A shell-based slurry bed hydrogenation catalyst and its preparation method and application

Abstract

The present invention discloses a method for preparing a shell-based slurry bed hydrogenation catalyst, comprising: washing, drying, coarsely crushing and pulverizing discarded shells to obtain shell powder; immersing the shell powder in an aqueous solution of ferric nitrate to obtain an iron shell powder mixture, drying to obtain iron-containing shell powder; immersing the iron-containing shell powder in an aqueous solution of anionic surfactant, drying to obtain a shell-based slurry bed hydrogenation catalyst. The present invention also discloses a shell-based slurry bed hydrogenation catalyst and its application. The preparation method of the present invention is simple and low in cost. The prepared shell-based hydrogenation catalyst has a rich pore structure and internal and external surface areas, which can maximize the loading or deposition of macromolecular compounds such as asphalt and colloid in inferior heavy oil, and can convert low-value-added inferior heavy oil into feed for fixed bed hydrogenation device, and finally into clean fuel products, which significantly improves its economy and has broad application prospects in the field of inferior heavy oil processing.

Description

Technical Field

[0001] The invention relates to the technical field of catalytic hydrogenation and the technical field of hydrogenation methods for inferior heavy oil in the petrochemical industry, and in particular to a shell-based slurry bed hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] The slurry bed hydrogenation process was developed from coal liquefaction technology in the 1940s. With high reaction temperature and reaction pressure, the raw materials are deeply cracked to obtain more light oil products. It can process inferior raw materials that cannot be processed by fixed bed and ebullating bed hydrogenation processes. The slurry bed hydrogenation process has basically no restrictions on the impurity content of the processed raw materials, and can even process asphalt and oil sands. Therefore, the slurry bed hydrogenation process plays an increasingly important role in the lightening of inferior heavy oil.

[0003] The patent document with the authorization announcement number CN 107670699 B discloses a heavy oil suspension bed hydrogenation catalyst using a composite carrier, which uses a blue carbon expansion material, a molecular sieve and a catalytic cracking waste catalyst as a composite carrier to prepare a heavy oil suspension bed hydrogenation catalyst. The patent document with the publication number CN 113145106 A discloses a transition metal hydrogenation catalyst and method supported on carbonaceous particles, which uses tungsten as the active component of the transition metal. The carriers of the above methods are all non-waste recycled materials, and the catalyst preparation cost is relatively high.

[0004] Ethylene tar is a byproduct of the ethylene cracking unit in the petrochemical industry. It has a high asphaltene content and belongs to the category of inferior heavy oil. At present, ethylene tar is mainly sold as heavy fuel oil or carbon black raw material. Patent documents with authorization announcement numbers CN 1970688 B and CN106883871 B and some companies have disclosed comprehensive utilization methods of ethylene tar, such as extracting naphthalene and its series of products from it, using light components to synthesize petroleum resins, heavy tar to produce carbon fiber pitch and carbon fiber, and heavy fractions above 540°C to produce activated carbon, etc., but its comprehensive utilization rate is only about 50%.

[0005] Patent document with publication number CN 109609182 A discloses a process for delayed coking of unadulterated full-fraction ethylene tar, which uses a delayed coking method to treat ethylene tar, with a high value-added product yield of about 80%, including more than 10% of heavier wax oil, and a low yield of high value-added light fuel.

[0006] As a by-product of catalytic cracking units in the petrochemical industry, catalytic oil slurry is mainly sold as cheap fuel oil or mixed with a small amount of coking units, resulting in a waste of oil resources. At present, the output of catalytic oil slurry in my country is about 7.5 million tons / year. In the current situation where refining profits are decreasing, developing a technical route with better comprehensive economic efficiency of catalytic oil slurry is an urgent problem that refineries need to solve.

