Production method and application of tooth spherical carrier

Abstract

The invention relates to the technical field of preparation of carriers, and discloses a production method and application of a tooth-spherical carrier, the production method comprises the following steps: (1) mixing and kneading an alumina precursor and a mixing and kneading solution, rolling and forming tooth balls to obtain a tooth-spherical formed substance; (2) carrying out first drying on the tooth-ball-shaped forming substance, so that the dry basis content of a dried product is 60-80wt%; (3) loading an enhancer on the dried product in a spraying and / or dipping manner; the reinforcer comprises silicon resin and polyacrylamide; and (4) performing secondary drying and roasting on the product obtained in the step (3). By controlling the first drying degree and the composition of the reinforcer, the strength of the tooth spherical carrier can be effectively improved, the material fragmentation proportion in the roasting process is reduced, and then the carrier yield is increased.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of carriers, and particularly relates to a production method and application of a tooth-shaped spherical carrier. Background Art

[0002] Tooth-shaped spherical catalysts have the advantages of high activity, large processing load, low initial reaction temperature, etc., and have been well industrially applied in the refining processes of gasoline and diesel with high sulfur and nitrogen, olefin, and gum contents. For example, CN103285842A discloses a tooth-shaped spherical alumina carrier, and by adding an anionic surfactant, the properties such as the bulk density, pore volume, crush strength, and pore size distribution of the carrier can be optimized. CN103160312A discloses the application of a tooth-shaped spherical fractionation oil hydrotreating catalyst. However, in the prior art, there is little research on the production process of tooth-shaped spherical catalyst carriers.

[0003] Compared with carriers of regular shapes, as a special-shaped carrier, the tooth-shaped spherical catalyst carrier is prone to breakage during the production process due to its special shape, resulting in a low yield. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problems of low strength and insufficient yield of tooth-shaped spherical carriers existing in the prior art, and to provide a production method and application of a tooth-shaped spherical carrier, which can effectively improve the strength of the carrier and increase the yield.

[0005] To achieve the above purpose, on the one hand, the present invention provides a production method of a tooth-shaped spherical carrier, including:

[0006] (1) Kneading, rolling, and tooth ball forming the alumina precursor and the kneading liquid to obtain a tooth-shaped spherical formed product;

[0007] (2) Performing first drying on the tooth-shaped spherical formed product so that the dry basis content of the dried product is 60 - 80 wt%;

[0008] (3) Loading the strengthening agent on the dried product by spraying and / or impregnation;

[0009] The strengthening agent includes silicone resin and polyacrylamide;

[0010] (4) Performing second drying and calcination on the product obtained in step (3).

[0011] Preferably, the mass ratio of the dried product based on the dry basis of alumina, silicone resin, and polyacrylamide is 1:(0.003 - 0.004):(0.002 - 0.003), preferably 1:(0.0031 - 0.0036):(0.0022 - 0.0025).

[0012] The second aspect of the present invention provides the application of the tooth-shaped spherical carrier prepared by the above production method in gasoline and / or diesel refining catalysts.

[0013] Compared with carriers of regular shapes, as an irregular-shaped carrier, the tooth-shaped spherical carrier is somewhat difficult to prepare, has poor strength, is prone to breakage and poor uniformity during the calcination and forming process, resulting in a low product yield. Through the above technical solution, the present invention first forms and performs the first drying on the alumina precursor, and then loads the strengthening agent on the dried product. By controlling the degree of the first drying and the composition of the strengthening agent, the strength of the tooth-shaped spherical carrier can be effectively improved, the proportion of material fragmentation during the calcination process can be reduced, and thus the carrier yield can be increased. Detailed Embodiments

[0014] The endpoints and any values disclosed in this article for a range are not limited to the exact range or value. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this article.

[0015] The first aspect of the present invention provides a production method of a tooth-shaped spherical carrier, including:

[0016] (1) Kneading, rolling and forming into tooth-shaped balls the alumina precursor and the kneading liquid to obtain a tooth-shaped spherical formed product;

[0017] (2) Performing the first drying on the tooth-shaped spherical formed product so that the dry basis content of the dried product is 60 - 80 wt%;

[0018] (3) Loading the strengthening agent on the dried product by means of spraying and / or impregnation;

[0019] The strengthening agent includes silicone resin and polyacrylamide;

[0020] (4) Performing the second drying and calcination on the product obtained in step (3).

