A method for regenerating a deactivated residual oil hydroprocessing catalyst

Abstract

The application discloses a regeneration method of deactivated residual oil hydroprocessing catalyst. The method comprises the following steps: deoiling and decarburization treatment of the deactivated residual oil hydroprocessing catalyst, ultrasonic cleaning of the catalyst by using a non-ionic surfactant, mixing of the catalyst with a binary system solution containing an organic acid and an oxidant, hydrothermal treatment of the mixture, impregnation of the mixture by using an impregnation solution containing a polyacid and a dihydric alcohol, and calcination of the impregnated mixture to obtain the regenerated hydroprocessing catalyst. The method can effectively leach poisoning substances such as V, Ni and Fe in the deactivated catalyst, maximally reduce the loss of catalytic active components, restore the pore structure of the waste catalyst, expose the active centers, and has the characteristics that the catalyst has a high initial sulfuration degree and high catalytic activity when applied to the residual oil hydrogenation reaction after the regeneration treatment.

Description

Technical Field

[0001] This invention belongs to the field of deactivated catalyst regeneration, specifically relating to a method for regenerating a deactivated residue oil hydrotreating catalyst. Background Technology

[0002] In the hydrotreating process of residual oil, the deactivation of hydrotreating catalysts is mainly caused by the blockage of catalyst channels and poisoning of active sites due to coking and metal impurity deposition. Residual oil contains a large amount of gums, asphaltenes, and metal impurities. Among these, gums and asphaltenes contain a large number of unstable polycyclic aromatic compounds. These unstable compounds easily undergo condensation reactions, forming coke deposits on the catalyst surface, covering and blocking metal active sites and clogging the catalyst's micropores. Metal impurities such as Fe, Ca, Ni, and V exist in the form of soluble organometallic compounds. After decomposition during hydrotreating, they deposit on the catalyst surface and within the channels, causing a loss of active sites and thus permanently deactivating the hydrotreating catalyst. Deactivation caused by coke can be regenerated by roasting in an oxygen-containing atmosphere; however, deactivation caused by metal deposition and blockage cannot be regenerated by roasting in an oxygen-containing atmosphere. Most deactivation of residual oil hydrotreating catalysts involves both of these factors. Therefore, regenerating deactivated residue hydrotreating catalysts to partially or completely replace fresh catalysts is of great practical significance for increasing the economic benefits of refineries, reducing energy consumption, and reducing environmental pollution.

[0003] CN102451774A discloses a method for regenerating a deactivated hydrotreating catalyst. The method includes: pre-treating the deactivated hydrotreating catalyst by degreasing, removing deposited metal impurities from the deactivated catalyst, and carbonizing the deactivated catalyst. The method for removing deposited metal impurities involves impregnating the deactivated hydrotreating catalyst with an alkaline solution, filtering, and then acid washing. This method first uses an alkaline solution to precipitate metal impurities such as vanadium, nickel, and iron, and then uses acid washing to remove the removed vanadium, nickel, and iron from the catalyst channels, thereby restoring the catalyst channels blocked by the deposition of metals such as vanadium, nickel, and iron. However, this method generates excessive types of molybdates and other crystalline species during the regeneration process, resulting in poor leaching of impurity metals and loss of some active metals, thus reducing the catalyst activity.

[0004] CN112337501A discloses a method for preparing a sulfide-type regenerated hydrogenation catalyst. The method includes: first, wetting the carbon-deactivated hydrogenation catalyst with an oxygen-containing organic solvent, then subjecting it to a mild sulfur-burning and carbon-burning treatment; after cooling, vacuum impregnating it with a water-soluble sulfur-containing composite solution; and finally, heat treatment to obtain the sulfide-type regenerated hydrogenation catalyst. This method uses a sulfur-containing composite solvent containing a complexing agent, which reacts and dissolves with the metal oxides formed during the regeneration process, further contacting with sulfides in the composite solvent to form sulfur-containing metal complexes. Under vacuum heating conditions, the sulfur-containing metal complexes decompose in situ to generate active metal sulfides. This method is costly, not feasible for large-scale industrial regeneration of deactivated catalysts, and the amount of type II Ni / CoMoS composite active phase in the regenerated catalyst is relatively small, resulting in a low degree of catalyst activity recovery.