[0007] Maximizing the utilization rate of renewable resources in nature is conducive to the country's low-carbon green development. At present, with the rapid development of shellfish farming and processing industry in my country, a large number of discarded shells are produced every year, which accumulate year by year and cause serious environmental pollution and occupy a large amount of precious land resources. At the same time, due to the decay of the flesh residues attached to the shells or the decomposition by microorganisms, such as NH 3 , H 2 S and amines, etc., causing secondary pollution to the environment and humans. According to statistics, every 1kg of shellfish processed will produce 0.3-0.7kg of discarded shellfish. The China Fisheries Statistical Yearbook shows that the total production of marine shellfish in China in 2020 was 14.8 million tons, and about 7.4 million tons of discarded shellfish were produced each year, a considerable amount, not including the number of freshwater shellfish. At present, discarded shellfish are mainly used as feed, curing agents, building materials and water treatment agents.

[0008] Patent document with authorization announcement number CN 106345448 B discloses an alkaline catalyst for preparing biodiesel, which uses shell powder as a carrier of the biodiesel catalyst. Patent document with publication number CN 110038564 A discloses a core-shell structure catalyst for efficiently purifying combustion exhaust gas, which uses shell powder as an enhancer in the catalyst for purifying combustion exhaust gas.

[0009] Although the above-mentioned prior art has a certain foundation for the research on using shells for catalyst preparation, there is still relatively little research on using shells for preparing hydrogenation catalysts. Therefore, finding a simple method to prepare shell-based hydrogenation catalysts with excellent hydrogenation performance is of great significance for reducing the cost of catalysts and improving the economic benefits of the plant. Summary of the invention

[0010] In view of the deficiencies of the prior art, the present invention provides a method for preparing a shell-based slurry bed hydrogenation catalyst, which uses waste shells as the main raw material, first prepares shell powder by combining roasting and pulverization, and then prepares the above-mentioned shell-based slurry bed hydrogenation catalyst by combining ferric nitrate and anionic surfactant modification. The method has a simple preparation process and low processing cost, and the prepared catalyst has excellent hydrogenation performance and can be used for large-scale industrial production.

[0011] A method for preparing a shell-based slurry bed hydrogenation catalyst comprises the following steps:

[0012] (1) washing, drying, coarsely crushing and pulverizing the discarded shells to obtain shell powder;

[0013] (2) immersing the shell powder in an aqueous solution of ferric nitrate to obtain an iron shell powder mixture, and drying to obtain an iron-containing shell powder;

[0014] (3) Immersing the iron-containing shell powder in an aqueous solution of anionic surfactant and drying it to obtain a shell-based slurry bed hydrogenation catalyst.

[0015] The present invention adopts a combination of roasting and pulverization to first prepare waste shell powder particles with suitable particle size, and then uses ferric nitrate and anionic surfactants for modification to prepare a shell-based slurry bed hydrogenation catalyst with more active sites and pores. Since the catalyst has abundant active sites and pore structures, more asphaltene molecules have the opportunity to be hydrogenated, loaded, and deposited when used for the conversion of inferior heavy oil, so that the catalyst prepared by the present invention has a higher liquid product yield and a lower gas yield than the existing catalyst when used for hydrogenation reaction, and optimizes product distribution.

[0016] Preferably, in step (1), the discarded shells refer to the mantles of aquatic mollusks that have been eaten or discarded after processing, i.e., the hard outer shells of shellfish, such as discarded oyster shells and mussel shells.

[0017] The present invention adopts environmentally polluting and discarded shells as main components, effectively utilizing the discarded shells, and has the advantages of turning waste into treasure, making full use of renewable resources, and increasing the output value of the shellfish processing industry.

[0018] Preferably, in step (1), the cleaning temperature is 20-35°C, the time is 1-5 hours, and the volume ratio of discarded shells to water is 1:1-1:3.

[0019] Preferably, in step (1), the drying temperature is 100-120° C., and the time is 1 to 5 hours.

[0020] Preferably, in step (1), the coarse crushing comprises: calcining at 900-1000° C. for 1-3 hours.

