阅读说明：本技术 一种脱硫催化剂及其制备方法 (Desulfurization catalyst and preparation method thereof ) 是由 杨成敏 刘丽 姚运海 段为宇 李扬 郭蓉 周勇 孙进 郑步梅 丁莉 于 2019-10-25 设计创作，主要内容包括：本发明公开了一种脱硫催化剂及其制备方法,包括氧化铝载体和活性金属组分,活性金属组分为硫化态第VIB族金属、氧化态第VIB族金属和氧化态第VIII族金属；表相与体相的硫化态第VIB族金属质量比为2.2:1～4.7:1；氧化态第VIB族金属氧化物和氧化态第VIII族金属氧化物分布于催化剂表相。制备方法包括：(1)将氧化态第VIB族金属前驱物原料、氧化铝、硝酸和水混合,挤出成型并经干燥处理,干燥后的物料进行硫化处理；(2)用含第VIB族和第族金属的浸渍液浸渍硫化后的物料,在惰性气氛下进行干燥和焙烧,得到脱硫催化剂。本发明催化剂具有更合理的金属状态分布,加氢脱硫活性高,适用于馏分油、蜡油、渣油、费托合成油、煤加氢生成油和煤焦化生成油等油品加氢脱硫过程。(The invention discloses a desulfurization catalyst and a preparation method thereof, wherein the desulfurization catalyst comprises an alumina carrier and active metal components, wherein the active metal components comprise a vulcanized state VIB group metal, an oxidized state VIB group metal and an oxidized state VIII group metal; sulfided group VIB metals in the surface and bulk phasesThe mass ratio is 2.2: 1-4.7: 1; the oxide state group VIB metal oxide and the oxide state group VIII metal oxide are distributed in the catalyst surface phase. The preparation method comprises the following steps: (1) mixing an oxidized VIB group metal precursor raw material, aluminum oxide, nitric acid and water, extruding, molding, drying, and vulcanizing the dried material; (2) by containing groups VIB and)

1. A desulfurization catalyst comprises an alumina carrier and an active metal component, and is characterized in that: the active metal components are a vulcanized state VIB group metal, an oxidized state VIB group metal and an oxidized state VIII group metal; the vulcanized VIB group metal is distributed in a bulk phase and a surface phase of the catalyst, and the mass ratio of the surface phase to the vulcanized VIB group metal in the bulk phase is 2.2: 1-4.7: 1; the oxide state VIB group metal oxide and the oxide state VIII group metal oxide are distributed in the catalyst surface phase; wherein the group VIB metal is preferably Mo and/or W, and the group VIII metal is preferably Co and/or Ni; based on the total weight of the catalyst, 1.3wt% -38.3wt% of sulfide-state VIB group metal, 0.2wt% -11.0wt% of oxidation-state VIB group metal, 0.2wt% -22.0wt% of oxidation-state VIII group metal and 39.7 wt% -98.3 wt% of alumina carrier.

2. The catalyst of claim 1, wherein: based on the total weight of the catalyst, the sulfurized VIB group metal accounts for 5.0wt% -29.0 wt%; the oxidation state group VIB metal is 0.5wt% -6.0 wt%; the oxidized group VIII metal is from 3.3wt% to 13.0 wt%; the weight percentage of the alumina carrier is 52-91.2 wt%.

3. A method for producing the desulfurization catalyst according to claim 1 or 2, characterized by comprising: (1) mixing an oxidized VIB group metal precursor raw material, aluminum oxide, nitric acid and water, then extruding and molding, drying, and vulcanizing the dried material; (2) by containing groups VIB andand (3) impregnating the vulcanized material in the step (1) with an impregnating solution of the group metal, and then drying and roasting the impregnated material in an inert atmosphere to obtain the desulfurization catalyst.

4. The method of claim 3, wherein: phosphates or ammonium salts of said group VIB metal in an oxidized state of step (1); the adding amount of the nitric acid is 0.2 to 8.9 weight percent of the dry basis of the alumina, and the adding amount of the water is 30 to 230 weight percent of the dry basis of the alumina.

5. The method of claim 3, wherein: the vulcanization treatment in the step (1) adopts dry vulcanization or wet vulcanization, and the vulcanization treatment conditions are as follows: the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h; the dry vulcanizing agent is hydrogen sulfide, and the wet vulcanizing agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide or n-butyl sulfide.

