Method for preparing composite aerogel using heavy energy hydrogenation tailings and halloysite

Abstract

This invention relates to the field of composite materials technology, and more particularly to a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite, thereby improving the added value of heavy energy hydrogenation tailings and the adsorption capacity of the aerogel. The method involves high-temperature graphitization of the toluene-soluble components of the heavy energy hydrogenation tailings, using the high-temperature graphitization product to prepare graphene oxide; amination and carboxylation of halloysite; mixing the carboxylated halloysite and graphene oxide in a specific ratio; adding ascorbic acid and stirring until homogeneous; and then subjecting the mixture to a hydrothermal reaction in an oven to obtain a hydrogel. The hydrogel is then freeze-dried to obtain the composite aerogel. This composite aerogel can be applied in the field of water purification, particularly as an adsorbent material for wastewater treatment, thereby increasing the added value of heavy energy hydrogenation tailings and the adsorption capacity of the aerogel. The aerogel exhibits strong adsorption performance and high stability in water.

Description

Technical Field

[0001] This invention relates to the field of composite materials technology, and in particular to a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite. Background Technology

[0002] my country possesses abundant coal resources. However, due to the complex composition of the raw materials used in the hydrogenation process of heavy energy, a considerable amount of liquefied tailings are generated after hydrogenation. Therefore, finding an effective way to utilize clean coal with high added value is of great significance for developing clean coal technology.

[0003] Graphene oxide is prepared using heavy energy hydrogenation tailings. Graphene oxide has strong adsorption capacity and is widely used in the adsorption field. Graphene oxide aerogel, as a porous three-dimensional material, and rich in various oxygen-containing functional groups, has great application value in the adsorption and removal of pollutants.

[0004] Halloysite nanotubes also possess strong adsorption capacity. Halloysite nanotubes are unique hollow tubular structures; the material is naturally occurring, readily available, inexpensive, non-toxic, and exhibits excellent biocompatibility. Due to the hydroxyl structure on its surface, halloysite nanotubes are easily modified, facilitating applied research. Therefore, preparing composite aerogels using graphene oxide and carboxylated halloysite can enhance the adsorption capacity of the aerogel, possessing significant research value. Summary of the Invention

[0005] This invention provides a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite. The heavy energy hydrogenation tailings are subjected to component separation and graphitization treatment. Graphene oxide is prepared using the high-temperature graphitization products and then subjected to a hydrothermal reaction with carboxylated halloysite to prepare composite aerogels, thereby improving the added value of heavy energy hydrogenation tailings and the adsorption capacity of the aerogels.

[0006] To achieve the above objectives, the present invention provides a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite, comprising the following steps:

[0007] (1) Preparation of graphitized carbon: Toluene is extracted from the tailings of heavy energy hydrogenation using toluene to obtain toluene-soluble matter. The toluene-soluble matter is carbonized in a tube furnace, and the carbonized product is placed in a graphitization furnace to obtain high-temperature graphitized product.

[0008] (2) Preparation of graphene oxide: Graphene oxide was prepared from the high-temperature graphitization product and washed to remove impurities until the pH value was 7. The graphene oxide was placed in a refrigerator and frozen at -45°C for 8 hours, and then placed in a freeze dryer and dried at 20°C for 2 days.

[0009] (3) Preparation of carboxylated halloysite: Halloysite, 3-aminopropyltriethoxysilane and anhydrous ethanol were added to a round-bottom flask at a ratio of 1g:4g:10ml and refluxed to obtain aminated halloysite; succinic anhydride was added to N,N-dimethylformamide at a volume ratio of 7:1000 to prepare a 0.1mol / L solution, and 2g of aminated halloysite was added to 100mL of the above solution and stirred to obtain carboxylated halloysite;

[0010] (4) Prepare a 4 mg / mL suspension with the prepared graphene oxide and deionized water, add carboxylated halloysite, wherein the mass ratio of graphene oxide to carboxylated halloysite is 9:1, then add 5 times the mass of ascorbic acid of graphene oxide and ultrasonically disperse at room temperature for 1 hour, and place in an oven to react to obtain hydrogel.

[0011] (5) The hydrogel was frozen in a refrigerator and then dried in a freeze dryer to obtain carboxylated halloysite / graphene oxide composite aerogel.

[0012] In the above-mentioned method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite, it is optional that the carbonization treatment of toluene-soluble substances in a tube furnace is carried out at a temperature of 800-1000℃ for 1 hour; and the carbonization product is placed in a graphitization furnace for graphitization at a temperature of 2500-3000℃ for 3 hours.

