A method for comprehensive recovery of nickel, vanadium and molybdenum from vanadium-containing oil hydrofining waste catalyst

Abstract

The application provides a method for comprehensively recovering nickel, vanadium and molybdenum from vanadium-containing residue oil hydrogenation waste catalyst, and relates to the field of metal resource recovery. The method comprises the following steps: the waste catalyst is subjected to deoiling, crushing, briquetting, smelting enrichment, atomization and powder spraying to obtain an alloy powder; the alloy powder is mixed with sodium carbonate to perform alkali fusion roasting and water immersion; the water immersion liquid is subjected to vanadium precipitation, drying and calcination to obtain vanadium pentoxide; the vanadium precipitation filtrate is subjected to ion exchange, elution, molybdenum precipitation, drying and calcination to obtain molybdenum trioxide; the water immersion residue is subjected to acid immersion, iron removal by oxidation, nickel extraction enrichment, back extraction, evaporation crystallization and centrifugal separation to obtain nickel nitrate crystals. The method realizes the synergistic and efficient recovery of nickel, vanadium and molybdenum, has high metal recovery rate, high product purity, compact process and is suitable for industrialized production.

Description

Technical Field

[0001] This application relates to the field of metal resource recovery, and in particular to a method for the comprehensive recovery of nickel, vanadium, and molybdenum from hydrogenation waste catalysts containing vanadium residue oil. Background Technology

[0002] Molybdenum-nickel and vanadium-containing residue hydrogenation catalyst waste is a typical solid waste from the petrochemical industry, containing valuable metals such as nickel, molybdenum, and vanadium. Global annual production reaches hundreds of thousands of tons, and direct landfilling or stockpiling would result in resource waste and environmental pollution.

[0003] Currently, recycling processes are mainly divided into pyrometallurgical processes and hydrometallurgical processes. Pyrometallurgical processes (such as reduction smelting and sodium roasting) suffer from high energy consumption, significant metal volatilization losses, and difficulties in flue gas treatment. Hydrometallurgical processes use acid or alkali leaching to dissolve the metal, followed by separation through precipitation, extraction, or ion exchange. However, existing methods are mostly designed for the recovery of single or two metals, making it difficult to achieve efficient and coordinated separation of nickel, molybdenum, and vanadium. Alkali leaching can preferentially leach vanadium and molybdenum, but the nickel residue requires separate treatment; acid leaching can leach all three metals simultaneously, but the leachate composition is complex, and the separation process is lengthy. Furthermore, existing processes generally suffer from high acid / alkali consumption, severe equipment corrosion, repeated pH adjustments, large additions of ammonium salts or extractants, and large emissions of wastewater and exhaust gases.

[0004] Existing technologies employ a combined pyrometallurgical and hydrometallurgical process, but this suffers from drawbacks such as poor unit integration, significant material transfer losses, and high auxiliary material consumption. For vanadium-containing residue oil hydrogenation waste catalysts, due to the significant differences in chemical properties between vanadium and nickel / molybdenum, a comprehensive recovery method that is compact, has a high recovery rate, and is clean and environmentally friendly is currently lacking. Summary of the Invention

[0005] The purpose of this application is to provide a method for the comprehensive recovery of nickel, vanadium, and molybdenum from hydrogenation waste catalysts containing vanadium residue oil, so as to solve the above-mentioned problems.

[0006] To achieve the above objectives, this application adopts the following technical solution: This application provides a method for the comprehensive recovery of nickel, vanadium, and molybdenum from vanadium-containing residue hydrotreating waste catalyst, comprising: The spent catalyst from the hydrogenation of vanadium-containing residue oil was subjected to a series of processes, including deoiling, crushing, pelletizing, smelting and enrichment, and atomization spraying, to obtain alloy powder. The alloy powder is mixed with sodium carbonate, and the resulting mixture is subjected to alkali fusion roasting treatment. The resulting alkali fusion product is then subjected to water leaching treatment to obtain water leaching solution and water leaching residue. The aqueous leaching solution is subjected to vanadium precipitation treatment, and the obtained vanadium precipitation product is subjected to a first drying treatment and a first calcination treatment in sequence to obtain vanadium pentoxide; the vanadium precipitation filtrate obtained from the vanadium precipitation treatment is subjected to ion exchange resin adsorption treatment, elution treatment, molybdenum precipitation treatment, a second drying treatment, and a second calcination treatment in sequence to obtain molybdenum trioxide. The filter residue produced by the water leaching treatment is subjected to acid leaching to obtain a leachate; the leachate is then subjected to oxidation to remove iron, extraction to enrich nickel, and back-extraction to obtain nickel nitrate crystals.

[0007] Optionally, based on the mass of the vanadium-containing residue oil hydrogenation waste catalyst, it includes 50-95% molybdenum-nickel waste catalyst and 5-50% molybdenum-nickel residue oil waste catalyst; The molybdenum-nickel waste catalyst, by mass fraction of chemical elements, comprises: 5-10% carbon, 40-50% aluminum, 1-6% nickel, and 8-15% molybdenum; The molybdenum-nickel residue catalyst, by mass fraction of chemical elements, includes: 10-20% carbon, 40-50% aluminum, and 5-15% vanadium.

[0008] Optionally, the particle size of the material obtained by the crushing process is no greater than 200 mesh.

