CN108276582A - A kind of application of metal-organic framework materials and preparation method and formaldehyde adsorption - Google Patents
A kind of application of metal-organic framework materials and preparation method and formaldehyde adsorption Download PDFInfo
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- CN108276582A CN108276582A CN201711446955.XA CN201711446955A CN108276582A CN 108276582 A CN108276582 A CN 108276582A CN 201711446955 A CN201711446955 A CN 201711446955A CN 108276582 A CN108276582 A CN 108276582A
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- 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
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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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- 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
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Abstract
The invention discloses the applications of a kind of metal-organic framework materials and preparation method and formaldehyde adsorption.The specific surface area of the metal-organic framework materials is 500 600m20.2 0.5cm of/g, Kong Rongwei3/ g, average pore size are 0.55 0.80nm.The metal-organic framework materials are used for formaldehyde adsorption, when concentration of formaldehyde is 90mg/m3‑110mg/m3When, the formaldehyde absorbing amount of the metal-organic framework materials is 0.3 0.4mol/kg.Organic framework material formaldehyde absorbing ability of the present invention is notable, reuses high effect, while thermal stability is higher, can be applied to the higher industrial waste gas purifying field of temperature, has high application value in industry and daily life.
Description
Technical field
The invention belongs to air purification fields, more particularly, to a kind of metal-organic framework materials and preparation method thereof
With the application of formaldehyde adsorption.
Background technology
Formaldehyde pollution is a kind of common air pollution, seriously affects human health.Formaldehyde can stimulate human body eye,
The organs such as nose, larynx, skin cause headache, dizziness, weak, sensory disturbance, immunity reduction, memory loss or even energy
Cause cancer.Common purifying formaldehyde method includes physisorphtion, chemical absorption method, biosorption process, photocatalytic method etc.,
In, physisorphtion has many advantages, such as that technical maturity, easily operated, low energy consumption, of low cost, removal rate is high, and application range is most
It is extensive.
The materials such as the active charcoal of purifying formaldehyde material common in daily life, zeolite, silica at present, however it is this kind of
Material causes formaldehyde absorbing amount small since formaldehyde selective adsorption capacity is weaker, while that there is also adsorption rate is slow, is difficult to regenerate
The problems such as utilization, in indoor air purification, the effect is unsatisfactory.Therefore, efficient, the repeatable purifying formaldehyde utilized is developed
Material has great importance.
Invention content
Adsorption capacity that the present invention solves material formaldehyde in the prior art is weak, adsorptive selectivity absorption is not high, is difficult to
The technical problems such as regeneration provide the application of a kind of metal-organic framework materials and preparation method and formaldehyde adsorption.
It is according to the invention in a first aspect, providing a kind of preparation method of metal-organic framework materials, including following step
Suddenly：
(1) in a solvent by the salt containing yttrium metal ion and trimesic acid dissolving；
(2) solution obtained in step (1) is placed in the reaction kettle that liner is high-molecular compound and is heated；
(3) it is dried to get to metal-organic framework materials after being washed the product obtained in step (2).
Preferably, the chemical reaction of the salt containing yttrium metal and trimesic acid generation is in step (1)：
Wherein Y3+For yttrium metal ion；N is the positive integer more than or equal to 2.
Preferably, before being heated described in step (2), further include the solution that is obtained into step (1) be added dropwise triethylamine and
Nitric acid.
Preferably, the salt containing yttrium metal ion described in step (1) is yttrium nitrate, yttrium sulfate, yttrium chloride or acetic acid yttrium
At least one of；The solvent is the mixed solution of N,N-dimethylformamide and deionized water；
High-molecular compound described in step (2) is polytetrafluoroethylene (PTFE)；The time heated described in step (2) is 12h-
For 24 hours, the temperature of the heating is 100 DEG C -150 DEG C；
It is deionized water, methanol, absolute ethyl alcohol, acetone, N, N- dimethyl methyls that washing described in step (3), which is with solvent,
One or more of amide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide (DMSO) are washed；The temperature of the drying be 60 DEG C-
80℃；The time of the drying is 6h-24h.
It is another aspect of this invention to provide that a kind of metal-organic framework materials are provided, it is any described by claim 1-4
Method is prepared.
Preferably, the specific surface area of the framework material is 500-600m2/ g, Kong Rongwei 0.2-0.5cm3/ g, aperture are
0.55-0.80nm。
It is another aspect of this invention to provide that providing the application that the metal-organic framework materials are used for formaldehyde adsorption.