[0013] In the above-mentioned method for preparing composite aerogels using hydrogenation tailings from heavy energy sources and halloysite, an alternative is to use the modified Hummers method to prepare graphene oxide.

[0014] In the above-mentioned method for preparing composite aerogels using hydrogenation tailings from heavy energy sources and halloysite, it is optional to prepare aminated halloysite by reflux at 80°C for 1 day, or to prepare carboxylated halloysite by stirring in a beaker at room temperature for 1 day.

[0015] In the above-mentioned method for preparing composite aerogels using hydrogenation tailings from heavy energy sources and halloysite, it is optional to place the mixture in an oven and perform a hydrothermal reaction at 95°C for 3 to 5 hours.

[0016] In the above method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite, it is optional to freeze the hydrogel in a -40°C freezer for 4 hours and then dry it in a freeze dryer for 2 days.

[0017] This invention provides a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite. The method involves high-temperature graphitization of the toluene-soluble components of the heavy energy hydrogenation tailings, followed by the preparation of graphene oxide from the high-temperature graphitization product. Halloysite is then aminated and carboxylated. The carboxylated halloysite and graphene oxide are mixed in a specific ratio, and ascorbic acid is added and stirred until homogeneous. The mixture is then placed in an oven for a hydrothermal reaction to obtain a hydrogel. The hydrogel is freeze-dried to obtain a composite aerogel. This composite aerogel can be applied in the field of water purification, particularly as an adsorbent material for wastewater treatment. It enhances the added value of heavy energy hydrogenation tailings and the adsorption capacity of the aerogel. The aerogel exhibits strong adsorption performance and high stability in water.

[0018] The structure of the present invention, as well as its other inventive objects and beneficial effects, will become more apparent from the description of preferred embodiments taken in conjunction with the accompanying drawings. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 Scanning electron microscope image of a composite aerogel prepared from heavy energy hydrogenation tailings and halloysite, provided in an embodiment of the present invention. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be described in more detail below with reference to the accompanying drawings of the preferred embodiments. In the drawings, the same or similar reference numerals denote the same or similar components or components having the same or similar functions throughout. The described embodiments are some, but not all, embodiments of the present invention. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention. The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0022] This invention provides a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite, comprising the following steps:

[0023] (1) Preparation of graphitized carbon: Toluene is extracted from the tailings of heavy energy hydrogenation using toluene to obtain toluene-soluble matter. The toluene-soluble matter is carbonized in a tube furnace, and the carbonized product is placed in a graphitization furnace to obtain high-temperature graphitized product.

[0024] (2) Preparation of graphene oxide: Graphene oxide was prepared from the high-temperature graphitization product and washed to remove impurities until the pH value was 7. The graphene oxide was placed in a refrigerator and frozen at -45°C for 8 hours, and then placed in a freeze dryer and dried at 20°C for 2 days.

[0025] (3) Preparation of carboxylated halloysite: Halloysite, 3-aminopropyltriethoxysilane and anhydrous ethanol were added to a round-bottom flask at a ratio of 1g:4g:10ml and refluxed to obtain aminated halloysite; succinic anhydride was added to N,N-dimethylformamide at a volume ratio of 7:1000 to prepare a 0.1mol / L solution, and 2g of aminated halloysite was added to 100mL of the above solution and stirred to obtain carboxylated halloysite;

[0026] (4) Prepare a 4 mg / mL suspension with the prepared graphene oxide and deionized water, add carboxylated halloysite, wherein the mass ratio of graphene oxide to carboxylated halloysite is 9:1, then add 5 times the mass of ascorbic acid of graphene oxide and ultrasonically disperse at room temperature for 1 hour, and place in an oven to react to obtain hydrogel.

[0027] (5) The hydrogel was frozen in a refrigerator and then dried in a freeze dryer to obtain carboxylated halloysite / graphene oxide composite aerogel.

[0028] Furthermore, in the method for preparing composite aerogel using heavy energy hydrogenation tailings and halloysite according to the present invention, in step (1), the carbonization treatment of toluene solubles in a tube furnace is carried out at a temperature of 800-1000℃ for 1 hour; the carbonization product is placed in a graphitization furnace for graphitization at a temperature of 2500-3000℃ for 3 hours.

[0029] Furthermore, in the method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite according to the present invention, graphene oxide is prepared in step (2) using the improved Hummers method.

