A porous material and its preparation method and application

Abstract

The present disclosure relates to a porous material, a preparation method and use thereof. The porous material comprises an alumina core, and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material, the content of the alumina core is 10 to 40% by weight, preferably 20 to 30% by weight; the content of the porous carbon layer is 60 to 90% by weight, preferably 70 to 80% by weight. The present disclosure provides a new porous material having a large specific surface area and pore volume, which can be used as an adsorbent, catalyst or catalyst carrier. The method for preparing the porous material provided by the present disclosure has the advantages of simple process flow and low cost, and is suitable for industrial large-scale production.

Description

Technical Field

[0001] The present disclosure relates to the field of material technology, and in particular to a porous material and a preparation method and application thereof. Background Art

[0002] Mesoporous carbon materials have the characteristics of high specific surface area, high porosity and adjustable pore size. As people's understanding of them gradually deepens, mesoporous carbon materials have been widely used in many fields. For example, mesoporous carbon materials can be used as catalysts, catalyst carriers or adsorbents.

[0003] Currently, the methods used to synthesize mesoporous carbon materials mainly include hard template method and soft template method. The hard template method uses a silicon oxide material with a mesoporous structure (for example, SBA-15) as a template agent to introduce a carbon source precursor into its mesopores. After high-temperature carbonization, the silicon template is removed with hydrofluoric acid or sodium hydroxide solution to produce the mesoporous carbon material. The preparation process of this method is relatively complicated, and the preparation process requires acid or alkaline washing, which produces a certain amount of waste liquid.

[0004] The soft template method uses block polymers and carbon source precursors (such as phenolic resins) to induce self-assembly, and then undergoes high-temperature thermal polycondensation and carbonization to produce mesoporous carbon materials. This method requires the use of organic templates, and the cost of raw materials is relatively high.

[0005] Therefore, there is an urgent need for a method for preparing porous materials with a simple preparation process and low cost. Summary of the Invention

[0006] The purpose of the present disclosure is to provide a porous material and a preparation method and use thereof.

[0007] In order to achieve the above-mentioned purpose, the present disclosure provides a porous material, which includes an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material, the content of the alumina core is 10 to 40 weight%, preferably 20 to 30 weight%; the content of the porous carbon layer is 60 to 90 weight%, preferably 70 to 80 weight%.

[0008] Optionally, the specific surface area of ​​the porous material is 150 to 1200 m 2 / g, pore volume is 0.5~1.3cm 3 / g, and the average pore size is 3 to 30 nm.

[0009] Optionally, the porous carbon layer contains carbon, oxygen, hydrogen, sulfur and nitrogen. Based on the total weight of the porous carbon layer, the carbon content is 83 to 95 weight%, preferably 85 to 91 weight%; the oxygen content is 2 to 6 weight%, preferably 3 to 5 weight%; the hydrogen content is 0.1 to 1 weight%, preferably 0.5 to 0.8 weight%; the sulfur content is 1 to 8 weight%, preferably 2 to 6 weight%; and the nitrogen content is 0.5 to 3 weight%, preferably 1 to 2 weight%.

[0010] Optionally, the alumina core contains a modifying element, and the modifying element is selected from at least one of group IIIA, IVA, VA, IIA, IIB, IIIB or IVB elements;

[0011] Based on the total weight of the alumina core, the content of the modifying element is 0.1 to 10 weight % in terms of element.

[0012] Optionally, the modifying element is selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium or zirconium;

[0013] Based on the total weight of the alumina core, the content of the modifying element is 0.3 to 5 weight % in terms of element.

[0014] The present disclosure also provides a method for preparing a porous material, the method comprising:

[0015] Mixing asphalt powder, an aluminum source, and a binder to obtain a mixed material, wherein the aluminum source contains aluminum oxide powder and / or an aluminum oxide powder precursor, and the binder includes at least one of cellulose ether, starch, or ene alcohol polymer;

[0016] The mixed material is subjected to heat treatment to obtain the porous material.

[0017] Optionally, the aluminum source further contains an auxiliary agent, the auxiliary agent contains a modifying element, and the modifying element is selected from at least one of the elements of Group IIIA, IVA, VA, IIA, IIB, IIIB or IVB;

[0018] The content of the modifying element is 0.1 to 10 wt % based on the total dry weight of the aluminum source, calculated as the element.

[0019] Optionally, the modifying element is at least one selected from phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium;

[0020] The content of the modifying element is 0.3 to 5 weight % based on the total dry weight of the aluminum source, calculated as the element.

[0021] Optionally, relative to 100 parts by weight of the asphalt powder, the amount of the aluminum source is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, calculated as alumina; the amount of the binder is 1 to 20 parts by weight, preferably 5 to 15 parts by weight.

[0022] Optionally, the particle size of the asphalt powder is 1 to 1000 μm, preferably 1 to 250 μm; the particle size of the aluminum source is 1 to 150 μm, preferably 1 to 75 μm.

[0023] Optionally, heat-treating the mixed material to obtain the porous material comprises:

[0024] In an oxygen-containing atmosphere, the temperature of the mixed material is raised from room temperature to 120-400° C. at a heating rate of 0.1-10° C. / min, and a first heat treatment is performed for 0.1-48 hours to obtain a first intermediate material;

[0025] Under an inert atmosphere, raising the temperature of the first intermediate material to 400-950° C. at a heating rate of 0.1-10° C. / min, and performing a second heat treatment for 0.1-24 hours to obtain a second intermediate material;

[0026] In an oxygen-containing atmosphere, the temperature of the second intermediate material is raised to 700-1000° C. at a heating rate of 0.1-10° C. / min, and a third heat treatment is performed for 0.1-12 hours to obtain the porous material.

