CN112029106B - Preparation method and application of modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane - Google Patents

Preparation method and application of modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane Download PDF

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CN112029106B
CN112029106B CN202010776919.5A CN202010776919A CN112029106B CN 112029106 B CN112029106 B CN 112029106B CN 202010776919 A CN202010776919 A CN 202010776919A CN 112029106 B CN112029106 B CN 112029106B
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宋夫交
许琦
岳仁亮
吴傲立
齐丛亮
严金龙
杨百忍
刘阳庆
曹燕
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Anhui Chenze Intellectual Property Service Co ltd
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Abstract

The invention discloses a preparation method and application of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane. The preparation method of the adsorbent comprises the following steps: mixing mixed solution containing dimethylformamide, ethanol and deionized water according to a certain proportion, and adding Cu (NO) according to a certain proportion3)2·3H2O, trimesic acid (H)3BTC) and organic amine, uniformly stirring, placing in a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 20 h at 85 ℃, cooling, washing and centrifuging a product by using DMF and ethanol, and finally drying and activating in vacuum at 120 ℃ to obtain a blue product, namely the amine modified HKUST-1. The invention introduces amino on the surface of HKUST-1 through amine modification, and protects the active adsorption site Cu of the adsorbent when adsorbing and separating n-hexane waste gas2+The sulfur poisoning of the adsorbent is avoided to inactivate, and the sulfur resistance and stability of the material are improved.

Description

Preparation method and application of modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane
Technical Field
The invention belongs to the technical field of organic waste gas adsorption and separation, and particularly relates to a preparation method and application of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane.
Background
In the past decades, with the rapid development of industrial economy such as petrifaction, medicine, printing and dyeing, paint spraying and leather making in China, great economic benefits are brought, and meanwhile, a large amount of organic waste gas, namely Volatile Organic Compounds (VOC), is discharged, so that serious harm is brought to the environment, the life of people and the health of people, and therefore VOC waste gas treatment is urgent.
The adsorption method is a treatment technology with development prospect, because the adsorption method can realize the recycling of waste gas components while reducing emission. Alkane is a common component in VOC waste gas, normal hexane is a typical representative, has good viscosity, is often used as an organic solvent in various industries such as pharmacy, shoemaking, leather and the like, can be used as an extraction solvent and a raw material for manufacturing polymers, has certain environmental and economic benefits by adsorbing, separating and recovering the normal hexane from the waste gas, and is a key technology for preparing the adsorbent.
In recent decades, metal-organic frameworks (MOFs) exhibit excellent performance in the field of gas adsorption separation and storage due to their large specific surface area and abnormally developed pore structure. HKUST-1 is a typical MOFs material synthesized by taking trimesic acid and copper nitrate as raw materials by adopting a solvothermal method, has multiple adsorption sites, and has gas adsorption performance higher than that of traditional adsorbents such as activated carbon, molecular sieves and the like. HKUST-1 is a typical microporous material, and has high adsorption capacity (0.65 cm) for small-molecule VOC gas such as n-hexane and the like according to the matching of pore size3More than g), the adsorption capacity to macromolecular gas is small, so that HKUST-1 has incomparable advantages with other adsorbents in the aspect of adsorbing and separating normal hexane.
SO is often accompanied in VOC waste gas containing n-hexane generated in industries such as medicine and breeding2Gas, SO compared with n-hexane2Has stronger polarity and larger dipole moment, thus being easier to adsorb Cu in HKUST-12+On the adsorption sites of equal polarity or alkalinitySulfite or sulfate, which are difficult to desorb, cause the adsorbent to be poisoned and deactivated. Investigation has found that in CO2In the field of adsorption, an organic amine modification method is commonly used for introducing an amino functional group into the surface of a porous material, so that the alkaline adsorption sites on the surface of the material are increased, and the CO content is improved2Adsorption capacity and selectivity.
CN201510674326.7 discloses an amine modified fiber membrane-shaped adsorbing material and a preparation method thereof. The invention takes polyacrylonitrile powder as a substrate, adopts solid-phase graft polymerization and amination reaction to prepare a liquid substrate, and then prepares a novel fiber membrane-shaped adsorption material through electrostatic spinning. The preparation method is simple, the amination efficiency is high, a large amount of swelling agents and amination reagents can be saved, the adsorption material has a high-hydrophilicity surface, the adsorption material can be applied to a flat membrane filter assembly, when water passes through the fiber membrane, surface groups can efficiently adsorb and remove various heavy metal ions in the water, and the fiber membrane after adsorption saturation can be repeatedly used after desorption and regeneration.