[0005] In summary, existing methods for treating deactivated residue hydrotreating catalysts suffer from drawbacks to varying degrees, including significant losses of active metal components during regeneration and low catalyst activity after regeneration. Therefore, further research and development of regeneration methods for deactivated residue hydrotreating catalysts is of great practical significance for residue oil hydrotreating catalysts. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a method for regenerating deactivated residue hydrotreating catalysts. This method effectively removes metal poisoning substances such as V, Ni, and Fe from the deactivated catalyst, minimizes the loss of catalytically active components, restores the pore structure of the spent catalyst, exposes the active sites, and the regenerated catalyst exhibits a high initial degree of sulfidation and high catalyst activity when applied to residue hydrotreating reactions.

[0007] This invention provides a method for regenerating a deactivated residue hydrotreating catalyst, comprising:

[0008] (1) Deoiling and decarbonizing the deactivated residue hydrotreating catalyst;

[0009] (2) The solid product after step (1) is placed in a solution containing a nonionic surfactant for ultrasonic cleaning;

[0010] (3) The solid product after ultrasonic treatment in step (2) is mixed with a binary system solution containing organic acid and oxidant and then subjected to hydrothermal treatment.

[0011] (4) Impregnate the solid product after hydrothermal treatment in step (3) with an impregnation solution containing polybasic acid and diol, and calcine to obtain the regenerated hydrogenation catalyst.

[0012] According to the present invention, the deactivated residue hydrotreating catalyst in step (1) is a hydrotreating catalyst that has been deactivated due to coke deposition and the deposition of metallic impurities such as nickel and vanadium; the deactivated hydrotreating catalyst contains deposited metallic impurities such as iron, calcium, nickel and vanadium. The waste hydrotreating catalyst comprises, by weight, 70% to 90% catalyst solids and 10% to 30% petroleum fraction.

[0013] According to the present invention, further, the composition of the hydrotreating catalyst for the deactivated residue oil after extraction and deoiling in step (1), based on the mass of the catalyst, includes:

[0014] The nickel content, calculated as oxides, is 0.5% to 11%.

[0015] The molybdenum content, calculated as oxides, is 10%–25%.

[0016] The aluminum content, calculated as oxides, ranges from 29% to 79%.

[0017] The iron content, calculated as oxides, is 0.2% to 5%.

[0018] Calcium content, based on oxides, is 0.2%–6%;

[0019] The vanadium content, calculated as oxides, is 0.3% to 10%.

[0020] Carbon content is 6%–14%.

[0021] According to the present invention, the catalyst for hydrotreating the deactivated residue oil after extraction and deoiling in step (1) further includes 3% to 11% sulfur.

[0022] According to the present invention, the deactivated residue hydrotreating catalyst described in step (1) has the following properties: a specific surface area of ​​20-120 m². 2 / g, pore volume 0.01~0.2cm 3 / g.

[0023] According to the present invention, the deoiling treatment in step (1) involves immersing the deactivated residue hydrotreating catalyst in an organic solvent for extraction. The organic solvent includes one or more of ethanol, petroleum ether, and toluene. The immersion temperature is 70–120°C, and the immersion time is 24–48 h. The volume ratio of the organic solvent to the deactivated residue hydrotreating catalyst is 6:1–12:1. After the deoiling treatment in step (1), the catalyst is dried. The drying temperature is 70–90°C, and the drying time is 4–8 h.

[0024] According to the present invention, the equipment for carbon removal treatment in step (1) is a coaxial non-thermal plasma reactor. The carbon removal treatment is performed by heat treatment. The heat treatment temperature is 200–300°C, and the treatment time is 2–6 hours. The atmosphere for heat treatment is oxygen-containing gas. The oxygen-containing gas ionizes into O2 in the plasma reactor. 2+ O - O 2– and O 3– The heating rate to the target heat treatment temperature is 3–6 °C / min. The carbon content in the product after decarbonization is 0.4 wt%–1.2 wt%, and / or the sulfur content is 0.1 wt%–1.0 wt%.

