Composite materials, their preparation methods and methods for removing heteroatoms

Abstract

A composite material comprises a metal oxide support, a metal-organic framework, and an interfacial crystalline layer disposed between the metal oxide support and the metal-organic framework, wherein the interfacial crystalline layer has a d-spacing of 0.290 nm to 0.360 nm. Furthermore, the present invention also provides a method for preparing the composite material and a method for removing heteroatoms.

Description

Technical Field

[0001] This invention relates to composite materials, their preparation methods, and methods for removing heteroatoms, particularly to composite materials of metal oxide-supported metal-organic frameworks, their preparation methods, and methods for removing heteroatoms. Background Technology

[0002] Compounds in waste plastic pyrolysis oil often contain heteroatoms such as sulfur, phosphorus, halogens, and silicon. These heteroatomic impurities limit the application of waste plastic pyrolysis oil as a feedstock for light oil pyrolysis. Sulfur, phosphorus, and halogens are also common heteroatoms in crude oil. Currently, commercial adsorbents (such as alumina) can remove some of these heteroatoms, but they cannot effectively remove organosilicon impurities.

[0003] Metal-organic frameworks (MOFs) possess both metal and organic structures, thus their unique metal-organic combination structure can be used to adsorb and remove organosilicon impurities (such as siloxanes) from waste plastic pyrolysis oil. However, due to mass transfer barriers in MOFs, the utilization of their internal adsorption sites is limited, reducing their efficiency in removing heteroatoms by adsorbing organosilicon atoms.

[0004] Besides waste plastic pyrolysis oil, other liquid organic materials (such as biomass, food, and waste) also require effective heteroatom adsorbents (such as nitrogen) for removal to facilitate their application. Therefore, in order to improve the quality of liquid organic materials and expand their potential in industrial applications, developing adsorbent materials that can effectively remove heteroatoms by adsorbing them is an important goal in this field. Summary of the Invention

[0005] One embodiment of the present invention provides a composite material comprising: a metal oxide carrier, a metal-organic framework, and an interfacial crystalline layer disposed between the metal oxide carrier and the metal-organic framework, wherein the interfacial crystalline layer has a d-spacing of 0.290 nanometers (nm) to 0.360 nanometers.

[0006] An embodiment of the present invention provides a method for preparing a composite material, comprising: adding a metal oxide support to an alkaline solution at a first temperature and a pressure to form a first mixed solution; introducing an organic ligand (from an organic binder) and a metal ion precursor into the first mixed solution at the first temperature and a pressure to react and form a second mixed solution; filtering the second mixed solution to obtain a solid product; and drying the solid product at a second temperature and a pressure (which may be the same as the aforementioned mixing pressure) to obtain the composite material, wherein the second temperature is greater than the first temperature.

[0007] An embodiment of the present invention provides a method for removing heteroatoms from liquid organic matter (e.g., waste plastic pyrolysis oil, liquid biomass, liquid food waste) using a composite material, comprising: filling the composite material of the present invention into a reactor; introducing the liquid organic matter containing heteroatoms into the reactor; and contacting the composite material with the liquid organic matter containing heteroatoms to adsorb the heteroatoms in the liquid organic matter, wherein the heteroatoms comprise silicon, phosphorus, bromine, chlorine, nitrogen or a combination thereof. Attached Figure Description

[0008] Figure 1 This is a TEM image of a composite material according to an embodiment of the present invention.

[0009] Figure 2 This is a TEM image of a composite material according to an embodiment of the present invention.

[0010] Figure 3 This is a TEM image of a composite material according to an embodiment of the present invention.

[0011] Figure 4 This is a TEM image of an adsorbent material according to a comparative example of the present invention. Detailed Implementation

[0012] The following embodiments describe in detail the features and advantages of the present invention, the content of which is sufficient to enable anyone skilled in the art to understand the technical content of the present invention and implement it accordingly. Furthermore, based on the disclosure, claims, and drawings in this specification, anyone skilled in the art can easily understand the related objectives and advantages of the present invention. The following embodiments are intended to further illustrate the points of the present invention, but are not intended to limit the scope of the present invention in any way.

[0013] The composite material of the present invention will now be described with reference to the accompanying drawings.

