A phenolic resin-based porous carbon and a method for preparing the same

Abstract

The present application relates to the technical field of porous carbon material, and proposes a phenolic resin-based porous carbon and a preparation method thereof.A phenolic resin-based porous carbon, raw materials including the following components in parts by weight: 85-100 parts of phenolic resin, 5-10 parts of curing agent, 10-18 parts of binder, and 17-21 parts of urea; the phenolic resin includes boron-modified phenolic resin and epoxy-vinyl-modified phenolic resin.Through the above technical solution, the problem of small specific surface area of the porous carbon in the related art is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of porous carbon materials, in particular to a phenolic resin-based porous carbon and a preparation method thereof. BACKGROUND

[0002] In the field of material science, porous carbon, as an adsorbent material with highly developed pore structure and large specific surface area, is widely used in many key fields such as water treatment, gas purification, catalyst carrier and supercapacitor electrode material. Its excellent adsorption performance and surface activity are mainly due to the rich pore structure and high specific surface area, which enables porous carbon to efficiently interact with external substances, realizing the adsorption removal of various pollutants and the catalytic promotion of chemical reactions.

[0003] Traditionally, phenolic resin carbonization is one of the important methods for preparing porous carbon. Phenolic resin, due to its unique molecular structure and abundant carbon source, can form a carbon skeleton during high-temperature carbonization, and by reasonably controlling the process parameters, a certain pore structure can be constructed. However, the existing methods for preparing porous carbon by carbonizing phenolic resin have many limitations. On the one hand, the specific surface area of the porous carbon prepared by conventional processes is often difficult to reach the ideal level, limiting its use in high-end application scenarios that require high adsorption performance. For example, in some high-precision gas separation processes, porous carbon needs to have a higher specific surface area to achieve efficient selective adsorption of specific gas molecules, and the porous carbon prepared by traditional methods cannot meet this demand. On the other hand, the existing technology has limited ability to regulate the pore structure during carbonization, resulting in uneven pore distribution, which affects the stability and consistency of the overall performance of the porous carbon.

[0004] Therefore, it is of great practical significance to develop a phenolic resin-based porous carbon with high specific surface area. SUMMARY

[0005] The present application provides a phenolic resin-based porous carbon and a preparation method thereof, solving the problem of small specific surface area of porous carbon in related technologies.

[0006] The technical scheme of the present application is as follows:

[0007] The present application provides a phenolic resin-based porous carbon, the raw materials including the following components by weight: phenolic resin 85-100 parts, curing agent 5-10 parts, binder 10-18 parts, and urea 17-21 parts.

[0008] The phenolic resin includes boron-modified phenolic resin and epoxy-vinyl-modified phenolic resin.

[0009] As a further technical scheme, the mass ratio of the boron-modified phenolic resin to the epoxy-vinyl-modified phenolic resin is 3-5:1.

[0010] In the application, by adjusting the mass ratio of boron-modified phenolic resin and epoxy vinyl-modified phenolic resin to 3-5:1, the specific surface area of the phenolic resin-based porous carbon is further improved.

[0011] As a further technical solution, the mass ratio of the boron-modified phenolic resin and the epoxy vinyl-modified phenolic resin is 4:1.

[0012] In the application, by adjusting the mass ratio of boron-modified phenolic resin and epoxy vinyl-modified phenolic resin to 4:1, the specific surface area of the phenolic resin-based porous carbon is further improved.

[0013] As a further technical solution, the curing agent includes urotropine;

[0014] The binder includes the following components by weight: coal tar 20-34 parts, starch 15-25 parts, and water 10-25 parts.

[0015] As a further technical solution, the starch includes one or more of corn starch, wheat starch, and sweet potato starch.

[0016] In the application, urotropine is used as a curing agent in the raw materials. When urotropine reacts with phenolic resin, it can form a highly cross-linked three-dimensional network structure. It can fully react with the active groups in the phenolic resin, tightly connecting the resin molecular chains through chemical bonds, thereby increasing the cross-linking density of the cured resin and enhancing the mechanical properties and heat resistance of the material.