[0009] Optionally, in the pelletizing process, the vanadium-containing residue hydrogenation waste catalyst, coke, glass powder, borax, limestone, sodium carbonate, and fluorite that have been pulverized are used for pelletizing, and the mass ratio of the vanadium-containing residue hydrogenation waste catalyst, the coke, the glass powder, the borax, the limestone, the sodium carbonate, and the fluorite is 100:50-15:60-100:2-10:20-60:20-60:1-8.

[0010] Optionally, the pellets obtained by the pelletizing process have a diameter of 4-8 cm.

[0011] Optionally, the smelting enrichment treatment is carried out at a temperature of 1300-1800℃ for 1-3 hours.

[0012] Optionally, the mass ratio of the alloy powder to the sodium carbonate is 1.5-2:1.

[0013] Optionally, the alkali fusion roasting treatment is carried out at a temperature of 500-600℃ for 2-4 hours.

[0014] Optionally, the liquid-to-solid ratio of the water immersion treatment is 5-8 mL:1 g, the immersion temperature is 60-100℃, and the immersion time is 3-5 h.

[0015] Optionally, the precipitant used in the vanadium precipitation treatment includes ammonium sulfate.

[0016] Optionally, the temperature of the first drying process is 80-100℃, and the time is 2-4 hours.

[0017] Optionally, the temperature of the first calcination treatment is 450-550℃, and the time is 2-3 hours.

[0018] Optionally, the ion exchange resin includes anion exchange resin.

[0019] Optionally, the eluent used in the elution process includes ammonia.

[0020] Optionally, the precipitant used in the molybdenum precipitation treatment includes sulfuric acid.

[0021] Optionally, the pH value of the molybdenum precipitation treatment is 1.5-2, and the precipitation temperature is 50-70℃.

[0022] Optionally, the temperature of the second drying process is 200-300℃, and the time is 1-3 hours.

[0023] Optionally, the second calcination treatment is carried out at a temperature of 450-550℃ for 2-3 hours.

[0024] Optionally, the acid leaching treatment includes: a normal pressure acid leaching treatment and a high pressure acid leaching treatment performed sequentially.

[0025] Optionally, the sulfuric acid concentration used in the atmospheric pressure acid leaching treatment is 3-5 mol / L, the leaching temperature is 60-70℃, and the leaching time is 6-8 h.

[0026] Optionally, the sulfuric acid concentration used in the high-pressure acid leaching treatment is 5-7 mol / L, the leaching temperature is 150-180℃, the pressure is 0.8-1.0 MPa, and the leaching time is 5-8 h.

[0027] Optionally, the oxidant used in the iron removal process includes H2O2.

[0028] Optionally, the pH of the iron removal oxidation treatment is 4.0-4.5, and the precipitation temperature is 70-80℃.

[0029] Optionally, the extractant used in the nickel extraction enrichment process includes P2O4, and the extraction ratio is O / A = 1:1-3.

[0030] Optionally, the extraction temperature for the nickel enrichment treatment is 30-40℃, and the extraction time is 5-8 min.

[0031] Optionally, the stripping agent used in the stripping process is a 3 mol / L nitric acid solution, and the stripping ratio O / A = 2-3:1.

[0032] Optionally, the back-extraction time for the back-extraction process is 8-10 minutes.

[0033] Optionally, after the back-extraction process, the process further includes sequential evaporation, cooling crystallization, and centrifugal separation. The evaporation process is carried out at a pressure of -0.06 to -0.08 MPa and a temperature of 50-70°C. The temperature for the cooling crystallization process is 30-40℃; The centrifugal separation process is carried out at a speed of 2000-2500 rpm.

[0034] Compared with the prior art, the beneficial effects of this application include: This application provides a method for the comprehensive recovery of nickel, vanadium, and molybdenum from spent catalysts in the hydrogenation of vanadium-containing residue oil. The method involves pre-enriching valuable metals in the spent catalyst into alloy powder using a pyrometallurgical unit, followed by alkaline fusion roasting and water leaching to achieve efficient separation of vanadium, molybdenum, and nickel. Vanadium and molybdenum are then recovered through two pathways in the water leaching solution: vanadium precipitation and ion exchange-molybdenum precipitation, respectively. Nickel is enriched in the water leaching residue and recovered as nickel nitrate crystals through acid leaching, iron removal, extraction, and back-extraction. This method organically combines pyrometallurgical and hydrometallurgical processes, enabling the recovery of nickel, vanadium, and molybdenum in the forms of vanadium pentoxide, molybdenum trioxide, and nickel nitrate crystals, respectively. The product forms are clearly defined, the overall metal recovery rate is high, and the operations of each unit are seamlessly integrated, eliminating the need for repeated transfer of intermediate materials and resulting in a compact process.

