CN-117363957-B - Method for preparing special steel by using waste hydrogenation catalyst in short process

Abstract

The invention discloses a method for preparing special steel by a short process of a waste hydrogenation catalyst, and relates to the field of solid waste recycling. The method uses waste hydrogenation catalyst as raw material, and according to its metal elements, the waste catalyst is divided into Mo-Ni system, mo-Co system, W-Ni system and W-Co system, and the waste hydrogenation catalyst, carbon reducing agent and fluxing agent are mixed according to the mixing ratio, smelted, reduced and separated to obtain alloy melt and slag phase, and the alloy melt is passed through the processes of oxidation, slagging and removing phosphorus, carbon and silicon, etc. so as to obtain the purified intermediate alloy melt for special steel, and according to the requirements for special steel component proportion the intermediate alloy melt can be regulated, and the intermediate alloy melt can be added into molten steel, and refined and cast so as to obtain the special steel. The method takes the waste hydrogenation catalyst as a raw material to produce the intermediate alloy melt for the special steel, prepares the high-value special steel in a short process, has the characteristics of simple process, high efficiency, low cost and the like, and is suitable for industrialization.

Inventors

• ZHANG SHENGEN
• SHI ZHISHENG
• DING YUNJI
• LIU BO

Assignees

• 北京科技大学

Dates

Publication Date

20260505

Application Date

20231008

Claims (3)

1. 1. A method for preparing special steel by using a waste hydrogenation catalyst in a short process is characterized by comprising the following steps: S1, classifying, namely sampling, and classifying the waste hydrogenation catalyst according to metal elements; S2, mixing and smelting, namely mixing the waste hydrogenation catalyst, the reducing agent and the fluxing agent according to a proportion, smelting, and separating to obtain an alloy melt and a slag phase; S3, alloy impurity removal, namely transferring the alloy melt into a converter, and obtaining a purified intermediate alloy melt for special steel through oxygen blowing, slag formation, dephosphorization, carbon and silicon impurity, wherein the oxygen blowing temperature is 1300-1700 ℃, the oxygen supply strength is 1.0-1.3N.m 3 /(min.t), and the purified intermediate alloy melt for special steel is obtained after the oxidation dephosphorization, decarburization, desilication and slag formation, wherein the P is less than or equal to 0.25wt%, the C is less than or equal to 0.90wt% and the Si is less than or equal to 0.30wt%; s4, preparing special steel, namely adding the intermediate alloy melt into molten steel, adjusting the addition amount of the intermediate alloy melt according to the component proportion requirement of the special steel, refining and casting to obtain the special steel; The waste hydrogenation catalyst is divided into Mo-Ni system, mo-Co system, W-Ni system and W-Co system according to the metal elements, wherein the residual oil and carbon deposit are 20-40wt%, fe 2 O 3 is 0-10wt% and the rest is Al 2 O 3 carrier; The Mo-Ni series waste hydrogenation catalyst contains 3-20wt% of MoO 3 , 1-8wt% of NiO and 0-10wt% of V 2 O 5 ; The Mo-Co waste hydrogenation catalyst contains 3-20wt% of MoO 3 , 1-8wt% of CoO and 0-10wt% of V 2 O 5 ; The W-Ni series waste hydrogenation catalyst contains 3-20wt% of WO 3 and 1-8wt% of NiO; the W-Co waste hydrogenation catalyst contains 3-20wt% of WO 3 and 1-8wt% of CoO; The mixing in the step S2 is to mix 80-100 parts of waste hydrogenation catalyst, 5-15 parts of carbon reducer, 30-45 parts of CaO, 5-15 parts of SiO 2 , 1-20 parts of Na 2 CO 3 , 1-10 parts of B 2 O 3 and 1-5 parts of CaF 2 .
2. 2. The method for preparing special steel by using the waste hydrogenation catalyst in a short process according to claim 1, wherein the smelting temperature in the step S2 is 1400-1700 ℃, and the heat preservation time is 0.5-2.0h.
3. 3. The method for preparing special steel by using the short process of the waste hydrogenation catalyst according to claim 1, wherein in the step S3, the intermediate alloy melt for the special steel is one of NiMo alloy, coMo alloy, niW alloy, coW alloy, niMoV alloy and CoMoV alloy.