CN201610409244.4 discloses a straw-based solid amine sulfur dioxide adsorbent and a preparation and use method thereof, which comprises the following contents: modifying polyvinylamine by adopting a Clark methylation reaction, and adding the polyvinylamine into a methanol solution for dissolving to obtain a mixed solution; the straws are washed, dried and crushed and then are added into the mixed solution for dipping, and the SO is prepared after drying2Adsorbed straw-based solid amine. When using the adsorbent, the SO is soaked by water2And (4) performing gas adsorption operation. In N2And heating and regenerating the adsorbent by airflow at 90-120 ℃. The application of the straw stalk of the invention opens up a brand new way, and simultaneously, the solid amine adsorbent is applied to the treatment process of sulfur dioxide, thereby improving the straw stalk value and also purifying SO for adsorption2The gas provides a new adsorbent, and SO is enriched2The type of adsorbent.
Disclosure of Invention
Aiming at active adsorption site Cu of HKUST-1 in process of adsorbing and separating n-hexane waste gas2+Preferably with SO2The invention aims to provide a preparation method of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexaneThe preparation method and the application thereof are characterized in that amino is introduced to the surface of HKUST-1 through amine modification, and the amino on the surface of the material is preferentially reacted with SO2Reacting to protect the adsorption site Cu2+Thereby avoiding the poisoning and inactivation of the adsorbent and improving the sulfur resistance and stability of the adsorbent.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a preparation method of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane comprises the following steps:
step 1, mixing dimethylformamide, ethanol and deionized water according to a volume ratio of 1:1:1 to prepare a mixed solution A, and mixing Cu (NO)3)2·3H2O and trimesic acid H3BTC is 2: 1, adding the mixed solution A and organic amine after mixing, and magnetically stirring for 5-10min to completely dissolve the mixture to obtain a precursor solution of the adsorbent;
step 2, transferring the precursor solution in the step 1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, covering and sealing the reaction kettle, transferring the reaction kettle into a drying box, carrying out solvothermal reaction for 20 hours at 85 ℃, cooling, washing and centrifuging the product repeatedly by using a mixed solution of DMF and ethanol to obtain a blue solid precipitate;
step 3, transferring the blue solid precipitate obtained in the step 2 to an oven for drying treatment at 100 ℃, and then transferring to a vacuum oven for vacuum drying and activation at 120 ℃ to obtain a blue product, namely the amine modified HKUST-1 adsorbent; wherein the mol ratio of the organic amine to the HKUST-1 is 1-3: 20.
The improvement is that the product obtained after the solvothermal reaction in the step 2 is washed by a mixed solution of DMF and ethanol and centrifuged for 3 to 5 times.
The improvement is that the organic amine in the step 1 is N, N-dimethylethylenediamine.
The improvement is that when the blue solid precipitate is subjected to vacuum drying in the step 3, in order to deeply remove the coordinated water and the bound water in the HKUST-1, the drying box is subjected to vacuum pumping treatment every 2 hours, and the operation is repeated for 5-6 times.
The modified HKUST-1 sulfur-resistant adsorbent is applied to the treatment of volatile organic compounds.
Has the advantages that:
compared with the prior art, the preparation method and the application of the modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane are characterized in that an amino functional group is introduced to the surface of the HKUST-1 by adopting an organic amine modification method to protect Cu at an adsorption site2+And the sulfur resistance and stability of the adsorbent are improved.
Drawings
FIG. 1 is SEM topography of HKUST-1 and amine modified HKUST-1 adsorbents, wherein A1 and A2 are SO-containing respectively2HKUST-1 before and after gas treatment, B1 and B2 are SO-containing2Organic amine EDA modified HKUST-1 before and after gas treatment, C1 and C2 are water and SO respectively2Organic amine mmen before and after gas treatment modifies HKUST-1.
Detailed Description
The invention is further described below with reference to the accompanying drawings and specific embodiments.
Example 1
A preparation method of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane comprises the following steps:
(1) preparing dimethyl formamide (DMF), ethanol and deionized water into a mixed solution according to the volume ratio of 1:1:1, and adding Cu (NO)3)2·3H2O and H3BTC as per 2: 1, adding organic amine N, N-dimethyl ethylenediamine (mmen) according to the molar ratio of 1:20, and magnetically stirring for 5-10min to completely dissolve the mixture to obtain a precursor solution of the adsorbent.
