A catalyst carrier for heavy oil hydrogenation and upgrading and its preparation method and application

Abstract

The present application relates to the field of catalytic technology, and specifically discloses a catalyst carrier for heavy oil hydrogenation and upgrading, and its preparation method and application. The preparation method of the catalyst carrier comprises the following steps: a. mixing diatomaceous earth with an anthracene oil fraction of coal tar in a weight ratio of (2-4): (6-8) at a temperature of not less than 80°C for 1-2 hours to obtain a mixture; b. ultrasonically separating the mixture at a power of 300-500W for 20-40 minutes, then filtering, washing, and drying to obtain a catalyst carrier. The present application uses diatomaceous earth and anthracene oil fraction of coal tar as raw materials to prepare a catalyst carrier. The catalyst carrier can fully disperse the catalyst in the heavy oil, expand the area of ​​the reactive region, and also has excellent temperature resistance, significantly improving the quality and efficiency of oil upgrading.

Description

Technical Field

[0001] The present application relates to the field of catalytic technology, and more specifically, to a catalyst carrier for heavy oil hydrogenation and upgrading, and a preparation method and application thereof. Background Art

[0002] The supports used in traditional hydro-upgrading catalysts cannot adequately ensure uniform dispersion of catalyst particles within heavy oil, resulting in a limited reactive zone, directly impacting the quality and efficiency of oil upgrading. While some researchers have employed various additives to improve catalyst dispersibility in an attempt to enhance reaction activity and efficiency, these approaches have significant drawbacks. These additives not only increase process complexity and production costs, but also have poor temperature resistance and impurity sensitivity, making them difficult to meet practical production requirements. Summary of the Invention

[0003] In order to solve the above technical problems, the present application provides a catalyst carrier for heavy oil hydrogenation and upgrading, and its preparation method and application. The catalyst carrier not only has good stability, but also promotes the effective dispersion of the catalyst active components, thereby significantly improving the quality and efficiency of oil upgrading.

[0004] In a first aspect, the present application provides a method for preparing a catalyst carrier for heavy oil hydro-upgrading, which adopts the following technical solution:

[0005] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0006] a. Mixing diatomaceous earth and anthracene oil fraction of coal tar in a weight ratio of (2-4):(6-8) at a temperature not lower than 80° C. and stirring for 1-2 hours to obtain a mixture;

[0007] b. The mixture is subjected to ultrasonic separation at a power of 300-500 W for 20-40 minutes, and then filtered, washed, and dried to obtain a catalyst carrier.

[0008] By adopting the above-mentioned technical scheme, the present application uses diatomaceous earth and the anthracene oil fraction of coal tar as raw materials, utilizes diatomaceous earth to provide a large specific surface area and a mesoporous structure, and utilizes the anthracene oil fraction of coal tar to form a hydrophobic layer, the contact angle of which can reach 105°, which can fully resist the infiltration of heavy oil, significantly improve the dispersibility of the catalyst carrier in the heavy oil, and enable the active ingredients loaded on the catalyst carrier to fully contact the heavy oil, thereby improving the utilization rate of the catalyst and expanding the area of ​​the reaction active region. At the same time, the catalyst carrier also has high temperature resistance, significantly improving the quality and efficiency of oil product upgrading, and conforming to the development trend of the green and low-carbon petrochemical industry.

[0009] Preferably, the weight ratio of the diatomaceous earth to the anthracene oil fraction of coal tar is 3:7.

[0010] By adopting the above technical solution, the present application further optimizes the ratio between diatomaceous earth and the anthracene oil fraction of coal tar, enabling the two to be fully mixed and contacted, better exerting the characteristics of both, and promoting the subsequent steps to generate a suitable catalyst carrier, thereby further improving the dispersibility of the catalyst carrier in heavy oil.

[0011] Preferably, the anthracene oil fraction of the coal tar is taken from a distillation range of 300-360° C., and the total content of anthracene and phenanthrene is ≥40 wt %, and the oxygen content is 8-12 wt %.

[0012] By adopting the above technical solution, the present application conducts vacuum distillation of coal tar in a true boiling point distillation tower, cuts the 300-360°C fraction, and then analyzes and determines by GC-MS that the total content of anthracene and phenanthrene is ≥40wt%, and elemental analysis shows that the oxygen content is 8-12wt%.