[0027] Optionally, the asphalt powder includes petroleum asphalt powder and / or coal asphalt powder, and the asphalt powder contains polycyclic aromatic hydrocarbons. Based on the total weight of the asphalt powder, the content of the polycyclic aromatic hydrocarbons is 70 to 100 weight%, preferably 85 to 100 weight%.

[0028] The present disclosure also provides use of any of the porous materials described above or a porous material prepared by any of the methods described above in preparing an adsorbent, a catalyst or a catalyst carrier.

[0029] Through the above technical solution, the present disclosure provides a new porous material with a large specific surface area and pore volume, which can be used as an adsorbent, catalyst, or catalyst support. The porous material preparation method provided by the present disclosure has the advantages of simple process flow and low cost, and is suitable for industrial large-scale production.

[0030] Other features and advantages of the present disclosure will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0031] The following describes the specific embodiments of the present disclosure in detail. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure and are not intended to limit the present disclosure.

[0032] A first aspect of the present disclosure provides a porous material, which includes an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material, the content of the alumina core is 10 to 40 weight%, preferably 20 to 30 weight%; the content of the porous carbon layer is 60 to 90 weight%, preferably 70 to 80 weight%.

[0033] Through the above technical solution, the present disclosure provides a new porous material, which is composed of an alumina core and a porous carbon layer. The alumina and the porous carbon layer are compounded in a specific proportion and a specific spatial structure to achieve the effect of 1+1>2. Therefore, the porous material has a large specific surface area and pore volume, and can be used as an adsorbent, catalyst or catalyst carrier.

[0034] According to the present disclosure, the specific surface area of ​​the porous material can be 150 to 1200 m 2 / g, and the pore volume can be 0.5~1.3cm 3 / g, and the average pore diameter can be 3 to 30 nm.

[0035] According to the present disclosure, the porous carbon layer of the porous material may contain carbon, oxygen, hydrogen, sulfur and nitrogen. Based on the total weight of the porous carbon layer, the carbon content may be 83 to 95 weight%, preferably 85 to 91 weight%; the oxygen content may be 2 to 6 weight%, preferably 3 to 5 weight%; the hydrogen content may be 0.1 to 1 weight%, preferably 0.5 to 0.8 weight%; the sulfur content may be 1 to 8 weight%, preferably 2 to 6 weight%; the nitrogen content may be 0.5 to 3 weight%, preferably 1 to 2 weight%.

[0036] According to the present disclosure, the alumina core may contain a modifying element, and the modifying element may be selected from at least one of group IIIA, IVA, VA, IIA, IIB, IIIB or IVB elements; based on the total weight of the alumina core, the content of the modifying element may be 0.1 to 10 weight % in terms of the element.

[0037] Preferably, the modifying element can be selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium or zirconium; based on the total weight of the alumina core, the content of the modifying element can be 0.3 to 5 weight %.

[0038] The second aspect of the present disclosure provides a method for preparing a porous material, which comprises: mixing asphalt powder, an aluminum source and a binder to obtain a mixture, wherein the aluminum source contains alumina powder and / or an alumina powder precursor, and the binder comprises at least one of cellulose ether, starch or ene alcohol polymer; and heat-treating the mixture to obtain the porous material.

[0039] In the present disclosure, specifically, the alumina powder precursor is capable of producing alumina powder during heat treatment. The specific type of the alumina powder precursor can be selected within a certain range. For example, the alumina powder precursor can be pseudo-boehmite powder, boehmite powder, or gibbsite powder. The alumina powder precursor can be commercially available products or prepared using any existing technology, without particular limitation. Preferably, the alumina powder and / or alumina powder precursor (on a dry basis) has a maximum pore diameter of 6-20 nm.

[0040] According to the present disclosure, the aluminum source may further contain an auxiliary agent, and the auxiliary agent contains a modifying element, and the modifying element may be selected from at least one of Group IIIA, IVA, VA, IIA, IIB, IIIB or IVB elements; based on the total dry weight of the aluminum source, the content of the modifying element may be 0.1 to 10 weight % in terms of the element.

[0041] Preferably, the modifying element can be selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium; based on the total dry weight of the aluminum source, the content of the modifying element can be 0.3 to 5 weight%, more preferably 0.3 to 4 weight%.

[0042] In the present disclosure, specifically, the auxiliary agent can be a water-soluble compound of a modifying element, for example, it can be boric acid, ammonium borate, ammonium metaborate, ammonium tetraborate, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, boric acid, ammonium tetraborate, silica sol, silicon tetrachloride, ammonium fluorosilicate and ethyl orthosilicate, magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate, magnesium chloride, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, zinc chloride, lanthanum nitrate, lanthanum carbonate, lanthanum chloride, cerium nitrate, cerium carbonate, cerium chloride, titanium sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate, zirconium nitrate, zirconyl nitrate and zirconium oxychloride, etc.

[0043] Among them, the method of introducing the auxiliary agent into the aluminum source can be selected within a certain range. For example, the compound containing the auxiliary agent component can be prepared into an aqueous solution, and the aqueous solution can be introduced into the aluminum source synthesis process; it can also be contacted with the aluminum source, impregnated or mixed into a slurry, and then dried at a temperature of 60°C-180°C and a time of 0.5 hour-24 hours; it can also be calcined at a condition of 300°C-1200°C and a time of 1-24 hours.

[0044] Preferably, the binder is cellulose ether, and the cellulose ether may include at least one of methyl cellulose, hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose.