[0014] One embodiment of the present invention provides a composite material comprising: a metal oxide support, a metal-organic framework, and an interfacial crystalline layer disposed between the metal oxide support and the metal-organic framework, wherein the interfacial crystalline layer has a d-spacing of 0.290 nm to 0.360 nm as analyzed by high-resolution TEM. The thickness of the interfacial crystalline layer can be 10 nm to 340 nm. In some embodiments of the present invention, the interfacial crystalline layer may partially cover the metal oxide support.

[0015] In some embodiments of the present invention, the metal oxide support may comprise alumina, zirconium oxide, cerium oxide, or a combination thereof. In some embodiments of the present invention, the metal oxide support has a non-porous structure and a median particle size of 10 micrometers (μm) to 150 micrometers. In some embodiments, the metal oxide support has a porous structure with a pore size of 10 nm to 180 nm and a specific surface area of ​​1 square meter per gram (m²).2 The concentration of the substance ranges from 0.002 cubic centimeters per gram (g) to 500 square meters per gram, and its pore volume is 0.002 cubic centimeters per gram (cm³). 3 / g) to 0.3 cubic centimeters / gram.

[0016] In some embodiments of the present invention, the metal-organic framework may include: a metal ion and an organic ligand, wherein the metal of the metal ion is selected from copper, aluminum, iron, zinc or a combination thereof, and can be introduced through a metal ion precursor; and the organic ligand includes at least one benzene ring and at least two carboxylic acid groups, and can be introduced through an organic linker.

[0017] In some embodiments of the present invention, the organic ligand may contain at least one amino group. In some embodiments of the present invention, the organic ligand may not contain an amino group. In some embodiments of the present invention, the organic ligand is derived from an organic linker, and the organic linker may contain trimesic acid (BTC), 2-aminoterephthalic acid (BDC-NH2), or a combination thereof.

[0018] In some embodiments of the present invention, the weight ratio of the metal-organic framework to the composite material is from 0.1:100 to 50:100.

[0019] This invention provides a method for preparing a composite material, comprising: adding a metal oxide support to an alkaline solution at a first temperature and a pressure to form a first mixed solution; introducing an organic binder and a metal ion precursor into the first mixed solution at the first temperature and a pressure to react and form a second mixed solution; and filtering the second mixed solution to obtain the composite material of this invention. Alternatively, the solid product can be dried at a second temperature and a pressure to obtain the composite material, wherein the second temperature is higher than the first temperature. In some embodiments of this invention, the first temperature may be room temperature, or may be from 15°C to 50°C, the second temperature may be from 60°C to 90°C, and the pressure may be from 0.5 bar to 10 bar. In some embodiments of this invention, the metal oxide comprises alumina, zirconium oxide, cerium oxide, or combinations thereof. In some embodiments of this invention, the metal ion precursor may be a copper salt (e.g., copper nitrate), an aluminum salt (e.g., aluminum nitrate), an iron salt (e.g., ferric nitrate), a zinc salt (e.g., zinc nitrate), or combinations thereof. In some embodiments of the present invention, a metal-organic framework is grown on the surface of a metal oxide support to form an interfacial crystalline layer with a specific interplanar spacing (d-spacing).

[0020] In some embodiments of the present invention, the organic binder may comprise trimesic acid (BTC), 2-aminoterephthalic acid (BDC-NH2), or a combination thereof.

[0021] In some embodiments of the present invention, the molar ratio of the metal oxide support to the metal ion precursor is 1:20 to 1:500. In some embodiments of the present invention, the molar ratio of the metal ion precursor to the organic binder is 77:100 to 1:1.

[0022] The composite material of the present invention uses metal oxide as a carrier, loads and appropriately disperses the metal-organic framework through the interfacial crystalline layer, thereby reducing the mass transfer barrier of the metal-organic framework and effectively improving the adsorption of heteroatoms and thus removing heteroatoms.

[0023] An embodiment of the present invention provides a method for removing heteroatoms from liquid organic matter using a composite material, comprising: filling the composite material of the present invention into a reactor; introducing liquid organic matter containing heteroatoms into the reactor; and contacting the composite material with the liquid organic matter containing heteroatoms to adsorb the heteroatoms in the liquid organic matter, wherein the heteroatoms comprise silicon, phosphorus, bromine, chlorine, nitrogen or a combination thereof.

[0024] In some embodiments of the present invention, the method for removing heteroatoms from liquid organic matter using a composite material can be carried out at room temperature or at a temperature of 15°C to 30°C and a pressure of 1 bar. In some embodiments of the present invention, the liquid organic matter includes waste plastic pyrolysis oil, liquid biomass, liquid food, waste, or combinations thereof. In some embodiments of the present invention, the composite material has an adsorption capacity for silicon atoms of 49–151 μg / g.