[0013] Preferably, when the diatomaceous earth and the anthracene oil fraction of coal tar are mixed, 1-3 wt% of the total amount of the system is also added with ZrO2 nanoparticles, the surface of which is modified with benzoic acid groups.

[0014] By adopting the above-mentioned technical solution, the present application also adds a certain amount of ZrO2 nanoparticles whose surfaces are modified with benzoic acid groups when mixing diatomaceous earth and the anthracene oil fraction of coal tar. The carboxyl groups on the benzoic acid groups can form ester bonds or amide bonds with the active groups of the matrix material to achieve covalent bond bridging. At the same time, the benzoic acid groups can increase the micro-nano structure on the surface of the ZrO2 nanoparticles and enhance the mechanical interlocking effect. The hydrophobic aromatic ring structure of the benzoic acid groups can also improve the dispersibility of the ZrO2 nanoparticles in the organic phase and reduce interface defects, thereby significantly improving the interface bonding strength between the diatomaceous earth and the anthracene oil fraction of coal tar.

[0015] Preferably, after the cleaning, the resultant is mixed evenly with γ-Al2O3 nanoparticles and then dried, and the amount of γ-Al2O3 nanoparticles added is 1-3 wt% of the total amount of diatomaceous earth and anthracene oil fraction of coal tar.

[0016] By adopting the above technical solution, the present application further adds a certain amount of γ-Al2O3 nanoparticles to blend with the resultant after cleaning, and uses γ-Al2O3 nanoparticles to modify the catalyst carrier, thereby further strengthening the structure of the catalyst carrier and improving the dispersibility and temperature resistance of the catalyst carrier.

[0017] Preferably, the diatomaceous earth is calcined diatomaceous earth.

[0018] By adopting the above technical solution, the present application further adopts calcined diatomaceous earth instead of ordinary diatomaceous earth. The calcined diatomaceous earth significantly optimizes the physical and chemical properties of ordinary diatomaceous earth through high-temperature treatment, and can provide a larger mesoporous structure, thereby further improving the dispersion ability of the catalyst carrier, while reducing the impurity content in the catalyst carrier, and improving the dispersibility and temperature resistance of the catalyst carrier.

[0019] Preferably, the cleaning process is specifically: cleaning with acetone at a temperature of 35-45° C. for 20-30 minutes.

[0020] By adopting the above technical solution, the present application uses 35-40°C acetone to wash the insoluble matter after filtration, which can fully remove the colloid, significantly reduce the TOC content, and improve the quality of the catalyst carrier.

[0021] Preferably, the drying process is specifically: vacuum drying at a temperature of 55-65° C. for 3-5 hours.

[0022] By adopting the above technical solution, the present application performs vacuum drying on the obtained product after washing at a certain temperature, which can protect the heat-sensitive components and thus improve the temperature resistance of the catalyst carrier.

[0023] In a second aspect, the present application provides a catalyst support prepared by the above-mentioned method for preparing a catalyst support for heavy oil hydrogenation and upgrading.

[0024] By adopting the above technical solution, the catalyst carrier prepared in this application was analyzed by XPS, and its surface Si-OC bond content was ≥15at%, and the specific surface area was 263-275m 2 / g, the dispersion index in heavy oil is 88-95%, the temperature resistance is 480-520℃, it can be fully dispersed in heavy oil and has excellent temperature resistance.

[0025] In a third aspect, the present application provides an application of a catalyst carrier for heavy oil hydrogenation upgrading, which adopts the following technical solution:

[0026] A catalyst carrier for heavy oil hydrogenation upgrading is used. The catalyst carrier is loaded with NiMo active components to prepare a catalyst, wherein the Ni content is 3-5wt% and the Mo content is 12-18wt%. The heavy oil hydrogenation upgrading process is then carried out at a temperature of 380-420°C and a pressure of 12-15MPa.

[0027] By adopting the above technical solution, the present application loads the NiMo active component on a catalyst support to prepare a catalyst and performs a heavy oil hydrogenation and upgrading process under certain conditions. The catalyst can be fully dispersed in the heavy oil, allowing the active component to fully contact the heavy oil, improving the utilization rate of the catalyst and expanding the area of ​​the reactive region. When using the catalyst of the present application for heavy oil hydrogenation and upgrading, no additional additives are required, significantly reducing process complexity and production costs. In addition, the catalyst has high temperature resistance and impurity sensitivity, which can meet actual production needs.

