Adsorptive material, method for preparing same, and use thereof

Abstract

The application provides an adsorbing material and a preparation method and application thereof. The adsorbing material comprises activated carbon and an additive material; the specific heat capacity and the thermal conductivity of the additive material are not lower than those of the activated carbon; the additive material comprises one-dimensional fiber material and / or two-dimensional layered material; and the mass ratio of the activated carbon to the additive material is 100:(0.1-10). The additive material in the adsorbing material provided by the application can form a thermal conduction path and a uniform heat storage / heat release network, and the activated carbon is surrounded in the network, so that the desorption performance to oil and gas is enhanced, the residual amount is reduced, and the mechanical performance of the material is improved without affecting the adsorption performance of the activated carbon.

Description

Technical Field

[0001] This invention belongs to the field of adsorption material preparation technology, specifically relating to an adsorption material, its preparation method, and its application. Background Technology

[0002] Currently, there are activated carbon canisters for vehicles that adsorb the vapors generated by the vehicle's fuel system, preventing fuel from being directly emitted into the atmosphere due to breathing. The fuel vapors can then be desorbed by purging air and introduced into the engine cylinders for combustion, thus controlling and regenerating the fuel vapors. When the vehicle is stationary, during the high-temperature period of the daytime temperature cycle, fuel vapors will escape from the canister, resulting in "daytime breathing loss" (DBL).

[0003] American researchers have disclosed a vehicle charcoal canister for controlling DBL (Damage Per Batch) loss. The canister material consists of main adsorption particles inside the canister and a honeycomb-shaped structure near the atmospheric vent outside. During fuel vapor adsorption, the main adsorption material, with its high working capacity, captures a large amount of volatile hydrocarbons, while the rear-end structure adsorbs residual small-molecule hydrocarbons. During desorption, purge air enters from the rear, regenerating the material inside the canister. Activated carbon undergoes thousands of adsorption / desorption cycles throughout a vehicle's lifespan. During each cycle, the purge air cannot desorb all fuel vapors adsorbed on the adsorbent. A small amount of residual fuel slowly increases, reducing the overall effective adsorption capacity and lifespan of the activated carbon. Currently, with increasingly stringent environmental regulations, activated carbon is required to have both high working capacity and low DBL values. This necessitates that the charcoal canister material maintain high adsorption performance, high desorption efficiency, low fuel residue, and high mechanical strength to ensure a long service life.

[0004] CN 111511681A discloses a method for preparing an activated carbon molded body for adsorbing evaporated fuel from automobiles. The method involves mixing powdered activated carbon, a lubricant, and an acid-soluble solid diluent. The resulting mixture is then kneaded with a thermoplastic or thermosetting resin binder, and the resulting compound is molded into a geometrically perforated body. After drying, the molded body is acid-washed to remove at least a portion of the solid diluent, forming micropores. Further drying yields the finished product. The product exhibits improved desorption performance through macroscopic geometrically perforated channels and micropores formed by acid dissolution. Furthermore, the resin binder contributes to a low wear rate. However, while the activated carbon molded body provided by this patent achieves enhanced desorption performance by forming micropores and ensuring strength through the incorporation of a high content of thermoplastic or thermosetting resin, the resin significantly reduces the material's adsorption capacity.

[0005] In CN 112154027A, the honeycomb molded body in the carbon canister improves the desorption performance of the material by adding metal oxide heat storage material to activated carbon and adding second fine pores (above 1μm) constructed by fusible core pulp fibers that can be removed during high-temperature heat treatment. However, the fusible core will affect the strength of the molded body.

[0006] In addition, US Patent 8759250B2 discloses that using chitosan and alginate as binders, supplemented by natural fibers, synthetic fibers and inorganic fibers, can only enhance the strength of activated carbon molded bodies.

[0007] In summary, the present invention provides an adsorption material for automotive charcoal canisters that, without affecting its adsorption performance, not only has a high desorption rate and low residue, but also high mechanical strength. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide an adsorbent material, its preparation method, and its applications. The adsorbent material provided by this invention can achieve the goals of increasing desorption rate, reducing residue, and improving mechanical strength without affecting its adsorption performance.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides an adsorption material comprising activated carbon and additives;

[0011] The specific heat capacity and thermal conductivity of the added material are not lower than those of the activated carbon.

[0012] The additive materials include one-dimensional fiber materials and / or two-dimensional layered materials;

[0013] The mass ratio of activated carbon to additives is 100:(0.1 to 10), for example, it can be 100:0.1, 100:1, 100:2, 100:4, 100:6, 100:8 or 100:10, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0014] The adsorption material provided by this invention can form a thermally conductive path and a uniform heat storage / release network, surrounding the activated carbon. This can enhance the desorption performance of oil and gas, reduce the residue, and improve the mechanical properties of the material without affecting the adsorption performance of the activated carbon.