6. The method of claim 3, wherein: group VIB and group VIB of step (2)The dipping solution of the group metal adopts nitrate, acetate or sulfate solution; the group VIB metal is preferably Mo and/or W, the second groupThe group metals are preferably Ni and/or Co.

7. The method of claim 3, wherein: the inert atmosphere in the step (2) is N₂And an inert gas; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.

8. Use of the desulfurization catalyst of claim 1 or 2 in a hydrotreating process of distillate oil, wax oil, residual oil, fischer-tropsch synthesis oil, coal hydrogenation-derived oil, or coal coking-derived oil.

9. A desulfurization catalyst as recited in claim 1 or 2, which is subjected to a sulfiding treatment before use, wherein: the vulcanization treatment conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide or n-butyl sulfide; the vulcanization pressure is 3.2-16.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

10. A desulfurization catalyst according to claim 1 or 2, characterized in that: and after the sulfurization treatment, XPS energy spectrum analysis is adopted, wherein the molar proportion of the +4 valence VIB group metal content in the total VIB group metal content is 70-100%.

Technical Field

The invention relates to a preparation method of a desulfurization catalyst, in particular to a desulfurization catalyst in oil products and a preparation method thereof.

Background

The hydrodesulfurization of oils containing sulfur feedstocks generally uses metals from group VIB and group VIII in the sulfurized state as the active components. At present, the main development direction of oil product hydrogenation catalysts is to pursue higher activity and higher stability. The highly active hydrogenation catalyst active phase is usually dominated by the class II active phase. The preparation method of the II-type active center catalyst is to introduce a chelating agent in the preparation process of the hydrofining catalyst to promote the generation of II-type active centers.

CN102465005A discloses a start-up method of a II-type active center catalyst, wherein vulcanized oil is introduced at 135 ℃, which is beneficial to the catalyst to generate more II-type active centers. The patent uses fine control of the vulcanization process to obtain the type II active centers, and the vulcanization process in the actual production process is often difficult to realize.

CN106669706A discloses a preparation method of a hydrotreating catalyst, wherein an organic additive is added into an impregnation solution and is subjected to microwave drying, so that more II-type active centers are generated. The method obtains the II-type active center by the way of drying organic auxiliary agents and microwaves, has more control factors, needs fine operation and has higher requirements on the production process of the catalyst.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a desulfurization catalyst and a preparation method thereof. The catalyst has more reasonable metal state distribution and high hydrodesulfurization activity, and is suitable for the hydrodesulfurization process of oil products such as distillate oil, wax oil, residual oil, Fischer-Tropsch synthetic oil, coal hydrogenation generated oil and coal coking generated oil.

The desulfurization catalyst comprises an alumina carrier and active metal components, wherein the active metal components comprise a vulcanized state VIB group metal, an oxidized state VIB group metal and an oxidized state VIII group metal; the vulcanized VIB group metal is distributed in a bulk phase and a surface phase of the catalyst, and the mass ratio of the surface phase to the vulcanized VIB group metal in the bulk phase is 2.2: 1-4.7: 1; the oxide state VIB group metal oxide and the oxide state VIII group metal oxide are distributed in the catalyst surface phase; wherein the group VIB metal is preferably Mo and/or W, and the group VIII metal is preferably Co and/or Ni; the group VIB metal in the sulfided state is from 1.3 wt.% to 38.3 wt.%, preferably from 5.0 wt.% to 29.0 wt.%, based on the total weight of the catalyst; the group VIB metal in the oxidized state is from 0.2wt% to 11.0wt%, preferably from 0.5wt% to 6.0 wt%; the group VIII metal in an oxidized state is from 0.2wt% to 22.0wt%, preferably from 3.3wt% to 13.0 wt%; the weight percent of the alumina carrier is 39.7-98.3%, preferably 52-91.2%.

The preparation method of the desulfurization catalyst comprises the following steps:

(1) mixing an oxidized VIB group metal precursor raw material, aluminum oxide, nitric acid and water, then extruding and molding, drying, and vulcanizing the dried material;

(2) by containing groups VIB andand (3) impregnating the vulcanized material in the step (1) with an impregnating solution of the group metal, and then drying and roasting the impregnated material in an inert atmosphere to obtain the desulfurization catalyst.

