A method for recovering sodium vanadate from a failed residual oil hydrogenation catalyst by using ultrasonic microbubbles

Abstract

A method for recovering sodium vanadate from spent residue hydrogenation catalyst using ultrasonic microbubbles includes the following steps: (1) mixing the spent residue hydrogenation catalyst and inorganic salt additive evenly and then performing graded ball milling; (2) calcining the ball-milled powder under oxygen-enriched gas; (3) introducing the calcined mixture, leaching agent, and leaching aid into oxygen microbubbles and applying ultrasonic treatment to separate and obtain leachate; (4) adding a purification agent to the leachate for separation to obtain vanadium-containing alkaline solution; (5) simultaneously applying ultrasonic waves and oxygen microbubbles to the vanadium-containing alkaline solution for enhanced oxidation, and finally performing evaporation concentration, crystallization, separation, washing, and drying to obtain sodium vanadate. Through the coordinated operation of the entire process, the process is simple, the operation is continuous, there is no secondary pollution, the energy consumption is low, and the reagent consumption is small. It is suitable for large-scale industrial treatment of spent residue hydrogenation catalyst, thereby achieving the dual goals of hazardous waste resource utilization and environmental governance.

Description

Technical Field

[0001] This application belongs to the field of spent residue hydrotreating catalyst recovery, specifically involving a method for recovering sodium vanadate from spent residue hydrotreating catalyst using ultrasonic microbubbles. Background Technology

[0002] Residue hydrotreating catalysts are core materials used in the petroleum refining industry for hydrodesulfurization, hydronitrogenation, and hydrometallurgical removal of residue oil. With the increasing trend of heavier and lower-quality crude oil, their usage has been increasing year by year, resulting in a large amount of spent residue hydrotreating catalysts. These spent catalysts are classified as hazardous waste, as their surfaces and interiors are deposited with large amounts of carbon and sulfur. The supported metals such as vanadium, molybdenum, and nickel exist in stable forms such as sulfides and oxides. Direct disposal would not only waste strategic metal resources but also cause serious pollution to the soil, water bodies, and other ecological environments. Vanadium, as an important strategic metal, is widely used in steel, chemical, new energy, and aerospace industries, with strong market demand.

[0003] Therefore, it is necessary to develop a method to recover sodium vanadate from spent residue hydrogenation catalysts, thereby realizing the resource utilization of hazardous waste and alleviating the vanadium resource shortage problem. Summary of the Invention

[0004] This application provides a method for recovering sodium vanadate from a spent residue hydrotreating catalyst using ultrasonic microbubbles. The spent residue hydrotreating catalyst is subjected to ball milling, oxygen-enriched roasting, ultrasonic microbubble leaching, and dealuminization and impurity removal, followed by preparation of sodium vanadate using ultrasonic microbubbles. Through synergistic enhancement throughout the entire process, efficient vanadium leaching and efficient aluminum removal are achieved simultaneously, thereby obtaining sodium vanadate.

[0005] In a first aspect, this application provides a method for recovering sodium vanadate from a spent residue hydrotreating catalyst using ultrasonic microbubbles, comprising the following steps:

[0006] Step S1: Mix the spent residue hydrogenation catalyst and inorganic salt additive evenly to obtain the material; ball mill the material to obtain activated ball milled powder;

[0007] Step S2: The activated ball-milled powder is calcined under oxygen-enriched gas to obtain a mixture of spent residue hydrogenation catalyst after oxygen-enriched calcination; the oxygen volume content of the oxygen-enriched gas is ≥80%.

[0008] Step S3: The mixture of the spent residue hydrogenation catalyst after oxygen-enriched roasting and the leaching agent are mixed at a liquid-to-solid ratio of mL:g = 5~10:1, and a leaching slurry is formed after uniform mixing; subsequently, a leaching aid is added to the leaching slurry under ultrasonic and oxygen microbubble conditions for oxidative leaching treatment; wherein the microbubble concentration is 10. 6 ~108 The concentration of the sample is 1 / mL, the ultrasonic frequency is 20~40kHz, the ultrasonic power is 300~600W, the temperature is 60~85℃, and the time is 60~120min; after the oxidation leaching is completed, the sample is separated to obtain leachate A and leachate residue B.

[0009] Step S4: Add a decontaminant to the leachate A for decontamination, and then perform solid-liquid separation to obtain vanadium-containing alkaline solution a and aluminum precipitate slag b;

[0010] Step S5: Enhanced oxidation is carried out in the vanadium-containing alkaline solution a under conditions of simultaneous ultrasound and oxygen microbubbles, wherein the microbubble concentration is 10. 6 ~10 8 The concentration of sodium vanadate was determined by ultrasonic treatment at a frequency of 20-40 kHz, an ultrasonic power of 200-400 W, a temperature of 70-90 °C, and a time of 30-60 min. The vanadium-containing alkaline solution a after enhanced oxidation was then evaporated and concentrated at a temperature of 100-110 °C for 12-24 h. Subsequently, the solution was cooled to room temperature for crystallization, separation, washing, and drying to obtain sodium vanadate.

[0011] This application describes a process for preparing sodium vanadate using controlled ball milling, oxygen-enriched roasting, ultrasonic microbubble leaching, aluminum removal, and ultrasonic microbubble technology. In the leaching process, ultrasonic oxygen microbubbles are used. When these microbubbles contact the liquid phase, a transformation reaction occurs, generating highly oxidizing active oxygen substances: hydroxyl groups, singlet oxygen, and superoxide radicals. Simultaneously, the cavitation effect of ultrasound generates active oxygen in the liquid phase and enhances mass transfer, increasing the contact efficiency between active oxygen and vanadium-containing materials, thus strengthening vanadium leaching kinetics. Furthermore, the ultrasonic microbubbles enhance the oxidation of low-valence vanadium after oxygen-enriched roasting, further improving the vanadium leaching rate. In the sodium vanadate preparation process, ultrasonic oxygen microbubbles are used. The active oxygen generated by the ultrasonic microbubbles enhances the oxidation of vanadium ions in the vanadium-containing alkaline solution a, converting low-valence vanadium ions into stable pentavalent vanadate ions, further improving the purity of sodium vanadate. Through the synergistic effect of the entire process, efficient vanadium leaching and efficient aluminum removal are achieved simultaneously, resulting in the preparation of sodium vanadate.