[0035] Compared with existing technologies: First, this application, through a stepwise separation strategy of pyrometallurgical pre-enrichment followed by alkali fusion and water leaching, avoids the difficulties and lengthy processes associated with the separation of vanadium, molybdenum, and nickel after co-dissolution in traditional acid leaching methods. This fundamentally reduces the complexity of metal ions in the leachate and alleviates the burden of subsequent separation and purification. Second, the filtrate generated after vanadium precipitation directly enters the ion exchange system. Utilizing the selective adsorption characteristics of anion exchange resin for molybdate, deep separation of molybdenum from residual impurities is achieved. Combined with ammonia elution and sulfuric acid precipitation of molybdenum, high-purity ammonium molybdate intermediates can be obtained without repeated pH adjustments or the addition of large amounts of ammonium salts. The process is clean and generates minimal waste. Third, after the water leaching residue leachate is oxidized to remove iron impurities, a back-extraction system is used for selective enrichment of nickel. After back-extraction, nickel nitrate crystals are directly obtained by evaporation and crystallization. This eliminates the need for additional precipitants or system conversion steps in conventional processes. The process is short, simple to operate, and easy to implement for industrial production. Attached Figure Description

[0036] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0037] Figure 1This is a schematic diagram of the process flow for the comprehensive recovery of nickel, vanadium, and molybdenum from hydrogenation waste catalyst of vanadium-containing residue oil, provided in the embodiments. Detailed Implementation

[0038] As used in this article: "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0039] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0040] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0041] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0042] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (where K is any number representing a multiplier). It is important to understand that, unlike parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0043] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0044] To better explain the technical solution provided in this application, the technical solution provided in this application will be described in general before the specific implementation.

[0045] This application provides a method for the comprehensive recovery of nickel, vanadium, and molybdenum from vanadium-containing residue hydrotreating waste catalyst, comprising: The spent catalyst from the hydrogenation of vanadium-containing residue oil was subjected to a series of processes, including deoiling, crushing, pelletizing, smelting and enrichment, and atomization spraying, to obtain alloy powder. The alloy powder is mixed with sodium carbonate, and the resulting mixture is subjected to alkali fusion roasting treatment. The resulting alkali fusion product is then subjected to water leaching treatment to obtain water leaching solution and water leaching residue. The aqueous leaching solution is subjected to vanadium precipitation treatment, and the obtained vanadium precipitation product is subjected to a first drying treatment and a first calcination treatment in sequence to obtain vanadium pentoxide; the vanadium precipitation filtrate obtained from the vanadium precipitation treatment is subjected to ion exchange resin adsorption treatment, elution treatment, molybdenum precipitation treatment, a second drying treatment, and a second calcination treatment in sequence to obtain molybdenum trioxide. The filter residue produced by the water leaching treatment is subjected to acid leaching to obtain a leachate; the leachate is then subjected to oxidation to remove iron, extraction to enrich nickel, and back-extraction to obtain nickel nitrate crystals.

[0046] Based on the mass of the vanadium-containing residue oil hydrogenation waste catalyst as 100%, it includes 50-95% molybdenum-nickel waste catalyst and 5-50% molybdenum-nickel residue oil waste catalyst; The molybdenum-nickel waste catalyst, by mass fraction of chemical elements, comprises: 5-10% carbon, 40-50% aluminum, 1-6% nickel, and 8-15% molybdenum; The molybdenum-nickel residue catalyst, by mass fraction of chemical elements, includes: 10-20% carbon, 40-50% aluminum, and 5-15% vanadium.

[0047] In one optional embodiment, the particle size of the material obtained by the pulverization process is no greater than 200 mesh.

[0048] In an optional embodiment, the pelletizing process uses the pulverized vanadium-containing residue hydrogenation waste catalyst, coke, glass powder, borax, limestone, sodium carbonate, and fluorite for pelletizing, wherein the mass ratio of the pulverized vanadium-containing residue hydrogenation waste catalyst, the coke, the glass powder, the borax, the limestone, the sodium carbonate, and the fluorite is 100:5-15:60-100:2-10:20-60:20-60:1-8.

[0049] In one optional embodiment, the pellets produced by the pelletizing process have a diameter of 4-8 cm.

[0050] In one optional embodiment, the smelting enrichment treatment is carried out at a temperature of 1300-1800°C for 1-3 hours.

[0051] Optionally, the temperature for the smelting enrichment treatment is 1300℃, 1400℃, 1500℃, 1600℃, 1700℃, 1800℃, or any value between 1300℃ and 1800℃; the time can be 1h, 2h, 3h, or any value between 1h and 3h.

[0052] In one optional embodiment, the mass ratio of the alloy powder to the sodium carbonate is 1.5-2:1.

[0053] Optionally, the mass ratio of alloy powder to sodium carbonate can be 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, or any value between 1.5 and 2:1.

[0054] In one optional embodiment, the alkali fusion roasting treatment is performed at a temperature of 500-600°C for 2-4 hours.

[0055] Optionally, the temperature of the alkali fusion roasting treatment can be 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃, or any value between 500℃ and 600℃; the alkali fusion roasting time can be 2h, 3h, 4h, or any value between 2h and 4h.

[0056] In one optional embodiment, the liquid-to-solid ratio of the water immersion treatment is 5-8 mL:1 g, the immersion temperature is 60-100 °C, and the immersion time is 3-5 h.

[0057] Optionally, the liquid-to-solid ratio for water immersion treatment can be 5 mL:1 g, 6 mL:1 g, 7 mL:1 g, 8 mL:1 g, or any value between 5 and 8 mL:1 g; the water immersion temperature can be 60℃, 70℃, 80℃, or any value between 60 and 100℃; and the immersion time can be 3 h, 4 h, 5 h, or any value between 3 and 5 h.

[0058] In an optional embodiment, the precipitant used in the vanadium precipitation treatment includes ammonium sulfate.

[0059] In one optional embodiment, the temperature of the first drying process is 80-100°C, and the time is 2-4 hours.