[0015] It is worth noting that the functions of the additives described in this invention include: (1) not affecting adsorption performance: one-dimensional fiber or / and two-dimensional layered materials do not occupy the space of activated carbon or block the pores of activated carbon, and have little impact on its adsorption capacity; in addition, it is easier to transfer and store the heat released by activated carbon during oil and gas adsorption, thus suppressing the temperature rise of activated carbon and maintaining adsorption performance; (2) improving desorption performance and reducing oil and gas residue: during oil and gas desorption, it can quickly release and supply heat to activated carbon, thus suppressing the temperature drop of activated carbon and helping activated carbon to desorb oil and gas; in addition, the heat storage / heat release network formed can make the temperature distribution of activated carbon more uniform, avoiding adsorbate residue caused by local temperature concentration; (3) improving mechanical properties: making it have better processability, support and wear resistance. In summary, the above three functions of the additives provided by this invention can enhance the desorption performance of oil and gas and reduce the residue without affecting the adsorption performance of activated carbon, while also improving the mechanical properties of the material, solving the problem that it is difficult to balance the adsorption performance, desorption performance and mechanical properties of automotive carbon canister materials.

[0016] As a preferred embodiment of the present invention, the specific heat capacity of the added material is ≥0.8×10⁻⁶. 3 J / kg·℃, for example, could be 0.8×10 3 J / kg·℃, 1×10 3 J / kg·℃, 1.2×10 3 J / kg·℃, 1.5×10 3 J / kg·℃, 2×10 3 J / kg·℃ or 3×10 3 J / kg·℃, but not limited to the listed values, other unlisted values ​​within the range also apply.

[0017] Preferably, the thermal conductivity of the added material is ≥0.8W / (m·K), for example, it can be 0.8W / (m·K), 1W / (m·K), 1.4W / (m·K), 1.8W / (m·K), 2.2W / (m·K) or 2.5W / (m·K), but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0018] As a preferred embodiment of the present invention, the diameter of the one-dimensional fiber material is 5nm to 40μm, for example, it can be 5nm, 50nm, 100nm, 10μm, 20μm, 30μm or 40μm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0019] Preferably, the average aspect ratio of the one-dimensional fiber material is 5 to 1000, for example, it can be 5, 10, 100, 200, 500, 700, 800, 900 or 1000, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0020] Preferably, the one-dimensional fiber material includes any one or a combination of at least two of carbon-based fibers, oxide fibers, silicate fibers, nitride fibers, or carbide fibers. Typical but non-limiting combinations include combinations of carbon-based fibers, oxide fibers, and carbide fibers; combinations of oxide fibers, silicate fibers, and nitride fibers; or combinations of carbon-based fibers, oxide fibers, silicate fibers, nitride fibers, and carbide fibers.

[0021] Preferably, the carbon-based fiber includes any one or a combination of at least two of carbon fibers, carbon nanorods, or carbon nanotubes. Typical but non-limiting combinations include a combination of carbon fibers and carbon nanorods, a combination of carbon nanorods and carbon nanotubes, a combination of carbon fibers and carbon nanotubes, or a combination of carbon fibers, carbon nanorods, and carbon nanotubes.

[0022] Preferably, the oxide fiber includes any one or a combination of at least two of titanium oxide fiber, alumina fiber, silicon oxide fiber, zirconium oxide fiber, mullite fiber, glass fiber, or zinc oxide fiber. Typical but non-limiting combinations include combinations of titanium oxide fiber, alumina fiber, and zirconium oxide fiber; combinations of silicon oxide fiber, mullite fiber, and glass fiber; combinations of titanium oxide fiber, alumina fiber, zirconium oxide fiber, and zinc oxide fiber; or combinations of titanium oxide fiber, alumina fiber, silicon oxide fiber, zirconium oxide fiber, mullite fiber, glass fiber, and zinc oxide fiber.

[0023] Preferably, the silicate fiber includes aluminum silicate fiber and / or calcium silicate fiber.

[0024] Preferably, the nitride fiber includes any one or a combination of at least two of boron nitride fiber, aluminum nitride fiber or silicon nitride fiber. Typical but non-limiting combinations include: a combination of boron nitride fiber and aluminum nitride fiber, a combination of boron nitride fiber and silicon nitride fiber, a combination of aluminum nitride fiber and silicon nitride fiber, or a combination of boron nitride fiber, aluminum nitride fiber and silicon nitride fiber.

[0025] Preferably, the carbonized fiber comprises silicon carbide fiber.

