A method for recycling spent hydrogenation catalyst

Abstract

The application discloses a method for recycling waste hydrogenation catalysts. The method comprises the following steps: (1) crushing the solid of the waste molybdenum-nickel catalyst after oil extraction; (2) after the catalyst powder is reacted with chlorine, the catalyst powder is transferred to anhydrous organic solvent for ultrasonic treatment after cooling, and solvent I and material II are separated; (3) after the material II is mixed with an ammonium bicarbonate solution and sealed for heat treatment, the treated material is shaped, dried and calcined in an inert gas atmosphere to obtain an alumina-based carrier; (4) the solvent I is added dropwise into a solution containing a nickel source, a phosphorus source and a complexing agent to obtain an impregnation solution; and (5) the impregnation solution obtained in the step (4) is impregnated into the alumina-based carrier, and then is aged and dried to obtain a hydrogenation catalyst. The method has the advantages of simple recycling steps, efficient utilization of metal components and alumina carriers of the waste molybdenum-nickel catalyst, and the prepared new catalyst has the characteristics of high activity and long service life when applied to a residue oil hydrogenation reaction.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of recycling of waste hydrogenation catalysts, and particularly relates to a method for recycling waste hydrogenation catalysts. BACKGROUND

[0002] Hydrogenation catalysts are large in quantity and difficult to regenerate, resulting in low metal recovery rate and waste of resources. The basic service life of a residue hydrogenation catalyst is currently 8000 hours, and several hundred tons of waste catalysts are generated by each residue hydrogenation device every year. China currently has more than a dozen residue hydrogenation devices, and the annual residue waste catalysts can reach tens of thousands of tons. The catalyst recovery enterprises currently mainly consider recycling the molybdenum-nickel active metals of the residue hydrogenation catalyst, and the alumina carrier is basically used as waste by cement or ceramic enterprises, and the carrier utilization rate is too low. Recycling and reuse of active metals and alumina carriers have become an important direction of current hydrogenation catalyst research.

[0003] CN108067272A discloses a method for preparing a hydrogenation treatment catalyst. The method comprises: (1) extracting, microwave treating and crushing a molybdenum-nickel waste hydrogenation catalyst; (2) uniformly mixing the crushed catalyst powder of step (1) with an alkali and high-temperature calcining; (3) hot water leaching the waste catalyst after step (2) calcining; (4) reacting the filtrate in step (3) with an acidic solution to prepare a pseudo-boehmite, and mixing, shaping and calcining the pseudo-boehmite to obtain a carrier; (5) adding a Na2S solution to the filtrate after step (4) to obtain MoO3; (6) adding an acid to the solid after step (3) filtration, and then removing Fe and Al in the solution by using an alkaline solution, and finally preparing an alkaline nickel carbonate; (7) preparing a molybdenum-nickel phosphorus solution by mixing the molybdenum oxide in step (5) and the alkaline nickel carbonate in step (6), and impregnating the carrier in step (4), and then drying and calcining to obtain a hydrogenation catalyst. The method is suitable for recycling and preparing a new catalyst from a molybdenum-nickel waste catalyst, but the process is too complex, and the carrier and metal recovery rate is low.

[0004] In summary, the existing methods for recycling and reusing hydrogenation catalysts have problems such as complex process steps, low recovery rate of active metals and / or carriers, and low activity and short service life of the prepared catalysts. Therefore, it is of great significance to further study the recycling and reuse of waste hydrogenation catalysts. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a method for recycling and reusing waste hydrogenation catalysts. The method of the present application has simple recovery steps, can efficiently utilize the metal components and alumina carriers of the nickel-molybdenum waste catalyst, and the prepared new catalyst has high activity and long service life when applied to residue hydrogenation reactions.

