Method for producing special steel by short process of spent hydrogenation catalyst

Abstract

This invention discloses a short-process method for preparing special steel from waste hydrogenation catalysts, relating to the field of solid waste resource utilization. The method uses waste hydrogenation catalysts as raw materials, classifying them into Mo-Ni, Mo-Co, W-Ni, and W-Co series based on their metal elements. The waste hydrogenation catalyst, carbon reducing agent, and flux are mixed and smelted according to a specific ratio, followed by reduction and separation to obtain an alloy melt and slag phase. The alloy melt is then purified by oxidation and slag formation to remove impurities such as phosphorus, carbon, and silicon, yielding a purified intermediate alloy melt for special steel. The amount of intermediate alloy melt added is adjusted according to the required proportions of special steel components, and the melt is added to molten steel. The special steel is then obtained through refining and casting. This method, using waste hydrogenation catalysts as raw materials to produce intermediate alloy melts for special steel, enables the short-process preparation of high-value special steel. It features simple technology, high efficiency, and low cost, making it suitable for industrialization.

Description

Technical Field

[0001] This invention relates to the field of solid waste resource utilization, specifically to a short-process method for preparing special steel from waste hydrogenation catalysts. Background Technology

[0002] The petrochemical industry is a pillar industry in my country. As of 2022, my country's petroleum processing volume reached 6.78 billion tons. Among them, catalytic processing accounted for 45% of the petroleum processing volume. Therefore, catalytic hydrogenation is an important process in the petrochemical field. The core of catalytic hydrogenation is the hydrogenation catalyst. The hydrogenation catalyst is composed of a support Al2O3 and active components such as Mo, W, Ni, and Co, and is used for hydrogenation deoxygenation, desulfurization, and demetallization. The service life of hydrogenation catalysts varies slightly depending on the raw materials used, generally ranging from 0.5 to 3 years, after which they are scrapped due to carbon buildup, sintering of the surface active phase, and other reasons. Waste hydrogenation catalysts are hazardous waste, with an annual generation exceeding 200,000 tons; in addition, waste catalysts contain more than 10 wt% of valuable metals such as Mo, W, Ni, Co, and V, which are important secondary resources. Therefore, the resource utilization of waste hydrogenation catalysts can not only avoid the environmental harm caused by waste catalysts, but also promote the sustainable development of metals such as Mo, W, Ni, Co, and V, and has significant environmental and economic benefits.

[0003] Methods for recovering spent hydrogenation catalysts include roasting-leaching and pyrometallurgical enrichment-leaching, in which valuable metals are leached into a solution and then recovered through precipitation, ion exchange, and solvent extraction.

[0004] Chinese invention patent (CN115074554B) discloses a method for separating and recovering molybdenum and nickel from spent hydrogenation catalysts. The method involves oxygen-enriched roasting of the spent hydrogenation catalyst, leaching with acetic acid, adding oxalic acid to the leachate to separate nickel oxalate, and then evaporating and crystallizing the leachate to recover molybdenum acetate. This method is simple, economical, and efficient, but the recovery process uses large amounts of organic acids, resulting in high costs and a heavy environmental burden.

[0005] Sulfation roasting can improve the leaching rate of subsequent metals. Chinese invention patent (CN114807606B) discloses a method for the complete recovery of waste hydrogenation catalysts. The waste hydrogenation catalyst undergoes vacuum thermal deoiling pretreatment, followed by sulfation roasting and water leaching to obtain a leachate. The leachate is then separated by solvent extraction-back-extraction to obtain vanadium oxysulfate, ammonium molybdate, nickel sulfate, and aluminum sulfate. This method achieves complete recovery of waste hydrogenation catalysts, but it suffers from a long process and a large volume of high-salt wastewater.

[0006] Pyrometallurgical smelting has advantages such as large-scale solid waste disposal and high efficiency, and is widely used in the resource utilization of solid waste. Chinese invention patent (CN106282570B) discloses a method for recovering metal elements from spent catalysts. This method involves obtaining a nickel-cobalt-tungsten-molybdenum-vanadium-iron alloy through pyrometallurgical smelting, and recovering the valuable metals through hydrometallurgical separation steps such as pressurized acid leaching, alkaline leaching, ion exchange, and precipitation. While this method can efficiently enrich metals through pyrometallurgical smelting and recover the valuable metals through hydrometallurgical separation, the leaching and separation processes are complex and generate a large amount of wastewater.

