CN108276582B - Metal organic framework material, preparation method and application of metal organic framework material in formaldehyde adsorption - Google Patents
Metal organic framework material, preparation method and application of metal organic framework material in formaldehyde adsorption Download PDFInfo
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- CN108276582B CN108276582B CN201711446955.XA CN201711446955A CN108276582B CN 108276582 B CN108276582 B CN 108276582B CN 201711446955 A CN201711446955 A CN 201711446955A CN 108276582 B CN108276582 B CN 108276582B
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
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- B01D2257/00—Components to be removed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
The invention discloses a metalAn organic framework material, a preparation method and application of adsorbing formaldehyde. The specific surface area of the metal-organic framework material is 500-600m2Per g, pore volume of 0.2-0.5cm3(ii)/g, the average pore diameter is 0.55-0.80 nm. The metal organic framework material is used for adsorbing formaldehyde, and when the concentration of the formaldehyde is 90mg/m3‑110mg/m3When the amount of formaldehyde adsorbed by the metal-organic framework material is 0.3-0.4 mol/kg. The organic framework material disclosed by the invention has the advantages of obvious formaldehyde adsorption capacity, high recycling effect and high thermal stability, can be applied to the field of industrial waste gas purification with high temperature, and has extremely high application value in industry and daily life.
Description
Technical Field
The invention belongs to the field of air purification, and particularly relates to a metal organic framework material, a preparation method thereof and application of the metal organic framework material in formaldehyde adsorption.
Background
Formaldehyde pollution is a common air pollution, and seriously affects human health. Formaldehyde can stimulate eyes, nose, throat, skin and other body organs of a human body to cause headache, dizziness, hypodynamia, sensory disturbance, immunity reduction, memory deterioration and even cancer. Common formaldehyde purification methods include physical adsorption methods, chemical absorption methods, biological absorption methods, photocatalytic methods and the like, wherein the physical adsorption methods have the advantages of mature process, easiness in operation, low energy consumption, low cost, high removal rate and the like, and the application range is the widest.
At present, common formaldehyde purification materials in daily life comprise materials such as activated carbon, zeolite and silica, but the materials have the problems of small formaldehyde adsorption amount due to weak formaldehyde selective adsorption capacity, low adsorption speed, difficult regeneration and the like, and the formaldehyde purification materials are not ideal in effect when used for purifying indoor air. Therefore, the development of the formaldehyde purification material which is efficient and can be recycled has important significance.
Disclosure of Invention
The invention solves the technical problems of weak adsorption capacity, low adsorption selectivity, difficult regeneration and the like of formaldehyde in the prior art, and provides a metal organic framework material, a preparation method and application thereof in formaldehyde adsorption.
According to a first aspect of the present invention, there is provided a method of preparing a metal organic framework material, comprising the steps of:
(1) dissolving a salt containing yttrium metal ions and trimesic acid in a solvent;
(2) putting the solution obtained in the step (1) into a reaction kettle with a high molecular compound lining for heating;
(3) and (3) washing and drying the product obtained in the step (2) to obtain the metal organic framework material.
Preferably, the chemical reaction between the yttrium metal-containing salt and trimesic acid in step (1) is:
wherein Y is3+Is yttrium metal ion; n is a positive integer of 2 or more.
Preferably, before the heating in the step (2), the method further comprises the step of dropwise adding triethylamine and nitric acid into the solution obtained in the step (1).
Preferably, the yttrium metal ion-containing salt in step (1) is at least one of yttrium nitrate, yttrium sulfate, yttrium chloride or yttrium acetate; the solvent is a mixed solution of N, N-dimethylformamide and deionized water;
in the step (2), the high molecular compound is polytetrafluoroethylene; the heating time in the step (2) is 12-24 h, and the heating temperature is 100-150 ℃;
the washing in the step (3) is carried out by using one or more solvents selected from deionized water, methanol, absolute ethyl alcohol, acetone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the drying temperature is 60-80 ℃; the drying time is 6-24 h.
According to another aspect of the present invention there is provided a metal organic framework material obtainable by a process as claimed in any one of claims 1 to 4.
Preferably, the specific surface area of the framework material is 500-600m2Per g, pore volume of 0.2-0.5cm3(ii)/g, pore diameter is 0.55-0.80 nm.