[0025] According to the present invention, the nonionic surfactant in step (2) is selected from at least one of long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxyethylene alkylolamide, polyoxyethylene alkylamine, and fatty acid polyoxyethylene ester. Preferably, the nonionic surfactant in step (2) includes at least one of dodecylphenol polyoxyethylene ether OP-10 and nonylphenol polyoxyethylene ether NP-10. The concentration of the solution containing the nonionic surfactant is 1 wt% to 3 wt%.

[0026] According to the present invention, the ultrasonic frequency in step (2) is 10kHz to 150kHz, and the ultrasonic treatment time is 0.5 to 2 hours. After ultrasonic treatment, drying is required. The drying conditions are drying at 100 to 140°C for 4 to 8 hours.

[0027] According to the present invention, the organic acid in step (3) is oxalic acid. The oxidant is ammonium persulfate. Preferably, in the binary system solution in step (3), the concentration of the organic acid is 2 wt% to 20 wt%, more preferably 7 to 17 wt%, and even more preferably 9 to 17 wt%; the concentration of the oxidant is 3 wt% to 30 wt%, preferably 4 wt% to 25 wt%.

[0028] According to the present invention, the temperature of the hydrothermal treatment in step (3) is 80–130°C. The hydrothermal treatment time is 3–5 hours. The heating rate to the hydrothermal treatment temperature is 5–15°C / min. The heat treatment is generally carried out in a high-pressure reactor. The pressure for heat treatment in the high-pressure reactor is autogenous pressure. After hydrothermal treatment, washing and drying are required. The drying conditions are 120–160°C, and the drying time is 2–6 hours.

[0029] According to the present invention, the polyacid in step (4) includes at least one of maleic acid and ethylenediaminetetraacetic acid. The diol includes at least one of diethylene glycol and triethylene glycol. In the impregnation solution in step (4), the concentration of the polyacid is 2wt% to 20wt%, preferably 4wt% to 16wt%; the concentration of the diol is 5wt% to 25wt%, preferably 7wt% to 18wt%. The impregnation is saturated impregnation or unsaturated impregnation. By volume, the amount of impregnation solution used for unsaturated impregnation is more than 70% of the saturated water absorption capacity of the catalyst; the amount of impregnation solution used for saturated impregnation is 100% of the saturated water absorption capacity of the catalyst. Preferably, after impregnation in step (4), a homogenization treatment is performed. The homogenization time is 0.5 to 3.0 h.

[0030] According to the present invention, drying is required before calcination in step (4). The drying temperature is 70-130°C, and the drying time is 2-6 hours. The calcination temperature in step (4) is 500-650°C, and the calcination time is 5-10 hours.

[0031] According to the present invention, the composition of the regenerated hydrotreating catalyst in step (4) includes: based on the mass of the catalyst,

[0032] The nickel content, calculated as oxides, is 0.5% to 8%.

[0033] The molybdenum content, calculated as oxides, is 10%–25%.

[0034] The aluminum content, calculated as oxides, is 57%–88%.

[0035] The iron content, calculated as oxides, is 0.2% to 3%.

[0036] Calcium content, based on oxides, is 0.2% to 2%;

[0037] The vanadium content, calculated as oxides, is 0.3% to 5%.

[0038] According to the present invention, the specific surface area of ​​the regenerated hydrotreating catalyst in step (4) is 130-250 m². 2 / g, pore volume 0.3~1.2cm 3 / g.

[0039] Compared with the prior art, the method of the present invention has the following advantages:

[0040] 1. In the regeneration method of the deactivated residue hydrotreating catalyst of this invention, ultrasonic cleaning with a nonionic surfactant solution first effectively promotes the peeling and removal of scale on the pore surface, facilitating the unblocking of catalyst pores. Then, the deactivated catalyst is hydrothermally treated in a binary system of organic acid and oxidant. This facilitates the complexation of impurity metals deposited in the catalyst pores with the organic acid to form water-soluble compounds, thereby leaching out metal poisoning substances such as V, Ni, and Fe and redistributing them on molybdates. This optimizes the aggregation state of active metal species, promoting the formation of highly active six-coordinate polymolybdates. Simultaneously, V can synergistically interact with Ni-Mo to form new active phase centers, promoting the reaction and minimizing the loss of catalytically active components. In this invention, the ultrasonic treatment with nonionic surfactant combined with hydrothermal treatment with organic acid and oxidant effectively regenerates the deactivated catalyst. The regenerated catalyst exhibits high catalytic activity when applied to residue hydrotreating reactions.