[0026] As a preferred embodiment of the present invention, the thickness of the two-dimensional layered material is 5nm-100μm, for example, it can be 5nm, 10nm, 100nm, 500nm, 800nm, 2μm, 10μm, 30μm, 500μm, 70μm or 100μm, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0027] Preferably, the lateral dimension of the two-dimensional layered material is 100nm to 800μm, for example, it can be 100nm, 500nm, 1μm, 50μm, 100μm, 300μm, 500μm or 800μm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0028] Preferably, the number of layers in the two-dimensional layered material is ≥1, for example, it can be 1, 2, 3, 4 or 5 layers, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0029] Preferably, the two-dimensional layered material comprises any one or a combination of at least two of carbon-based sheets, layered silicates, hexagonal boron nitride, zirconium hydrogen phosphate, layered hydroxides, or Mxene. Typical but non-limiting combinations include: a combination of carbon-based sheets, layered silicates, and layered hydroxides; a combination of hexagonal boron nitride, zirconium hydrogen phosphate, and Mxene; or a combination of carbon-based sheets, layered silicates, hexagonal boron nitride, zirconium hydrogen phosphate, layered hydroxides, and Mxene.

[0030] Preferably, the carbon-based sheet comprises any one or a combination of at least two of flake graphite, expanded graphite, graphene, reduced graphene, or nitrogen-doped graphene. Typical but non-limiting combinations include: a combination of flake graphite and expanded graphite, a combination of graphene, reduced graphene, and nitrogen-doped graphene, a combination of flake graphite, expanded graphite, and graphene, or a combination of flake graphite, expanded graphite, graphene, reduced graphene, and nitrogen-doped graphene.

[0031] Preferably, the layered silicate comprises any one or a combination of at least two of vermiculite, expanded vermiculite, mica, or calcium silicate. Typical but non-limiting combinations include: a combination of vermiculite and expanded vermiculite, a combination of vermiculite, expanded vermiculite, and mica, a combination of vermiculite, expanded vermiculite, and calcium silicate, a combination of mica and calcium silicate, or a combination of vermiculite, expanded vermiculite, mica, and calcium silicate.

[0032] Preferably, the layered hydroxide comprises any one or a combination of at least two of magnesium hydroxide, aluminum hydroxide, or layered composite metal hydroxides. Typical but non-limiting combinations include combinations of magnesium hydroxide and aluminum hydroxide, combinations of magnesium hydroxide and layered composite metal hydroxides, combinations of aluminum hydroxide and layered composite metal hydroxides, or combinations of magnesium hydroxide, aluminum hydroxide, and layered composite metal hydroxides.

[0033] As a preferred embodiment of the present invention, the specific surface area of ​​the activated carbon is >1200 m². 2 / g, for example, could be 1200m 2 / g、1300m 2 / g, 1400m 2 / g, 1500m 2 / g, 1600m 2 / g or 2000m 2 / g, but not limited to the listed values, other unlisted values ​​within the range also apply.

[0034] Preferably, the pore volume of the activated carbon is >1 cm³. 3 / g, for example, could be 1.5cm 3 / g、2cm 3 / g, 2.5cm 3 / g, 3cm 3 / g, 3.5cm 3 / g、4cm 3 / g or 5cm 3 / g, but not limited to the listed values, other unlisted values ​​within the range also apply.

[0035] Preferably, the mesopore volume of the activated carbon is >0.5 cm³. 3 / g, for example, could be 0.6cm 3 / g, 0.7cm 3 / g, 0.9cm 3 / g, 1.1cm 3 / g, 1.3cm 3 / g, 1.5cm 3 / g or 2cm 3 / g, but not limited to the listed values, other unlisted values ​​within the range also apply.

[0036] Preferably, the butane working capacity of the activated carbon is 10-18 g / 100 mL, for example, it can be 10 g / 100 mL, 11 g / 100 mL, 13 g / 100 mL, 15 g / 100 mL, 17 g / 100 mL or 18 g / 100 mL, but is not limited to the listed values, and other values ​​not listed in the value range are also applicable.

[0037] This invention does not specifically limit the raw materials for activated carbon; they can be selected from plant-based, mineral-based, natural, and synthetic raw materials. Commercially available automotive activated carbon is mainly derived from plant-based materials, such as any one or a combination of at least two of the following: wood, fruit or vegetable shells / kernels, algae, bamboo, or coffee beans.

[0038] In a second aspect, the present invention provides a method for preparing an adsorbent material as provided in the first aspect, the preparation method comprising scheme A or scheme B;

[0039] Scheme A includes: mixing activated carbon precursor and additives according to the formula amount and then kneading and molding to obtain a molded body; subsequently, the molded body is activated, washed and dried to obtain granular adsorbent material;

[0040] Scheme B includes: mixing activated carbon and binder, then mixing and adding materials and kneading to form a molded body; finally, drying the molded body to obtain granular adsorbent material or perforated adsorbent material.