(2) And (2) transferring the precursor solution in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, covering and sealing the reaction kettle, transferring the reaction kettle into a drying box, carrying out solvothermal reaction for 20 hours at 85 ℃, cooling, repeatedly washing and centrifuging the product for 3-5 times by using DMF and an ethanol solvent to obtain a blue solid precipitate.
(3) Transferring the blue solid precipitate obtained in the step (2) to an oven for drying treatment at 100 ℃, and then transferringTransferring into a vacuum oven, vacuum drying and activating at 120 deg.C to deeply remove coordinated water and bound water in HKUST-1, vacuumizing the oven every 2 h, and repeating the operation for 5-6 times to obtain a blue product labeled as mmen0.05@HKUST-1。
Example 2
A preparation method of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane comprises the following steps:
(1) preparing dimethyl formamide (DMF), ethanol and deionized water into a mixed solution according to the volume ratio of 1:1:1, and adding Cu (NO)3)2·3H2O and H3BTC as per 2: 1, adding a certain amount of organic amine N, N-dimethyl ethylenediamine (mmen), wherein the molar ratio of the organic amine to the HKUST-1 is 2:20, and magnetically stirring for 5-10min to completely dissolve the mixture to obtain a precursor solution of the adsorbent.
(2) And (2) transferring the precursor solution in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, covering and sealing the reaction kettle, transferring the reaction kettle into a drying box, carrying out solvothermal reaction for 20 hours at 85 ℃, cooling, repeatedly washing and centrifuging the product for 3-5 times by using DMF and an ethanol solvent to obtain a blue solid precipitate.
(3) Transferring the blue solid precipitate obtained in the step (2) to an oven for drying treatment at 100 ℃, then transferring to a vacuum oven for vacuum drying and activation at 120 ℃, carrying out vacuum pumping treatment on the oven every 2 h for deeply removing the coordinated water and the bound water in the HKUST-1, and repeating the operation for 5-6 times to obtain a blue product labeled as mmen0.10@HKUST-1。
Example 3
A preparation method of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane comprises the following steps:
(1) preparing dimethyl formamide (DMF), ethanol and deionized water into a mixed solution according to the volume ratio of 1:1:1, and adding Cu (NO)3)2·3H2O and H3BTC as per 2: 1, adding a certain amount of organic amine N, N-dimethyl ethylenediamine (mmen),the molar ratio of the organic amine to the HKUST-1 is 3:20, and the mixture is completely dissolved by magnetic stirring for 5-10min to obtain a precursor solution of the adsorbent.
(2) And (2) transferring the precursor solution in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, covering and sealing the reaction kettle, transferring the reaction kettle into a drying box, carrying out solvothermal reaction for 20 hours at 85 ℃, cooling, repeatedly washing and centrifuging the product for 3-5 times by using DMF and an ethanol solvent to obtain a blue solid precipitate.
(3) Transferring the blue solid precipitate obtained in the step (2) to an oven for drying treatment at 100 ℃, then transferring to a vacuum oven for vacuum drying and activation at 120 ℃, carrying out vacuum pumping treatment on the oven every 2 h for deeply removing the coordinated water and the bound water in the HKUST-1, and repeating the operation for 5-6 times to obtain a blue product labeled as mmen0.15@HKUST-1。
Comparative example 1
A preparation method of an anti-sulfur adsorbent for adsorbing n-hexane comprises the following steps:
(1) preparing dimethyl formamide (DMF), ethanol and deionized water into a mixed solution according to the volume ratio of 1:1:1, and adding Cu (NO)3)2·3H2O and H3BTC as per 2: adding the solution according to the mass ratio of 1, and magnetically stirring for 5-10min to completely dissolve the mixture to obtain a precursor solution of the adsorbent.
(2) And (2) transferring the precursor solution in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, covering and sealing the reaction kettle, transferring the reaction kettle into a drying box, carrying out solvothermal reaction for 20 hours at 85 ℃, cooling, repeatedly washing and centrifuging the product for 3-5 times by using DMF and an ethanol solvent to obtain a blue solid precipitate.
(3) And (3) transferring the blue solid precipitate obtained in the step (2) to an oven for drying treatment at 100 ℃, then transferring to a vacuum oven for vacuum drying and activation at 120 ℃, vacuumizing the oven every 2 hours for deeply removing the coordinated water and the bound water in the HKUST-1, and repeating the operation for 5-6 times to obtain a blue product marked as HKUST-1.