[0021] Preferably, in step (1), shell fragments with a particle size of 0.2 to 2 mm are obtained after coarse crushing.

[0022] Preferably, in step (1), the pulverization is performed by using a pulverizer with a rotation speed of 6800 r / min for 10-50 min.

[0023] Preferably, in step (1), shell powder with a mesh size of 160 to 300 is obtained after pulverization.

[0024] The present invention adopts a method combining roasting and pulverization to remove the flesh residues on the surface of the discarded shells and obtain hydrogenation catalyst particles with suitable particle size, so that the prepared slurry bed hydrogenation catalyst has abundant pores and internal and external surface areas, which can maximize the loading or deposition of macromolecular compounds such as asphalt and colloid in inferior heavy oil.

[0025] Preferably, in step (2), the concentration of the aqueous ferric nitrate solution is 5 to 10 wt %, and the volume ratio of the aqueous ferric nitrate solution to the shell powder is 1:1 to 3:1.

[0026] Preferably, in step (2), the immersion time is 1 to 7 hours.

[0027] The present invention uses ferric nitrate as an auxiliary component, and the active iron metal can work synergistically with the waste shells, so that the prepared slurry bed hydrogenation catalyst has good hydrogenation activity and deasphalting properties.

[0028] Preferably, in step (3), the anionic surfactant is sodium dodecylbenzene sulfonate or sodium butylnaphthalene sulfonate.

[0029] In the study of the coke formation mechanism in the hydrocracking process of inferior heavy oil, it was found that anisotropic and isotropic submicron particles and micron spheres appeared in the process of converting the coke precursor into solid coke. In the process of converting the coke precursor into coke, an anisotropic fine particle undergoes a polymerization process to become a large particle. Controlling this process will effectively reduce the amount of coke generated, even if the coke precursor maintains its original isotropic or anisotropic polymerization state. The present invention adds a surfactant during the preparation of the slurry bed hydrogenation catalyst, so that the coke precursor compound in the feed is more fully adsorbed on the active site, solidifies its original polymerization state, promotes its hydrogenation reaction, converts it into a small molecule compound, and prevents it from generating large particles of coke, thereby reducing the coke yield and optimizing the product distribution.

[0030] Preferably, in step (3), the concentration of the anionic surfactant aqueous solution is 1 to 4 wt %, and the volume ratio of the anionic surfactant aqueous solution to the iron-containing shell powder is 1:1 to 3:1.

[0031] Preferably, in step (3), the immersion temperature is 20 to 35° C., and the immersion time is 1 to 7 hours.

[0032] Preferably, in step (2) and step (3), the drying temperature is 100-130° C. and the time is 1-7 hours.

[0033] The present invention also provides a shell-based slurry bed hydrogenation catalyst prepared by the above preparation method. The shell-based slurry bed hydrogenation catalyst has abundant pores and internal and external surface areas, can be loaded or deposited with macromolecular compounds such as asphalt and colloid in inferior heavy oil to the maximum extent, and has excellent hydrogenation catalytic performance.

[0034] Preferably, the particle size of the shell-based slurry bed hydrogenation catalyst is 50 to 100 μm.

[0035] The present invention also provides the use of the shell-based slurry bed hydrogenation catalyst in the processing of low-quality heavy oil. The shell-based slurry bed hydrogenation catalyst can be well combined with low-quality heavy oil, converting low-value-added low-quality heavy oil into feed for a fixed bed hydrogenation unit, and finally into a clean fuel product, significantly improving its economic efficiency.

[0036] Preferably, when the shell-based slurry bed hydrogenation catalyst is used in the processing of low-quality heavy oil, low-quality heavy oil, sulfur and the shell-based slurry bed hydrogenation catalyst are mixed to form a slurry bed, and a hydrogenation reaction is carried out in an atmosphere containing hydrogen.