[0006] The present application provides a method for recycling waste hydrogenation catalyst, comprising the following steps:

[0007] (1) crushing the solid of the molybdenum-nickel waste catalyst after extraction of oil;

[0008] (2) after the reaction of the catalyst powder with chlorine, the cooled product is transferred to anhydrous organic solvent for ultrasonic treatment, and solvent I and material II are separated;

[0009] (3) after the mixture of material II and ammonium bicarbonate solution is sealed and heat treated, the treated material is shaped, dried, and calcined in an inert gas atmosphere to obtain an alumina-based carrier;

[0010] (4) dropping solvent I into a solution containing a nickel source, a phosphorus source, and a complexing agent to obtain an impregnation solution;

[0011] (5) impregnating the impregnation solution obtained in step (4) into the alumina-based carrier, and then aging and drying to obtain a hydrogenation catalyst.

[0012] According to the present application, the waste hydrogenation catalyst in step (1) is a molybdenum-nickel waste catalyst, i.e. the deactivated catalyst of a molybdenum-nickel catalyst after residual oil hydroprocessing. The waste hydrogenation catalyst includes 70% to 90% of catalyst solids and 10% to 30% of petroleum distillates by weight content. Further, the waste hydrogenation catalyst after extraction of oil includes, by mass fraction based on the mass of the catalyst:

[0013] 10% to 25% of molybdenum calculated as molybdenum trioxide;

[0014] 3% to 10% of nickel calculated as nickel oxide;

[0015] 3% to 10% of vanadium calculated as vanadium pentoxide;

[0016] 6% to 14% of carbon;

[0017] 41% to 77% of carrier alumina.

[0018] According to the present application, the extracted organic solvent in step (1) includes one or more of toluene, petroleum ether, and ethanol; the extraction temperature is 80 to 110°C, and the extraction time is 60 to 90 hours. The mass ratio of the organic solvent to the catalyst is 25 to 50:1. The extraction removes the petroleum distillates in the molybdenum-nickel waste catalyst.

[0019] According to the present application, the waste hydrogenation catalyst is dried and crushed after extraction in step (1). The drying temperature is 120 to 200°C, and the drying time is 3 to 8 hours. The crushing is to crush the waste hydrogenation catalyst to a particle size of 200 to 500 mesh, preferably 300 to 400 mesh.

[0020] According to the present application, the purity of the chlorine gas in step (2) is 96% or more by volume fraction. The flow rate of the chlorine gas in step (2) is 2.7-6.8 mL / (min-g catalyst); the reaction conditions are as follows: the reaction temperature is 300-400°C, and the reaction time is 40-90 min.

[0021] According to the present application, in step (2), cooling is performed to the temperature required for ultrasonic treatment. The anhydrous organic solvent is one or more selected from the group consisting of acetone, tetrahydrofuran, and acetic acid. The amount of the anhydrous organic solvent used is 3-5:1 by mass ratio relative to the mass of the catalyst powder.

[0022] According to the present application, in step (2), the ultrasonic frequency is 10 KHz-150 KHz, the ultrasonic treatment temperature is 20°C-70°C, and the treatment time is 0.5-2 h.

[0023] According to the present application, in step (3), the mass ratio of the amount of the material II to the amount of the ammonium bicarbonate solution is 1:4-1:7, and the mass concentration of the ammonium bicarbonate solution is 15%-25%.

[0024] According to the present application, in step (3), the sealing heat treatment temperature is 120-160°C, and the treatment time is 4-8 h. The heating rate for heating to the heat treatment temperature is 5°C / min-20°C / min. Preferably, a sealing pretreatment is performed before the sealing heat treatment, the pretreatment temperature is 60-100°C, the isothermal treatment time is 2-4 h, the heating rate before the pretreatment is 10-20°C / min, the heating rate after the pretreatment is 5-10°C / min, the heating rate after the pretreatment is at least 3°C / min lower than the heating rate before the pretreatment, preferably at least 5°C / min lower, and the heat treatment is generally performed in a high-pressure autoclave.

[0025] According to the present application, in step (3), the kneading and molding are performed by using a conventional method in the art, and an adhesive, an extrusion aid, and water can be added as needed during the molding. The adhesive can be at least one selected from the group consisting of nitric acid, acetic acid, and citric acid, and the extrusion aid can be amaranth powder. The amounts of the water, the adhesive, and the extrusion aid are added as needed for actual molding, and the present application does not have a specific requirement therefor. For example, the amount of the adhesive added is 0.5wt%-5wt% of the mass of the raw materials. The amount of the extrusion aid added is 0.5wt%-6wt% of the mass of the raw materials. The amount of the water added is 90wt%-150wt% of the mass of the raw materials.

