A method for reusing spent hydrogenation catalyst

Abstract

This invention belongs to the field of chemical technology and provides a method for reusing waste hydrogenation catalysts. The method includes mixing the waste hydrogenation catalyst with silica, boric acid, titanium dioxide, a lithium source, and an aluminum source, followed by ball milling. The resulting mixture is then sequentially smelted, annealed, and subjected to crystallization heat treatment to obtain microcrystalline glass. The waste hydrogenation catalyst contains aluminum. The crystallization heat treatment temperature is 635-735℃. This invention, through designing the microcrystalline glass system components and controlling the processing, prepares microcrystalline glass with low expansion properties. This method not only solves the environmental pollution problem caused by waste hydrogenation catalysts, but also produces microcrystalline glass with high economic value, achieving a win-win situation for both economic and environmental benefits compared to existing treatment technologies.

Description

Technical Field

[0001] This invention relates to the field of chemical technology, and in particular to a method for reusing waste hydrogenation catalysts. Background Technology

[0002] Hydrogenation catalysts are crucial in the petrochemical industry, primarily used in deoxygenation, denitrification, desulfurization, and demetallization reactions during petroleum refining to improve the quality and yield of refined petroleum products. Hydrogenation catalysts gradually deactivate and become unusable due to heavy metal deposition, carbon buildup, and active phase sintering, with a lifespan of approximately 2-3 years. Statistics show that over 800,000 tons of industrial waste catalysts are generated globally each year, with waste hydrogenation catalysts accounting for over 120,000 tons. However, the heavy metals and oily substances contained in waste hydrogenation catalysts seriously threaten the ecological environment and human health, and are classified as hazardous solid waste by many countries. Therefore, the harmless treatment of waste hydrogenation catalysts is extremely urgent. Furthermore, waste hydrogenation catalysts contain high concentrations of rare metals, representing a significant secondary resource. Therefore, the green and resource-efficient treatment of waste hydrogenation catalysts is highly beneficial for reducing environmental burden and alleviating resource shortages.

[0003] Recovering valuable metals from spent hydrogenation catalysts is a common treatment method. CN116751966A proposes a method for separating and recovering molybdenum and nickel from spent hydrogenation catalysts. The spent catalyst is placed in a tubular furnace for air roasting, where molybdenum trioxide is sublimated and vaporized at a certain temperature and recovered. The remaining roasting product reacts with a certain concentration of chlorine dioxide to produce nickel chloride, which is then recovered. However, this method requires very high reaction temperatures and expensive equipment. Furthermore, CN108067245A proposes a reuse method for spent hydrogenation catalysts, involving roasting, crushing, alkaline leaching, acid leaching, and re-roasting to prepare new catalysts. This method involves numerous steps to prepare new catalysts from spent hydrogenation catalysts. CN108609857A proposes a method for preparing microcrystalline glass using spent catalytic cracking catalysts. Using spent catalytic cracking catalysts as raw materials, the catalyst is first ground to control the particle size to 100–300 mesh, and the Si / Al ratio is adjusted. Then, it undergoes vitrification treatment in a thermal plasma arc reactor to obtain microcrystalline glass. However, this method uses a thermal plasma arc reactor, which increases production costs. Although the prepared glass-ceramics have similar physicochemical properties to ordinary glass-ceramics, they do not have the outstanding performance advantages of glass-ceramics, thus limiting their market application.

[0004] In summary, the research methods for utilizing spent hydrogenation catalysts mentioned above suffer from problems such as high cost, numerous process steps, and low utilization value. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a method for reusing spent hydrogenation catalysts. This method offers advantages such as a short process, low cost, environmental friendliness, and high-value utilization.

[0006] This invention provides a method for reusing spent hydrogenation catalysts, comprising:

[0007] Waste hydrogenation catalyst is mixed with silica, boric acid, titanium dioxide, lithium source and aluminum source, and ball-milled. The resulting mixture is then subjected to smelting, annealing and crystallization heat treatment to obtain microcrystalline glass. The waste hydrogenation catalyst contains aluminum. The temperature of the crystallization heat treatment is 635-735℃.