In the method, the oxidation state VIB group metal precursor in the step (1) is generally mixed with materials such as aluminum oxide, nitric acid, water and the like by adopting phosphate or ammonium salt and the like, and then is extruded and molded by a pore plate with a proper shape; the adding amount of nitric acid is 0.2 to 8.9 weight percent of the dry basis of alumina, and preferably 0.3 to 4.6 weight percent; water is added in an amount of 30 to 230wt%, preferably 70 to 190wt%, of the alumina dry basis; the group VIB metal is preferably Mo and/or W.

In the method of the invention, the drying conditions in the step (1) are as follows: the drying temperature is 90-220 ℃, and the drying time is 1-5 hours.

In the method of the present invention, the vulcanization treatment in step (1) may be dry vulcanization or wet vulcanization, and the vulcanization treatment conditions are as follows: the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h; the dry vulcanizing agent is hydrogen sulfide, and the wet vulcanizing agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide or n-butyl sulfide.

In the process of the present invention, the groups VIB and VIB in step (2)The preparation method of the impregnation solution of the group metals is well known to those skilled in the art, and if nitrate, acetate, sulfate solution and the like are generally adopted, equal volume impregnation or other impregnation methods can be adopted, wherein the group VIB metal is preferably Mo and/or W, and the group VIB metal is preferably Mo and/or WThe group metals are preferably Ni and/or Co.

In the method of the invention, the inert atmosphere in the step (2) is N₂And an inert gas;the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.

The desulfurization catalyst is applied to the hydrotreating process of oil products such as distillate oil, wax oil, residual oil, Fischer-Tropsch synthetic oil, coal hydrogenation generated oil or coal coking generated oil.

The desulfurization catalyst of the present invention needs to be subjected to a sulfidation treatment before application, and the general sulfidation treatment conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is generally 3.2-16.4MPa, the vulcanization pressure can be adjusted according to different reaction raw materials and reaction purposes, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

The catalyst is subjected to vulcanization and then is analyzed by XPS energy spectrum, wherein the molar proportion of the +4 valence VIB group metal content in the total VIB group metal content is 70-100%.

The traditional catalyst exists in an oxidation state before vulcanization, while VIB group metals are difficult to vulcanize, VIII group metals are easy to vulcanize, the phenomenon that the VIII group metals in a vulcanization state are wrapped by the VIB group metals in a vulcanization state is easy to cause, the VIII group metals cannot fully play the function of an auxiliary agent, and the activity of the catalyst is reduced. The inventor adopts the mode of adding and vulcanizing different active metals step by step to adjust the proportion of the active metals in a catalyst bulk phase and a surface phase, firstly adds a VIB group metal oxidation state precursor on a carrier and carries out presulfurization, and then impregnates the VIB group and the VIB group on a sulfideA group metal. By impregnation on a support containing a sulphide of a group VIB metal, it is possible to obtainThe group metal covers the surface of the VIB group metal in a vulcanized state to give full play to the secondThe group metal auxiliary agent acts to create the condition of interaction between the group metal auxiliary agent and the group metal auxiliary agent, promote the generation of II-type active centers and improve the activity of the catalyst; the VIB group elements in the second impregnation process can disperse the VIII group elements in the impregnation process, so that the promotion effect of the VIII group elements is further improved, and the activity of the catalyst is further improved.

Detailed Description

The scheme and effect of the invention are further illustrated by the following examples. The content and the state of bulk phase metals of the desulfurization catalyst are represented by SEM and TEM electron microscope, and the content and the state of surface phase metals are analyzed by XPS energy spectrum. The composition of the catalyst provided by the invention can be characterized by combining inductively coupled plasma ICP and XPS energy spectrums, and the total content of VIB group metals and the total content of the VIB group metals in the catalyst are firstly characterized by ICPAnd (3) quantitatively characterizing the content of metal elements with different valence states in the catalyst by an XPS spectrometer.

The metal species of the catalyst bulk phase is characterized by adopting an SEM energy spectrum and a TEM electron microscope, a Quanta 200FEG type scanning electron microscope (FEI company) is adopted, the cross section of the catalyst is directly stuck on a sample table by using conductive adhesive, an ultrahigh vacuum mode is adopted for observation, the accelerating voltage is 20.0kV, and meanwhile, the metal composition in the catalyst bulk phase is inspected by combining an EDX technology. The TEM is characterized by adopting a JEM-2100 high-resolution transmission electron microscope produced by JEOL company of Japan, the type of the electron gun is LaB6, the accelerating voltage is 200 kV, the dot resolution is 0.23 nm, and the line resolution is 0.14 nm. The metal species of the watch phase were characterized by XPS spectroscopy.