[0012] In some embodiments, the spent residue hydrotreating catalyst, by mass percentage, comprises the following components: 10-70% Al₂O₃, 3-25% vanadium-containing substances, 1-10% nickel-containing substances, and 1-15% molybdenum-containing substances; the vanadium-containing substances include VO₂, V₂S₃, and vanadium at least partially coated with carbonaceous material; the nickel-containing substances include NiS; and the molybdenum-containing substances include MoS₂ and MoO₂. When these conditions are met, efficient vanadium leaching and efficient aluminum removal can be achieved simultaneously, thereby preparing sodium vanadate.

[0013] In some implementations, step S1 satisfies at least one of the following conditions:

[0014] (1) The mass ratio of the spent residue hydrotreating catalyst to the inorganic salt additive is 100:5~15; the inorganic salt additive includes sodium carbonate and sodium nitrate, and the mass ratio of sodium carbonate to sodium nitrate is 3~5:1;

[0015] (2) The ball mill uses grinding balls, the mass ratio of the grinding balls to the material is 8~15:1, the rotation speed of the ball mill is 200~400 r / min, and the ball milling time is 60~120 min;

[0016] (3) The ball mill uses grinding balls, which include a first grinding ball, a second grinding ball and a third grinding ball in a mass ratio of (2~3):(3~4):(3~5). The diameter of the first grinding ball is 10~15mm, the diameter of the second grinding ball is 5~8mm and the diameter of the third grinding ball is 2~4mm.

[0017] By adjusting the ball milling process conditions to meet the above-mentioned range, this application can achieve efficient crushing of the depleted residue oil hydrogenation catalyst and full exposure of carbon and sulfur deposits, thereby obtaining activated ball milled powder. In synergy with the entire process, it can achieve efficient vanadium leaching and efficient aluminum removal, thereby preparing sodium vanadate.

[0018] In some embodiments, in step S2, the oxygen-enriched gas is introduced at a rate of 0.5~1.5 m / s. 3 The roasting process is carried out in stages. The first stage roasting temperature T1 is 350~450℃, and the time t1 is 30~60min. The second stage roasting temperature T2 is 550~700℃, and the time t2 is 60~120min. By adjusting the oxygen-enriched roasting process conditions to meet the above range, this application can fully burn and remove the carbon and sulfur deposits in the activated ball-milled powder. At the same time, vanadium, aluminum and other metals react with inorganic salt additives to generate soluble salts, thereby achieving full oxidation transformation of vanadium and generation of soluble salts. In synergy with the entire process, it can achieve efficient vanadium leaching and efficient aluminum removal, thereby preparing high-purity sodium vanadate.

[0019] In some embodiments, in step S3, the leaching agent is a sodium hydroxide solution with a concentration of 1.0~2.0 mol / L; the leaching aid includes hydrogen peroxide and sodium hydroxide in a mass ratio of 2~3:1; and the sum of the molar concentrations of the hydrogen peroxide and sodium hydroxide in the leaching aid is 0.5~1.5 mol / L. This application achieves efficient vanadium leaching by adjusting the ultrasonic microbubble leaching process conditions to meet the above ranges. In synergy with the entire process, it can achieve efficient aluminum removal while simultaneously achieving efficient vanadium leaching, thereby preparing sodium vanadate.

[0020] In some embodiments, in step S3, preferably, the microbubble concentration is 4.5 × 10⁻⁶. 7 ~5.5×10 7 The ultrasonic microbubble leaching process, with a concentration of 100 particles per mL, an ultrasonic frequency of 28–32 kHz, an ultrasonic power of 420–480 W, a temperature of 72–78 °C, and a time of 85–95 min, achieves efficient mass transfer of the mixture after oxygen-enriched roasting with the leaching agent and leaching aids through the synergistic effect of ultrasound and microbubbles. This further enhances the oxidation process and achieves efficient vanadium leaching. In conjunction with the entire process, it enables efficient aluminum removal while achieving efficient vanadium leaching, thereby preparing sodium vanadate.

[0021] In some embodiments, in step S4, the impurity remover is dilute sulfuric acid with a concentration of 1.0~2.0 mol / L, an addition rate of 5~10 mL / min, and the pH of the solution is adjusted to 8.5~9.5 by adding the impurity remover; the reaction temperature is 50~70℃, the stirring rate is 150~250 r / min, and the stirring time is 30~60 min. By controlling the aluminum removal process conditions to meet the above ranges, this application can ensure that aluminum in leaching solution A is fully precipitated as aluminum hydroxide. By controlling the addition rate of dilute sulfuric acid, it can avoid the loss of vanadium precipitation due to excessively low local pH. In synergy with the entire process, it can achieve efficient vanadium leaching while simultaneously achieving efficient aluminum removal, thereby preparing sodium vanadate.

[0022] In some embodiments, in step S5, preferably, the microbubble concentration is 4.5 × 10⁻⁶. 7 ~5.5×10 7The ultrasonic frequency is 28-32 kHz, the ultrasonic power is 290-320 W, the temperature is 79-82 °C, and the time is 42-48 min. This application, by controlling the ultrasonic microbubble process conditions to meet the above ranges, further enhances the oxidation process under the synergistic effect of ultrasound and microbubbles. This allows vanadium in the vanadium-containing alkaline solution a to be completely converted into high-valence vanadate ions. In synergy with the entire process, efficient vanadium leaching and efficient aluminum removal can be achieved simultaneously, thereby preparing sodium vanadate.

[0023] In some embodiments, in step S5, the vanadium-containing alkaline solution a is evaporated and concentrated to a solution concentration of 150-200 g / L. When this condition is met, in synergy with the entire process, efficient vanadium leaching and efficient aluminum removal can be achieved simultaneously, thereby preparing sodium vanadate.