[0060] Optionally, the temperature of the first drying treatment can be 80℃, 90℃, 100℃, or any value between 80℃ and 100℃; the time of the first drying treatment can be 2h, 3h, 4h, or any value between 2h and 4h.

[0061] In one optional embodiment, the temperature of the first calcination treatment is 450-550°C, and the time is 2-3 hours.

[0062] Optionally, the temperature of the first stage of treatment can be 450℃, 460℃, 470℃, 480℃, 490℃, 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, or any value between 450℃ and 550℃; the first calcination time can be 2h, 3h, or any value between 2h and 3h.

[0063] In an optional embodiment, the ion exchange resin comprises anion exchange resin (D314).

[0064] In one optional embodiment, the eluent used in the elution process includes ammonia.

[0065] In an optional embodiment, the precipitant used in the molybdenum precipitation treatment includes sulfuric acid.

[0066] In one optional embodiment, the precipitation pH of the molybdenum precipitation treatment is 1.5-2, and the precipitation temperature is 50-70°C.

[0067] Optionally, the precipitation pH value of the molybdenum precipitation treatment can be 1.5, 1.6, 1.7, 1.8, 1.9, 2, or any value between 1.5 and 2; the precipitation temperature can be 50℃, 60℃, 70℃, or any value between 50℃ and 70℃.

[0068] In one optional embodiment, the temperature of the second drying process is 200-300°C, and the time is 1-3 hours.

[0069] Optionally, the temperature of the second drying process can be 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, or any value between 200℃ and 300℃.

[0070] In one optional embodiment, the second calcination treatment is carried out at a temperature of 450-550°C for 2-3 hours.

[0071] Optional. The temperature of the second calcination treatment can be 450℃, 460℃, 470℃, 480℃, 490℃, 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, or any value between 450℃ and 550℃; the time of the second calcination treatment can be 2h, 3h, or any value between 2h and 3h.

[0072] In one optional embodiment, the acid leaching treatment includes: a normal pressure acid leaching treatment and a high pressure acid leaching treatment performed sequentially.

[0073] In one optional embodiment, the sulfuric acid concentration used in the atmospheric pressure acid leaching treatment is 3-5 mol / L, the leaching temperature is 60-70℃, and the leaching time is 6-8 h.

[0074] Optionally, the concentration of sulfuric acid used in the atmospheric pressure acid leaching treatment can be 3 mol / L, 4 mol / L, 1 mol / L, or any value between 3 and 5 mol / L; the leaching temperature can be 60℃, 62℃, 64℃, 66℃, 68℃, 70℃, or any value between 60 and 70℃; and the leaching time can be 67 h, 8 h, or any value between 6 and 8 h.

[0075] In one optional embodiment, the sulfuric acid concentration used in the high-pressure acid leaching treatment is 5-7 mol / L, the leaching temperature is 150-180℃, the pressure is 0.8-1.0 MPa, and the leaching time is 4-8 h.

[0076] Optionally, the concentration of sulfuric acid used in the high-pressure acid leaching treatment can be 5 mol / L, 6 mol / L, 7 mol / L, or any value between 5 and 7 mol / L; the pressure of the high-pressure acid leaching treatment can be 0.8 MPa, 0.9 MPa, 1.0 MPa, or any value between 0.8 and 1.0 MPa; and the leaching time can be 4 h, 5 h, 6 h, 7 h, 8 h, or any value between 4 and 8 h.

[0077] In an optional embodiment, the oxidant used in the iron removal process includes H2O2.

[0078] In one optional embodiment, the pH of the iron removal oxidation treatment is 4.0-4.5, and the precipitation temperature is 70-80℃.

[0079] Optionally, the pH value of the iron removal oxidation treatment can be 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, or any value between 4.0 and 4.5; the precipitation temperature can be 70℃, 72℃, 74℃, 76℃, 78℃, 80℃, or any value between 70 and 80℃.

[0080] In an optional embodiment, the extractant used in the nickel extraction enrichment process comprises P2O4, with an extraction ratio of O / A = 1:1-3.

[0081] Optionally, the extraction ratio O / A in the nickel extraction enrichment process can be 1:1, 1:2, 1:3, or any value between 1:1 and 3.

[0082] In one optional embodiment, the extraction temperature for the nickel enrichment treatment is 30-40°C, and the extraction time is 5-8 min.

[0083] Optionally, the extraction temperature for nickel enrichment treatment can be 30℃, 35℃, 40℃, or any value between 30℃ and 40℃; the extraction time can be 5 min, 6 min, 7 min, 8 min, or any value between 5 min and 8 min.

[0084] In an optional embodiment, the stripping agent used in the stripping process is a 3 mol / L nitric acid solution, and the stripping ratio O / A = 2-3:1.

[0085] Optionally, the back-extraction ratio in the back-extraction process can be 2:1, 3:1, or any value between 2 and 3:1.

[0086] In one optional implementation, the back-extraction time is 8-10 minutes.

[0087] Optionally, the back-extraction time can be 8 min, 9 min, 10 min, or any value between 8 and 10 min.

[0088] In an optional embodiment, after the back-extraction process, the process further includes sequential evaporation, cooling crystallization, and centrifugation. The evaporation process is carried out at a pressure of -0.06 to -0.08 MPa and a temperature of 50-70°C. The temperature for the cooling crystallization process is 30-40℃; The centrifugal separation process is carried out at a speed of 2000-2500 rpm.