[0037] The shell-based slurry bed hydrogenation catalyst prepared by the present invention is mixed with inferior heavy oil and sulfur powder, and then enters a slurry bed hydrogenation reactor for reaction. The hydrogenation product is separated to obtain combustible gas, liquid phase product and a small amount of coke. The liquid phase product with a dry point of less than 520°C is used as feed for a fixed bed hydrogenation device and can be further converted into clean motor fuel.

[0038] Preferably, the inferior heavy oil includes ethylene tar, catalytic oil slurry and coal tar.

[0039] Preferably, the mass fraction of the shell-based slurry bed hydrogenation catalyst in the slurry bed is 0.1-0.3% of the inferior heavy oil, and the mass fraction of the shell-based slurry bed hydrogenation catalyst in the slurry bed is 80-100%.

[0040] Preferably, the temperature of the slurry bed hydrogenation reaction is 400-460°C, the pressure is 12-24 MPa, the hydrogen-oil volume ratio is 1000-1600, and the space velocity is 0.5-2.5 h -1 .

[0041] Compared with the prior art, the present invention has at least the following beneficial effects:

[0042] (1) The present invention uses environmentally polluting, discarded shells as the main component and ferric nitrate as the auxiliary component, which effectively utilizes the discarded shells and has the advantages of turning waste into treasure, making full use of renewable resources, and increasing the output value of the shellfish processing industry; at the same time, the discarded shells and the iron active metal work together to make the prepared slurry bed hydrogenation catalyst have good hydrogenation activity and deasphalting properties.

[0043] (2) The present invention adopts a method combining roasting and pulverization to remove the flesh residues on the surface of the discarded shells and obtain hydrogenation catalyst particles with suitable particle size, so that the prepared slurry bed hydrogenation catalyst has abundant pores and internal and external surface areas, which can maximize the loading or deposition of macromolecular compounds such as asphalt and colloid in the inferior heavy oil, thereby achieving the purpose of treating inferior heavy oil in the slurry bed hydrogenation process, obtaining more and better quality feed for the downstream fixed bed hydrogenation device, and extending the operating life of the fixed bed hydrogenation device.

[0044] (3) The present invention uses anionic surfactants to treat the surface of the mixture of waste shell powder and ferric nitrate, so that the prepared slurry bed hydrogenation catalyst particles can better combine with inferior heavy oil, promote the tendency of ferric nitrate, shell powder and sulfiding agent to generate hydrogenation-active sulfides under slurry bed hydrogenation conditions, so that during the reaction, more active sites on the inner and outer surfaces of the sulfide particles adsorb more reactant molecules, including coke precursor compounds. When these molecules undergo hydrogenation reaction, the precursor compound molecules will be able to maintain their anisotropic aggregation state, rather than continue to polymerize into coke particles with larger molecules, thereby effectively reducing the amount of coke produced.

[0045] (4) The slurry bed hydrogenation catalyst provided by the present invention uses waste shell powder and ferric nitrate, has a simple preparation process, low processing cost, and low price, which is beneficial to improving the economy of the industrial equipment used.

[0046] (5) The slurry bed hydrogenation catalyst and slurry bed hydrogenation process provided by the present invention are used to treat low-quality heavy oil, so that low-value-added low-quality heavy oil is converted into feed for a fixed bed hydrogenation unit and finally converted into a clean fuel product, thereby significantly improving its economic efficiency. DETAILED DESCRIPTION

[0047] In view of the deficiencies in the prior art, the inventors of this case have proposed the technical solution of the present invention after long-term research and extensive practice. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can also be implemented in other ways different from those described herein. Therefore, the scope of protection of the present invention is not limited by the specific embodiments disclosed below. It should be understood that the order of the steps or the order in which specific actions are performed is not very important, as long as the teachings of the present invention remain operable. In addition, two or more steps or actions can be performed simultaneously.

