Method for recovering metals in slurry bed residual oil hydrogenation waste catalyst

Abstract

The invention relates to the technical field of metal recovery and extraction, and discloses a method for recovering metal in a slurry bed residual oil hydrogenation waste catalyst, which comprises the following steps: (1) taking the slurry bed residual oil hydrogenation waste catalyst as a raw material, and introducing water vapor and oxygen while heating to obtain a waste catalyst; (2) mixing the obtained waste catalyst with an alkaline reagent A and water, heating, leaching and filtering to obtain filtrate I; (3) adding an alkaline reagent B into the filtrate I, and adjusting the pH value to 8.0-11.0 to obtain filtrate II; (4) cooling and standing the filtrate II to separate out an ammonium metavanadate solid and obtain a filtrate III; (5) removing the filtrate III by using anion exchange resin to obtain molybdenum-rich filtrate; and (6) adjusting the pH value of the molybdenum-rich filtrate to be acidic, and performing evaporative crystallization to obtain a molybdic acid solid. After the slurry bed residual oil hydrogenation waste catalyst is subjected to high-temperature treatment in the presence of water vapor and oxygen, metal is leached and recovered by adopting alkali liquor, the process is simple, and the recovery rate is high.

Description

Technical Field

[0001] The invention relates to the technical field of metal recovery and extraction, in particular to a method for recovering metals from a slurry bed residual oil hydrogenation waste catalyst. Background Art

[0002] As people's awareness of environmental protection continues to improve, under the current increasingly stringent environmental regulations, the issue of recycling and reusing waste catalysts has received increasing attention. If waste catalysts are directly landfilled without recycling, it will cause waste of resources and large-scale environmental pollution. Most waste catalysts contain rich metal resources, which can be recycled. The recovered metal components can be recycled to prepare fresh catalysts. Therefore, the recovery and recycling of metal components in waste catalysts can not only achieve certain economic benefits, but also reduce environmental pollution. The main components of slurry bed residue oil hydrogenation waste catalysts include carbon, molybdenum and vanadium, among which the content of valuable metals such as molybdenum and vanadium is relatively high, and has a high recovery value.

[0003] CN111410229A discloses a method and equipment for preparing high-purity molybdenum oxide, including ball milling, preheat drying, oxidative roasting, sublimation and condensation processes, obtaining molybdenum trioxide gas at high temperature, and cooling the gaseous molybdenum trioxide with a quenching medium to obtain high-purity molybdenum trioxide solid. The purity of the molybdenum trioxide product obtained by this method can reach 99.5%, and the processing technology is simple and the process flow is short. However, this method is mostly used for purifying minerals or crude products, and has not yet been applied to recovering molybdenum components from waste catalysts.

[0004] CN115216650A discloses a method for separating and recovering molybdenum from waste hydrogenation catalysts. The waste hydrogenation catalyst and magnesium oxide are mixed in a certain proportion and then roasted once, and then mixed with sodium carbonate for secondary roasting; the final roasting product is mixed with an alkaline solution to extract the molybdenum component; and finally, the molybdenum component is selectively extracted using an organic extractant. This method uses a low eutectic solvent as an extractant, which is more environmentally friendly than traditional organic extractants and improves the extraction rate of molybdenum metal; however, the secondary roasting process consumes a lot of energy, and the large amount of use of the extractant increases the process cost.

[0005] CN113774220A discloses a method for recovering molybdenum / bismuth and vanadium from waste catalysts. The method comprises the following steps: oxidizing and roasting the waste catalyst with alkali, and then leaching it in water to separate bismuth from molybdenum and vanadium in the waste catalyst; precipitating vanadium with ammonium chloride to separate vanadium from molybdenum; subjecting the crude ammonium molybdate solution to acid precipitation, ammonia leaching, ion exchange, purification, and vacuum crystallization to obtain ammonium heptamolybdate; and subjecting the crude ammonium molybdate solution to ion exchange, ammonia desorption, and recrystallization to obtain an ammonium metavanadate product. The method has a high metal recovery rate, but the entire process is complicated, involves a wide variety of chemical reagents, and has a relatively high process cost, making it unsuitable for industrial production.