[0026] According to the present application, in step (3), the drying temperature is 110-160°C, the drying time is 4-8 h, the calcination temperature is 550-650°C, and the calcination time is 4-6 h; the inert protective gas can be an inert gas and / or nitrogen, wherein the inert gas is one or more selected from the group consisting of argon and helium.

[0027] According to the present application, the impregnation solution in step (4) is prepared by dissolving a nickel source, a phosphorus source and a complexing agent in water, and then dropping solvent I into the solution and stirring to mix. In the impregnation solution, the concentration of nickel, calculated as nickel oxide, is 40-120 g / L, the concentration of phosphorus is 10-100 g / L, and the concentration of the complexing agent is 20.0-200.0 g / L. The temperature during preparation of the impregnation solution is 50-100°C, preferably 60-90°C, and the time for dropping solvent I into the solution containing the nickel source, the phosphorus source and the complexing agent is 30-180 min, preferably 60-120 min.

[0028] According to the present application, the nickel source in step (4) includes one or more of nickel nitrate, nickel acetate, basic nickel carbonate and nickel chloride; the phosphorus source includes one or more of phosphoric acid, ammonium monohydrogen phosphate and ammonium dihydrogen phosphate, and the complexing agent is a compound containing a carboxyl group and / or a carbonyl group, including one or more of citric acid, tartaric acid, malic acid, acetic acid, formic acid, oxalic acid, malonic acid, succinic acid, glucose, fructose, galactose and gluconic acid.

[0029] According to the present application, the impregnation in step (5) can be carried out by a spray impregnation method, and the impregnation can be carried out by a saturation impregnation method or a supersaturation impregnation method.

[0030] According to the present application, the aging in step (5) is carried out by placing the impregnated sample in a closed condition at 10-30°C for 6-12 h, and the pressure during the aging is not particularly limited and can be autogenous pressure; and / or, the drying condition is drying at 100-160°C for 1-8 h.

[0031] According to the present application, the hydrogenation catalyst in step (5) comprises, by mass fraction based on the mass of the catalyst:

[0032] Mo, calculated as molybdenum trioxide, is 5.0%-22.0%,

[0033] Ni, calculated as nickel oxide, is 8.0%-13.0%,

[0034] vanadium, calculated as vanadium pentoxide, is 3%-10%,

[0035] phosphorus, calculated as phosphorus pentoxide, is 0.5%-4.0%,

[0036] carbon is 5.0%-7.0%,

[0037] the complexing agent is 0.5%-3.0%,

[0038] alumina is 41.0%-78.0%.

[0039] According to the present application, in the catalyst, part of the nickel exists in the form of nickel carbide, and the nickel element in the nickel carbide accounts for 30.0wt%-40.0wt% of the total amount of the nickel element.

[0040] According to the present application, the catalyst in step (5) has the following properties: a specific surface area of 180-280m 2 / g, a pore volume of 0.5-1.3mL / g, an average pore diameter of 10-15nm, and a mechanical strength of 130-180N / cm, preferably 140-180N / cm.

[0041] Another aspect of the present application provides a hydrogenation catalyst prepared by the above method, preferably, the hydrogenation catalyst is a residue hydrodesulfurization catalyst or a residue hydrodenitrogenation catalyst.