[0024] The beneficial effects of this application are at least as follows:

[0025] This technology deeply couples mechanochemical activation, oxygen-enriched roasting, and ultrasonic microbubble technology to recover sodium vanadate from exhausted residue hydrotreating catalysts through a synergistic process. It overcomes the limitations of traditional single-ball milling by employing graded ball milling with mechanochemical activation and inorganic salt additives. The rational gradation of grinding balls of different diameters achieves gradient fragmentation of the catalyst, which, combined with mechanochemical action, causes lattice distortion and exposes active sites. Simultaneously, the inorganic salt additives are pre-mixed with the catalyst, laying the foundation for the oxidation transformation of vanadium in subsequent oxygen-enriched roasting, significantly reducing roasting temperature and energy consumption, and improving vanadium conversion efficiency. A dual-field synergistic system of oxygen-enriched roasting and ultrasonic microbubble-enhanced leaching is constructed. Oxygen-enriched roasting achieves complete removal of carbon and sulfur deposits and preliminary oxidation transformation of vanadium. Ultrasonic microbubbles, through cavitation effects, break the passivation film at the solid-liquid interface during leaching, enhancing mass transfer efficiency. At the same time, oxygen microbubbles provide a sufficient oxidation atmosphere to promote deep oxidation leaching of vanadium, solving the problems of low leaching efficiency and incomplete oxidation in traditional methods. Precise pH control achieves selective dealuminization and impurity removal. Within the range of 8.5 to 9.5, aluminum is efficiently precipitated and removed as aluminum hydroxide, while vanadium is stably retained in the solution as vanadate. The vanadium loss rate is ≤2%, and the aluminum removal rate is ≥95%, solving the pain points of large vanadium loss and incomplete removal in traditional impurity removal processes. Through the strong oxidation and strong mass transfer effect of ultrasonic microbubbles, it is ensured that vanadium in the vanadium-containing alkaline solution is completely converted into high-valence vanadate, avoiding co-precipitation of impurities. At the same time, it promotes the uniform growth of sodium vanadate crystals during the crystallization process, improves product purity and crystallization efficiency, and finally obtains sodium vanadate product with a purity of ≥99%.

[0026] This application utilizes an ultrasonic microbubble-enhanced method to recover sodium vanadate from spent residue hydrogenation catalysts, forming a complete set of recovery technologies: from pretreatment, roasting, leaching, impurity removal to crystallization, the entire process is coordinated and linked, the process is simple, the operation is continuous, there is no secondary pollution, the energy consumption is low, and the reagent consumption is small. It is suitable for large-scale industrial treatment of spent residue hydrogenation catalysts, achieving the dual goals of hazardous waste resource utilization and environmental governance. Attached Figure Description

[0027] Figure 1 This is a simplified process flow diagram of a method for recovering sodium vanadate from a spent residue hydrogenation catalyst using ultrasonic microbubbles, as described in this application. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0029] The inventors discovered that conventional crushing or single ball milling methods are insufficient to completely break down the catalyst support structure, preventing the full exposure of carbon and sulfur deposits. This results in low vanadium conversion efficiency and slow leaching rates during subsequent roasting and leaching processes. Traditional leaching methods often employ single stirring leaching, leading to low mass transfer efficiency, incomplete oxidation, and vanadium leaching rates generally below 90%. Furthermore, these methods are time-consuming and require large amounts of reagents. Impurity removal is challenging because the leaching solution contains a large amount of impurities such as aluminum and iron. Conventional impurity removal processes struggle to achieve efficient separation of aluminum and vanadium, easily causing vanadium loss and affecting the purity of subsequent products. Product quality is also suboptimal because incomplete vanadium oxidation during crystallization easily leads to impurity co-precipitation, resulting in low purity sodium vanadate products that fail to meet the demands of high-end industrial applications. Existing processes often involve multi-stage roasting, multiple leaching, and complex impurity removal procedures, which are cumbersome, energy-intensive, and prone to secondary pollution, hindering large-scale industrial applications.

[0030] To address the aforementioned problems, this application provides a method for recovering sodium vanadate from spent residue hydrotreating catalysts using ultrasonic microbubbles, comprising the following steps:

[0031] Step S1: Mix the spent residue hydrogenation catalyst and inorganic salt additive evenly to obtain the material; ball mill the material to obtain activated ball milled powder;

[0032] Step S2: The activated ball-milled powder is calcined under oxygen-enriched gas to obtain a mixture of spent residue hydrogenation catalyst after oxygen-enriched calcination; the oxygen volume content of the oxygen-enriched gas is ≥80%.

[0033] Step S3: The mixture of the spent residue hydrogenation catalyst after oxygen-enriched roasting and the leaching agent are mixed at a liquid-to-solid ratio of mL:g = 5~10:1, and a leaching slurry is formed after uniform mixing; subsequently, a leaching aid is added to the leaching slurry under ultrasonic and oxygen microbubble conditions for oxidative leaching treatment; wherein the microbubble concentration is 10. 6 ~10 8 The concentration of the sample is 1 / mL, the ultrasonic frequency is 20~40kHz, the ultrasonic power is 300~600W, the temperature is 60~85℃, and the time is 60~120min; after the oxidation leaching is completed, the sample is separated to obtain leachate A and leachate residue B.

[0034] Step S4: Add a decontaminant to the leachate A for decontamination, and then perform solid-liquid separation to obtain vanadium-containing alkaline solution a and aluminum precipitate slag b;

[0035] Step S5: Enhanced oxidation is carried out in the vanadium-containing alkaline solution a under conditions of simultaneous ultrasound and oxygen microbubbles, wherein the microbubble concentration is 10. 6 ~10 8 The concentration of sodium vanadate was determined by ultrasonic treatment at a frequency of 20-40 kHz, an ultrasonic power of 200-400 W, a temperature of 70-90 °C, and a time of 30-60 min. The vanadium-containing alkaline solution a after enhanced oxidation was then evaporated and concentrated at a temperature of 100-110 °C for 12-24 h. Subsequently, the solution was cooled to room temperature for crystallization, separation, washing, and drying to obtain sodium vanadate.

[0036] Based on the above scheme, this application utilizes a combination of graded ball milling, oxygen-enriched calcination, and ultrasonic microbubble technology to achieve a stable vanadium leaching rate of over 95.9%, an aluminum removal rate of ≥95.1%, and a sodium vanadate product purity of ≥98.9%, meeting the needs of high-end industrial applications. The process is simple and continuous, requiring no complex steps, reducing energy consumption by 15%~25% compared to traditional processes, with lower reagent consumption and production costs. The process is clean and environmentally friendly, with no harmful wastewater or waste residue discharge; leaching residue and aluminum precipitate residue can be further recycled, achieving multi-resource synergistic recovery. It is compatible with hydrogenation catalysts for various complex components of spent residue oil, with mild process conditions and simple equipment requirements. It can be adapted to large-scale industrial production by modifying existing equipment, offering significant economic and environmental benefits and broad prospects for widespread application.