[0006] In summary, the existing methods for recovering molybdenum and vanadium from spent catalysts still have defects, mainly manifested in low metal recovery rate, poor environmental friendliness, complex process, high cost and other problems. Therefore, it is of great significance to develop an efficient, simple, environmentally friendly and economical method for recovering molybdenum and vanadium from metal ash of spent catalysts in slurry bed residual oil hydrogenation. Summary of the invention

[0007] In order to solve the above technical problems, the present invention provides a method for recovering metals from waste catalysts of slurry bed residual oil hydrogenation, which uses waste catalysts of slurry bed residual oil hydrogenation as raw materials, treats them at high temperature under the conditions of water vapor and oxygen, and then uses alkali solution leaching to obtain a leachate containing molybdenum and vanadium components, and obtains ammonium metavanadate and molybdic acid after a series of operations such as crystallization and separation. The method has a simple process flow, high metal recovery rate, is green and environmentally friendly, economical, and easy to achieve industrial-scale production.

[0008] The purpose of the present invention is achieved through the following technical solutions: The present invention provides a method for recovering metals from a spent catalyst for hydrogenation of residual oil in a slurry bed, comprising the following steps: (1) Using a slurry bed residual oil hydrogenation waste catalyst as a raw material, introducing water vapor and oxygen while heating the waste catalyst to obtain the waste catalyst; (2) mixing the waste catalyst obtained with alkaline reagent A and water, heating and leaching, filtering, and obtaining filtrate I; (3) adding alkaline reagent B to filtrate I to adjust the pH to 8.0-11.0 to obtain filtrate II; (4) cooling the filtrate II and allowing it to stand to precipitate ammonium metavanadate solid and obtain filtrate III; (5) removing the remaining metavanadate ions from the filtrate III using an anion exchange resin to obtain a molybdenum-rich filtrate; (6) After the pH of the molybdenum-rich filtrate is adjusted to acidic, it is evaporated and crystallized to obtain molybdic acid solid.

[0009] The present invention uses water vapor and oxygen to carry out calcination in an atmosphere where water vapor and oxygen coexist. Oxygen is used to change the metal elements in the waste catalyst from a reduced state to an oxidized state, which is beneficial for extracting the metal from the filtrate in the subsequent hydrometallurgical process. Water vapor is used to react with polycyclic aromatic hydrocarbons in the waste catalyst to generate hydrogen, thereby realizing the secondary utilization of polycyclic petroleum hydrocarbons attached to the surface of the waste catalyst, and is beneficial for reducing the influence of hydrocarbon impurities on the metal oxidation effect and improving the reaction efficiency. However, the ratio of water vapor and oxygen needs to be controlled within a reasonable range to obtain a better recovery and extraction effect. If the oxygen introduction ratio is too large, it is easy to oxidize to generate nickel molybdate, and it is difficult to separate molybdenum and nickel from nickel molybdate in the subsequent hydrometallurgical process; if the oxygen ratio is too small, the oxidation degree is too low, and the efficiency is too low, and the recovery rate will also be reduced. Therefore, the use of water vapor and oxygen atmosphere for calcination in the present invention is more conducive to separating vanadium and molybdenum metals, and obtaining a higher recovery rate and purity.

[0010] The material after heating treatment is directly extracted from molybdenum and vanadium by hydrometallurgy. Since carbon will remain in the material after heating treatment, as well as water remaining in the water vapor atmosphere, the material volume is large at this time. Compared with the material that undergoes subsequent drying and roasting treatment, the equipment required to extract the same molybdenum and vanadium is much larger, which will cause inconvenience in operation and high processing costs. However, during heating leaching, the metal ion concentration in the same solution volume is lower in this scheme, and the contact probability between the alkaline reagent and the metal oxide is higher, resulting in a higher recovery rate.

[0011] Add alkaline reagent A, the metal oxides in the waste catalyst react with the alkali to generate metal ions in the filtrate I. Add alkaline reagent B to the filtrate I to adjust the pH of the filtrate. In solutions with different pH values ​​and temperatures, the solubility of metavanadate and molybdate is different, and the difference in solubility is used to separate molybdenum and vanadium.

[0012] Preferably, in step (1), the slurry bed residue oil hydrogenation spent catalyst comprises iron, nickel, vanadium, molybdenum and hydrocarbon substances.