[0021] Compared with carriers of regular shapes, as an irregular-shaped carrier, the tooth-shaped spherical carrier is somewhat difficult to prepare, has poor strength, is prone to breakage and poor uniformity during the calcination and forming process, resulting in a low product yield. Through the above technical solution, the present invention first forms and performs the first drying on the alumina precursor, and then loads the strengthening agent on the dried product. By controlling the degree of the first drying and the composition of the strengthening agent, the strength of the tooth-shaped spherical carrier can be effectively improved, the proportion of material fragmentation during the calcination process can be reduced, and thus the carrier yield can be increased.

[0022] In the present invention, the alumina precursor refers to any substance that can be calcined to obtain alumina, which is well-known to those skilled in the art. For example, it can be pseudoboehmite. The present invention does not have any special limitation on the alumina content in the pseudoboehmite. For example, based on the total amount of the alumina precursor, the alumina content can be 42-45 wt%.

[0023] The present invention does not have any special limitation on the composition of the kneading liquid, which can be any auxiliary agent solution beneficial to kneading in the art and is well-known to those skilled in the art. The kneading liquid also contains a solvent. The present invention does not have any special limitation on the type of the solvent. For example, it can be water.

[0024] According to some preferred embodiments of the present invention, the kneading liquid includes water, an extrusion aid and / or peptizing agent. The present invention has a wide selection range for the extrusion aid, which can be any auxiliary agent beneficial to extrusion in the art. Preferably, the peptizing agent is selected from organic acids and / or inorganic acids, preferably at least one of nitric acid, citric acid, acetic acid and tartaric acid, and more preferably nitric acid.

[0025] Preferably, the extrusion aid is synthetic cellulose, preferably selected from at least one of carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxycellulose fatty alcohol polyethylene ether, and more preferably methyl cellulose.

[0026] According to some particularly preferred embodiments of the present invention, the kneading liquid includes water, an extrusion aid and a peptizing agent. Preferably, the mass ratio of the alumina precursor, extrusion aid and peptizing agent on a dry basis is 1:(0.001-0.006):(0.03-0.04), and more preferably 1:(0.003-0.005):(0.036-0.039). The present invention does not have any special requirement for the amount of water in the kneading liquid, which can be selected according to actual needs. Preferably, the amount of water is such that the total mass concentration of the extrusion aid and peptizing agent in the kneading liquid is 2-5 wt%.

[0027] In the present invention, there is no special limitation on the specific conditions of the kneading and rolling, which can be carried out in conventional kneading and rolling equipment in the art. In order to further improve the forming efficiency and product quality, preferably, the kneading frequency is 30-40 Hz, more preferably 35-37 Hz, and the kneading time is 20-30 min, more preferably 25-27 min.

[0028] Preferably, the rolling frequency is 15-25 Hz, more preferably 20-22 Hz, and the rolling time is 30-55 min, more preferably 35-40 min.

[0029] Controlling the conditions of kneading and rolling within the above-mentioned preferred ranges can further optimize the processing time and improve the product yield.

[0030] According to the present invention, after the material is kneaded and rolled, it can be formed into tooth balls by conventional tooth ball production equipment in the art. The present invention has no special requirements for the conditions of the forming, and those skilled in the art can select according to actual application needs. For example, tooth ball-shaped formed products with a cross-sectional area of quadrilateral, pentagonal or hexagonal can be obtained through tooth ball forming.

[0031] In the present invention, the dry basis content of the dried product after the first drying of the tooth ball-shaped formed product is controlled to be 60 - 80 wt%, and then the strengthening agent is loaded on the dried product. Controlling the dry basis content within the above-mentioned preferred range can ensure the effective loading of the strengthening agent and prevent the tooth balls from cracking. Preferably, the first drying makes the dry basis content of the dried product be 68 - 73 wt%.

[0032] In the present invention, the dry basis content of the dried product refers to roasting the dried product at 600 °C for 180 min, and the percentage of the mass after roasting to the mass before roasting is recorded as the dry basis content by calculation.

[0033] The present invention has no special limitation on the specific conditions of the first drying, as long as the above-mentioned dry basis content is satisfied. Preferably, the temperature is 30 - 40 °C; the heating rate is 0.2 - 0.3 °C / min; the drying time is 150 - 170 min. Adopting the above-mentioned preferred implementation mode can further improve the drying uniformity and avoid the generation of cracks in the tooth balls caused by too fast water evaporation.