The catalyst provided by the invention has metal vulcanization degree of Mo⁴⁺Or W⁴⁺The content represents the degree of metal sulfidation of the catalyst. Using 20mL/min of H at 320 DEG C₂S sulfurizing for 2h, characterizing the metal valence state of the surface of the sample by an XPS PEAK spectrometer, respectively fitting and peak-splitting Mo3d, W4f, Co2p and Ni2p energy spectrums by adopting XPS PEAK version4.0, and calculating according to the peak area to obtain the metal sulfurization degree.

Example 1

200g of alumina powder, 5mL of nitric acid with the concentration of 50m percent, 120g of water and a proper amount of ammonium molybdate are taken to ensure that MoO is coated on a section of semi-finished product₃Content 3% (using 470 ℃ C. roasting analysis as standard), thoroughly mixed and extruded through a 1.9mm diameter circular orifice plate, and then dried at 170 ℃ for 2h to obtain a semi-finished product A1. Then vulcanizing A1 by dry vulcanization to convert Mo into MoS₂And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 1.6 percent at the temperature of 360 ℃ and under the pressure of 3.3MPa to obtain a semi-finished product A2. Under the protection of nitrogen, adopting mixed aqueous solution of ammonium molybdate and cobalt nitrate to perform equal-volume impregnation on A2, so that MoO is newly added in the latter₃0.4% (using 470 ℃ roasting analysis as standard) and 0.9% (using 470 ℃ roasting analysis as standard), drying at 60 ℃ for 5h in nitrogen atmosphere, and roasting at 250 ℃ for 4h to obtain MoS₂-MoO₃-CoO/Al₂O₃Catalyst a 3.

Example 2

200g of alumina powder, 6mL of nitric acid with the concentration of 50m percent, 150g of water and a proper amount of ammonium molybdate are taken to ensure that MoO is coated on a section of semi-finished product₃Content 13% (based on 470 ℃ C. calcination analysis), thoroughly mixed and extruded through a 1.9mm diameter circular orifice plate, and then dried at 170 ℃ for 2 hours to obtain a semi-finished product B1. Then vulcanizing B1 by dry vulcanization to convert Mo into MoS₂And vulcanizing the mixture for 6 hours by using hydrogen with the hydrogen sulfide content of 1.6 percent at the temperature of 360 ℃ and under the pressure of 4.0MPa to obtain a semi-finished product B2. Under the protection of nitrogen, the mixed aqueous solution of ammonium molybdate and cobalt acetate is adopted to carry out equal-volume impregnation on B2, so that the MoO is newly added in the latter₃The content of 9.0 percent (analysis after roasting at 470 ℃ is taken as a standard) and the CoO content of 20.0 percent (analysis after roasting at 470 ℃ is taken as a standard), and then the mixture is dried for 5 hours at 60 ℃ in a nitrogen atmosphere and roasted for 4 hours at 280 ℃ to obtain MoS₂-MoO₃-CoO/Al₂O₃Catalyst B3.

Example 3

200g of alumina powder, 3mL of nitric acid with the concentration of 50m%, 140g of water and a proper amount of ammonium molybdate are taken to ensure that MoO is coated on a section of semi-finished product₃Content 24.0% (using 470 ℃ C. roasting analysis as standard), fully mixing and extruding with a circular orifice plate with diameter of 1.9mm,then dried at 170 ℃ for 2 hours to obtain a semi-finished product C1. Then C1 is vulcanized by dry vulcanization to convert Mo into MoS₂And vulcanizing the mixture for 8 hours by using hydrogen with the hydrogen sulfide content of 1.6 percent at the temperature of 360 ℃ and under the pressure of 5.0MPa to obtain a semi-finished product C2. Under the protection of nitrogen, C2 is subjected to equal-volume impregnation by using a mixed aqueous solution of ammonium metatungstate and nickel nitrate, so that WO is newly added to the C2₃The content of 7.0 percent (taking the analysis after roasting at 470 ℃ as a standard) and the NiO content of 11.0 percent (taking the analysis after roasting at 470 ℃ as a standard), and then the mixture is dried for 5 hours at 60 ℃ in a nitrogen atmosphere and roasted for 4 hours at 310 ℃ to obtain MoS₂-WO₃-NiO/Al₂O₃Catalyst C3.