[0007] The methods described above for recovering and separating valuable metals from spent hydrogenation catalysts are all wet separation processes, which suffer from problems such as large wastewater volumes and long process flows. Chinese invention patent (CN114959269B) uses pyrometallurgical enrichment to obtain a nickel-cobalt-molybdenum-tungsten-vanadium-iron alloy, selectively separates it into vanadium-iron slag and the nickel-cobalt-molybdenum alloy through oxygen blowing, and then prepares a vanadium-iron alloy through further aluminothermic reduction. This method is highly efficient, low-cost, and produces no wastewater; however, one of the products, the nickel-cobalt-molybdenum alloy, is still an intermediate alloy and requires further high-value recovery.

[0008] Existing methods for reusing spent hydrogenation catalysts fall into two main categories: one is wet extraction of valuable metals; the other is pyrometallurgical reduction to obtain alloys or further separation to obtain single valuable metals. In summary, existing methods for reusing spent hydrogenation catalysts involve lengthy processes, impose a heavy environmental burden, and fail to achieve green and high-value utilization. There is an urgent need to develop methods for the short-process recovery and high-value utilization of valuable metals.

[0009] To address the existing challenges in reusing spent hydrogenation catalysts, this application discloses a method for preparing an intermediate alloy melt using spent hydrogenation catalysts as raw materials through pyrometallurgical reduction, and then directly preparing special steel from the intermediate alloy melt. Summary of the Invention

[0010] This invention addresses the problems existing in the prior art by providing a short-process method for preparing special steel from waste hydrogenation catalysts. This method features simple process, high efficiency, and low cost, making it suitable for industrialization.

[0011] The present invention adopts the following technical solution:

[0012] A method for preparing special steel from spent hydrogenation catalyst using a short process, characterized by the following steps:

[0013] S1. Classification: Sampling and classifying the waste hydrogenation catalyst according to its metal element;

[0014] S2. Mixing and smelting: The waste hydrogenation catalyst, reducing agent and flux are mixed in proportion, smelted and separated to obtain alloy melt and slag phase;

[0015] S3. Alloy impurity removal: The alloy melt is transferred to a converter and purified by oxygen blowing and slag formation to remove impurities such as phosphorus, carbon, and silicon, to obtain a purified intermediate alloy melt for special steel.

[0016] S4. Preparation of special steel: The special steel is prepared by adding an intermediate alloy to the molten steel, adjusting the amount of intermediate alloy melt added according to the special steel composition ratio requirements, refining, and casting to obtain the special steel.

[0017] The spent hydrogenation catalyst is classified into Mo-Ni, Mo-Co, W-Ni, and W-Co series according to its metal elements; the residual oil and carbon deposits are 20-40 wt%, Fe2O3 is 0-10 wt%, and the remainder is Al2O3 support;

[0018] Mo-Ni based waste hydrogenation catalysts contain 3-20 wt% MoO3, 1-8 wt% NiO, and 0-10 wt% V2O5;

[0019] Mo-Co based waste hydrogenation catalysts contain 3-20 wt% MoO3, 1-8 wt% CoO, and 0-10 wt% V2O5;

[0020] W-Ni series waste hydrogenation catalysts contain 3-20 wt% WO3 and 1-8 wt% NiO;

[0021] W-Co series waste hydrogenation catalysts contain 3-20 wt% WO3 and 1-8 wt% CoO.

[0022] Further, the mixing described in step S2 involves mixing 80-100 parts of waste hydrogenation catalyst, 5-15 parts of carbon reducing agent, 30-45 parts of CaO, 5-15 parts of SiO2, 0-20 parts of Na2CO3, 0-10 parts of B2O3, and 0-5 parts of CaF2.

[0023] Furthermore, the melting temperature in step S2 is 1400-1700℃, and the holding time is 0.5-2.0h.

[0024] Furthermore, in step S3, the alloy impurity removal process involves an oxygen blowing temperature of 1300-1700℃ and an oxygen supply intensity of 1.0-1.3 N·m. 3 / (min·t); After oxidation, dephosphorization, decarburization, desiliconization and slag formation, a purified intermediate alloy melt for special steel is obtained, with P≤0.25wt%, C≤0.90wt%, and Si≤0.30wt%.

[0025] Furthermore, the intermediate alloy melt for special steel is one of NiMo alloy, CoMo alloy, NiW alloy, CoW alloy, NiMoV alloy, and CoMoV alloy.

[0026] Furthermore, the preparation of special steel in step S4 involves adding one or more intermediate alloy melts obtained in step S3 to molten steel, followed by refining and casting to obtain special steel.