[0089] Optionally, the pressure of the evaporation treatment can be -0.06 MPa, -0.07 MPa, -0.08 MPa, or any value between -0.06 and -0.08 MPa; the temperature of the evaporation treatment can be 50℃, 60℃, 70℃, or any value between 50℃ and 70℃.

[0090] Optionally, the temperature for the cooling crystallization process can be 30°C, 35°C, 40°C, or any value between 30°C and 40°C.

[0091] Optionally, the centrifugal separation speed can be 2000 rpm, 2100 rpm, 2200 rpm, 2300 rpm, 2400 rpm, 2500 rpm, or any value between 2000 and 2500 rpm.

[0092] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0093] The chemical composition of the vanadium-containing residue hydrotreating waste catalyst used in the examples and comparative examples is shown in the table below: Table 1 Chemical composition of spent catalyst from vanadium-containing residue hydrotreating

[0094] Example 1 This embodiment provides a method for the comprehensive recovery of nickel, vanadium, and molybdenum from spent catalyst from vanadium-containing hydrotreating oil. The process flow is as follows: Figure 1 As shown, the specific steps are as follows: Vanadium-containing slag oil hydrogenation waste catalyst was deoiled in a cracking kiln. The deoiled material was then pulverized to a particle size no larger than 200 mesh. The pulverized material was then mixed uniformly with coke, glass powder, borax, limestone, sodium carbonate, and fluorite in a mass ratio of 100:8:80:5:40:40:3, and pelletized to obtain pellets with a diameter of 5 cm. These pellets were placed in a melting furnace and smelted and enriched at 1600℃ for 2 hours. The enriched material was then atomized and sprayed to obtain alloy powder.

[0095] Alloy powder and sodium carbonate were mixed evenly at a mass ratio of 1.8:1. The resulting mixture was then subjected to alkali fusion roasting at 550℃ for 3 hours. The resulting alkali fusion product was then subjected to water leaching treatment with a water-to-solid ratio of 6.5:1 (L / kg), a leaching temperature of 80℃, and a leaching time of 4 hours, yielding water leaching solution and water leaching residue.

[0096] The aqueous leaching solution was subjected to vanadium precipitation treatment with ammonium sulfate as the vanadium precipitant. The resulting ammonium metavanadate precipitate was first dried at 90℃ for 3 hours, and then calcined at 500℃ for 2.5 hours to obtain vanadium pentoxide product with a purity of 98.6% and a vanadium recovery rate of 96.2%.

[0097] The vanadium precipitation filtrate obtained from the vanadium precipitation treatment was adsorbed onto an anion exchange resin (D314, purchased from Zhejiang Zhengguang Industry) using ammonia as the eluent. The eluent was then treated with sulfuric acid to precipitate molybdenum, controlling the pH of the precipitation at 1.8 and the precipitation temperature at 60℃. The resulting molybdic acid precipitate was then subjected to a second drying treatment at 250℃ for 1 hour, followed by a second calcination treatment at 500℃ for 2.5 hours to obtain molybdenum trioxide product with a purity of 99.1% and a molybdenum recovery rate of 97.5%.

[0098] The water-leached residue was subjected to acid leaching treatment. First, it was leached with 4 mol / L sulfuric acid at 65℃ under normal pressure for 7 hours, followed by high-pressure leaching with 6 mol / L sulfuric acid at 170℃ and 0.9 MPa for 6 hours. The two leachates were combined. H₂O₂ was added to the leachate for oxidation and iron removal, controlling the pH at 4.3 and the precipitation temperature at 75℃. The iron-removed liquid was then extracted with P₂O₄ extractant to enrich nickel, with an extraction ratio of O / A = 1:1, an extraction temperature of 35℃, and an extraction time of 6 minutes. The supported organic phase was back-extracted with 3 mol / L nitric acid solution, with a back-extraction ratio of O / A = 2.5:1 (L / L) and a back-extraction time of 9 minutes. The back-extraction solution was evaporated at -0.07 MPa and 60℃, cooled and crystallized at 35℃, and then centrifuged at 2250 rpm to obtain nickel nitrate crystals with a purity of 98.9% and a nickel recovery rate of 95.8%.

[0099] Example 2 This embodiment provides a method for the comprehensive recovery of nickel, vanadium, and molybdenum from vanadium-containing residue hydrotreating waste catalyst. The difference between this method and Example 1 is that: This embodiment provides a method for the comprehensive recovery of nickel, vanadium, and molybdenum from spent catalyst from vanadium-containing hydrotreating oil. The process flow is as follows: Figure 1 As shown, the specific steps are as follows: The first drying treatment was carried out at a temperature of 100℃ for 4 hours; the first calcination treatment was carried out at a temperature of 550℃ for 3 hours.

[0100] The precipitation pH value of the molybdenum precipitation treatment was 2, and the precipitation temperature was 70℃; the second drying treatment was at a temperature of 300℃ for 1 hour; and the second calcination treatment was at a temperature of 550℃ for 3 hours.

[0101] In the normal pressure acid leaching treatment, the sulfuric acid concentration was 5 mol / L, the leaching temperature was 70℃, and the leaching time was 8 h; in the high pressure acid leaching treatment, the sulfuric acid concentration was 7 mol / L, and the pressure was 1.0 MPa.

[0102] The pH for iron removal by oxidation was 4.5, and the precipitation temperature was 80℃; the extraction temperature for nickel enrichment by extraction was 40℃, and the extraction time was 8 min; the back-extraction treatment had a back-extraction ratio of O / A = 3:1, and the back-extraction time was 10 min.

