Iron-molybdenum hydrogenation catalyst for organic sulfur and preparation method of iron-molybdenum hydrogenation catalyst

Abstract

The invention relates to the technical field of organic chemical catalysts, in particular to a cylindrical iron-molybdenum hydrogenation catalyst for removing organic sulfur in coke oven gas through hydro-conversion and a preparation method of the cylindrical iron-molybdenum hydrogenation catalyst. The technical scheme adopted by the invention is as follows: the catalyst comprises the following components in parts by weight: 250-350 parts by weight of Al2O3 carrier in terms of Al2O3; 35 to 45 parts by weight of ZnO; 3-5 parts by weight of iron oxide in terms of Fe; 13-20 parts by weight of molybdenum oxide in terms of molybdenum; the Al2O3 carrier is prepared by drying, mixing, forming and roasting a neutralized material and a hydrate, and the hydrate is prepared by slurrying and filter-pressing pseudo-boehmite. The catalyst has the advantages that the usage amounts of the Al2O3 carrier, ZnO, Fe and Mo are limited, so that the catalyst keeps Mo as a main active phase, and a proper amount of Fe and ZnO assistants are matched with Mo, so that the synergistic effect of the assistants can be efficiently exerted.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemical catalysts, and in particular to a cylindrical iron-molybdenum hydrogenation catalyst for removing organic sulfur from coke oven gas by hydrogenation conversion and a preparation method thereof. Background Art

[0002] my country is the largest producer and exporter of coke. With the continuous improvement of my country's economic level, the coke industry has developed rapidly. However, a large amount of coke oven gas is produced as a by-product during the coking process. Coke oven gas contains toxic impurities such as H2S, CS2, thiophene, mercaptan, and sulfide. These impurities not only corrode equipment and clog pipelines, but also cause catalyst deactivation and affect the catalytic effect. Among them, H2S is the most typical impurity, while thiophene, mercaptan, and sulfide have high chemical stability and are difficult to remove. Therefore, how to improve the conversion rate of thiophene, mercaptan, and sulfide by organic sulfur hydrogenation catalysts, increase the service life of catalysts, and reduce production costs is a top priority.

[0003] The general methods for removing organic sulfur include oxidation, hydrolysis conversion and hydrogenation conversion. The most effective method currently solved by technology is hydrogenation conversion. In the prior art, Chinese patent document CN101797508A discloses a method for preparing a coke oven gas hydrogenation desulfurization catalyst, which includes the following steps: (1) Selecting a formed γ-Al2O3 carrier, and drying it at 120°C for 2-10 hours; (2) Weigh a certain amount of ammonium molybdate and dissolve it in deionized water. Add a certain amount of organic acid, then add cobalt salt, and finally add iron salt under constant stirring to prepare an impregnation solution. (3) The carrier obtained in step (1) is impregnated into the impregnation solution prepared in step (2) by an equal amount impregnation method for 2-12 hours, and then dried at 120°C and calcined at 500°C for 2-4 hours to obtain a coke oven gas hydrodesulfurization catalyst. The hydrodesulfurization catalyst is prepared by an impregnation method, and the active components are evenly distributed and have a high utilization rate. When the catalyst is used in coke oven gas, the hydrodesulfurization rate is greater than 90%, the low temperature 300°C hydrodesulfurization rate is about 80%, the methanation CO disproportionation carbon deposition reaction is small, and the long-term operation performance is stable. However, when the catalyst is used to remove organic sulfides such as thiophene in sulfides, the requirements for the initial reaction temperature and hydrogen partial pressure are relatively high. In order to solve the above technical problems, in the prior art, Chinese patent document CN1100004A discloses a coking crude benzene hydrorefining composite bed catalyst, which is composed of two parts of catalysts A and B, wherein the A catalyst contains the following components: CoO, 0.1-6wt%; ZnO, 0.1-6wt%; MoO3, 8-20wt%; the remainder is Al2O3; the preparation method of the A catalyst is to impregnate the alumina carrier with Co and Zn, Mo salt solutions respectively; the B catalyst is a ZnO independent catalyst. The above catalyst is used in combination with the A and B catalysts, and the A catalyst can promote the conversion of thiophene in the gas into H2S (C4H4S+4H2=C4H10+H2S), and the ZnO independent catalyst thereafter can absorb H2S in the gas, and the above catalyst can operate at a lower starting temperature.