Preferably, when concentration of formaldehyde is 90-110mg/m3When, the formaldehyde absorbing amount of the metal-organic framework materials is
0.3-0.4mol/kg。
Preferably, when the temperature residing for the formaldehyde is at 570 DEG C or less, the metal-organic framework materials holding structure is steady
It is fixed.
Preferably, after 2-5 times recycles, the adsorbance of formaldehyde maintains just the metal-organic framework materials
The 72%-99% of beginning adsorbance.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, has the following advantages and
Advantageous effect：
(1) a kind of metal-organic framework materials for purifying formaldehyde provided by the invention, specific surface area 500-
600m2/ g, Kong Rongwei 0.2-0.5cm3/ g, average pore size 0.55-0.80nm.The metal cluster and formaldehyde molecule that the material has
It is attached by Van der Waals force and Coulomb force interaction, interaction force bigger, specific surface area, Kong Rong also higher, it can be high
Effect quickly removes formaldehyde, and can recycle.It is tested by formaldehyde absorbing, when concentration of formaldehyde is 90-110mg/m3When, the metal
The formaldehyde absorbing amount of organic framework material is 0.3-0.4mol/kg, and purifying formaldehyde ability is notable, is far above activated carbon；Heat simultaneously
High stability can be applied to the higher industrial waste gas purifying field of temperature, be answered with high with daily life in industry
With value.
(2) a kind of metal-organic framework materials for purifying formaldehyde provided by the invention are recycled by formaldehyde absorbing and are surveyed
Examination experiment, the recycling effect of the 5th remain to maintain the 72% of the 1st time, it is shown that the material has preferable recycling
Effect reduces the application cost of the material.
(3) the present invention provides a kind of preparation method of the metal-organic framework materials for purifying formaldehyde, the preparation sides
Method step is simple, and controllability is strong, and can prepare the high metal-organic framework materials for purifying formaldehyde of purity, have compared with
High commercialization potentiality.
(4) a kind of metal-organic framework materials for purifying formaldehyde provided by the invention, the prices of raw materials of use are just
Preferably, preparation process is simple, and large-scale promotion is suitble to use.
Description of the drawings
Fig. 1 is the XRD spectrum of metal-organic framework materials prepared by embodiment 1；
Fig. 2 is the nitrogen adsorption curve of metal-organic framework materials prepared by embodiment 1；
Fig. 3 is the SEM figures of metal-organic framework materials prepared by embodiment 1；
Fig. 4 is the TGA figures of metal-organic framework materials prepared by embodiment 1；
Fig. 5 is metal-organic framework materials prepared by embodiment 1 and activated carbon in 100mg/m3Formaldehyde under concentration of formaldehyde
Adsorbance comparison diagram；
Fig. 6 is that metal-organic framework materials formaldehyde absorbing prepared by embodiment 1 recycles design sketch.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
Embodiment 1
By six nitric hydrate yttriums of 3.677g and 1.681g trimesic acids be dissolved in 50mL N,N-dimethylformamides and
In the mixed solution of 10mL deionized waters, after the rate stirring 15min of 500r/min, successively with the dropwise addition of 0.05mL/min speed
0.4mL triethylamines and 0.15mL nitric acid is added dropwise in rate, and the sealing of gained mixture is positioned over the high pressure with polytetrafluoroethyllining lining
In reaction kettle, it is placed in 17h in 100 DEG C of baking oven.Product is washed with absolute methanol is placed in 60 DEG C of baking oven dry 8h three times.
Fig. 1 is the XRD spectrum of metal-organic framework materials prepared by the present invention, it can be seen from the figure that the XRD of the material
Characteristic peak is substantially corresponding with theoretical value, shows ideal crystal structure；
Fig. 2 is the nitrogen adsorption desorption curve of metal-organic framework materials prepared by the present invention, is calculated by adsorpting data
The specific surface area of the material is 600m2/ g, Kong Rongwei 0.243cm3/ g, average pore size 0.70nm；
Fig. 3 is the SEM figures of metal-organic framework materials prepared by the present invention, and the material is in needle-shaped as can be seen from Figure；
Fig. 4 is the TGA collection of illustrative plates of metal-organic framework materials prepared by the present invention, and as can be seen from Figure, the material is 570
DEG C or less holding structure stablize；
Metal-organic framework materials of the present invention are suitable for the absorption of any concentration formaldehyde, when concentration of formaldehyde is 90-
110mg/m3When, the formaldehyde absorbing amount of the metal-organic framework materials is 0.3-0.4mol/kg.It is prepared by Fig. 5 present invention
Metal-organic framework materials are with activated carbon in 100mg/m3Formaldehyde absorbing amount comparison diagram under concentration of formaldehyde, as seen from the figure,
The formaldehyde absorbing amount of material prepared by the present invention is 0.382mol/kg, is 6 times or more of activated carbon adsorption amount 0.060mol/kg.