[0042] Compared with the prior art, the present application has the following advantages:

[0043] 1. In the method of the present application, by controlling the reaction conditions, the catalyst powder can be reacted with chlorine gas, the molybdenum can be extracted from the catalyst with high selectivity, and transferred to the solvent phase, then the solvent phase is added dropwise into a solution containing a nickel source, a phosphorus source and a complexing agent to prepare an impregnation solution, while effectively extracting the molybdenum, the carbon deposited in the waste catalyst can be effectively retained in the carrier component, part of the carbon is reacted with nickel to form nickel carbide, the carrier component is mixed with an ammonium bicarbonate solution and then sealed and heat-treated to prepare an alumina-based carrier, and finally the impregnation solution is loaded on the alumina-based carrier, thereby on the one hand, the pore structure of the catalyst is adjusted, and on the other hand, the number of acid sites on the carrier surface is increased, more coordination unsaturated sites are generated, the loading of the active components is adjusted, especially the molybdenum is more uniformly loaded on the carrier in the form of +5 valence molybdenum, which is more easily sulfided to +4 valence MoS2, thus accelerating the rate of Mo forming MoS2, and the use of the complexing agent delays the sulfuration of Ni, resulting in a high-efficiency hydrogenation active phase structure in which MoS2 is the skeleton and metal nickel is on the surface, which is beneficial to improving the activity and stability of the catalyst. 2. The specific treatment used in the present application can selectively remove the metal molybdenum from the deactivated hydrogenation catalyst without affecting other active metals loaded on the catalyst, and the deposited vanadium is sulfided to form a V-S type active phase during the hydrogenation process, which can maximize the self-catalytic activity of the deposited vanadium.

[0044] 3. The method of the present application recycles the carrier raw material alumina and carbon deposited in the waste hydrogenation catalyst to prepare a C-containing composite alumina carrier, and recycles the metals in the waste hydrogenation catalyst, thereby reducing the cost of preparing the carrier and reducing the harm to the environment.

[0045] 3. The method of the present application recycles the carrier raw material alumina and carbon deposited in the waste hydrogenation catalyst to prepare a C-containing composite alumina carrier, and recycles the metals in the waste hydrogenation catalyst, thereby reducing the cost of preparing the carrier and reducing the harm to the environment. DETAILED DESCRIPTION

[0046] The effects and advantages of the present application are further illustrated by the following examples, which do not limit the method of the present application.

[0047] In the present application, all the percentages are mass percentages unless otherwise specified.

[0048] In the present application, the specific surface area, pore volume and pore distribution are determined by using an ASAP2420 full-automatic physical adsorption instrument of American Micromeritics Company, and the determination method is as follows: after the sample is treated at 300℃ and 0.1MPa for 4h, liquid N2 is used as the adsorbate, the adsorption temperature is -196℃, and after accurate weighing, the sample is analyzed and tested. The specific surface area is calculated by BET method, and the pore volume and pore distribution are calculated by BJH method.

[0049] In the present application, the catalyst composition is tested by spectrophotometry. The testing instrument is Lambda 365 ultraviolet spectrophotometer.

[0050] In the present application, the composition and properties of the catalyst prepared in each example are shown in Table 1.

[0051] In the present application, the composition of the waste hydrogenation catalyst used in each example is 85% of catalyst solid and 15% of petroleum distillate in terms of mass percentage.

[0052] In the present application, the extraction oil removal conditions of each example are as follows: the organic solvent is toluene, the extraction temperature is 100℃, the extraction time is 72h, and the mass ratio of organic solvent to catalyst is 30:1. The composition of the waste hydrogenation catalyst after extraction oil removal is as follows in terms of mass percentage:

[0053] 19.2% of molybdenum calculated by molybdenum trioxide;

[0054] 8.6% of nickel calculated by nickel oxide;

[0055] 4.2% of vanadium calculated by vanadium pentoxide;

[0056] 9.1% of carbon,

[0057] The balance is carrier alumina.

[0058] Example 1

[0059] (1) The waste hydrogenation catalyst after industrial operation is extracted to remove oil, dried at 120℃ for 6h, and then crushed to 300 mesh.

[0060] (2) Take 124 g of catalyst powder into a container, and introduce 3.5 mL / (min.g catalyst) of chlorine gas with a purity of 98 vol% to react at a temperature of 400°C for 90 min. Cool the reacted catalyst to 30°C, and then move it into 434 g of acetone, mix uniformly, and then put it into an ultrasonic generator to treat at 30°C for 1 h with acetone as a medium and at an ultrasonic frequency of 50 kHz. Separate to obtain solvent I and material II, respectively. Material II is 100 g.