[0004] Although the above-mentioned hydrodesulfurization catalyst in the prior art can remove organic sulfur from the gas, the problem still exists that the organic sulfur conversion rate of the above-mentioned catalyst is low. In actual industrial production, the gas treated by the above-mentioned hydrodesulfurization catalyst still contains a certain amount of organic sulfur. How to improve the hydrodesulfurization catalyst to further improve the conversion and removal efficiency of organic sulfur is a technical problem that has not been solved in the prior art. Summary of the invention

[0005] The purpose of the present invention is to provide an organic sulfur iron-molybdenum hydrogenation catalyst, which can solve the problems of low conversion and removal efficiency of organic sulfides and serious carbon deposition in the prior art hydrodesulfurization catalyst when used to remove organic sulfides in coke oven gas, and further provide an organic sulfur hydrogenation catalyst with high organic sulfur conversion and removal efficiency and reduced carbon deposition. When used to remove organic sulfides in coke oven gas, it has high organic sulfur conversion and removal efficiency, and the reason is that ZnO, Fe and Mo can produce significant synergistic effects under the above weight ratio conditions; in the present invention, by limiting the amount of Al2O3 carrier, ZnO, Fe and Mo, the catalyst keeps Mo as its main active phase, and the appropriate amount of Fe and ZnO additives cooperate with Mo, which can effectively exert their synergistic effects and effectively control the acidity and alkalinity of the catalyst, thereby effectively improving the organic sulfur conversion and removal efficiency.

[0006] The technical solution of the present invention is as follows: An organic sulfur iron-molybdenum hydrogenation catalyst, characterized in that it comprises the following components in parts by weight: Al2O3 carrier: 250-350 parts by weight as Al2O3; ZnO, 35-45 parts by weight; Iron oxide, calculated as Fe, 3-5 parts by weight; Molybdenum oxide, calculated as molybdenum, 13-20 parts by weight; The Al2O3 carrier is prepared by drying, mixing, molding and calcining a neutralizing material and a hydrate, wherein the hydrate is prepared by slurrying and filter pressing of pseudo-boehmite; the preparation method of the neutralizing material is: (a) mixing aluminum hydroxide and an alkaline solution and reacting them at 120-150° C.; (b) adding acid to the solution prepared in step (a) for neutralization; (c) taking out the product generated after neutralization by the acid solution, washing it with water and filtering it to obtain a neutralized material; the mass ratio of the neutralized material to the hydrate is 1-1.5; the alkaline solution is one or more of NaOH, KOH, LiOH, Ca(OH)2 and ammonia solution; the acid solution is one or more of nitric acid, citric acid, acetic acid, oxalic acid, and tartaric acid; in the step (a), the equivalent concentration ratio of aluminum hydroxide to alkali is 2:3-2:4.5; the drying temperature is 115°C-125°C, the drying time is 2-5h, the roasting temperature is 450°C-550°C, and the roasting time is 2-4h.

[0007] Furthermore, the Al2O3 carrier is formed into tablets after mixing the neutralizing material and the hydrate.

[0008] Furthermore, graphite is added to the mixture of the neutralizing material and the hydrate before tableting.

[0009] Furthermore, the organic weak acid is citric acid with a mass fraction of 0.38wt%-0.55wt%.

[0010] Furthermore, the positioning safety molded connecting rod (3) is made of plastic material.

[0011] A method for preparing an organic sulfur iron-molybdenum hydrogenation catalyst, characterized in that it comprises the following steps: (1) weighing an initial raw material of iron oxide and adding it to an organic weak acid solution, heating and stirring until the precipitate is dissolved, wherein the amount of the initial raw material added is 3-5 parts by weight based on Fe; (2) adding ammonium molybdate to the solution prepared in step (1), and adding ammonia water while stirring until the precipitate is dissolved, wherein the amount of ammonium molybdate added is 13-20 parts by weight based on molybdenum, to prepare an active component solution; (3) In the process of preparing the Al2O3 carrier, the active component solution prepared in step (2) is added when mixing the neutralizing material and the hydrate, and then 35-45 parts by weight of zinc oxide is added after drying. After molding and calcination, the organic sulfur hydrogenation catalyst is obtained.

[0012] Furthermore, amorphous ferric hydroxide is also added in step (3), and the mass ratio of ferric nitrate to amorphous ferric hydroxide is 1:3-4:1.

[0013] Furthermore, in the step (3), one or both of attapulgite and hydroxymethyl cellulose are added.

