CN-121988336-A - Coke oven gas hydrodesulfurization catalyst and preparation method and application thereof

CN121988336ACN 121988336 ACN121988336 ACN 121988336ACN-121988336-A

Abstract

The invention relates to the technical field of catalysts, and particularly discloses a hydrodesulfurization catalyst for coke oven gas, a preparation method and application thereof, comprising a carrier added with an active component, wherein the carrier is yttrium doped mesoporous pseudo-ordered alumina, the active component comprises nickel nitrate hexahydrate and ammonium meta-tungstate, the mass transfer efficiency is improved through pore regulation and control of the yttrium doped mesoporous pseudo-ordered alumina carrier and an active component dispersing process assisted by a complexing agent, the organic sulfur diffusion requirement is met, the metal-carrier interaction is enhanced through yttrium doping, sintering and carbon deposition generation of the active component are inhibited, the high-temperature stability and long-period activity are improved, the deep desulfurization is realized, the severe purification requirement of the coke oven gas after the subsequent deep processing can be met by combining with the subsequent inorganic sulfur removal, the thermal stability of the carrier is enhanced through doping of yttrium element, the sintering and carbon deposition generation of the active component are inhibited through the strong interaction of metal-carrier, and the stability and the anti-attenuation capability of the catalyst are improved.

Inventors

Xia Xuefa
SUN SHUNPING
GAO YANG
ZHANG ZHAO
CHEN XIANG
ZHANG YUSHENG
MENG XIANGSHUAI
MA BOWEN
HE JIANHONG

Assignees

淮北矿业绿色化工新材料研究院有限公司

Dates

Publication Date: 20260508
Application Date: 20260403

Claims (10)

1. A hydrodesulfurization catalyst for coke oven gas is characterized by comprising a carrier added with an active component, wherein the carrier is yttrium doped mesoporous pseudo-ordered alumina, and the active component comprises nickel nitrate hexahydrate and ammonium metatungstate.
2. A coke oven gas hydrodesulfurization catalyst according to claim 1, characterized in that the active component comprises nickel cobalt nitrate hexahydrate and ammonium heptamolybdate tetrahydrate.
3. A catalyst for hydrodesulfurization of coke oven gas according to claim 1, characterized in that the mass ratio of the nickel nitrate hexahydrate to the carrier is 1.02:4 and the mass ratio of the ammonium metatungstate to the carrier is 1:4.
4. A catalyst for hydrodesulfurization of coke oven gas according to claim 2, characterized in that the mass ratio of the nickel cobalt nitrate hexahydrate to the carrier is 1:4 and the mass ratio of the ammonium heptamolybdate tetrahydrate to the carrier is 1.16:4.
5. A preparation method of a coke oven gas hydrodesulfurization catalyst is characterized by being applied to the coke oven gas hydrodesulfurization catalyst as claimed in any one of claims 1 to 4, and comprises the following steps: S1, dissolving a structure directing agent in ethanol, uniformly stirring at constant temperature until the structure directing agent is completely dissolved, slowly dripping acid, and continuously stirring to obtain a transparent and uniform surfactant solution A; s2, dissolving citric acid in ethanol, sequentially adding an aluminum source and an yttrium source, and stirring to obtain a solution B; S3, slowly pouring the surfactant solution A into the solution B, and continuously stirring to form sol; s4, aging, crystallizing and calcining to obtain the yttrium-doped mesoporous pseudo-ordered alumina carrier; S5, dissolving the active component precursor in deionized water to obtain an impregnating solution, dripping the impregnating solution into the yttrium-doped mesoporous pseudo-ordered alumina carrier, and then impregnating, drying, calcining at the temperature of 450 ℃ for 2 hours to obtain the coke oven gas hydrodesulfurization catalyst.
6. The method for preparing a hydrodesulfurization catalyst for coke oven gas according to claim 5, wherein the structure directing agent used in S1 is triblock copolymer P-123, the temperature of the constant temperature water bath is 40 ℃, the solution used in the process of dropwise adding acid is 0.5M HCl solution, and finally transparent and uniform surfactant solution A is obtained.
7. A process for preparing the hydrodesulfurization catalyst for coke oven gas according to claim 5, wherein the aluminum source and the yttrium source used in S2 are aluminum nitrate nonahydrate and yttrium nitrate hexahydrate, respectively.
8. A process for preparing a catalyst for hydrodesulfurization of coke oven gas according to claim 5, characterized in that the stirring temperature is maintained at 40℃in S3 and the stirring is vigorously carried out for 24 hours to form a sol.
9. The preparation method of the coke oven gas hydrodesulfurization catalyst according to claim 5, wherein the specific operation of aging, crystallization and calcination treatment in S4 is that the sol is transferred into a polytetrafluoroethylene container, the sol is subjected to constant temperature heat treatment for 24 hours at 80 ℃ to promote the ordering of a mesoporous structure, the sol is taken out and subjected to static crystallization in a 60 ℃ oven for 2 days, and then the sol is placed into a muffle furnace for calcination, and the muffle furnace is subjected to calcination at 400 ℃ and calcination at 800 ℃ for 3 hours in sequence, so that the yttrium-doped mesoporous pseudo-ordered alumina carrier is obtained.
10. The application of the coke oven gas hydrodesulfurization catalyst is characterized in that the coke oven gas hydrodesulfurization catalyst is applied to the hydrodesulfurization of coke oven gas according to any one of claims 1 to 4.