[0061] (3) Put the material II (100 g) prepared in step (2) into 550 g of an ammonium bicarbonate solution with a mass concentration of 20.0%, and then move the mixture into an autoclave to seal, heat to 100°C at a rate of 15°C / min, and then keep the temperature constant for 3 h. Then heat to 150°C at a rate of 10°C / min, and then keep the temperature constant for 6 h. Then dry at 110°C for 6 h, and then mix with 4 g of sesbania powder and 3 g of nitric acid and 120 g of water to form a shape, dry at 130°C for 4 h, and then calcine at 650°C for 4 h in a helium atmosphere to obtain catalyst carrier A-0.

[0062] (4) Take 10.3 g of nickel nitrate hexahydrate, 4.5 g of phosphoric acid, and 6.3 g of tartaric acid, and dissolve them in 60.0 mL of water to obtain a mixture. Then add the solvent I to the mixture dropwise, and the dropwise adding time is 70 min. The heating temperature is 80°C, and the heating time is 4 h. The obtained solution is recorded as L-0.

[0063] (5) Use a spraying method to impregnate the impregnating solution L-0 on the carrier A-0 to obtain A-1. Put A-1 in a closed container at room temperature of 20°C for 6 h, and then dry at 120°C for 4 h to obtain CA-1. The composition of the catalyst CA-1 is shown in Table 1.

[0064] In the catalyst CA-1, the nickel element in the nickel carbide accounts for 36.0% of the total amount of nickel element, calculated based on nickel.

[0065] Example 2

[0066] (1) Extract and remove oil from the waste hydrogenation catalyst after industrial operation, dry at 140°C for 4 h, and then crush to 400 mesh.

[0067] (2) Take 124 g of catalyst powder into a container, and introduce 3.5 mL / (min.g catalyst) of chlorine gas with a purity of 98 vol% to react at a temperature of 400°C for 90 min. Cool the reacted catalyst to 30°C, and then move it into 434 g of acetone, mix uniformly, and then put it into an ultrasonic generator to treat at 30°C for 1 h with acetone as a medium and at an ultrasonic frequency of 50 kHz. Separate to obtain solvent I and material II, respectively. Material II is 100 g.

[0068] (3) Put the material II (100 g) prepared in step (2) into 450 g of ammonium bicarbonate solution with a mass concentration of 17.5%, and then transfer the mixture into an autoclave and seal. Then, heat the mixture to 100℃ at a rate of 10℃ / min, and keep the temperature constant for 3 hours. Then, heat the mixture to 160℃ at a rate of 7℃ / min, and keep the temperature constant for 5 hours. Then, dry the mixture at 120℃ for 5 hours. Then, knead and shape the mixture with 5 g of sesbania powder, 4 g of nitric acid and 115 g of water, and then dry the mixture at 120℃ for 5 hours. Then, calcine the mixture at 650℃ for 4 hours in a helium atmosphere to obtain a catalyst carrier B-0.

[0069] (4) Take 10.3 g of nickel nitrate hexahydrate, 5.39 g of phosphoric acid and 4.16 g of tartaric acid, and dissolve them in 60.0 mL of water to obtain a mixture. Then, add the solvent I to the mixture dropwise, and the dropwise adding time is 120 min. The heating temperature is 80℃, and the heating time is 4 h. The obtained solution is recorded as L-0.

[0070] (5) Use a spraying method to impregnate the above impregnation solution L-0 on the carrier B-0 to obtain B-1. Then, place B-1 in a closed container at room temperature of 25℃ for 6 hours, and then dry B-1 at 110℃ for 5 hours to obtain CB-1. The composition of the catalyst CB-1 is shown in Table 1.

[0071] In the catalyst CB-1, the nickel element in the nickel carbide accounts for 37.9% of the total amount of the nickel element.

[0072] Example 3

[0073] (1) Take the waste hydrogenation catalyst after industrial operation, extract and remove oil, dry at 160℃ for 3 h, and then crush to 400 mesh.