[0027] Beneficial technical effects of the present invention:

[0028] (1) The method of the present invention prepares special steel in a short process using waste hydrogenation catalyst, efficiently recovers and utilizes valuable metals in waste, and has the characteristics of simple process, high efficiency and low cost, making it suitable for industrial production;

[0029] (2) The method described in this invention uses a pyrometallurgical process to produce intermediate alloy melt, and makes full use of the calorific value generated by the intermediate alloy melt, avoiding the wet separation of each metal to prepare corresponding compounds, generating no wastewater, with a small environmental burden and low energy consumption;

[0030] (3) The method described in this invention provides a new method for producing special steel with excellent performance and reduces the risk of raw material supply. Attached Figure Description

[0031] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0033] Conversely, this invention encompasses any substitutions, modifications, equivalent methods, and solutions made within the spirit and scope of the invention as defined in the claims. Furthermore, to provide a better understanding of the invention, certain specific details are described in detail below. However, those skilled in the art will fully understand the invention even without these detailed descriptions.

[0034] Example 1

[0035] The Mo-Ni based spent hydrogenation catalyst contained 3 wt% MoO3, 8 wt% NiO, 39 wt% residual oil and carbon deposits, and the remainder was an Al2O3 support. 80 parts of the spent hydrogenation catalyst, 5 parts of carbon reducing agent, 30 parts of CaO, 5 parts of SiO2, and 20 parts of Na2CO3 were mixed and smelted at 1550℃ for 1 hour, separating the NiMo alloy melt and slag phase. The NiMo alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1500℃ and an oxygen supply intensity of 1 N·m. 3After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiMo alloy for special steel is prepared with a P content of 0.05 wt%, a C content of 0.9 wt%, and a Si content of 0.3 wt%. The prepared NiMo alloy is added to molten steel, and the amount of NiMo alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0036] Example 2

[0037] The Mo-Ni based spent hydrogenation catalyst contained 6 wt% MoO3, 7 wt% NiO, 10 wt% V2O5, 28 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 81 parts of the spent hydrogenation catalyst, 6 parts of carbon reducing agent, 31 parts of CaO, 6 parts of SiO2, 19 parts of Na2CO3, 1 part of B2O3, and 1 part of CaF2 were mixed and smelted at 1680℃ for 0.6 h. The NiMoV alloy melt and slag phase were then separated. The NiMoV alloy melt was transferred to a converter for oxygen blowing to remove impurities. The oxygen blowing temperature was 1650℃, and the oxygen supply intensity was 1.1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiMoV alloy for special steel was prepared with a P content of 0.1 wt%, a C content of 0.8 wt%, and a Si content of 0.27 wt%. The prepared NiMoV alloy was added to the molten steel, and the amount of NiMoV alloy added was adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot was obtained.

[0038] Example 3

[0039] The Mo-Ni based spent hydrogenation catalyst contained 9 wt% MoO3, 6 wt% NiO, 8 wt% V2O5, 1 wt% Fe2O3, and 28 wt% residual oil, carbon deposits, and other components, with the remainder being an Al2O3 support. 82 parts of the spent hydrogenation catalyst, 7 parts of carbon reducing agent, 32 parts of CaO, 7 parts of SiO2, 18 parts of Na2CO3, 2 parts of B2O3, and 2 parts of CaF2 were mixed and smelted at 1660℃ for 0.7 h. The NiMoV alloy melt and slag phase were then separated. The NiMoV alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1610℃ and an oxygen supply intensity of 1.2 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiMoV alloy for special steel was prepared with a P content of 0.15 wt%, a C content of 0.7 wt%, and a Si content of 0.24 wt%. The prepared NiMoV alloy was added to the molten steel, and the amount of NiMoV alloy added was adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot was obtained.

[0040] Example 4

[0041] The Mo-Ni based spent hydrogenation catalyst contained 12 wt% MoO3, 5 wt% NiO, 6 wt% V2O5, 3 wt% Fe2O3, and 27 wt% residual oil, carbon deposits, and other components, with the remainder being an Al2O3 support. 83 parts of the spent hydrogenation catalyst, 8 parts of carbon reducing agent, 33 parts of CaO, 8 parts of SiO2, 17 parts of Na2CO3, 3 parts of B2O3, and 3 parts of CaF2 were mixed and smelted at 1640℃ for 0.8 h. The NiMoV alloy melt and slag phase were then separated. The NiMoV alloy melt was transferred to a converter for oxygen blowing to remove impurities. The oxygen blowing temperature was 1590℃, and the oxygen supply intensity was 1.3 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiMoV alloy for special steel was prepared with a P content of 0.2 wt%, a C content of 0.6 wt%, and a Si content of 0.21 wt%. The prepared NiMoV alloy was added to the molten steel, and the amount of NiMoV alloy added was adjusted according to the requirements of the special steel composition ratio. After refining and casting, a special steel ingot was obtained.