[0008] This invention, based on the component characteristics of spent hydrogenation catalysts, designs and introduces glass components. Through melting, Si-O-Si and [AlO4] form a stable structure, and Al is stably present in the glass phase. Simultaneously, Al... 3+ It complements the glass network structure, promotes the precipitation of low-expansion-coefficient crystalline phases after heat treatment, and improves the physicochemical properties of the glass-ceramic. Furthermore, by adding a lithium source, Li... + It functions as a charge compensation agent. The glass network also exhibits good containment of other impurity ions in the spent hydrogenation catalyst, Mo. 6+ It participates in the construction of the glass network structure, while lowering the melting point of the glass components.

[0009] The waste hydrogenation catalyst described in this invention can be selected from one or more of the waste hydrogenation catalysts containing Al, such as hydrorefining type 3936, hydrocracking type FF-26, and type 3824.

[0010] According to the recycling method provided by the present invention, the material composition is as follows by mass percentage: 5-25% waste hydrogenation catalyst, 50-63% silicon dioxide, 7-10% aluminum source (calculated as Al2O3), 2-3% titanium dioxide, 8.8-11% lithium source (calculated as Li2O), and 6.3-8% boric acid (calculated as B2O3).

[0011] In the above technical solution, silicon dioxide is the main component of the microcrystalline glass, and the parent glass is arranged in a [SiO4] array to form a glass network structure. A relatively large amount of waste hydrogenation catalyst is added, providing Al... 3+ The increase in concentration causes a change in the crystalline phase precipitated in the glass-ceramic. At this point, the glass-ceramic tends to precipitate a β-quartz solid solution phase. As the crystallization heat treatment temperature increases, a portion of the β-quartz solid solution phase transforms into the β-spodumene phase, which exhibits low or even negative expansion characteristics. Boric acid and the lithium source play a role in lowering the melting point of the components. In the above components, the spent hydrogenation catalyst contains a large amount of alumina, but the proportion is relatively insufficient; therefore, a portion of alumina is added as an intermediate in the glass network.

[0012] Furthermore, both lithium and aluminum sources can be selected from metal salts, hydroxides, oxides, etc.

[0013] In some embodiments of the present invention, the lithium source is selected from one or more of Li2CO3 and LiOH, preferably Li2CO3.

[0014] In some embodiments of the present invention, the aluminum source is selected from one or more of Al(OH)3 and Al2O3, preferably Al2O3.

[0015] Lithium carbonate provides cations for the glass structure and plays a role in compensating for the charges of the [SiO4], [BO4], and [AlO4] tetrahedral units in the parent glass. Heat treatment crystallization affects the precipitation of different crystal phases. Since more Si-O-Si structures are formed and less Si-O-Al is formed, some aluminum oxide is added to supplement it.

[0016] According to the method for reusing spent hydrogenation catalyst provided by the present invention, the melting temperature is 1500-1600℃, preferably 1530-1560℃; the melting time is 2-6 hours, preferably 2-3 hours. If the temperature is too low, the raw materials are difficult to melt evenly and clarify; if the melting temperature is too high, it is difficult for high-temperature equipment to achieve the required temperature.

[0017] Furthermore, the annealing temperature is 500-600℃, preferably 550-580℃; the annealing time is 2-6 hours, preferably 3-4 hours; the product after annealing needs to be cooled to room temperature.

[0018] Furthermore, the crystallization heat treatment time is 2-4 hours.

[0019] In some embodiments of the present invention, after ball milling, the particle size is controlled at 100-200 mesh.

[0020] In a preferred embodiment of the present invention, the reuse method includes the following steps:

[0021] (1) By mass percentage, 5-25% of waste hydrogenation catalyst, 50-63% of silicon dioxide, 7-10% of aluminum source (Al2O3), 2-3% of titanium dioxide, 8.8-11% of lithium source (Li2O), and 6.3-8% of boric acid (B2O3) are mixed together.

[0022] (2) The mixture obtained in step (1) is ball-milled and the particle size is controlled to be 100-200 mesh;

[0023] (3) Melt the mixture obtained in step (2) at 1500-1600℃ for 2-6 hours;

[0024] (4) Pour the melt obtained in step (3) into a mold, transfer it to a muffle furnace and anneal at 500-600℃ for 2-6 hours, then cool the product to room temperature;

[0025] (5) After the cooling product obtained in step (4) is subjected to crystallization heat treatment at 635-735℃ for 2-4 hours, it is cooled to room temperature to obtain microcrystalline glass.