[0041] 2. In the regeneration method of the deactivated residue hydrotreating catalyst of the present invention, the addition of maleic acid / ethylenediaminetetraacetic acid and diethylene glycol / triethylene glycol can reduce the number of crystalline species such as nickel molybdate. At the same time, the sulfidation of nickel can be delayed during the regeneration and reuse. The catalyst is more likely to form a highly efficient hydrogenation active phase structure with MoS2 as the framework and metallic nickel on the outer surface. The regenerated catalyst can basically meet the usage standards of fresh catalyst.

[0042] 3. In the regeneration method of the deactivated residue hydrotreating catalyst of the present invention, the decarbonization treatment is carried out under oxygen-containing plasma, such as O 2+ O - O 2– and O 3– It can oxidize heavy molecules (graphite or polyaromatic coke molecules) below 300℃ to restore the pore structure of spent catalysts, reduce oxide sintering, inhibit active metal agglomeration, limit the formation of crystalline species such as molybdates, and weaken the strong interaction between active metals and supports, which is conducive to improving the degree of catalyst activity recovery. Detailed Implementation

[0043] The method of the present invention will be described in detail below with reference to specific implementations, but this does not limit the scope of protection of the present invention.

[0044] In this invention, unless otherwise specified, all percentages (%) refer to mass content.

[0045] In this invention, the room temperature is 20°C.

[0046] In this invention, the catalyst composition was determined using spectrophotometry. The testing instrument was a Lambda 365 UV spectrophotometer.

[0047] In this invention, the waste hydrogenation catalyst used in each example has the following composition: 85% catalyst solid and 15% petroleum fraction.

[0048] In this invention, the specific surface area, pore volume, and pore distribution were measured using an ASAP2420 fully automated physical adsorption analyzer from Micron Instruments, Inc., USA. The measurement method is as follows: the sample was treated at 300℃ and 0.1MPa for 4 hours, with liquid N2 as the adsorbate and an adsorption temperature of -196℃. The sample was accurately weighed and then analyzed. The specific surface area was calculated using the BET method, and the pore volume and pore distribution were calculated using the BJH method.

[0049] In this invention, the composition and properties of the regenerated catalysts in Examples 1-4 are shown in Table 1. The composition and properties of the regenerated catalysts in Comparative Examples 1-3 and the fresh catalyst in Comparative Example 4 are shown in Table 1 (continued).

[0050] Example 1

[0051] (1) Take 150g of deactivated residue hydrotreating catalyst after industrial operation. The catalyst is NiMo / Al2O3, i.e., deactivator A-1. The composition of the deactivated residue hydrotreating catalyst after extraction and deoiling is: iron content 1.3wt%; calcium content 0.8wt%; nickel content 8.3wt%; vanadium content 2.6wt%; molybdenum content 12.4wt%; aluminum content 57.9wt%; sulfur content 7.5wt%; and carbon content 9.2wt%. The specific surface area of ​​the deactivated residue hydrotreating catalyst is 39.29m². 2 / g, pore volume is 0.09cm 3 / g.

[0052] With an organic solvent to deactivated residue hydrotreating catalyst volume ratio of 7:1, deactivator A-1 was placed in a fat extractor and extracted with a 1:1 volume ratio of ethanol-petroleum ether mixed solvent at 80°C for 48 hours. The soluble oil components were removed by filtration. The filtered solid was dried in an oven at 80°C for 8 hours and then placed in a coaxial non-thermal plasma reactor for coking, decarbonization, and desulfurization heat treatment. The heat treatment atmosphere was air. The heating rate was 5°C / min, and catalyst A-2 was obtained after holding at 250°C for 4 hours. The carbon content of the product after decarbonization and desulfurization treatment was 0.6 wt%, and the sulfur content was 0.8 wt%.