[0028] In summary, this application has the following beneficial technical effects:

[0029] 1. This application uses diatomaceous earth and the anthracene oil fraction of coal tar as raw materials to prepare a catalyst carrier. This catalyst carrier can fully disperse the catalyst in heavy oil, expand the area of ​​the reactive region, and also has excellent temperature resistance, significantly improving the quality and efficiency of oil upgrading.

[0030] 2. When the catalyst of the present application is used for hydrogenation and upgrading of heavy oil, no other additives need to be added, which significantly reduces the complexity of the process and reduces production costs. In addition, the catalyst has high temperature resistance and impurity sensitivity, which can meet actual production needs. DETAILED DESCRIPTION

[0031] The present application is further described in detail below with reference to the embodiments.

[0032] The raw materials used in this application are all commercially available products.

[0033] The anthracene oil fraction of coal tar of the present application is prepared by subjecting coal tar to vacuum distillation in a true boiling point distillation tower, cutting a fraction at 300-360°C, and then analyzing and determining the anthracene content, which is 32.1wt%, the phenanthrene content, and the benzofuran content, which is 9.7wt%, and the benzofuran content, by GC-MS. Elemental analysis shows that the oxygen content is 10wt%.

[0034] The ZrO2 nanoparticles modified with benzoic acid groups on the surface of the present application can be prepared using methods commonly used by those skilled in the art, such as direct modification (carboxyl coupling) or indirect modification (coupling agent bridging). In the specific embodiments of the present application, the direct modification method is used as an example. The direct modification method is a dehydration condensation reaction between benzoic acid and the hydroxyl groups (-OH) on the surface of ZrO2 through the carboxyl group (-COOH) to form a stable ester bond (-COO-Zr); specifically, the ZrO2 nanoparticles are dispersed in an organic solvent (such as ethanol or toluene), and then benzoic acid is added. The molar ratio of benzoic acid to ZrO2 nanoparticles is 1:1. The reaction is carried out at a temperature of 70°C for 10 hours, and then the unreacted benzoic acid is removed by centrifugation and washing to obtain a modified product.

[0035] Example 1

[0036] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0037] a. Mix 200 g of ordinary diatomaceous earth (SiO2 content of 88%), 800 g of anthracene oil fraction of coal tar, and 10 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 80°C and stir for 2 h to obtain a mixture;

[0038] b. The mixture was ultrasonically separated at a power of 300 W for 40 minutes, and then the insoluble matter was filtered out. The mixture was washed with acetone at a temperature of 35°C for 30 minutes and vacuum dried at a temperature of 55°C for 5 hours to obtain a catalyst support.

[0039] Example 2

[0040] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0041] a. Mix 400 g of ordinary diatomaceous earth (SiO2 content: 88%), 600 g of anthracene oil fraction of coal tar, and 30 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 120°C and stir for 1 hour to obtain a mixture;

[0042] b. The mixture was ultrasonically separated at a power of 500 W for 20 minutes, and then the insoluble matter was filtered out. The mixture was washed with acetone at a temperature of 45°C for 20 minutes and vacuum dried at a temperature of 65°C for 3 hours to obtain a catalyst support.

[0043] Example 3

[0044] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0045] a. Mix 300 g of ordinary diatomaceous earth (SiO2 content: 88%), 700 g of anthracene oil fraction of coal tar, and 20 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 100°C and stir for 1.5 h to obtain a mixture;

[0046] b. The mixture was ultrasonically separated at a power of 400 W for 25 minutes, and then the insoluble matter was filtered out. The mixture was washed with acetone at a temperature of 40°C for 25 minutes and vacuum dried at a temperature of 60°C for 4 hours to obtain a catalyst support.