[0017] In the application, coal tar and starch are used in the binder, which has certain fluidity and viscosity. When added to the phenolic resin system, it can improve the fluidity of the phenolic resin during processing, making it easier to uniformly mix with other additives and reinforcing materials, improving processing efficiency and product forming quality.

[0018] The application also provides a preparation method of the phenolic resin-based porous carbon, which includes the following steps:

[0019] S1, mix the phenolic resin and the curing agent, cure, and crush to obtain phenolic resin powder;

[0020] S2, grind and mix the phenolic resin powder and the remaining components of the phenolic resin-based porous carbon to obtain a mixture;

[0021] S3, shape the mixture, carbonize, and cool to room temperature to obtain the phenolic resin-based porous carbon.

[0022] As a further technical solution, the carbonization is divided into three stages, the first stage is to increase the temperature to 120-160 DEG C at 3-8 DEG C / min, and keep the temperature for 1-2h, the second stage is to increase the temperature to 450-520 DEG C at 14-17 DEG C / min, and keep the temperature for 0.5-1.5h, the third stage is to increase the temperature to 900-950 DEG C at 9-13 DEG C / min, and keep the temperature for 3-6h.

[0023] In the application, the specific carbonization method is used to improve the yield of the phenolic resin-based porous carbon.

[0024] As a further technical solution, the carbonization atmosphere is inert gas.

[0025] As a further technical solution, the inert gas includes one of nitrogen and argon.

[0026] As a further technical solution, the particle size of the solid particles in the mixture is 5-15um.

[0027] The working principle and beneficial effects of the application are as follows:

[0028] In the application, the introduction of boron element in the boron-modified phenolic resin can make the molecular structure of the phenolic resin more stable, and the resin skeleton structure can be better maintained in the carbonization process, and the structure collapse and damage are reduced. This is conducive to forming more and more regular pore structure, and improving the adsorption activity. The introduction of epoxy vinyl in the epoxy vinyl-modified phenolic resin gives the phenolic resin better flexibility and reactivity, and after compounding with the boron-modified phenolic resin, the processing performance and forming performance of the resin are improved, the pore structure of the porous carbon is further optimized, and the specific surface area of the porous carbon is improved. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are involved in the protection scope of the application.

[0030] In the following examples and comparative examples, the boron-modified phenolic resin is purchased from Jining Tangyi Chemical Co., Ltd.; the epoxy vinyl-modified phenolic resin, also known as phenolic epoxy vinyl resin, is of type 907; the coal tar is purchased from Hebei Derixin Material Technology Co., Ltd.; and the corn starch has a particle size of 15-25um.

[0031] Example 1

[0032] A phenolic resin-based porous carbon, raw materials comprising the following components in parts by weight: phenolic resin 100 parts, curing agent 10 parts, binder 18 parts, urea 21 parts;

[0033] The phenolic resin comprises boron-modified phenolic resin and epoxy vinyl-modified phenolic resin at a mass ratio of 8:1;

[0034] The curing agent comprises urotropine;

[0035] The binder comprises the following components in parts by weight: coal tar 34 parts, corn starch 25 parts, water 25 parts;

[0036] A preparation method of the phenolic resin-based porous carbon, comprising the following steps:

[0037] S1, mixing the phenolic resin and the curing agent, curing, and crushing to obtain phenolic resin powder;

[0038] S2, grinding the phenolic resin powder and the remaining components of the phenolic resin-based porous carbon to a particle size of 15 μm, mixing to obtain a mixture;

[0039] S3, shaping the mixture, carbonizing, and cooling to room temperature to obtain the phenolic resin-based porous carbon;

[0040] The carbonization is divided into three stages, the first stage is to heat to 140℃ at 2℃ / min, and keep for 1.5h, the second stage is to heat to 470℃ at 13℃ / min, and keep for 1h, and the third stage is to heat to 930℃ at 8℃ / min, and keep for 4h;

[0041] The atmosphere for carbonization is nitrogen.