[0026] Preferably, in step (3), the smelting is carried out in a high-temperature furnace. The ball-milled material is placed in a crucible and then melted in a high-temperature furnace within a preset temperature range. The crucible is selected from one of the following: alumina crucible, silica crucible, graphite crucible, and platinum crucible, with platinum crucible being preferred.

[0027] In step (4), the mold is selected from graphite mold and stainless steel mold, preferably graphite mold.

[0028] In step (5), the heat treatment is also carried out in a high-temperature furnace. The cooling to room temperature specifically involves naturally cooling the mother glass or microcrystalline glass to room temperature along with the furnace.

[0029] According to the recycling method of the present invention, the obtained microcrystalline glass has a coefficient of thermal expansion of less than 1.1 × 10⁻⁶ at 600 °C. -6 / ℃.

[0030] The present invention also provides the application of the above-mentioned method for reusing waste hydrogenation catalyst in the comprehensive utilization of solid waste.

[0031] The beneficial effects of this invention are as follows:

[0032] The method provided by this invention first melts the raw materials, then anneals them to relieve stress, and finally performs crystallization heat treatment to obtain microcrystalline glass. The preparation of microcrystalline glass requires simple ingredients, minimal equipment, and is easy to operate, making it suitable for industrial production. Microcrystalline glass fully utilizes the large amount of alumina in waste hydrogenation catalysts, and also solidifies all other impurity raw materials, achieving the utilization of all components of solid waste. Furthermore, the microcrystalline glass prepared by this invention using waste hydrogenation catalysts has properties such as low expansion, achieving both high economic value utilization of solid waste and avoiding environmental pollution. Attached Figure Description

[0033] Figure 1 XRD analysis of glass-ceramics prepared from spent hydrogenation catalysts;

[0034] Figure 2 SEM image of glass-ceramics prepared from waste hydrogenation catalyst. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0036] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0037] The main components of the spent hydrogenation catalysts used in the following examples and comparative examples are as follows:

[0038] Al2O3 (60~74%), MoO3 (11~26%) and NiO (3~7%).

[0039] In the following embodiments, a thermal expansion meter was used to test the length change of the microcrystalline glass within the range of 30 to 600°C, and the thermal expansion curve was obtained.

[0040] Example 1

[0041] This embodiment provides a method for reusing spent hydrogenation catalysts, the steps of which are as follows:

[0042] (1) The waste hydrogenation catalyst (20%), lithium carbonate (Li2O) (9.26%), Al2O3 (8.42%), SiO2 (53.05%), boric acid (B2O3) (6.74%) and TiO2 (2.53%) were mixed by mass fraction.

[0043] (2) The mixture from step (1) is ball-milled and mixed evenly, with the particle size controlled at 100-200 mesh.

[0044] (3) Melt the mixture obtained in step (2) at 1530°C for 3 hours.

[0045] (4) Pour the melt obtained in step (3) into a graphite mold and transfer it to a muffle furnace for annealing at 560°C for 3 hours.

[0046] (5) After the product of step (4) is subjected to crystallization heat treatment at 660°C for 2 hours, it is cooled to room temperature to obtain a low coefficient of thermal expansion microcrystalline glass.

[0047] The coefficient of thermal expansion of the glass-ceramic at 600℃ was determined to be 1.1 × 10⁻⁶. -6 / ℃.

[0048] Example 2

[0049] This embodiment provides a method for reusing spent hydrogenation catalysts, the steps of which are as follows:

[0050] (1) The waste hydrogenation catalyst (25%), lithium carbonate (Li2O) (8.68%), Al2O3 (7.89%), SiO2 (49.74%), boric acid (B2O3) (6.32%) and TiO2 (2.37%) were mixed by mass fraction.

[0051] (2) The mixture from step (1) is ball-milled and mixed evenly, with the particle size controlled at 100-200 mesh.

[0052] (3) Melt the mixture obtained in step (2) at 1560°C for 3 hours.

[0053] (4) Pour the melt obtained in step (3) into a graphite mold and transfer it to a muffle furnace for annealing at 580°C for 3 hours.

