CN110368902A - A kind of guard method of zeolitic imidazolate framework material - Google Patents

A kind of guard method of zeolitic imidazolate framework material Download PDF

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Publication number
CN110368902A
CN110368902A CN201810324002.4A CN201810324002A CN110368902A CN 110368902 A CN110368902 A CN 110368902A CN 201810324002 A CN201810324002 A CN 201810324002A CN 110368902 A CN110368902 A CN 110368902A
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China
Prior art keywords
framework material
zeolitic imidazolate
imidazolate framework
slurries
zif
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CN201810324002.4A
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Inventor
刘蓓
陈光进
孙长宇
陈婉
李海
贾翀之
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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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]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The present invention provides a kind of guard methods of zeolitic imidazolate framework material.This method is the organic ligand that addition synthesizes the zeolitic imidazolate framework material in the slurries of zeolitic imidazolate framework material.The present invention also provides a kind of methods of zeolitic imidazolate framework material for capturing sour gas recycled.The change of cellular structure can occur because of absorbing acid gases in the presence of water to avoid zeolitic imidazolate framework material for the above method of the invention, the recycled for multiple times of zeolitic imidazolate framework material may be implemented, and can preferably separate the sour gas in gaseous mixture.

Description

A kind of guard method of zeolitic imidazolate framework material
Technical field
The present invention relates to a kind of guard methods of zeolitic imidazolate framework material, belong to duct field of material technology.
Background technique
CO2The discharge of equal gases is to cause a principal element of climate change, SO2、SO3The discharge meeting of equal sour gas Generate acid rain, welding.These sour gas constitute people's lives and living environment and greatly threaten, therefore from gas In body mixture, trapping and separating acid gas seem particularly important.
In recent years, very fast to the research and development of zeolitic imidazolate framework material (ZIF material), it is widely used in gas It stores and separates, is catalyzed the fields such as reaction, medicine.Zeolitic imidazolate framework material (ZIF material) is due to the specific surface area of itself Big with pore volume, porosity is high, and structure aperture is adjustable, and brilliant chemical stability and thermal stability, makes it in gas point Greatly advantage is shown from field.Zeolitic imidazolate framework material (ZIF material) is to the large amount of adsorption of sour gas in other Light hydrocarbon gas, but in industrial process, acid gas mixture typically contains a certain amount of vapor, there is environment existing for steam In, zeolitic imidazolate framework material (ZIF material) is extremely sensitive to sour gas, in absorbing acid gases process, duct Irreversible change can occur for structure, make it industrially and cannot achieve continuous operation.
Summary of the invention
It is an object of the invention to be directed to zeolitic imidazolate framework material (ZIF material), skeleton is easy to collapse in water, mentions For a kind of guard method of zeolitic imidazolate framework material.
In order to achieve the above technical purposes, the present invention provides a kind of guard methods of zeolitic imidazolate framework material, should Guard method is the organic ligand that addition synthesizes the zeolitic imidazolate framework material in the slurries of zeolitic imidazolate framework material.
In guard method of the invention, it is preferable that the additive amount of organic ligand is the slurry of zeolitic imidazolate framework material The 5%-40% of the liquid phase quality of liquid；
It is highly preferred that the additive amount of organic ligand is the 10%- of the liquid phase quality of the slurries of zeolitic imidazolate framework material 20%.
In guard method of the invention, it is preferable that the slurries of zeolitic imidazolate framework material are zeolite imidazole ester skeleton Material is added to the slurry suspension formed in liquid medium.
In guard method of the invention, it is preferable that liquid medium is water or water and ethylene glycol, glycerine, in toluene The mixed solvent that one or more are mixed to get.