[0037] The following examples and comparative examples illustrate the implementation of this application in more detail. Unless otherwise specified, all raw materials used in the following examples and comparative examples are commercially available products, and all process conditions are standard operating conditions unless otherwise specified.

[0038] Example 1

[0039] Raw materials: By mass percentage, the spent residue hydrotreating catalyst comprises the following components: vanadium 6.8%, carbon 13.5%, sulfur 7.9%, nickel 4.12%, molybdenum 3.09%, and aluminum 37.08%.

[0040] The method for recovering sodium vanadate in this application includes the following steps:

[0041] Step S1: Mix 1000g of spent residue hydrogenation catalyst and 100g of inorganic salt additive (sodium carbonate and sodium nitrate in a mass ratio of 4:1) evenly to obtain the material, and add it to a ball mill jar; the mass ratio of grinding balls to material is 12:1, the ball mill speed is 300r / min, and the ball milling time is 90min; the grinding balls used for grinding include a first grinding ball, a second grinding ball, and a third grinding ball in a mass ratio of 2:3:5, the diameter of the first grinding ball is 12mm, the diameter of the second grinding ball is 6mm, and the diameter of the third grinding ball is 3mm, to obtain activated ball mill powder;

[0042] Step S2: The activated ball-milled powder is fed into a rotary kiln and kiln under oxygen-enriched gas conditions. The oxygen volume content of the oxygen-enriched gas is 85%, and the gas flow rate is 1.0 m. 3 / h; The roasting process adopts a staged roasting process. The first stage roasting temperature T1 is 400℃ and the time t1 is 45min. The second stage roasting temperature T2 is 650℃ and the time t2 is 90min, to obtain the mixture after oxygen-enriched roasting of the exhausted residue hydrogenation catalyst.

[0043] Step S3: The mixture after oxygen-enriched roasting of the spent residue hydrogenation catalyst is mixed with a 1.5 mol / L sodium hydroxide solution at a liquid-to-solid ratio of mL:g = 8:1 to form a leach slurry. The leach slurry is then placed in an ultrasonic microbubble reactor, and ultrasonic waves at 30 kHz and 450 W are applied to introduce oxygen microbubbles to achieve a concentration of 5 × 10⁻⁶. 7 The sample was prepared by adding 1.0 mol / L of leaching aid (hydrogen peroxide and sodium hydroxide in a mass ratio of 2.5:1), reacting at 75℃ for 90 min, and separating the solid and liquid to obtain leachate A and leachate residue B.

[0044] Step S4: Place the leachate A in a stirred reactor at a temperature of 60℃ and a stirring rate of 200r / min. Add 1.5mol / L dilute sulfuric acid (dropping rate of 8mL / min) to remove impurities. Adjust the pH to 9.0 and continue stirring for 45min. Then, separate the solid and liquid to obtain vanadium-containing alkaline solution a and aluminum precipitate slag b.

[0045] Step S5: Transfer the vanadium-containing alkaline solution a to the ultrasonic microbubble oxidation crystallization device, and introduce oxygen microbubbles to achieve a concentration of 5 × 10⁻⁶. 7The sample was subjected to ultrasonic treatment at 30 kHz and 300 W at 80 °C for 45 min to enhance oxidation; then concentrated by evaporation at 105 °C to a concentration of 180 g / L, and cooled to room temperature for 18 h to crystallize.

[0046] Sodium vanadate was then separated, washed three times with deionized water, and dried at 105°C for 2 hours.

[0047] Example 2

[0048] The difference between the sodium vanadate recovery process in this embodiment and that in Embodiment 1 is that the raw materials, by mass percentage, include the following components in the spent residue hydrotreating catalyst: vanadium content 5.9%, carbon content 15.3%, sulfur content 8.7%, nickel content 5.33%, molybdenum content 4.41%, and aluminum content 29.34%. Step S1: The mass ratio of spent residue hydrotreating catalyst to inorganic salt additive is 100:12, and the mass ratio of sodium carbonate to sodium nitrate is 5:1; the mass ratio of grinding balls to material is 15:1; the ball mill speed is 350 r / min, and the ball milling time is 120 min; the grinding balls used include a first grinding ball, a second grinding ball, and a third grinding ball with a mass ratio of 3:4:3, the diameter of the first grinding ball is 15 mm, the diameter of the second grinding ball is 8 mm, and the diameter of the third grinding ball is 4 mm; Step S2: The oxygen volume content in the oxygen-enriched gas is 90%, and the oxygen-enriched gas introduction rate is 1.2 m. 3 / h; The first stage roasting temperature T1 is 450℃, and the time t1 is 60min; the second stage roasting temperature T2 is 700℃, and the time t2 is 120min; Step S3: The sodium hydroxide solution concentration is 2mol / L, the liquid-solid ratio mL:g=10:1, and 40kHz, 600W ultrasound is applied, with an oxygen microbubble concentration of 8×10 7 The leaching agent concentration was 1.5 mol / L (hydrogen peroxide and sodium hydroxide mass ratio of 3:1), the reaction temperature was 85℃, and the leaching time was 120 min; Step S4: The temperature was 70℃, the stirring rate was 250 r / min, the impurity remover was 2 mol / L dilute sulfuric acid (dropping rate 10 mL / min), the pH was 9.5, and the stirring reaction was carried out for 60 min; Step S5: The oxygen microbubble concentration reached 8 × 10⁻⁶. 7 The sample was subjected to ultrasonic waves at 40 kHz and 400 W at 90 °C for 60 min to enhance oxidation. It was then evaporated and concentrated to a concentration of 200 g / L at 110 °C and cooled to room temperature for 24 h to crystallize.