[0053] (2) Catalyst A-2 was placed in an ultrasonic generator and treated in a 1.8wt% dodecylalkylphenol polyoxyethylene ether OP-10 solution for 60 minutes under ultrasonic frequency 45kHz assisted conditions. After drying in a drying oven at 120℃ for 4 hours, catalyst A-3 was obtained.

[0054] (3) Catalyst A-3 was placed in a polytetrafluoroethylene liner of an autoclave, and an organic acid-oxidant binary system solution was added simultaneously. The binary system solution contained 12 wt% oxalic acid and 8 wt% ammonium persulfate. After sealing the autoclave, it was heat-treated at 90°C for 4 hours. The heating rate to the hydrothermal treatment temperature was 10°C / min. After filtration, the treated catalyst was repeatedly sprayed three times with an equal volume of deionized water to remove the surface solution. After drying in a drying oven at 120°C for 4 hours, catalyst A-4 was obtained.

[0055] (4) Catalyst A-5 was obtained by spraying maleic acid solution containing diethylene glycol with an unsaturated impregnation method (85% saturated water absorption) for 10 minutes at room temperature and then homogenizing for 2 hours. The concentration of diethylene glycol in the maleic acid solution was 13 wt%, and the concentration of maleic acid was 15 wt%. Catalyst A-5 was dried in a drying oven at 120°C for 4 hours and then calcined at 550°C for 6 hours to obtain regenerated catalyst A-6.

[0056] Example 2

[0057] (1) Take 150g of deactivated residue hydrotreating catalyst after industrial operation. The catalyst is NiMo / Al2O3, i.e., deactivator B-1. The composition of the deactivated residue hydrotreating catalyst after extraction and deoiling is as follows: iron content 1.5wt%; calcium content 0.6wt%; nickel content 9.2wt%; vanadium content 2.3wt%; molybdenum content 12.8wt%; aluminum content 55.1wt%; sulfur content 8.2wt%; carbon content 10.3wt%. The specific surface area of ​​the deactivated residue hydrotreating catalyst is 25.35m². 2 / g, pore volume 0.05cm 3 / g.

[0058] Following a volume ratio of 6:1 between organic solvent and deactivated residue hydrotreating catalyst, deactivator B-1 was placed in a fat extractor and extracted at 110°C for 32 hours using a 1:1 volume ratio of ethanol to petroleum ether mixed solvent. The soluble oil components were then removed by filtration. The filtered solid was dried in an oven at 80°C for 6 hours and then placed in a coaxial non-thermal plasma reactor for decoking, decarbonization, and desulfurization heat treatment. The heat treatment atmosphere was air. The heating rate was 5°C / min, and catalyst B-2 was obtained after holding at 230°C for 5 hours. The carbon content of the product after decoking and desulfurization treatment was 0.6 wt%, and the sulfur content was 0.7 wt%.

[0059] (2) Catalyst B-2 was placed in an ultrasonic generator and treated in a 2.1 wt% nonylphenol polyoxyethylene ether NP-10 solution for 90 minutes under ultrasonic frequency 80 kHz assisted conditions. After drying in a drying oven at 130 °C for 5 hours, catalyst B-3 was obtained.

[0060] (3) Catalyst B-3 was placed in a polytetrafluoroethylene liner of an autoclave, and an organic acid-oxidant binary system solution was added simultaneously. The binary system solution contained 12 wt% oxalic acid and 8 wt% ammonium persulfate. After sealing the autoclave, it was heat-treated at 100°C for 3.5 hours. The heating rate to the hydrothermal treatment temperature was 10°C / min. After filtration, the treated catalyst was repeatedly sprayed three times with an equal volume of deionized water to remove the surface solution. After drying in a drying oven at 120°C for 4 hours, catalyst B-4 was obtained.

[0061] (4) Catalyst B-5 was obtained by spraying a triethylene glycol-containing ethylenediaminetetraacetic acid (EDTA) solution with an unsaturated impregnation method (85% saturated water absorption) for 10 minutes and homogenizing for 3 hours at room temperature. The triethylene glycol-containing EDTA solution contained 16 wt% triethylene glycol and 12 wt% EDTA. Catalyst B-5 was dried in a drying oven at 120°C for 4 hours and then calcined at 530°C for 6 hours to obtain regenerated catalyst B-6.