[0042] Example 2

[0043] A phenolic resin-based porous carbon, raw materials comprising the following components in parts by weight: phenolic resin 85 parts, curing agent 5 parts, binder 10 parts, urea 17 parts;

[0044] The phenolic resin comprises boron-modified phenolic resin and epoxy vinyl-modified phenolic resin at a mass ratio of 1:1;

[0045] The curing agent comprises urotropine;

[0046] The binder comprises the following components in parts by weight: coal tar 20 parts, wheat starch 15 parts, water 10 parts;

[0047] A preparation method of the phenolic resin-based porous carbon, comprising the following steps:

[0048] S1, mixing the phenolic resin and the curing agent, curing, and crushing to obtain phenolic resin powder;

[0049] S2, grinding the phenolic resin powder and the remaining components of the phenolic resin-based porous carbon to a particle size of 5 μm, mixing, to obtain a mixture;

[0050] S3, molding the mixture, carbonizing, and cooling to room temperature to obtain the phenolic resin-based porous carbon;

[0051] The carbonization is divided into three stages, the first stage is to increase the temperature to 140℃ at 2℃ / min, and keep for 1.5h, the second stage is to increase the temperature to 470℃ at 13℃ / min, and keep for 1h, the third stage is to increase the temperature to 930℃ at 8℃ / min, and keep for 4h;

[0052] The carbonization atmosphere is argon.

[0053] Example 3

[0054] A phenolic resin-based porous carbon, the raw materials include the following components by weight: phenolic resin 90 parts, curing agent 8 parts, binder 14 parts, urea 18 parts;

[0055] The phenolic resin includes boron-modified phenolic resin and epoxy vinyl-modified phenolic resin with a mass ratio of 6:1;

[0056] The curing agent includes urotropine;

[0057] The binder includes the following components by weight: coal tar 26 parts, sweet potato starch 20 parts, water 19 parts;

[0058] A method for preparing a phenolic resin-based porous carbon, including the following steps:

[0059] S1, mixing the phenolic resin and the curing agent, curing, and crushing to obtain a phenolic resin powder;

[0060] S2, grinding the phenolic resin powder and the remaining components of the phenolic resin-based porous carbon to a particle size of 10 μm, mixing, to obtain a mixture;

[0061] S3, molding the mixture, carbonizing, and cooling to room temperature to obtain the phenolic resin-based porous carbon;

[0062] The carbonization is divided into three stages, the first stage is to increase the temperature to 140℃ at 2℃ / min, and keep for 1.5h, the second stage is to increase the temperature to 470℃ at 13℃ / min, and keep for 1h, the third stage is to increase the temperature to 930℃ at 8℃ / min, and keep for 4h;

[0063] The carbonization atmosphere is nitrogen.

[0064] Example 4

[0065] The difference between this embodiment and Example 3 is that the phenolic resin of this embodiment includes boron-modified phenolic resin and epoxy vinyl-modified phenolic resin with a mass ratio of 2:1.

[0066] Example 5

[0067] The difference between this example and Example 3 is that the phenolic resin of this example comprises boron-modified phenolic resin and epoxy vinyl-modified phenolic resin in a mass ratio of 3:1.

[0068] Example 6

[0069] The difference between this example and Example 3 is that the phenolic resin of this example comprises boron-modified phenolic resin and epoxy vinyl-modified phenolic resin in a mass ratio of 4:1.

[0070] Example 7

[0071] The difference between this example and Example 3 is that the phenolic resin of this example comprises boron-modified phenolic resin and epoxy vinyl-modified phenolic resin in a mass ratio of 5:1.

[0072] Example 8

[0073] The difference between this example and Example 3 is that the carbonization of this example is divided into three stages, the first stage is to rise to 140℃ at 9℃ / min, keep for 1.5h, the second stage is to rise to 470℃ at 13℃ / min, keep for 1h, the third stage is to rise to 930℃ at 8℃ / min, keep for 4h.