[0049] Example 3

[0050] The difference between the sodium vanadate recovery process in this embodiment and that in Embodiment 1 is that the raw materials, by mass percentage, include the following components in the spent residue hydrotreating catalyst: vanadium content 4.5%, carbon content 11.2%, sulfur content 6.5%, nickel content 4.98%, molybdenum content 4.89%, and aluminum content 27.15%. Step S1: The mass ratio of spent residue hydrotreating catalyst to inorganic salt additive is 100:8, and the mass ratio of sodium carbonate to sodium nitrate is 3:1; the mass ratio of grinding balls to material is 10:1, the ball mill speed is 250 r / min, and the ball milling time is 60 min; the grinding balls used include a first grinding ball, a second grinding ball, and a third grinding ball with a mass ratio of 2:3:4, the diameter of the first grinding ball is 10 mm, the diameter of the second grinding ball is 5 mm, and the diameter of the third grinding ball is 2 mm; Step S2: The oxygen volume content in the oxygen-enriched gas is 80%, and the oxygen-enriched gas introduction rate is 0.8 m... 3 / h; The first stage roasting temperature T1 is 350℃, and the time t1 is 30min; the second stage roasting temperature T2 is 550℃, and the time t2 is 60min; Step S3: The sodium hydroxide solution concentration is 1mol / L, the liquid-solid ratio is mL:g=6:1, 20kHz, 300W ultrasound is applied, and the concentration of oxygen microbubbles is 3×10 7 The leaching agent concentration was 0.8 mol / L (hydrogen peroxide and sodium hydroxide mass ratio was 2:1), the reaction temperature was 65℃, and the leaching time was 75 min; Step S4: The temperature was 55℃, the stirring rate was 180 r / min, the impurity remover was 1 mol / L dilute sulfuric acid (dropping rate was 6 mL / min), the pH was 8.5, and the stirring reaction was carried out for 35 min; Step S5: The oxygen microbubble concentration reached 3 × 10⁻⁶. 7 The sample was subjected to ultrasonic waves at 20 kHz and 250 W at 75 °C for 35 min to enhance oxidation. It was then evaporated and concentrated to a concentration of 160 g / L at 100 °C and cooled to room temperature for 15 h to crystallize.

[0051] Example 4

[0052] The difference between the sodium vanadate recovery process in this embodiment and that in Embodiment 1 is that the raw materials, by mass percentage, include the following components in the spent residue hydrotreating catalyst: vanadium content 6.2%, carbon content 12.8%, sulfur content 7.2%, nickel content 5.15%, molybdenum content 4.85%, and aluminum content 27.18%. Step S1: The mass ratio of spent residue hydrotreating catalyst to inorganic salt additive is 100:9, and the mass ratio of sodium carbonate to sodium nitrate is 3.5:1; the mass ratio of grinding balls to material is 11:1, the ball mill speed is 280 r / min, and the ball milling time is 80 min; the grinding balls used include a first grinding ball, a second grinding ball, and a third grinding ball with a mass ratio of 2:3:4, the diameter of the first grinding ball is 11 mm, the diameter of the second grinding ball is 7 mm, and the diameter of the third grinding ball is 3 mm; Step S2: The oxygen volume content in the oxygen-enriched gas is 82%, and the oxygen-enriched gas introduction rate is 0.9 m. 3 / h; The first stage roasting temperature T1 is 380℃, and the time t1 is 40min; the second stage roasting temperature T2 is 620℃, and the time t2 is 80min; Step S3: The sodium hydroxide solution concentration is 1.2mol / L, the liquid-to-solid ratio is mL:g=7:1, and ultrasound at 25kHz and 380W is applied, with an oxygen microbubble concentration of 4×10 7 The leaching agent concentration was 0.9 mol / L (hydrogen peroxide and sodium hydroxide mass ratio was 2.2:1), the reaction temperature was 70℃, and the leaching time was 80 min; Step S4: The temperature was 58℃, the stirring rate was 190 r / min, the impurity remover was 1.2 mol / L dilute sulfuric acid (dropping rate 7 mL / min), the pH was 8.8, and the stirring reaction was carried out for 40 min; Step S5: The oxygen microbubble concentration reached 4 × 10⁻⁶. 7 The sample was subjected to ultrasonic waves at 25 kHz and 280 W at 78 °C for 40 min to enhance oxidation. It was then evaporated and concentrated to a concentration of 170 g / L at 102 °C and cooled to room temperature for 16 h to crystallize.

[0053] Example 5

[0054] The difference between the sodium vanadate recovery process in this embodiment and that in Embodiment 1 is that the raw materials, by mass percentage, include the following components in the spent residue hydrotreating catalyst: vanadium content 5.5%, carbon content 13.1%, sulfur content 7.5%, nickel content 5.21%, molybdenum content 5.02%, and aluminum content 29.53%. Step S1: The mass ratio of spent residue hydrotreating catalyst to inorganic salt additive is 100:11, and the mass ratio of sodium carbonate to sodium nitrate is 4.5:1; the mass ratio of grinding balls to material is 13:1, the ball mill speed is 320 r / min, and the ball milling time is 100 min; the grinding balls used include a first grinding ball, a second grinding ball, and a third grinding ball with a mass ratio of 2.5:3.5:4, the diameter of the first grinding ball is 13 mm, the diameter of the second grinding ball is 7 mm, and the diameter of the third grinding ball is 4 mm; Step S2: The oxygen volume content in the oxygen-enriched gas is 88%, and the oxygen-enriched gas introduction rate is 1.1 m. 3 / h; The first stage roasting temperature T1 is 420℃, and the time t1 is 50min; the second stage roasting temperature T2 is 680℃, and the time t2 is 100min; Step S3: The sodium hydroxide solution concentration is 1.8mol / L, the liquid-to-solid ratio is mL:g=9:1, and ultrasound at 35kHz and 500W is applied, with an oxygen microbubble concentration of 6×10 7 The leaching agent concentration was 1.2 mol / L (hydrogen peroxide and sodium hydroxide mass ratio was 2.8:1), the reaction temperature was 80℃, and the leaching time was 100 min; Step S4: The temperature was 65℃, the stirring rate was 220 r / min, the impurity remover was 1.8 mol / L dilute sulfuric acid (dropping rate 9 mL / min), the pH was 9.2, and the stirring reaction was carried out for 50 min; Step S5: The oxygen microbubble concentration reached 6 × 10⁻⁶. 7 The sample was subjected to ultrasonic waves at 35 kHz and 350 W at 85 °C for 50 min to enhance oxidation. It was then evaporated and concentrated to a concentration of 190 g / L at 108 °C and cooled to room temperature for 20 h to crystallize.