[0054] (5) After the product of step (4) is subjected to crystallization heat treatment at 660°C for 2 hours, it is cooled to room temperature to obtain a low coefficient of thermal expansion microcrystalline glass.

[0055] The coefficient of thermal expansion of the obtained microcrystalline glass at 600℃ was measured to be 0.98 × 10⁻⁶. -6 / ℃.

[0056] Example 3

[0057] This embodiment provides a method for reusing spent hydrogenation catalysts, the steps of which are as follows:

[0058] (1) The waste hydrogenation catalyst (25%), lithium carbonate (Li2O) (8.68%), Al2O3 (7.89%), SiO2 (49.74%), boric acid (B2O3) (6.32%) and TiO2 (2.37%) were mixed by mass fraction.

[0059] (2) The mixture from step (1) is ball-milled and mixed evenly, with the particle size controlled at 100-200 mesh.

[0060] (3) Melt the mixture obtained in step (2) at 1550°C for 3 hours.

[0061] (4) Pour the melt obtained in step (3) into a graphite mold and transfer it to a muffle furnace for annealing at 580°C for 3 hours.

[0062] (5) After the product of step (4) is subjected to crystallization heat treatment at 685℃ for 2 hours, it is cooled to room temperature to obtain a low expansion coefficient microcrystalline glass.

[0063] The microcrystalline glass phase precipitates as β-quartz phase (Li2Al2Si3O). 10) and β-spodumene phase (LiAl(SiO3)2), XRD patterns are shown below Figure 1 As shown, the crystal size is 20-40nm, and the SEM image is as follows. Figure 2 As shown, the coefficient of thermal expansion at 600℃ is 0.96 × 10⁻⁶. -6 / ℃.

[0064] Comparative Example 1

[0065] This comparative example provides a method for reusing spent hydrogenation catalysts, the steps of which are as follows:

[0066] (1) The waste hydrogenation catalyst (25%), lithium carbonate (Li2O) (8.68%), Al2O3 (7.89%), SiO2 (49.74%), boric acid (B2O3) (6.32%) and TiO2 (2.37%) were mixed by mass fraction.

[0067] (2) The mixture from step (1) is ball-milled and mixed evenly, with the particle size controlled at 100-200 mesh.

[0068] (3) Melt the mixture obtained in step (2) at 1550°C for 3 hours.

[0069] (4) Pour the melt obtained in step (3) into a graphite mold and cool it to room temperature.

[0070] (5) After the product of step (4) is subjected to crystallization heat treatment at 685°C for 2 hours, it is cooled to room temperature to obtain microcrystalline glass.

[0071] The microcrystalline glass phase precipitates as β-quartz phase (Li2Al2Si3O). 10 The coefficient of thermal expansion of the phases β-spodumene (LiAl(SiO3)2) and β-spodumene was determined to be 0.966 × 10⁻⁶ at 600 °C. -6 / ℃. Compared with annealed microcrystalline glass, the coefficient of thermal expansion of unannealed microcrystalline glass is not significantly different, but the unannealed base glass is prone to cracking, which is not conducive to the large-scale production of microcrystalline glass.

[0072] Comparative Example 2

[0073] This comparative example provides a method for reusing spent hydrogenation catalysts, the steps of which are as follows:

[0074] (1) The waste hydrogenation catalyst (25%), lithium carbonate (Li2O) (8.68%), Al2O3 (7.89%), SiO2 (49.74%), boric acid (B2O3) (6.32%) and TiO2 (2.37%) were mixed by mass fraction.

[0075] (2) The mixture from step (1) is ball-milled and mixed evenly, with the particle size controlled at 100-200 mesh.

[0076] (3) Melt the mixture obtained in step (2) at 1550°C for 3 hours.

[0077] (4) Pour the melt obtained in step (3) into a graphite mold and transfer it to a muffle furnace for annealing at 580°C for 3 hours.

[0078] (5) After the product of step (4) is subjected to crystallization heat treatment at 600℃ for 2 hours, it is cooled to room temperature to obtain glass product.

[0079] The glass product obtained in this comparative example did not crystallize and remained in the glass phase, failing to be prepared into a microcrystalline glass. Its coefficient of thermal expansion at 600℃ was 6.9 × 10⁻⁶. -6 / ℃.