[0025] An embodiment of the present invention further includes contacting the composite material with an organic solvent to clean the composite material, and returning the composite material to the reactor.

[0026] In some embodiments of the present invention, the organic solvent used to clean the composite material may include tetrahydrofuran, methanol, ethanol, toluene, or acetone. By cleaning the composite material adsorbed with heteroatoms using an organic solvent, the adsorption capacity of the composite material can be regenerated for reuse, which is beneficial for cost reduction and sustainable development.

[0027] To make the above-described contents and other objects, features and advantages of this disclosure more apparent and understandable, embodiments are described below in detail with reference to the accompanying drawings:

[0028] Material selection / preparation method

[0029] The alumina (Al2O3) used in the following examples and comparative examples was purchased from ACROS and had a specific surface area of ​​23 m². 2 / g, pore size 175nm, median particle size 10μm, pore volume 0.12cm³ 3 / g, and the crystalline phase is the gamma phase (γ-phase).

[0030] The zirconium oxide (ZrO2) used in the following examples and comparative examples was purchased from Sigma-Aldrich and had a specific surface area of ​​81.1 m². 2 / g, pore size 12.7nm, median particle size 15μm, pore volume 0.266cm³ 3 / g, and the crystalline phase is tetragonal.

[0031] The cerium oxide (CeO2) used in the following examples and comparative examples was purchased from Sigma-Aldrich and had a specific surface area of ​​8.2 m². 2 / g, pore size 23.6nm, median particle size 12μm, pore volume 0.05cm³ 3 / g, and the crystalline phase is cubic.

[0032] The trimesic acid (BTC) used in the following examples and comparative examples was purchased from Sigma-Aldrich.

[0033] The 2-aminoterephthalic acid (BDC-NH2) used in the following examples and comparative examples was purchased from Sigma-Aldrich.

[0034] Example 1 (Al-BTC@Al2O3)

[0035] An alkaline solution was prepared by dissolving 0.8 g of sodium hydroxide (NaOH) in 60 mL of water. 9 g of alumina was added to the alkaline solution, and the mixture was stirred at room temperature and 1 bar for 0.1 hours. Then, 1.12 g of trimesic acid was added, and the mixture was stirred for 1 hour to form a solid-liquid mixture. A 2.83 g aqueous solution of aluminum nitrate dissolved in 64.8 mL of water was added dropwise to the solid-liquid mixture, and the mixture was stirred for 24 hours. The reaction mixture was then filtered to obtain the crude product. The crude product was washed several times with deionized water to remove residues. Finally, the crude product was dried at 80 °C and 1.0 Bar to obtain the final product.

[0036] Example 2 (Cu-BDC-NH2@Al2O3)

[0037] 0.596 g of sodium hydroxide (NaOH) was dissolved in 50 mL of water to prepare an alkaline solution. 9 g of alumina (Al₂O₃) was added to the alkaline solution, and the mixture was stirred at room temperature and 1.0 Bar for 0.1 hours. Then, 1.0 g of 2-aminoterephthalic acid was added, and the mixture was stirred for 1 hour to form a solid-liquid mixture. A 1.335 g aqueous solution of copper nitrate dissolved in 8.0 mL of water was added dropwise to the solid-liquid mixture, and the mixture was stirred for 24 hours. The reaction mixture was then filtered to obtain the crude product. The crude product was washed several times with deionized water to remove residues. Finally, the crude product was dried at 80 °C and 1.0 Bar to obtain the final product.

[0038] Example 3 (Fe-BDC-NH2@Al2O3)

[0039] 1.7898 g of sodium hydroxide (NaOH) was dissolved in 150 mL of water to prepare an alkaline solution. 27 g of alumina was added to the alkaline solution, and the mixture was stirred for 0.1 hours at room temperature and 1 bar. Then, 3.0 g of 2-aminoterephthalic acid was added, and the mixture was stirred for 1 hour to form a solid-liquid mixture. 6.69 g of ferric nitrate aqueous solution dissolved in 24.0 mL of water was added dropwise to the solid-liquid mixture, and the mixture was stirred for 24 hours. The reaction mixture was then filtered to obtain a crude product. The crude product was washed several times with deionized water to remove residues. Finally, the crude product was dried at 80 °C and 1.0 Bar to obtain the final product.