[0055] Example 6

[0056] The difference between the sodium vanadate recovery process in this embodiment and that in Embodiment 1 is that the raw materials, by mass percentage, include the following components in the spent residue hydrotreating catalyst: vanadium content 6%, carbon content 11.5%, sulfur content 6.8%, nickel content 5.45%, molybdenum content 4.99%, and aluminum content 29.59%. Step S1: The mass ratio of spent residue hydrotreating catalyst to inorganic salt additive is 100:8.5, and the mass ratio of sodium carbonate to sodium nitrate is 3.2:1; the mass ratio of grinding balls to material is 10.5:1; the ball mill speed is 260 r / min, and the ball milling time is 70 min; the grinding balls used include a first grinding ball, a second grinding ball, and a third grinding ball with a mass ratio of 2:3:4.5, the diameter of the first grinding ball is 10 mm, the diameter of the second grinding ball is 6 mm, and the diameter of the third grinding ball is 2.5 mm; Step S2: The oxygen volume content in the oxygen-enriched gas is 81%, and the oxygen-enriched gas introduction rate is 0.7 m. 3 / h; The first stage roasting temperature T1 is 360℃, and the time t1 is 35min; the second stage roasting temperature T2 is 580℃, and the time t2 is 70min; Step S3: The sodium hydroxide solution concentration is 1.1mol / L, the liquid-to-solid ratio mL:g=5.5:1, and 22kHz, 320W ultrasound is applied, with an oxygen microbubble concentration of 3.5×10 7 The leaching agent concentration was 0.7 mol / L (hydrogen peroxide and sodium hydroxide mass ratio of 2.1:1), the reaction temperature was 68℃, and the leaching time was 70 min; Step S4: The temperature was 52℃, the stirring rate was 170 r / min, the impurity remover was 1.1 mol / L dilute sulfuric acid (dropping rate 5.5 mL / min), the pH was 8.6, and the stirring reaction was carried out for 32 min; Step S5: The oxygen microbubble concentration reached 3.5 × 10⁻⁶. 7 The sample was subjected to ultrasonic waves at 22 kHz and 230 W at 72 °C for 32 min to enhance oxidation. It was then evaporated and concentrated to a concentration of 155 g / L at 101 °C and cooled to room temperature for 14 h to crystallize.

[0057] Example 7

[0058] The difference between the sodium vanadate recovery process in this embodiment and that in Embodiment 1 is that the raw materials, by mass percentage, include the following components in the spent residue hydrotreating catalyst: vanadium content 5.8%, carbon content 8.8%, sulfur content 12.2%, nickel content 8.862%, molybdenum content 1.49%, and aluminum content 39.77%. Step S1: The mass ratio of spent residue hydrotreating catalyst to inorganic salt additive is 100:9.5, and the mass ratio of sodium carbonate to sodium nitrate is 4:1; the mass ratio of grinding balls to material is 12.5:1, the ball mill speed is 310 r / min, and the ball milling time is 95 min; the grinding balls used include a first grinding ball, a second grinding ball, and a third grinding ball with a mass ratio of 2.2:3.3:4.5, the diameter of the first grinding ball is 12 mm, the diameter of the second grinding ball is 7 mm, and the diameter of the third grinding ball is 3.5 mm; Step S2: The oxygen volume content in the oxygen-enriched gas is 86%, and the oxygen-enriched gas introduction rate is 1.05 m / s. 3 / h; The first stage roasting temperature T1 is 410℃, and the time t1 is 48min; the second stage roasting temperature T2 is 640℃, and the time t2 is 95min; Step S3: The sodium hydroxide solution concentration is 1.6mol / L, the liquid-to-solid ratio mL:g = 8.5:1, and ultrasound at 32kHz and 480W is applied, with an oxygen microbubble concentration of 5.5×10 7 The leaching agent concentration was 1.1 mol / L (hydrogen peroxide and sodium hydroxide mass ratio was 2.6:1), the reaction temperature was 78℃, and the leaching time was 95 min; Step S4: The temperature was 62℃, the stirring rate was 210 r / min, the impurity remover was 1.6 mol / L dilute sulfuric acid (dropping rate 8.5 mL / min), the pH was 9.1, and the stirring reaction was carried out for 48 min; Step S5: The oxygen microbubble concentration reached 5.5 × 10⁻⁶. 7 The sample was subjected to ultrasonic waves at 32 kHz and 320 W at 82 °C for 48 min to enhance oxidation. It was then evaporated and concentrated to a concentration of 185 g / L at 106 °C and cooled to room temperature for 19 h to crystallize.

[0059] Example 8

[0060] The difference between the sodium vanadate recovery process in this embodiment and that in Embodiment 1 is that the raw materials, by mass percentage, include the following components in the spent residue hydrotreating catalyst: vanadium content 4.8%, carbon content 14.5%, sulfur content 7.3%, nickel content 7.92%, molybdenum content 1.77%, and aluminum content 41.07%. Step S1: The mass ratio of spent residue hydrotreating catalyst to inorganic salt additive is 100:10.5, and the mass ratio of sodium carbonate to sodium nitrate is 4.8:1; the mass ratio of grinding balls to material is 14:1; the ball mill speed is 340 r / min, and the ball milling time is 110 min; the grinding balls used include a first grinding ball, a second grinding ball, and a third grinding ball with a mass ratio of 2.8:3.8:3.4, the diameter of the first grinding ball is 14 mm, the diameter of the second grinding ball is 8 mm, and the diameter of the third grinding ball is 3.5 mm; Step S2: The oxygen volume content in the oxygen-enriched gas is 89%, and the oxygen-enriched gas introduction rate is 1.3 m. 3 / h; The first stage roasting temperature T1 is 440℃, and the time t1 is 55min; the second stage roasting temperature T2 is 690℃, and the time t2 is 110min; Step S3: The sodium hydroxide solution concentration is 1.9mol / L, the liquid-to-solid ratio mL:g = 9.5:1, and ultrasound at 38kHz and 550W is applied, with an oxygen microbubble concentration of 7×10 7 The leaching agent concentration was 1.4 mol / L (hydrogen peroxide and sodium hydroxide mass ratio was 2.9:1), the reaction temperature was 83℃, and the leaching time was 110 min; Step S4: The temperature was 68℃, the stirring rate was 240 r / min, the impurity remover was 1.9 mol / L dilute sulfuric acid (dropping rate 9.5 mL / min), the pH was 9.4, and the stirring reaction was carried out for 55 min; Step S5: The oxygen microbubble concentration reached 7 × 10⁻⁶. 7 The sample was subjected to ultrasonic waves at 38 kHz and 380 W at a temperature of 88 °C for 55 min to enhance oxidation. It was then evaporated and concentrated to a concentration of 195 g / L at 109 °C and cooled to room temperature for 22 h to crystallize.