[0103] The evaporation process was carried out at a pressure of -0.08 MPa and a temperature of 70°C; the cooling crystallization process was carried out at a temperature of 40°C; and the centrifugal separation process was carried out at a speed of 2500 rpm.

[0104] The purity of vanadium pentoxide obtained in this example was determined to be 98.2%, with a vanadium recovery rate of 95.7%; the purity of molybdenum trioxide was 98.8%, with a molybdenum recovery rate of 96.9%; and the purity of nickel nitrate crystals was 98.5%, with a nickel recovery rate of 95.2%.

[0105] Example 3 This embodiment provides a method for the comprehensive recovery of nickel, vanadium, and molybdenum from vanadium-containing residue hydrotreating waste catalyst. The difference between this method and Example 1 is that: The mass ratio of alloy powder to sodium carbonate was 1.5:1; the alkali fusion roasting treatment was carried out at a temperature of 500℃ for 2 hours; the liquid-solid ratio of water immersion treatment was 5:1, and the leaching time was 3 hours.

[0106] The temperature of the first drying treatment is 80℃ and the time is 2 hours; the temperature of the first calcination treatment is 450℃ and the time is 2 hours.

[0107] The precipitation pH value of the molybdenum precipitation treatment was 1.5, and the precipitation temperature was 50℃; the second drying treatment was at a temperature of 200℃ for 1 hour; and the second calcination treatment was at a temperature of 450℃ for 2 hours.

[0108] In the normal pressure acid leaching treatment, the sulfuric acid concentration was 3 mol / L, the leaching temperature was 60℃, and the leaching time was 6 h; in the high pressure acid leaching treatment, the sulfuric acid concentration was 5 mol / L, and the pressure was 0.8 MPa.

[0109] The pH for iron removal by oxidation was 4.0, and the precipitation temperature was 70℃; the extraction temperature for nickel enrichment by extraction was 30℃, and the extraction time was 5 min; the back-extraction treatment had a back-extraction ratio of O / A = 2:1, and the back-extraction time was 8 min.

[0110] The evaporation process was carried out at a pressure of -0.06 MPa and a temperature of 50°C; the cooling crystallization process was carried out at a temperature of 30°C; and the centrifugal separation process was carried out at a speed of 2000 rpm.

[0111] The purity of vanadium pentoxide obtained in this example was determined to be 99.1%, with a vanadium recovery rate of 94.8%; the purity of molybdenum trioxide was 99.4%, with a molybdenum recovery rate of 96.1%; and the purity of nickel nitrate crystals was 99.2%, with a nickel recovery rate of 94.6%.

[0112] Comparative Example 1 The difference between this comparative example and Example 1 is as follows: Without pelletizing, the de-oiled and pulverized waste catalyst powder is directly mixed with coke, glass powder, borax, limestone, sodium carbonate and fluorite in a mass ratio of 100:8:80:5:40:40:3 and then fed into an electric arc furnace for smelting and enrichment. The remaining steps and conditions are the same as in Example 1.

[0113] The vanadium recovery rate of Comparative Example 1 was 88.12%, the molybdenum recovery rate was 89.57%, and the nickel recovery rate was 85.39%; the product purity was 98.21% for vanadium pentoxide, 98.05% for molybdenum trioxide, and 98.17% for nickel nitrate crystals.

[0114] The results showed that when the pelletizing process was omitted and the powder was smelted directly, the powder material was easily lost in large quantities with the flue gas at high temperatures. Furthermore, the contact between the metal and the auxiliary materials was insufficient during the smelting process, resulting in a decrease in the metal enrichment efficiency and a significant decrease in the recovery rates of nickel, molybdenum, and vanadium compared to Example 1.

[0115] Comparative Example 2 The difference between this comparative example and Example 1 is as follows: The molten alloy was not subjected to atomization powder spraying treatment, but was directly poured into cold water for water quenching to obtain alloy particles with a particle size of 5~20mm. The remaining steps and conditions were the same as in Example 1.

[0116] The vanadium recovery rate of Comparative Example 2 was 90.45%, the molybdenum recovery rate was 91.28%, and the nickel recovery rate was 87.63%; the product purity was 98.53% for vanadium pentoxide, 98.41% for molybdenum trioxide, and 98.35% for nickel nitrate crystals.

[0117] The results showed that the alloy particles obtained by water quenching of the alloy melt were too large (5~20mm). During the subsequent alkaline calcination process, the contact area between sodium carbonate and the alloy particles was insufficient, and the conversion reaction of vanadium and molybdenum was incomplete. As a result, some vanadium and molybdenum failed to leach out effectively and remained in the water leaching residue. The recovery rates of the three metals were all lower than those in Example 1.

[0118] Comparative Example 3 The difference between this comparative example and Example 1 is as follows: The vanadium precipitate filtrate was not subjected to anion exchange resin adsorption and ammonia elution treatment. Instead, sulfuric acid was added to adjust the pH to 1.8, and molybdenum precipitation was carried out at 60°C. The remaining steps and conditions were the same as in Example 1.

[0119] The vanadium recovery rate of Comparative Example 3 was 95.18%, the molybdenum recovery rate was 82.36%, and the nickel recovery rate was 93.15%; the product purity was: vanadium pentoxide 99.82%, molybdenum trioxide 96.03%, and nickel nitrate crystals 99.79%.