According to another aspect of the present invention, there is provided the use of said metal-organic framework material for adsorbing formaldehyde.
Preferably, when the concentration of formaldehyde is 90-110mg/m3In the case, the formaldehyde adsorption amount of the metal organic framework material is 0.3-0.4 mol/kg.
Preferably, the metal-organic framework material remains structurally stable when the formaldehyde is at a temperature below 570 ℃.
Preferably, after the metal organic framework material is recycled for 2-5 times, the adsorption amount of the formaldehyde is maintained to be 72% -99% of the initial adsorption amount.
Generally, compared with the prior art, the technical scheme of the invention has the following advantages and beneficial effects:
(1) the metal organic framework material for purifying formaldehyde provided by the invention has the specific surface area of 500-600m2Per g, pore volume of 0.2-0.5cm3(ii)/g, the average pore diameter is 0.55-0.80 nm. The metal cluster and formaldehyde molecules of the material are connected through the interaction of Van der Waals force and Coulomb force, the interaction force is larger, the specific surface area and the pore volume are also higher, the formaldehyde can be efficiently and quickly removed, and the material can be recycled. Through formaldehyde adsorption test, when the concentration of formaldehyde is 90-110mg/m3In the process, the formaldehyde adsorption amount of the metal organic framework material is 0.3-0.4mol/kg, and the formaldehyde purification capacity is obvious and far higher than that of activated carbon; meanwhile, the thermal stability is high, the method can be applied to the field of industrial waste gas purification with high temperature, and has extremely high application value in industry and daily life.
(2) According to the metal organic framework material for purifying formaldehyde, through a formaldehyde adsorption cycle test experiment, the 5 th recycling effect can still maintain 72% of the 1 st recycling effect, so that the material has a good recycling effect, and the application cost of the material is reduced.
(3) The preparation method of the metal organic framework material for formaldehyde purification provided by the invention is simple in steps and strong in controllability, can be used for preparing the metal organic framework material with high purity for formaldehyde purification, and has high productization potential.
(4) The metal organic framework material for purifying formaldehyde provided by the invention is low in price of adopted raw materials, simple in preparation process and suitable for large-scale popularization and use.
Drawings
FIG. 1 is an XRD pattern of a metal organic framework material prepared in example 1;
FIG. 2 is a nitrogen adsorption curve of the metal organic framework material prepared in example 1;
FIG. 3 is an SEM image of a metal-organic framework material prepared in example 1;
FIG. 4 is a TGA profile of a metal organic framework material prepared in example 1;
FIG. 5 shows that the metal organic framework material and the activated carbon prepared in example 1 are at 100mg/m3A comparison graph of formaldehyde adsorption amount under formaldehyde concentration;
FIG. 6 is a diagram showing the effect of formaldehyde adsorption and recycling in the metal-organic framework material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
3.677g of yttrium nitrate hexahydrate and 1.681g of trimesic acid are dissolved in a mixed solution of 50mL of N, N-dimethylformamide and 10mL of deionized water, the mixed solution is stirred at the speed of 500r/min for 15min, 0.4mL of triethylamine and 0.15mL of nitric acid are sequentially added dropwise at the dropping speed of 0.05mL/min, and the obtained mixture is hermetically placed in a high-pressure reaction kettle with a polytetrafluoroethylene lining and is placed in an oven at the temperature of 100 ℃ for 17 h. The product was washed three times with anhydrous methanol and dried in an oven at 60 ℃ for 8 h.
FIG. 1 is an XRD pattern of the metal organic framework material prepared by the present invention, and it can be seen from the pattern that the characteristic peaks of XRD of the material basically correspond to theoretical values, and shows a relatively ideal crystal structure;
FIG. 2 is a nitrogen adsorption and desorption curve of the metal organic framework material prepared by the invention, and the specific surface area of the material is calculated to be 600m through adsorption data2Per g, pore volume of 0.243cm3(ii)/g, average pore diameter of 0.70 nm;
FIG. 3 is an SEM image of a metal organic framework material prepared according to the present invention, wherein the material is seen to have a needle shape;
FIG. 4 is a TGA spectrum of a metal organic framework material prepared in accordance with the present invention, from which it can be seen that the material remains structurally stable below 570 ℃;
the metal organic framework material is suitable for adsorbing formaldehyde with any concentration, and when the concentration of the formaldehyde is 90-110mg/m3In the case, the formaldehyde adsorption amount of the metal organic framework material is 0.3-0.4 mol/kg. FIG. 5 shows that the metal organic framework material and the activated carbon prepared by the present invention are 100mg/m3The comparison of formaldehyde adsorption under formaldehyde concentration shows that the formaldehyde adsorption of the material prepared by the invention is 0.382mol/kg, which is more than 6 times of the adsorption of the activated carbon, namely 0.060 mol/kg.
