Regeneration method of waste hydrogenation catalyst carrier

Abstract

The invention belongs to the field of waste catalyst recovery, and particularly relates to a waste catalyst carrier regeneration method. The method comprises the four steps of oxidizing roasting, melt blending, mild leaching and drying regeneration. According to the method, organic matters in the waste hydrogenation catalyst are removed through oxidizing roasting, and valuable metals are converted into components which can be mildly leached; and a mild solvent is prepared to efficiently leach valuable metals, and meanwhile, the structure and form of the carrier are directly reserved, so that short-range regeneration of the carrier is realized, and good environmental and economic benefits are achieved.

Description

Technical Field

[0001] The invention belongs to the field of waste catalyst recovery, and particularly relates to a waste catalyst carrier regeneration method. Background Art

[0002] Hydrogenation catalysts are essential catalysts in petroleum refining and chemical production (such as hydrotreating, hydrocracking, and desulfurization and denitrification processes). They are primarily composed of active components (molybdenum and nickel) and an alumina or silica support. They catalyze hydrogenation reactions under high temperature and pressure to improve oil quality or produce high-value-added chemicals. However, over long-term operation, catalysts gradually deactivate due to loss of active components, surface carbon coking, poisoning by sulfur / metal impurities, structural sintering, or mechanical wear, leading to decreased reaction efficiency and even failure, necessitating regular scrapping and replacement. The high integrity of the support particles in spent hydrogenation catalysts and the well-preserved γ-Al₂O₃ phase make alumina supports highly valuable for recycling and reuse. However, the recycling of spent hydrogenation catalysts primarily focuses on the complete recovery of spent catalyst components, with limited research on the short-term regeneration of alumina supports, and even fewer on the short-term regeneration of alumina support particles. Therefore, the selective recovery of valuable metals from spent hydrogenation catalysts and the simultaneous short-term regeneration of support particles are of great significance for the resource recovery and high-value recovery of spent hydrogenation catalysts.

[0003] In the prior art, patent CN202210326342.7 discloses a method for recovering all components of spent hydrogenation catalysts. This method first deoils the spent hydrogenation catalyst by vacuum pyrolysis, then mixes the pyrolysis residue with concentrated sulfuric acid and roasts it to obtain a roasted clinker. The sulfate product is obtained through leaching, extraction and other steps. It has a high metal recovery efficiency, but does not consider the recovery of the alumina carrier. Patent CN202210846254.X discloses a method for separating and recovering molybdenum and nickel from spent hydrogenation catalysts. The spent catalyst is first calcined in oxygen-enriched water, and then the calcined product is leached with acetic acid. After leaching, oxalic acid is added to form a nickel oxalate precipitate. The nickel oxalate product is obtained by filtration and separation. The solution is then evaporated and crystallized to form molybdenum oxalate and molybdenum acetate. Finally, the molybdenum oxalate and molybdenum acetate are converted into molybdenum trioxide by thermal decomposition. Compared with the traditional method of recovering molybdenum from spent catalysts, this method has a simple process, a high yield of molybdenum and nickel, and does not produce saline wastewater, with good environmental and economic benefits. However, it does not recover the common metal vanadium in spent hydrogenation catalysts. Patent CN202110728404.2 discloses a method for extracting vanadium, nickel and molybdenum from spent catalysts by leaching them with ammonium sulfate solution. Ammonium sulfate and ammonium persulfate are used as a combined medium to react with spent catalysts under normal pressure. The strong oxidizing property of ammonium persulfate enables efficient oxidative leaching of vanadium, nickel and molybdenum in spent catalysts. It can be seen that in the existing technologies for the recovery of spent hydrogenation catalysts, most of them are carried out by destroying the shape or physical phase of the alumina carrier, and few consider the short-range regeneration of alumina carrier particles. Therefore, the development of a technology for the regeneration of spent hydrogenation catalyst carriers is of great reference significance for the development of the spent hydrogenation catalyst recovery industry. Summary of the Invention

[0004] To solve the above problems, the present invention provides a method for regenerating a spent hydrogenation catalyst carrier, the method comprising the following steps:

[0005] (1) Oxidation roasting: preheating a tubular furnace, then adding the spent hydrogenation catalyst into the tubular furnace for oxidation roasting to obtain a spent hydrogenation catalyst roasting material;

[0006] (2) Melt blending: hydrogen bond acceptor, hydrogen bond donor and deionized water are added to a round-bottom flask and melt blended to obtain a deep eutectic solvent;

[0007] (3) Mild leaching: placing the spent hydrogenation catalyst calcined material obtained in step (1) in the deep eutectic solvent obtained in step (2) for leaching to obtain leached residue and leachate;

[0008] (4) Drying and regeneration: The leaching residue obtained in step (3) is dried to obtain a regenerated carrier.

[0009] Furthermore, the spent hydrogenation catalyst in step (1) does not need to be ground, and the calcination temperature is 300° C.-750° C., the calcination time is 0.5 h-2.5 h, and the atmosphere is an oxidizing gas.

[0010] Furthermore, the hydrogen bond acceptor described in step (2) is one of choline chloride, betaine or choline lactate, the hydrogen bond donor is one of p-toluenesulfonic acid, oxalic acid, citric acid, malic acid or glycerol, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 0.5:1-4:1, the amount of deionized water added is 10% to 30% of the total mass of the hydrogen bond acceptor and the hydrogen bond donor, the preparation temperature is 50°C-90°C, the preparation time is 30min-120min, and the stirring speed is 500rpm-1000rpm.

[0011] Furthermore, the leaching temperature in step (3) is 45°C-100°C, the leaching time is 15min-120min, the stirring speed is 300rpm-800rpm, and the solid-liquid ratio is 5g / L-20g / L.

[0012] Furthermore, the drying conditions in step (4) are 90° C. and 12 h.

[0013] The present invention has the following beneficial effects:

[0014] (1) Through oxidative roasting, the problem of serious damage to the support caused by the traditional roasting process is solved, the organic matter in the spent hydrogenation catalyst is removed, and the valuable metals are converted into components that can be gently leached;

[0015] (2) By melt blending and preparing deep eutectic solvent, the problem of high aluminum leaching rate was solved, laying the foundation for short-range regeneration of the carrier;

[0016] (3) Through mild leaching, mild leaching of valuable metals and short-range regeneration and recovery of alumina carrier particles are achieved. DETAILED DESCRIPTION

[0017] Various exemplary embodiments of the present invention are now described in detail. Unless otherwise specified, the methods in the examples are conventional methods. Unless otherwise specified, the reagents used are conventional commercially available reagents or reagents prepared using conventional methods. This detailed description should not be considered a limitation of the present invention, but rather should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0018] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value within any stated value or stated range, and each smaller range between any other stated value or intermediate value within the stated range, is also encompassed within the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0019] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0020] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0021] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0022] Example 1

[0023] Leaching was performed as follows:

[0024] (1) Oxidation roasting: preheat the tubular furnace to 600°C, then add the spent hydrogenation catalyst into the tubular furnace for oxidation roasting. The roasting time is 0.5 h in an air atmosphere to obtain the spent hydrogenation catalyst roasting material.

[0025] (2) Melt blending: Choline chloride, p-toluenesulfonic acid and deionized water were added to a round-bottom flask for melt blending. The molar ratio of choline chloride to p-toluenesulfonic acid was 2:1, and the amount of deionized water added was 30% of the total mass of choline chloride and p-toluenesulfonic acid. The preparation temperature was 80°C, the preparation time was 60 min, and the stirring speed was 500 rpm to obtain a uniform and clear deep eutectic solvent.