[0062] Example 3

[0063] (1) Take 150g of deactivated residue hydrotreating catalyst after industrial operation. The catalyst is NiMo / Al2O3, i.e., deactivator C-1. The composition of the deactivated residue hydrotreating catalyst after extraction and deoiling is as follows: iron content 1.3wt%; calcium content 0.8wt%; nickel content 8.3wt%; vanadium content 2.6wt%; molybdenum content 12.4wt%; aluminum content 57.9wt%; sulfur content 7.5wt%; carbon content 9.2wt%. The specific surface area of ​​the deactivated residue hydrotreating catalyst is 39.29m². 2 / g, pore volume is 0.09cm 3 / g.

[0064] The deactivating agent C-1 was placed in a fat extractor and extracted with a 1:1 volume ratio of organic solvent to deactivated residue hydrotreating catalyst at 100°C for 32 hours. The soluble oil components were removed by filtration. The filtered solid was dried in an oven at 90°C for 8 hours and then placed in a coaxial non-thermal plasma reactor for decoking, decarbonization, and desulfurization heat treatment. The heat treatment atmosphere was air. The heating rate was 5°C / min, and the catalyst C-2 was obtained after holding at 220°C for 6 hours. The carbon content of the product after decoking and desulfurization treatment was 0.5 wt%, and the sulfur content was 0.4 wt%.

[0065] (2) Catalyst C-2 was placed in an ultrasonic generator and treated in a 2.5wt% nonylphenol polyoxyethylene ether NP-10 solution for 120 minutes under ultrasonic frequency 120kHz assisted conditions. After drying in a drying oven at 120℃ for 6 hours, catalyst C-3 was obtained.

[0066] (3) Catalyst C-3 was placed in a polytetrafluoroethylene liner of an autoclave, and an organic acid-oxidant binary system solution was added simultaneously. The binary system solution contained 15 wt% oxalic acid and 13 wt% ammonium persulfate. After sealing the autoclave, it was heat-treated at 120°C for 4 hours. The heating rate to the hydrothermal treatment temperature was 12°C / min. After filtration, the treated catalyst was repeatedly sprayed three times with an equal volume of deionized water to remove the surface solution. After drying in a drying oven at 140°C for 3 hours, catalyst C-4 was obtained.

[0067] (4) Catalyst C-5 was obtained by spraying maleic acid solution containing triethylene glycol with an unsaturated impregnation method (85% saturated water absorption) for 10 minutes at room temperature and then homogenizing for 2 hours. The concentration of triethylene glycol in the maleic acid solution was 16 wt%, and the concentration of maleic acid was 15 wt%. Catalyst C-5 was dried in a drying oven at 120°C for 4 hours and then calcined at 500°C for 7 hours to obtain regenerated catalyst C-6.

[0068] Example 4

[0069] (1) Take 150g of deactivated residue hydrotreating catalyst after industrial operation. The catalyst is NiMo / Al2O3, i.e., deactivator D-1. The composition of the deactivated residue hydrotreating catalyst after extraction and deoiling is as follows: iron content 1.3wt%; calcium content 0.4wt%; nickel content 9.5wt%; vanadium content 2.6wt%; molybdenum content 12.4wt%; aluminum content 56.1wt%; sulfur content 8.1wt%; carbon content 9.6wt%. The specific surface area of ​​the deactivated residue hydrotreating catalyst is 46.59m². 2 / g, pore volume 0.1cm 3 / g.

[0070] Following a volume ratio of 7:1 between organic solvent and deactivated residue hydrotreating catalyst, deactivator D-1 was placed in a fat extractor and extracted for 24 hours at 100°C using a 1:1 volume ratio of ethanol to petroleum ether mixed solvent. The soluble oil components were then removed by filtration. The filtered solid was dried in an oven at 80°C for 6 hours and then placed in a coaxial non-thermal plasma reactor for decoking, decarbonization, and desulfurization heat treatment. The heat treatment atmosphere was air. The heating rate was 5°C / min, and catalyst D-2 was obtained after holding at 240°C for 4 hours. The carbon content in the product after decoking and desulfurization treatment was 0.4 wt%, and the sulfur content was 0.3 wt%.