[0041] The preparation method of Scheme A of the present invention involves first mixing and molding the activated carbon precursor with additives, and then performing activation treatment. This method is suitable for preparing samples with high BWC (BWC ≥ 13g / 100ml) and placing them in the connected oil tank chamber. The preparation method of Scheme B involves first activating the activated carbon precursor, and then mixing and molding it with additives. This method is suitable for preparing samples with low BWC (0.2g / 100ml ≤ BWC ≤ 13g / 100ml) and high desorption rate (desorption rate ≥ 85%). Furthermore, the granular adsorbent material obtained by Scheme B is suitable for applications with 10g / 100ml ≤ BWC ≤ 13g / 100ml and can be placed in the connected atmospheric chamber. The perforated adsorbent material obtained by Scheme B is suitable for applications with 0.2g / 100ml ≤ BWC ≤ 10g / 100ml and can be placed in the adjacent area on the atmospheric side outside the carbon canister.

[0042] Generally, a vehicle charcoal canister contains two chambers. The chamber connected to the fuel tank requires an adsorbent material with a high BWC (granular adsorbent material prepared using scheme A), while the chamber connected to the atmosphere requires an adsorbent material with a low BWC (granular adsorbent material prepared using scheme B). The adjacent area on the atmospheric side outside the charcoal canister is then filled with an adsorbent material with the lowest BWC (perforated adsorbent material prepared using scheme B). The adsorbent material prepared by the method provided in this invention can meet the performance requirements of both the adsorbent material inside the vehicle charcoal canister and the adsorbent material in the adjacent area on the atmospheric side outside the charcoal canister.

[0043] As a preferred embodiment of the present invention, the activated carbon precursor in embodiment A is a carbon-based material that has not undergone activation treatment.

[0044] Preferably, the mixing described in Scheme A further includes mixing chemical reagents or adhesives.

[0045] Preferably, the chemical reagent includes phosphoric acid and / or zinc chloride.

[0046] Preferably, the adhesive comprises bitumen and / or tar.

[0047] As a preferred embodiment of the present invention, the activation process described in embodiment A includes carbonization and activation performed sequentially.

[0048] Preferably, the activation is carried out in an inert gas atmosphere.

[0049] It is worth noting that the temperature selection for the carbonization and activation processes described in this invention is related to the selection of the activated carbon precursor. When the activated carbon precursor is a plant-based material, the carbonization temperature is 30–160°C, for example, 30°C, 50°C, 70°C, 90°C, 120°C, 140°C, or 160°C, but is not limited to the listed values; other values ​​not listed within the range are also applicable. The activation temperature is 350–700°C, for example, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, or 700°C, but is not limited to the listed values; other values ​​not listed within the range are also applicable.

[0050] Preferably, the endpoint of the washing process described in Scheme A is a pH value of 5 to 7 for the washing solution, such as 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.6, 6.8 or 7, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0051] As a preferred embodiment of the present invention, when the granular adsorbent material is obtained using embodiment B, the binder includes an organic binder or an inorganic binder;

[0052] When obtaining the perforated adsorbent material using scheme B, the binder includes an inorganic binder or a mixture of an organic binder and an inorganic binder;

[0053] Preferably, when Scheme B yields a perforated adsorbent material, the mixing of the binder further includes mixing of fillers;

[0054] Preferably, the filler comprises any one or a combination of at least two of kaolin, alumina, silica, or iron oxide. Typical limiting combinations include a combination of kaolin and silica, a combination of alumina, silica, and iron oxide, a combination of alumina and iron oxide, or a combination of kaolin, alumina, silica, and iron oxide.

[0055] Preferably, the amount of filler added is 1 to 50 wt% of the total amount of activated carbon, for example, it can be 1 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt% or 50 wt%, but is not limited to the listed values. Other values ​​not listed within the range are also applicable.

[0056] The organic binder includes any one or a combination of at least two of carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, or hydroxyethyl methyl cellulose. Typical but non-limiting combinations include: a combination of carboxymethyl cellulose and methyl cellulose, a combination of hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, a combination of carboxymethyl cellulose, methyl cellulose, and hydroxypropyl methyl cellulose, or a combination of carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose.

[0057] Preferably, the amount of organic binder added is 1 to 10 wt% of the total amount of activated carbon, for example, it can be 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt% or 10 wt%, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0058] Preferably, the inorganic binder comprises a powder material or a colloidal material.

[0059] Preferably, the powder material includes any one or a combination of at least two of bentonite, kaolin, or wood-joint clay. Typical but non-limiting combinations include: a combination of bentonite, kaolin, and wood-joint clay; a combination of bentonite and kaolin; a combination of bentonite and wood-joint clay; or a combination of kaolin and wood-joint clay.

[0060] It is worth noting that in the process of preparing the hollowed-out adsorbent material using scheme B, when a colloidal material is selected as the inorganic binder, the filler does not need to be mixed; when a powder material is selected as the inorganic binder, the filler must be mixed.