[0045] In the method for preparing porous materials provided by the present invention, cheap asphalt powder is used as raw material, and alumina is used as a template, and there is no need to dissolve the alumina during the preparation process. When using this method to prepare porous materials, on the one hand, the use of high-cost organic templates can be avoided, and on the other hand, the use of environmentally unfriendly solvents to dissolve the templates can be avoided. Therefore, the method provided by the present invention has the advantages of simple process flow, low cost and good environmental protection, and is suitable for industrial large-scale production.

[0046] According to the present disclosure, when preparing porous materials using the method of the present disclosure, the amounts of asphalt powder, aluminum source and adhesive can vary within a certain range. For example, relative to 100 parts by weight of the asphalt powder, the amount of the aluminum source can be 1 to 20 parts by weight, preferably 3 to 15 parts by weight, calculated as alumina; the amount of the adhesive can be 1 to 20 parts by weight, preferably 5 to 15 parts by weight.

[0047] According to the present disclosure, in order to enable the asphalt powder, aluminum source and adhesive to be mixed faster and better, preferably, the asphalt powder and aluminum source can have a smaller particle size. For example, the particle size of the asphalt powder can be 1 to 1000 μm, preferably 1 to 250 μm; the particle size of the aluminum source can be 1 to 150 μm, preferably 1 to 75 μm.

[0048] In the present disclosure, specifically, in order to further improve the uniformity of mixing, when mixing asphalt powder, aluminum source and adhesive, the aluminum source and adhesive can be first made into a paste slurry, and then the asphalt powder is mixed with the prepared paste slurry, and finally stirred or extruded.

[0049] According to the present disclosure, the heat treatment of the mixed material to obtain the porous material may include: in an oxygen-containing atmosphere, raising the temperature of the mixed material from room temperature to 120-400°C at a heating rate of 0.1-10°C / minute, and performing a first heat treatment for 0.1-48 hours to obtain a first intermediate material; in an inert atmosphere, raising the temperature of the first intermediate material to 400-950°C at a heating rate of 0.1-10°C / minute, and performing a second heat treatment for 0.1-24 hours to obtain a second intermediate material; in an oxygen-containing atmosphere, raising the temperature of the second intermediate material to 700-1000°C at a heating rate of 0.1-10°C / minute, and performing a third heat treatment for 0.1-12 hours to obtain the porous material.

[0050] The oxygen-containing atmosphere contains an oxygen-containing gas or a mixture of an oxygen-containing gas and an inert gas, the inert atmosphere contains an inert gas, the oxygen-containing gas is selected from at least one of oxygen, carbon dioxide, carbon monoxide or water vapor, and the inert gas is selected from at least one of nitrogen, argon or helium.

[0051] Furthermore, the flow rate of the oxygen-containing gas stream during the first heat treatment can be 1 to 80 liters / hour, the flow rate of the inert gas stream during the second heat treatment can be 1 to 80 liters / hour, and the flow rate of the oxygen-containing gas stream during the third heat treatment can be 1 to 80 liters / hour.

[0052] According to the present disclosure, the asphalt powder can be selected within a certain range. For example, the asphalt powder can include petroleum asphalt powder and / or coal asphalt powder. The asphalt powder can contain polycyclic aromatic hydrocarbons (PAHs). The PAH content can be 70-100% by weight, preferably 85-100% by weight, based on the total weight of the asphalt powder. Furthermore, the asphalt powder can be obtained by physically pulverizing asphalt solids.

[0053] A third aspect of the present disclosure provides use of any of the porous materials described above or a porous material prepared by any of the methods described above in the preparation of an adsorbent, a catalyst or a catalyst carrier.

[0054] The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereto. Unless otherwise specified, the raw materials, reagents, instruments and equipment involved in the examples of the present disclosure can be purchased.

[0055] The pseudo-boehmite powder involved in the embodiments of the present disclosure has a dry basis weight of 70%. When introducing the modifying element, a compound containing an auxiliary component is formulated into an aqueous solution, and the aqueous solution is contacted with alumina powder and / or alumina powder precursor, impregnated or mixed into a slurry, and then dried at a temperature of 120°C for 12 hours. When an alumina powder precursor is used, only drying is performed without calcination. When an alumina powder precursor is used (a product obtained by heating the alumina powder precursor to 600°C at a heating rate of 4°C / minute in a muffle furnace under an air atmosphere and then maintaining the temperature at 600°C for 4 hours), drying is followed by calcination at 450°C for 8 hours.

[0056] The method for determining the dry basis content involved in the embodiments of the present disclosure is as follows: alumina or an alumina precursor is heated to 600°C at a heating rate of 4°C / minute in a muffle furnace under an air atmosphere, and then maintained at 600°C for 4 hours. The percentage of the weight of the product after calcination to the weight before calcination is the dry basis content.

[0057] Example 1

[0058] The porous material was prepared as follows:

[0059] Weigh 50 grams of methyl cellulose, add 260 milliliters of an aqueous solution containing 50 grams of pseudo-boehmite powder (dry basis content of 70 weight percent, particle size of 1 to 75 μm), stir and mix evenly, and then let stand for 2 hours. Then add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixture. Take 200 grams of the above-mentioned mixture and place it in a closed tube furnace. Under the condition of air ventilation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixture is raised from room temperature to 120°C at a heating rate of 3°C / min, and maintained at 120°C for 18 hours, then raised to 200°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 4 hours, then raised to 240°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 280°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 300°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 2 hours. , obtaining a first intermediate material; then, switching the air to nitrogen, and controlling the nitrogen flow rate to 40 liters / hour, raising the temperature of the above-mentioned first intermediate material to 700°C at a heating rate of 3°C / minute, and maintaining a constant temperature of 700°C for heat treatment for 2 hours, to obtain a second intermediate material; finally, switching the nitrogen to carbon dioxide gas, and controlling the carbon dioxide gas flow rate to 40 liters / hour, raising the temperature of the above-mentioned second intermediate material to 960°C at a heating rate of 5°C / minute, and maintaining a constant temperature of 960°C for heat treatment for 4 hours, to obtain porous material S1.