The guard method of zeolitic imidazolate framework material of the invention, can be to avoid zeolite imidazole ester skeleton in the presence of water The cellular structure of material changes, and can prevent zeolitic imidazolate framework material from meeting the collapsing that skeleton occurs for water.
Invention further provides a kind of methods of zeolitic imidazolate framework material for capturing sour gas recycled, should Method is the organic ligand that addition synthesizes the zeolitic imidazolate framework material in the slurries of zeolitic imidazolate framework material.
In the method for the zeolitic imidazolate framework material of capture sour gas of the invention recycled, it is preferable that The additive amount of organic ligand is the 5%-40% of the liquid phase quality of the slurries of zeolitic imidazolate framework material；It is highly preferred that organic The additive amount of ligand is the 10%-20% of the liquid phase quality of the slurries of zeolitic imidazolate framework material.
In the method for the zeolitic imidazolate framework material of capture sour gas of the invention recycled, it is preferable that Sour gas is aqueous sour gas.It should be noted that here aqueous can be to contain gaseous vapor or liquid water.
In a specific embodiment of the invention, aqueous sour gas includes acid natural gas, coal bed gas, coal or day So the steam reforming gas of gas, flue gas, oil refinery dry gas, oven gas, biogas etc..
In the method for the zeolitic imidazolate framework material of capture sour gas of the invention recycled, it is preferable that The slurries of zeolitic imidazolate framework material are that zeolitic imidazolate framework material is added to the slurry suspension formed in liquid medium.
In the method for the zeolitic imidazolate framework material of capture sour gas of the invention recycled, it is preferable that Liquid medium is the mixed solvent that water or water and one or more of ethylene glycol, glycerine, toluene are mixed to get.
The method of the zeolitic imidazolate framework material of capture sour gas of the invention recycled, can be to avoid zeolite The change of cellular structure occurs because of absorbing acid gases in the presence of water for imidazate framework material, and zeolite imidazole ester may be implemented The recycled for multiple times of framework material.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the high pressure all-transparent sapphire kettle device of the embodiment of the present invention 1.
Fig. 2 is the PXRD diffraction pattern of a variety of materials of the embodiment of the present invention 1.
Fig. 3 is the PXRD diffraction pattern of a variety of materials of the embodiment of the present invention 2.
Fig. 4 is the PXRD diffraction pattern of a variety of materials of the embodiment of the present invention 3.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
Present embodiments provide a kind of ZIF-8 material CO absorption2When, the method for protecting ZIF-8 material structure not collapse is adopted With device as shown in Figure 1, this method is followed the steps below:
Before experiment starts, sapphire kettle is unloaded first, with distilled water flushing, is then cleaned again with deionized water to no droplet Hang on kettle wall；
Water (vapor in simulation gaseous mixture), the ethylene glycol, dimethyl miaow of certain mass ratio are added into sapphire kettle Azoles, ZIF-8；
It stirs evenly, high-pressure sapphire kettle is fastened in constant temperature air bath；To sapphire kettle, equilibrium still and entire high pressure Pipe-line system vacuumizes, and the time is about 15 minutes；
The valve for closing connection vacuum pump is closing vacuum pump.By a certain amount of CO2Equilibrium still is put by high pressure gas cylinder In, after air bath temperature peace weighing apparatus kettle pressure is stablized, the shut-off valve among equilibrium still and sapphire kettle is opened, a certain amount of gas is put Body starts gas absorption experiment, with the progress of reaction, sapphire kettle pressure is begun to decline, to system pressure into sapphire kettle When power no longer changes in 1 hour, it is believed that reach vapor liquid equilibrium, record the pressure of equilibrium still and jewel kettle at this time.