[0047] Example 4

[0048] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0049] a. Mix 200 g of ordinary diatomaceous earth (SiO2 content: 88%), 800 g of anthracene oil fraction of coal tar, and 20 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 100°C and stir for 1.5 h to obtain a mixture;

[0050] b. The mixture was ultrasonically separated at a power of 400 W for 25 minutes, and then the insoluble matter was filtered out. The mixture was washed with acetone at a temperature of 40°C for 25 minutes and vacuum dried at a temperature of 60°C for 4 hours to obtain a catalyst support.

[0051] Example 5

[0052] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0053] a. Mix 400 g of ordinary diatomaceous earth (SiO2 content: 88%), 600 g of anthracene oil fraction of coal tar, and 20 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 100°C and stir for 1.5 h to obtain a mixture;

[0054] b. The mixture was ultrasonically separated at a power of 400 W for 25 minutes, and then the insoluble matter was filtered out. The mixture was washed with acetone at a temperature of 40°C for 25 minutes and vacuum dried at a temperature of 60°C for 4 hours to obtain a catalyst support.

[0055] Example 6

[0056] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0057] a. Mix 300 g of ordinary diatomaceous earth (SiO2 content: 88%), 700 g of anthracene oil fraction of coal tar, and 20 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 100°C and stir for 1.5 h to obtain a mixture;

[0058] b. The mixture was ultrasonically separated at a power of 500 W for 25 minutes, and then the insoluble matter was filtered out. The mixture was washed with acetone at a temperature of 40°C for 25 minutes and vacuum dried at a temperature of 60°C for 4 hours to obtain a catalyst support.

[0059] Example 7

[0060] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0061] a. Mix 300 g of ordinary diatomaceous earth (SiO2 content: 88%), 700 g of anthracene oil fraction of coal tar, and 20 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 100°C and stir for 1.5 h to obtain a mixture;

[0062] b. The mixture was ultrasonically separated at a power of 300 W for 25 minutes, and then the insoluble matter was filtered out. The mixture was washed with acetone at a temperature of 40°C for 25 minutes and vacuum dried at a temperature of 60°C for 4 hours to obtain a catalyst support.

[0063] Example 8

[0064] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0065] a. Mix 300 g of ordinary diatomaceous earth (SiO2 content: 88%), 700 g of anthracene oil fraction of coal tar, and 20 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 100°C and stir for 1.5 h to obtain a mixture;

[0066] b. Ultrasonic separation of the mixture was performed at a power of 300 W for 25 minutes, and then the insoluble matter was filtered out and washed with acetone at a temperature of 40°C for 25 minutes. After that, the mixture was mixed and stirred evenly with 10 g of γ-Al2O3 nanoparticles (particle size of 20 nm), and then vacuum dried at a temperature of 60°C for 4 hours to obtain a catalyst support.

[0067] Example 9

[0068] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0069] a. Mix 300 g of ordinary diatomaceous earth (SiO2 content: 88%), 700 g of anthracene oil fraction of coal tar, and 20 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 100°C and stir for 1.5 h to obtain a mixture;

[0070] b. Ultrasonic separation of the mixture was performed at a power of 300 W for 25 minutes, and then the insoluble matter was filtered out and washed with acetone at a temperature of 40°C for 25 minutes. After that, the mixture was mixed with 20 g of γ-Al2O3 nanoparticles (particle size of 20 nm) and stirred evenly. The mixture was then vacuum dried at a temperature of 60°C for 4 hours to obtain a catalyst support.

[0071] Example 10

[0072] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0073] a. Mix 300 g of ordinary diatomaceous earth (SiO2 content: 88%), 700 g of anthracene oil fraction of coal tar, and 20 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 100°C and stir for 1.5 h to obtain a mixture;

[0074] b. Ultrasonic separation of the mixture was performed at a power of 300 W for 25 minutes, and then the insoluble matter was filtered out and washed with acetone at a temperature of 40°C for 25 minutes. After that, the mixture was mixed and stirred evenly with 30 g of γ-Al2O3 nanoparticles (particle size of 20 nm), and then vacuum dried at a temperature of 60°C for 4 hours to obtain a catalyst support.

[0075] Example 11

[0076] A method for preparing a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0077] a. Mix 300 g of calcined diatomaceous earth (SiO2 content: 92%), 700 g of anthracene oil fraction of coal tar, and 20 g of ZrO2 nanoparticles surface-modified with benzoic acid groups at 100°C and stir for 1.5 h to obtain a mixture;

[0078] b. The mixture was ultrasonically separated at a power of 400 W for 25 minutes, and then the insoluble matter was filtered out. The mixture was washed with acetone at a temperature of 40°C for 25 minutes and vacuum dried at a temperature of 60°C for 4 hours to obtain a catalyst support.