[0060] In this embodiment, the aluminum source (pseudo-boehmite powder) contains a modifying element (phosphorus), and is modified using ammonium dihydrogen phosphate as a raw material. Based on the total dry weight of the aluminum source, the content of the modifying element (phosphorus) is 2 weight %.

[0061] The porous material S1 prepared in this embodiment consists of an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material S1, the content of the alumina core is 25 weight%, and the content of the porous carbon layer is 75 weight%.

[0062] Based on the total weight of the porous carbon layer, the carbon content, oxygen content, hydrogen content, sulfur content, and nitrogen content are 89.38 weight%, 3.45 weight%, 0.52 weight%, and 5.33 weight%, respectively. Based on the total weight of the alumina core, the content of the modifying element (phosphorus) is 2 weight%.

[0063] Example 2

[0064] The porous material was prepared as follows:

[0065] Weigh 50 grams of methyl cellulose, add 260 milliliters of an aqueous solution containing 50 grams of pseudo-boehmite powder (dry basis content of 70 weight percent, particle size of 1 to 75 μm), stir and mix evenly, and then let stand for 2 hours. Then add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixture. Take 200 grams of the above-mentioned mixture and place it in a closed tube furnace. Under the condition of air ventilation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixture is raised from room temperature to 120°C at a heating rate of 5°C / min, and maintained at 120°C for 18 hours, then raised to 200°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 4 hours, then raised to 240°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 280°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 300°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 2 hours. , obtaining a first intermediate material; then, switching the air to nitrogen, and controlling the nitrogen flow rate to 40 liters / hour, raising the temperature of the above-mentioned first intermediate material to 700°C at a heating rate of 3°C / minute, and maintaining a constant temperature of 700°C for heat treatment for 2 hours, to obtain a second intermediate material; finally, switching the nitrogen to carbon dioxide gas, and controlling the carbon dioxide gas flow rate to 40 liters / hour, raising the temperature of the above-mentioned second intermediate material to 960°C at a heating rate of 5°C / minute, and maintaining a constant temperature of 960°C for heat treatment for 4 hours, to obtain porous material S2.

[0066] The porous material S2 prepared in this embodiment consists of an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material S2, the content of the alumina core is 27 weight%, and the content of the porous carbon layer is 73 weight%.

[0067] Based on the total weight of the porous carbon layer, the carbon content is 88.78 weight %, the oxygen content is 3.78 weight %, the hydrogen content is 0.48 weight %, the sulfur content is 5.84 weight %, and the nitrogen content is 1.12 weight %.

[0068] Example 3

[0069] The porous material was prepared as follows:

[0070] Weigh 50 grams of methyl cellulose, add 230 milliliters of an aqueous solution containing 26 grams of pseudo-boehmite powder (dry basis content of 70 weight%, particle size of 1 to 75 μm), stir and mix evenly, and let it stand for 2 hours. Then, add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tubular furnace. Under the condition of air circulation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 280°C at a heating rate of 5°C / minute, and maintained at a constant temperature of 280°C for 12 hours to obtain a first intermediate material; then, the air is switched to nitrogen, and the nitrogen flow rate is controlled to 40 liters / hour, and the temperature of the above-mentioned first intermediate material is raised to 700°C at a heating rate of 3°C / minute, and maintained at a constant temperature of 700°C for 2 hours to obtain a second intermediate material; finally, the nitrogen is switched to carbon dioxide gas, and the carbon dioxide gas flow rate is controlled to 40 liters / hour, and the temperature of the above-mentioned second intermediate material is raised to 980°C at a heating rate of 5°C / minute, and maintained at a constant temperature of 980°C for 3 hours to obtain porous material S3.

[0071] The porous material S3 prepared in this embodiment consists of an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material S3, the content of the alumina core is 22 weight%, and the content of the porous carbon layer is 78 weight%.

[0072] Based on the total weight of the porous carbon layer, the carbon content is 89.65 weight %, the oxygen content is 3.25 weight %, the hydrogen content is 0.54 weight %, the sulfur content is 5.21 weight %, and the nitrogen content is 1.35 weight %.

[0073] Example 4

[0074] The porous material was prepared as follows:

[0075] Weigh 50 grams of methyl cellulose, add 240 milliliters of an aqueous solution containing 30 grams of alumina powder (dry basis content of 70 weight%, particle size of 1 to 75 μm) obtained after calcining at 600°C for 4 hours, stir and mix evenly, and let it stand for 2 hours. Then, add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tubular furnace. Under the condition of air circulation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 280°C at a heating rate of 5°C / minute, and maintained at a constant temperature of 280°C for 12 hours to obtain a first intermediate material; then, the air is switched to nitrogen, and the nitrogen flow rate is controlled to 40 liters / hour, and the temperature of the above-mentioned first intermediate material is raised to 700°C at a heating rate of 3°C / minute, and maintained at a constant temperature of 700°C for 3 hours to obtain a second intermediate material; finally, the nitrogen is switched to carbon dioxide gas, and the carbon dioxide gas flow rate is controlled to 40 liters / hour, and the temperature of the above-mentioned second intermediate material is raised to 940°C at a heating rate of 5°C / minute, and maintained at a constant temperature of 940°C for 8 hours to obtain porous material S4.