[0014] A method for using an organic sulfur iron-molybdenum hydrogenation catalyst, characterized in that the organic sulfur hydrogenation catalyst is pre-sulfurized before use.

[0015] Beneficial effects of the present invention: 1. In the process of preparing the Al2O3 carrier, an active component solution is added when mixing the neutralizing material and the hydrate, and ZnO is added after drying, and the organic sulfur hydrogenation catalyst is obtained by molding and calcining. Compared with the prior art that introduces the ZnO component into the system by impregnation, the preparation method of the organic sulfur hydrogenation catalyst of the present invention has the advantages that ZnO is directly added to the Al2O3 carrier added with the active component, and is molded by a physical method, so that the structure of ZnO is basically unchanged, and ZnO particles are evenly dispersed on the surface of the carrier, which can not only improve the activity of the Al2O3 carrier, but also promote the adsorption activation and overflow of hydrogen on the catalyst surface. In addition, ZnO can also effectively control the acidity and alkalinity of the catalyst.

[0016] 2. When used for removing organic sulfides in coke oven gas, it has a high organic sulfur conversion and removal efficiency, the reason being that under the above weight ratio conditions, ZnO, Fe and Mo can produce a significant synergistic effect; in the present invention, by limiting the amounts of Al2O3 carrier, ZnO, Fe and Mo, the catalyst maintains Mo as its main active phase, while appropriate amounts of Fe and ZnO additives are combined with Mo, which can effectively exert their synergistic effect and effectively control the acidity and alkalinity of the catalyst, thereby effectively improving the organic sulfur conversion and removal efficiency. DETAILED DESCRIPTION

[0017] An organic sulfur iron-molybdenum hydrogenation catalyst, characterized in that it comprises the following components in parts by weight: Al2O3 carrier: 250-350 parts by weight as Al2O3; ZnO, 35-45 parts by weight; Iron oxide, calculated as Fe, 3-5 parts by weight; Molybdenum oxide, calculated as molybdenum, 13-20 parts by weight; The Al2O3 carrier is prepared by drying, mixing, molding and calcining a neutralizing material and a hydrate, wherein the hydrate is prepared by slurrying and filter pressing of pseudo-boehmite; the preparation method of the neutralizing material is: (a) mixing aluminum hydroxide and an alkaline solution and reacting them at 120-150° C.; (b) adding acid to the solution prepared in step (a) for neutralization; (c) taking out the product generated after neutralization by the acid solution, washing it with water and filtering it to obtain a neutralized material; the mass ratio of the neutralized material to the hydrate is 1-1.5; the alkaline solution is one or more of NaOH, KOH, LiOH, Ca(OH)2 and ammonia solution; the acid solution is one or more of nitric acid, citric acid, acetic acid, oxalic acid, and tartaric acid; in the step (a), the equivalent concentration ratio of aluminum hydroxide to alkali is 2:3-2:4.5; the drying temperature is 115°C-125°C, the drying time is 2-5h, the roasting temperature is 450°C-550°C, and the roasting time is 2-4h.

[0018] A method for preparing an organic sulfur iron-molybdenum hydrogenation catalyst, characterized in that it comprises the following steps: (1) weighing an initial raw material of iron oxide and adding it to an organic weak acid solution, heating and stirring until the precipitate is dissolved, wherein the amount of the initial raw material added is 3-5 parts by weight based on Fe; (2) adding ammonium molybdate to the solution prepared in step (1), and adding ammonia water while stirring until the precipitate is dissolved, wherein the amount of ammonium molybdate added is 13-20 parts by weight based on molybdenum, to prepare an active component solution; (3) In the process of preparing the Al2O3 carrier, the active component solution prepared in step (2) is added when the neutralizing material and the hydrate are mixed, and then 35-45 parts by weight of zinc oxide is added after drying, and the organic sulfur hydrogenation catalyst is obtained after molding and roasting. The organic sulfur hydrogenation catalyst is pre-sulfurized before use.

[0019] The preparation method of the organic sulfur hydrogenation catalyst of the present invention is as follows: in the process of preparing the Al2O3 carrier, an active component solution is added when mixing the neutralizing material and the hydrate, and ZnO is added after drying, and the organic sulfur hydrogenation catalyst is obtained by molding and roasting. Compared with the prior art that introduces the ZnO component into the system by the impregnation method, the preparation method of the organic sulfur hydrogenation catalyst of the present invention has the advantages that ZnO is directly added to the Al2O3 carrier added with the active component, and the molding is performed by a physical method, so that the structure of ZnO is basically unchanged, and the ZnO particles are evenly dispersed on the surface of the carrier, which can not only improve the activity of the Al2O3 carrier, but also promote the adsorption activation and overflow of hydrogen on the catalyst surface, and ZnO can also effectively control the acidity and alkalinity of the catalyst.