[0034] The present invention has a relatively wide selection range for the dosage of the strengthening agent. According to some preferred implementation modes of the present invention, the mass ratio of the dried product based on alumina dry basis, silicone resin and polyacrylamide is 1:(0.003 - 0.004):(0.002 - 0.003), preferably 1:(0.0031 - 0.0036):(0.0022 - 0.0025). Controlling the dosages of the silicone resin and polyacrylamide within the above-mentioned preferred ranges is beneficial to further improving the carrier strength, reducing the proportion of material fragmentation during roasting, and thus improving the yield.

[0035] The present invention has no special limitation on the type of the silicone resin, and any conventional silicone resin with lubricating properties in the art can be applied to the present invention. Preferably, the silicone resin is selected from at least one of polymethyl silicone resin, amino silicone resin and methyl silicone resin.

[0036] According to some preferred implementation modes of the present invention, the weight average molecular weight of the polyacrylamide is 4×10 6 -6×10 6 .

[0037] The present invention also has no special requirements for the sources of the silicone resin and polyacrylamide, which can be commercially available or prepared by methods known in the art.

[0038] In the present invention, the strengthening agent is loaded onto the dried product by spraying and / or impregnation. Preferably, it is loaded onto the surface of the dried product. Subsequently, the dried product loaded with the strengthening agent is subjected to a second drying and calcination, which can reduce the proportion of material fragmentation during the calcination process. The strengthening agent can be provided by a dispersion of the strengthening agent. Preferably, the concentration of the dispersion containing the strengthening agent is 1-3 wt%. The concentration of the dispersion refers to the percentage of the total mass of the silicone resin and polyacrylamide in the mass of the dispersion.

[0039] According to some preferred embodiments of the present invention, the method of loading the strengthening agent onto the dried product in step (3) includes: preparing a dispersion containing the strengthening agent, and then spraying and impregnating the dispersion containing the strengthening agent onto the dried product. The spraying and impregnation can be carried out using conventional equipment in the art, and the present invention has no special limitations on the conditions of the spraying and impregnation, as long as the uniform loading of the strengthening agent is satisfied.

[0040] According to some preferred embodiments of the present invention, the spraying and impregnation is carried out in a double-cone impregnating machine, and the spraying and impregnation is preferably carried out under vacuum conditions. Preferably, the conditions of the spraying and impregnation include: the vacuum degree is 65-75 kPa, and the spraying and impregnation time is 30-40 min. Using the above preferred embodiments is beneficial to improving the uniform loading of the strengthening agent, thereby further improving the carrier strength and the yield.

[0041] According to the present invention, controlling the volatilization rate of the strengthening agent through the second drying and calcination is beneficial to further improving the strength of the carrier.

[0042] According to some preferred embodiments of the present invention, the second drying enables the volatilization amount of the strengthening agent to be not less than 30 wt%, preferably 30-35 wt%. In the present invention, the volatilization amount of the strengthening agent is measured by the method of fluorescence analysis of ion content. Using the above preferred embodiments is beneficial to further improving the strength of the carrier and preventing the volatilization rate and volatilization amount of the strengthening agent from being too high during the subsequent calcination process, resulting in cracking of the carrier.

[0043] According to some preferred embodiments of the present invention, the conditions of the second drying include: the temperature is 60-70 °C, preferably 65-68 °C; the heating rate is 0.5-0.7 °C / min, preferably 0.55-0.6 °C / min; the drying time is 100-200 min, preferably 120-150 min.

[0044] In the present invention, the "first" and "second" in the "first drying" and "second drying" are only used to distinguish different drying steps and conditions.

[0045] According to some preferred embodiments of the present invention, the conditions for the roasting include: the temperature is 700 - 800 °C, preferably 730 - 750 °C; the heating rate is 0.8 - 0.9 °C / min, preferably 0.82 - 0.85 °C / min; the roasting time is 200 - 320 min, preferably 240 - 300 min.

[0046] Preferably, the roasting is carried out in an air atmosphere. Relative to 375 g of the product of the second drying, the ventilation volume for the roasting is 0.1 - 0.15 m 3 / h. Controlling the air volume for roasting within the above - preferred range is beneficial to ensuring sufficient roasting of the carrier and sufficient volatilization of the additives, thereby being beneficial to improving the strength and yield of the tooth - spherical carrier.