Example 4

200g of alumina powder, 30g of silica sol with the silica content of 25m%, 6mL of nitric acid with the concentration of 50m%, 150g of water and a proper amount of ammonium molybdate are taken to ensure that MoO is formed on a section of semi-finished product₃Content 28.0% (based on 470 ℃ C. post-baking analysis), thoroughly mixed and extruded through a 1.9mm diameter circular orifice plate, and then dried at 170 ℃ for 2 hours to give a semi-finished product D1. Then D1 was sulfided using dry sulfiding to convert Mo therein to MoS₂And vulcanizing the mixture for 7 hours by using hydrogen with the hydrogen sulfide content of 1.6 percent at the temperature of 360 ℃ and under the pressure of 6.0MPa to obtain a semi-finished product D2. Under the protection of nitrogen, D2 was impregnated with a mixed aqueous solution of ammonium molybdate and nickel nitrate in equal volume, so that the latter was newly added with MoO₃The content of 1.0 percent (taking the analysis after roasting at 470 ℃ as a standard) and the NiO content of 5.0 percent (taking the analysis after roasting at 470 ℃ as a standard), then drying for 5 hours at 60 ℃ in a nitrogen atmosphere, and roasting for 4 hours at 400 ℃ to obtain MoS₂-MoO₃-NiO/Al₂O₃-SiO₂Catalyst D3.

Example 5

200g of alumina powder, 50g of silica sol with the silica content of 25m%, 6mL of nitric acid with the concentration of 50m%, 150g of water and a proper amount of ammonium metatungstate are taken, so that a section of semi-finished product is coated with WO₃Content 19.0% (based on 470 ℃ C. post-baking analysis), thoroughly mixed and extruded through a 1.9mm diameter circular orifice and then dried at 170 ℃ for 2 hours to give a semi-finished product E1. Then vulcanizing E1 by dry vulcanization to convert W intoBecome WS₂And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 1.6 percent at the temperature of 360 ℃ and under the pressure of 6.3MPa to obtain a semi-finished product E2. Under the protection of nitrogen, E2 is subjected to equal-volume impregnation by using a mixed aqueous solution of ammonium metatungstate and nickel nitrate, so that WO is newly added to the E2₃4.0% (using 470 ℃ roasting analysis as standard) and NiO content 7.0% (using 470 ℃ roasting analysis as standard), then drying at 60 ℃ for 5h under nitrogen atmosphere, roasting at 460 ℃ for 4h to obtain WS₂-WO₃-NiO/Al₂O₃-SiO₂Catalyst E3.

Example 6

200g of alumina powder, 20g of silica sol with the silica content of 25m%, 6mL of nitric acid with the concentration of 50m%, 150g of water and a proper amount of ammonium metatungstate are taken, so that a section of semi-finished product is coated with WO₃Content 17.0% (based on 470 ℃ C. post-baking analysis), thoroughly mixed and extruded through a 1.9mm diameter circular orifice and then dried at 170 ℃ for 2 hours to give a semi-finished product F1. And then vulcanizing F1 by dry vulcanization to convert W into WS₂And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 1.6 percent at the temperature of 360 ℃ and under the pressure of 4.7MPa to obtain a semi-finished product F2. Under the protection of nitrogen, the mixed aqueous solution of ammonium molybdate and nickel acetate is used for carrying out equal-volume impregnation on the F2, so that MoO is newly added to the latter₃2.0% (using 470 ℃ roasting analysis as standard) and NiO content 8.0% (using 470 ℃ roasting analysis as standard), drying at 60 deg.C for 5h in nitrogen atmosphere, and roasting at 360 deg.C for 4 hr to obtain WS₂-MoO₃-NiO/Al₂O₃-SiO₂Catalyst F3.