[0048] The discarded shells used in the embodiments of the present invention are discarded oyster shells or mussel shells. The roasting equipment uses a high-temperature box-type electric furnace of model ZCGWL with a heating element of silicon-molybdenum rod produced by Shandong Zhongchen Electric Furnace Co., Ltd. The pulverizing equipment uses a superfine pulverizer of model WFH-8 produced by Jiangyin Zhengze Machinery Co., Ltd. The raw materials, solvents and reagents used in the embodiments are all obtained through conventional commercial purchase.

[0049] (1) Preparation of Shell-Based Slurry Bed Hydrogenation Catalyst A

[0050] 1. Take 100g of discarded oyster shells, wash them at 27.5℃ with clean water at a volume ratio of 1:2 for 1h, then take them out; then dry them at 120℃ for 1h, and then roast the dried discarded oyster shells at 950℃ for 3h to obtain coarsely crushed shells with a particle size of about 1.1mm; then use an ultrafine grinder with a rotation speed of 6800r / min to crush for 30min to obtain shell powder with a particle size of about 60μm for standby use.

[0051] 2. Soak the product obtained in step 1 in 300 ml of 7.5 wt% ferric nitrate aqueous solution for 4 hours to obtain an iron shell powder mixture; then dry it at 115°C for 1 hour to obtain iron-containing shell powder.

[0052] 3. At 25°C, soak the product obtained in step 2 with 200 ml of 2.5 wt% sodium dodecylbenzene sulfonate aqueous solution for 7 hours to obtain iron-containing shell powder modified by surfactant; then dry it at 100°C for 7 hours to obtain shell-based slurry bed hydrogenation catalyst A with a particle size of about 70 μm.

[0053] (2) Preparation of Shell-based Slurry Bed Hydrogenation Catalyst B

[0054] 1. Take 100 g of discarded mussel shells, wash them at 35°C with clean water at a volume ratio of 1:3 for 5 hours, and then take them out; then dry them at 100°C for 3 hours, and then roast the dried discarded mussel shells at 900°C for 1 hour to obtain coarsely crushed shells with a particle size of about 1.8 mm; then use an ultrafine grinder with a rotation speed of 6800 r / min to crush for 10 minutes to obtain shell powder with a particle size of about 88 μm for use.

[0055] 2. Soak the product obtained in step 1 in 200 ml of 10 wt% ferric nitrate aqueous solution for 1 hour to obtain an iron shell powder mixture; then dry it at 130°C for 4 hours to obtain iron-containing shell powder.

[0056] 3. At 20°C, soak the product obtained in step 2 with 300 ml of 1 wt% sodium dodecylbenzene sulfonate aqueous solution for 4 hours to obtain iron-containing shell powder modified by surfactant; then dry it at 130°C for 4 hours to obtain shell-based slurry bed hydrogenation catalyst B with a particle size of about 95 μm.

[0057] (3) Preparation of Shell-Based Slurry Bed Hydrogenation Catalyst C

[0058] 1. Take 100g of discarded oyster shells, wash them with clean water at a volume ratio of 1:1 at 20°C for 3 hours, and then take them out; then dry them at 110°C for 5 hours, and then roast the dried discarded oyster shells at 1000°C for 2 hours to obtain coarsely crushed shells with a particle size of about 0.2mm; then use an ultrafine grinder with a rotation speed of 6800r / min to crush them for 50 minutes to obtain shell powder with a particle size of about 50μm for standby use.

[0059] 2. Soak the product obtained in step 1 in 100 ml of 5 wt% ferric nitrate aqueous solution for 7 hours to obtain an iron shell powder mixture; then dry it at 100°C for 7 hours to obtain iron-containing shell powder.

[0060] 3. At 35°C, soak the product obtained in step 2 with 100 ml of 4 wt% sodium dodecylbenzene sulfonate aqueous solution for 1 hour to obtain iron-containing shell powder modified by surfactant; then dry it at 115°C for 1 hour to obtain shell-based slurry bed hydrogenation catalyst C with a particle size of about 58 μm.

