Nickel-based metal organic framework material and application thereof in removal of fishy smell
Patent Information
- Application Number
- CN202410983295.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-22
- Publication Date
- 2026-10-30
- Estimated Expiration
- 2044-07-22
AI Technical Summary
[0005]基于此，为了解决现有技术中的材料对海产品的脱腥除臭效果差的问题，本发明提供了一种镍基金属有机框架材料及其在腥臭物脱除中的应用，具体技术方案如下：
[0015]上述方案中制备得到的镍基金属有机框架材料具有优异的水汽稳定性，暴露在88%相对湿度环境中24 h后，其孔结构无明显变化，且镍基金属有机框架材料能够有效去除海产品的腥臭味，效果显著。将本发明制备的镍基金属有机框架材料具有高度有序的多孔结构，赋予了材料高比表面积和选择性吸附特性，作为核心的吸附分离技术，应用于高效脱除海产品中的腥臭味物质，不仅能保证好产品的品质和感官，还能增加镍基金属有机框架材料的应用，使其具有更广的利用价值。
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Figure CN118904300B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of adsorption materials technology, and more specifically, to a nickel-based metal-organic framework material and its application in the removal of odorous substances. Background Technology
[0002] With the deepening of marine development policies, the development of marine resources is becoming increasingly "refined," "green," and "sustainable." Apart from some directly edible marine products that require no processing, most require processing before reaching the market. Furthermore, seafood is prone to developing a fishy odor during processing and storage, which not only affects product quality but also limits its application in food, cosmetics, and other fields. The fishy odor primarily originates from volatile organic compounds in seafood, including N,N-dimethylformamide, styrene, and 5-amino-1-methyl-1H-pyrazole-4-carboxamide. These substances have a strong, unpleasant smell, severely impacting the sensory quality of seafood.
[0003] Currently, methods for removing fishy odors from seafood mainly fall into three categories: chemical deodorization, physical deodorization, and biological deodorization. Chemical deodorization methods, such as acid-base balance methods and Maillard reactions, remove or transform fishy-smelling substances through chemical reactions, but may result in reagent residues and affect product quality. Physical deodorization methods, such as adsorption and masking methods, remove fishy-smelling substances using adsorbents such as activated carbon, but may suffer from low adsorption efficiency and easy saturation. Biological deodorization methods, such as microbial fermentation and enzymatic methods, remove fishy-smelling substances through biotransformation, but these require demanding conditions and are difficult to scale up.
[0004] Therefore, designing and synthesizing materials that can efficiently deodorize and remove the fishy smell from seafood presents a challenging technical problem. Summary of the Invention
[0005] Therefore, in order to solve the problem of poor deodorization effect of existing materials on seafood, this invention provides a nickel-based metal-organic framework material and its application in the removal of fishy and odorous substances. The specific technical solution is as follows: A nickel-based metal-organic framework material, wherein the nickel-based metal-organic framework material is used in products for removing odors; The preparation method of the nickel-based metal-organic framework material includes the following steps: Nickel acetate tetrahydrate and 2-methylpyridine-4-carboxylic acid were added sequentially to N,N-dimethylformamide and mixed thoroughly. Then, a solvent was added, and the mixture was dissolved by sonication. The mixture was then placed in an oven to react. After the reaction was completed, the solid was washed and then filtered. The green solid obtained by filtration was wrapped in aluminum foil and then vacuum dried to obtain a nickel-based metal-organic framework material.
[0006] Furthermore, the mass ratio of nickel acetate tetrahydrate to 2-methylpyridine-4-carboxylic acid is (1~3):(1~5).
[0007] Furthermore, the volume ratio of N,N-dimethylformamide to the solvent is 1:(1~4).
[0008] Furthermore, the ultrasonic dissolution time is 10 min to 15 min.
[0009] Furthermore, the reaction temperature is 130℃~150℃.
[0010] Furthermore, the washing treatment employs at least one of N,N-dimethylformamide, acetonitrile, ethanol, and acetone.