[0074] Example 9

[0075] The difference between this example and Example 3 is that the carbonization of this example is divided into three stages, the first stage is to rise to 140℃ at 3℃ / min, keep for 1.5h, the second stage is to rise to 470℃ at 13℃ / min, keep for 1h, the third stage is to rise to 930℃ at 8℃ / min, keep for 4h.

[0076] Example 10

[0077] The difference between this example and Example 3 is that the carbonization of this example is divided into three stages, the first stage is to rise to 140℃ at 2℃ / min, keep for 1.5h, the second stage is to rise to 470℃ at 18℃ / min, keep for 1h, the third stage is to rise to 930℃ at 8℃ / min, keep for 4h.

[0078] Example 11

[0079] The difference between this example and Example 3 is that the carbonization of this example is divided into three stages, the first stage is to rise to 140℃ at 2℃ / min, keep for 1.5h, the second stage is to rise to 470℃ at 14℃ / min, keep for 1h, the third stage is to rise to 930℃ at 8℃ / min, keep for 4h.

[0080] Example 12

[0081] The difference between this example and Example 3 is that the carbonization of this example is divided into three stages, the first stage is to increase the temperature to 140°C at a rate of 2°C / min, keep the temperature for 1.5h, the second stage is to increase the temperature to 470°C at a rate of 13°C / min, keep the temperature for 1h, and the third stage is to increase the temperature to 930°C at a rate of 14°C / min, keep the temperature for 4h.

[0082] Example 13

[0083] The difference between this example and Example 3 is that the carbonization of this example is divided into three stages, the first stage is to increase the temperature to 140°C at a rate of 2°C / min, keep the temperature for 1.5h, the second stage is to increase the temperature to 470°C at a rate of 13°C / min, keep the temperature for 1h, and the third stage is to increase the temperature to 930°C at a rate of 9°C / min, keep the temperature for 4h.

[0084] Example 14

[0085] The difference between this example and Example 3 is that the carbonization of this example is divided into three stages, the first stage is to increase the temperature to 120°C at a rate of 3°C / min, keep the temperature for 2h, the second stage is to increase the temperature to 450°C at a rate of 14°C / min, keep the temperature for 1.5h, and the third stage is to increase the temperature to 900°C at a rate of 9°C / min, keep the temperature for 3h.

[0086] Example 15

[0087] The difference between this example and Example 3 is that the carbonization of this example is divided into three stages, the first stage is to increase the temperature to 140°C at a rate of 5°C / min, keep the temperature for 1.5h, the second stage is to increase the temperature to 470°C at a rate of 15°C / min, keep the temperature for 1h, and the third stage is to increase the temperature to 930°C at a rate of 11°C / min, keep the temperature for 4h.

[0088] Example 16

[0089] The difference between this example and Example 3 is that the carbonization of this example is divided into three stages, the first stage is to increase the temperature to 160°C at a rate of 8°C / min, keep the temperature for 1h, the second stage is to increase the temperature to 520°C at a rate of 17°C / min, keep the temperature for 0.5h, and the third stage is to increase the temperature to 950°C at a rate of 13°C / min, keep the temperature for 3h.

[0090] Comparative Example 1

[0091] The difference between this comparative example and Example 2 is that the raw materials of this comparative example include the following components by weight: boron-modified phenolic resin 85 parts, curing agent 5 parts, adhesive 10 parts, and urea 17 parts.

[0092] Comparative Example 2

[0093] The difference between the present comparative example and Example 2 is only that the raw material of the present comparative example comprises the following components in parts by weight: epoxy vinyl modified phenolic resin 85 parts, curing agent 5 parts, adhesive 10 parts, urea 17 parts.

[0094] Experimental Example 1

[0095] The phenolic resin-based porous carbons prepared in Examples 1-7 and Comparative Examples 1-2 were tested for specific surface area, using the following test method: a 3H 2000 BET instrument was used to determine the specific surface area of the phenolic resin-based porous carbon from the nitrogen adsorption isotherm, according to the BET formula. The test results are shown in Table 1.