Comparative example 2
A preparation method of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane comprises the following steps:
(1) preparing dimethyl formamide (DMF), ethanol and deionized water into a mixed solution according to the volume ratio of 1:1:1, and adding Cu (NO)3)2·3H2O and H3BTC as per 2: 1, adding Ethylenediamine (EDA), wherein the molar ratio of the Ethylenediamine (EDA) to the HKUST-1 is 1:20, and magnetically stirring for 5-10min to completely dissolve the mixture to obtain a precursor solution of the adsorbent.
(2) And (2) transferring the precursor solution in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, covering and sealing the reaction kettle, transferring the reaction kettle into a drying box, carrying out solvothermal reaction for 20 hours at 85 ℃, cooling, repeatedly washing and centrifuging the product for 3-5 times by using DMF and an ethanol solvent to obtain a blue solid precipitate.
(3) Transferring the blue solid precipitate obtained in the step (2) into an oven to be dried at 100 ℃, then transferring into a vacuum oven to be dried and activated at 120 ℃ in vacuum, vacuumizing the oven every 2 h for deeply removing the coordinated water and the bound water in the HKUST-1, and repeating the operation for 5-6 times to obtain a blue product labeled as EDA0.05@HKUST-1。
Comparative example 3
A preparation method of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane comprises the following steps:
(1) preparing dimethyl formamide (DMF), ethanol and deionized water into a mixed solution according to the volume ratio of 1:1:1, and adding Cu (NO)3)2·3H2O and H3BTC as per 2: 1, adding Ethylenediamine (EDA), the molar ratio of the Ethylenediamine (EDA) to the HKUST-1 is 2:20, and magnetically stirring for 5-10min to completely dissolve the mixture to obtain a precursor solution of the adsorbent.
(2) And (2) transferring the precursor solution in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, covering and sealing the reaction kettle, transferring the reaction kettle into a drying box, carrying out solvothermal reaction for 20 hours at 85 ℃, cooling, repeatedly washing and centrifuging the product for 3-5 times by using DMF and an ethanol solvent to obtain a blue solid precipitate.
(3) Transferring the blue solid precipitate obtained in the step (2) into an oven to be dried at 100 ℃, then transferring into a vacuum oven to be dried and activated at 120 ℃ in vacuum, vacuumizing the oven every 2 h for deeply removing the coordinated water and the bound water in the HKUST-1, and repeating the operation for 5-6 times to obtain a blue product labeled as EDA0.10@HKUST-1。
Comparative example 4
A preparation method of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane comprises the following steps:
(1) preparing dimethyl formamide (DMF), ethanol and deionized water into a mixed solution according to the volume ratio of 1:1:1, and adding Cu (NO)3)2·3H2O and H3BTC as per 2: 1, adding Ethylenediamine (EDA), the molar ratio of the Ethylenediamine (EDA) to the HKUST-1 is 3:20, and magnetically stirring for 5-10min to completely dissolve the mixture to obtain a precursor solution of the adsorbent.
(2) And (2) transferring the precursor solution in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, covering and sealing the reaction kettle, transferring the reaction kettle into a drying box, carrying out solvothermal reaction for 20 hours at 85 ℃, cooling, repeatedly washing and centrifuging the product for 3-5 times by using DMF and an ethanol solvent to obtain a blue solid precipitate.
(3) Transferring the blue solid precipitate obtained in the step (2) into an oven to be dried at 100 ℃, then transferring into a vacuum oven to be dried and activated at 120 ℃ in vacuum, vacuumizing the oven every 2 h for deeply removing the coordinated water and the bound water in the HKUST-1, and repeating the operation for 5-6 times to obtain a blue product labeled as EDA0.15@HKUST-1。
The specific surface area and pore volume of the adsorbent are tested by an ASAP2020M full-automatic specific surface area and porosity analyzer (Mega instruments, USA), and low-temperature nitrogen physical adsorption desorption is tested at liquid nitrogen temperature (-196 deg.C)Calculating the specific surface area of the sample by using a BET equation with an isotherm according to N when the relative pressure is 0.992The pore volume of the sample was calculated. The n-hexane adsorption performance is also tested in the instrument, the testing pressure is controlled between 0 MPa and 0.12 MPa through a steel cylinder pressure reducing valve and an electromagnetic valve, the temperature is controlled at room temperature by a method of immersing the sample tube in a constant-temperature water bath, and the n-hexane adsorption isotherm is measured under the above conditions, so that the adsorption quantity of the n-hexane can be obtained.