[0020] Compared with the prior art, the organic sulfur hydrogenation catalyst of the present invention has the following advantages (1) The organic sulfur hydrogenation catalyst of the present invention comprises an Al2O3 carrier, in which Al2O3 accounts for 250-350 parts by weight; ZnO, in which ZnO accounts for 35-45 parts by weight; iron oxide, in which Fe accounts for 3-5 parts by weight; and molybdenum oxide, in which molybdenum accounts for 13-20 parts by weight. When used to remove organic sulfides in coke oven gas, it has a high organic sulfur conversion and removal efficiency. The reason is that under the above-mentioned weight ratio conditions, ZnO, Fe and Mo can produce a significant synergistic effect; 13-20 weight parts of Mo in the organic sulfur hydrogenation catalyst of the present invention is the main active phase of the catalyst. The higher the dispersion of Mo on the carrier, the better the catalyst performance. The addition of Fe produces a synergistic promotion effect on the catalysis of Mo. After pre-sulfurization, Fe and Mo form a tetrahedral complex Fe2(MoS2)3, which has a very high catalytic hydrogenation activity. At the same time, the presence of Fe separates MoS2 crystals from each other, reduces the probability of dissolution between crystals, increases the dispersion of Mo on the carrier without reducing the specific surface area of ​​the carrier, thereby improving the activity of the carrier. ; At the same time, 35-45 parts by weight of ZnO added to the organic sulfur hydrogenation catalyst as an auxiliary agent has excellent synergistic effect with the iron and molybdenum active components, specifically: the addition of ZnO, on the one hand, affects the Fe3+ in Fe2(MoS2)3, making the structure of Fe2(MoS2)3 more stable, reducing the generation of Fe2+ and FeMoS2, thereby improving the activity of the catalyst; on the other hand, it promotes the transformation of FeS to the sulfur-rich state of Fe2S3 with high hydrogenation activity, thereby enhancing the synergistic effect of Fe on Mo; in addition, ZnO itself can absorb H2S, thereby moving the reaction (C4H4S+4H2=C4H10+H2S) in the positive direction, thereby improving the conversion rate of organic sulfur; at the same time, the addition of ZnO can also promote the adsorption, activation and overflow of hydrogen on the catalyst surface. In the present invention, the amounts of Al2O3 carrier, ZnO, Fe and Mo are limited so that the catalyst maintains Mo as its main active phase, and appropriate amounts of Fe and ZnO additives are combined with Mo to effectively exert their synergistic effect and effectively control the acidity and alkalinity of the catalyst, thereby effectively improving the conversion and removal efficiency of organic sulfur.

[0021] (2) The organic sulfur hydrogenation catalyst of the present invention, the Al2O3 carrier is made by mixing, molding, drying and calcining a neutralizing material and a hydrate, wherein the hydrate is directly obtained by filter pressing with pseudo-boehmite, and mainly exists in the form of γ-Al2O3, and does not contain other impurities, thereby ensuring that the γ-Al2O3 carrier of the hydrogenation catalyst has better performance and more uniform adsorption of iron and molybdenum active components. The present invention stipulates that the neutralizing material uses aluminum hydroxide as a raw material, and is mixed with an alkaline solution at 120-150°C to react, which can effectively improve the activity of the carrier, thereby improving the catalytic performance of the hydrogenation catalyst. The neutralizing material in the present invention can significantly reduce the carbon deposition of the catalyst, thereby improving the activity of the catalyst.

[0022] (3) The organic sulfur hydrogenation catalyst of the present invention is formed by mixing the neutralizing material and the hydrate and then beating into tablets. The tableting is to mix several raw materials together by physical methods to keep the original state of the components. In addition, the tablets have high compressive strength, are not easy to break during use, and have a long service life.