After the completion of adsorption experiment, the slurries in sapphire kettle make CO in the case where heating stirring or vacuum stirring2Desorption Out, desorption operations temperature range is 353.15K to 373.15K.To there is no bubbles to emerge in slurries, it is complete to be considered as desorption. Shut-off valve is opened, makes pressure normal pressure in sapphire kettle, sapphire kettle is unloaded, slurries are poured into evaporating dish, by evaporating dish It is put into vacuum oven, it is 12 hours dry under the conditions of 393.15K.ZIF-8 material is recycled, and its skeleton is characterized by PXRD Structure.
CO is absorbed in water to verify this method to ZIF-8 material2When skeleton structure protection, give difference in Fig. 2 ZIF-8/ water/ethylene glycol/methylimidazole the slurries and ZIF-8/ water of methylimidazole content/ethylene glycol slurries complete primary inhale Receive desorption CO2PXRD diffraction pattern afterwards.In Fig. 2, curve (1) is not absorb CO2Fresh ZIF-8 PXRD diffraction curve, curve It (2) is the PXRD diffraction curve that ZIF-8 is recycled from 20 mass % slurries of ZIF-8/ water/ethylene glycol/methylimidazole, curve It (3) is the PXRD diffraction curve that ZIF-8 is recycled from 3 mass % slurries of ZIF-8/ water/ethylene glycol/methylimidazole, curve (4) For the PXRD diffraction curve for recycling ZIF-8 from ZIF-8/ water/ethylene glycol slurries.From ZIF-8/ it can be seen from experimental result The characteristic peak of the ZIF-8 material recycled in water/ethylene glycol slurries disappears, and skeleton structure is collapsed completely, from ZIF-8/ water/second two The ZIF-8 material structure section that recycles in 3 mass % slurries of alcohol/methylimidazole collapses, and from ZIF-8/ water/ethylene glycol/bis- The ZIF-8 material characteristics peak recycled in 20 mass % slurries of methylimidazole is complete, and skeleton structure still remains.Demonstrate in water and CO2Under the conditions of existing, the addition of a certain amount of methylimidazole effectively protects the skeleton structure of ZIF-8.
Embodiment 2
A kind of method recycled for present embodiments providing zeolitic imidazolate framework material for capturing sour gas, should Method is by ZIF-8/ water/ethylene glycol/methylimidazole slurries in embodiment 1 to CO2Multiple adsorption-desorption circulation is carried out, is tested Equipment, step embodiment 1 are identical.CO2Absorption result is as shown in table 1, from table 1 it follows that in circulation absorption experiment, slurry Liquid is to CO2Absorption property unanimously keep good.ZIF-8 material is recycled from slurries, is characterized by PXRD, it is final to test As a result as shown in figure 3, curve (1) is the PXRD diffraction curve of fresh ZIF-8 material in Fig. 3, curve (2) is after cyclic test times Receive the PXRD diffraction curve of ZIF-8 material.As seen from Figure 3, ZIF-8 material structure after multiple adsorption-desorption is still complete It is whole, illustrate that this method can be used for CO2To CO under conditions of being coexisted with water2Separation, and repeatedly after circulation, suspension slurry absorption point From CO2Effect stability.
Table 1
Embodiment 3
A kind of ZIF-11 material CO absorption2When, the method for protecting ZIF-11 material structure not collapse, this method is according to following Step carries out:
CO is absorbed in water to ZIF-11 material in order to verify the present invention2When skeleton structure protective effect, configure ZIF- 11/ water/ethylene glycol/benzimidazole slurries are to CO2Adsorption and desorption experiment is carried out, experimental facilities, step are same as Example 1.
Benzimidazole is the ligand for synthesizing ZIF-11.ZIF- will be recycled after fresh ZIF-11 material and absorption-desorption experiment 11 materials carry out PXRD diffraction characterization, and final experimental result is as shown in figure 4, curve (1) is fresh ZIF-11 material in Fig. 4 PXRD diffraction curve, curve (2) are the PXRD diffraction curve of recycling ZIF-11 material after absorption-desorption experiment.It can be seen by Fig. 4 Out, ZIF-11 material adsorption-desorption CO2Structure is still complete afterwards, illustrates that method of the invention can be used for CO2The item coexisted with water Part protects ZIFs material skeleton structure.
Above embodiments explanation synthesizes the zeolite imidazole ester bone by adding in the slurries of zeolitic imidazolate framework material Because of absorbing acid gases duct can occur for the organic ligand of frame material in the presence of water to avoid zeolitic imidazolate framework material The recycled for multiple times of zeolitic imidazolate framework material may be implemented in the change of structure, can preferably separate in gaseous mixture Sour gas.