[0080] Comparative Example 3

[0081] This comparative example provides a method for reusing spent hydrogenation catalysts, the steps of which are as follows:

[0082] (1) The waste hydrogenation catalyst (25%), lithium carbonate (Li2O) (8.68%), Al2O3 (7.89%), SiO2 (49.74%), boric acid (B2O3) (6.32%) and TiO2 (2.37%) were mixed by mass fraction.

[0083] (2) The mixture from step (1) is ball-milled and mixed evenly, with the particle size controlled at 100-200 mesh.

[0084] (3) Melt the mixture obtained in step (2) at 1550°C for 3 hours.

[0085] (4) Pour the melt obtained in step (3) into a graphite mold and transfer it to a muffle furnace for annealing at 580°C for 3 hours.

[0086] (5) After the product of step (4) is subjected to crystallization heat treatment at 750°C for 2 hours, it is cooled to room temperature to obtain microcrystalline glass.

[0087] The obtained microcrystalline glass phase precipitated a bulk β-spodumene phase (LiAl(SiO3)2), with crystal sizes ranging from 1 to 2 μm. The coefficient of thermal expansion at 600℃ was measured to be 2.8 × 10⁻⁶. -6 / ℃.

[0088] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention 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 of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for reusing spent hydrogenation catalyst, characterized in that, include: Waste hydrogenation catalyst is mixed with silica, boric acid, titanium dioxide, lithium source and aluminum source, and ball-milled. The resulting mixture is then subjected to melting, annealing and crystallization heat treatment to obtain microcrystalline glass. The waste hydrogenation catalyst contains aluminum. The temperature of the crystallization heat treatment is 635-735℃. The material composition is as follows by mass percentage: 5-25% waste hydrogenation catalyst, 50-63% silicon dioxide, 7-10% aluminum source (calculated as Al2O3), 2-3% titanium dioxide, 8.8-11% lithium source (calculated as Li2O), and 6.3-8% boric acid (calculated as B2O3).

2. The method for reusing spent hydrogenation catalyst according to claim 1, characterized in that, The melting temperature is 1500-1600℃; the melting time is 2-6 hours.

3. The method for reusing spent hydrogenation catalyst according to claim 1, characterized in that, The annealing temperature is 500-600℃; the annealing time is 2-6 hours; and the product after annealing needs to be cooled to room temperature.

4. The method for reusing spent hydrogenation catalyst according to claim 1, characterized in that, The crystallization heat treatment time is 2-4 hours.

5. The method for reusing spent hydrogenation catalyst according to any one of claims 1-4, characterized in that, The lithium source is selected from one or more of Li2CO3 and LiOH; And / or, the aluminum source is selected from one or more of Al(OH)3 and Al2O3.

6. The method for reusing spent hydrogenation catalyst according to any one of claims 1-4, characterized in that, The lithium source is Li2CO3; And / or, the aluminum source is Al2O3.

7. The method for reusing spent hydrogenation catalyst according to any one of claims 1-4, characterized in that, After ball milling, the particle size is controlled at 100-200 mesh.

8. The method for reusing spent hydrogenation catalyst according to any one of claims 1-4, characterized in that, The reuse method includes the following steps: (1) By mass percentage, 5-25% of waste hydrogenation catalyst, 50-63% of silicon dioxide, 7-10% of aluminum source (Al2O3), 2-3% of titanium dioxide, 8.8-11% of lithium source (Li2O), and 6.3-8% of boric acid (B2O3) are mixed. (2) The mixture obtained in step (1) is ball-milled and the particle size is controlled to be 100-200 mesh; (3) Melt the mixture obtained in step (2) at 1500-1600℃ for 2-6 hours; (4) Pour the melt obtained in step (3) into a mold, transfer it to a muffle furnace and anneal at 500-600℃ for 2-6 hours, then cool the product to room temperature; (5) After the cooling product obtained in step (4) is subjected to crystallization heat treatment at 635-735℃ for 2-4 hours, it is cooled to room temperature to obtain microcrystalline glass.