[0042] Example 5

[0043] The Mo-Ni based spent hydrogenation catalyst contained 15 wt% MoO3, 4 wt% NiO, 4 wt% V2O5, 5 wt% Fe2O3, 26 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 84 parts of the spent hydrogenation catalyst, 9 parts of carbon reducing agent, 34 parts of CaO, 9 parts of SiO2, 16 parts of Na2CO3, 4 parts of B2O3, and 4 parts of CaF2 were mixed and smelted at 1620℃ for 0.9 h. The NiMoV alloy melt and slag phase were then separated. The NiMoV alloy melt was transferred to a converter for oxygen blowing to remove impurities. The oxygen blowing temperature was 1570℃, and the oxygen supply intensity was 1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiMoV alloy for special steel was prepared with a P content of 0.25 wt%, a C content of 0.5 wt%, and a Si content of 0.18 wt%. The prepared NiMoV alloy was added to the molten steel, and the amount of NiMoV alloy added was adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot was obtained.

[0044] Example 6

[0045] The Mo-Ni based spent hydrogenation catalyst contained 18 wt% MoO3, 3 wt% NiO, 2 wt% V2O5, 7 wt% Fe2O3, and 25 wt% residual oil, carbon deposits, and other components, with the remainder being an Al2O3 support. 85 parts of the spent hydrogenation catalyst, 10 parts of carbon reducing agent, 35 parts of CaO, 10 parts of SiO2, 15 parts of Na2CO3, 5 parts of B2O3, and 5 parts of CaF2 were mixed and smelted at 1600℃ for 1 hour. The NiMoV alloy melt and slag phase were then separated. The NiMoV alloy melt was transferred to a converter for oxygen blowing to remove impurities. The oxygen blowing temperature was 1550℃, and the oxygen supply intensity was 1.1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiMoV alloy for special steel is prepared with a P content of 0.05 wt%, a C content of 0.4 wt%, and a Si content of 0.15 wt%. The prepared NiMoV alloy is added to the molten steel, and the amount of NiMoV alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0046] Example 7

[0047] The Mo-Ni based spent hydrogenation catalyst contained 20 wt% MoO3, 2 wt% NiO, 9 wt% Fe2O3, 25 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 86 parts of the spent hydrogenation catalyst, 11 parts of carbon reducing agent, 36 parts of CaO, 11 parts of SiO2, 14 parts of Na2CO3, 6 parts of B2O3, and 4 parts of CaF2 were mixed and smelted at 1580℃ for 1.1 h, resulting in the separation of NiMo alloy melt and slag phase. The NiMo alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1530℃ and an oxygen supply intensity of 1.2 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiMo alloy for special steel is prepared with a P content of 0.1 wt%, a C content of 0.3 wt%, and a Si content of 0.12 wt%. The prepared NiMo alloy is added to the molten steel, and the amount of NiMo alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0048] Example 8

[0049] The Mo-Co based spent hydrogenation catalyst contained 2 wt% MoO3, 10 wt% V2O5, 8 wt% CoO, and 37 wt% residual oil, carbon deposits, and other components, with the remainder being an Al2O3 support. 87 parts of the spent hydrogenation catalyst, 12 parts of carbon reducing agent, 37 parts of CaO, 12 parts of SiO2, 13 parts of Na2CO3, 7 parts of B2O3, and 3 parts of CaF2 were mixed and smelted at 1560℃ for 1.2 h. The resulting CoMoV alloy melt and slag phase were then separated. The CoMoV alloy melt was transferred to a converter for oxygen blowing to remove impurities. The oxygen blowing temperature was 1510℃, and the oxygen supply intensity was 1.3 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoMoV alloy for special steel was prepared with a P content of 0.15 wt%, a C content of 0.2 wt%, and a Si content of 0.09 wt%. The prepared CoMoV alloy was added to the molten steel, and the amount of CoMoV alloy added was adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot was obtained.

[0050] Example 9

[0051] The Mo-Co based spent hydrogenation catalyst contained 5 wt% MoO3, 9 wt% V2O5, 7 wt% CoO, and 37 wt% residual oil, carbon deposits, and other components, with the remainder being an Al2O3 support. 88 parts of the spent hydrogenation catalyst, 13 parts of carbon reducing agent, 38 parts of CaO, 13 parts of SiO2, 12 parts of Na2CO3, 8 parts of B2O3, and 2 parts of CaF2 were mixed and smelted at 1540℃ for 1.3 h. The resulting CoMoV alloy melt and slag phase were then separated. The CoMoV alloy melt was transferred to a converter for oxygen blowing to remove impurities. The oxygen blowing temperature was 1490℃, and the oxygen supply intensity was 1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoMoV alloy for special steel was prepared with a P content of 0.2 wt%, a C content of 0.1 wt%, and a Si content of 0.06 wt%. The prepared CoMoV alloy was added to the molten steel, and the amount of CoMoV alloy added was adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot was obtained.