[0071] (2) Catalyst D-2 was placed in an ultrasonic generator and treated in a 2.5wt% nonylphenol polyoxyethylene ether NP-10 solution for 100 minutes under ultrasonic frequency 140kHz assisted conditions. After drying in a drying oven at 120℃ for 5 hours, catalyst D-3 was obtained.

[0072] (3) Catalyst D-3 was placed in a polytetrafluoroethylene liner of an autoclave, and an organic acid-oxidant binary system solution was added simultaneously. The binary system solution contained 15 wt% oxalic acid and 17 wt% ammonium persulfate. After sealing the autoclave, it was heat-treated at 120°C for 4 hours. The heating rate to the hydrothermal treatment temperature was 15°C / min. After filtration, the treated catalyst was repeatedly sprayed three times with an equal volume of deionized water to remove the surface solution. After drying in a drying oven at 150°C for 2 hours, catalyst D-4 was obtained.

[0073] (4) Catalyst D-5 was obtained by spraying a triethylene glycol-containing ethylenediaminetetraacetic acid (EDTA) solution with an unsaturated impregnation method (85% saturated water absorption) for 10 minutes and homogenizing for 3 hours at room temperature. The triethylene glycol-containing EDTA solution contained 13 wt% triethylene glycol and 15 wt% EDTA. Catalyst D-5 was dried in a drying oven at 120°C for 4 hours and then calcined at 530°C for 6 hours to obtain regenerated catalyst D-6.

[0074] Comparative Example 1

[0075] Compared with Example 1, the difference is that in step (3), the material is not transferred to a high-pressure autoclave for sealed hydrothermal treatment. Instead, the waste catalyst is mechanically mixed with a solution containing oxalic acid and ammonium persulfate at room temperature for 4 hours. Other conditions are the same as in Example 1. In this example, catalyst DA-6 was finally obtained.

[0076] Comparative Example 2

[0077] Compared to Example 1, the difference lies in step (2), where the spent catalyst is ultrasonically cleaned in deionized water instead of being ultrasonically treated in a nonionic surfactant solution. Other conditions are the same as in Example 1. This example ultimately yielded catalyst DB-6.

[0078] Comparative Example 3

[0079] Compared to Example 1, the difference lies in the absence of the polybasic acid and diol impregnation treatment in step (4). Other conditions are the same as in Example 1. The final catalyst obtained is DC-6.

[0080] Comparative Example 4

[0081] The composition and properties of the fresh catalyst before deactivation of each waste hydrogenation catalyst are shown in Table 1 (continued).

[0082] Application examples

[0083] This application example demonstrates the catalyst activity tests of Examples 1-4 and Comparative Examples 1-4 in the residue oil hydrogenation reaction on a small fixed-bed hydrogenation unit. The feedstock properties and reaction conditions are shown in Table 2, and the evaluation results are shown in Table 3.

[0084] Table 1. Composition and properties of the regenerated catalysts in Examples 1-4

[0085]

[0086]

[0087] Continued from Table 1: Composition and properties of the catalysts after regeneration in Comparative Examples 1-3 and the catalyst after freshening in Comparative Example 4.

[0088] <![CDATA[Specific surface area / (m 2 / g)]]> 124 113 146 193 <![CDATA[Pore volume / (cm 3 / g)]]> 0.28 0.22 0.36 0.48 Composition / wt% Mo 10.3 10.4 10.2 10.3 Ni 7.3 6.7 7.5 3.4 V 2.3 1.9 1.8 0 Fe 0.32 0.34 0.37 0 Ca 0.52 0.56 0.62 0

[0089] Table 2. Properties of feedstock oil and reaction conditions

[0090] properties of crude oil <![CDATA[Density / kg·m -3 > 970.0 S / wt% 1.9 <![CDATA[Ni / μg·g -1 ]]> 28.7 <![CDATA[V / μg·g -1 ]]> 46.9 Reaction conditions Temperature / °C 320 Pressure / MPa 7.5 <![CDATA[Space velocity per hour -1 > 1.5 Hydrogen-to-oil volume ratio 500 Reaction time / h 200