9. The method for reusing spent hydrogenation catalyst according to claim 5, characterized in that, The reuse method includes the following steps: (1) By mass percentage, 5-25% of waste hydrogenation catalyst, 50-63% of silicon dioxide, 7-10% of aluminum source (Al2O3), 2-3% of titanium dioxide, 8.8-11% of lithium source (Li2O), and 6.3-8% of boric acid (B2O3) are mixed. (2) The mixture obtained in step (1) is ball-milled and the particle size is controlled to be 100-200 mesh; (3) Melt the mixture obtained in step (2) at 1500-1600℃ for 2-6 hours; (4) Pour the melt obtained in step (3) into a mold, transfer it to a muffle furnace and anneal at 500-600℃ for 2-6 hours, then cool the product to room temperature; (5) After the cooling product obtained in step (4) is subjected to crystallization heat treatment at 635-735℃ for 2-4 hours, it is cooled to room temperature to obtain microcrystalline glass.

10. The method for reusing spent hydrogenation catalyst according to claim 6, characterized in that, The reuse method includes the following steps: (1) By mass percentage, 5-25% of waste hydrogenation catalyst, 50-63% of silicon dioxide, 7-10% of aluminum source (Al2O3), 2-3% of titanium dioxide, 8.8-11% of lithium source (Li2O), and 6.3-8% of boric acid (B2O3) are mixed. (2) The mixture obtained in step (1) is ball-milled and the particle size is controlled to be 100-200 mesh; (3) Melt the mixture obtained in step (2) at 1500-1600℃ for 2-6 hours; (4) Pour the melt obtained in step (3) into a mold, transfer it to a muffle furnace and anneal at 500-600℃ for 2-6 hours, then cool the product to room temperature; (5) After the cooling product obtained in step (4) is subjected to crystallization heat treatment at 635-735℃ for 2-4 hours, it is cooled to room temperature to obtain microcrystalline glass.

11. The method for reusing spent hydrogenation catalyst according to claim 7, characterized in that, The reuse method includes the following steps: (1) By mass percentage, 5-25% of waste hydrogenation catalyst, 50-63% of silicon dioxide, 7-10% of aluminum source (Al2O3), 2-3% of titanium dioxide, 8.8-11% of lithium source (Li2O), and 6.3-8% of boric acid (B2O3) are mixed. (2) The mixture obtained in step (1) is ball-milled and the particle size is controlled to be 100-200 mesh; (3) Melt the mixture obtained in step (2) at 1500-1600℃ for 2-6 hours; (4) Pour the melt obtained in step (3) into a mold, transfer it to a muffle furnace and anneal at 500-600℃ for 2-6 hours, then cool the product to room temperature; (5) After the cooling product obtained in step (4) is subjected to crystallization heat treatment at 635-735℃ for 2-4 hours, it is cooled to room temperature to obtain microcrystalline glass.

12. The method for reusing spent hydrogenation catalyst according to claim 1, characterized in that, The melting temperature is 1530-1560℃, and the melting time is 2-3 hours.

13. The method for reusing spent hydrogenation catalyst according to claim 1, characterized in that, The annealing temperature is 550-580℃; the annealing time is 3-4 hours; and the product after annealing needs to be cooled to room temperature.

14. The method for reusing spent hydrogenation catalyst according to any one of claims 1-4, 9-13, characterized in that, The coefficient of thermal expansion of the microcrystalline glass at 600℃ is less than or equal to 1.1 × 10⁻⁶. -6 / ℃.

15. The method for reusing spent hydrogenation catalyst according to claim 5, characterized in that, The coefficient of thermal expansion of the microcrystalline glass at 600℃ is less than or equal to 1.1 × 10⁻⁶. -6 / ℃.

16. The method for reusing spent hydrogenation catalyst according to claim 6, characterized in that, The coefficient of thermal expansion of the microcrystalline glass at 600℃ is less than or equal to 1.1 × 10⁻⁶. -6 / ℃.

17. The method for reusing spent hydrogenation catalyst according to claim 7, characterized in that, The coefficient of thermal expansion of the microcrystalline glass at 600℃ is less than or equal to 1.1 × 10⁻⁶. -6 / ℃.

18. The method for reusing spent hydrogenation catalyst according to claim 8, characterized in that, The coefficient of thermal expansion of the microcrystalline glass at 600℃ is less than or equal to 1.1 × 10⁻⁶. -6 / ℃.

19. The application of the method for reusing the waste hydrogenation catalyst according to any one of claims 1-18 in the comprehensive utilization of solid waste.

Images