[0013] Preferably, in step (1), the slurry bed residue oil hydrogenation spent catalyst comprises iron, nickel, vanadium, molybdenum, aluminum, silicon, sodium, calcium and hydrocarbon substances.

[0014] The spent catalyst obtained in the slurry bed residue oil hydrogenation process mainly contains vanadium and molybdenum metals, followed by metal impurities such as nickel, aluminum, silicon, iron, sodium, calcium, and also contains hydrocarbon substances such as petroleum hydrocarbons.

[0015] Preferably, in step (1), the heating treatment is heating to 800-1400° C. and maintaining for 1-60 min. More preferably, the heating treatment is heating to 1000-1300° C. and maintaining for 2-30 min.

[0016] Preferably, in step (1), the flow ratio of water vapor to oxygen is 1.0-6.0:1.0, more preferably, the flow ratio of water vapor to oxygen is 2.0-4.0:1.0.

[0017] Preferably, in step (2), the molar ratio of the waste catalyst to the alkaline reagent A is 1.0:1.5-3.5, the molar amount of vanadium in the waste catalyst is calculated as V2O5, the molar amount of molybdenum in the waste catalyst is calculated as MoO3, and the molar ratio of the waste catalyst to the alkaline reagent A is calculated according to the total molar amount of V2O5 and MoO3 and the molar amount of the alkaline reagent A; more preferably, the molar ratio of the waste catalyst to the alkaline reagent A is 1.0:2.0-2.5.

[0018] Preferably, in step (2), the molar ratio of the alkaline reagent A to water is 1.0:50.0-100.0, and more preferably, the molar ratio of the alkaline reagent A to water is 1.0:60.0-80.0.

[0019] Preferably, in step (2), the alkaline reagent A comprises one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate. More preferably, the alkaline reagent A comprises one or more of ammonia water, sodium carbonate and sodium bicarbonate.

[0020] Preferably, in step (2), the heating leaching is performed at 40-130°C for 1-10 hours, and more preferably, the heating leaching is performed at 80-95°C for 2-5 hours.

[0021] Preferably, in step (3), the alkaline reagent B comprises ammonium chloride and / or aqueous ammonia.

[0022] Preferably, in step (3), after adding the alkaline reagent B, one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water are used to adjust the pH to 8.0-11.0.

[0023] Preferably, in step (4), the final temperature of the cooling treatment is 20-85°C, more preferably, the final temperature of the cooling treatment is 25-40°C; the standing time is 3-24h, more preferably, the standing time is 5-10h.

[0024] Preferably, in step (5), the mass ratio of the anion exchange resin to the filtrate III is 0.05-0.3:1.0, and more preferably, the mass ratio of the anion exchange resin to the filtrate III is 0.05-0.15:1.0.

[0025] Preferably, in step (5), the removal time of the anion exchange resin is 0.5-8 h, more preferably, the removal time is 1-5 h.

[0026] Preferably, in step (6), the pH value of the molybdenum-rich filtrate after pH adjustment is 0.4-3.5, and more preferably, the pH value is 1.5-2.5.

[0027] Preferably, in step (6), the temperature of the evaporation crystallization is 40-65°C, more preferably, the temperature of the evaporation crystallization is 55-65°C.

[0028] Compared with the prior art, the present invention has the following beneficial effects: (1) The metal recovery method provided by the present invention can improve the recovery rate of molybdenum and vanadium components, simplify the recovery process, reduce environmental pollution, and reduce the cost of the recovery process.

[0029] (2) The ammonium metavanadate solid and molybdic acid solid provided by the present invention have high purity, both above 98%. DETAILED DESCRIPTION

[0030] The technical solution of the present invention is described below with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0031] A method for recovering metals from a spent catalyst for slurry bed residual oil hydrogenation comprises the following steps: (1) using a slurry bed residual oil hydrogenation waste catalyst as a raw material, heating to 800-1400° C., maintaining for 1-60 minutes, and simultaneously introducing water vapor and oxygen (the flow ratio of water vapor to oxygen is 1.0-6.0:1.0) to remove hydrocarbon substances, thereby obtaining a waste catalyst; (2) The spent catalyst, alkaline reagent A (one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate) and water are mixed in a certain proportion, leached at 40 to 130° C. for 1 to 10 hours, filtered, and a filtrate I is obtained; (3) adding alkaline reagent B (ammonium chloride and / or aqueous ammonia) to filtrate I to adjust the pH to 8.0-11.0 to obtain filtrate II; (4) cooling the filtrate II to 20-85° C. and standing for 3-24 hours to precipitate ammonium metavanadate solid and obtain filtrate III; (5) removing the remaining metavanadate ions from the filtrate III using an anion exchange resin to obtain a molybdenum-rich filtrate with a pH value of 0.4-3.5; (6) adjusting the pH of the molybdenum-rich filtrate to an acidic state, evaporating and crystallizing, and obtaining molybdic acid solid.