[0076] The porous material S4 prepared in this embodiment consists of an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material S4, the content of the alumina core is 29 weight%, and the content of the porous carbon layer is 71 weight%.

[0077] Based on the total weight of the porous carbon layer, the carbon content is 89.09 weight %, the oxygen content is 4.12 weight %, the hydrogen content is 0.63 weight %, the sulfur content is 4.58 weight %, and the nitrogen content is 1.58 weight %.

[0078] Example 5

[0079] The porous material S5 was prepared according to the method of Example 2, except that: in this example, relative to 100 parts by weight of asphalt powder, the amount of aluminum source (pseudo-boehmite powder) used was 1 part by weight, and the amount of binder (methyl cellulose) used was 1 part by weight, calculated as alumina.

[0080] The porous material S5 prepared in this embodiment consists of an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material S5, the content of the alumina core is 35 weight%, and the content of the porous carbon layer is 65 weight%.

[0081] Example 6

[0082] The porous material S6 was prepared according to the method of Example 2, except that: in this example, relative to 100 parts by weight of asphalt powder, the amount of aluminum source (aluminum oxide) used was 20 parts by weight, and the amount of adhesive (starch) used was 20 parts by weight, calculated as alumina.

[0083] The porous material S6 prepared in this embodiment consists of an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material S6, the content of the alumina core is 40 weight%, and the content of the porous carbon layer is 60 weight%.

[0084] Example 7

[0085] The porous material S7 was prepared according to the method of Example 2, except that: in this example, relative to 100 parts by weight of asphalt powder, the amount of aluminum source (aluminum oxide) used was 3 parts by weight, and the amount of binder (enol polymer) used was 5 parts by weight, calculated as alumina.

[0086] The porous material S7 prepared in this embodiment consists of an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material S7, the content of the alumina core is 23 weight%, and the content of the porous carbon layer is 77 weight%.

[0087] Example 8

[0088] The porous material S8 was prepared according to the method of Example 2, except that: in this example, relative to 100 parts by weight of asphalt powder, the amount of aluminum source (alumina + pseudo-boehmite powder) used was 15 parts by weight, and the amount of binder (methyl cellulose) used was 15 parts by weight, calculated as alumina.

[0089] The porous material S8 prepared in this embodiment consists of an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material S8, the content of the alumina core is 37 weight%, and the content of the porous carbon layer is 63 weight%.

[0090] Example 9

[0091] The porous material S9 is prepared according to the method of Example 1, except that: in this example, the aluminum source (aluminum oxide powder) contains a modifying element (zirconium), and zirconium oxynitrate is used as a raw material for modification. Based on the total dry weight of the aluminum source, the content of the modifying element (zirconium) is 0.1 wt % in terms of the element.

[0092] Example 10

[0093] The porous material S10 was prepared according to the method of Example 1, except that: in this example, the aluminum source (pseudo-boehmite powder) contained a modifying element (silicon), and the modification was carried out using silica sol as a raw material. The content of the modifying element (silicon) was 10 wt % based on the total dry weight of the aluminum source, calculated as the element.

[0094] Example 11

[0095] The porous material S11 is prepared according to the method of Example 1, except that: in this example, the aluminum source (pseudo-boehmite powder) contains a modifying element (magnesium), and magnesium nitrate is used as the raw material for modification. Based on the total dry weight of the aluminum source, the content of the modifying element (magnesium) is 0.3 weight % in terms of element.

[0096] Example 12

[0097] The porous material S12 is prepared according to the method of Example 1, except that: in this example, the aluminum source (pseudo-boehmite powder) contains modifying elements (lanthanum and cerium), and is modified using lanthanum nitrate and cerium nitrate as raw materials. Based on the total dry weight of the aluminum source, the content of the modifying elements (2 weight% lanthanum and 3 weight% cerium) is 5 weight%.

[0098] Example 13

[0099] The porous material S13 is prepared according to the method of Example 1, except that: in this example, the aluminum source (pseudo-boehmite powder) contains a modifying element (boron), and is modified using boric acid as a raw material. Based on the total dry weight of the aluminum source, the content of the modifying element (boron) is 1.5 wt % in terms of element.

[0100] Example 14

[0101] The porous material S14 is prepared according to the method of Example 1, except that: in this example, the aluminum source (aluminum oxide powder) contains a modifying element (zinc), and zinc nitrate is used as the raw material for modification. Based on the total dry weight of the aluminum source, the content of the modifying element (zinc) is 2.5 weight % in terms of element.

[0102] Example 15

[0103] The porous material S15 is prepared according to the method of Example 1, except that: in this example, the aluminum source (pseudo-boehmite powder) contains a modifying element (titanium), and titanium sulfate is used as the raw material for modification. Based on the total dry weight of the aluminum source, the content of the modifying element (titanium) is 4 weight % in terms of element.