[0091] Table 3 Activity evaluation of regenerated catalysts

[0092]

[0093] The data above show that the pore structure of the regenerator obtained by the method of this invention is well restored. Activity evaluation results indicate that the regenerated catalyst has good desulfurization and demetallization activity, demonstrating that the method of this invention effectively improves the utilization rate of active metals in the regenerated catalyst and exhibits high activity. The catalyst regenerated in the embodiments of this invention basically meets the standards for use with fresh catalyst.

Claims

1. A method for regenerating a deactivated residue hydrotreating catalyst, comprising: (1) Deoiling and decarbonizing the deactivated residue hydrotreating catalyst; (2) Place the solid product after step (1) into a solution containing a nonionic surfactant for ultrasonic cleaning; (3) The solid product after ultrasonic treatment in step (2) is mixed with a binary system solution containing organic acid and oxidant and then subjected to hydrothermal treatment; (4) Impregnate the solid product after hydrothermal treatment in step (3) with an impregnation solution containing polybasic acid and diol, and calcine to obtain the regenerated hydrogenation catalyst; The organic acid mentioned in step (3) is oxalic acid; the oxidizing agent is ammonium persulfate; The polyacid mentioned in step (4) includes at least one of maleic acid and ethylenediaminetetraacetic acid; The diol mentioned in step (4) includes at least one of diethylene glycol and triethylene glycol; In step (4), the concentration of the polybasic acid in the impregnation solution is 2wt%~20wt%; In step (4), the concentration of the diol in the impregnation solution is 5 wt% to 25 wt%. The composition of the regenerated hydrotreating catalyst in step (4) includes: based on the catalyst mass, The nickel content, calculated as oxides, is 0.5% to 8%. The molybdenum content, calculated as oxides, is 10%–25%. The aluminum content, calculated as oxides, is 57%–88%. The iron content, calculated as oxides, is 0.2% to 3%. Calcium content, based on oxides, is 0.2% to 2%; The vanadium content, calculated as oxides, is 0.3% to 5%. The composition of the deactivated residue hydrotreating catalyst mentioned in step (1), based on catalyst mass, includes: The nickel content, calculated as oxides, ranges from 0.5% to 11%. The molybdenum content, calculated as oxides, is 10%–25%. The aluminum content, calculated as oxides, is 29%–79%. The iron content, calculated as oxides, is 0.2% to 5%. Calcium content, based on oxides, is 0.2% to 6%; The vanadium content, calculated as oxides, is 0.3% to 10%. Carbon content is 6%~14%.

2. The method according to claim 1, characterized in that, The nonionic surfactant mentioned in step (2) is selected from at least one of long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxyethylene alkylolamide, polyoxyethylene alkylamine, and fatty acid polyoxyethylene ester.

3. The method according to claim 1 or 2, characterized in that, The nonionic surfactant mentioned in step (2) includes at least one of dodecylphenol polyoxyethylene ether OP-10 and nonylphenol polyoxyethylene ether NP-10.

4. The method according to any one of claims 1 to 3, characterized in that, The temperature of the hydrothermal treatment in step (3) is 80~130℃; and / or the hydrothermal treatment time is 3~5h.

5. The method according to claim 1, characterized in that, In step (4), the concentration of polybasic acid in the impregnation solution is 4wt%~16wt%.

6. The method according to claim 1, characterized in that, In step (4), the concentration of the diol in the impregnation solution is 7wt%~18wt%.

7. The method according to claim 1, characterized in that, In step (4), the roasting temperature is 500~650℃ and the roasting time is 5~10h.

8. The method according to claim 1, characterized in that, The equipment for carbon removal in step (1) is a non-thermal plasma reactor with a coaxial structure.

9. The method according to claim 8, characterized in that, In step (1), the decarbonization process is carried out by heat treatment.

10. The method according to claim 9, characterized in that, In step (1), the heat treatment temperature is 200~300℃ and the treatment time is 2~6h; the heat treatment atmosphere is oxygen-containing gas.

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