[0061] Example 9

[0062] The difference between the sodium vanadate recovery process in this embodiment and that in Embodiment 1 is that the raw materials, by mass percentage, include the following components in the spent residue hydrotreating catalyst: vanadium content 6.5%, carbon content 12.6%, sulfur content 7.1%, nickel content 5.44%, molybdenum content 4.99%, and aluminum content 29.59%. Step S1: The mass ratio of spent residue hydrotreating catalyst to inorganic salt additive is 100:9.2, and the mass ratio of sodium carbonate to sodium nitrate is 3.8:1; the mass ratio of grinding balls to material is 11.5:1; the ball mill speed is 290 r / min, and the ball milling time is 85 min; the grinding balls used include a first grinding ball, a second grinding ball, and a third grinding ball with a mass ratio of 2.1:3.2:4.7, the diameter of the first grinding ball is 11.5 mm, the diameter of the second grinding ball is 6.5 mm, and the diameter of the third grinding ball is 3 mm; Step S2: The oxygen volume content in the oxygen-enriched gas is 84%, and the oxygen-enriched gas introduction rate is 0.95 m. 3 / h; The first stage roasting temperature T1 is 390℃, and the time t1 is 42min; the second stage roasting temperature T2 is 630℃, and the time t2 is 85min; Step S3: The sodium hydroxide solution concentration is 1.4mol / L, the liquid-to-solid ratio mL:g=7.5:1, and 28kHz, 420W ultrasound is applied, with an oxygen microbubble concentration of 4.5×10 7 The leaching agent concentration was 1 mol / L (hydrogen peroxide and sodium hydroxide mass ratio was 2.4:1), the reaction temperature was 7:2℃, and the leaching time was 85 min; Step S4: The temperature was 56℃, the stirring rate was 195 r / min, the impurity remover was 1.4 mol / L dilute sulfuric acid (dropping rate 7.5 mL / min), the pH was 8.9, and the stirring reaction was carried out for 42 min; Step S5: The oxygen microbubble concentration reached 4.5 × 10⁻⁶. 7 The sample was subjected to ultrasonic waves at 28 kHz and 290 W at a temperature of 79 °C for 42 min to enhance oxidation. It was then evaporated and concentrated to a concentration of 175 g / L at 103 °C and cooled to room temperature for 17 h to crystallize.

[0063] Example 10

[0064] The difference between the sodium vanadate recovery process in this embodiment and that in Embodiment 1 is that the raw materials, by mass percentage, include the following components in the spent residue hydrotreating catalyst: vanadium content 6.3%, carbon content 11.8%, sulfur content 6.6%, nickel content 7.93%, molybdenum content 1.77%, and aluminum content 41.07%. Step S1: The mass ratio of spent residue hydrotreating catalyst to inorganic salt additive is 100:8.8, and the mass ratio of sodium carbonate to sodium nitrate is 3.3:1; the mass ratio of grinding balls to material is 10.8:1; the ball mill speed is 270 r / min, and the ball milling time is 75 min; the grinding balls used include a first grinding ball, a second grinding ball, and a third grinding ball with a mass ratio of 2:3.1:4.9, the diameter of the first grinding ball is 10.5 mm, the diameter of the second grinding ball is 5.5 mm, and the diameter of the third grinding ball is 2.5 mm; Step S2: The oxygen volume content in the oxygen-enriched gas is 83%, and the oxygen-enriched gas introduction rate is 0.85 m / s. 3 / h; The first stage roasting temperature T1 is 370℃, and the time t1 is 38min; the second stage roasting temperature T2 is 600℃, and the time t2 is 75min; Step S3: The sodium hydroxide solution concentration is 1.3mol / L, the liquid-to-solid ratio mL:g = 6.5:1, and 24kHz, 350W ultrasound is applied, with an oxygen microbubble concentration of 3.8×10 7 The leaching agent concentration was 0.8 mol / L (hydrogen peroxide and sodium hydroxide mass ratio was 2.3:1), the reaction temperature was 66℃, and the leaching time was 78 min; Step S4: The temperature was 54℃, the stirring rate was 175 r / min, the impurity remover was 1.3 mol / L dilute sulfuric acid (dropping rate 6.5 mL / min), the pH was 8.7, and the stirring reaction was carried out for 36 min; Step S5: The oxygen microbubble concentration reached 3.8 × 10⁻⁶. 7 The sample was subjected to ultrasonic waves at 24 kHz and 240 W at 74 °C for 36 min to enhance oxidation. It was then evaporated and concentrated to a concentration of 165 g / L at 102 °C and cooled to room temperature for 15.5 h to crystallize.

[0065] Comparative Example 1

[0066] The difference between this comparative example of sodium vanadate recovery and Example 1 is that, by mass percentage, the spent residue hydrotreating catalyst comprises the following components: vanadium 6.8%, carbon 13.5%, sulfur 7.9%, nickel 4.12%, molybdenum 3.09%, and aluminum 37.08%. Step S1: Direct grinding is used without using the first, second, and third grinding balls and their corresponding proportions; Step S2: Oxygen-enriched gas is not introduced during the roasting process; Step S3: Conventional stirring leaching is used only, without applying ultrasonic microbubbles.

[0067] Comparative Example 2

[0068] The difference between this comparative example of sodium vanadate recovery and Example 1 is that, by mass percentage, the spent residue hydrotreating catalyst comprises the following components: vanadium 6.8%, carbon 13.5%, sulfur 7.9%, nickel 4.12%, molybdenum 3.09%, and aluminum 37.08%. Step S3: No ultrasonic microbubbles are applied; only conventional stirring leaching is used.