[0052] Example 10

[0053] The Mo-Co based spent hydrogenation catalyst contained 8 wt% MoO3, 7 wt% V2O5, 6 wt% CoO, 2 wt% Fe2O3, and 36 wt% residual oil, carbon deposits, and other components, with the remainder being Al2O3 support. 89 parts of the spent hydrogenation catalyst, 14 parts of carbon reducing agent, 39 parts of CaO, 14 parts of SiO2, 11 parts of Na2CO3, 9 parts of B2O3, and 1 part of CaF2 were mixed and smelted at 1520℃ for 1.4 h. The resulting CoMoV alloy melt and slag phase were then separated. The CoMoV alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1470℃ and an oxygen supply intensity of 1.1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoMoV alloy for special steel is prepared with a P content of 0.25 wt%, a C content of 0.1 wt%, and a Si content of 0.05 wt%. The prepared CoMoV alloy is added to the molten steel, and the amount of CoMoV alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0054] Example 11

[0055] The Mo-Co based spent hydrogenation catalyst contained 11 wt% MoO3, 5 wt% V2O5, 5 wt% CoO, 4 wt% Fe2O3, and 35 wt% residual oil, carbon deposits, and other components, with the remainder being an Al2O3 support. 90 parts of the spent hydrogenation catalyst, 15 parts of carbon reducing agent, 40 parts of CaO, 15 parts of SiO2, 10 parts of Na2CO3, and 10 parts of B2O3 were mixed and smelted at 1500℃ for 1.5 h, resulting in the separation of CoMoV alloy melt and slag phase. The CoMoV alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1450℃ and an oxygen supply intensity of 1.2 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoMoV alloy for special steel is prepared with a P content of 0.05 wt%, a C content of 0.1 wt%, and a Si content of 0.05 wt%. The prepared CoMoV alloy is added to the molten steel, and the amount of CoMoV alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0056] Example 12

[0057] The Mo-Co based spent hydrogenation catalyst contained 14 wt% MoO3, 4 wt% CoO, 6 wt% Fe2O3, 37 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 91 parts of the spent hydrogenation catalyst, 5 parts of carbon reducing agent, 41 parts of CaO, 14 parts of SiO2, 9 parts of Na2CO3, 9 parts of B2O3, and 1 part of CaF2 were mixed and smelted at 1480℃ for 1.6 h, resulting in the separation of CoMo alloy melt and slag phase. The CoMo alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1430℃ and an oxygen supply intensity of 1.3 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoMo alloy for special steel is prepared with a P content of 0.1 wt%, a C content of 0.1 wt%, and a Si content of 0.05 wt%. The prepared CoMo alloy is added to the molten steel, and the amount of CoMo alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0058] Example 13

[0059] The Mo-Co based spent hydrogenation catalyst contained 17 wt% MoO3, 3 wt% CoO, 8 wt% Fe2O3, 34 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 92 parts of spent hydrogenation catalyst, 6 parts of carbon reducing agent, 42 parts of CaO, 13 parts of SiO2, 8 parts of Na2CO3, 8 parts of B2O3, and 2 parts of CaF2 were mixed and smelted at 1460℃ for 1.7 h, separating the CoMo alloy melt and slag phase. The CoMo alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1400℃ and an oxygen supply intensity of 1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoMo alloy for special steel is prepared with a P content of 0.15 wt%, a C content of 0.1 wt%, and a Si content of 0.05 wt%. The prepared CoMo alloy is added to the molten steel, and the amount of CoMo alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0060] Example 14

[0061] The Mo-Co based spent hydrogenation catalyst contained 20 wt% MoO3, 2 wt% CoO, 10 wt% Fe2O3, 31 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 93 parts of the spent hydrogenation catalyst, 7 parts of carbon reducing agent, 43 parts of CaO, 12 parts of SiO2, 7 parts of Na2CO3, 7 parts of B2O3, and 3 parts of CaF2 were mixed and smelted at 1440℃ for 1.8 h. The resulting CoMo alloy melt and slag phase were then separated. The CoMo alloy melt was transferred to a converter for oxygen blowing to remove impurities. The oxygen blowing temperature was 1390℃, and the oxygen supply intensity was 1.1 N·m. 3After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoMo alloy for special steel is prepared with a P content of 0.2 wt%, a C content of 0.15 wt%, and a Si content of 0.05 wt%. The prepared CoMo alloy is added to the molten steel, and the amount of CoMo alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0062] Example 15