[0074] (2) Take 124 g of catalyst powder and place it in a container. Then, introduce 5.3 mL / (min·g catalyst) of chlorine gas with a purity of 98v% to react. The reaction temperature is 350℃, and the reaction time is 60 min. Then, cool the reacted catalyst to 25℃, and then move it into 400 g of tetrahydrofuran and mix uniformly. Then, place the mixture into an ultrasonic generator, and treat it in tetrahydrofuran as a medium at 30℃ and an ultrasonic frequency of 100 KHz for 1 hour. Then, separate to obtain solvent I and material II. The material II is 100 g.

[0075] (3) Put the material II (100 g) prepared in step (2) into 600 g of a 25% by mass ammonium bicarbonate solution, and then transfer the mixture into an autoclave and seal. Then, heat the mixture to 90°C at a rate of 15°C / min, and keep the temperature constant for 3 hours. Then, heat the mixture to 150°C at a rate of 10°C / min, and keep the temperature constant for 6 hours. Then, dry the mixture at 120°C for 5 hours. Then, knead the mixture with 3 g of sesbania powder and 4 g of nitric acid and 100 g of water to form a shape, dry the shape at 120°C for 4 hours, and then calcine the shape at 630°C for 5 hours in a helium atmosphere to obtain a catalyst carrier C-0.

[0076] (4) Weigh 10.3 g of nickel nitrate hexahydrate, 5.9 g of phosphoric acid, and 8.0 g of tartaric acid, and dissolve them in 60.0 mL of water to obtain a mixture. Then, add the solvent I dropwise to the mixture, and the dropwise addition is performed at a temperature of 60°C for 5 hours to obtain a solution, which is denoted as L-0.

[0077] (5) Use a spraying method to impregnate the impregnation solution L-0 on the carrier C-0 to obtain C-1. Then, place C-1 in a closed container at room temperature of 25°C for 6 hours, and then dry C-1 at 120°C for 4 hours to obtain CC-1. The composition of the catalyst CC-1 is shown in Table 1.

[0078] In the catalyst CC-1, the nickel element in the nickel carbide accounts for 35.5% of the total amount of the nickel element, in terms of nickel.

[0079] Example 4

[0080] (1) Extract and remove oil from the waste hydrogenation catalyst after industrial operation, dry at 160°C for 4 hours, and then crush to 500 mesh.

[0081] (2) Put 124 g of catalyst powder into a container, and then introduce 3.9 mL / (min·g catalyst) of chlorine gas with a purity of 99v% to react at a temperature of 300°C for 80 min. Then, cool the reacted catalyst to 30°C, and then mix the catalyst with 500 g of acetic acid, and then place the mixture into an ultrasonic generator to treat at 70°C for 2 hours with acetic acid as a medium and at an ultrasonic frequency of 50 KHz. Then, separate to obtain solvent I and material II. The material II is 100 g.

[0082] (3) Put the material II (100 g) prepared in step (2) into 550 g of ammonium bicarbonate solution with a mass concentration of 20.0%, and then transfer the mixture into an autoclave and seal. Then, heat the mixture to 100 ℃ at a rate of 14 ℃ / min, and keep the temperature constant for 3 hours. Then, heat the mixture to 160 ℃ at a rate of 9 ℃ / min, and keep the temperature constant for 6 hours. Then, dry the mixture at 110 ℃ for 6 hours. Then, knead and shape the mixture with 4 g of sesbania powder, 3 g of nitric acid and 120 g of water, dry the shaped mixture at 130 ℃ for 4 hours, and then calcine the shaped mixture at 600 ℃ for 4 hours in a helium atmosphere to obtain a catalyst carrier D-0.

[0083] (4) Take 10.3 g of nickel nitrate hexahydrate, 4.5 g of phosphoric acid and 6.3 g of tartaric acid, and dissolve them in 60.0 mL of water to obtain a mixture. Then, add the solvent I dropwise into the mixture, and the dropwise adding time is 60 min. The heating temperature is 80 ℃, and the heating time is 4 h. The obtained solution is recorded as L-0.