[0104] Example 16

[0105] In this example, the aluminum source (commercially available phosphorus-containing pseudo-boehmite powder) contained 3% by weight of the modifying element (phosphorus), calculated as the element, based on the total dry weight of the aluminum source. 50 g of methylcellulose was added to 260 ml of an aqueous solution containing 26 g of phosphorus-containing pseudo-boehmite powder (72% by weight on a dry basis, with a particle size of 1 to 75 μm). The mixture was stirred and mixed thoroughly, then allowed to stand for 2 hours. Then, 500 g of asphalt powder (particle size of 1 to 250 μm) was added and stirred and mixed thoroughly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tubular furnace. Under the condition of air circulation and an air flow rate of 20 liters / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 120°C at a heating rate of 5°C / min, and maintained at a constant temperature of 120°C for heat treatment for 8 hours, and then raised to 320°C at a heating rate of 0.5°C / min and maintained at a constant temperature for 4 hours to obtain the first intermediate material; then, the air is switched to nitrogen, and the nitrogen flow rate is controlled to 60 liters / hour, and the temperature of the above-mentioned first intermediate material is raised to 550°C at a heating rate of 5°C / min, and maintained at a constant temperature of 550°C for heat treatment for 3 hours to obtain the second intermediate material; finally, the nitrogen is switched to carbon dioxide gas, and the carbon dioxide gas flow rate is controlled to 40 liters / hour, and the temperature of the above-mentioned second intermediate material is raised to 950°C at a heating rate of 5°C / min, and maintained at a constant temperature of 950°C for heat treatment for 4 hours to obtain porous material S16.

[0106] Example 17

[0107] In this example, the aluminum source (commercially available phosphorus-containing pseudo-boehmite powder) contained 3% by weight of the modifying element (phosphorus), calculated as the element, based on the total dry weight of the aluminum source. 50 g of methylcellulose was added to 260 ml of an aqueous solution containing 26 g of phosphorus-containing pseudo-boehmite powder (72% by weight on a dry basis, with a particle size of 1 to 75 μm). The mixture was stirred and mixed thoroughly, then allowed to stand for 2 hours. Then, 500 g of asphalt powder (particle size of 1 to 250 μm) was added and stirred and mixed thoroughly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tubular furnace. Under the condition of air circulation and an air flow rate of 1 liter / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 120°C at a heating rate of 3°C / min, and maintained at a constant temperature of 120°C for heat treatment for 8 hours, and then raised to 300°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 4 hours to obtain a first intermediate material; then, the air is switched to nitrogen, and the nitrogen flow rate is controlled to 70 liters / hour, and the temperature of the above-mentioned first intermediate material is raised to 800°C at a heating rate of 3°C / min, and maintained at a constant temperature of 800°C for heat treatment for 2 hours to obtain a second intermediate material; finally, the nitrogen is switched to carbon dioxide gas, and the carbon dioxide gas flow rate is controlled to 50 liters / hour, and the temperature of the above-mentioned second intermediate material is raised to 950°C at a heating rate of 5°C / min, and maintained at a constant temperature of 950°C for heat treatment for 4 hours to obtain porous material S17.

[0108] Comparative Example 1

[0109] The porous material was prepared as follows:

[0110] 500 g of asphalt powder (particle size of 1-250 μm) and 50 g of methyl cellulose were stirred and mixed evenly, then soaked with 260 ml of water and stirred and mixed evenly, and allowed to stand for 2 hours to obtain a mixture. 200 g of the above mixture was placed in a closed tube furnace, and under the condition of air flow of 40 liters / hour, the temperature of the above mixture was raised from room temperature to 120°C at a heating rate of 5°C / min, and kept at 120°C for 18 hours, then raised to 200°C at a heating rate of 0.2°C / min and kept at this temperature for 4 hours, then raised to 240°C at a heating rate of 0.2°C / min and kept at this temperature for 8 hours, then raised to 280°C at a heating rate of 0.2°C / min and kept at this temperature for 8 hours, then raised to 300°C at a heating rate of 0.2°C / min and kept at this temperature for 2 hours, The first intermediate material is obtained; then, the air is switched to nitrogen, and the nitrogen flow rate is controlled to 40 liters / hour, the temperature of the above-mentioned first intermediate material is increased to 700°C at a heating rate of 3°C / minute, and maintained at 700°C for constant temperature heat treatment for 2 hours to obtain the second intermediate material; finally, the nitrogen is switched to carbon dioxide gas, and the carbon dioxide gas flow rate is controlled to 40 liters / hour, the temperature of the above-mentioned second intermediate material is increased to 960°C at a heating rate of 5°C / minute, and maintained at 960°C for constant temperature heat treatment for 4 hours to obtain the porous material DT-1.

[0111] Comparative Example 2

[0112] The porous material was prepared as follows:

[0113] 500 g of pseudo-boehmite powder (70 wt% dry basis content) and 50 g of methyl cellulose were stirred and mixed uniformly, then impregnated with 260 ml of water, stirred and mixed uniformly, and allowed to stand for 2 hours to obtain a mixture. 200 g of the mixture was placed in a sealed tube furnace, and under the condition of air flow of 40 liters / hour, the temperature of the mixture was raised from room temperature to 120° C. at a heating rate of 5° C. / min, and maintained at 120° C. for 18 hours, then raised to 200° C. at a heating rate of 0.2° C. / min and maintained at this temperature for 4 hours, then raised to 240° C. at a heating rate of 0.2° C. / min and maintained at this temperature for 8 hours, then raised to 280° C. at a heating rate of 0.2° C. / min and maintained at this temperature for 8 hours, then raised to 300° C. at a heating rate of 0.2° C. / min and maintained at this temperature for 2 hours. The first intermediate material is obtained; then, the air is switched to nitrogen, and the nitrogen flow rate is controlled to 40 liters / hour, the temperature of the above-mentioned first intermediate material is increased to 700°C at a heating rate of 3°C / minute, and maintained at 700°C for constant temperature heat treatment for 2 hours to obtain the second intermediate material; finally, the nitrogen is switched to carbon dioxide gas, and the carbon dioxide gas flow rate is controlled to 40 liters / hour, the temperature of the above-mentioned second intermediate material is increased to 960°C at a heating rate of 5°C / minute, and maintained at 960°C for constant temperature heat treatment for 4 hours to obtain the porous material DT-2.