[0023] (4) The organic sulfur hydrogenation catalyst of the present invention, based on the use of ferric nitrate as the raw material of iron oxide, further adds amorphous ferric hydroxide oxide as the initial raw material of iron oxide, and further controls the mass ratio of the ferric nitrate and the amorphous ferric hydroxide oxide to be 1:2.5-3.5:1, which can effectively improve the synergistic effect between Fe, Mo and ZnO, promote the adsorption of hydrogen on the surface of the organic sulfur hydrogenation catalyst, and at the same time enhance the conversion and removal of organic sulfides. Example 1

[0024] The organic sulfur hydrogenation catalyst described in this embodiment includes the following components by weight: Al2O3 carrier, calculated as Al2O3, 255g; ZnO, 45g; iron oxide, calculated as Fe, 7g; molybdenum oxide, calculated as molybdenum, 17g. The Al2O3 carrier described in this embodiment is prepared by a neutralizing material and a hydrate with a mass ratio of 1:1.5, which are dried at 125°C for 2.5h, mixed and formed into sheets, and calcined at 500°C for 3h; wherein the hydrate is prepared by slurrying and filter pressing of pseudo-boehmite; the preparation method of the neutralizing material is: (a) mixing aluminum hydroxide and Ca(OH)2 in an equivalent concentration ratio of 2:4 and reacting them at 120°C; (b) adding tartaric acid to the solution prepared in step (a) for neutralization; (c) taking out the product generated after the tartaric acid neutralization, washing it with water and filtering it to obtain a neutralized material. The preparation method of the organic sulfur hydrogenation catalyst comprises the following steps: (1) Prepare a citric acid solution with a mass fraction of 0.46 wt%; (2) Adding ferric nitrate to the above citric acid solution, heating and stirring until the precipitate is dissolved, the amount of ferric nitrate added as the initial raw material is 1.6 g in terms of Fe; (3) adding ammonium molybdate to the solution prepared in step (2), and adding ammonia water while stirring until the precipitate is dissolved, wherein the amount of ammonium molybdate added is 17 g based on molybdenum, to prepare an active component solution; (4) In the process of preparing the Al2O3 carrier, the active component solution prepared in step (3) is added when mixing the neutralizing material and the hydrate. After drying, 45g of zinc oxide and a certain amount of amorphous oxyhydroxide iron are added in succession, wherein the amount of the amorphous oxyhydroxide iron added is 4.4g based on Fe. 30g of attapulgite and 140g of hydroxymethyl cellulose are added and mixed evenly. The sample is dried at 125°C for 3h, and then an appropriate amount of graphite is added. Finally, the organic sulfur hydrogenation catalyst is obtained after the tableting and calcination.

[0025] The prepared organic sulfur hydrogenation catalyst has a particle size of 40-60 mesh and a loading amount of 1 mL. CS2 is introduced for pre-sulfurization before use, and the process is repeated 8-10 times. The injection amount of CS2 is 3-5 μL each time, so that the catalyst is fully pre-sulfurized; further, at a temperature of 350°C, carrier gas N2, reaction gas H2 and O2 are introduced into the catalyst at rates of 13 mL / min, 28 mL / min and 55 mL / min, respectively, and then 2-3 μL of organic sulfur standard is added to the catalyst. After the reaction, the organic sulfur conversion rate is measured by GC9890A gas chromatograph to be 97.62%. Example 2

[0026] The organic sulfur hydrogenation catalyst described in this embodiment includes the following components by weight: Al2O3 carrier, calculated as Al2O3, 350g; ZnO, 40g; iron oxide, calculated as Fe, 6g; molybdenum oxide, calculated as molybdenum, 16g. The Al2O3 carrier described in this embodiment is prepared by a neutralizing material and a hydrate with a mass ratio of 1:1.5, which are successively dried at 120°C for 3h, mixed and formed into sheets, and roasted at 550°C for 2h. The hydrate is prepared by slurrying and filter pressing of pseudo-boehmite; the preparation method of the neutralizing material is: (a) mixing aluminum hydroxide and an aqueous ammonia solution at an equivalent concentration ratio of 2:3.5, and reacting at 130° C.; (b) adding oxalic acid to the solution prepared in step (a) for neutralization; (c) taking out the product generated after the oxalic acid neutralization, washing it with water and filtering it to obtain a neutralized material. The preparation method of the organic sulfur hydrogenation catalyst comprises the following steps: (1) Prepare a citric acid solution with a mass fraction of 0.42wt%; (2) Adding ferric nitrate to the above citric acid solution, heating and stirring until the precipitate is dissolved, the amount of ferric nitrate added as the initial raw material is 4.8 g in terms of Fe; (3) adding ammonium molybdate to the solution prepared in step (2), and adding ammonia water while stirring until the precipitate is dissolved, wherein the amount of ammonium molybdate added is 16 g based on molybdenum, to prepare an active component solution; (4) In the process of preparing the Al2O3 carrier, the active component solution prepared in step (3) is added when mixing the neutralizing material and the hydrate, and after drying, 40g of zinc oxide and a certain amount of amorphous oxyhydroxide iron are added, wherein the amount of amorphous oxyhydroxide iron added is 1.2g based on Fe, and 35g of attapulgite and 150g of hydroxymethyl cellulose are added and mixed evenly. After being formed into tablets and calcined together, the organic sulfur hydrogenation catalyst is obtained.