[0047] According to a particularly preferred embodiment of the present invention, the production method includes:

[0048] (1) Kneading, rolling and tooth - ball forming the alumina precursor and the kneading liquid to obtain a tooth - spherical formed product;

[0049] (2) Performing the first drying on the tooth - spherical formed product so that the dry - basis content of the dried product is 60 - 80 wt%;

[0050] (3) Loading the strengthening agent on the dried product by spraying and / or impregnation;

[0051] The strengthening agent includes silicone resin and polyacrylamide; the mass ratio of the dried product calculated on the dry basis of alumina, silicone resin and polyacrylamide is 1:(0.003 - 0.004):(0.002 - 0.003), preferably 1:(0.0031 - 0.0036):(0.0022 - 0.0025);

[0052] (4) Performing the second drying on the product obtained in step (3) so that the volatilization amount of the strengthening agent is not less than 30 wt%; then roasting the product of the second drying;

[0053] The conditions for the roasting include: the temperature is 700 - 800 °C, preferably 720 - 750 °C; the heating rate is 0.8 - 0.9 °C / min, preferably 0.82 - 0.85 °C / min; the roasting time is 200 - 300 min, preferably 240 - 300 min.

[0054] The second aspect of the present invention provides the application of the tooth - spherical carrier prepared by the above production method in gasoline and / or diesel refining catalysts.

[0055] The present invention will be described in detail below with reference to embodiments.

[0056] In the following embodiments, unless otherwise specified, the raw materials used are all commercially available.

[0057] In the following embodiments, the strength of the carrier is determined by the method of testing the crushing strength with a ZQJ-III intelligent particle strength tester.

[0058] The yield of the carrier is the percentage of the mass of the qualified product in the theoretical output. Among them, the qualified product refers to the carrier with a complete shape and a strength not less than 30 N / particle.

[0059] Example 1

[0060] (1) Pseudoboehmite (aluminum oxide content 70 wt%) and kneading liquid are mixed and kneaded at a kneading frequency of 35 Hz for 25 min, and then rolled at a rolling frequency of 20 Hz for 35 min using a rolling device.

[0061] Among them, the kneading liquid includes water, nitric acid, and methylcellulose. The mass ratio of pseudoboehmite, water, methylcellulose, and nitric acid based on the dry basis is 1:1.6:0.003:0.036.

[0062] Then the mixture is sent into a tooth ball forming device for forming to obtain a tooth ball-shaped formed product with a pentagonal cross-section.

[0063] (2) The tooth ball-shaped formed product is heated to 30 °C at a heating rate of 0.2 °C / min and dried for 150 min. The dry basis content of the dried product is 69 wt%.

[0064] (3) A dispersion liquid with a concentration of 1 wt% containing silicone resin (methyl silicone resin) and polyacrylamide (weight average molecular weight of 5 million) is prepared, and the dispersion liquid is sprayed and impregnated on the dried product in a double-cone impregnating machine. The vacuum degree during this process is maintained at 65 kPa, and the time is controlled at 30 min. The mass ratio of the dried product, silicone resin, and polyacrylamide based on the dry basis of aluminum oxide is 1:0.0031:0.0022.

[0065] (4) The product obtained in step (3) is heated to 60 °C at a heating rate of 0.5 °C / min and dried for 120 min, so that the volatilization amount of the strengthening agent is 30 wt%; then in an air atmosphere, it is heated to 700 °C at a heating rate of 0.8 °C / min and calcined for 240 min. Relative to 375 g of the second dried product, the ventilation volume is controlled at 0.1 m 3 / h. A tooth ball-shaped carrier is obtained. The yield of the carrier is 93.5 wt%, and the average strength is 53 N / particle.

[0066] Example 2

[0067] (1) Mix pseudoboehmite (aluminum oxide content 70 wt%) with a kneading liquid, knead at a kneading frequency of 36 Hz for 26 min, and then roll at a rolling frequency of 21 Hz for 37 min using a rolling device.

[0068] Among them, the kneading liquid includes water, nitric acid, and methylcellulose. The mass ratio of pseudoboehmite, water, methylcellulose, and nitric acid based on dry basis is 1:1.6:0.004:0.0375.

[0069] Then send the mixture into a tooth ball forming device for forming to obtain a tooth ball-shaped formed product with a pentagonal cross-section.

[0070] (2) Heat the tooth ball-shaped formed product at a heating rate of 0.21 °C / min to 35 °C and dry for 160 min. The dry basis content of the dried product is 70 wt%.

