-11-02 | 大连理工大学盘锦产业技术研究院 | Microporous metal organic framework Cu (Qc)2Preparation method of (1) |
| CN113583252B (en) * | 2021-08-16 | 2022-08-05 | 大连理工大学盘锦产业技术研究院 | Microporous metal organic framework Cu (Qc) 2 Preparation method of (1) |
| CN115044050A (en) * | 2022-05-25 | 2022-09-13 | 华南理工大学 | Metal organic framework-organic molecular chain covalent modification material preferentially adsorbing alkane and preparation method thereof |
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