[0027] The prepared organic sulfur hydrogenation catalyst was pre-sulfurized by introducing CS2 before use, and the process was repeated 8-10 times, with the injection amount of CS2 being 3-5 μL each time, so that the catalyst was fully pre-sulfurized; further, at a temperature of 350°C, carrier gas N2, reaction gas H2 and O2 were introduced into the catalyst with a particle size of 40-60 mesh and a loading amount of 1 mL, and the introduction rates were 13 mL / min, 28 mL / min and 55 mL / min, respectively, and then 2-3 μL of organic sulfur standard was added to the catalyst. After the reaction, the organic sulfur conversion rate was measured by GC9890A gas chromatograph to be 98.21%. Example 3

[0028] The organic sulfur hydrogenation catalyst described in this embodiment includes the following components by weight: Al2O3 carrier, calculated as Al2O3, 360g; ZnO, 48g; iron oxide, calculated as Fe, 7g; molybdenum oxide, calculated as molybdenum, 20g. The Al2O3 carrier described in this embodiment is prepared by a neutralizing material and a hydrate with a mass ratio of 1:1.5, which are successively dried at 130°C for 3h, mixed and formed into sheets, and calcined at 500°C for 3h; wherein the hydrate is prepared by slurrying and filter pressing of pseudo-boehmite; the preparation method of the neutralizing material is: (a) mixing aluminum hydroxide and KOH in an equivalent concentration ratio of 2:4.5 and reacting at 135° C.; (b) adding citric acid to the solution prepared in step (a) for neutralization; (c) taking out the product generated after the citric acid neutralization, washing it with water and filtering it to obtain a neutralized material.

[0029] The preparation method of the organic sulfur hydrogenation catalyst comprises the following steps: (1) Prepare a citric acid solution with a mass fraction of 0.43wt%; (2) Adding ferric nitrate to the above citric acid solution, heating and stirring until the precipitate is dissolved, the amount of ferric nitrate added as the initial raw material is 7 g in terms of Fe; (3) adding ammonium molybdate to the solution prepared in step (2), and adding ammonia water while stirring until the precipitate is dissolved, wherein the amount of ammonium molybdate added is 20 g based on molybdenum, to prepare an active component solution; (4) In the process of preparing the Al2O3 carrier, the active component solution prepared in step (3) is added when mixing the neutralizing material and the hydrate, and then 48g of zinc oxide and 138g of hydroxymethyl cellulose are added after drying, and the mixture is mixed evenly. The sample is dried at 120°C for 4h, and then an appropriate amount of graphite is added. Finally, the mixture is subjected to the tableting and calcination to obtain the organic sulfur hydrogenation catalyst.

[0030] The prepared organic sulfur hydrogenation catalyst is pre-sulfurized by introducing CS2 before use, and the process is repeated 8-10 times, with the injection amount of CS2 being 3-5 μL each time, so that the catalyst is fully pre-sulfurized; further, at a temperature of 350°C, carrier gas N2, reaction gas H2 and O2 are introduced into the catalyst with a particle size of 40-60 mesh and a loading amount of 1 mL, and the introduction rates are 15 mL / min, 35 mL / min and 65 mL / min, respectively, and then 2-3 μL of organic sulfur standard is added to the catalyst. After the reaction, the organic sulfur conversion rate is measured by GC9890A gas chromatograph to be 96.77%.

[0031] In order to further demonstrate the technical effect of the technical solution described in the present invention, the present invention also sets the following comparative example Comparative Example 1 The organic sulfur hydrogenation catalyst in this comparative example is composed of two catalysts, A and B, wherein the B catalyst is ZnO, and the A catalyst includes the following components: CoO, 3.6wt%; ZnO, 3.5wt%; MoO, 14wt%; Al2O3 support, remainder.