[0032] In a specific embodiment of the present invention, in step (2), the molar ratio of the waste catalyst to the alkaline reagent A is 1.0:1.5-3.5, the molar amount of vanadium in the waste catalyst is calculated as V2O5, the molar amount of molybdenum in the waste catalyst is calculated as MoO3, and the molar ratio of the waste catalyst to the alkaline reagent A is calculated according to the total molar amount of V2O5 and MoO3 and the molar amount of the alkaline reagent A.

[0033] In a specific embodiment of the present invention, in step (2), the molar ratio of alkaline reagent A to water is 1.0:50.0-100.0.

[0034] In a specific embodiment of the present invention, in step (5), the mass ratio of the anion exchange resin to the filtrate III is 0.05-0.3:1.0.

[0035] In a specific embodiment of the present invention, in step (5), the removal time of the anion exchange resin is 0.5-8h.

[0036] In a specific embodiment of the present invention, in step (6), the temperature of evaporation crystallization is 40-65°C.

[0037] In a specific embodiment of the present invention, in step (1), the composition of the spent catalyst for slurry bed residue oil hydrogenation is as shown in Table 1 below.

[0038] Table 1 Composition of spent catalyst for slurry bed residue oil hydrogenation project unit Numeric Dynamic viscosity (150℃) cp 198 Carbon residue (including petroleum hydrocarbons) wt% 45.60 iron mg / kg 108.4 nickel mg / kg 619.3 Sulfur content wt% 2.54 vanadium mg / kg 2022.4 Tetrahydrofuran insoluble matter ％ 5.61 molybdenum mg / kg 2022.4 Initial distillation point ℃ 377 Iron + Nickel + Vanadium + Molybdenum mg / kg 5485.2 Example 1 The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation comprises the following steps: (1) 5 kg of slurry bed residue oil hydrogenation waste catalyst was placed in a heating furnace, and the heating furnace was heated to 1200°C. A mixed gas of water vapor and oxygen was continuously introduced at a flow ratio of water vapor to oxygen of 3.0:1.0. The waste catalyst was heated for 3 minutes to obtain the waste catalyst.

[0039] (2) 1500 g of the spent catalyst after hydrocarbon removal was mixed with 400 g of sodium carbonate (AR, 99%) and 5000 g of deionized water, stirred evenly, heated in a water bath at 85° C., heated for 3 h, and then filtered to obtain filtrate I.

[0040] (3) Add 300 g of aqueous ammonia (AR, 25-28%) to filtrate I and adjust the pH of the filtrate to 8.5 to obtain filtrate II.

[0041] (4) The filtrate II was cooled to 30°C and allowed to stand for 6 hours to precipitate ammonium metavanadate solid, which was filtered to obtain ammonium metavanadate solid and filtrate III.

[0042] (5) Add 400 g of anion exchange resin to the filtrate III and perform ion exchange for 3 h to obtain a molybdenum-rich filtrate.

[0043] (6) adding nitric acid solution (mass concentration 68%) to the molybdenum-rich filtrate, adjusting the pH value to 2.0, and then evaporating and crystallizing at 65° C. to obtain molybdic acid solid.

[0044] Tables 2 and 3 show the material composition of the waste catalyst obtained after the heating treatment in step (1), indicating that the waste catalyst contains more carbon and water components, has a larger volume, and has a lower metal content in the same volume, so that the contact probability between the alkaline reagent and the metal oxide is higher and the recovery rate is higher.