Through analysis, the metal organic framework material for formaldehyde purification prepared by the invention has the adsorption selectivity of 4151 for formaldehyde and the adsorption heat of about 40kJ/mol under the condition that the molar ratio of formaldehyde (formaldehyde), nitrogen (nitrogen) and oxygen (oxygen) mixed gas is 2:798:200, and shows excellent formaldehyde purification capability.
FIG. 6 is a diagram of formaldehyde adsorption recycling effect of the metal organic framework material prepared by the present invention, and it can be seen from the diagram that after the material is recycled for 5 times, the formaldehyde adsorption amount is maintained at 72% of the first adsorption amount (i.e. the initial adsorption amount), indicating that Y-BTC has better recycling effect.
Example 2
Dissolving 2g of yttrium nitrate hexahydrate and 4g of trimesic acid in a mixed solution of 80mL of N, N-dimethylformamide and 10mL of deionized water, stirring at the speed of 500r/min for 20min, then sequentially dropwise adding 0.6mL of triethylamine and 0.3mL of nitric acid at the dropwise adding speed of 0.05mL/min, hermetically placing the obtained mixture in a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an oven at the temperature of 110 ℃ for 18 h. The product was washed three times with anhydrous methanol and dried in an oven at 80 ℃ for 6 h.
Example 3
Dissolving 4g of yttrium nitrate hexahydrate and 2g of trimesic acid in a mixed solution of 50mL of N, N-dimethylformamide and 30mL of deionized water, stirring at the speed of 500r/min for 10min, then dropwise adding 0.3mL of triethylamine and 0.2mL of nitric acid at the dropwise adding speed of 0.05mL/min in sequence, sealing and placing the obtained mixture in a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an oven at the temperature of 90 ℃ for 20 h. The product was washed three times with anhydrous methanol and dried in an oven at 80 ℃ for 6 h.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (2)
1. The preparation method of the metal organic framework material is characterized by comprising the following steps:
(1) dissolving a salt containing yttrium metal ions and trimesic acid in a solvent;
(2) putting the solution obtained in the step (1) into a reaction kettle with a high molecular compound lining for heating; the macromolecular compound is polytetrafluoroethylene; the heating time is 12h-24h, and the heating temperature is 100 ℃ to 150 ℃;
(3) washing and drying the product obtained in the step (2) to obtain the metal organic framework material;
the chemical reaction between the yttrium metal-containing salt and trimesic acid in the step (2) is as follows:
wherein Y is3+Is yttrium metal ion; n is a positive integer greater than or equal to 2;
before the heating in the step (2), adding triethylamine and nitric acid dropwise into the solution obtained in the step (1);
in the step (1), the solvent is a mixed solution of N, N-dimethylformamide and deionized water.
2. The process for the preparation of a metal-organic framework material according to claim 1,
the salt containing yttrium metal ions in the step (1) is at least one of yttrium nitrate, yttrium sulfate, yttrium chloride or yttrium acetate;
the washing in the step (3) is carried out by using one or more solvents selected from deionized water, methanol, absolute ethyl alcohol, acetone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the drying temperature is 60-80 ℃; the drying time is 6-24 h.
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| 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 |
| CN110339791B (en) * | 2019-06-28 | 2020-06-02 | 华中科技大学 | Multifunctional synthesis equipment suitable for metal organic framework material |
| CN110327978B (en) * | 2019-07-01 | 2022-02-08 | 华侨大学 | Preparation method of yttrium metal organic framework supported noble metal catalyst |
| CN111495181B (en) * | 2020-04-29 | 2022-06-07 | 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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| CN106866985B (en) * | 2017-01-07 | 2019-11-26 | 青岛科技大学 | A kind of metal-organic framework materials and preparation method thereof separated for acetylene and methane adsorption |
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