[0032] The preparation steps of catalyst A are as follows: take 220g of γ-Al2O3 calcined at 500℃×3.5hr, first soak Co and Zn, take 62.07g of cobalt nitrate and 55.21g of zinc nitrate and dissolve them in deionized water to form 300mL of Co and Zn nitrate solution, soak the above γ-Al2O3, the water absorption rate is 0.51mL / g, the wet ball is dried at 100-120℃×13hr, and then decomposes the nitrate at 360℃×5hr to obtain 221g of Co-Zn-Al2O3 soaked balls; the second step is to soak Mo, take 128.3g of ammonium molybdate and dissolve it in 1:1 ammonia water to 280mL of ammonium molybdate solution, soak the above Co-Zn-Al2O3 decomposition and dry ball, the water absorption rate is 0.47mL / g, dry at 90-120℃×14hr, and then activate and calcine at 550℃ to obtain 252.12g of catalyst A.

[0033] Catalysts A and B were loaded into a reactor, wherein catalyst A was located at the upper part with a particle size of 45-55 mesh, and catalyst B ZnO was located at the lower part with a particle size of 45-55 mesh. The loading ratio (volume ratio) of catalysts A and B was 1:1. Before use, CS2 was introduced into the reactor for presulfurization, which was repeated 8-10 times, with each CS2 injection volume of 3-5 μL to allow the catalyst to be fully presulfurized. Further, at a temperature of 350°C, carrier gas N2, reaction gas H2 and O2 were introduced into the catalyst at rates of 13 mL / min, 28 mL / min and 55 mL / min, respectively. Subsequently, 2-3 μL of an organic sulfur standard was added to the catalyst. After the reaction, the organic sulfur conversion rate was measured by GC9890A gas chromatograph to be 85.21%.

[0034] The organic sulfur conversion rate of the catalyst in this comparative example 1 is lower than that of Examples 1 and 2 of the present invention. It can be seen that the catalyst in Example 1 of the present invention has better technical effect than that of Comparative Example 1.

[0035] Comparative Example 2 The organic sulfur hydrogenation catalyst in this comparative example has the same component contents as those in Example 3, and includes the following components in parts by weight: Al2O3 carrier, 360 g in terms of Al2O3; 48 g of ZnO; 7 g of iron oxide in terms of Fe; and 20 g of molybdenum oxide in terms of molybdenum.

[0036] The Al2O3 carrier in this comparative example is prepared by successively drying a neutralizing material and a hydrate in a mass ratio of 1:1.5 at 130°C for 3h, mixing and forming a sheet, and calcining at 500°C for 3h; wherein the hydrate is prepared by slurrying and filter pressing of pseudo-boehmite; the preparation method of the neutralizing material is: (a) mixing aluminum hydroxide and KOH at an equivalent concentration ratio of 2:4.5 and reacting at 135°C; (b) adding tartaric acid to the solution prepared in step (a) for neutralization; (c) taking out the product generated after the tartaric acid neutralization, washing it with water and filtering it to obtain a neutralized material.

[0037] The preparation method of the organic sulfur hydrogenation catalyst comprises the following steps: (1) Prepare a citric acid solution with a mass fraction of 0.43wt%; (2) Adding ferric nitrate to the above citric acid solution, heating and stirring until the precipitate is dissolved, the amount of ferric nitrate added as the initial raw material is 7 g in terms of Fe; (3) adding ammonium molybdate to the solution prepared in step (2), and adding ammonia water while stirring until the precipitate is dissolved, wherein the amount of ammonium molybdate added is 20 g based on molybdenum, to prepare an active component solution; (4) In the process of preparing the Al2O3 carrier, the active component solution prepared in step (3) is added when mixing the neutralizing material and the hydrate, and 155g of zinc nitrate and 138g of hydroxymethyl cellulose are added at the same time. The mixture is evenly mixed, and the sample is dried at 120°C for 4h. Then, an appropriate amount of graphite is added. Finally, the mixture is subjected to the tableting and calcination to obtain an organic sulfur hydrogenation catalyst.

[0038] The above-mentioned organic sulfur hydrogenation catalyst has a particle size of 40-60 mesh and a loading amount of 1 mL. CS2 is introduced for pre-sulfurization before use, and the process is repeated 8-10 times. The injection amount of CS2 each time is 3-5 μL, so that the catalyst is fully pre-sulfurized; further, at a temperature of 350°C, carrier gas N2, reaction gas H2 and O2 are introduced into the catalyst at rates of 15 mL / min, 35 mL / min and 65 mL / min, respectively, and then 2-3 μL of organic sulfur standard is added to the catalyst. After the reaction, the organic sulfur conversion rate is measured by GC9890A gas chromatograph to be 86.35%.