[0096]

[0097] Comparing Example 2 with Comparative Examples 1-2 shows that the use of both boron-modified phenolic resin and epoxy vinyl-modified phenolic resin as raw materials for the phenolic resin-based porous carbon in the present application improves the specific surface area of the phenolic resin-based porous carbon.

[0098] Comparing Examples 5-7 with Examples 3-4 shows that when the mass ratio of boron-modified phenolic resin to epoxy vinyl-modified phenolic resin is 3-5:1, the specific surface area of the phenolic resin-based porous carbon is further improved.

[0099] Experimental Example 2

[0100] The phenolic resin-based porous carbons prepared in Example 3 and Examples 8-16 were calculated for yield, using the following formula:

[0101] A = m1 / m;

[0102] A is the yield of the phenolic resin-based porous carbon;

[0103] m1 is the mass of the phenolic resin-based porous carbon;

[0104] m is the mass of the raw material;

[0105] The test results are shown in Table 2.

[0106]

[0107] Comparing Examples 9, 11, 13-16 with Examples 3, 8, 10, 12 shows that the use of the specific carbonization method in the present application improves the yield of the phenolic resin-based porous carbon.

[0108] The above merely describes preferred embodiments of the present application and is not intended to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A phenolic resin-based porous carbon, characterized in that, The raw materials include the following components in parts by weight: 85-100 parts phenolic resin, 5-10 parts curing agent, 10-18 parts binder, and 17-21 parts urea; The phenolic resin includes boron-modified phenolic resin and epoxy vinyl-modified phenolic resin. The method for preparing the phenolic resin-based porous carbon includes the following steps: S1. Mix the phenolic resin and the curing agent, cure, and pulverize to obtain phenolic resin powder; S2. Grind and mix the phenolic resin powder with the remaining components of the phenolic resin-based porous carbon to obtain a mixture; S3. The mixture is shaped, carbonized, and cooled to room temperature to obtain phenolic resin-based porous carbon. The mass ratio of boron-modified phenolic resin to epoxy vinyl-modified phenolic resin is 3~5:1; The curing agent includes hexamethylenetetramine; The binder comprises the following components in parts by weight: 20-34 parts coal tar, 15-25 parts starch, and 10-25 parts water.

2. The phenolic resin-based porous carbon according to claim 1, characterized in that, The mass ratio of boron-modified phenolic resin to epoxy vinyl-modified phenolic resin is 4:

1.

3. The phenolic resin-based porous carbon according to claim 1, characterized in that, The starch includes one or more of corn starch, wheat starch, and sweet potato starch.

4. A method for preparing phenolic resin-based porous carbon according to any one of claims 1 to 3, characterized in that, Includes the following steps: S1. Mix the phenolic resin and the curing agent, cure, and pulverize to obtain phenolic resin powder; S2. Grind and mix the phenolic resin powder with the remaining components of the phenolic resin-based porous carbon to obtain a mixture; S3. The mixture is shaped, carbonized, and cooled to room temperature to obtain phenolic resin-based porous carbon.

5. The method for preparing phenolic resin-based porous carbon according to claim 4, characterized in that, The carbonization process is divided into three stages: in the first stage, the temperature is increased to 120-160℃ at a rate of 3-8℃ / min and held for 1-2 hours; in the second stage, the temperature is increased to 450-520℃ at a rate of 14-17℃ / min and held for 0.5-1.5 hours; and in the third stage, the temperature is increased to 900-950℃ at a rate of 9-13℃ / min and held for 3-6 hours.

6. The method for preparing phenolic resin-based porous carbon according to claim 4, characterized in that, The carbonization atmosphere is an inert gas.

7. The method for preparing phenolic resin-based porous carbon according to claim 6, characterized in that, The inert gas includes either nitrogen or argon.

8. The method for preparing phenolic resin-based porous carbon according to claim 4, characterized in that, The particle size of the solid particles in the mixture is 5~15μm.

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