[0045] Table 2 Material composition of spent catalyst Serial number composition Mass percentage, % 1 water 75.5 2 carbon 19.2 3 Metal oxides 5.3 Table 3 Metal element composition of spent catalyst Serial number element Mass percentage, % 1 Al 0.0023 2 Ca 0.0326 3 Fe 0.0716 4 Mo 2.3404 5 Na 0.0659 6 Ni 0.4216 7 S 0.4240 8 Si 0.0009 9 V 1.1717 10 Zn 0.0039 11 K 0.0039 12 Mg 0.0043 13 Cr 0.0017 Example 2 The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation comprises the following steps: (1) 5 kg of slurry bed residue oil hydrogenation waste catalyst was placed in a heating furnace, and the heating furnace was heated to 1100°C. A mixed gas of water vapor and oxygen was continuously introduced at a flow ratio of water vapor to oxygen of 2.0:1.0. The waste catalyst was heated for 2 minutes to obtain the waste catalyst.

[0046] (2) 1500 g of the spent catalyst after hydrocarbon removal was mixed with 390 g of sodium bicarbonate (AR, 99%) and 5500 g of deionized water, stirred evenly, heated in a water bath at 80° C., heated and leached for 4 h, and then filtered to obtain filtrate I.

[0047] (3) Add 320 g of ammonium chloride (AR, 99.5%) to filtrate I, stir evenly, then add an appropriate amount of potassium hydroxide (AR, 95%), adjust the pH of the filtrate to 9.0, and obtain filtrate II.

[0048] (4) The filtrate II was cooled to 25°C and allowed to stand for 8 hours to precipitate ammonium metavanadate solid, which was filtered to obtain ammonium metavanadate solid and filtrate III.

[0049] (5) Add 450 g of anion exchange resin to the filtrate III and perform ion exchange for 4 h to obtain a molybdenum-rich filtrate.

[0050] (6) adding nitric acid solution (mass concentration 68%) to the molybdenum-rich filtrate, adjusting the pH value to 1.5, and then evaporating and crystallizing at 60° C. to obtain molybdic acid solid.

[0051] Example 3 The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation comprises the following steps: (1) 5 kg of slurry bed residual oil hydrogenation waste catalyst was placed in a heating furnace, and the heating furnace was heated to 1300°C. At the same time, a mixed gas of water vapor and oxygen was continuously introduced, and the flow ratio of water vapor to oxygen was 4.0:1.0. The waste catalyst was heated for 2 minutes to obtain the waste catalyst.

[0052] (2) 1500 g of the spent catalyst after hydrocarbon removal was mixed with 420 g of sodium bicarbonate (AR, 99%) and 4800 g of deionized water, stirred evenly, heated in a water bath at 80° C., heated for 3 h, and then filtered to obtain filtrate I.

[0053] (3) Add 340 g of ammonium chloride (AR, 99.5%) to filtrate I, stir evenly, then add an appropriate amount of ammonia water (AR, 25-28%), adjust the pH of the filtrate to 8.5, and obtain filtrate II.

[0054] (4) The filtrate II is cooled to 40°C and allowed to stand for 10 hours to precipitate ammonium metavanadate solid, which is then filtered to obtain ammonium metavanadate solid and filtrate III.

[0055] (5) Add 350 g of anion exchange resin to the filtrate III and perform ion exchange for 5 h to obtain a molybdenum-rich filtrate.

[0056] (6) Sulfuric acid (5 mol / L) was added to the molybdenum-rich filtrate to adjust the pH value to 2.0, and then evaporated and crystallized at 55° C. to obtain molybdic acid solid.

[0057] Example 4 The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation comprises the following steps: (1) 5 kg of slurry bed residual oil hydrogenation waste catalyst was placed in a heating furnace, and the heating furnace was heated to 1200°C. At the same time, a mixed gas of water vapor and oxygen was continuously introduced, and the flow ratio of water vapor to oxygen was 2.0:1.0. The waste catalyst was heated for 2 minutes to obtain the waste catalyst.

[0058] (2) 1500 g of the spent catalyst after hydrocarbon removal was mixed with 400 g of ammonia water (AR, 25-28%) and 4800 g of deionized water, stirred evenly, heated in a water bath at 85° C., heated for 4 h, and then filtered to obtain filtrate I.

[0059] (3) Add 330 g of aqueous ammonia (AR, 25-28%) to filtrate I, stir evenly, then add an appropriate amount of sodium carbonate (AR, 99%), adjust the pH of the filtrate to 9.0, and obtain filtrate II.