[0084] (5) Use a spraying method to impregnate the carrier D-0 with the impregnation solution L-0 to obtain D-1. Then, place D-1 in a closed container at room temperature of 20 ℃ for 6 hours, and then dry D-1 at 120 ℃ for 4 hours to obtain CD-1. The composition of the catalyst CD-1 is shown in Table 1.

[0085] In the catalyst CD-1, the nickel element in the nickel carbide accounts for 36.1% of the total amount of the nickel element, calculated based on the nickel.

[0086] Comparative Example 1

[0087] Compared with Example 1, only air is used to replace the chlorine gas in step (2). The other steps are the same as those in Example 1.

[0088] The comparative hydrogenation catalyst DCA-1 is prepared.

[0089] In the catalyst DCA-1, the nickel element in the nickel carbide accounts for 10.1% of the total amount of the nickel element, calculated based on the nickel.

[0090] Comparative Example 2

[0091] Compared with Example 1, the comparative hydrogenation catalyst DCA-2 is prepared by using a fresh catalyst before deactivation as a comparison.

[0092] Comparative Example 3

[0093] Compared with Example 1, only the ammonium bicarbonate heat treatment step is omitted to directly prepare a carrier, and the comparative hydrogenation catalyst DCA-3 is prepared.

[0094] In the catalyst DCA-3, the nickel element in the nickel carbide accounts for 34.8% of the total amount of the nickel element, calculated based on the nickel.

[0095] Comparative Example 4

[0096] Comparative hydrogenation catalyst DCA-4 was prepared in the same way as in Example 1 except that no complexing agent was added during the preparation of the impregnation solution.

[0097] The nickel content of the nickel carbide in the catalyst DCA-4 was 34.4% of the total nickel content, based on nickel.

[0098] Composition of the catalysts obtained in the Examples of Table 1

[0099]

[0100] Properties of the catalysts obtained in the Examples of Table 2

[0101]

[0102] Catalyst evaluation

[0103] The catalysts obtained in the Examples and Comparative Examples were evaluated using the feedstocks of Table 3, under the reaction conditions of Table 3, and the results of the evaluation are shown in Table 4.

[0104] Properties of the feedstocks and reaction conditions of Table 3

[0105] Item Property Feed oil property Density / kg m -3 ]] 970.0 S / wt% 2.2 N / wt% 0.54 [Ni + V] / μg·g -1 ]] 72 Reaction condition Reaction temperature / °C 350 Pressure / MPa 7.5 Liquid hourly space velocity / h -1 ]] 0.5 Hydrogen / oil volume ratio 550

[0106] Evaluation results of the catalysts of Table 4

[0107] Removal rate Operation time, h Example 1 Example 2 Example 3 Example 4 HDS, % 200 98.3 98.1 98.6 98.1 HDS, % 2000 86.6 88.8 86.4 87.5 HDN, % 200 94.2 91.5 92.3 93.4 HDN, % 2000 81.4 82.4 83.1 82.8

[0108] Table 4 (continued)

[0109] Removal rate Operation time, h Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 HDS, % 200 61.4 98.2 62.4 65.4 HDS, % 2000 42.8 86.6 45.1 47.1 HDN, % 200 54.5 91.7 54.3 55.6 HDN, % 2000 30.2 81.6 31.1 32.5

[0110] The above detailed the specific embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A method for recycling spent hydrogenation catalyst, comprising the following steps: (1) The solids after oil removal from the molybdenum-nickel waste catalyst are crushed; (2) After reacting the catalyst powder with chlorine, the mixture was cooled and then transferred to an anhydrous organic solvent for ultrasonic treatment to separate solvent I and material II. (3) After mixing material II with ammonium bicarbonate solution, the mixture is sealed and heat-treated. After the treated material is shaped, it is dried and calcined in an inert gas atmosphere to obtain an alumina-based carrier. (4) Solvent I is added dropwise to a solution containing a nickel source, a phosphorus source and a complexing agent to obtain an impregnation solution; (5) The impregnation solution obtained in step (4) is impregnated into an alumina-based support, and then cured and dried to obtain a hydrogenation catalyst; The flow rate of chlorine gas in step (2) is 2.7~6.8 mL / (min·g catalyst); The reaction conditions described in step (2) are as follows: the reaction temperature is 300~400℃ and the reaction time is 40~90min; In step (3), the mass ratio of material II to ammonium bicarbonate solution is 1:4 to 1:7, and the mass concentration of ammonium bicarbonate solution is 15% to 25%. In step (3), the sealing heat treatment temperature is 120~160℃ and the treatment time is 4~8h; In the hydrogenation catalyst described in step (5), some nickel exists in the form of nickel carbide, and the nickel element in nickel carbide accounts for 30.0wt%~40.0wt% of the total nickel element.