Example 7

200g of alumina powder, 16g of mixed hydrocracking catalyst powder, 9mL of nitric acid with the concentration of 50m%, 150g of water and a proper amount of ammonium metatungstate are taken, so that a section of semi-finished product is coated with WO₃22.0% NiO content and 0.2% NiO content (both based on 470 ℃ C. roasting analysis), mixed thoroughly and extruded through a 1.9mm diameter circular orifice plate, and then dried at 170 ℃ for 2 hours to give a semi-finished product G1. Then vulcanizing G1 by dry vulcanization to convert W into WS₂The strip is prepared by hydrogen with the hydrogen sulfide content of 1.6 percent at 360 ℃ and 5.2MPaVulcanization was carried out under the condition for 6 hours to obtain a semi-finished product G2. Under the protection of nitrogen, G2 is subjected to equal-volume impregnation by using a mixed aqueous solution of ammonium metatungstate and nickel nitrate, so that WO is newly added to the G2₃3.0% (using 470 ℃ roasting analysis as standard) and NiO content 6.0% (using 470 ℃ roasting analysis as standard), drying at 60 deg.C for 5h in nitrogen atmosphere, and roasting at 340 deg.C for 4 hr to obtain WS₂-Ni₂S₃-WO₃-NiO/Al₂O₃-SiO₂Catalyst G3.

Comparative example 1

This comparative example is compared to example 2.

200g of alumina powder, 6mL of nitric acid with the concentration of 50m percent and 150g of water are taken, fully mixed, extruded and molded by a circular orifice plate with the diameter of 1.9mm, and then dried and roasted to obtain the alumina carrier. Soaking ammonium molybdate and cobalt acetate aqueous solution on alumina carrier in equal volume to make MoO on a section of semi-finished product₃22 percent of content and 20.0 percent of CoO content (both are analyzed as a standard after roasting at 470 ℃), then drying for 2h at 170 ℃, and roasting for 4h at 280 ℃ to obtain MoO₃-CoO/Al₂O₃And (4) catalyst DB.

Comparative example 2

This comparative example is compared to example 5.

200g of alumina powder, 50g of silica sol with the silica content of 25m%, 6mL of nitric acid with the concentration of 50m% and 150g of water are taken, fully mixed and extruded by a circular orifice plate with the diameter of 1.9mm, and then dried and roasted to obtain the silicon-containing alumina carrier. Equal volume impregnation of ammonium metatungstate and nickel nitrate aqueous solution on a silicon-containing alumina support, such that a section of the semi-finished product is coated with WO₃23.0 percent of NiO (both taking the analysis after roasting at 470 ℃ as a standard), then drying at 170 ℃ for 2h, roasting at 460 ℃ for 4h to obtain WO₃-NiO/Al₂O₃-SiO₂Catalyst DE.

TABLE 1 catalyst active Metal content and distribution

Example 8

This example illustrates the hydrodesulfurization reaction performance of the catalyst of the present invention on diesel fuel.

The adopted evaluation raw oil is mixed diesel oil provided by a certain refinery of China Petroleum chemical. The sulfur content was 13800. mu.g/g, and the nitrogen content was 750. mu.g/g.

Catalysts A3 to G3, comparative examples DB and DE were each evaluated for reaction performance using a 200mL trickle bed hydrogenation unit.

Presulfurizing conditions of the catalyst: using a catalyst containing 2.1wt% CS₂The space velocity of the aviation kerosene is 1.1h^-1Presulfurizing the catalyst at the pressure of 8.2MPa with the hydrogen-oil volume ratio of 350: 1.

The prevulcanisation process is as follows: feeding pre-vulcanized oil at 110 ℃, feeding oil for 2h, vulcanizing at constant temperature for 2h, heating to 140 ℃ at 15 ℃/h, vulcanizing at constant temperature for 4h, heating to 220 ℃ at 6 ℃/h, vulcanizing at constant temperature for 10h, heating to 270 ℃ at 6 ℃/h, vulcanizing at constant temperature for 6h, heating to 350 ℃ at 12 ℃/h, vulcanizing at constant temperature for 6h, naturally cooling to 110 ℃, and finishing the pre-vulcanization.

The evaluation reaction conditions were: the operating pressure is 9.5MPa, the reaction temperature is 340 ℃, and the volume space velocity is 1.5h^-1The hydrogen-oil volume ratio was 350:1, and the evaluation results are shown in Table 1.

TABLE 1 Properties of catalyst and evaluation results

The evaluation results in the table show that the active metal of the catalyst of the present invention has a high degree of sulfidation and the desulfurization activity of the catalyst is high.