Description

Coke oven gas hydrodesulfurization catalyst and preparation method and application thereof Technical Field The invention relates to the technical field of catalysts, in particular to a coke oven gas hydrodesulfurization catalyst and a preparation method and application thereof. Background Coke oven gas is an important byproduct in the coking industry, is rich in various effective components such as hydrogen, methane, carbon monoxide and the like, and is an important chemical raw material. The method is increasingly widely applied in the fields of ammonia synthesis, methanol, high-purity hydrogen and the like, and has important significance for promoting energy structure optimization and chemical industry upgrading. However, coke oven gas generally contains a certain amount of sulfides, and the existence of the sulfides can cause serious harm to a catalyst in the subsequent processing process, so that the catalytic reaction efficiency and the product quality are obviously reduced, the problems of equipment corrosion and the like are also caused, and the production and maintenance cost and the safety risk are increased. Therefore, the coke oven gas needs to be subjected to deep desulfurization treatment. Inorganic sulfur (hydrogen sulfide) in coke oven gas can be removed by desulfurizing agents such as zinc oxide, and organic sulfur such as thiophene, carbonyl sulfide, thioether, carbon disulfide and the like are required to be converted into hydrogen sulfide by hydrodesulfurization, and then are removed by the desulfurizing agents. The current common hydrodesulfurization catalyst takes alumina as a carrier to load active components such as cobalt, molybdenum, nickel and the like. However, the existing catalyst still has some problems in practical application, namely, on one hand, the activity and stability of the catalyst are required to be further improved, the catalytic performance is easy to be reduced due to sintering of active components, carbon deposition and the like in the long-term operation process, and on the other hand, pore canal blocking phenomenon is easy to occur in the preparation or use process of part of the catalyst, the diffusion of reactants and products is influenced, and the desulfurization efficiency is further reduced. These problems limit to some extent the effectiveness of hydrodesulfurization technology in coke oven gas purification. Chinese patent CN112742362B discloses a catalyst for hydrodesulfurization of coke oven gas and a preparation method thereof, wherein the active metal component comprises molybdenum and VIII metal, and the carrier is raspberry oxide microsphere. The prepared catalyst has better mass transfer and heat transfer characteristics and has obviously higher strength than the existing products with similar structures. However, due to the introduction of the blasting agent, serious potential safety hazards exist in industrial production, meanwhile, the carrier drying is required to be carried out at a high temperature of 400-1200 ℃, multiple times of dipping-calcining are required, and the energy consumption of the preparation process is high. Chinese patent CN118179538a discloses a double-function catalyst for hydrodesulfurization of coke oven gas and its preparation method. The catalyst contains a pore canal structure with more large pore diameters, and can absorb, contain and partially convert macromolecular organic matters. However, due to the lack of short-range ordered mesopores and weak metal-support interactions, the thermodynamic stability against sintering is lacking. Chinese patent CN114433112B discloses a catalyst for hydrodesulfurization of coke oven gas and a method for preparing the same. The hydrodesulfurization catalyst for coke oven gas can realize the thiophene conversion rate of more than or equal to 90% at 200 ℃ and the thiophene conversion rate of more than or equal to 95% at 300 ℃. However, the defects of poor safety and economy of a solvent system, overlong preparation period and the like exist, and the large-scale application of the solvent system is restricted. Chinese patent CN108404901B discloses a catalyst for hydrodesulfurization of coke oven gas and a method for preparing the same. The coke oven gas hydrodesulfurization catalyst is a silicon-molybdenum catalyst, has high initial activity, good heat resistance, simple preparation method, convenient operation and easy industrial production, and can reduce the usage amount of vulcanizing agent because the vulcanizing agent is not needed before the accelerator is used. However, the catalyst has single active component system and limited catalytic activity, and the non-metal auxiliary agent has weak carbon deposition resistance. In summary, the existing hydrodesulfurization catalyst for coke oven gas has the main problems of low mass transfer efficiency, easy sintering of active components, carbon deposition and the like caused by the defect of carrier structure design. Therefore, the