[0063] The W-Ni series spent hydrogenation catalyst contained 8 wt% NiO, 20 wt% WO3, 37 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 94 parts of the spent hydrogenation catalyst, 8 parts of carbon reducing agent, 44 parts of CaO, 11 parts of SiO2, 6 parts of Na2CO3, 6 parts of B2O3, and 4 parts of CaF2 were mixed and smelted at 1420℃ for 1.9 h, resulting in the separation of NiW alloy melt and slag phase. The NiW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1370℃ and an oxygen supply intensity of 1.2 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiW alloy for special steel is prepared with a P content of 0.25 wt%, a C content of 0.2 wt%, and a Si content of 0.08 wt%. The prepared NiW alloy is added to molten steel, and the amount of NiW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0064] Example 16

[0065] The W-Ni series spent hydrogenation catalyst contained 7 wt% NiO, 18 wt% WO3, 38 wt% residual oil and carbon deposits, and the remainder was an Al2O3 support. 95 parts of the spent hydrogenation catalyst, 9 parts of carbon reducing agent, 45 parts of CaO, 10 parts of SiO2, 5 parts of Na2CO3, 5 parts of B2O3, and 5 parts of CaF2 were mixed and smelted at 1400℃ for 2 hours. The NiW alloy melt and slag phase were then separated. The NiW alloy melt was transferred to a converter for oxygen blowing to remove impurities. The oxygen blowing temperature was 1300℃, and the oxygen supply intensity was 1.3 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiW alloy for special steel is prepared with a P content of 0.05 wt%, a C content of 0.25 wt%, and a Si content of 0.11 wt%. The prepared NiW alloy is added to molten steel, and the amount of NiW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0066] Example 17

[0067] The W-Ni series spent hydrogenation catalyst contained 6 wt% NiO, 15 wt% WO3, 1 wt% Fe2O3, 40 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 96 parts of the spent hydrogenation catalyst, 10 parts of carbon reducing agent, 44 parts of CaO, 9 parts of SiO2, 4 parts of Na2CO3, 4 parts of B2O3, and 4 parts of CaF2 were mixed and smelted at 1430℃ for 1.8 h, separating the NiW alloy melt and slag phase. The NiW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1380℃ and an oxygen supply intensity of 1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiW alloy for special steel is prepared with a P content of 0.1 wt%, a C content of 0.3 wt%, and a Si content of 0.14 wt%. The prepared NiW alloy is added to molten steel, and the amount of NiW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0068] Example 18

[0069] The W-Ni series spent hydrogenation catalyst contained 5 wt% NiO, 12 wt% WO3, 3 wt% Fe2O3, 30 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 97 parts of the spent hydrogenation catalyst, 11 parts of carbon reducing agent, 43 parts of CaO, 8 parts of SiO2, 3 parts of Na2CO3, 3 parts of B2O3, and 3 parts of CaF2 were mixed and smelted at 1460℃ for 1.6 h, separating the NiW alloy melt and slag phase. The NiW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1410℃ and an oxygen supply intensity of 1.1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiW alloy for special steel is prepared with a P content of 0.15 wt%, a C content of 0.35 wt%, and a Si content of 0.17 wt%. The prepared NiW alloy is added to molten steel, and the amount of NiW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0070] Example 19

[0071] The W-Ni series spent hydrogenation catalyst contained 4 wt% NiO, 9 wt% WO3, 5 wt% Fe2O3, 34 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 98 parts of the spent hydrogenation catalyst, 12 parts of carbon reducing agent, 42 parts of CaO, 7 parts of SiO2, 2 parts of Na2CO3, 2 parts of B2O3, and 2 parts of CaF2 were mixed and smelted at 1490℃ for 1.4 h, separating the NiW alloy melt and slag phase. The NiW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1440℃ and an oxygen supply intensity of 1.2 N·m. 3After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiW alloy for special steel is prepared with a P content of 0.2 wt%, a C content of 0.4 wt%, and a Si content of 0.2 wt%. The prepared NiW alloy is added to molten steel, and the amount of NiW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0072] Example 20

[0073] The W-Ni series spent hydrogenation catalyst contained 3wt% NiO, 6wt% WO3, 7wt% Fe2O3, 38wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 99 parts of the spent hydrogenation catalyst, 13 parts of carbon reducing agent, 41 parts of CaO, 6 parts of SiO2, 1 part of Na2CO3, 1 part of B2O3, and 1 part of CaF2 were mixed and smelted at 1520℃ for 1.2 h, separating the NiW alloy melt and slag phase. The NiW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1470℃ and an oxygen supply intensity of 1.3 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiW alloy for special steel is prepared with a P content of 0.25 wt%, a C content of 0.45 wt%, and a Si content of 0.23 wt%. The prepared NiW alloy is added to molten steel, and the amount of NiW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0074] Example 21