[0069] Comparative Example 3

[0070] The difference between this comparative example of sodium vanadate recovery and Example 1 is that, by mass percentage, the spent residue hydrotreating catalyst comprises the following components: vanadium 6.8%, carbon 13.5%, sulfur 7.9%, nickel 4.12%, molybdenum 3.09%, and aluminum 37.08%. Step S1: Direct grinding is used instead of the first, second, and third grinding balls and their corresponding proportions; Step S2: Oxygen-enriched gas is not introduced during the roasting process.

[0071] Test case

[0072] Vanadium leaching rate, aluminum removal rate, and sodium vanadate purity were calculated for each embodiment and comparative example.

[0073]

[0074] As shown in the table above, the sodium vanadate recovery method of this application, in synergy with the entire process, can achieve efficient vanadium leaching and efficient aluminum removal simultaneously, thereby preparing high-purity sodium vanadate. In particular, when the ultrasonic microbubble process conditions of this application are met, efficient vanadium leaching and efficient aluminum removal are further achieved, further improving the purity of sodium vanadate.

[0075] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the principles of this application should be included within the protection scope of this application.

Claims

1. A method for recovering sodium vanadate from spent residue hydrotreating catalyst using ultrasonic microbubbles, characterized in that, Includes the following steps: Step S1: Mix the spent residue hydrogenation catalyst and inorganic salt additive evenly to obtain the material; ball mill the material to obtain activated ball milled powder; Step S2: The activated ball-milled powder is calcined under oxygen-enriched gas to obtain a mixture of spent residue hydrogenation catalyst after oxygen-enriched calcination; the oxygen volume content of the oxygen-enriched gas is ≥80%. Step S3: The mixture of the spent residue hydrogenation catalyst after oxygen-enriched roasting and the leaching agent are mixed at a liquid-to-solid ratio of mL:g = 5~10:1, and a leaching slurry is formed after uniform mixing; subsequently, a leaching aid is added to the leaching slurry under ultrasonic and oxygen microbubble conditions for oxidative leaching treatment; wherein the microbubble concentration is 10. 6 ~10 8 The concentration of the sample is 1 / mL, the ultrasonic frequency is 20~40kHz, the ultrasonic power is 300~600W, the temperature is 60~85℃, and the time is 60~120min; after the oxidation leaching is completed, the sample is separated to obtain leachate A and leachate residue B. Step S4: Add a decontaminant to the leachate A for decontamination, and then perform solid-liquid separation to obtain vanadium-containing alkaline solution a and aluminum precipitate slag b; Step S5: Enhanced oxidation is carried out in the vanadium-containing alkaline solution a under conditions of simultaneous ultrasonic waves and oxygen microbubbles, wherein the microbubble concentration is 10. 6 ~10 8 The concentration of sodium vanadate was determined by ultrasonic treatment at a frequency of 20-40 kHz, an ultrasonic power of 200-400 W, a temperature of 70-90 °C, and a time of 30-60 min. The vanadium-containing alkaline solution a after enhanced oxidation was then evaporated and concentrated at a temperature of 100-110 °C for 12-24 h. Subsequently, the solution was cooled to room temperature for crystallization, separation, washing, and drying to obtain the sodium vanadate.

2. The method according to claim 1, characterized in that, The spent residue hydrotreating catalyst, by mass percentage, comprises the following components: 10-70% Al2O3, 3-25% vanadium-containing substances, 1-10% nickel-containing substances, and 1-15% molybdenum-containing substances; the vanadium-containing substances include VO2 and V2S3; the nickel-containing substances include NiS; and the molybdenum-containing substances include MoS2 and MoO2.

3. The method according to claim 2, characterized in that, Step S1 satisfies at least one of the following conditions: (1) The mass ratio of the spent residue hydrotreating catalyst to the inorganic salt additive is 100:5~15; the inorganic salt additive includes sodium carbonate and sodium nitrate, and the mass ratio of sodium carbonate to sodium nitrate is 3~5:1; (2) The ball mill uses grinding balls, the mass ratio of the grinding balls to the material is 8~15:1, the rotation speed of the ball mill is 200~400 r / min, and the ball milling time is 60~120 min; (3) The ball mill uses grinding balls, which include a first grinding ball, a second grinding ball and a third grinding ball in a mass ratio of (2~3):(3~4):(3~5). The diameter of the first grinding ball is 10~15mm, the diameter of the second grinding ball is 5~8mm and the diameter of the third grinding ball is 2~4mm.

4. The method according to claim 3, characterized in that, In step S2, the oxygen-enriched gas is introduced at a rate of 0.5~1.5m. 3 / h; The roasting process adopts a staged roasting process. The first stage roasting temperature T1 is 350~450℃ and the time t1 is 30~60min. The second stage roasting temperature T2 is 550~700℃ and the time t2 is 60~120min.

5. The method according to claim 4, characterized in that, In step S3, the leaching agent is a sodium hydroxide solution with a concentration of 1.0~2.0 mol / L; the leaching aid includes hydrogen peroxide and sodium hydroxide in a mass ratio of 2~3:1; and the sum of the molar concentrations of the hydrogen peroxide and sodium hydroxide in the leaching aid is 0.5~1.5 mol / L.

6. The method according to claim 5, characterized in that, In step S3, preferably, the microbubble concentration is 4.5 × 10⁻⁶. 7 ~5.5×10 7 The ultrasonic frequency was 28~32kHz, the ultrasonic power was 420~480W, the temperature was 72~78℃, and the time was 85~95min.

7. The method according to claim 6, characterized in that, In step S4, the impurity remover is dilute sulfuric acid with a concentration of 1.0~2.0 mol / L and an addition rate of 5~10 mL / min. The pH of the solution is adjusted to 8.5~9.5 by adding the impurity remover.

8. The method according to claim 7, characterized in that, In step S4, the reaction temperature is 50~70℃, the stirring rate is 150~250 r / min, and the stirring time is 30~60 min.

9. The method according to claim 8, characterized in that, In step S5, preferably, the microbubble concentration is 4.5 × 10⁻⁶. 7 ~5.5×10 7 The ultrasonic frequency was 28~32kHz, the ultrasonic power was 290~320W, the temperature was 79~82℃, and the time was 42~48min.

10. The method according to claim 9, characterized in that, In step S5, the vanadium-containing alkaline solution a is evaporated and concentrated until the solution concentration is 150~200g / L.

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