By analysis, a kind of metal-organic framework materials for purifying formaldehyde prepared by the present invention are in formaldehyde
(formaldehyde), the molar ratio of nitrogen (nitrogen), oxygen (oxygen) gaseous mixture is 2:798:Under conditions of 200,
Adsorptive selectivity for formaldehyde is 4151, and heat of adsorption is about 40kJ/mol, shows the outstanding purifying formaldehyde ability of the material.
Fig. 6 is that metal-organic framework materials formaldehyde absorbing prepared by the present invention recycles design sketch, as seen from the figure,
When the material is after recycling 5 times, the adsorbance of formaldehyde maintains the 72% of adsorbance (i.e. initial adsorption amount) for the first time, shows
Y-BTC has preferable recycling effect.
Embodiment 2
Six nitric hydrate yttriums of 2g and 4g trimesic acids are dissolved in 80mL N,N-dimethylformamides and 10mL deionizations
In the mixed solution of water, after the rate stirring 20min of 500r/min, it is added dropwise successively with the drop rate of 0.05mL/min
The sealing of gained mixture is positioned over the autoclave with polytetrafluoroethyllining lining by 0.6mL triethylamines and 0.3mL nitric acid
It is interior, it is placed in 18h in 110 DEG C of baking oven.Product is washed with absolute methanol is placed in 80 DEG C of baking oven dry 6h three times.
Embodiment 3
Six nitric hydrate yttriums of 4g and 2g trimesic acids are dissolved in 50mL N,N-dimethylformamides and 30mL deionizations
In the mixed solution of water, after the rate stirring 10min of 500r/min, it is added dropwise successively with the drop rate of 0.05mL/min
The sealing of gained mixture is positioned over the autoclave with polytetrafluoroethyllining lining by 0.3mL triethylamines and 0.2mL nitric acid
It is interior, it is placed in 20h in 90 DEG C of baking oven.Product is washed with absolute methanol is placed in 80 DEG C of baking oven dry 6h three times.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of metal-organic framework materials, which is characterized in that include the following steps：
(1) in a solvent by the salt containing yttrium metal ion and trimesic acid dissolving；
(2) solution obtained in step (1) is placed in the reaction kettle that liner is high-molecular compound and is heated；
(3) it is dried to get to metal-organic framework materials after being washed the product obtained in step (2).
2. the preparation method of metal-organic framework materials as described in claim 1, which is characterized in that step contains yttrium in (1)
The chemical reaction that the salt and trimesic acid of metal occur is：
Wherein Y3+For yttrium metal ion；N is the positive integer more than or equal to 2.
3. the preparation method of metal-organic framework materials as described in claim 1, which is characterized in that add described in step (2)
Further include that triethylamine and nitric acid are added dropwise in the solution obtained into step (1) before heat.
4. the preparation method of metal-organic framework materials as described in any one of claims 1-3, which is characterized in that in step (1)
The salt containing yttrium metal ion is at least one of yttrium nitrate, yttrium sulfate, yttrium chloride or acetic acid yttrium；The solvent is N,
The mixed solution of dinethylformamide and deionized water；
High-molecular compound described in step (2) is polytetrafluoroethylene (PTFE)；The time heated described in step (2) is 12h-24h, institute
The temperature for stating heating is 100 DEG C -150 DEG C；
It is deionized water, methanol, absolute ethyl alcohol, acetone, N, N- dimethyl formyls that washing described in step (3), which is with solvent,
One or more of amine, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide (DMSO) are washed；The temperature of the drying is 60 DEG C -80
℃；The time of the drying is 6h-24h.
5. a kind of metal-organic framework materials, which is characterized in that be prepared by any the methods of claim 1-4.