[0011] Furthermore, the solvent is at least one selected from acetonitrile, methanol, and ethanol.
[0012] Furthermore, the vacuum drying process is carried out at a temperature of 30°C to 40°C for a duration of 12 hours to 24 hours.
[0013] Furthermore, the molar ratio of nickel-based metal to organic framework material in the nickel-based metal-organic framework material is 1:(1~4).
[0014] In addition, this application also provides an application of a nickel-based metal-organic framework material, namely, the application of the nickel-based metal-organic framework material in the processing of seafood.
[0015] The nickel-based metal-organic framework material prepared by the above method exhibits excellent water vapor stability. After exposure to an environment with 88% relative humidity for 24 hours, its pore structure shows no significant change. Furthermore, the nickel-based metal-organic framework material effectively removes the fishy odor from seafood, demonstrating remarkable results. The highly ordered porous structure of the nickel-based metal-organic framework material prepared by this invention endows it with high specific surface area and selective adsorption properties. As a core adsorption and separation technology, its application in the efficient removal of fishy odor substances from seafood not only ensures the quality and sensory appeal of the product but also expands the applications of nickel-based metal-organic framework materials, giving them broader utilization value. Attached Figure Description
[0016] Figure 1 This is a schematic diagram of the crystal structure of Ni(mla)2 prepared in Example 1 of the present invention; Figure 2 This is a schematic diagram of the crystal morphology of Ni(mla)2 prepared in Example 1 of the present invention; Figure 3The X-ray powder diffraction (PXRD) spectra of Ni(mla)2-1, Ni(mla)2-2, Ni(mla)2-3, and Ni(mla)2-4 prepared in Examples 1-4 of this invention are shown below. Figure 4 This is a schematic diagram of the adsorption isotherms of Ni(mla)2-1 prepared in Example 1 of the present invention before and after exposure to an environment with 88% relative humidity for 24 hours at room temperature for CO2 adsorption. Figure 5 Abundance diagram of oyster peptide powder solution obtained after deodorization treatment of Ni(mla)2-1 prepared in Example 1 of the present invention (abundance shown by scanning time (RT value 6.47-7.78 min) for N,N-dimethylformamide).
[0017] Figure 6 The adsorption isotherms of Ni(mla)2-1, Ni(mla)2-2, Ni(mla)2-3, and Ni(mla)2-4 prepared in Examples 1-4 of this invention for styrene, a typical fishy-smelling substance, at room temperature are shown. Detailed Implementation
[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to its embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of protection of the invention.
[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.
[0020] One embodiment of the present invention provides a nickel-based metal-organic framework material, which is used in a product for removing odor and fishy smell. The preparation method of the nickel-based metal-organic framework material includes the following steps: Nickel acetate tetrahydrate and 2-methylpyridine-4-carboxylic acid were added sequentially to N,N-dimethylformamide and mixed thoroughly. Then, a solvent was added, and the mixture was dissolved by sonication. The mixture was then placed in an oven to react. After the reaction was completed, the solid was washed and then filtered. The green solid obtained by filtration was wrapped in aluminum foil and then vacuum dried to obtain a nickel-based metal-organic framework material.
[0021] In one embodiment, the mass ratio of nickel acetate tetrahydrate to 2-methylpyridine-4-carboxylic acid is (1~3):(1~5).
[0022] In one embodiment, the volume ratio of N,N-dimethylformamide to the solvent is 1:(1~4).
[0023] In one embodiment, the ultrasonic dissolution time is 10 min to 15 min.
[0024] In one embodiment, the reaction temperature is 130°C to 150°C.
[0025] In one embodiment, the washing treatment uses at least one of N,N-dimethylformamide, acetonitrile, ethanol, and acetone.
[0026] In one embodiment, the solvent is at least one of acetonitrile, methanol, and ethanol.
[0027] In one embodiment, the vacuum drying process is performed at a temperature of 30°C to 40°C for a duration of 12 hours to 24 hours.