[0114] Comparative Example 3

[0115] The porous material was prepared as follows:

[0116] Weigh 50 grams of methyl cellulose, add 260 milliliters of an aqueous solution containing 50 grams of pseudo-boehmite powder (dry basis content of 70 weight percent, particle size of 1 to 75 μm), stir and mix evenly, and let stand for 2 hours. Then, add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tubular furnace. Under the condition of air circulation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 120°C at a heating rate of 5°C / min, and maintained at a constant temperature of 120°C for 18 hours, then raised to 200°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 4 hours, then raised to 240°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 280°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 300°C at a heating rate of 0.2°C / min and maintained at a constant temperature for 2 hours to obtain a first intermediate material; then, switch the air to carbon dioxide gas, and control the carbon dioxide gas flow rate to 40 liters / hour, raise the temperature of the above-mentioned first intermediate material to 960°C at a heating rate of 5°C / min, and maintain a constant temperature of 960°C for 4 hours to obtain the porous material DT-3.

[0117] Comparative Example 4

[0118] The porous material was prepared as follows:

[0119] Weigh 50 grams of methyl cellulose, add 260 milliliters of an aqueous solution containing 50 grams of pseudo-boehmite powder (dry basis content of 70% by weight, particle size of 1 to 75 μm), stir and mix evenly, and then let it stand for 2 hours. Then, add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixed material. Take 200 grams of the above mixed material and place it in a closed tube furnace. Under nitrogen flow conditions, control the nitrogen flow rate to 40 liters / hour, increase the temperature of the above mixed material to 700°C at a heating rate of 3°C / minute, and maintain a constant temperature of 700°C for 2 hours to obtain a first intermediate material; finally, switch the nitrogen gas to carbon dioxide gas, control the carbon dioxide gas flow rate to 40 liters / hour, increase the temperature of the above first intermediate material to 960°C at a heating rate of 5°C / minute, and maintain a constant temperature of 960°C for 4 hours to obtain a porous material DT-4.

[0120] Comparative Example 5

[0121] The porous material was prepared as follows:

[0122] Weigh 50 grams of methyl cellulose, add 260 milliliters of an aqueous solution containing 50 grams of pseudo-boehmite powder (dry basis content of 70 weight percent, particle size of 1 to 75 μm), stir and mix evenly, and let stand for 2 hours. Then, add 500 grams of asphalt powder (particle size of 1 to 250 μm), stir and mix evenly to obtain a mixed material. Take 200 grams of the above-mentioned mixed material and place it in a closed tubular furnace. Under the condition of air circulation and an air flow rate of 40 liters / hour, the temperature of the above-mentioned mixed material is raised from room temperature to 120°C at a heating rate of 5°C / min, and maintained at a constant temperature of 120°C for 18 hours, then raised to 200°C at 0.2°C / min and maintained at a constant temperature for 4 hours, then raised to 240°C at 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 280°C at 0.2°C / min and maintained at a constant temperature for 8 hours, then raised to 300°C at 0.2°C / min and maintained at a constant temperature for 2 hours to obtain the first intermediate material; then, switch the air to nitrogen, and control the nitrogen flow rate to 40 liters / hour, raise the temperature of the above-mentioned first intermediate material to 700°C at a heating rate of 3°C / min, and maintain a constant temperature of 700°C for 2 hours to obtain material DT-5.

[0123] Comparative Example 6

[0124] The porous material was prepared as follows:

[0125] 500 g of asphalt powder (particle size of 1-250 μm) and 50 g of methyl cellulose were stirred and mixed uniformly, then impregnated with 260 ml of an aqueous solution containing 7 g of titanium sulfate and stirred and mixed uniformly, and allowed to stand for 2 hours to obtain a mixed material. 200 g of the mixed material was placed in a sealed tube furnace, and under the condition of air flow of 40 liters / hour, the temperature of the mixed material was raised from room temperature to 120°C at a heating rate of 5°C / min, and maintained at 120°C for 18 hours, then raised to 200°C at a heating rate of 0.2°C / min and maintained at this temperature for 4 hours, then raised to 240°C at a heating rate of 0.2°C / min and maintained at this temperature for 8 hours, then raised to 280°C at a heating rate of 0.2°C / min and maintained at this temperature for 8 hours, then raised to 300°C at a heating rate of 0.2°C / min and maintained at this temperature for 2 hours, A first intermediate material is obtained; then, the air is switched to nitrogen, and the nitrogen flow rate is controlled to 40 liters / hour, the temperature of the above-mentioned first intermediate material is increased to 700°C at a heating rate of 3°C / minute, and maintained at 700°C for constant temperature heat treatment for 2 hours to obtain a second intermediate material; finally, the nitrogen is switched to carbon dioxide gas, and the carbon dioxide gas flow rate is controlled to 40 liters / hour, the temperature of the above-mentioned second intermediate material is increased to 960°C at a heating rate of 5°C / minute, and maintained at 960°C for constant temperature heat treatment for 4 hours to obtain the porous material DT-6.

[0126] Test Case

[0127] The pore structures of the porous materials prepared in Examples 1-17 and Comparative Examples 1-6 were measured. The results are shown in Table 1.

[0128] Table 1

[0129]

[0130] As can be seen from Table 1, the porous material disclosed in the present invention has a large specific surface area and pore volume, and is suitable for use as an adsorbent, catalyst or catalyst carrier.