[0040] Example 4 (Al-BTC@ZrO2)

[0041] 0.8 g of sodium hydroxide (NaOH) was dissolved in 60 mL of water to prepare an alkaline solution. 9 g of zirconium oxide (ZrO2) was added to the alkaline solution, and the mixture was stirred at room temperature and 1.0 Bar for 0.1 hours. Then, 1.12 g of trimesic acid was added, and the mixture was stirred for 1 hour to form a solid-liquid mixture. A 2.83 g aqueous solution of aluminum nitrate dissolved in 64.8 mL of water was added dropwise to the solid-liquid mixture, and the mixture was stirred for 24 hours. The reaction mixture was then filtered to obtain a crude product. The crude product was washed several times with deionized water to remove residues. Finally, the crude product was dried at 80 °C and 1.0 Bar to obtain the final product.

[0042] Example 5 (Cu-BDC-NH2@CeO2)

[0043] 0.596 g of sodium hydroxide (NaOH) was dissolved in 50 mL of water to prepare an alkaline solution. 9 g of cerium oxide (CeO2) was added to the alkaline solution, and the mixture was stirred at room temperature and 1.0 Bar for 0.1 hours. Then, 1.0 g of 2-aminoterephthalic acid was added, and the mixture was stirred for 1 hour to form a solid-liquid mixture. A 1.335 g aqueous solution of copper nitrate dissolved in 8.0 mL of water was added dropwise to the solid-liquid mixture, and the mixture was stirred for 24 hours. The reaction mixture was then filtered to obtain a crude product. The crude product was washed several times with deionized water to remove residues. Finally, the crude product was dried at 80 °C and 1.0 Bar to obtain the final product.

[0044] Example 6 (Zn-BDC-NH2@CeO2)

[0045] 0.596 g of sodium hydroxide (NaOH) was dissolved in 50 mL of water to prepare an alkaline solution. 9 g of cerium oxide (CeO2) was added to the alkaline solution, and the mixture was stirred at room temperature and 1.0 Bar for 0.1 hours. Then, 1.0 g of 2-aminoterephthalic acid was added, and the mixture was stirred for 1 hour to form a solid-liquid mixture. 1.664 g of zinc nitrate aqueous solution dissolved in 8.0 mL of water was added dropwise to the solid-liquid mixture, and the mixture was stirred for 24 hours. The reaction mixture was then filtered to obtain the crude product. The crude product was washed several times with deionized water to remove residues. Finally, the crude product was dried at 80 °C and 1.0 Bar to obtain the final product.

[0046] Example 7 (Cu-BDC-NH2@Al2O3)

[0047] Except for changing the amount of 2-aminoterephthalic acid to 0.16g and the amount of copper nitrate to 0.2136g, the same preparation conditions as in Example 2 above were used.

[0048] Example 8 (Cu-BDC-NH2@Al2O3)

[0049] Except for changing the amount of 2-aminoterephthalic acid to 0.65g and the amount of copper nitrate to 0.868g, the same preparation conditions as in Example 2 above were used.

[0050] Example 9 (Cu-BDC-NH2@Al2O3)

[0051] Except for changing the amount of 2-aminoterephthalic acid to 3.0g and the amount of copper nitrate to 4.01g, the same preparation conditions as in Example 2 above were used.

[0052] Example 10 (Cu-BDC-NH2@Al2O3)

[0053] Except for changing the amount of 2-aminoterephthalic acid to 5.0g and the amount of copper nitrate to 6.68g, the same preparation conditions as in Example 2 above were used.

[0054] Example 11 (Cu-BDC-NH2@Al2O3)

[0055] Except for changing the amount of 2-aminoterephthalic acid to 20.0g and the amount of copper nitrate to 26.7g, the same preparation conditions as in Example 2 above were used.

[0056] Example 12 (Cu-BDC-NH2@Al2O3)

[0057] Except for changing the amount of 2-aminoterephthalic acid to 50.0g and the amount of copper nitrate to 66.8g, the same preparation conditions as in Example 2 above were used.

[0058] Comparative Example 1 (Al2O3)

[0059] As mentioned above, alumina purchased from ACROS was used as adsorbent material I.