[0060] (4) The filtrate II was cooled to 30°C and allowed to stand for 8 hours to precipitate ammonium metavanadate solid, which was filtered to obtain ammonium metavanadate solid and filtrate III.

[0061] (5) Add 380 g of anion exchange resin to the filtrate III and perform ion exchange for 4 h to obtain a molybdenum-rich filtrate.

[0062] (6) Add nitric acid solution (volume concentration 68%) to the molybdenum-rich filtrate, adjust the pH value to 1.5, and then evaporate and crystallize at 65° C. to obtain molybdic acid solid.

[0063] Example 5 The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation comprises the following steps: (1) 5 kg of slurry bed residual oil hydrogenation waste catalyst was placed in a heating furnace, and the heating furnace was heated to 1100° C. At the same time, a mixed gas of water vapor and oxygen was continuously introduced, and the flow ratio of water vapor to oxygen was 3.0:1.0. The waste catalyst was heated for 2 minutes to obtain the waste catalyst.

[0064] (2) 1500 g of the spent catalyst after hydrocarbon removal was mixed with 450 g of sodium carbonate (AR, 99%) and 5600 g of deionized water, stirred evenly, heated in a water bath at 80° C., heated for 4 h, and then filtered to obtain filtrate I.

[0065] (3) Add 330 g of ammonium chloride (AR, 99.5%) to filtrate I, stir evenly, then add an appropriate amount of sodium hydroxide (AR, 96%), adjust the pH of the filtrate to 8.5, and obtain filtrate II.

[0066] (4) The filtrate II is cooled to 45°C and allowed to stand for 10 hours to precipitate ammonium metavanadate solid, which is then filtered to obtain ammonium metavanadate solid and filtrate III.

[0067] (5) Add 450 g of anion exchange resin to the filtrate III and perform ion exchange for 5 h to obtain a molybdenum-rich filtrate.

[0068] (6) Add hydrochloric acid solution (volume concentration 36%) to the molybdenum-rich filtrate to adjust the pH value to 2.0, and then evaporate and crystallize at 60° C. to obtain molybdic acid solid.

[0069] Example 6 The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation comprises the following steps: (1) 5 kg of slurry bed residual oil hydrogenation waste catalyst was placed in a heating furnace, and the heating furnace was heated to 1100° C. At the same time, a mixed gas of water vapor and oxygen was continuously introduced, and the flow ratio of water vapor to oxygen was 3.0:1.0. The waste catalyst was heated for 2 minutes to obtain the waste catalyst.

[0070] (2) 1500 g of the spent catalyst after hydrocarbon removal was mixed with 450 g of sodium carbonate (AR, 99%) and 5600 g of deionized water, stirred evenly, heated in a water bath at 70° C., heated for 4 h, and then filtered to obtain filtrate I.

[0071] (3) Add 330 g of ammonium chloride (AR, 99.5%) to filtrate I, stir evenly, then add an appropriate amount of sodium hydroxide (AR, 96%), adjust the pH of the filtrate to 9.5, and obtain filtrate II.

[0072] (4) The filtrate II is cooled to 15°C and allowed to stand for 10 hours to precipitate ammonium metavanadate solid, which is then filtered to obtain ammonium metavanadate solid and filtrate III.

[0073] (5) Add 450 g of anion exchange resin to the filtrate III and perform ion exchange for 5 h to obtain a molybdenum-rich filtrate.

[0074] (6) Add hydrochloric acid solution (volume concentration 36%) to the molybdenum-rich filtrate to adjust the pH value to 2.0, and then evaporate and crystallize at 60° C. to obtain molybdic acid solid.

[0075] Comparative Example 1 The difference from Example 1 is that in step (1), the flow ratio of water vapor to oxygen is too large.

[0076] The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation comprises the following steps: (1) 5 kg of slurry bed residual oil hydrogenation waste catalyst was put into a heating furnace, and the heating furnace was heated to 1200°C. At the same time, a mixed gas of water vapor and oxygen was continuously introduced, and the flow ratio of water vapor to oxygen was 20.0:1.0. The waste catalyst was heated for 3 minutes to obtain the waste catalyst.