[0079] The catalyst carrier prepared in the above embodiment is loaded with NiMo active component to prepare a catalyst, and the catalyst is applied to the heavy oil hydrogenation and upgrading process. The method for loading the NiMo active component on the catalyst carrier can be an impregnation method, a coprecipitation method, etc. well known to those skilled in the art. In the specific embodiment of the present application, ultrasonic-assisted impregnation is used as an example for illustration.

[0080] Application Example 1

[0081] An application of a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0082] The catalyst support prepared in Example 1 was immersed in a Ni-Mo mixed solution and ultrasonically vibrated at a frequency of 40 kHz for 30 min to obtain a catalyst with a Ni content of 3 wt% and a Mo content of 12 wt%. The heavy oil was then hydrogenated and upgraded in a microreactor, wherein the reactor was a fixed bed φ10×300 mm, the raw material was heavy residual oil (sulfur content of 3.8 wt%), the reaction temperature was 380°C, the pressure was 15 MPa, and the LHSV was 1.0 h -1 .

[0083] Application Example 2

[0084] An application of a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0085] The catalyst support prepared in Example 2 was immersed in a Ni-Mo mixed solution and ultrasonically vibrated at a frequency of 40 kHz for 30 min to obtain a catalyst with a Ni content of 5 wt% and a Mo content of 18 wt%. The heavy oil was then hydrogenated and upgraded in a microreactor, wherein the reactor was a fixed bed of φ10×300 mm, the raw material was heavy residual oil (sulfur content of 3.8 wt%), the reaction temperature was 420°C, the pressure was 12 MPa, and the LHSV was 1.0 h -1 .

[0086] Application Example 3

[0087] An application of a catalyst carrier for heavy oil hydrogenation and upgrading comprises the following steps:

[0088] The catalyst support prepared in Example 3 was immersed in a Ni-Mo mixed solution and ultrasonically vibrated at a frequency of 40 kHz for 30 min to obtain a catalyst with a Ni content of 4 wt% and a Mo content of 15 wt%. The heavy oil was then hydrogenated and upgraded in a microreactor, wherein the reactor was a fixed bed φ10×300 mm, the raw material was heavy residual oil (sulfur content of 3.8 wt%), the reaction temperature was 400°C, the pressure was 14 MPa, and the LHSV was 1.0 h -1 .

[0089] Application Example 4-11

[0090] The application of a catalyst carrier for heavy oil hydrogenation and upgrading is different from that of Application Example 3 in that the catalyst carrier prepared in Example 3 is replaced by the catalyst carriers prepared in Examples 4-11 respectively, and the rest is the same as that of Application Example 3.

[0091] Comparative Application Example 1

[0092] The difference from Application Example 3 is that the catalyst carrier prepared in Example 3 is replaced by a commercial γ-Al2O3 carrier, and the rest is the same as Application Example 3.

[0093] Comparative Application Example 2

[0094] The difference from Application Example 3 is that the catalyst carrier prepared in Example 3 is replaced by a pure diatomaceous earth carrier made from anthracene oil fraction without using coal tar, and the rest is the same as Application Example 3.

[0095] Performance testing

[0096] 1. Dispersion Index Determination (Laser Particle Size Method): The instrument was a Malvern Mastersizer 3000, and the dispersion medium was heavy oil (API 12.5). 1 g of the catalyst support prepared in the above example, a commercial γ-Al2O3 support, and a pure diatomaceous earth support obtained from anthracene oil fraction without coal tar were dispersed in the heavy oil. The mixture was stirred at 150°C for 1 hour, and then a sample was taken and diluted. The sample was analyzed by laser particle size analysis, and the dispersion index was calculated according to the dispersion index formula and recorded in Table 1.

[0097] The dispersion index formula is .