[0030] The improved Hummers process treats the raw material with an inorganic strong protic acid, such as concentrated sulfuric acid, which allows small molecules of the strong acid to enter the interlayer of graphite. Then, it is oxidized with a strong oxidizing agent (such as potassium permanganate) to obtain a layered structure with wrinkles and rich oxygen-containing functional groups, which has good dispersibility in aqueous solution.

[0031] Furthermore, in the method for preparing composite aerogel using heavy energy hydrogenation tailings and halloysite according to the present invention, in step (3), aminated halloysite is prepared by reflux at 80°C for 1 day; and carboxylated halloysite is prepared by stirring in a beaker at room temperature for 1 day.

[0032] Furthermore, in the method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite according to the present invention, the mixture placed in the oven in step (4) undergoes a hydrothermal reaction at 95°C for 3 to 5 hours.

[0033] Furthermore, in the method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite according to the present invention, in step (5), the hydrogel is placed in a freezer at -40°C for 4 hours and then placed in a freeze dryer for 2 days.

[0034] This invention provides a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite. The method involves separating and graphitizing the heavy energy hydrogenation tailings, preparing graphene oxide using the high-temperature graphitization products, and then reacting it with carboxylated halloysite via a hydrothermal reaction to prepare a carboxylated halloysite / graphene oxide composite aerogel. The composite aerogel can be applied in the field of water purification, especially as an adsorbent material for wastewater treatment, thereby increasing the added value of heavy energy hydrogenation tailings and the adsorption capacity of the aerogel.

[0035] The following will describe in detail a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite, with reference to specific embodiments.

[0036] Example 1

[0037] This invention discloses a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite. The aerogel is prepared using coal tar hydrogenation tailings as raw material, and the specific preparation method is as follows:

[0038] The toluene-soluble residue of hydrogenated coal tar was extracted with toluene. This toluene-soluble residue was then carbonized in a tube furnace at 800°C. The carbonized product was then subjected to high-temperature graphitization in a graphitization furnace at 2500°C to obtain a high-temperature graphitized product. Graphene oxide was prepared from the high-temperature graphitized product and washed to remove impurities until the pH reached 7. The graphene oxide was then frozen at -45°C for 8 hours and then dried in a freeze dryer at -20°C for 2 days. A 4 mg / mL suspension of the graphene oxide was prepared with deionized water. Five times the mass of ascorbic acid (based on the graphene oxide's mass) was added and ultrasonically dispersed at room temperature for 1 hour. The mixture was then reacted in an oven at 95°C for 5 hours to obtain a hydrogel. The hydrogel was frozen for 4 hours and then dried in a freeze dryer for 2 days to obtain a carbon aerogel.

[0039] Example 2

[0040] A method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite, using coal / heavy oil hydrogenation tailings as raw materials, is as follows:

[0041] The toluene-soluble residue of the coal / heavy oil hydrotreating tailings was extracted with toluene. The toluene-soluble residue was placed in a tube furnace and carbonized at 800°C. The carbonized product was then placed in a graphitization furnace and graphitized at 2500°C to obtain the high-temperature graphitized product.

[0042] Graphene oxide was prepared from the high-temperature graphitization product and washed to remove impurities until the pH value reached 7. The graphene oxide was then frozen at -45°C for 8 hours and subsequently dried at -20°C for 2 days. A 4 mg / mL suspension of the graphene oxide was prepared with deionized water, and ascorbic acid (5 times the mass of the graphene oxide) was added and ultrasonically dispersed at room temperature for 1 hour. The suspension was then reacted at 95°C for 5 hours to obtain a hydrogel. The hydrogel was frozen for 4 hours and then dried in a freeze dryer for 2 days to obtain a carbon aerogel. Scanning electron micrographs of the obtained material are shown below. Figure 1 As shown, the prepared aerogel has a typical wrinkled layered structure, which is due to the stacking of graphene oxide nanosheets and the reduced number of oxygen-containing functional groups on its surface after chemical reduction.

[0043] Example 3

[0044] This invention discloses a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite. The composite aerogel is prepared using coal / heavy oil hydrogenation tailings as raw materials, and the specific preparation method is as follows:

[0045] Graphene oxide was prepared according to the steps of Example 2. A suspension of 4 mg / mL was prepared with the above graphene oxide and deionized water, and carboxylated halloysite was added. The mass ratio of graphene oxide to carboxylated halloysite was 9:1. Ascorbic acid with a mass of 5 times that of graphene oxide was added and ultrasonically dispersed at room temperature for 1 hour. The mixture was then placed in an oven and reacted at 95°C for 5 hours to obtain a hydrogel. The hydrogel was frozen in a refrigerator for 4 hours and then dried in a freeze dryer for 2 days to obtain a composite aerogel.