[0071] (3) Prepare a dispersion liquid with a concentration of 2 wt% containing silicone resin (methyl silicone resin) and polyacrylamide (weight average molecular weight of 5 million), and spray and immerse the dispersion liquid on the dried product in a double-cone impregnator. The vacuum degree during this process is maintained at 70 kPa, and the time is controlled at 35 min. The mass ratio of the dried product, silicone resin, and polyacrylamide based on dry aluminum oxide is 1:0.0033:0.0023.

[0072] (4) Heat the product obtained in step (3) at a heating rate of 0.60 °C / min to 65 °C and dry for 135 min to make the volatilization amount of the strengthening agent 33 wt%; then in an air atmosphere, heat it at a heating rate of 0.85 °C / min to 750 °C and calcine for 270 min. For 375 g of the second dried product, the ventilation rate is controlled at 0.12 m 3 / h. Obtain a tooth ball-shaped carrier. The yield of the carrier is 95.8 wt%, and the average strength is 59 N / particle.

[0073] Example 3

[0074] (1) Mix pseudoboehmite (aluminum oxide content 70 wt%) with a kneading liquid, knead at a kneading frequency of 37 Hz for 27 min, and then roll at a rolling frequency of 22 Hz for 40 min using a rolling device.

[0075] Among them, the kneading liquid includes water, nitric acid, and methylcellulose. The mass ratio of pseudoboehmite, water, methylcellulose, and nitric acid based on dry basis is 1:1.6:0.005:0.039.

[0076] Then send the mixture into a tooth ball forming device for forming to obtain a tooth ball-shaped formed product with a pentagonal cross-section.

[0077] (2) Heat the tooth-spherical shaped product at a heating rate of 0.23 °C / min to 40 °C and dry it for 170 min. The dry basis content of the dried product is 71 wt%.

[0078] (3) Prepare a dispersion with a concentration of 3 wt% containing silicone resin (methyl silicone resin) and polyacrylamide (weight average molecular weight of 5 million). Spray and immerse the dispersion on the dried product in a double-cone impregnator. During this process, the vacuum is maintained at 75 kPa and the time is controlled at 40 min. The mass ratio of the dried product, silicone resin, and polyacrylamide based on the dry basis of alumina is 1:0.0036:0.0025.

[0079] (4) Heat the product obtained in step (3) at a heating rate of 0.70 °C / min to 70 °C and dry it for 150 min, so that the volatilization amount of the strengthening agent is 35 wt%. Then, in an air atmosphere, heat it at a heating rate of 0.9 °C / min to 800 °C and calcine it for 300 min. For 375 g of the second dried product, the ventilation rate is controlled at 0.15 m 3 / h. A tooth-spherical carrier is obtained. The yield of the carrier is 94.1 wt%, and the average strength is 55 N / particle.

[0080] Example 4

[0081] According to the method of Example 1, except that the amount of the strengthening agent is such that the mass ratio of the dried product, silicone resin, and polyacrylamide based on the dry basis of alumina is 1:0.004:0.003. Then, perform the second drying and calcination in the same method to obtain a tooth-spherical carrier. The yield of the carrier is 92.6 wt%, and the average strength is 49 N / particle.

[0082] Example 5

[0083] According to the method of Example 1, except that an equal mass of ethyl cellulose is used to replace methyl cellulose.

[0084] A tooth-spherical carrier is obtained. The yield of the carrier is 92.8 wt%, and the average strength is 53 N / particle.

[0085] Example 6

[0086] According to the method of Example 1, except that in step (4), the product obtained in step (3) is heated at a heating rate of 0.8 °C / min to 75 °C and dried for 170 min, so that the volatilization amount of the strengthening agent is 45 wt%. Then, perform the calcination in the same method. A tooth-spherical carrier is obtained. The yield of the carrier is 90.2 wt%, and the average strength is 47 N / particle.

[0087] Comparative Example 1

[0088] According to the method of Example 1, except that in step (2), the tooth-shaped spherical molding is heated to 70 °C at a heating rate of 0.3 °C / min and dried for 180 min, and the dry basis content of the dried product is 90 wt%. Then, the strengthening agent spraying and impregnation, the second drying, and the calcination are carried out in the same method. A tooth-shaped spherical carrier is obtained, and the yield of the carrier is 89.6 wt%, and the average strength is 45 N / particle.

[0089] Comparative Example 2

[0090] According to the method of Example 1, except that step (3) is not carried out. The yield of the carrier is 80.3 wt%, and the average strength is 31 N / particle.