[0098] 2. Temperature resistance test (high-temperature calcination method): The catalyst supports prepared in the above examples, as well as commercial γ-Al2O3 supports and pure diatomaceous earth supports obtained from anthracene oil fractions without using coal tar, were heated to the target temperature in N2 at a heating rate of 5°C / min. After maintaining the temperature for 24 h, the specific surface area retention rate was measured, and the temperature resistance threshold (the highest temperature at which the specific surface area loss was ≤20%) was recorded in Table 1.

[0099] 3. The desulfurization rates of the above application examples and comparative application examples are recorded in Table 1. The desulfurization rate formula is:

[0100] Desulfurization rate = (S in - S out) / S in × 100%.

[0101] Table 1

[0102]

[0103] Data Analysis:

[0104] As can be seen from Table 1, the dispersion index of the catalyst carriers prepared in Examples 1-3 of the present application in heavy oil is 88.0-91.5%, the temperature resistance threshold is 480-485°C, and the desulfurization rate of Application Examples 1-3 is 89.5-91.8%; while the dispersion index of the commercial γ-Al2O3 carrier in heavy oil is 62.0%, the temperature resistance threshold is 450°C, and the desulfurization rate of Comparative Application Example 1 is 82.3%; the dispersion index of the pure diatomaceous earth carrier in heavy oil is 71.0%, the temperature resistance threshold is 490°C, and the desulfurization rate of Comparative Application Example 2 is 85.6%; and it has been verified that the catalyst carriers prepared in this application have a dispersion index of 88.0-91.5% in heavy oil, a ... Comparative Application Example 2 is 89.5-91.8%; The catalyst has an operating cycle of 8,500 hours, which is 20% longer than that of traditional commercial γ-Al2O3 carriers. The processing cost of each ton of residual oil can be reduced by 8.5 yuan. Experimental results show that the catalyst carrier prepared by the application using diatomaceous earth and anthracene oil fraction of coal tar as raw materials has good dispersibility in heavy oil, can expand the area of ​​the catalyst reaction active region, and has high temperature resistance. Without adding other additives, it has a high desulfurization rate, significantly improves the quality and efficiency of oil upgrading, reduces the complexity of the process, and is in line with the development trend of green and low-carbon petrochemical industry.

[0105] The difference between Application Example 4-5 and Application Example 3 is that the ratio of diatomaceous earth and the anthracene oil fraction of coal tar is different when preparing the catalyst carrier. As can be seen from Table 1, the dispersion index of the catalyst carrier prepared in Example 4-5 in heavy oil is lower than that in Example 3, and the temperature resistance threshold is also lower than that in Example 3. The desulfurization rate of Application Example 4-5 is lower than that of Application Example 3. The experimental results show that further optimizing the ratio of diatomaceous earth and the anthracene oil fraction of coal tar can further improve the dispersion performance of the catalyst carrier in heavy oil, thereby improving the utilization rate of the catalyst and further improving the desulfurization rate.

[0106] The difference between Application Examples 6-7 and Application Example 3 is that the power during ultrasonic separation during the preparation of the catalyst carrier is different. It can be seen from Table 1 that the dispersion index of the catalyst carrier prepared in Example 6 in heavy oil is higher than that in Example 3, and the temperature resistance threshold is also higher than that in Example 3. The desulfurization rate of Application Example 6 is higher than that in Application Example 3. The dispersion index of the catalyst carrier prepared in Example 7 in heavy oil is lower than that in Example 3, and the temperature resistance threshold is also lower than that in Example 3. The desulfurization rate of Application Example 7 is lower than that in Application Example 3. The experimental results show that further optimizing the power during ultrasonic separation can further improve the dispersion performance of the catalyst carrier in heavy oil, thereby improving the utilization rate of the catalyst and further improving the desulfurization rate.

[0107] The difference between Application Examples 8-10 and Application Example 3 is that γ-Al2O3 nanoparticles are also added during the preparation of the catalyst carrier. As can be seen from Table 1, the catalyst carrier prepared in Examples 8-10 has a higher dispersion index in heavy oil than that in Example 3, and a higher temperature resistance threshold than that in Example 3. The desulfurization rate of Application Examples 8-10 is higher than that of Application Example 3. The experimental results show that the further addition of γ-Al2O3 nanoparticles can further improve the dispersion performance and temperature resistance of the catalyst carrier, thereby improving the utilization rate of the catalyst and further improving the desulfurization rate.