[0026] (3) Mild leaching: The spent hydrogenation catalyst calcined material obtained in step (1) is placed in the deep eutectic solvent obtained in step (2) for mild leaching at a leaching temperature of 90° C., a leaching time of 80 min, a stirring speed of 600 rpm, and a solid-liquid ratio of 5 g / L to obtain leaching residue and leachate, which are then centrally processed;

[0027] (4) Drying and regeneration: drying the leaching residue obtained in step (3) at 90°C for 12 hours to obtain a regenerated carrier;

[0028] Example 2

[0029] Leaching was performed as follows:

[0030] (1) Oxidative calcination: preheat the tubular furnace to 650°C, then add the spent hydrogenation catalyst into the tubular furnace for oxidative calcination for 1.5 hours in an atmosphere of a mixed gas consisting of 20% oxygen and 80% nitrogen to obtain a spent hydrogenation catalyst calcined material;

[0031] (2) Melt blending: betaine, oxalic acid and deionized water were added to a round-bottom flask for melt blending. The molar ratio of betaine to oxalic acid was 4:1, and the amount of deionized water added was 10% of the total mass of betaine and oxalic acid. The preparation temperature was 50°C, the preparation time was 120 min, and the stirring speed was 700 rpm to obtain a uniform and clear deep eutectic solvent.

[0032] (3) Mild leaching: The spent hydrogenation catalyst calcined material obtained in step (1) is placed in the deep eutectic solvent obtained in step (2) for mild leaching, with a leaching temperature of 60° C., a leaching time of 90 min, a stirring speed of 800 rpm, and a solid-liquid ratio of 10 g / L to obtain leaching residue and leachate, which are then centrally processed;

[0033] (4) Drying and regeneration: drying the leaching residue obtained in step (3) at 90°C for 12 hours to obtain a regenerated carrier;

[0034] Example 3

[0035] Leaching was performed as follows:

[0036] (1) Oxidative calcination: preheat the tubular furnace to 700°C, then add the spent hydrogenation catalyst into the tubular furnace for oxidative calcination for 1 hour in an atmosphere of a mixed gas consisting of 30% oxygen and 70% nitrogen to obtain a spent hydrogenation catalyst calcined material;

[0037] (2) Melt blending: Choline lactate, glycerol and deionized water were added to a round-bottom flask for melt blending. The molar ratio of choline lactate to glycerol was 2:1, and the amount of deionized water added was 15% of the total mass of choline lactate and glycerol. The preparation temperature was 60°C, the preparation time was 90 min, and the stirring speed was 900 rpm to obtain a uniform and clear deep eutectic solvent.

[0038] (3) Mild leaching: The spent hydrogenation catalyst calcined material obtained in step (1) is placed in the deep eutectic solvent obtained in step (2) for mild leaching, with a leaching temperature of 100° C., a leaching time of 60 min, a stirring speed of 300 rpm, and a solid-liquid ratio of 20 g / L to obtain leaching residue and leachate, which are then centrally processed;

[0039] (4) Drying and regeneration: drying the leaching residue obtained in step (3) at 90°C for 12 hours to obtain a regenerated carrier;

[0040] Example 4

[0041] Leaching was performed as follows:

[0042] (1) Oxidation roasting: preheat the tubular furnace to 400°C, then add the spent hydrogenation catalyst into the tubular furnace for oxidation roasting for 2 hours in an air atmosphere to obtain the spent hydrogenation catalyst roasting material;

[0043] (2) Melt blending: Choline chloride, malic acid and deionized water were added to a round-bottom flask for melt blending. The molar ratio of choline chloride to malic acid was 0.5:1, and the amount of deionized water added was 25% of the total mass of choline chloride and malic acid. The preparation temperature was 90°C, the preparation time was 60 min, and the stirring speed was 1000 rpm to obtain a uniform and clear deep eutectic solvent.

[0044] (3) Mild leaching: The spent hydrogenation catalyst calcined material obtained in step (1) is placed in the deep eutectic solvent obtained in step (2) for mild leaching, with a leaching temperature of 80° C., a leaching time of 15 min, a stirring speed of 600 rpm, and a solid-liquid ratio of 15 g / L to obtain leaching residue and leachate, which are then centrally processed;

[0045] (4) Drying and regeneration: drying the leaching residue obtained in step (3) at 90°C for 12 hours to obtain a regenerated carrier;

[0046] Example 5

[0047] Leaching was performed as follows:

[0048] (1) Oxidative calcination: preheat the tubular furnace to 300°C, then add the spent hydrogenation catalyst into the tubular furnace for oxidative calcination for 2.5 hours in an atmosphere of a mixed gas consisting of 25% oxygen and 75% nitrogen to obtain a spent hydrogenation catalyst calcined material;

[0049] (2) Melt blending: Choline chloride, p-toluenesulfonic acid and deionized water were added to a round-bottom flask for melt blending. The molar ratio of choline chloride to p-toluenesulfonic acid was 3:1, and the amount of deionized water added was 20% of the total mass of choline chloride and p-toluenesulfonic acid. The preparation temperature was 80°C, the preparation time was 90 min, and the stirring speed was 700 rpm to obtain a uniform and clear deep eutectic solvent.