[0061] The present invention uses ethylene tar and catalytic oil slurry provided by a refinery in the south to evaluate the activity of the prepared shell-based slurry bed hydrogenation catalyst. The specific properties of the ethylene tar and catalytic oil slurry used are shown in Table 1. The experimental evaluation indicators are feedstock conversion rate, distillate oil yield, and coke production rate, and the calculation method is as follows:

[0062] Feedstock conversion rate = (1-unconverted oil / feed amount) x 100%.

[0063] Distillate oil yield = distillate oil less than 520℃ / raw oil × 100%

[0064] The coke yield is the data obtained by detecting the toluene insoluble matter in the liquid product.

[0065] Example 1

[0066] The slurry bed hydrogenation reaction of this embodiment adopts a fully mixed return slurry bed hydrogenation reactor, uses a shell-based slurry bed hydrogenation catalyst A as a catalyst for the hydrogenation reaction, and the raw material used is ethylene tar. The hydrogenation process conditions, the amount of catalyst added relative to the raw material, and the amount of sulfur added are shown in Table 2. The hydrogenation product separation adopts a SH / T 0165 vacuum distillation apparatus produced by Xi'an Lianxing Experimental Instrument Co., Ltd.

[0067] Example 2

[0068] The slurry bed hydrogenation reaction of this embodiment adopts a fully mixed return slurry bed hydrogenation reactor, uses a shell-based slurry bed hydrogenation catalyst B as a catalyst for the hydrogenation reaction, and the raw material used is ethylene tar. The hydrogenation process conditions, the amount of catalyst added relative to the raw material, and the amount of sulfur added are shown in Table 2. The hydrogenation product separation adopts a SH / T 0165 vacuum distillation apparatus produced by Xi'an Lianxing Experimental Instrument Co., Ltd.

[0069] Example 3

[0070] The slurry bed hydrogenation reaction of this embodiment adopts a fully mixed return slurry bed hydrogenation reactor, uses a shell-based slurry bed hydrogenation catalyst C as a catalyst for the hydrogenation reaction, and the raw material used is catalytic oil slurry. The hydrogenation process conditions, the amount of catalyst added relative to the raw material, and the amount of sulfur added are shown in Table 2. The hydrogenation product separation adopts a SH / T 0165 vacuum distillation apparatus produced by Xi'an Lianxing Experimental Instrument Co., Ltd.

[0071] Comparative Example 1

[0072] This comparative example uses the catalyst in the invention patent with authorization announcement number CN 106622268 B, and other conditions are the same as those in Example 1.

[0073] The evaluation results of the catalysts in Examples 1-3 and Comparative Example 1 are shown in Table 2. As can be seen from Table 2, the shell-based slurry bed hydrogenation catalysts prepared from waste shells and ferric nitrate in Examples 1-3 showed good catalytic activity when treating ethylene tar or catalytic oil slurry, with high feedstock conversion rate and distillate oil yield, especially high distillate oil yield below 520°C, which means that the activity stability of the catalyst can be better protected during the next fixed bed hydrogenation reaction, and more high value-added clean gasoline and diesel products are finally obtained, so that the economy of low value-added inferior heavy oil is improved; on the other hand, the coking rate is less than 1%, indicating that the catalysts in Examples 1-3 have broad industrial application prospects, and when applied to industrial devices, the devices can be stably operated.

[0074] Based on the above embodiments and comparative examples, it is clear that the shell-based slurry bed hydrogenation catalyst provided in the embodiments of the present invention has a relatively good catalytic effect, and the waste shells and ferric nitrate used in the slurry bed hydrogenation catalyst provided in the present invention are cheap, and the catalyst preparation process is simple and the processing cost is low, which is beneficial to improving the economic efficiency of the industrial device used. In addition, the shell-based slurry bed hydrogenation catalyst and slurry bed hydrogenation process provided in the embodiments of the present invention are used to treat low-quality heavy oil, so that low-value-added petrochemical by-products such as ethylene tar and catalytic oil slurry can be converted into fixed bed hydrogenation unit feed, and finally can be converted into clean fuel oil products, which significantly improves its economic efficiency.