[0060] Comparative Example 2 (Al-BTC)

[0061] 0.8 g of sodium hydroxide (NaOH) was dissolved in 60 mL of water to prepare an alkaline solution. Then, 1.12 g of trimesic acid was added and the mixture was stirred at room temperature and 1.0 Bar for 0.1 hours to form a solid-liquid mixture. 2.83 g of aluminum nitrate aqueous solution dissolved in 64.8 mL of water was added dropwise to the mixture, and the mixture was stirred at room temperature and 1 bar for 24 hours. The reaction mixture was then filtered to obtain a crude product. The crude product was washed several times with deionized water to remove residues. Finally, it was dried at 80 °C and 1.0 Bar to obtain the final product (adsorbent material II).

[0062] Comparative Example 3 (Cu-BDC-NH2)

[0063] 0.596 g of sodium hydroxide (NaOH) was dissolved in 50 mL of water to prepare an alkaline solution. Then, 1.0 g of 2-aminoterephthalic acid was added, and the mixture was stirred at room temperature and 1.0 Bar for 0.1 hours to form a mixture. 2.446 g of copper nitrate aqueous solution dissolved in 8.0 mL of water was added dropwise to the mixture, and the mixture was stirred at room temperature and 1.0 Bar for 24 hours. The reaction mixture was then filtered to obtain a crude product. The crude product was washed several times with deionized water to remove residues. It was then dried at 80 °C and 1.0 Bar to obtain the final product (adsorbent III).

[0064] Comparative Example 4 (Fe-BDC-NH2)

[0065] 1.7898 g of sodium hydroxide (NaOH) was dissolved in 150 mL of water to prepare an alkaline solution. Then, 3.0 g of 2-aminoterephthalic acid was added, and the mixture was stirred at room temperature and 1 bar for 1 hour to form a mixture. 6.69 g of ferric nitrate aqueous solution dissolved in 24.0 mL of water was added dropwise to the mixture, and the mixture was stirred at room temperature and 1 bar for 24 hours. The reaction mixture was then filtered to obtain a crude product. The crude product was washed several times with deionized water to remove residues. It was then dried at 80 °C and 1.0 Bar to obtain the final product (adsorbent IV).

[0066] Comparative Example 5 (Al-BTC+Al2O3)

[0067] 1.00g of adsorbent material II was physically mixed with 99.0g of adsorbent material I.

[0068] Comparative Example 6 (Cu-BDC-NH2+Al2O3)

[0069] 1.00 g of adsorbent III was physically mixed with 99.0 g of adsorbent I.

[0070] Comparative Example 7 (Fe-BDC-NH2+Al2O3)

[0071] 1.00 g of adsorbent IV was physically mixed with 99.0 g of adsorbent I.

[0072] Comparative Example 8 (Acid Synthesis of Al-BTC@Al2O3)

[0073] 9.0 g of Al₂O₃ was dissolved in 20 mL of 1 M HNO₃ to prepare an acid solution, which was stirred at room temperature and 1.0 Bar for 0.1 hours. Then, 1.12 g of trimesic acid was added and stirred for 1 hour to form a solid-liquid mixture. A 2.83 g aqueous solution of aluminum nitrate dissolved in 64.8 mL of water was added dropwise to the solid-liquid mixture, and the mixture was stirred at room temperature and 1.0 Bar for 24 hours. The reaction mixture was then filtered to obtain the crude product. The crude product was washed several times with deionized water to remove residues. Finally, it was dried at 80 °C and 1.0 Bar to obtain the final product.

[0074] Comparative Example 9 (Acid Synthesis of Cu-BDC-NH2@Al2O3)

[0075] 9.0 g of Al₂O₃ was dissolved in 20 mL of 1 M HNO₃ to prepare an acid solution, which was stirred at room temperature and 1.0 Bar for 0.1 hours. Then, 1.0 g of 2-aminoterephthalic acid was added and stirred for 1 hour to form a solid-liquid mixture. 1.335 g of copper nitrate aqueous solution dissolved in 8.0 mL of water was added dropwise to the solid-liquid mixture, and the mixture was stirred at room temperature and 1.0 Bar for 24 hours. The reaction mixture was then filtered to obtain the crude product. The crude product was washed several times with deionized water to remove residues. Finally, it was dried at 80 °C and 1.0 Bar to obtain the final product.