The SEM morphologies of the various adsorbents prepared in the above examples and comparative examples are shown in fig. 1:
the shape of HKUST-1 is regular octahedral structure with smooth surface and clear edges, a small amount of cuprous oxide particles are attached to the surface, and the size is about 15-20 microns; by using a gas containing SO2After the gas treatment for a period of time, the octahedral structure collapsed, the surface became rough, and small particles agglomerated and agglomerated, indicating that the sulfur resistance of HKUST-1 was poor. After organic amine EDA and mmen are adopted for modification, EDA0.10@ HKUST-1 and mmen0.10The @ HKUST-1 basically keeps the original octahedral structure and size and does not have obvious shape change; in the presence of SO2After the gas treatment is carried out for a period of time, the octahedral structure and the size are hardly changed or destroyed, and the small particles attached to the surface are enlarged or increased, which is probably attributed to the amino groups and SO on the surface of the sample2Stacking and agglomerating the ammonium sulfate salt generated by the reaction.
The specific surface area, pore volume and n-hexane adsorption performance test results of the adsorbents prepared in the above examples are shown in table 1:
TABLE 1 specific surface area, pore volume and n-hexane adsorption of organoamine-modified adsorbents to unmodified adsorbents
Figure 143821DEST_PATH_IMAGE001
TABLE 2 use of SO2Physicochemical Properties of organic amine-modified treated adsorbent after gas treatment and unmodified adsorbent
Figure 861242DEST_PATH_IMAGE002
As can be seen from Table 1, the parent HKUST-1 had a specific surface area of 1353.27 m2Per g, pore volume 0.68 m3The n-hexane adsorption amount was 3.87 mmol/g. After EDA and mmen are adopted for modification, the specific surface area, the pore volume and the n-hexane adsorption quantity of the HKUST-1 are slightly reduced, which shows that the organic amine modification has little influence on the pore structure and the adsorption quantity of the HKUST-1.
As can be seen from Table 2, SO was used2After the gas is used for treating the adsorbent, the specific surface area and the pore volume of the parent HKUST-1 are both greatly reduced, and the n-hexane adsorption capacity is reduced by 41.60%. The specific surface area and the pore volume of the EDA and the mmen modified HKUST-1 are only reduced to a small extent, and the adsorption capacity of n-hexane is respectively reduced by 10 percent and 4.5 percent, so that the sulfur resistance and the stability of the HKUST-1 adsorbent are effectively improved by amine modification.

Claims (4)

1. A preparation method of a modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane is characterized by comprising the following steps: step 1, mixing dimethylformamide, ethanol and deionized water according to a volume ratio of 1:1:1 to prepare a mixed solution A, and mixing Cu (NO)3)2·3H2O and trimesic acid H3BTC is 2: 1, adding the mixed solution A after mixing, adding organic amine, and magnetically stirring for 5-10min to completely dissolve the mixture to obtain a precursor solution of the adsorbent, wherein the organic amine is N, N-dimethylethylenediamine; step 2, transferring the precursor solution in the step 1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, covering and sealing the reaction kettle, transferring the reaction kettle into a drying box, carrying out solvothermal reaction for 20 hours at 85 ℃, cooling, washing and centrifuging the product repeatedly by using a mixed solution of DMF and ethanol to obtain a blue solid precipitate; step 3, transferring the blue solid precipitate obtained in the step 2 to an oven for drying treatment at 100 ℃, and then transferring to a vacuum oven for vacuum drying and activation at 120 ℃ to obtain a blue product, namely the amine modified HKUST-1 adsorbent; wherein the mol ratio of the organic amine to the HKUST-1 is 1-3: 20.
2. The preparation method of the modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane according to claim 1, wherein the method comprises the following steps: and (3) carrying out solvothermal reaction for 20 hours in the step (2) to obtain a product, washing the product with a mixed solution of DMF and ethanol, and centrifuging the product for 3-5 times.
3. The preparation method of the modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane according to claim 1, wherein the method comprises the following steps: and 3, when the blue solid precipitate is subjected to vacuum drying in the step 3, vacuumizing the drying box every 2 hours for deeply removing the coordination water and the bound water in the HKUST-1, and repeating the operation for 5-6 times.
4. Application of the modified HKUST-1 sulfur-resistant adsorbent prepared by the preparation method according to claim 1 in treating volatile organic n-hexane.
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