[0120] The results showed that the vanadium precipitation filtrate contained residual vanadate, iron, aluminum and other impurity ions in addition to molybdate ions. When molybdenum was precipitated directly without adsorption treatment by ion exchange resin, these impurity ions would co-precipitate with molybdate, significantly reducing the purity of the molybdenum trioxide product (from 99.1% in Example 1 to 96.03%). At the same time, due to the interference of impurity ions on the molybdenum precipitation process, the molybdenum recovery rate was also greatly reduced to 82.36%.

[0121] Comparative Example 4 The difference between this comparative example and Example 1 is as follows: The water-leached residue was not subjected to atmospheric pressure acid leaching treatment, but only high-pressure acid leaching (sulfuric acid concentration 6 mol / L, 170℃, 0.9 MPa, 6h), and the remaining steps and conditions were the same as in Example 1.

[0122] The vanadium recovery rate of Comparative Example 4 was 85.25%, the molybdenum recovery rate was 87.68%, and the nickel recovery rate was 88.74%; the product purity was 99.85% for vanadium pentoxide, 99.81% for molybdenum trioxide, and 98.62% for nickel nitrate crystals.

[0123] The results showed that although the leaching intensity of a single acid leaching was high when atmospheric pressure acid leaching was eliminated and only a single high pressure acid leaching was used, it was not conducive to the leaching kinetics of some sparingly soluble nickel compounds in the water leaching residue. The acid leaching process did not form a gradient leaching environment from low concentration acid to high concentration acid, resulting in incomplete nickel leaching and a significant decrease in nickel recovery rate (from 95.8% in Example 1 to 88.74%).

[0124] Comparative Example 5 The difference between this comparative example and Example 1 is as follows: The water-leached residue was first subjected to high-pressure acid leaching (sulfuric acid concentration 6 mol / L, 170℃, 0.9MPa, 6h), and then subjected to normal-pressure acid leaching (sulfuric acid concentration 4 mol / L, 65℃, 7h). The total amount of sulfuric acid used and the total acid leaching time were the same as in Example 1, and the remaining steps and conditions were the same as in Example 1.

[0125] The vanadium recovery rate was 95.21%, the molybdenum recovery rate was 96.70%, and the nickel recovery rate was 90.58%. The product purity was 99.83% for vanadium pentoxide, 99.80% for molybdenum trioxide, and 99.14% for nickel nitrate crystals.

[0126] The results show that placing high-pressure acid leaching before atmospheric-pressure acid leaching, although keeping the total acid concentration and total leaching time unchanged, results in a significant amount of metal rapidly dissolving under strong acid and high-temperature conditions during high-pressure leaching. This leads to a sharp increase in the metal concentration of the mother liquor and a rapid decrease in acidity. Consequently, the leaching driving force in the subsequent atmospheric-pressure acid leaching stage is insufficient, making it difficult to effectively supplement the leaching of residual nickel not leached in the high-pressure stage. This results in a nickel recovery rate significantly lower than in Example 1. This indicates that the order of atmospheric-pressure and high-pressure acid leaching has a significant impact on nickel leaching efficiency, and a gradient leaching method of atmospheric-pressure followed by high-pressure leaching is more conducive to deep nickel recovery.

[0127] The results of the examples and comparative examples are summarized in Table 2: Table 2 Summary of Results from Examples and Comparative Examples

[0128] It is evident that both pelletizing and atomized powder spraying in the pyrometallurgical unit of this application significantly contribute to the metal recovery rate, and their synergistic effect results in uniform alloy powder particle size and high reactivity. In the wet vanadium-molybdenum unit, ion exchange treatment is crucial for ensuring the purity and recovery rate of molybdenum trioxide. In the wet nickel unit, the gradient sequence of atmospheric and high-pressure acid leaching (atmospheric pressure first, then high pressure) is a key technical means to ensure high nickel recovery. Omission, substitution, or reversal of any step will significantly degrade the recovery rate or product purity.

[0129] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0130] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, in the foregoing claims, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A method for the comprehensive recovery of nickel, vanadium, and molybdenum from vanadium-containing residual oil hydrotreating waste catalyst, characterized in that, include: The spent catalyst from the hydrogenation of vanadium-containing residue oil was subjected to a series of processes, including deoiling, crushing, pelletizing, smelting and enrichment, and atomization spraying, to obtain alloy powder. The alloy powder is mixed with sodium carbonate, and the resulting mixture is subjected to alkali fusion roasting treatment. The resulting alkali fusion product is then subjected to water leaching treatment to obtain water leaching solution and water leaching residue. The aqueous leaching solution is subjected to vanadium precipitation treatment, and the obtained vanadium precipitation product is subjected to a first drying treatment and a first calcination treatment in sequence to obtain vanadium pentoxide; the vanadium precipitation filtrate obtained from the vanadium precipitation treatment is subjected to ion exchange resin adsorption treatment, elution treatment, molybdenum precipitation treatment, a second drying treatment, and a second calcination treatment in sequence to obtain molybdenum trioxide. The filter residue produced by the water leaching treatment is subjected to acid leaching to obtain a leachate; the leachate is then subjected to oxidation to remove iron, extraction to enrich nickel, and back-extraction to obtain nickel nitrate crystals.