[0075] The W-Ni series spent hydrogenation catalyst contained 2wt% NiO, 3wt% WO3, 9wt% Fe2O3, 36wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 100 parts of spent hydrogenation catalyst, 14 parts of carbon reducing agent, 40 parts of CaO, 5 parts of SiO2, 20 parts of Na2CO3, 10 parts of B2O3, and 5 parts of CaF2 were mixed and smelted at 1550℃ for 1 hour, separating the NiW alloy melt and slag phase. The NiW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1500℃ and an oxygen supply intensity of 1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a NiW alloy for special steel is prepared with a P content of 0.05 wt%, a C content of 0.5 wt%, and a Si content of 0.26 wt%. The prepared NiW alloy is added to molten steel, and the amount of NiW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0076] Example 22

[0077] The W-Co series spent hydrogenation catalyst contained 8 wt% CoO, 2 wt% WO3, 40 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 97 parts of spent hydrogenation catalyst, 15 parts of carbon reducing agent, 39 parts of CaO, 6 parts of SiO2, 18 parts of Na2CO3, 10 parts of B2O3, and 5 parts of CaF2 were mixed and smelted at 1580℃ for 0.8 h, resulting in the separation of CoW alloy melt and slag phase. The CoW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1530℃ and an oxygen supply intensity of 1.1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoW alloy for special steel is prepared with a P content of 0.1 wt%, a C content of 0.55 wt%, and a Si content of 0.28 wt%. The prepared CoW alloy is added to the molten steel, and the amount of CoW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0078] Example 23

[0079] The W-Co series spent hydrogenation catalyst contained 7 wt% CoO, 5 wt% WO3, 38 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 94 parts of spent hydrogenation catalyst, 5 parts of carbon reducing agent, 38 parts of CaO, 7 parts of SiO2, 16 parts of Na2CO3, 2 parts of B2O3, and 2 parts of CaF2 were mixed and smelted at 1610℃ for 0.6 h, separating the CoW alloy melt and slag phase. The CoW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1560℃ and an oxygen supply intensity of 1.2 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoW alloy for special steel is prepared with a P content of 0.15 wt%, a C content of 0.45 wt%, and a Si content of 0.3 wt%. The prepared CoW alloy is added to the molten steel, and the amount of CoW alloy added is adjusted according to the requirements of the special steel composition ratio. After refining and casting, a special steel ingot is obtained.

[0080] Example 24

[0081] The W-Co series spent hydrogenation catalyst contained 6 wt% CoO, 8 wt% WO3, 2 wt% Fe2O3, 34 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 91 parts of spent hydrogenation catalyst, 7 parts of carbon reducing agent, 37 parts of CaO, 8 parts of SiO2, 12 parts of Na2CO3, 3 parts of B2O3, and 3 parts of CaF2 were mixed and smelted at 1640℃ for 0.5 h, resulting in the separation of CoW alloy melt and slag phase. The CoW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1590℃ and an oxygen supply intensity of 1.3 N·m. 3After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoW alloy for special steel is prepared with a P content of 0.2 wt%, a C content of 0.35 wt%, and a Si content of 0.25 wt%. The prepared CoW alloy is added to the molten steel, and the amount of CoW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0082] Example 25

[0083] The W-Co series spent hydrogenation catalyst contained 5 wt% CoO, 11 wt% WO3, 4 wt% Fe2O3, 30 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 88 parts of spent hydrogenation catalyst, 9 parts of carbon reducing agent, 36 parts of CaO, 9 parts of SiO2, 8 parts of Na2CO3, 4 parts of B2O3, and 4 parts of CaF2 were mixed and smelted at 1670℃ for 0.5 h, separating the CoW alloy melt and slag phase. The CoW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1620℃ and an oxygen supply intensity of 1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoW alloy for special steel is prepared with a P content of 0.25 wt%, a C content of 0.25 wt%, and a Si content of 0.2 wt%. The prepared CoW alloy is added to the molten steel, and the amount of CoW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0084] Example 26

[0085] The W-Co series spent hydrogenation catalyst contained 4 wt% CoO, 14 wt% WO3, 10 wt% Fe2O3, 22 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 85 parts of spent hydrogenation catalyst, 11 parts of carbon reducing agent, 35 parts of CaO, 10 parts of SiO2, 4 parts of Na2CO3, 5 parts of B2O3, and 5 parts of CaF2 were mixed and smelted at 1700℃ for 0.5 h, separating the CoW alloy melt and slag phase. The CoW alloy melt was transferred to a converter for oxygen blowing to remove impurities at 1700℃ and an oxygen supply intensity of 1.1 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoW alloy for special steel is prepared with a P content of 0.05 wt%, a C content of 0.1 wt%, and a Si content of 0.1 wt%. The prepared CoW alloy is added to the molten steel, and the amount of CoW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0086] Example 27