[0108] In addition, in the temperature resistance test of Example 9, when the temperature is raised to 450°C, the specific surface area retention rate is 98%; when the temperature is raised to 500°C, the specific surface area retention rate is 95%; when the temperature is raised to 520°C, the specific surface area retention rate is 89%. In the temperature resistance test of the commercial γ-Al2O3 carrier, when the temperature is raised to 450°C, the specific surface area retention rate is 92%; when the temperature is raised to 500°C, the specific surface area retention rate is <80%. It can be seen that compared with the traditional commercial γ-Al2O3 carrier, Example 9 significantly improves the temperature resistance of the catalyst carrier, thereby improving the service life of the catalyst carrier.

[0109] The difference between Application Example 11 and Application Example 3 is that calcined diatomaceous earth is used instead of ordinary diatomaceous earth in the preparation of the catalyst carrier. As can be seen from Table 1, the catalyst carrier prepared in Example 11 has a higher dispersion index in heavy oil than that in Example 3, and a higher temperature resistance threshold than that in Example 3. The desulfurization rate of Application Example 11 is higher than that of Application Example 3. The experimental results show that compared with ordinary diatomaceous earth, calcined diatomaceous earth can further improve the dispersion performance and temperature resistance of the catalyst carrier, thereby improving the utilization rate of the catalyst and further improving the desulfurization rate.

[0110] The embodiments of this specific implementation method are all preferred embodiments of the present application and are not intended to limit the scope of protection of the present application. Therefore, any equivalent changes made based on the structure, shape, and principle of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing a catalyst carrier for heavy oil hydrogenation upgrading, characterized in that: The following steps are involved: a. mixing diatomaceous earth and an anthracene oil fraction of coal tar in a weight ratio of (2-4):(6-8) at a temperature not lower than 80° C. and stirring for 1-2 hours to obtain a mixture; and adding 1-3 wt % of the total amount of the system to the mixing of the diatomaceous earth and the anthracene oil fraction of coal tar, ZrO2 nanoparticles whose surface is modified with benzoic acid groups; b. The mixture is subjected to ultrasonic separation at a power of 300-500 W for 20-40 minutes, and then filtered, washed, and dried to obtain a catalyst carrier.

2. The method for preparing a catalyst carrier for heavy oil hydro-upgrading according to claim 1, characterized in that: The weight ratio of the diatomaceous earth to the anthracene oil fraction of coal tar is 3:

7.

3. The method for preparing a catalyst carrier for heavy oil hydro-upgrading according to claim 1, characterized in that: The anthracene oil fraction of the coal tar is taken from a distillation range of 300-360° C., and the total content of anthracene and phenanthrene is ≥40 wt %, and the oxygen content is 8-12 wt %.

4. The method for preparing a catalyst carrier for heavy oil hydro-upgrading according to claim 1, characterized in that: After the cleaning, the resultant is mixed evenly with γ-Al2O3 nanoparticles and then dried. The amount of γ-Al2O3 nanoparticles added is 1-3 wt% of the total amount of diatomaceous earth and anthracene oil fraction of coal tar.

5. The method for preparing a catalyst carrier for heavy oil hydro-upgrading according to claim 1, characterized in that: The diatomaceous earth is calcined diatomaceous earth.

6. The method for preparing a catalyst carrier for heavy oil hydro-upgrading according to claim 1, characterized in that: The cleaning process is specifically as follows: cleaning with acetone at a temperature of 35-45° C. for 20-30 minutes.

7. The method for preparing a catalyst carrier for heavy oil hydro-upgrading according to claim 1, characterized in that: The drying process is specifically as follows: vacuum drying at a temperature of 55-65° C. for 3-5 hours.

8. A catalyst support prepared by the method for preparing a catalyst support for heavy oil hydro-upgrading according to any one of claims 1 to 7.

9. Use of the catalyst carrier for heavy oil hydrogenation upgrading according to claim 8, characterized in that: First, the NiMo active component is loaded on a catalyst carrier to prepare a catalyst, wherein the Ni content is 3-5wt% and the Mo content is 12-18wt%. Then, the heavy oil is hydrogenated and upgraded at a temperature of 380-420°C and a pressure of 12-15MPa.

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