[0046] Example 4

[0047] This invention discloses a method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite. The aerogel is prepared using coal / heavy oil hydrogenation tailings as raw material. The specific preparation method is as follows:

[0048] Graphene oxide was prepared according to the steps of Example 2. A suspension of 4 mg / mL was prepared with the above graphene oxide and deionized water, and carboxylated halloysite was added. The mass ratio of graphene oxide to carboxylated halloysite was 9:1. Ascorbic acid with a mass of 5 times that of graphene oxide was added and ultrasonically dispersed at room temperature for 1 hour. The mixture was then placed in an oven and reacted at 95°C for 5 hours to obtain a hydrogel. The hydrogel was frozen in a refrigerator for 4 hours and then dried in a freeze dryer for 2 days to obtain a composite aerogel.

[0049] A solution of methyl orange, malachite green, and methylene blue with a concentration of 50 mg / L was prepared, and then aerogel was added. The mixture was kept at 30°C and shaken for 6 hours. The aerogel was then removed, and its adsorption capacity for dyes in water was measured using a UV spectrophotometer. The adsorption capacity of the aerogel for dyes in water was used to determine its adsorption characteristics. The adsorption capacities (qm, unit: mg / g) of the aerogels prepared in Examples 1-4 for dyes in water are shown in Table 1.

[0050] Table 1. Adsorption capacity of different aerogels for dyes in water (qm, unit: mg / g)

[0051]

[0052] As can be seen from the data comparison in Table 1, composite aerogels can be used as adsorbent materials in the field of water purification and treatment, which increases the added value of heavy energy hydrogenation tailings and enhances the adsorption performance of composite aerogels.

[0053] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite, characterized in that, Includes the following steps: (1) Preparation of graphitized carbon: Toluene is extracted from the tailings of heavy energy hydrogenation using toluene to obtain toluene-soluble matter. The toluene-soluble matter is carbonized in a tube furnace, and the carbonized product is placed in a graphitization furnace to obtain high-temperature graphitized product. (2) Preparation of graphene oxide: Graphene oxide was prepared from the high-temperature graphitization product and washed to remove impurities until the pH value was 7. The graphene oxide was placed in a refrigerator and frozen at -45°C for 8 hours, and then placed in a freeze dryer and dried at 20°C for 2 days. (3) Preparation of carboxylated halloysite: Halloysite, 3-aminopropyltriethoxysilane and anhydrous ethanol were added to a round-bottom flask at a ratio of 1g:4g:10ml and refluxed to obtain aminated halloysite; succinic anhydride was added to N,N-dimethylformamide at a volume ratio of 7:1000 to prepare a 0.1mol / L solution, and 2g of aminated halloysite was added to 100mL of the above solution and stirred to obtain carboxylated halloysite; (4) Prepare a 4 mg / mL suspension with the prepared graphene oxide and deionized water, add carboxylated halloysite, wherein the mass ratio of graphene oxide to carboxylated halloysite is 9:1, then add 5 times the mass of ascorbic acid of graphene oxide and ultrasonically disperse at room temperature for 1 hour, and place in an oven to react to obtain hydrogel. (5) The hydrogel was frozen in a refrigerator and then dried in a freeze dryer to obtain carboxylated halloysite / graphene oxide composite aerogel.

2. The method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite according to claim 1, characterized in that, The carbonization of toluene-soluble substances in a tubular furnace is carried out at a temperature of 800–1000℃ for 1 hour; the carbonized products are then placed in a graphitization furnace for graphitization at a temperature of 2500–3000℃ for 3 hours.

3. The method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite according to claim 1, characterized in that, Graphene oxide was prepared using a modified Hummers method.

4. The method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite according to claim 1, characterized in that, Aminated halloysite was prepared by reflux at 80°C for 1 day; carboxylated halloysite was prepared by stirring in a beaker at room temperature for 1 day.

5. The method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite according to claim 1, characterized in that, The mixture placed in an oven undergoes a hydrothermal reaction at 95°C for 3–5 hours.

6. The method for preparing composite aerogels using heavy energy hydrogenation tailings and halloysite according to claim 1, characterized in that, The hydrogel was frozen in a -40°C freezer for 4 hours, and then dried in a freeze dryer for 2 days.

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