[0091] It can be seen from the comparison of the above examples and comparative examples that the preparation method provided in the examples of the present invention can effectively improve the strength of the tooth-shaped spherical carrier, reduce the proportion of material fragmentation during the calcination process, and thus improve the carrier yield.

[0092] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A production method of a toothed spherical carrier, comprising: (1) Kneading, rolling and toothed ball forming of an alumina precursor and a kneading liquid to obtain a toothed spherical formed product; (2) Performing first drying on the toothed spherical formed product so that the dry basis content of the dried product is 60 - 80 wt%; (3) Loading a strengthening agent on the dried product by spraying and / or impregnation; The strengthening agent includes silicone resin and polyacrylamide; (4) Performing second drying and roasting on the product obtained in step (3).

2. The production method according to claim 1, wherein, The mass ratio of the dried product based on the dry basis of alumina, silicone resin and polyacrylamide is 1:(0.003 - 0.004):(0.002 - 0.003), preferably 1:(0.0031 - 0.0036):(0.0022 - 0.0025); Preferably, the silicone resin is selected from at least one of polymethyl silicone resin, amino silicone resin and methyl silicone resin; Preferably, the weight-average molecular weight of the polyacrylamide is 4×10 6 -6×10 6 .

3. The production method according to claim 1 or 2, wherein, The method of loading the strengthening agent on the dried product in step (3) includes: preparing a dispersion liquid containing the strengthening agent, and then spraying and impregnating the dispersion liquid containing the strengthening agent on the dried product; Preferably, the concentration of the dispersion liquid containing the strengthening agent is 1 - 3 wt%; Preferably, the spraying and impregnation is carried out in a double - cone impregnating machine, and the spraying and impregnation is preferably carried out under vacuum conditions; Preferably, the conditions of the spraying and impregnation include: the vacuum degree is 65 - 75 kPa, and the spraying and impregnation time is 30 - 40 min.

4. The production method according to any one of claims 1 - 3, wherein, The kneading liquid includes water, an extrusion aid and / or a peptizing agent; Preferably, the peptizing agent is selected from organic acids and / or inorganic acids, preferably at least one of nitric acid, citric acid, acetic acid and tartaric acid, more preferably nitric acid; Preferably, the extrusion aid is synthetic cellulose, preferably selected from at least one of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy - cellulose fatty alcohol polyethylene ether, preferably methyl cellulose; Preferably, the mass ratio of the alumina precursor, extrusion aid and peptizing agent based on the dry basis is 1:(0.001 - 0.006):(0.03 - 0.04), preferably 1:(0.003 - 0.005):(0.036 - 0.039).

5. The production method according to any one of claims 1 - 4, wherein, The conditions of the kneading include: the kneading frequency is 30 - 40 Hz, preferably 35 - 37 Hz, the kneading time is 20 - 30 min, preferably 25 - 27 min; Preferably, the rolling frequency is 15 - 25 Hz, preferably 20 - 22 Hz, and the rolling time is 30 - 55 min, preferably 35 - 40 min.

6. The production method according to any one of claims 1 - 5, wherein, The toothed ball forming is carried out in a toothed ball production device, and a toothed spherical formed product with a cross - sectional area of a quadrilateral, pentagon or hexagon is obtained through toothed ball forming.

7. The production method according to any one of claims 1 - 6, wherein, The first drying makes the dry basis content of the dried product be 68 - 73 wt%; Preferably, the conditions of the first drying include: temperature is 30 - 40 °C, heating rate is 0.2 - 0.3 °C / min, and drying time is 120 - 200 min.

8. The production method according to any one of claims 1 - 7, wherein, the second drying makes the volatilization amount of the intensifier be not less than 30 wt%, preferably 30 - 35 wt%; Preferably, the conditions of the second drying include: temperature is 60 - 70 °C, heating rate is 0.5 - 0.7 °C / min, and drying time is 120 - 150 min.

9. The production method according to any one of claims 1 - 8, the conditions of the roasting include: temperature is 700 - 800 °C, heating rate is 0.8 - 0.9 °C / min, and roasting time is 200 - 320 min; Preferably, the roasting is carried out in an air atmosphere, and the ventilation volume of the roasting is 0.1 - 0.15 m 3 / h with respect to 375 g of the second dried product.

10. Application of the tooth - spherical carrier prepared by the production method according to any one of claims 1 - 9 in gasoline and / or diesel refining catalysts.