[0028] In one embodiment, the molar ratio of nickel-based metal to organic framework material in the nickel-based metal-organic framework material is 1:(1~4).
[0029] In addition, this application also provides an application of a nickel-based metal-organic framework material, namely, the application of the nickel-based metal-organic framework material in the processing of seafood.
[0030] In one embodiment, the nickel-based metal-organic framework material is used in the cosmetics and food industries.
[0031] The nickel-based metal-organic framework material prepared by this invention has good water vapor stability. After being exposed to an environment with 88% relative humidity for 24 hours, its pore structure does not change significantly. It can effectively remove the fishy smell of seafood with remarkable effect. Moreover, the method for removing the fishy smell is green, simple to operate, highly efficient, and leaves no chemical residue. It has important commercial application value and environmental friendliness.
[0032] The nickel-based metal-organic framework material prepared in this invention has 1.86 times the adsorption performance of traditional commercial activated carbon for styrene.
[0033] Furthermore, the nickel-based metal-organic framework material prepared in this invention is a three-dimensional porous metal-organic framework material that is self-assembled from nickel acetate tetrahydrate and 2-methylpyridine-4-carboxylic acid through a hydrothermal reaction. The excellent water vapor stability of the nickel-based metal-organic framework material is due to its strong hydrophobicity, which prevents water vapor from attacking the metal-ligand bonds, thus giving it superior application value.
[0034] The implementation schemes of the present invention will now be described in detail with reference to specific embodiments.
[0035] Example 1: A method for preparing a nickel-based metal-organic framework material includes the following steps: 0.0166 g of nickel acetate tetrahydrate and 0.0366 g of 2-methylpyridine-4-carboxylic acid were added sequentially to 4 mL of N,N-dimethylformamide and mixed thoroughly. Then, 2.6 mL of acetonitrile was added, and the mixture was sonicated for 15 min. The mixture was then placed in an oven at 140 °C and reacted for 24 h. After the reaction was completed, the mixture was washed with N,N-dimethylformamide at 8500 r / min for 3 min in a centrifuge. The collected solid was then filtered. The green solid obtained by filtration was wrapped in aluminum foil and vacuum dried at 40 °C for 24 h to obtain a nickel-based metal-organic framework material, labeled Ni(mla)2-1.
[0036] Example 2: A method for preparing a nickel-based metal-organic framework material includes the following steps: 0.0166 g of nickel acetate tetrahydrate and 0.0258 g of 2-methylpyridine-4-carboxylic acid were added sequentially to 4 mL of N,N-dimethylformamide and mixed thoroughly. Then, 3.2 mL of acetonitrile was added, and the mixture was sonicated for 15 min. The mixture was then placed in an oven at 140 °C and reacted for 24 h. After the reaction was completed, the mixture was washed with acetonitrile at 8500 r / min for 3 min in a centrifuge. The collected solid was then filtered. The green solid obtained by filtration was wrapped in aluminum foil and vacuum dried at 35 °C for 24 h to obtain a nickel-based metal-organic framework material, labeled as Ni(mla)2-2.
[0037] Example 3: A method for preparing a nickel-based metal-organic framework material includes the following steps: 0.0166 g of nickel acetate tetrahydrate and 0.0455 g of 2-methylpyridine-4-carboxylic acid were added sequentially to 4 mL of N,N-dimethylformamide and mixed thoroughly. Then, 2.6 mL of acetonitrile was added, and the mixture was sonicated for 15 min. The mixture was then placed in an oven at 130 °C and reacted for 24 h. After the reaction was completed, the mixture was washed with acetonitrile at 8500 r / min for 3 min in a centrifuge. The collected solid was then filtered. The green solid obtained by filtration was wrapped in aluminum foil and vacuum dried at 30 °C for 24 h to obtain a nickel-based metal-organic framework material, labeled Ni(mla)2-3.