[0075] Table 1 Properties of low-quality heavy oil used for slurry bed hydrogenation

[0076] Crude oil name Ethylene tar Catalytic slurry <![CDATA[Density (20 °C), kg·m -3 > 1021.5 987.8 <![CDATA[S,μg·g -1 ]]> 322 11090 <![CDATA[N,μg·g -1 ]]> 150 2004 Four components, wt% Carbon residue / % 17.1 5.9 Saturation 4.1 35.8 Aroma 39.0 36.1 Gel 27.8 21.5 Asphaltene 29.1 6.6 Distillation range, ℃ IBP-EBP 119-518(95v％) 150-421(90v％)

[0077] Table 2 Slurry bed hydrogenation process conditions and reaction results

[0078]

[0079] It should also be noted that the various reaction participants and process conditions used in the above embodiments are relatively typical examples, but after a large number of experiments and verifications by the inventors of this case, other types of reaction participants and other process conditions listed above are also applicable and can also achieve the technical effects claimed in the present invention.

[0080] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0081] In summary, the catalyst provided by the embodiments of the present invention, its preparation method and application will produce good economic and social benefits after industrialization.

[0082] It should be understood that the above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a shell-based slurry bed hydrogenation catalyst, It is characterized in that The following steps are involved: (1) washing, drying, coarsely crushing and pulverizing the discarded shells to obtain shell powder; The coarse crushing is performed by roasting at 900-1000°C for 1-3 hours, and shell pieces with a particle size of 0.2-2 mm are obtained after coarse crushing; shell powder with a particle size of 160-300 mesh is obtained after pulverization; (2) soaking the shell powder in an aqueous solution of ferric nitrate to obtain an iron shell powder mixture, and drying to obtain iron-containing shell powder; (3) impregnating the iron-containing shell powder in an aqueous solution of anionic surfactant and drying to obtain a shell-based slurry bed hydrogenation catalyst; The anionic surfactant is sodium dodecylbenzene sulfonate; the concentration of the anionic surfactant aqueous solution is 1-4wt%, and the volume ratio of the anionic surfactant aqueous solution to the iron-containing shell powder is 1:1-3:

1.

2. The preparation method according to claim 1, It is characterized in that In step (2), the concentration of the ferric nitrate aqueous solution is 5-10 wt %, the volume ratio of the ferric nitrate aqueous solution to the shell powder is 1:1-3:1; and the immersion time is 1-7 h.

3. The preparation method according to claim 1, It is characterized in that In step (3), the immersion temperature is 20-35° C., and the immersion time is 1-7 hours.

4. A shell-based slurry bed hydrogenation catalyst prepared according to the preparation method described in any one of claims 1 to 3.

5. The shell-based slurry bed hydrogenation catalyst according to claim 4, It is characterized in that The particle size of the shell-based slurry bed hydrogenation catalyst is 50-100 μm.

6. Use of the shell-based slurry bed hydrogenation catalyst according to claim 4 or 5 in the processing of inferior heavy oil.

7. Use of the shell-based slurry bed hydrogenation catalyst according to claim 6 in processing low-quality heavy oil, It is characterized in that A slurry bed is formed by mixing inferior heavy oil, sulfur and the shell-based slurry bed hydrogenation catalyst according to claim 4 or 5, and a hydrogenation reaction is carried out in an atmosphere containing hydrogen.

8. Use of the shell-based slurry bed hydrogenation catalyst according to claim 7 in processing low-quality heavy oil, It is characterized in that The mass fraction of the shell-based slurry bed hydrogenation catalyst in the slurry bed is 0.1-0.3% of the inferior heavy oil and the mass fraction of the shell-based slurry bed hydrogenation catalyst in the slurry bed is 80-100%.

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