[0061] Preferably, the colloidal material comprises a solid component of silica sol and / or alumina sol.

[0062] Preferably, the amount of inorganic binder added is 1 to 50 wt% of the total amount of activated carbon, for example, it can be 1 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt% or 50 wt%, but is not limited to the listed values, and other values ​​not listed in the range are also applicable.

[0063] Preferably, the drying process described in Scheme B includes drying or calcination.

[0064] Preferably, the drying temperature is 150-200°C, for example, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0065] Calcination is carried out in an inert atmosphere at a temperature of 350–1000°C, for example, 350°C, 450°C, 550°C, 650°C, 750°C, 850°C, or 1000°C, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0066] Thirdly, the present invention provides an application of the adsorbent material as described in the first aspect, wherein the adsorbent material is filled in the interior of a vehicle charcoal canister or in an adjacent area on the atmospheric side outside the charcoal canister.

[0067] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0068] Compared with the prior art, the present invention has the following beneficial effects:

[0069] (1) The one-dimensional fiber or / and two-dimensional layered material in the adsorption material provided by the present invention can form a heat conduction path and a uniform heat storage / heat release network, which surrounds the activated carbon. Without affecting the adsorption performance of the activated carbon, it can enhance the desorption performance of oil and gas, reduce the residual amount, and improve the mechanical properties of the material.

[0070] (2) The preparation method provided by the present invention is simple and can not only meet the performance requirements of the adsorbent materials required in the two chambers of the vehicle carbon canister at the same time, but also meet the performance requirements of the adsorbent materials in the adjacent area of ​​the outdoor atmosphere side of the carbon canister. Attached Figure Description

[0071] Figure 1 This is a scanning electron microscope image of the adsorption material provided in Comparative Example 1 of the present invention;

[0072] Figure 2 This is a scanning electron microscope image of the adsorption material provided in Embodiment 1 of the present invention;

[0073] Figure 3 This is a scanning electron microscope image of the adsorption material provided in Embodiment 2 of the present invention;

[0074] Figure 4 This is a scanning electron microscope image of the adsorption material provided in Embodiment 3 of the present invention. Detailed Implementation

[0075] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be considered as specific limitations thereof.

[0076] The properties of the adsorbent materials provided in the following examples and comparative examples were evaluated according to the following standards: adsorption capacity, working capacity (BWC) of butane, desorption rate and residual amount were obtained according to GB / T 20449-2006 Test Method for Working Capacity of Butane in Activated Carbon; the strength test method was obtained according to GB / T 12496.6-1999 Test Method for Strength of Wood-based Activated Carbon.

[0077] Example 1

[0078] This embodiment provides an adsorption material, and the preparation method of the adsorption material is scheme A;

[0079] Scheme A includes the following steps:

[0080] (1) Mix 100 parts by weight of wood chips, 10 parts by weight of carbon fiber and 150 parts by weight of phosphoric acid with a mass concentration of 85 wt%, and then let them stand and extrude them to obtain the molding material.

[0081] The carbon fiber is a one-dimensional material with an average diameter of 6 μm and an average aspect ratio of 5.

[0082] (2) The molding material obtained in step (1) is carbonized at 150°C, then activated at 450°C in a nitrogen atmosphere, rinsed until pH is 5.4, and then dried at 150°C to obtain the adsorbent material.

[0083] The scanning electron microscope image of the adsorbent material provided in this embodiment is as follows: Figure 2 As shown, the adsorbent material is granular material filled in the chamber of the charcoal canister connected to the oil tank.

[0084] Example 2

[0085] This embodiment provides an adsorption material, and the preparation method of the adsorption material is scheme A;

[0086] The only difference between Scheme A and Example 1 is that:

[0087] In this embodiment, the carbon fiber mentioned in step (1) is modified to: 4 parts by weight of two-dimensional layered material expanded vermiculite; the expanded vermiculite has a thickness of 500 nm and a lateral dimension of 30 μm.

[0088] The scanning electron microscope image of the adsorbent material provided in this embodiment is as follows: Figure 3 As shown, the adsorbent material is granular material filled in the chamber of the charcoal canister connected to the oil tank.

[0089] Example 3

[0090] This embodiment provides an adsorption material, and the preparation method of the adsorption material is scheme A;

[0091] The only difference between Scheme A and Example 1 is that:

[0092] In this embodiment, the carbon fiber described in step (1) is modified to be: 5 parts by weight of one-dimensional carbon fiber and 2 parts by weight of two-dimensional expanded vermiculite;

[0093] The carbon fiber has an average diameter of 6 μm and an average aspect ratio of 5; the expanded vermiculite has a thickness of 500 nm and a transverse dimension of 30 μm.

[0094] The scanning electron microscope image of the adsorbent material provided in this embodiment is as follows: Figure 4 As shown, the adsorbent material is granular material filled in the chamber of the charcoal canister connected to the oil tank.