[0077] (2) 1500 g of the spent catalyst after hydrocarbon removal was mixed with 400 g of sodium carbonate (AR, 99%) and 5000 g of deionized water, stirred evenly, heated in a water bath at 85° C., heated for 3 h, and then filtered to obtain filtrate I.

[0078] (3) Add 300 g of aqueous ammonia (AR, 25-28%) to filtrate I and adjust the pH of the filtrate to 8.5 to obtain filtrate II.

[0079] (4) The filtrate II was cooled to 30°C and allowed to stand for 6 hours to precipitate ammonium metavanadate solid, which was filtered to obtain ammonium metavanadate solid and filtrate III.

[0080] (5) Add 400 g of anion exchange resin to the filtrate III and perform ion exchange for 3 h to obtain a molybdenum-rich filtrate.

[0081] (6) adding nitric acid solution (mass concentration 68%) to the molybdenum-rich filtrate, adjusting the pH value to 2.0, and then evaporating and crystallizing at 65° C. to obtain molybdic acid solid.

[0082] Comparative Example 2 The difference from Example 1 is that in step (1), the flow ratio of water vapor to oxygen is too small.

[0083] The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation comprises the following steps: (1) 5 kg of slurry bed residue oil hydrogenation waste catalyst was placed in a heating furnace, and the heating furnace was heated to 1200°C. A mixed gas of water vapor and oxygen was continuously introduced at a flow ratio of water vapor to oxygen of 0.2:1.0. The waste catalyst was heated for 3 minutes to obtain the waste catalyst.

[0084] (2) 1500 g of the spent catalyst after hydrocarbon removal was mixed with 400 g of sodium carbonate (AR, 99%) and 5000 g of deionized water, stirred evenly, heated in a water bath at 85° C., heated for 3 h, and then filtered to obtain filtrate I.

[0085] (3) Add 300 g of aqueous ammonia (AR, 25-28%) to filtrate I and adjust the pH of the filtrate to 8.5 to obtain filtrate II.

[0086] (4) The filtrate II was cooled to 30°C and allowed to stand for 6 hours to precipitate ammonium metavanadate solid, which was filtered to obtain ammonium metavanadate solid and filtrate III.

[0087] (5) Add 400 g of anion exchange resin to the filtrate III and perform ion exchange for 3 h to obtain a molybdenum-rich filtrate.

[0088] (6) adding nitric acid solution (mass concentration 68%) to the molybdenum-rich filtrate, adjusting the pH value to 2.0, and then evaporating and crystallizing at 65° C. to obtain molybdic acid solid.

[0089] Comparative Example 3 The difference from Example 1 is that in step (1), the heating treatment time is too long.

[0090] The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation comprises the following steps: (1) 5 kg of slurry bed residue oil hydrogenation waste catalyst was placed in a heating furnace, and the heating furnace was heated to 1200°C. A mixed gas of water vapor and oxygen was continuously introduced at a flow ratio of water vapor to oxygen of 3.0:1.0. The waste catalyst was heated for 100 minutes to obtain the waste catalyst.

[0091] (2) 1500 g of the spent catalyst after hydrocarbon removal was mixed with 400 g of sodium carbonate (AR, 99%) and 5000 g of deionized water, stirred evenly, heated in a water bath at 85° C., heated for 3 h, and then filtered to obtain filtrate I.

[0092] (3) Add 300 g of aqueous ammonia (AR, 25-28%) to filtrate I and adjust the pH of the filtrate to 8.5 to obtain filtrate II.

[0093] (4) The filtrate II was cooled to 30°C and allowed to stand for 6 hours to precipitate ammonium metavanadate solid, which was filtered to obtain ammonium metavanadate solid and filtrate III.

[0094] (5) Add 400 g of anion exchange resin to the filtrate III and perform ion exchange for 3 h to obtain a molybdenum-rich filtrate.

[0095] (6) adding nitric acid solution (mass concentration 68%) to the molybdenum-rich filtrate, adjusting the pH value to 2.0, and then evaporating and crystallizing at 65° C. to obtain molybdic acid solid.