[0087] The W-Co series spent hydrogenation catalyst contained 3 wt% CoO, 17 wt% WO3, 9 wt% Fe2O3, 21 wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 82 parts of spent hydrogenation catalyst, 13 parts of carbon reducing agent, 34 parts of CaO, 11 parts of SiO2, 6 parts of B2O3, and 4 parts of CaF2 were mixed and smelted at 1500℃ for 1.5 h, resulting in the separation of CoW alloy melt and slag phase. The CoW alloy melt was transferred to a converter for oxygen blowing to remove impurities at a temperature of 1350℃ and an oxygen supply intensity of 1.2 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoW alloy for special steel is prepared with a P content of 0.15 wt%, a C content of 0.2 wt%, and a Si content of 0.15 wt%. The prepared CoW alloy is added to the molten steel, and the amount of CoW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

[0088] Example 28

[0089] The W-Co series spent hydrogenation catalyst contained 2wt% CoO, 20wt% WO3, 10wt% Fe2O3, 20wt% residual oil and carbon deposits, and the remainder was Al2O3 support. 80 parts of the spent hydrogenation catalyst, 15 parts of carbon reducing agent, 33 parts of CaO, 12 parts of SiO2, 20 parts of Na2CO3, 7 parts of B2O3, and 3 parts of CaF2 were mixed and smelted at 1700℃ for 0.5 h, resulting in the separation of CoW alloy melt and slag phase. The CoW alloy melt was transferred to a converter for oxygen blowing to remove impurities at 1700℃ and an oxygen supply intensity of 1.3 N·m. 3 After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a CoW alloy for special steel is prepared with a P content of 0.25 wt%, a C content of 0.3 wt%, and a Si content of 0.25 wt%. The prepared CoW alloy is added to the molten steel, and the amount of CoW alloy added is adjusted according to the special steel composition ratio requirements. After refining and casting, a special steel ingot is obtained.

Claims

1. A method for short-process preparation of special steel from spent hydrogenation catalyst, characterized in that, It has the following steps: S1. Classification: Sampling and classifying the waste hydrogenation catalyst according to its metal element; S2. Mixing and smelting: The waste hydrogenation catalyst, reducing agent and flux are mixed in proportion, smelted and separated to obtain alloy melt and slag phase; S3. Alloy impurity removal: The alloy melt is transferred to a converter, where it undergoes oxygen blowing and slag formation to remove phosphorus, carbon, and silicon impurities, resulting in a purified intermediate alloy melt for special steel. The oxygen blowing temperature for this alloy impurity removal is 1300-1700℃, and the oxygen supply intensity is 1.0-1.3 N·m. 3 / (min·t); After oxidation, dephosphorization, decarburization, desiliconization, and slag formation, a purified intermediate alloy melt for special steel is obtained, with P≤0.25wt%, C≤0.90wt%, and Si≤0.30wt%; S4. Preparation of special steel: Add intermediate alloy melt to molten steel, adjust the amount of intermediate alloy melt added according to the special steel composition ratio requirements, and refine and cast to obtain special steel; The waste hydrogenation catalyst is classified into Mo-Ni, Mo-Co, W-Ni, and W-Co series according to its metal element; the residual oil and carbon deposits are 20-40 wt%, Fe2O3 is 0-10 wt%, and the remainder is Al2O3 support; Mo-Ni based spent hydrogenation catalysts contain 3-20 wt% MoO3, 1-8 wt% NiO, and 0-10 wt% V2O5. Mo-Co based spent hydrogenation catalysts contain 3-20 wt% MoO3, 1-8 wt% CoO, and 0-10 wt% V2O5. W-Ni series spent hydrogenation catalysts contain 3-20 wt% WO3 and 1-8 wt% NiO; W-Co series spent hydrogenation catalysts contain 3-20 wt% WO3 and 1-8 wt% CoO; The mixing described in step S2 involves mixing 80-100 parts of waste hydrogenation catalyst, 5-15 parts of carbon reducing agent, 30-45 parts of CaO, 5-15 parts of SiO2, 1-20 parts of Na2CO3, 1-10 parts of B2O3, and 1-5 parts of CaF2.

2. The method for short-process preparation of special steel from waste hydrogenation catalyst according to claim 1, characterized in that, The melting temperature in step S2 is 1400-1700℃, and the holding time is 0.5-2.0h.

3. The method for short-process preparation of special steel from waste hydrogenation catalyst according to claim 1, characterized in that, In step S3, the intermediate alloy melt for special steel is one of NiMo alloy, CoMo alloy, NiW alloy, CoW alloy, NiMoV alloy, and CoMoV alloy.

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