2. The method according to claim 1, characterized in that, In step (2), the ultrasonic frequency is 10KHz~150KHz, the ultrasonic treatment temperature is 20℃~70℃, and the treatment time is 0.5~2h.

3. The method according to claim 1, characterized in that, Before the heat treatment of sealing in step (3), a sealing pretreatment is performed. The pretreatment temperature is 60~100℃ and the constant temperature treatment time is 2~4h.

4. The method according to claim 3, characterized in that, The heating rate before pretreatment is 10~20℃ / min, and the heating rate after pretreatment is 5~10℃ / min. Moreover, the heating rate after pretreatment is at least 3℃ / min lower than that before pretreatment.

5. The method according to claim 3, characterized in that, The heating rate after pretreatment in step (3) should be lower than that before pretreatment, by at least 5°C / min.

6. The method according to claim 1, characterized in that, In step (3), the drying temperature is 110~160℃ and the drying time is 4~8h; and / or, the calcination temperature is 550~650℃ and the calcination time is 4~6h.

7. The method according to claim 1, characterized in that, In step (4), the concentration of nickel (calculated as nickel oxide) in the impregnation solution is 40~120 g / L, the concentration of phosphorus is 10~100 g / L, and the concentration of complexing agent is 20.0~200.0 g / L. And / or, the time for adding solvent I to the solution containing nickel source, phosphorus source and complexing agent is 30~180 min.

8. The method according to claim 7, characterized in that, In step (4), solvent I is added dropwise to the solution containing nickel source, phosphorus source and complexing agent for 60~120 minutes.

9. The method according to claim 1, characterized in that, The complexing agent mentioned in step (4) is a compound containing a carboxyl group and / or a carbonyl group, including one or more of citric acid, tartaric acid, malic acid, acetic acid, formic acid, oxalic acid, malonic acid, succinic acid, glucose, fructose, galactose, and gluconic acid.

10. The method according to claim 1, characterized in that, The conditioning in step (5) involves placing the soaked sample under sealed conditions at 10~30℃ for 6~12h; and / or, the drying conditions are drying at 100~160℃ for 1~8h.

11. The method according to claim 1, characterized in that, The composition of the hydrogenation catalyst described in step (5), based on the mass of the catalyst and expressed as a mass fraction, includes: Based on molybdenum trioxide, the Mo content ranges from 5.0% to 22.0%. The Ni content, calculated as nickel oxide, is 8.0%~13.0%. Based on vanadium pentoxide, the vanadium content is 3%~10%. The phosphorus content, calculated as phosphorus pentoxide, ranges from 0.5% to 4.0%. The carbon content is 5.0%~7.0%. The content of the complexing agent is 0.5%~3.0%. The alumina content is 41.0%~78.0%.

12. The method according to claim 1, characterized in that, The properties of the catalyst described in step (5) are as follows: specific surface area of ​​180~280 m². 2 / g; and / or, pore volume of 0.5~1.3mL / g; and / or, average pore size of 10~15nm; and / or, mechanical strength of 130~180N / cm.

13. A hydrogenation catalyst prepared by the method of recycling waste hydrogenation catalyst according to any one of claims 1-12.

14. The catalyst according to claim 13, characterized in that, The hydrogenation catalyst is a residual oil hydrodesulfurization catalyst or a residual oil hydronitrogenation catalyst.

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