[0095] Comparative Example 1

[0096] This comparative example provides an adsorbent material, and the preparation method of the adsorbent material is scheme A;

[0097] The only difference between Scheme A and Example 1 is that:

[0098] The carbon fiber mentioned in step (1) is omitted in this comparative example. That is, the adsorbent material provided in this comparative example is pure activated carbon particles obtained by the lignophosphoric acid activation method.

[0099] The scanning electron microscope image of the adsorbent material provided in this comparative example is as follows: Figure 1 As shown.

[0100] The performance evaluation results of the adsorption materials provided in Examples 1-3 and Comparative Example 1 are shown in Table 1.

[0101] Table 1

[0102]

[0103] As shown in Table 1, the results of Examples 1 and 2 indicate that the adsorption capacity and BWC decreased slightly after the addition of one-dimensional carbon fiber and two-dimensional expanded vermiculite, indicating that the effect on adsorption performance was limited; the desorption rate was significantly improved and the residue was significantly reduced, indicating that the desorption performance was significantly improved; the strength was improved, indicating that the mechanical properties were improved; in particular, as shown in Example 3, when carbon fiber and expanded vermiculite were added simultaneously, the desorption rate was further improved, the residue was further reduced, and the strength was further enhanced compared with the addition of the two alone. This is due to the multi-dimensional thermal conduction pathways and heat storage / release network composed of one-dimensional carbon fiber and two-dimensional sheet layered vermiculite.

[0104] Comprehensive analysis Figure 2-4 and Figure 1 It can be seen that, Figure 2 Medium carbon fibers are evenly distributed between activated carbon particles, forming a heat conduction pathway and a heat storage / release network on a one-dimensional spatial scale; Figure 3 The thin, layered vermiculite particles are uniformly distributed between the activated carbon particles, forming a heat conduction pathway and a heat storage / release network on a two-dimensional spatial scale. Figure 4 The layered vermiculite, composed of one-dimensional carbon fibers and two-dimensional sheets, forms a multi-dimensional thermal conduction pathway and heat storage / release network.

[0105] Example 4

[0106] This embodiment provides an adsorbent material, and the preparation method of the adsorbent material is scheme B, which yields a granular adsorbent material.

[0107] Scheme B includes the following steps:

[0108] (a) Mix 100 parts by weight of activated carbon powder and 6 parts by weight of aluminum silicate fiber; then mix with 5 parts by weight of hydroxymethyl ethyl cellulose and 200 parts by weight of water to obtain a mixture.

[0109] The average diameter of the aluminum silicate fiber is 10 μm and the average aspect ratio is 20.

[0110] (b) The mixture obtained in step (a) is extruded into cylinders with a diameter of 2 mm using a hydraulic extruder and then cut into pellets to obtain granules;

[0111] (c) Dry the granules obtained in step (b) at 150°C to obtain the adsorbent material.

[0112] The adsorbent material obtained in this embodiment is granular material filled in the carbon canister connected to the atmospheric chamber.

[0113] Example 5

[0114] This embodiment provides an adsorption material, and the preparation method of the adsorption material is scheme B.

[0115] The only difference between Scheme B and Example 4 is that:

[0116] In this embodiment, aluminum silicate fiber is replaced with 1 part by weight of graphene oxide; the graphene oxide has a thickness of 8 μm and a lateral dimension of 16 μm.

[0117] The adsorbent material obtained in this embodiment is granular material filled in the carbon canister connected to the atmospheric chamber.

[0118] Example 6

[0119] This embodiment provides an adsorption material, and the preparation method of the adsorption material is scheme B.

[0120] The only difference between Scheme B and Example 4 is that:

[0121] In this embodiment, the aluminum silicate fiber is modified to consist of 3 parts by weight of aluminum silicate fiber and 0.5 parts by weight of graphene oxide.

[0122] The adsorbent material obtained in this embodiment is granular material filled in the carbon canister connected to the atmospheric chamber.

[0123] Comparative Example 2

[0124] This comparative example provides an adsorbent material, and the preparation method of the adsorbent material is scheme B.

[0125] The only difference between Scheme B and Example 4 is that:

[0126] The aluminum silicate fiber described in step (a) is omitted in this comparative example.

[0127] The performance evaluation results of the adsorption materials provided in Examples 4-6 and Comparative Example 2 are shown in Table 2.

[0128] Table 2

[0129]

[0130] As shown in Table 2, the results of Examples 4 and 5 indicate that the adsorption capacity and BWC slightly decreased after the addition of one-dimensional aluminosilicate fibers and two-dimensional layered graphene oxide, indicating that the effect on adsorption performance was limited; the desorption rate was significantly improved and the residual amount was significantly reduced, indicating that the desorption performance was significantly improved; the strength was improved, indicating that the mechanical properties were improved; in particular, as shown in Example 6, when aluminosilicate fibers and graphene oxide were added simultaneously, the desorption rate was further improved, the residual amount was further reduced, and the strength was further enhanced compared with the addition of the two alone, indicating that the simultaneous addition of the two has a synergistic effect.