[0076] Comparative Example 10 (Acid Synthesis of Fe-BDC-NH2@Al2O3)

[0077] 9.0 g of Al₂O₃ was dissolved in 20 mL of 1 M HNO₃ to prepare an acid solution, which was stirred at room temperature and 1.0 Bar for 0.1 hours. Then, 3.0 g of 2-aminoterephthalic acid was added and stirred for 1 hour to form a solid-liquid mixture. 6.68 g of ferric nitrate aqueous solution dissolved in 24.0 mL of water was added dropwise to the mixture, and the mixture was stirred at room temperature and 1.0 Bar for 24 hours. The reaction mixture was then filtered to obtain the crude product. The crude product was washed several times with deionized water to remove residues. Finally, it was dried at 80 °C and 1.0 Bar to obtain the final product.

[0078] Comparative Example 11 (ZrO2)

[0079] Zirconia, purchased from Sigma-Aldrich as mentioned above, was used as the adsorbent material V.

[0080] Comparative Example 12 (Al-BTC+ZrO2)

[0081] 1.00g of adsorbent material II was physically mixed with 99.0g of adsorbent material V.

[0082] Comparative Example 13 (CeO2)

[0083] As mentioned above, cerium oxide purchased from Sigma-Aldrich was used as adsorbent material VI.

[0084] Comparative Example 14 (Cu-BDC-NH2+CeO2)

[0085] 1.00g of adsorbent III was physically mixed with 99.0g of adsorbent VI.

[0086] Comparative Example 15 (Zn-BDC-NH2)

[0087] 0.596 g of sodium hydroxide (NaOH) was dissolved in 50 mL of water to prepare an alkaline solution. Then, 1.0 g of 2-aminoterephthalic acid was added, and the mixture was stirred at room temperature and 1.0 Bar for 1 hour to form a mixture. 1.664 g of zinc nitrate aqueous solution dissolved in 8.0 mL of water was added dropwise to the mixture, and the mixture was stirred at room temperature and 1.0 Bar for 24 hours. The reaction mixture was then filtered to obtain a crude product. The crude product was washed several times with deionized water to remove residues. It was then dried at 80 °C and 1.0 Bar to obtain the final product (adsorbent VII).

[0088] Comparative Example 16 (Zn-BDC-NH2+CeO2)

[0089] 1.00g of adsorbent VII was physically mixed with 99.0g of adsorbent VI.

[0090] Figure 1 This is a TEM image of the composite material according to an embodiment (Example 2) of the present invention.

[0091] Please refer to Figure 1 The composite material in Example 2 comprises three parts: pure Cu-BDC-NH2, Cu-BDC-NH2 supported on Al2O3 (interfacial crystalline layer), and pure Al2O3. The thickness of the interfacial crystalline layer reaches 340 nm in some regions, and the interplanar spacing (d-spacing) is 0.287 nm to 0.301 nm, while the interplanar spacing of Al2O3 is 0.229 nm. Due to the mismatch in lattice constants between Al2O3 and Cu-BDC-NH2, although the interfacial crystalline layer has an ordered crystalline structure, its interplanar spacing gradually increases from 0.287 nm near the Al2O3 region to 0.301 nm further away from the Al2O3 region. Furthermore, according to... Figure 1 The single-element (Cu, Al) distribution diagram on the right shows that the copper-containing metal-organic framework Cu-BDC-NH2 covers at least part of the metal oxide, but the aluminum-containing metal oxide support does not significantly diffuse or grow towards the metal-organic framework Cu-BDC-NH2.

[0092] Figure 2 This is a TEM image of the composite material according to an embodiment (Example 4) of the present invention.

[0093] Please refer to Figure 2The composite material in Example 4 comprises three parts: pure Al-BTC, Al-BTC (interfacial crystalline layer) supported on ZrO2, and pure ZrO2. The thickness of the interfacial crystalline layer reaches 51 nm in some regions, with a crystal interplanar spacing of 0.351 nm to 0.360 nm, while the ZrO2 crystal interplanar spacing is 0.293 nm. Due to the mismatch in lattice constants between ZrO2 and Al-BTC, although the interfacial crystalline layer has an ordered crystalline structure, its crystal interplanar spacing gradually increases from 0.351 nm near the ZrO2 region to 0.360 nm further away from the ZrO2 region. Furthermore, according to... Figure 2 The single-element (Al, Zr) distribution diagram on the right shows that the aluminum-containing metal-organic framework covers at least part of the metal oxide, but the zirconium-containing metal oxide support does not significantly diffuse or grow towards the metal-organic framework Al-BTC.

[0094] Figure 3 This is a TEM image of the composite material according to an embodiment (Example 5) of the present invention.