[0096] Table 4 Recovery and purity of vanadium and molybdenum Vanadium component recovery rate (%) Molybdenum component recovery rate (%) Purity of ammonium metavanadate (%) Molybdic acid purity (%) Example 1 97.2 97.4 97.5 97.1 Example 2 96.6 96.7 97.4 97.7 Example 3 96.2 97.4 97.3 97.2 Example 4 96.6 97.3 97.5 97.6 Example 5 96.7 96.9 97.4 97.8 Example 6 97.9 98.7 97.5 97.5 Comparative Example 1 75.6 70.7 96.9 95.3 Comparative Example 2 85.7 72.8 97.5 95.4 Comparative Example 3 88.4 71.3 98.9 95.8 *Calculation method: vanadium component recovery rate (%) = (mass of vanadium in product / mass of vanadium in raw material) * 100; Molybdenum component recovery rate (%) = (mass of molybdenum in product / mass of molybdenum in raw material) * 100; The purity test method of ammonium metavanadate shall be in accordance with HG / T 3445-2003; Molybdic acid purity (%) = (mass fraction of molybdenum obtained by ICP method) / (mass fraction of molybdenum in theoretical molybdic acid) * 100.

[0097] As shown in Table 4, the scheme of the present invention can effectively recover vanadium and molybdenum metals, and obtain a high metal recovery rate and a high-purity product. Comparative Examples 1-2 show that the ratio of water vapor and oxygen needs to be controlled within a reasonable range to obtain a better recovery and extraction effect. If the oxygen introduction ratio is too large, it is easy to oxidize to form nickel molybdate, and nickel molybdate is difficult to separate molybdenum and nickel in the subsequent hydrometallurgical process; if the oxygen ratio is too small, the oxidation degree is too low, and the efficiency is too low, and the recovery rate will also be reduced. Comparative Example 3 shows that the heating treatment time under water vapor and oxygen atmosphere is too long, and it is also easy to oxidize to form nickel molybdate, which increases the difficulty of subsequent hydrometallurgy and reduces the recovery rate.

[0098] The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the specification of the present invention, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation, characterized in that: The steps include: (1) Using the spent catalyst from slurry bed residue oil hydrogenation as raw material, steam and oxygen are introduced into the catalyst during heating to obtain the spent catalyst; (2) The waste catalyst obtained is mixed with alkaline reagent A and water, heated for leaching, and filtered to obtain filtrate I; (3) Add alkaline reagent B to filtrate I and adjust the pH to 8.0-11.0 to obtain filtrate II; (4) Cooling the filtrate II and allowing it to stand to precipitate ammonium metavanadate solid and obtain filtrate III; (5) removing the remaining metavanadate ions from the filtrate III using an anion exchange resin to obtain a molybdenum-rich filtrate; (6) The pH of the molybdenum-rich filtrate is adjusted to acidic, and then evaporated and crystallized to obtain molybdic acid solid.

2. The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation according to claim 1, characterized in that: The heating treatment is heating to 800-1400° C. and maintaining for 1-60 minutes; the flow ratio of water vapor and oxygen is 1.0-6.0:1.

0.

3. The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation according to claim 1, characterized in that: The molar ratio of the waste catalyst to the alkaline reagent A is 1.0:1.5-3.5, the molar amount of vanadium in the waste catalyst is calculated as V2O5, the molar amount of molybdenum in the waste catalyst is calculated as MoO3, and the molar ratio of the waste catalyst to the alkaline reagent A is calculated according to the total molar amount of V2O5 and MoO3 and the molar amount of the alkaline reagent A.

4. The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation according to claim 1, characterized in that: The molar ratio of the alkaline reagent A to water is 1.0:50.0-100.

0.

5. The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation according to any one of claims 1 to 4, characterized in that: The heating leaching is performed at 40-130° C. for 1-10 hours.

6. The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation according to claim 1, characterized in that: The alkaline agent B includes ammonium chloride and / or ammonia water.

7. The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation according to claim 1 or 6, characterized in that: The final temperature of the cooling treatment is 20-85°C; the standing time is 3-24h.

8. The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation according to claim 1, characterized in that: The mass ratio of the anion exchange resin to the filtrate III is 0.05-0.3:1.

0.

9. The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation according to claim 1, characterized in that: The pH value of the molybdenum-rich filtrate after pH adjustment is 0.4-3.

5.

10. The method for recovering metals from spent catalysts for slurry bed residue oil hydrogenation according to claim 1, 8 or 9, characterized in that: The temperature of the evaporation crystallization is 40-65°C.