[0050] (3) Mild leaching: The spent hydrogenation catalyst calcined material obtained in step (1) is placed in the deep eutectic solvent obtained in step (2) for mild leaching, the leaching temperature is 45°C, the leaching time is 120 min, the stirring speed is 400 rpm, the solid-liquid ratio is 20 g / L, and leaching residue and leachate are obtained, and the leachate is centrally processed;

[0051] (4) Drying and regeneration: drying the leaching residue obtained in step (3) at 90°C for 12 hours to obtain a regenerated carrier;

[0052] Example 6

[0053] Leaching was performed as follows:

[0054] (1) Oxidative calcination: preheat the tubular furnace to 550°C, then add the spent hydrogenation catalyst into the tubular furnace for oxidative calcination for 1 hour in an atmosphere of a mixed gas consisting of 40% oxygen and 60% nitrogen to obtain a spent hydrogenation catalyst calcined material;

[0055] (2) Melt blending: Choline lactate, malic acid and deionized water were added to a round-bottom flask for melt blending. The molar ratio of choline lactate to malic acid was 1:1, and the amount of deionized water added was 20% of the total mass of choline lactate and malic acid. The preparation temperature was 90°C, the preparation time was 30 min, and the stirring speed was 900 rpm to obtain a uniform and clear deep eutectic solvent.

[0056] (3) Mild leaching: The spent hydrogenation catalyst calcined material obtained in step (1) is placed in the deep eutectic solvent obtained in step (2) for mild leaching, with a leaching temperature of 100° C., a leaching time of 120 min, a stirring speed of 500 rpm, and a solid-liquid ratio of 5 g / L to obtain leaching residue and leachate, which are then centrally processed;

[0057] (4) Drying and regeneration: The leaching residue obtained in step (3) is dried at 90°C for 12 hours to obtain a regenerated carrier.

[0058] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for regenerating a spent hydrogenation catalyst carrier, characterized in that: The method comprises the following steps: (1) Oxidation roasting: preheating a tubular furnace, then adding the spent hydrogenation catalyst into the tubular furnace for oxidation roasting to obtain a spent hydrogenation catalyst roasting material; (2) Melt blending: hydrogen bond acceptor, hydrogen bond donor and deionized water are added to a round-bottom flask and melt blended to obtain a deep eutectic solvent; (3) Mild leaching: placing the spent hydrogenation catalyst calcined material obtained in step (1) in the deep eutectic solvent obtained in step (2) for leaching to obtain leached residue and leachate; (4) Drying and regeneration: The leaching residue obtained in step (3) is dried to obtain a regenerated carrier.

2. The method according to claim 1, characterized in that The spent hydrogenation catalyst in step (1) does not need to be ground, the calcination temperature is 300° C.-750° C., the calcination time is 0.5 h-2.5 h, and the atmosphere is an oxidizing gas.

3. The method according to claim 1, characterized in that The hydrogen bond acceptor described in step (2) is one of choline chloride, betaine or choline lactate, the hydrogen bond donor is one of p-toluenesulfonic acid, oxalic acid, citric acid, malic acid or glycerol, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 0.5:1-4:1, the amount of deionized water added is 10% to 30% of the total mass of the hydrogen bond acceptor and the hydrogen bond donor, the preparation temperature is 50°C-90°C, the preparation time is 30min-120min, and the stirring speed is 500rpm-1000rpm.

4. The method according to claim 1, wherein The leaching temperature in step (3) is 45° C.-100° C., the leaching time is 15 min-120 min, the stirring speed is 300 rpm-800 rpm, and the solid-liquid ratio is 5 g / L-20 g / L.

5. The method according to claim 1, wherein The drying conditions in step (4) are 90° C. and 12 h.