[0095] Please refer to Figure 3 The composite material in Example 4 comprises three parts: pure Cu-BDC-NH2, Cu-BDC-NH2 supported on CeO2 (interfacial crystalline layer), and pure CeO2. The thickness of the interfacial crystalline layer reaches 43 nm in some regions, with a crystal interplanar spacing of 0.330 nm to 0.344 nm, while the crystal interplanar spacing of CeO2 is 0.270 nm. Due to the mismatch in lattice constants between CeO2 and Cu-BDC-NH2, although the interfacial crystalline layer has an ordered crystalline structure, its crystal interplanar spacing gradually increases from 0.330 nm near the CeO2 region to 0.344 nm further away from the CeO2 region. Furthermore, according to... Figure 3 The single-element (Cu, Ce) distribution diagram on the left shows that the copper-containing metal-organic framework covers at least part of the metal oxide, but the cerium-containing metal oxide support does not significantly diffuse or grow towards the metal-organic framework Cu-BDC-NH2.

[0096] Figure 4 This is a TEM image of the adsorbent material according to a comparative example (Comparative Example 6) of the present invention.

[0097] Please refer to Figure 4 Comparative Example 6, the adsorbent material after physical mixing, contains only two parts: pure Cu-BDC-NH2 and pure Al2O3, and these two parts are not connected and do not have an interfacial crystalline layer. Furthermore, according to... Figure 4 The single-element (Cu, Al) distribution diagram on the right shows that the copper-containing metal-organic framework is not covered by metal oxides.

[0098] Test for adsorbed heteroatoms

[0099] Nine g of the composite materials of Examples 1 to 12 and the adsorbent materials of Comparative Examples 1 to 16 were placed in a fixed-bed vacuum filtration system, and 30 mL of polypropylene plastic pyrolysis oil was added to each for adsorption heteroatom testing. The product composition was analyzed by XRF and the adsorption capacity (the weight of impurities that can be adsorbed per gram of material) was calculated.

[0100] Table 1 below reveals the adsorption heteroatom test results of the materials in each embodiment and comparative example of the present invention.

[0101] Table 1

[0102]

[0103]

[0104] Based on the test results in Table 1, the following phenomena can be observed.

[0105] By comparing Examples 1 to 3 and Comparative Examples 1 to 7, it can be confirmed that the composite material of the present invention has better silicon adsorption capacity than using metal oxides or metal-organic frameworks alone or simply a mixture of both. Furthermore, the composite material of the present invention also has excellent phosphorus, halogen, and nitrogen adsorption capacity. The composite material of the present invention can simultaneously achieve the effect of having excellent silicon, phosphorus, halogen, and nitrogen adsorption capacity, that is, it has the effect of having excellent heteroatom adsorption capacity.

[0106] By comparing Examples 1 to 3 and Comparative Examples 8 to 10, it was confirmed that the composite material of the present invention has better heteroatom (including silicon, phosphorus, halogen, and nitrogen) adsorption capacity compared to the material synthesized under acidic conditions. Furthermore, it was found that the adsorption capacity of various heteroatoms in Comparative Examples 8 to 10 was similar to that of the alumina in Comparative Example 1. During the preparation of Comparative Examples 8 to 10, it was found that the organic ligands were difficult to dissolve in acidic aqueous solutions, therefore it is speculated that the metal-organic framework of Comparative Examples 8 to 10 may not have been effectively formed.

[0107] By comparing Example 4 with Comparative Examples 2, 11, and 12, it can be confirmed that the composite material of the present invention has better adsorption capacity for silicon, phosphorus, halogens, and nitrogen compared to using metal oxides or metal-organic frameworks alone or simply a mixture of both.

[0108] By comparing Example 5 with Comparative Examples 3, 13, and 14, it can be confirmed that the composite material of the present invention has better adsorption capacity for silicon, phosphorus, halogens, and nitrogen compared to using metal oxides or metal-organic frameworks alone or simply a mixture of both.

[0109] By comparing Example 6 and Comparative Examples 13, 15, and 16, it can be confirmed that the composite material of the present invention has better adsorption capacity for silicon, phosphorus, halogens, and nitrogen compared to using metal oxides or metal-organic frameworks alone or simply a mixture of both.

[0110] By comparing Examples 2, 7-12, it can be confirmed that the composite material with 1 wt% metal-organic framework (Example 2) has better adsorption capacity for silicon, phosphorus, halogens and nitrogen.