6. metal-organic framework materials as claimed in claim 5, which is characterized in that the specific surface area of the framework material is
500-600m2/ g, Kong Rongwei 0.2-0.5cm3/ g, aperture 0.55-0.80nm.
7. metal-organic framework materials described in claim 5 or 6 are used for the application of formaldehyde adsorption.
8. the use as claimed in claim 7, which is characterized in that when concentration of formaldehyde is 90-110mg/m3When, the metal is organic
The formaldehyde absorbing amount of framework material is 0.3-0.4mol/kg.
9. the use as claimed in claim 7, which is characterized in that when temperature residing for the formaldehyde is at 570 DEG C or less, the metal
Organic framework material holding structure is stablized.
10. the use as claimed in claim 7, which is characterized in that the metal-organic framework materials are by 2-5 cycle profit
With rear, the adsorbance of formaldehyde maintains the 72%-99% of initial adsorption amount.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038517A (en) * | 2019-03-21 | 2019-07-23 | 中山大学 | A kind of UiO-66 Base Metal organic framework material of room temperature purifying indoor formaldehyde and its application |
| CN110327978A (en) * | 2019-07-01 | 2019-10-15 | 华侨大学 | A kind of preparation method of yttrium metal organic framework supported precious metal catalyst |
| CN110339791A (en) * | 2019-06-28 | 2019-10-18 | 华中科技大学 | A kind of multi-functional synthesis device suitable for metal-organic framework material |
| CN111495181A (en) * | 2020-04-29 | 2020-08-07 | 成都市美康三杉木业有限公司 | Composite formaldehyde capture agent and preparation method thereof, artificial board formaldehyde removal method and artificial board |
| CN111790209A (en) * | 2020-07-23 | 2020-10-20 | 张宗洲 | Automobile air conditioner filter screen and interlayer preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080121105A1 (en) * | 2006-11-24 | 2008-05-29 | Basf Aktiengesellschaft | Method for the separation of carbon dioxide using a porous metal-organic framework material |
| CN106866985A (en) * | 2017-01-07 | 2017-06-20 | 青岛科技大学 | A kind of metal-organic framework materials for for acetylene and methane adsorption separate and preparation method thereof |
-
2017
- 2017-12-27 CN CN201711446955.XA patent/CN108276582B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080121105A1 (en) * | 2006-11-24 | 2008-05-29 | Basf Aktiengesellschaft | Method for the separation of carbon dioxide using a porous metal-organic framework material |
| CN106866985A (en) * | 2017-01-07 | 2017-06-20 | 青岛科技大学 | A kind of metal-organic framework materials for for acetylene and methane adsorption separate and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LIU XIANG: "Synthesis of rare earth metal-organic frameworks (Ln-MOFs) and their properties of adsorption desulfurization", 《JOURNAL OF RARE EARTHS》 * |
| 李金洋: "金属一有机骨架材料MOF-199对甲醛气体吸附行为的研究", 《材料导报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038517A (en) * | 2019-03-21 | 2019-07-23 | 中山大学 | A kind of UiO-66 Base Metal organic framework material of room temperature purifying indoor formaldehyde and its application |
| CN110038517B (en) * | 2019-03-21 | 2022-03-15 | 中山大学 | UiO-66-based metal organic framework material for indoor formaldehyde purification and application thereof |
| CN110339791A (en) * | 2019-06-28 | 2019-10-18 | 华中科技大学 | A kind of multi-functional synthesis device suitable for metal-organic framework material |
| CN110339791B (en) * | 2019-06-28 | 2020-06-02 | 华中科技大学 | Multifunctional synthesis equipment suitable for metal organic framework material |
| CN110327978A (en) * | 2019-07-01 | 2019-10-15 | 华侨大学 | A kind of preparation method of yttrium metal organic framework supported precious metal catalyst |
| CN110327978B (en) * | 2019-07-01 | 2022-02-08 | 华侨大学 | Preparation method of yttrium metal organic framework supported noble metal catalyst |
| CN111495181A (en) * | 2020-04-29 | 2020-08-07 | 成都市美康三杉木业有限公司 | Composite formaldehyde capture agent and preparation method thereof, artificial board formaldehyde removal method and artificial board |
| CN111790209A (en) * | 2020-07-23 | 2020-10-20 | 张宗洲 | Automobile air conditioner filter screen and interlayer preparation method thereof |
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