[0039] The organic sulfur conversion rate of the catalyst in this comparative example 2 is lower than that of Example 3 of the present invention. It can be seen that the technical solution of preparing the catalyst by directly doping ZnO in the present invention has a higher organic sulfur conversion rate than the catalyst prepared by loading ZnO by the impregnation method in Comparative Example 2. Obviously, the above examples are only examples for clear explanation and are not limitations on the implementation methods. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description.

[0040] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements or substitutions can be made without departing from the principles of the present invention. These improvements or substitutions should also be regarded as the scope of protection of the present invention.

Claims

1. An organosulfur iron-molybdenum hydrogenation catalyst, characterized in that: It includes the following components by weight: Al2O3 carrier: 250-350 parts by weight as Al2O3; ZnO, 35-45 parts by weight; Iron oxide, calculated as Fe, 3-5 parts by weight; Molybdenum oxide, calculated as molybdenum, 13-20 parts by weight; The Al2O3 carrier is prepared by drying, mixing, molding and calcining a neutralizing material and a hydrate, wherein the hydrate is prepared by slurrying and filter pressing of pseudo-boehmite; the preparation method of the neutralizing material is: (a) mixing aluminum hydroxide and an alkaline solution and reacting them at 120-150° C.; (b) adding acid to the solution prepared in step (a) for neutralization; (c) taking out the product generated after neutralization by the acid solution, washing it with water and filtering it to obtain a neutralized material; the mass ratio of the neutralized material to the hydrate is 1-1.5; the alkaline solution is one or more of NaOH, KOH, LiOH, Ca(OH)2 and ammonia solution; the acid solution is one or more of nitric acid, citric acid, acetic acid, oxalic acid, and tartaric acid; in the step (a), the equivalent concentration ratio of aluminum hydroxide to alkali is 2:3-2:4.5; the drying temperature is 115°C-125°C, the drying time is 2-5h, the roasting temperature is 450°C-550°C, and the roasting time is 2-4h.

2. An organic sulfur iron-molybdenum hydrogenation catalyst according to claim 1, characterized in that: The Al2O3 carrier is formed into tablets after mixing the neutralizing material and the hydrate.

3. An organosulfur iron-molybdenum hydrogenation catalyst according to claim 1, characterized in that: Graphite is added to the mixture of the neutralizing material and the hydrate before tableting.

4. An organosulfur iron-molybdenum hydrogenation catalyst according to claim 1, characterized in that: The organic weak acid is citric acid with a mass fraction of 0.38wt%-0.55wt%.

5. The organosulfur iron-molybdenum hydrogenation catalyst according to claim 1, characterized in that: The positioning safety molded connecting rod (3) is made of plastic material.

6. A method for preparing an organosulfur iron-molybdenum hydrogenation catalyst according to any one of claims 1 to 5, characterized in that: The steps include: (1) weighing an initial raw material of iron oxide and adding it to an organic weak acid solution, heating and stirring until the precipitate is dissolved, wherein the amount of the initial raw material added is 3-5 parts by weight based on Fe; (2) adding ammonium molybdate to the solution prepared in step (1), and adding ammonia water while stirring until the precipitate is dissolved, wherein the amount of ammonium molybdate added is 13-20 parts by weight based on molybdenum, to prepare an active component solution; (3) In the process of preparing the Al2O3 carrier, the active component solution prepared in step (2) is added when mixing the neutralizing material and the hydrate, and then 35-45 parts by weight of zinc oxide is added after drying. After molding and calcination, the organic sulfur hydrogenation catalyst is obtained.

7. An organosulfur iron-molybdenum hydrogenation catalyst according to claim 6, characterized in that: Amorphous ferric hydroxide is also added in the step (3), and the mass ratio of the ferric nitrate to the amorphous ferric hydroxide is 1:3-4:

1.

8. An organosulfur iron-molybdenum hydrogenation catalyst according to claim 6, characterized in that: In the step (3), one or both of attapulgite and hydroxymethyl cellulose are also added.

9. A method for using an organosulfur iron-molybdenum hydrogenation catalyst according to any one of claims 1 to 5, characterized in that: The organic sulfur hydrogenation catalyst is presulfided before use.