[0111] In summary, the composite material, its preparation method, and the method for removing heteroatoms provided by this invention reduce the mass transfer barrier of the metal-organic framework and enhance the effect of removing heteroatoms by adsorbing them by using metal oxides as a carrier to disperse the metal-organic framework.

Claims

1. A composite material comprising: A metal oxide support; A metal-organic framework; and An interfacial crystalline layer is disposed between the metal oxide support and the metal-organic framework, wherein the interfacial crystalline layer has a d-spacing of 0.290 nanometers (nm) to 0.360 nanometers.

2. The composite material according to claim 1, wherein the interfacial crystalline layer covers at least a portion of the surface of the metal oxide carrier.

3. The composite material according to claim 1, wherein the metal oxide carrier comprises alumina, zirconium oxide, cerium oxide, or a combination thereof.

4. The composite material according to claim 1, wherein the metal oxide carrier is a non-porous structure and its median particle size is between 10 micrometers (μm) and 150 micrometers.

5. The composite material according to claim 1, wherein the metal oxide carrier has a porous structure and its pore size is 10 nanometers to 180 nanometers.

6. The composite material according to claim 1, wherein the metal oxide carrier has a porous structure and its specific surface area is 1 square meter per gram (m²). 2 / g) to 500 square meters / gram.

7. The composite material according to claim 1, wherein the metal oxide carrier has a porous structure and its pore volume is 0.002 cubic centimeters / gram (cm³). 3 / g) to 0.3 cubic centimeters / gram.

8. The composite material according to claim 1, wherein the weight ratio of the metal-organic framework to the composite material is from 0.1:100 to 50:

100.

9. The composite material according to claim 1, wherein the metal-organic framework comprises: A metal ion and an organic ligand, The metal ion is selected from copper, aluminum, iron, zinc, or combinations thereof, and The organic ligand contains at least one benzene ring and at least two carboxylic acid groups.

10. The composite material according to claim 9, wherein the organic ligand comprises at least one amine group.

11. The composite material according to claim 1, wherein the thickness of the interfacial crystalline layer is from 10 nanometers to 340 nanometers.

12. A method for preparing a composite material, comprising: A metal oxide support is added to an alkaline solution at a first temperature and a first pressure to form a first mixed solution; An organic binder and a metal ion precursor are introduced into the first mixed solution at the first temperature and the first pressure to react and form a second mixed solution. The second mixed solution is filtered to obtain a solid product, thereby obtaining the composite material of claim 1.

13. The method for preparing composite materials according to claim 12, further comprising: A second temperature is provided to dry the solid product to obtain the composite material of claim 1.

14. The method for preparing the composite material according to claim 12, wherein the first temperature ranges from 15°C to 50°C.

15. The method for preparing the composite material according to claim 13, wherein the second temperature ranges from 60°C to 90°C.

16. The method for preparing the composite material according to claim 12, wherein the pressure ranges from 0.5 Bar to 10 Bar.

17. The method for preparing a composite material according to claim 12, wherein the metal oxide comprises aluminum oxide, zirconium oxide, cerium oxide, or a combination thereof.

18. The method for preparing a composite material according to claim 12, wherein the metal ion precursor is a copper salt, aluminum salt, iron salt, zinc salt, or a combination thereof.

19. The method for preparing a composite material according to claim 12, wherein the organic binder comprises pyromellitic acid, 2-aminoterephthalic acid, or a combination thereof.

20. The method for preparing a composite material according to claim 12, wherein the molar ratio of the metal oxide carrier to the metal ion precursor is 1:20 to 1:500, and the molar ratio of the metal ion precursor to the organic binder is 77:100 to 100:

100.

21. A method for removing heteroatoms, comprising: The composite material according to any one of claims 1 to 11 is filled into a reactor; A liquid organic compound containing heteroatoms is introduced into the reactor; and The composite material is brought into contact with the liquid organic material containing heteroatoms to adsorb one heteroatom from the liquid organic material containing heteroatoms, wherein the heteroatom comprises silicon, phosphorus, bromine, chlorine, nitrogen or a combination thereof.

22. The method for removing heteroatoms according to claim 21, wherein the liquid organic matter comprises waste plastic pyrolysis oil, liquid biomass, liquid food, liquid waste, or a combination thereof.

23. The method for removing heteroatoms according to claim 21 further comprises: contacting the composite material with an organic solvent to clean the composite material, and returning the composite material to the reactor.

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