[0131] Example 7

[0132] This embodiment provides an adsorbent material, and the preparation method of the adsorbent material is scheme B, which yields a perforated adsorbent material; scheme B includes the following steps:

[0133] (a) Mix 60 parts by weight of activated carbon powder, 8 parts by weight of mullite fiber, 9 parts by weight of bentonite and 32 parts by weight of kaolin; then mix with 5 parts by weight of hydroxymethyl ethyl cellulose and 120 parts by weight of water to obtain a mixture.

[0134] The mullite fibers have an average diameter of 5 μm and an average aspect ratio of 50.

[0135] (b) Extruding the mixture obtained in step (a) into a cylindrical honeycomb structure;

[0136] (c) The cylindrical honeycomb obtained in step (b) is calcined at 900°C for 2 hours under a nitrogen atmosphere to obtain the adsorbent material.

[0137] The adsorbent material obtained in this embodiment is located in the adjacent area of ​​the outdoor atmospheric side of the carbon canister.

[0138] Example 8

[0139] This embodiment provides an adsorbent material, and the preparation method of the adsorbent material is Scheme B; the only difference between Scheme B and Embodiment 7 is that:

[0140] In this embodiment, the added material in step (a) is modified to: 8 parts by weight of boron nitride; the thickness of the boron nitride is 8 μm and the lateral dimension is 50 μm.

[0141] The adsorbent obtained in this embodiment is the adsorbent material in the outdoor atmospheric side adjacent area of ​​the carbon canister adsorbent material.

[0142] Example 9

[0143] This embodiment provides an adsorbent material, and the preparation method of the adsorbent material is Scheme B; the only difference between Scheme B and Embodiment 7 is that:

[0144] In this embodiment, the added material described in step (a) is modified to: 4 parts by weight of mullite fiber and 4 parts by weight of boron nitride.

[0145] The adsorbent obtained in this embodiment is the adsorbent material in the outdoor atmospheric side adjacent area of ​​the carbon canister adsorbent material.

[0146] Comparative Example 3

[0147] This comparative example provides an adsorbent material, the preparation method of which is Scheme B; the only difference between Scheme B and Example 7 is:

[0148] This comparative example omits the addition of materials described in step (a).

[0149] The adsorbent obtained in this comparative example is from the adjacent area of ​​the outdoor atmospheric side of the carbon canister.

[0150] The performance evaluation results of the adsorption materials provided in Examples 7-9 and Comparative Example 3 are shown in Table 3.

[0151] Table 3

[0152]

[0153] As shown in Table 3, the results of Examples 7 and 8 indicate that the adsorption capacity and BWC slightly decreased after the addition of one-dimensional mullite fibers and two-dimensional layered boron nitride, indicating a limited impact on adsorption performance. The desorption rate significantly increased, and the residue significantly decreased, indicating a significant improvement in desorption performance. The increased strength indicates improved mechanical properties. In particular, Example 9 shows that when mullite fibers and layered boron nitride were added simultaneously, the desorption rate further increased, the residue further decreased, and the strength further increased compared to adding either material alone, indicating a synergistic effect when both are added simultaneously.

[0154] The applicant declares that the detailed structural features of the present invention are illustrated through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the components selected in the present invention, additions of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0155] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. An adsorbent material, characterized in that, The adsorption material includes activated carbon and additives; The added material in the adsorbent can form a thermally conductive path and a uniform heat storage / release network, surrounding the activated carbon within it; The specific heat capacity and thermal conductivity of the added material are not lower than those of the activated carbon. The additive materials include one-dimensional fiber materials and two-dimensional layered materials; The one-dimensional fiber material includes any one or a combination of at least two of oxide fibers, silicate fibers, nitride fibers, or carbide fibers; The two-dimensional layered material includes any one or a combination of at least two of layered silicates, hexagonal boron nitride, zirconium hydrogen phosphate, layered hydroxides, or Mxene; The mass ratio of activated carbon to additives is 100:(0.1~10); The diameter of the one-dimensional fiber material is 5 nm to 40 μm; The average aspect ratio of the one-dimensional fiber material is 5 to 1000. The thickness of the two-dimensional layered material is 5 nm-100 μm; The lateral dimension of the two-dimensional layered material is 100nm~800μm.

2. The adsorbent material according to claim 1, characterized in that, The specific heat capacity of the added material is ≥0.8×10⁻⁶. 3 J / kg·℃.

3. The adsorbent material according to claim 1, characterized in that, The thermal conductivity of the added material is ≥0.8 W / (m·K).