Description

Method for preparing special steel by using waste hydrogenation catalyst in short process Technical Field The invention relates to the field of solid waste recycling, in particular to a method for preparing special steel by a short process of a waste hydrogenation catalyst. Background The petrochemical industry is the pillar industry in China. By 2022, the petroleum processing amount of China reaches 6.78 tons. Wherein the catalytic processing treatment amount accounts for 45% of the petroleum processing amount. Catalytic hydrogenation is therefore an important process in the petrochemical field. The core of catalytic hydrogenation is a hydrogenation catalyst. The hydrogenation catalyst consists of active components such as carriers Al 2O3 and Mo, W, ni, co and is used for hydrodeoxygenation, desulfurization, demetallization and the like. The service life of the hydrogenation catalyst is slightly different due to different treatment raw materials, and is generally 0.5-3 years, and the hydrogenation catalyst is scrapped due to carbon deposition, surface active phase sintering and the like. The waste hydrogenation catalyst is dangerous waste, the annual production amount is more than 20 ten thousand tons, and in addition, the waste catalyst contains more than 10 weight percent of valuable metals such as Mo, W, ni, co, V and the like, and is an important secondary resource. Therefore, the recycling utilization of the waste hydrogenation catalyst can avoid the harm of the waste catalyst to the environment, is beneficial to the sustainable development of Mo, W, ni, co, V and other metals, and has important environmental and economic benefits. The recovery method of the waste hydrogenation catalyst comprises a roasting-leaching method and a pyrogenic enrichment-leaching method, valuable metals are leached into a solution, and recovery of the valuable metals is realized through precipitation, ion exchange and solvent extraction separation methods. Chinese patent (CN 115074554B) discloses a method for separating and recovering molybdenum and nickel from waste hydrogenation catalyst, the waste hydrogenation catalyst is roasted in an oxygen-enriched mode, acetic acid is adopted for leaching, oxalic acid is added into the leaching solution for separating nickel oxalate, and the leaching solution is subjected to evaporation crystallization to recover molybdenum acetate. The method has simple flow, economy and high efficiency, but the recovery process uses a large amount of organic acid, and has high cost and heavy environmental burden. Sulfating roasting can improve the leaching rate of subsequent metals. Chinese patent (CN 114807606B) discloses a full-component recovery method of waste hydrogenation catalyst, the waste hydrogenation catalyst is pretreated by vacuum pyrolysis deoiling, sulfating roasting water leaching to obtain leaching solution, and vanadyl sulfate, ammonium molybdate, nickel sulfate and aluminum sulfate are obtained by solvent extraction-back extraction separation. The method realizes the full-component recovery of the waste hydrogenation catalyst, but has the problems of long flow, high salt and large wastewater amount. The pyrometallurgy has the advantages of large solid waste disposal amount, greenness, high efficiency and the like, and is widely applied to the recycling of solid waste. Chinese patent (CN 106282570B) discloses a method for recovering metal elements from waste catalyst, obtaining nickel-cobalt-tungsten-molybdenum-vanadium-iron alloy by pyrometallurgy, and recovering valuable metals by wet separation steps of pressure acid leaching, alkaline leaching, ion exchange, precipitation, etc. The method can efficiently enrich alloy through pyrometallurgy, and realize recovery of valuable metals through wet separation, but the leaching and separation processes are complex, and a large amount of wastewater is generated. The method for recovering and separating valuable metals of the waste hydrogenation catalyst is wet separation, and has the problems of large waste water amount and long process flow. The Chinese patent (CN 114959269B) adopts a pyrogenic process to enrich and obtain the nickel-cobalt-molybdenum-tungsten-vanadium-iron alloy, and adopts oxygen blowing to selectively separate and obtain vanadium iron slag and nickel-cobalt-molybdenum alloy, and adopts further aluminothermic reduction to prepare the vanadium-iron alloy. The method has high efficiency, low cost and no wastewater discharge, but one of the products is still intermediate alloy, and the intermediate alloy is to be recovered in a high-value way. The existing recycling modes of the waste hydrogenation catalyst are two main types, namely, wet extraction of valuable metals, and pyrogenic reduction to obtain alloys or further separation to obtain single valuable metals. In summary, the existing recycling method of the waste hydrogenation catalyst has long flow, heavy environmental load and no realization of green high-valu