[0038] Example 4: A method for preparing a nickel-based metal-organic framework material includes the following steps: 0.0166 g of nickel acetate tetrahydrate and 0.0366 g of 2-methylpyridine-4-carboxylic acid were added sequentially to 4 mL of N,N-dimethylformamide and mixed thoroughly. Then, 2.6 mL of acetonitrile was added, and the mixture was sonicated for 15 min. The mixture was then placed in an oven at 100 °C and reacted for 24 h. After the reaction was completed, the solid was washed with acetone at 8500 r / min for 3 min in a centrifuge. The collected solid was then filtered. The green solid obtained by filtration was wrapped in aluminum foil and vacuum dried at 40 °C for 24 h to obtain the nickel-based metal-organic framework material, Ni(mla)2-4.
[0039] Test Example 1: The single-crystal structure of Ni(mla)2-1 prepared in Example 1 was analyzed using a Smart Apex single-crystal diffractometer from Bruker GmbH, Germany. The crystallographic data are shown in Table 1.
[0040] Table 1: Crystallographic Data
[0041] As shown in Table 1, the relative molecular mass of Ni(mla)2-1 is 561.13, the crystal belongs to the triclinic crystal system, and the space group of the crystal is P1.
[0042] Figure 1 This is the crystal structure diagram of Ni(mla)2-1. Each Ni metal center is 4-coordinated, connecting N and O atoms on 4 different organic ligands; each organic ligand is 2-coordinated, coordinated with two different Ni metal centers.
[0043] Figure 2 The image shows the crystal morphology of Ni(mla)₂ prepared in Example 1 of this invention. As can be seen from the image, the overall morphology of the Ni(mla)₂-1 crystal is a bulk crystal.
[0044] Test Example 2: The pore structures of Ni(mla)2-1, Ni(mla)2-2, Ni(mla)2-3, and Ni(mla)2-4 prepared in Examples 1-4 of this invention were tested using a BSD-PM pore size analyzer from Beijing Best Instruments Co., Ltd. The results are shown in Table 2.
[0045] Table 2: Pore Structure and Specific Surface Area
[0046] As shown in Table 2, the BET specific surface area of the Ni(mla)2 material synthesized in this invention is 422.1-452.4 m². 2 / g, total pore volume is 0.15-0.18 cm³ 3 / g, with a pore size of 0.62-0.65 nm. This indicates that the invented material has excellent adsorption properties.
[0047] Test Example 3: X-ray Powder Diffraction (PXRD) Analysis of Nickel-based Metal-Organic Framework Material Ni(mla)2 X-ray diffractometer manufactured by Rigaku, Japan, was used to characterize the structures of Ni(m1a)2-1, Ni(m1a)2-2, Ni(m1a)2-3, and Ni(m1a)2-4 materials prepared in Examples 1-4. The scanning speed was 10° / min, the double diffraction angle range was 5-90°, and the test voltage and current were 40 kV and 15 mA, respectively. Cu-K α ray.
[0048] Figure 3 The PXRD spectra of Ni(m1a)2-1, Ni(m1a)2-2, Ni(m1a)2-3, and Ni(m1a)2-4 prepared in Examples 1-4 of this invention are shown. As can be seen from the figures, the PXRD spectra of the four Ni(m1a)2 samples synthesized in Examples 1-4 are basically the same, indicating that these four Ni(m1a)2 samples have the same crystal structure, and samples with high crystallinity can be synthesized using the methods of Examples 1-4.
[0049] Test Example 4: Water vapor stability of nickel-based metal-organic framework material Ni(mla)2 The Ni(mla)2-1 prepared in Example 1 of this invention was placed at 25 °C in an environment with a relative humidity of 88% for 24 h, and then the adsorption effect of the sample on CO2 was compared. Figure 4 The figure shows the adsorption isotherms of Ni(mla)2-1 prepared in Example 1 of this invention for CO2 adsorption before and after 24 hours in air with a relative humidity of 88%. As can be seen from the figure, after 24 hours of exposure to humid air, the adsorption capacity of the material for CO2 not only did not decrease, but actually increased slightly. This indicates that the material prepared in this invention has good water vapor stability. This may be because water vapor molecules replace the solvent molecules remaining in the pores of the material. These solvent molecules are difficult to remove by heating and vacuuming during adsorption testing, but water molecules can be removed by heating and vacuuming, thus releasing the pores of the material.