2. The method for comprehensively recovering nickel, vanadium, and molybdenum from vanadium-containing residual oil hydrogenation waste catalyst according to claim 1, characterized in that, Based on the mass of the vanadium-containing residue oil hydrogenation waste catalyst as 100%, it includes 50-95% molybdenum-nickel waste catalyst and 5-50% molybdenum-nickel residue oil waste catalyst; The molybdenum-nickel waste catalyst, by mass fraction of chemical elements, comprises: 5-10% carbon, 40-50% aluminum, 1-6% nickel, and 8-15% molybdenum; The molybdenum-nickel residue catalyst, by mass fraction of chemical elements, includes: 10-20% carbon, 40-50% aluminum, and 5-15% vanadium.

3. The method for comprehensively recovering nickel, vanadium, and molybdenum from hydrogenation waste 50AC of vanadium-containing residue oil according to claim 1, characterized in that, At least one of the following conditions must be met: A. The particle size of the material obtained by the crushing process is no greater than 200 mesh; B. In the pelletizing process, the vanadium-containing residue hydrogenation waste catalyst, coke, glass powder, borax, limestone, sodium carbonate, and fluorite that have been pulverized are used for pelletizing. The mass ratio of the vanadium-containing residue hydrogenation waste catalyst, coke, glass powder, borax, limestone, sodium carbonate, and fluorite is 100:5-15:60-100:2-10:20-60:20-60:1-8. C. The pellets obtained by the pelletizing process have a diameter of 4-8 cm; D. The temperature of the smelting enrichment treatment is 1300-1800℃, and the time is 1-3h.

4. The method for comprehensively recovering nickel, vanadium, and molybdenum from vanadium-containing residue oil hydrotreating waste catalyst according to claim 1, characterized in that, The mass ratio of the alloy powder to the sodium carbonate is 1.5-2:

1.

5. The method for comprehensively recovering nickel, vanadium, and molybdenum from vanadium-containing residual oil hydrogenation waste catalyst according to claim 1, characterized in that, At least one of the following conditions must be met: E. The alkali fusion roasting treatment is performed at a temperature of 500-600℃ for 2-4 hours; F. The liquid-to-solid ratio of the water immersion treatment is 5-8 mL:1 g, the immersion temperature is 60-100℃, and the immersion time is 3-5 h.

6. The method for comprehensively recovering nickel, vanadium, and molybdenum from vanadium-containing residue oil hydrotreating waste catalyst according to claim 1, characterized in that, At least one of the following conditions must be met: G. The precipitant used in the vanadium precipitation treatment includes ammonium sulfate; H. The temperature of the first drying treatment is 80-100℃, and the time is 2-4 hours; I. The temperature of the first calcination treatment is 450-550℃, and the time is 2-3h.

7. The method for comprehensively recovering nickel, vanadium, and molybdenum from vanadium-containing residue oil hydrotreating waste catalyst according to claim 1, characterized in that, At least one of the following conditions must be met: J. The ion exchange resin includes anion exchange resin; K. The eluent used in the elution process includes ammonia; L. The precipitant used in the molybdenum precipitation treatment includes sulfuric acid; M. The pH value of the molybdenum precipitation treatment is 1.5-2, and the precipitation temperature is 50-70℃; N. The temperature of the second drying treatment is 200-300℃, and the time is 1-3 hours; O. The second calcination treatment is carried out at a temperature of 450-550℃ for 2-3 hours.

8. The method for comprehensively recovering nickel, vanadium, and molybdenum from vanadium-containing residue oil hydrotreating waste catalyst according to claim 1, characterized in that, The acid leaching treatment includes: sequential atmospheric pressure acid leaching treatment and high pressure acid leaching treatment; and satisfies at least one of the following conditions: P. The sulfuric acid concentration used in the atmospheric pressure acid leaching treatment is 3-5 mol / L, the leaching temperature is 60-70℃, and the leaching time is 6-8h; Q. The sulfuric acid concentration used in the high-pressure acid leaching treatment is 5-7 mol / L, the leaching temperature is 150-180℃, the pressure is 0.8-1.0 MPa, and the leaching time is 4-8 h.

9. The method for comprehensively recovering nickel, vanadium, and molybdenum from vanadium-containing residual oil hydrotreating waste catalyst according to claim 1, characterized in that, At least one of the following conditions must be met: R. The oxidant used in the iron removal oxidation process includes H2O2; S. The pH of the iron removal oxidation treatment is 4.0-4.5, and the precipitation temperature is 70-80℃; T. The extractant used in the nickel extraction enrichment process includes P2O4, and the extraction ratio is O / A = 1:1-3; U. The extraction temperature for the nickel enrichment treatment is 30-40℃, and the extraction time is 5-8 min; V. The stripping agent used in the stripping process is a 3 mol / L nitric acid solution, and the stripping ratio O / A = 2-3:1; W. The back-extraction time for the back-extraction process is 8-10 min.

10. The method for comprehensively recovering nickel, vanadium, and molybdenum from vanadium-containing residue hydrotreating waste catalyst according to any one of claims 1-9, characterized in that, Following the back-extraction process, the process further includes sequential evaporation, cooling crystallization, and centrifugation; and must also meet at least one of the following conditions: X. The evaporation process is carried out at a pressure of -0.06 to -0.08 MPa and a temperature of 50-70°C. Y. The temperature for the cooling crystallization process is 30-40℃; Z. The centrifugal separation process is carried out at a speed of 2000-2500 rpm.

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