4. The adsorbent material according to claim 1, characterized in that, The oxide fibers include any one or a combination of at least two of the following: titanium oxide fibers, alumina fibers, silicon oxide fibers, zirconium oxide fibers, mullite fibers, glass fibers, or zinc oxide fibers.

5. The adsorbent material according to claim 1, characterized in that, The silicate fibers include aluminum silicate fibers and / or calcium silicate fibers.

6. The adsorbent material according to claim 1, characterized in that, The nitride fibers include any one or a combination of at least two of boron nitride fibers, aluminum nitride fibers, or silicon nitride fibers.

7. The adsorbent material according to claim 1, characterized in that, The carbonized fibers include silicon carbide fibers.

8. The adsorbent material according to claim 1, characterized in that, The two-dimensional layered material has ≥1 layer.

9. The adsorbent material according to claim 1, characterized in that, The layered silicate includes any one or a combination of at least two of vermiculite, mica, or calcium silicate.

10. The adsorbent material according to claim 1, characterized in that, The layered hydroxide includes any one or a combination of at least two of magnesium hydroxide, aluminum hydroxide, or layered composite metal hydroxides.

11. The adsorbent material according to claim 1, characterized in that, The specific surface area of ​​the activated carbon is >1200m². 2 / g.

12. The adsorbent material according to claim 1, characterized in that, The activated carbon has a pore volume >1 cm³. 3 / g.

13. The adsorbent material according to claim 1, characterized in that, The activated carbon has a mesopore volume > 0.5 cm³. 3 / g.

14. The adsorbent material according to claim 1, characterized in that, The working capacity of the activated carbon in butane is 10~18g / 100mL.

15. A method for preparing the adsorbent material according to any one of claims 1-14, characterized in that, The preparation method includes scheme A or scheme B; Scheme A includes: mixing activated carbon precursor and additives according to the formula amount and then kneading and molding to obtain a molded body; subsequently, the molded body is activated, washed and dried to obtain granular adsorbent material; Scheme B includes: mixing activated carbon and binder, then mixing and adding materials and kneading to form a molded body; finally, drying the molded body to obtain granular adsorbent material or perforated adsorbent material.

16. The preparation method according to claim 15, characterized in that, The activated carbon precursor described in Scheme A is a carbon-based material that has not undergone activation treatment.

17. The preparation method according to claim 15, characterized in that, The mixing described in Scheme A also includes mixing chemical reagents or adhesives.

18. The preparation method according to claim 17, characterized in that, The chemical reagents include phosphoric acid and / or zinc chloride.

19. The preparation method according to claim 17, characterized in that, The adhesive includes bitumen and / or tar.

20. The preparation method according to claim 15, characterized in that, The activation process described in Scheme A includes sequential carbonization and activation.

21. The preparation method according to claim 20, characterized in that, The activation is carried out in an inert gas atmosphere.

22. The preparation method according to claim 15, characterized in that, The endpoint of the washing process described in Scheme A is when the pH value of the washing solution is 5-7.

23. The preparation method according to claim 15, characterized in that, When using Scheme B to obtain granular adsorbent material, the binder includes organic binders or inorganic binders.

24. The preparation method according to claim 15, characterized in that, When obtaining the perforated adsorbent material using scheme B, the binder includes a mixture of organic and inorganic binders or an inorganic binder.

25. The preparation method according to claim 15, characterized in that, When obtaining the hollowed-out adsorbent material in Scheme B, the mixing of the binder also includes mixing of fillers.

26. The preparation method according to claim 25, characterized in that, The filler includes any one or a combination of at least two of kaolin, alumina, silica, or iron oxide.

27. The preparation method according to claim 25, characterized in that, The amount of filler added is 1 to 50 wt% of the total amount of activated carbon.

28. The preparation method according to claim 23, characterized in that, The organic binder includes any one or a combination of at least two of carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, or hydroxyethyl methyl cellulose.

29. The preparation method according to claim 23, characterized in that, The amount of the organic binder added is 1 to 10 wt% of the total amount of activated carbon.

30. The preparation method according to claim 23, characterized in that, The inorganic binder includes powder materials or colloidal materials.

31. The preparation method according to claim 30, characterized in that, The powder material includes any one or a combination of at least two of bentonite, kaolin, or wood knot clay.

32. The preparation method according to claim 30, characterized in that, The colloidal material includes solid components of silica sol and / or alumina sol.

33. The preparation method according to claim 23, characterized in that, The amount of inorganic binder added is 1 to 50 wt% of the total amount of activated carbon.

34. An application of the adsorbent material as described in any one of claims 1-14, characterized in that, The adsorbent material is filled in the interior of the vehicle charcoal canister or in the adjacent area on the atmospheric side outside the charcoal canister.

Images