[0050] Test Example 5: Deodorizing and deodorizing effect of nickel-based metal-organic framework material Ni(mla)2 on oyster peptide powder solution Qualitative and quantitative analysis of odor substances in seafood was performed using gas chromatography-mass spectrometry (G3540A, Agilent Technologies). Figure 4To introduce abundance analysis, the absolute content of N,N-dimethylformamide in oyster peptides after Ni(mla)2-1 treatment was analyzed. The abundance of N,N-dimethylformamide was observed to decrease by an order of magnitude after treatment, and the abundance of Ni(mla)2 dropped to approximately 0 after 7.1 min of scanning time. This indicates a significant reduction in the absolute content of N,N-dimethylformamide before and after adsorption.
[0051] Table 3 shows the changes in the content of substances in the oyster peptide powder solution before and after adsorption, determined by gas chromatography-mass spectrometry. As can be seen from the table, Ni(mla)2-1 has a certain adsorption effect on various volatile substances in the oyster peptide powder solution. Styrene in the oyster peptide powder solution was completely adsorbed by Ni(mla)2-1; the relative content of N,N-dimethylformamide decreased by 3.1% after adsorption by Ni(mla)2-1; 5-amino-1-methyl-1H-pyrazole-4-carboxamide was completely adsorbed by Ni(mla)2-1; and the relative content of octamethylcyclotetrasiloxane decreased by 22.6% after adsorption by Ni(mla)2-1.
[0052] Table 3: Content Changes
[0053] Figure 6 The figure shows the adsorption isotherms of Ni(mla)2-1, Ni(mla)2-2, Ni(mla)2-3, and Ni(mla)2-4 for styrene, a typical odorous substance, at 25 °C. As can be seen from the figure, Ni(mla)2-1 adsorbs 128.60 mg / g of styrene at 0.09 kPa and 165.70 mg / g at the highest pressure of 0.73 kPa, which is 1.86 times that of commercial activated carbon.
[0054] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0055] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.
Claims
1. The application of a nickel-based metal-organic framework material in the removal of odorous substances, characterized in that, The odorous substances include N,N-dimethylformamide, styrene, 5-amino-1-methyl-1H-pyrazole-4-carboxamide and octamethylcyclotetrasiloxane; The preparation method of the nickel-based metal-organic framework material includes the following steps: Nickel acetate tetrahydrate and 2-methylpyridine-4-carboxylic acid were added sequentially to N,N-dimethylformamide and mixed thoroughly. Then, a solvent was added, and the mixture was sonicated for 10 to 15 minutes. The mixture was then placed in an oven at 130°C to 150°C to react. After the reaction was completed, the solid was washed and then filtered. The green solid obtained by filtration was wrapped in aluminum foil and then vacuum dried to obtain a nickel-based metal-organic framework material. The nickel-based metal-organic framework material has a three-dimensional porous structure with pore sizes of 0.62–0.65 nm and a specific surface area of 422.1–452.4 m². 2 / g.
2. The application according to claim 1, characterized in that, The mass ratio of nickel acetate tetrahydrate to 2-methylpyridine-4-carboxylic acid is (1~3):(1~5).
3. The application according to claim 1, characterized in that, In the preparation method of the nickel-based metal-organic framework material, the volume ratio of N,N-dimethylformamide to the solvent is 1:(1~4).
4. The application according to claim 1, characterized in that, The washing process uses at least one of N,N-dimethylformamide, acetonitrile, ethanol, and acetone.
5. The application according to claim 3, characterized in that, The solvent is at least one of acetonitrile, methanol, and ethanol.
6. The application according to claim 1, characterized in that, The vacuum drying process is performed at a temperature of 30℃~40℃ for 12h~24h.