Claims (10)

1. a kind of guard method of zeolitic imidazolate framework material, which is characterized in that this method is in zeolite imidazole ester skeleton material Addition synthesizes the organic ligand of the zeolitic imidazolate framework material in the slurries of material.
2. guard method according to claim 1, which is characterized in that the additive amount of the organic ligand is the zeolite miaow The 5%-40% of the liquid phase quality of the slurries of azoles ester framework material.
3. guard method according to claim 1 or 2, which is characterized in that the additive amount of the organic ligand is the boiling The 10%-20% of the liquid phase quality of the slurries of stone imidazate framework material.
4. guard method according to claim 1, which is characterized in that the slurries of the zeolitic imidazolate framework material are boiling Stone imidazate framework material is added to the slurry suspension formed in liquid medium.
5. guard method according to claim 4, which is characterized in that the liquid medium is water or water and ethylene glycol, third The mixed solvent that one or more of triol, toluene are mixed to get.
6. a kind of method of the zeolitic imidazolate framework material for capturing sour gas recycled, which is characterized in that this method It is the organic ligand that addition synthesizes the zeolitic imidazolate framework material in the slurries of zeolitic imidazolate framework material.
7. according to the method described in claim 6, it is characterized in that, the additive amount of the organic ligand is the zeolite imidazole ester The 5%-40% of the liquid phase quality of the slurries of framework material.
8. the method according to the description of claim 7 is characterized in that the additive amount of the organic ligand is the zeolite imidazole ester The 10%-20% of the liquid phase quality of the slurries of framework material.
9. according to the method described in claim 6, it is characterized in that, the sour gas is aqueous sour gas.
10. according to the method described in claim 6, it is characterized in that, the slurries of the zeolitic imidazolate framework material are zeolite Imidazate framework material is added to the slurry suspension formed in liquid medium.
CN201810324002.4A 2018-04-12 2018-04-12 A kind of guard method of zeolitic imidazolate framework material Pending CN110368902A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113908664A (en) * 2021-10-11 2022-01-11 中国石油大学(北京) Adsorbent for propylene-propane separation, preparation method thereof and propylene-propane separation method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102389686A (en) * 2011-09-22 2012-03-28 中国石油大学(北京) Separating method for CO2-containing mixed gas
CN102600716A (en) * 2012-03-30 2012-07-25 北京化工大学 Method for absorbing CO2 gas by using imidazole ionic liquid at low temperature
CN103058189A (en) * 2013-01-28 2013-04-24 北京化工大学 Absorption and adsorption coupling method for capturing carbon dioxide
CN105013292A (en) * 2014-04-28 2015-11-04 中国石油大学(北京) Combined method for gathering CO2 in gas mixture
CN105149002A (en) * 2015-10-14 2015-12-16 太原理工大学 ZIF-8 encapsulated amino ionic liquid type carbon dioxide adsorbing-catalyzing agent
CN106390768A (en) * 2016-11-14 2017-02-15 中国工程物理研究院化工材料研究所 Zeolite imidazate framework/polyamide composite membrane and preparation method thereof
CN106732390A (en) * 2016-12-02 2017-05-31 太原理工大学 CO high2Modified ZIFs materials of absorption property and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102389686A (en) * 2011-09-22 2012-03-28 中国石油大学(北京) Separating method for CO2-containing mixed gas
CN102600716A (en) * 2012-03-30 2012-07-25 北京化工大学 Method for absorbing CO2 gas by using imidazole ionic liquid at low temperature
CN103058189A (en) * 2013-01-28 2013-04-24 北京化工大学 Absorption and adsorption coupling method for capturing carbon dioxide
CN105013292A (en) * 2014-04-28 2015-11-04 中国石油大学(北京) Combined method for gathering CO2 in gas mixture
CN105149002A (en) * 2015-10-14 2015-12-16 太原理工大学 ZIF-8 encapsulated amino ionic liquid type carbon dioxide adsorbing-catalyzing agent
CN106390768A (en) * 2016-11-14 2017-02-15 中国工程物理研究院化工材料研究所 Zeolite imidazate framework/polyamide composite membrane and preparation method thereof
CN106732390A (en) * 2016-12-02 2017-05-31 太原理工大学 CO high2Modified ZIFs materials of absorption property and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAI LI ET AL.: "CO2 capture using ZIF-8/water-glycol-2-methylimidazole slurry with high capacity and low desorption heat", 《CHEMICAL ENGINEERING SCIENCE》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113908664A (en) * 2021-10-11 2022-01-11 中国石油大学(北京) Adsorbent for propylene-propane separation, preparation method thereof and propylene-propane separation method

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Application publication date: 20191025