[0131] The preferred embodiments of the present disclosure are described in detail above. However, the present disclosure is not limited to the specific details of the above embodiments. Within the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the scope of protection of the present disclosure.

[0132] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0133] In addition, the various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A porous material, characterized in that The porous material comprises an alumina core and a porous carbon layer distributed on the outer surface of the alumina core and the inner wall of the pores. Based on the total weight of the porous material, the content of the alumina core is 10 to 40% by weight; the content of the porous carbon layer is 60 to 90% by weight; The specific surface area of ​​the porous material is 150 to 1200 m 2 / g, pore volume of 0.5~1.3 cm 3 / g, average pore size is 3-30nm; The preparation method of the porous material comprises the following steps: Mixing asphalt powder, an aluminum source, and a binder to obtain a mixed material, wherein the aluminum source contains aluminum oxide powder and / or an aluminum oxide powder precursor, and the binder includes at least one of cellulose ether, starch, or ene alcohol polymer; The mixed material is subjected to heat treatment to obtain the porous material.

2. The porous material according to claim 1, characterized in that The content of the alumina core is 20 to 30% by weight; the content of the porous carbon layer is 70 to 80% by weight.

3. The porous material according to claim 1, characterized in that The porous carbon layer contains carbon, oxygen, hydrogen, sulfur and nitrogen. Based on the total weight of the porous carbon layer, the carbon content is 83-95% by weight; the oxygen content is 2-6% by weight; the hydrogen content is 0.1-1% by weight; the sulfur content is 1-8% by weight; and the nitrogen content is 0.5-3% by weight.

4. The porous material according to claim 3, characterized in that Based on the total weight of the porous carbon layer, the content of the carbon element is 85 to 91 weight %; the content of the oxygen element is 3 to 5 weight %; the content of the hydrogen element is 0.5 to 0.8 weight %; the content of the sulfur element is 2 to 6 weight %; and the content of the nitrogen element is 1 to 2 weight %.

5. The porous material according to claim 1, characterized in that The alumina core contains a modifying element, and the modifying element is selected from at least one of group IIIA, IVA, VA, IIA, IIB, IIIB or IVB elements; Based on the total weight of the alumina core, the content of the modifying element is 0.1 to 10% by weight.

6. The porous material according to claim 5, characterized in that The modifying element is selected from at least one of phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium or zirconium; Based on the total weight of the alumina core, the content of the modifying element is 0.3 to 5% by weight.

7. A method for preparing the porous material according to any one of claims 1 to 6, characterized in that: The method includes: Mixing asphalt powder, an aluminum source, and a binder to obtain a mixed material, wherein the aluminum source contains aluminum oxide powder and / or an aluminum oxide powder precursor, and the binder includes at least one of cellulose ether, starch, or ene alcohol polymer; heat-treating the mixed material to obtain the porous material; The heat treatment comprises: In an oxygen-containing atmosphere, the temperature of the mixed material is raised from room temperature to 120-400° C. at a heating rate of 0.1-10° C. / min, and a first heat treatment is performed for 0.1-48 hours to obtain a first intermediate material; Under an inert atmosphere, raising the temperature of the first intermediate material to 400-950° C. at a heating rate of 0.1-10° C. / min, and performing a second heat treatment for 0.1-24 hours to obtain a second intermediate material; In an oxygen-containing atmosphere, the temperature of the second intermediate material is raised to 700-1000° C. at a heating rate of 0.1-10° C. / min, and a third heat treatment is performed for 0.1-12 hours to obtain the porous material.

8. The method according to claim 7, characterized in that The aluminum source further contains an auxiliary agent, the auxiliary agent contains a modifying element, and the modifying element is selected from at least one of the elements of Group IIIA, IVA, VA, IIA, IIB, IIIB or IVB; The content of the modifying element is 0.1 to 10 wt % based on the total dry weight of the aluminum source, calculated as the element.

9. The method according to claim 8, characterized in that The modifying element is at least one element selected from phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium; The content of the modifying element is 0.3 to 5 wt % based on the total dry weight of the aluminum source, calculated as the element.

10. The method according to claim 7, characterized in that Relative to 100 parts by weight of the asphalt powder, the amount of the aluminum source is 1 to 20 parts by weight, calculated as aluminum oxide; the amount of the binder is 1 to 20 parts by weight.

11. The method according to claim 10, characterized in that Relative to 100 parts by weight of the asphalt powder, the amount of the aluminum source is 3 to 15 parts by weight, calculated as aluminum oxide; the amount of the binder is 5 to 15 parts by weight.

12. The method according to claim 7, characterized in that The particle size of the asphalt powder is 1 to 1000 μm; the particle size of the aluminum source is 1 to 75 μm.

13. The method according to claim 12, characterized in that The particle size of the asphalt powder is 1 to 250 μm; the particle size of the aluminum source is 1 to 75 μm.

14. The method according to any one of claims 7 to 13, characterized in that The asphalt powder includes petroleum asphalt powder and / or coal asphalt powder. The asphalt powder contains polycyclic aromatic hydrocarbons. Based on the total weight of the asphalt powder, the content of the polycyclic aromatic hydrocarbons is 70 to 100% by weight.

15. The method according to claim 14, characterized in that Based on the total weight of the asphalt powder, the content of the polycyclic aromatic hydrocarbons is 85 to 100 weight %.

16. Use of the porous material according to any one of claims 1 to 6 or the porous material prepared by the method according to any one of claims 7 to 15 in the preparation of an adsorbent, a catalyst or a catalyst carrier.

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